CN113769733B - Catalyst system for preparing carbon dioxide by oxidative coupling of methane and application thereof - Google Patents
Catalyst system for preparing carbon dioxide by oxidative coupling of methane and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 194
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 29
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000011049 filling Methods 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000376 reactant Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 77
- 239000001301 oxygen Substances 0.000 claims description 76
- 229910052760 oxygen Inorganic materials 0.000 claims description 76
- 230000003197 catalytic effect Effects 0.000 claims description 31
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000153 supplemental effect Effects 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 230000008676 import Effects 0.000 description 10
- 230000001706 oxygenating effect Effects 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- ARJFOGOIGWNNPB-UHFFFAOYSA-N [C].O1CCOCC1 Chemical compound [C].O1CCOCC1 ARJFOGOIGWNNPB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004876 x-ray fluorescence 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to the field of catalysts, and discloses a catalyst system for preparing carbon dioxide by oxidative coupling of methane and application thereof, wherein the catalyst system sequentially comprises a first catalyst section, a filling section and a second catalyst section in the direction of a reactant flow, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the direction of the reactant flow; the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active component comprises a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn. The methane conversion rate is improved, the selectivity and the yield of the carbon dioxide are improved, and the method has good industrial application prospect.
Description
Technical Field
The application relates to the field of catalysts, in particular to a catalyst system for preparing carbon dioxide by oxidative coupling of methane and application thereof.
Background
With the breakthrough of exploration technology, the discovery of new gas fields and the continuous improvement of the deep sea exploration and development technology level, the global natural gas exploration reserve is continuously increased. The method has unique geological background, various natural gas types, rich total resources and huge potential. With increasing emphasis on environmental protection, clean replacement of energy is a necessary trend of global primary energy supply structure change. Olefin raw materials are basic raw materials in the chemical industry, and the current development trend of olefin raw material diversification is shown, for example, the yield of propylene prepared by propane dehydrogenation is rapidly increased worldwide; coal-to-olefin is also rapidly developing in China; in the context of increased natural gas production, methane conversion to lower Olefins (OCM) technology is again of academic and industrial interest. The production of ethylene by using natural gas is the shortest route for producing ethylene by using methane with abundant reserves in hydrocarbon compounds as raw materials, so that the production cost of ethylene is greatly reduced, and the route is most economical in theory. However, the process is still a research hotspot for natural gas chemical industry and catalysis at present because of the great difficulty in directional activation of methane.
At present, the methane oxidative coupling catalyst can be mostly carried out at the reaction temperature of 750-850 ℃, and in the industrial scale-up stage, the methane is deeply oxidized, and the reaction selectivity is low, so that the yield of the carbon-to-carbon hydrocarbons is reduced.
Disclosure of Invention
The application aims to solve the problems of deep oxidation of methane and reduced reaction selectivity, so that the yield of olefin is reduced, and provides a catalyst system for preparing carbon dioxide by oxidative coupling of methane and application thereof.
The inventor of the application discovers in the research that the catalyst system adopts two sections of filling, the two sections of catalysts are separated by the filler, and the ratio of the length of the filling section to the total length of the first catalyst section and the second catalyst section is controlled to reduce the temperature of the catalytic reaction, thereby inhibiting the deep oxidation of methane to a certain extent, improving the selectivity and the yield of the carbon dioxide, and having good industrial application prospect.
In order to achieve the above object, according to one aspect of the present application, there is provided a catalyst system for preparing a carbon dioxide by oxidative coupling of methane, comprising a first catalyst section, a packing section, and a second catalyst section in that order in a reactant flow direction, wherein the length of the packing section is 0.3 to 5 times as long as the total length of the first catalyst section and the second catalyst section in the reactant flow direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn.
In a second aspect, the present application provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the second catalystThe catalysts in the paragraphs are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
(2) Methane and oxygen are introduced into a catalytic reactor to contact the catalyst for catalytic reaction.
