CN1113905A - Process for the production of hydrocarbons - Google Patents
Process for the production of hydrocarbons Download PDFInfo
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- CN1113905A CN1113905A CN 94106734 CN94106734A CN1113905A CN 1113905 A CN1113905 A CN 1113905A CN 94106734 CN94106734 CN 94106734 CN 94106734 A CN94106734 A CN 94106734A CN 1113905 A CN1113905 A CN 1113905A
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- Prior art keywords
- hydrocarbon
- gas
- carbonic acid
- carbon
- fischer
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- 150000002430 hydrocarbons Chemical class 0.000 title claims description 138
- 229930195733 hydrocarbon Natural products 0.000 title claims description 137
- 238000000034 method Methods 0.000 title claims description 93
- 230000008569 process Effects 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 168
- 239000004215 Carbon black (E152) Substances 0.000 claims description 130
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 106
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 103
- 239000000047 product Substances 0.000 claims description 84
- 235000011089 carbon dioxide Nutrition 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 52
- 229910052742 iron Inorganic materials 0.000 claims description 49
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000002283 diesel fuel Substances 0.000 claims description 33
- 235000014347 soups Nutrition 0.000 claims description 32
- 238000000629 steam reforming Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 30
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 230000036961 partial effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001994 activation Methods 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- -1 alkali metal salt Chemical class 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000006872 improvement Effects 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 5
- 230000001186 cumulative effect Effects 0.000 claims 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910002549 Fe–Cu Inorganic materials 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 238000005844 autocatalytic reaction Methods 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 238000006356 dehydrogenation reaction Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000005194 fractionation Methods 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000012263 liquid product Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 30
- 239000003502 gasoline Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 42
- 238000007254 oxidation reaction Methods 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 19
- 239000001993 wax Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 15
- 238000013461 design Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical group [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910001567 cementite Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
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- 239000000376 reactant Substances 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 101100272412 Arabidopsis thaliana BIA1 gene Proteins 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 240000004064 Poterium sanguisorba Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000006392 deoxygenation reaction Methods 0.000 description 1
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- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
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- 239000002737 fuel gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N n-nonadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
In the slurry reactor, several Fischer Tropsch reaction systems using Fe-catalyst for promoting catalysis produce the oxidized coarse gasoline and distilled fuel oil fraction for reducing the particle discharging rate in diesel engine. The features of said technology are fairly high carbon conversion rate and optimized chain propagation rate.
Description
The present invention relates to a kind of method and system that hydrocarbon and hydrocarbon mixture are produced, comprise and use Fischer-Tropsch synthesis reactor and technology, a kind of ferrum-based catalyst of this technology utilization, and with general gas with hydrocarbonaceous, the gas reforming that especially is rich in methane is H
2Combine with the technology of CO.
Past is industrial to be starting raw material with many carbonaceous materials and hydrocarbon, uses Fischer-Tropsch synthesis technique production hydrocarbon and has carried out extensive studies and development.
The communique 544(1955 of Department of Mines) comprised some early stage summaries of working of Fischer-Tropsch synthetic technology, exercise question is: the synthetic and related process catalogue of Fischer-Tropsch, author H.C.Anderson, J.L.Wiley and A.Newell.
At " catalysis magazine " (the 73rd volume, the 187-197 page or leaf, 1982) in the article that a piece is entitled as " carbon number distribution of the Fischer-Tropsch product that iron catalyst forms in the slurry-phase reactor ", Charles N.Satterfield and George A.Huff, Jr have scrutinized products distribution and the productive rate that reacts with the catalytic specific Fischer-Tropsch of iron catalyst.This article has also been studied the Shultz-Flory distribution in different catalyst systems.
In addition, Baird, Schehl and Haynes are at " industry and engineering chemistry, product research and exploitation " (1980, the 19th volume, the 175th～191) one piece is entitled as in the article of " the Fischer-Tropsch technology of Pittsburgh's energy technology center research over 1994 ", has described the structure of many Fischer-Tropsch reactors.
Aforementioned article has described in detail in the reactor of varied structure, how to use specific catalyst under conditions suitable, makes CO and H
2Change specific product into.
Several examples are only arranged, and the Fischer-Tropsch reaction is used solid-state or gaseous feed is formed a holonomic system.Germany is in the 1930's and the forties, and making several factories is that raw material is produced (with reference to " catalyzed conversion CO and H with the coal
225 years of synthetic gasoline ", Helmut Pichler, " catalyzer progress ", 1952, the 4 volumes, 272-341 page or leaf).Except above-mentioned example, South Africa is based on the research of Germany, 's raw material in 35 years of past always, use the Fischer-Tropsch technology to produce gasoline and the (reference " the Sasol refining techniques improves the synthol grade " of many other products, J.S.Swart, G.J.Czajkowski and R.E.Conser, oil and natural gas magazine, on August 31st, 1991, technology).G.Weber is at " oil and gas magazine " (the 47th volume, the 47th phase, 1949, the 248～250) one piece is entitled as has described among the Carthage Hydrocol Project that 1940's later stage-Fischer-Tropsch factory is the example of gasoline and diesel oil fuel with conversion of natural gas.These early stage effort have confirmed that from hydrocarbon-containing feedstock gas commercialization ground uses the synthetic hydrocarbon arts demand of Fischer-Tropsch and solve a series of challenges relevant with holonomic system in the mode of economy.For example, at first, hydrocarbon-containing feedstock changed into mainly by H before introducing the Fischer-Tropsch reactor
2With the mixture that CO forms, this is very important.The economical operation general requirement H of the Fischer-Tropsch reactor of specific size
2The ratio of/CO is in predefined scope.Hydrocol As mentioned above factory, the partial oxidation of Sweet natural gas reaches H
2The ratio of/CO is about 2.0.Another kind of partial oxidation uses vapour stream to reform to make and contains light hydrocarbon gas and be converted into H
2Mixture with CO.For the latter, use steam and CO
2, methane and water are raw material, CO
2Can return its import to reduce the H that forms from the outlet recirculation of converter
2To CO
2Ratio.
Therefore from the methane production synthetic gas two basic skills are arranged: steam reforming and partial oxidation process.
The steam reforming of methane is undertaken by following reaction:
Because steam and CO exist, so water gas shift reaction has also taken place:
These two reactions all are reversible reaction, and promptly their degree of reacting by above-mentioned wirtiting formula depend on used temperature and pressure condition.High temperature and low pressure help the generation of synthetic gas.
Partial oxidation reaction uses limited amount O
2With contain the hydrocarbon gas (as methane) and produce H
2And CO, as equation (3) expression, rather than the water of complete oxidation and CO
2
In fact, this reaction is difficult to be undertaken by the wirtiting formula, and some water and CO are always arranged
2Generation, so water gas shift reaction (2) also will take place.Transform situation as steam, higher temperature and lower pressure help the generation of synthetic gas.
Compare with steam reforming, the major advantage of partial oxidation is: in case after the reactant preheating, reaction just can self be kept and needn't continue heating.
Another advantage of partial oxidation is: H in the normal synthetic gas that forms
2The ratio of/CO is lower, and this ratio ratio required with being used for the synthetic whole process of Fischer-Tropsch liquid hydrocarbon mates very much.
Partial oxidation also has another advantage: needn't remove CO before synthetic gas is input to synthesis reactor from synthetic gas
2And/or H
2
Adjust H
2The ratio of/CO can be by removing excessive H
2(as using membrane separation apparatus) reaches., this method needs extra fixture, and owing to H in the technology
2Loss make the productive rate of oil or liquid hydrocarbon lower.
Consider that for whole process in order to use the method that can produce economical effectiveness, no matter be the steam reforming or the partial oxidation of raw material, the Fischer-Tropsch reactor must typically make the CO at least 90% of input be transformed.If unidirectional operation and air-flow are not removed H before being input into reactor
2Can reach 90% transformation efficiency, so because excessive H
2Cause H
2Accumulation will need bigger retort to keep sufficiently long residence time in reactor.Frequent unreacted H with the Fischer-Tropsch reactor outlet
2Circulation turns back to import to reach desired conversion with CO., when using excessive H
2, under this circular flow, the unreacted H that accumulation is how excessive
2, this condition large reactor otherwise must remove H more as a result
2
The main drawback of previous many commercial process is product cost height, and the carbonaceous of need specific catalyst and input is converted into the omnidistance transformation efficiency of liquid hydrocarbon output and can't accepts, especially when using cheap catalyzer.
Cause most two catalyst types or the cobalt catalyst or the iron catalyst of the real Fischer-Tropsch reaction of noting of people.In fact, cobalt catalyst helps following reaction
And iron catalyst helps following omnidistance reaction (because the high conversion vigor of water-gas):
In theory, cobalt catalyst can produce higher transformation efficiency than iron catalyst, because Co is near 100% efficiency of carbon conversion, and iron trends towards 50% efficiency of carbon conversion in the Fischer-Tropsch building-up reactions, because reaction (5) helps to generate CO
2The carbon of form.Here the shortcoming that runs at first is: compare with iron catalyst, cobalt catalyst is very expensive; Secondly, if the Fischer-Tropsch technology is used in the whole world on a large scale, higher to the needs of rare relatively Co, this will make cost higher.
Use cobalt catalyst that tail gas stream is recycled to the import of Fischer-Tropsch reactor, because Co helps the formation of water, so can reach 90% transformation efficiency substantially.Water is known potent inhibitor to two catalyzed reaction flow processs.Therefore, when carrying out under being reflected at the water existence, not only concentration of reactants is lower, and it is also bigger to play inhibiting water vapor concentration.In fact, use cobalt catalyst, unidirectional operation, the accessible maximum conversion rate of CO is generally 70%.Iron catalyst helps CO
2Formation, unidirectional operation can make CO reach the CO theoretical yield 90% and do not have a too big difficulty.This method does not form extra water, has therefore eliminated the necessity that tail gas stream is recycled to the Fischer-Tropsch reactor inlet.
