CN117003609A - Reactor for oxidative coupling reaction of methane and method for preparing carbon dioxide - Google Patents
Reactor for oxidative coupling reaction of methane and method for preparing carbon dioxide Download PDFInfo
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- CN117003609A CN117003609A CN202210473929.0A CN202210473929A CN117003609A CN 117003609 A CN117003609 A CN 117003609A CN 202210473929 A CN202210473929 A CN 202210473929A CN 117003609 A CN117003609 A CN 117003609A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 157
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000000945 filler Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000012495 reaction gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 2
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 150000003254 radicals Chemical class 0.000 abstract description 9
- 238000003379 elimination reaction Methods 0.000 abstract description 7
- 238000011049 filling Methods 0.000 abstract description 7
- 230000002411 adverse Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 55
- 229920000034 Plastomer Polymers 0.000 description 30
- 238000000465 moulding Methods 0.000 description 30
- 238000001035 drying Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000002156 mixing Methods 0.000 description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000006004 Quartz sand Substances 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 229910021538 borax Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 235000010339 sodium tetraborate Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 241000219793 Trifolium Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- -1 polyethylene, ethylene propylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates toAnd the technical field of methane oxidative coupling reaction, and discloses a reactor for methane oxidative coupling reaction and a method for preparing carbon dioxide. The reactor provided by the invention adopts a filling mode that the catalyst and the filling agent are mixed and then are filled in the catalyst bed, and fills the gap generated by filling the catalyst in the catalyst bed through the filling agent with smaller particle size, thereby avoiding the contact between free radicals generated in the reaction process and the wall of the reactor cavity, reducing the adverse effect of the free radical elimination reaction and effectively improving C 2 Yield and selectivity of hydrocarbons. In addition, the reactor provided by the invention is filled with the formed catalyst, can be directly applied to industrial production, and avoids the influence on the catalytic effect of the catalyst in the catalyst forming process.
Description
Technical Field
The invention relates to the technical field of methane oxidative coupling reaction, in particular to a reactor for methane oxidative coupling reaction and a method for preparing carbon dioxide.
Background
Ethylene is one of the chemicals with the largest yield in the world, is an important organic chemical raw material for producing polyethylene, ethylene propylene rubber, polyvinyl chloride and other products, has important application in medicine, dye, pesticide, chemical industry and other aspects, is the organic chemical raw material with the widest application, has very important status in national economy, and the production scale and level thereof are one of important marks for measuring the strength and technical level of enterprises, so the development of the ethylene industry is always the focus of attention, and the demand of China for ethylene is also increasing with the rapid development of the economy of China.
Technology for producing olefins using natural gas (methane as a main component) as a carbon source has been a recent research focus. Methane is the main component in natural gas, and currently, two utilization paths for methane are mainly available, namely indirect utilization of methane and direct utilization of methane. The indirect utilization of methane is that the synthesis gas generated by the steam reforming reaction of methane is further converted into methanol, synthetic ammonia, dimethyl ether and the like, which is the most main utilization way of methane. However, since a large amount of energy is consumed in both processes of indirect conversion of methane, direct utilization of methane, oxidative coupling to produce ethylene and ethane, is a focus of attention of various countries.
Oxidative coupling of methane is a complex surface-gas phase reaction due to the C produced 2 Product ratio CH 4 Is easily oxidized deeply, thus limiting C 2 Further improving the single pass yield of hydrocarbon. With the continuous and deep research on oxidative coupling of methane, how to increase C in the reaction 2 The hydrocarbon once-through yield is a concern for researchers in various countries.
Disclosure of Invention
The invention aims to overcome the defects in the prior art that C is in the oxidative coupling reaction process of methane 2 The problem of low single pass hydrocarbon yield is to provide a reactor for oxidative coupling of methane and a method for preparing carbon dioxide. The catalyst bed in the reactor adopts a mode of filling the catalyst and (small particles) filler, and fills the gap of the catalyst filled in the bed in the reactor cavity by the filler with smaller particle diameter, thereby reducing the adverse effect of free radical elimination reaction and effectively improving C 2 Yield and selectivity of hydrocarbons.
In order to achieve the above object, according to one aspect of the present invention, there is provided a reactor for oxidative coupling reaction of methane, the reactor comprising a reactor cavity and a catalyst and a filler filled in the cavity at a catalyst bed, wherein the reactor cavity is made of quartz;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
In a second 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 cavity for methane oxidative coupling reaction;
the reactor cavity is made of quartz, and a catalyst bed layer in the reactor cavity is filled with a catalyst and a filler;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The reactor provided by the invention is filled with the formed catalyst, can be directly applied to industrial production, and avoids the influence on the catalytic effect of the catalyst in the catalyst forming process. Meanwhile, the catalyst bed layer of the reactor is filled with the catalyst and the filler, and the filler with small particle size is used for further filling the gaps in the reaction area, so that the adverse effect of the free radical elimination reaction on the OCM reaction effect is reduced, and the C is improved 2 Yield and selectivity of hydrocarbons.
