TLHX Design PDF

Steam Cracking of Complex Hydrocarbon Mixtures
Steven Vandermeersch
Promotor: prof. dr. ir. Kevin Van Geem

Begeleider: Thomas Dijkmans
Masterproef ingediend tot het behalen van de academische graad van

Master in de ingenieurswetenschappen: chemische technologie
Vakgroep Chemische Proceskunde en Technische Chemie

Voorzitter: prof. dr. ir. Guy Marin
Faculteit Ingenieurswetenschappen en Architectuur
Academiejaar 2011-2012
Steam Cracking of Complex Hydrocarbon Mixtures
Promotor: prof. dr. ir Kevin M. Van Geem
Coach: ir. Thomas Dijkmans
Thesis submitted to obtain the degree of

Master of Science in Chemical Engineering

Voorzitter: prof. dr. ir. G.B. Marin
Faculteit Ingenieurswetenschappen en Architectuur
Universiteit Gent
Academiejaar 2011-2012
Summary
Due to the depleting reserves of high quality petroleum, there is a growing interest for using
heavy hydrocarbon mixtures such as gas oils and vacuum gas oils for steam cracking. The
microkinetic network included in steam cracking simulation models needs to be extended to
account for the changing feedstock. Therefore, detailed information about these heavy fractions
is necessary and can be provided by GC × GC analyses. Two VGOs have been analyzed with
different injectors and the sulfur composition of one gas oil has been investigated by using GC ×
GC coupled with an SCD. Apart from the microkinetic network, the software for reactor
simulation, i.e. COILSIM1D, can be improved. Secondary reactions can occur in the TLE
leading to lower selectivities and loss of valuable products. By including a TLE module in
COILSIM1D, this effect can be taken into account.
Keywords
Steam cracking, GC × GC, split/splitless, cold-on column, injector, Vacuum Gas Oil, Sulfur
Chemiluminescence Detector, gasoil, Transfer Line Exchanger, modeling, simulation
Confidential
FACULTEIT INGENIEURSWETENSCHAPPEN
EN ARCHITECTUUR
Laboratorium voor Chemische Technologie
Directeur: Prof. Dr. Ir. Guy B. Marin
Laboratorium voor Chemische Technologie
Verklaring in verband met de toegankelijkheid van de scriptie
Ondergetekende, Steven Vandermeersch

afgestudeerd aan de UGent in het academiejaar 2011-2012 en auteur van de
scriptie met als titel: Steam Cracking of Complex Hydrocarbon Mixtures
verklaart hierbij:
1. dat hij geopteerd heeft voor de hierna aangestipte mogelijkheid in verband
met de consultatie van zijn scriptie:
de scriptie mag steeds ter beschikking gesteld worden van elke

aanvrager
de scriptie mag enkel ter beschikking gesteld worden met uitdrukkelijke,

schriftelijke goedkeuring van de auteur
de scriptie mag ter beschikking gesteld worden van een aanvrager na

een wachttijd van…………jaar
de scriptie mag nooit ter beschikking gesteld worden van een aanvrager
2. dat elke gebruiker te allen tijde gehouden is aan een correcte en volledige
bronverwijzing
Gent,
(Handtekening)
Laboratorium voor Chemische Technologie • Krijgslaan 281 S5, B-9000 Gent • www.lct.ugent.be
Secretariaat : T +32 (0)9 264 45 16 • F +32 (0)9 264 49 99 • Petra.Vereecken@UGent.be
Dankwoord
In dit dankwoord wens ik iedereen te bedanken die direct of indirect heeft bijgedragen aan
deze masterproef.
Allereerst wil ik prof. dr. ir. Kevin Van Geem bedanken om mij bij te staan met raad en om
een antwoord te bieden op al mijn vragen.
Ook mijn begeleider, Thomas Dijkmans, verdient een oprecht woord van dank om me
opnieuw op weg te helpen bij problemen, om steeds uitleg te willen geven en om mijn teksten
grondig na te lezen en te corrigeren.
Ik wil graag prof. dr. ir. Guy B. Marin bedanken omdat hij mij de kans heeft gegeven om
tijdens het jaar van de masterproef een Erasmus uitwisseling aan te vatten, wat niet evident is.
Mijn collega’s thesisstudenten en doctoraatstudenten in gebouw 918 wil ik bedanken voor

hun bijdrage aan de goede sfeer tijdens de pauzes. In het bijzonder de buitenlandse
doctoraatsstudenten ben ik dankbaar voor hun openheid en spontaniteit.
Ten slotte wil ik zeker ook mijn ouders bedanken om me steeds alle kansen te geven en om
me goed te ‘soigneren’ zodat ik me in optimale omstandigheden op deze masterproef heb
kunnen focussen. Mijn broer Lukas bedank ik voor de hechte band die we in de loop der jaren
hebben opgebouwd en mijn vriendin Greta voor haar vertrouwen, humor en onuitputtelijk
enthousiasme.
Juni 2012
Steam cracking of complex hydrocarbon mixtures
Promotor: prof. dr. ir. Kevin M. Van Geem

Coach: ir. Thomas Dijkmans
Abstract: Due to the depleting reserves of high There are however still several possibilities to
quality petroleum, there is a growing interest for improve this simulation model.
using heavy hydrocarbon mixtures such as gas oils Firstly, more detailed information of the feedstock
and vacuum gas oils for steam cracking. The on a molecular level obtained through comprehensive
microkinetic network included in steam cracking GC × GC analyses is necessary to develop a more
simulation models needs to be extended to account rigorous kinetic network. In addition, heavy
for the changing feedstock. Therefore, detailed feedstocks contain more heteroelements such as
information about these heavy fractions is sulfur whose influence on the conversion and
necessary and can be provided by GC × GC selectivity are insufficiently known and investigated.
analyses. Two VGOs have been analyzed with Accurately determining the sulfur composition of
different injectors and the sulfur composition of one those mixtures using the GC × GC coupled with a
gas oil has been investigated by using GC × GC Sulfur Chemiluminescence Detector (SCD) and
coupled with an SCD. Apart from the microkinetic measuring the sulfur content with a Flame
network, the software for reactor simulation, i.e. Photometric Detector (FPD) will provide new
COILSIM1D, can be improved. Secondary information.
reactions can occur in the TLE leading to lower Another issue with COILSIM1D is the lack of a
selectivities and loss of valuable products. By module that is able to simulate the cracking behavior
including a TLE module in COILSIM1D, this effect inside a TLE. Despite the fast cooling, reactions still
can be taken into account. take place in the adiabatic inlet section at the inlet of
the TLE and inside the TLE itself. Extending the
I. INTRODUCTION program with a module that takes this influence into
account will allow even better predictions of the
product composition.
Steam cracking of hydrocarbons is one of the main
processes for the production of olefins which are the
building blocks for the petrochemical industry. II. FEEDSTOCK ANALYSIS
Conventional feedstocks are light alkanes such as
ethane and propane and more complex mixtures like A. Comprehensive GC × GC – FID
naphtha and gas oil. The endothermic cracking During the last decade, GC × GC has proven to be
process is carried out in radiant coils suspended in a powerful technique for analyzing the composition
large furnaces where the hydrocarbon feedstock and of heavy petroleum cuts as it gives near molecular
dilute steam are heated to 750-900 °C. To prevent the information about the feedstock. The GCs can be
degradation of the highly reactive products, the equipped with different injectors (split/splitless and
process gas is quickly cooled to 500-600 °C in a cold-on column) and detectors (FID, TOF-MS,
Transfer Line Exchanger (TLE). SCD). Two VGOs have been analyzed with the GC ×
Due to the increasing depletion of the conventional GC coupled with an FID, both using a split/splitless
high quality petroleum and the decreasing demand and a cold-on column injector. The influence of these
for heavy hydrocarbon mixtures, there is a tendency injectors has been investigated and a group type
towards the use of heavier feedstocks for steam quantification per carbon number for vacuum gas oils
cracking. As the cracking behavior of these fractions has been developed.
differs from that of the conventional feeds,
extrapolating the existing simulation models for light
feedstocks to allow the modeling of complex
hydrocarbon mixtures is not straightforward.
Nevertheless, the most advanced simulation models
allow modeling of not only steam cracking of light
fractions such as naphthas but also of heavier
fractions like gas oils and vacuum gas oils (VGOs).
Such a simulation model has been developed at the
Laboratory of Chemical Technology, namely
COILSIM1D, which describes cracking of
hydrocarbon mixtures up to gas condensates [1].
Figure 1: GC × GC – FID contour plot of a VGO with
cold-on column injector
Steven Vandermeersch, master thesis student at Ghent University,
Ghent, Belgium. E-mail: vandermeersch.steven@gmail.com
Confidential
B. Sulfur analysis with GC × GC - SCD Several correlations for this heat transfer coefficient
A Sulfur Chemiluminescence Detector detects the are available in the literature of which two methods
photons that are formed during the reaction of ozone are chosen to be implemented in COILSIM1D.
with SO. Excited SO2* species are formed which fall The validity of the TLE module introduced in the
back to their ground state by emitting light in the new version of COILSIM1D for TLE simulations is
frequency range of 280-420 nm. An important feature tested by comparing the simulation results with data
of this detector is that the signal deduced from the for industrial TLEs.
photon emissions is linear and equimolar to the sulfur
content of the sample. A GC × GC analysis with
SCD detector of two calibration mixtures composed
of sulfur containing compounds like thiophenes,
benzothiophenes and thiols has been performed. The
results are used to verify the linear response of the
SCD and subsequently, a gas oil is analyzed on its
sulfur composition. The sulfur compounds are
identified by comparing with TOF-MS results and
quantified based on internal normalization. To
achieve this, the total sulfur content of the gas oil was
determined using the elemental analyzer.
Figure 2: Temperature profiles in the TLE for the
simulation of an industrial TLE
III. TLE MODELING
Transfer line exchangers (TLEs) are used in steam
cracking installations to quickly cool the effluent gas IV. CONCLUSIONS
below reaction temperature and to prepare the Newly developed conditions for comprehensive
effluent for further processing. The effluent generally GC × GC were applied on two VGO samples. The
leaves the reactor between 750 and 900 °C [2], conditions allow for a quantification of the sample by
depending on the feedstock and the process chemical group and carbon number. Additionally it
conditions. The (primary) TLE then cools the gas to has been demonstrated that the results obtained when
500-650 °C in case two cooling steps are used or using the cold-on column injector have a lower
straight down to 300-400 °C when only one TLE is standard deviation than those obtained using the
present. The exchanged heat is used to produce high split/splitless injector.
pressure steam which allows recovering up to 45% of A GC × GC analysis with SCD detector of one gas
the fired input duty [3]. oil is performed. The sulfur present in the gas oil
In general two types of TLEs are in use: those mainly originates from benzothiophenes and
based on a double pipe system and those based on the dibenzothiophenes. This has been confirmed with
shell and tube configuration. These TLEs can either TOF-MS chromatograms.
be coupled individually to a reactor coil, or they can The developed TLE module for COILSIM1D is
accept gas flows from multiple reactor coils. In a successfully compared to the data for industrial TLEs
double pipe system, the gas flows in the inner pipe provided by Borsig and to the data obtained from the
whereas the water flows in the annulus between the PhD thesis of professor Heynderickx.
inner and outer pipe. For the shell and tube based
TLEs the effluent gas flows through the tubes REFERENCES
whereas water flows in the shell and is evaporated.
COILSIM1D is a program written in FORTRAN 1. Van Geem, K.M., M.F. Reyniers, and G.B.
that simulates the cracking furnace of an industrial Marin, Challenges of modeling steam
steam cracker. One-dimensional equations for the cracking of heavy feedstocks. Oil & Gas
conservation of mass, energy and momentum in a Science and Technology-Revue D Ifp
tubular plug flow reactor are combined with the Energies Nouvelles, 2008. 63(1): p. 79-94.
microkinetic network called CRACKSIM to simulate 2. Heinz Zimmermann, R.W., Ethylene, in
the product yields, coke formation and run lengths. Ullmann's Encyclopedia of Industrial
The program was modified to include the simulation Chemistry, Wiley. p. 66.
of an industrial TLE based on the double pipe 3. G. Schmidt, D.S.U., Dr. C. Geipel, Olefin
system. The equations used in the original Academy 2010 Cracking Furnace
COILSIM1D program for modeling the coil can now Technology, L. Engineering, Editor. 2010.
be applied to model the hydrocarbon side of the TLE.
The main focus hence lies on determining the
coefficient for convective heat transfer from the tube
wall to the water/steam mixture in the annulus.
Confidential
Stoomkraken van complexe koolwaterstofmengsels
Promotor: prof. dr. ir. Kevin M. Van Geem

Begeleider: ir. Thomas Dijkmans
Samenvatting: Door de dalende reserves aan simulatiemodel ontwikkeld, COILSIM1D genaamd,

petroleum van hoge kwaliteit is er een toenemende dat ook het kraakgedrag van zware voedingen als
interesse naar het gebruik van zware petroleum gascondensaten kan beschrijven [1]. Toch kan dit
fracties zoals gasolies en vacuüm gasolies als model nog verder verbeterd worden.
voeding voor stoomkrakers. Het microkinetisch Gedetailleerde informatie van de voeding op
model dat vervat zit in de simulatiemodellen voor moleculaire schaal, zoals verkregen bij GC × GC
stoomkraken dient te worden uitgebreid om de analyses, is noodzakelijk om het kinetisch netwerk
invloed van de veranderende voedingssamenstelling verder te ontwikkelen. Daarnaast bevatten zware
in rekening te brengen. Hiertoe is er gedetailleerde voedingen meer heteroelementen zoals zwavel,
informatie nodig over deze voedingen die kan waarvan de invloed op de conversie en de
verkregen worden door middel van GC × GC selectiviteit onvoldoende gekend en onderzocht zijn.
analyses. Twee VGO’s zijn geanalyseerd met Nieuwe informatie kan verkregen worden door de
verschillende injectors en de zwavelsamenstelling zwavelhoudende componenten in deze mengsels
van een gasolie is onderzocht via een GC × GC nauwkeurig te bepalen met behulp van GC × GC
analyse met een SCD. Niet alleen het analyses gekoppeld met een Zwavel
microkinetisch netwerk, maar ook de software voor Chemiluminescentie Detector (SCD) en door de
reactorsimulaties, i.e. COILSIM1D, kan worden zwavelinhoud nauwkeurig te meten met een Vlam
verbeterd. In de TLE kunnen secundaire reacties Fotometrische Detector (FPD).
leiden tot lagere selectiviteiten en het verlies van Een ander tekort aan COILSIM1D is het ontbreken
waardevolle producten. Door een TLE module in van een module die in staat is om het krakingsgedrag
COILSIM1D op te nemen wordt dit effect mee in in een TLE te modelleren. Ondanks de snelle koeling
rekening gebracht. gaan er nog steeds reacties door ter hoogte van de
adiabatische inlaatzone en in de TLE zelf. Door het
I. INLEIDING programma uit te breiden met een module die dit in
rekening brengt kan de productsamenstelling nog
beter worden voorspeld.
Stoomkraken van koolwaterstoffen is één van de
voornaamste processen voor de productie van
alkenen, de bouwstenen van de petrochemische II. VOEDINGSANALYSE
industrie. Conventionele voedingen zijn lichte
alkanen, zoals ethaan en propaan, en meer complexe A. GC × GC – FID analyse
mengsels zoals nafta en gasolie. De endotherme De laatste jaren is gebleken dat GC × GC analyse
krakingsreacties vinden plaats in buisreactoren die in een krachtige techniek is om de samenstelling van
een oven verhit worden door branders. De voeding aardoliefracties op moleculaire schaal te analyseren.
verlaat de reactor op 700-900 °C en wordt snel GC’s kunnen uitgerust worden met verschillende
gekoeld tot 500-600 °C in een Transfer Line injectoren (Split-Splitless en Cold-on column) en
Exchanger (TLE) om verlies van waardevolle detectoren (FID, TOF-MS, SCD). Twee VGO’s zijn
producten te voorkomen. geanalyseerd met de GC × GC gekoppeld met een
Wegens het toenemend tekort aan aardolie van FID, zowel gebruik makende van een Split-Splitless
hoge kwaliteit en door de dalende vraag naar zware injector als van een Cold-on columninjector. De
koolwaterstof-mengsels worden steeds vaker zware invloed van deze injectoren is onderzocht en een
voedingen gebruikt voor stoomkraken. Aangezien het kwantificatiemethode voor VGO’s op basis van
krakingsgedrag van deze fracties verschilt van dat groep type en koolstofgetal is ontwikkeld.
van conventionele voedingen is het niet
vanzelfsprekend om de bestaande simulatiemodellen
voor lichte voedingen te extrapoleren zodat ook
complexe voedingen kunnen gemodelleerd worden.
Desondanks zijn de meeste geavanceerde
simulatiemodellen niet beperkt tot het modelleren
van stoomkraken van lichte fracties, maar werken ze
ook voor zware fracties zoals gasolies en vacuüm
gasolies (VGO’s). In het Laboratorium voor
Chemische Technologie (LCT) is een dergelijk
Steven Vandermeersch, thesisstudent aan de Universiteit Gent,

Figuur 1: GC × GC – FID contour plot van een VGO cold-
Gent, België. E-mail: vandermeersch.steven@gmail.com on column injector
Confidentieel
B. Zwavel analyse met GC × GC – SCD twee methodes zijn gekozen om in COILSIM1D te
Een Zwavel Chemiluminescentie Detector worden geïmplementeerd.
detecteert de fotonen die gevormd worden tijdens de De geldigheid van de TLE module die in de nieuwe
reactie van ozon met SO. Hierbij worden versie van COILSIM1D is ingevoerd is nagegaan
geëxciteerde SO2* deeltjes gevormd die tijdens de door simulatieresultaten te vergelijken met data voor
relaxatie licht uitzenden in het frequentiebereik van industriële TLE’s.
280-420 nm. Een belangrijke eigenschap van deze
detector is dat het verkregen signaal lineair en
equimolair is met de zwavelinhoud van het monster.
Twee kalibratiemengsels bestaande uit
zwavelhoudende componenten zijn geanalyseerd met
de SCD. De resultaten zijn gebruikt om de lineaire
respons van de SCD na te gaan en vervolgens is de
zwavelsamenstelling van een gasolie onderzocht.
Door te vergelijken met TOF-MS resultaten werden
de zwavelcomponenten geïdentificeerd. De totale
zwavelinhoud is bepaald met de element analyzer
zodat de kwantificatie mogelijk is door middel van
interne normalisatie. Figuur 2: Temperatuursprofielen in de TLE voor de
simulatie van een industriële TLE
III. TLE MODELLERING
Transfer line exchangers (TLEs) worden gebruikt
in stoomkrakers om het gasmengsel snel te koelen IV. BESLUIT
onder de reactietemperatuur. Het mengsel verlaat de
Nieuw ontwikkelde condities voor GC × GC
reactor tussen de 750 en de 900 °C [2], afhankelijk
analyses zijn toegepast op twee VGO’s. Met deze
van de gebruikte voeding en de procescondities. De
(eerste) TLE koelt het gas dan tot 500-650 °C indien condities is een kwantificatiemethode gebaseerd op
het gas in twee stappen wordt gekoeld, of tot 400-500 groep type en koolstofgetal verkregen voor VGO’s.
°C als er slechts één TLE wordt gebruikt. De Daarnaast is aangetoond dat de resultaten verkregen
door het gebruik van een cold-on column injector een
overgedragen warmte wordt gebruikt om hoge druk
lagere standaard afwijking tonen dat die verkregen
stoom te produceren. Zo kan tot 45% van de
met een split/splitless injector.
verbrandingswarmte gerecupereerd worden [3].
In de industrie worden twee types TLE’s gebruikt: Er is een GC × GC analyse van een gasolie
dubbele pijp TLE’s en mantel en-buis TLE’s. De uitgevoerd met een SCD detector. Daaruit blijkt dat
TLE’s kunnen individueel gekoppeld worden aan een de zwavel aanwezig in de gasolie voornamelijk
afkomstig is van benzothiophenen en
reactorbuis, of ze kunnen de gasstroom van meerdere
dibenzothiophenen. Dit is bevestigd met TOF-MS
reactoren ontvangen. In een dubbele pijp configuratie
chromatogrammen.
stroomt het gas in de binnenste buis terwijl het water
in de ring vloeit tussen binnenste en buitenste buis. De ontwikkelde TLE module voor COILSIM1D is
Bij mantel-buis TLEs stroomt het gas in de buizen en met succes vergeleken met zowel de data van Borsig
voor industriële TLE’s als met de data vermeld in het
wordt water verdampt in de mantel.
doctoraat van professor Heynderickx.
COILSIM1D is een programma geschreven in
FORTRAN dat de reactor van een industriële
stoomkraker simuleert. Vergelijkingen voor het REFERENTIES
behoud van massa, energie en moment opgesteld 1. Van Geem, K.M., M.F. Reyniers, and G.B.
voor een eendimensionale propstroomreactor worden Marin, Challenges of modeling steam
gecombineerd met het microkinetisch model cracking of heavy feedstocks. Oil & Gas
CRACKSIM om de productsamenstelling, de Science and Technology-Revue D Ifp
cokesvorming en de run length te simuleren. Het Energies Nouvelles, 2008. 63(1): p. 79-94.
programma is zo aangepast dat het een industriële 2. Heinz Zimmermann, R.W., Ethylene, in
dubbele pijp TLE kan modelleren. De vergelijkingen Ullmann's Encyclopedia of Industrial
die in de oorspronkelijke COILSIM1D de reactorbuis Chemistry, Wiley. p. 66.
simuleerden kunnen nu worden toegepast om de 3. G. Schmidt, D.S.U., Dr. C. Geipel, Olefin
binnenste buis van de TLE modelleren. De nadruk Academy 2010 Cracking Furnace
ligt dus vooral op het modelleren van de coëfficiënt Technology, L. Engineering, Editor. 2010.
voor convectieve warmteoverdracht aan de
buitenwand van de binnenste buis. Er zijn
verschillende correlaties beschikbaar in de literatuur
voor deze warmteoverdrachtscoëfficiënt waarvan er
Confidentieel
Table of Contents
List of Acronyms ...................................................................................................................................... iv
List of Symbols ..........................................................................................................................................v
Chapter 1 ................................................................................................................................................. 1
Introduction............................................................................................................................................. 1
1.1 Objectives ................................................................................................................................ 3
1.2 Outline ..................................................................................................................................... 3
References ........................................................................................................................................... 4
Chapter 2 ................................................................................................................................................. 6
Feedstock analysis ................................................................................................................................... 6
2.1 Introduction ............................................................................................................................. 6
2.2 GC x GC analysis of the feedstock ........................................................................................... 8
2.2.1 Analysis of polyethylene and VGO .................................................................................. 8
2.2.2 Calibration mixtures for SCD ......................................................................................... 10
2.2.3 Gas oil ............................................................................................................................ 11
2.2.4 Elemental analyzer ........................................................................................................ 12
2.3 Samples ................................................................................................................................. 15
2.3.1 Polywax sample preparation ......................................................................................... 16
2.3.2 Vacuum gas oil sample preparation .............................................................................. 16
2.3.3 Gas oil sample preparation ........................................................................................... 16
2.4 Data treatment ...................................................................................................................... 17
2.4.1 VGO and polyethylene sample ...................................................................................... 17
2.4.2 Gas oil analysis............................................................................................................... 18
2.5 Results and discussion ........................................................................................................... 18
2.5.1 Polywax analysis ............................................................................................................ 18
2.5.2 Vacuum gas oil analysis ................................................................................................. 21
2.5.3 Calibration mixtures ...................................................................................................... 26
2.5.4 Gas oil ............................................................................................................................ 30
2.6 Future work ........................................................................................................................... 34
2.7 Conclusion ............................................................................................................................. 34
2.8 References ............................................................................................................................. 35
Chapter 3 ............................................................................................................................................... 37
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Literature review TLEs ........................................................................................................................... 37
3.1 Introduction ........................................................................................................................... 37
3.2 Transfer line exchanger ......................................................................................................... 38
3.3 Alstom Exchangers ................................................................................................................ 43
3.3.1 Multi-tube exchangers .................................................................................................. 45
3.3.2 Linear closed-coupled Exchangers ................................................................................ 48
3.3.3 Overview........................................................................................................................ 50
3.4 Borsig Exchangers .................................................................................................................. 51
3.4.1 “Tunnelflow” Transfer Line Exchanger .......................................................................... 51
3.4.2 Linear Transfer Line Exchanger ..................................................................................... 53
3.4.3 Examples with typical dimensions................................................................................. 55
3.5 References ............................................................................................................................. 56
Chapter 4 ............................................................................................................................................... 57
Correlations ........................................................................................................................................... 57
4.1 Introduction ........................................................................................................................... 57
4.2 Convective heat transfer coefficient h .................................................................................. 57
4.2.1 Introduction ................................................................................................................... 57
4.2.2 Single phase turbulent flow........................................................................................... 58
4.2.3 Two phase boiling heat transfer .................................................................................... 60
4.3 Physical properties of water/steam ...................................................................................... 69
4.3.1 Density and heat capacity at constant pressure ........................................................... 69
4.3.2 Viscosity ......................................................................................................................... 75
4.3.3 Surface tension .............................................................................................................. 76
4.3.4 Thermal conductivity ..................................................................................................... 77
4.4 References ............................................................................................................................. 77
Chapter 5 ............................................................................................................................................... 79
Modeling of a TLE .................................................................................................................................. 79
5.1 Introduction ........................................................................................................................... 79
5.2 Review COILSIM1D ................................................................................................................ 80
5.3 Modifying COILSIM1D ........................................................................................................... 81
5.3.1 Case 1: fixed geometry and water inlet conditions ....................................................... 82
5.3.2 Case 2: shooting for gas outlet temperature ................................................................ 88
5.4 Results ................................................................................................................................... 89
5.4.1 Simulation based on Borsig data ................................................................................... 89
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5.4.2 Simulations based on data from Heynderickx (1993) ................................................... 95
5.5 Future work ......................................................................................................................... 101
5.6 Conclusion ........................................................................................................................... 101
5.7 References ........................................................................................................................... 101
Chapter 6 ............................................................................................................................................. 102
Conclusions and future work............................................................................................................... 102
6.1 Future work ......................................................................................................................... 104
References ....................................................................................................................................... 104
Annex A: Correlation coefficients........................................................................................................ 105
Annex B: Elemental analysis and density measurements ................................................................... 110
Annex C: Detailed GC × GC composition of the VGOs and gasoil ....................................................... 113
Confidential
iv
List of Acronyms
Arconym Description
1D First dimension
1D-GC One dimensional Gas Chromatography
2D Second dimension
Avg Average
ASTM American Society for Testing and Materials
BBOT 2,5-bis-2-(5-tert-Butylbenzoxazolyl)-thiophene
CFD Computational Fluid Dynamics
CHNS Carbon Hydrogen Nitrogen Sulfur
COC Cold-on column
COP Coil Outlet Pressure
COT Coil Outlet Temperature
FID Flame Ionization Detector
FPD Flame Photometric Detector
GC Gas Chromatograph
GC × GC Comprehensive two Dimensional Gas Chromatography
HT-2D-GC High Temperature two Dimentional Gas Chromatography
IAPWS International Association for the Properties of Water and Steam
ID Internal Diameter
IS Internal Standard
PIONA Paraffins Isoparaffins Olefines Naphthenes Aromatics
PTV Programmed Temperature Vaporization injector
RF Response Factor
SCD Sulfur Chemiluminescence Detector
SQE Secondary Quench Exchanger
SS Split/Splitless
STD Standard
TOF-MS Time Of Flight Mass Spectrometer
TLE Transfer Line Exchanger
VGO Vacuum Gas Oil
Confidential
v
List of Symbols
Roman symbols Description Unit
A Surface available for heat exchange (Chapter 5) m2
Ai Peak volume of component i
Ast Peak volume for the internal standard
B Reference surface tension N m-1
B Dimensionless constant
B0 Boiling number
C0 Correction factor for the convective boiling coefficient
C1 Intermediate result in a symbolic calculation kW m-2
C2 Intermediate result in a symbolic calculation
cp Heat capacity at constant pressure of the fluid J kg-1 K-1 *
cpg Specific heat of the gas mixture kJ kg-1 K-1
cpL Heat capacity at constant pressure of the liquid kJ kg-1 K-1
D Constant
Dev Sum of squares of the difference between the newly calculated
and the ‘old’ heat flux profile
di Internal diameter m
di,0 Standard tube reference diameter m
e Pipe roughness m
E Constant
f Friction factor
F Constant
F(M) Residual molar weight correction factor
fG Fanning friction factor for the vapor
fi Relative response factor for component i
fL Fanning friction factor
Fnb Nucleate boiling correction factor
Fpf Pressure correction factor
fst Relative response factor for the internal standard
Ftp Two-phase multiplier
fturb Friction factor for turbulent flow
g Specific Gibbs free energy kJ kg-1
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G Constant
h Convective heat transfer coefficient W m-2 K-1
hconv,i Convection coefficient in section i W m-2 K-1
Hi Constant, dimensionless coefficient
hi(T) Enthalpy of component i in the gas mixture at temperature T kJ kg-1
Hij Constant, dimensionless coefficient
hLG Latent heat of vaporization J kg-1 *
Ii Constant, dimensionless exponent
Ji Constant, dimensionless exponent
k Thermal conductivity coefficient of the fluid W m-1 K-1
kG Thermal conductivity coefficient of the vapor W m-1 K-1
Ki Constant of proportionality for compound i
kL Thermal conductivity coefficient of the liquid W m-1 K-1
L Characteristic length m
L Length of the TLE m
Mfi Weight fraction of component i
Mi Molecular weight g mol-1
mi Weight of component i g
Mass flow kg s-1
Mass flow of the fluid kg s-1
Mass flow of the gas kg s-1
Steam production rate kg s-1
Mass flow water/steam mixture kg s-1
N Exponent
NC,i Number of carbon atoms in the molecule
nf Nucleate boiling exponent
ni Number of moles of component i (paragraph 2.5.4)
ni Constant, dimensionless coefficient (elsewhere)
nS,i Number of moles sulfur originating from group i
Nu Nusselt number
P Pressure bar*
p* Reference pressure bar
pc Critical pressure Pa
Pr Prandtl number
pr Reduced pressure
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vii
PrG Prandtl number for the vapor phase

