CN113952970A - Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof - Google Patents
Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 33
- 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 title claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000002407 reforming Methods 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000725 suspension Substances 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 238000003828 vacuum filtration Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- 239000012876 carrier material Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- B01J35/40—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
Abstract
The invention discloses a nickel-loaded hydroxyapatite (MeHAP) catalyst, a preparation method and an application thereof, wherein the catalyst comprises a hydroxyapatite carrier component and an active metal nickel component, and the components in percentage by mass are as follows: 85.0 to 99.0 percent; ni: 1-15%, wherein Me in MeHAP material = one or more than two elements of Mg, Ca, Sr and Zn, and the atomic ratio of Me to P is controlled at 1.67. The catalyst prepared by the invention can be used in the reaction of preparing synthesis gas by dry reforming of methane and carbon dioxide, and has the advantages of high activity, high stability, cheap and easily available raw materials, simple synthesis process and easy realization of batch production.
Description
Technical Field
The invention relates to a nickel-loaded hydroxyapatite catalyst, a preparation method and application thereof, and belongs to the technical field of catalyst preparation and application.
Background
Methane carbon dioxide dry reforming reaction (DRM) uses two main greenhouse gases CH4And CO2As raw material, produce lower H2Syngas with/CO ratio is one of the key research topics in the fields of heterogeneous catalysis, C1 chemistry and energy catalysis. The way is a comprehensive and efficient utilization mode of natural gas and is also CO2An efficient way of chemical conversion is to use,not only can make full use of CH4、CO2The carbon, hydrogen and oxygen resources in the synthesis gas are used for preparing the synthesis gas suitable for Fischer-Tropsch synthesis and carbonyl synthesis, the increasingly serious greenhouse effect can be relieved, the economic benefit and the environmental benefit are remarkable, and the method is also one of important ways for realizing the target tasks of carbon peak reaching and carbon neutralization in China.
Studies have shown that metals active for methane carbon dioxide reforming contain almost all elements of group VIII (except Os). Among them, noble metal Catalysts represented by Pt, Pd, Ru, Rh, Ir, etc. have relatively high activity, and they show good characteristics in terms of carbon deposition resistance and sintering resistance of the catalyst, thus showing good stability in DRM reaction (Pakhare d. et al. chem. soc. rev. 2014, 43, 7813; Wysocka i. et al. Catalysts 2019, 9, 540.). However, the abundance of noble metals is low, the price is high, and the large-scale industrial application is not economically feasible. The nickel (Ni) based and cobalt (Co) based catalysts in non-noble metals, particularly Ni based catalysts, have the best activity, and the catalytic activity of the catalysts can be even comparable with that of noble metal catalysts after being properly modulated, and the raw materials required for preparing the Ni based catalysts are cheap and easy to obtain, so that the industrial application potential is huge.
Since the reforming reaction generally needs to be operated at high temperature, the main problems faced by the Ni-based catalyst at present are that the active component is easy to deactivate due to high-temperature sintering and severe carbon deposition on the surface of the catalyst, and the stability of the catalyst is far less than that of the noble metal catalyst. Considerable research has shown that increasing Ni dispersion, making embedded Ni or making Ni in a clad structure can largely suppress the sintering growth of Ni particles (Zhang m. et al., energy. converters. manage., 2020, 216, 112950; Zhang x.p. et al., Fuel, 2015,147, 1, 243). The main reason for the deactivation of the catalyst caused by carbon deposition is that the cracking rate of methane on the surface of the catalyst is higher than the carbon elimination rate of carbon dioxide, so that a large amount of carbon deposition is not removed in time and graphitized to cover active sites on the surface.