(2) The molded catalyst adopted in the method 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.
(3) 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 yields, good catalytic stability and it has been demonstrated in pilot reactions that under the preferred reaction process conditions of the present invention, methane conversion and C can be obtained according to the process of the present invention using the reactor of the present invention (using specific catalyst loadings) 2 The hydrocarbon selectivity reaches more than 35 percent of excellent reaction effect.
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.
The present inventors have skillfully found during the course of the study that, for an OCM catalyst having W, mn, B and alkali metal as active components, by adjusting the filling manner of the catalyst, the OCM reaction efficiency can be further improved, the methane conversion rate can be increased or the C can be increased 2 Selectivity to hydrocarbons. Wherein the inventors found that when a catalyst (particularly a shaped catalyst) is packed in a reactor, certain voids are generated during the packing due to the shape and particle size limitations of the catalyst itself, so that free radicals generated during the reaction process are lost due to touching the exposed reaction chamber walls, i.e., radical elimination reaction occurs, resulting in methane conversion and/or C 2 The selectivity of hydrocarbons decreases, limiting the reaction efficiency. By mixing the proper filler and the catalyst, the gaps in the reaction area are reduced when the catalyst is filled into the reactor, thereby greatly reducing the adverse effect on the reaction activity caused by the free radical elimination reaction, further effectively improving the OCM reaction efficiency, improving the methane conversion rate or improving the C 2 Selectivity to hydrocarbons. The inventors have further found that selection of filler type, particle size, shape, etc. is effective for OCM reaction, increasing methane conversion, and increasing C 2 There is also a certain effect on the selectivity of the hydrocarbons.
Based on the above findings, the present invention provides in one aspect a reactor for oxidative coupling reaction of methane, the reactor comprising a reactor cavity and a catalyst and a filler filled in the cavity at a catalyst bed, wherein the reactor cavity is made of quartz;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
The shape of the catalyst is not particularly limited, and may be a regular shape such as a sphere, a cylinder, a cube, a sheet, or an irregular shape such as a clover, a star, or an irregular sphere. The catalyst size refers to its diameter when the catalyst shape is regular spherical and the catalyst size refers to its equivalent diameter when the catalyst shape is not spherical. 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.
It should be noted that, the existence form of W in the catalyst loaded in the reactor 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 only for the convenience of description and the calculation of the content and the proportion of the active components. The existence form of B in the catalyst filled in the reactor provided by the invention can be B simple substance or borate (such as boric acid and/or borate) when the catalyst plays a role, and the B is written as B only for the convenience of description and the calculation of the content and the proportion of active components.
According to a preferred embodiment of the invention, wherein the ratio of the inner diameter of the reaction chamber to the catalyst size is 3-9:1, the length-diameter ratio of the reactor cavity is 20-50.
According to a preferred embodiment of the invention, the filler is selected from quartz particles having a particle size of not more than 2 mm. That is, the quartz particles can pass through a screen of 10 mesh or more.
Preferably, the filler is 0.4-1mm quartz particles, i.e., the quartz particles can pass through an 18 mesh screen, but cannot pass through a 50 mesh screen.
In order to further enhance the catalytic effect of the catalyst while reducing the adverse effect of the radical elimination reaction on the reactivity by using the filler, it is preferable that the weight ratio of the catalyst to the filler packed in the reactor cavity is 10 to 20:1. It will be appreciated that the catalyst and filler are packed in a mixed manner.
According to a preferred embodiment of the invention, wherein the weight ratio of alkali metals (preferably K and/or Na), W, mn and B in elemental terms in the catalyst is 1:4-12:2.5-7:0.8-2. Preferably 1:5-11:2.5-5.5:0.8-1. More preferably 1:5-5.3:2.5-3.5:0.9-0.95.
Preferably, in the catalyst, siO 2 The alkali metal content is 0.5-5 wt.%, based on the weight of the composition. Preferably 0.5 to 4.5% by weight. More preferably 4 to 4.5% by weight.
Preferably, in the catalyst, siO 2 W is present in an amount of 5 to 25% by weight, based on the weight of the composition. Preferably 6 to 22% by weight. More preferably 15-22% by weight.
