JP5662162B2 - ガス流からの汚染物質除去 - Google Patents
ガス流からの汚染物質除去 Download PDFInfo
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- JP5662162B2 JP5662162B2 JP2010544968A JP2010544968A JP5662162B2 JP 5662162 B2 JP5662162 B2 JP 5662162B2 JP 2010544968 A JP2010544968 A JP 2010544968A JP 2010544968 A JP2010544968 A JP 2010544968A JP 5662162 B2 JP5662162 B2 JP 5662162B2
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- adsorbent
- sulfur
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- 239000000356 contaminant Substances 0.000 title description 25
- 239000003463 adsorbent Substances 0.000 claims description 128
- 239000007789 gas Substances 0.000 claims description 122
- 230000008929 regeneration Effects 0.000 claims description 81
- 238000011069 regeneration method Methods 0.000 claims description 81
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 73
- 229910052717 sulfur Inorganic materials 0.000 claims description 73
- 239000011593 sulfur Substances 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 55
- 238000001179 sorption measurement Methods 0.000 claims description 50
- 230000008569 process Effects 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000006104 solid solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 description 20
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 150000003464 sulfur compounds Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- -1 for example Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- YOXKVLXOLWOQBK-UHFFFAOYSA-N sulfur monoxide zinc Chemical compound [Zn].S=O YOXKVLXOLWOQBK-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002343 natural gas well Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
- Gas Separation By Absorption (AREA)
Description
本発明は概して、ガス流からの汚染物質除去に関する。別の面において、本発明は、再生可能な吸着剤との接触によりガス流から1種以上の汚染物質を除去するためのプロセスに関する。
近年になって、天然ガスおよびその他の気相燃料の需要がかなり高まってきた。同時に、特定の成分(例:硫黄種、酸性ガス、および環境面で懸念のあるその他の化合物)の許容可能なレベルに関して、さらに厳格な規制が課せられ、燃料ガス生産者には、準拠したガス製品を生産する経済的な方法の開発が求められている。
