CN108722411B - Catalyst of alpha-aluminum oxide loaded ferroferric oxide and preparation method thereof - Google Patents
Catalyst of alpha-aluminum oxide loaded ferroferric oxide and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 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
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
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- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
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- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 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
- 238000007865 diluting Methods 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052786 argon 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 230000001419 dependent effect Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- -1 comprises Co Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012084 conversion product Substances 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
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- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
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- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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Images
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 alpha-Al for high-efficiency conversion of synthesis gas2O3Fe load3O4And a process for preparing the same. Firstly utilizing high-temperature cracking method to prepare Fe3O4Nanoparticles and loading thereof to alpha-Al2O3The carrier is simultaneously applied to a reaction system for directly preparing low-carbon olefin from synthesis gas, the preparation process of the catalyst is divided into two steps, and the first step is to prepare Fe by using a high-temperature cracking method3O4Nanoparticles, second step of loading the nanoparticles to alpha-Al2O3And (3) a carrier. The invention has the beneficial effect that the active component has Fe3O4A crystalline phase, the preparation being such that the particle size of the active component is dependent only on the pyrolysis process and not on the loading of the active component.
Description
Technical Field
The invention relates to synthesis gas (CO/H)2) In particular to alpha-Al for high-efficiency conversion of synthesis gas2O3Fe load3O4And a process for preparing the same.
Background
The synthesis gas can be used for preparing various chemical raw materials such as methane, low-carbon olefin, low-carbon alkane, gasoline, diesel oil and the like and liquid fuel, is an important chemical raw material gas, is mainly derived from petroleum cracking, and depends heavily on petroleum resources. However, the current energy structure situation of China is 'lean oil, little gas and relatively rich coal', the dependence of oil in China on the outside is over 50% of the internationally recognized safety warning line since 2008, and over 60% in 2013, so that the energy safety of China is seriously threatened. Therefore, the research on the related technology of the high-efficiency conversion of the non-petroleum route synthetic gas with coal as the source accords with the excessive dependence of China on imported petroleum resources.
The high-efficiency conversion of the synthesis gas is to convert CO and H2Directly synthesizing hydrocarbon under the action of catalyst by using raw material as raw material, and its reaction equation is (2n +1) H2+n CO→CnH2n+2+n H2O；2n H2+n CO→CnH2n+n H2O; accompanied by a water-vapor shift reaction H2O+CO→CO2+H2. The product composition is complex and is distributed in Anderson-Schulz-Flory (ASF). According to the distribution of ASF model products, the synthesis gas conversion products are difficult to be concentrated to a certain carbon number, and the active component sintering and lower mechanical strength caused by the conversion of the catalyst active phase, surface carbon and high temperature also become the bottleneck of industrialization.
At present, the conversion process of the synthesis gas is mainly used for synthesizing oil products and low-carbon olefins, and the catalyst mainly comprises Co, Fe, Ru, Ni and the like, wherein the Co and Fe catalysts have good reaction performance and low price, and are beneficial to large-scale application in industrial production. In contrast, the Fe-based catalyst has a wide process operation range, and can selectively generate olefins, aromatics and oxygenates according to the modulation of the reaction temperature and pressure. alpha-Al2O3Because the surface inertia of the carrier is beneficial to the reduction and carbonization of the Fe component, the carrier is a good carrier for preparing low-carbon olefin by using the synthesis gas.
The traditional supported Fe-based catalyst mostly adopts an impregnation method to load active components, and the method is easy to cause the active components and a carrier to generate stronger interaction in the high-temperature roasting process of the active components, thereby reducing the activity and stability of the catalyst. On the other hand, at high Fe loading, the obtained particle size is also large, which is not beneficial to the improvement of the conversion rate and the generation of low-carbon olefin. There is therefore a need to design more efficient supported catalysts and methods for their preparation.
Disclosure of Invention
The invention aims to provide a high-efficiency synthesis gas aiming at the technical defects in the prior artConverted alpha-Al2O3Fe load3O4And a process for preparing the same. Firstly utilizing high-temperature cracking method to prepare Fe3O4Nanoparticles and loading thereof to alpha-Al2O3The carrier is simultaneously applied to a reaction system for directly preparing low-carbon olefin from synthesis gas, the preparation process of the catalyst is divided into two steps, and the first step is to prepare Fe by using a high-temperature cracking method3O4Nanoparticles, second step of loading the nanoparticles to alpha-Al2O3And (3) a carrier. This process allows the particle size of the active component to be dependent only on the pyrolysis process and not on the loading. The catalyst can be prepared in different particle sizes and different loading amounts according to the use requirement. The catalyst prepared by the method has the advantages of high selectivity, long service life, low preparation cost and relatively simple process.
