CN108722411A - The catalyst and preparation method thereof of α-alundum (Al2O3) load ferroso-ferric oxide - Google Patents
The catalyst and preparation method thereof of α-alundum (Al2O3) load ferroso-ferric oxide Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title description 5
- 229910052593 corundum Inorganic materials 0.000 title description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 title description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 title description 2
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 16
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- -1 octadecylene Chemical group 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 238000005336 cracking Methods 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000001802 infusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HDDSHPAODJUKPD-UHFFFAOYSA-N fenbendazole Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1SC1=CC=CC=C1 HDDSHPAODJUKPD-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J23/745—Iron
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of α-Al of synthesis gas Efficient Conversion2O3Load Fe3O4Catalyst and preparation method thereof.High-temperature cracking method is utilized to prepare Fe for the first time3O4Nano particle is simultaneously loaded to α-Al2O3Carrier, while being applied to the direct reaction for preparing light olefins system of synthesis gas, catalyst preparation process is divided into two steps, and the first step is to prepare Fe using high-temperature cracking method3O4Nano particle is loaded to α-Al by nano particle, second step2O3Carrier.The invention has the advantages that active component has Fe3O4Crystalline phase, the preparation process make the particle size of active component only related with Pintsch process process, and unrelated with the load capacity of active component.
Description
Technical field
The present invention relates to synthesis gas (CO/H2) catalysis technical field, more particularly to a kind of synthesis gas Efficient Conversion
α-Al2O3Load Fe3O4Catalyst and preparation method thereof.
Background technology
Synthesis gas can be used for preparing numerous industrial chemicals such as methane, low-carbon alkene, low-carbon alkanes, gasoline, diesel oil and liquid
Fluid fuel is a kind of important material gas, and main source is petroleum cracking, depends critically upon petroleum resources.However, I
State's energy resource structure present situation is " oil-poor, few gas, coal relative abundance ", and the dependence on foreign countries for oil from 2008 China Nian Qi has been more than
Internationally recognized safe-guard line 50%, and in 2013 more than 60%, seriously threaten the energy security in China.Therefore, it studies
Meet China to the excessive of Imported oil resource by the relevant technologies of the Non oil-based route synthesis gas Efficient Conversion in source of coal
It relies on.
The Efficient Conversion of synthesis gas is with CO, H2For raw material, direct Synthin under the effect of the catalyst, reactional equation
For (2n+1) H2+n CO→CnH2n+2+n H2O；2n H2+n CO→CnH2n+n H2O；And along with water gas shift reation H2O+CO
→CO2+H2.Its product composition is complicated, is distributed in Anderson-Schulz-Flory (ASF).It is distributed according to ASF model products,
Synthesis gas converted product is difficult to focus on certain carbon number, and the transformation of catalyst activity phase, area carbon, high temperature cause activity
Component is sintered and lower mechanical strength also becomes industrialized bottleneck.
Synthesis gas conversion process is mainly used for synthetic oil and low-carbon alkene at present, and catalyst includes mainly Co, Fe,
Ru, Ni etc., wherein Co, Fe series catalysts have good reactivity worth and cheap, are conducive to large-scale application in industry
Production.In contrast, Fe series catalysts technological operation range is wide, according to the modulation of reaction temperature and pressure, optionally gives birth to
At alkene, aromatic hydrocarbon and oxygenatedchemicals.α-Al2O3Due to its surface inertness, be conducive to the reduction and carbonization of Fe components, thus
It is a kind of good carrier of preparation of low carbon olefines by synthetic gas.
Traditional support type Fe series catalysts mostly use infusion process and upload active component, and the method is roasted in active component high temperature
Burning process is easy so that active component and the stronger interaction of carrier generation, reduce the activity and stability of catalyst.It is another
Aspect, in high Fe load capacity, obtained particle size is also bigger, is unfavorable for the raising of conversion ratio and the life of low-carbon alkene
At.It is therefore desirable to design more efficient loaded catalyst and preparation method thereof.
