GTC Technology Day 16 April  Hotel Le Meridien  New Delhi

Isomalk℠ Technologies for Light Naphtha Isomerization

Naphtha Processing Technology by GTC

n-C4
Isomalk-3 i-C4

Light Naphtha
Isomalk-2 C5/C6 Isomerate

C7 Paraffins
Isomalk-4 C7 Isomerate

Heavy Naphtha Semi-

Regenerative Reformate
Reforming

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Isomerization Technology Requirements
Efficiency
• Low operating temperature (100-150ºС)
• High octane product (possibility of 92-93 RON)
• Low H2 consumption and operating costs
• Long service life (up to 10 years)
Environmental
• Avoidance of acid and alkali wastes
Operations and Safety
• No acid agents
• Tolerance to catalytic poisons and excursions of feedstock impurities
• Activity recovery after contaminants removal from the feed
• Regenerable catalyst

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Technology Choices
Three light gasoline isomerization processes
• Chlorinated alumina catalysts
• Reasonable octane increase
• Regular organochloride additions required
• Spent caustic disposal also required
• Extreme measures for H20 and impurity removal
• Zeolite catalysts
• High operating temperature
• Less favorable for formation of high-branched isomers
• Mixed metal oxide catalysts
• Advantages of chlorinated alumina plus zeolite,
with none of the disadvantages
• Isomalk-2 leading mixed metal oxide catalyst

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 Temperature Range and Efficiency
of Different Isomerization Catalysts
80 Unstable,
disqualified
70
MF5 (MF6)/HF

60

50
2.2DMB/
∑С6Н14, % SI-2 and
40 Pt/Al2O3-C l
First generation,
Pt/ZrO2-SO4 obsolete
30
Pt/zeolite
20
Pt/Al2O3-F

10

0
0 50 100 150 200 250 300 350 400 450
Temperature °C

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Thermodynamic and Kinetic Limitations
equilibrium curve

SI-2 curve

chlorinated catalyst curve

oxide catalyst curve

2,2 DMB/ zeolite catalyst curve

ΣС6Н14,%

Temperature °C

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Isomerization Comparison
Chlorinated Catalysts Zeolite Catalysts Isomalk-2
Parameter Pt/Sulfated Oxides
Pt/Al2O5-Cl Pt/Zeolite Pt/ZrO2-MxOy-SO4
Operating temperature (°C) 120-180 250 – 280 140-200 120-180
Pressure (kg/cm2) 30 – 40 20 – 30 30 – 35 25 – 30
H2/HC 0.2 – 0.5 / 1 1–2/1 2–3/1 2–3/1
Octane Number (RON)
Once-through 82 – 85 78 – 79 80 – 81 82 – 85
DIH 86 – 88 81 – 82 84 86 – 88
DIP + DIH 89 – 90 83 – 86 86 – 87 89 – 90
DIP + DP + DIH 91 – 93 84 – 87 89 – 90 91 – 93
Trace Contaminant Limits
Sulfur (ppm) < 1.0 < 10 < 1.0 < 2.0
Nitrogen (ppm) < 0.5 < 2.0 < 0.5 < 1.0
Water (ppm) < 0.5 < 50 < 3.0 < 10.0
Capability to Regenerate No Yes Yes Yes
Water Poisoning Irreversible Recoverable Recoverable Recoverable

Isomalk-2SM is a low-temperature high performance isomerization technology with impressive tolerance to process impurities.

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 High Naphthenic Hydrocarbons -
Higher Conversion on SI-2
Naphthenic hydrocarbons conversion to paraffins over chlorinated and SI-2;
more benzene allowed in feed.
70

60

50
SI-2 oxide catalyst
Conversion,%
40

30

20

10
Pt/Al2O3-Cl

0
100 110 120 130 140 150 160 170 180 190

Temperature °C

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 Lower C7+ Formation on SI-2
Formation of low-octane С7+ hydrocarbons in isomerization
over chlorinated and SI-2 catalysts; better overall octane
3

Pt/Al2O3-Cl
Yield, C7+ , %

1
SI-2 oxide catalyst

0
100 110 120 130 140 150 160 170 180 190

Temperature °C

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Tolerance of the SI-2 Catalyst to Process Impurities

40
SI-2 oxide catalyst

30

Activity, 2,2-DMB/∑С6Н14, %
Pt/Al2O3-Cl
20

10

H2O, Н2S, ppm

0

0 1 2 3 4 5 6
Minimum risk, high-performance operation;
optimized shut-down and start-up procedures
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SI-2 and Chlorinated Aluminum Operation Cost Comparison
Benchmark cost study of the processes over
chlorinated and SI-2 catalysts.

