CN112973694A - Aluminum element promoted disordered mesoporous silica-supported cobalt-based catalyst and preparation and application thereof - Google Patents
Aluminum element promoted disordered mesoporous silica-supported cobalt-based catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 37
- 239000010941 cobalt Substances 0.000 title claims abstract description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000005580 one pot reaction Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 14
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- QFIGQGUHYKRFAI-UHFFFAOYSA-K aluminum;trichlorate Chemical compound [Al+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O QFIGQGUHYKRFAI-UHFFFAOYSA-K 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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 provides an aluminum element promoted disordered mesoporous silica loaded cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method and application thereof, and the preparation method comprises the following steps: firstly dissolving aluminum salt, then adding a precursor of silicon, then adding a template agent and the like, and carrying out drying, hydrothermal treatment, roasting and other processes, and adopting a one-pot method to synthesize the aluminum-modified disordered mesoporous silica material with high specific surface area in situ, wherein the specific surface area of the aluminum-modified disordered mesoporous silica material reaches 300-800 m-2The pore diameter is 3-10 nm. The Fischer-Tropsch synthesis catalyst is obtained by loading an active component cobalt salt. The Fischer-Tropsch synthesis catalyst prepared by the method has good dispersion of active phase and activityHigh stability, simple preparation method, easy control and suitability for industrial application.
Description
Technical Field
The invention belongs to the field of Fischer-Tropsch synthesis, and particularly relates to an aluminum element promoted disordered mesoporous silica supported cobalt-based Fischer-Tropsch synthesis catalyst, and a preparation method and application thereof.
Background
Fischer-Tropsch synthesis (F-T) to synthesize gas (syngas, CO/H)2) The catalyst is used as raw material gas to generate olefin and alkane with different carbon chain distributions by the catalysis of supported catalysts such as iron (Fe), cobalt (Co), ruthenium (Ru) and the like, and is an important way for converting non-fossil fuel into clean energy and chemicals. The cobalt-based catalyst has high stability, high liquid phase hydrocarbon selectivity, good oxidation resistance and low water vapor conversion rate, and is widely used for Fischer-Tropsch synthesis reaction. The traditional industrial cobalt-based Fischer-Tropsch synthesis catalyst is generally prepared from alpha-Al2O3And the activated carbon is used as a carrier, has the characteristic of low CO conversion rate, and generally improves the reaction activity by adding a noble metal auxiliary agent, but increases the industrial cost of Fischer-Tropsch synthesis. In the catalytic reaction, the carrier can effectively regulate and control the geometric configuration and the electronic structure of an active center, thereby realizing the aim of regulating and controlling the activity of the catalyst. Under the condition of not adding a noble metal auxiliary agent, how to improve the activity of Fischer-Tropsch synthesis by changing the physical and chemical properties of a carrier and obtain an oil product with high alkane-olefin ratio is the key point of cobalt-based Fischer-Tropsch synthesis research.
Attempts have been made by researchers to improve the activity of cobalt based fischer-tropsch synthesis by modifying the support or incorporating promoters. CN102441391A reports a method of modifying a modified silica gel carrier with 1-2 transition metals, and then loading an active component Co. The cobalt-based catalyst prepared by the method is placed in a high-pressure continuous stirred tank reactor, and the reaction condition is 2.5N m3/h/kg cat,2.0MPa,H2when/C0 was 2 (molar ratio), the CO conversion was 66.5% after 100h of reaction, CH4The selectivity was 8.3%.
CN102861583B reports that a supported cobalt-based fischer-tropsch synthesis catalyst for slurry bed and ebullated bed is prepared by first loading carbon nanofibers on a silica gel carrier in situ, and then impregnating with a transition metal promoter and an active component Co. The prepared catalyst is put in a high-pressure continuous stirred tank reactor, and the reaction condition is 2.5N m3/h/kg cat,2.0MPa,H2when/C0 was 2 (molar ratio), the CO conversion was 63.9% after 100h of reaction, CH4The selectivity was 7.9%.
