CN117000231A - Catalyst, reactor and method for preparing carbon dioxide - Google Patents
Catalyst, reactor and method for preparing carbon dioxide Download PDFInfo
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- CN117000231A CN117000231A CN202210473044.0A CN202210473044A CN117000231A CN 117000231 A CN117000231 A CN 117000231A CN 202210473044 A CN202210473044 A CN 202210473044A CN 117000231 A CN117000231 A CN 117000231A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 229920000034 Plastomer Polymers 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000012495 reaction gas Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002991 molded plastic Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of methane oxidative coupling reaction, and discloses a catalyst, a reactor and a method for preparing carbon dioxide. The catalyst provided by the invention has high reaction activity, high methane conversion rate and C 2 The preferred preparation method of the invention can further improve C 2 Hydrocarbon single pass yield. At the bookUnder the preferred reaction process conditions of the invention, the methane conversion and C can be obtained according to the preferred reaction conditions of the invention using the reactor of the invention 2 The hydrocarbon selectivity reaches over 40 percent.
Description
Technical Field
The invention relates to the technical field of methane oxidative coupling reaction, in particular to a catalyst, a reactor and a method for preparing carbon dioxide.
Background
Ethylene is a basic raw material for petrochemical industry, and the yield, the production scale and the production technology are important marks for measuring the level of the petrochemical industry in one country. The capacity and production continue to increase as the worldwide demand for ethylene increases. Ethylene is currently mainly from naphtha steam cracking. However, since the naphtha source of the petroleum processing route is single and is greatly influenced by petroleum economy and price, a new route for preparing ethylene from non-petroleum resources such as methane is developed, the raw material source of ethylene production is expanded, and the dependence on petroleum resources is reduced, so that the method has important academic significance and application value.
Methane Oxidative Coupling (OCM) reactions are a technological route to the activation of methane under aerobic conditions and the direct production of ethane and ethylene. The concept of oxidative coupling of methane was first proposed by Keller et al in 1982 and has been in the last 40 years. Although methane oxidative coupling reactions have been studied for a long time, there is currently no successful example of industrial application worldwide. The key to the current application is how to achieve higher C 2 Hydrocarbon single pass yield. However, the existing catalyst and the production mode C 2 The single pass yield of hydrocarbon is still not ideal and cannot meet the requirements of industrial application.
Disclosure of Invention
The invention aims to overcome the defect of C in the prior art of methane oxidative coupling reaction 2 The problems of non-ideal single-pass yield of hydrocarbon and the like, and provides a catalyst, a reactor and a method for preparing carbon dioxide. The catalyst provided by the invention has high reaction activity, high methane conversion rate and C 2 The preferred preparation method of the invention can further improve C 2 Hydrocarbon single pass yield.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing a catalyst for preparing a carbon dioxide by directly oxidizing methane, the method comprising mixing and molding a cristobalite carrier, an active component precursor, a molding agent and water to obtain a molded plastic body, and then sequentially performing first drying and first calcination on the molded plastic body to obtain the catalyst for preparing a carbon dioxide by directly oxidizing methane;
wherein the active component precursor comprises a tungsten precursor and/or a manganese precursor.
The second aspect of the invention provides a catalyst for preparing carbon dioxide by directly oxidizing methane, wherein the catalyst is prepared by the method;
alternatively, the catalyst comprises a cristobalite support and an active component selected from W, mn and alkali metals supported on the cristobalite support.
The invention provides a reactor for oxidative coupling reaction of methane, which comprises a reactor cavity made of quartz, and a catalyst and a filler filled in the cavity;
wherein the catalyst is the catalyst as described above;
the particle size of the filler is not more than 1/3 of the catalyst size.
In a fourth aspect, the invention provides a process for preparing a carbon dioxide comprising reacting a carbon dioxide containing CH 4 And O 2 Introducing the reaction gas into a reactor for performing methane oxidative coupling reaction;
wherein the reactor is the reactor as described above.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The catalyst provided by the invention is a molded catalyst, can be directly applied to industrial production, and avoids catalysis in the catalyst molding processInfluence of the chemical effect. In addition, the catalyst has high catalytic activity, high methane conversion rate and C 2 High hydrocarbon yield, and the like.
(2) The reactor provided by the invention is filled with the catalyst and the filler simultaneously in the reactor cavity, and the gap in the reactor cavity is further filled with the filler with small particle diameter, so that the adverse effect of the free radical elimination reaction on the OCM reaction effect is reduced, and the C is further improved 2 Yield and selectivity of hydrocarbons.
