Livia Sierra Llorens lisl@topsoe.com WSA Technology a competitive solution for sulfur management
Agenda A few words about Haldor Topsoe Handling sulfurous streams the traditional way the WSA way Introduction to WSA technology WSA process and lay-outs References Summary 2
Haldor Topsoe Company Established in 1940 by Dr. Haldor Topsoe. Private 100% family owned company Global market leader in heterogeneous catalysis with a 75 year long track record ~2,700 employees in 11 countries across five continents. HQ in Lyngby, Denmark, HT Inc. located in Houston ~250 employees Revenue about $ 1 billion. 3 Active phase Pore structure Catalyst Reactor Services: Catalysts Technology/licensing Engineering Hardware Operation assistance
Synergies in the Topsoe business model Founded on the belief that applied fundamental research is key to build and retain a leading position in catalysis and technology supply Basic research and catalyst characterization done by 300+ world class scientists Approx. 10% of revenues annually applied to support R&D efforts Bringing science to the market Improving our products through costumer interaction Marketing, sales and support Process design R&D Engineering & Hardware Catalyst production 4
Visbreaker Delayed coker Vacuum distillation Atmospheric distillation Refinery Overview Topsoe WSA plant Gas, LPG Alkylation Spent/fresh H 2 SO 4 H2S SRU SRU Tailgas Crude oil Naphta Kero Gas oil HDT Gasoline, jet fuels Steam H 2 SO 4 Vacuum Gas oil HDT MHC FCC Fuel Oils Steam HC H2S Lubricating oils Power H 2 SO 4 Topsoe SNOX TM plant 5
What to do with H 2 S? The traditional way Other uses of sulfur ~ 10 % H 2 S Claus plant Sulfur ~ 90 % of all sulfur 6 Sulfuric acid Sulfuric acid plant
What to do with H 2 S? The direct way H 2 S Sulfuric acid plant (WSA) 7 Sulfuric acid
Four times more energy when producing sulfuric acid instead of sulfur H 2 S 222 Sulfur: 222 kj/mole S (solid) H H 2 S SO 2 SO 2 SO 99 101 4 3 519 85 Sulfuric acid: 804 kj/mole (gas) H 2 SO 4 (liquid) 8-2 0 +4 +6 +6 +6 Oxidation state of sulfur
Limitations when producing sulfur in a Claus plant Minimum H 2 S content in feed gas of 20 vol.-% Other combustibles than H 2 S (like NH 3 and hydrocarbons) make air control more complex Ammonia requires very high furnace temperature Hydrocarbons give risk of carbon formation and catalyst deactivation COS and CS 2 require special design 9 Sulfur solidifies below 120 C and gets viscous above 160 C.
Comparison WSA vs. Claus Operating expenses (OPEX) 3 x more steam and better quality 10
Comparison WSA vs. Claus Summary WSA offers larger revenues and less CAPEX WSA produces 3 times as much steam; this means saving in fuel consumption and CO2 emissions WSA produces HP steam; Claus produces mostly MP steam WSA handles NH3, COS and hydrocarbons DeNOx is conveniently included in the WSA process, when required Smaller plot area for WSA than for Claus Less equipment is required WSA is simple and easy to operate. 11
What is WSA - Wet gas Sulfuric Acid A process for cleaning sulfur containing streams under production of concentrated sulfuric acid Lean H 2 S gas Rich H 2 S gas SRU tail gas Clean gas No need to dry the gas SWS gas No water consumption SO 2 SO 3 Elemental sulfur CS 2 / COS WSA H 2 SO 4 HP steam No need to use chemicals or other additives No generation of waste products With high energy efficiency. Spent H 2 SO 4 12
WSA process lay-out H 2 S gas Superheated steam Combustion air Blower Reaction: H 2 SO 4 (g) H 2 SO 4 (liq) + heat Cleaned gas BFW H 2 S gas WHB Steam drum SO 2 converter Interbed cooler Interbed cooler Blower WSA condenser Air 13 Combustor Reaction: H 2 S + 1½O 2 SO 2 + H 2 O + heat Reaction: SO 2 + ½O 2 SO 3 + heat Reaction: Gas cooler SO 3 + H 2 O H 2 SO 4 (g) + heat CW Acid cooler Product acid
WSA process lay-out H 2 S gas + SWS gas Superheated steam Combustion air Blower Cleaned gas BFW H 2 S gas WHB Steam drum SCR SO 2 converter Interbed cooler Interbed cooler Blower WSA condenser Air SWS gas Combustor Gas cooler 14 Additional reaction: NH 3 + 1.25 O 2 NO + 1.5 H 2 O + heat Reaction: NO + NH 3 + 0.25 O 2 N 2 + 1.5 H 2 O + heat CW Acid cooler Product acid
WSA process lay-out Spent acid regeneration Superheated steam Combustion air Blower Cleaned gas BFW H 2 S gas Spent acid Atom. air Fuel gas WHB Combustor Steam drum Dust ESP SO 2 converter Interbed cooler Interbed cooler Gas cooler CW Blower WSA condenser Acid cooler Air Product acid 15
SO 2 conversion catalyst series VK-W VK-WSX / VK-WL 9 mm Daisy VK-WSA 25 mm Daisy VK-WSA / VK-WH 12 mm Daisy 16
WSA condenser Clean gas outlet Cooling air inlet SO 3 gas inlet Hot air outlet 17 Sulfuric acid
WSA condenser modular construction Clean Gas Outlet Cooling Air Inlet Acid Gas Inlet Hot Air Outlet Product Acid Outlet 18
WSA condenser design 19
WSA/SNOX TM references March 2018 Acid production: 4 1,140 MTPD 155+ references Oil refining Coking Gasification 5 27 26 10 2 9 10 1 1 2 3 1 8 5 4 1 29 6 4 3 14 2 5 7 4 4 17 2 4 2 28 6 41 11 13 5 24 26 12 16 1 14 8 2 15 25 31 10 8 9 19 6 7 51 18 30 12 32 14 11 35 23 22 24 24 16 17 30 19 31 29 17 8 18 10 47 20 11 12 33 37 23 26 3 3 11 22 3 38 40 28 27 8 7 46 25 5 18 19 6 13 25 45 21 15 16 32 21 13 29 28 20 9 39 15 31 7 6 33 32 4 Metallurgy 27 22 23 8 1 5 6 7 42 9 Viscose Sundry applications 13 21 12 14 44 34 3 9 43 36 7 20
Refinery WSA plants 21 Irving Oil Limited, NB, Canada Claus plant tail gas treatment 40 t/d sulfuric acid OSC Slavneft (YaNOS) Yaroslavl, Russia Spent acid regeneration 260 t/d sulfuric acid
Too good to be true?? Conclusions Traditional SRU WSA technology a better solution Attractive OPEX and CAPEX Simple process and easy to operate Proven and reliable technology (155+ references) Low emissions and no waste materials No issues with NH 3 and hydrocarbons. 22