Preferably, in the catalyst, siO 2 The Mn content is 3-15 wt.%, based on the weight of (C). Preferably 3 to 12% by weight. More preferably 10 to 12% by weight.
Preferably, in the catalyst, siO 2 The content of B is 0.5-5 wt% based on the weight of the composition. Preferably 0.5 to 4.5% by weight. More preferably 4 to 4.5% by weight.
In view of the requirements in terms of particle size and strength of the shaped catalyst in the reactor (especially in commercial reactors), according to a preferred embodiment of the present invention, the catalyst is a cylindrical shaped catalyst having the dimensions: 3-6mm in diameter and 2-5mm in length. Preferably the aspect ratio of the catalyst is from 1:1 to 2.
According to a preferred embodiment of the invention, the strength of the catalyst is 20-30N/particle for a catalyst having the above-mentioned dimensions.
In order to minimize the packing porosity of the catalyst bed in the reactor and thereby better avoid the adverse effects of radical elimination reactions, it is preferred that the catalyst has a size of 5 to 10 times the filler particle size. For example 5 times, 6 times, 7 times, 8 times, 9 times or 10 times, or any intermediate value between any two of the above values.
The catalyst filled in the reactor provided by the invention can be a commercial product with the characteristics, or can be a self-prepared related catalyst with the characteristics.
The catalyst and the filling agent are mixed (uniformly) according to the proportion and then are filled in the cavity of the reactor, so that the reactor provided by the invention can be obtained.
According to a preferred embodiment of the present invention, the catalyst may be prepared by the following method: siO is made of 2 Mixing a carrier, an active component precursor, a forming agent and water, kneading and forming to obtain a formed plastic body, and sequentially drying and roasting the formed plastic body to obtain a formed catalyst;
wherein the active component precursor is at least one selected from tungsten precursor, manganese precursor, boron precursor and alkali metal 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), boric acid (salt), nitrate, etc. In order to avoid the influence of the catalyst performance/stability caused by the introduction of foreign elements into the catalyst, which are detrimental to the OCM reaction, the method provided by the invention does not use salts containing other elements, such as sulfates, chlorides, and the like, of the active components as active component precursors.
Preferably, the alkali metal precursor is selected from water-soluble inorganic salts of K and/or Na. Preferably sodium borate and/or potassium borate (i.e., the boron precursor and the alkali metal precursor are the same compound).
In order to make the distribution of the active ingredient more uniform, according to a preferred embodiment of the present invention, wherein the active ingredient is selected from at least one of ammonium tungstate, manganese nitrate, sodium borate and potassium borate.
Any SiO known in the art as being useful in the preparation of OCM catalysts 2 The carrier is suitable for use in the present invention, and may be a commercially available related product or a related product prepared by itself according to the prior art. According to a preferred embodiment of the present invention, wherein the SiO 2 The carrier is SiO with average grain diameter of 0.05-0.2mm 2 Particles (e.g., amorphous spherical particles).
Preferably, the SiO 2 The average particle size of the carrier is 0.06-0.15mm.
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, relative to 100 parts by weight of SiO 2 And the total dosage of the active component precursors is 3-60 parts by weight of carrier. The total amount of the active component precursors refers to the amount of all active component precursors used, and if one active component precursor is used, the amount of the active component precursor is the amount; if multiple active component precursors are used, the sum of the amounts of the active component precursors is the sum of the amounts of the active component precursors.
In the method provided by the invention, in order to obtain the OCM formed catalyst with better catalytic activity, the dosage of the precursor of the active component is different when the precursor of the active component is different.
Preferably, relative to 100 parts by weight of SiO 2 The carrier, the tungsten precursor (such as ammonium tungstate) is used in an amount of 10-50 parts by weight. Preferably 10 to 35 parts by weight. More preferably 30 to 35 parts by weight.
Preferably, relative to 100 parts by weight of SiO 2 And a carrier, wherein the manganese precursor (such as manganese nitrate) is used in an amount of 10-50 parts by weight. Preferably 10 to 40 parts by weight. More preferably 35 to 40 parts by weight.
Preferably, S is used in an amount of 100 parts by weightiO 2 The carrier, the sodium borate and/or potassium borate (i.e. alkali metal precursor and boron precursor) is used in an amount of 1-20 parts by weight. Preferably 3 to 20 parts by weight. More preferably 15 to 20 parts by weight.
More preferably, the active component precursors are used in amounts such that a weight ratio of alkali metal, W, mn and B of 1:4 to 12:2.5 to 7:0.8 to 2 is obtained in the catalyst. Preferably 1:5-11:2.5-5.5:0.8-1. More preferably 1:5-5.3:2.5-3.5:0.9-0.95.
