CN114425272B - Reactor provided with alumina reaction cavity and application thereof - Google Patents

Reactor provided with alumina reaction cavity and application thereof Download PDF

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Publication number
CN114425272B
CN114425272B CN202010943418.1A CN202010943418A CN114425272B CN 114425272 B CN114425272 B CN 114425272B CN 202010943418 A CN202010943418 A CN 202010943418A CN 114425272 B CN114425272 B CN 114425272B
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reaction
active component
methane
alumina
reaction cavity
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CN114425272A (en
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赵清锐
王雪
韦力
武洁花
邵芸
冯静
张明森
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

Abstract

The invention relates to the field of catalysis, and discloses a reactor provided with an alumina reaction cavity and application thereof, wherein the reactor comprises the alumina reaction cavity, a catalyst filled in the reaction cavity and a stainless steel support sleeve fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding manner, and the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 reactor has the advantages of firm quality, long service life, smooth inner surface of the alumina reaction cavity, small resistance, good heat preservation performance, high raw material conversion rate, less side reaction, high selectivity and yield of the carbon dioxide and easy industrial mass production and application.

Description

Reactor provided with alumina reaction cavity and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to a reactor provided with an alumina reaction cavity and application thereof.
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 a focus of attention, and the demand of China for ethylene is also increasing with the rapid development of the economy of China.
The technology for preparing ethylene by oxidative coupling of methane has certain academic significance and potential economic value, and is one of the most challenging and focused research subjects in the catalytic field at present. Since Keller et al first proposed a methane oxidative coupling technology in 1982, the technology has been the focus of attention in the catalytic world, the chemical industry, and the petroleum and natural gas fields. With the breakthrough of the united states in the shale gas field, a large amount of methane which is difficult to mine is mined, and chemical utilization of methane is highly paid attention to the industry, wherein research on oxidative coupling of methane which is considered to be the most promising is once again a research hotspot worldwide.
The methane oxidative coupling reaction is a high-temperature strong exothermic reaction, and the heat released by the whole reaction can be more together with side reactions generated by methane oxidation. At present, the reactor used for preparing ethylene by oxidative coupling of methane in laboratory research is made of quartz or stainless steel, and because the stainless steel reactor has strong oxygen adsorption capacity, the oxidative coupling of methane generates larger side reaction, and the heated quartz reactor has lower strength and short service life, and is not suitable for industrial amplification stages.
Thus, the existing reactors for oxidative coupling of methane are in need of further improvement.
Disclosure of Invention
The invention aims to solve the technical problems of more side reactions, intolerance to high temperature and low mechanical strength of a reactor in methane oxidative coupling reaction in the prior art, and provides a reactor provided with an alumina reaction cavity and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a reactor provided with an alumina reaction chamber, the reactor comprising an alumina reaction chamber, a catalyst filled in the reaction chamber, and a stainless steel support sleeve fixedly disposed around an outer wall of the alumina reaction chamber, and a roughness of an inner surface of the alumina reaction chamber being 0.2 to 0.8 μm;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 reactor provided by the invention is firm in quality, long in service life and suitable for high-temperature reaction of methane oxidative coupling. The outer wall is set as stainless steel support sleeve, is more easy to be connected with other devices of methane oxidative coupling in industry, and the inner surface of the alumina reaction cavity is smooth, the resistance is small, the heat preservation performance is good, the reactor is used for methane oxidative coupling reaction, the raw material conversion rate is high, the side reaction is less, the selectivity and the yield of the carbon dioxide are high, and the reactor is easy to be applied to industrial mass production.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) The method comprises the steps that a catalyst is filled in an alumina reaction cavity, a stainless steel supporting sleeve is fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding mode, and the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 the alumina reaction cavity to contact with the catalyst for catalytic reaction.
The method for preparing the carbon dioxide by oxidative coupling of methane has the advantages of high conversion rate of raw materials of catalytic reaction, 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.