The method for preparing the carbon dioxide by oxidative coupling of methane has the advantages of low catalytic reaction temperature, high raw material conversion rate, less side reaction, high selectivity and yield of the carbon dioxide and easiness in large-scale production and application.
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 one aspect, the application provides a catalyst system for preparing carbon dioxide by oxidative coupling of methane, which sequentially comprises a first catalyst section, a filling section and a second catalyst section in the direction of reactant flow, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the direction of reactant flow;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active component comprises a first active component and a second active componentAn active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn.
In some embodiments of the application, the filler in the filler section may be alpha-Al 2 O 3 。
In some embodiments of the application, the catalysts used are prepared by methods commercially available or using prior art techniques.
In some embodiments of the application, preferably, the ratio of the lengths of the first catalyst section and the second catalyst section in the direction of the reactant flow is from 0.5 to 6:1, more preferably from 0.8 to 2:1.
In some embodiments of the application, preferably, the volume ratio of the first catalyst section to the second catalyst section is from 0.5 to 6:1, more preferably from 0.8 to 2:1.
In some embodiments of the application, preferably, the length of the packed section is 2-5 times the total length of the first and second catalyst sections.
In some embodiments of the application, the catalyst in the first catalyst stage and/or the catalyst in the second catalyst stage may further contain an auxiliary agent, preferably at least one selected from the group consisting of oxides of Ce, la, sr, sm and Y; more preferably, the content of the auxiliary agent is 0.2-4g based on 100g of the carrier.
In some embodiments of the application, the first active component is preferably present in an amount of 1 to 20g and the second active component is preferably present in an amount of 1 to 10g, based on 100g of the carrier.
In some embodiments of the present application, a first oxygen supplementing inlet is further provided at the first catalyst section, and is used for delivering the first-section oxygen into the catalytic reactor, and may also be used as a gas raw material (methane and partial oxygen) inlet.
In some embodiments of the application, to control the conversion degree of the catalytic reaction and improve the yield and selectivity of the product carbon dioxide, the filling section is further provided with a second oxygen supplementing inlet for delivering the second section of oxygen into the catalytic reactor.
In some embodiments of the application, to further reduce the occurrence of side reactions, the distance of the second oxygen-compensating inlet from the cross-section of the upstream end of the second catalyst section in the reverse direction of the reactant stream may be from 0.3 to 0.7 times the length of the packed section.
In a second aspect, the application provides a process for the oxidative coupling of methane to produce a carbon dioxide, the process comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
(2) Methane and oxygen are introduced into a catalytic reactor to contact the catalyst for catalytic reaction.
In some embodiments of the present application, the type of the catalytic reactor is not limited as long as the catalytic reaction for preparing the carbon dioxide by oxidative coupling of methane can be performed, and specifically, a batch tank reactor, a continuous tank reactor or a semi-continuous tank reactor, and preferably, the catalytic reactor is a fixed bed reactor.
In some embodiments of the present application, preferably, the length ratio of the first catalyst section and the second catalyst section may be from 0.5 to 6:1, more preferably from 0.8 to 2:1.
In some embodiments of the present application, preferably, the volume ratio of the first catalyst section to the second catalyst section may be from 0.5 to 6:1, more preferably from 0.8 to 2:1.
In some embodiments of the application, preferably, the length of the packed section is 2-5 times the total length of the first and second catalyst sections.
In some embodiments of the application, the catalyst in the first catalyst stage and/or the catalyst in the second catalyst stage may further contain an auxiliary agent, preferably at least one selected from the group consisting of oxides of Ce, la, sr, sm and Y; more preferably, the content of the auxiliary agent is 0.2-4g based on 100g of the carrier.
In some embodiments of the application, the first active component is preferably present in an amount of 1 to 20g and the second active component is preferably present in an amount of 1 to 10g, based on 100g of the carrier.
