CN114471636A - Preparation method and application of supported nickel-based catalyst - Google Patents
Preparation method and application of supported nickel-based catalyst Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 229910017677 NH4H2 Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 62
- 239000011575 calcium Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 229910052791 calcium Inorganic materials 0.000 claims description 24
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 24
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- 230000002950 deficient Effects 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 238000002407 reforming Methods 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 29
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000008021 deposition Effects 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The application discloses a preparation method and application of a supported nickel-based catalyst, Ca (NO) is added3)2·4H2O，NH4H2PO4Respectively dissolving the two solutions in deionized water, mixing the two solutions, dropwise adding 25% vol ammonia water, heating and stirring, filtering and washing the obtained suspension to be neutral, drying at 80-100 ℃, and calcining the solid in air at 400 ℃ for 3-5 hours to obtain a carrier; ni (NO)3)2·6H2Dissolving O in deionized water, pouring the carrier into the nickel precursor solution, violently stirring at room temperature, dropwise adding 25% vol ammonia water, and stirring at room temperature; filtering and washing the suspension until the filtrate is neutral, drying the obtained solid at 80-100 ℃, calcining the dried solid in air at 400-500 ℃ for 3-5 hours to obtain the supported nickel-based catalyst Nix/Ca10‑x(PO4)6(OH)2。
Description
Technical Field
The application relates to the technical field of preparation of nickel-based catalysts, in particular to a preparation method and application of a supported nickel-based catalyst.
Background
The problem of greenhouse effect caused by the large consumption of fossil energy has been brought for a long time. CO as the most predominant greenhouse gas2The cyclic and efficient utilization of the waste water is widely regarded. Wherein CO is2And CH4Reaction for producing CO and H2The dry reforming of methane technology has received great attention. The methane dry reforming technology not only simultaneously utilizes CH4And CO2Two greenhouse gases, CO and H in their products2The theoretical ratio of the carbon-containing liquid fuel is 1:1, and the carbon-containing liquid fuel is an ideal raw material for synthesizing the carbon-containing liquid fuel by Fischer-Tropsch synthesis and other technologies, and has great application potential.
The methane dry reforming catalyst is mainly divided into a noble metal catalyst (Ru, Pt, Pd, Rh) and a non-noble metal catalyst (Ni, Co, Cu, Fe). Noble metal catalysts have excellent catalytic activity for dry reforming of methane and have good anti-carbon deposition performance, but the expensive cost of noble metals limits large-scale industrial application. The nickel-based catalyst has the highest cracking activity on methane in the non-noble metal catalyst, but the dry reforming of methane by the nickel-based catalyst still has two problems. On one hand, the nickel-based catalyst is easy to sinter and deactivate during a high-temperature reaction process (the dry reforming reaction of methane is generally required to be carried out at a temperature of more than 700 ℃), and on the other hand, the nickel active sites are easily covered by carbon deposition generated by methane cracking during the reaction process, so that the catalyst is deactivated. The two problems are caused by the unstable nickel active site, sintering caused by migration of polymer in the reaction process and CH4The rate of cleavage is too fast, resulting in the formation of large amounts of inert carbon species, covering the active sites. Thus, the preparation has a strong metal-support interaction and ensures CH4Cracking rate and CO2A conversion rate matched catalyst is critical.
In order to solve the problems of high-temperature sintering and carbon deposition in the dry reforming reaction of methane, the invention aims to prepare a supported nickel-based catalyst with strong metal-carrier interaction, high catalytic activity, high catalytic stability and carbon deposition resistance by using calcium-deficient hydroxyapatite as a carrier.
Content of application
The technical problem to be solved is as follows:
the technical problem to be solved in the application is that high-temperature sintering, carbon deposition and the like exist in the dry reforming reaction of methane in the prior art, and a preparation method and application of the supported nickel-based catalyst are provided.