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.
Any binder known in the art that can be used in the preparation of an OCM shaped catalyst can be suitable for use in the present invention. For catalyst performance reasons, it is preferred that the binder is a silica sol.
More preferably, siO in the silica sol 2 The content of (2) is 25-30 wt% of the total weight of the silica sol. The silica sol may be a commercially available related product or a related product prepared by itself according to the prior art.
In order to achieve the object that the binder can be uniformly dispersed in the prepared shaped catalyst, it is further preferred that the silica sol has an average particle diameter of 10 to 20nm.
In the method provided by the invention, siO 2 The proportions of the raw materials such as the carrier, the active component precursor, the molding agent, and water are not particularly limited as long as the OCM molded catalyst can be obtained. In order to be able to obtain shaped catalysts with better mechanical strength with as much catalytic activity as possible, preference is given to SiO in an amount of 100 parts by weight 2 And the carrier, the dosage of the forming agent is 5-40 parts by weight. The "amount of the molding agent" means all the molding agents used(e.g., binder, extrusion aid, etc.).
More preferably, relative to 100 parts by weight of SiO 2 The carrier, the dosage of the extrusion aid is 8-20 parts by weight.
In order to make the shaped plastomer easier to extrude and more suitable for drying and calcination treatment to obtain a catalyst of regular shape and high strength, more preferably, relative to 100 parts by weight of SiO 2 The carrier, the binder (preferably silica sol) is used in an amount of 5 to 20 parts by weight, preferably 5 to 15 parts by weight.
In the present invention, the water added has a role of allowing the molding precursor and the molding agent to be kneaded into a plastic body, and therefore, the amount of water in step (1) is not particularly limited as long as the purpose can be achieved. Preferably, relative to 100 parts by weight of SiO 2 The carrier may be 150 to 200 parts by weight of water. The term "water amount" refers to the total amount of water used in the preparation process of the shaped catalyst, and includes water contained in raw materials such as silica sol and the like, and also includes additional water.
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, wherein the shaping is selected from extrusion and/or spray shaping, preferably extrusion, i.e. the catalyst is preferably in the form of a cylinder.
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 the present invention, the size of the molded plastic body is not particularly limited as long as it can satisfy the industrial reactor filling requirement. Preferably, the shaping is performed in such a way that the dimensions of the shaped plastomer are: diameter 3-6mm, length 2-5mm, preferred aspect ratio is 1:1-2. The "aspect ratio" refers to the ratio of the length of the formed plastomer to its diameter.
In the present invention, the manner and condition of drying are not particularly limited. According to a preferred embodiment of the invention, the drying means are selected from drying and/or vacuum drying.
In view of obtaining as great a molding strength as possible, it is preferable that the drying is performed in a step-drying operation.
More preferably, the step-drying comprises the steps of:
(A) First drying: the temperature is 20-40 ℃ and the time is 2-6h;
(B) And (3) second drying: the temperature is 100-160 ℃ and the time is 4-10h.
In the method provided by the invention, the drying treatment can be carried out in an inert atmosphere (for example, under the protection of inert gas and/or nitrogen) or in an air atmosphere. Drying is preferably carried out under an air atmosphere.
In the method of the present invention, the conditions (modes) of firing are not particularly limited. According to a preferred embodiment of the present invention, the 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.
The inventor of the present invention found in the course of research that the method provided by the present invention was used for preparing a molded catalystIn the preparation, if SiO is firstly used 2 The carrier and the active component precursor are mixed to prepare a molding precursor, and then the molding precursor is mixed with other materials to prepare the molding catalyst.
Therefore, in the method provided by the invention, the mixing can be performed in a one-step mixing mode or a step-by-step mixing mode. Preferably by means of stepwise mixing.
According to a preferred embodiment of the invention, the mixing is carried out in a stepwise mixing manner, according to the following steps:
(1) SiO is made of 2 The carrier is mixed with the active component precursor such that the SiO 2 The carrier is loaded on the active component precursor to obtain a molding precursor;
(2) Mixing the molding precursor, a molding agent and water.
In the present invention, the shaped precursor is a laboratory OCM catalyst precursor, that is, a semi-finished product obtained before the calcination step in the preparation process of the laboratory OCM catalyst, and may be prepared by any method existing in the art. According to a preferred embodiment of the present invention, wherein the firing operation is not included in step (1). The shaped precursor is obtained only by simple impregnation (and drying) (without calcination after impregnation), e.g. by impregnating SiO 2 The carrier is placed in an impregnating solution containing an active component precursor (and then dried).