PrL Prandtl number for the liquid phase
ps Saturation pressure bar
psat Local saturation pressure bar*
pt Pressure at the triple point Mpa
q Local heat flux from the tube wall into the fluid W m-2 *
Q Heat flux kW m-2
q0 Reference heat flux W m-2
Qi Heat flux in section i kW m-2
Qi,new Newly calculated heat flux in section i kW m-2
Qi,old ‘Old’ heat flux in section i kW m-2
Qmax The maximum local heat flux at the TLE inlet kW m-2
qONB Heat flux corresponding to the onset of nucleate boiling
Qtot Total amount of heat exchanged over the entire TLE per second kW
R Specific gas constant of ordinary water kJ kg-1 K-1
R Ratio of the heat flux at the inlet over the heat flux at the outlet
of the TLE
r0 Critical nucleation radius for a boiling site m
Re Tubular Reynolds number
ReGt Reynolds number for the vapor phase calculated assuming the
entire mass flow is pure vapor
ReL Reynolds number for the liquid phase, based on the liquid mass
flow
ReLt Reynolds number for the liquid phase calculated assuming the
entire mass flow is pure liquid
Rp,0 Mean surface roughness m
T Temperature K*
T* Reference temperature K
Tc Critical temperature K
Tg Gas temperature K
Tg,inlet Gas temperature at the inlet of the TLE K
Ti Water temperature in section i K
Tsat Local saturation temperature K*
Tt Triple point temperature K
Tw/s,i Temperature of the water/steam mixture in section i K
Twall Wall temperature K*
Twall,i External wall temperature in section i K
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viii
dimensionless temperature
x Steam quality
xcrit Critical vapor quality
xi Vapor quality in section i (Chapter 5)
xi Mass fraction of component I (elsewhere)
xst Mass fraction of the internal standard
z Axial coordinate m
*unless specified differently in the text
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ix
Greek symbols Description Unit

αcb Heat transfer coefficient for convective boiling W m-2 K-1
αGt Local liquid phase forced convection coefficient based on the W m-2 K-1
total flow as vapor
αi Mass fraction of component i in the gas mixture
αL Single phase convection coefficient W m-2 K-1
αLt Local liquid phase forced convection coefficient based on the W m-2 K-1
total flow as liquid
αnb Heat transfer coefficient for nucleate boiling W m-2 K-1
αnb,0 Local nucleate pool boiling coefficient at a reference heat flux q0 W m-2 K-1
at the reduced pressure pr equal to 0.1
αtp Local two-phase flow boiling heat transfer coefficient for W m-2 K-1
evaporation inside a tube
β Dimensionless parameter
γ Dimensionless specific Gibbs free energy
γ0 Ideal gas part of the dimensionless Gibbs free energy
γr Ideal gas part of the dimensionless Gibbs free energy
δi Relative change in mass fraction of component i
μ Dynamic viscosity of the fluid Pa s
μL Dynamic viscosity of the liquid Pa s
μs Dimensionless constant
Dimensionless viscosity
Dimensionless viscosity in the dilute-gas limit
Dimensionless factor representing the contribution to viscosity
due to finite density
Dimensionless factor representing the critical enhancement of

the viscosity
ν Specific volume (section 4.3.1.1) m3 kg-1

π Dimensionless pressure
ρG Density of the gas kg m-3
ρL Density of the liquid kg m-3
Dimensionless density
σ Surface tension N m-1
τ Dimensionless temperature
τs Dimensionless temperature
Φ Mass velocity kg m-2 s-1
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x
ΦG Mass flux of the gas kg m-2 s-1

Ω Circumference of the tube m
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Chapter 1: Introduction 1
Chapter 1
Introduction
Steam cracking of hydrocarbons is one of the main processes for the production of olefins (e.g.
ethene, propene, butadiene) and aromatics (e.g. benzene) which are the building blocks for the
petrochemical industry. The endothermic cracking process is carried out in radiant coils
suspended in large furnaces. Conventional feedstocks are light alkanes such as ethane and
propane and more complex mixtures like naphtha and gas oils. The furnace consists of two main
parts: the convection section and the radiant section. In the convection section, the hydrocarbon
feedstock and dilute steam is preheated to 600-650 °C. The process gas then enters the radiant
section, where the temperature rises to 750-900 °C at the reactor outlet. To prevent the
degradation of the highly reactive products, the process gas is quickly cooled to 500-600 °C in a
Transfer Line Exchanger (TLE). Despite the fast cooling, reactions still take place in the
adiabatic inlet section of the TLE and inside the TLE itself. Steam cracking is one of the most
energy consuming processes in the petrochemical industry. The second main function of the TLE
is therefore to recover energy by producing high pressure steam from the released heat to reduce
the overall energy consumption.
For process optimization and design purposes mathematical models have been developed to
simulate the steam cracking coil and to predict the product yields. At the Laboratory for
Chemical Technology (LCT) a plug flow reactor model has been proposed [1-2] and a
microkinetic model (CRACKSIM) has been developed [3] and continuously improved [4-6].
Coke formation has been investigated [7-9] and a reaction mechanisms for coke formation have
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been suggested [10]. The microkinetic model CRACKSIM and a one dimensional reactor model
have been combined in COILSIM1D which successfully simulates the cracking coil of an
industrial steam cracking installation. The program lacks however a module that is able to
simulate the cracking behavior inside a TLE. This is necessary to account for the reactions that
take place after the process gas has left the radiant coil as well as to calculate the amount of high
pressure steam that can be produced.
Due to the increasing depletion of the conventional high quality petroleum, there is a tendency
towards the use of heavier feedstocks like gas oils and vacuum gas oils (VGOs) for steam
cracking. The cracking behavior of these fractions differs from that of the conventional feeds.
This is mainly related to the difference in composition between the lighter and the heavier cuts.
VGOs for example, contain significant amounts of di-, tri- and poly-aromatic compounds that are
not present in light fractions [6]. To extend CRACKSIM for steam cracking both a detailed
molecular feedstock composition and a detailed molecular composition of the effluent are
required. Heavy feedstocks are very complex mixtures and contain thousands of different
compounds. Currently no analytical technique is powerful enough to identify and quantify these
components on a molecular basis. Therefore numerical “reconstruction” methods for simulating
the molecular composition of these complex mixtures are often used. Most of these methods
require a library of representative molecules which is usually based on experimental data [6].
Comprehensive two dimensional gas chromatography (GC × GC) is a powerful technique for
analyzing the composition of heavy petroleum cuts and it gives near molecular information about
the feedstock. Thus it is useful in both expanding the library of these reconstruction methods as
well as providing detailed information about the feed which can be used together with the
effluent composition to extend the current microkinetic models. At the LCT several in-house
adjusted comprehensive two dimensional gas chromatographs (GC × GC) are available for both
online characterization of the cracked gas and for offline inspection of the feedstock. A range of
different injectors (split/splitless and cold-on column) and detectors (FID, TOF-MS, SCD) are
available on these GCs [11].
Another issue related to the use of heavy feedstocks in the petrochemical industry lies in the
higher sulfur content of these fractions. If these fractions are converted to transportation fuels
(e.g. by fluid catalytic cracking of hydrocracking), combustion of the sulfur content will give rise
to harmful SOx emission in the atmosphere. In addition, sulfur species promote corrosion in fuels
and have a poisoning effect on car catalytic converters [12] and on metallic catalysts in general
[13]. Hydrodesulfurization processes are applied to reduce the sulfur content of products
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obtained from heavy feedstocks. In order to improve these processes the kinetics of S-
compounds need to be well known [14]. Sulfur also has an influence on the coke formation in
steam cracking coils and transfer line exchangers [8-9]. For these reasons, it is interesting to
investigate the sulfur content of heavy fractions on a molecular scale by performing analyses
with GC × GC coupled with an SCD. This information can also be used to study the effect of the
sulfur content on the conversion and selectivity for the steam cracking process and on coke
formation.
1.1 Objectives
The first objective is to develop a GC × GC method for the group type quantification per carbon
number for vacuum gas oils. The influence of the injector will be investigated by using both a
Split/Splitless injector as a Cold-on column injector for the analysis of two VGOs. A
polyethylene sample will be analyzed to determine the maximum detectable carbon number and
repeatability of the methods. The total amount of sulfur of both VGOs will be determined with
an element analyzer coupled with a flame photometric detector. A calibration method for the
newly installed sulfur chemiluminescence detector (SCD) coupled with the GC × GC will be
developed and the SCD will be used to analyze the sulfur compounds present in a gas oil.
The second objective is to develop a module for the COILSIM1D program that allows for the
simulation of a TLE. The module should be able to predict the outlet composition of the TLE
and to calculate the amount of high pressure steam that is formed.
1.2 Outline
The outline of this master thesis does not follow the conventional structure of literature review,
methodology and results. This is due to the two very distinct subjects that are treated in this
work: feedstock characterization and TLE modeling. In order to avoid repeatedly switching from
the one subject to the other, the feedstock characterization is treated first and everything related
to the TLE modeling comes next. A brief summary of the content of each chapter is given below.
Chapter 2 contains the experimental work regarding the feedstock analysis with the GC × GC.
The analysis of the two VGOs, the polyethylene sample, the calibration of the SCD and the
analysis of the gas oil is presented.
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In Chapter 3 a more detailed description of the working of a TLE is presented and the
configurations proposed by the two main producers for industrial TLEs are discussed.
Chapter 4 gives an overview of the correlations used to determine the coefficient for convective
heat transfer used in Chapter 5 and discusses the calculation of the properties of water and steam
needed in Chapter 5.
Chapter 5 is devoted to the modeling of the TLE. The approach and calculation method is
explained and the simulation results are discussed and compared with data from the industry.
References
1. Sundaram, K.M. and G.F. Froment, COMPARISON OF SIMULATION-MODELS FOR
EMPTY TUBULAR REACTORS. Chemical Engineering Science, 1979. 34(1): p. 117-
124.
2. Sundaram, K.M. and G.F. Froment, 2 DIMENSIONAL MODEL FOR THE SIMULATION
OF TUBULAR REACTORS FOR THERMAL-CRACKING. Chemical Engineering
Science, 1980. 35(1-2): p. 364-371.
3. Froment, G.F., KINETICS AND REACTOR DESIGN IN THE THERMAL-CRACKING
FOR OLEFINS PRODUCTION. Chemical Engineering Science, 1992. 47(9-11): p. 2163-
2177.
4. Van Geem, K.M., G.J. Heynderickx, and G.B. Marin, Effect of radial temperature
profiles on yields in steam cracking. Aiche Journal, 2004. 50(1): p. 173-183.
5. Van Geem, K.M., et al., Automatic reaction network generation using RMG for steam
cracking of n-hexane. Aiche Journal, 2006. 52(2): p. 718-730.
6. Van Geem, K.M., M.F. Reyniers, and G.B. Marin, Challenges of modeling steam
cracking of heavy feedstocks. Oil & Gas Science and Technology-Revue D Ifp Energies
Nouvelles, 2008. 63(1): p. 79-94.
7. Reyniers, G.C., et al., COKE FORMATION IN THE THERMAL-CRACKING OF
HYDROCARBONS .4. MODELING OF COKE FORMATION IN NAPHTHA
CRACKING. Industrial & Engineering Chemistry Research, 1994. 33(11): p. 2584-2590.
8. Dhuyvetter, I., et al., The influence of dimethyl disulfide on naphtha steam cracking.
Industrial & Engineering Chemistry Research, 2001. 40(20): p. 4353-4362.
9. Wang, J., et al., Influence of silicon and silicon/sulfur-containing additives on coke
formation during steam cracking of hydrocarbons. Industrial & Engineering Chemistry
Research, 2008. 47(5): p. 1468-1482.
10. Wauters, S. and G.B. Marin, Kinetic modeling of coke formation during steam cracking.
Industrial & Engineering Chemistry Research, 2002. 41(10): p. 2379-2391.
11. Van Geem, K.M., et al., On-line analysis of complex hydrocarbon mixtures using
comprehensive two-dimensional gas chromatography. Journal of Chromatography A,
2010. 1217(43): p. 6623-6633.
12. Mahe, L., et al., Global approach for the selection of high temperature comprehensive
two-dimensional gas chromatography experimental conditions and quantitative analysis
in regards to sulfur-containing compounds in heavy petroleum cuts. Journal of
Chromatography A, 2011. 1218(3): p. 534-544.
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13. Bartholomew, C.H., Mechanisms of catalyst deactivation. Applied Catalysis a-General,

2001. 212(1-2): p. 17-60.
14. Charon-Revellin, N., et al., Kinetic Modeling of Vacuum Gas Oil Hydrotreatment using a
Molecular Reconstruction Approach. Oil & Gas Science and Technology-Revue D Ifp
Energies Nouvelles, 2011. 66(3): p. 479-490.
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Chapter 2: Feedstock analysis 6
Chapter 2
Feedstock analysis
2.1 Introduction
Due to the increasing depletion of the conventional high quality petroleum feedstocks, there is a
tendency towards the use of heavier feedstocks (e.g. gas oils) for steam cracking [1]. These
feedstocks bring along new issues like more severe coking and the lack of available models
which are able to simulate the product yields. Figure 2-1 shows how the steam cracking model
developed at the LCT can predict the product yields for conventional feedstocks based on the
microkinetic model “Cracksim”, the one dimensional reactor model “Coilsim1D” and
information about the process conditions. Since the microkinetic model is based on elementary
reactions, it requires detailed molecular information about the feedstock. As currently no
analytical technique is powerful enough to identify and quantify the different components
present in heavy feeds, numerical “reconstruction” methods are applied to simulate the
composition of these feeds. The “reconstruction” methods vary the mole fractions of a set of
representative molecules in order to obtain the same global characteristics as the ones that have
been determined experimentally [2]. In order to successfully model the cracking of heavy
feedstocks, an extended library with representative molecules is needed. Hence, in addition to
experimental pilot data, a detailed molecular characterization of the feedstock is necessary.
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Figure 2-1: Overview of the different elements needed to model steam cracking
Another point of interest is the higher sulfur content present in heavy petroleum cuts. If these
cuts are used to produce fuels, the sulfur content will give rise to SOx emission. Sulfur species
also have a poisoning effect on metallic catalysts [3]. Hence, information on the sulfur content of
heavy fractions on a molecular scale is needed.
The characterization of heavy petroleum fractions is however an important challenge for

analytical chemists. Complex fractions such as atmospheric and vacuum gas oils can easily
contain over one million different compounds. These fractions are therefore often distinguished
using global characteristics such as simulated distillation, elementary and/or structural analysis
[4]. Other techniques include liquid chromatography [5-6] or supercritical fluid chromatography
[7-8] where fractions are separated into different chemical classes. Mass spectrometric
techniques which divide the sample in to different groups such as alkanes, single and multi-cycle
aromatic hydrocarbons (monoaromatics, diaromatics, triaromatics and polyaromatic
hydrocarbons) and sulfur containing molecules [9] are also available.
Characterization of these fractions based on global characteristics or chemical groups is

insufficient for process optimization or design thus there is a need for a new more detailed
“molecular” analysis. Due to the sheer number of compounds in complex fractions (e.g. heavy
and vacuum gas oils) individual molecular quantification of these fractions remains impossible.
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Quantification based on both chemical family and carbon number can be considered as the next
best thing.
The influence of sulfur components on the yields during steam cracking and their influence on
coking is still a topic of research. Recently GC × GC has been coupled to a sulfur
chemiluminescence detector [10-11] to allow for the detection of sulfur components in heavy
petroleum cuts.
In the next paragraphs a GC × GC method is suggested for the group type quantification per
carbon number for vacuum gas oils. In the literature, in most cases a split/splitless injector (SS)
is used for the analysis of heavy fractions such as heavy and vacuum gas oils. From conventional
1D-GC it is known that the injection technique is critical for cuts with a broad boiling point
range [12]. Therefore a GC × GC analysis of two VGOs has been performed with an FID
detector and different injectors (split/splitless and cold-on column) were tried out and compared
to get optimal results. A polyethylene sample is analyzed with the GC × GC coupled with an FID
detector to determine the maximum detectable carbon number and to check the impact of
injector discrimination and the repeatability of both methods. The total amount of sulfur for both
VGOs has been determined using an elemental analyzer coupled with a flame photometric
detector (FPD) which is able to detect trace amounts of sulfur. A quantification method for an
SCD detector coupled to a GC × GC setup is proposed and validated using different calibration
mixtures. The mixtures consist of sulfur containing compounds like thiols and thiophenes. The
SCD detector has been used for the GC × GC analysis of one gas oil. For the identification of the
sulfur components inside the gas oil a chromatogram of the GC × GC coupled with a TOF-MS is
used.
2.2 GC x GC analysis of the feedstock

2.2.1 Analysis of polyethylene and VGO
The experiments with the VGOs and the polyethylene sample were carried out using a Thermo
Scientific TRACE GC × GC (Interscience, Belgium) [13]. The device is equipped with a dual
stage cryogenic liquid CO2 modulator, a flame ionization detector (FID) and a sulfur
chemiluminescence detector (SCD) for the detection of components containing sulfur.
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Figure 2-2: Schematic overview of the GC × GC-FID/SCD setup
H2, air and N2 (make-up gas) flow rates were set at respectively 35, 350 and 35 ml/min. The
detector temperature was set at 350 °C and its acquisition rate is set at 100 Hz. The GC × GC is
equipped with both a split/splitless injector and a cold-on column injector. The split/splitless
injector was set at 350 °C and a split flow rate of 10 ml/min. Higher injector temperatures are not
advisable because cracking of the heavy molecules in the studied samples would occur [14]. This
temperature also corresponds to the maximum temperature used in the atmospheric distillation
section of a refinery. The cold-on column injector is air cooled to about 10 °C below oven
temperature and is connected to a retention gap (MXT®-guard column 0.53mm ID). The column
set consisted of a non-polar first dimension column (MXT-1, Restek, 60 m × 0.25 mm, 0.25 µm)
and a mid-polar second dimension column (BPX-50, SGE, 2 m × 0.25 m, 0.25 µm) placed in
the same oven. Helium was used as a carrier gas in constant flow rate mode (flow rate
corresponding to 271 kPa at 90 °C). The GC system was operated in programmed temperature
conditions which differed slightly depending on the injector that had been used. In case the
split/splitless injector is used the oven program starts at 40 °C and goes up to 370 °C at a rate of
3 °C/min. The temperature is held constant at 370 °C for 10 min. In case of the cold-on column
injector the oven temperature starts at 40 °C and is heated rapidly (20 °C/min) until 50 °C to
vaporize the solvent. From 50 °C it is heated to 370 °C at a rate of 3 °C/min where it is held for
10 min. The maximum temperature is limited by the second dimension column which has a
maximum operating temperature of 370 °C. 2D modulation was carried out on the piece of
deactivated fused silica column which was placed between the first and second dimension
column. The modulation period was optimized to allow a maximal separation in second
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dimension. This resulted for the column combination used for these experiments to a modulation
time of 8 seconds.
Table 2-1: Settings used for the GC × GC analysis of the VGOs and the polyethylene
sample
SS COC
Injector temperature 350 °C 10 °C below oven temperature
Split flow 10 ml/min -
Oven program 40 to 370 °C at 3 °C/min 40 to 50 °C at 20 °C/min