In some embodiments of the application, preferably, a first supplemental oxygen inlet is also provided at the first catalyst section to introduce methane and first stage oxygen into the catalytic reactor.
In some embodiments of the present application, to control the conversion degree of the catalytic reaction and to improve the yield and selectivity of the product carbon dioxide, it is preferable that the filling section is further provided with a second oxygen supplementing inlet to introduce the second section of oxygen into the catalytic reactor.
In some embodiments of the application, to further reduce the occurrence of side reactions, the distance of the second oxygen-compensating inlet from the cross-section of the upstream end of the second catalyst section in the reverse direction of the reactant stream may be from 0.3 to 0.7 times the length of the packed section.
In some embodiments of the present application, preferably, the temperature of the oxygen inlet point of the second stage oxygen is 780-830 ℃, more preferably 790-810 ℃. The volume ratio of the first section of oxygen to the second section of oxygen is preferably 1-10:1, more preferably 4-10:1. the inventor of the application discovers that oxygen matched with each section of bed layer after the sectional oxygen feeding is smaller than that of the single section of oxygen feeding, thereby controlling the temperature rise of the catalyst bed layer, modulating the methane conversion rate and selectivity of the reaction, further inhibiting the occurrence of side reaction and further improving the yield and selectivity of the product carbon dioxide.
In some embodiments of the application, preferably, the volume ratio of methane to total oxygen input to the catalytic reactor is from 2 to 6:1, more preferably 2.2-4:1.
in some embodiments of the application, the conditions of the catalytic reaction include: the reaction temperature may be 780-840 ℃, preferably 800-830 ℃. The catalytic reaction pressure may be 0-0.02MPa. The catalytic reaction time can be 0.5-8h. The reaction gas hourly space velocity in terms of methane and oxygen may be 10000-25000 mL/(g.h). Specifically, the reaction temperature was a temperature 1cm above the first stage catalyst bed.
In the present application, the unit "mL/(g.h)" is the amount of the total gas of methane and oxygen (mL) used for 1 hour with respect to 1g of the catalyst.
In the present application, the pressures refer to gauge pressure.
In the present application, the carbon dioxide may be ethane and/or ethylene.
The present application will be described in detail by examples. In both examples and comparative examples, the reagents used were commercially available analytically pure reagents. The method for measuring the element composition of the catalyst is an X-ray fluorescence method, and specific detection is referred to GB/T30905-2014.
Preparation example 1
Adding manganese nitrate into deionized water with the temperature of 20 ℃ and the weight of 25g, adding a carrier, stirring for 4 hours, and drying at the temperature of 120 ℃ for 24 hours to obtain a solid A; then dissolving sodium tungstate/potassium tungstate into 25g deionized water at 20 ℃, adding the solid A, stirring for 4 hours, and drying at 120 ℃ for 24 hours to obtain a solid B; then dissolving the precursor of the auxiliary agent in 50 ℃ and 25g of deionized water, adding the solid B, stirring for 2 hours, drying at 120 ℃ for 24 hours, roasting at 550 ℃ for 5 hours, and then heating to 850 ℃ for 5 hours to obtain the catalyst used by the application.
The precursors of the auxiliary agents all refer to nitrate, and the usage amount of each component is such that the content of active components and the auxiliary agents in the catalyst are shown in table 1:
TABLE 1
Note that: the content of each component in the catalyst is based on 100g of carrier;
"/" indicates that no promoter is present in the catalyst.
