CN106947511A - F- T synthesis prepares the method for liquid hydrocarbon and prepares the method for catalyst - Google Patents
F- T synthesis prepares the method for liquid hydrocarbon and prepares the method for catalyst Download PDFInfo
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- CN106947511A CN106947511A CN201710132253.8A CN201710132253A CN106947511A CN 106947511 A CN106947511 A CN 106947511A CN 201710132253 A CN201710132253 A CN 201710132253A CN 106947511 A CN106947511 A CN 106947511A
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- catalyst
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- liquid hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 95
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 74
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 74
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 41
- 239000010941 cobalt Substances 0.000 claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000000446 fuel Substances 0.000 abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000001993 wax Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002737 fuel gas Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The method of liquid hydrocarbon is prepared the invention discloses F- T synthesis and prepares the method for catalyst, wherein, the method that F- T synthesis prepares liquid hydrocarbon includes：Catalyst is fitted into fixed bed reactors, and reduces in reducing atmosphere the catalyst；H is passed through into the fixed bed reactors2F- T synthesis is carried out with CO synthesis gas, to obtain hydrocarbon product, wherein, the carrier of metallic cobalt of the catalyst comprising 5 25 parts by weight, the auxiliary agent of 0.01 10 parts by weight and 75 95 parts by weight, the carrier is made up of the carborundum of the indifferent oxide, the molecular sieve of 20 40 parts by weight and 20 40 parts by weight of 40 60 parts by weight.The method that liquid hydrocarbon is prepared by using the F- T synthesis, can significantly improve the reaction rate of Fischer-Tropsch synthesis, it is particularly possible to significantly improve the conversion ratio of carbon monoxide and the yield of target liq HC fuel, reduce the generation of heavy hydrocarbon.
Description
Technical field
The invention belongs to chemical field, specifically, the present invention relates to the method and system that F- T synthesis prepares liquid hydrocarbon
The method of standby catalyst.
Background technology
Nineteen twenty-three, German scholar F.Fischer and H.Tropsch are found that and can be produced by CO catalytic hydrogenations with Synthin
The method of product, afterwards Fiscber-Tropscb synthesis developed rapidly.Germany built up first Fisher-Tropsch synthesis fuels factory in the world in 1934,
South Africa Sasol companies built up in nineteen fifty-five first coal-to-oil factory and operate so far, its three from synthesis gas production fuel and
The factory of chemicals, produces 5200000 tons of liquid fuel, 2,800,000 tons of other chemicals per year.The early 1990s, Shell companies propose
Heavy hydrocarbon is first converted synthesis gas to, intermediate oil (diesel oil, aviation kerosine, naphtha are produced in then heavy hydrocarbon cracking
Deng) SMDS (Shell Middle Distillate Synthesis) technique, and realized 50 in Malaysia in 1993 years
Ten thousand tons/year of commercial scales.
F- T synthesis is most characterized in significantly that product distribution is wide, and the selectivity of single product is low.Traditional Fischer-Tropsch Synthesis is
Using cobalt as catalyst, products obtained therefrom composition is complicated, and poor selectivity, light liquids hydrocarbon is few, and heavy paraffinic waxes hydrocarbon is more.Its main component
It is linear paraffin, alkene, a small amount of aromatic hydrocarbons and byproduct water and carbon dioxide.Traditional Fischer-Tropsch synthetic meets the ASF regularities of distribution,
The more wax of generation, and the liquid fuel selectivity largely for industrial production needs is relatively low.At present Fischer Tropsch waxes again through adding
The procedure of hydrogen process production liquid fuel is cumbersome, and cost is higher.Therefore the generation of heavy wax is reduced, with high selectivity
Generation target hydro carbons (liquid fuel, heavy hydrocarbon or alkene) is the direction of F- T synthesis and catalyst research and development all the time.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is to propose that F- T synthesis prepares the method for liquid hydrocarbon and prepares the method for catalyst, is closed by using the Fischer-Tropsch
Liquid hydrocarbon can be prepared with high selectivity into the method for preparing liquid hydrocarbon.Meanwhile, the method system that catalyst is prepared using this
Standby catalyst has higher catalytic activity, catalysis can prepare liquid fuel with high selectivity, and this prepares catalyst
Method is simple, low cost, environment-friendly, with heavy industrialization prospect.