Research work shows that the cobalt of the hcp phase has higher Fischer-Tropsch synthesis reaction activity than that of the fcc phase, and different functional groups on the surface of the carrier have certain influence on the crystal phase of the Co. Research work by the professor K.P.de Jong university of Utremulin, the Netherlands showed that characterization techniques with XAS/XRPD in situ showed that the untreated CNT surface was more conducive to the formation of hcp phase cobalt nanoparticles than the oxidized treated CNT surface. However, cobalt nanoparticles are more prone to agglomeration due to the lack of anchoring sites for metallic Co for untreated CNTs.
The activity of the catalyst is improved by modifying the carrier or introducing the transition metal auxiliary agent, but the activity is still low, and the controllability of the carrier is weak by utilizing the carriers such as commercial silica gel and the like. Aiming at the problems, the carrier is synthesized in situ, and the properties of the carrier are regulated and controlled by regulating various parameters in the preparation process according to the activity and product distribution of the Fischer-Tropsch reaction, so that the optimal Fischer-Tropsch synthesis performance is obtained, and the supported cobalt-based Fischer-Tropsch synthesis catalyst with high activity, high stability and low cost is further obtained, so that the method has very important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method for preparing a cobalt-based Fischer-Tropsch synthesis catalyst with low cost, high activity and high stability by using modified mesoporous silica as a carrier.
The preparation method of the Fischer-Tropsch synthesis catalyst comprises the following steps: firstly, preparing the aluminum modified amorphous mesoporous silica in situ, enabling aluminum elements to enter a framework structure of the silica, and then loading an active component Co by adopting an impregnation method.
Based on the above technical scheme, preferably, the preparation of the aluminum-modified amorphous mesoporous silica adopts a one-pot method, and the preparation process thereof is as follows, wherein the one-pot method comprises the specific steps of in-situ synthesis of the aluminum-modified disordered mesoporous silica: firstly dissolving an Al precursor, then adding an Si precursor, stirring for 20-40 minutes at 20-40 ℃, adding a template agent, continuing to stir for 20-40 minutes, adding a pore-forming agent, stirring for 48 hours at 20-40 ℃, drying, carrying out hydrothermal treatment, and roasting to obtain the aluminum-modified disordered mesoporous silica; the aluminum source is as follows: silicon source: template agent: the mol ratio of the pore-forming agent is 0.3-4% and 1:1: 0.3.
Based on the above technical scheme, preferably, the precursor of the Al salt includes aluminum sulfate, aluminum isopropoxide, aluminum nitrate, aluminum chlorate and the like.
Based on the above technical solution, preferably, the solution of the precursor of Al includes water, methanol, ethanol, propanol, and isopropanol, wherein ethanol is preferred.
Based on the technical scheme, preferably, the precursor of the Si comprises one of tetraethoxysilane, sodium metasilicate and silica sol.
Based on the above technical solution, preferably, the selection of the template agent comprises one of Triethanolamine (TEA), tetraethylene glycol (TEG), and diethanolamine.
Based on the above technical solution, preferably, the pore-forming agent is selected from one of tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH).
Based on the technical scheme, preferably, the drying temperature of the carrier is 70-120 ℃, and the time is 2-24 h; the hydrothermal treatment temperature is 120-180 ℃, and the time is 2-15 h; the roasting temperature is 600-800 ℃, and the time is 4-12 h.
Based on the technical scheme, preferably, the drying temperature of the supported cobalt-based catalyst is 70-120 ℃, and the time is 4-48 h; the roasting temperature is 300-450 ℃, and the time is 2-24 h.
The invention also provides an aluminum-promoted cobalt-based Fischer-Tropsch synthesis catalyst loaded by disordered mesoporous silica, which is prepared by the method.
Based on the technical scheme, the specific surface area of the cobalt-based Fischer-Tropsch catalyst is preferably 300-800m2Per g, the pore diameter is 3-10nm, and the pore volume is 0.5-1.5cm3/g。
Based on the technical scheme, the cobalt-based Fischer-Tropsch catalyst preferably contains 0.01-5% of Al, 10-30% of active component Co and the balance of SiO2。
The invention also provides application of the cobalt-based Fischer-Tropsch synthesis catalyst, wherein the reaction conditions are 220 ℃, 12Nm3/h/kg cat，2.0MPa，H 22/CO (molar ratio) in the presence of a catalystWhen the Al content is 0.1-1.5 wt%, the conversion rate of CO can reach 67.8% after 100h of reaction.
