socnnms ‘i poss ipa te ee cpa Claus process From Wikipedia, the fee eneylopedia ‘The Claus process isthe most significant gas desulfuriing process, recovering elemental sulfur from gaseous hydrogen sulfide. First patented in 1883 by the scientist Carl Friedrich Claus, the Claus process has become the industry standard, ‘The muli-step Claus process recovers sulfur from the gaseous hydrogen sulfide found in raw natural gus and from the by-product gases containing hydrogen sulfide derived from refining crude oil and other industrial processes. The by-product gases mainly originate from physical and chemical gas treatment units {Selexol, Recisol,Purisol and amine scrubbers) in refineries, natural gas processing plans and gasification or symthesis gas plants. These by-product gases may also contain hydrogen eyanide, hydrocarbons, sulfur dioxide or ammonia ‘Gases with an HyS content of over 25% are suitable forthe recovery of sulfur in straight-through Claus plants while alternate configurations such as a split-flow set up or feed and air preheating can be used to process leaner feeds Piles of ular progusod in Alberta by the Claus process, Hydrogen sulfide produced, for example, in the hydo-desulfvzation af refinery naphthas and other pewoleum oil, is converted to sulfur in Clas plants The svoting sie at ds in Vanover, Can ‘overall main reaction equation is 2HS+0,28+21,0 In fac, he vast majority ofthe 64,000,000 metric tons of sulfa produced worldwide in 2005 was byproduct sulfur fom refineries and other hydrocarbon processing plans [ISI sulfur is used for manufacturing sul cid, medicine, cosmetis, fetlizers and rubber products. Elemental sulfur is used as fertilizer and pesticide Contents #1 History + Process description 2.1 Thermal step © 2.11 Side reactions + 2.1 2 Detailed Chemical Kinetic Modeling + 22 .Catalyte step + 23 Sub dew point Claus process * 3 Process performance #4 Seealso + 5 References History The process was invented by Carl Friedrich Claus, a chemist working in England. A British patent was issued to him in 1883. The process was later significantly modified by a German company called 1G Farben! Process description ‘A schematic process flow diagram of abasic 2+1-reactr (converte) SuperClaus unit is shown below. esenumesa cme post‘acne cme pac np tetany Schematic Now diagram ofa staightthrough, 3 reator (converte), Claus sulfur The Claus technology can be divided into two process steps, thermal and catalytic. Thermal step Inthe thermal step, hydrogen sulfide-laden gas reacts ina substoichiometric combustion at temperatures above 850 °C II such that elemental sulfur precipitates in the downstream provess gas cooler. le components (hydrocarbons or ammonia) determine the location where the feed gas is burned, Claus gases (acid gas) with no further combustible contents apart The H,S content and the concentration of other comby from HS are burned in lances surrounding central mufile by the following chemical 2H,S+30,+280,+21,0 (AN=-41472 KI mol” This isa strongly exothermic fiee-flame total oxidation of hydrogen sulfide generating sulfur dioxide that reacts away in subsequent reactions. The most important one isthe Claus reaction: 2H,S +80, +35 21,0 The overall equation i: 1OH,S + 5 0, + 21S + $0, + 722 S, + 8 HO This equation shows that in the thermal step alone two-thirds of the hydrogen sulfide can be converted to sulfur Gases containing ammonia, such as the gas from the refinery’s sour water stripper (SWS), or hydrocarbons are converted inthe burner muffle Sufficient aris injected ino the mufMe for the complete combustion of all hydrocarbons and ammonia. The air to the acid gas ratio is controlled such that in total 1/3 ofall hydrogen sulfide (I1,S) is converted to SO). This ensures a stoichiometric reaction forthe Claus reaction inthe second catalytic step (see next section below) The