CN104607190B - 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 - Google Patents
用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN104607190B CN104607190B CN201510050801.3A CN201510050801A CN104607190B CN 104607190 B CN104607190 B CN 104607190B CN 201510050801 A CN201510050801 A CN 201510050801A CN 104607190 B CN104607190 B CN 104607190B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- transition metal
- synthesis
- nano
- single dispersing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 39
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000013528 metallic particle Substances 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000003891 oxalate salts Chemical group 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 8
- 235000013495 cobalt Nutrition 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical class [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical class [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- B01J35/23—
-
- B01J35/27—
-
- B01J35/40—
-
- B01J35/612—
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/643—
-
- B01J35/651—
-
- 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
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/04—Mixing
-
- 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
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/005—Catalytic metals
-
- 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
- C07C2523/75—Cobalt
-
- 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
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
Abstract
本发明公开了一种用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用，该催化剂包括过渡金属，所述过渡金属以单分散纳米金属颗粒状态稳定分散于有机溶剂中；所述过渡金属的粒径为1～100nm；所述催化剂的比表面积为5～300m2/g。本发明方法能够实现活性组分颗粒粒径大小的调节控制，使得纳米金属颗粒尺寸大小可控，纳米金属颗粒无需嵌合在载体表面，从而增大了活性组分的比表面积，提升了催化剂的催化性能；本发明的催化剂，其纳米金属颗粒分散度高，用于浆态床反应系统时，无需经过繁琐的滤分离，清洗，高温焙烧及活化还原就能够直接应用于费托合成反应，并具有极其优异的催化活性。
Description
技术领域
本发明涉及费托合成催化剂，具体地指一种用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用。
背景技术
通过费托合成技术可将由煤炭，天然气及生物质等含碳原料气化获得的合成气转化为以烷烃和烯烃为主要组成的目标产物，这些产物中几乎不含有硫，氮和芳烃化合物，易加工成环境友好的清洁燃料，是充分利用可循环含碳原料替代传统石化燃料的理想途径。费托合成技术在我国原油进口量以及环境要求逐步提高的背景下具有重要的能源安全和环保意义，获得了广泛的关注和研究。