Invention content
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide a kind of synthesis gas Efficient Conversions
α-Al2O3Load Fe3O4Catalyst and preparation method thereof.High-temperature cracking method is utilized to prepare Fe for the first time3O4Nano particle and by its
Load to α-Al2O3Carrier, while being applied to the direct reaction for preparing light olefins system of synthesis gas, catalyst preparation process is divided into two
Step, the first step are to prepare Fe using high-temperature cracking method3O4Nano particle is loaded to α-Al by nano particle, second step2O3Carrier.
The process makes the particle size of active component only related with Pintsch process process, unrelated with load capacity.It can be according to using need
Prepare the catalyst of varying particle size and different loads amount.Catalyst choice prepared by the method is higher, and service life is long,
Manufacturing cost is low, and process is relatively easy.
The technical solution adopted to achieve the purpose of the present invention is：
α-the Al of the present invention2O3Load Fe3O4Catalyst, wherein carrier α-Al2O3Account for the 70- of catalyst weight
99wt%, active component Fe3O4Nano particle accounts for the 1wt%-30wt% of catalyst weight, and the catalyst contains Fe3O4It is brilliant
Phase, Fe3O4The grain size of nano particle be 5-20nm, the catalyst activity will not decline in 60h, the catalyst according to
It is prepared by following step：
S1：Iron oleate and oleic acid are dissolved in high boiling solvent, wherein the mass ratio (5-50) of iron oleate and oleic acid：1, first
With inert gas degassing 30-60min；It is raised to 280-340 DEG C with the heating rate of 3-5 DEG C/min, and keeps 10-60min, then from
So it is cooled to room temperature；
S2：Ethyl alcohol is added to be precipitated, centrifugation is taken；It in redisperse to hexane, is precipitated with ethyl alcohol, centrifugation point
From with hexamethylene constant volume in volumetric flask so that iron-holder 1-3mg/mL obtains Fe3O4The cyclohexane solution of nano particle；
S3：Take what is quantitatively prepared to contain Fe3O4The cyclohexane solution of nano particle, mixes with carrier, wherein cyclohexane solution body
Product is (10~100) with carrier quality ratio：12-36h is stirred at room temperature in 1mL/g, is spin-dried for using Rotary Evaporators, then in air
The lower 300-500 DEG C of roasting 2-6h of purging, finally obtains α-Al2O3Load Fe3O4The catalyst of nano particle.
Preferably, the Fe3O4The grain size of nano particle is 11.3-12.7nm.
Preferably, by adjusting the mass ratio of iron oleate and oleic acid in S1, identical load amount varying particle size can be obtained
Fe3O4Load to α-Al2O3On catalyst.
Preferably, carrier accounts for the 90-95wt% of catalyst weight, active component Fe3O4Account for the preferred of catalyst weight
5wt%~10%.
Another aspect of the present invention further includes a kind of preparing α-Al2O3Load Fe3O4The method of catalyst, including following step
Suddenly：
S1：Iron oleate and oleic acid are dissolved in high boiling solvent, wherein the mass ratio (5-50) of iron oleate and oleic acid：1, first
With inert gas degassing 30-60min；It is raised to 280-340 DEG C with the heating rate of 3-5 DEG C/min, and keeps 10-60min, then from
So it is cooled to room temperature；
S2：Ethyl alcohol is added to be precipitated, centrifugation is taken；It in redisperse to hexane, is precipitated with ethyl alcohol, centrifugation point
From with hexamethylene constant volume in volumetric flask so that iron-holder 1-3mg/mL obtains Fe3O4The cyclohexane solution of nano particle；
S3：Take what is quantitatively prepared to contain Fe3O4The cyclohexane solution of nano particle, mixes with carrier, wherein cyclohexane solution with
Carrier quality ratio is (10~100)：12-36h is stirred at room temperature in 1mL/g, is spin-dried for using Rotary Evaporators, is then purged in air
Lower 300-500 DEG C of roasting 2-6h, finally obtains α-Al2O3Load Fe3O4The catalyst of nano particle.