10 min at 370 °C 50 to 370 °C at 3 °C/min
10 min at 370 °C
Modulation time 8s 8s
Detector temperature 350 °C 350 °C
2.2.2 Calibration mixtures for SCD

The calibration mixtures have been analyzed with the same device and the same columns as the
VGOs and the polyethylene sample. All experiments were carried out using the split/splitless
injector. For every experiment, 0.2 µl was injected. The applied GC × GC settings are
summarized in Table 2-2.
Figure 2-3 show an overview of an Agilent Technologies 355 Sulfur Chemiluminescence

Detector which is used in combination with the GC × GC to identify compounds containing
sulfur. A dual plasma burner and controller ensure the very high temperature combustion of the
sample. During the combustion, the sulfur present in the sample is converted to SO. The reaction
products are collected by means of a vacuum pump and are transferred to the reaction cell. An
ozone generator produces the ozone necessary for the chemiluminescence reaction of SO and
ozone that gives rise to excited SO2*. During the subsequent relaxation, equimolar amounts of
photons are produced in a frequency range of 280 – 420 nm. The light is filtered, detected by a
photomultiplier tube and converted into an electronic signal which varies linearly with the sulfur
content [15-16].
The pressure of the air flow used by the ozone generator is set at 350 torr (0.47 bar) and the
burner temperature is set at 800 °C. The hydrogen and oxygen flow rates are set at 40 and 7
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standard cubic centimeters per minute respectively. The background noise remains lower than 2
mV throughout the experiment.
Figure 2-3: schematic overview of the SCD
Table 2-2: Settings used for the GC × GC analysis of the calibration samples and gas oil
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Standard 1 and 2 Gas oil
Injector temperature 300 °C 280 °C
Split flow 10 ml/min 10 ml/min
Oven program 40 to 160 °C at 3 °C/min 40 to 300 °C

160 to 300 °C at 20 °C/min at 3 °C/min
5 min at 300 °C
Modulation time 5s 5s
Detector temperature 300 °C 280 °C
2.2.3 Gas oil

For the detection of sulfur components in the gas oil again the same setup for the GC × GC is
used. All experiments were carried out using the split/splitless injector. For every experiment,
0.2 µl was injected. The applied GC × GC settings are summarized in Table 2-2.
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2.2.4 Elemental analyzer

A Thermo Scientific FLASH 2000 CHNS elemental analyzer gives information about the
carbon, hydrogen, nitrogen and sulfur content of a sample. VGOs, gas oils and other mixtures
like gas condensates and bio-oils have been analyzed. All these results are included in annex B.
More accurate measurement of the total sulfur content of the VGOs and the gas oil can be
obtained with the elemental analyzer coupled with a flame photometric detector (FPD) for
sensitive sulfur detection. The sample is injected in a tin capsule which is folded, weighed and
introduced into the autosampler. Sample, oxygen and a helium carrier flow are brought to a
combustion room where combustion at a high temperature takes place. The high temperature is
attained thanks to the very exothermal oxidation of tin. This also ensures the complete
combustion of the sample. The effluent is sent to the reactor where oxygen in excess is trapped
and where nitrogen oxides are reduced to N2 and SO3 is reduced to SO2. The gas mixture is then
sent to a chromatographic column to be separated and to a detector for the quantification. In case
of CHNS analyses, a thermal conductivity detector is used. The FPD detector applied for
sensitive sulfur analyses consists of a combustion chamber, a narrow band interferential filter,
and a photomultiplier tube for measuring the photons emission. Sulfur containing compounds
(mainly SO2) form the gas mixture are introduced in a hydrogen rich flame where they
decompose, giving rise to excited S2* molecular species. An optical filter focused at 394 nm
isolates the photons released by the relaxation of S2* to its ground state. In the photomultiplier
tube, the photons are detected and converted into measurable electrical signals [17].
The helium carrier gas flow is fixed at 140 ml/min, the oxygen flow is set at 250 ml/min. The run
time of the experiment is 720 s, sampling delay is 15 s and oxygen injection lasts 10 s. The
furnace temperature is set at 950 °C and the oven for the chromatographic column is fixed at 65
°C. These conditions apply for both CHNS as sensitive sulfur analyses.
Before the actual measurements can start the elemental analyzer has to be calibrated. The
calibration procedure involves the injection of ‘blank’ samples followed by standards with
known composition according to the scheme shown in Table 2-3. For the calibration of the FPD
samples of the ‘Soil’ standard with different weights are needed, whereas for the regular CHNS
analysis the at least 4 measurements of 2-3 mg of the ‘BBOT’ standard are used.
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Table 2-3: Calibration scheme for sensitive sulfur and regular CHNS analyses
Type FPD calibration CHNS calibration
Sample Weight Sample Weight
By-pass Soil standard* 2-3 mg BBOT standard** 2-3 mg
Blank Blank - Blank -
STD Soil standard 0.5 mg BBOT standard 2-3 mg
Unknown Soil standard 1-2 mg BBOT standard 2-3 mg
*Soil standard: 1.755 wt% carbon, 0.195 wt% nitrogen, 0.039 wt% sulfur
**BBOT standard: 72.53 wt% carbon, 6.09 wt% hydrogen, 7.44 wt% sulfur, 6.51 wt% nitrogen, 7.43 wt% oxygen
‘By-pass’ means that the sample is introduced, combusted and sent to the reactor but there is no
data processing done by the software. By-pass is used to check if everything is in working order.
‘Blank’ means that a tin cup is introduced without adding any sample. Soil or BBOT standard
samples injected as ‘Unknown’ are used to check the calibration.
Based on the measurements of the standards, a calibration curve is fitted. For CHNS analysis the
peak area is proportional to the concentration so a linear curve is fitted as displayed in Figure
2-4. In case of FPD calibration the peak area varies quadratically with respect to the sulfur
concentration. If the average deviation is small enough, measurement can start. If not, the
calibration procedure must be repeated. Figure 2-5 shows a calibration curve for the FPD and
gives the parameters for the equation of the quadratic curve: Peak area = Ka C2 + Kb C + Kc
with C the concentration of sulfur.
Minimum requirement for a good calibration curve is a coefficient of determination of at least

0.9999. Only measurements with sulfur concentrations within the range of the sulfur
concentration of the standards used to set up the calibration curve are valid. This requires that a
specific standard is necessary based on an estimation of the amount of sulfur present in the
sample.
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Figure 2-4: Linear calibration curve for CHNS analysis
Figure 2-5: Quadratic calibration curve for the FPD
An example of a FPD analysis of a gas oil can be found in Table 2-4. Other results obtained with
the FPD are not shown here since they are unreliable due to calibration problems.
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Table 2-4: Results of an FPD analysis of gas oil 1191
Measurement number S [ppm]

1191_1 180
1191_2 230
1191_3 170
2.3 Samples
Analytical gases were provided at a minimum purity of 99.99% (Air Liquide, Belgium).
Polywax655® was obtained from Restek. It consists of pure polyethylene with a number average
molecular weight of 655 g/mole. Carbon disulfide, benzene and toluene were also purchased
from Sigma-Aldrich with a minimum purity of 99.9%. VGO A was supplied by the Total
refinery (Antwerp, Belgium) and VGO B by the ExxonMobil refinery (Antwerp, Belgium).
VGO A has an initial boiling point of 150 °C and a final boiling point of 500 °C while VGO B
has an initial boiling point of 120 °C and a final boiling point of 570 °C. The density of VGO A
at 40 °C is 0.862 kg/m³ while that of VGO B is 0.886 kg/m³. The elemental composition of these
vacuum gas oils was determined using a Flash EA2000 and can be found in Table 2-5. The gas
oil was supplied by Total (Feluy, Belgium). Its elemental composition was determined using a
Flash EA2000 and can also be found in Table 2-5.
Table 2-5: Elemental composition of the vacuum gas oils and the gas oil [wt%]
VGO A VGO B Gas oil
C 87.39 87.35 86.42
H 12.46 12.39 13.15
N <0.01 <0.01 0.09
S 0.14 0.25 0.33
The molecular composition of the two sulfur calibration mixtures is shown in Table 2-6.
Calibration mixture 1 is ASTM D5623 standard 2 and is delivered in a 2 ml ampoule containing
10 sulfur components diluted in 90 wt% isooctane and 10 wt% toluene. Calibration mixture 2 is
Sulfur Simulated Distillate Standard and is also delivered in a 2 ml ampoule. It contains 13 sulfur
components diluted in 93.75 wt% isooctane and 6.25 wt% toluene. Both mixtures were provided
by DCG Partnership.
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Table 2-6: Composition of standards 1 and 2
Standard 1 Standard 2
Component Conc [ppm wt] Component Conc [ppm wt]
dimethyl sulfide 103.11 ethanethiol 29.96
ethyl methyl sulfide 50.66 1-propanethiol 59.88
thiophene 111.96 1-butanethiol 30.07
diethyl sulfide 80.71 1-pentanethiol 59.89
dimethyl disulfide 27.76 1-hexanethiol 29.71
2-methyl thiophene 75.86 1-heptanethiol 59.84
3-methyl thiophene 104.87 3,5-dimethyl benzenethiol 29.63
diethyl disulfide 24.24 1-octanethiol 59.54
benzothiophene 78.98 1-nonanethiol 29.78
3- methylbenzothiophene 107.37 1-decanethiol 59.91
1-pentadecanethiol 31.39
1-hexadecanethiol 60.45
1-octadecanethiol 30.99
2.3.1 Polywax sample preparation

20 mg of Polywax was weighed and put inside a glass vial. 7 mg of naphthalene was added as an
internal standard. The mixture was then dissolved in 1.5 ml of benzene. Prior to injection the
sample was heated to 60 °C to make the sample less viscous. In case of the cold-on column
injection additional benzene was added until the peak height of naphthalene corresponded to that
of the split/splitless injection. This was done to prevent differences in the standard deviation of
the two techniques due to higher sensitivity (higher injection volume) when using the cold-on
column injector.
2.3.2 Vacuum gas oil sample preparation

In case of a split/splitless injection VGO A was injected undiluted. VGO B was heated until
40 °C and then dissolved in carbon disulfide (1v/1v) since the high viscosity of VGO B did not
allow an undiluted injection. For the cold-on column injections of VGO A and VGO B, the
samples were first heated until 40 °C and then dissolved in carbon disulfide (1v/5v).
2.3.3 Gas oil sample preparation

The gas oil sample was injected undiluted.
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2.4 Data treatment

2.4.1 VGO and polyethylene sample
Data acquisition of the GC × GC analysis was performed using Thermo Scientific’s Chrom-Card
data system. Results obtained with the FID detector were exported to a cdf file and imported into
GCImage (Zoex, USA). GCImage performed the contour plotting, retention time measurement,
peak fitting and peak integration.
For the FID data, each peak (or blob) was identified by both a group and a carbon number. The
peak name, 1D retention time, 2D retention time and peak volume were exported as a csv file.
This csv file was imported in an in-house written excel macro. Together with a library containing
the response factors the macro can then calculate the mass fraction of each component. This can
be done either by internal normalization [18]:
.
(2-1)
∑ .
or by means of an internal standard:
.
. (2-2)

.

Where fi is the relative response factor for component i. It has been demonstrated that various
isomeric hydrocarbons, produce only slightly different relative FID responses, and hence that a
fair approximation of the relative response factor may be written as [18]:

(2-3)
. ,
Additionally this macro determines a detailed PIONA group type composition, a boiling point
curve and the elemental composition of the sample using data included in the library (group type,
molecular weight and elemental formula) and the detailed composition of the GC × GC analysis.
The different groups defined in the library are n-paraffins, i-paraffins, mononaphthenes,
dinaphthenes, monoaromatics, naphthenoaromatics, diaromatics, naphthenodiaromatics,
triaromatics, naphthenotriaromatics, tetra-aromatics, naphthenotetra-aromatics and terpanes.
Terpanes are a group of highly saturated cyclic compounds which contain 4 (e.g. steranes), 5
(e.g. hopanes) or more rings together with some aliphatic side chains. The internal standard
method was used for the analysis of Polywax while the internal normalization method was used
for the analysis of the VGO samples.
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2.4.2 Gas oil analysis

For the SCD data, no library with response factors is available.. To facilitate peak identification
and to develop a calibration method,
method, analysis of two calibration mixtures with known
concentrations has been performed. Each calibration mixture has been injected five times.
Combining the results of the integrated chromatograms of the calibration mixtures with the
known concentrations of the
he sulfur components in the mixtures allows to calculate average
response factors over four runs for the components present in the mixtures. The fifth run has
been used to check the results.
One gas oil (numbered 3778) has been analyzed with the SCD detector.
detector. To facilitate the peak
identification, the chromatogram is compared with results obtained on a GC × GC coupled with
a TOF-MS.
MS. In order to filter the sulfur containing compounds, m/z ratios of 147, 161, 175 have
been used to trace the peaks originating from benzothiophenes [19] and 184, 198, 212, 226, 240
for the dibenzothiophenes [20].
[20] Each peak (or blob) was identified by both a group
(benzothiophenes or dibenzothiophenes) and a carbon number representing the number of
carbons present in the sample as a alkyl substituent. The C1 dibenzothiophenes for example can
be 1-, 2-, 3- or 4- methyldibenzothiophene. The peak name, 1D retention time, 2D retention time
and peak volume were
re exported as a csv file. No internal standard was added so the internal
normalization method is used to determine the concentrations. The total sulfur concentration is
obtained with the elemental analyzer coupled with a flame photometric sulfur detector (Table
2-5).
Figure 2-6:: Benzothiophene (left) and dibenzothiophene (right)
2.5 Results and discussion

2.5.1 Polywax analysis
Polywax polyethylenes are fully saturated homopolymers of ethylene that exhibit a high degree
of linearity and crystallinity. These synthetic waxes have narrow molecular weight distributions
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with a typical polydispersity (Mw/Mn) of 1.08. Polywax was analyzed multiple times to test the
maximum detectable carbon number, injector discrimination and repeatability of the methods.
Both split/splitless and cold-on column injections were carried out. Naphthalene was used as an
internal standard. The detailed composition
Figure 2-7: GC × GC chromatogram of Polywax injected on a cold-on column injector
Figure 2-7 shows the GC × GC contour plot of Polywax injected on the cold-on column injector.
Table 2-7 shows the average mass fraction of all injections for some of the n-paraffins present in
Polywax as well as the total sum of all visible Polywax components. The maximum visible
carbon number using this method is 46 or hexatetracontane for both split/splitless and cold-on
column injection. Because the average molecular weight of the Polywax is 655 g/mole which
corresponds to C47-C48 n-paraffin, it is clear that the major part of the sample has not eluted. It
was either trapped on the retention gap (cold-on column injection), was vented (split/splitless
injection) or retained on the column. There is a distinct difference between the measured
fractions when using the cold-on column injector and those measured when using the
split/splitless injector based on the known amount of internal standard (naphthalene) added to the
Polywax. The higher the carbon number the more significant the difference between the fractions
measured when using split/splitless injection and the cold-on column injection becomes.
Ranging from a difference of 0.04 wt% at a carbon number of 14 to a difference of 7.57 wt% at a
carbon number of 46. This clearly shows that mass discrimination in the split/splitless injector
plays an important role when analyzing heavier hydrocarbon samples.
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Table 2-7: GC × GC analysis of Polywax655™ on the split/splitless injector and the

cold-on column injector (average and standard deviation of three injections)
Component Mass fraction Mass fraction St. dev. SS St. dev. COC
SS (wt%) COC (wt%) (wt%) (wt%)
tetradecane 0.03 0.07 0.01 0.00
hexadecane 0.03 0.15 0.00 0.04
octadecane 0.04 0.32 0.00 0.08
eicosane 0.04 0.51 0.00 0.16
docosane 0.06 0.63 0.01 0.15
tetracosane 0.07 0.81 0.03 0.12
hexacosane 0.10 0.63 0.05 0.11
octacosane 0.15 0.85 0.07 0.03
triacontane 0.25 0.91 0.09 0.09
dotriacontane 0.41 1.16 0.25 0.08
tetratriacontane 0.59 1.60 0.34 0.13
hexatriacontane 0.78 1.86 0.47 0.09
octatriacontane 1.02 2.72 0.57 0.04
tetracontane 1.33 3.41 0.65 0.15
dotetracontane 1.65 5.15 0.70 0.08
tetratetracontane 1.95 7.23 0.43 0.10
hexatetracontane 1.59 9.16 0.56 0.05
Total 10.09 37.18 3.98 1.19
Mass discrimination is not the only problem with the use of the split/splitless injector, also the
standard deviation of the different injections is a lot higher at higher carbon numbers when
compared to the cold-on column injector.
Taking both facts into account it is clear that for heavy hydrocarbon samples (e.g. gas oils) the
use of a cold-on column injector over a split/splitless injector is recommended. There are also
other injectors available which minimize mass discrimination effects e.g. PTV-injector that have
not been evaluated [12] and it is expected that similar conclusions could be drawn when
comparing the PTV-injector with a split/splitless injector.
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2.5.2 Vacuum gas oil analysis

A GC × GC analysis with FID detector of each of the vacuum gas oil samples has been
performed using the conditions described in paragraph 2.2.1. Both a cold-on column injection
and a split/splitless injection have been carried out. 2D contour plots of VGO A injected on both
the cold-on column injector and the split/splitless injector are shown in Figure 2-8. A 3D contour
plot of VGO B on the cold-on column injector is shown in Figure 2-9. Different 2D elution
zones of important compounds groups have been marked on the chromatograms. Both the
split/splitless and the cold-on column color plots of VGO A show a high resemblance. The main
difference is the shift in first dimension retention time. Each chemical group is reasonably well
separated from the other group in the second dimension column. There is however some minor
overlap between groups at the boundaries of these groups. Each peak is assigned both a group
and a carbon number. The group is assigned based on the group type separation which is
depicted in Figure 2-8. The carbon number is assigned using the so called “roof tile” structure or
ascending bands of isomeric compounds [21] combined with the knowledge of some of the
important components inside each group (e.g. naphthalene for the diaromatics). Combining this
information allows to determine a very detailed PIONA (see Table 2-8 for an example using the
cold-on column injector) which combines a group type analysis of over 10 different groups with
the assigned carbon number providing very detailed but lumped composition of the sample.
Lumping is however inevitable due to the high amount of isomers present inside the samples.
For example tricosane has almost 6 million structural isomers.
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Figure 2-8: GC × GC contour plot of VGO A (a) cold-on column injection and (b)
split/splitless injection
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Table 2-8: Detailed Carbon number distribution of VGO A (Average over three runs) determined using the cold-on column injector
N A
P I O Terpanes Total
mono- di- mono naphthenodi- naphthenodi- tri- naphthenotri-
8 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01
9 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.03
10 0.00 0.01 0.00 0.05 0.02 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.14
11 0.02 0.03 0.00 0.12 0.07 0.09 0.06 0.07 0.00 0.00 0.00 0.00 0.45
12 0.06 0.09 0.00 0.23 0.17 0.16 0.15 0.34 0.00 0.00 0.00 0.00 1.21
13 0.17 0.26 0.00 0.46 0.25 0.23 0.34 0.64 0.05 0.00 0.00 0.00 2.39
14 0.36 0.43 0.00 0.74 0.19 0.47 0.46 0.84 0.35 0.03 0.00 0.00 3.88
15 0.55 0.59 0.00 0.92 0.31 1.14 0.56 0.62 0.76 0.23 0.00 0.00 5.68
16 0.90 0.75 0.00 0.97 0.51 0.67 0.66 0.74 1.24 0.56 0.04 0.00 7.05
17 1.02 0.99 0.00 1.56 0.43 0.89 0.57 0.69 1.21 0.69 0.09 0.00 8.12
18 1.60 1.52 0.00 1.24 0.38 0.94 0.78 0.73 1.27 0.76 0.15 0.00 9.36
19 1.75 1.85 0.00 1.71 0.41 1.09 1.44 0.50 0.84 0.73 0.25 0.00 10.57
20 1.62 1.24 0.00 1.70 0.21 1.46 1.25 0.59 0.54 0.71 0.26 0.00 9.59
21 1.63 1.54 0.00 1.70 0.21 1.34 0.80 0.47 0.00 0.09 0.15 0.00 7.94
22 1.50 1.44 0.00 1.33 0.06 1.41 0.54 0.25 0.00 0.00 0.00 0.00 6.53
23 1.28 1.55 0.00 1.25 0.00 1.98 0.19 0.00 0.00 0.00 0.00 0.00 6.25
24 1.44 1.50 0.00 0.96 0.00 2.38 0.00 0.00 0.00 0.00 0.00 0.00 6.28
25 0.88 1.14 0.00 0.63 0.00 1.09 0.00 0.00 0.00 0.00 0.00 0.00 3.74
26 0.45 1.19 0.00 0.48 0.00 0.34 0.00 0.00 0.00 0.00 0.00 0.00 2.45
27 0.19 0.82 0.00 0.16 0.00 0.18 0.00 0.00 0.00 0.00 0.00 0.00 1.36
28 0.19 0.70 0.00 0.09 0.00 0.16 0.00 0.00 0.00 0.00 0.00 0.00 1.14
29 0.15 0.51 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.66
30 0.08 0.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.48
31 0.06 0.34 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.39
32 0.04 0.51 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.54
33 0.02 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.22
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.53 3.53
Total 15.97 19.60 0.00 16.31 3.20 16.10 7.80 6.49 6.26 3.80 0.94 3.53 100.00
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Figure 2-9: GC × GC 3D plot of VGO B with cold-on column injection
Figure 2-10 shows the carbon number distribution derived from this detailed PIONA analysis of
the two VGOs for both the split/splitless injection and the cold-on column injection.
Discrimination effects are visible starting from carbon number 30 in all samples when comparing
both injections. Hydrocarbons with a carbon number of 30 or higher are underestimated on the
split/splitless injector. Table 2-9 shows the PIONA analysis that has been derived from Table
2-8. In most groups there is only a small difference between the split/splitless injection and the
cold-on column injection. The groups that deviate the most are the naphthenoaromatics,
naphthenodiaromatics and the naphthenotriaromatics. These groups are located between the
monoaromatics and diaromatics, diaromatics and triaromatics and triaromatics and tetra-
aromatics respectively and are hard to differentiate from these groups which could explain the
larger error margin on their quantification. In case of VGO B there is also some deviation on the
paraffins. Since the heaviest components are mostly paraffins this can be explained due to mass
discrimination effects. These effects are also visible in Figure 2-10 which shows the carbon
number distribution derived from Table 2-8. It shows that mass discrimination becomes
significant starting from a carbon number of 30. Table 2-9 and Table 2-10 show the standard
deviation of the PIONA analysis and carbon number distribution when VGO A is injected
multiple times. The standard deviation of the cold-on column injection is in overall lower than
the split/splitless injection. An exception here are the terpanes where the standard deviation is
slightly higher on the cold-on column.
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12
VGO A
10
Mass Fraction (-)
6
SS
4
COC
2
0
7 9 11 13 15 17 19 21 23 25 27 29 31 33 35
Carbon number (-)

7
6
VGO B
Mass fraxtion (wt%)
3 SS
COC
2
0
7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45
Carbon number (-)
Figure 2-10: Carbon number distribution of VGO A and VGO B on both split/splitless
injector and cold-on column injector
Taken all these considerations into account it is clear that there is a clear benefit in using the
cold-on column injector when injecting heavier hydrocarbon samples (Carbon number 30 and
up) on the GC × GC. The detailed reconstructed composition of VGO A and VGO B is included
in Annex C, both for the split/splitless injection as for the cold-on column injection.
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Table 2-9: Detailed PIONA analysis of the two VGOs both on split/splitless injector and
cold-on column injector [wt%]
VGO A VGO B
Group type Average (3 runs) Standard deviation Single run
SS COC SS COC SS COC
Paraffins 15.97 15.66 0.90 0.24 20.14 18.82
Isoparaffins 19.60 19.28 1.39 0.77 22.69 23.29
Olefins 0.00 0.00 0.00 0.00 0.00 0.00
mono- 16.31 15.47 1.95 0.11 12.54 11.82