催化剂在费托合成反应中的性能表现与其化学元素组成密切相关。第VIII族过渡金属中的铁，钴，镍，钌和铑等元素对费托合成反应具有较强催化作用，可作为催化剂的主金属元素。工业费托合成催化剂多选用铁或钴作为元素主金属，并添加其它金属元素作为助剂，以调节或改善催化剂的综合性能。
费托合成催化剂的常见制备方法已为领域内研究人员所熟知。钴基费托合成催化剂常通过浸渍法将活性金属组分负载于氧化物载体表面获得，而铁基费托合成催化剂则利用共沉淀法或熔融法获得。不同制备方法所得催化剂在性能方面存在显著差异，这些差异往往因催化剂微观结构不同而导致。催化剂颗粒内部的孔结构特性以及表面金属颗粒的粒径分布对于其催化性能具有重要的影响。浸渍法和共沉淀法制备的催化剂具有丰富的孔结构，因此，孔道内活性金属的催化性能将受到原料浓度及内扩散的制约影响。另外，金属颗粒活性组分嵌合在载体表面，裸露活性组分的比表面积较少，制约了催化剂性能的 充分发挥。同时，越来越多的研究结果表明，当金属颗粒粒径尺寸处于特定的范围时，催化剂进行费托合成反应时将具有最佳的活性和产物选择性。然而，受传统制备方法限制，催化剂表面的金属颗粒尺寸大小难以进行有效调控。
基于上述原因，为改善催化剂的催化性能，研究人员开始考虑合成无负载型纳米颗粒催化剂，但这类催化剂普遍存在适用温度低，有效产物的时空收率低，及活性金属成分尺寸过大的缺点，如：申请号为CN 200710099011的中国专利申请公开了一种进行费托合成反应的方法及其专用催化剂，其将过渡金属盐(Ru、Co、Ni、Fe和Rh中的至少一种)与高分子稳定剂(聚乙烯基吡咯烷酮或[BVIMPVP]Cl)混合分散于液体介质中，在100～200℃下用H2还原，得到1～10nm的过渡金属纳米催化剂，在100～200℃下即可进行费托合成反应。该方法制备的纳米粒子浓度较低，过渡金属盐在液体介质中的最高浓度仅为0.014mol/L；而且，需要采用高分子化合物作稳定剂，仅可适用于反应温度低于200℃的费托合成反应；另外，有效产物的时空收率较低，这些缺点限制了其工业应用前景。再如：申请号为CN200810055122的中国专利申请公开了一种适合于浆态床反应器的催化剂及制备方法和应用，其将过渡金属硝酸盐(铁、钴或镍)溶于C6-C8的直链醇溶液后加热回流，以获得粒径尺寸在5～200nm的过渡金属纳米氧化物颗粒，在浆态床反应器内经活化还原后进行费托合成反应。然而，由于硝酸盐中结晶水的存在，一方面增加了金属晶粒表面的氢键，加剧了一次晶粒间的团聚作用(T.He,D.Chen,X.Jiao,Controlled Synthesis of Co3O4Nanoparticlesthrough Oriented Aggregation,Chem.Mater.,16(2004)737-743)，另一方面导致硝酸钴的分解温度升高，使金属晶核的快速形成和长大，两种因素相互作用导致最终获得尺寸较大的二次团聚晶粒(李泽壮，陈建刚，王月伦，孙予罕，单分散Co/SiO2催化剂的制备及其F-T合成性能[J]，《工业 催化》2009(9)，第17卷，43-47)。
发明内容
本发明的目的就是要提供一种用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用，该催化剂的活性金属颗粒尺寸可控，催化活性高。
为实现上述目的，本发明采用的技术方案是：一种用于费托合成的单分散过渡金属纳米催化剂，包括过渡金属，所述过渡金属以单分散纳米金属颗粒状态稳定分散于有机溶剂中；所述过渡金属的粒径为1～100nm；所述催化剂的比表面积为5～300m2/g。
进一步地，所述过渡金属为Mn，Fe，Co或Ru中的一种或几种。
进一步地，所述有机溶剂为苄醚，芳醇，吡咯烷酮或液体石蜡。
进一步地，所述过渡金属的颗粒粒径为5～20nm。
一种上述用于费托合成的单分散过渡金属纳米催化剂的制备方法，包括以下步骤：
1)将所述过渡金属的有机盐溶解于含有多元醇的有机溶剂中，制得混合液；
2)在空气或惰性气体氛围中对所述混合液进行加热并搅拌，将所述混合液温度升至150～250℃后进行保温，保温时间为30～240min，即可制得所述用于费托合成的单分散过渡金属纳米催化剂。
进一步地，所述步骤1)中，所述过渡金属为Mn，Fe，Co或Ru中的一种或几种，所述有机盐为草酸盐，乙酰丙酮盐或羰基金属盐。
进一步地，所述步骤1)中，所述多元醇为C3-C18的二元醇或三元醇；所述有机溶剂为苄醚，芳醇，吡咯烷酮或液体石蜡。
进一步地，所述步骤1)中，所述多元醇与所述过渡金属的有机盐的摩尔比为1～5∶1；所述有机溶剂与所述过渡金属的有机盐的摩尔比为30～500∶1。多元醇与过渡金属的有机盐的摩尔比为1～5∶1，以使有机金属盐分解后的金属化合物还原至零价金属态，同时维持纳米金属颗粒的稳定性；有机溶剂主要作为反应分散溶剂。
进一步地，所述步骤2)中，所述混合液升温速率为1～10℃/min；所述保温时间为60～120min。
一种上述用于费托合成的单分散过渡金属纳米催化剂的应用，无需过滤分离，清洗，高温焙烧及活化还原，直接将所述催化剂用于费托合成反应，反应温度为180～300℃，反应压力为1～3MPa，H2与CO进料体积比为1～2.5，反应器总空速为0.5～15L/h/g催化剂。
