CN112569990A - Composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst and application thereof, and Fischer-Tropsch synthesis method - Google Patents
Composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst and application thereof, and Fischer-Tropsch synthesis method Download PDFInfo
- Publication number
- CN112569990A CN112569990A CN202011064089.XA CN202011064089A CN112569990A CN 112569990 A CN112569990 A CN 112569990A CN 202011064089 A CN202011064089 A CN 202011064089A CN 112569990 A CN112569990 A CN 112569990A
- Authority
- CN
- China
- Prior art keywords
- epsilon
- iron
- iron carbide
- carbide
- theta
- 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.)
- Granted
Links
- 229910001567 cementite Inorganic materials 0.000 title claims abstract description 248
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000001308 synthesis method Methods 0.000 title abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 200
- 229910052742 iron Inorganic materials 0.000 claims abstract description 73
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 54
- 239000012535 impurity Substances 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 39
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 6
- 239000004313 iron ammonium citrate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- -1 iron carbides Chemical class 0.000 claims description 3
- 159000000014 iron salts Chemical class 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 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 claims 1
- 235000013980 iron oxide Nutrition 0.000 claims 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 99
- 229910002092 carbon dioxide Inorganic materials 0.000 description 56
- 239000001569 carbon dioxide Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- 239000013078 crystal Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- AUALKMYBYGCYNY-UHFFFAOYSA-E triazanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(3+) Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[Fe+3].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O AUALKMYBYGCYNY-UHFFFAOYSA-E 0.000 description 5
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 235000014872 manganese citrate Nutrition 0.000 description 4
- 239000011564 manganese citrate Substances 0.000 description 4
- 229940097206 manganese citrate Drugs 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000001669 Mossbauer spectrum Methods 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910000704 hexaferrum Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/613—10-100 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
- B01J35/615—100-500 m2/g
-
- 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
Landscapes
- 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)
Abstract
The invention relates to the field of Fischer-Tropsch synthesis reaction, and discloses a composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, a preparation method, a catalyst and application thereof, and a Fischer-Tropsch synthesis method. A composition comprising supported epsilon/epsilon ' iron carbide and theta iron carbide, the composition comprising 55-90 wt.% of a carrier and 10-45 wt.% of an iron component, based on the total amount of the composition, wherein the iron component comprises 95-100 mol% of epsilon/epsilon ' iron carbide and theta iron carbide, and 0-5 mol% of an Fe-containing impurity, the Fe-containing impurity being an iron-containing substance other than epsilon/epsilon ' iron carbide and theta iron carbide, based on the total amount of the iron component. Can simply prepare epsilon/epsilon' iron carbide and theta iron carbide, can be used as active components to obtain continuous and stable Fischer-Tropsch synthesis reaction, and has high selectivity of effective products.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis reaction, in particular to a composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, a preparation method, a catalyst and application thereof, and a Fischer-Tropsch synthesis method.
Background
The primary energy structure of China is characterized by rich coal, lack of oil and little gas. With the development of economy in China, the dependence of petroleum on the outside is continuously rising.
Fischer-Tropsch synthesis is an increasingly important energy conversion way in recent years, and can convert carbon monoxide and H2The syngas is converted into liquid fuels and chemicals.
The reaction equation for fischer-tropsch synthesis is as follows:
(2n+1)H2+nCO→CnH2n+2+nH2O (1)，
2nH2+nCO→CnH2n+nH2O (2)。
in addition to alkanes and alkenes, industrial fischer-tropsch synthesis can also produce carbon dioxide (CO) as a by-product2) And methane (CH)4). The Fischer-Tropsch synthesis reaction has complex mechanism and multiple steps, such as CO dissociation, carbon (C) hydrogenation and CHxChain growth, and hydrogenation and dehydrogenation reactions that result in hydrocarbon product desorption and oxygen (O) removal.
Iron is the cheapest transition metal used in making fischer-tropsch synthesis catalysts. The traditional iron-based catalyst has high water gas shift (CO + H)2O→CO2+H2) Active, therefore, conventional iron-based catalysts typically have a higher CO by-product2Selectivity, typically 25% to 45% of the carbon monoxide of the conversion feedstock. This is one of the major disadvantages of iron-based fischer-tropsch catalysts.
The active phase of the iron-based catalyst is very complicated to change, which causes considerable debate between the nature of the active phase and the Fischer-Tropsch synthesis reaction mechanism of the iron-based catalyst.
CN104399501A discloses epsilon-Fe suitable for low-temperature Fischer-Tropsch synthesis reaction2C, a preparation method of the nano-particles. The initial precursor is skeleton iron, and the reaction system is intermittent discontinuous reaction of polyethylene glycol solvent. CO of this catalyst2Selectivity 18.9%, CH4The selectivity of (2) is 17.3%. The disadvantage is that the method can only be applied to low temperature below 200 ℃, and the reaction can not be continuously completed. This means that such catalysts are not suitable for continuous production under modern Fischer-Tropsch synthesis industrial conditions. However, since the skeleton iron cannot be completely carbonized, epsilon-Fe described in the above document2The nanoparticles of C contain a considerable amount of iron impurity components of the non-iron carbide type, and in fact, the prior art cannot obtain pure phase materials of iron carbide free of iron impurities, which are various Fe (element) -containing phase components of non-iron carbide.
Accordingly, there is a need for an improved iron-based catalyst for use in fischer-tropsch synthesis reactions.
Disclosure of Invention
The invention aims to solve the problem of how to obtain a pure-phase iron carbide substance without Fe impurities by using an iron-based catalyst, improve the stability of Fischer-Tropsch synthesis reaction, and simultaneously reduce CO2Or CH4The problem of over-high selectivity of byproducts, and provides a composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, a preparation method, a catalyst and application thereof, and a Fischer-Tropsch synthesis method.
In order to achieve the above object, a first aspect of the present invention provides a supported epsilon/epsilon ' iron carbide and theta iron carbide-containing composition comprising 55 to 90% by weight of a carrier and 10 to 45% by weight of an iron component, based on the total amount of the composition, wherein the iron component comprises 95 to 100 mol% of epsilon/epsilon ' iron carbide and theta iron carbide, and 0 to 5 mol% of an Fe-containing impurity, which is an iron-containing substance other than epsilon/epsilon ' iron carbide and theta iron carbide, based on the total amount of the iron component.
In a second aspect, the present invention provides a method of preparing a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide, comprising:
soaking the carrier in a ferric salt water solution, and drying and roasting the soaked carrier to obtain a precursor;
(1) preparing a supported epsilon/epsilon' iron carbide, comprising:
(1-1) reacting the precursor with H2Performing a first reduction at a temperature of 300-550 ℃;
(1-2) mixing the material obtained in the step (1-1) with H2Pre-treating CO at 90-185 deg.C, and H2The molar ratio to CO is 1.2-2.8: 1;
(1-3) mixing the material obtained in the step (1-2) with H2CO at a temperature of 200-2The molar ratio to CO is 1-3.2: 1, obtaining load type epsilon/epsilon' iron carbide;
(2) preparing a supported theta iron carbide comprising:
(2-1) reacting the precursor with H2At a temperature T1Performing a second reduction at 340 ℃. + 600 ℃;
(2-2) subjecting the product obtained in the step (2-1)Materials and H2CO at temperature T2The second carbide preparation is carried out at the temperature of 280-430 ℃ for 20-120H, wherein H2The molar ratio to CO is 5-120: 1, obtaining load type theta iron carbide;
(3) mixing the load type epsilon/epsilon' iron carbide and theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the supported epsilon/epsilon' iron carbide and theta iron carbide are used in an amount and the Fe-containing impurities are used in an amount so as to obtain the composition, wherein the composition comprises 55-90 wt% of the carrier and 10-45 wt% of the iron component based on the total amount of the composition; the iron component comprises 95 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 5 mol% of Fe-containing impurities, based on the total amount of the iron component;
wherein the Fe-containing impurities are iron-containing substances except epsilon/epsilon' iron carbide and theta iron carbide.
In a third aspect, the invention provides a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide, made by the method of the invention.
In a fourth aspect, the invention provides a catalyst comprising a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide as provided by the invention.
In a fifth aspect, the invention provides an application of the composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide in the Fischer-Tropsch synthesis reaction.
In a sixth aspect, the invention provides a use of the supported epsilon/epsilon' iron carbide and theta iron carbide-containing composition or catalyst provided by the invention in synthesis reactions of C, H fuels and/or chemicals based on the fischer-tropsch principle.
In a seventh aspect, the invention provides a fischer-tropsch synthesis process comprising: under the condition of Fischer-Tropsch synthesis reaction, the synthesis gas is contacted with the composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide provided by the invention.
An eighth aspect of the present invention provides a fischer-tropsch synthesis method, comprising: contacting the synthesis gas with a fischer-tropsch catalyst under fischer-tropsch synthesis reaction conditions, wherein the fischer-tropsch catalyst comprises a Mn component and a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide as provided by the present invention.
Through the technical scheme, the invention has the following technical effects:
(1) the required raw materials are simple and easy to obtain, and the cost is low: the iron source of the main raw material for synthesizing the precursor can be commercial iron salt, and when active phase carbide is synthesized, only original reaction gas (carbon monoxide and hydrogen) of a Fischer-Tropsch synthesis reaction system is used, so that no inorganic or organic reaction raw material is involved, and the method is greatly simplified compared with the prior art;
(2) the operation steps are simple, and in a preferred embodiment, the whole process of preparing each crystal phase iron carbide can be realized in the same reactor, and then the crystal phase iron carbide and the active phase iron carbide are mixed to form the composition.
(3) The invention can respectively prepare 100% purity epsilon/epsilon 'iron carbide and theta iron carbide loaded on a carrier through the steps provided by the method, and then the epsilon/epsilon' iron carbide and the theta iron carbide form a composition with Fe-containing impurities to further prepare the catalyst. The above iron carbide or composition or catalyst can be used at high temperatures and pressures (e.g., temperatures of 235 ℃.;, pressures of 1.9-2.5MPa, H)21.5-2.0) continuous reactor, the reaction stability is extremely high, the theoretical technical barrier of the traditional literature theory that pure iron carbide can not stably exist under the reaction condition is broken through, the stable temperature can reach 260 ℃, and CO can be realized2Very low selectivity: under the condition of industrial Fischer-Tropsch synthesis reaction, a high-pressure continuous reactor can be used for keeping continuous and stable reaction for more than 400h, and CO is generated2The selectivity is below 8% (preferably, 4% or below can be achieved); at the same time, its by-product CH4The selectivity is kept below 12 percent (preferably below 7 percent), the selectivity of the effective product can reach above 81 percent (preferably above 86 percent), and the method is very suitable for the high-efficiency production of oil wax products in the Fischer-Tropsch synthesis industry of the modern coal chemical industry.
Drawings
FIG. 1 is an XRD spectrum of a supported epsilon/epsilon' iron carbide prepared in preparation example 1 provided by the invention;
fig. 2 is an XRD spectrum of the supported iron theta carbide prepared in preparation example 2 provided in the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a composition containing supported epsilon/epsilon ' iron carbide and theta iron carbide, which comprises 55-90 wt% of a carrier and 10-45 wt% of an iron component based on the total amount of the composition, wherein the iron component comprises 95-100 mol% of epsilon/epsilon ' iron carbide and theta iron carbide and 0-5 mol% of Fe-containing impurities based on the total amount of the iron component, and the Fe-containing impurities are iron-containing substances except the epsilon/epsilon ' iron carbide and the theta iron carbide.
The invention provides a composition, which comprises 100% purity epsilon-iron carbide and/or 100% purity epsilon' -iron carbide and 100% purity theta-iron carbide loaded on a carrier. Further, the supported epsilon/epsilon' iron carbide and theta iron carbide may constitute the composition with other Fe-containing impurities. Under the limit of the content, the composition containing the supported epsilon/epsilon' iron carbide and the theta iron carbide provided by the invention can be used alone or combined with other components when being applied to a Fischer-Tropsch synthesis catalyst, so that the stability of the Fischer-Tropsch synthesis reaction of the Fischer-Tropsch synthesis catalyst is improved, and CO is reduced2Or CH4Selectivity of by-products.
In some embodiments of the invention, the composition comprises high purity epsilon/epsilon 'iron carbide and theta iron carbide supported on a carrier, and mossbauer spectroscopy is performed to observe that the crystalline phase comprises pure epsilon/epsilon' iron carbide and theta iron carbide on the obtained mossbauer spectroscopy results. Preferably, the specific surface area of the composition is from 40 to 500m2Per g, preferably from 45 to 350m2(ii) in terms of/g. The specific surface area may be represented by N2The BET adsorption and desorption method (2). The composition comprises hexagonal, pseudo-hexagonal or trigonal epsilon/epsilon' iron carbide and orthorhombic theta iron carbide.
In some embodiments of the invention, it is further preferred that the composition comprises 60 to 85 wt.% of the carrier and 15 to 40 wt.% of the iron component, based on the total amount of the composition. Can be determined by elemental analysis. The support may be selected from at least one of silica, alumina, titania, niobium pentoxide, and zirconia.
In a preferred embodiment of the present invention, the iron component preferably comprises 97 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 3 mol% of impurities containing Fe, based on the total amount of the iron component. Can be determined by XRD and Mossbauer spectrometry analysis, and can also be determined according to the preparation charge of the composition.
In some embodiments of the invention, the Fe-containing impurities are at least one of iron carbide, iron oxide, iron hydroxide, iron sulfide, iron salt other than epsilon/epsilon' iron carbide and theta iron carbide. The Fe-containing impurities may be introduced by solution impregnation, sputtering, atomic deposition or mixing.
In a specific embodiment provided by the present invention, the mole ratio of epsilon/epsilon' iron carbide to theta iron carbide is a: b, wherein a is more than 0 and less than 100, b is more than 0 and less than 100, preferably, a is more than 0 and less than or equal to 85, and b is more than 0 and less than or equal to 85. The molar ratio of the iron carbides of the two phases in the above range can produce a synergistic effect, optimizing the dissociation path of CO and the hydrogenation path of the C species and CHxIncrease the catalytic activity and decrease CH4With CO2And adjusting the product distribution.
In a second aspect, the present invention provides a process for preparing a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide, comprising:
soaking the carrier in a ferric salt water solution, and drying and roasting the soaked carrier to obtain a precursor;
(1) preparing a supported epsilon/epsilon' iron carbide, comprising:
(1-1) reacting the precursor with H2Performing a first reduction at a temperature of 300-550 ℃;
(1-2) mixing the material obtained in the step (1-1) with H2Pre-treating CO at 90-185 deg.C, and H2The molar ratio to CO is 1.2-2.8: 1;
(1-3) mixing the material obtained in the step (1-2) with H2CO at a temperature of 200-2The molar ratio to CO is 1-3.2: 1, obtaining load type epsilon/epsilon' iron carbide;
(2) preparing a supported theta iron carbide comprising:
(2-1) reacting the precursor with H2At a temperature T1Performing a second reduction at 340 ℃. + 600 ℃;
(2-2) mixing the material obtained in the step (2-1) with H2CO at temperature T2The second carbide preparation is carried out at the temperature of 280-430 ℃ for 20-120H, wherein H2The molar ratio to CO is 5-120: 1, obtaining load type theta iron carbide;
(3) mixing the load type epsilon/epsilon' iron carbide and theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the supported epsilon/epsilon' iron carbide and theta iron carbide are used in an amount and the Fe-containing impurities are used in an amount so as to obtain the composition, wherein the composition comprises 55-90 wt% of the carrier and 10-45 wt% of the iron component based on the total amount of the composition; the iron component comprises 95 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 5 mol% of Fe-containing impurities, based on the total amount of the iron component;
wherein the Fe-containing impurities are iron-containing substances except epsilon/epsilon' iron carbide and theta iron carbide.
One embodiment provided by the present invention first prepares the precursor. In the preparation process, preferably, the iron salt may be a water-soluble iron salt commonly used in the art, and the iron salt is selected from water-soluble iron salts, which may be commercially available products, for example, at least one of ferric nitrate, ferric chloride, ferrous ammonium sulfate and ferric ammonium citrate.
In some embodiments of the present invention, the catalyst support may be a conventional choice in the art, for example, the catalyst support is at least one of silica, alumina, titania, niobium pentoxide, and zirconia. In the present invention, it is preferable that the particle size of the carrier is 30 to 200. mu.m.
In some embodiments of the invention, preferably, the impregnation is such that the iron content in the impregnated support after drying is from 10 to 30% by weight. The impregnation may be a routine choice in the art as long as the loading of iron in the impregnated support is achieved, preferably the impregnation is a saturated impregnation.
In a preferred embodiment of the present invention, the drying and baking process comprises: firstly, drying the impregnated carrier at 20-30 ℃ for 0.5-4h, then drying at 35-80 ℃ and a vacuum degree of 250-. The above drying process can be performed in an oven, and the roasting process can be performed in a muffle furnace.
One embodiment provided by the invention prepares the supported epsilon/epsilon' iron carbide.
In some embodiments of the present invention, step (1-1) may simultaneously perform in-situ generation of nano iron powder from iron element in the precursor and reduction of the generated nano iron powder.
In some embodiments of the invention, H in step (1-1)2Can be represented by H2Introducing the mixture into the reaction system in the form of a flow, and simultaneously controlling H2The pressure of the stream is controlled to control the pressure of the first reduction, preferably, the pressure of the first reduction is 0.1 to 15atm, preferably 0.3 to 2.6atm, and the time is 0.7 to 15 hours, preferably 1 to 12 hours in step (1 to 2).
In some embodiments of the invention, H2The amount of H to be used may be selected depending on the amount of the precursor to be treated, and preferably, in step (1-1), H2The gas flow rate of (b) is 600-25000mL/h/g, more preferably 2800-22000 mL/h/g.
In step (1-2) of the process provided by the present invention, H2And CO may be (H)2+ CO) mixed gas flow to participate in the pretreatment process; at the same time, by controlling (H)2+ CO) mixed gas stream pressure to control the pressure of the pretreatment process. Preferably, in the step (1-2), the pressure of the pretreatment is0.05-7atm, preferably 0.08-4.5atm, for 15-120min, preferably 20-90 min.
In some embodiments of the present invention, preferably, in step (1-2), H2The total gas flow rate with CO is 300-12000mL/h/g, more preferably 1500-9000 mL/h/g.
In the step (1-3) of the method provided by the invention, the conditions for realizing the preparation of the first carbide are provided so as to obtain the supported epsilon/epsilon' iron carbide. H2And CO may be (H)2+ CO) in the form of a mixed gas stream into the first carbide production process; at the same time, by controlling (H)2+ CO) mixed gas stream pressure to control the pressure of the first carbide making process. Preferably, in the step (1-4), the first carbide is prepared at a pressure of 0.1-10atm, preferably 0.2-4.5atm, for a time of 1.5-15h, preferably 2.5-12 h.