Naphthenes
di- 3.20 3.25 0.36 0.02 0.53 1.19
mono- 16.10 16.63 1.78 1.27 12.37 12.58
naphtheno- 7.80 6.87 0.77 0.83 2.31 3.57
di- 6.49 6.82 0.27 0.03 3.92 3.31
naphthenodi- 6.26 6.80 0.94 0.43 3.10 5.16

Aromatics
tri- 3.80 3.98 0.42 0.25 2.92 2.13
naphthenotri- 0.94 1.35 0.43 0.07 1.62 0.87
tetra- 0.00 0.10 0.03 0.00 1.25 0.90
naphthenotetra- 0.00 0.00 0.00 0.00 0.53 0.00
Terpanes 3.53 3.81 0.30 0.60 16.42 16.35
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Table 2-10: Standard deviation of carbon number distribution of VGO A on both

split/splitless injector and cold-on column injector [wt%]
Carbon number SS COC

10 0.11 0.2
15 0.35 0.25
20 0.73 0.12
25 0.48 0.06
30 0.11 0.02
2.5.3 Calibration mixtures

A GC × GC analysis with SCD detector of the calibration mixtures has been performed using the
conditions described in paragraph 2.2.2. Figure 2-11 and Figure 2-12 give the contour plots of
the individual mixtures. The blobs are well separated and can easily be identified based on
volatility. The thiols show a similar structure as the hydrocarbons typically do. Aromatic
compounds are longer retained in the polar column and hence show later on the second
dimension of the plot. This is also in agreement with the experiences with hydrocarbons.
Figure 2-11: GC × GC contour plot of calibration standard 1 with SCD detector
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Note that in Figure 2-12 wrap-around occurs for the benzothiophenes. A higher modulation time
would resolve this but this is not necessary since there is no peak overlap.
Figure 2-12: GC × GC contour plot of calibration standard 2 with SCD detector
The second column of Table 2-11 and Table 2-12 shows the average response factors for every
component calculated by the internal standard method based on four injections. The SCD yields
a signal that is linear and equimolar to the sulfur content of the sample [22]. The response factors
should hence be close to 1 which is confirmed in Table 2-11 and Table 2-12. Only for 3,5-
dimethyl benzenethiol there is a significant deviation. This is probably due to absorption of this
compound by the needle used for the injection and by the liner inside the split/splitless injector.
The results of the fifth run have been used to test the method by calculating the weight fraction
of the components in the standard, both by using the internal standard method (columns 4 and 5)
and internal normalization (columns 6 and 7). 1-butanethiol was chosen as internal standard. For
some compounds, the internal standard method gives better results, and for the others internal
normalization is preferred. Since the response factors are close to 1, there is little difference in
the concentrations calculated with the average response factor and those calculated with a
response factor equal to 1. This result indicates that the response factor can be set equal to 1 for
the calculation of the concentrations of the sulfur components in the gas oil.
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Table 2-11: Response factors, measured sulfur concentration and calculated sulfur
concentration for calibration mixture 1
Calculated S concentration
Sulfur
Name component Avg RF concentration Internal Standard Normalized
[ppm]
Avg RF RF = 1 Avg RF RF = 1
1-butanethiol (I.S.) 1.00 30.07 30.07 30.07 29.59 31.66
1-decanethiol 0.93 59.91 65.85 57.95 64.80 61.02
1-heptanethiol 0.99 59.84 61.06 59.17 60.08 62.30
1-hexanethiol 0.91 29.71 30.86 27.45 30.37 28.91
1-nonanethiol 0.94 29.78 30.89 27.92 30.40 29.40
1-octanethiol 1.00 59.54 62.04 60.47 61.05 63.67
1-pentanethiol 0.99 59.89 60.26 59.36 59.30 62.51
1-propanethiol 0.99 59.88 58.34 58.58 57.41 61.68
3,5-dimethyl benzenethiol 0.66 29.63 26.92 17.93 26.49 18.88
ethanethiol 0.91 29.96 29.19 26.77 28.72 28.19
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Table 2-12: Response factors, measured sulfur concentration and calculated sulfur
concentration for calibration mixture 2
Calculated S concentration
Sulfur
Name component Avg RF concentration Internal Standard Normalized
[ppm]
Avg RF RF = 1 Avg RF RF = 1
2-methyl thiophene (IS) 1.00 75.86 75.86 75.86 75.75 75.90
3-methyl thiophene 0.96 104.87 105.48 101.21 105.33 101.27
3-methylbenzothiophene 1.00 107.37 70.91 71.05 70.81 71.08
benzothiophene 1.02 78.98 48.26 49.22 48.19 49.24
diethyl disulfide 1.03 24.24 33.97 34.96 33.92 34.98
diethyl sulfide 1.00 80.71 79.51 79.87 79.40 79.91
dimethyl disulfide 1.01 27.76 49.71 50.41 49.63 50.44
dimethyl sulfide 1.00 103.11 128.38 128.49 128.20 128.56
ethyl methyl sulfide 1.00 50.66 55.88 56.15 55.80 56.17
thiophene 0.99 111.96 118.67 117.91 118.50 117.97
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2.5.4 Gas oil

A GC × GC analysis with SCD detector of one gas oil is performed according to the conditions
discussed in 2.2.3. The 2D contour plot of the gas oil is shown in Figure 2-13.
There is a clear resemblance in the structure for the dibenzothiophenes as for the
benzothiophenes in the chromatogram obtained with the SCD detector and in the filtered
chromatogram obtained with the mass spectrometer (Figure 2-14 and Figure 2-15).
Confirmation of the carbon number assigned to the peaks by the mass spectrometer was possible
for all dibenzothiophenes and for C1 to C4 for the benzothiophenes. The C5 to C9 carbon
numbers were assigned based on the so-called roof tile principle that has been used for
identification of hydrocarbon chromatograms.
Figure 2-16 shows the contour plot as obtained with the FID. This figure clearly shows that the
dibenzothiophenes are situated in the elution area of the diaromatics. It is therefore impossible to
identify and quantify the sulfur containing compounds based on a chromatogram obtained with
an FID.
Figure 2-13: GC × GC contour plot of gas oil 3778 with SCD detector
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Figure 2-14: GC × GC contour plot of gas oil 3625 with TOF-MS detector (filtered m/z:
184, 198, 212, 266, 240) used for identification of dibenzothiophenes
Figure 2-15: GC × GC contour plot of gas oil 3625 with TOF-MS detector (filtered m/z:
147, 161, 175) used for identification of benzothiophenes
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Figure 2-16: GC × GC contour plot of gas oil 3778 with FID detector
The signal and hence the peak volume of one group (compound) obtained from the SCD is linear
and equimolar to the amount of sulfur originating from that group:
, (2-4)
with
, the number of moles sulfur originating from group i
the constant of proportionality for compound i
the peak volume of group i
The results of the analysis of the calibration mixtures have shown that the response of the SCD
to the sulfur is independent of the molecule in which the sulfur is present. In other words, the
proportionality constant K is independent of the compound i. Assuming that every sulfur
containing component only contains one atom of sulfur, the signal is also proportional to the
number of moles of compound i: , . Multiplying by the molar mass yields a measure for
the total weight of the component present in the sample:
(2-5)
with
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a measure for the weight of the component in the sample
the molecular mass of the compound
The sum of the peak volumes indicates the total number of moles sulfur present in the sample.
Multiplying by the molar mass of sulfur yields a measure for the weight of sulfur in the sample:
,

, (2-6)
The ratio of the total weight of sulfur in the sample to the total weight of the sample is given by
the weight percentage of sulfur present in the sample obtained from the elemental analyzer. The
weight fraction of each sulfur containing compound in the gas oil can then by calculated as
,

,
! (2-7)
,

,

, ∑
with
the weight percentage of sulfur present in the sample obtained from the elemental analyzer
Table 2-13 lists the calculated mass fractions of the sulfur components in the gas oil.
Table 2-13: Calculated concentration of sulfur containing compounds in gas oil 3778
Group Name Mass fraction of the group

in the gas oil [wt %]
C1 benzothiophene 0.00
dibenzothiophene 0.10
C1 dibenzothiophene 0.29
SUM 2.22
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The detailed reconstructed composition (including the hydrocarbons) of gas oil 3778 can be
found in Annex C.
2.6 Future work

To be able check the results of the gas oil, new injections with an appropriate compound as
internal standard would be useful.
As shown in Table 2-5 the two VGOs contain a fraction of sulfur components. It is impossible to
separate these sulfur components from the normal hydrocarbons with the results obtained from
the FID detector (e.g. benzothiophene and analogues are located in the diaromatics group). An
analysis of the VGOs with the SCD detector would overcome this problem. Mass fractions can
be calculated based on internal normalization where the total sulfur content is obtained with the
elemental analyzer. Adding an appropriate compound as internal standard would allow to check
these results with those obtained with an internal standard method.
2.7 Conclusion
Newly developed conditions for HT-2D-GC were applied on two VGO samples. The conditions
allow for a quantification of the sample by chemical group and carbon number. The maximum
detectable carbon number was established at 46. Two VGOs showed that the heavier
hydrocarbons (carbon number 30 and up) are slightly discriminated. Additionally the results
obtained when using the cold-on column injector have a lower standard deviation than those
obtained using the split/splitless injector.
Experimental confirmation of the linear and equimolar character of the SCD signal has been
provided. This results in response factors equal to 1 and allows for straightforward calculations
of weight fractions in the sample.
A GC × GC analysis with SCD detector of one gas oil is performed. The sulfur present in the gas
oil mainly originates from benzothiophenes and dibenzothiophenes. This has been confirmed
with TOF-MS.
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2.8 References
1. Singh, J., et al., Reaction pathways and product yields in mild thermal cracking of
vacuum residues: A multi-lump kinetic model. Chemical Engineering Journal, 2005.
108(3): p. 239-248.
2. Van Geem, K.M., M.F. Reyniers, and G.B. Marin, Challenges of modeling steam
cracking of heavy feedstocks. Oil & Gas Science and Technology-Revue D Ifp Energies
Nouvelles, 2008. 63(1): p. 79-94.
3. Bartholomew, C.H., Mechanisms of catalyst deactivation. Applied Catalysis a-General,
2001. 212(1-2): p. 17-60.
4. Dutriez, T., et al., Extended characterization of a vacuum gas oil by offline LC-high-
temperature comprehensive two-dimensional gas chromatography. Journal of Separation
Science, 2010. 33(12): p. 1787-1796.
5. Herod, A.A., K.D. Bartle, and R. Kandiyoti, Characterization of heavy hydrocarbons by
chromatographic and mass spectrometric methods: An overview. Energy & Fuels, 2007.
21(4): p. 2176-2203.
6. Oro, N.E. and C.A. Lucy, High performance liquid chromatographic separations of gas
oil samples and their hydrotreated products using commercial normal phases. Journal of
7. Andersson, P.E., M. Demirbüker, and L.G. Blomberg, Quantitative hydrocarbon group
analysis of gasoline and diesel fuel by supercritical fluid chromatography. Journal of
Chromatography A, 1992. 595(1–2): p. 301-311.
8. Andersson, P.E., M. Demirbüker, and L.G. Blomberg, Characterization of fuels by multi-
dimensional supercritical fluid chromatography and supercritical fluid
chromatography—mass spectrometry. Journal of Chromatography A, 1993. 641(2): p.
347-355.
9. Fafet, A., J. Bonnard, and F. Prigent, Nouveaux développements en spectrométrie de
masse pour l'analyse quantitative par famille chimique des coupes pétrolières (Première
partie). Oil & Gas Science and Technology - Rev. IFP, 1999. 54(4): p. 439-452.
10. Mahe, L., et al., Global approach for the selection of high temperature comprehensive
two-dimensional gas chromatography experimental conditions and quantitative analysis
in regards to sulfur-containing compounds in heavy petroleum cuts. Journal of
11. Ruiz-Guerrero, R., et al., Comparison of comprehensive two-dimensional gas
chromatography coupled with sulfur-chemiluminescence detector to standard methods
for speciation of sulfur-containing compounds in middle distillates. Journal of
Chromatographic Science, 2006. 44(9): p. 566-573.
12. Bailey, R., Injectors for capillary gas chromatography and their application to
environmental analysis. Journal of Environmental Monitoring, 2005. 7(11).
2010. 1217(43): p. 6623-6633.
14. Hernandez-Baez, D.M., et al., Establishing the Maximum Carbon Number for Reliable
Quantitative Gas Chromatographic Analysis of Heavy Ends Hydrocarbons. Part 1: Low-
Conversion Thermal Cracking Modeling. Energy & Fuels, 2011.
15. Richard Godec, N.J., Donald H. Stedman, Process for simultaneous measurement of
sulfur and non-sulfur containing compounds. 1991, Sievers Research Inc.: U.S.
16. John D. Ray, N.J., Method and apparatus for chemiluminescent detection of sulfur. 1993,
Sievers Instruments, Inc.: U.S.
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17. Scientific, T., OEA/FPD System Instruction Manual. 7th ed. 2009, Cambridge: Thermo
Fisher Scientific.
18. Beens, J., et al., Quantitative Aspects of Comprehensive Two-Dimensional Gas
Chromatography (GC×GC). Journal of High Resolution Chromatography, 1998. 21(1):
p. 47-54.
19. Gallegos, E.J., Gas-Chromatography Mass-Spectrometry Analysis of Normal-
Alkylbenzothiophenes Identified in Arabian Heavy Asphaltenes, Pyrolysis Oil. Novel
Techniques in Fossil Fuel Mass Spectrometry, 1989. 1019: p. 94-115.
20. Jack Cochran, J.P. (2011) GCxGC Analysis of Complex Petroleum Hydrocarbons: Sulfur
Speciation in Diesel 2.
2010. In Press, Corrected Proof.
22. Agilent, T., Dual Plasma Sulfur and Nitrogen Chemiluminescence Detectors, A.T. Inc.,
Editor. 2006.
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Chapter 3: Literature review TLEs 37
Chapter 3
Literature review TLEs
3.1 Introduction
Steam cracking is an important process in the petrochemical industry. The purpose is to convert
gaseous (e.g. ethane, propane) or liquid (e.g. naphtha, gas condensates) feedstocks coming from
the refinery to more valuable products (olefins and aromatics) which are base materials for other
petrochemical processes (e.g. polyethylene production). “Cracking” refers to the scission of
bonds to form radicals. These radicals can dissociate and form shorter unsaturated molecules.
Steam is added to the mixture to lower the partial pressure of the hydrocarbons. This partially
suppresses the bimolecular reactions and results in higher olefin yields. For the same reason, the
total pressure is kept as low as possible. An additional benefit of steam is that it helps reduce
coke formation. Because scission reactions are highly endothermic, both the feedstock and steam
are send to a tubular reactors inside a furnace. The mixture is heated until 750-875 °C for a very
short time (0.1-0.5 s). The heating takes place in two steps. In the convection section the
feedstock is heated to 500-680 °C. At these temperatures, cracking reactions start to occur. In the
radiant section the diluted feedstock is further heated and a high heat flux provides the energy
required for the endothermic reactions to take place. A short residence time is necessary to have
optimal yields and to avoid secondary reactions. The temperature profile in the radiant coils
should remain high because oligomerization reactions involved in the formation of secondary
products are favored by low temperatures. The steam to hydrocarbon ratio depends on the
feedstock and ranges from 0.25-0.35 for ethane cracking to 0.4-0.5 for naphta and 0.4-0.6 for gas
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Figure 3-1: Energy recovery in a steam cracker, Linde Engineering [3]
condensates and even higher for heavier feedstocks. The pressure drop should be low to keep the
coil inlet pressure as low as possible. One of the major problems for the steam cracking process
is coke formation. The coke layer leads to a higher pressure drop over the reactor and an
increased heat-transfer resistance in the coil. Steam cracking is one of the most energy
consuming reaction in petrochemical industry [2]. To reduce the energy consumption of the
process energy recovery is important. In the convection section, excess heat is used to heat
process steam, boiler feed water and high pressure steam (Figure 3-1). A transfer line exchanger
(TLE) recovers energy by rapidly cooling down the effluent and producing high pressure steam
from the released heat. For naphtha cracking, up to 45 % of the fired input duty can be recovered
in the form of high pressure steam. 30 % is consumed by the reaction and 18.5 % of the energy is
still present after the TLE. The remaining 6.5 % are cracking losses and stack losses [3].
3.2 Transfer line exchanger

Transfer line exchangers (TLEs) or quench coolers are used in steam cracking installations to
cool the effluent gas quickly below reaction temperature and to prepare the effluent for further
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Figure 3-2: Schematical overview of a cracking furnace with a TLE [4]
processing. Fast cooling is necessary to avoid secondary reactions. The second purpose of
modern TLEs is to recover energy by producing high pressure steam. The effluent generally
leaves the reactor between 750 and 900 °C [5], depending on the feedstock and the process
conditions. As shown in Figure 3-3 different setups and combination of TLEs can be used to
achieve the required cooling capacity. In case two cooling steps are used, the primary quench
typically cools the gas to 500-650 °C in 20 to 200 ms. The secondary quench can operate at a
different water pressure to produce lower pressure steam and cools further down to 400-300°C.
Reaction stops at a temperature around 500-650 °C, depending on the feedstock that has been
used. The lowest temperature to which the cracked gas can be cooled also depends on the
feedstock. Heavier feeds produce heavier products which condense at higher temperatures and
contribute to coke formation and TLE fouling [5].
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Figure 3-3: possible TLE combinations [3]
The cracked gas should not be cooled lower than 350 °C. This is why high pressure water and
steam is used. High pressure water has a higher saturation temperature so steam is generated at a
higher temperature inside the TLE. This causes the tube wall temperature to be higher than
would be the case when low pressure water is used. This reduces the probability of condensation
of heavy molecules on the tube. To produce high pressure steam, high pressure (±140 bar) water
is preheated in the convection section and is fed to the steam drum. Saturated water (300-340 °C)
flows to the bottom of the TLE through vertical pipes (
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Figure 3-2). Water is evaporated and a steam/water mixture comes out at the top of the TLE. The
water/steam ratio at the outlet of the TLE usually lies around 10. The mixture flows back to the
steam drum where water and steam are separated. The steam is led towards the furnace where it
is superheated and the water is reintroduced into the TLE. A continuous blow-down flow is used
to control the concentration of particles in the water. The TLE is a thermosyphon system so the
water/steam mixture flows by natural circulation. As the mixture contains more steam near the
top of the TLE, the density of the mixture is lower. The heavier water that is sent to the bottom
of the TLE pushes the water/steam mixture further. However, to keep this natural circulation
going, it is necessary for the steam drum to be placed on a position higher than the top of the
TLE. A natural circulation model for a closed loop, two-phase thermosyphon system is presented
in [6]. Discussing this model and including it in the calculation falls however out of the scope of
this master thesis.
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Figure 3-4: Quench system [1]
Due to the hydrocarbon flow, fouling of the TLE and coke formation can occur. This will lower
the cooling capacity of the TLE and limit the amount of steam that can be produced. It will also
cause an increase of the pressure drop and make the tube wall temperature rise. Several types of
TLE fouling or coking have been observed [5]. Firstly, fouling can be caused by coke produced
in the radiant coil that is carried into the TLE inlet cone where it blocks some of the tubes on the
TLE entry tube sheet. Such fouling is most serious in ethane cracking. A reason for extra coke
formation in the TLE is poor flow distribution in the entry cone and at the tube sheet that causes
eddies and backmixing.
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Figure 3-5: Simulated coke formation in a TLE [3]
Gas that remains trapped experiences long residence time at high temperature, which increases
tar and coke production. A third way for fouling originates from heavy polycyclic aromatics and
other high boiling components in the cracked gas that condense on the cool TLE tube walls. This
is particularly true for heavy naphthas, kerosenes and gasoils. These condensed high-boiling
substances are gradually converted to cokes.
Typically, TLE outlet temperatures increases by 50-100°C during the first day or two in gas oil
cracking. This can be explained by rapid coking according to a catalytic mechanism where nickel
or iron atoms from the metallic surface of the tube act as a catalyst for the formation of
filamentous cokes. When the metallic surface is completely covered with cokes, another, slower
mechanism allows the coke to continue growing (thermal cokes). This mechanism does no
longer depend on the presence of metal atoms, but is based on free radical reactions between the
coke layer and entities from the vapor phase. Since the free-radical mechanism is temperature
dependent, it will mainly contribute to coke formation in the radiant coil and near the entrance of
the TLE where the temperature is high.
When the pressure drop or the tube wall temperature gets to high, the cokes need to be removed.
Usually, a technique where the coke is burned out with a mixture of steam and air is preferred
over mechanical techniques [5].
Cooling of the cracked gas should start as quickly as possible. The effluent needs to be
transferred from the coil outlet to the inlet of the TLE. This adiabatic residence time should be
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limited as much as possible. Different inlet structures for a TLE can have a significant impact on
the adiabatic residence time. The main challenges for TLE producers are dealing with the
intensive heat flux, the high temperatures and the erosive effect of coke particles.
Two of the main TLE producers are Alstom and Borsig. In the following sections a brief
overview of the different types of TLE developed by these manufacturers is given.
Table 3-1: Typical dimensions and values for the double pipe system
Property Typical value Unit

Inner diameter gas tube 0.051 m
Inner diameter outer tube 0.073 m
Thickness tubes 0.005 m
Water inlet pressure 140 bar
Heat flux at the inlet 170 kW m-2
3.3 Alstom Exchangers

Alstom proposes several types of heat exchangers. They are all based on a double pipe system
[4]. In this double pipe configuration, the hot effluent of the reactor flows through the inner pipe
and the water/steam mixture flows concurrent in the annulus between the inner and the outer
pipe. High pressure water (up to 140 bars) is fed through the downcomer manifold (Figure 3-7a)
to individual bottom oval headers for distribution to the annulus between the inner and outer
tubes (Figure 3-7b). Typical values for the dimensions of the double pipe system are given in
Table 3-1 and a typical temperature profile in the TLE is shown in Figure 3-6.
Figure 3-6: Temperature profile for the gas and the water/steam mixture
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Figure 3-7: Water inlet section (a) with detailed double pipe arrangement (b) [4]
Steam is generated in the annulus and the water/steam mixture flows to the top oval header and
returns to the steam drum through the risers [4]. The water side of the exchanger operates in
natural circulation. This design ensures high velocities on the bottom oval header and in the
annulus between the inner and the outer tubes, which results in turbulent flow and a high heat
transfer coefficient. The high velocities also allow for removal and transport of particles carried
over by the feed water.
The oval headers act as flexible members that compensate for the difference in thermal
expansion between the inner and the outer tubes and therefore reduces the mechanical stresses on
the system. Mechanical and thermal stresses are also reduced due to the use of thin-walled oval
headers, pipes and tubes. A thin wall is more flexible and the temperature gradient across the
wall is lower than would be the case when a thick wall was used.
The TLEs all have a pressure drop which is lower than 0.1 bar. Alstom offers two categories of
TLEs: multi-tube exchangers and linear closed-coupled exchangers. Three dimensional CFD
tools are used to design TLEs which optimize the gas flow distribution through the exchanger.
Finite element analysis give prior information about the thermal stresses in the headers, pipes
and tubes of the designed TLE.
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3.3.1 Multi-tube exchangers

The conventional round-type multi-tube exchangers consist of several double tubes welded
together to form a compact exchanger (Figure 3-8). The TLE typically has a single gas inlet
connected to multiple furnace coils. In most furnaces a so-called split radiant coil arrangement is
used (Figure 3-9).
Figure 3-8: Conventional round-type multi tube exchanger [4]
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Figure 3-9: Split radiant coil arrangement [5]
In a split coil parallel small-diameter tubes are combined into a larger diameter tubes to form a
single coil. For multitube exchangers several of these coils are combined and connected to a
single tube inside the TLE. The small diameter tubes at the inlet of the furnace allow for a rapid
temperature increase, which results in slightly higher yields compared to a uniform diameter coil
of the same residence time. The larger diameter furnace coil outlet is connected to the TLE gas
inlet by flanges. After this inlet, the gas flow is divided over several double tube elements
through the holes in the “tube sheet” to have efficient cooling (Figure 3-10). The “tube sheets”
are formed by welding the oval headers together, at the bottom as well as at the top of the TLE
(Figure 3-8). The inlet channel is internally coated to protect the shell from high gas
temperatures and corrosion. The outlet channel is not internally insulated unless the cracked gas
temperature is higher than 530 to 550 °C.
Figure 3-10: Conventional TLE inlet with tube sheet [4]