Preferably, the iron oleate in the S1 is prepared by following steps：
1)：It is 20 to take volume ratio:16:35 ethyl alcohol, deionized water and hexane prepares mixed solvent, weighs FeCl3, oil
Sour sodium is dissolved in the mixed solvent and obtains mixed liquor, wherein：FeCl3Molar ratio with enuatrol is 1:3；
2)：Mixed liquor in step 1) is heated to 58-70 DEG C, and keeps 3-5h, after reaction, is washed with water and sharp
It is detached with separatory funnel, takes supernatant, washed repeatedly, vacuum distillation removes excessive solvent, obtained iron oleate.
Preferably, the high boiling solvent in the step S1 is octadecylene or trioctylamine.
Preferably, the inert gas used in the step S1 is nitrogen, argon gas or helium.
Preferably, the rotating speed centrifuged in the step S2 is 9500rpm, time 10min.
Another aspect of the present invention further includes Al2O3Load Fe3O4Catalyst is utilizing preparing hydrocarbon from synthetic gas compound
On application.
Preferably, usage ratio of the reaction using preparing hydrocarbon from synthetic gas compound in gas flow rate and catalyst
For 10000-60000mLg-1·h-1It is carried out under conditions of lower, reducing condition is normal pressure H2, flow is 30-180mLmin-1,
Temperature is 350-450 DEG C, feedstock mol ratio n (H2:CO=1-2), reaction temperature is 300-350 DEG C, and reaction pressure is
Under 0.5-2.5MPa and catalyst existence condition, reaction synthesis is realized.
Compared with prior art, the beneficial effects of the invention are as follows：
Active component is more disperseed and is stablized, and by the dosage of adjusting oleic acid, the control accurate of particle size may be implemented,
And it is unrelated with the load capacity of active component.By regulating and controlling particle size, the activity and stability of catalyst can be effectively improved.It should
Catalyst choice prepared by method is higher, and service life is long, and activity will not decline in 60h, and manufacturing cost is low, and process is relatively simple
It is single.
Description of the drawings
Fig. 1 is the Fe of varying particle size3O4Load to α-Al2O3Catalyst TEM figures, wherein：
Fig. 1 a are the Fe that embodiment 2 obtains3O4/α-Al2O3Catalyst, wherein Fe3O4Grain size be 8.3 ± 0.6nm；
Fig. 1 b are the Fe that embodiment 1 obtains3O4/α-Al2O3Catalyst, wherein Fe3O4Grain size be 12.0 ± 0.7nm；
Fig. 1 c are the Fe that embodiment 3 obtains3O4/α-Al2O3Catalyst, wherein Fe3O4Grain size be 15.2 ± 1.3nm；
Fig. 1 d are the Fe that embodiment 4 obtains3O4/α-Al2O3Catalyst, wherein Fe3O4Grain size be 17.3 ± 1.2nm；
Fig. 2 is varying particle size Fe3O4Load to α-Al2O3Catalyst XRD diagram, wherein：
A is the Fe that embodiment 4 obtains3O4/α-Al2O3Catalyst；
B is the Fe that embodiment 3 obtains3O4/α-Al2O3Catalyst；
C is the Fe that embodiment 1 obtains3O4/α-Al2O3Catalyst；
D is the Fe that embodiment 2 obtains3O4/α-Al2O3Catalyst.