The technical scheme adopted for realizing the purpose of the invention is as follows:
alpha-Al of the invention2O3Fe load3O4Wherein the carrier is alpha-Al2O370-99 wt% of catalyst weight, active component Fe3O4The nanoparticles comprise 1 wt% to 30 wt% of the catalyst weight, the catalyst comprising Fe3O4Crystalline phase, Fe3O4The particle size of the nano particles is 5-20nm, the activity of the catalyst is not reduced within 60h, and the catalyst is prepared according to the following steps:
s1: dissolving iron oleate and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the iron oleate to the oleic acid (5-50): 1, degassing for 30-60min by using inert gas; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting with cyclohexane to constant volume in volumetric flask to obtain Fe with iron content of 1-3mg/mL3O4A cyclohexane solution of nanoparticles;
s3: taking the prepared Fe3O4Cyclohexane solution of nanoparticles, mixed with a carrier, whichThe mass ratio of the cyclohexane solution volume to the carrier is (10-100): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then roasting at the temperature of 300 ℃ and 500 ℃ for 2-6h under air blowing to finally obtain alpha-Al2O3Fe load3O4A catalyst of nanoparticles.
Preferably, said Fe3O4The particle size of the nano-particles is 11.3-12.7 nm.
Preferably, the same loading of Fe with different particle sizes can be obtained by adjusting the mass ratio of ferric oleate to oleic acid in S13O4Loaded on alpha-Al2O3A catalyst on a support.
Preferably, the carrier accounts for 90-95 wt% of the weight of the catalyst, and the active component Fe3O4Preferably 5 to 10% by weight of the catalyst.
In another aspect of the invention, the method also comprises a step of preparing alpha-Al2O3Fe load3O4A process for the preparation of a catalyst comprising the steps of:
s1: dissolving iron oleate and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the iron oleate to the oleic acid (5-50): 1, degassing for 30-60min by using inert gas; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting with cyclohexane to constant volume in volumetric flask to obtain Fe with iron content of 1-3mg/mL3O4A cyclohexane solution of nanoparticles;
s3: taking the prepared Fe3O4Mixing a cyclohexane solution of nanoparticles with a carrier, wherein the mass ratio of the cyclohexane solution to the carrier is (10-100): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then roasting at the temperature of 300 ℃ and 500 ℃ for 2-6h under air blowing to finally obtain alpha-Al2O3Fe load3O4A catalyst of nanoparticles.
Preferably, the iron oleate in S1 is prepared by the following steps:
1): preparing a mixed solvent by taking ethanol, deionized water and hexane in a volume ratio of 20:16:35, and weighing FeCl3And dissolving sodium oleate in the mixed solvent to obtain a mixed solution, wherein: FeCl3And sodium oleate in a molar ratio of 1: 3;
2): heating the mixed solution in the step 1) to 58-70 ℃, keeping the temperature for 3-5h, washing with water after the reaction is finished, separating by using a separating funnel, taking supernate, repeatedly washing, and distilling under reduced pressure to remove excessive solvent to obtain the iron oleate.
Preferably, the high-boiling solvent in step S1 is octadecene or trioctylamine.
Preferably, the inert gas used in step S1 is nitrogen, argon or helium.
Preferably, the rotation speed of the centrifugal separation in the step S2 is 9500rpm, and the time is 10 min.
In another aspect of the present invention, Al is further included2O3Fe load3O4The application of the catalyst in preparing hydrocarbon compounds by using synthesis gas.
Preferably, the reaction for preparing the hydrocarbon compound by using the synthesis gas has a gas flow rate and the dosage ratio of the catalyst of 10000--1·h-1Under the condition that the reduction condition is normal pressure H2The flow rate is 30-180 mL/min-1The temperature is 350-450 ℃, and the raw material feeding molar ratio n (H)2CO is 1-2), the reaction temperature is 300-350 ℃, the reaction pressure is 0.5-2.5MPa, and the reaction synthesis is realized under the existence of a catalyst.