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Bathtub TLEs (Figure 3-11a) are similar to conventional TLEs but the inlet structure is different.
In contrast to conventional exchangers, a bathtub TLE has two to four gas inlet connections. The
“tube sheet”, formed by the oval headers, is installed in a step-like arrangement (Figure 3-11a).
The advantage is that the inlet channel volume is reduced by a factor two compared to a
conventional TLE. This reduces the adiabatic residence time and coke formation and enhances
the olefin selectivity. The adiabatic residence time is about 20 milliseconds whereas in a
conventional TLE it is 40 milliseconds. Additionally, the geometric shape offers better gas flow
patterns which reduce recirculation and improve gas distribution to the tubes. The use of a
multiple inlet TLE also eliminates unnecessary Y-pieces and manifolds.
Just like Bathtub TLEs, Quick Quencher multi tube exchangers (Figure 3-11 b) have two to four
gas inlets that connect to a set of furnace coils. The inlet structure is further developed to
decrease the adiabatic residence time by using an aerodynamic ceramic insert. The insert first
decelerates the gas through a diffuser and then distributes it uniformly to the tubes as the gas
reaccelerates through a nozzle section.
Figure 3-11: Bathtub TLE with multiple inlets and a step-like "tube sheet" (a) and
Quick Quencher with ceramic insert (b) [4]
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The contour of the insert is designed to eliminate dead zones. The Quick Quencher connects up
to twelve TLE tubes to one coil outlet. This arrangement provides a high heat exchange surface
area to volume ratio and translates to rapid quenching of the gas. The adiabatic residence time is
further reduced to 10-12 milliseconds thanks to the Quick Quencher inlet design. This TLE does
not have a “tube sheet” facing the gas flow so the inherent erosion of the tube sheet, pressure
drop through the tube and coke formation on the tube sheet are minimized.
3.3.2 Linear closed-coupled Exchangers

The linear exchangers are closed-coupled to individual coil outlets (Figure 3-12). The number of
double pipes are determined by the coil outlet configuration and limited by overall transport
dimensions. Modules of up to thirteen double tubes are not uncommon.
Figure 3-12: Linear closed-coupled exchangers [4]
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Short inlet transition pieces connect the individual radiant coils to one double tube. The inlet
transition piece is designed to gradually reduce the skin metal temperature between the hot coils
outlets and the cooled exchanger oval header form approximately 900 °C to around 320 °C.
Thermal stresses that could cause premature failure are avoided by having a moderate
temperature gradient in the transition piece. The top and bottom oval headers of the linear
exchanger are connected to the riser and downcomer piping respectively. There is no tube sheet
and the adiabatic zone in the transition between the furnace and the exchanger tubes is reduced
to the bare minimum. The inner diameter of the exchanger tubes is the same as the inner
diameter of the coil outlet. Therefore, the internal diameters are usually larger than the ones used
for multi-tube exchangers. To provide a similar cooling capacity, the linear exchangers have to
be longer, which results in a higher pressure drop and longer residence times. Due to the large
nature of this TLE a second stage is often necessary to achieve the desired outlet temperature
without exceeding the available space inside the production unit. The second stage also operates
as a steam generator. The secondary quench exchanger can be a conventional multi-tube TLE
operating in vertical position with gas flow from top to bottom (Figure 3-13) or a horizontal shell
and tube heat exchanger. In some installations, a second linear exchanger leg is used instead of a
secondary TLE.
Figure 3-13: Linear closed coupled TLE with secondary quench exchanger (SQE) [4]
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3.3.3 Overview
In Figure 3-14 a comparison is made of the residence times in the different TLEs. During the
first milliseconds no cooling occurs because the gas is in the adiabatic inlet section. For linear
TLEs, the adiabatic section is the shortest because the double pipes are directly coupled to the
radiant coils. The cooling rate is however a lot lower due to the larger diameters of the pipes.
The Quick Quencher has the most advanced inlet structure resulting in the lowest adiabatic
residence time compared to the other multi-tube exchangers. Compared to the conventional TLE,
the Bathtub TLE lowers the adiabatic residence time by a factor 2. For all exchangers, the
cooling rate decreases with residence time, or with TLE length because of the lower temperature
gradient between the gas temperature and the water/steam temperature which is the driving force
for the heat transfer.
Figure 3-14: Residence time of the cracked gas in the different TLEs [4]
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3.4 Borsig Exchangers

As with Alstom, the Borsig quench system also consists of one or more parallel TLEs for each
furnace cell, which are connected by riser and downcomer piping to one common elevated steam
drum. Borsig offers two different designs: the “Tunnelflow” TLE and the Linear TLE. The
“Tunnelflow” TLE is basically a shell and tube heat exchanger whereas the Linear TLE is very
similar to the Alstom Linear TLE.
Figure 3-15: Tunnelflow TLE [1]
3.4.1 “Tunnelflow” Transfer Line Exchanger

The vertical arrangement of the TLE is the most common one. A horizontal arrangement of the
“Tunnelflow” TLE is also possible. The steam drum can be installed on top of the quench cooler
or at an elevated location in the steel structure.
The water inlet design of the “Tunnelflow” TLE consists of a thin tube sheet of
10-15 mm thickness (1, Figure 3-15), combined with a thick forged anchoring plate (2) to
provide additional strength for the water pressure. Anchoring ribs (3) transfer the water pressure
load from the tube sheet to the anchoring plate and to the cooler shell (4). The anchoring ribs are
machined out of the thin tube sheets and the thick forged plate thereby forming tunnels. The
water leaving the downcomer (1, Figure 3-16) flows into an internal water chamber (2). In the
water chamber, the water flows downwards and enters the flow tunnel (3) through inlet holes (4).
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There is one inlet hole for every tunnel. In the tunnel, the water flows to the other side of the
TLE with high velocity, hereby avoiding settling of solids on the thin tube sheet. On the opposite
side, water flows upwards through the outlet holes (5) to the main shell space. A certain portion
of the water enters the main shell space via annular gaps (6) around the tubes in the thick
anchoring plate. The high water velocity prevents solids from settling, and overheating and hot
water corrosion to occur.
Figure 3-16: Water flow in Tunnelflow TLE [1]

Solid particles may be present in the feedwater and additionally, the waterside surface produces
magnetite (Fe3O4). The magnetite layer protects the steel and constantly renews itself slowly
from the metal surface at operation temperature, hereby releasing a small amount of magnetite
particles into the water.
Like Alstom, Borsig also used CFD calculations to optimize the gas inlet channel design to
ensure uniform gas flow to the tubes, minimum residence time within the channel and low
pressure drop. The refractory of the gas inlet channel is provided with a protection shield to deal
with erosion caused by hard coke particles in the gas flow. Stresses and temperatures acting on
the “Tunnelflow” gas inlet tube sheet assembly are analyzed using finite element methods.
Feedwater is added to the system in the steam drum. There is a demister package operating as
steam/water separator.
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3.4.2 Linear Transfer Line Exchanger

The linear quencher consists of a number of linearly arranged double pipe elements of which
each is directly coupled to one of the furnace radiant coil outlets. The double pipes (Figure 3-17,
7) provide individual cooling for each radiant coil. A common downcomer header (11)
uniformly distributes the water coming from the steam drum to the “Turboflow” inlet chambers
(10). A riser header (5) sends the water/steam from the upper outer chambers (1) back to the
steam drum. Guides (6), a supporting frame (9) and supporting brackets (8) keep the TLE in
position. The gas collection header (3) accumulates the cooled gas and sends it towards the
downstream equipment. The pipe spacing can be as close as the outer diameter of the outer pipe,
if required.
Figure 3-17: Linear TLE arrangement [1]
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The “Turboflow” chambers use a water inlet nozzle which ensures a rotating water flow around
the process gas pipe. This ensures that any potential solid deposition is eliminated at the hot inlet
of the exchanger. Every “Turboflow” chambers has its own solid ejection nozzle located at the
lowest point of the quench system. Any debris can easily be ejected during start-up or operation
and cleaning fluids can be removed. It can also be used as drain and to inspect the “Turboflow”
chamber during routine maintenance. The individual ejection nozzles can be piped to a common
location for blowdown purposes.
Gas tube diameters are chosen to match the radiant coil dimensions. Often a single exchanger
suffices to perform the required heat recovery duty. For ethane and propane cracking, larger
diameter coils are common and a second leg can be necessary. The length of the exchanger is
limited by the location of the steam drum in the furnace structure. The centerline of the drum
must be above the top water chamber for the thermosyphon system to operate adequately.
Designs with lengths of 20 m have already been built. A twin leg configuration (Figure 3-18) can
be useful to have sufficient long pipes when the available place in the furnace structure is
limited.
Linear exchangers have several advantages: they are directly and individually coupled to the
radiant coil outlet. Therefore, additional fittings in the furnace are unnecessary. There is no hot
tube sheet so typical fouling or erosion at the tube sheet cannot take place. The adiabatic
residence time is very low. For these reasons the linear TLEs are most used today. Recently,
Borsig won an order for 70 linear quench coolers for the construction of one of the largest ethane
crackers in the world, located in Abu Dhabi (UAE) [7-8].
Figure 3-18: Twin leg linear TLE [1]
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3.4.3 Examples with typical dimensions

Two examples will be discussed, one with Tunnelflow TLEs and one with linear TLEs.
A furnace is coupled with two Tunnelflow TLEs which both consist of 50 to 60 bundle tubes.
The effluent gas stream flow is 8000 kg h-1 for one TLE and about 8500 kg h-1 steam is
produced. Water is fed at 120 bars and the water to steam ratio at the outlet of the TLE is around
10. The cracked gas is cooled from 800-850 °C to 400 °C and has an inlet pressure of 3 bar.
Table 3-2: Dimensions Tunnelflow TLE

Inner diameter gas tube 0.040 - 0.050 m
Thickness gas tube 0.005 m
Outer diameter shell 0.8 m
TLE length 6-7 m
A furnace is coupled to 4 TLE modules, each being composed of 18 double pipes. The effluent
gas stream flow is 15000 – 16000 kg h-1 for one TLE module which allows a steam production
rate of 16000 – 17000 kg h-1. Water is fed at 110 bar and the water to steam ratio at the outlet of
the TLE is around 10. The cracked gas is cooled from 800-850 °C to 350 °C and has an inlet
pressure of 1.89 bar.
Table 3-3: Dimensions linear TLE

Inner diameter gas tube 0.08 - 0.09 m
Thickness outer tube 0.0125 m
TLE length 20-25 m
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3.5 References
1. Borsig, P.H.E.G., Borsig Transfer Line Exchangers for Ethylene Cracking Furnaces.
2003.
2. Ren, T., M. Patel, and K. Blok, Olefins from conventional and heavy feedstocks: Energy
use in steam cracking and alternative processes. Energy, 2006. 31(4): p. 425-451.
3. G. Schmidt, D.S.U., Dr. C. Geipel, Olefin Academy 2010 Cracking Furnace Technology,
L. Engineering, Editor. 2010.
4. Alstom, P.E.R.G., Transfer Line Exchangers for Ethylene Plants. 2009.
5. Heinz Zimmermann, R.W., Ethylene, in Ullmann's Encyclopedia of Industrial Chemistry,
Wiley. p. 66.
6. Haider, S.I., Y.K. Joshi, and W. Nakayama, A natural circulation model of the closed
loop, two-phase thermosyphon for electronics cooling. Journal of Heat Transfer-
Transactions of the Asme, 2002. 124(5): p. 881-890.
7. Borsig, P.H.E.G. 2010; Available from: http://phe.borsig.de/en/inside/news/newsdetail/-
////news-bphe-test.html.
8. Bourouge. 2010; Available from: http://www.borouge.com/aboutus/Pages/Plants.aspx.
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Chapter 4: Correlations 57
Chapter 4
Correlations
4.1 Introduction
In the next chapter an attempt is made to implement calculation for modeling a transfer line
exchanger (TLE) in the COILSIM1D simulation code for steam cracking coils. In this chapter
the correlations implemented in the TLE module for the calculation of the coefficient for
convective heat transfer are presented. As discussed in Chapter 3, double pipe TLEs consist of
two concentric tubes where the hot gas flows in the inner tube and the water/steam mixture in the
annulus between both tubes. Models for the inner tube are already included in COILSIM1D so
the focus is on modeling the water/steam side of the TLE and on calculating the convection
coefficient at the water/steam side in particular.
4.2 Convective heat transfer coefficient h

4.2.1 Introduction
In the literature, there are many correlations for heat transfer coefficients. They are basically all
based on the determination of the dimensionless Nusselt number (Nu)

(4-1)
with
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h the convective heat transfer coefficient [W m-2 K-1]
L a characteristic length, often the internal or equivalent diameter of the tube [m]
k the thermal conductivity coefficient of the fluid [W m-1 K-1]
Correlations for the Nusselt number depend on the flow type (laminar, turbulent), heat exchanger
configuration (horizontal tubes, vertical tubes, shell and tube, …) and convection type (natural or
forced). Keeping the TLE modeling end purpose in mind, the most useful correlations for this
thesis are the ones for vertical tubes with forced convection and turbulent flow. Furthermore,
correlations for single phase flow heat transfer (water and steam) and for two phase boiling heat
transfer (water/steam mixture) are needed.
4.2.2 Single phase turbulent flow

In the TLE, water is introduced at the bottom and a water/steam mixture leaves the top. The high
pressure water that is introduced into the TLE is close to its saturation temperature, but it is
possible that in the first section of the TLE some of the heat is used to bring the water to its
saturation temperature. To be able to take this into account, single phase flow heat transfer
correlations are needed.
4.2.2.1 Plain smooth tubes

The correlations [1] presented in this section are valid for tubes as in double pipe heat exchanger
as for tubes in shell and tube heat exchangers. However, since our main focus is on the water
side of the TLEs, the following correlation will only be applied to calculate the water side
convective heat transfer coefficient in the double pipe TLE.
A commonly used correlation for to determine heat transfer coefficients for turbulent flow in
round tubes is known as the Dittus-Boelter equation [2]:
0.023 . (4-2)
The tubular Reynolds number Re is defined as

(4-3)
with
the mass velocity [kg m-2 s-1] obtained by dividing the mass flow rate in kg s-1 by the cross
section area of the tube in m2
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the dynamic viscosity of the fluid [Pa s]
The Prandtl number Pr is defined as

(4-4)
with the heat capacity at constant pressure of the fluid [J kg-1 K-1]
The exponent of the Prandtl number n is usually taken equal to 0.4 for heating a fluid.
The expression is valid for 0.7 < Pr < 600, Re > 104 and L/di > 10 where L is the length from the
inlet of the tube. Deviations up to 25% are possible.
For fully developed turbulent flow, more accurate results can be obtained by using the Petukhov
heat transfer correlation [3] that is valid for 0.5 < Pr < 2000 and 104 < Re < 5 106

2
$%&' .*+

. ()&&
1.07 12.7 2 " 1#
(4-5)
.!!
The friction factor f can be obtained from the Moody diagram or from Petukhov’s friction factor
correlation for smooth tubes valid for 3000 < Re < 5 106
1.58 ./ # " 3.28#01 (4-6)
.*+
The factor 234567 :
3
corrects for property variations for liquid flows caused by temperature
8966
differences in the bulk and near the wall.
Another heat transfer coefficient correlation is that of Gnielinski [4], which extends the
Petukhov correlation down into the transition regime:

2 " 1000#
$%&' .*+

.
1 12.7 2 .!! " 1#
(4-7)
()&&
It is valid for 0.5 < Pr < 2000 and 3 103 < Re < 5 106. The transition regime lies in between the
laminar and turbulent regime. In the region near the entrance, flow tends to be more laminar, it is
only after about 10 to 60 tube diameters from the entrance that fully developed turbulent flow
starts to occur.
Ghajar and Tam [5] proposed a method to predict the behavior of heat transfer in the transition
regime for three different inlet structures. These correlations however are no longer within the
scope of this literature review.
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Another widely used correlation for the calculation of the friction factor is proposed by Ghadjar
and Tam [6]:
0.0791 $%&' 0.1

;%<$
.1 ()&&
(4-8)
4.2.2.2 Enhanced tubes

The internal roughness of the tube surface is well known to increase the turbulent heat transfer
coefficient. The Churchill [7] correlation can be solved for the friction factor of rough tubes with
a commercial pipe roughness of e:
2 7 .B
> "2.46 ./ A C

(4-9)
Other correlations exist for tubes with twisted tape inserts, corrugated tubes and internally finned
or ribbed tubes. These correlations however fall out of the scope of this literature review.
4.2.3 Two phase boiling heat transfer

In a vertical tube heated uniformly along its length, several flow regimes can exist depending on
liquid-vapor ratio of the fluid. These are discussed in [1] and will briefly be summarized below.
At the bottom of the tube, subcooled liquid enters. As the wall temperature initially is below the
temperature needed for nucleation, the heat transfer mechanism near the inlet of the tube is
ordinary single phase convective heat transfer. At a certain point, the wall temperature will
however rise above the nucleation temperature and vapor bubbles will start to form at nucleation
sites on the tube surface. At first, the liquid in the core will still be subcooled, so the vapor
bubbles will condense shortly after leaving the tube wall. Once the core itself also has reached
the saturation temperature, saturated boiling will occur combined with a slug flow regime as
shown in Figure 4-1. Slug flow will change to annular flow when the amount of liquid in the
bulk flow decreases. When the vapor core entrains liquid droplets and the liquid film at the tube
wall is evaporated completely, drop flow arises. This point is referred to as the onset of dryout or
simply dryout. Heat transfer decreases drastically and the tube wall temperature rises suddenly.
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Figure 4-1: flow regimes in vertical tube with boiling liquid [8]
For high heat fluxes, another boiling mechanism is possible. At the so-called critical heat flux,
nucleate boiling makes place for saturated film boiling. The flow pattern for film boiling is an
inverted annular flow, with vapor forming an annular film near the wall and liquid in the center
core. The heat transfer for film boiling and in liquid deficient regions are significantly smaller
than heat transfer with a wet wall. These situations should hence be avoided in applications as a
TLE and the corresponding mechanisms are not included in the correlation shown in the
following section.
The local two-phase flow boiling heat transfer coefficient for evaporation inside a tube D; is
defined [1] as
Confidential
E
D;
F()&& " FG); #
(4-10)
with
q the local heat flux from the tube wall into the fluid [J m-2 s-1]
Tsat the local saturation temperature at the local saturation pressure psat [K]
Twall the local wall temperature at the axial position along the evaporator tube, assumed to be
uniform around the perimeter of the tube [K].
Normally, two heat transfer mechanisms are considered to be important for flow boiling models:
nucleate boiling heat transfer and convective boiling heat transfer. Nucleate boiling corresponds
to the boiling regime where bubbles of water vapor are formed at certain nucleation sites on the
tube surface. Convective boiling refers to the convective process between the heated wall and the
liquid phase. For example for annular flow without nucleate boiling at the tube surface, the
convective heat transfer can be seen as single phase forced convection at the liquid-wall
interface. Evaporation then takes place at the liquid-vapor interface of the central core.
There is one heat transfer coefficient associated with each of both mechanisms: D$ for nucleate
boiling and DH$ for convective boiling. The resulting global heat transfer coefficient is obtained
by using a power law relation:
D; I D$ # DH$ #

J
(4-11)
The value of the exponent n determines whether both mechanisms are always considered equally
important (n = 1) or whether one mechanism should be made dominant when its heat transfer
coefficient is larger than the other one (n = 2, 3, ∞).
There are different approaches to determine the values for the heat transfer coefficients for
nucleate boiling and for convective boiling. Below, two possibilities are discussed.
4.2.3.1 Shah correlation

Shah’s method for vertical tubes is presented in this paragraph [1, 9]. He suggested to choose the
two-phase flow boiling heat transfer coefficient equal to the largest of the two contributing
mechanisms. He uses the Dittus-Boetler correlation for single phase convection coefficient DK
[2] both for calculating the convective boiling coefficient DH$ and the nucleate boiling coefficient
D$ :
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K
DK 0.023 K. K.+

(4-12)
ReL and PrL are calculated as
Φ 1 " x#
K
K
K K
K
K
with
Φ the mass velocity of the liquid plus the vapor [kg m-2 s-1]
x the steam quality
the internal diameter of the tube [m]
The correction factor C0 for the convective boiling coefficient accounts for the influence of the
density and the vapor quality:
1 " O . PQ .

N
O PK
(4-13)
The convective heat transfer coefficient DH$ is then calculated as
DH$ 1.8 DK N 0. (4-14)
For the nucleate boiling coefficient the Boiling number R is introduced to determine the effect
of the heat flux:
E
R
Φ KQ
(4-15)
with
q the heat flux [W m-2]
KQ the latent heat of vaporization [J kg-1]
Shah now proposes four equations to calculate the nucleate boiling coefficient:
D$ 230 R . DK (4-16)
D$ 1 46 R . # DK (4-17)
D$ S R . exp 2.74 N " 0.1 # (4-18)
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D$ S R . exp 2.74 N " 0.15# (4-19)
with F a constant equal to 14.7 if R > 0.0011 and equal to 15.43 when R < 0.0011.
The nucleate boiling coefficient is given by the equation that yields the largest value.
One issue with the correlation proposed by Shah is that it does not give continuous values for
changing parameters. This is inherent to the fact that the coefficients are chosen as the maximum
of different values obtained with different calculation methods. Another reason for the
discontinuity is found in equation (4-13) where the steam quality is in the denominator. When
the steam quality is equal to zero, the correlation is not valid and the single phase convective
boiling coefficient DK given by (4-12) has to be used. For applications as a TLE where pure
liquid water is fed, this discontinuity can show up in the results.
4.2.3.2 Steiner and Taborek

An interesting model has been developed by Steiner and Taborek [10] and is presented in this
section. Steiner and Taborek wanted a model capable of representing following observations: for
(low) heat fluxes below the onset of nucleate boiling (qONB), the only heat transfer mechanism is
the convective one. For very large heat fluxes, the nucleate boiling contribution should dominate.
When there is no vapor (quality x = 0), D; should be equal to the single phase liquid convective
heat transfer coefficient when q < qONB, but D; should correspond to that plus D$ when q >
qONB. When there is only vapor (x = 1), D; should be equal to the vapor-phase convective
coefficient DQ; .
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Figure 4-2: Overview of the boiling proces in a vertical tube according to Steiner and
Taborek [10]
The top graph of Figure 4-2 shows the variation of the convective heat transfer coefficient D;
along the tube length. In region A the liquid is subcooled and D; corresponds to the single phase
liquid convective heat transfer coefficient, as long as q < qONB. If q > qONB, D; increases rapidly
due to the contribution of (subcooled) nucleate boiling. The higher the heat flux, the faster D;
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starts to increase. In the saturated boiling regime the coefficient for pure convective boiling DH$
quickly increases with increasing vapor quality. For very high heat fluxes, the contribution of
D$ is dominant and D; barely changes with increasing vapor quality. Once the critical vapor
quality is reached, dryout occurs and D; decreases drastically to equal the gas phase heat
convective coefficient DQ; for x = 1. The dashed lines for x > xcrit are not predicted by the model
of Steiner and Taborek.
In their model, they use an asymptotic approximation with exponent n equal to 3:
D; VWD$, S$ Y WDK; S; Y

[ Z Z
(4-20)
with
D$, the local nucleate pool boiling coefficient at a reference heat flux q0 at the reduced pressure
pr equal to 0.1 [W m-2 K-1]
S$ the nucleate boiling correction factor [-]
DK; the local liquid phase forced convection coefficient based on the total flow as liquid and is
obtained with the Gnielinski [4] correlation [W m-2 K-1]
S; the two-phase multiplier that accounts for the enhancement of liquid convection by higher
velocity of a two-phase flow compared to single-phase flow of the liquid in the channel [-]
The Gnielinski correlation for DK; is
K
DK;
8 K; " 1000# K
K K .
1 12.7 8 W K .!! " 1Y
(4-21)
The Fanning friction factor, K , for the liquid is:
K 0.7904 ./ K; # " 1.64#01

(4-22)
This expression is valid when 4000 < ReLt < 5 000 000 and 0.5 < PrL < 2000 for single-phase
flows. The total mass velocity of liquid plus vapor is used for evaluating the liquid Reynolds
number.
\]
K;
K
(4-23)
The two phase multiplier Ftp is for convective evaporation, which will occur if x < xcrit and q >
qONB or over the entire range of x if q < qONB.
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For applications where if x < xcrit and q > qONB, the following equation is used:
PK .Z
*.*
S; A 1 " O# *.
1.9 O .!
C
PQ
(4-24)
with
PK the density of the fluid in liquid phase [kg m-3]
PQ the density of the fluid in gaseous phase [kg m-3]
This expression is valid for PK ⁄PQ from 3.75 to 5000 and converges to 1.0 as x goes to 0. xcrit is
often assumed to occur at around 0.5 for these applications.
When q < qONB, only pure convective evaporation is present, extending from x = 0.0 to x = 1.0.
At the limiting case of x = 1.0, the value of D; corresponds to DQ; , which is the forced
convection coefficient with the total flow as all vapor. The Gnielinski correlation is also used for
obtaining DQ; :
Q
DQ;
8 Q; " 1000# Q
Q .
1 12.7 Q W Q .!! " 1Y
(4-25)
8
The Fanning friction factor for the vapor, Q , is given by
Q 0.7904 ./ Q; # " 1.64#01