The catalyst surface hydroxyl groups also have a significant effect on the activation of the reactant molecules and the conversion of intermediates during the DRM reaction. The reaction of hydroxyl groups with carbon species is effective in inhibiting the formation of carbon deposits on the surface of the catalyst, thereby retarding the deactivation of the catalyst (O' Connor A.M. et al. Catal. Today 2006, 115, 191; Ferreira-Aparicio P. et al., J. Catal. 1999, 184, 202; Schuurman Y. et al., Catal. Today 1998, 46, 185). Meanwhile, the weak alkaline sites on the surface of the catalyst are also considered as important active sites for adsorbing and activating carbon dioxide. Therefore, the construction of the Ni catalyst which is rich in hydroxyl and has a suitable alkaline site on the surface to realize the stable operation of the methane carbon dioxide dry reforming catalyst system with high activity and long period is an important step for promoting the industrial application of the catalyst.
Disclosure of Invention
The invention aims to provide a hydroxyapatite nickel-loaded catalyst which is high in activity, good in selectivity, low in cost and easy to prepare, and also provides a preparation method and application of the catalyst.
The invention provides a catalyst of nickel loaded hydroxyapatite, which is catalyst hydroxyapatite (Me)10(OH)2(PO4)6Abbreviated as MeHAP, wherein Me = one of the four cations Mg, Ca, Sr, Zn or) is a supported metallic nickel catalytic material.
Hydroxyapatite (Me)10(OH)2(PO4)6MeHAP) belongs to the hexagonal system, theoretically with a Me/P molar ratio of 1.67, but the preparation process can significantly affect its structure and Me/P ratio, and thus its surface properties. From the viewpoint of crystal phase composition and structure, MeHAP has both acid-base property and rich hydroxyl group. In addition, MeHAP has the characteristics of high thermal stability and the like, and the preparation process is simple, so the MeHAP has the characteristics of low cost, low toxicity and the like.
The catalyst comprises a hydroxyapatite carrier (MeHAP) and an active metal Ni, wherein the mass percentage of the active metal Ni is as follows: 85.0 to 99.0 percent; ni: 1-15%, wherein Me in MeHAP material = one or more than two elements of Mg, Ca, Sr, Zn, etc., and the atomic ratio of Me to P is controlled at 1.67.
The invention provides a preparation method of the hydroxyapatite nickel-loaded catalyst, which comprises the following steps: (1) preparation of MeHAP support Material
When Me is Ca, the compound (I) is,firstly, Ca (NO) with the concentration of 0.2-0.4 mol/L is prepared3)2Solution A and (NH) with a concentration of 0.2-0.4 mol/L4)2HPO4Solution B with n (Ca) in a metering ratio2+)/n(PO4 3-) =5/3, add solution B drop by drop to solution a with vigorous stirring in a thermostatic water bath at 40-60 ℃. After the dropwise addition is finished, the pH value of the solution is adjusted to 9-11 by using strong ammonia water, and the solution is continuously stirred for 6-10 h; the resulting white suspension was then transferred to a reaction vessel and hydrothermally treated at 100 ℃ and 140 ℃ for 12-24 h. Naturally cooling, carrying out vacuum filtration on the obtained white precipitate, washing with 50mL of distilled water for 3-5 times, drying at 110 ℃ overnight, and roasting at 600-800 ℃ for 3-6 h to obtain the CaHAP carrier. The preparation of other metal cation materials is similar to the preparation process of CaHAP.
(2) Preparation of nickel-based catalyst loaded with hydroxyapatite
Firstly, a catalyst is prepared by a deposition precipitation method. The method comprises weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Heating the solution with the concentration of 0.03-0.05 mol/L to 40-60 ℃ in a water bath kettle by stirring; then, the CaHAP carrier prepared in (1) was added to the above solution at one time to obtain a suspension. The amount of Ni used in the solution herein is calculated by controlling the amount thereof to be in the range of 1 to 15 wt%; subsequently, saturated Na was pumped through a peristaltic pump2CO3Adding the solution into the suspension drop by drop until the pH is 9-11; after stirring for 4-8 h, centrifugally separating the suspension, washing the suspension with distilled water for 3-5 times, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 400-600 ℃ for 3-6 h;
and secondly, tabletting, crushing and screening the raw catalyst powder prepared in the step I into particles of 20-40 meshes to obtain the catalyst.