E is α-Al2O3。
Specific implementation mode
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
【Embodiment 1】
Prepare the Fe for the 12nm particle sizes that iron content is 10%3O4/α-Al2O3Catalyst.Preparation process is as follows：Compounding
Liquid (80mL ethyl alcohol, 64mL deionized waters, 140mL hexanes) is closed, 6.50g FeCl are weighed3, 36.5g enuatrols are dissolved in mixed liquor
In；Mixed liquor is heated to 60 DEG C, and keeps 4h, after reaction, detaches, takes with 100mL water washings and using separatory funnel
Supernatant washes repeatedly five times, and excessive solvent is removed using vacuum distillation；Iron oleate 36g and the 3.0g oleic acid that will be obtained
It is dissolved in 100g octadecylenes；First use N2Deaerate 30min；320 DEG C are raised to the heating rate of 3.3 DEG C/min, and keeps 30min
(series reaction having occurred, initial transparent solution becomes muddy and brown solution), then naturally cool to room temperature；It is added
250mL ethyl alcohol is precipitated, and is centrifuged (9500rpm, 10min)；In being distributed to 100mL hexanes, carried out with 250mL ethyl alcohol
Precipitation centrifuges (9500rpm, 10min), and hexamethylene constant volume is used in 500ml volumetric flasks；Take what 150mL prepared to contain Fe3O4
Cyclohexane solution and 4g α-Al2O3Carrier mixing, be stirred at room temperature for 24 hours, be spin-dried for using Rotary Evaporators, then blown in air
Lower 350 DEG C of roastings 4h is swept, Fe is finally obtained3O4/α-Al2O3Catalyst, TEM spectrograms are as shown in Figure 1 b, XRD spectra such as Fig. 2 e institutes
Show.
Wherein：TEM uses the Tecnai G2F20 field emission microscopes of Dutch FEI Co..With Schottky types field
Ejecting gun is electron source, and instrument point resolution and linear resolution are 0.248nm, 0.102nm, accelerating potential 200kV, and highest is put
Big multiple is 190,000 times.Sample preparation procedure is：Sample is carefully ground in the agate mortar, takes and is dispersed in absolute ethyl alcohol on a small quantity
In, disperseed using ultrasonic oscillation, drops in naturally dry on the copper mesh with carbon film；
XRD is characterized using RigakuD/Max-2500 types X-ray diffractometer (Rigaku company), instrument work ginseng
Number is as follows：Using Cu K α as radiographic source (λ=0.154nm), operating voltage 40kV, operating current 200mA, scanning range 10-
90 °, sweep speed is 8 °/min.
【Embodiment 2-4】
In the case where other experiment conditions are identical with embodiment 1, oleic acid amount is changed to 2.4g (embodiments respectively
2), 3.4g (embodiment 3), 5.70g (embodiment 4), obtains the Fe of varying particle size3O4Nano particle finally obtains identical negative
The Fe of carrying capacity varying particle size3O4/α-Al2O3Catalyst, the Fe that embodiment 2-4 is obtained3O4/α-Al2O3The TEM of catalyst is composed
Figure is respectively as shown in Fig. 1 a, 1c, 1d, and XRD spectra is respectively as shown in Fig. 2 d, 2c, 2a.
As seen from Figure 1, the Fe for taking high-temperature cracking method to be prepared3O4Nanoparticle size distributes very evenly (error
Within 10%).Meanwhile the ratio by changing oleic acid and iron oleate, various sizes of Fe can be obtained3O4Nano particle.
As seen from Figure 2, varying particle size and metal-doped obtained catalyst mainly contain Fe3O4Crystalline phase passes
The mainly Fe that the infusion process and the precipitation method of system obtain2O3Crystalline phase, and Fe3O4Crystalline phase ratio Fe2O3Crystalline phase is easier to restore and be carbonized,
To obtain higher activity.
【Embodiment 5-8】
Dry catalyst fines tabletting is sized to 40~60 mesh, measuring the catalyst that embodiment 1-4 is obtained, (Fe is being urged
Mass fraction in agent is 10%), loadings 0.2g carries out catalyst activity evaluation in pressurization minisize reaction system, point
Embodiment 5-8 is not obtained.It is passed through reactant 45mL/min CO, 45mL/minH2And interior standard gas 10mL/min Ar, at 340 DEG C,
The usage ratio of 1.0Mpa, reaction gas flow velocity and catalyst is 27000mLg-1·h-1Under reacted, using gas phase color
Spectrum analyzes product.Gained reactivity worth is as shown in table 1.
The Fe of 1 varying particle size of table3O4Load to α-Al2O3On catalyst synthesis gas Efficient Conversion reaction result
Wherein：FTY indicates that the molal quantity of the iron of unit mass conversion CO per second, O/P (2-4) indicate C2~C4In compound
The ratio of alkene and alkane.
Wherein：Fe3O4(12.0)/α-Al2O3Indicate Fe3O4The grain size of nano particle is 12.0nm.
【Embodiment 9-11】
Under other conditions reaction condition same as Example 5, reaction pressure is changed to 2.0MPa, and reduction temperature is respectively
350 DEG C, 400 DEG C, 450 DEG C, respectively obtain embodiment 9-11.
The Fe of the different reduction temperatures of table 33O4(12.0nm)/α-Al2O3Catalyst synthesis gas Efficient Conversion reaction result
Different reduction temperatures influences the conversion ratio of catalyst and selectivity less notable as seen from Table 3.
【Comparative example 1】
Fe is prepared using traditional infusion process2O3/α-Al2O3Catalyst.Process is as follows：Weigh 3.2g ferric citrates
(NH4)3Fe(C6H5O7)2, it is dissolved in 100mL deionized waters.4.0g α-Al are added2O3, it stirs for 24 hours, is spin-dried for using Rotary Evaporators,
120 DEG C drying over night, and then 500 DEG C of roasting 4h (5 DEG C/min) under air purging, finally obtain 10Fe/ α-Al2O3Catalyst.
Catalyst performance evaluation is carried out under the reaction condition of embodiment 5.FTY is 42 × 10-6molCO gFe -1s-1, well below implementation
The catalyst activity of example 1-4, also, this catalyst has apparent deactivation phenomenom in 30h.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (10)
1.α-Al2O3Load Fe3O4Catalyst, it is characterised in that：Wherein carrier α-Al2O3Account for the 70- of catalyst weight
99wt%, active component Fe3O4Nano particle accounts for the 1wt%-30wt% of catalyst weight, and the catalyst contains Fe3O4It is brilliant
Phase, Fe3O4The grain size of nano particle be 5-20nm, the catalyst activity will not decline in 60h, the catalyst according to
It is prepared by following step：
S1：Iron oleate and oleic acid are dissolved in high boiling solvent, wherein the mass ratio (5-50) of iron oleate and oleic acid：1, first with lazy
Property gas deaerate 30-60min；It is raised to 280-340 DEG C with the heating rate of 3-5 DEG C/min, and keeps 10-60min, then is naturally cold
But room temperature is arrived；
S2：Ethyl alcohol is added to be precipitated, centrifugation is taken；It in redisperse to hexane, is precipitated, is centrifuged with ethyl alcohol,
Hexamethylene constant volume is used in volumetric flask so that iron-holder 1-3mg/mL obtains Fe3O4The cyclohexane solution of nano particle；
S3：Take what is quantitatively prepared to contain Fe3O4Cyclohexane solution, mixed with carrier, wherein cyclohexane solution volume and carrier quality
Than for (10~100)：12-36h is stirred at room temperature in 1mL/g, is spin-dried for using Rotary Evaporators, then the 300-500 under air purging
DEG C roasting 2-6h, finally obtain α-Al2O3Load Fe3O4The catalyst of nano particle.
2. α-Al according to claim 12O3Load Fe3O4Catalyst, it is characterised in that：By adjusting iron oleate in S1
With the mass ratio of oleic acid, the Fe of identical load amount varying particle size can be obtained3O4Load to α-Al2O3On catalyst.
3. α-Al according to claim 12O3Load Fe3O4Catalyst, it is characterised in that：Wherein carrier accounts for catalyst weight
The 90-95wt% of amount, active component Fe3O4Account for preferred 5wt%~10% of catalyst weight.
