CN109529905A - A kind of method of the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst - Google Patents
A kind of method of the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst Download PDFInfo
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- CN109529905A CN109529905A CN201811567763.9A CN201811567763A CN109529905A CN 109529905 A CN109529905 A CN 109529905A CN 201811567763 A CN201811567763 A CN 201811567763A CN 109529905 A CN109529905 A CN 109529905A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 title claims abstract description 15
- 238000009826 distribution Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003502 gasoline Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 239000004711 α-olefin Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000013495 cobalt Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [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
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- -1 Carbon olefin Chemical class 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/617—500-1000 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- C10G2/331—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 group VIII-metals
- C10G2/332—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 group VIII-metals of the iron-group
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Abstract
The invention discloses a kind of methods of the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst, the each element mass percentage of the active component of Co base catalyst in this method are as follows: Co 10%~30%, Mn 0.1%~10%, Zr 0.1%~10%, Ce 0.1%~10%, C 0.02%~0.1%, N 0.02%~0.1%, remaining is oxygen element；Carrier is silica or aluminium oxide.The control accurate of synthesis gas F- T synthesis hydrocarbon product distribution can be realized by the simple adjustment to reaction temperature, pressure and air speed using preparation catalyst, including realize low-carbon alkene (C respectively2‑C4 =), alpha-olefin (α-C≥4 =), gasoline component (C5‑C11), diesel component (C10‑C20) and solid wax (C20+) high selectivity.The features such as catalyst is active high, long period stability is good, target product yield is high, catalyst preparation is simple, raw material sources are extensive, prepare with scale enlarge-effect is small.
Description
Technical field
The invention belongs to co hydrogenation technical fields, and in particular to a kind of controllable modulation Fischer-Tropsch reaction of Co base catalyst
The method of product distribution.
Background technique
Fischer-Tropsch (Fischer-Tropsch) synthesis is by coal, natural gas, biomass etc. through synthesis gas (CO+H2) be converted into
The process of clean fuel liquid or high valuable chemicals is occupied an important position in coal resources clean and effective use aspects.But
It is that Fischer-Tropsch synthetic is complicated, the wide (C of carbon number distribution1-C120) and it is dynamic by Anderson-Schulz-Flory (ASF) polymerization
The limitation of mechanics, it is poor to the specific objectives selectivity of product such as alkene, gasoline, diesel oil.Therefore, it is living that synthesizing high-stability, height are designed
Property catalyst and highly selective controllable adjustment can be carried out to target product, be the key that current Fischer-Tropsch reaction correlative study
And the emphasis that difficult point and the process industrialization are applied.
In recent years, grinding in terms of synthesis gas prepares highly selective high value added product through the direct one-step method of F- T synthesis
Study carefully, constantly acquirement new progress.K.P.de Jong reports the Fe base catalyst of S and Na modification, the selectivity of low-carbon alkene
Reach 60% (Science 2012,335,835-838)；Patent CN 105107523A is urged using the Mn-Co of coprecipitation preparation
Agent, in-situ preparation diamond shape Co during the catalyst reaction2C has excellent selectivity of light olefin (60.8C%, CO2-
free).Patent CN108144613A discloses a kind of fischer-tropsch synthetic catalyst preparation method of hollow microsphere shape, and the catalyst is logical
The shell for crossing meso-hole structure screens reaction product, and the macromolecular limited in product molecule passes through, and can make gasoline component
(C5-C11) selectively reach 60%.Patent CN 101224425 reports a kind of Fischer-Tropsch product and is distributed controllable Co base catalyst
Preparation method adjusts catalyst cobalt particle size, different cobalts by addition complexing agent in catalyst preparation process
The catalyst of particle size respectively reaches 45% and 46% to gasoline and diesel component optimal selectivity towards.