Chlorinated catalysts
- 15%
SI-2 catalyst

Recycle and product

separation

Reactor block
operation costs

Costs of feed water

removal and sour
gas caustic treatment

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Isomalk-2℠ Once-through
No Caustic
Treatment Block

Gas C1-C4
No Perchloroethylene Compressor
Addition
Dryer

Reactor
Make-up
Section
Hydrogen

Stabilizer
Feed

No Feed
Dryers Needed

Product
Product RON
81-85
RON 82-84

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Isomalk-2℠ with Full Recycles
Isopentane fraction Product
Product RON 92-93
RON 91-92
n-pentane recycle

Compressor C1-C4
H2 gas
Dryer
Reactor Section

Make-up
H2
Deisopentanizer

Deisohexanizer
Depentanizer
Stabilizer
H/T feed

Low
Octane Residue
reduced 10 times

n-hexane recycle

Unwanted
Naphthene
Recycle minimized
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Plant I Case Study, World-Scale Grass-Root Isomalk-2℠ Unit.

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Plant I, Case Study, World-Scale
Grass Roots Isomalk-2℠ Unit

Full Recycle
Capacity, t/y 1,100,000
Isomerate yield, % 99
i-Pentane cut, RON 92.0-93.0
Light Isomerate, RON 91.5-92.5
Space velocity in the reactor block, hour-1 2.0 -2.5

Start-up year Q4 2010

First World-Scale isomerization unit to use non-chlorinated catalyst

and achieve 92.5 RON for final isomerate

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Plant II Case Study, World-Scale
Revamp to Isomalk-2℠ Unit at BPCL Mumbai

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Revamp Objectives at BPCL Mumbai

• Convert existing Semi Regenerative Catalytic Reforming Unit (CRU)

to an Isomerization (ISOM) / revamp existing Naphtha Hydro
desulfurization (NHDS) unit
• Increase processing capacity
• Maximize Isomerate Yield & Octane
• To produce special products such as Food Grade Hexane (FGH),
Special Boiling Point (SBP)
• Maximize the use of existing equipment

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Revamp to Isomalk-2℠ Unit at BPCL Mumbai

• Revamped existing Naphtha Hydrodesulfurization unit by replacing catalyst to

hydrotreat Naphtha streams
• Revamped existing Reformate Splitter to be used as Naphtha Splitter for splitting
hydrotreated naphtha into
− Top cut as Isomerization Feed
− Side cut for blending into MS
− Bottom cut for blending into HSD
• Revamped existing idle CRU to an Isomerization unit using SI-2 catalyst
• New DWC combining Deisohexanizer and FGH column to produce Food Grade
Hexane product and Isomerate.

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Plant II Case Study, World-Scale Revamp to
Isomalk-2℠ Unit at BPCL Mumbai
• Feed from various sources with high x-factor
– Benzene up to 5%
– C7 and Naphthenes up to 10%
• Successfully commissioned with the overall annual capacity of the isomerization section
being 680 KTA.

Once Through
Capacity, t/y 680,000
Isomerate yield, % 97
Stabilized Isomerate, RON 84
Space velocity in the reactor block, hour-1 2.0 -2.5
Start-up year Q1 2017

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Isomalk-2℠ Applications: Revamp of Other Technologies
Company, Year Type of Project Capacity Process Scheme Octane, RON

Plant A, 2003 Revamp of Reforming Unit to Isomalk-2 Technology 500 KTA DIH 86-87

Plant B, 2005 Revamp of a Zeolite unit to Isomalk-2 Technology 400 KTA Once-through 82-83

Plant C, 2005 Revamp of a Zeolite Unit to Isomalk-2 Technology 500 KTA Once-through 83-84

Plant D 2005 Revamp of Reforming Unit to Isomalk-2 Technology 400 KTA DIP+DIH 86-87

