CN1177018C - Catalyst for preparing heavy hydrocarbon from synthetic gas and its prepn. and application - Google Patents
Catalyst for preparing heavy hydrocarbon from synthetic gas and its prepn. and applicationInfo
- Publication number
- CN1177018C CN1177018C CNB011115831A CN01111583A CN1177018C CN 1177018 C CN1177018 C CN 1177018C CN B011115831 A CNB011115831 A CN B011115831A CN 01111583 A CN01111583 A CN 01111583A CN 1177018 C CN1177018 C CN 1177018C
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- catalyzer
- catalyst
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- hours
- heavy hydrocarbon
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- 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 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 45
- 238000007654 immersion Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 28
- 230000009466 transformation Effects 0.000 description 14
- -1 hexadecyl primary amine Chemical class 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 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 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241001415846 Procellariidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a catalyst for preparing heavy hydrocarbon by synthetic gas, a preparation method and an application of the catalyst. The catalyst comprises the constituents by weight percent: 50 to 95% of carrier and 5 to 50% of metallic cobalt, wherein the carrier can be pure silicon hexagon mesoporous molecular sieve HMS or amorphous silica; the 5 to 50 % of cobalt is loaded on the carrier by an immersion method. The present invention comprises the application conditions: the catalyst is loaded in a fixed bed reactor, the raw gas H2 /CO molar ratio is from 1.5 to 3.5, and the preferred molar ratio is from 1.8 to 2.2; the reaction temperature is 150 to 300 DEG C, and the preferred reaction temperature is from 180 to 260 DEG C; the reaction pressure is from 0.1 to 5.0MPa, and the preferred reaction pressure is from 1.0 to 4.5MPa; the raw gas air speed is from 250 to 2500NL/(L *h), and the preferred raw gas air speed is from 350 to 1000NL/(L *h). The heavy hydrocarbon selectivity reaches up to 88%, and the catalyst has favorable stability.
Description
The invention belongs to Catalysts and its preparation method and application, relate in particular to a kind of Catalysts and its preparation method and application that synthetic gas is produced heavy hydrocarbon that be used for.
Fischer-Tropsch synthetic (Fischer-Tropsch Synthesis) is the reaction that synthetic gas is converted into hydrocarbon under the effect of catalyzer, and the synthetic hydrocarbon product that obtains of Fischer-Tropsch can obtain the hard wax of gasoline, diesel oil, aviation kerosene, petroleum naphtha and high added value after deep processing.Because synthetic gas (refers to that carbon number at the hydro carbons more than 5, is designated as C at the heavy hydrocarbon that cobalt-base catalyst can obtain highly selective
5 +), heavy hydrocarbon is obtainable middle distillate oil behind hydrocracking and isomery upgrading, comprise diesel oil, aviation kerosene and petroleum naphtha, these liquid feuls have excellent combustionproperty, and not sulfur-bearing nitrogen oxygen and aromatic hydrocarbons, can significantly reduce exhaust pollution, thereby cause the very big concern of each major oil companies of the world in recent years, and dropped into huge man power and material's development of new cobalt-base catalyst, the cobalt-base catalyst of wherein Dutch Shell company exploitation has been realized the industrialization that the natural gas via synthetic gas is produced middle distillate oil in Malaysia.
Exxon (Exxon) company announces that in Chinese patent CN10433G7A the rhenium of being developed (Re) makes the cobalt-base catalyst preparation method of auxiliary agent, and carrier adopts titanium dioxide (TiO
2), immersion process for preparing; Consist of 12%Co/0.5%Re/TiO at catalyzer
2(weight percent), 200 ℃ of temperature of reaction, reaction pressure 1.93MPa, H
2/ CO mol ratio is 2.15, and under the operational condition of unstripped gas air speed 1000NL/ (Lh), operation in 200 hours drops to below 80% from 98% with interior CO transformation efficiency, actively descends very soon, and catalyst stability can be relatively poor.