In the Fischer-Tropsch building-up reactions, use catalyzer and form CO
2, be commonly considered as unwelcome.Therefore many process programs use cobalt-base catalyst, comprise that the fluid with reactor is recycled directly to the Fischer-Tropsch reactor.In sum, although iron catalyst is very efficient with the product that CO is converted in the equation (2), because they help CO
2Formation, so in the past overall carbon conversion efficiency is limited.Therefore, they do not resemble aspect total efficiency of carbon conversion the cobalt catalyst process program effective.
Therefore Fischer-Tropsch is synthesized with upstream steam reforming furnace accretion and use altogether, then CO and the H that produces at steam reforming reaction
2The catalytic Fischer-Tropsch reaction of experience cobalt is before from CO and H
2Remove CO in the reactant
2
When selecting for use appropriate catalyst to be used for helping the system of reaction (5), it is important that several considerations are arranged.In Fischer-Tropsch is synthetic, use the suitably equipment of design, be input to the H of Fischer-Tropsch reactor
2The charge ratio of/CO is preferably between 1.0～2.0.So require is that the CO that the energy acquisition is made us accepting is converted into the transformation efficiency of hydrocarbon for each Fischer-Tropsch reactor that passes through.And on catalyst bed, do not have unwanted carbonaceous to form.
For selected catalyzer, in order to adjust H
2/ CO ratio is removed H with film or analogue in above-mentioned optimum range
2, be very necessary among this additional deoxygenation step is inserted into product flow, also be very typical.Product flow is between steam reforming stove and Fischer-Tropsch reactor.In entering the steam reforming reaction product vapor of Fischer-Tropsch reactor, must take off H
2To obtain suitable H
2/ CO ratio.
Although it has been observed by the present inventors that to have above-mentioned difficulties, being to use the Fischer-Tropsch of steam reforming or partial oxidation and iron catalyst synthetic is that the economic viability of the technology of oil product can realize with conversion of natural gas.The present invention includes the iron catalyst that uses special preparation and solve reduction converter or the excessive H of partial oxidation equipment
2Formation and the increase problem that is input in the system total efficiency of carbon conversion of input carbon.As hereinafter showing, the CO that this iron catalyst produces
2(its generation has caused the problem of low efficiency of carbon conversion previously discussed) can be used to solve excessive H
2The problem low with total efficiency of carbon conversion.
Therefore an object of the present invention is to use specific low-cost catalyzer.In the Fischer-Tropsch reactor, this catalyzer helps CO
2Formation, produce hydrocarbon effectively, be necessary or need not circulating current and directly turn back to the Fischer-Tropsch reaction zone.
Further purpose of the present invention is to use and produces H
2And CO
2Reaction (as steam reforming and partial oxidation reaction), the H that produced of these reactions
2The ratio of/CO can directly use in the Fischer-Tropsch synthesis reactor of the suitable design of using specific iron catalyst, need not the additional H that removes
2Step.
Further purpose of the present invention is: use competent CO in steam reforming or partial oxidation reaction
2, the H of production specific equipment design code in the Fischer-Tropsch building-up reactions
2The ratio of/CO is converted into H to improve the gas containing hydrocarbon reaction
2Efficiency of carbon conversion with CO.
Further purpose of the present invention is to produce the required H of Fischer-Tropsch building-up reactions
2And CO.Should be synthetic with CO
2And the light hydrocarbon gas that forms of Fischer-Tropsch reaction in case of necessity is recycled in the feedstream of steam reforming reaction device or partial oxidation equipment and removes CO with production
2After contain required H
2The synthetic gas of/CO ratio.
A further object of the present invention is that complete process that effective conversion gas containing hydrocarbon and low B.T.U. gas will be provided (as has the CO of higher concentration
2The hydrocarbonaceous conversion of natural gas is the hydrocarbon product that contains that has more than 5 carbon atoms, comprises liquid hydrocarbon (comprising raw gasline, diesel oil and chloroflo)).This technology has high-level efficiency to the carbon that the whole carbon in the input process is converted into hydrocarbon product.
Another purpose of the present invention is will improve the tail gas circulation that Fischer-Tropsch reaction generates the selectivity of higher molecular weight compound and will be rich in the alkene alcohols and aldehydes to turn back to the Fischer-Tropsch Reactor inlet to improve efficiency of carbon conversion.Round-robin alkene, alcohols and aldehydes are absorbed on the catalyzer again, participate in further chain growth.
Another object of the present invention is will improve the selectivity of Fischer-Tropsch reaction production higher molecular weight compound and the raw gasline circulation that will be rich in alkene and contain a large amount of alcohol turns back to the Fischer-Tropsch Reactor inlet, increases efficiency of carbon conversion.Round-robin alkene and alcohol are absorbed on the catalyzer again, participate in further chain growth.
Further purpose of the present invention is to use secondary Fischer-Tropsch reactor, with emptying or the remaining H that uses as fuel
2And CO
2Be converted into liquid hydrocarbon, thereby improved efficiency of carbon conversion.
A further object of the invention is to produce a kind of catalyzer, and it has high reactivity and highly selective to the hydrocarbon product that contains that main production has greater than 5 carbon atoms.
The inventive method is applicable to that the gas containing hydrocarbon that comprises low B.T.U. appropriate hydrocarbon gas of any resource being derived and coming is converted into the liquid hydrocarbon product.This gas is in case acquisition at first is converted into H in steam reforming reaction device or partial oxidation equipment
2And CO, these gases are converted into CO in the Fischer-Tropsch reactor that uses specific iron catalyst then
2With the hydrocarbon product that contains 5 above carbon atoms, it comprises hydrocarbon gas, liquid hydrocarbon, pure and mild wax.Be converted into H
2Before CO, some or all CO that the Fischer-Tropsch reaction is produced
2Mix with initial gas containing hydrocarbon.In preferred embodiments, at H
2Before CO steam introducing Fischer-Tropsch reactor, CO
2H from generating
2With remove among the CO.If desired or necessary, for obtaining required H
2/ CO ratio, the CO that also this can be removed in case of necessity
2Join in the starting raw material.
Developed the whole system of implementing aforementioned technology, by this system, the air-flow that contains methane can be converted into the liquid hydrocarbon product, and the equipment of use comprises: steam reformer or partial oxidation equipment contain H with production
2, CO and CO
2Air-flow; CO
2Removing equipment is removed the CO in the air-flow
2; The Fischer-Tropsch slurry-phase reactor, this reactor uses iron catalyst, with H
2Be catalytically conveted to hydrocarbon and the CO that contains 5 above carbon atoms with CO
2; CO
2Removing equipment is removed the CO that the Fischer-Tropsch reactor produces
2, recycle unit is with the CO that removes of predetermined amount
2Be incorporated in the air-flow that enters steam reformer or partial oxidation equipment,, enter the H of Fischer-Tropsch reactor in the selective system by this system
2/ CO ratio can improve total efficiency of carbon conversion of technology.
Secondary Fischer-Tropsch slurry-phase reactor uses iron catalyst and uses and is suitable for H
2And CO
2Be catalytically conveted to hydrocarbon product and water and pure reaction conditions with 5 above carbon atoms.
The sketch of a kind of embodiment of the inventive method of Fig. 1;
Fig. 2 is the sketch that another embodiment of the inventive method is used partial oxidation process;
Fig. 3 is the detailed sketch of system of the present invention;
Fig. 4 is the sketch of another embodiment of system of the present invention;
Fig. 5 and 5a remove the diagram of wax for transverse flow strainer of the present invention;
Fig. 6 and 6a are for implementing the diagram of the used catalyst filter of the present invention;
Fig. 7 is emission-free round-robin steam reforming and a CO for the present invention adopts
2The process diagram of resorber;
Fig. 8 is emission-free round-robin steam reforming and two CO for the present invention uses
2The process diagram of resorber;
Fig. 9 has tail gas circulation and a CO for the present invention uses
2The process diagram of the steam reforming of resorber;
Figure 10 has tail gas circulation and two CO for the present invention uses
2The process diagram of the steam reforming of resorber;
Figure 11 has tail gas circulation and two CO for the present invention uses
2The process diagram of the steam reforming of resorber;
Figure 12 removes H for the present invention's employing comprises
2Remove CO in case of necessity
2The partial oxidation technology sketch.
With reference to figure 1, introduce gas containing hydrocarbon (as methane) 1.Gases usedly must be applicable to the inventive method, before introducing steam reforming reaction device 5, preferably pass through desulfurizer 2.Desulfurization can be used conventional equipment such as packed bed, typically can use the ZnO of grain bed as the 32-4 that obtains from Katalco, and diameter is at 1/8～3/16 inch (spheroidal particle bed of 3～5mm).Can be in sulfur removal technology using system pressure, typically this method is moved between 200 ℃～500 ℃, and is better between 350 ℃～400 ℃, with about 375 ℃ best.Space velocity by reactor should be advisable 400～1000 cubic feet/hour/cubic foot of bed, and 600～800 cubic feet/hour/cubic foot of bed is better, and about 700 cubic feet/hour/cubic foot of bed is best.
Then the hydrocarbon gas after the desulfurization was mixed with air-flow 6 before being incorporated into steam reforming stove 5.
Distinct advantages of the present invention is that special processes as herein described has production air-flow 6 or the used H to entering steam reforming stove or other producer
2Can allow predefined high levels of CO with the CO raw material
2, this is desired really.Under previously selected system pressure, use high concentration CO
2The hydrocarbon gas be favourable.This method allows to use air-flow from drilling well, and (this gas is because CO
2The concentration height, so B.T.U. amount is low) and the gas of hydrocarbon feed pyrolysis generation.Typically, the air-flow 6 that enters converter can contain a hydrocarbon gas carbon atom to the sum CO of 4 molecules nearly
2And the water (CO of about 3 molecules
2Better with water).Here, CO
2The number of molecule is less than or equals 2 times of carbonatoms of institute's hydrocarbonaceous in the flow of feed gas 6.Selecting these ratios mainly is to reduce the formation of elemental carbon in the steam reforming stove.Can use different proportionings when additionally using air-flow.As long as the generation of excessive elemental carbon in the converter is not quickened in omnidistance reaction, just can use to be less than 4 parts CO
2And water.9(contains from CO with circulating current
2The CO of removing equipment and recovery zone 24
2) merge previously selected carbon/water of generation and CO with air-flow 6
2Ratio, enter converter 5 then.According to the CO in the initial hydrocarbon gas 1
2The CO concentration or the initial hydrocarbon gas 1 and light hydrocarbon gases circulation 17
2Total amount is by controlling from CO
2The CO of removing equipment and recovery zone 24
2 Input 8, can adjust in air-flow 6 CO that adds
2
The concrete application of another of Fischer-Tropsch technology described herein is to be used for town gas (or coal gas), the content of deleterious carbon monoxide dropped to the level of regulation, as the 10%(volume).