Compared with the prior art, the invention has the beneficial effects that:
the active components are more dispersed and stable, the precise regulation and control of the particle size can be realized by regulating the using amount of oleic acid, and the active components are irrelevant to the loading amount of the active components. The activity and stability of the catalyst can be effectively improved by regulating and controlling the particle size. The catalyst prepared by the method has the advantages of high selectivity, long service life, no reduction of activity within 60 hours, low preparation cost and relatively simple process.
Drawings
FIG. 1 is Fe of different particle sizes3O4Loaded on alpha-Al2O3TEM image of catalyst, wherein:
FIG. 1a shows Fe obtained in example 23O4/α-Al2O3Catalyst of which Fe3O4The particle size of (A) is 8.3 +/-0.6 nm;
FIG. 1b shows Fe obtained in example 13O4/α-Al2O3Catalyst of which Fe3O4The particle size of (A) is 12.0 +/-0.7 nm;
FIG. 1c shows Fe obtained in example 33O4/α-Al2O3Catalyst of which Fe3O4The grain diameter of the nano-particles is 15.2 +/-1.3 nm;
FIG. 1d is Fe obtained in example 43O4/α-Al2O3Catalyst of which Fe3O4The particle size of the particles is 17.3 +/-1.2 nm;
FIG. 2 shows different particle sizes of Fe3O4Loaded on alpha-Al2O3A catalyst XRD pattern, wherein:
a is Fe obtained in example 43O4/α-Al2O3A catalyst;
b is Fe obtained in example 33O4/α-Al2O3A catalyst;
c is Fe obtained in example 13O4/α-Al2O3A catalyst;
d is Fe obtained in example 23O4/α-Al2O3A catalyst.
e is alpha-Al2O3。
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[ example 1 ]
Preparation of 12nm particle size Fe with 10% iron content3O4/α-Al2O3A catalyst. The preparation process comprises the following steps: the mixture (80mL ethanol, 64mL deionized water, 140mL hexane) was weighed and 6.50g FeCl was added336.5g of sodium oleate is dissolved in the mixed solution; heating the mixed solution to 60 ℃, keeping the temperature for 4 hours, washing the mixed solution with 100mL of water after the reaction is finished, separating the mixed solution by using a separating funnel, taking supernate, repeatedly washing the supernate for five times, and removing excessive solvent by using reduced pressure distillation; dissolving 36g of the obtained iron oleate and 3.0g of oleic acid in 100g of octadecene; firstly using N2Degassing for 30 min; heating to 320 deg.C at a rate of 3.3 deg.C/min, maintaining for 30min (after a series of reactions, the initial transparent solution becomes turbid and brown), and naturally cooling to room temperature; adding 250mL of ethanol for precipitation, and performing centrifugal separation (9500rpm, 10 min); dispersing in 100mL hexane, precipitating with 250mL ethanol, centrifuging (9500rpm, 10min), and adding cyclohexane to the volume in a 500mL volumetric flask; 150mL of prepared cyclohexane solution containing Fe3O4 and 4g of alpha-Al2O3Mixing the carriers, stirring for 24h at room temperature, spin-drying by using a rotary evaporator, and roasting for 4h at 350 ℃ under air blowing to finally obtain Fe3O4/α-Al2O3The catalyst has a TEM spectrum as shown in figure 1b and an XRD spectrum as shown in figure 2 e.
Wherein: the TEM employed a Tecnai G2F20 field emission electron microscope from FEI, the Netherlands. A Schottky type field emission gun is used as an electron source, the point resolution and the line resolution of the instrument are 0.248nm and 0.102nm, the acceleration voltage is 200kV, and the maximum amplification factor is 19 ten thousand times. The sample preparation process comprises the following steps: carefully grinding the sample in an agate mortar, taking a small amount of the ground sample, dispersing the ground sample in absolute ethyl alcohol, dispersing the ground sample by ultrasonic oscillation, and dripping the ground sample on a copper net attached with a carbon film for naturally drying;
XRD was characterized using a RigakuD/Max-2500X-ray diffractometer (Japan science Inc.) with the following operating parameters: cu Kalpha is used as a ray source (lambda is 0.154nm), the working voltage is 40kV, the working current is 200mA, the scanning range is 10-90 degrees, and the scanning speed is 8 degrees/min.
