CN113019439A - Molybdenum-modified molecular sieve-loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof - Google Patents
Molybdenum-modified molecular sieve-loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 67
- 238000002407 reforming Methods 0.000 title claims abstract description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 63
- 239000011733 molybdenum Substances 0.000 claims abstract description 63
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- -1 molybdenum modified molecular sieve Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 29
- 238000006722 reduction reaction Methods 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- 241000269350 Anura Species 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
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 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
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052799 carbon Inorganic materials 0.000 abstract description 28
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 230000008021 deposition Effects 0.000 abstract description 22
- 239000006185 dispersion Substances 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 8
- 238000005470 impregnation Methods 0.000 abstract description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910039444 MoC Inorganic materials 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 238000013112 stability test Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910015711 MoOx Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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Abstract
The invention relates to a preparation method of a molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst. The catalyst takes a molecular sieve as a carrier, and nickel and molybdenum are respectively loaded on the molecular sieve by a sequential impregnation method, so that the dispersion of active species and the strong interaction with the carrier are realized. And then drying, calcining at high temperature and reducing by programmed heating to obtain the molybdenum modified molecular sieve loaded nickel catalyst, which can effectively improve the catalytic activity, and effectively eliminate carbon deposition in the reaction by the dynamic conversion of molybdenum oxide and molybdenum carbide on the molecular sieve constructed in the reaction. Finally, the catalytic material with high sintering resistance and carbon deposition resistance is obtained. The invention has the advantages of simple preparation process, lower cost and high catalytic efficiency.
Description
Technical Field
The invention relates to a molybdenum modified molecular sieve loaded nickel-based catalyst, a preparation method and application, belonging to the technical field of nano catalyst preparation process and environmental protection. The catalyst can effectively solve the problems of sintering of reaction active components under high temperature conditions and carbon deposition in the reaction.
Background
With the rapid development of society, the burning consumption of fossil energy brings about increasingly serious environmental problems, wherein carbon dioxide and methane gas are one of the main causes of the drastic effect of greenhouse. The dry reforming reaction of methane can effectively utilize CH4And CO2Conversion to syngas CO and H2The reaction can reduce the use of fossil fuel to relieve greenhouse effect, and the product H2Syngas with a/CO of 1 is the main feedstock for carrying out a series of chemical reactions, such as Fischer-Tropsch reactions. The catalyst is the core of the technology for preparing the synthesis gas by dry reforming the methane. A great deal of research finds that the nickel-based catalyst has the most industrial application potential and presents high activity and selectivity, but the biggest defects of the nickel-based catalyst are easy carbon deposition and easy sintering of active nickel particles, which causes the degradation of the catalyst and limits the practical industrial application of the catalyst.
For nickel-based catalysts, the active component is usually supported on an oxide support which is resistant to high temperatures or has an abundance of oxygen vacancies, such as γ -Al, by means of reduction by impregnation calcination2O3、SiO2、ZrO2. However, the nickel nanoparticles on the surface of the carrier are still easy to agglomerate and sinter, the particles are enlarged and carbon deposition is generated, and the activity of the catalyst is further reduced. Recently, the addition of a second metal modification active component has been found to be a method capable of significantly improving the activity and stability of the catalyst. The addition of the second metal can not only improve the dispersion degree of the active component and improve the high-temperature sintering resistance, but also improve the carbon deposition resistance, thereby obtaining the catalyst with high activity and high stability. In patent CN110813341A, isovolumetric immersion and microwave are assisted by ultrasoundThe reduction method for preparing Fe, Co and other modified nickel-based catalysts is complex in preparation method, long in preparation time and to-be-improved in catalytic performance. Therefore, the search for a high-performance nickel-based methane dry catalyst with good active component dispersion, excellent carbon deposition resistance and simple preparation process is still a challenging task.
