Dow Solvent Technologies for CO 2 Removal



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Dow Oil & Gas Jan Lambrichts AIChE Netherlands / Belgium Section 21 January 2014 Novotel, Antwerp Dow Solvent Technologies for CO 2 Removal

Who We Are Dow combines the power of science and technology to passionately innovate what is essential to human progress. 1897 Founded by Herbert H. Dow in Midland, Michigan Serve customers in 160 countries Manufacture more than 5000 products at 188 sites in 36 countries Employ approximately 54000 people worldwide

Dow Oil & Gas : Aligned to Industry Needs We maximize value for our customers by providing comprehensive solutions across the oil,,gas and mining value chains through chemistry expertise, industry knowledge and advanced innovation. Recently aligned with our business to bring together Dow's industryleading mineral extraction and processing technologies with our growing portfolio of technology offerings for oil and gas

Acid Gas Removal Technologies 100% Membrane followed by UCARSOL Membranes 10% SELEXOL, UCARSOL, Commodity Amines SELEXOL Membranes, SELEXOL 1% 1000 ppm 100 ppm 10 ppm INLET GAS CONCEN NTRATION SulFerox Pr rocess SELEXOL, UCARSOL, Com. Amines Commodity Amines, UCARSOL,, Direct Oxidation Commodity Amines, UCARSOL, Direct Oxidation, Batch Processes, Mol Sieves Batch Processes, UCARSOL, Mol Sieves, Direct Oxidation OUTLET GAS CONCENTRATION Commodity Amines, UCARSOL, SELEXOL, BenField Equal Inlet and Outlet 10 ppm 100 ppm 1000 ppm 1% 10%

Key Offerings for Amine Sweetening UCARSOL Solvents Multiple formulations used for gas treating; each provides key benefits, depending on customer specifications Selective H 2 S preferentially absorbing H 2 S while allowing CO 2 to slip UCARSOL HS-101 for gas treating UCARSOL HS-102 for acid gas enrichment UCARSOL HS-103 for tail gas treating UCARSOL HS-115 for liquid hydrocarbon treating Tunable CO 2 removal removal of CO 2 to a desired specification UCARSOL AP-802, AP-804, AP-806 removal of CO 2 to pipeline specification UCARSOL AP-810, AP-814 removal of CO 2 to cryogenic UCARSOL NH-608, for removal of CO 2 in ammonia applications CO 2 capture in coal based power plants using UCARSOL FGC-3000 Mercaptan and organic sulfur removal capturing organic sulfur compounds requires unique solutions UCARSOL LE-701, LE-702 removal of organic sulfur and meeting total sulfur specification Refinery, low-energy solvents where removal of bulk components is desired, but minimizing energy is key UCARSOL LE-713, LE-777, LE-801 maximize energy savings SELEXOL Solvent Removal of acid gas, organic sulfur and hydrocarbons when there is a high partial pressure of target components

UCARSOL AP Solvents UCARSOL AP-800 Solvents are the latest generation of Dow solvents to remove carbon dioxide MDEA based solvents with different levels of activator, depending on the required sweet gas specification CO 2 removal applications include Natural Gas, LNG, Ammonia, IGCC, and Cryogenic Processing units. The AP-800 Solvents are advanced performance CO 2 removal products, outperforming other competitive solvents in the market place Technology can be offered on a non-licensed basis. For licensed approach, UOP can offer an Amine Guard FS license 15-Year Track Record More than 250 References

LNG and Large Middle East References UOP Amine Guard TM FS, UCARSOL TM AP-800 Solvents LNG Start-up MMSCFD RasGas Train 3 LNG 2004 750 RasGas Train 4 LNG 2005 750 RasGas Train 5 LNG 2006 750 RasGas Train 6 LNG 2008 1600 RasGas Train 7 LNG 2008 1600 Large Mid-East Gas Plants Start-upt MMSCFD RasGas Train AKG-1 2005 750 RasGas Train AKG-2 2008 1600 Dolphin, Train1,2 2007 4 x 800 GASCO, OGD3, Train 1,2 2010 2 x 630 GASCO, ADG2, Train 1,2 2010 2 x 400 UCARSOL TM and SELEXOL TM Solvents in 5 World Scale LNG Plants in Ras Laffan, Qatar

Conventional Process Scheme

One Stage Process Scheme

Two Stage Process Scheme

Flash Regeneration Scheme

Comparing DEA and UCARSOL AP-814 Performance Capacity Increase 33% DEA 45 % AP-814 Processing capacity, knm 3 /hr 152 188 Circulation Rate, m 3 /hr 217 230 Solvent CO 2 loading, mol/mol Lean 006 0.06 003 0.03 Rich 0.49 0.46 Reboiler Duty, Gcal/hr 12.6 12.6 Treated Gas CO 2 Outlet from absorber 2%v 100 ppmv

