CN114425276B - Reactor and application thereof in preparation of carbon dioxide by oxidative coupling of methane - Google Patents

Reactor and application thereof in preparation of carbon dioxide by oxidative coupling of methane Download PDF

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Publication number
CN114425276B
CN114425276B CN202010989114.9A CN202010989114A CN114425276B CN 114425276 B CN114425276 B CN 114425276B CN 202010989114 A CN202010989114 A CN 202010989114A CN 114425276 B CN114425276 B CN 114425276B
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layer wall
middle layer
inner layer
wall
methane
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CN114425276A (en
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武洁花
薛伟
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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Sinopec Beijing Research Institute of Chemical Industry
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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • 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
    • 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
    • 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 and application thereof in preparing carbon dioxide by oxidative coupling of methane, wherein the reactor comprises the following components: an inner layer wall provided with a first opening; the middle layer wall is sleeved outside the inner layer wall at intervals, and the inner layer wall and the middle layer wall are movably connected, so that the volume of a cavity formed by the inner layer wall and the middle layer wall can be adjusted, and the middle layer wall is provided with a second opening; the outer layer wall is sleeved outside the middle layer wall at intervals; wherein the opening ratios of the inner layer wall and the middle layer wall are the same or different and are not less than 50%; the inner layer wall and the middle layer wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramic. The reactor can avoid side reaction, improve the conversion rate of the reaction, improve the yield and selectivity of reaction products, and is easy for industrial application.

Description

Reactor and application thereof in preparation of carbon dioxide by oxidative coupling of methane
Technical Field
The invention relates to the field of catalysis, in particular to a reactor and application thereof in preparing carbon dioxide by oxidative coupling of methane.
Background
The oxidative coupling of methane to ethylene and ethane is one of the most challenging and focused research subjects in the catalytic field at present because of its academic significance and potential great economic value. Since the papers of Keller and Bhasin in 1982, the papers have been focused on the fields of catalysis, chemical industry and petroleum and natural gas, and the research activity reaches a peak before and after 1992, and then the research heat is slightly reduced for a period of time. By 2010, along 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 attracts great importance to the industry, wherein research on oxidative coupling of methane to prepare ethylene and ethane, which is considered to be the most promising, is a hot spot subject worldwide.
In view of the currently reported catalyst reaction types, the catalyst reaction type is mainly a fixed bed reaction bed reactor, some documents report that the membrane reactor is used for memorizing plasmas and the like, and when the catalyst loading is increased, the thickness of the fixed bed layer is increased, and as the reaction releases heat, the temperature of the central hot spot of the catalyst bed layer is high, the side reaction is increased, the selectivity of carbon dioxide generated by methane oxidative coupling reaction is reduced, and the reaction yield is further reduced. Other types of reactors have difficulty achieving engineering scale-up due to thermal effects caused by increased catalyst loading.
Disclosure of Invention
The invention aims to solve the problems of the prior art that the methane oxidative coupling reaction has a plurality of side reactions, low selectivity, low yield of the carbon dioxide and difficult industrial scale-up, and provides a reactor and application thereof in preparing the carbon dioxide by methane oxidative coupling.
The inventor of the invention discovers in the research that in the three-layer sleeve type reactor, the problems of more side reactions of the oxidative coupling reaction of methane can be obviously improved by maintaining the thickness of the catalyst bed layer basically unchanged and controlling the aperture ratio and the material of the sleeve, the conversion rate of the reaction can be improved, the yield and the selectivity of the reaction product are improved, and the method is easy for industrial application. Accordingly, in order to achieve the above object, an aspect of the present invention provides a reactor comprising:
an inner wall provided with a first aperture;
the middle layer wall is sleeved outside the inner layer wall at intervals, the inner layer wall and the middle layer wall are movably connected, so that the volume of a cavity formed by the inner layer wall and the middle layer wall can be adjusted, and the middle layer wall is provided with a second opening;
the outer layer wall is sleeved outside the middle layer wall at intervals;
wherein the opening ratios of the inner layer wall and the middle layer wall are the same or different and are not less than 50%; the inner layer wall and the middle layer wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramic.
According to the reactor provided by the invention, the reactor adopts a three-layer structure, the inner layer wall and the middle layer wall are movably connected, the thickness of the catalyst bed layer is unchanged on the premise of increasing the catalyst consumption, and the material is contacted with the catalyst through the openings on the inner layer wall and the middle layer wall, so that the contact area of the catalyst and the raw material is increased, the problem of uneven temperature distribution of the bed layer caused by the thickening of the catalyst bed layer thickness due to the increase of the catalyst loading amount of the traditional fixed bed reactor is avoided, the occurrence of side reaction is avoided, the conversion rate of the reaction is improved, the yield and the selectivity of a reaction product are improved, and the reactor is easy for industrial application.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising: methane and oxygen are introduced into a reactor to be contacted with a catalyst for catalytic reaction, wherein the reactor is the reactor, and the catalyst is filled between the inner layer wall and the middle layer wall.
The method for preparing the carbon dioxide by oxidative coupling of methane has the advantages of high raw material conversion rate, less side reaction, high selectivity and yield of the carbon dioxide and easiness in large-scale production and application.
Drawings
FIG. 1 is a schematic structural view of a reactor according to an embodiment of the present invention;
FIG. 2 is a left side view of an inner wall according to one embodiment of the invention;
FIG. 3 is a left side view of a middle layer wall according to one embodiment of the invention;
fig. 4 is a top view of a reactor according to one embodiment of the invention.
Description of the reference numerals
100 inner walls, 101 first holes, 200 middle walls, 201 second holes, 300 outer walls, 400 movable devices, 500 sealing devices, 501 fixing bolts, 502 air inlets and 503 air outlets.
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 present invention provides a reactor comprising:
an inner wall provided with a first aperture;
the middle layer wall is sleeved outside the inner layer wall at intervals, the inner layer wall and the middle layer wall are movably connected, so that the volume of a cavity formed by the inner layer wall and the middle layer wall can be adjusted, and the middle layer wall is provided with a second opening;
the outer layer wall is sleeved outside the middle layer wall at intervals;
wherein the opening ratios of the inner layer wall and the middle layer wall are the same or different and are not less than 50%; the inner layer wall and the middle layer wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramic.
In some embodiments of the invention, the open porosity of the inner and middle layer walls is each independently preferably 50-80%.
In the present invention, the aperture ratio is defined as the ratio of the total area of the mesh openings on the screen plate to the area of the open area (also known as the effective mass transfer area), i.e., Φ=a 0 /A a The method comprises the steps of carrying out a first treatment on the surface of the Wherein: phi-aperture ratio (%); a is that 0 Is the total area of the sieve holes on the sieve plate; a is that a Area of the open area.
In the present invention, the material of the outer wall is not limited, but is preferably a dense material, and more preferably at least one of stainless steel, ceramic, alumina, and quartz.
In the present invention, the reactor may further include a catalyst packed between the inner wall and the middle wall, and the catalytic reaction temperature of the catalyst is preferably 750 to 850 ℃. Specifically, the catalyst is at least one selected from sodium tungstate-manganese oxide/silicon dioxide, sodium tungstate-manganese oxide/barium titanate, sodium tungstate-manganese oxide-rare earth element/silicon dioxide, sodium tungstate-manganese oxide-rare earth element/barium titanate and a catalyst obtained by modifying the above catalysts. Wherein the sodium salt may be replaced by a potassium salt.
In some embodiments of the invention, it is preferred that the first and second apertures are the same or different in shape and each is independently a regular or irregular shape. More preferably, the first and second openings are the same shape and are both circular. Further preferably, the diameter of the first and second openings is preferably no more than 500 microns, more preferably 50-500 microns.
In some embodiments of the invention, the middle layer wall is preferably coaxially sleeved outside the inner layer wall with a spacing.
In some embodiments of the invention, the outer wall is preferably coaxially sleeved outside the middle wall with a spacing.
In some embodiments of the invention, the thickness ratio of the inner layer wall to the middle layer wall is preferably 1:0.2-5. More preferably, the thickness of the inner layer wall is 2-5mm. The thickness of the outer wall is 2-6mm.
In some embodiments of the invention, the distance between the inner layer wall and the middle layer wall in the radial direction is preferably 1-10mm.
In the present invention, the manner of movably connecting the inner wall and the middle wall is not particularly limited, as long as the volume of the cavity formed by the inner wall and the middle wall can be adjusted, in particular, the connection manner can be adjusted in the axial direction (that is, the manner of maintaining the distance between the inner wall and the middle wall in the radial direction unchanged). In some embodiments of the present invention, at least two pairs of structures for fixing the card are oppositely disposed on the inner wall and the middle wall, and the inner wall is movably connected with the middle wall through the card, so that the volume of the cavity formed by the inner wall and the middle wall can be adjusted along the axial direction. In particular, the card is a radially placed axially adjustable card having a radial length equal to the distance between the inner and middle walls in the radial direction. The structure for fixing the card can be a clamping groove or a sliding bolt with a track, wherein the number of the clamping grooves or the bolts for fixing the card in one group is 2-6. The material of the card is not limited, so long as the inner layer wall and the cavity formed by the middle layer wall can be sealed, and the axial position can be adjusted, and the material is not repeated here. In the present invention, the sealing manner of the two ends of the reactor is not limited as long as the sealing function is achieved, and preferably, the sealing is achieved by a flange.
In the invention, temperature measuring elements (such as thermocouples) are arranged between the inner layer wall and the middle layer wall and between the middle layer wall and the outer layer wall to measure the temperature of the catalyst bed layer and the temperature of the product, the specific positions of the temperature measuring elements are not limited, and the positions of the temperature measuring elements can be determined according to a constant temperature zone determination method in the conventional technology. Preferably, the temperature measuring element is made of quartz or ceramic.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising: methane and oxygen are introduced into a reactor to be contacted with a catalyst for catalytic reaction, wherein the reactor is the reactor, and the catalyst is filled between the inner layer wall and the middle layer wall.
In some embodiments of the invention, when using the above-described reactor, the ratio of the distance between the inner layer wall and the middle layer wall in the radial direction to the filling height of the catalyst in the axial direction is preferably 1:0.25 to 10, more preferably 1:1-9.
In the invention, the movable connection of the inner layer wall and the middle layer wall can realize the filling of different amounts of catalysts with the same dispersion degree.
In the present invention, optionally, an inert material is filled between the middle layer wall and the outer layer wall.
In some embodiments of the invention, it is preferred that an inert material is filled between the middle layer wall and the outer layer wall. More preferably, the inert material is selected from at least one of quartz sand, ceramic, and alumina. The inert material preferably has an average particle size of 300-500 microns.
In some embodiments of the invention, the catalyst preferably has an average particle size of 300 to 500 microns.
In the present invention, the catalyst used is at least one selected from the group consisting of sodium tungstate-manganese oxide/silica, sodium tungstate-manganese oxide/barium titanate, sodium tungstate-manganese oxide-rare earth element/silica, sodium tungstate-manganese oxide-rare earth element/barium titanate, and a modified catalyst of each of the above. Wherein the sodium salt may be replaced by a potassium salt.
In some embodiments of the invention, the catalysts used are prepared by methods commercially available or using prior art techniques.
According to a preferred embodiment of the present invention, the catalyst is prepared by the following steps:
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 and/or potassium tungstate in 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 roasting for 4-5 hours at 500-550 ℃, and then roasting for 4-5 hours at 850-880 ℃ at a heating rate of 2-10 ℃/min, so as to obtain the catalyst of the invention, wherein water used is not limited, preferably deionized water, and more preferably deionized water at 50-70 ℃.
In some embodiments of the invention, the molar ratio of methane to oxygen is preferably 1-10:1, more preferably 2-5:1.
According to a preferred embodiment of the present invention, according to fig. 1 to 4, a catalyst is filled between the inner wall 100 and the middle wall 200, an inert material is filled between the middle wall 200 and the outer wall 300, methane and oxygen enter into a closed space formed by the inner wall 100 through the gas inlet 502 and contact with the catalyst through the first opening 101, are discharged into the inert material through the second opening 201 after reaction, and are discharged out of the reactor through the gas outlet 503, and both ends of the reactor are sealed by the sealing means 500 and fixedly connected with the reaction chamber through the fixing bolts 501. Specifically, the movable device 400 is an axially adjustable card placed in a radial direction, and the radial length of the card is equal to the distance between the inner wall 100 and the middle wall 200, and a person skilled in the art can control the thickness of the catalyst bed according to the amount of the catalyst used, for example, by adjusting the adjustable card to adjust the length of the inner wall 100 (i.e. the volume of the cavity formed by the inner wall and the middle wall) in the axial direction.
In some embodiments of the invention, the conditions of the catalytic reaction include: the reaction pressure of the catalytic reaction is preferably 0.001 to 0.05MPa. The reaction gas hourly space velocity in terms of methane and oxygen is preferably 5000 to 100000 mL/(g.h).
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. Quartz sand was purchased from Qingdao ocean chemical Co. Alumina is purchased from world chemical filler limited.
Preparation example 1
Catalyst Na 2 WO 4 -Mn/SiO 2 Is prepared from the following steps:
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 in 25g of deionized water at 60 ℃, adding the solid A, stirring for 4 hours, and drying at 120 ℃ for 12 hours to obtain a solid B; then, the catalyst was calcined at 550℃for 5 hours, and then calcined at 850℃for 5 hours at a temperature increase rate of 5℃per minute, to obtain the catalyst used in the examples.
Example 1
The thickness of the inner layer wall of the reactor is 2mm, the thickness of the middle layer wall is 6mm, the materials are quartz, the bottom is provided with a raw material gas inlet, round holes with the diameter of 250 micrometers are formed in the inner layer wall and the middle layer wall, the opening ratio of the inner layer wall is 55%, the opening ratio of the middle layer wall is 65%, the outer layer wall is a quartz tube, the thickness of the outer layer wall is 5mm, and the inner layer wall and the middle layer wall are movably connected through a card (namely the card is clamped on the inner layer wall and the middle layer wall through a clamping groove) so as to adjust the length of the inner layer along the axial direction (namely the volume of a cavity formed by the inner layer wall and the middle layer wall). The catalyst is filled between the inner layer wall and the middle layer wall, the average grain diameter of the catalyst is 300 microns, the inert material quartz sand is filled between the middle layer wall and the outer layer wall, the average grain diameter of the quartz sand is 300 microns, and the two ends of the reactor are sealed by stainless steel flanges. The material outlets are arranged at the upper end and the lower end between the middle layer wall and the outer layer wall. The reaction materials pass through the inlet of the reactor through a mixing preheating heating furnace, react through a catalyst bed layer and are discharged out of the reactor through an air outlet.
1g of the catalyst obtained in preparation example 1 was charged between the middle layer wall and the inner layer wall, the distance between the inner layer wall and the middle layer wall (i.e., the catalyst thickness) was 5mm in the radial direction, the card was adjusted so that the charging height of the catalyst was 4mm, the hourly space velocity of the reaction gas in terms of methane and oxygen was 10000 mL/(g.h), and the molar ratio of methane to oxygen was 3:1, the catalytic reaction temperature is 800 ℃, the reaction pressure is 0.001MPa, raw material gas passes through the inlet of the reactor, the catalyst bed layer is reacted, the raw material gas passes through the inert material zone, the inert material zone is collected from the outlet, and the reaction product is collected after the reaction is carried out for 1 hour.
Example 2
The thickness of the inner layer wall of the reactor is 5mm, the thickness of the middle layer wall is 1mm, the materials are quartz, a raw material gas inlet is formed in the bottom of the reactor, round holes with the diameter of 350 microns are formed in the inner layer wall and the middle layer wall, the aperture ratio of the inner layer wall is 65%, the aperture ratio of the middle layer wall is 55%, the outer layer wall is an alumina tube, the thickness of the outer layer wall is 3mm, the inner layer wall and the middle layer wall are movably connected through a card (namely, the card is clamped on the inner layer wall and the middle layer wall through a clamping groove), and two ends of the inner layer wall are movably connected through the card so as to adjust the length of the inner layer along the axial direction (namely, the volume of a cavity formed by the inner layer wall and the middle layer wall). The catalyst is filled between the inner layer wall and the middle layer wall, the average grain diameter of the catalyst is 400 microns, the inert material alumina is filled between the middle layer wall and the outer layer wall, the average grain diameter of the alumina is 400 microns, and the two ends of the reactor are sealed by stainless steel flanges. The material outlets are arranged at the upper end and the lower end between the middle layer wall and the outer layer wall. The reaction materials pass through the inlet of the reactor through a mixing preheating heating furnace, react through a catalyst bed layer and are discharged out of the reactor through an air outlet.
5g of the catalyst obtained in preparation example 1 was charged between the middle layer wall and the inner layer wall, the distance between the inner layer wall and the middle layer wall (i.e., the catalyst thickness) was 6mm in the radial direction, the card was adjusted so that the charging height of the catalyst was 18mm, the hourly space velocity of the reaction gas in terms of methane and oxygen was 5000 mL/(g.h), and the molar ratio of methane to oxygen was 2:1, the catalytic reaction temperature is 760 ℃, the reaction pressure is 0.009MPa, then the reaction product is collected after passing through an inert material area and an outlet after passing through a catalyst bed for reaction at the inlet of a reactor and reacting for 1 hour.
Example 3
The thickness of the inner layer wall of the reactor is 2mm, the thickness of the middle layer wall is 10mm, the materials are quartz, the bottom is provided with a raw material gas inlet, round holes with the diameter of 400 microns are formed in the inner layer wall and the middle layer wall, the aperture ratio of the inner layer wall is 75%, the aperture ratio of the middle layer wall is 80%, the outer layer wall is an alumina tube, the thickness of the outer layer wall is 6mm, and the inner layer wall and the middle layer wall are movably connected through a card (namely the card is clamped on the inner layer wall and the middle layer wall through a clamping groove) so as to adjust the length of the inner layer along the axial direction (namely the volume of a cavity formed by the inner layer wall and the middle layer wall). The catalyst is filled between the inner layer wall and the middle layer wall, the average grain diameter of the catalyst is 450 microns, the inert material alumina is filled between the middle layer wall and the outer layer wall, the average grain diameter of the alumina is 450 microns, and the two ends of the reactor are sealed by stainless steel flanges. The material outlets are arranged at the upper end and the lower end between the middle layer wall and the outer layer wall. The reaction materials pass through the inlet of the reactor through a mixing preheating heating furnace, react through a catalyst bed layer and are discharged out of the reactor through an air outlet.
10g of the catalyst obtained in preparation example 1 was charged between the middle layer wall and the inner layer wall, the distance between the inner layer wall and the middle layer wall (i.e., the catalyst thickness) was 9mm in the radial direction, the card was adjusted so that the charging height of the catalyst was 30mm, the hourly space velocity of the reaction gas in terms of methane and oxygen was 100000 mL/(g.h), and the molar ratio of methane to oxygen was 5:1, the catalytic reaction temperature is 850 ℃, the reaction pressure is 0.02MPa, then the reaction product is collected after the reaction is carried out for 0.5 hour through an inlet of a reactor, a catalyst bed layer and an inert material zone.
Example 4
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 distance between the inner layer wall and the middle layer wall in the radial direction was 8mm and the length of the inner layer wall in the axial direction was 2mm.
Example 5
The oxidative coupling of methane to make a carbon dioxide was performed as in example 1, except that circular holes having a diameter of 600 μm were formed in the inner and middle walls.
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 catalyst loading was 10g and the catalyst loading height was 40mm.
Example 7
The reaction for producing a carbon dioxide by oxidative coupling of methane was carried out in the same manner as in example 2 except that the catalyst loading was 15g and the catalyst loading height was 54mm.
Example 8
The reaction for producing a carbon dioxide by oxidative coupling of methane was carried out in the same manner as in example 3 except that the catalyst loading was 20g and the catalyst loading height was 60mm.
Comparative example 1
The reaction of preparing the carbon dioxide by the oxidative coupling of methane is carried out by adopting a traditional fixed bed quartz tube reactor, the inner diameter of the reactor is 8mm, 1g of the catalyst obtained in the preparation example 1 is filled in the reactor, the thickness of the catalyst bed layer is 7mm, the space velocity of methane is 10000 mL/(g.h), and the molar ratio of methane to oxygen is 3:1, the catalytic reaction temperature is 800 ℃, the reaction pressure is 0.001MPa, and the reaction product is collected after 1 hour of reaction.
Comparative example 2
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 loading was 5g and the catalyst bed thickness was 35mm.
Comparative example 3
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 inner wall and the middle wall of the reactor were each made of 316L stainless steel.
Comparative example 4
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 opening ratio of the inner layer wall was 40% and the opening ratio of the middle layer wall was 45%.
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
Carbon dioxane yield = methane conversion x (ethane selectivity + ethylene selectivity) x 100%
The results obtained are shown in Table 1.
TABLE 1
As can be seen from table 1, in examples 1 to 8, the opening ratio of the inner and middle walls of the reactor was not less than 50%, and the reactor of examples 1 to 8 was used for the oxidative coupling reaction of methane, which had a higher methane conversion and selectivity of hydrocarbons of two or more, example 1 was compared with example 5, example 2 was compared with example 7, example 3 was compared with example 8, and the catalyst loading was increased, the thickness of the catalyst bed (i.e., the distance between the middle and inner walls in the radial direction) was not changed, the methane conversion and selectivity of hydrocarbons of two or more were substantially unchanged and the side reaction was less in the reaction product collected after the same time of reaction, whereas the reactor of comparative examples 3 to 4 was not using the technical means of the present invention, and the opening ratio of the inner wall was 40%, the opening ratio of the middle wall was 45%, which was lower than 50%, the methane conversion and selectivity of hydrocarbons of two or more were obtained was lower, and the side reaction was more, and in addition, from table 1, the effect of methane conversion and hydrocarbons of two or more was obtained, and the catalyst loading was not changed, as compared with example 1, the catalyst loading ratio was 1, which was not higher than that of the catalyst loading ratio 1, and the catalyst loading ratio was 1 was not changed, compared with the comparative example 1. However, as is clear from comparison of comparative example 1 and comparative example 2, the catalyst bed thickness becomes thicker as the catalyst loading increases, the methane conversion and selectivity of hydrocarbons with more than two carbons obtained are lower, and side reactions are more, indicating that the change in catalyst bed thickness has a great influence on the oxidative coupling reaction of methane. When the catalyst loading is increased, the thickness of the catalyst bed layer (namely the distance between the middle layer wall and the inner layer wall along the radial direction) is unchanged, so that the reactor is favorable for the methane oxidative coupling reaction, has higher methane conversion rate and selectivity of more than two hydrocarbons, and has less side reaction and is favorable for industrialized amplified production.
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: introducing methane and oxygen into a reactor to contact a catalyst for catalytic reaction, wherein the catalyst is selected from sodium tungstate-manganese oxide/silicon dioxide; the average particle diameter of the catalyst is 300-500 microns, and the catalyst is filled between the inner layer wall and the middle layer wall; wherein the reactor comprises:
an inner wall provided with a first aperture;
the middle layer wall is sleeved outside the inner layer wall at intervals, the inner layer wall and the middle layer wall are movably connected, so that the volume of a cavity formed by the inner layer wall and the middle layer wall can be adjusted, and the middle layer wall is provided with a second opening;
the outer layer wall is sleeved outside the middle layer wall at intervals;
at least two pairs of structures for fixing the cards are oppositely arranged on the inner layer wall and the middle layer wall, and the inner layer wall is movably connected with the middle layer wall through the cards, so that the volume of a cavity formed by the inner layer wall and the middle layer wall can be adjusted along the axial direction; the opening ratios of the inner layer wall and the middle layer wall are the same or different and are not less than 50%; the first and second openings have a diameter of no greater than 500 microns; the inner layer wall and the middle layer wall are the same or different in material and are each independently selected from at least one of quartz, alumina and ceramic; and an inert material is filled between the middle layer wall and the outer layer wall, wherein the inert material is at least one selected from quartz sand, ceramic and alumina, and the average particle size of the inert material is 300-500 microns.
2. The method of claim 1, wherein the open cell content of the inner and middle layer walls is each independently 50-80%;
and/or the first and second apertures are the same or different in shape and are each independently regular or irregular in shape.
3. The method of claim 1, wherein the first aperture and the second aperture are the same shape and are both circular.
4. The method of claim 1, wherein the first and second openings have a diameter of 50-500 microns.
5. The method of claim 1, wherein the thickness ratio of the inner layer wall and the middle layer wall is 1:0.2-5.
6. The method of claim 1, wherein the inner layer wall has a thickness of 2-5mm.
7. The method of claim 1, wherein the distance between the inner layer wall and the middle layer wall is 1-10mm in the radial direction.
8. The method according to any one of claims 1 to 7, wherein, when the above-described reactor is used, a ratio of a distance between the inner layer wall and the middle layer wall in a radial direction to a filling height of the catalyst in an axial direction is 1:0.25-10.
9. The method according to any one of claims 1 to 7, wherein, when the above-described reactor is used, a ratio of a distance between the inner layer wall and the middle layer wall in a radial direction to a filling height of the catalyst in an axial direction is 1:1-9.
10. The method of any of claims 1-7, wherein the molar ratio of methane to oxygen is 1-10:1.
11. the method of any of claims 1-7, wherein the molar ratio of methane to oxygen is 2-5:1.
12. The method of any one of claims 1-7, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 750-850 ℃, the reaction pressure is 0.001-0.05MPa, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 5000-100000 mL/(g.h).
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