In some embodiments of the present invention, preferably, in step (1-3), H2The total gas flow rate with CO is 500-30000mL/h/g, more preferably 3000-25000 mL/h/g.
In a preferred embodiment of the present invention, the first carbide preparation further comprises: in the step (1-3), the temperature is simultaneously raised from the pretreatment temperature to 200-230 ℃ at a temperature raising rate of 0.2-5 ℃/min. In the preferred embodiment, the obtained supported epsilon/epsilon' iron carbide can have better effective product selectivity in the Fischer-Tropsch synthesis reaction. Further preferably, the temperature is raised from the temperature of the pretreatment to 210-290 ℃ at a temperature raising rate of 0.2-2.5 ℃/min. In the temperature raising operation, the temperature of the pretreatment is 90-185 ℃ in the step (1-2). Namely, the temperature raising operation is: raising the temperature from 90-185 ℃ to 200-300 ℃ at a temperature raising rate of 0.2-5 ℃/min, preferably from 90-185 ℃ to 210-290 ℃ at a temperature raising rate of 0.2-2.5 ℃/min.
In another embodiment of the present invention, a supported theta iron carbide is prepared.
In some embodiments of the present invention, it is preferred that H in step (2-1)2Can be represented by H2Introducing the mixture into the reaction system in the form of a flow, and simultaneously controlling H2Pressure of the flow to controlA pressure of the second reduction, preferably, in the step (2-1), the pressure of the second reduction is 0.1 to 15atm, preferably 0.3 to 2.6 atm; the time is 0.7-15h, preferably 1-12 h.
In some embodiments of the invention, H2The amount of H to be used may be selected depending on the amount of the precursor to be treated, and preferably, in step (2-1), H is2The gas flow rate of (b) is 600-25000mL/h/g, more preferably 2800-22000 mL/h/g.
In the step (2-2) of the method provided by the invention, conditions for realizing the preparation of the second carbide are provided so as to obtain the supported theta iron carbide. H2And CO may be (H)2+ CO) in the form of a mixed gas stream into the second carbide production process; at the same time, by controlling (H)2+ CO) mixed gas stream to control the pressure of the second carbide making process. Preferably, in the step (2-2), the second carbide is prepared at a pressure of 0 to 28atm, preferably 0.01 to 20atm, for a time of 20 to 120 hours, preferably 24 to 80 hours.
In some embodiments of the present invention, preferably, in step (2-2), H2The total gas flow rate with CO is 200-.
In a preferred embodiment of the present invention, the second carbide preparation further comprises: in the step (2-2), the temperature change operation is carried out at the same time from the temperature T1Cooling or heating to temperature T at variable temperature rate of 0.2-5 deg.C/min2(ii) a Preferably, from the temperature T1Cooling or heating to 300-400 ℃ at a temperature change rate of 0.2-2.5 ℃/min.
In the present invention, "mL/h/g" in the iron carbide production process means the volume of gas introduced per gram of the material per hour, unless otherwise specified.
In another preferred embodiment of the present invention, the first reduction, pretreatment and first carbide preparation may be performed in the same fischer-tropsch synthesis reactor during the preparation of the supported epsilon/epsilon' iron carbide. In the process of preparing the supported theta iron carbide, the second reduction and the second carbide preparation can be carried out in the same fischer-tropsch synthesis reactor. In-situ characterization equipment can be used to track the crystal phase transition of the material during the preparation process.
In the invention, the steps (1) and (2) in the method provided by the invention can realize the obtainment of the load type epsilon/epsilon' iron carbide and the load type theta iron carbide.
In the step (3) of the method provided by the invention, the load type epsilon/epsilon' iron carbide and the load type theta iron carbide are mixed into the load type iron carbide. The result of said mixing is preferably such that the mole ratio of epsilon/epsilon' iron carbide and theta iron carbide is a: b, wherein a is more than 0 and less than 100, b is more than 0 and less than 100, preferably, a is more than 0 and less than or equal to 85, and b is more than 0 and less than or equal to 85.
In some embodiments of the invention, the supported epsilon/epsilon' iron carbide and theta iron carbide-containing composition comprises Fe impurities that can be incorporated by external means. Preferably, step (3) comprises 60-85 wt.% of the carrier and 15-40 wt.% of the iron component, based on the total amount of the composition; the iron component comprises 97 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 3 mol% of Fe-containing impurities, based on the total amount of the iron component.
In the step (3) of the method provided by the invention, the mixing is carried out by mixing the powders of the supported epsilon/epsilon' iron carbide and the theta iron carbide and the Fe-containing impurity powder in a glove box according to the dosage requirement under the inert gas protection condition.
In a third aspect, the invention provides a composition of supported epsilon/epsilon' iron carbide and theta iron carbide made by the process of the invention. The composition comprises 55-90 wt% of a carrier and 10-45 wt% of an iron component, based on the total amount of the composition, wherein the iron component comprises 95-100 mol% of epsilon/epsilon 'iron carbide and theta iron carbide, and 0-5 mol% of Fe-containing impurities, wherein the Fe-containing impurities are iron-containing substances except epsilon/epsilon' iron carbide and theta iron carbide, based on the total amount of the iron component.
Preferably, the composition comprises 60 to 85 wt.% of the carrier and 15 to 40 wt.% of the iron component, based on the total amount of the composition; the iron component comprises 97 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 3 mol% of Fe-containing impurities, based on the total amount of the iron component.
Preferably, the compositionHas a specific surface area of 40-500m2Per g, preferably from 45 to 350m2/g。
Preferably, the mole ratio of epsilon/epsilon' iron carbide to theta iron carbide is a: b, wherein a is more than 0 and less than 100, b is more than 0 and less than 100, preferably, a is more than 0 and less than or equal to 85, and b is more than 0 and less than or equal to 85.
In a fourth aspect, the invention provides a catalyst comprising a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide as provided by the invention. Preferably, the catalyst may also comprise other components, such as promoters.
In the embodiment provided by the present invention, preferably, the composition containing the supported epsilon/epsilon' iron carbide and the theta iron carbide is contained in an amount of 75 wt% or more and less than 100 wt%, and the auxiliary is contained in an amount of more than 0 wt% and 25 wt% or less, based on the total amount of the catalyst.
In the embodiment provided by the invention, preferably, the catalyst can be prepared by introducing the auxiliary agent by a method of impregnation, atomic deposition, sputtering or chemical deposition.
In a fifth aspect, the invention provides an application of the composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide in the Fischer-Tropsch synthesis reaction.
In a sixth aspect, the invention provides the use of a supported iron epsilon/epsilon' carbide and iron theta carbide-containing composition or catalyst in the synthesis of C, H fuels and/or chemicals based on the fischer-tropsch synthesis principle.
In a seventh aspect, the present invention provides a fischer-tropsch synthesis reaction process, comprising: under the condition of Fischer-Tropsch synthesis reaction, the synthesis gas is contacted with the composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide provided by the invention.
The fischer-tropsch synthesis reaction carried out by using the composition or catalyst containing epsilon/epsilon' iron carbide and theta iron carbide of the invention can be carried out at high temperature and high pressure, for example, the conditions of the fischer-tropsch synthesis reaction include: the temperature is 235 ℃ and 250 ℃, and the pressure is 2.3-2.5 MPa. But also can be used for realizing better effective product selectivity; the effective product is prepared from CO and H2Produced by reactionRemoving CH4With CO2Products containing carbon other than C, including but not limited to2And C2The above hydrocarbons, alcohols, aldehydes, ketones, esters, and the like.
In the present invention, the pressure refers to gauge pressure unless otherwise specified.
In the present invention, preferably, the fischer-tropsch synthesis reaction is carried out in a high temperature and high pressure continuous reactor. The composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide can realize that the Fischer-Tropsch synthesis reaction can be continuously and stably carried out for more than 400 hours in a high-temperature high-pressure continuous reactor.
An eighth aspect of the present invention provides a fischer-tropsch synthesis method, comprising: contacting the synthesis gas with a fischer-tropsch catalyst under fischer-tropsch synthesis reaction conditions, wherein the fischer-tropsch catalyst comprises a Mn component and a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide as provided by the present invention.
In a specific embodiment provided by the present invention, the composition of the fischer-tropsch catalyst may further comprise, based on the total amount of the fischer-tropsch catalyst, 75 wt% or more and less than 100 wt% of the composition containing the supported epsilon/epsilon' iron carbide and theta iron carbide, and more than 0 wt% and less than 25 wt% of Mn. In the fischer-tropsch catalyst, Mn may be present as an oxide and may be incorporated into the fischer-tropsch catalyst by methods including, but not limited to, impregnation, chemical deposition, sputtering, atomic deposition.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
in-situ XRD detection in the process of preparing the iron carbide, an X-ray diffractometer (Rigaku company, model D/max-2600/PC) is used for monitoring the crystal phase change of the material;
the obtained iron carbide and iron carbide composition were subjected to Mossbauer spectrometer (Transmission)57Fe，57A Co (Rh) source sinusoidal velocity spectrometer) to perform Mossbauer spectrum detection;
the BET specific surface area of the iron carbide composition was measured by a nitrogen adsorption method;
carrying out Fischer-Tropsch synthesis reaction:
carrying out gas chromatography (Agilent 6890 gas chromatography) on the product obtained by the reaction;
the effect of the reaction is calculated by the following formula:
CO2selectivity%2Mole number/(moles of CO in feed-moles of CO in discharge)]×100％；
CH4Selectivity%4Mole/(mole of CO in the feed x CO conversion% (1-CO)2Selectivity%))]×100％；
Effective product selectivity ═ 1-CO2Selective% CH4Selectivity%]×100％
Space-time conversion rate (mmol/h/g) of raw material COFe) (moles of CO in feed-moles of CO in discharge)/reaction time/weight of Fe element;
space-time yield (mmol/h/g) for efficient product formationFe) Reaction of C2And C2The above number of moles of hydrocarbon/reaction time/weight of Fe element.
Preparation example 1
(1) Weighing 10g of silicon oxide as a carrier, and then impregnating with an aqueous ferric ammonium citrate solution, wherein the aqueous ferric ammonium citrate solution is weighed and prepared according to the content of 30 wt% of the simple substance iron in the final carrier. Drying the impregnated carrier at 35 ℃ for 2h, then drying the impregnated carrier in a vacuum drying oven at 30 ℃ and a vacuum degree of 300Pa for 8h, drying the dried material in an oven at 120 ℃ for 24h, and roasting the obtained material in a muffle furnace at 500 ℃ for 5 h. Obtaining a load type iron-based precursor;
(2) mixing the precursor with H2At a pressure of 2.0atm, H2The flow rate of the first reduction is 20000mL/h/g, and the first reduction is carried out at the temperature of 420 ℃ for 12 h;
(3) cooling the product obtained in the step (2) to 160 ℃, and reacting the product with H at 160 DEG C2Mixed gas with CO (pressure 2.5atm, total gas flow 10000mL/H/g, H)2Contacting with CO at a molar ratio of 2:1) for pretreatment for 90 min;
(4) h is to be2The conditions of the mixed gas with CO are firstly changed as follows: pressure 3.0atm, total gas flow 14000 mL/H/g, H2And (3) heating the mixture to 250 ℃ from 160 ℃ at a heating rate of 2.5 ℃/min under the condition that the molar ratio of the mixture to CO is 1.5:1, then carrying out first carbide preparation on the mixture and the material obtained in the step (3), wherein the carbonization time is 5h, so as to obtain loaded iron carbide, and determining that the loaded iron carbide is pure epsilon/epsilon' iron carbide through Mossbauer spectroscopy and is marked as iron carbide 1.
The preparation method of the supported epsilon/epsilon ' iron carbide provided by the invention is not limited to the preparation example 1, and the specific implementation method for preparing the supported epsilon/epsilon ' iron carbide is described in the embodiment of Chinese patent application ' composition containing the supported epsilon/epsilon ' iron carbide, preparation method thereof, catalyst and application thereof and Fischer-Tropsch synthesis method ', and the whole content of the method is introduced into the invention.