The invention provides a reactor provided with an alumina reaction cavity, which comprises an alumina reaction cavity, a catalyst filled in the reaction cavity and a stainless steel support sleeve fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding manner, wherein the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 some embodiments of the invention, the roughness of the inner surface of the alumina reaction chamber is 0.2 to 0.8 microns, preferably 0.3 to 0.5 microns. Roughness refers to the small pitch and the unevenness of the minute peaks and valleys of the machined surface. Measured by needle-drawing method. Specifically, the roughness of the inner surface of the cavity is small, the side reaction of the oxidative coupling reaction of methane is less, and the selectivity of carbon dioxide is relatively high.
In some embodiments of the invention, the length ratio of the alumina reaction chamber to the stainless steel support sleeve in the direction of reactant flow is preferably 0.8-1:1.
in some embodiments of the invention, the ratio of the thickness of the alumina reaction chamber to the inner diameter of the alumina reaction chamber is preferably from 0.12 to 0.25:1.
in some embodiments of the present invention, the alumina reaction chamber is made of a commercially available common alumina product, preferably α -Al 2 O 3 。
In some embodiments of the present invention, the stainless steel support sleeve is not particularly limited, and is preferably at least one of 314L stainless steel, 316 stainless steel and 304 stainless steel. In the invention, a gap is not reserved between the stainless steel support sleeve and the alumina reaction cavity, and the stainless steel support sleeve and the alumina reaction cavity are tightly attached.
In some embodiments of the invention, the catalysts used are prepared by methods commercially available or using prior art techniques.
According to one embodiment of the invention, the catalyst is prepared by: adding manganese nitrate into water, adding a carrier, stirring for 2-4 hours, and drying at 100-120 ℃ for 10-12 hours to obtain a solid A; then dissolving sodium tungstate/potassium tungstate in the deionized water, adding the solid A, stirring for 2-4 hours, and drying for 10-12 hours at 100-120 ℃ to obtain the solid B; then dissolving the precursor of the auxiliary agent in water, adding the solid B, stirring for 2-4 hours, drying for 10-12 hours at 100-120 ℃, then roasting for 4-5 hours at 500-550 ℃, and then heating to 850-880 ℃ for roasting for 4-5 hours to obtain the catalyst of the invention, wherein the water used is not limited, preferably deionized water, more preferably deionized water at 50-70 ℃.
In some embodiments of the present invention, preferably, the catalyst further comprises 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 preferably 0.5 to 5g, more preferably 1 to 2g, based on 100g of the carrier.
In some embodiments of the invention, the first active component is preferably present in an amount of 1 to 25g, more preferably 5 to 10g, based on 100g of the carrier. The content of the second active component is preferably 1 to 12g, more preferably 2 to 5g.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) The method comprises the steps that a catalyst is filled in an alumina reaction cavity, a stainless steel supporting sleeve is fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding mode, and the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns, preferably 0.3-0.5 microns;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 the alumina reaction cavity to contact with the catalyst for catalytic reaction.
In the present invention, the description of the structure of the reactor is not repeated here as described above.
In some embodiments of the present invention, preferably, the catalyst further comprises 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 preferably 0.5 to 5g, more preferably 1 to 2g, based on 100g of the carrier.
In some embodiments of the invention, the first active component is preferably present in an amount of 1 to 25g, more preferably 5 to 10g, based on 100g of the carrier. The content of the second active component is preferably 1 to 12g, more preferably 2 to 5g.
In some embodiments of the invention, to reduce bed hot spots. The catalytic reaction is carried out in the presence of a solvent. In the present invention, the bed hot spot refers to the highest temperature of the catalyst bed.
In some embodiments of the invention, preferably, the solvent is water, more preferably deionized water.
In some embodiments of the invention, the volume ratio of methane to solvent is preferably 1:0.5-2, more preferably 1:1-1.5.
