CN113477273A - Preparation method of catalyst for methanation reaction of carbon dioxide - Google Patents
Preparation method of catalyst for methanation reaction of carbon dioxide Download PDFInfo
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- CN113477273A CN113477273A CN202110731842.4A CN202110731842A CN113477273A CN 113477273 A CN113477273 A CN 113477273A CN 202110731842 A CN202110731842 A CN 202110731842A CN 113477273 A CN113477273 A CN 113477273A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910001868 water Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- WOSOOWIGVAKGOC-UHFFFAOYSA-N azanylidyneoxidanium;ruthenium(2+);trinitrate Chemical compound [Ru+2].[O+]#N.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WOSOOWIGVAKGOC-UHFFFAOYSA-N 0.000 claims description 2
- XKTGKMXHQPHUOL-UHFFFAOYSA-N nitrosyl chloride;ruthenium(3+);hydrate Chemical compound O.[Ru+3].ClN=O XKTGKMXHQPHUOL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
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- B01J35/393—
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- B01J35/396—
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention relates to a preparation method of a catalyst for methanation reaction of carbon dioxide by using a nickel and ruthenium loaded zeolite molecular sieve. The invention uses molecular sieve as carrier, and nickel and ruthenium nanometer particles are loaded on the surface of the carrier, and the catalyst is used for Sabatier reaction. The invention also discloses a method for effectively controlling nickel and ruthenium to be uniformly dispersed on the surface and the inner pore channels of the molecular sieve, and the catalyst prepared by the method can be used for the Sabatier reaction. The method is a rotary evaporation dipping method. The method takes a zeolite molecular sieve as a carrier, nickel and ruthenium precursors are loaded on the surface of the treated molecular sieve by a rotary impregnation method to realize uniform dispersion and strong interaction of metals, and then the catalytic material with high sintering resistance and carbon deposition resistance is obtained by negative pressure rotary evaporation drying, high temperature calcination and continuous heating reduction. The invention has the advantages of simple preparation process, lower cost, no environmental pollution, high catalytic efficiency and the like.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a catalyst for methanation reaction of carbon dioxide.
Background
To limit the climate of global warming, reducing carbon dioxide emissions has become a formidable challenge in all countries. Over the past many years, CO has been utilized2There is a great deal of interest in producing renewable energy carriers. CO22Can be converted into a variety of synthetic fuels, including methane, methanol, and dimethyl ether. Future large-scale production of fuels and chemicals, feedstock CO2And H2Is of crucial importance. Large amount of CO2Available in industrial facilities such as coal fired power plants, this technology is currently referred to as CCU (carbon capture utilization). Direct CO separation from air2The technology has also advanced greatly, and H2Can be obtained continuously by electrolyzing water. By Sabatier reaction, H2And CO2Methane can be synthesized, and the reaction equation is as follows:
this reaction is currently only used for air regeneration in the sealed capsule of the national aeronautics and astronautics administration (NASA) manned spacecraft.
This reaction is accompanied by side reactions, which generate toxic CO.
CO2+H2→CO+H2O；ΔH0r(298K)＝41kJ/mol
In order to solve these problems, many studies have been reported, among which silica, α -alumina, titania, magnesia, zirconia and the like are used as a carrier, and nickel, iron, zirconium, cobalt, lanthanum and the like are used as an active metal. The noble metal catalyst has excellent catalytic performance and carbon deposition resistance, but has high price and limited resources, is greatly limited in industrial application, has low price and easy obtainment of nickel, and has catalytic activity equivalent to that of noble metal, so the nickel-based catalyst has very deep industrial application potential. In the Sabatier reaction, nickel favors the reverse water gas shift Reaction (RWGS), ruthenium shows higher activity for the CO hydrogenation reaction, and nickel ruthenium synergizes to promote the carbon dioxide methanation reaction, however, fewer reports are made on this bimetallic catalyst. The molecular sieve is used as a carrier, so that the report on the catalyst used for the Sabatier reaction is less, the molecular sieve can provide a porous environment as the carrier, the reaction is rapidly carried out, carbon deposition is not easy to occur, water produced by the reaction can be selectively absorbed, and the reaction conversion rate is improved. Therefore, it is still a difficult task to find a low-cost, anti-carbon deposition, high conversion and selectivity carbon dioxide methanation catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for methanation reaction of carbon dioxide, which aims to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
1. a preparation method of a catalyst for methanation reaction of carbon dioxide comprises the following steps:
a. drying the molecular sieve in an oven for later use;
b. dissolving precursor salts of nickel and ruthenium in deionized water to prepare a precursor solution with the mass percentage of 1-20%;
c. adding the molecular sieve obtained in the step a into the precursor salt solution obtained in the step b, and performing ultrasonic dispersion to obtain a mixed suspension, wherein the liquid-solid mass ratio is 25-50: 1;
d. c, transferring the suspension obtained in the step c into a rotary steaming bottle, and performing rotary steaming at room temperature;
e. d, rotationally evaporating the suspension treated in the step d to remove deionized water, and drying to obtain a mixture;
f. continuously heating and calcining the mixture obtained in the step e in the air atmosphere;
g. drying the product obtained in step f in Ar, then in 5% H2And (Ar) carrying out reduction reaction of the metal oxide in the atmosphere to finish the preparation of the catalyst.
Further, the molecular sieve is one of A type, X type or Y type.
Further, the nickel precursor salt is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate and nickel citrate, and the ruthenium precursor salt is one of ruthenium (III) nitrosyl nitrate solution or ruthenium (III) nitrosyl chloride hydrate.
Further, the particle size of the molecular sieve is 100-200 nm; the drying conditions were 100 ℃ for 12 h.
Further, the ultrasonic dispersion time in the step b is 30-60 min; in the step c, the rotary evaporation speed is 5-10 rpm, and the rotary evaporation time is 6-12 h.
Further, in the step e, the rotary evaporation environment is 50 ℃, and the water ring vacuum pump is used for pumping out; the drying temperature is 100 ℃, and the drying time is 12 h.
Further, the specific temperature rise and calcination conditions in the step f are as follows:
heating to 250-300 ℃, maintaining the final temperature for 40-60 min, wherein the heating rate is 4.5 ℃/min; and then heating to 500-600 ℃, calcining for 3-5 h, wherein the air flow rate is 50ml/min, the heating rate is 2 ℃/min, and cooling to room temperature for 4-6 h.
Further, in the step g, the drying condition in Ar gas is 250 ℃ for 1 h; the conditions of the metal oxide reduction reaction are as follows: at 5% H2Continuously heating to 500-800 ℃ at the speed of 5 ℃/min in the (Ar) atmosphere, and reacting for 3-6 h.
Compared with the prior art, the invention has the following technical effects:
the invention uses molecular sieve as carrier, and nickel and ruthenium nanometer particles are loaded on the surface of the carrier, and the catalyst is used for Sabatier reaction. The invention also discloses a method for effectively controlling nickel and ruthenium to be uniformly dispersed on the surface and the inner pore channels of the molecular sieve, and the catalyst prepared by the method can be used for the Sabatier reaction. The method is a rotary evaporation dipping method. The method takes a zeolite molecular sieve as a carrier, nickel and ruthenium precursors are loaded on the surface of the treated molecular sieve by a rotary impregnation method to realize uniform dispersion and strong interaction of metals, and then the catalytic material with high sintering resistance and carbon deposition resistance is obtained by negative pressure rotary evaporation drying, high temperature calcination and continuous heating reduction. The invention has the advantages of simple preparation process, lower cost, no environmental pollution, high catalytic efficiency and the like.
The preparation method has the advantages of low cost, high operability and environmental friendliness. The catalyst can be used for solving the problem of high-temperature sintering agglomeration of active components in the methanation reaction of CO2, and ensures high conversion rate of CO2 and high selectivity to CH 4.
Drawings
FIG. 1 shows the application of the X-type molecular sieve loaded with nickel and ruthenium in CO obtained in example 1 of the present invention2CO in methanation reactions2Conversion and p-CH4Selectivity as a function of reaction time scatter plot.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1
10g of 13X molecular sieve was weighed into a crucible and dried overnight at 100 ℃. 2.477g of nickel nitrate hexahydrate and 0.314g of ruthenium trinitronitrosyl were weighed out and dissolved in 250ml of deionized water. Slowly adding the dried 13X molecular sieve into the aqueous solution containing the nickel and the ruthenium in the ultrasonic process, and continuing to perform ultrasonic dispersion for 30 min. The supernatant was transferred to a rotary evaporator and rotary evaporated at 10rpm for 8h at room temperature. And starting a water circulation vacuum pump, heating the water bath kettle to 50 ℃, performing rotary evaporation for 2 hours, and evaporating the deionized water in the suspension to dryness. The rotary-dried powder was moved to an oven for drying at 100 ℃ for 12 h. Calcining the dried powder, in an air atmosphere, raising the temperature to 300 ℃ at the air flow rate of 50ml/min and the heating rate of 4.5 ℃/min, maintaining for 40min, then adjusting the heating rate to 500 ℃ at the heating rate of 2 ℃/min, maintaining for 5h, and naturally cooling to room temperature. And (3) continuously heating and reducing the calcined powder by hydrogen, firstly drying the calcined powder in Ar at 250 ℃ for 1H, then continuously heating the calcined powder to 500 ℃ at the speed of 5 ℃/min in the atmosphere of 5% H2(Ar) to perform a reduction reaction for 5H, and cooling the calcined powder to room temperature in the atmosphere of Ar to finish the preparation of the catalyst.
The catalysts described above were tested for catalytic activity: weighing 0.9g of upper catalyst powder, placing in a fixed bed quartz tube reactor, and introducing CO2、H2And N2Mixed gas, H2 flow rate 40ml/min, CO2Flow rate 10ml/min, N2The flow rate was 150 ml/min. The activity test temperature is 400 ℃ and CO2The conversion rate is as high as 80, is close to the reaction equilibrium conversion rate, and is used for treating CH4The selectivity reaches 98.5%, and the reaction lasts for 4 hours, and the conversion rate and the selectivity are not changed.
Example 2
10g of 13X molecular sieve was weighed into a crucible and dried overnight at 100 ℃. 2.477g of nickel nitrate hexahydrate and 0.314g of ruthenium trinitronitrosyl were weighed out and dissolved in 250ml of deionized water. Slowly adding the dried 13X molecular sieve into the aqueous solution containing the nickel and the ruthenium in the ultrasonic process, and continuing to perform ultrasonic dispersion for 40 min. The supernatant was transferred to a rotary evaporator and rotary evaporated at 5rpm for 8h at room temperature. And starting a water circulation vacuum pump, heating the water bath kettle to 50 ℃, performing rotary evaporation for 2 hours, and evaporating the deionized water in the suspension to dryness. The rotary-dried powder was moved to an oven for drying at 100 ℃ for 12 h. Calcining the dried powder, in an air atmosphere, raising the temperature to 300 ℃ at the air flow rate of 50ml/min and the heating rate of 4.5 ℃/min, maintaining for 40min, then adjusting the heating rate to 500 ℃ at the heating rate of 2 ℃/min, maintaining for 5h, and naturally cooling to room temperature. And (3) continuously heating and reducing the calcined powder by hydrogen, firstly drying the calcined powder in Ar at 250 ℃ for 1H, then continuously heating the calcined powder to 500 ℃ at the speed of 5 ℃/min in the atmosphere of 5% H2(Ar) to perform a reduction reaction for 5H, and cooling the calcined powder to room temperature in the atmosphere of Ar to finish the preparation of the 13X molecular sieve catalyst with 5% of nickel load and 1% of ruthenium load.
The catalysts described above were tested for catalytic activity: weighing 0.9g of upper catalyst powder, placing in a fixed bed quartz tube reactor, and introducing CO2、H2And N2Mixed gas, H2 flow rate 40ml/min, CO2Flow rate 10ml/min, N2The flow rate was 150 ml/min. The activity test temperature is 400 ℃ and CO2The conversion rate is as high as 80, is close to the reaction equilibrium conversion rate, and is used for treating CH4The selectivity reaches 98.5%, and the reaction lasts for 4 hours, and the conversion rate and the selectivity are not changed.
Example 3
10g of type A molecular sieve was weighed into a crucible and dried overnight at 100 ℃. 4.240g of nickel acetate tetrahydrate and 0.157g of ruthenium trinitronitrosyl were weighed out and dissolved in 300ml of deionized water. Slowly adding the dried A-type molecular sieve into the aqueous solution containing the nickel and the ruthenium in the ultrasonic treatment, and continuing to perform ultrasonic dispersion for 50 min. The supernatant was transferred to a rotary evaporator and rotary evaporated at 5rpm for 10h at room temperature. And starting a water circulation vacuum pump, heating the water bath kettle to 50 ℃, performing rotary evaporation for 3 hours, and evaporating the deionized water in the suspension to dryness. The rotary-dried powder was moved to an oven for drying at 100 ℃ for 12 h. Calcining the dried powder, in an air atmosphere, raising the temperature at a speed of 50ml/min and at a speed of 4.5 ℃/min to 250 ℃ for 60min, then adjusting the temperature at a speed of 2 ℃/min to 600 ℃ for 3h, and naturally cooling to room temperature. And (3) continuously heating and reducing the calcined powder by hydrogen, firstly drying the calcined powder in Ar at 250 ℃ for 1H, then continuously heating the calcined powder to 750 ℃ at the speed of 5 ℃/min in the atmosphere of 5% H2(Ar) to perform a reduction reaction for 3H, and cooling the calcined powder to room temperature in the atmosphere of Ar to finish the preparation of the A-type molecular sieve catalyst with the nickel load of 10% and the ruthenium load of 0.5%.
The catalysts described above were tested for catalytic activity: weighing 0.9g of upper catalyst powder, placing in a fixed bed quartz tube reactor, and introducing CO2、H2And N2Mixed gas, H2 flow rate 40ml/min, CO2Flow rate 10ml/min, N2The flow rate was 150 ml/min. The activity test temperature is 360 ℃, and CO is2The conversion rate is as high as 80, is close to the reaction equilibrium conversion rate, and is used for treating CH4The selectivity reaches 95 percent.
Example 4
Molecular sieve type 10gY was weighed into a crucible and dried overnight at 100 ℃. 2.519g of hydrated nickel citrate and 0.157g of ruthenium trinitronitrosyl were weighed out and dissolved in 200ml of deionized water. Slowly adding the dried Y-type molecular sieve into the aqueous solution containing the nickel and the ruthenium in the ultrasonic process, and continuing to perform ultrasonic dispersion for 50 min. The supernatant was transferred to a rotary evaporator and rotary evaporated at 10rpm for 6h at room temperature. And starting a water circulation vacuum pump, heating the water bath kettle to 50 ℃, performing rotary evaporation for 2 hours, and evaporating the deionized water in the suspension to dryness. The rotary-dried powder was moved to an oven for drying at 100 ℃ for 12 h. Calcining the dried powder, in an air atmosphere, raising the temperature at a speed of 50ml/min and at a speed of 4.5 ℃/min to 300 ℃ for 50min, then adjusting the temperature at a speed of 2 ℃/min to 500 ℃ for 4h, and naturally cooling to room temperature. And (3) continuously heating and reducing the calcined powder by hydrogen, firstly drying the calcined powder in Ar at 250 ℃ for 1H, then continuously heating the calcined powder to 600 ℃ at the speed of 5 ℃/min in the atmosphere of 5% H2(Ar) to perform a reduction reaction for 4H, and cooling the calcined powder to room temperature in the atmosphere of Ar to finish the preparation of the Y-type molecular sieve catalyst with 8% of nickel load and 0.5% of ruthenium load.
The catalysts described above were tested for catalytic activity: weighing 0.9g of upper catalyst powder, placing in a fixed bed quartz tube reactor, and introducing CO2、H2And N2Mixed gas, H2 flow rate 40ml/min, CO2Flow rate 10ml/min, N2Flow rate of flow150 ml/min. The activity test temperature is 360 ℃, and CO is2The conversion rate is as high as 80, is close to the reaction equilibrium conversion rate, and is used for treating CH4The selectivity reaches 97 percent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, substitutions, modifications and variations may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a catalyst for methanation reaction of carbon dioxide is characterized by comprising the following steps:
a. drying the molecular sieve in an oven for later use;
b. dissolving precursor salts of nickel and ruthenium in deionized water to prepare a precursor solution with the mass percentage of 1-20%;
c. adding the molecular sieve obtained in the step a into the precursor salt solution obtained in the step b, and performing ultrasonic dispersion to obtain a mixed suspension, wherein the liquid-solid mass ratio is 25-50: 1;
d. c, transferring the suspension obtained in the step c into a rotary steaming bottle, and performing rotary steaming at room temperature;
e. d, rotationally evaporating the suspension treated in the step d to remove deionized water, and drying to obtain a mixture;
f. continuously heating and calcining the mixture obtained in the step e in the air atmosphere;
g. drying the product obtained in step f in Ar, then in 5% H2And (Ar) carrying out reduction reaction of the metal oxide in the atmosphere to finish the preparation of the catalyst.
2. The preparation method of the catalyst for methanation of carbon dioxide according to claim 1, wherein the molecular sieve is one of type A, type X or type Y.
3. The method according to claim 1, wherein the nickel precursor salt is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate and nickel citrate, and the ruthenium precursor salt is one of a ruthenium (III) nitrosyl nitrate solution and a ruthenium (III) nitrosyl chloride hydrate.
4. The preparation method of the catalyst for methanation reaction of carbon dioxide as claimed in claim 1, wherein the particle size of the molecular sieve is 100-200 nm; the drying conditions were 100 ℃ for 12 h.
5. The preparation method of the catalyst for methanation reaction of carbon dioxide according to claim 1, wherein the ultrasonic dispersion time in the step b is 30-60 min; in the step c, the rotary evaporation speed is 5-10 rpm, and the rotary evaporation time is 6-12 h.
6. The preparation method of the catalyst for the methanation reaction of carbon dioxide according to claim 1, wherein in the step e, the rotary evaporation environment is 50 ℃, and the water ring vacuum pump is used for evacuating; the drying temperature is 100 ℃, and the drying time is 12 h.
7. The preparation method of the catalyst for methanation reaction of carbon dioxide according to claim 1, wherein the specific temperature rise and calcination conditions in step f are as follows:
heating to 250-300 ℃, maintaining the final temperature for 40-60 min, wherein the heating rate is 4.5 ℃/min; and then heating to 500-600 ℃, calcining for 3-5 h, wherein the air flow rate is 50ml/min, the heating rate is 2 ℃/min, and cooling to room temperature for 4-6 h.
8. The preparation method of the catalyst for methanation of carbon dioxide according to claim 1, wherein in the step g, the drying condition in Ar gas is 250 ℃, 1 h; the conditions of the metal oxide reduction reaction are as follows: at 5% H2Continuously heating to 500-800 ℃ at the speed of 5 ℃/min in the (Ar) atmosphere, and reacting for 3-6 h.
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