According to an aspect of the present invention, the present invention proposes a kind of method that F- T synthesis prepares liquid hydrocarbon, according to
Embodiments of the invention, including：
Catalyst is fitted into fixed bed reactors, and reduces in reducing atmosphere the catalyst；
H is passed through into the fixed bed reactors2F- T synthesis is carried out with CO synthesis gas, to obtain hydrocarbon product,
Wherein, catalyst includes the metallic cobalt, the auxiliary agent of 0.01-10 parts by weight and 75-95 parts by weight of 5-25 parts by weight
Carrier,
Carrier by 40-60 parts by weight indifferent oxide, the molecular sieve of 20-40 parts by weight and 20-40 parts by weight carbonization
Silicon is constituted.
According to a particular embodiment of the invention, first, fischer-tropsch synthetic catalyst is reduced in fixed bed reactors, profit
With the catalyst H after reduction2F- T synthesis is carried out with CO, hydrocarbon product is finally given.Wherein, catalyst is used as work using cobalt
Property composition, using indifferent oxide, three kinds of components of molecular sieve and carborundum collectively as carrier, and adds a small amount of auxiliary agent.Pass through
The method that liquid hydrocarbon is prepared using the F- T synthesis, can not only significantly improve the reaction rate and an oxygen of Fischer-Tropsch synthesis
Change charcoal percent conversion, target liq HC fuel yield can also be improved, and reduce the generation of the solid products such as wax.Thus, lead to
The method that liquid hydrocarbon is prepared using the F- T synthesis is crossed, the efficiency that F- T synthesis prepares liquid hydrocarbon can be significantly improved, made
Liquid hydrocarbon is accounted for more than 60 weight % in hydrocarbon product.
In addition, the method that F- T synthesis according to the above embodiment of the present invention prepares liquid hydrocarbon can also be with following attached
Plus technical characteristic：
In some embodiments of the invention, H2Mol ratio with CO is (1-3)：1.
In some embodiments of the invention, the pressure of F- T synthesis is 0.5-3.0MPa.
In some embodiments of the invention, indifferent oxide is in silica, aluminum oxide, zirconium oxide and titanium oxide
At least one.
In some embodiments of the invention, molecular sieve is selected from SBA-15, MCM-41, MCM-48, beta-molecular sieve, super steady Y
At least one in type molecular sieve, ZSM-5, ZSM-22, SAPO-34 and SAPO-11.
In some embodiments of the invention, auxiliary agent be in Ca, Mg, Cu, Mn, Fe, Zn, La, Zr, Ru and Pt extremely
Few one kind.
According to another aspect of the present invention, F- T synthesis described in preceding embodiment is prepared the invention allows for one kind to prepare
The method of used catalyst in the method for liquid hydrocarbon, embodiments in accordance with the present invention, this method includes：
Soluble cobalt and builder salts are subjected to mixed dissolution, to obtain solutions preparatory；
Indifferent oxide, molecular sieve and carborundum are mixed according to predetermined ratio, to obtain carrier；
The carrier is subjected to impregnation process in the solutions preparatory, makes the soluble cobalt and the builder salts negative
Carry on the carrier, to obtain catalyst preparation body；
The catalyst preparation body is dried and calcination process, to obtain fischer-tropsch synthetic catalyst.
Catalyst can be effectively prepared by using the above method, this method preparation process is simple, production cost
It is low and environment-friendly, it is pollution-free.The catalyst prepared by the above method is using cobalt as active component, with inertia oxygen
Compound, three kinds of components of molecular sieve and carborundum have a small amount of auxiliary agent collectively as carrier.Thus, by using party's legal system
Standby obtained catalyst has good catalytic activity, can significantly improve the reaction rate and carbon monoxide of Fischer-Tropsch synthesis
Conversion ratio.In addition, the longer liquid hydrocarbon fuel of the being also an option that property of catalyst catalysis F- T synthesis carbochain, reduces methane
Deng the generation of gaseous fuel and solid wax.Therefore, the method for preparing catalyst of the above embodiment of the present invention is closed in production Fischer-Tropsch
There is widely application prospect and market value into liquefied hydrocarbon aspect.
In addition, the method according to the above embodiment of the present invention for preparing catalyst can also have technology additional as follows special
Levy：
In some embodiments of the invention, builder salts are selected from calcium nitrate, magnesium nitrate, copper nitrate, manganese nitrate, nitric acid
At least one in iron, zinc nitrate, lanthanum nitrate, zirconium nitrate, ruthenium trichloride, nitric acid ruthenium, chloroplatinic acid and zirconium oxychloride,
In some embodiments of the invention, soluble cobalt is selected from cobalt nitrate, cobalt acetate, cobalt oxalate and citric acid cobalt
In at least one.
In some embodiments of the invention, the soluble cobalt and the builder salts are carried out using water and/or alcohol
Mixed dissolution.