In some embodiments of the invention, the volume ratio of methane to oxygen is preferably 2-10:1, more preferably 2.2-4:1.
in some embodiments of the invention, the conditions of the catalytic reaction include: the reaction temperature of the catalytic reaction is preferably 790 to 850 ℃, more preferably 800 to 830 ℃. The reaction pressure of the catalytic reaction is preferably 0.001 to 0.02MPa. The reaction time of the catalytic reaction is 0.5-40h. The reaction gas hourly space velocity in terms of methane and oxygen is preferably from 5000 to 25000 mL/(g.h).
In the invention, the fillers at the two ends of the catalyst are inert materials, and the inert materials only play a role of supporting the catalyst and do not participate in the reaction. Preferably, the inert material is silica and/or alumina, the silica being derived from quartz sand.
In the present invention, 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 invention, the pressures refer to gauge pressure.
In the present invention, the carbon dioxide may be ethane and/or ethylene.
The present invention 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 the specific detection reference GB/T 30905-2014。SiO 2 From quartz sand, which was purchased from Qingdao ocean chemical Co. Alumina is purchased from world chemical filler limited.
Preparation example 1
Adding manganese nitrate into deionized water with the temperature of 60 ℃ and the weight of 25g, adding a carrier, stirring for 4 hours, and drying at the temperature of 120 ℃ for 12 hours to obtain a solid A; then dissolving sodium tungstate/potassium tungstate in 25g deionized water at 60 ℃, adding solid A, stirring for 4 hours, and drying at 120 ℃ for 12 hours to obtain solid B; then, the precursor of the auxiliary agent was dissolved in deionized water at 60℃and 25g, and solid B was added, stirred for 2 hours, dried at 120℃for 12 hours, then calcined at 550℃for 5 hours, and then calcined at 850℃for 5 hours, to obtain the catalyst used in the examples or comparative examples.
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:
note that: the content of each component in the catalyst is the relative content calculated by taking 100g of carrier as a reference;
"/" indicates that no promoter is present in the catalyst.
Example 1
The reactor comprises alumina (alpha-Al 2 O 3 ) The reaction cavity and along the fixed stainless steel (314L stainless steel) supporting sleeve that sets up of outer wall encirclement of aluminium oxide reaction cavity, the internal diameter of aluminium oxide reaction cavity is 10mm, length is 530mm, the catalyst loading is 0.2g in the aluminium oxide reaction cavity, the roughness of the internal surface of aluminium oxide reaction cavity is 0.3 micron, the length of stainless steel supporting sleeve is 530mm, the thickness of aluminium oxide reaction cavity is 1.5mm, the reaction pressure is the pressure that raw materials self produced, namely 0.01MPa, reaction temperature is 800 ℃, methane and oxygen volume ratio is 2.2:1, the volume ratio of methane to water is 1:1.5, the reaction gas hourly space velocity in terms of methane and oxygen was 12000 mL/(g.h), and the reaction product was collected after 1 hour of reaction.
Example 2
The reactor comprises alumina (alpha-Al 2 O 3 ) The reaction cavity and along the outer wall of aluminium oxide reaction cavity encircle fixed stainless steel (314L stainless steel) supporting sleeve that sets up, the internal diameter of aluminium oxide reaction cavity is 8mm, length is 530mm, the catalyst loading is 0.2g in the aluminium oxide reaction cavity, the roughness of the internal surface of aluminium oxide reaction cavity is 0.4 micron, the length of stainless steel supporting sleeve is 660mm, the thickness of aluminium oxide reaction cavity is 2mm, the reaction pressure is the pressure that raw materials self produced, 0.009MPa promptly, the reaction temperature is 790 ℃, the volume ratio of methane to oxygen is 3:1, the volume ratio of methane to water is 1:1, the reaction gas hourly space velocity calculated by methane and oxygen is 10000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 3
The reactor comprises alumina (alpha-Al 2 O 3 ) The reaction cavity and along the outer wall of aluminium oxide reaction cavity encircle fixed stainless steel (314L stainless steel) supporting sleeve that sets up, the internal diameter of aluminium oxide reaction cavity is 10mm, length is 530mm, the catalyst loading is 0.2g in the aluminium oxide reaction cavity, the roughness of the internal surface of aluminium oxide reaction cavity is 0.5 micron, stainless steel supporting sleeve's length is 590mm, the thickness of aluminium oxide reaction cavity is 2mm, the reaction pressure is the pressure that raw materials self produced, namely 0.013MPa, the reaction temperature is 810 ℃, methane and oxygen's volume ratio is 2.2:1, the volume ratio of methane to water is 1:2, the reaction gas hourly space velocity in terms of methane and oxygen was 15000 mL/(g.h), and the reaction product was collected after 1 hour of reaction.