Disclosure of Invention
The invention relates to a molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst, a preparation method and application thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst comprises the following process steps:
a. weighing nickel precursor salt and a molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 2-10 wt%, dispersing in deionized water, and violently stirring for 4-8 hours; then evaporating the solvent, and drying at 60-80 ℃ for 10-12 hours; then, under the air atmosphere, heating at a heating rate of 1-2 ℃/min, heating to 500-600 ℃, and calcining for 4-6 h to obtain a powder product A;
b. b, dispersing the powder product A obtained in the step a and molybdenum precursor salt in deionized water, and violently stirring for 4-8 hours; then evaporating the solvent, and drying at 60-80 ℃ for 10-12 hours; then, under the air atmosphere, heating at a heating rate of 1-2 ℃/min, heating to 500-600 ℃, and calcining for 4-6 h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C or higher for at least 30min, cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min or higher2/N2And carrying out reduction reaction on the mixed gas at the temperature of 700-800 ℃ for 0.5-1 h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Preferably, in the step a, the molecular sieve is at least one of an HZSM-5 molecular sieve, an HY molecular sieve, a SAPO molecular sieve and a beta molecular sieve.
Preferably, in the step a, the nickel precursor salt is at least one of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate. The dispersion degree and the particle size of different nickel precursor loaded on the carrier are different, and high-dispersion active nickel species can be obtained by utilizing the regulation and control selection of various nickel precursor salts provided by the invention.
Preferably, in the step b, at least one of ammonium molybdate, molybdenum acetylacetonate and sodium molybdate is used as the molybdenum precursor salt. The dispersion degree and the particle size of different molybdenum salts loaded on the carrier are different, and high-dispersion active nickel species can be obtained by utilizing the regulation and control selection of various molybdenum precursor salts.
Preferably, the molar ratio of nickel to molybdenum in the molybdenum-modified molecular sieve supported nickel catalyst is 5: 1. Too high or too low a molybdenum content can lead to poor dispersion of the active components, carbon deposition and catalyst deactivation.
In the air atmosphere, the temperature is raised at the rate of 1-2 ℃/min, and the temperature is raised to 500-600 ℃ for calcining for 4-6 h to obtain a powder product. The calcination temperature is too high, and the calcination time is too long, which can cause the agglomeration and sintering of nickel metal and the damage of the shape structure of the carrier. Reduction of the catalyst, i.e. H, according to the invention2And during TPR reduction, the adopted temperature is 700-800 ℃, and the reduction reaction time is 0.5-1 h. Too high a reduction temperature or too long a reduction time may cause high-temperature sintering of the active component.
The invention discloses a nickel catalyst loaded by a molybdenum modified molecular sieve, which is prepared by the preparation method of the nickel-based methane dry reforming catalyst loaded by the molybdenum modified molecular sieve.
The invention relates to an application of a nickel catalyst loaded by a molybdenum modified molecular sieve, which applies the nickel catalyst loaded by the molybdenum modified molecular sieve to a methane dry reforming process.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. according to the method, the molybdenum metal is loaded on the molecular sieve, so that stable carbon circulation can be constructed in alkane reaction, and the carbon deposition resistance of the catalyst is improved; the method uses a simple dipping method to adjust the content of molybdenum to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, thereby obtaining the catalyst with high activity and high stability;
2. the method has simple preparation process and does not cause secondary pollution to the environment. The catalyst can be used for solving the problems of sintering of active components and serious carbon deposition in the dry reforming reaction of methane.
Description of the drawings:
FIG. 1 is a TEM image of a molybdenum-modified molecular sieve-supported nickel catalyst obtained in example 1 of the present invention.
FIG. 2 is an activity diagram of a molybdenum-modified molecular sieve-supported nickel catalyst obtained in example 1 of the present invention.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1
In this embodiment, a preparation method of a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst includes the following process steps:
a. weighing nickel nitrate and an HZSM-5 molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 6 wt%, dispersing in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at a heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product A;
b. b, according to the molar ratio of nickel to molybdenum of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst being 5:1, dispersing the powder product A obtained in the step a and ammonium molybdate in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at the heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C for 30min, then cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min2/N2And carrying out reduction reaction on the mixed gas at the temperature of 800 ℃ for 1h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Experimental test analysis:
microscopic observation is performed on the molybdenum-modified molecular sieve-supported nickel catalyst composite material prepared by the method in this example, referring to fig. 1, fig. 1 is a TEM image of the molybdenum-modified molecular sieve-supported nickel catalyst obtained in this example. NiMo alloy particles and polymorphous MoOxThe particles are uniformly dispersed on the molecular sieve carrier.
The catalyst prepared in this example was tested for catalytic activity: weighing 0.120g of prepared catalyst with the granularity of 40-60 meshes, putting the catalyst into a fixed bed quartz tube reactor for catalyst performance test, and measuring the content of CH4And CO2The flow is 25mL/min, the activity test temperature range is set to be 450-750 ℃, the catalyst has lower catalytic activity at the temperature of 450 ℃, the catalyst shows the highest catalytic activity at the temperature of 750 ℃, and the catalyst has CH4The conversion rate of the catalyst can reach 91 percent, and CO is2The conversion of (c) can reach about 94%. The catalyst stability test is carried out at a temperature of 750 ℃, and after 100h of stability test reaction, CH4And CO2The conversion rates are still kept at 89% and 94% respectively, and the catalyst has good catalytic activity and can effectively inhibit the generation of carbon deposition.
FIG. 2 is an activity diagram of the molybdenum-modified molecular sieve-supported nickel catalyst obtained in the example, wherein within 20h, CH is4And CO2The conversion rate is maintained to be not less than 89%, the method of the embodiment loads the molybdenum metal on the molecular sieve, and stable carbon can be constructed in alkane reactionCirculating to improve the carbon deposition resistance of the catalyst; the invention uses a simple dipping method to adjust the content of molybdenum, so as to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, and further obtain the catalyst with high activity and high stability.
Example 2
In this embodiment, a preparation method of a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst includes the following process steps:
a. weighing nickel acetylacetonate and an HZSM-5 molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 6 wt%, dispersing in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at a heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product A;
b. b, according to the molar ratio of nickel to molybdenum of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst being 5:1, dispersing the powder product A obtained in the step a and ammonium molybdate in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at the heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C for 30min, then cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min2/N2And carrying out reduction reaction on the mixed gas at the temperature of 800 ℃ for 1h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Experimental test analysis:
the catalysts prepared by the method of this example were tested for catalytic activity: weighing 0.120g of prepared catalyst with the granularity of 40-60 meshes, putting the catalyst into a fixed bed quartz tube reactor for catalyst performance test, and measuring the content of CH4And CO2The flow rate is 25mL/min, and the activity test temperatureThe range is set to be 450-750 ℃, the catalyst has lower catalytic activity at the temperature of 450 ℃, the highest catalytic activity is shown at the temperature of 750 ℃, and the catalyst has CH4The conversion rate of the catalyst can reach 90 percent, and CO2The conversion of (c) can reach about 93%. The catalyst stability test is carried out at a temperature of 750 ℃, and after 20h of stability test reaction, CH4And CO2The conversion rate is still kept at 88 percent and 92 percent respectively, and the catalyst has good catalytic activity and effectively inhibits the generation of carbon deposition. In the method, the molybdenum metal is loaded on the molecular sieve, so that stable carbon circulation can be constructed in alkane reaction, and the carbon deposition resistance of the catalyst is improved; the invention uses a simple dipping method to adjust the content of molybdenum, so as to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, and further obtain the catalyst with high activity and high stability.
Example 3
In this embodiment, a preparation method of a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst includes the following process steps:
a. weighing nickel acetate and an HY molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 6 wt%, dispersing in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at a heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product A;
b. b, according to the molar ratio of nickel to molybdenum of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst being 5:1, dispersing the powder product A obtained in the step a and ammonium molybdate in deionized water, and violently stirring for 8 hours; then evaporating the solvent, and drying at 80 ℃ for 12 hours; then, under the air atmosphere, heating at the heating rate of 2 ℃/min, heating to 600 ℃ and calcining for 4h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreatment at 300 ℃ 30min, then after cooling to room temperature, 10 vol% H was bubbled at a gassing rate of 30mL/min2/N2And carrying out reduction reaction on the mixed gas at the temperature of 800 ℃ for 1h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Experimental test analysis:
the catalysts prepared by the method of this example were tested for catalytic activity: weighing 0.120g of prepared catalyst with the granularity of 40-60 meshes, putting the catalyst into a fixed bed quartz tube reactor for catalyst performance test, and measuring the content of CH4And CO2The flow is 25mL/min, the activity test temperature range is set to be 450-750 ℃, the catalyst has lower catalytic activity at the temperature of 450 ℃, the catalyst shows the highest catalytic activity at the temperature of 750 ℃, and the catalyst has CH4The conversion rate of the catalyst can reach 89 percent, and CO is2The conversion of (c) can reach about 91%. The catalyst stability test is carried out at a temperature of 750 ℃, and after 20h of stability test reaction, CH4And CO2The conversion rate is still kept at 86% and 90% respectively, and the catalyst has good catalytic activity and can effectively inhibit the generation of carbon deposition. In the method, the molybdenum metal is loaded on the molecular sieve, so that stable carbon circulation can be constructed in alkane reaction, and the carbon deposition resistance of the catalyst is improved; the invention uses a simple dipping method to adjust the content of molybdenum, so as to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, and further obtain the catalyst with high activity and high stability.