(4-26)
The total mass velocity of liquid plus vapor is used for evaluating the vapor Reynolds number, so
Q; is:
\]
Q;
Q
(4-27)
For this case (q < qONB), the following expression is used for S; :
01 0.
PK .Z DQ .* PK .!`
01.1
S; _A 1 " O# *.
1.9 O .!
1 " O#
.*
C A O 1 8 1 " O#.` # C a
PQ DK PQ
(4-28)
This expression is valid for values of PK ⁄PQ from 3.75 to 1017. The terms with exponent of 0.01
make this expression go to its proper limits for x = 0 and x = 1. Note that this model does not
give results for D; in case q > qONB and x > xcrit.
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The minimum heat flux for determining the onset of nucleate boiling qONB is given by the
following expression using the liquid-phase heat transfer coefficient DK; :
2 e FG); DK;
Ebcd
PQ KQ
(4-29)
with
e the surface tension [N m-1]
FG); the saturation temperature [K]
the critical nucleation radius for a boiling site [m], recommended value = 3 10-7 m
KQ the latent heat of vaporization [J kg-1]
The nucleate boiling coefficient is determined here with a method similar to the nucleate pool
boiling method of Gorenflo [11]. The standard nucleate boiling coefficient for the Steiner and
Taborek flow boiling correlation D$, is determined at following standard conditions: reduced
pressure pr = 0.1, a mean surface roughness of Rp,0 = 1 10-6 m and the heat flux q0 equal to one
specific value for every fluid used during the experiments. For water this value is 150 000 W m-2
and the corresponding value for D$, is 25 580 W m-2 K-1.
The nucleate boiling correction factor Fn,b includes effects of reduced pressure, heat flux, tube
diameter, surface roughness and a residual molecular weight correction factor on D$, as
follows:
E f
0.+ .*ZZ
S$ Sf g h g h S i#
E , ,
(4-30)
The pressure correction factor, Fpf, valid for pr < 0.95, accounts for the increase in nucleate
boiling coefficient with increasing pressure:
1.7
Sf 2.816 j< .+ k3.4 l j< Z.`
1 " j< `
(4-31)
with
pr the reduced pressure, defined by p/pc with pc the critical pressure which equals 22 064 000 Pa
The nucleate boiling exponent, nf, on the normalized heat flux term is:
/ 0.8 " 0.1 Oj 1.75 j< #

(4-32)
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The standard tube reference diameter , is 0.01 m, the standard value for the surface roughness
, is 1 µm and the surface roughness term covers values of Rp from 0.1 to 18 µm. The residual
molar weight correction factor is in terms of the liquid molecular weight M (valid for 10 < M <
187):
S i# 0.377 0.199 ./ i# 0.000028427 i1

(4-33)
For water, the value of S i# reduces to 0.962.
The Steiner and Taborek method is based on an extensive database containing 10 262 data points
for water and 2345 additional data points for other refrigerants, hydrocarbons, cryogens and
ammonia.
4.3 Physical properties of water/steam

In order to evaluate the above correlations, the physical properties of water and steam need to be
known for various condition of temperature and pressure. The International Association for the
Properties of Water and Steam (IAPWS) is a non-profit association that provides recommended
formulations for numerous properties of water, steam, and aqueous solutions [12].
4.3.1 Density and heat capacity at constant pressure

In their online available Revised Release on the IAPWS Industrial Formulation 1997 for the
Thermodynamic Properties of Water and Steam [13], the IAPWS presents correlations for,
among others, specific volume and specific isobaric heat capacity. The publication consists of a
set of equations for different regions which cover the following range of validity:
273.15 m n F n 1073.15 m j n 100 io
1073.15 m n F n 2273.15 m j n 50 io
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Figure 4-3: Water phase diagram divided in 5 regions for correlations [13]
The IAPWS divides the phase diagram of water into five regions and supplies with one
fundamental equation for each region from which all the thermodynamic properties can be
derived. The regions of interest for water and steam used in applications as a TLE are region 1
for the properties of water, region 2 for the properties of steam and region 4 for the liquid-vapor
saturation line. In regions 1 and 2, a fundamental equation for the Gibbs free energy g(p,T) is
given.
4.3.1.1 Properties of water

The basic equation for this region is a fundamental equation for the specific Gibbs free energy g.
this equation is expressed in dimensionless form, p q⁄ F, and reads:
Z+
q j, F#
p r, s# t / 7.1 " r#uv s " 1.222# wv
F
(4-34)
x*
with
g(p,T) the specific Gibbs free energy [kJ kg-1]
R the specific gas constant of ordinary water = 0.462 kJ kg-1 K-1
T the temperature [K]
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π the dimensionless pressure = p/p* with p the pressure [bar] and p* a reference pressure equal to
165.3 bar
τ the dimensionless temperature = T*/T with T the temperature [K] and T* a reference
temperature equal to 1386 K
ni fitted dimensionless coefficients, listed in Annex A, Table A-1.
Ii, Ji fitted exponents, listed in Annex A, Table A-2.
All thermodynamic properties can be derived from (4-34) by using the appropriate combination
of the dimensionless Gibbs free energy and its derivatives.
The thermodynamic relation that links the specific volume and the specific Gibbs free energy is:
zq
y
zj {
(4-35)
with
ν the specific volume [m3 kg-1]
Rearranging and substituting (4-34) yields:
y 1 zq zp

F F zj { zj |
(4-36)
Applying the chain rule for derivatives and rearranging gives:
y zp zr 1 zp

F zr | zj 100 j zr |
}
(4-37)
Evaluating the derivative 2 : in terms of the power series in (4-34) gives:

~
~ |
Z+
zp
t " / 7.1 " r#uv 0* s " 1.222# wv
zr |
(4-38)
x*
To obtain the density, it is sufficient to take the inverse of the specific volume:
1 100 j} zp 0*
P j, F#
y F zr |
(4-39)
with
ρ the density [kg m-3]
In a similar way, it can be shown that the relation that links the specific isobaric heat capacity
with the specific Gibbs free energy is:
Confidential
z 1p
j, F# " s 1 g h
zs 1
(4-40)
Evaluating the derivative 2 : in terms of the power series in (4-34) gives:

~
~|
Z+
z 1p
g 1 h t / 7.1 " r#uv " 1# s " 1.222# wv 01
zs
(4-41)
x*
The values of the coefficients ni , Ii and Ji can be found in Annex A, Table A-3. Equations (4-38)
to (4-41) can be implemented in COILSIM1D to calculate cp(p,T) and ρ(p,T) for water.
Equation (4-34) and all derived equations are valid for
0 °N n F n 350 °N jG F# n j n 100 io
IAPWS estimates that the uncertainties on the specific volume in this region are ± 0.05% and
that the uncertainties on the specific heat capacities in this region are ± 0. 5%.
4.3.1.2 Properties of steam

The basic equation for this region is a fundamental equation for the specific Gibbs free energy g,
as in 4.3.1.1, and consists of two parts, an ideal gas part p and a residual part p < :
q j, F#
p r, s# p r, s# p < r, s#
F
(4-42)
with again R= 0.46 kJ kg-1 K-1, π = p/p* with p* = 10 bar and τ = T*/T with T* = 540 K.
The equation for the ideal gas part of the dimensionless Gibbs free energy reads:
B
p ln r t / s wv

(4-43)
x*
The coefficients ni0 and exponents Ji0 are listed in Annex A, Table A-2.
The equation for the residual part of the dimensionless Gibbs free energy is:
+Z
p < t / r uv s " 0.5# wv (4-44)

x*
The coefficients ni and exponents Ii and Ji are listed in Annex A, Table A-3.
The relations for the specific volume and specific isobaric heat capacity are similar to the ones
encountered in section 4.3.1.1:
Confidential
1 100 j} zp zp <
0*
P j, F# Ag h C
y F zr | zr |
(4-45)
z 1p z 1p <
j, F# " s 1 A g 1 h g 1 h C
zs zs (4-46)
The expressions for the derivatives in (4-45) and (4-46) are:
zp 1
g h
zr | r (4-47)
+Z
zp <
t / r uv 0* s " 0.5# wv
zr |
(4-48)
x*
B
z 1p
g 1 h t / W " 1Y s wv 01

zs
(4-49)
x*
+Z
z 1p <
g 1 h t / r uv " 1# s " 0.5# wv 01
zs
(4-50)
x*
Equation (4-42) and all derived equations are valid for
0 °N n F n 350 °N 0 j n jG F#
350 °N F n 550 °N 0 j n j$%)< <G 1 ) Z F#
However, this is true for the stable single-phase vapor region. In the metastable-vapor region
near the saturation line, the equations still gives reasonable values for pressures above 100 bar.
For pressures below 100 bar, an additional equation is presented below.
IAPWS estimates that the uncertainties on the specific volume in the above defined region are ±
0.1% and that the uncertainties on the specific heat capacities in this region are ± 0. 5%.
The supplementary equation to calculate the properties of steam in the metastable region yields
the specific Gibbs free energy g and consists of an ideal-gas part and a residual part:
q j, F#
p r, s# p r, s# p < r, s#
F
with once more R= 0.46 kJ kg-1 K-1, π = p/p* with p* = 10 bar and τ = T*/T with T* = 540 K.
The equation for the ideal-gas part is identical to (4-43), but has different values for /* and /1
(cfr Annex A Table A-2). For the residual part, following equation should be used:
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*Z
p t / r uv s " 0.5# wv
< (4-51)
x*
with R= 0.46 kJ kg-1 K-1, π = p/p* with p* = 10 bar and τ = T*/T with T* = 540 K.
The values of the coefficients ni and the exponents Ii and Ji can be found in Annex A Table A-4.
The relations for the specific volume and specific isobaric heat capacity and the derivatives are
identical to the ones presented above, cfr (4-45) to (4-50), with however index i going from 1 to
13 in (4-48) and (4-50).
4.3.1.3 Water/steam saturation line

The IAPWS provides two equations, one for calculating psat as a function of T, and one to
calculate Tsat as a function of p. In a TLE, the pressure of the water/steam system is fixed (except
for the pressure differences related to pressure drop in the TLE). Therefore, it is useful to be able
to calculate the corresponding saturation temperature for a given pressure. Below, only the
equation for Tsat as a function of p is presented.
The saturation-temperature equation reads:
FG /* " I /* #1 " 4 /B /* #

F} 2
(4-52)
with
Ts the saturation temperature [K]
T* a reference temperature equal to 1 K
2

"S " √S 1 " 4
(4-53)
1 /Z /! (4-54)
S /* 1 /+ /`
(4-55)
/1 1 / / (4-56)
*
jG +
}
j
ps the saturation pressure [bar]
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p* a reference pressure equal to 10 bar
n1, n2, n3, n4, n5, n6, n7, n8, n9, n10 coefficients listed in Annex A Table A-5.
Equation (4-52) is valid along the entire vapor-liquid saturation line from the triple point
temperature Tt (251 K) to the critical temperature Tc (647.096 K) and can be simply extrapolated
to 273.15 K so that it covers the temperature range
273.15 m n F n 647.096 m
4.3.2 Viscosity
In the release on the IAPWS Formulation 2008 for the Viscosity of Ordinary Water Substance
[14], the IAPWS shows correlations for the calculation of the viscosity of water in all
thermodynamically stable fluid states. The viscosity is calculated with the equation
F# * F, P # 1 F, P # (4-57)
with
the dimensionless viscosity = µ/µ* with µ* a reference viscosity equal to 1 10-6 Pa s
the dimensionless viscosity in the dilute-gas limit
* the dimensionless factor representing the contribution to viscosity due to finite density
1 the dimensionless factor representing the critical enhancement of the viscosity
F the dimensionless temperature = T/T* with T* a reference temperature equal to 647.096 K
P the dimensionless density = P/P * with P * a reference density equal to 322.0 kg m-3
The first factor of the product is given by
100 IF
F#

∑Zx
(4-58)
F
The coefficient Hi are given in Annex A Table A-6.
The second factor * F, P # is calculated by
Confidential
!
1
* F, P # exp P t " 1 t P " 1#
F
(4-59)
x x
The coefficient Hij are given in Annex A Table A-7.
The contribution of second factor 1 F, P # is only significant in a small region around the critical
point. So for industrial uses where greater computing speed is needed, the second factor 1 F, P #
can be neglected and set equal to 1.
Equation (4-57) is at least valid for all thermodynamically stable fluid states in the following
range of temperature and pressure:
273.16 m n F n 1173.15 m 0 n j n j;
where pt is the pressure at the triple point (210 MPa).
The estimated uncertainty on the viscosity of water for conditions encountered in a TLE is 2%.
The viscosity as presented here is a function of the temperature and the density. This means that
near the saturation line, the density of liquid water needs to be used to obtain the viscosity of
liquid water, and the density of steam needs to be used for the viscosity of steam.
4.3.3 Surface tension

To calculate the onset of nucleate boiling qONB using equation (4-29), the surface tension needs
to be known. IAPWS has another release [15] in which a correlation is presented to calculate the
water surface tension:
e R s G 3 1 s G # (4-60)
with
e the water surface tension [N m-1]
B a reference surface tension equal to 0.2358 N m-1
sG the dimensionless temperature = 1-T/Tc with Tc a reference temperature equal to 647.096 K
G a dimensionless constant equal to 1.256
b a dimensionless constant equal to -0.625
Equation (4-60) is valid for temperatures ranging from the triple point (0.01°C) to the reference
temperature (647.096 K).
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The estimated uncertainty on the surface tension of water for conditions encountered in a TLE is
3%.
4.3.4 Thermal conductivity

The IAPWS also provides a correlation for the thermal conductivity, but it is a very long and
complicated one depending on many different thermodynamic properties like temperature,
density, viscosity, isobaric and isochoric specific heat capacity. Therefore, it will not be
discussed but it can be found in [16].
4.4 References
1. Thome, J.R., Engineering Data Book III. 2004.
2. Dittus, B., Publications on Engineering, 1930. 2: p. 443.
3. Petukhov, B.S., V.A. Kurganov, and A.I. Gladuntsov, Experimental study of heat transfer
to a turbulent flow of a multiatomic gas when there is a large temperature drop. High
Temperature, 1970. 8(6): p. 1235-12371237.
4. Gnielinski, V., NEW EQUATIONS FOR HEAT AND MASS-TRANSFER IN
TURBULENT PIPE AND CHANNEL FLOW. International Chemical Engineering, 1976.
16(2): p. 359-368.
5. Ghajar, A.J. and L.M. Tam, HEAT-TRANSFER MEASUREMENTS AND
CORRELATIONS IN THE TRANSITION REGION FOR A CIRCULAR TUBE WITH 3
DIFFERENT INLET CONFIGURATIONS. Experimental Thermal and Fluid Science,
1994. 8(1): p. 79-90.
6. Tam, L.M. and A.J. Ghajar, Effect of inlet geometry and heating on the fully developed
friction factor in the transition region of a horizontal tube. Experimental Thermal and
Fluid Science, 1997. 15(1): p. 52-64.
7. Churchill, S.W., COMPREHENSIVE, THEORETICALLY BASED, CORRELATING
EQUATIONS FOR FREE CONVECTION FROM ISOTHERMAL SPHERES. Chemical
Engineering Communications, 1983. 24(4-6): p. 339-352.
8. Collier, J.G. and J.R. Thome, Convective boiling and condensation. 3rd ed. Oxford
science publications. 1994, Oxford
New York: Clarendon Press ;
Oxford University Press. xliii, 596 p.
9. Shah, M.M., Evaluation of general correlations for heat transfer during boiling of
saturated liquids in tubes and annuli. HT2005: Proceedings of the ASME Summer Heat
Transfer Conference 2005, Vol 2, 2005: p. 1-11.
10. Steiner, D. and J. Taborek, FLOW BOILING HEAT-TRANSFER IN VERTICAL TUBES
CORRELATED BY AN ASYMPTOTIC MODEL. Heat Transfer Engineering, 1992. 13(2):
p. 43-69.
11. Grorenflo, D., Pool Boiling. VDI-Heat Atlas. 1993, Düsseldorf.
12. IAPWS. Available from: http://www.iapws.org/.
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13. IAPWS (1997) Revised Release on the IAPWS Industrial Formulation 1997 for the
Thermodynamic Properties of Water and Steam.
14. IAPWS (2008) Release on the IAPWS Formulation 2008 for the Viscosity of Ordinary
Water Substance.
15. IAPWS (1994) Release: "Surface Tension of Ordinary Water Substance".
16. IAPWS, Release on the IAPWS Formulation 2011 for the Thermal Conductivity of
Ordinary Water Substance. 2011.
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Chapter 5: Modeling of a TLE 79
Chapter 5
Modeling of a TLE
5.1 Introduction
COILSIM1D is a program written in FORTRAN that simulates the cracking furnace of an
industrial steam cracker. However in the transfer line exchanger (TLE) after the coil secondary
reactions still occur which are currently not modeled in COILSIM1D. The goal of this chapter is
to modify COILSIM1D and extend it with a module called ‘TLEsim’ to make it able to simulate
an industrial TLE. The module will simulate a TLE with a double pipe configuration. Firstly, the
program has to be capable to calculate the temperature profile for the water/steam side of the
TLE and the steam production rate, when the user defines the TLE geometry and the water inlet
pressure in an input file. The updated version of COILSIM1D is then able to predict the gas
temperature profile and the composition of the cracked gas at the outlet of the TLE. In a second
stage, the module should be capable of determining the TLE length that is necessary to achieve a
certain gas outlet temperature that is given by the user.
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5.2 Review COILSIM1D

In COILSIM1D, the reactor coil of a steam cracker is modeled. The model consists of equations
for a one dimensional tubular reactor and it assumes a plug flow regime inside the reactor. A
microkinetic network called CRACKSIM is used to model the reactions. It consists of a free
radical mechanism and is based on elementary reactions. In the input files for the software the
user gives the molecular composition of the feedstock, the geometry of the reactor and the
process conditions. Based on this information, COILSIM1D integrates the continuity equations
for the different species, the energy balance and a pressure equation along the reactor coil. In the
output files, the product distribution, temperature, pressure and heat flux at different axial
positions throughout the reactor are written.
The process conditions for the simulations can be provide in a number of different ways. A first
option is to give both the gas temperature and the pressure profile along the coil. In this case the
energy and momentum equation do not need to be solved. The second option is to give either a
heat flux profile or an external wall temperature profile. In this case COILSIM1D solves the
energy equation and the momentum equation to get information about the temperature profile,
pressure profile, heat flux, wall temperature, composition, etc. The third option is to specify two
severity indices at the outlet of the reactor. One temperature related severity (e.g.
propylene/ethylene P/E , coil outlet temperature COT) and one pressure related severity (coil
outlet pressure COP or ethylene/ethane E/E). COILSIM1D will start an iterative procedure
where it imposes a certain shape of the heat flux profile (chosen by the user). COILSIM1D
linearly increases or decreases the heat flux profile and varies the coil inlet pressure until the
desired severity indices are reached.
The differential equations are solved by applying the Runge-Kutta method. For this method the
reactor is divided into different junctions along the axis. In each junction the composition,
temperature and pressure is calculated based on previous junctions, the heat flux or temperature
at the current junction. Figure 1 shows an example of how the temperature in the current junction
is calculated when a heat flux profile is specified.
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Figure 5-1: Calculation of the new temperature in one junction of the radiant coil
Multiple geometries of cracking furnaces that are common in the industry have been pre-defined
in COILSIM1D. Only limited input is required for these type of geometries to fully specify the
reactor.
5.3 Modifying COILSIM1D

This chapter will explain how the TLE module is modeled inside COILSIM1D. The equations
used in the original COILSIM1D program for modeling the coil can now be applied to model the
hydrocarbon side of the TLE because the latter can also be seen as a tubular reactor. A solver for
these equations is readily available in COILSIM1D as described in paragraph 5.2. The output
files of the original COILSIM1D that give the gas composition, mass flow, temperature and
pressure at the outlet of the coil can be used as input files for the new version of COILSIM1D. It
has to be checked whether the correlation used in the original COILSIM1D still apply at the low
temperatures which are obtained inside the TLE. In first approximation however, it is fair to say
that the gas tube in the TLE is made of the same material and has the same wall properties etc as
the radiant coils so that the correlations can be copied. The new version of COILSIM1D also has
to be able to calculate the amount of high pressure steam that is generated. New subroutines have
been written for this purpose which will be able to determine the temperature profile of the water
side of the TLE and to predict how much steam is generated. The main ideas behind these
subroutine are explained in the next sections.
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5.3.1 Case 1: fixed geometry and water inlet conditions

When the user defines the geometry of the inner and outer tubes (length and diameter) and gives
information about the water entering the annulus between the inner and the outer tube (pressure
and temperature) the program can calculate the amount of steam produced based on the heat flux
profile.
As discussed in section 5.2, one way to introduce the process conditions in COILSIM1D is by
imposing the heat flux profile. Once an initial guess of the heat flux profile is provided,
COILSIM1D can do a simulation of the radiant coil, or in this case the hydrocarbon side of the
TLE, using the information about the geometry. The temperature profile on the water/steam side
can be calculated based on the heat flux profile and the water conditions at the entrance of the
TLE provided by the user. Just like the radiant coil, the TLE is divided in several intervals. The
temperature at the first junction is the given inlet temperature T0 = Tentrance. If this temperature is
below the boiling point temperature, the temperatures in the other junctions are calculated as:

(5-1)
with
Ti the water temperature in section i [K]
Qi the heat flux in section i [kW m-2]
A the surface available for heat exchange [m2]
cp the heat capacity of the fluid [kJ kg-1 K-1]
the mass flow of the fluid [kg s-1]
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Figure 5-2: Calculation of the water side temperature in the TLE module
The sign of Qi in the TLE module is chosen positive when heat flows from the exterior to the gas
tube, as shown in Figure 5-2. In the TLE module, the heat flux profile will always be negative
because heat will flow from the gas towards the water/steam mixture in the annulus. Hence, the
minus sign in (5-1) is valid for the calculation of the water temperature. The hydrocarbon side
temperature is calculated using the equations present in the original version of COILSIM1D.
Under normal operating conditions, the water introduced at the bottom of the TLE is near its
boiling point. When the saturation temperature is reached, water will evaporate and steam is
formed. The steam quality increases according to

/
(5-2)
with
xi the vapor quality in section i [-]
/ the mass flow water/steam mixture [kg s-1]
hLG the latent heat of vaporization of water in [kJ kg-1]
Again, the minus compensates the negative sign of the heat flux Qi. Assuming that pure water is
fed to the TLE, x0 can be set equal to 0.
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As long as evaporation occurs the temperature of the water/steam mixture will remain at the
boiling point temperature corresponding to the water pressure. In case all the water is
evaporated, steam is being superheated. The temperature is then calculated in a similar way is in
(5-1). This is unlikely however, since the water/steam ratios normally lie around 10 as seen in
Chapter 3. In case water is very near its saturation temperature, and the heat flux is larger than
the heat needed to reach the saturation temperature, the heat flux is divided into the amount
needed to reach the saturation temperature and the part that is left. The latter part is then used to
start evaporating. Similarly, when evaporation is almost complete, the heat flux is divided into
the amount needed to complete the evaporation and the part that is left. The latter part is then
used to start superheating the steam.
When the temperature profile is known for the entire TLE, the local convection coefficient hconv,i
for convective heat transfer from the gas tube towards the water/steam mixture can be calculated.
The calculation of hconv is discussed in Chapter 4. With the local convection coefficient known,
the heat flux can be recalculated as
, /, ,

1000
(5-3)
with
hconv,i the convection coefficient in section i [W m-2]
Twall,i the external wall temperature [K]
This heat flux can then be used to start a new iteration in the process. This procedure is repeated
until a convergence criteria is met. The convergence is checked by evaluating the sum of the
squares of the ‘new’ values for the heat flux minus the ‘old’ values:
!"# $,% ,& ' (5-4)