separation ofthe combustion processes ensures an accurate dosage a the required air volume needed as @ function of the feed gas composition. To reduce the process gas volume or obtain higher combustion temperatures, the air requirement can also be covered by injecting pure oxygen. Several technologies utilizing high-level and low-level oxygen enrichment are avaiable in industry, which requires the use of «special burner inthe reaction furnace for this process option, ‘Usually, 60 to 70% ofthe total amount of elemental sulfur produced inthe process are obtained inthe thermal process step. The main portion of the hot gas from the combustion chamber flows through the tube of the process gas cooler and is cooled down such that the sulfur formed in the reaction step condenses. The heat given off by the process gas and the condensation heat evolved are utilized to produce medium or low-pressure steam, The condensed sulfur is removed atthe liquid oullt section of the process gas cooler esenumesa cme post‘acme ‘i poss -ipaa te ence “The sulfur forms in the thermal phase as highly reactive Sdiradicals which combine exclusively tothe Sg allotrope 48;985 Side rea ‘Other chemical processes taking place in the thermal step of the Claus reaction are 5 1 The formation of hydrogen gas 2HS+S8,+21, (AH>0) CH, 421,04 C0; +41 1» The formation of carbonyl sulfide HS + CO, + S-C-0 + H,0 1 The formation of carbon disulfide: CH #28; SCS +218 Detailed Chemical Kinetic Modeling Recent efforts to develop complex chemical kinetic models for the thetmal reactions of Hydrogen sulfide under conditions of the Claus process furnace ean now be found. The models consist of hundreds of elementary reactions including kinetic coefficients and thermochemical data. Such efforts can be found in the following references: a. LA, Gargurevich, Hydrogen Sulfide Combustion: Relevant Issues under Claus Furnace Conditions Ind Eng Chem Res, 44 (2005), pp. 7706-7729 (hip: /wwww freescience infa/notes php?id=15) ‘Selim, HM. ME. (2012), Characteristics and chemical kinetics of hydrogen sulfide combustion in thermal Claus reactor (Doctoral dissertation, UNIVERSITY OF MARYLAND, COLLEGE PARK), ‘hip: drum lib.umd edwhandle/1903/13531) «, Manent,F., Papasidero, D., & Ranzi, E, (2013), Revised Kinetic Scheme for Thermal Furnace of Sulfur Recovery Units, Chemical Engineering Transactions, 32, 2013, 1185-1290 ( hitp:fwww aid, ieet/13/32/218,pa) ‘The most significant effort isin the development of sound chemistry (elementary reactions) for the mechanism since it must explain formation af intermediate chemical species and final products. Development of the kinetic coefficients involves experimental data, computational chemistry (eg. reaction activation energy via Quantum Chemistry) as well as estimation methods such as kinetie theory, transition state theory. Reactions ean involve chemical activation and methods are available to teat such reactions. A simple presentation of such methods cam be found in Gargurevich, Ivan A., Reaction Kineties & Chemical Reaction Models, itp /iwww-cheresourees com/reactionkineties pdf, 2001 BBimolecular chemical activation, an important reaction in combustion for example, ean be explained by the illustration below ({rom Gargurevich (2001) referenced above) esenumesa cme post »socnnms ‘i poss ipa te ee cpa Reaction Coordinate In the case ofa bimolecular activation reaction is meant that as the result ofa bimolecular reaction (addition of fee radical toa double bonded species for example) an intermediate A* is formed possessing excess energy ‘over the ground state that can more easily lead to some final product by decomposition or, RER’ > Products Activated Molecule (A*) < ‘Annice introduction to Computational Chemisty is given by David C, Young in his book “Computational Chemistry: A Practical Guide for Applying Techniques to Real World