[ examples 2 to 4 ]
Under the same other experimental conditions as those in example 1, the amounts of oleic acid were adjusted to give respective amounts of oleic acidVarying to 2.4g (example 2), 3.4g (example 3), 5.70g (example 4) gave Fe of different particle sizes3O4Nano particles, finally obtaining Fe with the same load and different particle sizes3O4/α-Al2O3Catalyst, Fe obtained in examples 2 to 43O4/α-Al2O3The TEM spectrum of the catalyst is shown in FIGS. 1a, 1c and 1d, and the XRD spectrum is shown in FIGS. 2d, 2c and 2 a.
As can be seen from FIG. 1, Fe was prepared by high temperature pyrolysis3O4The nanoparticle size distribution is very uniform (within 10%). Meanwhile, by changing the proportion of oleic acid and iron oleate, Fe with different sizes can be obtained3O4And (3) nanoparticles.
As can be seen from FIG. 2, the catalysts obtained with different particle sizes and metal doping all contain mainly Fe3O4The crystalline phase, mainly Fe, being obtained by conventional impregnation and precipitation methods2O3Crystalline phase of Fe3O4Crystal phase ratio of Fe2O3The crystal phase is more easily reduced and carbonized, resulting in higher activity.
[ examples 5 to 8 ]
The dried catalyst powder was pressed into tablets and sieved to 40-60 mesh, the catalyst obtained in example 1-4 was measured (mass fraction of Fe in the catalyst was 10%), the loading was 0.2g, and the catalyst activity evaluation was performed in a pressurized micro-reaction system to obtain examples 5-8, respectively. The reactants were introduced at 45mL/min CO and 45mL/minH2And internal standard gas 10mL/min Ar at 340 deg.C and 1.0Mpa, and the ratio of reaction gas flow rate to catalyst amount is 27000 mL-g-1·h-1The reaction was carried out and the product was analyzed by gas chromatography. The resulting reaction properties are shown in table 1.
TABLE 1 Fe of different particle sizes3O4Loaded on alpha-Al2O3High efficiency conversion reaction result of synthesis gas with catalyst
Wherein: FTY represents the moles of iron per second converted to CO per unit mass, O/P (2-4) represents C2～C4The ratio of alkene to alkane in the compound.
Wherein: fe3O4(12.0)/α-Al2O3Represents Fe3O4The particle size of the nanoparticles was 12.0 nm.
[ examples 9 to 11 ]
Examples 9 to 11 were obtained under the same reaction conditions as in example 5 except that the reaction pressure was changed to 2.0MPa, and the reduction temperatures were 350 ℃ and 400 ℃ and 450 ℃ respectively.
TABLE 3 Fe at different reduction temperatures3O4(12.0nm)/α-Al2O3High efficiency conversion reaction result of catalyst synthesis gas
It can be seen from table 3 that different reduction temperatures have less significant effect on the conversion and selectivity of the catalyst.
Comparative example 1
The traditional dipping method is adopted to prepare Fe2O3/α-Al2O3A catalyst. The process is as follows: 3.2g of ferric ammonium citrate (NH) are weighed4)3Fe(C6H5O7)2Dissolved in 100mL of deionized water. 4.0g of alpha-Al was added2O3Stirring for 24h, spin-drying with a rotary evaporator at 120 ℃ overnight, and calcining at 500 ℃ for 4h (5 ℃/min) under air purge to obtain 10 Fe/alpha-Al2O3A catalyst. The catalyst performance evaluation was performed under the reaction conditions of example 5. FTY is 42 multiplied by 10-6molCO gFe -1s-1It is much lower than the activity of the catalysts of examples 1-4, and the catalyst has obvious deactivation phenomenon in 30 h.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1.α-Al2O3Fe load3O4The catalyst of (2), characterized in that: wherein the carrier is alpha-Al2O370-99 wt% of catalyst weight, active component Fe3O4The nanoparticles comprise 1 wt% to 30 wt% of the catalyst weight, the catalyst comprising Fe3O4Crystalline phase, Fe3O4The particle size of the nano particles is 5-20nm, the activity of the catalyst is not reduced within 60h, and the catalyst is prepared according to the following steps:
s1: dissolving iron oleate and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the iron oleate to the oleic acid (5-50): 1, degassing for 30-60min by using inert gas; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting with cyclohexane to constant volume in volumetric flask to obtain Fe with iron content of 1-3mg/mL3O4A cyclohexane solution of nanoparticles;
s3: taking the prepared Fe3O4The cyclohexane solution is mixed with a carrier, wherein the mass ratio of the volume of the cyclohexane solution to the carrier is (10-100): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then roasting at the temperature of 300 ℃ and 500 ℃ for 2-6h under air blowing to finally obtain alpha-Al2O3Fe load3O4A catalyst of nanoparticles;
wherein the iron oleate in S1 is prepared by the following steps:
1): preparing a mixed solvent by taking ethanol, deionized water and hexane in a volume ratio of 20:16:35, and weighing FeCl3And dissolving sodium oleate in the mixed solvent to obtain a mixed solution, wherein: FeCl3And sodium oleate in a molar ratio of 1: 3;
2): heating the mixed solution in the step 1) to 58-70 ℃, keeping the temperature for 3-5h, washing with water after the reaction is finished, separating by using a separating funnel, taking supernate, repeatedly washing, and distilling under reduced pressure to remove excessive solvent to obtain iron oleate; the high-boiling-point solvent in the S1 is octadecene or trioctylamine.