Ammonia Applications UCARSOL NH Solvents

Ammonia Plant Ukraine Comparing MEA with UCARSOL NH-608 Performance Recirculation Flow 1 Recirculation Flow 2 Regenerator Mid Column Temp Regenerator Overhead Temp CO2 in Treated Gas Reboiler Steam MEA System Performance 650-670 m 3 /hr 550-570 m 3 /hr 115-116 o C 91-93 93 o C 50-80 ppm 17+17+3 MT/hr Total = 37 MT/hr UCARSOL NH-608 Performance 450-460 m 3 /hr 430-450 m 3 /hr 109 o C 82 o C 18-27 ppm 3.5+3.5 + 0.0 MT/hr Total = 7 MT/hr

CO 2 Capture from Coal Based Power Plants UCARSOL FGC Solvent 3000 First Pilot Plant at Dow Chemical Site in Charleston, WV Designed to capture 1,800 t CO 2 /year using TM UCARSOL TM FGC-3000 solvent Installation on commercial coal-fired boiler Project progression - Operation began in September 2009 - Validation of overall performance and unit operation - Implementation of 2 nd generation improved flow scheme in February 2011 - Focus on solvent management and emissions measurements, as well as proving concepts of the 3 rd generation flow scheme Completed more than 14,000 hrs of operation, 24/7, before pilot was shut down in October 2011

Advanced Amine Field Pilot Demonstration Unit at EDF Power Plant Le Havre Designed to capture 25 t CO 2 / day, 90% CO2 capture Advanced flow scheme & operation validation Flue gas: slipstream from 600 MWe coal plant (EDF host facility) French funding by ADEME (French Environment and denergy Management ta Agency) ) Project schedule - Overall 2010-20132013 program - Test from Q2 2013 to Q2 2014

SELEXOL Solvent Polyalkylene lk l Glycol l Dimethyl Ether R O (CH 2 - CH 2 -O) n R Invented by Allied Signal in 1950 s Purchased by Norton in 1982, then by Union Carbide in 1990 Became a Dow solvent after the merger in 2001 About 115 units were built of which still many in operation

SELEXOL Solvent : Applications Purification of lean natural gas Low-energy ammonia/urea production Gasification Heavy oil partial oxidation Landfill gas purification Light hydrocarbon dew point control

DOW and UOP SELEXOL TM Solvent Relationship UOP is the exclusive licensor of SELEXOL TM in Gasification and Ammonia applications UOP provides license/warranty, Dow provides solvent If no license involved, Dow can work directly with customers Dow and UOP cooperatively develop solvent and design improvements

SELEXOL is a Physical Solvent How is Physical Absorption Affected? Pressure High Pressure Increases the Driving Force for Absorption Temperature Low Temperature Increases the Solubility of the Acid Gases in the Liquid Phase Capacity For Physical Solvents, the Higher the Pressure, the Greater the Capacity Mass Transfer Packing Height or Number of Trays has an Effect, but it is Smaller Than the Effect of Temperature, Pressure or Solvent Flow

Relative Solubility of Various Gases in SELEXOL Component R= K CH4. Component R= K CH4. K Component K Component H 2 0.20 H 2 S 134 N 2 0.30 C 6 H 14 167 CO 0.43 CH 3 SH 340 CH 4 1.00 C 7 H 16 360 C 2 H 6 7.20 CS 2 360 CO 2 15.2 C 2 H 3 Cl 400 C 3 H 8 15.4 SO 2 1,400 i-c 4 H 10 28 C 6 H 6 3,800 n-c 4 H 10 36 C 2 H 5 OH 3,900 COS 35 CH 2 Cl 2 5,000 i-c 5 H 12 68 CH 2 Cl 3 5,000 C 2 H 2 68 C 4 H 4 S 8,200 NH 3 73 H 2 O 11,000 n-c 5 H 12 83 HCN 19,000

SELEXOL Solvent Design for CO 2 Removal

SELEXOL Solvent Design for H 2 S Removal

Regeneration Methods for SELEXOL Regeneration Method Treated Gas Specification Flash Only - No Heat 3-4% CO 2 Vacuum Flash or Heated Flash 1-2% CO 2 Inert Gas Stripping < 1% CO 2 < 4 ppm H 2 S Steam Stripping < 500 ppm CO 2 < 4 ppm H 2 S

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