Example 1
The catalytic reactor is a quartz tube with an inner diameter of 10mm and a length of 530mm, the total catalyst loading is 0.4g, the reactor is divided into two sections, the loading of each section is 0.2g, the length of each section is 9mm, the interval between the two sections is 4cm, and SiO is used for the catalyst 2 Filling. Methane and first section oxygen mix and get into at the reaction tube top, and the second oxygenating import is established at first catalyst section and the spaced filling section of second catalyst section, and the distance of second oxygenating import with the cross section of second catalyst section upstream end is 2.5cm. And the temperature of the oxygen inlet point of the second section of oxygen is 800 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 800 ℃, the volume ratio of methane to the total oxygen input into the catalytic reactor is 2.2, the volume ratio of the first-stage oxygen to the second-stage oxygen is 10, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 12000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 2
The catalytic reactor is a quartz tube with the inner diameter of 10mm and the length of 530mm, the total catalyst loading is 0.4g, the catalytic reactor is divided into two sections, the first section loading is 0.27g, the second section loading is 0.13g, the length of the first catalyst section reaches 12mm, the length of the second catalyst section is 6mm, and SiO is used for the catalyst 2 Filling. The filling section is up to 6cm in height. Methane and first section oxygen mix and get into at the reaction tube top, and the second oxygenating import is established at first catalyst section and the packing section of second catalyst section interval, and the distance of second oxygenating import with the cross section of second catalyst section upstream end is 2cm. And the temperature of the oxygen inlet point of the second stage oxygen is 830 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.02Mpa, the reaction temperature is 780 ℃, the volume ratio of methane to the total oxygen input into the catalytic reactor is 3, the firstThe volume ratio of the oxygen in the first stage to the oxygen in the second stage is 1, the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 3
The catalytic reactor is a quartz tube with an inner diameter of 10mm and a length of 530mm, the total catalyst loading is 0.4g, the reactor is divided into two sections, the first section loading is 0.14g, the length of the first catalyst section is 7mm, the second section loading is 0.26g, the length of the first catalyst section is 11mm, the interval between the two sections is 9cm, and alpha-Al is used for preparing the catalyst 2 O 3 Filling. Methane and first section oxygen mix and get into at the reaction tube top, and the second oxygenating import is established at first catalyst section and the spaced filling section of second catalyst section, and the distance of second oxygenating import with the cross section of second catalyst section upstream end is 3cm. And the temperature of the oxygen inlet point of the second section of oxygen is 780 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.01Mpa, the reaction temperature is 810 ℃, the volume ratio of methane to the total oxygen input into the catalytic reactor is 2, the volume ratio of the first-stage oxygen to the second-stage oxygen is 8, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 25000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 4
The catalytic reactor is a quartz tube with the inner diameter of 10mm and the length of 530mm, the total catalyst loading is 0.4g, the reactor is divided into two sections, the loading of each section is 0.2g, the height of each section bed layer reaches 9mm, the interval between the two sections of catalyst is 8cm, and SiO is used for preparing the catalyst 2 Filling. Methane and first section oxygen mix and get into at the reaction tube top, and the second oxygenating import is established at first catalyst section and the packing section of second catalyst section interval, and the distance of second oxygenating import with the cross section of second catalyst section upstream end is 5cm. And the temperature of the oxygen inlet point of the second stage oxygen is 810 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.015Mpa, the reaction temperature is 830 ℃, the volume ratio of methane to the total oxygen input into the catalytic reactor is 6, the volume ratio of the first-stage oxygen to the second-stage oxygen is 4, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 20000 mL/(g.h), and the reaction product is collected after the reaction for 1 hour.
Example 5
The catalytic reactor isA quartz tube with an inner diameter of 10mm and a length of 530mm, wherein the total catalyst loading is 1g, the quartz tube is divided into two sections, the first section loading is 0.85g, the length of the first catalyst section is 3.8cm, the second section loading is 0.15g, the length of the first catalyst section is 7mm, the interval between the two sections is 1.4cm, and SiO is used for preparing the catalyst 2 Filling. Methane and first section oxygen mix and get into at the reaction tube top, and the second oxygenating import is established at first catalyst section and the packing section of second catalyst section interval, and the distance of second oxygenating import with the cross section of second catalyst section upstream end is 1cm. And the temperature of the oxygen inlet point of the second stage oxygen is 810 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.013Mpa, the reaction temperature is 840 ℃, the volume ratio of methane to the total oxygen input into the catalytic reactor is 4, the volume ratio of the first section of oxygen to the second section of oxygen is 5, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 15000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 6
The reaction for producing a carbon dioxide by oxidative coupling of methane was carried out in the same manner as in example 1, except that the composition of the catalyst used was as shown in Table 1.