The technical scheme is as follows:
a preparation method of a supported nickel-based catalyst comprises the following steps of firstly preparing a calcium-deficient hydroxyapatite carrier by adopting a coprecipitation method, and then loading active metal nickel by adopting an impregnation method, wherein the preparation method comprises the following steps:
the first step is as follows: ca (NO)3)2·4H2O，NH4H2PO4Respectively dissolving in deionized water, controlling the molar ratio of Ca/P to be 8-10/6, mixing the two solutions after the two solutions are completely dissolved, dropwise adding 25% vol ammonia water under vigorous stirring at room temperature to adjust the pH value of the mixed solution to 10 +/-1, heating and stirring, controlling the heating temperature to be 60-90 ℃, and controlling the stirring time to be 2-4 hours;
the second step is that: after stirring, filtering and washing the obtained suspension to neutrality, drying at 80-100 ℃, calcining the dried solid in air at 300-400 ℃ for 3-5 hours to prepare the calcium-deficient hydroxyapatite carrier (chemical formula: Ca)10-x(PO4)6(OH)2，0<x<2)；
The third step: ni (NO)3)2·6H2Dissolving O in deionized water to prepare a nickel precursor solution, pouring the calcium-deficient hydroxyapatite carrier into the nickel precursor solution, wherein the sum of the mole numbers of Ni and Ca is 10;
the fourth step: stirring vigorously at room temperature, adding 25% vol ammonia water dropwise to adjust the pH of the mixed solution to 10 +/-1, and stirring for 2-4 hours at 80 ℃;
the fifth step: filtering and washing the suspension until the filtrate is neutral, drying the obtained solid, calcining the dried solid in air at 400-500 ℃ for 3-5 hours to obtain the supported nickel-based catalyst Nix/Ca10-x(PO4)6(OH)2；0<x<2。
As a preferred technical scheme of the application: calcium nitrate tetrahydrate Ca (NO) in the first step3)2·4H2The mass ratio of O to deionized water is 1:1-2 respectively, ammonium dihydrogen phosphate NH4H2PO4The mass ratio of the deionized water to the deionized water is 1:1-2 respectively.
As a preferred technical scheme of the application: and drying for 24 hours in the second step until the water content is less than 5 percent.
As a preferred technical scheme of the application: nickel nitrate hexahydrate Ni (NO) in the third step3)2·6H2The mass ratio of the O, the deionized water and the calcium-deficient hydroxyapatite is 1:2-10: 2-10.
As a preferred technical scheme of this application: the molar ratio of Ni/Ca in the third step is controlled to be 0.001-2/8-9.999.
As a preferred technical scheme of this application: the stirring speed of the vigorous stirring in the fourth step is 400-600 rpm/min.
As a preferred technical scheme of the application: and in the fifth step, the drying condition is drying for 24 hours at the temperature of 80-100 ℃ until the water content is less than 5%.
The application also discloses an application of the supported nickel-based catalyst prepared by the preparation method in methane dry reforming.
As a preferred technical scheme of the application: the specific application method is that the mixed gas of methane and carbon dioxide passes through a catalyst bed layer at the temperature of 800 ℃ according to the molar ratio of 1:1, and the obtained products are carbon monoxide and hydrogen.
Has the beneficial effects that:
compared with the prior art, the preparation method and the application of the supported nickel-based catalyst have the following technical effects:
1. the preparation condition is simple, and the application of the supported nickel-based catalyst is easy to amplify;
2. the carrier is calcium-deficient hydroxyapatite (chemical formula: Ca)10-x(PO4)6(OH)2，0<x<2) The mass percent of the nickel is 0-10 percent;
3. when the catalyst is used for dry reforming reaction of methane, the reaction temperature is 800 ℃, and the gas hourly space velocity is 30000mL gcat - 1h-1The service life of the catalyst is as long as 200h, the deactivation tendency does not occur, and carbon deposition is not observed in a TEM image of the catalyst after reaction;
4. in the supported nickel-based catalyst prepared by the method, more than 75% of Ni nano-particles are dispersed in a hydroxyapatite structure. The structure ensures the stability of Ni in the high-temperature reaction process, effectively prevents the sintering of the catalyst, improves the stability of the catalyst, and reduces the methane conversion rate by less than 3 percent after 200 hours.
5. The catalyst prepared by the method has better catalytic activity and anti-carbon deposition performance on methane dry reforming, and no carbon deposition is found in a catalyst TEM image after reaction.
6. In the reaction of the catalyst for 200 hours, the deactivation rate of methane is 0.008 percent h-1In comparative example, the deactivation rate of methane was 0.014% h-1。
Drawings
FIG. 1 is a TEM image of the catalyst obtained in example 1 of the present application after reduction.
FIG. 2 shows CH in DMR lifetime investigation reaction for example 1 and comparative example4Conversion as a function of reaction time.