In summary document and patent analysis, it can be found that the catalyst reported at present only has advantage to a certain product
Selectivity, i.e., can only produce one of low-carbon alkene, gasoline, diesel oil product with high selectivity on same catalyst.Patent
CN 106362737A report it is a kind of regulation Fischer-Tropsch synthetic in vapour, Determination of Diesel Oil method, this method is in batch tank
In reactor, heterogeneous gas-liquid-solid reaction is carried out, it is secondary to liquid product progress by adding dressing agent appropriate in the liquid phase
Reaction, may be implemented the adjusting of product gasoline and Determination of Diesel Oil.But dressing agent that this method is added in reaction system (organic,
Inorganic acid alkali and metal salt etc.), it improves product and isolates and purifies the technology difficulty recycled with catalyst.
The controllable adjustment for realizing product distribution that can be simple and efficient on a catalyst is had not been reported at present.
Summary of the invention
The present invention is distributed uncontrollable crucial problem for product in Fischer-Tropsch synthesis, provides a kind of Co base catalyst,
The controllable adjustment of Fischer-Tropsch reaction product distribution can be realized in temperature, pressure, the air speed reacted by simple modulation.
For above-mentioned purpose, the technical solution adopted by the present invention are as follows:
1, Co base catalyst is prepared using infusion process, each element quality percentage of the active component of the Co base catalyst contains
Amount are as follows: Co 10%~30%, Mn 0.1%~10%, Zr 0.1%~10%, Ce 0.1%~10%, C 0.02%~
0.1%, N 0.02%~0.1%, remaining is oxygen element；Carrier is silica or aluminium oxide；It is specific to be catalyzed the preparation method comprises the following steps: pressing
Agent composition, Co, Mn, Zr, Ce are dissolved in solvent in the form of metal salt, mixed liquor is made；Mixed liquor is mixed with carrier,
Vacuum impregnation, then by separation of solid and liquid, washing, drying, obtained solid powder is mixed with the presoma containing N and C, high temperature roasting
It burns, obtains Co base catalyst.
2, to contain H2Synthesis gas with CO is unstripped gas, is reacted in hydro carbons synthesis reactor, using above-mentioned Co
Base catalyst, modulation Fischer-Tropsch synthesis condition, comprising: 200~250 DEG C of reaction temperature, 0.3~3.0MPa of reaction pressure, H2/
Volume ratio=1.0~4.0 CO, volume space velocity=1~15Lgcat -1·h-1, C is realized respectively2-C4 =Low-carbon alkene, α-C≥4 =
Alpha-olefin, C5-C11Gasoline component, C10-C20Diesel component and C20+Solid wax high selectivity.
The each element mass percentage of the active component of above-mentioned Co base catalyst is preferred are as follows: Co 10%~30%,
Mn0.5%~5%, Zr 0.5%~5%, Ce 0.5%~5%, C 0.02%~0.1%, N 0.02%~0.1%.
The diameter of carrier of above-mentioned Co base catalyst is 0.5~500 μm, and specific surface area is 50~900m2/ g, Kong Rongwei 0.1
~10mL/g, aperture are 5nm~1 μm.
In above-mentioned steps 1, the metal salt be oxalates, acetate, carbonyl salt, alkoxide, ionic liquid, nitrate,
Any one in carbonate；The solvent is water, at least one in methanol, ethyl alcohol, acetone, toluene, N,N-dimethylformamide
Kind；The presoma containing N and C is at least one of amino acid, melamine, urea.
Compared with existing F- T synthesis technology, beneficial effects of the present invention are as follows:
1, Co base catalyst used by the method for the present invention, Co species particle size uniformity are with higher at low temperature
Reactivity and olefine selective, secondary response and carbochain growth theory based on alkene, only need simple adjustment reaction condition, adjust
CO conversion ratio and suitable residence time are controlled, catalyst surface olefin partial pressures are improved, the second adsorption of alkene and carbochain is promoted to increase
It is long, product can be realized in low-carbon alkene (C2-C4 =), Long carbon chain alpha-olefin (α-C≥4 =), gasoline component (C5-C11), diesel oil group
Divide (C10-C20) and solid wax (C20+)) between highly selective accurate switching.Wherein low temperature, low pressure, low H2/ CO ratio, Gao Tiji
Air speed is conducive to the generation that alkene includes low-carbon alkene and Long carbon chain alpha-olefin；High temperature, high pressure, high H2/ CO ratio, low volume air speed
Be conducive to the generation of gasoline component, diesel component and solid wax.