Advantageous effects
1. The modified amorphous mesoporous silica carrier prepared by the one-pot method has strong controllability, for example, the acidity of the carrier can be adjusted and controlled by changing the content of aluminum, and the specific surface area and the pore diameter can be adjusted and controlled by the time and the temperature of hydrothermal treatment.
2. The aluminum modified amorphous mesoporous silica carrier prepared by the one-pot method has simple preparation process and low cost.
3. The catalyst is simple to prepare, the process is mature, and the industrial production of the catalyst is facilitated.
4. The invention prepares the Fischer-Tropsch synthesis catalyst with high activity and high stability on the premise of not using a noble metal auxiliary agent, reduces the cost of the catalyst and is beneficial to the popularization and the application of the catalyst.
Drawings
FIG. 1 is a graph showing (a) nitrogen adsorption isotherm and (b) pore size distribution of the cobalt-based catalyst in example 4.
Figure 2 is the XRD pattern of the catalysts in examples 1, 2, 3, 6, 7.
FIG. 3 is a transmission electron microscope and particle size distribution chart of the catalyst in example 3.
FIG. 4 is a transmission electron microscope and particle size distribution chart of the catalyst in example 4.
FIG. 5 is a transmission electron microscope and particle size distribution chart of the catalyst in example 5.
Detailed Description
The process and effect of the present invention will be further described with reference to examples.
Example 1
0.2063g of aluminum isopropoxide was weighed, dissolved in ethanol, and after complete dissolution, ethyl orthosilicate (TEOS, 21.0443g) was added, followed by dropwise addition of a mixed solution of triethanolamine (TEA, 14.8982g) and water (11.4345 g). After the addition was complete, stirring was carried out for about 20min and 17.3707g of tetraethylammonium hydroxide (TEAOH) were added dropwise. Stirring at room temperature until a transparent gel is formed, then drying at 110 ℃ for 24h, carrying out hydrothermal treatment at 180 ℃ for 3h, and roasting at 600 ℃ for 8h in the air atmosphere to obtain the Al-modified amorphous mesoporous silica.
The finally obtained amorphous mesoporous silica modified by aluminum is sieved, and 1.5g of particles with the particle size of 160-400 mu m are weighed. 0.8235g of cobalt nitrate hexahydrate is weighed according to the content of the final catalyst cobalt of 10 percent and dissolved in a mixed solution of 1.5mL of water and 1.5mL of ethanol, the cobalt nitrate hexahydrate is easily dripped on 1.5g of aluminum modified amorphous mesoporous silica, the amorphous mesoporous silica is dried for 12 hours at the temperature of 110 ℃, and is roasted for 2 hours at the temperature of 350 ℃ in an air atmosphere. The resulting catalyst was labeled CFT-1.
The catalyst evaluation experiment was carried out in a high-pressure gas-solid fixed bed reaction apparatus, and the reduction was carried out under normal pressure in a pure hydrogen atmosphere at 350 ℃ for 6 hours. And cutting the cooled synthesis gas into synthesis gas for reaction, wherein the synthesis gas is introduced at a low temperature (190-. The reaction effluent is collected by a hot trap and a cold trap respectively. The reaction conditions were 220 ℃ and 12Nm3/h/kg cat,2.0MPa,H2and/CO is 2 (molar ratio). The results of the Fischer-Tropsch synthesis reaction (after 100 h) using the C-1 catalyst are shown in Table 1.
Example 2
0.0692g of aluminum isopropoxide was weighed, dissolved in ethanol, and after complete dissolution, ethyl orthosilicate (TEOS, 21.1630g) was added, followed by dropwise addition of a mixed solution of triethanolamine (TEA, 14.9822g) and water (11.4989 g). After the addition was complete, stirring was carried out for about 20min and 17.4686g of tetraethylammonium hydroxide (TEAOH) were added dropwise. Stirring at room temperature until a transparent gel is formed, then drying at 110 ℃ for 24h, carrying out hydrothermal treatment at 180 ℃ for 3h, and roasting at 600 ℃ for 8h in the air atmosphere to obtain the Al-modified amorphous mesoporous silica.