A kind of method that reduces the town gas CO content of coal generation is to use water-gas shift reactor.Water gas shift reaction can be write as following formula:
For all situations described below, the gas composition that typical gas furnace produces is consistent.
The situation I, all gas that gas furnace is produced is input in the converter, for town gas CO percentage by volume is dropped to 10%, the CO57.1% of input must be converted into CO
2
Air-flow is composed as follows before and after the conversion reaction.
The air-flow of situation I is formed
Because this reaction is thermopositive reaction, air-flow is through the about 7MMBTU of converter total energy loss.
In the situation II, gas is therefrom removed CO through behind the converter
2Can increase gas heating value.In this situation, must could keep town gas CO content to drop to 10% to the degree bigger (63.3%) gas reforming than situation I.This situation flow groups becomes to see Table 2.
The air-flow of situation II is formed
Other method situation III (this is the object of the invention) is to replace converter to remove CO with a kind of Fischer-Tropsch reactor process described herein.The gas that the part of coal steam stove is produced is input in the Fischer-Tropsch reactor, the 21.4%(volume) gas is walked around the Fischer-Tropsch reactor, this gas of walking around is mixed with the tail gas of Fischer-Tropsch reactor, obtains following air-flow and form:
The air-flow of situation III is formed
Except town gas, the Fischer-Tropsch reactor also produces 11.8 barrels and contains 5 or greater than the liquid hydrocarbon of 5 carbon atoms.
In the situation III, remove the CO in the mixed gas
2, can resemble increases calorific value the situation II.Remove CO in order to make
2After coal gas 10%CO is arranged, must increase gas volume by the Fischer-Tropsch reactor.The air-flow composition of situation IV is expressed as follows.
The air-flow of situation IV is formed
Except coal gas, the Fischer-Tropsch reactor also produced 12.6 barrels contain 5 or greater than the hydrocarbon of 5 carbon atoms.
During other is used at some, need a standby converter in case the Fischer-Tropsch reactor can not use.In this situation, the gas that must keep a certain amount of low discharge passes through converter, even under the situation that the Fischer-Tropsch reactor can move.When the Fischer-Tropsch reactor was moving, 40% of the output gas that gas furnace should be produced flow through converter.The percent by volume of CO drops to 10% in the coal gas in order to make, must will be input to conversion reactor CO 33.8% be converted into CO
2In this situation, air-flow is composed as follows:
The air-flow of situation V is formed
In this situation, the Fischer-Tropsch reactor produces 9.0 barrels of liquid hydrocarbons.
A kind of variation of situation V is that the situation VI shows and increased a CO
2Removing equipment.For the CO content that makes coal gas drops to 10%, CO is had transform (44.8%) greatly.The air-flow of this situation is composed as follows.
The air-flow of situation VI is formed
As the situation V, the Fischer-Tropsch reactor has also produced 9.0 barrels of liquid hydrocarbon products.
With reference to figure 1 and omnidistance technology, steam reforming stove 5 can be the conventional design mode again, and commercial nickel catalyzator is used in this design, can obtain from Katalco as this catalyzer, is designed to 23-1.This reactor preferably should be in the temperature range of about 1292 (700 ℃)～1652 (900 ℃).About 12Psia(82.7KPa)～500Psia(3447KPa) operation in the system pressure scope.Input gas flow rate by the reactor catalyst bed should be about 300lbs/hr/ft
3Catalyzer.
As previously mentioned, can move air- flow 6,10,12 and 16 down at system pressure or other pressure (available decompression or supercharging device are regulated).If desired, the composition of system can design to such an extent that allow the variation of relative broad range under working pressure.Found that the said system pressure of this paper can produce mentioned benefit and advantage.
Roughly show as Fig. 2, can use partial oxidation reaction or replace steam reforming section in the technology that shows among Fig. 1 with it.
After the steam reforming step, contain H
2, CO and CO
2Air-flow 10 through absorbing and eliminating CO
2Step.Then with CO
2The gas (being designated as 12) that content reduces is transported to the Fischer-Tropsch reactor.In order to make Fischer-Tropsch reactor 15 reach optimum utility, this CO
2Removing equipment should make CO in the air-flow 12
2Concentration be reduced to be lower than about 5%(volume), remove CO
2One of best approach is to contain CO
2Gas by about 30% wet chemical bubbling.This absorption should be advisable in aforementioned system pressure and about 100 ℃～115 ℃ temperature range, about 105 ℃～110 ℃ better, about 105 ℃ best.Certainly, for given absorption dose, in order to make CO in the air-flow 12
2It is same or similar with desired reduction that concentration reaches, and higher or lower pressure will need temperature and through-put are carried out optimum optimization.Heating contains dissolving CO in separating tank then
2Solution of potassium carbonate be that rich solution is to remove the CO of absorption
2, will remove CO again
2Solution be that lean solution turns back to tourie with the CO in the gas 10 that absorbs steaminess converter more 5 and produce
2
Also can use other CO
2Removing method is as using the removing method of amine.
To contain H then
2Be incorporated in the Fischer-Tropsch reactor with the air-flow 12 of CO, this reactor uses the pulpous state iron catalyst, but sedimentary iron catalyst is better, and with by the amount of predetermined potassium of the probability of the molecular weight distribution of previously selected linear condensation and requirement and copper and helped catalytic precipitated iron catalyst best.
The catalyzer of production special purpose comprises three basic sides: form the step of preparation method and deactivated catalyst.
Be difficult to determine the optimal activation step of catalyzer, even know that need do which change to catalyzer just can obtain required activity, selectivity and stability.
Good catalyzer should be DNAcarrier freely to have copper and potassium to help catalytic precipitated iron catalyst.This catalyzer is done the starting raw material preparation with elemental iron and copper.
The first step of technology: metal is dissolved in the mixture that nitric acid forms Iron nitrate, iron nitrate and cupric nitrate with suitable proportion.Water/acid should be adjusted weight ratio by about 6: 1 than being an important parameter.Dissolving metal is behind nitric acid, and association has oxynitride, mainly is nitrogen protoxide and nitrogen peroxide.Nitrogen protoxide solubleness in acid is limited, but behind ingress of air or the oxygen, the very easy nitrogen peroxide that is oxidized to.Nitrogen peroxide is dissolved in water and forms nitric acid and nitrogen protoxide.Therefore, from retort, overflow, reduce the consumption of nitric acid simultaneously in order to reduce oxynitride, in the time of dissolving metal in solution aerating oxygen.The small amount of N O that from retort, overflows
2Available KOH solution absorption is removed.Stir the mixture until whole dissolving metals.The temperature of solution increases with the dissolving of metal, but temperature control is to the highest about 150 ℃.
Second step of technology: use NH
4OH is settled out catalyst precursor from nitrate solution.With the water-soluble NH that makes of anhydrous ammonia
4OH.Room temperature is with NH
4It is 7.4 that OH is added in the hot nitrate solution up to the solution pH value.At this moment, all metals are precipitated out with oxide form.Cooling mixture to 80, final pH value transfers to 7.2.
Post precipitation must be with free from chloride high quality water washing catalyst precursor to there not being ammonium nitrate.At first soup compound is pumped into the storer that is arranged in vacuum drums strainer upstream from settling bath.Allow catalyst precursor sedimentation in storer, form one deck concentrated nitric acid ammonium solution above the solid.Inhale before washing, the filtration soup compound and remove this layer solution.With the precursor of the vacuum drums filter wash catalyzer that water jet standpipe is housed, and concentrated soup compound.The specific conductivity of monitoring filtrate is to guarantee to remove fully the ammonium nitrate in the soup compound.
After having washed catalyst precursor, add the last component of catalyzer: salt of wormwood, added amount adapts with the middle ferruginous amount that feeds intake.Saltpetre is dissolved in the less water, and this solution thoroughly mixes with soup compound makes the potassium uniform distribution.At this moment, the weight percentage of catalyzer in soup compound should be between 8～12.
Remove most of moisture content in the catalyzer with spray-dryer, form the spherical catalyst particle simultaneously roughly.Its diameter range is 5～50 microns.
The final step of technology: in air, catalyzer is heated to about 600 °F removing remaining moisture content, and make catalyzer stable.This step carries out in electrically heated fluidized-bed.In addition, the annealed catalyzer is very easy induces or activates and use.
For the catalytic iron catalyst that helps of Fischer-Tropsch reaction, introduced many different activation methods in the document.For example, Pichler and Merkel have delivered the research of used iron Fischer-Tropsch catalyst activation process in the fixed-bed reactor, this is one of the clearest and the most definite research (U.S. Department of Mines state inside, technical article 718, author H.Pickler and H.Merkel, Ruth Brinkley and Preface translation, L.J.E.Hefer contributes a foreword, U.S. Government Publication, Washington DC, 1949, the chemistry and the pyromagnetic research of synthetic hydrocarbon iron catalyst).In this research, the existence of iron carbide after the high reactivity of catalyzer and the activation treatment has been connected each other.The most effective step is at 325 ℃, and 0.1 normal atmosphere uses CO down.This research has shown also how the existence of copper and potassium influences activity of such catalysts in the catalyzer.
Following equation has illustrated the stoichiometry of some reactions that take place in the reactivation process.
H is rich in use
2Synthetic gas produce cementite from rhombohedral iron ore:
Only use CO to produce cementite from rhombohedral iron ore:
In the presence of iron catalyst, following reaction takes place:
(alkene)
(paraffinic hydrocarbons)
Water gas shift reaction:
May there be such problem in the synthetic gas activation of using CO or being rich in CO: make the excessive carbonization of catalyzer produce uncombined carbon or non-carbonized carbonaceous thereby reduce activity of such catalysts.