Plant E, 2006 Revamp of a ZrO2 based Unit into the Isomalk-2 Technology 180 KTA DIP+DIH 86-87

Plant F, 2008 Revamp of a Zeolite unit to Isomalk-2 Technology 300 KTA DIH 86-88

Plant G, 2009 Revamp of a Zeolite unit to Isomalk-2 Technology 500 KTA DIH 87-88

Plant H, 2015 Revamp of Reforming Unit to Isomalk-2 Technology 300 KTA DIH 86-88

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Isomalk-2℠ Highlights
• Leading low-temperature C5-C6 isomerization technology
• Based on a use a mixed metal oxide catalyst (non-chlorinated)
• Low-operating temperatures - high RON, high yields, optimum OPEX
• There is no need for chlorine injection, off-gas caustic scrubbing, feed dryers
• Water, Sulfur, Nitrogen specs are significantly relaxed
• Operation is simple and robust.
• Minimal start-up, turn-around, shutdown time minimal due to resistance to catalytic
poisons
• >15% CAPEX and OPEX advantage over competing technologies
• In the last 10 years, Isomalk-2℠ has been preferred for 30 refinery projects

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Naphtha Processing Technology by GTC

n-C4
Isomalk-3 i-C4

Light Naphtha
Isomalk-2 C5/C6 Isomerate

C7 Paraffins
Isomalk-4 C7 Isomerate

Heavy Naphtha Semi-

Regenerative Reformate
Reforming

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Isomalk-3℠ Highlights

• Isomalk-3℠ is the leading low-temperature C4 isomerization technology based on a using a mixed

metal oxide catalyst (non-chlorinated)
• Isomalk-3℠ was developed as the analogue of Isomalk-2 (C5-C6) for C4 isomerization.
• A recent award for Isomalk-3 is the first ever non-chlorinated unit in Asia.
• Operating temperatures of 160-180oC achieve high conversion, yield and have optimum OPEX
• The expected catalyst lifetime of Isomalk-3℠ is 10 years, Pt recovery minimized
• There is no need for chlorine injection, off-gas caustic scrubbing, only one reactor
design.
• Water, Sulfur, Nitrogen specs are significantly relaxed
• Operation is simple and robust. Start-up, turn-around, shutdown time are minimal due to
resistance to catalytic poisons

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Isomalk-3℠ Highlights
Process parameter Isomalk-3℠

Temperature, оС 160-180

Pressure, MPa 1.5-1.8

H2/Feed ratio 0,05-0,1

LHSV, h-1 8-10

N-butane conversion, per pass 50-55

Selectivity for C3+, wt % 98-99

Chlorine injection no

Off-gas scrubbing no
Life-time of the catalyst, years 8-10

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Block Flow Diagram for Isomalk-3℠
No Caustic
Treatment Block

Hydrocarbon Gas
DA-2/1,2 C-3

RD-3
H2 gas
One Reactor Design

No Perchloroethylene P-2/A, B
Addition
DA-2 -1/1,2

HE-1 R-1 SC
n-butane
fraction HE-2

HE-3
P-1/A, B
No Additional Trap C-4 Stable Isomerate
Beds Required

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Catalyst Impurity Limits

Parameter SI-3™

Trace Contaminant Limits

Sulfur (ppm) < 2.0

Nitrogen (ppm) < 1.0

Water (ppm) < 10.0

Olefins, wt.% <1.0

Capability to Regenerate Yes

Water Poisoning Recoverable

Isomalk-3℠ is a high performance C4 isomerization technology

with impressive tolerance to process impurities

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Isomalk-3℠ Commercial Units

No. Company Process Scheme

1 Liaoning Hualu, China n-butane Isomerization

With propane and butane
2 Shandong Sincier, China
dehydrogenation unit
3 Haike Ruilin, China n-butane Isomerization

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Isomalk-3℠ Summary

• Based on the use of a non-chlorinated high performance mixed oxide

SI-3™ catalyst.
• Offers competitive yield of final product.
• Significantly reduced CAPEX > 25% excludes chlorine injection
equipment and caustic scrubbing, only one-reactor design.
• Significantly reduced OPEX provides longer catalyst life-time, reliable
operation, no need for chloride supply and no corrosion or wastes
produced.

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GTC Technology Day