Problems (Wiley, 2001)", and his website hitp:/wwwcol net/eca/documents!dyoung/topics-orgl. It isnot the intention here ta present a discussion on such complex subject. A description of available quantum chemistry software is given by this Encyclopedia and found at https fen. wikipedia orgwikiList_of_quantum_chemistry_and_solid-sate_physics_software. Computational Chemistry methods can be used to estimate thermochemical properties of molecules such as Heat of Formation as well. However, Semi-empirical methods sach as group additive are described By S. W. Benson in his book "Thermochemical Kinetics " in Modeling of Chemical Reactions, vol. 42, Chapter 5, p. 187, W. R ‘The overall process of constructing such Detaled Chemical Kinetic Models is ilustrated by Swiart, Mark, T, "Constructing Reaction Mechanisms, Carr Editor, 2007 ( Comprehensive Chemical Kinetics Series (N. J.B. Green Series Editor, by Elsevier, a copy ofthe volume is found at ‘imps rads files wordpress com/2010/09/comprehensive_chemical_kineties_volume_42”- modeling of chemical reactions] pdf, ‘The diagram below depicts the major steps in constructing complex or detailed chemical kinetic reaction models, Itis self-explanatory and depicts quite well the major steps in building a detailed chemical kinetic model starting with the assembly ofthe elementary chemical reactions, followed by estimating chemical kinetic parameters and thermochemical parameters. The validation ofthe reaction model must be conducted with an ‘appropriate experimental apparatus. Eventually, the development and design ofa pilotcommercal size reactor must be considered including simulation by CFD including chemical reactions. The seal up parameters for ‘the reactor must also be determined esenumesa cme post‘acne cme pac np tetany CONSTRUCTING DETAILED REACTION MECHANISMS ASSEMBLE ELEMENTARY REACTIONS: ‘A. EXPERIMENTAL DATA ANALOGY TO OTHER MECHANISMS © FUNDAMENTAL CHEMICAL LAWS, ESTIMATE THERMODYNAMIC DATA A. EXPERIMENTAL DATA 8 QUANTUM CHEMISTRY © GROUP ADDITIVITY D. FUNDAMENTAL CHEMICAL LAWS ESTIMATE REACTION RATE COEFFICIENTS| EXPERIMENTAL DATA ANALOGY TO SIMILAR REACTIONS QUANTUM CHEMISTRY’ REACTION RATE THEORIES opp REACTION MODEL VALIDATION SELECTION OF EXPERIMENTAL SET UP 5 CONDUCTING DATA GATHERING FOR COMPONENTS OF INTEREST ¢ SENSITIVITY ANALYSIS: D RATE ANALYSIS I LARGE SCALE REACTOR DEVELOPMENTIDESIGN A. SCALE UP 8. REACTOR CONFIGURATION SELECTION © HEAT/MASSIMOMENTUM TRANSPORT (CFD) SIMULATION Two other excellent references for detailed chemical kinetic modeling are and 1 ‘As an illustration of such modeling, a reduced mechanism for the oxidation of Hydrogen Sulfide can be constructed as below (but lfenu kz/repository/2009/A1AA-2009-1392 pal 1 H2S+M =S+H2+M— 1 60B424 2.61 44800 H=H2 - 1 206407 2.1 350 SH=OH 7:50E+07 1.75 1460,‘ocwnms ‘i poss ipa te ee cpa 4, H2S+OH= SH#H20 2,70E+12 00 5. H2S+S=2SH 8 30E+13 0.3700 6, H2S+S = HS2+H 2.03613 0 9723.84 i SH+H 1.40E+14 09700 8 9. 10, SH+02= HS0-0 1.90E+13 0.9000 11, SHOH=H+S0 4.00E=13 00 12, S$H02= S00 5.208406 1.81 -600 13. SH+S=S2+H 1.005+13 00 14, S2+11414= HS2+M 1 00E+16 00 15, S240 SO+S 1.00E+13 00 16, SO*OH = SO2+H 1,08E+17-1.35 0 17, SO+02= $0240 7.60+03 2.37 1500 18, 280 $0248 2.03E+12 0 2000 19, HS0+02= $02+0H 1.00B+12 0 5000, 20. 28H=S24112 1.006+1200 21, S2#M= 2S+M 4,80E+13 0 38800 $2+H2 1.20E+07 21 352.42 23, HS2+0- S2HOH 7.505+07 1.8 1460 24, HS2+OH = S2+H20 2.70E+12.00 25. H52+5= S2+SH 8.3013 0 3700 26, SO+O(+M) = S02(+M) 3.206+13 0.0 27. SO*M-= S#0+M 4005+ 14 0 $4000, 28, SO+HeM 29. HSOH 30. HSOH 31. HSOH 32. HSOH 33. HSOW 34, HS0+0= OH#SO 1408413 0.15 150 435. HSO+OH = SO+H20 1.705109 1.03 235, 36. SHOH = SH+0 6.30E+11 05 4030.55, 137, SH#02= SO+OH L.00E+12 503 248, ‘The mechanism with chemical kinetic data and thermodynamic properties isan input to software (es a batch file) to simulate a plug flow