CN110075844A - Nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded and its preparation method and application - Google Patents
Nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded and its preparation method and application Download PDFInfo
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- CN110075844A CN110075844A CN201910359142.XA CN201910359142A CN110075844A CN 110075844 A CN110075844 A CN 110075844A CN 201910359142 A CN201910359142 A CN 201910359142A CN 110075844 A CN110075844 A CN 110075844A
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- catalyst
- mesoporous carbon
- iron
- tropsch synthetic
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229960002413 ferric citrate Drugs 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 238000005242 forging Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- 239000007789 gas Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000009467 reduction Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910001567 cementite Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 6
- 229920003987 resole Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 235000014413 iron hydroxide Nutrition 0.000 description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910017356 Fe2C Inorganic materials 0.000 description 2
- 238000013313 FeNO test Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000626 liquid-phase infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- 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
- C10G2300/10—Feedstock materials
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to catalysis material fields, more particularly to nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded and its preparation method and application, the catalyst is using nonionic surfactant as structure directing agent, self assembly mesoporous polymer polymer is carried out using source of iron and soluble resin, then is obtained by calcining.Compared with prior art, catalyst aperture of the invention is uniform, large specific surface area, and the mass transfer of unstrpped gas can be improved, and reduces resistance to mass tranfer, improves catalytic activity, and preparation method can be such that active component particles are evenly distributed on the hole wall of mesoporous carbon, process is simple.
Description
Technical field
The invention belongs to catalysis material fields, and in particular to a kind of nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded and
Preparation method and application.
Background technique
F- T synthesis is an important technical for converting synthesis gas under the effect of the catalyst hydrocarbon compound
And chemical process, using Fischer-Tropsch synthesis high added value can be converted by the carbon containing resource high-efficiency such as coal, biomass, natural gas
Chemicals and clean fuel.China is the country of the few oil of coal more than one, can be by China's coal abundant by F- T synthesis technology
Charcoal resource conversion is the low-carbon alkene of high added value, reduces China's oil import volume, ensures that national resources security has great meaning
Justice.
Currently, the research hotspot of F- T synthesis is still the development of catalyst.The research of fischer-tropsch synthetic catalyst mainly collects
In in iron-based, cobalt-based, ruthenium-based catalyst, since ruthenium is expensive, with industrial value predominantly iron-based and cobalt-base catalyst.
Wherein cobalt-base catalyst has preferable carbochain growth ability, is generally used for Low Temperature Fischer Tropsch synthesis C5+, including diesel oil and stone
Cerebrol.Synthesis gas based on sources such as coal, biomass directly prepares low-carbon alkene through F- T synthesis (FTO), is very important
Chemical process.Fe base catalyst has cheap and easy to get, higher Water gas shift/WGS living compared to other fischer-tropsch catalysts such as Co, Ru
The advantages that property, flexible operating condition.Ferrum-based catalyst is typically chosen in low-carbon alkene fischer-tropsch synthetic catalyst at present, however
There is sintering phenomenon easy to reunite in ferrum-based catalyst, lead to catalyst activity reduction during the reaction.On the other hand, Fe base is catalyzed
Often there is more phase (Fe during the reaction for agent2O3, Fe3O4, FeO, Fe, ε-Fe2C, ε-Fe2.2C, Fe7C3, χ-
Fe5C2, and θ-Fe3C), wherein χ-Fe5C2, ε-Fe2C, ε-Fe2.2C is considered as the active phase of F- T synthesis, and θ-Fe3C
It is then considered as inactivation phase iron species phase.
Carbon-based supports are a kind of good inert carriers, and the active force between iron species is moderate, are conducive to iron species
Fixed and reduction, by adjusting the structure of carbon-based supports it is possible to prevente effectively from going out for metal species high temperature reunion sintering deactivation phenomenon
It is existing.Since carbon material has biggish specific surface area and regulatable aperture, the dispersion of metal component, Jin Erti may advantageously facilitate
High catalyst activity.The iron species of high degree of dispersion surface energy with higher, and general carbon carrier lacks anchoring metal species
Ability, lead to iron species inactivation easy to reunite.The catalytic activity and stability of catalyst can be improved using carbon-based supports, inhibit
Ferrum-based catalyst is reacted in high temperature fischer-tropsch to be inactivated.