Embodiment
Embodiments of the invention are described below in detail, it is intended to for explaining the present invention, and it is not intended that to the present invention's
Limitation.
According to an aspect of the present invention, the present invention proposes a kind of method that F- T synthesis prepares liquid hydrocarbon, according to
Embodiments of the invention, including：
Catalyst is fitted into fixed bed reactors, and reduces in reducing atmosphere the catalyst；
H is passed through into the fixed bed reactors2F- T synthesis is carried out with CO synthesis gas, to obtain hydrocarbon product,
Wherein, catalyst includes the metallic cobalt, the auxiliary agent of 0.01-10 parts by weight and 75-95 parts by weight of 5-25 parts by weight
Carrier,
Carrier by 40-60 parts by weight indifferent oxide, the molecular sieve of 20-40 parts by weight and 20-40 parts by weight carbonization
Silicon is constituted.
According to a particular embodiment of the invention, first, fischer-tropsch synthetic catalyst is reduced in fixed bed reactors, connect
The synthesis gas for being passed through H2 and CO using the catalyst after reduction and carry out F- T synthesis, finally give hydrocarbon product liquid hydrocarbon
Class.Wherein, catalyst is using cobalt as active component, using indifferent oxide, three kinds of components of molecular sieve and carborundum collectively as
Carrier, and add a small amount of auxiliary agent.The method that liquid hydrocarbon is prepared by using the F- T synthesis, can not only significantly improve Fischer-Tropsch
The reaction rate of synthetic reaction and the conversion ratio of carbon monoxide, can also improve target liq HC fuel yield, and reduce first
The generation of the gaseous fuels such as alkane and solid wax.Thus, the method that liquid hydrocarbon is prepared by using the F- T synthesis, can be notable
The efficiency that F- T synthesis prepares liquid hydrocarbon is improved, liquid hydrocarbon in hydrocarbon product is accounted for more than 60 weight %.
According to a particular embodiment of the invention, F- T synthesis prepares the carrier of catalyst in the method for liquid hydrocarbon by inertia
Oxide, molecular sieve and carborundum composition.Wherein, indifferent oxide is conventional F- T synthesis carrier, can reduce catalyst
Cost；Molecular sieve has larger specific surface area, it is possible thereby to significantly improve the load capacity of active component cobalt, and then significantly carries
The catalytic activity of high fischer-tropsch synthetic catalyst；And carborundum thermal conductivity is good, it can be prevented effectively from Fischer-Tropsch synthesis due to putting
Hot-spot phenomenon and thing followed reactivity hot and produce decline.Inventor find, by by indifferent oxide,
Molecular sieve and carborundum are combined the carrier of catalyst in the method that liquid hydrocarbon is prepared as F- T synthesis, can significantly carry
The load capacity of active component cobalt in high catalyst, and then significantly improve the catalytic activity of catalyst, it is ensured that Fischer-Tropsch synthesis
It is smoothed out.In addition, inventor also found, by using above-mentioned carrier combination cobalt as active component, catalyst can be caused
With good catalytic selectivity, CO conversion when F- T synthesis prepares liquid hydrocarbon is significantly improved, expense is effectively catalyzed
Synthesizing liquid fuel is held in the palm, the generation of the fuel gas such as methane is reduced.
According to a particular embodiment of the invention, in carrier, the content of indifferent oxide is 40-60 weight %, molecular sieve
Content is 20-40 weight %, and the content of carborundum is 20-40 weight %.Inventor has found, passes through indifferent oxide, molecular sieve
Be combined carrier as catalyst according to above-mentioned content with three kinds of components of carborundum, can significantly improve catalyst activity into
Divide the load capacity of cobalt and the stability of catalyst.According to the present invention specific example, it is above-mentioned by indifferent oxide, molecular sieve and
In the carrier of carborundum composition, inventor has found so that wherein the quality of two kinds of less components of content and account for carrier gross mass
10-50%.According to the specific example of the present invention, the 40% or 50% of carrier gross mass is preferably accounted for.For example, molecular sieve and carbonization
The quality of silicon and account for the 40% of carrier gross mass.It is possible thereby to which molecular sieve and carborundum occupy less ratio, indifferent oxide is accounted for
There is larger proportion, it is possible thereby to significantly improve the load capacity and load stability of the carrier in fischer-tropsch synthetic catalyst, and drop
Low production cost.
According to a particular embodiment of the invention, as one of carrier component indifferent oxide particular type not by spy
Do not limit, such as, according to the specific example of the present invention, indifferent oxide can be selected from silica, aluminum oxide, zirconium oxide and oxygen
Change at least one in titanium.Inventor is had found, F- T synthesis can be further improved by using above-mentioned several indifferent oxides
The stability of reacting middle catalyst, while reaching the purpose of reduction production cost.