与现有技术相比，本发明具有以下优点：
其一，本发明方法制备的催化剂为无负载型纳米金属颗粒催化剂，纳米金属颗粒在反应过程中可以自由移动，无需嵌合在载体表面，从而增大了活性组分的比表面积，提升了催化剂的催化性能；而且本发明方法制得的纳米金属颗粒浓度高。
其二，本发明方法能够实现活性组分颗粒粒径大小的调节控制，使得纳米金属颗粒尺寸大小可控。
其三，本发明方法简单便捷，环境友好，操作工艺简单，不但能够对纳米金属颗粒尺寸实现有效的调节控制，同时，本催化剂的金属活性成分以单分散纳米金属颗粒形式稳定分散于有机溶剂中，分散溶剂可以回收并重复利用。
其四，本发明的催化剂，其纳米金属颗粒分散度高，用于浆态床反应系统时，无需经过繁琐的滤分离，清洗，高温焙烧及活化还原就能够直接应用于费托合成反应，并具有极其优异的催化活性和产物选择性。
附图说明
图1为实施例1中制得的催化剂的透射电镜图片。
具体实施方式
下面结合具体实施例和附图对本发明作进一步的详细说明，便于更清楚地了解本发明，但它们不对本发明构成限定。
实施例1：
先将6g乙酰丙酮铁(III)溶于550ml的2-吡咯烷酮溶液(密度为1.116g/ml)中，然后往溶液中添加3.5g的1,2-十二烷二醇，得混合溶液；接着，在机械搅拌条件下，空气气氛中，以1℃/min的升温速率将混合溶液的温度升至160℃；在160℃温度下保温120min后，自然冷却至室温，即获得灰黑色纳米铁胶体溶液，添加250ml液体石蜡封存待用。
将制得的纳米铁胶体溶液与液体石蜡一起转移至浆态床反应器内，直接进行费托合成反应，其中，反应温度为260℃，氢气与一氧化碳进料比范围1.2，进气空速为13.7L/h/g催化剂(进气流速为13L/h)，反应压力为2MPa。在上述条件下，该催化剂的性能评价结果见下表1；该催化剂的微观结构见图1。
实施例2：
先将2.6g草酸钴(II)和0.01g亚硝酰基硝酸合钌(III)溶于250ml的二苄醚溶液(密度为1.04g/ml)中，然后往溶液中添加10g的1,2-十六烷二醇，得混合溶液；接着，在机械搅拌条件下，氩气气氛中，以10℃/min的升温速率将混合溶液的温度升至250℃；在250℃温度下保温80min后，自然冷却至室温，即获得深紫色纳米钴胶体溶液，添加250ml液体石蜡封存待用。
将制得的纳米钴胶体溶液与液体石蜡一起转移至浆态床反应器内，直接进行费托合成反应，其中，反应温度为180℃，氢气与一氧化碳进料比范围2.4，进气空速为4.8L/h/g催化剂(进气流速为5L/h)，反应压力为3MPa。在上述条件下，该催化剂的性能评价结果见下表1。
实施例3：
先将4g乙酰丙酮铁(III)和2g乙酰丙酮钴(II)溶于450ml的苯甲醇溶液(密度为1.04g/ml)中，然后往溶液中添加9g的1,2,4-丁三醇，得混合溶液；接着，在机械搅拌的条件下，空气气氛中，以5℃/min的升温速率将混合溶液的温度升至200℃；在200℃温度下保温60min后，自然冷却至室温，即获得深灰色铁钴合金纳米胶体溶液，添加250ml液体石蜡封存待用。
将制得的铁钴合金纳米胶体溶液与液体石蜡一起转移至浆态床反应器内，直接进行费托合成反应，其中，反应温度为200℃，氢气与一氧化碳进料比范围2，进气空速为7.3L/h/g催化剂(进气流速为8L/h)，反应压力为1MPa。在上述条件下，该催化剂的性能评价结果见下表1。
实施例4：
先将3.1g五羰基铁和2.6g十羰基二锰溶于250ml的液体石蜡(密度为:0.87g/ml)中，然后往溶液中添加5g的1,2,8-辛三醇，得混合溶液；接着，在机械搅拌的条件下，氮气气氛中，以8℃/min的升温速率将混合溶液的温度升至235℃；在235℃温度下保温100min后，自然冷却至室温，即获得灰黑色纳米铁锰胶体溶液，封存待用。
将制得的纳米铁锰胶体溶液转移至浆态床反应器内，直接进行费托合成反应，其中，反应温度为240℃，氢气与一氧化碳进料比范围1.8，进气空速为0.8L/h/g催化剂(进气流速为1L/h)，反应压力为2MPa。在上述条件下，该催化剂的性能评价结果见下表1。
表1
由表1中催化剂的物化性质和催化性质参数可以看出：采用本发明方法能够便捷地制备不同粒径的高活性金属纳米颗粒催化剂。通常，催化剂的粒径越小，其活性比表面积越大，催化活性越高，但催化剂稳定性将会降低。将金属纳米催化剂粒径范围控制在5-20nm具有较好的综合性能优势。这些催化剂与同类型的工业催化剂相比较， 具有更好的催化活性，更低的甲烷选择性，同时C2-C4轻质烃选择性相对较高，显示出该方法获得的催化剂具有很好的应用前景。
Claims (9)
1.一种用于费托合成的单分散过渡金属纳米催化剂，包括过渡金属，其特征在于：所述过渡金属以单分散纳米金属颗粒状态稳定分散于有机溶剂中；所述过渡金属的颗粒粒径为5～20nm；所述催化剂的比表面积为5～300m2/g；所述催化剂的制备方法，包括以下步骤：
1)将所述过渡金属的有机盐溶解于含有多元醇的有机溶剂中，制得混合液；