It is nano combined that patent CN104226353A discloses a kind of cementite containing potassium for high-temperature Fischer-Tropsch synthesis reaction/carbon
The preparation method and its catalyst of catalyst and a kind of method and its liquid hydrocarbon using catalyst manufacture liquid hydrocarbon.Its
In, a kind of porous carbonaceous supports are uniformly infiltrated by melt infiltration process with iron hydroxide, and it is uniform that potassium passes through a variety of addition manners
It loads together, the pre- addition manner including carrying out iron hydroxide infiltration after mixing ground sylvite in advance again, Yi Ji
After iron hydroxide infiltration, then mix the intermediate addition manner or rear addition manner using potassium solution made from incipient wetness.It should
Patent is generally iron hydroxide solid powder or flocculent deposit, the effect of load is still using iron hydroxide source of iron
It is good not as good as liquid source of iron, and the effect loaded can directly or indirectly influence the performance of catalyst.
Summary of the invention
For carbon-based supports load chalybeate catalyst under the conditions of pyroreaction iron nano-particle phase easy to reunite and active
The disadvantage of state complexity, the object of the invention is to provide a kind of nanometer iron-based Fischer-Tropsch conjunction of mesoporous carbon-loaded in order to solve this problem
At catalyst and its preparation method and application, the catalytic activity height in high temperature fischer-tropsch synthesis, stability are good.
The purpose of the present invention is achieved through the following technical solutions:
A kind of nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded, the catalyst is using nonionic surfactant as structure
Directed agents carry out self assembly mesoporous polymer polymer using source of iron and soluble resin, then are obtained by calcining.
The catalyst has 2-dimensional mesoscopic structure or three-dimensional cubic structure, and the mesoporous carbon content of catalyst is 60-93
Wt%, specific surface area 150-600m2/ g, Kong Rongwei 0.1-0.5cm3/ g, aperture 3-6nm, active nano carbide content are
7-60wt%, partial size 2-10nm.
Preferably, it is poly- to be selected from polyethylene oxide-polypropylene oxide, polyethylene oxide-for the nonionic surfactant
Epoxy butane, alkane-one of polyethylene oxide diblock or triblock copolymer surfactant or more than one are mixed
Close object, general formula CaH2a+1EOb、EOcPOdEOc、EOcBOdEOc、EOcBOd、EOcPOd, wherein a=10~18, b=5~25；C=
5~135, d=25~135.
Preferably, the nonionic surfactant is selected from C12H25EO23、C16H33EO10、C18H37EO10、
EO20PO70EO20、EO106PO70EO106Or EO132PO50EO132One of or it is a variety of.
Preferably, the source of iron is in ferric nitrate, iron chloride, ferric acetyl acetonade, ironic citrate or ferric citrate
It is one or more.
Preferably, the soluble resin is phenolic resin of the molecular weight between 150-2500.
A kind of preparation method of the nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded, comprising the following steps:
(1) nonionic surfactant, soluble resin and source of iron are sequentially added in solvent, are stirred evenly, reaction one
Solvent is volatilized after the section time, obtains solid product；
(2) solid for obtaining step (1) carries out low temperature thermosetting, and the calcining removal nonionic table under inert atmosphere protection
Face activating agent to get arrive product.
Preferably, the solvent in step (1) is selected from one of water, alcohols, tetrahydrofuran or ether or a variety of；
Preferably, the mass concentration of the nonionic surfactant in step (1) be 0.5%-25%, soluble resin with
The molar ratio of nonionic surface active agent dosage is 10-35:1, and reaction temperature is 15-45 DEG C, reaction time 1-5h, volatilization
Time is 5-8h.