According to a particular embodiment of the invention, do not limited especially as the particular type of the molecular sieve of one of carrier component
System, such as, according to the specific example of the present invention, molecular sieve is selected from SBA-15, MCM-41, MCM-48, beta-molecular sieve, superstable gamma-type
At least one in molecular sieve, ZSM-5, ZSM-22, SAPO-34 and SAPO-11.Molecular sieve has larger specific surface area,
By using molecular sieve as one of component of carrier in the present invention, the load capacity of active component cobalt can be significantly improved, and then
Significantly improve the catalytic activity of fischer-tropsch synthetic catalyst, it is particularly possible to significantly improve catalytic selectivity, improve catalysis F- T synthesis
The yield of liquefied hydrocarbon, reduces the generation of the fuel gas such as methane.
According to a particular embodiment of the invention, the particular type of auxiliary agent is not particularly restricted, such as according to the present invention's
Specific example, auxiliary agent is at least one in Ca, Mg, Cu, Mn, Fe, Zn, La, Zr, Ru and Pt.In the present invention, by
A small amount of auxiliary agent is added in catalyst further to improve the stability and catalytic activity of catalyst, weakens active component cobalt with carrying
The conversion ratio and the yield of liquid hydrocarbon fuel of carbon monoxide in interaction between body, and then raising Fischer-Tropsch synthesis,
The generation of the fuel gas such as methane is reduced, promotes the efficient progress of Fischer-Tropsch synthesis.
The method that liquid hydrocarbon is prepared according to the F- T synthesis of the specific embodiment of the invention, including：Catalyst is loaded solid
In fixed bed reactor, and reduce in reducing atmosphere the catalyst；H is passed through into the fixed bed reactors2With CO conjunction
F- T synthesis is carried out into gas, to obtain hydrocarbon product.
According to a particular embodiment of the invention, wherein, above-mentioned H2Mol ratio with CO is (1-3)：1.Thus, not only can be with
Significantly improve the conversion ratio of carbon monoxide, moreover it is possible to improve the utilization rate of raw material, it is to avoid wastage of material.
According to a particular embodiment of the invention, the pressure of F- T synthesis is 0.5-3.0MPa.Inventor has found, using Fischer-Tropsch
During the method for synthetically prepared liquid hydrocarbon, under the pressure condition, CO conversion is higher, and is conducive to liquefied hydrocarbon
Generation, thus, it is possible to improve the efficiency that F- T synthesis prepares liquid hydrocarbon by controlling reaction pressure.
According to a particular embodiment of the invention, the temperature of F- T synthesis is 200-260 degrees Celsius.Thus, it is possible to ensure expense
Hold in the palm being smoothed out for synthetically prepared liquid hydrocarbon, it is to avoid excessive gaseous product is produced when temperature is too high and temperature is too low causes
The problem of reactivity is low, and then ensure the yield of liquefied hydrocarbon.
The method that liquid hydrocarbon is prepared by using the F- T synthesis of the embodiment of the present invention, can not only significantly improve Fischer-Tropsch
The reaction rate of synthetic reaction and the conversion ratio of carbon monoxide, can also improve target liq HC fuel yield, and reduce first
The generation of the gaseous fuels such as alkane and solid wax.Thus, the method that liquid hydrocarbon is prepared by using the F- T synthesis, can be notable
The efficiency that F- T synthesis prepares liquid hydrocarbon is improved, liquid hydrocarbon in hydrocarbon product is accounted for more than 60 weight %.
According to another aspect of the present invention, F- T synthesis described in preceding embodiment is prepared the invention allows for one kind to prepare
The method of used catalyst in the method for liquid hydrocarbon.
Embodiments in accordance with the present invention, this method includes：Soluble cobalt and builder salts are subjected to mixed dissolution, so as to
To solutions preparatory；Indifferent oxide, molecular sieve and carborundum are mixed according to predetermined ratio, to obtain carrier；It will carry
Body carries out impregnation process in solutions preparatory, soluble cobalt and builder salts is supported on carrier, pre- to obtain catalyst
Standby body；Catalyst preparation body is dried and calcination process, to obtain fischer-tropsch synthetic catalyst.