2)在空气或惰性气体氛围中对所述混合液进行加热并搅拌，将所述混合液温度升至150～250℃后进行保温，保温时间为30～240min，即可制得所述用于费托合成的单分散过渡金属纳米催化剂。
2.根据权利要求1所述用于费托合成的单分散过渡金属纳米催化剂，其特征在于：所述过渡金属为Mn，Fe，Co或Ru中的一种或几种。
3.根据权利要求1或2所述用于费托合成的单分散过渡金属纳米催化剂，其特征在于：所述有机溶剂为苄醚，芳醇，吡咯烷酮或液体石蜡。
4.一种权利要求1所述用于费托合成的单分散过渡金属纳米催化剂的制备方法，包括以下步骤：
1)将所述过渡金属的有机盐溶解于含有多元醇的有机溶剂中，制得混合液；
2)在空气或惰性气体氛围中对所述混合液进行加热并搅拌，将所述混合液温度升至150～250℃后进行保温，保温时间为30～240min，即可制得所述用于费托合成的单分散过渡金属纳米催化剂。
5.根据权利要求4所述用于费托合成的单分散过渡金属纳米催化剂的制备方法，其特征在于：所述1)中，所述过渡金属为Mn，Fe，Co或Ru中的一种或几种，所述有机盐为草酸盐，乙酰丙酮盐或羰基金属盐。
6.根据权利要求4或5所述用于费托合成的单分散过渡金属纳米催化剂的制备方法，其特征在于：所述1)中，所述多元醇为C3-C18的二元醇或三元醇；所述有机溶剂为苄醚，芳醇，吡咯烷酮或液体石蜡。
7.根据权利要求4或5所述用于费托合成的单分散过渡金属纳米催化剂的制备方法，其特征在于：所述1)中，所述多元醇与所述过渡金属的有机盐的摩尔比为1～5∶1；所述有机溶剂与所述过渡金属的有机盐的摩尔比为30～500∶1。
8.根据权利要求4或5所述用于费托合成的单分散过渡金属纳米催化剂的制备方法，其特征在于：所述2)中，所述混合液升温速率为1～10℃/min；所述保温时间为60～120min。
9.一种权利要求1所述用于费托合成的单分散过渡金属纳米催化剂的应用，其特征在于：无需过滤分离，清洗，高温焙烧及活化还原，直接将所述催化剂用于费托合成反应，反应温度为180～300℃，反应压力为1～3MPa，H2与CO进料体积比为1～2.5，反应器总空速为0.5～15L/h/g催化剂。
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050801.3A CN104607190B (zh) | 2015-01-30 | 2015-01-30 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
| RU2017130496A RU2675839C1 (ru) | 2015-01-30 | 2016-01-26 | Нанокатализатор из монодисперсного переходного металла для синтеза фишера-тропша, способ его приготовления и его применение |
| JP2017538345A JP6653709B2 (ja) | 2015-01-30 | 2016-01-26 | フィッシャー・トロプシュ合成のための単分散遷移金属ナノ触媒の調製方法 |
| EP16742731.9A EP3251745A4 (en) | 2015-01-30 | 2016-01-26 | Monodisperse transition metal nano-catalyst for fischer-tropsch synthesis and preparation method therefor and application thereof |
| CA2975160A CA2975160A1 (en) | 2015-01-30 | 2016-01-26 | Monodisperse transition metal nano-catalyst for fischer-tropsch synthesis and preparation method therefor and application thereof |
| KR1020177024375A KR20170110121A (ko) | 2015-01-30 | 2016-01-26 | 피셔-트롭쉬 합성용 단분산 전이 금속 나노-촉매제 및 그의 제조 방법 및 응용 |
| PCT/CN2016/072081 WO2016119669A1 (zh) | 2015-01-30 | 2016-01-26 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
| AU2016212495A AU2016212495A1 (en) | 2015-01-30 | 2016-01-26 | Monodisperse transition metal nano-catalyst for fischer-tropsch synthesis and preparation method therefor and application thereof |