Example 4
In this embodiment, a preparation method of a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst includes the following process steps:
a. weighing nickel chloride and SAPO molecular sieves according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 10 wt%, dispersing in deionized water, and violently stirring for 4 hours; then evaporating the solvent, and drying at 60 ℃ for 10 hours; then, under the air atmosphere, heating at a heating rate of 1 ℃/min, heating to 500 ℃ and calcining for 6h to obtain a powder product A;
b. b, according to the molar ratio of nickel to molybdenum of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst being 5:1, dispersing the powder product A obtained in the step a and molybdenum acetylacetonate in deionized water, and violently stirring for 4 hours; then evaporating the solvent, and drying at 60 ℃ for 10 hours; then, under the air atmosphere, heating at a heating rate of 1 ℃/min, heating to 500 ℃ and calcining for 6h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C for 30min, then cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min2/N2And carrying out reduction reaction on the mixed gas at the temperature of 700 ℃ for 0.5h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Experimental test analysis:
the catalysts prepared by the method of this example were tested for catalytic activity: weighing 0.120g of prepared catalyst with the granularity of 40-60 meshes, putting the catalyst into a fixed bed quartz tube reactor for catalyst performance test, and measuring the content of CH4And CO2The flow is 25mL/min, the activity test temperature range is set to be 450-750 ℃, the catalyst has lower catalytic activity at the temperature of 450 ℃, the catalyst shows the highest catalytic activity at the temperature of 750 ℃, and the catalyst has CH4The conversion rate of the catalyst can reach 85 percent, and CO is obtained2The conversion of (c) can reach about 89%. The catalyst stability test is carried out at a temperature of 750 ℃, and after 20h of stability test reaction, CH4And CO2The conversion rate is still maintained at 81% and 85% respectively, and the catalyst has good catalytic activity and can effectively inhibit the generation of carbon deposition. In the method, the molybdenum metal is loaded on the molecular sieve, so that stable carbon circulation can be constructed in alkane reaction, and the carbon deposition resistance of the catalyst is improved; the invention uses a simple dipping method to adjust the content of molybdenum, so as to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, and further obtain the catalyst with high activity and high stability.
Example 5
In this embodiment, a preparation method of a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst includes the following process steps:
a. weighing nickel chloride and a beta molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 2 wt%, dispersing in deionized water, and violently stirring for 4 hours; then evaporating the solvent, and drying at 60 ℃ for 10 hours; then, under the air atmosphere, heating at a heating rate of 1 ℃/min, heating to 500 ℃ and calcining for 6h to obtain a powder product A;
b. b, according to the molar ratio of nickel to molybdenum of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst being 5:1, dispersing the powder product A obtained in the step a and sodium molybdate in deionized water, and violently stirring for 4 hours; then evaporating the solvent, and drying at 60 ℃ for 10 hours; then, under the air atmosphere, heating at a heating rate of 1 ℃/min, heating to 500 ℃ and calcining for 6h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C for 30min, then cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min2/N2And carrying out reduction reaction on the mixed gas at the temperature of 700 ℃ for 0.5h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
Experimental test analysis:
the catalysts prepared by the method of this example were tested for catalytic activity: weighing 0.120g of prepared catalyst with the granularity of 40-60 meshes, putting the catalyst into a fixed bed quartz tube reactor for catalyst performance test, and measuring the content of CH4And CO2The flow is 25mL/min, the activity test temperature range is set to be 450-750 ℃, the catalyst has lower catalytic activity at the temperature of 450 ℃, the catalyst shows the highest catalytic activity at the temperature of 750 ℃, and the catalyst has CH4The conversion rate of the catalyst can reach 82 percent, and CO is obtained2The conversion of (c) can reach about 85%. The catalyst stability test is carried out at a temperature of 750 ℃, and after 20h of stability test reaction, CH4And CO2Transformation ofThe rate is still kept at 79 percent and 80 percent respectively, and the catalyst has good catalytic activity and effectively inhibits the generation of carbon deposition. In the method, the molybdenum metal is loaded on the molecular sieve, so that stable carbon circulation can be constructed in alkane reaction, and the carbon deposition resistance of the catalyst is improved; the invention uses a simple dipping method to adjust the content of molybdenum, so as to obtain the nickel catalyst loaded by the molybdenum modified molecular sieve with high activity, and further obtain the catalyst with high activity and high stability.
