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BASF - Technologies for Syngas Purification

Ekkehard Schwab BASF SE D-67056 Ludwigshafen Germany
Copyright by BASF SE Reproduction and distribution not allowed without written permission from BASF SE

BASF Business fields Gas scrubbing process (aMDEA®) Purification catalysts and absorbents 2 .

History of aMDEA® gas treatment Before 1971 Use of several gas treatment systems like MEA. DEA and Benfield 1st application in BASF’s ammonia plant No. 3 (1200 MTPD) 9 BASF synthesis gas plants (Oxo syngas as well as ammonia syngas ) Start of aMDEA® process licensing outside of BASF 1971 1971 – 1982 1982 Status 12/2008 > 250 reference plants (15 BASF owned plants) and > 30 under design/construction 3 .

preferably at low temperatures and high pressure The loaded solvent (rich solvent) moves to the regenerator Feed Gas Acid gases will be desorbed from the solvent in the regenerator at elevated temperatures and ambient pressure Absorber High Pressure Low Temperature Regenerator Ambient Pressure High Temperature The regenerated solvent (lean solvent) is returned to the absorber Gas stream H2S / CO2 Solvent 4 . such as H2S and CO2. are chemically or physically absorbed by the solvent in the absorber.Acid Gas Removal Unit (AGRU) Acid Off Gas Treated Gas Prin(simples) of an Acid Gas Removal Unit Acid gases.

Solvents & Technologies INDUSTRIES TECHNOLOGIES aMDEA ® sMDEA PuraTreat™ R / A1 Omnisulf ® (with Lurgi) Morphysorb ® (with Uhde) SOLVENTS MEA (Monoethanolamine) DEA (Diethanolamine) MDEA (N-Methyldiethanolamine) DIPA (Diisopropanolamine) ADEG ® (Diethyleneglycol) 1 NATURAL GAS LNG REFINERIES LPG SYNGAS AMMONIA FLUE GAS PuraTreat A technology is marketed through Toyo Eng. Co. 5 .

00% 10.00% 9.12% 2.60% 15.07% 0.94% 19.67% 2.86% 0.48% 32.73% 1.97% 780 Saturated <100 <100 39 Variuos gasfier technologies and different feedstock sources lead to a wide variety of crude syngas specifiations 6 .64% 0.23% 200 saturated <100 <100 30 B 66.10% 0.94% 1.Various Syngas Composition Gasifier CO H2 CO2 Ar CH4 N2 H2S COS H2O NH3 HCN pressure mol% mol% mol% mol% mol% mol% mol% ppmv% mg/Nm3 mg/Nm3 bar A 59.11% 0.19% 28.48% 0.18% 100 saturated <100 <100 38 C 47.58% 0.

gas CO2-off-gas S S ---varies > 30vol% -- < 50-500 ppmv --varies > 30vol% spec varies --High purity varies > 30vol% spec varies -High purity High purity varies > 30vol% spec varies Different applications required adapted outlet specifications 7 .1 ppmv Chemicals/Liquids methanol < 1-0. in gas turbines + process ecconomics --varies > 30vol% < 10 ppmv ?? NH3 < 0. CCS S < 5-30 ppmv incl. CCS < 5-30 ppmv depends on max.1 ppmv FTsynthesis < 0. H2 conc.1 ppmv CO2 process gas HCN NH3 Hg S-off.Outlet Specification Requirements IGCC excl.

Various Solvent Properties Chemical solvent kinetics selectivity based on equilibrium + Physical solvent + Hybrids + 0 H2 and CO losses via co-absorption acid off gas at elevated pressure Organic sulfur removal COS mercaptans low (0) - high + + + + medium + + 8 Split in H2S and COS rich off gas .

Potential Process Setup H2S (25% Minimum) e.g. to Sulfuric Acid Plant sMDEA (AGRU 2) H2S + CO2 Acid Gas CO2-off-gas Cooled Shifted Syngas aMDEA (AGRU 1) Clean Syngas 9 .

Experiences in Syngas Applications Today more than 260 reference plants worldwide (incl. 15 BASF owned plants) Thereof 28 operating Syngas Plants and 7 under design or construction Cooperation with PuraTreat A technology PuraTreat A (physical absorption process) specifically designed for coal gasification market 10 .

if the synthesis gas is derived from gasification of solids (e. especially. COS. Phosphorous (PH3). AGAINST Oxygen. solid or liquid organic waste streams 11 . Acetylene. Sulfur (H2S..Application fields TO PROTECT Highly active methanol production catalysts Efficient hydroformylation catalysts (oxo alcohol production) Highly efficient shift catalysts in ammonia plants Highly efficient Gas-to-Liquids (GTL) production catalysts . Chlorides (HCl). Arsine (AsH3).g... Ethylene.R-SH). Mercury and others . carbon-containing slurries. from iomass..BASF Puristar® Purification catalysts Why synthesis Gas Polishing ? .

For Example Methanol Production Impurity Effect.. .. on Methanol production Oxygen Ethylene Sulfur Acetylene Metals organic acid formation Organic acid formation Copper sulfidation Organic acid formation Metal deposition * * Methanol catalyst deactivation * Methanol catalyst deactivation * Acid formation on Methanol catalyst has two consequences Mechanical degradation of the MeOH catalyst Accumulation of corrosive acids in MeOH product 12 ...BASF Puristar® R0-23 & R3-15 Why synthesis Gas Polishing ? .

BASF Puristar® R0-23 Catalyst Specification 13 .

BASF Puristar® R3-15 Catalyst Specification 14 .

BASF Puristar® R0-23 & R3-15 Process Design Basis 15 .

BASF Puristar® R0-23 & R3-15 Process Conditions & Performance 16 .

BASF Puristar® R0-23 & R3-15 How do they work ? 17 .