| US15/662,310 US20170335202A1 (en) | 2015-01-30 | 2017-07-28 | Nanocatalyst for fischer-tropsch synthesis and methods for preparing and using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510050801.3A CN104607190B (zh) | 2015-01-30 | 2015-01-30 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104607190A CN104607190A (zh) | 2015-05-13 |
| CN104607190B true CN104607190B (zh) | 2018-01-16 |
Family
ID=53141994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510050801.3A Active CN104607190B (zh) | 2015-01-30 | 2015-01-30 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20170335202A1 (zh) |
| EP (1) | EP3251745A4 (zh) |
| JP (1) | JP6653709B2 (zh) |
| KR (1) | KR20170110121A (zh) |
| CN (1) | CN104607190B (zh) |
| AU (1) | AU2016212495A1 (zh) |
| CA (1) | CA2975160A1 (zh) |
| RU (1) | RU2675839C1 (zh) |
| WO (1) | WO2016119669A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607190B (zh) * | 2015-01-30 | 2018-01-16 | 武汉凯迪工程技术研究总院有限公司 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
| CN105056944B (zh) * | 2015-08-07 | 2018-01-30 | 北京华福工程有限公司 | 一种高分散催化体系及其制备方法和应用 |
| CN108570667A (zh) * | 2017-03-14 | 2018-09-25 | 中国科学技术大学 | 一种金属膜、反应器及其制备方法和化合物的制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045206A (zh) * | 2007-05-08 | 2007-10-03 | 北京大学 | 一种进行费托合成反应的方法及其专用催化剂 |
| CN101269330A (zh) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | 一种适合于浆态床用纳米催化剂及制法和应用 |
| CN102179255A (zh) * | 2011-03-02 | 2011-09-14 | 浙江工业大学 | 一种负载型钴合金催化剂及其在费托合成中的应用 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7575621B2 (en) * | 2005-01-14 | 2009-08-18 | Cabot Corporation | Separation of metal nanoparticles |
| JP5355095B2 (ja) * | 2006-02-16 | 2013-11-27 | ブリガム・ヤング・ユニバーシティ | 超高純度の金属酸化物、混合金属酸化物、金属、および合金の均一なナノ粒子の製造 |
| CN1943855A (zh) * | 2006-10-11 | 2007-04-11 | 大连理工大学 | 温控两相纳米催化体系及应用 |
| US20100054981A1 (en) * | 2007-12-21 | 2010-03-04 | Board Of Regents, The University Of Texas System | Magnetic nanoparticles, bulk nanocomposite magnets, and production thereof |
| CN101406961B (zh) * | 2008-11-25 | 2011-06-22 | 哈尔滨工业大学 | 水溶性金纳米团簇的制备方法 |
| JP5574761B2 (ja) * | 2009-04-17 | 2014-08-20 | 国立大学法人山形大学 | 被覆銀超微粒子とその製造方法 |