If this sum of squares is larger than the maximum allowed value for convergence, then the
procedure is restarted.
Equation (5-3) shows how the heat flux profile can be recalculated. When the newly calculated
heat flux profile is very different than the previous one however, errors can occur. To ensure the
stability of the program the “updated” heat flux is a weighted average of the newly calculate one
and the ‘old’ one. Different weight factors have been tested and it has been found that 0.99 for
the ‘old’ value and 0.01 for the ‘new’ value yield acceptable results.
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When convergence is reached, the results are written and the steam production ratio is calculated
by multiplying the steam quality at the outlet of the TLE by the water flow rate at the inlet. In
section 5.4 the results of a simulation are shown.
5.3.1.1 Initial guess for the heat flux profile

A good initial guess for the heat flux profile is important to find a solution. In Chapter 3 a typical
heat flux profile in Alstom TLEs is shown (Figure 3-6). The profile is exponentially decreasing,
which can be explained by following reasoning. The temperature of the gas decreases with
increasing length of the TLE, and this proportional to the heat transfer Q from the gas to the
water/steam mixture. Neglecting terms related to heat transfer losses and reaction enthalpy (so
assuming no reaction takes place) this can be written as:
+)
()
*) Ω
+,
(5-5)
with
() the mass flux of the gas [kg m-2 s-1]
cpg the specific heat of the gas mixture [kJ kg-1 K-1]
Tg the gas temperature [K]
z the axial coordinate [m]
Q the heat flux from the gas towards the water/steam mixture (negative) [kW m-2]
. the circumference of the tube [m]
Combining (5-3) with (5-5) results in:
+) , Ω

+,
) ()
*) 1000
(5-6)
Twall is assumed to be independent of z, which is a reasonable approximation since the

temperature at the waterside under normal conditions is fixed at the saturation temperature.
Integrating and rearranging yields:
, Ω
) , / ),%0 "* 1 ,2
()
*) 1000
(5-7)
The convection coefficient, circumference, gas mass flux and specific heat are also assumed to
be independent of z. Combining (5-7) with (5-5) then gives following expression for Q:
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, 3 "*3' , (5-8)
with
456,789:; 5<=99 > ?@A8B,7

3 =
CCC
?@A8B,7 Ω
3' =
D6 6 CCC
In first approximation, expression (5-8) can be used to determine an initial guess for the heat flux
profile. The constant 3 is the heat flux at z = 0, and is the maximum heat flux.
To determine 3' , a ratio of Q at the entrance and Q at the exit can be suggested. Say for example
that Q at z = L is 10 times lower then Q at z = 0 with L the length of the TLE. This results in:
E 0.1 0

(5-9)
or
3 "*3' E 0.1 3
(5-10)
And hence
GH10
3'
E
(5-11)
Or more general, with R = Q(0)/Q(L):
GHI
3'
E
(5-12)
The expression for Q in equation (5-8) then becomes:
GHI
, JK "* 1 ,2
E
(5-13)
Or
M
, JK I L N (5-14)
Since the TLE is divided in several discrete intervals the heat flux profile must also consist of
discrete values. It is enough to replace z by a running index i and L by the total number of
junctions in (5-14) to obtain these discrete values Qi.
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It is possible to estimate a value for Qmax based on the total amount of heat exchanged over the
entire TLE Qtot:

00 O , ., +, (5-15)

C
with
Qtot the total amount of heat exchanged over the entire TLE [kW]
Ω(z) the local outer perimeter of the tube [m], it is assumed to be constant in what follows
Using (5-14) yields:

M E JK . I 1
00 O JK I L N . +,
lnI I
(5-16)
C
Rearranging for Qmax gives:
lnI I 00
JK
. E I 1
(5-17)
The advantage of working with R is that one parameter can be used to modify the shape of the
initial heat flux profile in a predictable way. R is usually taken in the range of 10 to 50. The total
heat flux can be estimated by proposing a gas outlet temperature and by using enthalpy of the gas
mixture which can be calculated with the thermodynamic data present in COILSIM1D:
00 ) R$ S0 T $ T U (5-18)

with
) the mass flow of the gas [kg s-1]
enthalpy of component i in the gas mixture at temperature T [kJ kg-1]
T mass fraction of component i in the gas mixture [-]
Qtot calculated by (5-18) usually underestimates the actual heat flux. For the stability of the
calculations, this is convenient because too large heat flux profiles have more chances on causing
errors than values that are too low.
5.3.1.2 Water mass flow

The water mass flow can be estimated based on the total heat flux and a value for the
water/steam ratio at the outlet of the TLE (usually around 10, this corresponds to a vapor quality
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equal to 0.091). A global energy balance over the water/steam side of the TLE shows that the
amount of steam formed is:
00
0%J

(5-19)
with
0%J the steam production rate [kg s-1]
the latent heat of vaporization for the high pressure water [kJ kg-1]
The water flow at the entrance of the TLE then follows from:
0%J
0%V
0.091
(5-20)
The model can be further improved by taking into account that the water/steam flow is actually a
flow based on natural circulation. In this case, the water/steam mass flow is calculated from a
momentum equation over the thermosyphon system formed by the steam drum, the riser and
downcomer tubes and the annulus of the TLE in which the water/steam mixture is heated. A
natural circulation model for a closed loop, two-phase thermosyphon system is presented in [1]
but including these calculations falls out of the scope of this master thesis.
5.3.2 Case 2: shooting for gas outlet temperature

Another way to look at the problem is to say that the user does not fix the geometry, but rather
fixes the gas outlet temperature. In this case, a shooting method can be applied for determining
the TLE length needed to obtain the necessary amount of cooling. The program then starts with
an initial guess of the TLE length and goes through the same procedure as described in 5.3.1. If
the gas outlet temperature is too low (high), the TLE length is increased (decreased) and
calculations restart.
It is also possible to work with a fixed geometry and change the mass flow of the water/steam
instead. Then, the value of hconv will change and a different heat flux profile will be obtained.
This is however a less physically correct way to solve the problem. In addition, the value of hconv
does not entirely determine the heat flux profile. There are three resistances for heat transfer
included in the model: convective heat transfer at the gas-wall interface, conduction through the
tube wall and convection at the wall-water/steam interface. The values obtained for hconv are very
high, so it is few likely that this heat transfer mechanism is the limiting one. Therefore changing
the water mass flow in order to alter hconv to obtain better cooling will not be very efficient.
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5.4 Results
5.4.1 Simulation based on Borsig data
A simulation has been performed with input data for the geometry and the inlet conditions based
on the values obtained from Borsig (cfr section 3.4.3 and Table 3-3) and for the gas composition
at the inlet of the TLE based on simulation results for ethane cracking. A summary of the
conditions is given in Table 5-1. The composition of the cracked gas at the inlet of the TLE can
be found in Table 5-2.
Table 5-1: Input data for TLE simulation, data from Borsig
Property Value Unit

TLE length 24 m
Gas flow for one double pipe 855 kg h-1
Steam dilution 0.25
Inlet temperature gas 830 °C
Inlet pressure gas 1.888 bar
Inlet pressure water 110 bar
Inlet temperature water 318 °C
5.4.1.1 Shah correlation

In this simulation the Shah correlation (cfr paragraph 4.2.3.1) was used to calculate the two-
phase flow boiling heat transfer coefficient.
Figure 5-3 gives the temperature profiles in the TLE. The blue curve shows the temperature
profile of the cracked gas. At the outlet of the TLE the gas is cooled to 362 °C, which is a good
approximation of the 350 °C reported by Borsig. The purple curve displays the temperature of
the water/steam mixture. As expected, its temperature is constant during the steam formation.
The boiling point of water at 110 bar is 318.08 °C, and water is introduced at 318 °C so
evaporation starts right away. The temperature at the interface between the gas tube and the
water/steam mixture is given by the green curve. It is almost constant and is very close to the
water/steam temperature. This is due to the high values for the coefficient for convective mass
transfer at the wall-water/steam interface. The graph also illustrates that the main resistance for
the heat flux is located at the convective heat transfer from the gas to the gas tube wall, because
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the temperature differences between the gas and the gas/wall interface are larger than the
temperature differences in the gas tube wall. This is confirmed by Figure 5-4 which shows the
heat transfer coefficients.
Figure 5-3: Temperature profiles in the TLE, data from Borsig, use of Shah correlation
The green curve in Figure 5-4 shows the convection coefficient at the water/steam side. The
value of the convection coefficient at the inlet deviates from the general trend followed by the
other values. A related deviation is observed in the temperature profile of the external wall in
Figure 5-3. This is due to the Shah calculation method for the coefficient for convective heat
transfer. In paragraph 4.2.3.1 this discontinuity in the calculation of the convection coefficient is
explained. The convection coefficient at the water/steam side decreases along the TLE because
the value is dependent on the heat flux in the Shah calculation method. Equations (4-15) to
(4-19) explain the heat flux dependence of the convection coefficient.
The red curve represents the heat transfer coefficient for conduction. The conduction coefficient
has been divided by the wall thickness to be able to compare is with the convection coefficients.
The blue curve is the convection coefficient at the gas side and shows the lowest values.
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Figure 5-4: Heat transfer coefficients, data from Borsig, use of Shah correlation
The heat flux profile in the TLE is shown in Figure 5-5. The heat flux at the entrance of the TLE
is 240 kW m-2 and decreases with increasing axial position as the gas is cooled and the driving
force for heat transfer decreases.
Figure 5-5: Heat flux profile in the TLE, data from Borsig, use of Shah correlation
Figure 5-6 shows the evolution of the steam quality in the TLE. Pure liquid water is fed at the
inlet of the TLE. The method proposed in 5.3.1.2 to calculate the water mass flow is not
accurate. Therefore, it was used as an initial guess and it was modified in order to get a steam
quality at the outlet of the TLE in the range of 0.09-0.11. The steam quality at the TLE outlet in
this simulation equals 0.107. The corresponding water mass flow in the TLE is 4.21 kg s-1 so the
steam production rate is 0.452 kg s-1 or 1627 kg h-1 which twice as high as reported by Borsig. At
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present, it is not completely clear where this difference comes from. The calculated water
velocity at the inlet of the TLE is 0.941 m s-1 and the velocity of the water/steam mixture at the
outlet of the TLE is 1.658 m s-1.
Figure 5-6: Steam quality profile, data from Borsig, use of Shah correlation
Another goal of the TLE module was to investigate the influence of the cooling on the
composition of the gas. In Figure 5-7, the change in mass fraction of the main components of the
gas at the inlet and the outlet is compared. The relative change of component i is calculated as
The differences are very low, so not many reactions still occur in the TLE. The complete
composition of the gas feed at the in- and outlet of the TLE is shown in Table 5-2.
Figure 5-7: Change in composition of the gas due to TLE cooling, data from Borsig
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Table 5-2: Composition of the gas at the in- and outlet of the TLE, simulation data
from Borsig
Name component TLE inlet (wt%) TLE outlet (wt%)

H2 3.336 3.347
CH4 7.238 7.319
C2H2 0.294 0.309
C2H4 45.28 45.328
C2H6 40.751 40.573
C3H4(MA) 0.015 0.017
C3H4(PD) 0.003 0.004
C3H6 0.747 0.75
C3H8 0.17 0.17
1;3-C4H6 1.07 1.066
1C4H8 0.244 0.235
2C4H8 0.018 0.014
iC4H8 0.001 0.001
iC4H10 0.001 0.001
nC4H10 0.453 0.482
13C5di 0.016 0.016
14C5di 0.004 0.001
Isoprene 0.017 0.016
1C5H10 0.013 0.019
2C5H10 0.002 0.002
iC6ol 0.013 0.006
iC7di 0 0.001
cyC5ol 0 0.006
CPD 0.05 0.063
mCPD 0.021 0.014
cyC6ol 0.005 0.002
cyC6di 0.005 0
mcyC6di 0 0.001
Benzene 0.177 0.187
Toluene 0.011 0.011
Xylene 0.003 0.003
Styrene 0.004 0.004
Naphth 0 0.002
mNaphth 0.015 0.017
phenantr 0.012 0.012
In order to check the above results, the simulations are repeated with the calculation method for
the two-phase flow boiling heat transfer coefficient proposed by Steiner and Taborek.
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5.4.1.2 Steiner and Taborek correlation

Figure 5-8 shows the temperature profiles in the TLE. The trend is very similar as the one shown
in Figure 5-3 when the Shah correlation is used. The gas temperature at the outlet of the TLE
now is 363 °C, which is the same as in the previous case. It can however be noticed that the
external wall temperature and the temperature at the gas/wall interface are slightly lower here
than in Figure 5-3.
Figure 5-8: Temperature profiles in the TLE, data from Borsig, Steiner and Taborek
correlation
This is confirmed by Figure 5-9 which makes clear that the convection coefficient at the water
side has a distinct different profile than the one shown in Figure 5-4. When the Steiner-Taborek
correlation is used, the convection coefficient increases with increasing axial position because
the vapor quality increases. The minimum heat flux for determining the onset of nucleate boiling
qONB (cfr equation (4-29)) is in this simulation equal to 4237 kW, so only convective boiling heat
transfer takes place (cfr section 4.3.2). The influence of the vapor quality on the convection
coefficient then follows from equation (4.21) for the calculation of the two phase multiplier Ftp
which increases for increasing vapor quality. For the first five meters of the TLE, the values of
the convection coefficient given by Shah are higher, and from then on the values obtained with
the Steiner-Taborek method are the highest. These differences however barely have any
influence as long as the values way higher than the ones for the conduction coefficient and
especially the convection coefficient at the gas side.
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Figure 5-9: Heat transfer coefficients, data from Borsig, Steiner and Taborek
correlation
5.4.2 Simulations based on data from Heynderickx (1993)

In this section, simulations will be performed with data obtained from the PhD thesis of
professor Heynderickx [2]. In the PhD, steam cracking of a propane feed with a Kellogg
Millisecond furnace design and a primary and secondary quench is simulated. Every four reactor
tubes are coupled to one double pipe TLE by means of an adiabatic „Tetrafit‟. A summary of the
TLE geometry and the applied conditions is given in Table 5-3. The inlet pressure of the water in
the TLE is not specified and is chosen equal to 110 bar. The water flow or the steam production
rate are not specified. The effluent gas is cooled to 575 °C after the primary quench. The
secondary quench is performed in a shell and tube heat exchanger and is therefore not modeled.
The composition of the cracked gas at the in- and outlet of the TLE as reported in the PhD thesis
can be found in Table 5-4.
Table 5-3: Input data for TLE simulation with, data taken from [2]
Property Value Unit

TLE length 9.369 m
Gas flow for one double pipe 557.5 kg h-1
Steam dilution 0.3
Inlet temperature gas 910 °C
Inlet pressure gas 1.747 bar
Inlet pressure water 110 bar
Inlet temperature water 318 °C
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Table 5-4: Composition of the gas at the in- and outlet of the TLE. Input data for the
simulation is the composition after the reactor as reported in [2].
Name component After reactor (wt%) After tetrafit(wt%) After TLE (wt%)
H2 1.54 1.64
CH4 22.09 23.23 24.86
C2H2 1.54 1.40
C2H4 38.29 39.86 41.09
C2H6 3.51 3.90
C3H4(MA) 0.83 0.84
C3H4(PD) 0.20 0.17
C3H6 15.07 13.8 12.04
C3H8 11.07 5.77
1;3-C4H6 1.56 1.79 1.54
1C4H8 0.54 0.36
iC4H8 0.21 0.17
nC4H10 0.11 0.06
iC4H10 0.06 0.02
Benzene 1.17 1.45 0.00
SUM 97.79 80.13 93.86
In a first simulation, the composition after the reactor is used as input for the TLE modeling
(second column in Table 5-4). The Shah correlation was used to calculate the two-phase flow
boiling heat transfer coefficient.
The temperature profiles in the TLE are presented in Figure 5-10. The temperature of the gas
effluent at the outlet of the TLE is 525 °C, which is 50 °C lower than the value presented in the
PhD thesis but nevertheless is a good approximation. A second simulation with a higher water
inlet pressure would yield a higher gas outlet temperature.
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Figure 5-10: Temperature profiles in the TLE, data from PhD thesis
The heat flux profile is shown in Figure 5-11.
Figure 5-11: Heat flux profile, data from PhD thesis
The water flow is 2.5 kg s-1 and 968 kg steam is produced per hour. There is no information
about the steam production rate in the PhD so no comparison can be made.
The influence of the TLE on the gas composition however can be compared. In Figure 5-12 the
relative change in composition is shown as calculated with Error! Reference source not
found.. Here clearly reactions take place as deviations up to 25 % are possible. The reason why
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these deviations are more clear here with respect to Figure 5-7 is probably the higher temperature
at the reactor outlet in this case.
Figure 5-12: Change in composition of the gas due to TLE cooling, data from the PhD
thesis
In Table 5-5 the composition of the gas at the outlet of the TLE as reported in the PhD is
compared with the results of the first simulation. The simulated values tend to the reported
values but these are not reached. Probably this is due to the adiabatic tetra fit which is not
included in the program. A second simulation is done in which the composition of the gas after
the „Tetrafit‟ as shown in the third column of Table 5-4 is used. However, only for five
components the weight percentage is given, so for the other components the values of the first
column (i.e. the composition at the reactor outlet) are taken. Figure 5-13 shows the same results
in a graphical way. For the most components, the results of the second simulation are better.
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Table 5-5: Comparison of the reported and the simulated outlet composition. The
results of simulation 1 are the same as those in Table 5-4. The input data for simulation
2 is the composition after the ‘Tetrafit’ as reported in [2]
Name component Reported (wt%) Simulation 1 (wt%) Simulation 2 (wt%)

H2 1.64 1.587 1.558
CH4 24.86 23.494 24.152
C2H2 1.40 1.7 1.678
C2H4 41.09 40.14 40.849
C2H6 3.90 3.651 3.593
C3H4(MA) 0.84 1.03 0.987
C3H4(PD) 0.17 0.222 0.213
C3H6 12.04 13.78 12.4
C3H8 5.77 9.979 9.763
1;3-C4H6 1.54 1.544 1.721
1C4H8 0.36 0.449 0.433
iC4H8 0.17 0.195 0.194
nC4H10 0.06 0.048 0.057
iC4H10 0.02 1.429 0.084
Benzene 0.00 0.099 1.687
SUM 93.86 99.35 99.37
Figure 5-13: Comparison of the reported and the simulated outlet composition
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Another possibility is to use the original COILSIM1D program for reactor coil modeling. In this
program, it is possible to include an adiabatic section after the reactor coil in the calculations. A
more complete composition of the gas after the „Tetrafit‟ than the one shown in Table 5-4 can
then be simulated based on the composition of the propane feed. This composition, the geometry
of the reactor and the process conditions are given in the PhD thesis and supply enough
information to start the simulation. Based on the result of this COILSIM1D simulation, the
composition at the outlet of the TLE can be modeled by using the modified COILSIM1D
program described in this chapter. The results of these simulations are shown in Table 5-6 and
are compared with the data reported in the PhD. The last column in Table 5-6 gives the design
values of the Kellogg Millisecond furnace.
The results of COILSIM1D after the „Tetrafit‟ are in good agreement with those reported in the
PhD, except for propene (C3H6) whose value is overestimated. The results obtained with the
COILSIM1D calculations are closer to the Kellogg design values than the simulation results
reported in the PhD.
Table 5-6: Comparison of the reported and the simulated outlet composition. The
simulated results are obtained based on a COILSIM1D simulation of the propane feed.
Name component After the ‘Tetrafit’ After the TLE Design Kellogg
COILSIM1D PhD COILSIM1D for PhD
TLE modeling
H2 1.644 1.648 1.64
CH4 21.635 23.23 22.593 24.86 21.7
C2H2 0.459 0.649 1.40
C2H4 38.119 39.86 39.006 41.09 38.2
C2H6 3.739 3.765 3.90
C3H4(MA) 1.01 1.181 0.84
C3H4(PD) 0.242 0.255 0.17
C3H6 17.056 13.8 15.432 12.04 13
C3H8 8.664 7.699 5.77
1;3-C4H6 1.798 1.79 1.69 1.54 2.8
1C4H8 0.532 0.448 0.36
iC4H8 0.241 0.222 0.17
iC4H10 0.041 0.032 0.02
nC4H10 0.085 0.075 0.06
Benzene 1.01 1.45 1.343 0.00 2.2
Other 3.687 3.96
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5.5 Future work

The current calculation method for determining the water flow is not accurate. Ideally, a
calculation method that account for the natural circulation of water should be used. It would be
interesting to investigate this option in the future.
In section 5.4.1.1 the steam production rate is overestimated by a factor two whereas the other
simulations results show a very good agreement with the data from Borsig. The reason why the
program fails to correctly predict the steam production rate should be further examined.
Currently, COILSIM1D is modified to perform TLE simulations instead of reactor coil

simulations. In the future, the TLE module should be fully integrated in COILSIM1D to
facilitate the coupled simulation of reactor coil and TLE.
5.6 Conclusion
TLE module for COILSIM1D has been designed and successfully compared to the data for
industrial TLEs provided by Borsig and to the data obtained from the PhD thesis of professor
Heynderickx. Nevertheless, there are still some shortcomings which are listed in the future work
section.
5.7 References
1. Haider, S.I., Y.K. Joshi, and W. Nakayama, A natural circulation model of the closed
loop, two-phase thermosyphon for electronics cooling. Journal of Heat Transfer-
Transactions of the Asme, 2002. 124(5): p. 881-890.
2. Heynderickx, G.J., Modellering en Simulatie van Huidige en Nieuwe Technologieën voor
de Thermische Kraking van Koolwaterstoffen. 1993, UGent: Ghent.
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Chapter 6: Conclusions and future work 102
Chapter 6
Conclusions and future work
In Chapter 2 the experimental work related to feedstock characterization is presented. Newly
developed conditions for HT-2D-GC were applied on two VGO samples. The conditions allow
for a quantification of the sample by chemical group and carbon number. The maximum
detectable carbon number was established at 46. Two VGOs showed that the heavier
hydrocarbons (carbon number 30 and up) are slightly discriminated. Additionally the results
obtained when using the cold-on column injector have a lower standard deviation than those
obtained using the split/splitless injector.
Experimental confirmation of the linear and equimolar character of the SCD signal has been
provided. This results in response factors equal to 1 and allows for straightforward calculations
of weight fractions in the sample.
A GC × GC analysis with SCD detector of one gas oil is performed. The sulfur present in the gas
oil mainly originates from benzothiophenes and dibenzothiophenes. This has been confirmed
with TOF-MS.
Chapter 3 is an introduction to the TLE modeling section of this master thesis. The cracked gas
generally leaves the reactor between 750 and 900 °C [1], depending on the feedstock and the
process conditions. TLEs are used in steam cracking installations to cool the effluent gas quickly
below reaction temperature and to prepare the effluent for further processing. The gas is typically
cooled to 300-400 °C and the exchanged heat is used to produce high pressure steam which
allows to recover up to 45% of the fired input duty [2]. Different setups and combination of
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TLEs can be used to achieve the required cooling capacity. Two types of TLEs are used in the
industry: those based on a double pipe system and those based on the shell and tube
configuration.
Chapter 4 gives an overview of the correlations used to determine the coefficient for convective
heat transfer used in Chapter 5. Two such calculation methods are given by Shah [3] and Steiner
and Taborek [4]. In both methods two contributions to the boiling flow heat transfer are
considered: nucleate boiling heat transfer and convective boiling heat transfer. Shah suggests to
choose the two-phase flow boiling heat transfer coefficient equal to the largest of the two
contributing mechanisms, whereas Steiner and Taborek give more weight to the dominant
mechanism but always take both mechanisms in consideration. Shah method is based on the
Dittus-Boetler correlation for single phase convection [5] while Steiner and Taborek use the
Gnielinski correlation [6]. The Shah correlation has as an advantage that it is easier and requires
less calculations compared to Steiner and Taborek’s method. The disadvantage for the use in
TLE modeling is that a discontinuity arises when the steam quality is equal to zero, which is the
case at the inlet of the TLE.
In the second part of Chapter 4 recommended formulations supplied by the International

Association for the Properties of Water and Steam (IAPWS) [7] for the calculation of the
physical properties of water and steam are discussed. Correlations for the density, specific
isobaric heat capacity, viscosity, surface tension and thermal conductivity are presented since
these are the parameters arising in the correlations for the heat transfer coefficient.
In Chapter 5 is devoted to the modeling of a TLE module inside COILSIM1D. In COILSIM1D,

the reactor coil of a steam cracker is modeled. The model consists of equations for a one
dimensional tubular reactor and it assumes a plug flow regime inside the reactor. A microkinetic
network called CRACKSIM is used to model the reactions. The equations used in the original
COILSIM1D program for modeling the coil can now be applied to model the hydrocarbon side
of the TLE. Subroutines able to determine temperature profile of the water side of the TLE and
to predict the steam production rate have been developed. A calculation method for an initial
guess for the heat flux profile inside the TLE is proposed. Based on this heat flux profile, the
temperature profiles inside the TLE can be calculated. In turn, these temperature profiles are
applied to calculate the convection coefficient at the water/steam side and to calculate a better
estimation of the heat flux profile. This iterative procedure is repeated until a convergence
criterion is met. The evolution of the steam quality along the TLE, the water flow at the inlet of
the TLE and hence the steam production rate are calculated. Finally, the developed TLE module
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for COILSIM1D is successfully compared to the data for industrial TLEs provided by Borsig
and to the data obtained from the PhD thesis of professor Heynderickx.
6.1 Future work