According to a preferred embodiment of the invention, in step (1), the loading is preferably carried out by impregnation and/or ion exchange.
Preferably, the loading mode is an isovolumetric impregnation method.
In the present invention, the molding precursor, the molding agent, and the water raw materials in the step (2) may be mixed together and then kneaded, or may be mixed (and kneaded) stepwise. In order to obtain a molded catalyst having a better catalytic activity and a higher mechanical strength, it is preferable to use a stepwise addition and mixing method.
According to a preferred embodiment of the present invention, in the step (2), the following steps are performed:
(a) Mixing and kneading the molding precursor, an extrusion aid and water to obtain a plastomer I;
(b) Plastomer I is mixed with a pre-mixed binder, preferably a silica sol, and optionally water, and kneaded to give plastomer II.
In the process according to the invention, in step (b), the optional amount of water is additionally added, if the binder (e.g. silica sol) contains water and the water content is sufficient for kneading to form plastomer II, no additional water is required.
In the method provided by the invention, in the steps (a) and (b), the total amount of water is as described above, and will not be described herein.
In a second 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 cavity for methane oxidative coupling reaction;
the reactor cavity is made of quartz, and a catalyst bed layer in the reactor cavity is filled with a catalyst and a filler;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
According to a preferred embodiment of the invention, wherein the ratio of the inner diameter of the reaction chamber to the catalyst size is 3-9:1, the length-diameter ratio of the reactor cavity is 20-50.
In the method provided by the invention, the characteristics of the catalyst and the filler are as described above, and are not described in detail herein.
The inventors of the present invention have also found during the course of the study that CH in the reaction gas when OCM reaction is carried out using the reactor provided by the present invention 4 And O 2 The effect of the volume ratio of (e.g. CH) on the final reaction 4 Is used for the conversion of the (c) to the (c),C 2 hydrocarbon selectivity, etc.) has a significant impact.
According to a preferred embodiment of the present invention, wherein the CH 4 And O 2 The volume ratio of (2) to (10) to (1), preferably (2) to (5) to (1).
The inventors of the present invention have also found that when the reactor provided by the present invention is used for OCM reaction, the reaction effect can be further improved by matching specific reaction conditions.
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 air space of the reaction gas is 8000-15000 mL.g -1 ·h -1 . By "hourly space velocity" is meant the mass (or volume) of reactant passing through a unit mass (or volume) of catalyst per unit time. Unit "mL.g -1 ·h -1 "means: the total amount of reaction gases (i.e., methane and oxygen) used (mL) was 1h over a period of time relative to 1g of the catalyst.
In view of the stable reaction time of the catalyst packed in the reactor provided by the present invention, it is preferable that the reaction time of the oxidative coupling reaction of methane is 0.5 to 25 hours, preferably 2 to 25 hours, more preferably 2 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 The carrier, silica sol and quartz sand were all purchased from Qingdao ocean chemical plant, where SiO 2 The carrier is amorphous spherical particles with average particle diameter of 0.1+/-0.05 mm, the average particle diameter of silica sol is 15+/-5 nm, wherein SiO 2 The content of (2) was 25% by weight. 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
Preparing a molding precursor: 34g of ammonium tungstate, 39g of Mn (NO) 3 ) 2 Adding 19g of sodium borate into 180g of distilled water, completely dissolving, adding 100g of SiO 2 Dipping for 2 hours to obtain a molding precursor A1.
(1) Preparing a molded plastomer:
(a) The molded precursor A1 was mixed with 8g of sesbania powder (stirring at 100rpm for 15 min) to obtain plastomer I-1.
(b) 5g of SiO 2 The silica sol and plastomer I-1 were stirred and mixed at 100rpm for 15 minutes, and put into a bar extruder and kneaded for 20 minutes to obtain plastomer II-1.
(c) And (3) extruding the plastomer II-1 through an orifice plate with the diameter of 4mm by using an extruder, and cutting into granules with the length of 2mm under the conditions that the extrusion speed is 100rpm, the temperature is 30 ℃ and the pressure is 15MPa to obtain the molded plastomer-1.
(2) Preparing a formed catalyst:
drying the shaped plastomer-1:
(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 reactor cavity in the catalytic reactor is a quartz tube with an inner diameter of 20mm and a length of 900mm, wherein 10g of formed catalyst-1 and 1g of quartz sand with a particle size of 0.4+/-0.05 mm (which can pass through a 35-mesh sieve but cannot pass through a 50-mesh sieve) which are uniformly mixed are filled in the catalyst bed layer.