FIG. 3 shows CO in the DMR lifetime investigation reaction of example 1 and comparative example2Conversion as a function of reaction time.
FIG. 4 shows the DMR lifetime test reaction of example 1 and comparative example in H2Plot of the/CO conversion as a function of reaction time.
FIG. 5 is a TEM image of the nickel-based catalysts prepared in example 1 and comparative example after the life span investigation reaction.
FIG. 6 shows examples 1, 2, 3 andh of Nickel-based catalyst prepared in comparative example2-TPR characterization.
Figure 7 is an XPS characterization of the nickel-based catalysts prepared in examples 1, 2, 3 and comparative examples.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention, but it should not be understood that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1:
a preparation method of a supported nickel-based catalyst comprises the steps of firstly preparing a calcium-deficient hydroxyapatite carrier by adopting a coprecipitation method, and then loading active metal nickel by adopting an impregnation method, and specifically comprises the following steps:
step one, preparing a calcium-deficient hydroxyapatite carrier: 44.87g Ca (NO)3)2·4H2O (0.19mol, molecular weight 236.15g/mol) and 13.80g NH4H2PO4(0.12mol, molecular weight 115.03g/mol) are respectively dissolved in 50mL and 20mL deionized water, and after complete dissolution, the two solutions are mixed in a beaker; dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the second step is that: after stirring, filtering and washing the obtained suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
the third step: calcining the solid obtained in the second step in a muffle furnace for 4 hours at 400 ℃ in air atmosphere to obtain the calcium-deficient hydroxyapatite carrier with the molecular formula of Ca9.5(PO4)6(OH)2；
The fourth step: 2.91g of Ni (NO)3)2·6H2O (0.01mol, molecular weight 290.81g/mol) was dissolved in 15mL of water, and 19.68g of Ca was added9.5(PO4)6(OH)2(0.02mol, molecular weight 984g/mol), dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting the pH to 10, then controlling the heating temperature to 80 ℃, and continuing stirring for 2 hours;
the fifth step: filtering and washing the suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
and a sixth step: calcining the obtained solid in a muffle furnace at 500 ℃ for 4 hours in an air atmosphere to obtain Ni0.5/Ca9.5(PO4)6(OH)2Catalyst D, denoted catalyst A.
As shown in FIG. 1, which is a TEM image of the catalyst of example 1 after reduction, it can be seen from FIG. 1 that Ni is dispersed relatively uniformly in the catalyst of example 1, and the average particle size is 15.4 nm.
The catalyst is subjected to dry reforming reaction with methane, the catalyst is ground to 40-80 meshes, 400mg of the catalyst is put into a constant temperature region of a quartz tube reactor, and N is firstly introduced2And (3) raising the temperature, switching to the raw material gas after the temperature is raised to the reaction temperature, wherein the sampling amount of methane, carbon dioxide and nitrogen is 1:1:8(20mL, 20mL and 160mL), and the test is carried out at 800 ℃. The average conversion of methane and carbon dioxide was 98.7% and 98.5%, respectively. The catalyst stability test of example 1 was conducted at 800 deg.C and the results are shown in FIGS. 2-4. After 200h of reaction, the deactivation rate of methane is 0.008 percent h-1. The inactivation rate of carbon dioxide is 0.007 percent h-1. The catalyst maintains good activity. No carbon deposition was observed in the TEM image of the catalyst after the reaction (see FIG. 5).
Example 2
A preparation method of a supported nickel-based catalyst comprises the following steps of firstly preparing a calcium-deficient hydroxyapatite carrier by adopting a coprecipitation method, and then loading active metal nickel by adopting an impregnation method, wherein the preparation method comprises the following steps:
step one, preparing a calcium-deficient hydroxyapatite carrier: 42.51g Ca (NO)3)2·4H2O (0.18mol, molecular weight 236.15g/mol) and 13.80g NH4H2PO4(0.12mol, molecular weight 115.03g/mol) are respectively dissolved in 50mL and 20mL deionized water, and after complete dissolution, the two solutions are mixed in a beaker(ii) a Dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the second step is that: after stirring, filtering and washing the obtained suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
the third step: calcining the solid obtained in the second step in a muffle furnace for 4 hours at 400 ℃ in air atmosphere to obtain the calcium-deficient hydroxyapatite carrier with the molecular formula of Ca9(PO4)6(OH)2；
The fourth step: 5.82g of Ni (NO)3)2·6H2O (0.02mol, molecular weight 290.81g/mol) was dissolved in 30mL of water, and 19.28g of Ca was added9(PO4)6(OH)2(0.02mol, molecular weight 964g/mol), dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the fifth step: filtering and washing the suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
and a sixth step: calcining the obtained solid in a muffle furnace at 500 ℃ for 4 hours in an air atmosphere to obtain Ni1/Ca9(PO4)6(OH)2Catalyst D, denoted catalyst B.