Catalyst can be effectively prepared by using the above method, this method preparation process is simple, production cost
It is low and environment-friendly, it is pollution-free.The catalyst prepared by the above method is using cobalt as active component, with inertia oxygen
Compound, three kinds of components of molecular sieve and carborundum have a small amount of auxiliary agent collectively as carrier.Thus, by using party's legal system
Standby obtained catalyst has good catalytic activity, can significantly improve the reaction rate and carbon monoxide of Fischer-Tropsch synthesis
Conversion ratio.In addition, the longer liquid hydrocarbon fuel of the being also an option that property of catalyst catalysis F- T synthesis carbochain, reduces methane
Deng the generation of gaseous fuel.Therefore, the method for preparing catalyst of the above embodiment of the present invention is in production F- T synthesis liquid hydrocarbon
There is widely application prospect and market value in terms of class.
According to a particular embodiment of the invention, the method for preparing catalyst below to the above embodiment of the present invention is carried out in detail
Thin description.
First, the raw material for preparing catalyst is soluble cobalt, builder salts and carrier, and wherein carrier is aoxidized by inertia
Thing, molecular sieve and carborundum are mixed to get according to predetermined ratio.
According to a particular embodiment of the invention, soluble cobalt is selected from cobalt nitrate, cobalt acetate, cobalt oxalate and citric acid cobalt
In at least one.From there through above-mentioned soluble cobalt is used, cobalt can be enable successfully to be supported on carrier, so as to make
The standby catalyst obtained with cobalt as active component.The catalyst prepared by the above method using cobalt as activity into
Point, and using indifferent oxide, three kinds of components of molecular sieve and carborundum collectively as carrier, and containing a small amount of auxiliary agent, thus may be used
Make it that catalyst has preferable stability, catalytic activity and catalytic selectivity.Thus, it can show by using the catalyst
The yield for improving liquid hydrocarbon fuel in Fischer-Tropsch synthesis is write, the generation of the fuel gas such as methane is reduced.
According to a particular embodiment of the invention, builder salts are selected from calcium nitrate, magnesium nitrate, copper nitrate, manganese nitrate, nitric acid
At least one in iron, zinc nitrate, lanthanum nitrate, zirconium nitrate, ruthenium trichloride, nitric acid ruthenium, chloroplatinic acid and zirconium oxychloride, above-mentioned auxiliary agent
Salt is converted into auxiliary agent Ca, Mg, Cu, Mn, Fe, Zn, La, Zr, Ru and Pt etc. oxide by follow-up calcination process.Pass through
It can weaken the interaction between active component cobalt and carrier in the above-mentioned auxiliary agent of supported on carriers, further improve catalyst
The conversion ratio and the yield of liquid hydrocarbon fuel of carbon monoxide in stability and catalytic activity, and then raising Fischer-Tropsch synthesis,
The generation of the fuel gas such as methane is reduced, promotes the efficient progress of Fischer-Tropsch synthesis.
According to a particular embodiment of the invention, soluble cobalt and builder salts are subjected to mixed dissolution, to be prepared
Solution.
According to a particular embodiment of the invention, soluble cobalt and builder salts can be mixed using water and/or alcohol
Dissolving.Specifically, alcohol is at least one in methanol, ethanol, propyl alcohol, isopropanol and n-butanol.Thus using above-mentioned molten
Agent is more environmentally-friendly, to environment non-hazardous after roasting volatilization.
According to a particular embodiment of the invention, indifferent oxide, molecular sieve and carborundum are mixed according to predetermined ratio
Close, to obtain carrier.
Inventor has found, by the way that indifferent oxide, molecular sieve and carborundum three to be combined and be used as F- T synthesis system
The carrier of catalyst, can significantly improve the load capacity of active component cobalt in catalyst, Jin Erxian in the method for standby liquid hydrocarbon
Write the catalytic activity for improving catalyst, it is ensured that Fischer-Tropsch synthesis is smoothed out.And inventor also found, in three kinds of components
The catalytic performance of catalyst can all be influenceed by lacking any one.The thermal conductivity of catalyst can be influenceed by for example saving carborundum so that
The heated inequality of catalyst, and then influence catalytic performance；And Carriers Active composition cobalt and auxiliary agent can then be significantly affected by saving molecular sieve
Load capacity, and then reduce catalyst catalytic activity and liquid hydrocarbon selectivity.
According to a particular embodiment of the invention, in carrier, the content of indifferent oxide is 40-60 weight %, molecular sieve
Content is 20-40 weight %, and the content of carborundum is 20-40 weight %.Inventor has found, passes through indifferent oxide, molecular sieve
Be combined carrier as catalyst according to above-mentioned content with three kinds of components of carborundum, can significantly improve catalyst activity into
Divide the load capacity of cobalt and the stability of catalyst.