Preferably, the low temperature thermoset temperature in step (2) is 80-120 DEG C, time 12-36h, calcination temperature 200-
600 DEG C, heating rate is 1-5 DEG C/min.
A kind of application of the nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded on F- T synthesis.It is first when concrete application
First reduction temperature is 200-400 DEG C, pressure 1bar, also Primordial Qi are the gaseous mixture of hydrogen and High Purity Nitrogen and flow is 20ml/
To catalyst reduction 8h under conditions of min, then temperature is adjusted to reaction temperature again and reducing gas is switched to unstripped gas,
Unstripped gas H2: the volume ratio of CO is 1:1-2:1, and reaction pressure is 1-20 bar.
The present invention has high reference area using mesoporous carbon, and orderly is mesoporous, and Fe nanometer particles are in the form of half exposure
It is fixed on hole wall, can not only guarantee that catalyst has good thermal stability, the mass transfer of unstrpped gas can also be improved, subtracted
Few resistance to mass tranfer, improves catalytic activity, further increases the selectivity to low-carbon alkene.Use surfactant for structure directing
Agent carries out self assembly mesoporous polymer with nonionic surfactant using source of iron and resol resin and polymerize
Object, then the calcining through different temperatures obtain ordered mesopore carbon load nano silicon carbide iron catalyst.
Compared with prior art, the invention has the following beneficial effects:
(1) aperture of the catalyst is uniform, large specific surface area, and the mass transfer of unstrpped gas can be improved, and reduces resistance to mass tranfer,
Catalytic activity is improved, by Fig. 1 it can be found that the catalyst has high conversion ratio and high selectivity of light olefin.
(2) present invention uses in-situ carburization mode, and active component particles are evenly distributed on the hole wall of mesoporous carbon, and with
The mode of half exposure exists, and so as to reinforce the stability of active component in catalyst, inhibits the reunion of nano iron particles, and half
Exposed nano silicon carbide iron can be easier and feed gas, to improve catalytic activity.
(3) preparation method overall flow of the invention is more simple, and used raw material is both from commercialization raw material, easily
The advantages that amplification, equipment requirement is easy.
Detailed description of the invention
Fig. 1 is the nitrogen adsorption desorption of the prepared mesoporous carbon-loaded cementite with two-dimentional six side's p6mm structures of embodiment 1
Curve；
Fig. 2 is the nitrogen adsorption desorption of the prepared mesoporous carbon-loaded cementite with two-dimentional six side's p6mm structures of embodiment 2
Curve；
Fig. 3 is the small angle X-ray of the prepared mesoporous carbon-loaded cementite with two-dimentional six side's p6mm structures of embodiment 3
Diffraction (XRD) map；
Fig. 4 is the X-ray diffraction of the prepared mesoporous carbon-loaded cementite with two-dimentional six side's p6mm structures of embodiment 4
(XRD) map；
Fig. 5 is that the prepared mesoporous carbon-loaded cementite feature X- ray with two-dimentional six side's p6mm structures of embodiment 5 spreads out
Penetrate (XRD) map.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
At 40 DEG C, by 1.0g F127 (EO106PO70EO106) (0.075mmol) be dissolved in 10.00g dehydrated alcohol, stir
It mixes 1 hour；It is added 1g solubility resol (2mmol), 1 hour is stirred at 40 DEG C；0.3g FeNO is added3 9H2O
(0.75mmol)；Continue to stir 1 hour.Then this mixed liquor is uniformly laid in culture dish, is placed at room temperature for 7 hours, makes to have
Solvent volatilization；It is finally transferred to 100 DEG C of baking ovens to scrape product after 24 hours, obtains membranaceous solid.Obtained solid is straight
It connects and is placed in quartz boat, 400 DEG C of roasting 3h under nitrogen atmosphere in tube furnace, heating rate is 3 DEG C/min.Then roasting is collected
Product afterwards, with mortar grinder to 80-140 mesh.The catalyst quality percent composition are as follows: ferriferous oxide 10.1%, mesoporous carbon
89.9%.