The invention provides application of the hydroxyapatite nickel-loaded catalyst in preparation of synthesis gas by dry reforming of methane and carbon dioxide.
The application of the catalyst comprises the following steps: the catalytic reaction is carried out in a fixed bed reactor. The catalyst was first at 10% H2Reduction treatment for 1-3 h under Ar; in the process of catalysisDuring the reaction, the molar ratio of the raw material methane to the carbon dioxide is 1:1, the volume fraction of the methane is 10-50%, the volume fraction of the carbon dioxide is 10-50%, the volume fraction of the nitrogen is 0-80%, and the volume space velocity is 10000-catH), controlling the reaction temperature at 600-850 ℃ and the reaction pressure at normal pressure.
The invention has the beneficial effects that:
in the catalytic system, different cationic hydroxyapatite materials are used as catalyst carriers, the material has good thermal stability and rich and adjustable surface hydroxyl groups, and the used components of the material are non-noble metals, so the material has low cost, simple synthesis process and easy realization of batch production. When Ni is introduced into the material, the synthesis and preparation method of the catalyst is simple. Under the catalytic action of the catalyst, when the methane and the carbon dioxide react, the highest conversion rate of the methane and the carbon dioxide can reach more than 95% under the reaction optimization condition, and the catalyst has good catalytic activity and stability after running for 240 hours; the catalyst with the best activity performance has the methane conversion rate not to be reduced by more than 5 percent after 240 hours of reaction evaluation.
Detailed Description
The following examples are presented to further illustrate the present invention, but the present invention is not limited by the following examples. Moreover, the examples only show some conditions for achieving the object of the present invention, and do not mean that these conditions must be satisfied for achieving the object of the present invention.
Example 1
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(1) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Ca, Ca (NO) is first prepared at a concentration of 0.2mol/L3)2Solution A and (NH) with a concentration of 0.3mol/L4)2HPO4Solution B with n (Ca) in a metering ratio2+)/n(PO4 3-) =5/3, 100mL of B solution was added dropwise to 250 mL of a solution under vigorous stirring in a thermostatic water bath at 40 ℃. After the dropwise addition, the pH of the solution is adjusted to 10 by using strong ammonia water, and the solution is continuously stirred for 6 hours; the resulting white suspension was subsequently transferred to the reversePutting the mixture into a kettle, and carrying out hydrothermal treatment at 100 ℃ for 24 hours. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 3 times, drying at 110 ℃ overnight, and roasting at 700 ℃ for 5 h to obtain the CaHAP carrier.
(2) Preparation of CaHAP loaded nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 100mL of 0.03 mol/L solution, stirring and heating the solution to 50 ℃ in a water bath kettle; then, 3.5 g of the CaHAP carrier prepared in (1) was added to the above solution at once; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 10; after stirring for 5 hours, centrifugally separating the suspension, washing the suspension for 4 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 600 ℃ for 6 hours to obtain a 5% Ni/CaHAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 1 h, and reducing and activating the catalyst. After the reduction is finished, the temperature of the reactor is adjusted to 800 ℃, and the inlet gas is switched into the feed gas for reaction, wherein the feed gas has the composition (volume fraction) of 10 percent CH4、10%CO2、80%N2The reaction space velocity of the mixed gas of the three is controlled to be 200000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. The calculated conversion of methane was 94.2%, CO2The conversion rate of (2) was 92.3%, and the catalyst was operated for 240 hours without significant deactivation.