Performance on dry reforming of methane using the process of example 1. The average conversion of methane and carbon dioxide was 98.8% and 98.5%, respectively.
Example 3
A preparation method of a supported nickel-based catalyst comprises the steps of firstly preparing a calcium-deficient hydroxyapatite carrier by adopting a coprecipitation method, and then loading active metal nickel by adopting an impregnation method, and specifically comprises the following steps:
step one, preparing a calcium-deficient hydroxyapatite carrier: 40.15g Ca (NO)3)2·4H2O (0.17mol, molecular weight 236.15g/mol) and 13.80g NH4H2PO4(0.12mol, molecular weight 115.03g/mol) dissolved in 50mL and 20mL respectivelyMixing the two solutions in a beaker after the two solutions are completely dissolved in the water; dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the second step: after stirring, filtering and washing the obtained suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
the third step: calcining the solid obtained in the second step in a muffle furnace for 4 hours at 400 ℃ in air atmosphere to obtain the calcium-deficient hydroxyapatite carrier with the molecular formula of Ca8.5(PO4)6(OH)2；
The fourth step: mixing 8.72g of Ni (NO)3)2·6H2O (0.03mol, molecular weight 290.81g/mol) was dissolved in 45mL of water, 18.88g of Ca was added8.5(PO4)6(OH)2(0.02mol, molecular weight of 944g/mol), dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the fifth step: filtering and washing the suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
and a sixth step: calcining the obtained solid in a muffle furnace at 500 ℃ for 4 hours in an air atmosphere to obtain Ni1.5/Ca8.5(PO4)6(OH)2Catalyst D, denoted as catalyst C.
Performance on dry reforming of methane using the method of example 1. The average conversion of methane and carbon dioxide was 96.3% and 98.7%, respectively.
Comparative examples
A preparation method of a supported nickel-based catalyst comprises the steps of firstly preparing a calcium-deficient hydroxyapatite carrier by adopting a coprecipitation method, and then loading active metal nickel by adopting an impregnation method, and specifically comprises the following steps:
step one, preparing a calcium-deficient hydroxyapatite carrier: 47.23g Ca (NO)3)2·4H2O (0.2mol, molecular weight 236.15g/mol) and 13.80g NH4H2PO4(0.12mol, molecular weight 115.03g/mol) are respectively dissolved in 50mL and 20mL deionized water, and after complete dissolution, the two solutions are mixed in a beaker; dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the second step is that: after stirring, filtering and washing the obtained suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
the third step: calcining the solid obtained in the second step in a muffle furnace for 4 hours at 400 ℃ in air atmosphere to obtain the calcium-deficient hydroxyapatite carrier with the molecular formula of Ca10(PO4)6(OH)2；
The fourth step: 2.91g of Ni (NO)3)2·6H2O (0.01mol, molecular weight 290.81g/mol) was dissolved in 30mL of water, and 20.08g of Ca was added10(PO4)6(OH)2(0.02mol, molecular weight 1004g/mol), dropwise adding 25 vol% ammonia water solution into the solution at room temperature under vigorous stirring, adjusting pH to 10, controlling heating temperature to 80 ℃, and continuing stirring for 2 hours;
the fifth step: filtering and washing the suspension until the filtrate is neutral, and drying the solid obtained by filtering at 80 ℃ for 24 hours;
and a sixth step: calcining the obtained solid in a muffle furnace at 500 ℃ for 4 hours in an air atmosphere to obtain Ni0.5/Ca10(PO4)6(OH)2Catalyst, designated catalyst D.
Performance on dry reforming of methane using the method of example 1. The average conversion of methane and carbon dioxide was 84.9% and 91.1%, respectively. The catalyst stability test of the comparative example was performed at 800 deg.c, and the results are shown in fig. 2 to 4. After 118h of reaction, the methane deactivation rate was 0.087%, which was 10.9 times that of the catalyst of example 1. The carbon dioxide deactivation rate was 0.069%, which was 9.9 times that of the catalyst of example 1. In the TEM pattern after the reaction (see fig. 5), it was found that metallic Ni was surrounded by carbon deposit.