The finally obtained amorphous mesoporous silica modified by aluminum is sieved, and 1.5g of particles with the particle size of 160-400 mu m are weighed. 0.8235g of cobalt nitrate hexahydrate is weighed according to the content of the final catalyst cobalt of 10 percent and dissolved in a mixed solution of 1.5mL of water and 1.5mL of ethanol, the cobalt nitrate hexahydrate is easily dripped on 1.5g of aluminum modified amorphous mesoporous silica, the amorphous mesoporous silica is dried for 12 hours at the temperature of 110 ℃, and is roasted for 2 hours at the temperature of 350 ℃ in an air atmosphere. The resulting catalyst was labeled CFT-2. Evaluation of catalyst Activity the experimental conditions were the same as in example 1. The results of the Fischer-Tropsch synthesis reaction using the CFT-2 catalyst are shown in Table 1.
Example 3
0.1036g of aluminum isopropoxide was weighed, dissolved in ethanol, and after complete dissolution, ethyl orthosilicate (TEOS, 21.1332g) was added, followed by dropwise addition of a mixed solution of triethanolamine (TEA, 14.9611g) and water (11.4828 g). After the addition was complete, stirring was carried out for about 20min and 17.4440g of tetraethylammonium hydroxide (TEAOH) were added dropwise. Stirring at room temperature until a transparent gel is formed, then drying at 110 ℃ for 24h, carrying out hydrothermal treatment at 180 ℃ for 3h, and roasting at 600 ℃ for 8h in the air atmosphere to obtain the Al-modified amorphous mesoporous silica.
The finally obtained amorphous mesoporous silica modified by aluminum is sieved, and 1.5g of particles with the particle size of 160-400 mu m are weighed. 0.8235g of cobalt nitrate hexahydrate is weighed according to the content of the final catalyst cobalt of 10 percent and dissolved in a mixed solution of 1.5mL of water and 1.5mL of ethanol, the cobalt nitrate hexahydrate is easily dripped on 1.5g of aluminum modified amorphous mesoporous silica, the amorphous mesoporous silica is dried for 12 hours at the temperature of 110 ℃, and is roasted for 2 hours at the temperature of 350 ℃ in an air atmosphere. The resulting catalyst was labeled CFT-3. Evaluation of catalyst Activity the experimental conditions were the same as in example 1. The results of the Fischer-Tropsch synthesis reaction using the CFT-3 catalyst are shown in Table 1.
Example 4
0.8050g of aluminum isopropoxide was weighed, dissolved in ethanol, and after complete dissolution, ethyl orthosilicate (TEOS, 20.5263g) was added, and then a mixed solution of triethanolamine (TEA, 14.5315g) and water (11.1530g) was added dropwise. After the addition was complete, stirring was carried out for about 20min and 16.9431g of tetraethylammonium hydroxide (TEAOH) were added dropwise. Stirring at room temperature until a transparent gel is formed, then drying at 110 ℃ for 24h, carrying out hydrothermal treatment at 180 ℃ for 3h, and roasting at 600 ℃ for 8h in the air atmosphere to obtain the Al-modified amorphous mesoporous silica.
The finally obtained amorphous mesoporous silica modified by aluminum is sieved, and 1.5g of particles with the particle size of 160-400 mu m are weighed. 0.8235g of cobalt nitrate hexahydrate is weighed according to the content of the final catalyst cobalt of 10 percent and dissolved in a mixed solution of 1.5mL of water and 1.5mL of ethanol, the cobalt nitrate hexahydrate is easily dripped on 1.5g of aluminum modified amorphous mesoporous silica, the amorphous mesoporous silica is dried for 12 hours at the temperature of 110 ℃, and is roasted for 2 hours at the temperature of 350 ℃ in an air atmosphere. The resulting catalyst was labeled CFT-4. TheN of catalyst2The adsorption isotherm and pore size distribution are shown in fig. 1, from which it can be seen that the catalyst is mainly mesoporous and has a narrow pore size distribution of about 4 nm.
Evaluation of catalyst Activity the experimental conditions were the same as in example 1. The results of the Fischer-Tropsch synthesis reaction using the CFT-4 catalyst are shown in Table 1.