According to a particular embodiment of the invention, carrier is subjected to impregnation process in solutions preparatory, make soluble cobalt and
Builder salts are supported on carrier, to obtain catalyst preparation body.
According to a particular embodiment of the invention, impregnation process can carry out completing for 6-50 hours under 10-60 degrees Celsius.By
This can make it that soluble cobalt and builder salts are equably supported on carrier by using above-mentioned immersion condition.
According to a particular embodiment of the invention, processing and calcination process finally is dried in catalyst preparation body, so as to
Obtain fischer-tropsch synthetic catalyst.Solvent etc. can be removed from there through calcination process, and causes soluble cobalt and builder salts warp
Cross roasting and be converted into cobalt and auxiliary agent.
According to a particular embodiment of the invention, drying process is to carry out completing for 6-48 hours under 70-150 degrees Celsius.
According to a particular embodiment of the invention, calcination process is to carry out completing for 3-24 hours under 350-600 degrees Celsius.From there through
Active component Load Balanced can be made using above-mentioned drying process and calcination process condition, the catalyst heat endurance prepared
It is good.
The catalyst that method according to the above embodiment of the present invention is prepared, not only with preferable stability, also has
Higher catalytic activity and catalytic selectivity, and then be conducive to selective catalysis Fischer-Tropsch synthesis and generate the longer liquid of carbochain
State HC fuel, reduces the generation of the gaseous fuels such as methane and solid wax.
Embodiment 1
Carrier is the complex carrier of titanium oxide, SBA-15 and carborundum composition.Weigh 20g titanium oxide, SBA-15 points of 20g
Son sieve, 10g carborundum is well mixed.1.86g zirconium nitrates, 43.52g cabaltous nitrate hexahydrates are weighed, 100ml deionizations are dissolved in
Water, adds above-mentioned titanium dioxide carrier 50g, stands 24h, then 110 DEG C of dried overnights in baking oven, and dried solid is placed in horse
Not 400 DEG C of roasting 4h of stove, the solid powder after roasting is molded, crushed, and screening obtains catalyst 1.
Weigh above catalyst to be fitted into fixed bed reactors, N is used at ambient pressure2The H of dilution2(H2Molar content 5%, it is empty
Fast 2000h-1) reduce 10h at 450 DEG C.Less than 100 DEG C, switching and merging gas are cooled to after temperature programming to 450 DEG C of reduction.Reaction
Condition is：230 DEG C, 2.0MPa, 1000h-1, H2/ CO (V/V)=2/1.Reached at reaction conditions after induction 5-10h optimal anti-
Answer state, chromatography product and tail gas composition.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 2
Carrier is the complex carrier of zirconium oxide, super-stable Y molecular sieves and carborundum composition.10g zirconium oxides are weighed, 10g surpasses
Stabilization Y-type molecular sieve (USY), 30g carborundum is well mixed.4.32g manganese nitrates are weighed, 43.52g cabaltous nitrate hexahydrates are dissolved in
The mixed liquor of 100ml deionized waters and 100ml ethanol, adds above-mentioned carrier 50g, stands 24h, then 110 DEG C of mistakes in baking oven
Night is dried, and dried solid is placed in 400 DEG C of roasting 5h of Muffle furnace, and the solid powder after roasting is molded, crushed, screening is obtained
To catalyst 2.
Weigh above catalyst to be fitted into fixed bed reactors, N is used at ambient pressure2The H of dilution2(H2Molar content 10%,
Air speed 2000h-1) reduce 6h at 450 DEG C.Less than 100 DEG C, switching and merging gas are cooled to after temperature programming to 450 DEG C of reduction.Reaction
Condition is：230 DEG C, 2.0MPa, 1000h-1, H2/ CO (V/V)=2/1.Reached at reaction conditions after induction 5-10h optimal anti-
Answer state, chromatography product and tail gas composition.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 3
Carrier is the complex carrier of silica, MCM-48 molecular sieves and carborundum composition.Weigh the unformed titanium dioxides of 30g
Silicon, 12g MCM-48 molecular sieves, 8g carborundum is well mixed.Weigh 43.52g cabaltous nitrate hexahydrates, 2.31g ferric nitrates,
0.67g nitric acid rutheniums, are dissolved in 250ml absolute ethyl alcohols, add above-mentioned carrier 50g, stand 24h, then 110 DEG C of mistakes in baking oven
Night is dried, and dried solid is placed in 500 DEG C of roasting 5h of Muffle furnace, and the solid powder after roasting is molded, crushed, screening is obtained
To catalyst 3.