As shown in FIG. 6, examples 1, 2 and 3 and comparative exampleExample catalyst H2And TPR (thermal Plastic rubber) representation, as can be seen from FIG. 6, the reduction temperatures of the catalysts of examples 1, 2 and 3 are obviously higher than those of the comparative examples, which shows that the interaction between Ni and the carrier in the catalysts of examples 1, 2 and 3 is stronger, so that the stability of the catalysts is increased, the sintering of Ni in the reaction process is inhibited, and the service life of the catalysts is prolonged.
As shown in FIG. 7, in order to XPS characterisation of the catalysts of examples 1, 2, 3 and comparative examples, it can be seen from FIG. 7 that Ni is contained in examples 1, 2, 32+[I]And Ni2+[II]Is much higher than the comparative examples, which shows that Ni in the catalysts of examples 1, 2 and 3 is mainly present in hydroxyapatite crystal lattices, provides more stable active sites and CH with higher matching degree for the catalysts4And CO2The rate of reaction.
Claims (9)
1. A preparation method of a supported nickel-based catalyst is characterized in that a calcium-deficient hydroxyapatite carrier is prepared by a coprecipitation method, and then active metal nickel is loaded by an impregnation method, and the preparation method specifically comprises the following steps:
the first step is as follows: ca (NO)3)2·4H2O，NH4H2PO4Respectively dissolving in deionized water, controlling the molar ratio of Ca/P to be 8-10/6, mixing the two solutions after the two solutions are completely dissolved, dropwise adding 25% vol ammonia water under vigorous stirring at room temperature to adjust the pH value of the mixed solution to 10 +/-1, heating and stirring, controlling the heating temperature to be 60-90 ℃, and controlling the stirring time to be 2-4 hours;
the second step is that: after stirring, filtering and washing the obtained suspension to neutrality, drying at 80-100 ℃, calcining the dried solid in air at 300-400 ℃ for 3-5 hours to prepare the calcium-deficient hydroxyapatite carrier (chemical formula: Ca)10-x(PO4)6(OH)2，0<x<2)；
The third step: ni (NO)3)2·6H2Dissolving O in deionized water to prepare a nickel precursor solution, pouring the calcium-deficient hydroxyapatite carrier into the nickel precursor solution, wherein the sum of the mole numbers of Ni and Ca is 10;
the fourth step: stirring vigorously at room temperature, adding 25% vol ammonia water dropwise to adjust the pH of the mixed solution to 10 +/-1, and stirring for 2-4 hours at 80 ℃;
the fifth step: filtering and washing the suspension until the filtrate is neutral, drying the obtained solid, calcining the dried solid in air at 400-500 ℃ for 3-5 hours to obtain the supported nickel-based catalyst Nix/Ca10-x(PO4)6(OH)2；0<x<2。
2. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: calcium nitrate tetrahydrate Ca (NO) in the first step3)2·4H2The mass ratio of O to deionized water is 1:1-2 respectively, ammonium dihydrogen phosphate NH4H2PO4The mass ratio of the deionized water to the deionized water is 1:1-2 respectively.
3. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: and drying for 24 hours in the second step until the water content is less than 5 percent.
4. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: nickel nitrate hexahydrate Ni (NO) in the third step3)2·6H2The mass ratio of the O, the deionized water and the calcium-deficient hydroxyapatite is 1:2-10: 2-10.
5. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: the molar ratio of Ni/Ca in the third step is controlled to be 0.001-2/8-9.999.
6. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: the stirring speed of the vigorous stirring in the fourth step is 400-600 rpm/min.
7. The method for preparing a supported nickel-based catalyst according to claim 1, wherein: and in the fifth step, the drying condition is drying for 24 hours at the temperature of 80-100 ℃ until the water content is less than 5%.
8. Use of a supported nickel-based catalyst prepared by the preparation process according to any one of claims 1 to 7 in the dry reforming of methane.
9. Use of a supported nickel-based catalyst according to claim 8 in the dry reforming of methane, characterized in that: the mixed gas of methane and carbon dioxide is passed through a catalyst bed layer according to the molar ratio of 1:1 at the temperature of 800 ℃, and the obtained products are carbon monoxide and hydrogen.
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