Example 4
The reactor comprises alumina (alpha-Al 2 O 3 ) The reaction cavity and the stainless steel (304 stainless steel) supporting sleeve which is fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding way, wherein the inner diameter of the alumina reaction cavity is 10mm, the length is 530mm, the catalyst loading amount in the alumina reaction cavity is 0.2g, the roughness of the inner surface of the alumina reaction cavity is 0.8 micrometer, the length of the stainless steel supporting sleeve is 540mm, the thickness of the alumina reaction cavity is 2.5mm, the reaction pressure is the pressure generated by the raw material, namely 0.009MPa, the reaction temperature is 850 ℃, and the volume ratio of methane to oxygen is6:1, the volume ratio of methane to water is 1:0.5, the hourly space velocity of the reaction gas based on methane and oxygen is 8000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 5
The reactor comprises alumina (alpha-Al 2 O 3 ) The reaction cavity and along the outer wall of aluminium oxide reaction cavity encircle fixed stainless steel (316 stainless steel) supporting sleeve that sets up, the internal diameter of aluminium oxide reaction cavity is 12mm, length is 530mm, the catalyst loading is 0.2g in the aluminium oxide reaction cavity, the roughness of the internal surface of aluminium oxide reaction cavity is 0.7 micron, stainless steel supporting sleeve's length is 530mm, the thickness of aluminium oxide reaction cavity is 3mm, the reaction pressure is the pressure that raw materials self produced, 0.005MPa promptly, reaction temperature is 830 ℃, methane and oxygen's volume ratio is 4:1, the volume ratio of methane to water is 1:1.2, the reaction gas hourly space velocity in terms of methane and oxygen was 5000 mL/(g.h), and the reaction product was collected after 1 hour of reaction.
Example 6
The oxidative coupling of methane to make carbon dioxide was performed as in example 1, except that the catalyst was replaced with the catalyst shown in example 6 of table 1.
Comparative example 1
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 reactor was a single tube and the material of the reactor was quartz.
Comparative example 2
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 reactor was a single tube and the material of the reactor was 314L stainless steel.
Comparative example 3
The oxidative coupling of methane to make carbon dioxide was performed as in example 1, except that the roughness of the inner surface of the alumina reaction chamber was 2 μm.