In summary, the catalyst prepared by the preparation method of the molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst in the above embodiment uses the molecular sieve as the carrier, and nickel and molybdenum are respectively supported on the molecular sieve by a sequential impregnation method, so as to realize dispersion of active species and strong interaction with the carrier. And then drying, calcining at high temperature and reducing by programmed heating to obtain the molybdenum modified molecular sieve loaded nickel catalyst, which can effectively improve the catalytic activity, and effectively eliminate carbon deposition in the reaction by the dynamic conversion of molybdenum oxide and molybdenum carbide on the molecular sieve constructed in the reaction. Finally, the catalytic material with high sintering resistance and carbon deposition resistance is obtained. The method of the embodiment has the advantages of simple preparation process, low cost and high catalytic efficiency.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (7)
1. A preparation method of a molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is characterized by comprising the following process steps:
a. weighing nickel precursor salt and a molecular sieve according to the proportion that the nickel loading amount of the target prepared molybdenum modified molecular sieve loaded nickel-based methane dry reforming catalyst is 2-10 wt%, dispersing in deionized water, and violently stirring for 4-8 hours; then evaporating the solvent, and drying at 60-80 ℃ for 10-12 hours; then, under the air atmosphere, heating at a heating rate of 1-2 ℃/min, heating to 500-600 ℃, and calcining for 4-6 h to obtain a powder product A;
b. b, dispersing the powder product A obtained in the step a and molybdenum precursor salt in deionized water, and violently stirring for 4-8 hours; then evaporating the solvent, and drying at 60-80 ℃ for 10-12 hours; then, under the air atmosphere, heating at a heating rate of 1-2 ℃/min, heating to 500-600 ℃, and calcining for 4-6 h to obtain a powder product B;
c. and (3) reduction of the catalyst:
b, performing temperature programming reduction on the powder product B obtained in the step B by using hydrogen, and introducing N firstly2Pretreating at 300 deg.C or higher for at least 30min, cooling to room temperature, and introducing 10 vol% H at an aeration rate of 30mL/min or higher2/N2And carrying out reduction reaction on the mixed gas at the temperature of 700-800 ℃ for 0.5-1 h to obtain the molybdenum modified molecular sieve loaded nickel catalyst.
2. The method of claim 1 for preparing a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst, wherein the molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst comprises: in the step a, the molecular sieve is at least one of an HZSM-5 molecular sieve, an HY molecular sieve, an SAPO molecular sieve and a beta molecular sieve.
3. The method of claim 1 for preparing a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst, wherein the molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst comprises: in the step a, the nickel precursor salt is at least one of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate.
4. The method of claim 1 for preparing a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst, wherein the molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst comprises: in the step b, the molybdenum precursor salt is at least one of ammonium molybdate, molybdenum acetylacetonate and sodium molybdate.
5. The method of claim 1 for preparing a molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst, wherein the molybdenum-modified molecular sieve-supported nickel-based methane dry reforming catalyst comprises: the molar ratio of nickel to molybdenum in the molybdenum modified molecular sieve-loaded nickel catalyst is 5: 1.
6. A molybdenum modified molecular sieve supported nickel catalyst is characterized in that: the molybdenum-modified molecular sieve-loaded nickel-based methane dry reforming catalyst is prepared by the preparation method of the molybdenum-modified molecular sieve-loaded nickel-based methane dry reforming catalyst in claim 1.
7. The use of the molybdenum-modified molecular sieve supported nickel catalyst of claim 6, wherein: the nickel catalyst loaded by the molybdenum modified molecular sieve is applied to the dry reforming process of methane.
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