Use the business equipment of slurries phase Fischer-Tropsch reactor, between its on-stream period, it is very important having handiness in the activation step.For example, when slurry-phase reactor that wax and catalyzer are packed into, must make the fluidised form gas stream cross gas distributor to stop catalyst sedimentation.During soup compound is heated to activation temperature, also must keep gas flow.Therefore, run duration, it is favourable using synthetic gas at the very start, because it expands outwardly, and obtains rare gas element (N
2Or CO
2) may be difficulty or expensive.
Have been found that if catalyzer acts under high temperature and high pressure and be rich in H
2Synthetic gas, can improve the activity and the selectivity of Fischer-Tropsch iron catalyst.H is rich in use
2Synthetic gas, the carburizing reagent of iron catalyst precursor (mainly being rhombohedral iron ore) and Fischer-Tropsch subsequently reaction all produces water.The existence of believing this water has stoped the excessive carbonization of catalyzer, so has improved activity of such catalysts and selectivity.(referring to " water and alkali promotor are to the influence of the catalytic Fischer-Tropsch reaction product of iron carbon number distribution ", people such as author L.Konig, Ber.Bunsenges.Physical chemistry 91,116-121(1987)-CVHC Verlagsgesells chaft mbH, D-6940 Weinheim, 1987).
Also find when soup compound just is being heated to about 200 ℃ the available H that is rich in
2Synthetic gas replace rare gas element, keep the suspension of catalyzer.Here, with rare gas element (N
2Or CO
2) replace synthetic gas up to reaching activation temperature, at this moment, activate with synthetic gas.
Also find, use the synthetic gas pretreatment catalyst, a large amount of N
2Exist (20%, by volume) harmless to activation method.Containing 20%N
2Atmosphere in, the catalyst activation time kept 2 hours.
The catalyzer of packing at first in holding the technical grade slurry-phase reactor of several kips is preferably in pre-treatment in the slurry-phase reactor of life size.But run duration, a part of catalyzer can need an independent pretreatment reaction device to keep activity in the catalyst replaced reactor that only needs several centals of pre-treatment.Should be similar in the design of pretreatment reaction device with big Fischer-Tropsch reactor, but littler.The soup compound available pump that contains pretreatment catalyst is input in the big reactor.
, find little amount of catalyst, be up to 10% of catalyst reactor total amount by weight, can be by catalyst material be directly joined in-situ activation in the reactor under operational conditions.
Example 1
Conventional activation method
H
2∶CO＝0.7
P＝35
T＝280～290℃
SV＝6NL/g????Fe/h
Time=3～5 hour
Example 2
Activation method of the present invention
H
2∶CO＝1.4
P＝150Psig
T＝280℃
SV＝4NL/g????Fe/h
Time=2 hour
Preheating soup compound to 200 ℃ uses synthetic gas
From 200～280 ℃ of heating, use CO
2
Synthetic gas is used in activation
The inventive method can be used the Fischer-Tropsch reactor of many different designs.With similar in appearance to M.D.Schlesinger, J.H.Crowell, Max Leva and H.H.Storch are at " engineering and technological development " (the 43rd volume, the 6th phase, 1951.6, the 1474th～1479 page) in described in the article that is entitled as " slurries mutually in Fischer-Tropsch synthetic " delivered be designed to suitable.In this article, synthesis reactor is used the precipitated iron catalyst that is suspended in the cooling oil, and this reactor is the representative of Known designs.Under certain conditions, this reactor starching operation be can give, CO hydrocarbon product and carbonic acid gas are converted into, transformation efficiency Yue Keda 90%.The reactor that the inventive method is used should be at about 100Psia(689KPa)～about 500Psia(3447KPa), about 428 (220 ℃)～about 536 (280 ℃) time move.But at about 150Psia(1034KPa)～about 300Psia(2068KPa), down operation is better for about 464 (240 ℃)～about 500 (260 ℃); About 225Psia(1551KPa) and about 482 °F (250 ℃) best.Must make synthetic raw gas on the cross section of reactor uniform distribution so that the bubble that rises and contain dispersed catalyst particulate pasty media and mix well.Gas distributor is made up of orifice plate or porous metal atomizer.The orifice plate of optimum design comprises concentric ring or annular manifold, is arranged in such a way ring: ring should coincide with the profile phase of reactor underframe, promptly places the ring of maximum diameter at highest point, and lowest part is placed the ring of minimum diameter.Orifice plate or can place up or can place down or both all can.Each orifice plate should be placed near the center of the reactor cross-section with equal areas.Preferred porous metal atomizer comprises the end cap of inner ovalize, in the bottom of reactor, makes the end cap convex surface up, and the hole on the dispenser panel of the porous plate of minor diameter and bending fuses.Smooth dispenser panel is used in another kind of design, makes being more evenly distributed of bubble, but requires plate thicker in to resist bending.For making the reactor transformation efficiency the most desirable, the air speed of selecting should be advisable between 100～300 cubic feet/hour/cubic feet of swelling catalyst beds, better between 200～270 cubic feet/hour/cubic feet of expanded beds, about 240 cubic feet/hour/cubic feet of expanded beds are best.Diameter that should selecting reactor makes charging superficial velocity (the empty cross-sectional reactor area of the actual volume flow velocity ÷ of unstripped gas) between about 0.33～0.66 feet per second (0.1～0.2 meter per second).These conditions will make selected catalyst bed height increase by 30～40% than no thermopnore height.In addition, for the thermopositive reaction that takes place, soup compound is an effective heat transmission medium.
The preferred method of a large amount of heats that cleaning reaction is emitted is the heat exchangers in the slurry-phase reactor.Heat exchanger tube should be on the gas distributor eminence of about 3 feet (1 meters) extend to the top of expansion soup compound.The best heat transfer medium is a water, is introduced into the pipe end by the concentric annular manifold, and water seethes with excitement in pipe, and a very a large amount of Heat transfer coefficient is provided.Net heat from the soup compound to the boiled water shifts and makes the soup compound temperature uniformity almost of whole reactor.The temperature of soup compound can be controlled with combining of vapor pressure (this moment, temperature was the vapo(u)rous temperature) in the height of water in the pipe and the pipe.
Under extensively preferred operational conditions described herein, the particle size of selected iron catalyst should be between about 5 μ～40 μ, and about 10 μ～40 μ are better, and about 30 μ are best.
Can expect to have any catalyzer that helps reaction (5) can effectively use in the present invention.Aforementioned iron catalyst cost is low, is desirable so use them.According to previously selected α, promptly desired polymerization probability uses precipitated iron catalyst the best.Here, the weight ratio of potassium (being carbonate)/iron is between 0.005～0.015; Better between 0.0075～0.0125, about 0.010 is best.Relatively large alkali metal promoter makes product distribute and trends towards more long chain molecule, and the small amount of alkali master metal will produce the hydrocarbon gas product.The weight ratio of copper/iron should be between about 0.005～0.050, and better between about 0.0075～0.0125, about 0.010 is best.Copper is used as induces promotor, uses aforementioned range can obtain high conversion.What describe later is the Fischer-Tropsch slurry-phase reactor, the life-span that the product of acquisition distributes and catalyzer is long relatively.
The weight percentage of aforementioned iron catalyst should be pressed the weight of iron in the soup compound at 5～15%() between, 7.5～12.5% is better, and about 10% is best.
Production than one of characteristics of the slurry Fischer-Tropsch reactor of heavy products is: because the volatility of heavier wax is low, so the soup compound height continues to increase.The level of keeping soup compound is by air-flow 29 in a method of a steady state value, when catalyzer is turned back to reactor, uses transverse flow strainer 27(such as Fig. 1) remove filterable wax, air-flow 28.
The advantage of transverse flow strainer is: will the slow down speed of catalyzer lamination on tube wall of the flow velocity that soup compound flows through about 10 feet per seconds (3M/S) of porous filtering pipe.When filtering flow velocity that wax flows through perforated tube and drop to predetermined level, with rare gas element (as CO
2) filter the wax pressurization for transverse flow filter tube border spatial, the catalyzer that impacts lamination makes it enter pulpous state logistics 29.This logistics 29 is backflowed into Fischer-Tropsch reactor 15.For an example relevant with flow velocity.For the commercially available Mott (Farmington of Usiminas, Conneticut) transverse flow strainer, if it is 2gpm that the stream via barrel is removed the speed of filtering wax, so from Fischer-Tropsch reactor 15 to transverse flow strainer 27, the soup compound flow velocity will be 65gpm, and the flow velocity that slurries return the Fischer-Tropsch reactor is 63gpm, and the speed of 10fps is provided for the Kong Guanzhong soup compound, produce desired shearing action, stoped the lamination of catalyzer.Mott transverse flow strainer and installation sketch are as shown in Figure 5.In order periodically from reactor, to remove catalyzer, the slip-stream 30 of soup compound is input to another porous metal filter, the catalyzer of this strainer collection hole pipe inside.Periodically impact catalyzer with rare gas element its " pump " gone into bottom collector.The Mott strainer sketch that is used to remove catalyzer as shown in Figure 6.
The segregation section 18 of present method can be shaped in a different manner, distributes with different variant productions that form and the product that reclaims owing to gaseous hydrocarbon feedstock, reaction conditions and catalyzer.
In the preferred embodiment of Miao Shuing, segregation section 18 can use cold-trap, and/or distillation plant in the back.By this way, comprise CO
2Air-flow 20 in gas can be recycled by air-flow 19, and/or a part of gas can be used as the unstripped gas 17 of fuel gas stream 25 or steam reforming step 5.
Use described reaction conditions, can be with light hydrocarbon gases and CO
2Separate; The carbon containing high product can be separated with pre-separation product flow 16.Gaseous product flow 20 after advantageously separating is rich in light hydrocarbon, can be directly as producing heat.The C content of 21 hydrocarbonaceous of product flow is at C
5～C
20Between, generally be saturated and unsaturated fatty hydrocarbons product, can be used as the substitute of diesel oil etc.Determined that this product flow can obtain high hexadecane value, it is used separately for this or mixes use with other diesel oil absorbent especially.Typically contain C
11～C
19The engineering test of diesel oil distillate show: the commercially available diesel oil that comes with deriving from raw petroleum is compared, and this fuel combustion gets cleaner.In addition, discharge lower particle than ordinary diesel oil, partly cause is to compare with ordinary diesel oil, and the aromatic hydrocarbons weight content of this fuel is less than 1% approximately, and the aromaticity content of ordinary diesel oil about 32%.