(3) The molded catalyst provided by the invention is matched with the catalyst C provided by the invention 2 The hydrocarbon preparation method has the characteristics of clean production, low-cost and easily-obtained raw materials, low processing cost, simplified process, convenience in realizing industrial production and the like.
(4) The molded catalyst provided by the invention is matched with the catalyst C provided by the invention 2 Hydrocarbon production process capable of obtaining higher C 2 Hydrocarbon yield, and has good catalytic stability. It has been demonstrated in a pilot reaction that under the preferred reaction process conditions, methane conversion and C can be obtained using the reactor of the present invention, according to the preferred reaction conditions of the present invention 2 The hydrocarbon selectivity reaches over 40 percent.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, "first" and "second" in "first drying", "second drying", "first firing", "second firing" are used only for descriptive convenience to distinguish between drying and firing operations in different operation steps, and are not limited to specific operation modes, sequences, and the like.
In the present invention, "C 2 The hydrocarbon "is a shorthand for" carbo-dio ",the two meanings are the same and can be used interchangeably.
The invention provides a method for preparing a carbon dioxide catalyst by directly oxidizing methane, which comprises the steps of mixing and forming a cristobalite carrier, an active component precursor, a forming agent and water to obtain a formed plastic body, and sequentially carrying out first drying and first roasting on the formed plastic body to obtain the carbon dioxide catalyst by directly oxidizing methane;
wherein the active component precursor comprises a tungsten precursor and/or a manganese precursor.
In the method provided by the present invention, there is no particular limitation on the active ingredient precursor. According to a preferred embodiment of the invention, the active ingredient precursor is a water-soluble acid and/or water-soluble salt of the active ingredient. Such as tungstic acid (salt), nitrate, etc. In order to avoid the influence of the introduction of foreign elements into the catalyst and the influence on the catalytic performance/stability of the catalyst, the method provided by the invention does not adopt salts containing other elements such as sulfate, chloride and the like of active components as active component precursors. According to a preferred embodiment of the present invention, wherein the active component precursor is selected from at least one of sodium tungstate, potassium tungstate, ammonium tungstate, and manganese nitrate.
In the method provided by the present invention, the amount of the active ingredient precursor is not particularly limited. To obtain better catalytic activity (e.g. higher methane conversion, C 2 Better hydrocarbon selectivity, etc.), according to a preferred embodiment of the present invention, wherein, compared to 100 parts by weight of the catalyst in SiO 2 The amount of the carrier and the tungsten precursor is 5-25 parts by weight. Preferably 5 to 20 parts by weight. More preferably 7 to 12 parts by weight.
According to a preferred embodiment of the invention, wherein the SiO is present in an amount of 100 parts by weight 2 The amount of the manganese precursor is 5-30 parts by weight of the carrier. Preferably 5 to 28 parts by weight. More preferably 8 to 15 parts by weight.
In the present invention, the molding agent is not particularly limited, and may be any agent for catalyst molding added in the preparation process of the OCM molding catalyst existing in the art, and the specific kind and amount thereof may be adjusted according to the actual situation.
According to a preferred embodiment of the invention, the shaping agent is selected from extrusion aids and/or binders.
Preferably, the extrusion aid is selected from sesbania powder and/or starch.
Preferably, the binder is selected from water glass. Preferably water glass with specific gravity of 1.35-1.45 and modulus of 1.5-2.
According to a preferred embodiment of the invention, wherein the SiO is present in an amount of 100 parts by weight 2 The carrier and the forming agent are calculated in 5-45 weight parts. The "amount of the molding agent" refers to the total amount of all molding agents (e.g., binders, extrusion aids, etc.) employed.
Preferably, the amount of SiO is greater than 100 parts by weight 2 The amount of the carrier and the extrusion aid is 5-25 parts by weight. Preferably 5 to 20 parts by weight. More preferably 8 to 12 parts by weight.
Preferably, the amount of SiO is greater than 100 parts by weight 2 The carrier and the binder are used in an amount of 5 to 20 parts by weight. Preferably 5 to 18 parts by weight. More preferably 8 to 10 parts by weight.
According to a preferred embodiment of the invention, wherein the SiO is present in an amount of 100 parts by weight 2 The total amount of water used is 120-180 parts by weight based on the carrier. "total amount of water" refers to the total amount of water used during mixing, including the water used to formulate the active ingredient precursor solution, as well as the water added during mixing.
According to a preferred embodiment of the invention, the shaping is performed in such a way that the dimensions of the shaped plastomer are: 3-7mm in diameter and 3-6mm in length. Preferably, the shaped plastomer has an aspect ratio of 1:1 to 2. For example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, or any intermediate value of any two ratios may be used.
In the methods provided herein, the mixing may be performed in any manner known in the art. In order to uniformly mix the raw materials and to facilitate extrusion into strips (molding) of the plastomer viscosity obtained by the subsequent kneading treatment, so that the molded plastomer is more suitable for subsequent drying and calcination treatment and is more suitable for forming a molded catalyst with better specific surface area, pore structure and strength, preferably, the mixing process can be carried out by adopting grinding, sieving, mixing, stirring, mixing and the like, and then kneading the mixed materials. Stirring mixing is preferably employed, and for example, mixing may be carried out under stirring conditions of 50 to 150 rpm. Further, in order to obtain a better kneading effect, the kneading operation in the present invention may be carried out for 15 to 60 minutes.
In the present invention, the molding method is not particularly limited. According to a preferred embodiment of the invention, the shaping is selected from extrusion and/or spray shaping, preferably extrusion.
The inventor of the present invention found in the research process that when the OCM molded catalyst is prepared by extrusion molding, the extrusion molding of the plastomer into a rod can be facilitated by adopting specific molding conditions, and the molded catalyst with better mechanical strength, specific surface area, pore structure, etc. can be obtained.
According to a preferred embodiment of the present invention, wherein the molding conditions include: the extrusion speed is 100-500rpm, the temperature is 10-30 ℃, and the pressure is 10-30MPa.
In order to further increase the strength of the shaped catalyst, according to a preferred embodiment of the invention, the first drying is selected from drying and/or vacuum drying, preferably by means of stepwise drying.
Preferably, the step drying mode comprises:
(1) And (3) drying at low temperature: the temperature is 20-40 ℃ and the time is 2-6h;
(2) And (5) high-temperature drying: the temperature is 100-160 ℃ and the time is 4-10h.
According to a preferred embodiment of the present invention, the first firing means includes: raising the temperature to 750-900 ℃ at a heating rate of 4-10 ℃/min, and roasting at the temperature for 6-10h.
According to a preferred embodiment of the present invention, wherein the method further comprises a step of preparing a cristobalite carrier: siO is made of 2 And sodium salt (in the presence of water) and then subjected to secondary drying and secondary calcination.
Any SiO known in the art as being useful for the preparation of OCM catalysts (supports) 2 Are applicable to the present invention, and can be related products obtained by commercial use or self-preparation according to the prior art. Preferably, the SiO 2 SiO with average particle diameter of 0.05-0.18mm 2 Particles (e.g., amorphous spherical particles). More preferably 0.08-0.15mm.
Preferably, the sodium salt is selected from sodium nitrate and/or sodium tungstate.
Preferably, the SiO 2 And sodium salt in a weight ratio of 10-50:1.
preferably, the second drying conditions include: the temperature is 80-150 ℃ and the time is 5-10h.
Preferably, the conditions of the second firing include: raising the temperature to 800-900 ℃ at a heating rate of 3-10 ℃/min, and roasting at the temperature for 5-12h.
The second aspect of the invention provides a catalyst for preparing carbon dioxide by directly oxidizing methane, wherein the catalyst is prepared by the method;
alternatively, the catalyst comprises a cristobalite support and an active component selected from W, mn and alkali metals supported on the cristobalite support.
Preferably, in the catalyst, siO in a cristobalite carrier is used 2 W is present in an amount of 5 to 18.5 wt.%, based on the weight of the composition. Preferably 5.5 to 15% by weight. More preferably 8 to 10% by weight.
Preferably, in the catalyst, siO in a cristobalite carrier is used 2 The Mn content is 1-10 wt.%, based on the weight of the composition. Preferably 1.5 to 9% by weight. More preferably 2 to 4% by weight.
Preferably, in the catalyst, siO in a cristobalite carrier is used 2 The alkali metal content is 0.5-5 wt.%, based on the weight of the composition. Preferably 0.8 to 4% by weight. More preferably 1.5 to 3% by weight.
It is to be noted here that the above content of W and alkali metal is the total content of W and alkali metal supported on the cristobalite carrier and (possibly present in) the cristobalite carrier.
It should be specifically noted that the existence form of W in the catalyst provided by the invention can be W simple substance or tungstate (such as tungstic acid and/or tungstate), and the W is written as W in the invention only for convenience of description and calculation of the content and proportion of the active components.
Preferably, the catalyst has the following dimensions: 3-7mm in diameter and 3-6mm in length. Preferably the aspect ratio of the catalyst is from 1:1 to 2.
Preferably, the mechanical strength of the catalyst is not less than 20N/particle. Preferably 25-30N/granule.
The invention provides a reactor for oxidative coupling reaction of methane, which comprises a reactor cavity made of quartz, and a catalyst and a filler filled in the cavity;
wherein the catalyst is the catalyst as described above;
the particle size of the filler is not more than 1/3 of the catalyst size.