High petrels etc. (the tenth national catalysis academic meeting paper collection, volumes such as ZhongBing, in October, 2000, Zhangjiajie, Shanxi science tech publishing house, 467 pages-468 pages) in the tenth national catalysis academic conference have been reported a kind of Co/ZrO
2-SiO
2Catalyzer, wherein silicon-dioxide (SiO
2) prepare by sol-gel (Sol-gel) method, with zirconium nitrate Dipping SiO
2Obtain complex carrier ZrO
2-SiO
2, flood Xiao Suangu again and obtain catalyzer.This report is at unstripped gas hydrogen and carbon monoxide mol ratio 2.0 (H
2/ CO=2.0), pressure P=2.0MPa, under the condition of unstripped gas air speed 500NL/ (Lh), the CO per pass conversion is controlled at 70%-85%, between 185 ℃-193 ℃ of temperature, 524 hours have been moved, the result shows: catalyst activity is on a declining curve, needs to improve temperature of reaction and just can keep activity.
The purpose of this invention is to provide a kind of synthetic gas that is used for and produce good Catalysts and its preparation method of heavy hydrocarbon reaction stability and application.
Catalyst weight per-cent of the present invention consists of:
Carrier: 50%-95% cobalt metal: 5%-50%
Wherein carrier is pure silicon six side's mesoporous molecular sieves (Hexagonal Mesoporous Silica is called for short HMS) or soft silica.
Preparation of catalysts method concrete steps of the present invention are as follows:
1. the preparation method of carrier
Joining mole proportioning is water: the mixing solutions of kiber alkyl amine: organosilicon=18-45: 0.15-0.40: 0.5-2.0, solution left standstill 18-60 hour, filter, thorough washing, temperature 450-800 ℃ roasting 5-24 hour, the gained solid product is pure silicon six side's mesoporous molecular sieve HMS;
Or to join mole proportioning be water: dehydrated alcohol: the mixing solutions of organic alcohol: kiber alkyl amine: organosilicon=18-45: 0.01-8.5: 0.01-2: 0.15-0.40: 0.5-2.0, solution left standstill 18-60 hour, filtration, thorough washing, temperature 450-800 ℃ roasting 5-24 hour, the gained solid product is pure silicon six side's mesoporous molecular sieve HMS;
Or with above-mentioned synthetic pure silicon six side's mesoporous molecular sieve HMS soft silica that processing obtained in 10-72 hour under temperature is 500 ℃-1000 ℃, or synthetic pure silicon six side's mesoporous molecular sieve HMS are to handle the soft silica that obtained in 4-150 hour in 50 ℃ of-100 ℃ of following water in temperature.
In the above-mentioned preparing carriers, organosilicon can be tetraethoxy, methyl silicate, positive silicic acid propyl ester etc.; Kiber alkyl amine is the long-chain fat primary amine of eight to 20 carbon numbers;
Above-mentioned organic alcohol can be ethanol, glycerine, Virahol, n-propyl alcohol etc.
2. Preparation of catalysts
With the aqueous solution of Xiao Suangu as steeping fluid, the above-mentioned carrier that makes is joined in the solution that is dissolved with Xiao Suangu, evaporating solns is to doing on 30 ℃ of-100 ℃ of temperature, and the catalyzer that makes obtains containing the catalyzer that weight of cobalt per-cent is 5-50% 350 ℃-600 ℃ of temperature after roasting 2-6 hour; Roasting, compressing tablet gets the catalyzer finished product after the screening.
Catalyzer of the present invention is used for the reaction that synthetic gas is produced heavy hydrocarbon, and reaction conditions is as follows:
The catalyzer fixed-bed reactor of packing into, unstripped gas H
2/ CO (mol ratio) is 1.5-3.5, preferred 1.8-2.2,150 ℃-300 ℃ of temperature of reaction, preferred 180 ℃-260 ℃, reaction pressure 0.1-5.0MPa, preferred 1.0-4.5MPa, unstripped gas air speed 250-2500NL/ (Lh), preferred 350-1000NL/ (Lh).
Catalyzer of the present invention compared with prior art has the following advantages:
1. among the preparation method, raw material all can commercially availablely obtain, the simple and easy handling of carrier and Preparation of catalysts, and pickling process is classical catalyst preparation technology, the catalyzer good reproducibility of preparation.
2. catalyzer of the present invention adopts the mesoporous molecular sieve of high-specific surface area, because it has very high specific surface area and particular structure, therefore can obtain the cobalt-base catalyst of high dispersing, and this must produce unique influence to catalyst activity and selectivity.