Weigh above catalyst to be fitted into fixed bed reactors, N is used at ambient pressure2The H of dilution2(H2Molar content 5%, it is empty
Fast 2000h-1) reduce 6h at 450 DEG C.Less than 100 DEG C, switching and merging gas are cooled to after temperature programming to 450 DEG C of reduction.React bar
Part is：240 DEG C, 2.0MPa, 1000h-1, H2/ CO (V/V)=2/1.At reaction conditions optimum response is reached after induction 5-10h
State, chromatography product and tail gas composition.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 4
Carrier is the complex carrier of inert alumina, SAPO-34 molecular sieves and carborundum composition.Weigh the oxidation of 25g inertia
Aluminium, 15g SAPO-34 molecular sieves, 10g carborundum is well mixed.Weigh 43.52g cabaltous nitrate hexahydrates, 9.31g zirconium oxychlorides,
150ml deionized waters are dissolved in, above-mentioned carrier 50g is added, 24h are stood, then 110 DEG C of dried overnights in baking oven, after drying
Solid be placed in 400 DEG C of Muffle furnace roasting 4h, the solid powder after roasting is molded, crushed, screening obtains catalyst 4.
Weigh above catalyst to be fitted into fixed bed reactors, N is used at ambient pressure2The H of dilution2(H2Molar content 5%, it is empty
Fast 2000h-1) reduce 10h at 450 DEG C.Less than 100 DEG C, switching and merging gas are cooled to after temperature programming to 450 DEG C of reduction.Reaction
Condition is：220 DEG C, 2.0MPa, 1000h-1, H2/ CO (V/V)=2/1.Reached at reaction conditions after induction 5-10h optimal anti-
Answer state, chromatography product and tail gas composition.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 5
The preparation method and use condition be the same as Example 1 of catalyst, except that the reaction condition of F- T synthesis is：Temperature
240 DEG C of degree, pressure 2.0MPa, air speed 1000h-1.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 6
The preparation method and use condition be the same as Example 2 of catalyst, except that the reaction condition of F- T synthesis is：Temperature
240 DEG C of degree, pressure 2.0MPa, air speed 1000h-1.Fischer-Tropsch synthesis the results are shown in Table 1.
Embodiment 7
The preparation method and use condition be the same as Example 3 of catalyst, except that the reaction condition of F- T synthesis is：Temperature
230 DEG C of degree, pressure 2.0MPa, air speed 1000h-1.Fischer-Tropsch synthesis the results are shown in Table 1.
Comparative example 1
The basic be the same as Example 1 of preparation method of catalyst, difference is complex carrier by 25g titanium oxide and 25g SBA-15
Molecular sieve is constituted, and eliminates carborundum.
Fischer-Tropsch synthesis condition be the same as Example 1.Fischer-Tropsch synthesis the results are shown in Table 1.
Comparative example 2
The basic be the same as Example 1 of preparation method of catalyst, difference is complex carrier by 25g titanium oxide and 25g carborundum
Composition, eliminates molecular sieve.
Fischer-Tropsch synthesis condition be the same as Example 1.Fischer-Tropsch synthesis the results are shown in Table 1.
Table 1
Thus, the method for preparing liquid hydrocarbon by using the F- T synthesis of several embodiments above can be with selective catalysis
Fischer-Tropsch synthesis simultaneously generates the longer liquid hydrocarbon fuel of carbochain, reduces the generation of the gaseous fuel such as methane, enable in particular to by
CO conversion is improved to more than 80%, and the yield of liquefied hydrocarbon is above more than 74 weight %.
Pass through the comparison of comparative example 1 and 2 and the reaction result of embodiment 1, it can be deduced that following results：In catalyst carrier
Eliminate carborundum so that liquefied hydrocarbon yield is reduced to less than 62% in catalyst Fischer-Tropsch synthesis.Eliminate point
Son sieve so that the conversion ratio of carbon monoxide is reduced to less than 70% in catalyst Fischer-Tropsch synthesis.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be any
Combined in an appropriate manner in individual or multiple embodiments or example.In addition, in the case of not conflicting, the technology of this area
Not be the same as Example or the feature of example and non-be the same as Example or example described in this specification can be combined by personnel
And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of method that F- T synthesis prepares liquid hydrocarbon, it is characterised in that
Catalyst is fitted into fixed bed reactors, and reduces in reducing atmosphere the catalyst；
H is passed through into the fixed bed reactors2F- T synthesis is carried out with CO synthesis gas, to obtain hydrocarbon product,
Wherein, the catalyst includes the metallic cobalt, the auxiliary agent of 0.01-10 parts by weight and 75-95 parts by weight of 5-25 parts by weight
Carrier,
The carrier by 40-60 parts by weight indifferent oxide, the molecular sieve of 20-40 parts by weight and 20-40 parts by weight carbonization
Silicon is constituted.