2, catalyst of the present invention is tested through the reversible online switchover operation of long period 1000h, and catalyst performance stabilised, product is cut
Sensitive, target product yield height is answered in commutation.Test result shows, at 200~250 DEG C of reaction temperature, reaction pressure 0.3~
3.0MPa, H2Volume ratio=1.0~4.0 /CO, volume space velocity=1~15Lgcat -1·h-1Section modulation can be achieved low respectively
Carbon olefin (C2-C4 =) selective greater than 40%, Long carbon chain alpha-olefin (α-C≥4 =) selectivity is greater than 40%, gasoline component (C5-
C11) selectivity is greater than 60%, diesel component (C10-C20) selectivity is greater than 60%, solid wax (C20+) be selectively greater than
35%, CH4Selectivity≤10%, CO2Selectivity≤2%.
3, present invention process process is simple, and reaction condition is mild, easy to operate, and key advantages are can be according to the market demand
Variability, to product carry out fast accurate regulation.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
By 0.74g Co (NO3)2·6H2O, the Mn (NO that 0.04mL mass fraction is 50%3)3·4H2O aqueous solution, 0.05g
Zr(NO3)4·5H2O、0.015g Ce(NO3)3·6H2O is dissolved in 20mL water, is stirred evenly, and mixed liquor is made.Weigh 0.85g
SiO2Mixed liquor is uniformly mixed by carrier with carrier, and room temperature in vacuo impregnates 5h, is separated by solid-liquid separation, washing, 100 DEG C of dry 12h, is obtained
To solid powder；Obtained solid powder is mixed with 0.5g phenylalanine, mixed powder is through 500 DEG C of roasting 5h, grinding, pressure
Piece, screening, obtain 15%Co-1%Mn-1%Zr-0.5%Ce-0.05%N-0.1%C/SiO2Catalyst.
By 0.5g 15%Co-1%Mn-1%Zr-0.5%Ce-0.05%N-0.1%C/SiO2Catalyst and isometric stone
Sand mixing, is placed in fixed bed reactors, is passed through pure H2Gas (H2=99.9%) 450, are warming up to the rate of 5 DEG C/min
DEG C, 5h is maintained, 180 DEG C is then cooled to, is passed through synthesis gas, carries out producing hydrocarbon with synthetic gas product according to the reaction condition of table 1
Fischer-Tropsch reaction, reaction result are shown in Table 1.
The regulation that 1 embodiment of table, 1 catalyst is distributed Fischer-Tropsch reaction product
| H2/CO | Temperature/DEG C | Pressure/PMa | Air speed/Lgcat -1·h-1 | C2-C4 = | α-C≥4 = | C5-C11 | C10-C20 | C20+ |
| 1 | 210 | 0.6 | 7.2 | 45% | 12% | 21% | 2% | -- |
| 1 | 210 | 1.0 | 7.2 | 18% | 41% | 61% | 10% | -- |
| 2 | 220 | 1.0 | 4.8 | 10% | 25% | 65% | 15% | -- |
| 2 | 230 | 2 | 4.8 | 5% | 8% | 11% | 65% | 6% |
| 2 | 230 | 2 | 4.8 | 3% | 6% | 15% | 35% | 40% |
Embodiment 2
By 0.50g Co2(CO)8、0.09g Mn(Ac)2、0.047g Zr(NO3)3·6H2O、0.03g Ce(NO3)3·
6H2O is dissolved in 20mL ethyl alcohol, is stirred evenly, and mixed liquor is made.Weigh 1.0g SiO2Carrier mixes mixed liquor with carrier
Even, room temperature in vacuo impregnates 5h, is separated by solid-liquid separation, washing, 100 DEG C of dry 12h, obtains solid powder；By obtained solid powder with
The mixing of 1.0g phenylalanine, for mixed powder through 500 DEG C of roasting 5h, grinding, tabletting, screening obtain 20%Co-2%Mn-
1%Zr-1%Ce-0.1%N-0.1%C/SiO2Catalyst.