And mixing and introducing raw material gas consisting of methane and oxygen 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 in the reactor cavity to be 830 ℃, wherein the volume ratio of the introduced methane to the introduced oxygen is 2:1, the hourly space velocity of the reaction gas is 12000 mL.g -1 ·h -1 。
Example 2
Preparing a molding precursor: 10g of ammonium tungstate, 10g of Mn (NO) 3 ) 2 Adding 3g of sodium borate into 190g of distilled water, completely dissolving, adding 100g of SiO 2 Dipping for 2 hours to obtain a molding precursor A-2.
(1) Preparing a molded plastomer:
(a) The molded precursor A-2 was mixed with 20g of starch (stirring at 50rpm for 20 min) to obtain plastomer I-2.
(b) 10g of SiO 2 The silica sol and plastomer I-2 are stirred and mixed at 150rpm for 20min, and then put into a bar extruder for kneading for 30min to obtain plastomer II-2.
(c) And (3) extruding the plastomer II-2 through an orifice plate with the diameter of 5mm by using an extruder, and cutting into granules with the length of 3mm under the conditions of the extrusion speed of 500rpm, the temperature of 15 ℃ and the pressure of 10MPa to obtain the molded plastomer-2.
(2) Preparing a formed catalyst:
drying the shaped plastomer-2:
(A) First drying: the temperature is 30 ℃ and the time is 4 hours;
(B) And (3) second drying: the temperature is 150 ℃ and the time is 4 hours, and the dry product is obtained.
And (3) placing the dried product in a muffle furnace, heating to 900 ℃ at a heating rate of 8 ℃/min under the air atmosphere, and roasting for 8 hours. A shaped catalyst-2 was obtained.
Methane oxidative coupling reaction: the reactor cavity in the catalytic reactor is a quartz tube with an inner diameter of 20mm and a length of 900mm, wherein 10g of formed catalyst-2 and 0.5g of quartz sand with a particle size of 0.6+/-0.05 mm (which can pass through a 25-mesh sieve but cannot pass through a 35-mesh sieve) which are uniformly mixed are filled in the catalyst bed layer.
And mixing and introducing raw material gas consisting of methane and oxygen at the top end of a reaction tube. The reaction pressure was the pressure generated by the raw material itself (0.020 MPa). The reaction temperature in the reactor cavity is controlled to be 780 ℃, and the volume ratio of the introduced methane to the oxygen is 4:1, the hourly space velocity of the reaction gas is 15000 mL.g -1 ·h -1 。
Example 3
Preparing a molding precursor: 14g of ammonium tungstate, 20g of Mn (NO) 3 ) 2 7.5g of sodium borate is added into 160g of distilled water, and 100g of SiO is added after complete dissolution 2 Dipping for 2 hours to obtain a molding precursor A-3.
(1) Preparing a molded plastomer:
(a) The molded precursor A-3 was mixed with 10g of sesbania powder (stirring at 150rpm for 15 min) to obtain plastomer I-3.
(b) 8g of SiO 2 The silica sol and plastomer I-3 are stirred and mixed at 150rpm for 15min, and then put into a strip extruder for kneading for 45min to obtain plastomer II-3.
(c) And extruding the plastomer II-3 through an orifice plate with the diameter of 6mm by using an extruder, extruding a strip-shaped solid cylinder at the extrusion speed of 500rpm and the temperature of 25 ℃ under the pressure of 28MPa, and cutting into particles with the length of 4mm to obtain the molded plastomer-3.
(2) Preparing a formed catalyst:
drying the shaped plastomer-3:
(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 6 hours, and the dry product is obtained.
The dried product is placed in a muffle furnace, heated to 850 ℃ at a heating rate of 10 ℃/min under the air atmosphere, and baked for 10 hours. A shaped catalyst-3 was obtained.
Methane oxidative coupling reaction: the reactor cavity in the catalytic reactor is a quartz tube with an inner diameter of 20mm and a length of 900mm, wherein 10g of formed catalyst-3 and 0.8g of quartz sand with a particle size of 0.9+/-0.05 mm (which can pass through an 18-mesh sieve but cannot pass through a 20-mesh sieve) which are uniformly mixed are filled in the catalyst bed layer.
And mixing and introducing raw material gas consisting of methane and oxygen 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 in the reactor cavity to be 800 ℃, wherein the volume ratio of the introduced methane to the introduced oxygen is 3:1, the hourly space velocity of the reaction gas is 8000mL g -1 ·h -1 。
Example 4
Preparing a molding precursor: will 21Ammonium tungstate, 30g Mn (NO) 3 ) 2 Adding 11g of sodium borate into 180g of distilled water, completely dissolving, adding 100g of SiO 2 Dipping for 2 hours to obtain a molding precursor A-4.