3. support of the catalyst of the present invention adopts by the mesoporous molecular sieve HMS soft silica that obtains that sets out and makes carrier, because its source is different from traditional silicon-dioxide as silicon-dioxide that commercial silica gel and sol-gel process obtain, obtains the cobalt-base catalyst of excellent performance.
4. catalyzer of the present invention is not adding any auxiliary agent particularly under the situation of precious metal additive, the methane selectively that obtains can be lower than 8%, the heavy hydrocarbon selectivity is up to 88%, reached the purpose that improves catalyzer heavy hydrocarbon selectivity, forces down methane selectively, and catalyzer has satisfactory stability.
Embodiments of the invention are as follows:
Embodiment one
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the hexadecyl primary amine: tetraethoxy=36: 6.5: 1: 0.27: 1, the mixing solutions room temperature left standstill 24 hours, product after filtration, after washing and the dry air, slowly be warming up to 550 ℃ of roastings 10 hours at muffle furnace, products therefrom is HMS; 3.92g Xiao Suangu is dissolved in the 40mL water, adds the carrier HMS 4.5g of preparation, room temperature leaves standstill to be placed in 12 hours evaporates mixing solutions to doing on 40 ℃ of water temperatures, make 15% (weight of cobalt per-cent) cobalt-base catalyst.450 ℃ of roastings are 4 hours in the catalyzer muffle furnace, load the 5mL catalyzer on fixed-bed reactor, and reaction conditions is H
2/ CO mol ratio is 2.0, reaction pressure 2.0MPa, and unstripped gas air speed 500NL/ (Lh), in the time of 210 ℃, reaction result is as follows: CO transformation efficiency 87%, methane weight selectivity 6.8%, C
5 +Weight selectivity 88%; 210 ℃ of temperature, pressure 2.0MPa, unstripped gas air speed 500NL/ (Lh), H
2/ CO mol ratio is under 2.0 the condition, to investigate this catalyst life, steady running 500 hours, and the CO transformation efficiency is between 88%-82%, and methane weight selectivity maintains 6.8%, C
5 +The weight selectivity maintains 88%, and catalyzer has extraordinary stability.
Embodiment two
Mixing solutions mole proportioning is a water: eight kiber alkyl amines: methyl silicate=45: 0.40: 2.0, the mixing solutions room temperature left standstill 60 hours, product after filtration, after washing and the dry air, slowly be warming up to 800 ℃ of roastings 5 hours at muffle furnace, make dipping 5% (weight of cobalt per-cent) cobalt-base catalyst as embodiment one, the 5mL catalyzer is loaded in catalyzer 450 ℃ of roastings 4 hours in muffle furnace on fixed-bed reactor, reaction conditions is H
2/ CO mol ratio is 2.0, reaction pressure 5.0MPa, and unstripped gas air speed 500NL/ (Lh), in the time of 240 ℃, CO transformation efficiency 90%, methane weight selectivity 7%, C
5 +Weight selectivity 84%.
Embodiment three
Mixing solutions mole proportioning is a water: the undecyl primary amine: tetraethoxy=36: 0.18: 1.5, the mixing solutions room temperature left standstill 40 hours, product after filtration, after washing and the dry air, slowly being warming up to 550 ℃ in muffle furnace kept 10 hours, make dipping 25% (weight of cobalt per-cent) cobalt-base catalyst as embodiment one, catalyzer loads the 5mL catalyzer 450 ℃ of roastings of muffle furnace 4 hours on fixed-bed reactor, reaction conditions is H
2/ CO mol ratio is 2.0, reaction pressure 1.5MPa, and unstripped gas air speed 1500NL/ (Lh), in the time of 220 ℃, CO transformation efficiency 87%, methane weight selectivity 6%, C
5 +Weight selectivity 86%.