By 0.5g 20%Co-2%Mn-1%Zr-1%Ce-0.1%N-0.1%C/SiO2Catalyst and isometric quartz
Sand mixing, is placed in fixed bed reactors, is passed through pure H2Gas (H2=99.9%) 450 DEG C, are warming up to the rate of 5 DEG C/min,
5h is maintained, 180 DEG C is then cooled to, is passed through synthesis gas, the Fischer-Tropsch of producing hydrocarbon with synthetic gas product is carried out according to the reaction condition of table 2
Reaction, reaction result are shown in Table 2.
The regulation that 2 embodiment of table, 2 catalyst is distributed Fischer-Tropsch reaction product
| H2/CO | Temperature/DEG C | Pressure/PMa | Air speed/Lgcat -1·h-1 | C2-C4 = | α-C≥4 = | C5-C11 | C10-C20 | C20+ |
| 1 | 210 | 0.6 | 7.2 | 42% | 15% | 23% | 3% | -- |
| 1 | 210 | 1.0 | 7.2 | 20% | 42% | 60% | 8% | -- |
| 2 | 220 | 1.0 | 4.8 | 11% | 30% | 66% | 10% | -- |
| 2 | 230 | 2 | 4.8 | 5% | 8% | 14% | 62% | 10% |
| 2 | 230 | 2 | 4.8 | 4% | 8% | 17% | 35% | 36% |
Embodiment 3
By 0.50g Co (NO3)2·6H2O, 0.02mL 50%Mn (NO3)3·4H2O、0.10g Zr(NO3)4·5H2O、
0.031g Ce(NO3)3·6H2O is dissolved in 20mL water, is stirred evenly, and mixed liquor is made.Weigh 1.0g Al2O3Carrier will mix
Liquid is uniformly mixed with carrier, and room temperature in vacuo impregnates 5h, is separated by solid-liquid separation, washing, 100 DEG C of dry 5h, is obtained solid powder；By gained
Solid powder is mixed with 0.5g melamine, and for mixed powder through 500 DEG C of roasting 5h, grinding, tabletting, screening obtain 10%
Co-0.5%Mn-2%Zr-1%Ce-0.08%N-0.05%C/Al2O3Catalyst.
By 0.5g 10%Co-0.5%Mn-2%Zr-1%Ce-0.08%N-0.05%C/Al2O3Catalyst and isometric
Quartz sand mixing, is placed in fixed bed reactors, is passed through pure H2Gas (H2=99.9%) it, is warming up to the rate of 5 DEG C/min
450 DEG C, 5h is maintained, 180 DEG C is then cooled to, is passed through synthesis gas, carries out producing hydrocarbon with synthetic gas product according to the reaction condition of table 3
Fischer-Tropsch reaction, reaction result is shown in Table 3.
The regulation that 3 embodiment of table, 3 catalyst is distributed Fischer-Tropsch reaction product
| H2/CO | Temperature/DEG C | Pressure/PMa | Air speed/Lgcat -1·h-1 | C2-C4 = | α-C≥4 = | C5-C11 | C10-C20 | C20+ |
| 1 | 210 | 0.6 | 7.2 | 50% | 22% | 35% | 3% | -- |
| 1 | 210 | 1.0 | 7.2 | 25% | 43% | 55% | 8% | -- |
| 2 | 220 | 1.0 | 4.8 | 10% | 25% | 60% | 12% | 8% |
| 2 | 230 | 2 | 4.8 | 6% | 6% | 15% | 60% | 9% |
| 2 | 230 | 2 | 4.8 | 4% | 6% | 20% | 25% | 38% |
Embodiment 4
By 0.62g Co2(CO)8、0.045g Mn(Ac)2、0.14g Zr(NO3)3·6H2O、0.015g Ce(NO3)3·
6H2O is dissolved in 20mL water, is stirred evenly, and mixed liquor is made.Weigh 1.0g Al2O3Carrier mixes mixed liquor with carrier
Even, room temperature in vacuo impregnates 5h, is separated by solid-liquid separation, washing, 100 DEG C of dry 5h, obtains solid powder；By obtained solid powder and 1.0g
Urea mixing, for mixed powder through 500 DEG C of roasting 5h, grinding, tabletting, screening obtain 25%Co-1%Mn-3%Zr-
0.5%Ce-0.05%N-0.05%C/Al2O3Catalyst.