好ましくない成分を除去するための公知のガス流処理方法の1つは、ガス流を物理的または化学的な溶剤に接触させることである。化学的な溶剤の例には、メチルジエタノールアミン(MDEA)およびジエタノールアミン(DEA)などのアミンが含まれる。しばしば、化学的な溶剤の選択性が問題となることがある。例えば、アミンには硫化水素(H2S)をガス流から効果的に除去する能力があるが、一般にアミンには、例えば硫化カルボニル(COS)など、その他の好ましくない硫黄含有化合物を吸収する能力はない。その結果、ガス流が燃料として使用できるようになる前に、追加的なプロセス手順(例:COS加水分解)を実行する必要がある。H2Sの除去に加え、ほとんどのアミンは二酸化炭素も除去するが、これはその後の廃ガス設備に対して不必要なプロセス負荷をかけることがある。さらに、化学的な溶剤を利用するほとんどのプロセスでは、流入するガス流の大規模な冷却が必要で、吸収した汚染物質を溶剤から除去するために、しばしば大量の蒸気を使用し、これらのプロセスをエネルギー集約的なものにしている。物理的な溶剤ベースのプロセスも、エネルギー集約性が非常に高く、しばしば高い動作圧力および/または低い動作温度を必要とする。
従って、ガス流から汚染物質を除去するための経済的なプロセスのニーズが存在する。
本発明の一実施態様において、(a)硫黄を含有するガス流を吸着ゾーン内で最初の吸着剤に接触させ、それにより硫黄を除去した製品流と硫黄含有吸着剤を生成する手順(ここで最初の吸着剤がZnおよびプロモーター(助触媒)金属から構成される)、ならびに(b)再生条件下の再生ゾーン内で硫黄含有吸着剤の少なくとも一部分を再生ガス流と接触させ、それにより、再生吸着剤と排ガス流を生成する手順(ここで、手順(b)の接触には約100〜約100,000h-1の範囲の最初の標準ガスの時間当たり空間速度(SGHSV)で再生ガスを再生ゾーンに導入する手順が含まれ、また手順(b)の接触には、再生ガスのSGHSVを最初のSGHSVより少なくとも1,000h-1高い最終的なSGHSVに増大させる手順が含まれる)から構成されるプロセスを提供している。
図1を参照するが、汚染物質除去システム10は、概して、ガス供給源12、吸着ゾーン14、製品ガス利用者16、乾燥ゾーン18、再生ゾーン20、および排ガス利用者22から構成されるものとして図示している。一般に、ガス供給源12から排出される原料ガス流を吸着ゾーン14で吸着剤と接触させ、それによりガス流から1種以上の汚染物質を除去することができる。その結果、吸着ゾーン14から排出される汚染物質を除去した製品ガス流は、製品ガス利用者16に送ることができ、一方、汚染物質を含有する吸着剤の少なくとも一部分は、再生ゾーン20で再生ガスと接触して再生される前に、乾燥ゾーン18で乾燥させることができる。結果的に生じる再生ゾーン20から排出される排ガス流は、排ガス利用者22に送ることができ、一方その後、再生吸着剤の少なくとも一部分は、吸着ゾーン14に戻して再利用が可能である。一実施態様において、吸着ゾーン14、乾燥ゾーン18、および再生ゾーン20の少なくとも1つは、同一のプロセス容器内に含めることができる。別の実施態様において、吸着ゾーン14、乾燥ゾーン18、および再生ゾーン20の少なくとも1つは、2つ以上の別個のプロセス容器に含めることができる。さらに、図1に図示した汚染物質除去システム10は、連続モード、半連続モード、半一括処理モード、または一括処理モードで運転できる。ここで、汚染物質除去システム10の動作について、下記にさらに詳しく説明する。
未還元のZnプロモーター金属吸着剤(ケンタッキー州ルイビル市、Sud-Chemie Inc.から市販のSZorbTM Generation IV吸着剤)を、粉砕し篩い分けして、メッシュサイズ100+/200の粒子を得た。粉砕した吸着剤15グラムをアランダム45グラムと混合して、結果的に生じる混合物を固定ベッド下降流反応容器に入れた。原料ガス流(その組成は下記の表4にまとめられている)を、反応容器を通過させて、420℃の温度および約2813.16kPa(408psig)の圧力で吸着剤の混合物と接触させた。
本説明では、本発明に関連する一定のパラメーターを数量化するために数値範囲を使用する。数値範囲が提示されるとき、そうした範囲は、範囲の下限値を単に列挙する請求範囲の限定、また範囲の上限値を単に列挙する請求範囲の限定について文字通りの裏付けを提供するものとして解釈されるものと理解されるべきである。例えば、開示された数値範囲10〜100は、「10より大きい」(上限なし)と列挙された請求範囲および「100より小さい」(下限なし)と列挙された請求範囲についての文字通りの裏付けを提供する。
本書で使用するとき、原文で「a」、「an」、「the」、および「the」という用語は、1つ以上を意味する。