Comparative example 1
The catalytic reactor is a quartz tube with an inner diameter of 10mm and a length of 530mm, the total loading of the catalyst is 0.4g, the catalytic reactor is a single-stage loading, and the bed layer is 18mm high. The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane at 800℃and a reaction gas hourly space velocity of 12000 mL/(g.h) in terms of methane and oxygen in accordance with the method of example 1, and the reaction product was collected after 1 hour of reaction.
Comparative example 2
The oxidative coupling of methane to make carbon dioxide was performed as in example 5, except that the two catalyst sections were spaced 0.5cm apart.
Comparative example 3
The oxidative coupling of methane to make carbon dioxide was performed as in example 5, except that the two catalyst sections were spaced 24cm apart.
Comparative example 4
The oxidative coupling of methane to make carbon dioxide was performed as in example 1, except that the catalyst was replaced with another catalyst, as shown in table 1.
Comparative example 5
The reaction for producing a carbon dioxide by oxidative coupling of methane was carried out in the same manner as in comparative example 1, except that the catalyst of comparative example 4 was used.
Test example 1
The reaction product components obtained in examples and test examples were tested on a gas chromatograph available from Agilent under the model number 7890A. The product was assayed using a double detection channel three-valve four column system in which the FID detector was attached to an alumina column for CH analysis 4 、C 2 H 6 、C 2 H 4 、C 3 H 8 、C 3 H 6 、C 4 H 10 、C 4 H 8 、C n H m Isocompositions, TCD detector is mainly used for detecting CO and CO 2 、N 2 、O 2 、CH 4 。
The calculation method of methane conversion rate and the like is as follows:
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%
Carbon dioxane 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
Yield of carbon diolefms = methane conversion x (ethane selectivity + ethylene selectivity)
The results obtained are shown in Table 2.
TABLE 2
As shown in Table 2, the methane conversion rate, the selectivity and the yield of the carbon dioxide and the CO of examples 1 to 6 were higher when the length of the packed section was 0.3 to 5 times the total length of the first catalyst section and the second catalyst section, respectively, as compared with comparative examples 1 to 4 x The selectivity is relatively low, which indicates that the catalyst system of the application can inhibit the deep oxidation of methane and reduce the occurrence of side reactions when being used for preparing the carbon dioxide by oxidative coupling of methane. The methane conversion, selectivity to carbon dioxide, and yield to carbon dioxide were all higher for examples 1-6 than for comparative examples 4-5 (SiC as the support), and the effect of the multi-stage loading for comparative example 4 was similar to that of the single-stage loading for comparative example 5, indicating that superior catalytic effect could be obtained only for the specific catalyst by the multi-stage loading.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application 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 application, all falling within the scope of protection of the application.
Claims (28)
1. A catalyst system for preparing carbon dioxide by oxidative coupling of methane, which is characterized by comprising a first catalyst section, a filling section and a second catalyst section in sequence in the direction of reactant flow, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the direction of reactant flow;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; filling in the filling sectionThe filler is selected from silicon dioxide and/or aluminum oxide; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
the length ratio of the first catalyst section to the second catalyst section is 0.5-6:1.
2. The catalyst system of claim 1, wherein the first catalyst section and the second catalyst section have a length ratio of 0.8-2:1.
3. The catalyst system according to claim 1 or 2, wherein the volume ratio of the first catalyst section and the second catalyst section is from 0.5 to 6:1.
4. a catalyst system according to claim 3, wherein the volume ratio of the first catalyst section and the second catalyst section is 0.8-2:1.
5. The catalyst system of claim 1 or 2, wherein the length of the packed section is 2-5 times the total length of the first and second catalyst sections.