By 0.5g 25%Co-1%Mn-3%Zr-0.5%Ce-0.05%N-0.05%C/Al2O3Catalyst and isometric
Quartz sand mixing, is placed in fixed bed reactors, is passed through pure H2Gas (H2=99.9%) it, is warming up to the rate of 5 DEG C/min
450 DEG C, 5h is maintained, 180 DEG C is then cooled to, is passed through synthesis gas, carries out producing hydrocarbon with synthetic gas product according to the reaction condition of table 4
Fischer-Tropsch reaction, reaction result is shown in Table 4.
The regulation that 4 embodiment of table, 4 catalyst is distributed Fischer-Tropsch reaction product
Claims (6)
1. a kind of method of the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst, it is characterised in that:
(1) Co base catalyst, each element mass percentage of the active component of the Co base catalyst are prepared using infusion process
Are as follows: Co 10%~30%, Mn 0.1%~10%, Zr 0.1%~10%, Ce 0.1%~10%, C 0.02%~
0.1%, N 0.02%~0.1%, remaining is oxygen element；Carrier is silica or aluminium oxide；It is specific to be catalyzed the preparation method comprises the following steps: pressing
Agent composition, Co, Mn, Zr, Ce are dissolved in solvent in the form of metal salt, mixed liquor is made；Mixed liquor is mixed with carrier,
Vacuum impregnation, then by separation of solid and liquid, washing, drying, obtained solid powder is mixed with the presoma containing N and C, high temperature roasting
It burns, obtains Co base catalyst；
(2) to contain H2Synthesis gas with CO is unstripped gas, is reacted in hydro carbons synthesis reactor, is urged using above-mentioned Co base
Agent, modulation Fischer-Tropsch synthesis condition, comprising: 200~250 DEG C of reaction temperature, 0.3~3.0MPa of reaction pressure, H2/ CO body
Product ratio=1.0~4.0, volume space velocity=1~15Lgcat -1·h-1, C is realized respectively2-C4 =Low-carbon alkene, α-C≥4 =α-
Alkene, C5-C11Gasoline component, C10-C20Diesel component and C20+Solid wax high selectivity.
2. the method for the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst according to claim 1, it is characterised in that:
The each element mass percentage of the active component of the Co base catalyst are as follows: Co 10%~30%, Mn 0.5%~5%, Zr
0.5%~5%, Ce 0.5%~5%, C 0.02%~0.1%, N 0.02%~0.1%, remaining is oxygen element.
3. the method for the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst according to claim 2, it is characterised in that:
The diameter of carrier of the Co base catalyst is 0.5~500 μm, and specific surface area is 50~900m20.1~10mL/g of/g, Kong Rongwei,
Aperture is 5nm~1 μm.
4. the method for the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst according to any one of claims 1 to 3,
It is characterized by: in step (1), the metal salt be oxalates, acetate, carbonyl salt, alkoxide, ionic liquid, nitrate,
Any one in carbonate.
5. the method for the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst according to any one of claims 1 to 3,
It is characterized by: in step (1), the solvent be water, methanol, ethyl alcohol, acetone, toluene, in n,N-Dimethylformamide extremely
Few one kind.
6. the method for the controllable modulation Fischer-Tropsch reaction product distribution of Co base catalyst according to any one of claims 1 to 3,
It is characterized by: the presoma containing N and C is at least one of amino acid, melamine, urea in step (1).
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