Example 2
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(2) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Mg, Mg (NO) is first prepared at a concentration of 0.3mol/L3)2Solution A and (NH) with a concentration of 0.2mol/L4)2HPO4Solution B with n (Mg) in a metering ratio2+)/n(PO4 3-) =5/3, 100mL of the B solution was added dropwise to 112 mL of the a solution under vigorous stirring in a thermostatic water bath at 60 ℃. After the dropwise addition, the pH of the solution is adjusted to 11 by using strong ammonia water, and the solution is continuously stirred for 8 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally treated at 100 ℃ for 12 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 5 times, drying at 110 ℃ overnight, and roasting at 600 ℃ for 6 h to obtain the MgHAP carrier.
(2) Preparation of MgHAP supported nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 100mL of 0.05 mol/L solution, stirring and heating the solution to 40 ℃ in a water bath kettle; then, 2.9 g of the MgHAP carrier prepared in (1) was added to the above solution at a time; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 9; after stirring for 8 hours, centrifugally separating the suspension, washing the suspension for 3 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 600 ℃ for 4 hours to obtain a 10% Ni/MgHAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 1 h, and reducing and activating the catalyst. After the reduction is finished, the inlet gas is switched into the raw material gas for reaction, the reaction is carried out at 700 ℃, and the raw material gas composition (volume fraction) is 25% CH4、25%CO2、50%N2The reaction space velocity of the mixed gas of the three is controlled to be 60000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. The calculated conversion of methane was 83.3%, CO2The conversion rate of (1) is 76.3%, the catalyst runs for 20h, the conversion rate of methane is reduced to 78%, and CO is2The conversion rate drops to 70%.
Example 3
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(1) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Zn, first, Zn (NO) is prepared at a concentration of 0.4 mol/L3)2Solution A and (NH) with a concentration of 0.2mol/L4)2HPO4Solution B with n (Mg) in a metering ratio2+)/n(PO4 3-) =5/3, 100mL of the B solution was added dropwise to 83 mL of the a solution under vigorous stirring in a thermostatic water bath at 60 ℃. After the dropwise addition, the pH of the solution is adjusted to 9 by using strong ammonia water, and the solution is continuously stirred for 6 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally treated at 100 ℃ for 16 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 3 times, drying at 110 ℃ overnight, and roasting at 750 ℃ for 4 h to obtain the ZnHAP carrier.
(2) Preparation of ZnHAP loaded nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 200mL of 0.03 mol/L solution, stirring and heating the solution to 40 ℃ in a water bath kettle; then, 2.5 g of the ZnHAP carrier prepared in (1) was added to the above solution at a time; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 9; after stirring for 8 hours, centrifugally separating the suspension, washing the suspension for 3 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 600 ℃ for 4 hours to obtain a 14% Ni/ZnHAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 3 h, and reducing and activating the catalyst. After the reduction is finished, the inlet gas is switched into the raw material gas for reaction, the reaction temperature is adjusted to 750 ℃ for reaction, and the raw material gas has the composition (volume fraction) of 40 percent CH4、40%CO2、20%N2The reaction space velocity of the mixed gas of the three is controlled to be 10000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. The initial conversion of methane calculated was 88.3%, CO2The initial conversion rate of the catalyst is 80.2 percent, the catalyst runs for 10 hours, the conversion rate of methane is reduced to 68 percent, and CO is reduced2The conversion rate is reduced to 53%.
Analysis of the reason for the faster deactivation of the catalyst may be related to the low activation capacity of the catalyst for carbon dioxide. Here, the weak carbon dioxide activation ability causes intermediate carbon species generated by methane cracking to be not removed in time, thereby causing a large amount of carbon deposition on the surface of the catalyst to be deactivated.
Example 4
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(1) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Sr, Sr (NO) is first prepared at a concentration of 0.3mol/L3)2Solution A and (NH) with a concentration of 0.4 mol/L4)2HPO4Solution B, n (Sr) in a certain ratio2+)/n(PO4 3-) =5/3, 100mL of B solution was added dropwise to 223 mL of a solution under vigorous stirring in a thermostatic water bath at 50 ℃. After the dropwise addition, the pH of the solution is adjusted to 10 by using strong ammonia water, and the solution is continuously stirred for 6 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally heated at 100 ℃ for 14 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 4 times, drying at 110 ℃ overnight, and roasting at 800 ℃ for 5 h to obtain the SrHAP carrier.
(2) Preparation of SrHAP supported nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 200mL of 0.05 mol/L solution, stirring and heating the solution to 60 ℃ in a water bath kettle; then, 8 g of the SrHAP carrier prepared in (1) was added to the above solution at once; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 11; after stirring for 5 hours, the suspension was centrifuged and washed 5 times with distilled water, and finally the resulting sample was dried overnight at 110 ℃ and calcined in a muffle furnace at 500 ℃ for 5 hours to produce 3.6% Ni/SrHAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 2 h, and reducing and activating the catalyst. After the reduction is finished, the inlet gas is switched into the raw material gas for reaction, the reaction temperature is adjusted to 850 ℃ for reaction, and the raw material gas has the composition (volume fraction) of 50 percent CH4、50%CO2、0%N2The reaction space velocity of the mixed gas of the three is controlled at 48000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. Initial conversion of methane calculated as 91.3%, CO2The initial conversion rate of the catalyst is 90.2 percent, the catalyst runs for 100 hours, the conversion rate of methane is reduced to 84.1 percent, and CO is reduced2The conversion rate is reduced to 80.9%.
Example 5
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(1) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Ca, Ca (NO) is first prepared at a concentration of 0.3mol/L3)2Solution A and (NH) with a concentration of 0.3mol/L4)2HPO4Solution B with n (Ca) in a metering ratio2+)/n(PO4 3-) =5/3, 400 mL of B solution was added dropwise to 670 mL of a solution under vigorous stirring in a thermostatic water bath at 50 ℃. After the dropwise addition, the pH of the solution is adjusted to 11 by using strong ammonia water, and the solution is continuously stirred for 10 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally treated at 140 ℃ for 20 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 200mL of distilled water for 3 times, drying at 110 ℃ overnight, and roasting at 800 ℃ for 3 hours to obtain the CaHAP carrier.
(2) Preparation of CaHAP loaded nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 100mL of 0.03 mol/L solution, stirring and heating the solution to 60 ℃ in a water bath kettle; then, 17.6 g of the CaHAP carrier prepared in (1) was added to the above solution at a time; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 11; after stirring for 4 hours, centrifugally separating the suspension, washing the suspension for 4 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 700 ℃ for 5 hours to obtain a 1% Ni/CaHAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 2 h, and reducing and activating the catalyst. After the reduction is finished, the temperature of the reactor is regulated to 850 ℃, and the inlet gas is switched into the feed gas for reaction, wherein the feed gas composition (volume fraction) is 25 percent CH4、25%CO2、50%N2The reaction space velocity of the mixed gas of the three is controlled to 24000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. ComputingConversion of methane of 91.7%, CO2The conversion rate of (A) is 90.3%, and the catalyst runs for 150h without obvious inactivation.
Example 6
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(2) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Sr + Zn, Me (Sr (NO) is first placed3)2+Zn(NO3)2) Solution A having a total concentration of 0.2mol/L (wherein Sr: zn atomic ratio =7: 1) and (NH) at a concentration of 0.3mol/L4)2HPO4Solution B, at a metering ratio of n (Me)2+)/n(PO4 3-) =5/3, 100mL of B solution was added dropwise to 250 mL of a solution under vigorous stirring in a thermostatic water bath at 40 ℃. After the dropwise addition, the pH of the solution is adjusted to 9 by using strong ammonia water, and the solution is continuously stirred for 8 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally treated at 100 ℃ for 12 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 3 times, drying at 110 ℃ overnight, and roasting at 600 ℃ for 5 h to obtain the (Sr + Zn) HAP carrier.
(2) Preparation of (Sr + Zn) HAP-loaded nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 200mL of 0.05 mol/L solution, stirring and heating the solution to 60 ℃ in a water bath kettle; then, 3.9 g of the SrHAP carrier prepared in (1) was added to the above solution at once; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 11; after stirring for 5 hours, centrifugally separating the suspension, washing the suspension for 5 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 500 ℃ for 5 hours to obtain a 15% Ni/(Sr + Zn) HAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 3 h, and reducing and activating the catalyst. After the reduction is finished, the inlet gas is switched into the raw material gas for reaction, the reaction temperature is adjusted to 800 ℃ for reaction, and the raw material gas has the composition (volume fraction) of 10 percent CH4、10%CO2、80%N2The reaction space velocity of the mixed gas of the three is controlled to be 70000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. The initial conversion of methane was calculated to be 92.3%, CO2The initial conversion rate of the catalyst is 90.0 percent, the catalyst runs for 30 hours, the conversion rate of methane is reduced to 89.1 percent, and CO is reduced2The conversion rate is reduced to 85.3%.
Example 7
1. Preparation of hydroxyapatite (MeHAP) supported Ni catalyst
(3) Preparation of hydroxyapatite (MeHAP) carrier material
When Me is Mg + Ca, Me (Ca (NO) is first prepared3)2+Mg(NO3)2) Solution A having a total concentration of 0.3mol/L (wherein Mg: ca atomic ratio =1: 2) and (NH) at a concentration of 0.2mol/L4)2HPO4Solution B, at a metering ratio of n (Me)2+)/n(PO4 3-) =5/3, 100mL of B solution was added dropwise to 111 mL of a solution under vigorous stirring in a thermostatic water bath at 60 ℃. After the dropwise addition, the pH of the solution is adjusted to 10 by using strong ammonia water, and the solution is continuously stirred for 6 hours; the resulting white suspension was then transferred to a reaction kettle and hydrothermally treated at 120 ℃ for 24 h. And naturally cooling, carrying out vacuum filtration and recovery on the obtained white precipitate, washing with 50mL of distilled water for 5 times, drying at 110 ℃ overnight, and roasting at 800 ℃ for 3 h to obtain the (Mg + Ca) HAP carrier.
(2) Preparation of (Mg + Ca) HAP-Supported Nickel-based catalyst
(A) Weighing stoichiometric ratio of Ni (NO)3)2·6H2Dissolving O in distilled water to obtain Ni2+Taking 100mL of 0.04 mol/L solution, stirring and heating the solution to 60 ℃ in a water bath kettle; then, the user can use the device to perform the operation,adding 3.35 g of SrHAP carrier prepared in the step (1) into the solution in one step; subsequently, saturated Na was pumped through a peristaltic pump2CO3Dropwise adding the solution into the suspension, and detecting in real time by using a pH meter until the pH value is approximately equal to 10; after stirring for 8 hours, centrifugally separating the suspension, washing the suspension for 5 times by using distilled water, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 400 ℃ for 4 hours to obtain a 7% Ni/(Mg + Ca) HAP catalyst;
(B) tabletting, crushing and screening the raw catalyst powder prepared in the step (A) into particles of 20-40 meshes to obtain the catalyst.
2. Test for catalytic Performance
0.4 g of the catalyst is taken and placed in a self-built fixed bed reactor. 10 vol.% of H was added before the reaction2Heating the mixed gas/Ar (flow: 30 mL min-1) to 700 ℃ within 100 min, keeping the temperature for 2 h, and reducing and activating the catalyst. After the reduction is finished, the inlet gas is switched into the raw material gas for reaction, the reaction temperature is adjusted to 850 ℃ for reaction, and the raw material gas has the composition (volume fraction) of 40 percent CH4、40%CO2、20%N2The reaction space velocity of the mixed gas of the three is controlled to be 120000 mL/(g)catH). And (3) carrying out on-line detection on reaction outlet gas by using a gas chromatography after the reaction outlet gas passes through a cold trap. The initial conversion of methane calculated was 95.9%, CO2The initial conversion rate of the catalyst is 94.1 percent, the catalyst runs for 240 hours, the conversion rate of methane is reduced to 94.9 percent, and CO is reduced2The conversion rate is reduced to 93.3%.