Embodiment four
Mixing solutions mole proportioning is a water: the octadecyl primary amine: positive silicic acid propyl ester=18: 0.15: 0.5, the mixing solutions room temperature left standstill 18 hours, product after filtration, after washing and the dry air, slowly be warming up to 450 ℃ of roastings 24 hours at muffle furnace, 3.92g Xiao Suangu is dissolved in the 60mL water, the carrier HMS 4.5g that adds preparation, room temperature leaves standstill to be placed in 12 hours evaporates mixing solutions to doing on 100 ℃ of water temperatures, make 15% (weight of cobalt per-cent) cobalt-base catalyst, the catalyzer that makes 600 ℃ of roastings 2 hours in muffle furnace, load the 5mL catalyzer on fixed-bed reactor, reaction conditions is H
2/ CO mol ratio is 3.5, reaction pressure 0.10MPa, and unstripped gas air speed 500NL/ (Lh), in the time of 260 ℃, reaction result is as follows: CO transformation efficiency 90%, methane weight selectivity is 15%, C
5 +Weight selectivity 69%.
Embodiment five
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the eicosyl primary amine: tetraethoxy=36: 6.5: 1: 0.27: 1, the mixing solutions room temperature left standstill 52 hours, product after filtration, after washing and the dry air, solid product places 100 ℃ of water to handle 10 hours, filter the back drying at room temperature, 450 ℃ of roastings of muffle furnace reason 4 hours to remove template, the product that obtains is a soft silica, then as embodiment one dipping 18% (weight percent) cobalt, 450 ℃ of roastings are 4 hours in the catalyzer muffle furnace that makes.On fixed-bed reactor, load the 5mL catalyzer, at reaction pressure 2.0MPa, 210 ℃ of temperature of reaction, unstripped gas air speed 2500NL/ (Lh), H
2/ CO mol ratio is under 2.0 the condition, the stability of catalyzer to be investigated, the catalyzer steady running 1000 hours, the CO transformation efficiency is between 92%-82%, methane weight selectivity maintains 7.5%, C
5 +The weight selectivity maintains 86%.
Embodiment six
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the heptadecyl primary amine: tetraethoxy=18: 8.5: 2: 0.40: 2.0, the mixing solutions room temperature left standstill 24 hours, product after filtration, after washing and the dry air, solid product places 100 ℃ of water to handle 18 hours, filter the back drying at room temperature, to remove template, obtaining product was soft silica 550 ℃ of roastings of muffle furnace reason 10 hours, then as embodiment one flood 12% (weight percent) cobalt.500 ℃ of roastings are 4 hours in the catalyzer muffle furnace that makes, and load the 5mL catalyzer on fixed-bed reactor, at reaction pressure 2.0MPa, and unstripped gas air speed 1500NL/ (Lh), H
2/ CO mol ratio is under 1.5 the condition, and when 230 ℃ of temperature of reaction, the CO transformation efficiency is 90%, methane weight selectivity 10%, C
5 +The weight selectivity maintains 84%.
Embodiment seven
Mixing solutions mole proportioning is a water: dehydrated alcohol: propyl carbinol: the hexadecyl primary amine: tetraethoxy=36: 6.5: 1: 0.27: 1, the mixing solutions room temperature left standstill 60 hours, product after filtration, after washing and the dry air, solid product was 1000 ℃ of roastings 10 hours, the solid matter that obtains is a soft silica, then as embodiment one, carrier impregnation 15% (weight of cobalt per-cent) cobalt-base catalyst.350 ℃ of roastings are 6 hours in the catalyzer muffle furnace that makes, and are H at reaction conditions
2/ CO mol ratio is 1.5,180 ℃ of temperature of reaction, and reaction pressure 2.0MPa, under the condition of unstripped gas air speed 250NL/ (Lh), CO transformation efficiency 85%, methane weight selectivity 6%, C
5 +Weight selectivity 85%.
Embodiment eight
Mixing solutions mole proportioning is a water: dehydrated alcohol: n-propyl alcohol: the hexadecyl primary amine: positive silicic acid propyl ester=36: 6.5: 1: 0.15: 1, the mixing solutions room temperature left standstill 18 hours, product after filtration, after washing and the dry air, solid product in muffle furnace 550 ℃ of roastings 5 hours to remove template, the solid product that obtains was handled 150 hours in 50 ℃ of water, filter, drying at room temperature, obtaining product is soft silica, then as embodiment one, immersion process for preparing 20% (weight percent) cobalt-base catalyst.450 ℃ of roastings are 4 hours in the catalyzer muffle furnace that makes, and are H at reaction conditions
2/ CO mol ratio is 2.0,190 ℃ of temperature of reaction, reaction pressure 2.0MPa, under the condition of unstripped gas air speed 500NL/ (Lh), life of catalyst is investigated catalyzer steady running 800 hours, the CO transformation efficiency maintains between the 93%-85%, and methane weight maintains selectivity 7.2%, C
5 +The weight selectivity maintains 84%.