Preparation example 2
(a) Weighing 10g of silicon oxide as a carrier, and then impregnating with an aqueous ferric ammonium citrate solution, wherein the aqueous ferric ammonium citrate solution is weighed and prepared according to the content of 30 wt% of the simple substance iron in the final carrier. Drying the impregnated carrier at 35 ℃ for 2h, then drying the impregnated carrier in a vacuum drying oven at 30 ℃ and a vacuum degree of 300Pa for 8h, drying the dried material in an oven at 120 ℃ for 24h, and roasting the obtained material in a muffle furnace at 500 ℃ for 5 h. Obtaining a load type iron-based precursor;
(b) mixing the precursor with H2At a pressure of 2.2atm, H2The flow rate of the second reduction is 12000mL/h/g, and the temperature is 460 ℃ for 12 h;
(c) cooling the product of step (b) from 460 ℃ to 380 ℃ at a rate of 1.5 ℃/min and reacting with H at this temperature2And contacting with CO mixed gas to prepare a second carbide, wherein the conditions are as follows: pressure 2.0atm, total gas flow 10000mL/H/g, H2The molar ratio of the iron carbide to CO is 50:1, the treatment time is 8 hours, the loaded iron carbide is obtained, and the loaded iron carbide is pure theta iron carbide determined by Mossbauer spectroscopy and is marked as iron carbide 2.
The preparation method of the supported theta iron carbide provided by the invention is not limited to the preparation example 2, and the specific implementation method for preparing the supported theta iron carbide is described in the embodiment of the Chinese patent application 'composition containing the supported theta iron carbide, the preparation method, the catalyst and the application thereof and the Fischer-Tropsch synthesis method', and the whole content of the method is introduced into the invention.
Example 1
Under the protection of Ar gas, 83 parts by mole (in terms of iron element, the same applies hereinafter) of iron carbide 1, 16 parts by mole of iron carbide 2 was mixed with 1 part by mole of ferrous oxide (i.e., Fe-containing impurities). After mixing, it is designated as iron carbide composition 1.
Example 2
Under the protection of Ar gas, 14 molar parts of iron carbide 1, 84 molar parts of iron carbide 2 and 2 molar parts of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, it is designated as iron carbide composition 2.
Example 3
Under the protection of Ar gas, 90 molar parts of iron carbide 1, 9 molar parts of iron carbide 2 and 1 molar part of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, it was designated as iron carbide composition 3.
Example 4
Under Ar gas protection, 10 molar parts of iron carbide 1, 87 molar parts of iron carbide 2 and 3 molar parts of ferrous oxide (i.e. Fe-containing impurities) are mixed. After mixing, it was designated as iron carbide composition 4.
Comparative example 1
Under the protection of Ar gas, 79 mol parts of iron carbide 1, 14 mol parts of iron carbide 2 and 7 mol parts of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, it was designated as iron carbide composition D1.
Comparative example 2
Under the protection of Ar gas, 14 molar parts of iron carbide 1, 80 molar parts of iron carbide 2 and 6 molar parts of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, it was designated as iron carbide composition D2.
Examples 5 to 8
Respectively taking 1-4 parts of iron carbide composition in N2Adding manganese citrate solution by immersion method under protection, and adding N at 25 deg.C2And drying the gas flow for 24 hours to obtain the Fischer-Tropsch catalyst 1-4 correspondingly. Wherein the amount of the added manganese citrate solution is impregnated, so that the obtained Fischer-Tropsch catalysts 1-4 respectively and correspondingly contain 85 wt% of iron carbide composition 1-4 and 15 wt% of MnO2。
Comparative examples 3 to 4
Respectively taking iron carbide compositions D1-D2 as the balance of N2Adding manganese citrate solution by immersion method under protection, and adding N at 25 deg.C2And drying the gas flow for 24h to obtain the Fischer-Tropsch catalysts D1-D2. Wherein the added manganese citrate solution is impregnated in an amount which enables the obtained Fischer-Tropsch catalysts D1-D2 to respectively contain 85 wt% of iron carbide composition D1-D2 and 15 wt% of MnO2。
Test example
Mossbauer spectroscopy was performed on iron carbide 1-2, and the results of the determination of the Fe compound content are shown in Table 1. Wherein the content of the Fe compound is expressed in mol percent.
TABLE 1
In the preparation examples 1 and 2, in-situ XRD detection technology is adopted, and an X-ray diffractometer (Rigaku company, model D/max-2600/PC) is used for monitoring the crystal phase change of the material. The XRD test result of preparation example 1 is shown in FIG. 1, in which the curve is such that carbide 1 having a crystal phase of ε -Fe with a purity of 100% is obtained after all the carbonization steps are completed2C and epsilon-Fe2.2C, i.e. epsilon/epsilon' iron carbide, and together an XRD standard card PDF-89-2005 showing 2 theta equal to 37.7 °, 41.4 °, 43.2 °, 57.2 °, 68.0 °, 76.8 °, 82.9 ° in full agreement with the standard card. The crystallinity of the generated target product epsilon/epsilon 'iron carbide is good, all characteristic peaks of the epsilon/epsilon' iron carbide are well corresponded, the purity is extremely high, and no other impurities exist.
The XRD test result of preparation example 2 is shown in FIG. 2, in which the curve is that carbide 2 obtained after completion of all the carbonization steps has a crystal phase of 100% purity of the orthorhombic system theta-Fe3C, that is, θ iron carbide, has all characteristic peaks at 36.6 °, 37.8 °, 42.9 °, 43.8 °, 44.6 °, 45.0 °, 45.9 °, 48.6 °, and 49.1 ° of 2 θ main peak, and θ -Fe3The C standard card PDF-65-2142 is completely consistent. The generated target product theta iron carbide has good crystallinity, well corresponds to all characteristic peaks of the theta iron carbide, has extremely high purity and does not contain any other impurities.
Mossbauer spectra and BET specific surface area measurements were performed for iron carbide compositions 1-4 and D1-D2, respectively, and the results are shown in Table 2.
TABLE 2
Evaluation example
In a fixed bed continuous reactor, the performance evaluation of the catalytic reaction is respectively carried out on Fischer-Tropsch catalysts 1-4, D1-D2 and iron carbide compositions 1-2. The catalyst loading was 10.0 g.
Evaluation conditions were as follows: t is 241 deg.C, P is 2.35MPa, H2：CO＝1.9：1，(H2+ CO) total amount 42000mL/h/g-Fe(standard state flux, relative to Fe element). The reaction products were analyzed by gas chromatography, and the evaluation data of the reaction performance for the reactions of 24 hours and 400 hours are shown in tables 3 and 4.
TABLE 3
TABLE 4
As can be seen from the above examples, comparative examples and data in tables 1 to 4, the supported epsilon/epsilon' iron carbide and theta iron carbide composition or catalyst prepared by the invention has high space-time conversion rate of raw material CO, better reaction performance and ultralow CO content in limited condition range when the Fischer-Tropsch synthesis reaction is carried out under industrial conditions2And (4) selectivity. At the same time, CH4Low selectivity and high selectivity of effective products.