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 the catalyst shown in comparative example 4 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 the examples and comparative examples were tested on a gas chromatograph available from Agilent company 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
Numbering device Methane conversion/% Carbon Dihydrocarbon Selectivity/% CO x Selectivity/% Yield of carbon diolefms/%
Example 1 58.4 34.03 62.3 19.9
Example 2 59.6 33.6 62.7 20.0
Example 3 43.5 45.5 57.1 19.8
Example 4 47.1 42.2 53.5 19.9
Example 5 46.8 41.9 54.8 19.6
Example 6 52.4 31.8 66.2 16.7
Comparative example 1 58.2 33.5 65.5 19.5
Comparative example 2 31.9 18.4 80.4 5.9
Comparative example 3 51.5 30.1 65.3 15.5
Comparative example 4 43.7 28.9 67.5 12.6
Comparative example 5 40.2 30 64.6 12.1
As can be seen from the test results in Table 2, the selectivity of the carbon dioxide is higher, the yield of the carbon dioxide is higher, and the CO is higher in examples 1 to 5, compared with comparative example 2 x The selectivity is relatively low, which indicates that the reactor and the method of the invention inhibit the deep oxidation of methane and reduce the occurrence of side reactions when the reactor and the method are used for preparing the carbon dioxide through oxidative coupling of methane. Compared with comparative example 3, the selectivity and the yield of the carbon dioxide in examples 1-5 are both higher, which shows that the catalyst of the invention has fewer side reactions for preparing the carbon dioxide by catalyzing the oxidative coupling of methane and has high yield of the carbon dioxide only when the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns. Compared with comparative examples 4 and 5, examples 1 to 5 have higher selectivity and higher yield of the carbon dioxide, which means that the better catalytic effect can be obtained only by adopting the technical scheme of the invention for the specific catalyst.
Example 1 is inferior to comparative example 1 in data in Table 2, but the quartz tube used in comparative example 1 is brittle, is brittle when connected to stainless steel joints at both ends, and is not well secured in gas tightness at the joints, and collision is avoided in use. The composite reaction tube used in example 1 has the advantages of firm quality, long service life, good heat preservation performance and easy large-scale use.
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 (12)

1. A method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) The method comprises the steps that a catalyst is filled in an alumina reaction cavity, a stainless steel supporting sleeve is fixedly arranged along the outer wall of the alumina reaction cavity in a surrounding mode, and the roughness of the inner surface of the alumina reaction cavity is 0.2-0.8 microns;
the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; 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 catalyst also contains an auxiliary agent, wherein the auxiliary agent is at least one selected from Ce oxide, la oxide, sr oxide, sm oxide and Y oxide; the content of the first active component is 1-25g based on 100g of the carrier; the content of the second active component is 1-12g; the content of the auxiliary agent is 0.5-5g;
(2) Methane and oxygen are introduced into the alumina reaction cavity to contact with the catalyst for catalytic reaction;
wherein the catalytic reaction is carried out in the presence of a solvent, which is water.
2. The method of claim 1, wherein the roughness of the inner surface of the alumina reaction chamber is 0.3-0.5 microns;
and/or, in the reactant flow direction, the length ratio of the alumina reaction chamber to the stainless steel support sleeve is 0.8-1:1, a step of;
and/or the ratio of the thickness of the alumina reaction chamber to the inner diameter of the alumina reaction chamber is 0.12-0.25:1, a step of;
and/or the material of the alumina reaction cavity is alpha-Al 2 O 3 ；
And/or the stainless steel support sleeve is made of at least one of 314L stainless steel, 316 stainless steel and 304 stainless steel.
3. The process according to claim 1, wherein the auxiliary is present in an amount of 1-2g based on 100g of the carrier.
4. A method according to any one of claims 1 to 3, wherein the first active ingredient is present in an amount of 5 to 10g based on 100g of the carrier.
5. A method according to any one of claims 1 to 3, wherein the second active ingredient is present in an amount of 2 to 5g based on 100g of the carrier.
6. A method according to any one of claims 1-3, wherein the solvent is deionized water.
7. A process according to any one of claims 1 to 3, wherein the volume ratio of methane to solvent is 1:0.5-2.
8. A process according to any one of claims 1 to 3, wherein the volume ratio of methane to solvent is 1:1-1.5.
9. A method according to any one of claims 1-3, wherein the volume ratio of methane to oxygen is 2-10:1.
10. a method according to any one of claims 1-3, wherein the volume ratio of methane to oxygen is 2.2-4:1.
11. a method according to any one of claims 1-3, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 790-850 ℃, the reaction pressure is 0.001-0.02MPa, the reaction time is 0.5-40h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 5000-25000 mL/(g.h).
12. A method according to any one of claims 1-3, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 800-830 ℃.
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