Embodiment nine
Mixing solutions mole proportioning is a water: dehydrated alcohol: glycerine: the tetradecyl primary amine: tetraethoxy=36: 6.5: 1: 0.27: 1, the mixing solutions room temperature left standstill 18 hours, product after filtration, after washing and the dry air, solid product 550 ℃ of roastings 5 hours in muffle furnace, get white solid product, solid product was handled 24 hours in 80 ℃ of water, the material that obtains is a soft silica, then as embodiment one dipping 10% (weight of cobalt per-cent) cobalt-base catalyst, 450 ℃ of roastings are 4 hours in the catalyzer muffle furnace that makes, catalyzer loading amount 5ml is H at reaction conditions
2/ CO mol ratio is 2.0,220 ℃ of temperature of reaction, and reaction pressure 2.0MPa, under the condition of unstripped gas air speed 500NL/ (Lh), CO transformation efficiency 86%, methane weight selectivity 10%, C
5 +Weight selectivity 80%.
Embodiment ten
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the hexadecyl primary amine: tetraethoxy=36: 6.5: 1: 0.27: 1, the mixing solutions room temperature left standstill 48 hours, product after filtration, after washing and the dry air, slowly being warming up to 500 ℃ at muffle furnace kept 72 hours, the solid matter that obtains is a soft silica, 3.92g Xiao Suangu is dissolved in the 100mL water, the carrier 4.5g that adds preparation, room temperature leaves standstill to be placed in 12 hours evaporates mixing solutions to doing on 30 ℃ of water temperatures, make 15% (weight percent) cobalt, 450 ℃ of roastings are 4 hours in the catalyzer muffle furnace, load the 5mL catalyzer on fixed-bed reactor, and reaction conditions is H
2/ CO mol ratio is 3.5, reaction pressure 2.0MPa, and unstripped gas air speed 1000NL/ (Lh), in the time of 200 ℃, reaction result is as follows: CO transformation efficiency 80%, methane weight selectivity 11%, C
5 +Weight selectivity 80%.
Embodiment 11
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the hexadecyl primary amine: tetraethoxy=36: 0.01: 0.01: 0.27: 0.5, the mixing solutions room temperature left standstill 36 hours, product after filtration, after washing and the dry air, solid product was 1000 ℃ of roastings 10 hours, the solid matter that obtains is a soft silica, then as embodiment one, carrier impregnation 15% (weight of cobalt per-cent) cobalt-base catalyst.550 ℃ of roastings are 4 hours in the catalyzer muffle furnace that makes, and are H at reaction conditions
2/ CO mol ratio is 1.5,230 ℃ of temperature of reaction, and reaction pressure 2.0MPa, under the condition of unstripped gas air speed 800NL/ (Lh), CO transformation efficiency 85%, methane weight selectivity 8%, C
5 +Weight selectivity 86%.
Embodiment 12
Mixing solutions mole proportioning is a water: dehydrated alcohol: Virahol: the heptadecyl primary amine: tetraethoxy=45: 8.5: 2: 0.27: 2.0, the mixing solutions room temperature left standstill 24 hours, product after filtration, after washing and the dry air, solid product places 100 ℃ of water to handle 20 hours, filter the back drying at room temperature, to remove template, obtaining product was soft silica 550 ℃ of roastings of muffle furnace reason 10 hours, then as embodiment one flood 50% (weight percent) cobalt.350 ℃ of roastings are 6 hours in the catalyzer muffle furnace that makes, and load the 5mL catalyzer on fixed-bed reactor, at reaction pressure 2.0MPa, and unstripped gas air speed 1500NL/ (Lh), H
2/ CO mol ratio is under 1.5 the condition, and when 230 ℃ of temperature of reaction, the CO transformation efficiency is 65%, methane weight selectivity 18%, C
5 +The weight selectivity maintains 72%.