Further long-period experiments are carried out, and the data of the reaction for 400h in the table 4 show that after the composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide prepared under the limited conditions provided by the invention runs for a long time, the CO conversion rate and the product selectivity are stable and have no obvious change, and the stability is greatly superior to that of the iron carbide in the prior art.
The composition or the catalyst containing the supported epsilon/epsilon' iron carbide and the theta iron carbide prepared by the invention can be suitable for a high-temperature high-pressure continuous reactor, has high reaction stability, and contains CO2Very low selectivity: under the condition of industrial Fischer-Tropsch synthesis reaction, a high-pressure continuous reactor can be used for keeping continuous and stable reaction for more than 400h, and CO is generated2The selectivity is below 8% (preferably, 4% or below can be achieved); at the same time, its by-product CH4The selectivity is also kept below 12 percent (preferably below 7 percent), and the selectivity of the effective product can reach above 81 percent (preferably above 86 percent). Wherein the catalyst effective product formation space-time yield of the preferred conditions (catalyst 1-2) can reach 210mmol/h/g-FeThe method is very suitable for the high-efficiency production of products such as gasoline and diesel oil in the large modern chemical Fischer-Tropsch synthesis industry.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (23)
1. A composition comprising supported epsilon/epsilon ' iron carbide and theta iron carbide, which comprises 55-90 wt.% of a carrier and 10-45 wt.% of an iron component, based on the total amount of the composition, wherein the iron component comprises 95-100 mol% of epsilon/epsilon ' iron carbide and theta iron carbide, and 0-5 mol% of an Fe-containing impurity which is an iron-containing substance other than epsilon/epsilon ' iron carbide and theta iron carbide, based on the total amount of the iron component.
2. According to claimThe composition of claim 1, wherein the composition has a specific surface area of 40 to 500m2Per g, preferably from 45 to 350m2/g。
3. The composition according to claim 1 or 2, wherein the composition comprises 60-85 wt.% of the carrier and 15-40 wt.% of the iron component, based on the total amount of the composition;
preferably, the iron component comprises 97 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 3 mol% of Fe-containing impurities, based on the total amount of the iron component.
4. The composition of any one of claims 1-3, wherein the Fe-containing impurities are at least one of iron carbides other than epsilon/epsilon' and theta iron carbides, iron oxides, iron hydroxides, iron sulfides, iron salts.
5. The composition according to any one of claims 1 to 4, wherein the molar ratio of epsilon/epsilon' iron carbide and theta iron carbide is a: b, wherein a is more than 0 and less than 100, b is more than 0 and less than 100, preferably, a is more than 0 and less than or equal to 85, and b is more than 0 and less than or equal to 85.
6. A method of making a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide comprising:
soaking the carrier in a ferric salt water solution, and drying and roasting the soaked carrier to obtain a precursor;
(1) preparing a supported epsilon/epsilon' iron carbide, comprising:
(1-1) reacting the precursor with H2Performing a first reduction at a temperature of 300-550 ℃;
(1-2) mixing the material obtained in the step (1-1) with H2Pre-treating CO at 90-185 deg.C, and H2The molar ratio to CO is 1.2-2.8: 1;
(1-3) mixing the material obtained in the step (1-2) with H2CO at a temperature of 200-2The molar ratio to CO is 1-3.2: 1, obtaining a load typeEpsilon/epsilon' iron carbide;
(2) preparing a supported theta iron carbide comprising:
(2-1) reacting the precursor with H2At a temperature T1Performing a second reduction at 340 ℃. + 600 ℃;
(2-2) mixing the material obtained in the step (2-1) with H2CO at temperature T2The second carbide preparation is carried out at the temperature of 280-430 ℃ for 20-120H, wherein H2The molar ratio to CO is 5-120: 1, obtaining load type theta iron carbide;
(3) mixing the load type epsilon/epsilon' iron carbide and theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the supported epsilon/epsilon' iron carbide and theta iron carbide are used in an amount and the Fe-containing impurities are used in an amount so as to obtain the composition, wherein the composition comprises 55-90 wt% of the carrier and 10-45 wt% of the iron component based on the total amount of the composition; the iron component comprises 95 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 5 mol% of Fe-containing impurities, based on the total amount of the iron component;
wherein the Fe-containing impurities are iron-containing substances except epsilon/epsilon' iron carbide and theta iron carbide.
7. The method according to claim 6, wherein in the step (3), the mole ratio of epsilon/epsilon' iron carbide to theta iron carbide is a: b, wherein a is more than 0 and less than 100, b is more than 0 and less than 100, preferably, a is more than 0 and less than or equal to 85, and b is more than 0 and less than or equal to 85.
8. The method according to claim 6 or 7, wherein the iron salt is selected from water soluble iron salts, preferably at least one of ferric nitrate, ferric chloride, ferrous ammonium sulfate and ferric ammonium citrate;
preferably, the impregnation is such that the iron content in the dried impregnated support is from 10 to 30% by weight;
preferably, the drying and roasting process comprises the following steps: firstly, drying the impregnated carrier at 20-30 ℃ for 0.5-4h, then drying at 35-80 ℃ and a vacuum degree of 250-.
9. The method of any one of claims 6-8, wherein the support is at least one of silica, alumina, titania, niobium pentoxide, and zirconia;
preferably, the particle size of the support is 30-200 μm.
10. The process according to any one of claims 6 to 9, wherein in step (1-1), the pressure of the first reduction is 0.1 to 15atm, preferably 0.3 to 2.6atm, and the time is 0.7 to 15h, preferably 1 to 12 h;
further preferably, in step (1-1), H2The gas flow rate of (b) is 600-25000mL/h/g, more preferably 2800-22000 mL/h/g.
11. The method according to any one of claims 6 to 9, wherein in step (1-2), the pressure of the pretreatment is 0.05 to 7atm, preferably 0.08 to 4.5atm, and the time is 15 to 120min, preferably 20 to 90 min;
further preferably, in step (1-2), H2The total gas flow rate with CO is 300-12000mL/h/g, more preferably 1500-9000 mL/h/g.
12. The method according to any one of claims 6 to 9, wherein in step (1-3), the first carbide is prepared at a pressure of 0.1 to 10atm, preferably 0.2 to 4.5atm, for a time of 1.5 to 15h, preferably 2.5 to 12 h;
further preferably, in step (1-3), H2The total gas flow rate with CO is 500-30000mL/h/g, more preferably 3000-25000 mL/h/g.