2. alpha-Al according to claim 12O3Fe load3O4The catalyst of (2), characterized in that: by adjusting the mass ratio of the ferric oleate to the oleic acid in S1, Fe with the same loading and different particle sizes can be obtained3O4Loaded on alpha-Al2O3A catalyst on a support.
3. alpha-Al according to claim 12O3Fe load3O4The catalyst of (2), characterized in that: wherein the carrier accounts for 90-95 wt% of the catalyst, and the active component Fe3O45 to 10 percent of the weight of the catalyst.
4. Preparation of alpha-Al2O3Fe load3O4A process for the preparation of a catalyst comprising the steps of:
s1: dissolving iron oleate and oleic acid in a high-boiling-point solvent, wherein the mass ratio of the iron oleate to the oleic acid (5-50): 1, degassing for 30-60min by using inert gas; heating to 280-340 deg.C at a temperature rising rate of 3-5 deg.C/min, maintaining for 10-60min, and naturally cooling to room temperature;
s2: adding ethanol for precipitation, and performing centrifugal separation; dispersing in hexane, precipitating with ethanol, centrifuging, and diluting with cyclohexane to constant volume in volumetric flask to obtain Fe with iron content of 1-3mg/mL3O4A cyclohexane solution of nanoparticles;
s3: taking the prepared Fe3O4Mixing a cyclohexane solution of nanoparticles with a carrier, wherein the mass ratio of the cyclohexane solution to the carrier is (10-100): 1mL/g, stirring at room temperature for 12-36h, spin-drying by using a rotary evaporator, and then blowing at 300 ℃ under air purgeRoasting for 2-6h to finally obtain alpha-Al2O3Fe load3O4The catalyst of (1);
wherein the iron oleate in S1 is prepared by the following steps:
1): preparing a mixed solvent by taking ethanol, deionized water and hexane in a volume ratio of 20:16:35, and weighing FeCl3And dissolving sodium oleate in the mixed solvent to obtain a mixed solution, wherein: FeCl3And sodium oleate in a molar ratio of 1: 3;
2): heating the mixed solution in the step 1) to 58-70 ℃, keeping the temperature for 3-5h, washing with water after the reaction is finished, separating by using a separating funnel, taking supernate, repeatedly washing, and distilling under reduced pressure to remove excessive solvent to obtain iron oleate; the high-boiling-point solvent in the S1 is octadecene or trioctylamine.
5. Production of α -Al according to claim 42O3Fe load3O4A process for the preparation of a catalyst, characterized by: the inert gas used in step S1 is nitrogen, argon or helium.
6. A method of producing alpha-Al according to claim 42O3Fe load3O4A process for the preparation of a catalyst, characterized by: the rotation speed of the centrifugal separation in the step S2 is 9500rpm, and the time is 10 min.
7. alpha-Al according to claim 12O3Fe load3O4The application of the catalyst in preparing hydrocarbon compounds by using synthesis gas is characterized in that: the ratio of the gas flow rate to the catalyst dosage in the reaction is 10000-60000 mL-g-1·h-1Under the condition that the reduction condition is normal pressure H2The flow rate is 30-180 mL/min-1The temperature is 350-450 ℃, and the raw material feeding molar ratio is H2CO ═ 1-2: 1, the reaction temperature is 300-350 ℃, the reaction pressure is 0.5-2.5MPa and the reaction synthesis is realized under the existence of a catalyst.
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