6. The catalyst system according to claim 1 or 2, wherein the catalyst in the first catalyst stage and/or the catalyst in the second catalyst stage further comprises an auxiliary agent.
7. The catalyst system of claim 6, wherein the promoter is selected from at least one of an oxide of Ce, an oxide of La, an oxide of Sr, an oxide of Sm, and an oxide of Y.
8. Catalyst system according to claim 6 or 7, wherein the promoter is present in an amount of 0.2-4g based on 100g of the support.
9. The catalyst system of claim 1, wherein the first active component is present in an amount of 1 to 20g and the second active component is present in an amount of 1 to 10g based on 100g of the support.
10. The catalyst system of claim 1, wherein the first catalyst section is further provided with a first oxygen make-up inlet;
and/or the filling section is provided with a second oxygen supplementing inlet;
and/or, in the reverse direction of the reactant stream, the distance between the second oxygen-supplementing inlet and the cross section of the upstream end of the second catalyst section is 0.3-0.7 times the length of the filling section.
11. A method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 0.3-5 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise a support and an active component supported on the support, wherein the support is selected from silica and/or barium titanate; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
(2) Introducing methane and oxygen into a catalytic reactor to contact with a catalyst for catalytic reaction;
the length ratio of the first catalyst section to the second catalyst section is 0.5-6:1.
12. The method of claim 11, wherein the first catalyst section and the second catalyst section have a length ratio of 0.8-2:1.
13. The method of claim 11 or 12, wherein the volume ratio of the first catalyst section and the second catalyst section is 0.5-6:1.
14. the method of claim 13, wherein the volume ratio of the first catalyst section to the second catalyst section is 0.8-2:1.
15. The method of claim 11 or 12, wherein the length of the packed section is 2-5 times the total length of the first and second catalyst sections.
16. The process according to claim 11 or 12, wherein the catalyst in the first catalyst section and/or the catalyst in the second catalyst section further comprises an auxiliary agent.
17. The method of claim 16, wherein the promoter is selected from at least one of an oxide of Ce, an oxide of La, an oxide of Sr, an oxide of Sm, and an oxide of Y.
18. The process according to claim 16, wherein the adjuvant is present in an amount of 0.2-4g based on 100g of the carrier.
19. The method of claim 11, wherein the first active component is present in an amount of 1-20g and the second active component is present in an amount of 1-10g based on 100g of the carrier.
20. The method of claim 11, wherein a first supplemental oxygen inlet is further provided at the first catalyst section to introduce methane and a first section of oxygen into the catalytic reactor;
and/or the filling section is provided with a second oxygen supplementing inlet for introducing second-section oxygen into the catalytic reactor;
and/or, the distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 0.3-0.7 times of the length of the filling section along the reverse direction of the reactant flow.
21. The method of claim 20, wherein the second stage oxygen has an oxygen inlet point temperature of 780-830 ℃.
22. The method of claim 21, wherein the second stage oxygen has an oxygen inlet point temperature of 790-810 ℃.
23. The method of claim 20, wherein the volume ratio of the first stage oxygen to the second stage oxygen is 1-10:1.
24. the method of claim 23, wherein the volume ratio of the first stage oxygen to the second stage oxygen is 4-10:1.
25. the method of claim 11 or 21, wherein the volume ratio of methane to total oxygen input to the catalytic reactor is 2-6:1.
26. the method of claim 25, wherein the volume ratio of methane to total oxygen input to the catalytic reactor is from 2.2 to 4:1.
27. the method of claim 11, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 780-840 ℃, the reaction pressure is 0-0.02MPa, the reaction time is 0.5-8h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000-25000 mL/(g.h).
28. The method of claim 27, wherein the reaction temperature is 800-830 ℃.
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| CN103657640A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Load catalyst and preparation method and application thereof as well as method for preparing low carbon olefin by methane oxidative coupling |
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