13. The method of any of claims 6-9, wherein the first carbide making further comprises: simultaneously performing temperature rise operation in the step (1-3), wherein the temperature is raised from the pretreatment temperature to 200-300 ℃ at the temperature rise rate of 0.2-5 ℃/min;
preferably, the temperature is raised from the temperature of the pretreatment to 210-290 ℃ at a temperature raising rate of 0.2-2.5 ℃/min.
14. The process according to any one of claims 6 to 9, wherein in step (2-1), the pressure of the second reduction is 0.1 to 15atm, preferably 0.3 to 2.6 atm; the time is 0.7 to 15 hours, preferably 1 to 12 hours;
further preferably, in step (2-1), H2The gas flow rate of (b) is 600-25000mL/h/g, more preferably 2800-22000 mL/h/g.
15. The method according to any one of claims 6 to 9, wherein in step (2-2), the second carbide is prepared at a pressure of 0 to 28atm, preferably 0.01 to 20atm, for a time of 20 to 120h, preferably 24 to 80 h;
further preferably, in step (2-2), H2The total gas flow rate with CO is 200-.
16. The method of any of claims 6-9, wherein the second carbide making further comprises: in the step (2-2), temperature change operation is carried out at the same time from the temperature T1Cooling or heating to temperature T at variable temperature rate of 0.2-5 deg.C/min2；
Preferably, from the temperature T1Cooling or heating to 300-400 ℃ at a temperature change rate of 0.2-2.5 ℃/min.
17. The method according to any one of claims 6 to 20, wherein in step (3), 60 to 85% by weight of the carrier and 15 to 40% by weight of the iron component, based on the total amount of the composition;
the iron component comprises 97 to 100 mol% of epsilon/epsilon' iron carbide and theta iron carbide, and 0 to 3 mol% of Fe-containing impurities, based on the total amount of the iron component.
18. A composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide made by the process of any of claims 6-17.
19. A catalyst comprising the composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide of any of claims 1-5 and 18.
20. Use of a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide according to any one of claims 1 to 5 and 18 or a catalyst according to claim 19 in a fischer-tropsch synthesis reaction.
21. Use of a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide according to any one of claims 1 to 5 and 18 or a catalyst according to claim 19 in the synthesis of C, H fuels and/or chemicals based on the fischer-tropsch principle.
22. A process for fischer-tropsch synthesis comprising: contacting synthesis gas with a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide according to any one of claims 1 to 5 and 18 or a catalyst according to claim 19 under fischer-tropsch synthesis reaction conditions;
preferably, the fischer-tropsch synthesis is carried out in a high temperature high pressure continuous reactor.
23. A process for fischer-tropsch synthesis comprising: contacting synthesis gas with a fischer-tropsch catalyst under fischer-tropsch synthesis reaction conditions, wherein the fischer-tropsch catalyst comprises a Mn component and a composition comprising supported epsilon/epsilon' iron carbide and theta iron carbide according to any one of claims 1 to 5 and 18.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019109432380 | 2019-09-30 | ||
| CN201910943238 | 2019-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112569990A true CN112569990A (en) | 2021-03-30 |
| CN112569990B CN112569990B (en) | 2023-07-11 |
Family
ID=75119760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011064089.XA Active CN112569990B (en) | 2019-09-30 | 2020-09-30 | Composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112569990B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361349A2 (en) * | 1988-09-26 | 1990-04-04 | Seisan Kaihatsu Kagaku Kenkyusho | Magnetic fine particles of epsilon' iron carbide |
| CN104399501A (en) * | 2014-11-09 | 2015-03-11 | 复旦大学 | High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof |
| US20160045901A1 (en) * | 2013-03-19 | 2016-02-18 | Korea Institute Of Energy Research | Iron-based catalyst and method for preparing the same and use thereof |
-
2020
- 2020-09-30 CN CN202011064089.XA patent/CN112569990B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361349A2 (en) * | 1988-09-26 | 1990-04-04 | Seisan Kaihatsu Kagaku Kenkyusho | Magnetic fine particles of epsilon' iron carbide |
| US20160045901A1 (en) * | 2013-03-19 | 2016-02-18 | Korea Institute Of Energy Research | Iron-based catalyst and method for preparing the same and use thereof |
| CN104399501A (en) * | 2014-11-09 | 2015-03-11 | 复旦大学 | High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘润雪;刘任杰;徐艳;吕静;李振花;: "铁基费托合成催化剂研究进展", 化工进展 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112569990B (en) | 2023-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al2O3 in methane catalytic partial oxidation | |
| CN110339848B (en) | Supported/' iron carbide catalyst for Fischer-Tropsch synthesis reaction, preparation method thereof and Fischer-Tropsch synthesis reaction method | |
| CN112569993B (en) | Supported epsilon/epsilon' iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569988B (en) | Composition containing precipitated epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569978B (en) | Composition containing supported epsilon/epsilon' iron carbide and chi iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569990B (en) | Composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569979B (en) | Composition containing supported multi-phase iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569976B (en) | Composition containing supported χ -iron carbide and θ -iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569984B (en) | Supported theta iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569983B (en) | Supported χ -iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| Grabchenko et al. | Study of Nickel Catalysts Supported on MnO x–CeO 2 Mixed Oxides in Dry Reforming of Methane | |
| CN112569977B (en) | Composition containing precipitated type χ -iron carbide and theta-iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569989B (en) | Composition containing X iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569980B (en) | Composition containing precipitated epsilon/epsilon' iron carbide and chi iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569987B (en) | Composition containing epsilon/epsilon' iron carbide, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569982B (en) | Precipitated epsilon/epsilon iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569994B (en) | Composition containing multi-phase iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569995B (en) | Composition containing epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569975B (en) | Composition containing precipitated multi-phase iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569991B (en) | Composition containing epsilon/epsilon' iron carbide and chi iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method | |
| CN112569981B (en) | Composition containing precipitated theta iron carbide, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569985B (en) | Composition containing χ -iron carbide, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569986B (en) | Composition containing theta iron carbide, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| CN112569992A (en) | Composition containing precipitated X-type iron carbide, preparation method, catalyst and application thereof, and Fischer-Tropsch synthesis method | |
| KR101220759B1 (en) | Nickel catalyst supported on xerogel alumina and method for amnufacturing the same, and method for manufacturing methane using said catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |