CN110711587A - Nickel tungstate-based methanation catalyst with hollow structure - Google Patents
Nickel tungstate-based methanation catalyst with hollow structure Download PDFInfo
- Publication number
- CN110711587A CN110711587A CN201910966102.1A CN201910966102A CN110711587A CN 110711587 A CN110711587 A CN 110711587A CN 201910966102 A CN201910966102 A CN 201910966102A CN 110711587 A CN110711587 A CN 110711587A
- Authority
- CN
- China
- Prior art keywords
- pollen
- catalyst
- nickel
- solution
- suspension
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910006167 NiWO4 Inorganic materials 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 49
- 239000000725 suspension Substances 0.000 claims description 29
- 241000196324 Embryophyta Species 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 244000017020 Ipomoea batatas Species 0.000 claims description 9
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 9
- 240000002853 Nelumbo nucifera Species 0.000 claims description 9
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 9
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 235000003222 Helianthus annuus Nutrition 0.000 claims description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 244000020551 Helianthus annuus Species 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 241000208818 Helianthus Species 0.000 description 7
- 239000003245 coal Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 235000019772 Sunflower meal Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000000385 Brassica napus var. napus Species 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 244000247747 Coptis groenlandica Species 0.000 description 1
- 235000002991 Coptis groenlandica Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/888—Tungsten
Abstract
The invention relates to the field of energy catalysis, in particular to a nickel tungstate-based methanation catalyst with a hollow structure. The catalyst takes different plant pollen as a hard template agent and adopts a continuous adsorption reaction method to prepare NiWO4A catalyst. The methanation catalyst obtained by the invention has the advantages of hollow appearance, high specific surface area, high mechanical strength, high activity, good thermal stability, carbon deposition resistance, strong sintering resistance and low cost.
Description
Technical Field
The invention relates to the field of energy catalysis, in particular to a nickel tungstate-based methanation catalyst with a hollow structure.
Background
Natural gas is considered the cleanest fossil fuel that can meet industry stringent air emission standards. However, in view of the energy resource characteristics of rich coal, poor oil and less gas in China, coal is still the main body of energy consumption in China, but about 80% of coal consumption is directly converted through combustion, the heat energy utilization rate is low, and a large amount of pollutants are discharged. Therefore, the development of a high-efficiency, low-carbon and clean coal resource utilization technology has very important significance. The gas obtained by pyrolyzing and gasifying coal or biomass mainly contains H2And CO, the main components of the coke oven gas in the coking industry areIs also H2And CO, wherein the mixed gas containing CO can be subjected to conversion, purification and other processes and then can be subjected to methanation reaction to generate CH4. The method can promote the efficient and clean comprehensive utilization of coal, improve the heat density of fuel gas and provide a feasible way for filling the gap of natural gas requirements in China. The methanation process mainly involves the following reactions:
CO + 3H2→ CH4+ H2O Δr H m= –206 kJ/mol
the reaction is a strong exothermic reaction, and excessive reaction heat easily causes local overheating and temperature runaway phenomena, so that sintering and carbon deposition of active components are caused. Obviously, the carbon deposition resistance and high temperature resistance of the catalyst will directly affect the life of the catalyst. Therefore, the development of a methanation catalyst which is highly active and capable of operating stably at high temperatures for a long time is one of the key factors of the synthesis gas methanation process.
Carried on Al2O3、SiO2、TiO2、ZrO2Ni-based metal catalysts on oxides such as MgO are widely used as CO methanation catalysts. The catalysts can basically achieve ideal effects in applications of ammonia synthesis and low-concentration CO removal in the fuel cell industry, but the carbon deposition and sintering phenomena are serious due to the fact that the CO concentration in the methanation reaction of the synthesis gas obtained by coal or biomass gasification is high, and the heat release of the methanation reaction is strong. Therefore, the development of a novel catalyst suitable for high-concentration CO methanation is of great significance.
Nickel tungstate (NiWO)4) Is one of the important inorganic materials in the metal tungstate family, and is widely applied due to the high activity of the inorganic materials on the hydrodesulfurization of crude oil fractions, the preparation of propylene by the hydrogenation of propylene oxide and humidity sensors. In addition, NiWO4Have been explored in other potential applications, such as photoanodes. However, NiWO4The application of the material in the methanation reaction of CO is rarely reported, so the material has a very wide application prospect.
Disclosure of Invention
The invention uses plant pollen as a hard template agent and adopts coptis rootNiWO with hollow appearance, high specific surface area, high activity, sintering resistance and carbon deposition resistance prepared by continuous adsorption reaction method4A CO-based methanation catalyst. The invention not only improves the activity and stability of the catalyst, but also widens the application of the tungstate material in the field of catalysis.
Based on the above, one of the purposes of the invention is to provide a nickel tungstate-based methanation catalyst with a hollow structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nickel tungstate-based methanation catalyst with a hollow structure, wherein active components of the catalyst exist in NiWO4Wherein the active component is Ni.
The invention relates to a nickel tungstate-based methanation catalyst with a hollow structure, which is NiWO prepared by using plant pollen as a hard template agent and adopting a continuous adsorption reaction method4Has excellent mechanical strength and thermal stability; the NiWO formed by adopting plant pollen as a hard template agent4The catalyst has a certain micro-nano structure, so that the specific surface area of the catalyst is increased, and the catalytic performance of the catalyst is further improved.
The second object of the present invention is to provide a process for producing the above catalyst.
The invention relates to a nickel tungstate-based methanation catalyst with a hollow structure, which is prepared by the following steps:
(1) pretreatment of plant pollen with hard template agent
(1-1) crushing plant pollen by using a universal crusher, and screening parts with the size of less than 58 mu m;
(1-2) washing the plant pollen obtained in the step (1-1) with an ethanol solution for 4 ~ 7 times under ultrasonic radiation, each time for 20 ~ 50 min;
(1-3) filtering the suspension obtained in the step (1-2) to obtain plant pollen at 40 ~ 70oAnd drying for 24 hours at the temperature of C to obtain the required pollen serving as the hard template agent.
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
(2-1) dispersing plant pollen with a certain mass in 100mL of ethanol solution to form suspension;
(2-2) preparing 100mL of soluble nickel salt aqueous solution with a certain concentration, and marking as A solution. Adding the solution A into the suspension of the step (2-1), and mixing the mixture at 40oSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 ~ 70oDrying for 8 ~ 12 h under C;
(2-3) dispersing the plant pollen obtained in the step (2-2) in 100mL of ethanol solution again to form a suspension;
and (2-4) preparing 100mL of sodium tungstate aqueous solution with a certain concentration, and recording as a solution B. Adding the solution B into the suspension obtained in the step (2-3), and mixing the mixture at 40oSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 ~ 70oDrying for 8 ~ 12 h under C;
(2-5) recording the plant pollen obtained in the step (2-4) as a circulation unit, and then repeating the operation of the step (2-1) ~ (2-4) on the plant pollen for 3 ~ 7 cycles;
(2-6) placing the plant pollen finally obtained in the step (2-5) in a muffle furnace 500 ~ 650oCalcining for 2 ~ 5 h to obtain NiWO4A catalyst.
Preferably, the plant pollen selected in the step (1-1) is any one of lotus pollen, rape pollen, sweet potato pollen or sunflower pollen.
Preferably, the mass of the plant pollen in the step (2-1) is 1 ~ 4 g.
Preferably, the ethanol solution in the steps (2-1) and (2-3) is EtOH/H2O =1:1, volume ratio.
Preferably, the soluble nickel salt used in step (2-2) is any one of nickel acetate, nickel sulfate, nickel nitrate and nickel chloride.
Preferably, the concentration of the soluble nickel salt in the step (2-2) is 0.0005 ~ 0.001.001 mol/L.
Preferably, the concentration of sodium tungstate in the step (2-4) is 0.0005 ~ 0.001.001 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes different plant pollen as hard template agent and adopts a continuous adsorption reaction method to prepare NiWO4The catalyst has the characteristics of hollow appearance, high specific surface area, high mechanical strength, high catalytic activity, good thermal stability, carbon deposition resistance, strong sintering resistance and the like, and shows excellent catalytic performance in the methanation reaction of CO.
Drawings
Figure 1 is an XRD spectrum of the sample of example 1.
FIG. 2 is a 240000-fold SEM image of the magnification of a sample of example 1.
Detailed Description
The following examples further illustrate the technical solution of the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Pretreating plant pollen by using a hard template agent.
Size of the product<Washing 58 μm lotus pollen with ethanol solution under ultrasonic irradiation for 4 times, each for 20 min, filtering the suspension to obtain lotus pollen powder, and standing at 40 deg.CoAnd drying for 24 hours at the temperature of C to obtain the required lotus powder serving as the hard template agent.
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
1 g of lotus powder was dispersed in 100mL of ethanol solution to form a suspension. Then preparing 100mL nickel acetate aqueous solution of 0.0005 mol/L, and marking as A solution; and preparing 0.0005 mol/L100 mL of sodium tungstate aqueous solution, and marking as a B solution. Adding solution A to the suspension, and mixing the above solutions at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 deg.CoAnd C, drying for 8 h. Subsequently, the lotus powder obtained at this time was dispersed again in 100mL of an ethanol solution to form a suspension. Adding solution B to the suspension, and mixing the mixture at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 deg.CoC, drying for 8 hours; the lotus powder obtained at this time was counted as one cycle unit, and the above operation was repeated for 3 cycles. The lotus powder obtained in the last circulation is in a muffleIn a furnace 500oCalcining C for 2 h to obtain NiWO4A catalyst.
Example 2
(1) Pretreating plant pollen by using a hard template agent.
Size of the product<Washing 58 μm rape pollen with ethanol solution under ultrasonic radiation for 5 times, each for 30 min, filtering the suspension to obtain rape pollen, and standing at 50 deg.CoAnd drying for 24 hours at the C to obtain the required hard template agent rape pollen.
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
2 g of canola pollen was dispersed in 100mL of ethanol solution to form a suspension. Then preparing 100mL nickel sulfate aqueous solution of 0.0007 mol/L, and marking as A solution; and preparing 0.0007 mol/L100 mL of sodium tungstate aqueous solution, and marking as a B solution. Adding solution A to the suspension, and mixing the above solutions at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 50 deg.CoAnd C, drying for 9 h. Next, the rape pollen thus obtained was dispersed again in 100mL of an ethanol solution to form a suspension. Adding solution B to the suspension, and mixing the mixture at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 50 deg.CoC, drying for 9 hours; the rape pollen obtained at this time was counted as one cycle unit, and the above operation was repeated for 4 cycles. Placing the last time of the circulation to obtain rape pollen in a muffle furnace 550oCalcining C for 3 h to obtain NiWO4A catalyst.
Example 3
(1) Pretreating plant pollen by using a hard template agent.
Size of the product<Washing 58 μm sweet potato pollen with ethanol solution under ultrasonic radiation for 6 times, each for 40 min, filtering the suspension to obtain sweet potato pollen, and standing at 60 deg.CoAnd drying for 24 hours at the temperature of C to obtain the required sweet potato pollen serving as the hard template agent.
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
Dispersing 3 g sweet potato pollen in 100mL ethanol solution to formAnd (4) suspending the solution. Then preparing 100mL nickel nitrate aqueous solution of 0.0008 mol/L, and marking as A solution; and preparing 0.0008 mol/L100 mL of sodium tungstate aqueous solution, and marking as a B solution. Adding solution A to the suspension, and mixing the above solutions at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 60 deg.CoAnd C, drying for 10 hours. Then, the sweet potato pollen obtained at this time was dispersed again in 100mL of an ethanol solution to form a suspension. Adding solution B to the suspension, and mixing the mixture at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 60 deg.CoC, drying for 10 hours; the sweet potato pollen obtained at this time was counted as one cycle unit, and the above operation was repeated for 5 cycles. Placing sweet potato pollen obtained from the last circulation in a muffle furnace 600oCalcining C for 4 h to obtain NiWO4A catalyst.
Example 4
(1) Pretreating plant pollen by using a hard template agent.
Size of the product<Washing 58 μm sunflower pollen with ethanol solution under ultrasonic irradiation for 7 times, each for 50min, filtering the suspension to obtain sunflower pollen, and standing at 70 deg.CoAnd drying for 24 hours at the temperature of C to obtain the needed sunflower pollen serving as the hard template agent.
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
4 g of sunflower pollen was dispersed in 100mL of ethanol solution to form a suspension. Then preparing 0.001 mol/L100 mL nickel chloride aqueous solution, and marking as A solution; meanwhile, 0.001 mol/L100 mL of sodium tungstate aqueous solution is marked as solution B. Adding solution A to the suspension, and mixing the above solutions at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 70 deg.CoAnd C, drying for 12 h. Then, the sunflower meal obtained at this time was dispersed again in 100mL of an ethanol solution to form a suspension. Adding solution B to the suspension, and mixing the mixture at 40 deg.CoSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 70 deg.CoC, drying for 12 h; the sunflower meal obtained at this point was recorded as a circulating unitThen, the above operation was repeated for the sunflower pollen for 7 cycles. Placing the sunflower pollen obtained from the last cycle in muffle furnace 650oCalcining C for 5 h to obtain NiWO4A catalyst.
Evaluation of catalyst Performance
The catalytic performance tests of examples 1, 2, 3 and 4, the catalytic stability of the prepared catalyst in the methanation reaction of CO, 500 mg of the catalyst with 20 ~ 40 meshes is put into a quartz reaction tube, temperature programming reduction is carried out by introducing (flow: 30 mL/min), and the heating rate is 2oAnd C/min. The composition of the reaction raw material gas is H2∶CO∶N2The volume flow rate ratio is 3: 1, the reaction pressure is normal pressure, the mass space velocity is 60000 mL/h.g, and the reaction temperature is 450oC。
Table 1 shows the CO conversion and CH conversion in the methanation reaction of the catalysts of examples 1, 2, 3 and 44Yield of
| Serial number | CO conversion (%) | CH4Selectivity (%) | CH4Yield (%) |
| Example 1 | 87 | 84 | 82 |
| Example 2 | 90 | 85 | 85 |
| Example 3 | 88 | 83 | 83 |
| Example 4 | 86 | 81 | 81 |
As mentioned above, the nickel tungstate-based methanation catalyst with the hollow structure provided by the invention has high activity and good application prospect in industrial application.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A nickel tungstate-based methanation catalyst with a hollow structure is characterized in that an active component precursor of the catalyst is NiWO4。
2. The hollow structure nickel tungstate based methanation catalyst as claimed in claim 1, wherein the catalyst active component is Ni.
3. A nickel tungstate-based methanation catalyst with a hollow structure is characterized by being prepared by the following method:
(1) pretreatment of plant pollen with hard template agent
(1-1) using <58 μm size plant pollen as a hard template;
(1-2) ultrasonically washing the plant pollen obtained in the step (1-1) with an ethanol solution for 4 ~ 7 times, each time for 20 ~ 50 min;
(1-3) filtering the suspension obtained in the step (1-2) at 40 ~ 70oDrying for 24 h at C to obtain required pollen as hard template agent;
(2) NiWO prepared by hard template continuous adsorption reaction method4Catalyst and process for preparing same
(2-1) dispersing plant pollen with a certain mass in 100mL of ethanol solution to form suspension;
(2-2) preparing 100mL of soluble nickel salt aqueous solution with a certain concentration, and marking as A solution;
adding the solution A into the suspension of the step (2-1), and mixing the mixture at 40oSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 ~ 70oDrying for 8 ~ 12 h under C;
(2-3) dispersing the plant pollen obtained in the step (2-2) in 100mL of ethanol solution again to form a suspension;
(2-4) preparing 100mL of sodium tungstate aqueous solution with a certain concentration, and recording as a solution B;
adding the solution B into the suspension obtained in the step (2-3), and mixing the mixture at 40oSoaking for 12 hr, centrifuging, washing with water and ethanol, and soaking at 40 ~ 70oDrying for 8 ~ 12 h under C;
(2-5) recording the plant pollen obtained in the step (2-4) as a circulation unit, and then repeating the operation of the step (2-1) ~ (2-4) on the plant pollen for 3 ~ 7 cycles;
(2-6) placing the plant pollen finally obtained in the step (2-5) in a muffle furnace at 500 ~ 650oCalcining for 2 ~ 5 h to obtain the target NiWO4A catalyst.
4. The hollow structure nickel tungstate-based methanation catalyst as claimed in claim 3, wherein the plant pollen in the steps (1) and (2) is lotus pollen, rape pollen, sweet potato pollen or sunflower pollen.
5. The hollow structure nickel tungstate-based methanation catalyst as claimed in claim 3, wherein the soluble nickel salt in step (2-2) is nickel acetate, nickel sulfate, nickel nitrate or nickel chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910966102.1A CN110711587A (en) | 2019-10-12 | 2019-10-12 | Nickel tungstate-based methanation catalyst with hollow structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910966102.1A CN110711587A (en) | 2019-10-12 | 2019-10-12 | Nickel tungstate-based methanation catalyst with hollow structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110711587A true CN110711587A (en) | 2020-01-21 |
Family
ID=69211450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910966102.1A Pending CN110711587A (en) | 2019-10-12 | 2019-10-12 | Nickel tungstate-based methanation catalyst with hollow structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110711587A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468309A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing non-supported hydrogenation catalyst |
| CN103008015A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of fuel battery catalyst carrier WO3 (Tungsten Trioxide) |
| US20170341935A1 (en) * | 2015-05-13 | 2017-11-30 | Shaanxi University Of Science & Technology | Porous hollow shell wo3/ws2 nanomaterial and method of preparing same |
-
2019
- 2019-10-12 CN CN201910966102.1A patent/CN110711587A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468309A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for preparing non-supported hydrogenation catalyst |
| CN103008015A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of fuel battery catalyst carrier WO3 (Tungsten Trioxide) |
| US20170341935A1 (en) * | 2015-05-13 | 2017-11-30 | Shaanxi University Of Science & Technology | Porous hollow shell wo3/ws2 nanomaterial and method of preparing same |
Non-Patent Citations (4)
| Title |
|---|
| JONGMIN SHIN ET AL.: ""Catalytic Activity of Ni1-xLi2xWO4 Particles for Carbon Dioxide Photoreduction"", 《CATALYSTS》 * |
| LI YANG ET AL.: ""Novel Biotemplating Synthesis of ZnWO4 Hollow Microspheres and Its Photocatalytic Degradation of Auramine O"", 《INTEGRATED FERROELECTRICS: AN INTERNATIONAL JOURNAL》 * |
| 国家知识产权局专利局专利审查协作江苏中心 主编: "《热点专利技术分析与运用（第3辑）》", 30 September 2017, 知识产权出版社 * |
| 酒红芳 著: "《中空结构微纳米材料的制备与应用研究》", 31 December 2013, 国防工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102950006B (en) | High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof | |
| CN104588023B (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN105013506B (en) | Bifunctional catalyst and its preparation method and hydrogen production process for methane catalytic decomposition | |
| CN103272604A (en) | Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst | |
| CN107519911B (en) | Nickel-based catalyst prepared by using organic micromolecular additive and application of nickel-based catalyst in methanation reaction | |
| CN109621939A (en) | Ternary composite metal oxide solid base catalyst and its preparation method and application | |
| CN104039440A (en) | Catalyst for hydrolysis of carbonyl sulfide and hydrogen cyanide and use of titanium oxide-based composition | |
| CN101219392B (en) | Catalyst for producing gas rich in hydrogen with coke oven gas and method for producing the same | |
| CN107500296A (en) | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation | |
| CN103464163A (en) | Method for preparing methanation catalyst by inorganic ammonium salt combustion method | |
| CN103933991A (en) | Perovskite type composite oxide catalyst for producing controllable synthesis gas | |
| CN106669743A (en) | Catalyst for hydrogen production from reforming and preparation method thereof | |
| CN104511281A (en) | Water gas wide temperature shift catalyst, preparation and application thereof | |
| CN107233888B (en) | Multifunctional catalyst for preparing fuel gas from biomass and preparation method thereof | |
| CN106563453A (en) | Composite catalyst for biomass gasification for preparing hydrogen-rich combustion gas, and preparation method thereof | |
| CN110711587A (en) | Nickel tungstate-based methanation catalyst with hollow structure | |
| CN102139215B (en) | Method for preparing synthesis gas methanation catalyst | |
| CN104549324A (en) | Magnesium-aluminum-carbon composite support sulfur-tolerant shift catalyst and preparation method thereof | |
| CN109126799B (en) | Red brick powder loaded nickel catalyst for biomass tar cracking and reforming and preparation method thereof | |
| CN114870846B (en) | Carbon dioxide methanation catalyst and preparation method and application thereof | |
| CN104525210A (en) | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix | |
| CN109453778A (en) | A kind of volcanic rock catalyst and its preparation method and application preparing methyl methanol syngas for biomass gasified gas | |
| CN106311253A (en) | Composite catalyst for preparing hydrogen-rich gas through biomass gasification and preparation method thereof | |
| CN104841435A (en) | Alkali metal-doped modified coal-to-natural gas methane synthesis catalyst and preparation method thereof | |
| CN111974441B (en) | Three-dimensional porous structure nickel modified HY molecular sieve oxygen carrier and preparation and application thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200121 |