(1) Preparing a molded plastomer:
(a) The molded precursor A-4 was mixed with 15g of sesbania powder (stirring at 120rpm for 15 min) to obtain plastomer I-4.
(b) 10g of SiO 2 The silica sol and plastomer I-4 are stirred and mixed at 150rpm for 15min, and then put into a bar extruder for kneading for 30min to obtain plastomer II-4.
(c) And (3) extruding the plastomer II-4 through an orifice plate with the diameter of 5mm by using an extruder, and cutting into granules with the length of 3mm under the conditions of the extrusion speed of 500rpm, the temperature of 30 ℃ and the pressure of 20MPa to obtain the molded plastomer-4.
(2) Preparing a formed catalyst:
drying the shaped plastomer-4:
(A) First drying: the temperature is 30 ℃ and the time is 4 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 was placed in a muffle furnace, heated to 830℃at a heating rate of 5℃per minute under an air atmosphere, and calcined for 10 hours. Shaped catalyst-4 was obtained.
Methane oxidative coupling reaction: the reactor cavity in the catalytic reactor is a quartz tube with an inner diameter of 20mm and a length of 900mm, wherein 10g of formed catalyst-4 and 0.6g of quartz sand with a particle size of 0.5+/-0.05 mm (which can pass through a 30-mesh sieve but cannot pass through a 40-mesh sieve) which are uniformly mixed are filled in the catalyst bed layer.
And mixing and introducing raw material gas consisting of methane and oxygen at the top end of a reaction tube. The reaction pressure is the pressure generated by the raw materials, namely 0.020MPa. The reaction temperature of the catalyst section is controlled to be 810 ℃ and the volume ratio of methane to total oxygen is 4:1, the hourly space velocity of the reaction gas is 12000 mL.g -1 ·h -1 。
Example 5
The procedure of example 1 was used, except that the amount of active component precursor was adjusted so that the weight ratio of Na, W, mn and B in the catalyst was 1:1:0.5:0.5.
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 (a), the amount of sesbania powder used was 30g, and the other steps and operations were the same as 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 procedure of example 1 was employed, except that in step (b), the silica sol was used in an amount of 30g (as SiO 2 Meter), the rest of the procedure and operation were the same as in example 1. Shaped catalyst-7 was obtained.
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 8
The procedure of example 1 was employed, except that 10g of molded catalyst-1 and 1g of quartz sand having a particle diameter of 0.1.+ -. 0.05mm (capable of passing through a 120-mesh sieve but incapable of passing through a 170-mesh sieve) were packed uniformly mixed at the catalyst bed in the reactor, and the other conditions and operations were the same as those in example 1.
Example 9
The procedure of example 1 was employed, except that 10g of molded catalyst-1 and 1g of quartz sand having a particle diameter of 2.+ -. 0.05mm (capable of passing through an 8-mesh sieve but incapable of passing through a 12-mesh sieve) were packed uniformly mixed at the catalyst bed in the reactor, and the other conditions and operations were the same as those in example 1.
Example 10
The procedure of example 1 was employed, except that 10g of molded catalyst-1 and 3g of quartz sand having a particle diameter of 0.4.+ -. 0.05mm (capable of passing through a 35-mesh sieve but incapable of passing through a 50-mesh sieve) were packed uniformly mixed at the catalyst bed in the reactor, and the other conditions and operations were the same as those in example 1.
Example 11
The procedure of example 1 was employed, except that 10g of molded catalyst-1 and 0.1g of quartz sand (capable of passing through a 35-mesh sieve but incapable of passing through a 50-mesh sieve) having a particle diameter of 0.4.+ -. 0.05mm, which were uniformly mixed, were charged at the catalyst bed in the reactor, and the other conditions and operations were the same as those in example 1.
Example 12
The procedure in example 1 was employed, except that sodium borate was replaced with sodium chloride in such an amount that the Na content in the obtained molded catalyst was the same as that in molded catalyst-1, and the other steps and operations were the same as those in example 1, to obtain 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 molded catalyst-1 is adopted to carry out methane oxidative coupling reaction according to the following conditions: with the same catalytic reactor as in example 1, only 10g of the molded catalyst-1 was packed at the catalyst bed in the reactor, and no silica sand was packed. The other conditions and operations were the same as in example 1.
Comparative example 2
The procedure of example 3 was employed, except that 10g of molded catalyst-3 and 0.8g of quartz sand having a particle size of 2.+ -. 0.05mm (capable of passing through an 8-mesh sieve but incapable of passing through a 12-mesh sieve) were packed uniformly mixed at the catalyst bed in the reactor, and the other conditions and operations were the same as those in example 3.