本書で使用するとき、「および/または」(「and/or」)という用語は、2つ以上の項目のリストで用いられるとき、リストされた項目のどれか1つがそれ自体を使用できるか、またはリストされた項目の2つ以上の任意の組合せで使用できることを意味する。例えば、ある組成が、構成要素A、B、および/またはCを含むものとして記述された場合、その組成には、Aのみ、Bのみ、Cのみ、AおよびBの組合せ、AおよびCの組合せ、BおよびCの組合せ、またはA、B、およびCの組合せが含まれうる。
上記に記載した本発明の好ましい形態は、例証のみとして使用されるもので、本発明の範囲を限定的な意味で解釈するために使用されるべきではない。上記に記載した模範的な実施態様に対する修正は、本発明の精神から逸脱することなく、当業者によって容易に行うことができる。
Claims (11)
- (a)硫黄を含有するガス流を吸着剤と吸着ゾーン内で接触させ、それにより硫黄を除去した製品流および硫黄含有吸着剤を生成するステップであって、前記吸着剤は、Znおよびプロモーター金属から構成されるステップと、
(b)前記の硫黄含有吸着剤の少なくとも一部分を酸素を含有する再生ガス流と再生ゾーン内で、再生条件下で接触させ、それにより再生吸着剤および排ガス流を生成するステップとを有し、
上記ステップ(b)の前記接触には、前記再生ガスを前記再生ゾーンに、100〜100,000h-1の範囲の標準ガスの時間当たり空間速度(SGHSV)で導入するステップが含まれ、またここで、ステップ(b)の前記接触には、前記再生ガスのSGHSVを、前記最初のSGHSVよりも少なくとも1,000h-1多い最終的なSGHSVに増加させるステップが含まれ、ステップ(b)の前記接触が、650℃より低い温度で、24時間未満の時間にわたり実施されるプロセス。 - 請求項1のプロセスで、ここでステップ(b)の前記接触がさらに、前記再生ゾーンの温度を少なくとも75℃だけ増加させるステップから構成されるプロセス。
- 請求項2のプロセスで、ここでステップ(b)の前記接触がさらに、前記再生ゾーンの温度の前記増加と前記再生ガスのSGHSV前記増加を交互に行うステップから構成され、ここで前記の交互に行うステップは、前記排ガス流が0.05体積パーセント未満の二酸化硫黄(SO2)から構成されるようになるまで実施されるプロセス。
- 請求項1のプロセスで、ここで前記硫黄含有吸着剤は、1〜27重量パーセントの範囲の硫黄負荷を持ち、またここで前記再生した吸着剤は、10重量パーセント未満の硫黄負荷を持つプロセス。
- 請求項1のプロセスで、ここで前記プロモーター金属がニッケルであるプロセス。
- 請求項1のプロセスで、ここで前記吸着剤が、式MAZnBを特徴とする置換型金属固溶体で構成され、ここでMは前記プロモーター金属であり、またここでAおよびBは、0.01〜0.99の範囲であるプロセス。
- 請求項1のプロセスで、ステップ(b)の前に、前記硫黄含有吸着剤の少なくとも一部分を乾燥させ、それにより乾燥した硫黄含有吸着剤を得るステップ、および前記の乾燥した硫黄含有吸着剤の少なくとも一部分をステップ(b)の前記接触を受けさせるステップから構成されるプロセス。
- 請求項7のプロセスで、ここで前記硫黄を含有するガス流が、4〜40体積パーセントの範囲の水で構成され、またここで前記の再生吸着剤が、ステップ(b)の前記接触中に生成される0〜10重量パーセントの範囲の吸着剤に有害な化合物で構成されるプロセス。
- 請求項8のプロセスで、ここで前記硫黄を含有するガス流はさらに、10〜75体積パーセントの範囲の一酸化炭素(CO)および8〜50体積パーセントの範囲の水素(H2)で構成されるプロセス。
- 請求項1のプロセスで、ここで前記硫黄を含有するガス流が、0.001〜5体積パーセントの範囲のH2Sで構成され、ここで前記硫黄を除去した製品流が50ppmv未満のH2Sから構成されるプロセス。
- 請求項1のプロセスで、さらに前記再生吸着剤の少なくとも一部分を前記吸着ゾーンに導入する手順から構成され、ここで前記吸着ゾーンに導入された前記再生吸着剤は、式MXZnYOを特徴とする置換型の金属酸化物固溶体で構成され、ここでMは前記プロモーター金属であり、ここでXおよびYは0.01〜0.99の範囲であるプロセス。
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EP2829315A2 (en) | 2015-01-28 |
CN104107617B (zh) | 2017-04-12 |
EP2234698A1 (en) | 2010-10-06 |
CA2709803C (en) | 2016-03-22 |
KR20100118570A (ko) | 2010-11-05 |
SA08290687B1 (ar) | 2011-10-29 |
PL2234698T3 (pl) | 2015-02-27 |
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