Comparative example 1
A mixed solution of triethanolamine (TEA, 15.0246g) and water (11.5315g) was added dropwise to 21.2228g of Tetraethylorthosilicate (TEOS). After the addition was complete, stirring was carried out for about 20min and 17.5180g of tetraethylammonium hydroxide (TEAOH) were added dropwise. Stirring at room temperature until a transparent gel is formed, then drying at 110 ℃ for 24h, carrying out hydrothermal treatment at 180 ℃ for 3h, and roasting at 600 ℃ for 8h in the air atmosphere to obtain the amorphous mesoporous silica.
The amorphous mesoporous silica obtained finally is sieved, and 1.5g of particles with the particle size of 160-400 mu m are weighed. 0.8235g of cobalt nitrate hexahydrate is weighed according to the content of the final catalyst cobalt which is 10 percent and dissolved in a mixed solution of 1.5mL of water and 1.5mL of ethanol, the cobalt nitrate hexahydrate is easily dripped on 1.5g of amorphous mesoporous silica, the amorphous mesoporous silica is dried for 12 hours at the temperature of 110 ℃, and the amorphous mesoporous silica is roasted for 2 hours at the temperature of 350 ℃ in the air atmosphere. The resulting catalyst was labeled CFT-5. Evaluation of catalyst Activity the experimental conditions were the same as in example 1. The results of the Fischer-Tropsch synthesis reaction using the CFT-5 catalyst are shown in Table 1.
It can be seen from the XRD pattern of fig. 2 that the active component cobalt is well dispersed, and from fig. 3 to 5 that the particle size of cobalt is 3 to 6 nm.
TABLE 1 evaluation results of catalysts
Claims (10)
1. A preparation method of a cobalt-based Fischer-Tropsch synthesis catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) in-situ synthesizing aluminum modified disordered mesoporous silicon dioxide by adopting a one-pot method;
(2) and then loading metal cobalt on the aluminum modified disordered mesoporous silica by adopting an impregnation method, drying and roasting to obtain the cobalt-based Fischer-Tropsch synthesis catalyst.
2. The method of claim 1, wherein: in the cobalt-based Fischer-Tropsch synthesis catalyst, the weight percentage of Al is 0.01-5 wt%, and the weight percentage of Co is 10-30 wt%.
3. The method according to claim 1, wherein the one-pot method for in-situ synthesis of the aluminum-modified disordered mesoporous silica comprises the following specific steps: firstly dissolving an Al precursor, then adding an Si precursor, stirring for 20-40 minutes at 20-40 ℃, adding a template agent, continuously stirring for 20-40 minutes, adding a pore-forming agent, stirring for 48 hours at 20-40 ℃, drying, carrying out hydrothermal treatment, and roasting to obtain the aluminum-modified disordered mesoporous silica; the aluminum source is as follows: silicon source: template agent: the mol ratio of the pore-forming agent is 0.3-4% and 1:1: 0.3.
4. The method according to claim 3, wherein the precursor of Al salt is aluminum sulfate, aluminum isopropoxide, aluminum nitrate, aluminum chlorate.
5. The method according to claim 3, wherein the precursor of Si is tetraethoxysilane, sodium metasilicate, or silica sol.
6. The method of claim 3, wherein the templating agent is Triethanolamine (TEA), tetraethylene glycol (TEG), diethanolamine; the pore-forming agent is one of tetraethylammonium hydroxide (TEAOH) and tetrapropylammonium hydroxide (TPAOH).
7. A process according to claim 3, characterized in that the drying temperature is 70-120 ℃ and the time is 2-24 h; the hydrothermal treatment temperature is 120-180 ℃, and the time is 2-15 h; the roasting temperature is 600-800 ℃, and the time is 4-12 h.
8. The method according to claim 1, wherein the drying temperature in the step (2) is 70-120 ℃ and the time is 4-48 h; the roasting temperature is 300-450 ℃, and the time is 2-24 h.
9. A cobalt based fischer-tropsch synthesis catalyst prepared by the process of any one of claims 1 to 8.
10. A cobalt-based fischer-tropsch catalyst according to claim 9, wherein the cobalt-based fischer-tropsch catalyst has a specific surface area of 300-800m2Per g, the pore diameter is 3-10nm, and the pore volume is 0.5-1.5cm3(ii)/g; the particle size of the cobalt particles is 3-15 nm.
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