2. the method that F- T synthesis according to claim 1 prepares liquid hydrocarbon, it is characterised in that the H2With rubbing for CO
You are than being (1-3)：1.
3. the method that F- T synthesis according to claim 1 prepares liquid hydrocarbon, it is characterised in that the F- T synthesis
Pressure is 0.5-3.0MPa.
4. the method that F- T synthesis according to claim 1 prepares liquid hydrocarbon, it is characterised in that the indifferent oxide
For at least one in silica, aluminum oxide, zirconium oxide and titanium oxide.
5. the method that F- T synthesis according to claim 1 prepares liquid hydrocarbon, it is characterised in that the molecular sieve is choosing
From in SBA-15, MCM-41, MCM-48, beta-molecular sieve, super-stable Y molecular sieves, ZSM-5, ZSM-22, SAPO-34 and SAPO-11
At least one.
6. the method that F- T synthesis according to claim 1 prepares liquid hydrocarbon, it is characterised in that the auxiliary agent be selected from
At least one in Ca, Mg, Cu, Mn, Fe, Zn, La, Zr, Ru and Pt.
7. a kind of method for preparing catalyst, the catalyst is that any one of the claim 1-6 F- T synthesis prepares liquid
Used catalyst in the method for hydro carbons, it is characterised in that including：
Soluble cobalt and builder salts are subjected to mixed dissolution, to obtain solutions preparatory；
Indifferent oxide, molecular sieve and carborundum are mixed according to predetermined ratio, to obtain carrier；
The carrier is subjected to impregnation process in the solutions preparatory, the soluble cobalt and the builder salts are supported on
On the carrier, to obtain catalyst preparation body；
The catalyst preparation body is dried and calcination process, to obtain fischer-tropsch synthetic catalyst.
8. the method for catalyst is prepared according to claim 7, it is characterised in that the builder salts are selected from calcium nitrate, nitre
Sour magnesium, copper nitrate, manganese nitrate, ferric nitrate, zinc nitrate, lanthanum nitrate, zirconium nitrate, ruthenium trichloride, nitric acid ruthenium, chloroplatinic acid and oxychlorination
At least one in zirconium.
9. the method for catalyst is prepared according to claim 7, it is characterised in that the soluble cobalt is selected from nitric acid
At least one in cobalt, cobalt acetate, cobalt oxalate and citric acid cobalt.
10. the method for catalyst is prepared according to claim 7, it is characterised in that use water and/or alcohol by the solubility
Cobalt salt and the builder salts carry out mixed dissolution.
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| WO2020125488A1 (en) * | 2018-12-21 | 2020-06-25 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by direct conversion of synthesis gas |
| CN114247443A (en) * | 2021-12-31 | 2022-03-29 | 南宁师范大学 | Preparation method of easily-reduced metal-doped cobalt-based catalyst |
| RU2772383C1 (en) * | 2018-12-21 | 2022-05-19 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Экэдеми Оф Сайенсиз | Catalyst and a method for producing liquid fuel with a low content of aromatic hydrocarbons by direct conversion of synthesis gas |
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| CN111068766B (en) * | 2018-10-18 | 2022-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and application thereof |
| CN111068765B (en) * | 2018-10-18 | 2022-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and application thereof |
| WO2020125488A1 (en) * | 2018-12-21 | 2020-06-25 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by direct conversion of synthesis gas |
| JP2022512467A (en) * | 2018-12-21 | 2022-02-04 | 中国科学院大▲連▼化学物理研究所 | Method for producing low-grade arene liquid fuel by direct conversion of catalyst and syngas |
| RU2772383C1 (en) * | 2018-12-21 | 2022-05-19 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Экэдеми Оф Сайенсиз | Catalyst and a method for producing liquid fuel with a low content of aromatic hydrocarbons by direct conversion of synthesis gas |
| JP7205943B2 (en) | 2018-12-21 | 2023-01-17 | 中国科学院大▲連▼化学物理研究所 | Method for producing lower arene liquid fuels by direct conversion of catalyst and synthesis gas |
| US11999910B2 (en) | 2018-12-21 | 2024-06-04 | Dalian Institute Of Chemical Physics, Cas | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel through direct conversion of syngas |
| CN114247443A (en) * | 2021-12-31 | 2022-03-29 | 南宁师范大学 | Preparation method of easily-reduced metal-doped cobalt-based catalyst |
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