reactor, or CSTR for example satisfying hea, component and mass balances. Note ‘that atthe high temperature typical of @ Claus furnace, the mechanism involves a radical chain reaction mechanism for the devomposition and oxidation of Hydrogen sulfide. More ean be found in references [8} and [9] piven below Catalytic step ‘The Claus reaction continues inthe catalytic step with activated aluminumiIIl) or ttanium(1V) oxide, and serves to boost the sulfur yield, More hydrogen sulfide (H,S) reacts with the SO formed during combustion i the reaction furnace in the Claus reaction, and results in gaseous, elemental sulfur 2H,S+S0,-13$+2H,0 (AMI=-1165.6 5) mol“) ‘This sulfur can be Sg, $7, Sg or Ss ‘A recent mechanism forthe formation of sulfur ona catalyst surface is given in a recent publication by T-K. Khanmamedox and RH. Welland tiled "How Sulphur Really Forms on The Catalyst Surface ", Sulphur, 345, March-April 2013, p62. Their conclusion is as follows: "A mechanism path for catalytic oxidation of Hydrogen Sulfide has been discussed. The mechanism involves $(6) and S(8) that desorb form the catalyst’ active sites with simultaneous formation of stable cyclic elemental sulfur. Kinetic models that identify the main peculiarities of catalytic oxidation in the Claus reaction and the oxidation of Hydrogen Sulfide with Oxygen have been suggested." esenumesa cme post «‘acne ‘i pos ipa te eect ‘The catalytic recovery of sulfur consists of three substeps: heating, catalytic reaction and cooling plus condensation. These three steps are normally repeated a maximum of thre times. Where an incineration or tail-gas ‘treatment unit (TGTU) is added downstream of the Claus plant, only two catalytic stages are usually installed inthe “The frst process step in the catalytic stage isthe gas heating process. Iti nevessary to prevent sulfur condensation inthe catalyst bed, which can lead to catalyst fouling, The required bed operating temperatur individual catalytic stages is achieved by heating the process gas ina reheater until the desired operating bed temperature is reached Several methods of reheating are used in industry: = Hot-gas bypass: whi ‘= Indizect steam reheatets: the gas can also be heated with high-pressure steam ina heat exchanger. = Gas/gas exchangers: whereby the cooled gas Irom the process gas cooler is indtectly heated from the hot gas coming out of an upstream catalytic reactor ina gas-to-gas exchanger = Ditecttired heaters. fired reheaters utilizing acid gas of fuel gas, which is burned substoichiometscaly to avoid oxygen breakthrough which can damage Claus catalyst involves mixing the two process gas streams from the process gas cooler (eold gas) and the bypass (hot gas) ftom the fist pass ofthe waste-heat boiler ‘The typically recommended operating temperature ofthe first catalyst stage is 315 °C to 330°°C (bottom bed temperature), The high temperature inthe first stage also helps to hydrolyze COS and CS, which is formed in the furnace and would not otherwise be converted in the modified Claus process ‘The catalytic conversion is maximized at lower temperatures, but care must be taken to ensure that each bed is operated above the dew point of sulfur. The operating temperatures ofthe subsequent catalytic stages are typically 240 °C forthe second stage and 200 °C forthe third stage (bottom bed temperatures) In the sulfur condenser, the process gas coming from the catalytic reactor is cooled to between 150 and 130 °C. The condensation heat is used to generate steam at the shell side ofthe condenser. Before storage, liguid sulfur streams fom the process gas cooler, the sulfur condensers and from the final sulfur separator are routed tothe degassing unit, where the gases (primarily 1,S) dissolved in the sulfur are removed ‘The tal gas from the Claus process still containing combustible components and sufar