Typically, the diesel product that this technology produces is compared with ASTM diesel fuel grades standard, has following physical features.
Final product stream 22 hydrocarbon product that are rich in greater than 20 carbon atoms, this product is generally as paraffin (seeing Table I, II, III, IV and V).
The table I
* analytical results is below detectability
(1) ASTM D975-81 #1 diesel oil
(2) ASTM D975-81 #2 diesel oil
Following table is the more detailed analytical results of diesel oil in the table I
The table II
Except aforementioned, also F/T diesel oil of the present invention has been done further to analyze.
Test result:
Gas chromatography/mass spectrometry is measured the relative percentage ratio (approximation) of the alcohol that exists
Alcohol (approximation) percentage ratio
Propyl alcohol 0.02
Butanols 0.1
Amylalcohol 0.3
3-methyl amyl alcohol 0.3
Alcohol 0.1
Octanol 0.9
Decyl alcohol 1.0
Lauryl alcohol 0.9
Tetradecyl alcohol 1.0
Pentadecanol 0.9
Hexadecanol 0.7
Heptadecyl alcohol 0.2
Stearyl alcohol 0.6
Nonadecanol 0.1
Other branched-chain alcoho 1.0
Total pure 8-9
Speak of common discharging and special particulate emission, although the alcohol that exists in the F/T diesel oil also not exclusively understands at present that to the contribution of its excellent performance following analysis has clearly illustrated that the superiority of F/T diesel fuel characteristics among the present invention.
The table III
Combined diesel oil fuel
The table IV
Emission result (g/bhp-hr)
From the listed date, compare with the standard of the regulations that the purify air amendment of nineteen ninety, use synthol F/T diesel oil of the present invention to improve significantly.
The emission behavior that has improved shows strongly, can prepare oxygenated additive, improves performance thus.Synthesis technique of the present invention not only produces oxidiferous synthetic F/T diesel oil, and produces the raw gasline that contains the oxygen carrier that comprises alcohol.Following analysis has illustrated some typical physicochemical properties of the raw gasline that is produced by technology of the present invention.
The table V
Now understand, the synthetic raw gasline of being produced by the inventive method that adds q.s makes oxygen level account for ordinary diesel oil weight 2% or more, will obviously improve the emission result that produces in the standard engine test.
Must carefully add this raw gasline, not change other specifications parameter again, be no more than the allowed band of the suitability defined of this fuel expectation function so that promptly improved the oxygen level in the fuel.
Wax product promptly can be used for producing and also can be used for cracking and produce other combined diesel oil and raw gasline.
According to the finished product of expectation, wax is expected product here, so plan to remove any catalyzer of carrying secretly less than porous metal filter element aperture (0.2～0.5 micron) with the wax cleanup step in transverse flow strainer 27.
When needing to add diesel oil, can heat wax to 410 ℃ (770) and produce other raw gasline and diesel oil.Be described typical wax thermally splitting result's analysis below, also can use other conventional steps.
From table VI, VII as seen, the diesel oil and the raw gasline oxygen concentration that are produced by the wax thermally splitting are quite low, if the result needs, can contain the oxygen raw gasline or contain oxygen diesel oil and mix the concentration of adjusting oxygen with this technology produces.
The table VI
The diesel oil crackate
The table VII
The raw gasline crackate
As previously mentioned, characteristics of the present invention are, when carbonic acid gas partly derives from the Fischer-Tropsch reaction, for improving total efficiency of carbon conversion of this technology, use carbon dioxide generating hydrogen and carbon monoxide in steam converter or other reactor.
Similar decarbonation by absorption and aforesaid general follow-up stripping in 8, takes place in the air-flow 19 that contains hydrogen matter appropriate hydrocarbon gas and carbonic acid gas.Preferably will be from steam converter and Fischer-Tropsch reactor isolating carbonic acid gas (air-flow 9), incorporate input air-flow 6 again into, enter steam reforming reaction device 5 and obtain aforesaid ratio.Excess carbon dioxide can emptying or compression and be stored as after again with or sell.
After light hydrocarbon air-flow 23 and the carbon dioxide separation, recyclablely use as petroleum chemistry raw material or fuel, or as the fuel of steam converter; Also capable of circulationly enter the F/T reactor to inlet steam flow 12 and make alkene and further chainpropagation of alcohol, if need, shown in dotted line 17, in addition capable of circulation to inlet air flow 6, to improve total efficiency of carbon conversion and to regulate the productive rate of higher hydrocarbon product stream 21.
The present invention uses the vote of aforementioned technology to be shown in Fig. 3 generally.
If desired, the air-flow 100 of input is in the desulfurization of 102 places.Gas reacts in steam converter 105 in after the desulfurization and steam importing air-flow 106 backs.
From mainly containing hydrogen, the reacting product stream 107 that obtains in the steam converter of carbon monoxide and carbonic acid gas is introduced into carbon dioxide adsorber 108, and the gaseous product carbon dioxide content is better less than 10%, less than the 5%(volume) better.This product gas is transferred to Fischer-Tropsch reactor 110 through pipeline 109 then, after getting rid of by pipeline 113 and valve 114 through carbonic acid gas stripping device 112, the solution of the useless carbonic acid gas of aforementioned absorption preferably 111 is introduced adsorber by the road by pump 115, and the solution that is rich in carbonic acid gas in the adsorber 108 is transferred to stripper 112 by pipeline 116.
After the reaction, reaction product moves to distillation tower 120 by pipeline 119 in Fischer-Tropsch reactor 110, hydrocarbon product wax 120 with diesel oil, water and alcohol, raw gasline and light hydrocarbon gas, carbonic acid gas, carbon monoxide and Hydrogen Separation.
Then, the light hydrocarbon product pipeline 121 of flowing through is transferred to carbon dioxide adsorber 125, is further utilization, light hydrocarbon gas and carbon dioxide separation, and the carbonic acid gas of absorption is stripping in stripper 112,130 and 104 is circulated to convertor 105 by the road then.Light hydrocarbon gas (air-flow 137) also can circulate and turn back to the Fischer-Tropsch reactor inlet, so that wherein contained alkene and alcohol participate in further chainpropagation.In some cases, may need absorption unit of dioxide carbon 125 and resorber 108 are merged to reduce facility investment and complicacy.Any needn't circulation returned a part of air-flow 137(air-flow 138 of Fischer-Tropsch reactor), can be used in reformer fuel or the adding convertor raw material 106.
For using in each composition of system, selected condition must be passed through and the aforementioned identical judge of the present invention.
The following example uses listed condition design in the table, and simulated experiment is the experience based on the employed various conditions of research of pilot scale production equipment, and has shown used condition expected result.
Technology whole process efficiency of carbon conversion is defined as C in the Fischer-Tropsch reactor
5+The ratio of product carbon content.
C by the generation of Fischer-Tropsch reactor
5+Product volume calculates with following method:
The hydrogen of known quantity and reaction of carbon monoxide form the product flow of being made up of hydrogen, carbon monoxide, carbonic acid gas, water, hydrocarbon and oxide compound.Any gas supposition only the plaing a part diluent gas that enters reactor of non-hydrogen and carbon monoxide.Determining that product flow relates to completely separates 6 unknown numbers; 1) mole number of hydrogen; 2) carbon monoxide mole number; 3) carbonic acid gas mole number; 4) mole number of water; 5) hydrocarbon and terms of oxide moles; 6) leave the hydrocarbon of reactor and the composition of oxide compound.
Separate these 6 unknown numbers and need 6 equatioies, first three equation comes carbon, hydrogen and this condition of oxygen conservation in the autoreactor.The 4th equation supposed to produce thus: 90% of the raw material carbon monoxide of known quantity is participated in reaction, the 5th equation is from the experimental data of pilot plant, data show, the hydrogen that consumes when changing into hydrocarbon product and water, depend on hydrogen and the ratio of carbon monoxide and the carbon monoxide of consumption of input:
(H
2The change of mole number)/(change of CO mole number)
The 6th equation derives from the argumentation of Schultg-Flory theory: carbon number is that to equal carbon number be that the mole number of the hydrocarbon of n-1 multiply by alpha (α) mutually for the mole number of the hydrocarbon of n in the product gas flow, α is the chainpropagation probability, under given catalyst system and a whole set of operational condition, α is a constant.Articles of reference as above-mentioned Satterfield and Hnff is sayed.Have only when each carbon number of whole compounds is all included, the theory of Schultz-Flory is only correct.So react a spot of pure and mild other oxide compound of generation (mainly at C by Fischer-Tropsch
2-C
4Scope), when distributing, counting yield all included.
Mandatory declaration is similar to the situation of actual expectation based on the analysis of above-mentioned equation.Hydrocarbon product stream is believed to comprise oxide compound, and for few, these analyze the productive rates that obtain and are suitable for than than usefulness its output with respect to hydrocarbon (especially carbon number is greater than 4 hydrocarbon).
Table 1 has been listed on aforementioned system, in a different mode of operation with in following parameter and result who does analysis of different condition.
Referring to Fig. 3, every day 1 Million standard cubic feet (28316M
3) Sweet natural gas (supposition is a methane), adjusting to pressure is 230psia(1590kpa), in preheater PH1, be heated to 700 °F (371 ℃), with every M per hour
3Catalyzer 700M
3Space velocity flow through desulfurization bed S1.S1 is the fixed bed of commercially available zinc oxide bead, and the bead diameter range is 1/8 inch (3mm)～3/16 inch (5mm).This class sulfur removal technology is suitable for the lower concentration sulphur compound, such as being lower than 25ppm.