Claims (5)
1. A nickel-supported hydroxyapatite catalyst is characterized in that: the catalyst comprises a hydroxyapatite carrier MeHAP and an active metal Ni, wherein the mass percentage of the hydroxyapatite carrier MeHAP is as follows: 85.0-99.0%, Ni: 1-15%, wherein Me in MeHAP material = one or more than two elements of Mg, Ca, Sr and Zn, and the atomic ratio of Me to P is controlled at 1.67.
2. A method for preparing the nickel-on-hydroxyapatite catalyst according to claim 1, comprising the steps of:
(1) preparation of MeHAP support Material
When Me is Ca, Ca (NO) is first prepared in a concentration of 0.2 to 0.4 mol/L3)2Solution A and (NH) with a concentration of 0.2-0.4 mol/L4)2HPO4Solution B with molar ratio of n (Ca)2+)/n(PO4 3-) =5/3, adding the solution B dropwise into the solution A in a constant-temperature water bath at 40-60 ℃ under strong stirring; after the dropwise addition is finished, the pH value of the solution is adjusted to 9-11 by using strong ammonia water, and the solution is continuously stirred for 6-10 h; then transferring the obtained white suspension into a reaction kettle, and carrying out hydrothermal treatment at 100-140 ℃ for 12-24 h; naturally cooling, carrying out vacuum filtration on the obtained white precipitate, washing with 50mL of distilled water for 3-5 times, drying at 110 ℃ overnight, and roasting at 600-800 ℃ for 3-6 h to obtain a CaHAP carrier; the preparation of other metal cation materials is similar to the preparation process of CaHAP;
(2) preparation of nickel-based catalyst loaded with hydroxyapatite
Firstly, preparing a catalyst by a deposition precipitation method: the method comprises weighing a certain amount of Ni (NO)3)2·6H2Dissolving O in distilled water to prepare Ni2+Heating the solution with the concentration of 0.03-0.05 mol/L to 40-60 ℃ in a water bath kettle by stirring; then, adding the CaHAP carrier prepared in the step (1) into the solution at one time to obtain suspension; the amount of Ni used in the solution herein is calculated by controlling the amount thereof to be in the range of 1 to 15 wt%; subsequently, saturated Na was pumped through a peristaltic pump2CO3Adding the solution into the suspension drop by drop until the pH is 9-11; after stirring for 4-8 h, centrifugally separating the suspension, washing the suspension with distilled water for 3-5 times, finally drying the obtained sample at 110 ℃ overnight, and roasting the sample in a muffle furnace at 400-600 ℃ for 3-6 h;
and secondly, tabletting, crushing and screening the raw catalyst powder prepared in the step I into particles of 20-40 meshes to obtain the catalyst.
3. Use of the nickel hydroxyapatite-supported catalyst according to claim 1 in the preparation of synthesis gas by dry reforming of methane and carbon dioxide.
4. According to the claimsThe use according to claim 3, characterized in that it comprises the following steps: the catalytic reaction is carried out in a fixed bed reactor; the catalyst was first at 10% H2Reduction treatment for 1-3 h under Ar; when the catalytic reaction is carried out, the molar ratio of the raw material methane to the carbon dioxide is 1:1, the volume fraction of the methane is 10-50%, the volume fraction of the carbon dioxide is 10-50%, the volume fraction of the nitrogen is 0-80%, and the volume space velocity is 10000-120000 mL/(g-ncatH), controlling the reaction temperature at 600-850 ℃ and the reaction pressure at normal pressure.
5. Use according to claim 3, characterized in that: the conversion rate of methane and carbon dioxide can reach more than 95 percent.
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