The method developed for the quantification of VGOs by chemical group and carbon number
can be further applied to other samples.
To be able check the results of the GC × GC – SCD analysis of the gas oil, new injections with
an appropriate compound as internal standard would be useful. The same method should also be
applied on other heavy hydrocarbon mixtures like VGOs and can in the future be used for on-
line analysis of the pilot plant effluent during steam cracking experiments.
The TLE module still experiences some shortcomings. The current calculation method for
determining the water flow for example, is not very accurate. These issues should be further
analyzed and resolved.
Currently, COILSIM1D is modified to perform TLE simulations instead of reactor coil

simulations. In the future, the TLE module should be fully integrated in COILSIM1D to
facilitate the coupled simulation of reactor coil and TLE.
References
1. Heinz Zimmermann, R.W., Ethylene, in Ullmann's Encyclopedia of Industrial Chemistry,
Wiley. p. 66.
2. G. Schmidt, D.S.U., Dr. C. Geipel, Olefin Academy 2010 Cracking Furnace Technology,
L. Engineering, Editor. 2010.
3. Shah, M.M., Evaluation of general correlations for heat transfer during boiling of
saturated liquids in tubes and annuli. HT2005: Proceedings of the ASME Summer Heat
Transfer Conference 2005, Vol 2, 2005: p. 1-11.
4. Steiner, D. and J. Taborek, Flow Boiling Heat-Transfer in Vertical Tubes Correlated by
an Asymptotic Model. Heat Transfer Engineering, 1992. 13(2): p. 43-69.
5. Dittus, B., Publications on Engineering, 1930. 2: p. 443.
6. Gnielinski, V., NEW EQUATIONS FOR HEAT AND MASS-TRANSFER IN
TURBULENT PIPE AND CHANNEL FLOW. International Chemical Engineering, 1976.
16(2): p. 359-368.
7. IAPWS. Available from: http://www.iapws.org/.
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Annex A: Correlation coefficient 105
Annex A: Correlation coefficients
Table A-1: Coefficients for equation (4-41)
i Ii Ji ni
1 0 -2 1.4632971213167 10-1
2 0 -1 -8.4548187169114 10-1
3 0 0 -3.7563603672040 100
4 0 1 3.3855169168385 100
5 0 2 -9.5791963387872 10-1
6 0 3 1.5772038513228 10-1
7 0 4 -1.6616417199501 10-2
8 0 5 8.1214629983568 10-4
9 1 -9 2.8319080123804 10-4
10 1 -7 -6.0706301565874 10-4
11 1 -1 -1.8990068218419 10-2
12 1 0 -3.2529748770505 10-2
13 1 1 -2.1841717175414 10-2
14 1 3 -5.2838357969930 10-5
15 2 -3 -4.7184321073267 10-4
16 2 0 -3.0001780793026 10-4
17 2 1 4.7661393906987 10-5
18 2 3 -4.4141845330846 10-6
19 2 17 -7.2694996297594 10-16
20 3 -4 -3.1679644845054 10-5
21 3 0 -2.8270797985312 10-6
22 3 6 -8.5205128120103 10-10
23 4 -5 -2.2425281908000 10-6
24 4 -2 -6.5171222895601 10-7
25 4 10 -1.4341729937924 10-13
26 5 -8 -4.0516996860117 10-7
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27 8 -11 -1.2734301741641 10-9

28 8 -6 -1.7424871230634 10-10
29 21 -29 -6.8762131295531 10-19
30 23 -31 1.4478307828521 10-20
31 29 -38 2.6335781662795 10-23
32 30 -39 -1.1947622640071 10-23
33 31 -40 1.8228094581404 10-24
34 32 -41 -9.3537087292458 10-26
i Ji0 ni0 (1)

1 0 -0.96927686500217 101
2 1 0.10086655968018 102
3 -5 -0.56087911283020 10−2
4 -4 0.71452738081455 10−1
5 -3 -0.40710498223928 100
6 -2 0.14240819171444 101
7 -1 -0.43839511319450 101
8 2 -0.28408632460772 100
9 3 0.21268463753307 10−1
(1) if the coefficients are used to calculate the properties of steam in the metastable region
following values for should be used:
–0.96937268393049 101 for ݊ଵ ଴ and 0.10087275970006 102 for ݊ଶ ଴
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Table A-3: Coefficients for equations (4-48) and (4-50)
i Ii Ji ni
1 1 0 -1.773174247321 10-3
2 1 1 -1.783486229236 10-2
3 1 2 -4.599601369637 10-2
4 1 3 -5.758125908343 10-2
5 1 6 -5.032527872793 10-2
6 2 1 -3.303264167020 10-5
7 2 2 -1.894898751632 10-4
8 2 4 -3.939277724336 10-3
9 2 7 -4.379729565057 10-2
10 2 36 -2.667454791409 10-5
11 3 0 2.048173769231 10-8
12 3 1 4.387066728444 10-7
13 3 3 -3.227767723857 10-5
14 3 6 -1.503392454215 10-3
15 3 35 -4.066825356265 10-2
16 4 1 -7.884730955937 10-10
17 4 2 1.279071785229 10-8
18 4 3 4.822537271851 10-7
19 5 7 2.292207633766 10-6
20 6 3 -1.671476645106 10-11
21 6 16 -2.117147232136 10-3
22 6 35 -2.389574193410 101
23 7 0 -5.905956432427 10-18
24 7 11 -1.262180889910 10-6
25 7 25 -3.894684243574 10-2
26 8 8 1.125621136046 10-11
27 8 36 -8.231134089800 100
28 9 13 1.980971280209 10-8
29 10 4 1.040696521017 10-19
30 10 10 -1.023474709593 10-13
31 10 14 -1.001817937951 10-9
32 16 29 -8.088290864699 10-11
33 16 50 1.069303187941 10-1
34 18 57 -3.366225057417 10-1
35 20 20 8.918584535542 10-25
36 20 35 3.062931687623 10-13
37 20 48 -4.200246769821 10-6
38 21 21 -5.905602968564 10-26
39 22 53 3.782694761346 10-6
40 23 39 -1.276860893468 10-15
41 24 26 7.308761059506 10-29
42 24 40 5.541471535078 10-17
43 24 58 -9.436970724121 10-7
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Table A-4: Coefficients for equations (4-51)
i Ii Ji ni
1 1 0 –0.73362260186506 10-2
2 1 2 –0.88223831943146 10-1
3 1 5 –0.72334555213245 10-1
4 1 11 –0.40813178534455 10-2
5 2 1 0.20097803380207 10-2
6 2 7 –0.53045921898642 10-1
7 2 16 –0.76190409086970 10-2
8 3 4 –0.63498037657313 10-2
9 3 16 –0.86043093028588 10-1
10 4 7 0.75321581522770 10-2
11 4 10 –0.79238375446139 10-2
12 5 9 –0.22888160778447 10-3
13 5 10 –0.26456501482810 10-2
Table A-5: Coefficients for equations (4-52) to (4-56)
i ni
1 1.1670521452767 103
2 -7.2421316703206 105
3 -1.7073846940092 101
4 1.2020824702470 104
5 -3.2325550322333 106
6 1.4915108613530 101
7 -4.8232657361591 103
8 4.0511340542057 105
9 -2.3855557567849 10-1
10 6.5017534844798 102
i Hi
0 1.67752
1 2.20462
2 0.6366564
3 -0.241605
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i j Hij (2)
0 0 5.20094 10-1
1 0 8.50895 10-2
2 0 -1.08374 100
3 0 -2.89555 10-1
0 1 2.22531 10-1
1 1 9.99115 10-1
2 1 1.88797 100
3 1 1.26613 100
5 1 1.20573 10-1
0 2 -2.81378 10-1
1 2 -9.06851 10-1
2 2 -7.72479 10-1
3 2 -4.89837 10-1
4 2 -2.57040 10-1
0 3 1.61913 10-1
1 3 2.57399 10-1
0 4 -3.25372 10-2
3 4 6.98452 10-2
4 5 8.72 102 10-3
3 6 -4.35673 10-3
5 6 -5.93264 10-4
(2) The coefficients Hij that are not present in Table A-7 are identically equal to 0
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Annex B: Elemental analysis and density measurements 110
Annex B: Elemental analysis and density

measurements
Table B-1: CHNSO analysis of DTO bio oil
Sample N [wt %] C [wt %] H [wt %] S [wt %] O[wt%]

DTO_1 0.24 86.30 13.22 0 0.25
DTO_2 0.12 85.52 14.13 0 0.23
DTO_3 0.26 85.48 14.01 0 0.25
DTO_4 0.48 85.36 13.91 0 0.25
DTO_5 1.30 85.77 12.93 0 -
DTO_6 1.26 85.84 12.89 0 -
DTO_7 0.50 86.27 13.23 0 -
DTO_8 1.24 86.08 12.68 0 -
Average 0.67 85.72 13.36 0 0.24
Table B-2: CHNSO analysis of TOFA bio oil
Sample N [wt %] C [wt %] H [wt %] S [wt %] O[wt%]

TOFA_1 0.02 85.05 14.76 0.00 0.17
TOFA_2 0.03 84.99 14.81 0.00 0.16
TOFA_3 0.12 84.90 14.79 0.00 0.19
TOFA_4 0.10 84.71 15.02 0.00 0.17
Average 0.07 84.91 14.85 0.00 0.17
Table B-3: Density measurement bio oils at 40 °C
Sample Experiment 1 [kg/l] Experiment 2 [kg/l] Experiment 3 [kg/l]

TOFA 0.753 0.752 -
DTO 0.79 0.79 0.79
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Table B-4: CHNS analysis of VTT nafta
Sample N [wt %] C [wt %] H [wt %] S [wt %]

VTT_Nafta_1 0.044 84.448 15.508 0
VTT_Nafta_2 0.042 84.673 15.285 0
VTT_Nafta_3 0.027 84.831 15.143 0
VTT_Nafta_4 0.022 84.207 15.771 0
Table B-5: CHNS analysis of three VGOs

FINA1 0 87.43 12.39 0.18
FINA2 0 87.66 12.19 0.15
FINA3 0 87.26 12.60 0.15
FINA4 0 87.27 12.60 0.13
Average 0 87.40 12.44 0.15
Exxon1 0 87.36 12.40 0.24

Exxon2 0 87.26 12.43 0.31
Exxon3 0 87.46 12.28 0.26
Exxon4 0 87.24 12.50 0.26
Average 0 87.33 12.40 0.27
Shell1 0 86.46 12.35 1.19

Shell2 0 86.49 12.33 1.18
Shell3 0 86.47 12.36 1.17
Shell4 0 86.34 12.44 1.21
Average 0 86.44 12.37 1.19
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Table B-6: CHNS analysis gas condensates

GC1180_1 0.17 85.65 14.18 0
GC1180_2 0.00 86.00 14.00 0
GC1180_3 0.14 85.93 13.92 0
GC1180_4 0.06 85.24 14.71 0
Average 0.09 85.70 14.20 0
GC1181_1 1.11 85.77 13.12 0

GC1181_2 0.08 85.43 14.49 0
GC1181_3 0.05 84.74 15.21 0
GC1181_4 0.10 86.11 13.79 0
Average 0.34 85.51 14.15 0
GC1182_1 0.10 86.11 13.78 0

GC1182_2 0.03 86.58 13.39 0
GC1182_3 0.24 86.65 13.11 0
Average 0.13 86.45 13.43 0
NA1183_1 0.05 84.84 15.11 0

NA1183_2 0.01 84.23 15.76 0
NA1183_3 0.02 84.26 15.72 0
Average 0.03 84.44 15.53 0
NA1191_1 0.61 84.60 14.80 0

NA1191_2 0.21 84.62 15.16 0
NA1191_3 0.06 84.12 15.82 0
Average 0.29 84.45 15.26 0
GC1196_1 0.70 86.21 13.09 0

GC1196_2 0.28 85.97 13.74 0
GC1196_3 0.86 85.99 13.15 0
GC1196_4 1.32 85.85 12.82 0
Average 0.79 86.01 13.20 0
GC1218_1 0.07 84.63 15.30 0

GC1218_2 0.09 84.71 15.20 0
GC1218_3 0.06 84.40 15.53 0
GC1218_4 0.02 84.76 15.22 0
Average 0.06 84.63 15.31 0
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Annex C: Detailed GC × GC composition of the VGOs and gasoil 113
Annex C: Detailed GC × GC composition

of the VGOs and gasoil
Table C-1: Detailed composition of VGO A with COC injection – run 1
Compound Name type #C wt%

naphthalene diaromatics 10 0.15
1-methyl naphthalene diaromatics 11 0.11
C12 diaromatics diaromatics 12 0.53
C10 dinaphthenes dinaphthenes 10 0.01
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isoparaffines C9 isoparaffines 9 0.01
p/m-xylene monoaromatics 8 0.00
o-xylene monoaromatics 8 0.01
C9 monoaromatics monoaromatics 9 0.04
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C9 mononaphthenes naphthenes 9 0.01
n-C3 cyclohexane naphthenes 9 0.00
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C10 naphthenoaromatics naphthenoaromatics 10 0.03
C13 naphthenodiaromatics naphthenodiaromatics 13 0.07
C16 naphthenotriaromatics naphthenotriaromatics 16 0.03
octane paraffines 8 0.00
nonane paraffines 9 0.01
decane paraffines 10 0.02
undecane paraffines 11 0.06
dodecane paraffines 12 0.13
tridecane paraffines 13 0.22
tetradecane paraffines 14 0.39
pentadecane paraffines 15 0.53
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hexadecane paraffines 16 0.76

heptadecane paraffines 17 0.93
octadecane paraffines 18 1.24
nonadecane paraffines 19 1.70
eicosane paraffines 20 1.35
heneicosane paraffines 21 1.20
docosane paraffines 22 1.01
tricosane paraffines 23 1.06
tetracosane paraffines 24 0.97
pentacosane paraffines 25 0.90
hexacosane paraffines 26 0.62
heptacosane paraffines 27 0.44
octacosane paraffines 28 0.28
nonacosane paraffines 29 0.23
triacontane paraffines 30 0.21
hentriacontane paraffines 31 0.12
dotriacontane paraffines 32 0.12
tritriacontane paraffines 33 0.08
tetratriacontane paraffines 34 0.11
pentatriacontane paraffines 35 0.08
hexatriacontane paraffines 36 0.12
heptatriacontane paraffines 37 0.08
octatriacontane paraffines 38 0.08
steranes terpanes 27 1.46
hopanes terpanes 27 2.92
C17 tetraaromatics tetra-aromatics 17 0.04
phenanthrene triaromatics 14 0.07
anthracene triaromatics 14 0.02
C15 triaromatics triaromatics 15 0.35
SUM 100
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Table C-2: Detailed composition of VGO A with SS injection – run 1

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toluene monoaromatics 7 0.00
ethylbenzene monoaromatics 8 0.00
p/m-xylene monoaromatics 8 0.00
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Phenanthrene triaromatics 14 0.07
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SUM 100
Table C-3: Detailed composition of VGO B with COC injection

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nonatriacontane paraffines 39 0.28
tetracontane paraffines 40 0.56
heneitetracontane paraffines 41 0.67
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dotetracontane paraffines 42 0.52

tritetracontane paraffines 43 0.37
tetratetracontane paraffines 44 0.23
hexacyclic terpanes terpanes 22 2.59
SUM 100
Table C-4: Detailed composition of VGO B with SS injection

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C17 naphthenotetraaromatics naphthenotetra-aromatics 17 0.00
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nonatriacontane paraffines 39 0.27
tetracontane paraffines 40 0.27
heneitetracontane paraffines 41 0.26
dotetracontane paraffines 42 0.20
tritetracontane paraffines 43 0.67
tetratetracontane paraffines 44 0.56
pentatetracontane paraffines 45 0.17
hexatetracontane paraffines 46 0.10
heptatetracontane paraffines 47 0.09
hexacyclic terpanes terpanes 22 3.38
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SUM 100
Table C-5: Detailed composition of gasoil 3778

Benzo(b)thiophene, 7-ethyl- benzothiophenes 10 0.004
C3 Benzo(b)thiophene benzothiophenes 11 0.106
naphthalene, 2-methyl- diaromatics 11 0.133
naphthalene, 1-methyl- diaromatics 11 0.098
C2 naphthalene diaromatics 12 0.628
Dibenzothiophene dibenzothiophenes 12 0.020
C13H10S dibenzothiophenes 13 0.069
C9H16 dinaphthenes dinaphthenes 9 0.017
C10H18 dinaphthenes dinaphthenes 10 0.027
decaline dinaphthenes 10 0.033
methyl decaline dinaphthenes 11 0.101
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C2 decaline dinaphthenes 12 0.231

butane, 3-methyl- isoparaffines 5 0.008
Pentane, 2-methyl- isoparaffines 6 0.021
Pentane, 3-methyl- isoparaffines 6 0.011
hexane, 3-methyl- isoparaffines 7 0.023
2,3-dimethyl-hexane isoparaffines 8 0.004
2-methyl heptane isoparaffines 8 0.041
3-methyl heptane isoparaffines 8 0.022
2,4-dimethylhexane isoparaffines 8 0.008
heptane, 2,3-dimethyl- isoparaffines 9 0.003
octane, 4-methyl- isoparaffines 9 0.034
hexane, 3-ethyl-2-methyl- isoparaffines 9 0.020
octane, 3-methyl- isoparaffines 9 0.027
isoparaffin C10 isoparaffines 10 0.172
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benzene monoaromatics 6 0.011
toluene monoaromatics 7 0.053
ethylbenzene monoaromatics 8 0.021
p-xylene monoaromatics 8 0.083
benzene, 1-ethyl-4-methyl- monoaromatics 9 0.008
propyl benzene monoaromatics 9 0.015
benzene, 1,2,3-trimethyl- monoaromatics 9 0.042
1,2,4 trimethylbenzene monoaromatics 9 0.059
benzene, 1,3,5-trimethyl- monoaromatics 9 0.022
benzene, 1,2,4,5-tetramethyl- monoaromatics 10 0.013
C10 aromatics monoaromatics 10 0.179
n-C5 cyclopentane naphthenes 5 0.025
cyclopentane, methyl- naphthenes 6 0.030
cyclohexane naphthenes 6 0.064
n-C6 cyclopentane naphthenes 6 0.011
cyclopentane, 1,2-dimethyl, cis- naphthenes 7 0.032
cyclohexane, methyl- naphthenes 7 0.122
1,3,4-trimethyl cyclopentane naphthenes 8 0.007
1,2,4 trimethylcyclopentane naphthenes 8 0.007
1,2,3-cyclopentane naphthenes 8 0.008
1,3-dimethylcyclohexane,c&t naphthenes 8 0.049
cyclopentane, 1-ethyl-2-methyl- naphthenes 8 0.018
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1-ethyl-3-methyl-cyclopentane naphthenes 8 0.003

cyclohexane, 1,2-dimethyl-, trans- naphthenes 8 0.020
cyclohexane, 1,4-dimethyl- naphthenes 8 0.010
cyclopentane, propyl- naphthenes 8 0.035
cyclohexane, ethyl- naphthenes 8 0.056
cycloheptane, methyl- naphthenes 8 0.006
1-ethyl-3-methyl-cyclohexane naphthenes 9 0.034
i-C3 cyclohexane naphthenes 9 0.138
cyclopentane, 1-methyl-3-(2-methylpropyl) naphthenes 10 0.064
n-C4 Cyclohexane naphthenes 10 0.047
C11 decaline naphthenes 11 0.126
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indane naphthenoaromatics 9 0.004
indene naphthenoaromatics 9 0.001
1-methyl indane naphthenoaromatics 10 0.004
2-methyl indane naphthenoaromatics 10 0.009
tetraline naphthenoaromatics 10 0.009
C11H14 naphthenoaromatics naphthenoaromatics 11 0.062
C13H10 naphthenodiaromatics naphthenodiaromatics 13 0.067
pentane paraffines 5 0.007
Confidential
hexane paraffines 6 0.587

heptane paraffines 7 0.047
Dotriacontane paraffines 32 0.017
Phenanthrene triaromatics 14 0.085
Methyl phenanthrene triaromatics 15 0.096
Methyl anthracene triaromatics 15 0.125
C16H14 triaromatics triaromatics 16 0.265
SUM 100
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Steam Cracking of Complex Hydrocarbon Mixtures

Promotor: prof. dr. ir. Kevin Van Geem

Masterproef ingediend tot het behalen van de academische graad van

Vakgroep Chemische Proceskunde en Technische Chemie

Thesis submitted to obtain the degree of

Vakgroep Chemische Proceskunde en Technische Chemie

Laboratorium voor Chemische Technologie

Verklaring in verband met de toegankelijkheid van de scriptie

Ondergetekende, Steven Vandermeersch

de scriptie mag steeds ter beschikking gesteld worden van elke

de scriptie mag enkel ter beschikking gesteld worden met uitdrukkelijke,

de scriptie mag ter beschikking gesteld worden van een aanvrager na

Mijn collega’s thesisstudenten en doctoraatstudenten in gebouw 918 wil ik bedanken voor

Promotor: prof. dr. ir. Kevin M. Van Geem

Promotor: prof. dr. ir. Kevin M. Van Geem

Samenvatting: Door de dalende reserves aan simulatiemodel ontwikkeld, COILSIM1D genaamd,

Steven Vandermeersch, thesisstudent aan de Universiteit Gent,

PrG Prandtl number for the vapor phase

Greek symbols Description Unit

Dimensionless factor representing the critical enhancement of

ν Specific volume (section 4.3.1.1) m3 kg-1

ΦG Mass flux of the gas kg m-2 s-1

13. Bartholomew, C.H., Mechanisms of catalyst deactivation. Applied Catalysis a-General,

The characterization of heavy petroleum fractions is however an important challenge for

Characterization of these fractions based on global characteristics or chemical groups is

2.2 GC x GC analysis of the feedstock

Figure 2-2: Schematic overview of the GC × GC-FID/SCD setup

Injector temperature 350 °C 10 °C below oven temperature

Split flow 10 ml/min -

Oven program 40 to 370 °C at 3 °C/min 40 to 50 °C at 20 °C/min

2.2.2 Calibration mixtures for SCD

Figure 2-3 show an overview of an Agilent Technologies 355 Sulfur Chemiluminescence

Figure 2-3: schematic overview of the SCD

Standard 1 and 2 Gas oil

Injector temperature 300 °C 280 °C

Split flow 10 ml/min 10 ml/min

Oven program 40 to 160 °C at 3 °C/min 40 to 300 °C

2.2.3 Gas oil

2.2.4 Elemental analyzer

Type FPD calibration CHNS calibration

Sample Weight Sample Weight

By-pass Soil standard* 2-3 mg BBOT standard** 2-3 mg

Blank Blank - Blank -

STD Soil standard 0.5 mg BBOT standard 2-3 mg

STD Soil standard 1.3 mg BBOT standard 2-3 mg

STD Soil standard 1.9 mg BBOT standard 2-3 mg

STD Soil standard 2.5 mg BBOT standard 2-3 mg

Unknown Soil standard 1-2 mg BBOT standard 2-3 mg

Unknown Soil standard 1-2 mg BBOT standard 2-3 mg

Unknown Soil standard 1-2 mg BBOT standard 2-3 mg

Minimum requirement for a good calibration curve is a coefficient of determination of at least

Figure 2-4: Linear calibration curve for CHNS analysis

Figure 2-5: Quadratic calibration curve for the FPD

Table 2-4: Results of an FPD analysis of gas oil 1191

Measurement number S [ppm]

VGO A VGO B Gas oil

C 87.39 87.35 86.42

H 12.46 12.39 13.15

N <0.01 <0.01 0.09

S 0.14 0.25 0.33

Table 2-6: Composition of standards 1 and 2

2.3.1 Polywax sample preparation

2.3.2 Vacuum gas oil sample preparation

, the number of moles sulfur originating from group i

the constant of proportionality for compound i

the peak volume of group i

a measure for the weight of the component in the sample

the molecular mass of the compound