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 from the molded catalysts obtained in each example, respectively, and the average was taken). Adsorption isotherms were fully analyzed using a fully automatic physico-chemical adsorption analyzer ASAP2020, MICROMERITIS Instrument Co., U.S.A., and the specific surface area and average pore size of the shaped catalysts obtained in the above examples and comparative examples were calculated from the isotherms.
The results are detailed in Table 1. Wherein the content of the active component is relative to the carrier SiO 2 Is defined as weight percent.
TABLE 1
* In the catalyst 8, siO relative to the carrier 2 Contains 6.6 wt% Cl.
Test example 2
The collected reaction products of the above examples and comparative examples were analyzed for components and contents using a gas chromatograph (Agilent, 7890A) and methane conversion, C, was calculated using the following formula 2 Hydrocarbon selectivity, CO X Selectivity, C 2 Hydrocarbon yield (data in the table are averages over stable reaction time). The results are detailed in Table 2.
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 stable reaction time is defined byReactivity 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 reactor for the oxidative coupling reaction of methane is characterized by comprising a reactor cavity, and a catalyst and a filler filled in a catalyst bed layer in the cavity, wherein the reactor cavity is made of quartz;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
2. The reactor of claim 1, wherein the ratio of the inner diameter of the reaction chamber to the catalyst size is 3-9:1, the length-diameter ratio of the reactor cavity is 20-50;
and/or the filler is selected from quartz particles having a particle size of not more than 2mm, preferably 0.4-1 mm;
preferably, the weight ratio of the catalyst to the filler filled in the catalyst bed layer in the reactor cavity is 10-20:1.
3. The reactor of claim 1, wherein the weight ratio of alkali metal, W, mn and B, on an elemental basis, in the catalyst is 1:4-12:2.5-7:0.8-2;
preferably, in the catalyst, siO 2 The alkali metal content is 0.5-5 wt%, based on the weight of the composition;
preferably, in the catalyst, siO 2 W is present in an amount of 5 to 25% by weight based on the weight of (a);
preferably, in the catalyst, siO 2 Based on the weight of the alloy, the Mn content is 3-15 wt%;
preferably, in the catalyst, siO 2 The content of B is 0.5-5 wt% based on the weight of the composition.
4. A reactor according to claim 1 or 3, wherein the catalyst is of the size: 3-6mm in diameter and 2-5mm in length, preferably the aspect ratio of the catalyst is 1:1-2;
and/or the strength of the catalyst is 20-30N/particle.
5. 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 cavity for methane oxidative coupling reaction;
the reactor cavity is made of quartz, and a catalyst bed layer in the reactor cavity is filled with a catalyst and a filler;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from SiO 2 A shaped support, the active component comprising at least one of W, mn, B and an alkali metal;
the size of the catalyst is 4-10 times of the particle size of the filler.
6. The method of claim 5, wherein the ratio of the inner diameter of the reaction chamber to the catalyst size is 3-9:1, the length-diameter ratio of the reactor cavity is 20-50;
and/or the filler is selected from quartz particles having a particle size of not more than 2mm, preferably 0.4-1 mm;
preferably, the weight ratio of the catalyst to the filler filled in the catalyst bed layer in the reactor cavity is 10-20:1.
7. The process according to claim 5, wherein the weight ratio of alkali metal, W, mn and B, on an elemental basis, in the catalyst is 1:4-12:2.5-7:0.8-2;
preferably, in the catalyst, siO 2 The alkali metal content is 0.5-5 wt%, based on the weight of the composition;
preferably, in the catalyst, siO 2 W is present in an amount of 5 to 25% by weight based on the weight of (a);
preferably, in the catalyst, siO 2 Based on the weight of the alloy, the Mn content is 3-15 wt%;
preferably, in the catalyst, siO 2 The content of B is 0.5-5 wt% based on the weight of the composition.
8. The method of claim 5 or 7, wherein the catalyst is sized to: 3-6mm in diameter and 2-5mm in length, preferably the aspect ratio of the catalyst is 1:1-2;
and/or the strength of the catalyst is 20-30N/particle.
9. The method of claim 5, wherein the CH 4 And O 2 The volume ratio of (2) to (10) to (1), preferably (2) to (5) to (1).
10. The method of claim 5, wherein the conditions of the methane oxidative coupling reaction comprise: the reaction temperature of the catalyst section is 750-850 ℃, and the air space of the reaction gas is 8000-15000 mL.g -1 ·h -1 ；
Preferably, the reaction time of the oxidative coupling reaction of methane is 0.5-25h.
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