It should be noted that, when the catalyst outer shape is a regular sphere, the catalyst size means its diameter, and when the catalyst outer shape is not a sphere, the catalyst size means its equivalent diameter. Equivalent diameter means that a particle that is not spherical is converted to a sphere in some equivalent way, and the diameter of this converted sphere is used to represent the particle size of the particle. Common equivalent methods include an equal volume method, an equal surface area method, an equal projected perimeter method, and the like. The invention is not particularly limited to the specific choice of the equivalent method, and can be chosen according to actual conditions and needs.
The shape of the filler is not particularly limited, and may be any shape such as spherical particles, round plate-like particles, or amorphous particles. The present invention screens out the filler suitable for filling in the reactor provided by the present invention by selecting a screen that meets the above particle size conditions according to the size of the catalyst.
According to a preferred embodiment of the present invention, wherein the aspect ratio of the reactor cavity is 15-40, and the ratio of the inner diameter of the reaction cavity to the catalyst size is 5-8:1.
according to a preferred embodiment of the invention, the filler particle size is 1/10-1/3 of the size of the catalyst.
Preferably, the filler is selected from alpha-Al having a particle size of not more than 1mm 2 O 3 . That is, the alpha-Al 2 O 3 Can pass through a screen mesh of 18 meshes or more.
More preferably, the filler is selected from alpha-Al with a particle size of 0.4-1mm 2 O 3 . That is, the alpha-Al 2 O 3 Can pass through an 18 mesh screen but cannot pass through a 50 mesh screen.
Preferably, the weight ratio of the catalyst to the filler filled in the reactor cavity is 10-20:1.
A fourth aspect of the invention provides a process for preparing a carbon dioxide comprising reacting a hydrocarbon containing CH 4 And O 2 Introducing the reaction gas into a reactor for performing methane oxidative coupling reaction;
wherein the reactor is the reactor as described above.
According to a preferred embodiment of the present invention, wherein the CH 4 And O 2 The volume ratio of (2) to (6) to (1).
According to a preferred embodiment of the present invention, wherein the conditions for the oxidative coupling reaction of methane include: the reaction temperature of the catalyst section is 750-850 ℃, and the space-time of the reaction gas is 9000-15000 mL.g -1 ·h -1 。
Preferably, the reaction time of the oxidative coupling reaction of methane is 0.5 to 25 hours, preferably 5 to 20 hours.
The present invention will be described in detail by examples. It should be understood that the following examples are illustrative only and are not intended to limit the invention.
In the following examples, siO 2 Is purchased from Qingdao ocean chemical plant and is amorphous spherical particle with average particle diameter of 0.1 + -0.05 mmAnd (5) granulating. Tianfen (soluble sesbania powder bulk powder) was purchased from Hubei Yuyi biotechnology limited. The chemicals used in the remaining examples, unless specifically stated, were purchased from regular chemical suppliers and were chemically pure in purity.
In the following examples, shaped catalyst preparation was carried out using a twin screw extruder (type F-26) from the general technical industry Co., ltd. Of the university of North China.
Example 1
(1) Preparing a cristobalite carrier: adding 6g of sodium tungstate into 150g of distilled water, completely dissolving, adding 100g of SiO 2 After 2 hours of impregnation, the mixture was dried at 120℃for 6 hours. And (3) placing the dried product in a muffle furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the air atmosphere, and roasting for 10 hours to obtain the carrier A1.
(2) Preparing a molded plastomer:
(a) The carrier A1 was mixed with 8g of sodium tungstate, 10g of manganese nitrate, 10g of water glass (specific gravity 1.35, modulus 1.5), 10g of starch and 25g of deionized water (stirring at 100rpm for 35 min), to obtain a plastomer B1.
(b) The plastic body B1 was passed through a 4mm diameter orifice plate by means of a bar extruder, and a bar-shaped solid cylinder was extruded at an extrusion rate of 100rpm and a temperature of 30℃and a pressure of 15MPa, and cut into pellets having a length of 3mm, to obtain a molded plastic body C1.
(3) Preparing a formed catalyst:
drying the molded plastomer C1:
(A) First drying: the temperature is 20 ℃ and the time is 6 hours;
(B) And (3) second drying: the temperature is 100 ℃ and the time is 8 hours, and the dry product is obtained.
And (3) placing the dried product in a muffle furnace, heating to 750 ℃ at a heating rate of 4 ℃/min under the air atmosphere, and roasting for 10 hours. A shaped catalyst-1 was obtained.
Methane oxidative coupling reaction: the catalytic reactor was a quartz tube of 20mm inside diameter and 800mm length, 10g of the molded catalyst-1 and 1g of alpha-Al of 0.4.+ -. 0.05mm particle diameter were mixed 2 O 3 (can pass through a 35-mesh sieve, but can not pass through a 50-mesh sieve) and is filled at the catalyst bed of the reaction tube.
The feed gas consisting of methane and oxygen (volume ratio is 3:1) is mixed and introduced at the top end of the reaction tube. The reaction pressure was the pressure generated by the raw material itself (0.02 MPa). The reaction temperature of the catalyst section is controlled to be 805 ℃, and the hourly space velocity of the reaction gas is 9000 mL.g -1 ·h -1 。
Example 2
(1) Preparing a cristobalite carrier: adding 3g sodium tungstate into 160g distilled water, completely dissolving, adding 100g SiO 2 After 2 hours of impregnation, the mixture was dried at 120℃for 6 hours. And (3) placing the dried product in a muffle furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the air atmosphere, and roasting for 10 hours to obtain the carrier A2.
(2) Preparing a molded plastomer:
(a) The carrier A2 was mixed with 6g of sodium tungstate, 5g of manganese nitrate, 5g of water glass (specific gravity 1.4, modulus 1.8), 5g of starch and 10g of deionized water (stirring at 60rpm for 55 min), to obtain a plastomer B2.
(b) The plastic body B2 was extruded into a solid cylinder in a long shape by a bar extruder through an orifice plate having a diameter of 5mm at an extrusion rate of 200rpm at a temperature of 10℃and a pressure of 15MPa, and cut into particles having a length of 4mm to obtain a molded plastic body C2.
(3) Preparing a formed catalyst:
drying the molded plastomer C2:
(A) First drying: the temperature is 40 ℃ and the time is 4 hours;
(B) And (3) second drying: the temperature is 120 ℃ and the time is 6 hours, and the dry product is obtained.
And (3) placing the dried product in a muffle furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under the air atmosphere, and roasting for 8 hours. A shaped catalyst-2 was obtained.
Methane oxidative coupling reaction: the catalytic reactor was a quartz tube with an inner diameter of 25mm and a length of 800mm, and 10g of the molded catalyst-2 and 0.7g of alpha-Al with a particle diameter of 0.6.+ -. 0.05mm were mixed 2 O 3 (can pass through a 25-mesh sieve, but can not pass through a 35-mesh sieve) and is filled at the catalyst bed of the reaction tube.
Mixing and introducing raw gas consisting of methane and oxygen (volume ratio is 2.5:1) at the top end of a reaction tube. The reaction pressure was the pressure generated by the raw material itself (0.020 MPa). Controlling the reaction temperature of the catalyst section to 790 ℃ and the hourly space velocity of the reaction gas to 10000mL g -1 ·h -1 。
Example 3
(1) Preparing cristobalite: 9g of sodium tungstate is added into 120g of distilled water, and 100g of SiO is added after complete dissolution 2 After 2 hours of immersion, drying for 6 hours at 120 ℃, placing the dried product in a muffle furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under air atmosphere, and roasting for 10 hours to obtain A3.
(2) Preparing a molded plastomer:
(a) The carrier A3 was mixed with 15g of sodium tungstate, 16g of manganese nitrate, 18g of water glass (specific gravity 1.45, modulus 2), 15g of starch and 10g of deionized water (stirring at 120rpm for 45 min), to obtain a plastomer B3.
(b) The plastic body B3 was extruded into a solid cylinder in a long shape by a bar extruder through an orifice plate having a diameter of 3mm at an extrusion rate of 300rpm at a temperature of 20℃and a pressure of 15MPa, and cut into particles having a length of 3mm to obtain a molded plastic body C3.
(3) Preparing a formed catalyst:
drying the molded plastomer C3:
(A) First drying: the temperature is 30 ℃ and the time is 6 hours;
(B) And (3) second drying: the temperature is 150 ℃ and the time is 4 hours, and the dry product is obtained.
The dried product is placed in a muffle furnace, heated to 880 ℃ at a heating rate of 6 ℃/min under the air atmosphere, and baked for 10 hours. A shaped catalyst-3 was obtained.
Methane oxidative coupling reaction: the catalytic reactor was a quartz tube with an inner diameter of 20mm and a length of 700mm, and 10g of the molded catalyst-3 and 0.5g of alpha-Al with a particle diameter of 0.8.+ -. 0.05mm were mixed 2 O 3 (can pass through a 20-mesh sieve, but can not pass through a 24-mesh sieve) and is filled at the catalyst bed of the reaction tube.
The feed gas consisting of methane and oxygen (volume ratio is 6:1) is mixed and introduced at the top end of the reaction tube. The reaction pressure was the pressure generated by the raw material itself (0.020 MPa). Controlling the reaction temperature of the catalyst section to be 830 ℃ and the hourly space velocity of the reaction gas to be15000mL·g -1 ·h -1 。
Example 4
(1) Preparing a cristobalite carrier: adding 3g sodium tungstate into 120g distilled water, completely dissolving, adding 100g SiO 2 After 2 hours of immersion, drying for 6 hours at 120 ℃, placing the dried product in a muffle furnace, heating to 850 ℃ at a heating rate of 5 ℃/min under air atmosphere, and roasting for 10 hours to obtain a carrier A4.
(2) Preparing a molded plastomer:
(a) The carrier A1 was mixed with 20g of sodium tungstate, 28g of manganese nitrate, 12g of water glass (specific gravity 1.4, modulus 1.6), 18g of sesbania powder and 10g of deionized water (stirring at 100rpm for 35 min), to obtain a plastomer B4.
(b) The plastic body B4 was extruded into a solid cylinder in a long shape by a bar extruder through an orifice plate having a diameter of 5mm at an extrusion rate of 150rpm at a temperature of 30℃and a pressure of 15MPa, and cut into particles having a length of 3mm to obtain a molded plastic body C4.
(3) Preparing a formed catalyst:
drying the shaped plastomer C4:
(A) First drying: the temperature is 20 ℃ and the time is 6 hours;
(B) And (3) second drying: the temperature is 120 ℃ and the time is 8 hours, and the dry product is obtained.
And (3) placing the dried product in a muffle furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the air atmosphere, and roasting for 10 hours. Shaped catalyst-4 was obtained.
Methane oxidative coupling reaction: the catalytic reactor was a quartz tube with an inner diameter of 25mm and a length of 900mm, 10g of the molded catalyst-4 and 0.8g of alpha-Al with a particle diameter of 0.9.+ -. 0.05mm were mixed 2 O 3 (can pass through an 18-mesh sieve, but can not pass through a 20-mesh sieve) and is filled at the catalyst bed of the reaction tube.
The feed gas consisting of methane and oxygen (volume ratio is 4:1) is mixed and introduced at the top end of the reaction tube. The reaction pressure was the pressure generated by the raw material itself (0.020 MPa). The reaction temperature of the catalyst section is controlled to be 810 ℃, and the hourly space velocity of the reaction gas is 12000 mL.g -1 ·h -1 。
Example 5
The procedure of example 1 was followed, except that in step (a), the amount of starch used was 40g, and the remaining steps and operations were the same as in example 1. A shaped catalyst-5 was obtained.
The methane oxidative coupling reaction was carried out using the molded catalyst-5 under the same conditions and in the same manner as in example 1.
Example 6
The procedure of example 1 was employed, except that in step (b), the amount of water glass used was 40g, and the other steps and operations were the same as those in example 1. Shaped catalyst-6 was obtained.
The methane oxidative coupling reaction was carried out using the molded catalyst-6 under the same conditions and in the same manner as in example 1.
Example 7
The molded catalyst-1 is adopted to carry out methane oxidative coupling reaction according to the following conditions: the same catalytic reactor as in example 1 was used, in which only 10g of the molded catalyst-1 was packed, and no α -Al was packed 2 O 3 . The other conditions and operations were the same as in example 1.
Example 8
The molded catalyst-1 is adopted to carry out methane oxidative coupling reaction according to the following conditions: 10g of the shaped catalyst-1 and 1g of alpha-Al having a particle size of 0.1.+ -. 0.05mm were reacted in the same catalytic reactor as in example 1 2 O 3 (can pass through a 120-mesh sieve, but can not pass through a 170-mesh sieve) and are uniformly mixed and filled at the catalyst bed layer of the reaction tube. The other conditions and operations were the same as in example 1.
Example 9
The molded catalyst-1 is adopted to carry out methane oxidative coupling reaction according to the following conditions: 10g of the shaped catalyst-1 and 1g of alpha-Al having a particle size of 2.+ -. 0.05mm were reacted in the same catalytic reactor as in example 1 2 O 3 (can pass through an 8-mesh sieve, but can not pass through a 12-mesh sieve) and are uniformly mixed and filled at the catalyst bed layer of the reaction tube. The other conditions and operations were the same as in example 1.
Example 10
The methane oxidative coupling reaction is carried out by using the formed catalyst-1 according to the following conditions: 10g of the shaped catalyst-1 and 3g of alpha-Al having a particle size of 0.4.+ -. 0.05mm were reacted in the same catalytic reactor as in example 1 2 O 3 (can pass through a 35-mesh sieve, but can not pass through a 50-mesh sieve) and are uniformly mixed and filled at the catalyst bed layer of the reaction tube. The other conditions and operations were the same as in example 1.
Example 11
The method of example 1 was used, except that the specific gravity of the water glass used in step (a) was 1.45 and the modulus was 2.8. The other conditions and operations were the same as in example 1, to obtain a molded catalyst-7.
The methane oxidative coupling reaction was carried out using the molded catalyst-7 under the same conditions and in the same manner as in example 1.
Example 12
The method of example 1 was used, except that an equal weight of manganese sulfate was used instead of manganese nitrate. The other conditions and the operation were the same as in example 1, to obtain a molded catalyst-8.
The methane oxidative coupling reaction was carried out using the molded catalyst-8 under the same conditions and in the same manner as in example 1.
Comparative example 1
The procedure of example 1 was employed, except that 100g of SiO was directly reacted without step (1) 2 Is mixed with 14g of sodium tungstate, 10g of manganese nitrate, 10g of water glass, 10g of starch and 175g of deionized water. The remaining steps and operations were the same as in example 1. A shaped catalyst-9 was obtained.
The methane oxidative coupling reaction was carried out using the molded catalyst-9 under the same conditions and in the same manner as in example 1.
Test example 1
The content of the active component in the shaped catalysts obtained in the above examples and comparative examples was calculated by the amount of the raw materials, ignoring trace impurities. The mechanical strength of the molded catalysts obtained in the above examples and comparative examples was measured by a catalyst particle strength tester (50 were randomly selected for measurement, respectively, and averaged). Adsorption isotherm full analysis was performed using ASAP2020 fully automatic physical and chemical adsorption Analyzer from MICromerites instruments, USA, according to isotherm metersThe specific surface areas of the molded catalysts obtained in the above examples and comparative examples were calculated. The results are detailed in Table 1. Wherein the content of the active component is relative to SiO in the carrier 2 Is defined as weight percent.
TABLE 1
* In catalyst-8, relative to SiO in the carrier 2 Contains 3.39 wt% S.
Test example 2
The components and contents of the collected reaction products of the above examples and comparative examples were analyzed by a gas chromatograph (Agilent company model 7890A), and methane conversion and C were calculated by the following formula 2 Hydrocarbon selectivity, CO X Selectivity, C 2 Hydrocarbon yield. The results are detailed in Table 2 (values in the tables are averages over the stable reaction time).
Methane conversion = amount of methane consumed by the reaction/initial amount of methane x 100%
Ethylene selectivity = amount of methane consumed by ethylene produced/total amount of methane consumed x 100%
Ethane selectivity = amount of methane consumed by ethane produced/total amount of methane consumed x 100%
C 2 Hydrocarbon selectivity = ethane selectivity + ethylene selectivity
CO X (CO+CO 2 ) Selectivity = CO and CO produced 2 Total methane consumption x 100% of total methane consumption
C 2 Hydrocarbon yield = methane conversion x (ethane selectivity + ethylene selectivity)
TABLE 2
* The stabilization reaction time is determined by the reactivity of the catalyst (methane conversion and C 2 Hydrocarbon selectivity) determination as to methane conversion and C 2 If any one of the hydrocarbon selectivities is continuously decreased (the decrease amount reaches or exceeds 5%), the reaction is stopped, and the time between the start of the reaction and the stop of the reaction is the stable reaction time.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The method for preparing the catalyst for preparing the carbon dioxide by directly oxidizing methane is characterized by comprising the steps of mixing and forming a cristobalite carrier, an active component precursor, a forming agent and water to obtain a formed plastic body, and then sequentially carrying out first drying and first roasting on the formed plastic body to obtain the catalyst for preparing the carbon dioxide by directly oxidizing methane;
wherein the active component precursor comprises a tungsten precursor and/or a manganese precursor.
2. The method of claim 1, wherein the active component precursor is selected from at least one of sodium tungstate, potassium tungstate, ammonium tungstate, and manganese nitrate;
and/or the forming agent is selected from extrusion aids and/or binders;
preferably, the extrusion aid is selected from sesbania powder and/or starch;
preferably, the binder is selected from water glass, preferably water glass having a specific gravity of 1.35-1.45 and a modulus of 1.5-2.
3. The method according to claim 1, wherein the amount of SiO is greater than 100 parts by weight 2 The amount of the carrier and the tungsten precursor is 5-25 parts by weight, preferably 5-20 parts by weight;
and/or, in terms of SiO, in relation to 100 parts by weight 2 The amount of the manganese precursor is 5-30 parts by weight of the carrierPreferably 5 to 28 parts by weight;
and/or, in terms of SiO, in relation to 100 parts by weight 2 The calculated carrier and the dosage of the forming agent are 5-45 parts by weight;
and/or, in terms of SiO, in relation to 100 parts by weight 2 The total amount of water in the carrier is 120-180 parts by weight;
preferably, the amount of SiO is greater than 100 parts by weight 2 The amount of the carrier and the extrusion aid is 5-25 parts by weight, preferably 5-20 parts by weight;
preferably, the amount of SiO is greater than 100 parts by weight 2 The amount of the carrier and the binder is 5 to 20 parts by weight, preferably 5 to 18 parts by weight.
4. The method of claim 1, wherein the shaping is performed in such a way that the dimensions of the shaped plastomer are: 3-7mm in diameter and 3-6mm in length, preferably the aspect ratio of the shaped plastomer is 1:1-2;
and/or the first drying mode is selected from drying and/or vacuum drying, preferably a step drying mode is adopted;
and/or, the first roasting mode comprises: raising the temperature to 750-900 ℃ at a heating rate of 4-10 ℃/min, and roasting at the temperature for 6-10h;
preferably, the step drying mode comprises:
(1) And (3) drying at low temperature: the temperature is 20-40 ℃ and the time is 2-6h;
(2) And (5) high-temperature drying: the temperature is 100-160 ℃ and the time is 4-10h.
5. The method according to any one of claims 1 to 4, wherein the method further comprises the step of preparing a cristobalite carrier: siO is made of 2 Mixing with sodium salt, and then carrying out second drying and second roasting;
preferably, the SiO 2 The average particle diameter of (2) is 0.05 to 0.18mm, more preferably 0.08 to 0.15mm;
preferably, the sodium salt is selected from sodium nitrate and/or sodium tungstate;
preferably, the SiO 2 And sodium salt weight ratio10-50:1, a step of;
preferably, the second drying conditions include: the temperature is 80-150 ℃ and the time is 5-10h;
preferably, the conditions of the second firing include: raising the temperature to 800-900 ℃ at a heating rate of 3-10 ℃/min, and roasting at the temperature for 5-12h.
6. A catalyst for preparing carbon dioxide by direct oxidation of methane, which is prepared by the method according to any one of claims 1 to 5;
alternatively, the catalyst comprises a cristobalite carrier and an active component supported on the cristobalite carrier, the active component selected from W, mn and alkali metals;
preferably, in the catalyst, siO in a cristobalite carrier is used 2 W is present in an amount of 5 to 18.5 wt.%, preferably 5.5 to 15 wt.%;
preferably, in the catalyst, siO in a cristobalite carrier is used 2 The Mn content is 1 to 10 wt%, preferably 1.5 to 9 wt%, based on the weight of (C);
preferably, in the catalyst, siO in a cristobalite carrier is used 2 The alkali metal content is 0.5 to 5 wt.%, preferably 0.8 to 4 wt.%;
preferably, the catalyst has the following dimensions: 3-7mm in diameter and 3-6mm in length, preferably the aspect ratio of the catalyst is 1:1-2;
7. a reactor for oxidative coupling reaction of methane, which is characterized by comprising a reactor cavity made of quartz, and a catalyst and a filler filled in the reactor cavity;
wherein the catalyst is the catalyst of claim 5 or 6;
the particle size of the filler is not more than 1/3 of the catalyst size.
8. The reactor of claim 7, wherein the aspect ratio of the reactor cavity is 15-40, and the ratio of the inner diameter of the reaction cavity to the catalyst size is 5-8:1, a step of;
and/or the filler particle size is 1/10-1/3 of the size of the catalyst;
preferably, the weight ratio of the catalyst to the filler filled in the reactor cavity is 10-20:1;
preferably, the filler is selected from alpha-Al having a particle size of not more than 1mm 2 O 3 alpha-Al with a particle size of 0.4-1mm is preferred 2 O 3 。
9. A process for preparing a carbon dioxide comprising reacting a carbon dioxide containing compound containing CH 4 And O 2 Introducing the reaction gas into a reactor for performing methane oxidative coupling reaction;
wherein the reactor is the reactor of claim 7 or 8.
10. The method of claim 9, wherein the CH 4 And O 2 The volume ratio of (2) to (6) to (1);
and/or, the conditions of the oxidative coupling reaction of methane include: the reaction temperature of the catalyst section is 750-850 ℃, and the space-time of the reaction gas is 9000-15000 mL.g -1 ·h -1 ；
Preferably, the reaction time of the oxidative coupling reaction of methane is 0.5 to 25 hours, preferably 5 to 20 hours.
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