Obtained material has two-dimentional hexagonal structure (space group p6mm), aperture 4.7nm, Kong Rongwei 0.39cm3/ g compares table
Area is 566m2/g。
The catalyst synthesis gas high temperature fischer-tropsch synthesis in activity rating condition and evaluation results are shown in Table 1, specific steps
It is as follows:
Catalyst 100mg is uniformly mixed with 80-140 mesh quartz sand 900mg first, it is anti-then to place it in fixed bed
It answers in device, is 400 DEG C, pressure 1bar, goes back the gaseous mixture that Primordial Qi is hydrogen and High Purity Nitrogen in reduction temperature, and flow is 20ml/
Reductase 12 4h under the conditions of min.Then reduction autogenous cutting is changed into unstripped gas, unstripped gas H again2: the volume ratio of CO is 1:1, then anti-
Answering temperature is 350 DEG C, reaction pressure carries out F- T synthesis under being 10bar and certain space velocities, and reaction terminates for 24 hours.
Its nitrogen adsorption-desorption isotherm figure such as Fig. 1.
Embodiment 2
At 40 DEG C, by 1.0g F127 (EO106PO70EO106) (0.075mmol) be dissolved in 10.00g dehydrated alcohol, stir
It mixes 1 hour；It is added 1g solubility resol (2mmol), 1 hour is stirred at 40 DEG C；0.5g FeNO is added3 9H2O
(0.75mmol)；Continue to stir 1 hour.Then this mixed liquor is uniformly laid in culture dish, is placed at room temperature for 7 hours, makes to have
Solvent volatilization；It is finally transferred to 100 DEG C of baking ovens to scrape product after 24 hours, obtains membranaceous solid.Obtained solid is straight
It connects and is placed in quartz boat, 400 DEG C of roasting 3h under nitrogen atmosphere in tube furnace, heating rate is 3 DEG C/min.Then roasting is collected
Product afterwards, with mortar grinder to 80-140 mesh.The catalyst quality percent composition are as follows: ferriferous oxide 17.5%, mesoporous carbon
82.5%.
Obtained material has two-dimentional hexagonal structure (space group p6mm), aperture 4.6nm, Kong Rongwei 0.36cm3/ g compares table
Area is 496m2/g。
The catalyst synthesis gas high temperature fischer-tropsch synthesis in activity rating condition and evaluation results are shown in Table 1, specific steps
It is as follows:
Catalyst 100mg is uniformly mixed with 80-140 mesh quartz sand 900mg first, it is anti-then to place it in fixed bed
It answers in device, is 400 DEG C, pressure 1bar, goes back the gaseous mixture that Primordial Qi is hydrogen and High Purity Nitrogen in reduction temperature, and flow is 20ml/
Reductase 12 4h under the conditions of min.Then reduction autogenous cutting is changed into unstripped gas, unstripped gas H again2: the volume ratio of CO is 1:1, then anti-
Answering temperature is 350 DEG C, reaction pressure carries out F- T synthesis under being 10bar and certain space velocities, and reaction terminates for 24 hours.
Its nitrogen adsorption-desorption isotherm figure such as Fig. 2.
Embodiment 3
At 40 DEG C, by 1.0g F127 (EO106PO70EO106) (0.075mmol) be dissolved in 10.00g dehydrated alcohol, stir
It mixes 1 hour；It is added 1g solubility resol (2mmol), 1 hour is stirred at 40 DEG C；By 0.265g ferric acetyl acetonade
Above-mentioned solution is added in (0.75mmol)；Continue to stir 1 hour.Then this mixed liquor is uniformly laid in culture dish, room temperature is put
It sets 7 hours, organic solvent is made to volatilize；It is finally transferred to 100 DEG C of baking ovens to scrape product after 24 hours, obtains membranaceous solid.
Obtained solid is placed directly in quartz boat, 400 DEG C of roasting 3h under nitrogen atmosphere in tube furnace, heating rate is 3 DEG C/min.
Then product after roasting is collected, with mortar grinder to 80-140 mesh.The catalyst quality percent composition are as follows: ferriferous oxide
9.8%, mesoporous carbon 90.2%.
The catalyst synthesis gas high temperature fischer-tropsch synthesis in activity rating condition and evaluation results are shown in Table 1, specific steps
It is as follows:
Catalyst 100mg is uniformly mixed with 80-140 mesh quartz sand 900mg first, it is anti-then to place it in fixed bed
It answers in device, is 400 DEG C, pressure 1bar, goes back the gaseous mixture that Primordial Qi is hydrogen and High Purity Nitrogen in reduction temperature, and flow is 20ml/
Reductase 12 4h under the conditions of min.Then reduction autogenous cutting is changed into unstripped gas, unstripped gas H again2: the volume ratio of CO is 1:1, then anti-
Answering temperature is 340 DEG C, reaction pressure carries out F- T synthesis under being 10bar and certain space velocities, and reaction terminates for 24 hours.