The Sweet natural gas sulphur content of leaving S1 is lower than 0.5ppm, every day and the 1.46MMSCF(41343M that comes from stripper ST1 circulation
3) carbonic acid gas and 1.73MMSCF(48987M
3) vapor mixing, mixture in preheater PH2 by leaving conversion reactor R
1Gas be preheating to 968 °F (520 ℃).The gaseous mixture of heating is at catalytic conversion reactor R
1In carry out chemical reaction.Catalyzer is commercial conversion catalyst, for example at the nickel of loading with the form of Raschig rings on aluminum oxide (for example Katalco sells catalyzer 23-1).Because what take place relates to methane, steam and CO
2Chemical reaction be thermo-negative reaction, so need to contain the pipe outer wall heating of catalyst rings.Because the restriction on heat passage, the diameter of pipe must less (for example 5 inches (12.7Cm)), and number pipe boundling is integral again.For the flow velocity of present embodiment, needing 12 long 24 feet (7.3m), internal diameters altogether is the pipe of 5 inches (17.7Cm).
The effect of conversion reactor is to produce synthesis gas as much as possible (mixture of hydrocarbon and CO), especially carbon monoxide.The transforming degree that carbon in methane and carbonic acid gas changes into carbon contained in the carbon monoxide is determined by the thermodynamic(al)equilibrium of water-gas shift reaction:
（11）
And steam-methane reaction
（12）
These equilibrium constant of reaction depend on the temperature of the gas that leaves converter.Because reaction (12) relates to when reaction consumes methane, the increase of product mole number, higher pressure has disadvantageous effect to the transforming degree of methane.Water-gas shift reaction is the very easy balance that reaches on nickel catalyzator, simultaneously steam-methane reaction all at about 16 ℃ (29 °F) near balance, the result of expectation is promptly based on this phenomenon.In the present embodiment, Outlet Gas Temperature is 850 ℃ (1562 °F), and pressure is 225psia(1550kpa), the gas that leaves converter contains 2.15MMSCFD(60879M
3/ sky) hydrogen, 1.52MMSCFD(43040M
3/ sky) carbon monoxide, 0.80MMSCFD(22653M
3/ sky) carbonic acid gas, 0.08MMSCFD(2265M
3/ sky) methane and 1.29MMSCFD(36528M
3/ sky) water.
Gas is cooled to about 200 ℃ (392 °F) in preheater PH 2, continue to be cooled to 25 ℃ (77 °F) then in water-cooled condenser C1, and water condensation is therein also got rid of in separator SV1.
Concerning the raw material of building-up reactions, the gas of not wishing to leave SV1 contains in a large number the carbonic acid gas of (about 18%).So the next step of preparation synthesis gas is with CO
2Content is reduced to and is lower than the 5%(volume), in this example, reduced to 2%.This process uses the wet chemical of heat to finish in carbonic acid gas adsorption column ABS1.Salt of wormwood and carbon dioxide reaction change saleratus into.Solution reduces (flash distillation) to about 2psig(138kpa by pressure then) and in stripping columns ST1, seethe with excitement and cyclic regeneration.The carbonic acid gas of removing from ST1 is compressed into 230psia(1590kpa), the convertor inlet is got back in recirculation.The gas that leaves adsorber ABS1 is at water cooled condenser C
2In be cooled to 25 ℃ (77 °F) from 105 ℃ (221 °F), water vapor is at condenser C
2Middle condensation is got rid of from separator SV2 then.
Remove carbonic acid gas and can use other method, for example the thanomin system.But these systems usually need a large amount of steam to come regeneration soln.This two classes industrial system all is ready-made.After removing carbonic acid gas, except carbonic acid gas is reduced to 0.016MMSCFD(453M
3/ day) in addition, gas flow rate is identical.Gas enters synthesis reactor SR1, SR1 is a class bubble tower slurry-phase reactor, and its type Kolbel and Ralek once were described in detail in " liquid phase Fischer-Tropsch is synthetic ", the catalyzer summary, Science Engineering Vol.21(2), pp.225-274(1980).Reactor SR1 contains the sedimentary iron catalyst that granular size is the 5-40 micron, and this catalyzer is suspended in the no sulphur high melting-point wax (m.p.〉60 ℃ (140 °F)).Soup compound contains about 10%(weight) iron, space velocity is the per hour every volumetric expansion catalyzer of 240 a volumes pulpous state thing bed volume.
In this example, the reactor overall size is: 4.5 feet of internal diameters (1.37m), high 45 feet (13.7m).Reactor contains about 20,000 pounds of waxes, 3500 pounds of catalyzer.This volume provides the expansion space of the isolation portion of soup compound, catalyzer and soup compound top wax.Reactor has the internal cooling pipe to remove about 7000/Btu/(b) a large amount of reaction heat of (16249KJ/Kg) institute's production fluid body.Pump into water generates in the pipe and can be used as the high pressure steam of flow process heat.
The gas stream that enters synthesis reactor SR1 bottom is crossed a spout cover plate that produces diameter less than the vesicle of 1mm.The bubble of emerging in the soup compound can make between the gas-liquid phase and between the solid-liquid phase and mix well.Temperature of reactor maintains 250 ℃ (482 °F), by back pressure regulator BPR, red-tape operati pressure is 210psia(1450kpa), the product that produces in SR1 enters separation column with unconverted gas, and product is divided into three parts at this: 36.0 barrels comprise that carbon value is C
5-C
10The raw gasline of molecule, 27.7 barrels of diesel oil (C
11-C
19) and 17.0 barrels of wax (C
20+).
Cat head distillates gas and contain the carbonic acid gas that produces in a large number in synthesis reactor SR1.In order to recycle these carbonic acid gas, gas is imported carbon dioxide adsorber ABS2.In condenser C4 separate with separator SV4 dewater after, all the other light hydrocarbon gas: hydrogen and the carbon monoxide back pressure regulator of flowing through arrives the converter burner.The combustion air of converter is used heating by the exhaust gases with air compressor B1 compression in PH3.
Each routine product yield and efficiency of carbon conversion and operating parameters that the table VIII has been listed embodiment 1 and hereinafter discussed.
Embodiment 3
Embodiment 3 is identical with example 1, do not exist together for: have only the carbonic acid gas that comes from convertor just to be circulated back to the convertor inlet.The transformation efficiency of this situation carbon is 43.6%, 5 above product (C of carbon
5+) productive rate is 61.3 barrels.Comparing embodiment 1,2,3 has proved the advantage that is circulated back to (embodiment 2) convertor inlet from the carbonic acid gas of Fischer-Tropsch reactor.If carbonic acid gas does not circulate, transformation efficiency is very low, only is 36.8%, C
5+Productive rate is also very low, 51.8 barrels.From the circulation (example 3) of convertor increase carbonic acid gas, efficiency of carbon conversion and C
5+Productive rate has improvement slightly, is respectively 43.6% and 61.3 barrel.Only the carbonic acid gas from Fischer-Tropsch participates in circulation time, as the system of preferred embodiment 1, and efficiency of carbon conversion and C
5+Productive rate just is significantly increased, and attention only in vote, just has 50% efficiency of carbon conversion, as equation 2 expectations.
Embodiment 5
In this embodiment, in fact utilized all carbonic acid gas in the Fischer-Tropsch tail gas, obtained on some improved bases some improvement are arranged again at embodiment 4.But formerly separated after the carbonic acid gas of tail gas stream, had 50% tail gas to be recycled.In this way, 98% carbonic acid gas recirculation enters convertor in the tail gas.Efficiency of carbon conversion and C
5+Productive rate improves again greatly, is respectively 71.3% and 94.6 barrel.It should be noted that also that the gas flow rate that enters convertor and Fischer-Tropsch is compared with example 4 has reduced, and therefore not needing to enlarge equipment size improves productive rate.And the high hydrogen of example 4 and the ratio of carbon monoxide have been reduced to 2.50 from 3.54.
Embodiment 6
In the present embodiment, expand 70% to participating in round-robin Fischer-Tropsch tail gas in the example 4, this will make efficiency of carbon conversion and C
5+Productive rate greatly improves, but that cost is a gas flow rate is very big, and hydrogen and carbon monoxide ratio are too high.Probably on a set of equipment, in very economical ground designed system, C
5+In fact productive rate can not be realized.This be because, the input of the heat of convertor will improve, having surpassed does not circulate returns the producible heat of exhaust combustion that convertor enters the mouth.Therefore, as if comparatively economical and practical limit more approaches the circulation of 50% tail gas of example 4.
Embodiment 7
Present embodiment has shown the result who uses other method, promptly for example uses membrane separation apparatus to remove some hydrogen in air-flow, is input to the hydrogen of Fischer-Tropsch reactor and the high ratio of carbonic acid gas with reduction.Embodiment 7 has expressed the hydrogen of removing capacity and has been limited to result after about 1.5: 1 with the ratio with hydrogen and carbon monoxide.4 results compare with example, the transformation efficiency of carbon and C
5+Productive rate has all reduced.This is attributable to this fact: just no longer the generation of hydrocarbon is contributed to some extent after hydrogen is removed from reaction gas flow.With example 5 comparative descriptions, how effective the method for carbonic acid gas from the Fischer-Tropsch reactor cycles to convertor is with the present embodiment ratio.In example 5, not only hydrogen is retained in the system, and can utilize the carbon of input better.
Present embodiment can compare with example 4, and demonstrates the variation of α value, the influence of promptly linear condensation probability, and α has dropped to 0.7, and the result is that lighter hydrocarbon output improves greatly.Because α reduces to 0.7, has greatly increased C
1-C
4The generation of hydrocarbon, but it is with C
5+Part is a cost, so efficiency of carbon conversion and C
5+Productive rate is reduced to 43.7% and 60.0 barrel respectively.Yet, also it should be noted that, though C
5+Part has reduced, and these light hydrocarbons still can be used as chemical feedstocks.
The experiment of embodiment 4 as described above, this example brings up to 70% with the global cycle of example 4, and keeps only 0.7 low α value of example 8.In addition, the light hydrocarbon of capacity circulates and reacts, and obtains 79.3 barrels C respectively
5+Productive rate and 54.6% efficiency of carbon conversion.So it is a kind of change C that reduction α value is used in combination with the global cycle of Fischer-Tropsch tail gas
5+The method that hydrocarbon distributes.Here, discuss as embodiment 6, need once more to consider to produce bigger gas flow rate and since convertor add the restriction that heat request causes.