4. a kind of preparing α-Al2O3Load Fe3O4The method of catalyst, includes the following steps：
S1：Iron oleate and oleic acid are dissolved in high boiling solvent, wherein the mass ratio (5-50) of iron oleate and oleic acid：1, first with lazy
Property gas deaerate 30-60min；It is raised to 280-340 DEG C with the heating rate of 3-5 DEG C/min, and keeps 10-60min, then is naturally cold
But room temperature is arrived；
S2：Ethyl alcohol is added to be precipitated, centrifugation is taken；It in redisperse to hexane, is precipitated, is centrifuged with ethyl alcohol,
Hexamethylene constant volume is used in volumetric flask so that iron-holder 1-3mg/mL obtains Fe3O4The cyclohexane solution of nano particle；
S3：Take what is quantitatively prepared to contain Fe3O4The cyclohexane solution of nano particle, mixes with carrier, wherein cyclohexane solution and carrier
Mass ratio is (10~100)：12-36h is stirred at room temperature in 1mL/g, is spin-dried for using Rotary Evaporators, then under air purging
300-500 DEG C of roasting 2-6h, finally obtains α-Al2O3Load Fe3O4Catalyst.
5. preparation α-Al according to claim 42O3Load Fe3O4The method of catalyst, it is characterised in that：In the S1
Iron oleate is prepared by following steps：
1)：It is 20 to take volume ratio:16:35 ethyl alcohol, deionized water and hexane prepares mixed solvent, weighs FeCl3, enuatrol,
It is dissolved in the mixed solvent and obtains mixed liquor, wherein：FeCl3Molar ratio with enuatrol is 1:3；
2)：Mixed liquor in step 1) is heated to 58-70 DEG C, and keeps 3-5h, after reaction, is washed with water and utilizes and divide
Liquid funnel detaches, and takes supernatant, washes repeatedly, and vacuum distillation removes excessive solvent, obtains iron oleate.
6. a kind of α-Al are prepared according to claim 42O3Load Fe3O4The method of catalyst, it is characterised in that：The S1
In high boiling solvent be octadecylene or trioctylamine.
7. a kind of α-Al are prepared according to claim 42O3Load Fe3O4The method of catalyst, it is characterised in that：The step
The inert gas used in rapid S1 is nitrogen, argon gas or helium.
8. a kind of α-Al are prepared according to claim 42O3Load Fe3O4The method of catalyst, it is characterised in that：The step
The rotating speed centrifuged in rapid S2 is 9500rpm, time 10min.
9. α-Al as claimed in claim 12O3Load Fe3O4Catalyst is utilizing the application in preparing hydrocarbon from synthetic gas compound.
10. α-Al according to claim 92O3Load Fe3O4Catalyst is using in preparing hydrocarbon from synthetic gas compound
Using, it is characterised in that：The reaction is 10000-60000mLg in the usage ratio of gas flow rate and catalyst-1·h-1
It is carried out under conditions of lower, reducing condition is normal pressure H2, flow is 30-180mLmin-1, temperature is 350-450 DEG C, feedstock
Mol ratio H2:CO=(1-2)：1, reaction temperature is 300-350 DEG C, and reaction pressure is that there are items for 0.5-2.5MPa and catalyst
Under part, reaction synthesis is realized.
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| CN105032450A (en) * | 2015-07-29 | 2015-11-11 | 中国科学院山西煤炭化学研究所 | Catalyst suitable for Fischer-Tropsch synthesis medium circulation process, and preparation method and application of catalyst |
| EP3075450A1 (en) * | 2013-11-28 | 2016-10-05 | Korea Research Institute of Chemical Technology | Method for storing activated fischer-tropsch synthesis catalyst |
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| EP2669007A1 (en) * | 2012-05-30 | 2013-12-04 | IFP Energies nouvelles | Method for preparing a catalyst using at least one quick-drying step and at least one step of fluidised-bed drying and use thereof for Fischer-Tropsch synthesis |
| EP3075450A1 (en) * | 2013-11-28 | 2016-10-05 | Korea Research Institute of Chemical Technology | Method for storing activated fischer-tropsch synthesis catalyst |
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