Obtained material has two-dimentional hexagonal structure (space group p6mm), aperture 4.8nm, Kong Rongwei 0.31cm3/ g compares table
Area is 452m2/g。
Small angle X-ray diffraction (SXRD) the map such as Fig. 3 of its feature.
Embodiment 4
At 40 DEG C, by 1.0g F127 (EO106PO70EO106) (0.075mmol) be dissolved in 10.00g dehydrated alcohol, stir
It mixes 1 hour；It is added 1g solubility resol (2mmol), 1 hour is stirred at 40 DEG C；By 0.275g ferric citrate
(Fe%=16.5%) it is dissolved in 5g H2Then above-mentioned solution is added in O；Continue to stir 1 hour.Then this mixed liquor is uniform
It is laid in culture dish, is placed at room temperature for 7 hours, organic solvent is made to volatilize；100 DEG C of baking ovens are finally transferred to, after 24 hours, by product
It scrapes, obtains membranaceous solid.Obtained solid is placed directly in quartz boat, 400 DEG C of roasting 3h under nitrogen atmosphere in tube furnace,
Heating rate is 3 DEG C/min.Then product after roasting is collected, with mortar grinder to 80-140 mesh.The catalyst quality percentage
Component are as follows: ferriferous oxide 11.5%, mesoporous carbon 88.5%.
The catalyst synthesis gas high temperature fischer-tropsch synthesis in activity rating condition and evaluation results are shown in Table 1, specific steps
It is as follows:
Catalyst 100mg is uniformly mixed with 80-140 mesh quartz sand 900mg first, it is anti-then to place it in fixed bed
It answers in device, is 400 DEG C, pressure 1bar, goes back the gaseous mixture that Primordial Qi is hydrogen and High Purity Nitrogen in reduction temperature, and flow is 20ml/
Reductase 12 4h under the conditions of min.Then reduction autogenous cutting is changed into unstripped gas, unstripped gas H again2: the volume ratio of CO is 1:1, then anti-
Answering temperature is 350 DEG C, reaction pressure carries out F- T synthesis under being 10bar and certain space velocities, and reaction terminates for 24 hours.
Obtained material has two-dimentional hexagonal structure (space group p6mm), aperture 4.8nm, Kong Rongwei 0.31cm3/ g compares table
Area is 452m2/g。
Its distinctive X-ray diffraction (XRD) map such as Fig. 4.
Embodiment 5
At 40 DEG C, by 1.0g F127 (EO106PO70EO106) (0.075mmol) be dissolved in 10.00g dehydrated alcohol, stir
It mixes 1 hour；It is added 1g solubility resol (2mmol), 1 hour is stirred at 40 DEG C；By 0.275g ferric citrate
(Fe%=16.5%) it is dissolved in 5g H2Then above-mentioned solution is added in O；Continue to stir 1 hour.Then this mixed liquor is uniform
It is laid in culture dish, is placed at room temperature for 7 hours, organic solvent is made to volatilize；100 DEG C of baking ovens are finally transferred to, after 24 hours, by product
It scrapes, obtains membranaceous solid.Obtained solid is placed directly in quartz boat, 400 DEG C of roasting 3h under nitrogen atmosphere in tube furnace,
Heating rate is 3 DEG C/min.Then product after roasting is collected, with mortar grinder to 80-140 mesh.The catalyst quality percentage
Component are as follows: ferriferous oxide 11.5%, mesoporous carbon 88.5%.
The catalyst synthesis gas high temperature fischer-tropsch synthesis in activity rating condition and evaluation results are shown in Table 1, specific steps
It is as follows:
Catalyst 100mg is uniformly mixed with 80-140 mesh quartz sand 900mg first, it is anti-then to place it in fixed bed
It answers in device, is 400 DEG C, pressure 1bar, goes back the gaseous mixture that Primordial Qi is hydrogen and High Purity Nitrogen in reduction temperature, and flow is 20ml/
Reductase 12 4h under the conditions of min.Then reduction autogenous cutting is changed into unstripped gas, unstripped gas H again2: the volume ratio of CO is 2:1, then anti-
Answering temperature is 350 DEG C, reaction pressure carries out F- T synthesis under being 10bar and certain space velocities, and reaction terminates for 24 hours.
Obtained material has two-dimentional hexagonal structure (space group p6mm), aperture 4.8nm, Kong Rongwei 0.31cm3/ g compares table
Area is 452m2/g.Its distinctive X-ray diffraction (XRD) map such as Fig. 5.
Activity rating condition and evaluation result in 1 embodiment 1-5 of table in the synthesis of synthesis gas high temperature fischer-tropsch
Note: C2-C4 =Represent low-carbon alkene, C2-C4 0Represent low-carbon alkanes.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded, which is characterized in that the catalyst is living with non-ionic surface
Property agent be structure directing agent, carry out self assembly mesoporous polymer polymer using source of iron and soluble resin, then by forging
Burning obtains.
2. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded according to claim 1, which is characterized in that described
Catalyst has 2-dimensional mesoscopic structure or three-dimensional cubic structure, and the mesoporous carbon content of catalyst is 60-93wt%, and specific surface area is
150-600m2/ g, Kong Rongwei 0.1-0.5cm3/ g, aperture 3-6nm, active nano carbide content are 7-60wt%, and partial size is
2-10nm。
3. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded according to claim 1, which is characterized in that described
Nonionic surfactant is selected from polyethylene oxide-polypropylene oxide, polyethylene oxide-polybutylene oxide, alkane-polycyclic
One of oxidative ethane diblock or triblock copolymer surfactant or more than one mixtures, general formula CaH2a+ 1EOb、EOcPOdEOc、EOcBOdEOc、EOcBOd、EOcPOd, wherein a=10~18, b=5~25；C=5~135, d=25~
135。
4. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded according to claim 3, which is characterized in that described
Nonionic surfactant is selected from C12H25EO23、C16H33EO10、C18H37EO10、EO20PO70EO20、EO106PO70EO106Or
EO132PO50EO132One of or it is a variety of.
5. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded according to claim 1, which is characterized in that described
Source of iron is selected from one of ferric nitrate, iron chloride, ferric acetyl acetonade, ironic citrate or ferric citrate or a variety of.
6. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded according to claim 1, which is characterized in that described
Soluble resin is phenolic resin of the molecular weight between 150-2500g/mol.
7. a kind of preparation side of the nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded as claimed in any one of claims 1 to 6
Method, which comprises the following steps:
(1) nonionic surfactant, soluble resin and source of iron are sequentially added in solvent, is stirred evenly, when reacting one section
Between after solvent is volatilized, obtain solid product；
(2) solid for obtaining step (1) carries out low temperature thermosetting, and calcining removal non-ionic surface is living under inert atmosphere protection
Property agent to get arrive product.
8. a kind of preparation method of the nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded according to claim 7, special
Sign is that the solvent in step (1) is selected from one of water, alcohols, tetrahydrofuran or ether or a variety of；
The mass concentration of nonionic surfactant in step (1) is 0.5%-25%, soluble resin and non-ionic table
The molar ratio of face activating agent dosage is 10-35:1, and reaction temperature is 15-45 DEG C, reaction time 1-5h, and the volatilization time is 5-
8h。
9. a kind of preparation method of the nanometer iron-based fischer-tropsch synthetic catalyst of mesoporous carbon-loaded according to claim 7, special
Sign is that the low temperature thermoset temperature in step (2) is 80-120 DEG C, time 12-36h, and calcination temperature is 200-600 DEG C, rises
Warm rate is 1-5 DEG C/min.
10. the nanometer iron-based fischer-tropsch synthetic catalyst of a kind of mesoporous carbon-loaded as claimed in any one of claims 1 to 6 is closed in Fischer-Tropsch
At upper application.
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