Present embodiment proves, improves the service temperature of convertor, has just improved its performance, also is the performance of a complete set of system.Preferred systems service temperature (example 1) has been brought up to 875 ℃ concerning this example.Compare with example 1, this example is approximate to have produced the carbon monoxide more than 5.5%, thereby efficiency of carbon conversion is brought up to 61.4%, C
5+Productive rate is brought up to 85.1 barrels.The actual execution and obtain that this raising need consider be not only high-temperature operation the time high energy consumption, to consider that also the life-span that transforms organ pipe reduces, the latter is the main cost of system.
Found the method (see figure 4) that another utilizes the carbon dioxide to improve efficiency of carbon conversion of Fischer-Tropsch reactor generation.Have now found that mainly the tail gas of being made up of hydrogen and carbonic acid gas from the Fischer-Tropsch reactor can change into liquid hydrocarbon according to following reaction in second Fischer-Tropsch reactor.
Paraffinic hydrocarbons
Alkene
In this case, initial reaction is a water gas shift reaction, is equivalent to during molecular balance at 250 ℃, and the degree that reaction is from left to right carried out is about 0.25.The carbon monoxide that forms in conversion reaction generates hydrocarbon by Fischer-Tropsch reaction and excess hydrogen reaction.In a small-sized slurry-phase reactor, test, promptly use synthetic identical ferrum-based catalyst with normal Fischer-Tropsch.Keep same temperature, pressure and space velocity.Ratio for hydrogen and carbonic acid gas is 2: 1, also is 1.5: 1 raw material, and carbon dioxide conversion is 25%.In the Fischer-Tropsch reaction, hydrogen conversion is 42%, and 88% of the carbon monoxide that water-gas shift reaction generates changes into hydrocarbon, and it is synthetic that chainpropagation (α) is same as normal Fischer-Tropsch.
This discussion is especially favourable in the system with excess carbon dioxide and hydrogen, and carbonic acid gas is discharged into atmosphere usually, and hydrogen is removed in membrane separation apparatus or reservoir pressure absorbing unit (pressure saving adsorption unit).
Following table has been concluded the various graphic extensions of Fig. 7-14, they with every day bucket be the possible productive rate that unit shows expectation.
The table VIII
Other process condition equipment requirements and product yield
Condition:
* 1.0 MMCFPD methane (CH
4)
* deliver to the maximum CO of F-T reactor
2Content 8%
* 1.5: 1 H
2/ CO ratio
* * equipment * * *
CO
2CO
2CO
2CO
2H
2F-T tail gas F-T
FIG. converter partial oxidation resorber resorber stripper compresses and washes and washs compressor
The #1 #2 device device that contracts
7 have or not nothing
8 have or not nothing
9 have or not
10 have
11 have
12 nothings have or not have to be had
13 nothings have
* * product * * *
FIG. YIELD B/D (C7+) dump energy (MMBTUPD-LHV)
7????2039.97????226
8????69.38????0
9????60.98????0
10????77.96????0
11????82.93????0
12????2500.05????0
13????106.03????0
Observe at last, distillation is removed contains the compound (seeing Table IX) that water contains a large amount of pure and mild other oxidations, in general, attempts to concentrate and reclaims these alcohol and uneconomical.Handling this a kind of method that contains water is to be recycled in the convertor raw material, provides demand and the compound of oxidation of water vapor to water to react in convertor and produce extra hydrogen and carbon monoxide thus.
The table IX
Typical F-T contains water-phase component
Foregoing description and example are the example operation of system and method for the present invention.The scope of the invention is not limited thereto.The accompanying Claim book was represented the expectation scope of the present invention's description as former process technology limit.
Claims (35)
1, a kind of hydrocarbon gas feed is changed into the method for the higher hydrocarbon product of molecular weight, this hydrocarbon comprises the liquid hydrocarbon product that is suitable as fuel or fuel dope, and this method may further comprise the steps:
In the presence of carbonic acid gas, raw material hydrocarbon gas is changed into hydrogen and carbon monoxide with predetermined proportion;
In the liquid hydrocarbon soup compound, helping in the presence of the catalytic iron catalyst, hydrogen and carbon monoxide are reacted in the Fischer-Tropsch building-up reactions;
Liquid state with 5 above carbon atoms and gaseous state hydrocarbon product that recovery is produced by above-mentioned Fischer-Tropsch reaction;
The gaseous product that comprises carbonic acid gas that above-mentioned reaction is produced separates with liquid product;
The gaseous product (comprising carbonic acid gas) that at least a portion is generated is before it is converted into hydrogen and carbon monoxide, in the incoming stock appropriate hydrocarbon gas that circulates.
2, the process of claim 1 wherein Fischer-Tropsch synthetic be at about 100 psia(689kpa)～500psia(3447kpa) pressure under and the temperature of about 220 ℃ (428)～280 ℃ (536) and with every cubic metre of expansion slurry volume 100～300M
3Carry out under the space velocity condition of/hr.
The process of claim 1 wherein that 3, the catalyzer of selection is sedimentary Fe-Cu catalyzer by an alkali metal salt promotor.
4, the method for claim 3, wherein, an alkali metal salt is a salt of wormwood.
5, the method for claim 4, wherein, catalyst consumption is: the 5-15% of soup compound gross weight is an iron.
6, the method for claim 4, wherein, the particle size of catalyzer is between the 5-40 micron.
7, the method for claim 5, wherein, the liquid hydrocarbon product of recovery has following feature: saturated, the undersaturated aliphatic hydrocarbon and the alcohol that consist essentially of about 5-20 carbon atom chain length.
8, the method for claim 7, wherein, the liquid hydrocarbon section of boiling of recovery is about 122 °F (50 ℃)-662 °F (350 ℃).
9, the method for claim 8, wherein, what the Fischer-Tropsch building-up reactions obtained generates the transformation efficiency the most nearly 90% of the carbon of hydrocarbon product and carbonic acid gas by carbon monoxide.
The process of claim 1 wherein that 10, the carbon more than 50% of introducing step of converting when forming hydrocarbon is converted to the final hydrocarbon product that contains 5 carbon atoms at least.
11, a kind of carbonaceous material is transformed into comprises and is applicable to and acts as a fuel or the method for the product of the hydrocarbon that fuel dope uses, and may further comprise the steps:
In the presence of carbonic acid gas, carbonaceous material is changed into volume ratio and be about 0.5-2.0: 1 hydrogen and carbon monoxide;
In the hydrogen that produces and carbon monoxide, remove carbonic acid gas;
Contain the hydrocarbon soup compound that helps catalytic iron catalyst in the presence of, by the Fischer-Tropsch building-up reactions, make hydrogen and reaction of carbon monoxide;
Be the purpose of follow-up use, reclaim gaseous state and liquid hydrocarbon product that above-mentioned Fischer-Tropsch reaction produces;
To separate with other products by the hydrocarbon that contains the gaseous state product that above-mentioned reaction produces;
At least a portion gaseous product that produces is circulated to the Fischer-Tropsch synthesis reactor.
12, a kind of hydrocarbon stream that will contain changes into the method that comprises the liquid hydrocarbon product with larger molecular weight, and this method may further comprise the steps:
At first, in the presence of water and capacity carbonic acid gas, in a reaction zone, make the appropriate hydrocarbon gas reaction, produce hydrogen and carbon monoxide product with predetermined proportion;
The second, at second reaction zone, in the presence of the soup compound that contains the catalytic ferrum-based catalyst of alkaline auxiliary, helping forming carbonic acid gas, light hydrocarbon gas normally contains under the condition of the liquid hydrocarbon of 5 carbon atoms and chloroflo at least, carries out the catalyzed reaction of hydrogen and carbon monoxide;
The 3rd, with gaseous state and liquid hydrocarbon fractionation by distillation; With
The 4th, be recycled to major general's light hydrocarbon gas in the reaction of hydrogen and carbon monoxide.
13, the method for claim 12, wherein, the ratio of the carbon of appropriate hydrocarbon gas and carbonic acid gas and water is a carbon and the ratio of maximum four parts of carbonic acid gas and water.
14, the method for claim 13, wherein, keep a in flow of feed gas hydrocarbon carbon and the volume ratio of maximum two parts of carbonic acid gas, and keep the ratio of carbon and the cumulative volume of maximum four parts of carbonic acid gas and water in a hydrocarbon.
15, hydrocarbon stream is changed into the method for the product that comprises liquid hydrocarbon, the method includes the steps of:
The first, in the presence of water and capacity carbonic acid gas, in a reaction zone, the reaction of catalytic hydrocarbon gas generates hydrogen and carbon monoxide, and its ratio is 0.5-2.0: 1;
Second, contain the catalytic ferrum-based catalyst soup compound of alkaline auxiliary in the presence of, helping forming carbonic acid gas, light hydrocarbon gas and contain the normal liquid hydrocarbon of 5 carbon atoms at least and the condition of chloroflo under, carry out the catalyzed reaction of hydrogen and carbon monoxide at second reaction zone, then liquid hydrocarbon product is separated with gaseous product; With
The 3rd, in the presence of the soup compound that contains the catalytic ferrum-based catalyst of alkaline auxiliary, make the gaseous product reaction produce extra liquid hydrocarbon product at the 3rd reaction zone.
16, the method for claim 15, wherein, earlier the ratio of the carbon in the appropriate hydrocarbon gas of reaction and carbonic acid gas is a carbon and the ratio of maximum two parts of carbonic acid gas.
17, the method for claim 16, wherein, the ratio of carbon in the appropriate hydrocarbon gas and carbonic acid gas and water is 1: 4.
18, the method for claim 17 wherein keeps the carbon of hydrocarbon in a feedstream and the volume ratio of maximum two parts of carbonic acid gas, keeps the cumulative volume ratio of a hydrocarbon carbon and carbonic acid gas and water simultaneously.
19, a kind of adjustment enters the ratio of the hydrogen of Fischer-Tropsch reactor and carbon monoxide and don't removes the method for dehydrogenation, and it comprises following steps:
From the Fischer-Tropsch reactor, carbonic acid gas is separated with product flow; With
The carbonic acid gas of telling of pre-selected part is introduced the steam reforming reaction device, with the feedstream of hydrocarbonaceous and water with of the ratio merging of predetermined hydrocarbon with water and carbonic acid gas, the product flow of coming out, produce the hydrogen and the carbon monoxide of pre-selected ratio from the steam reforming reaction device.
20, the method for claim 19, wherein, the carbon in the appropriate hydrocarbon gas and the ratio of carbonic acid gas are a carbon and the ratio of maximum two parts of carbonic acid gas.
21, the method for claim 20, wherein, the ratio of the carbon of appropriate hydrocarbon gas and carbonic acid gas that enters the steam reforming reaction device and water is a carbon and the ratio of maximum four parts of carbonic acid gas and water.
22, the method for claim 21 wherein keeps the hydrocarbon carbon in a feedstream and the volume ratio of maximum two parts of carbonic acid gas, keeps the cumulative volume ratio of a carbon and maximum four parts of carbonic acid gas and water simultaneously.
23, the method for claim 22, wherein, in steam converter, the hydrocarbon gas changes into hydrogen and carbon monoxide is to carry out between about 1292 (700 ℃)-1652 (900 ℃).
24, the method for claim 23, wherein, steam reforming reaction is at about 12psia(827kpa)-carry out under 500psia(3447kpa) the pressure.
25, a kind of appropriate hydrocarbon gas is changed into the system of the liquid hydrocarbon product that contains 5 or 5 above carbon atoms, wherein the carbon of the appropriate hydrocarbon gas transformation efficiency that is transformed into the hydrocarbon product that contains 5 or 5 above carbon atoms is at least 50%, and this system comprises:
With appropriate hydrocarbon gas, water and carbonic acid gas are transformed into hydrogen, and the catalyticing conversioning equipment of carbon monoxide and carbonic acid gas also comprises gas is introduced the device of above-mentioned converting apparatus and the device that product is shifted out from above-mentioned converting apparatus;
Hydrogen and carbon monoxide are transformed into the Fischer-Tropsch synthesis device of liquid hydrocarbon compound and carbonic acid gas;
With the carbonic acid gas of at least a portion by the synthetic generation of Fischer-Tropsch, with its recycle unit with predetermined q.s (in case elemental carbon formation) introducing catalyticing conversioning equipment, generation ratio simultaneously is 0.5: 1～2.0: 1 hydrogen that enters the Fischer-Tropsch synthesis device and a carbon monoxide.
26, the system of claim 25, wherein, above-mentioned recycle unit comprises:
From carbonic acid gas absorption and recovery system from absorption the product flow of Fischer-Tropsch synthesis device and recovery carbonic acid gas.
27, the system of claim 26 further comprises:
Absorption of extra carbonic acid gas and recovery system are in order to absorption with retrieve carbonic acid gas in the autocatalysis converting apparatus product flow with in the feedstream with its input catalyticing conversioning equipment.
28, the system of claim 27 further comprises, separates the separating device from the liquid hydrocarbon in the Fischer-Tropsch synthesis device.
29, the system of claim 28, wherein, above-mentioned catalyticing conversioning equipment can be transformed into carbon monoxide and hydrogen with hydrocarbon so that the ratio of maximum two mole of carbon dioxide of carbon atomic ratio is initial.
30, the system of claim 29, wherein, the ratio of carbon and water and carbonic acid gas is a carbon and the ratio of maximum four parts of carbonic acid gas and water.
31, a kind of adding catalytic activity of being used for the Fischer-Tropsch slurry-phase reactor helps the method for catalytic iron catalyst, this method comprises: activation comprises ferriferous oxide and helps the potassium of catalytic amount and the nonactive catalyst precursor of copper, above-mentioned ferriferous oxide is selected from ferric hydrous oxide and mainly contains the precipitated iron oxide compound of rhombohedral iron ore, above-mentioned activation is to be contacted under the temperature and pressure that improves with carbon monoxide mixtures and worked by above-mentioned nonactive catalyst precursor and gaseous hydrogen, and its improvement comprises:
Under combination condition, carry out above-mentioned contact, activate above-mentioned catalyst precursor, combination condition comprises: the about 250-300 of temperature ℃, about 0.5-5hr, the about 1psig of steam partial pressure, hydrogen is about 1.3-1.5 with the carbon monoxide ratio, and this combination condition can improve the selectivity of deactivated catalyst effectively in the Fischer-Tropsch of follow-up generation liquid hydrocarbon reaction.
32, a kind of Fischer-Tropsch for preparing catalytic activity helps the method for catalytic iron catalyst, this method comprises, activate oxides-containing iron and help the potassium of catalytic amount and the nonactive catalyst precursor of copper, above-mentioned ferriferous oxide is selected from hydrous iron oxide and mainly contains the deposition of iron oxide of rhombohedral iron ore, above-mentioned activation is contacted under the temperature and pressure that improves with the mixture of gaseous hydrogen and carbon monoxide by above-mentioned nonactive catalyst precursor and works, and its improvement comprises:
Under combination condition, make this catalyst precursor activation by carrying out above-mentioned contact, combination condition comprises: the about 250-300 of temperature ℃, 0.5-5hr, the 1psig steam partial pressure, hydrogen and the about 1.3-1.5 of carbon monoxide ratio, this combination condition can improve the selectivity of deactivated catalyst effectively in the Fischer-Tropsch of follow-up generation liquid hydrocarbon reaction.
33, a kind of preparation is used for the method that helps catalytic iron catalyst of slurry Fischer-Tropsch reactor, and it comprises following steps:
Below 150 ℃ the copper and the dissolved ferric iron of predetermined amount formed Iron nitrate in nitric acid, iron nitrate and copper nitrate solution;
During dissolving step, stir this solution with the oxygen-containing gas bubbling;
The sufficient hydrogen ammonium oxide is added precipitated catalyst precursor in the solution that forms;
The ammonium nitrate that forms when removing precipitation;
Wash this catalyst precursor;
Mix the aqueous slurry that contains salt of wormwood, it is added in the catalyst precursor can fully help this catalyst consumption of catalysis;
The catalyst precursor of dry mixed and salt of wormwood promotor, and screening is into about the particle of 5-50 micron;
This solid that obtains in air heats the fully long time to drive away residual moisture at about 600 °F, then, cools off this catalyzer gradually, makes it be suitable for inducing in the Fischer-Tropsch slurry reaction activation also to use continuously.
34, a kind of diesel-dope that reduces the particulate emission rate, comprise synthetic pulpous state raw gasline or diesel oil or the mixture of the two, this additive contains by the Fischer-Tropsch reaction alkylol cpd that contains 5 carbon atoms that helps catalytic ferrum-based catalyst to produce at least, this additive adds diesel oil fuel with enough amount, produces in diesel oil and is at least 2%(weight) oxygen level and be no more than the viscosity criterion restriction of diesel oil.
35, the method for the wax that helps catalytic ferrum-based catalyst generation is used in a kind of cracking in slurry-phase reactor by the Fischer-Tropsch building-up reactions, this method comprises, wax is heated to 770 (410 ℃) fully long time to produce the diesel oil part, raw gasline part and remaining wax.
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| CN 94106734 CN1113905A (en) | 1994-06-21 | 1994-06-21 | Process for the production of hydrocarbons |
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| CN 94106734 CN1113905A (en) | 1994-06-21 | 1994-06-21 | Process for the production of hydrocarbons |
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| WO2010066129A1 (en) * | 2008-12-11 | 2010-06-17 | 中科合成油技术有限公司 | Method for continuously preparing metal oxides catalyst and apparatus thereof |
| WO2010094226A1 (en) * | 2009-02-20 | 2010-08-26 | 中科合成油技术有限公司 | Fischer-tropsch synthesis fe-based catalyst, process of preparation and application thereof |
| CN102601057A (en) * | 2012-03-12 | 2012-07-25 | 神华集团有限责任公司 | Method for screening catalyst for Fischer Tropsch synthesis |
| CN101965321B (en) * | 2008-01-04 | 2013-09-25 | 艾尼股份公司 | Process for stabilizing the performances of a catalyst for fischer tropsch reaction |
| CN104053501A (en) * | 2011-10-26 | 2014-09-17 | 瑞恩泰克公司 | Iron-based Fischer-Tropsch catalyst |
| CN108545759A (en) * | 2018-04-18 | 2018-09-18 | 中国天辰工程有限公司 | A kind of preparation method and its evaluating apparatus of the sial phosphorus molecular sieve of modification |
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1994
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| CN101965321B (en) * | 2008-01-04 | 2013-09-25 | 艾尼股份公司 | Process for stabilizing the performances of a catalyst for fischer tropsch reaction |
| WO2010066129A1 (en) * | 2008-12-11 | 2010-06-17 | 中科合成油技术有限公司 | Method for continuously preparing metal oxides catalyst and apparatus thereof |
| RU2477653C2 (en) * | 2008-12-11 | 2013-03-20 | Синфьюэлс Чайна Текнолоджи Ко., Лтд. | Method and device for continuous production of metal oxide catalyst |
| US9012351B2 (en) | 2008-12-11 | 2015-04-21 | Synfuels China Technology Co., Ltd. | Method for continuously preparing metal oxides catalyst and apparatus thereof |
| WO2010094226A1 (en) * | 2009-02-20 | 2010-08-26 | 中科合成油技术有限公司 | Fischer-tropsch synthesis fe-based catalyst, process of preparation and application thereof |
| CN104053501A (en) * | 2011-10-26 | 2014-09-17 | 瑞恩泰克公司 | Iron-based Fischer-Tropsch catalyst |
| CN102601057A (en) * | 2012-03-12 | 2012-07-25 | 神华集团有限责任公司 | Method for screening catalyst for Fischer Tropsch synthesis |
| CN102601057B (en) * | 2012-03-12 | 2013-11-20 | 神华集团有限责任公司 | Method for screening catalyst for Fischer Tropsch synthesis |
| CN108545759A (en) * | 2018-04-18 | 2018-09-18 | 中国天辰工程有限公司 | A kind of preparation method and its evaluating apparatus of the sial phosphorus molecular sieve of modification |
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