Response data reaches in system and gathers after stable state has good material balance among the embodiment.Liquid phase and solid product adopt cold and hot trap system to collect respectively, unstripped gas and react equal off-line analysis, CO
2Adopt external standard method, H
2, O
2, N
2, CO and CH
4Use gas chromatograph to analyze, TCD detects, carbonaceous molecular sieve post, C
1-C
6Hydro carbons uses the analysis of GC-920 gas chromatograph, the octadecane post, and FID detects.
Claims (3)
1. one kind is used for the Preparation of catalysts method that synthetic gas is produced heavy hydrocarbon, it is characterized in that concrete steps are as follows:
(1). the preparation method of carrier
Joining mole proportioning is water: dehydrated alcohol: the mixing solutions of organic alcohol: kiber alkyl amine: organosilicon=18-45: 0.01-8.5: 0.01-2: 0.15-0.40: 0.5-2.0, solution left standstill 18-60 hour, filtration, thorough washing, temperature 450-800 ℃ roasting 5-24 hour, the gained solid product is pure silicon six side's mesoporous molecular sieve HMS;
Or with above-mentioned synthetic pure silicon six side's mesoporous molecular sieve HMS soft silica that processing obtained in 10-72 hour under temperature is 500 ℃-1000 ℃, or synthetic pure silicon six side's mesoporous molecular sieve HMS are to handle the soft silica that obtained in 4-150 hour in 50 ℃ of-100 ℃ of following water in temperature;
(2). Preparation of catalysts
With the aqueous solution of Xiao Suangu as steeping fluid, the above-mentioned carrier that makes is joined the solution that is dissolved with Xiao Suangu, evaporating solns is to doing on 30 ℃ of-100 ℃ of temperature, and the catalyzer that makes 350 ℃-600 ℃ maintenances in air atmosphere obtained containing the catalyzer that weight of cobalt per-cent is 5-50% after 2-6 hour; Roasting, compressing tablet gets the catalyzer finished product after the screening.
2. a kind of Preparation of catalysts method that synthetic gas is produced heavy hydrocarbon that is used for as claimed in claim 1 is characterized in that described organosilicon is that tetraethoxy, methyl silicate, positive silicic acid propyl ester or kiber alkyl amine are the long-chain fat primary amine of eight to 20 carbon numbers.
3, a kind of Preparation of catalysts method that synthetic gas is produced heavy hydrocarbon that is used for as claimed in claim 1 is characterized in that described organic alcohol is glycerine, Virahol or n-propyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011115831A CN1177018C (en) | 2001-03-21 | 2001-03-21 | Catalyst for preparing heavy hydrocarbon from synthetic gas and its prepn. and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011115831A CN1177018C (en) | 2001-03-21 | 2001-03-21 | Catalyst for preparing heavy hydrocarbon from synthetic gas and its prepn. and application |
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| CN1375542A CN1375542A (en) | 2002-10-23 |
| CN1177018C true CN1177018C (en) | 2004-11-24 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297345C (en) * | 2004-01-13 | 2007-01-31 | 厦门大学 | Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method |
| CN101462059B (en) * | 2007-12-20 | 2011-07-20 | 中国石油化工股份有限公司 | FT synthetic catalyst containing metal support body, preparation and use thereof |
| CN101735872B (en) * | 2008-11-12 | 2013-01-30 | 中科合成油技术有限公司 | Non-steady state reactor and method for producing synthesis gas |
| CN102211034B (en) * | 2011-04-02 | 2013-08-28 | 万华实业集团有限公司 | Catalyst for preparing high-quality gasoline fraction by virtue of syngas high selectivity and preparation method thereof |
| CN107670666A (en) * | 2017-09-30 | 2018-02-09 | 中南民族大学 | A kind of Co based Fischer-Tropsch synthesis catalyst and its synthetic method |
| WO2021115244A1 (en) * | 2019-12-12 | 2021-06-17 | 中国科学院大连化学物理研究所 | Zirconium- or aluminum-modified amorphous mesoporous sio2-supported cobalt-based fischer-tropsch catalyst and preparation method therefor |
| CN111468097B (en) * | 2020-03-24 | 2023-03-03 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee before: Zhongke Synthetic Oil Technology Co., Ltd. |
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