| CN102371151B (zh) * | 2010-08-26 | 2013-05-01 | 中国石油化工股份有限公司 | 一种纳米贵金属催化剂及其制备方法 |
| CN102489312B (zh) * | 2011-11-24 | 2013-06-19 | 武汉凯迪工程技术研究总院有限公司 | 基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 |
| FR2999956B1 (fr) * | 2012-12-21 | 2015-12-25 | Centre Nat Rech Scient | Nano-catalyseurs metalliques dans le glycerol et applications en synthese organique |
| KR20140104636A (ko) * | 2013-02-20 | 2014-08-29 | 한국화학연구원 | 피셔 트롭시 합성용 코발트 촉매, 제조방법 및 이를 이용한 액체 탄화수소 제조방법 |
| RU2537850C1 (ru) * | 2013-09-12 | 2015-01-10 | Общество с ограниченной ответственностью "АНИКО" | Катализатор и способ получения синтетических углеводородов алифатического ряда из оксида углерода и водорода в его присутствии |
| CN103736487B (zh) * | 2013-12-29 | 2016-02-24 | 浙江工业大学 | 一种无溶剂机械混合制备负载型金属催化剂的方法 |
| CN104607190B (zh) * | 2015-01-30 | 2018-01-16 | 武汉凯迪工程技术研究总院有限公司 | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 |
-
2015
- 2015-01-30 CN CN201510050801.3A patent/CN104607190B/zh active Active
-
2016
- 2016-01-26 EP EP16742731.9A patent/EP3251745A4/en not_active Withdrawn
- 2016-01-26 JP JP2017538345A patent/JP6653709B2/ja active Active
- 2016-01-26 KR KR1020177024375A patent/KR20170110121A/ko not_active Application Discontinuation
- 2016-01-26 RU RU2017130496A patent/RU2675839C1/ru not_active IP Right Cessation
- 2016-01-26 AU AU2016212495A patent/AU2016212495A1/en not_active Abandoned
- 2016-01-26 CA CA2975160A patent/CA2975160A1/en not_active Abandoned
- 2016-01-26 WO PCT/CN2016/072081 patent/WO2016119669A1/zh active Application Filing
-
2017
- 2017-07-28 US US15/662,310 patent/US20170335202A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045206A (zh) * | 2007-05-08 | 2007-10-03 | 北京大学 | 一种进行费托合成反应的方法及其专用催化剂 |
| CN101269330A (zh) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | 一种适合于浆态床用纳米催化剂及制法和应用 |
| CN102179255A (zh) * | 2011-03-02 | 2011-09-14 | 浙江工业大学 | 一种负载型钴合金催化剂及其在费托合成中的应用 |
Non-Patent Citations (1)
| Title |
|---|
| Controlled Synthesis of Co3O4 Nanoparticles through Oriented Aggregation;Tao He et al;《Chem.Mater》;20040121;第16卷;第737-743页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104607190A (zh) | 2015-05-13 |