compounds (HS, Hand CO) is either burned inan incineration unit or futher desulfurized ina downstream tal gas treatment unit Sub dew point Claus process ‘The conventional Claus process described above is limited in its conversion due to the reaction equilibrium being reached, Like all exothermic reactions, greater conversion ean be achieved at lower temperatures, however 8s mentioned the Claus reactor must be operated above the sulfur dew point (120-150 °C) to avoid liquid sulfur physically deactivating the eatalyst. To overcome this problem, the sub dew point Claus process operates ‘with reactors in parallel. When one reaetor as become saturated with adsorbed sulfur, the process flow is diverted tothe standby reactor. The reactor is then regenerated by sending process gas that has been heated to 300-350 °C to vaporize the sulfur. This steam is sent toa condenser to recover the sulfur Process performance Using two catalytic stages, the process will typically yield over 97% of the sulfur inthe input stream. Over 2.6 tons of steam will be generated for each ton of sulfur yield. “The physical properties of elemental sulfur obtained in the Claus process can differ fom that obtained by other processes] Sulfur is usualy transported asa lguid (melting point 115 °C). In ordinary sulfur vscasity can increase rapidly at temperatures in excess of 160 °C de tothe formation of polymer sulfur chains but not so in Claus-sulfur, Another anomaly is found inthe solubility of residual HS mn liquid sulfur asa unetion of temperature. Ordinarily the solubility ofa gas decreases wit increasing temperature but now itis the opposite. This means that oxi an explosive HS gas can build up inthe headspace of any cooling liquid sulfur teservot. The explanation for his anomaly isthe endothermic reaction of sul with H,S to polysulfane See also Amine treating Hydro-desulfurizaion Crystasult Hydrogenation Acid gas Sour gas esenumesa cme post tesocnnms ‘i poss ipa te ee cpa References Gas Processors Association Data Book, 10th Fulton, Volume I, Section 22 (Gary, LH. and Handwerk, GE. (1984). Petroleum Refining Technology and Economics (2nd ation e.). Mace! Dekker, Ine. ISBN 0-8247-71508 ‘Sulfr production repo (ip minerals usgs gownineal/pubsteommediysulfa/suumes06 pt) by the United States Geological Survey Discussion of recovered byproduct sult (ip ww give onggotimes)uly/tesources Hi!) er Claus-Prazess. Reich an Jahron nd bedeutender dem je, Berbard Schein, Cherie in Unsere Zeit, Volume 42 Issue 6, Pages 378-392 2008 [Bibliographic Citation (hp ww ost gowenergyetations product bibliojspost,s&~5599725) Sul Recovery Technolgy. BG Gr, American Instie of Chemical Enginers Spring National Meeting, New Orleans, Louisiana, April 6, 1986 ‘Or between 950 and 1200 °C and even hatter near the ame, as stated in Der Claus-Pracess. Reich an laren wed Bedewtender den je, Bernhard Schreiner, Chemie in Unserer Zeit, Volume 42 Ise 8, 2009 Battin-Leclere, Frederique eal, Cleaner Combustion: Developing Detailed Chemical Kinet Models, 2013, Springer 8. Garguevich, Ivan A, Combustion Models and he Prediction of Polycyclic Aromatic Hvdrocarbons (PAH) in laminar lames of simple hysrocarbons: Methane. Met Chloride, and I,1 Dchlorothane, Doctoral Dissertation, Univesity of (California at Los Angeles (UICLA),1997 (bps academia. ed 7889827/ Combustion, Models_and_The_Prediction_of_Polyeyslic_Aromatc_ Hydrocarbons Flames) Retrieved from "hitps/en wikipedia.org/whindex php itle=Claus_processéeoldid=664526902" Categories: Sulfur | Chemical processes 1» This page was last modified on 29 May 2015, a 06:43. 1» Texts available under the Creative Commons Attribution-ShareAlike License, additional terms may apply. By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia® is registered trademark ofthe Wikimedia Foundation, Inc, a nor-profit organization esenumesa cme post a