| EP3251745A4 (en) | 2018-10-03 |
| KR20170110121A (ko) | 2017-10-10 |
| AU2016212495A1 (en) | 2017-09-21 |
| JP6653709B2 (ja) | 2020-02-26 |
| US20170335202A1 (en) | 2017-11-23 |
| RU2675839C1 (ru) | 2018-12-25 |
| WO2016119669A1 (zh) | 2016-08-04 |
| EP3251745A1 (en) | 2017-12-06 |
| JP2018505045A (ja) | 2018-02-22 |
| CA2975160A1 (en) | 2016-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Rh–Ni nanoparticles immobilized on Ce (OH) CO3 nanorods as highly efficient catalysts for hydrogen generation from alkaline solution of hydrazine | |
| CN104307530B (zh) | 一种氧化石墨烯基稀土复合物催化材料及其制备方法 | |
| CN107570155B (zh) | 多孔氧化铁/氧化石墨烯纳米复合材料在催化费托合成中的应用 | |
| CN103192086A (zh) | 一种可控的双金属合金纳米颗粒的制备方法 | |
| CN104707604A (zh) | 一种含金属或金属氧化物粒子的CeO2纤维催化剂的制备方法 | |
| CN104607190B (zh) | 用于费托合成的单分散过渡金属纳米催化剂及其制备方法和应用 | |
| CN109622000B (zh) | 一种非贵金属乙炔选择性加氢催化剂及其制备方法和应用 | |
| CN1970143A (zh) | 一种高活性加氢催化剂纳米Ru/C的制备方法 | |
| CN103041826A (zh) | 一种双金属纳米催化剂及其制备和应用方法 | |
| CN110327933A (zh) | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 | |
| CN104646025A (zh) | 一种中空Pt/Ni合金与石墨烯气凝胶复合材料的制备方法 | |
| Zhou et al. | Engineering nano-ordered of Ni nanoparticles on KIT-6 for enhanced catalytic hydrogenation of nitrobenzene | |
| CN109364931A (zh) | 一种核壳结构的二氧化碳加氢制甲醇催化剂及其制备方法 | |
| CN109364936B (zh) | 一种多壳层空心核壳立方结构的M1.8M′1.2O4@CeO2复合材料及其制备方法 | |
| CN106984314A (zh) | 一种高分散负载型铜基纳米催化剂的制备方法 | |
| CN102872870A (zh) | 一种合成气制馏分油联产高碳醇的催化剂及制备方法和应用 | |
| CN102974350A (zh) | 一种石墨烯负载金属氧化物纳米材料及其制备方法和应用 | |
| CA2671729C (en) | Preparation of iron-titanium nanoparticles | |
| CN103055869B (zh) | 一种多孔金属纳米颗粒催化剂及其制备方法 | |
| CN110773214A (zh) | 一种碳层嵌入式的碳化铁及其制备方法和碳层嵌入式的碳化铁作为费托合成催化剂的应用 | |
| Zhou et al. | Unsupported NiPt alloy metal catalysts prepared by water-in-oil (W/O) microemulsion method for methane cracking | |
| Zhu et al. | Facile synthesis of magnetic recyclable Fe3O4@ PDA@ MoS2 nanocomposites for effectively hydrocracking of residue | |
| CN106475101B (zh) | 含二氧化硅助剂的多孔炭载钴基费托合成催化剂及其制备方法 | |
| CN112774690A (zh) | 一种负载型单原子贵金属催化剂及其制备方法和应用 | |
| CN115888785A (zh) | 一种杂原子掺杂碳包覆的金属型催化剂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |