CN114425276A - Reactor and application thereof in preparation of carbon dioxide hydrocarbon by oxidative coupling of methane - Google Patents

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

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CN114425276A
CN114425276A CN202010989114.9A CN202010989114A CN114425276A CN 114425276 A CN114425276 A CN 114425276A CN 202010989114 A CN202010989114 A CN 202010989114A CN 114425276 A CN114425276 A CN 114425276A
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wall
reactor
layer wall
methane
catalyst
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CN114425276B (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

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  • 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 invention relates to the field of catalysis, and discloses a reactor and application thereof in preparing carbo-dihydrocarb through methane oxidative coupling, wherein the reactor comprises: the inner layer wall is provided with a first opening; 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 aperture ratios of the inner layer wall and the middle layer wall are the same or different and are not less than 50%; the inner wall and the middle wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramics. The reactor can avoid side reaction, improve the conversion rate of the reaction, improve the yield and the selectivity of reaction products, and is easy for industrial application.

Description

Reactor and application thereof in preparation of carbon dioxide hydrocarbon 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 carbo-dihydrocarb through methane oxidative coupling.
Background
The oxidative coupling of methane to produce ethylene and ethane is one of the most challenging and most concerned research topics in the field of catalysis at present due to its academic significance and potential huge economic value. Since the report of Keller and Bhasin in 1982, the interest in the fields of catalysis, chemical industry and petroleum and natural gas has been the focus, and the research activity reaches a peak before and after 1992, and the research heat is slightly reduced for a while later. By the year 2010 or later, along with the breakthrough of the united states in the shale gas field, a large amount of methane which is difficult to recover is recovered, the chemical utilization of methane draws high attention from the industry, and the research of preparing ethylene and ethane by the most promising methane oxidative coupling is considered to be a hot topic worldwide again.
From the current reported catalyst reaction types, the catalyst reaction type is mainly a fixed bed reaction bed reactor, and some documents on the aspects of plasma memory of a membrane reactor fluidized bed reactor and the like are reported. Other types of reactors have difficulty in achieving engineering scale-up due to thermal effects caused by increased catalyst loading.
Disclosure of Invention
The invention aims to overcome the technical problems of more side reactions, low selectivity, low yield of the carbo-dylic hydrocarbon and difficult industrial amplification of the prior art in the methane oxidative coupling reaction, and provides a reactor and application thereof in preparing the carbo-dylic hydrocarbon through methane oxidative coupling.
The inventor of the invention finds in research that in a three-wall shell reactor, the problem of more side reactions of the methane oxidative coupling reaction can be remarkably improved by maintaining the thickness of a catalyst bed layer basically unchanged and controlling the aperture ratio and the material of a sleeve, the conversion rate of the reaction can be improved, the yield and the selectivity of reaction products can be improved, and the method is easy for industrial application. Accordingly, in order to achieve the above objects, an aspect of the present invention provides a reactor comprising:
the inner layer wall is provided with a first opening;
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 inner layer wall and the middle layer wall have the same or different opening rate and are not less than 50%; the inner wall and the middle wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramics.
The reactor provided by the invention adopts a three-layer wall structure, and the inner layer wall and the middle layer wall are movably connected, so that the thickness of a catalyst bed layer is unchanged on the premise of increasing the using amount of a catalyst, and materials are contacted with the catalyst through the open holes by arranging the open holes on the inner layer wall and the middle layer wall, so that the contact area of the catalyst and raw materials is increased, the problem of uneven bed layer temperature distribution caused by the thickening of the catalyst bed layer due to the increase of the catalyst loading amount of a traditional fixed bed reactor is avoided, the occurrence of side reactions is avoided, the conversion rate of the reaction is improved, the yield and the selectivity of reaction products are improved, and the reactor is easy to industrially apply.
In a second aspect, the present invention provides a method for preparing a carbo-carbyl hydrocarbon by oxidative coupling of methane, the method comprising: introducing methane and oxygen into a reactor to contact with a catalyst to perform 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 carbo-dydrocarbon by oxidative coupling of the methane has the advantages of high conversion rate of raw materials, less side reactions, high selectivity and yield of the carbo-dydrocarbon and easy large-scale production and application.
Drawings
FIG. 1 is a schematic diagram of the structure of a reactor according to one 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 mid-level wall according to one embodiment of the present invention;
FIG. 4 is a top view of a reactor according to one embodiment of the invention.
Description of the reference numerals
100 inner layer wall, 101 first opening, 200 middle layer wall, 201 second opening, 300 outer layer wall, 400 movable device, 500 sealing device, 501 fixed bolt, 502 air inlet, 503 air outlet.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a reactor comprising:
the inner layer wall is provided with a first opening;
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 inner layer wall and the middle layer wall have the same or different opening rate and are not less than 50%; the inner wall and the middle wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramics.
In some embodiments of the invention, the inner wall and the middle wall each independently preferably have an open porosity of 50-80%.
In the present invention, the opening ratio is defined as the ratio of the total area of the sieve holes on the sieve plate to the area of the opening area (also called effective mass transfer area), i.e. phi ═ A0/Aa(ii) a In the formula: Φ — opening ratio (%); a. the0The total area of the sieve pores on the sieve plate; a. theaArea 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 filled 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 selected from at least one of 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 catalysts obtained by modifying the above catalysts. Wherein the sodium salt can be replaced by potassium salt.
In some embodiments of the present invention, preferably, the first and second apertures are the same or different in shape and are each 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 greater than 500 microns, more preferably 50-500 microns.
In some embodiments of the present invention, preferably, the middle layer wall is coaxially sleeved outside the inner layer wall at a spacing.
In some embodiments of the present invention, preferably, the outer wall is coaxially sleeved outside the middle wall at a spacing.
In some embodiments of the invention, the ratio of the thicknesses of the inner wall and the middle wall is preferably 1: 0.2-5. More preferably, the thickness of the inner wall is 2-5 mm. The thickness of the outer wall is 2-6 mm.
In some embodiments of the invention, the distance between the inner wall and the middle wall in the radial direction is preferably 1-10 mm.
In the present invention, there is no particular limitation on the movable connection manner of the inner wall and the middle wall, as long as the volume of the cavity formed by the inner wall and the middle wall can be adjusted, and particularly, the connection manner can be adjusted in the axial direction (i.e., the connection manner can be adjusted in a manner of maintaining the distance between the inner wall and the middle wall in the radial direction). In some embodiments of the present invention, at least two pairs of structures for fixing a card are oppositely disposed on the inner layer wall and the middle layer wall, and the inner layer wall is movably connected to the middle layer wall through the card, so that the volume of the cavity formed by the inner layer wall and the middle layer wall can be adjusted along the axial direction. Specifically, the card is an axially adjustable card placed along the radial direction, and the length of the radial direction of the card is equal to the distance between the inner layer wall and the middle layer wall along the radial direction. The structure for fixing the card can be a clamping groove or a slidable 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, as long as the cavity formed by the inner layer wall and the middle layer wall can be sealed, and the axial position can be adjusted, which is not described in detail herein. In the present invention, the sealing manner of the two ends of the reactor is not limited as long as the sealing effect can be achieved, and preferably, the sealing manner can be sealed by a flange.
In the present invention, temperature measuring elements (e.g., thermocouples) are disposed between the inner wall and the middle wall and between the middle wall and the outer wall to measure the temperature of the catalyst bed and the temperature of the product, and the specific positions of the temperature measuring elements are not limited, and the positions of the temperature measuring elements may be determined according to a constant temperature zone determination method in the conventional art. Preferably, the material of the temperature measuring element is quartz or ceramic.
In a second aspect, the present invention provides a method for preparing a carbo-carbyl hydrocarbon by oxidative coupling of methane, the method comprising: introducing methane and oxygen into a reactor to contact with a catalyst to perform 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 present invention, when the above reactor is used, the ratio of the distance between the inner wall and the middle wall in the radial direction to the packing 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 that different amounts of catalyst are filled with the same dispersion degree.
In the present invention, an inert material is optionally filled between the middle layer wall and the outer layer wall.
In some embodiments of the present invention, it is preferable 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 to 500 microns.
In some embodiments of the invention, the catalyst preferably has an average particle size of from 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 catalysts obtained by modifying the above catalysts. Wherein the sodium salt can be replaced by potassium salt.
In some embodiments of the invention, the catalyst used is commercially available or prepared by methods known in the art.
According to a preferred embodiment of the present invention, the specific preparation method of the catalyst is:
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 at 100-120 ℃ for 10-12 hours to obtain a solid B; then roasting at 500-550 ℃ for 4-5 hours, and then heating to 850-880 ℃ at the heating rate of 2-10 ℃/min for 4-5 hours to obtain the catalyst of the invention, wherein the water used is not limited, preferably the water is deionized water, and more preferably the deionized water with the temperature of 50-70 ℃.
In some embodiments of the invention, the molar ratio of methane to oxygen is preferably 1 to 10: 1, more preferably 2-5: 1.
According to a preferred embodiment of the present invention, according to fig. 1-4, 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 the closed space formed by the inner wall 100 through the gas inlet 502 and contact with the catalyst through the first opening 101, after reaction, the methane and oxygen are discharged into the inert material through the second opening 201 and discharged out of the reactor through the gas outlet 503, and both ends of the reactor are sealed by the sealing device 500 and fixedly connected with the reaction cavity through the fixing bolt 501. Specifically, the movable device 400 is an axially adjustable card disposed along the 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 the skilled person can control the thickness of the catalyst bed 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) along the axial direction according to the amount of the catalyst used, for example.
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 0.05 MPa. The hourly space velocity of the reaction gas, in terms of methane and oxygen, is preferably from 5000 to 100000 mL/(g.h).
In the present invention, the unit "mL/(g.h)" is the amount (mL) of the total gas of methane and oxygen used at a time of 1 hour, relative to 1g of the catalyst by mass.
In the present invention, the pressure means gauge pressure.
In the present invention, the carbo-hydrocarbon may be ethane and/or ethylene.
The present invention will be described in detail below by way of examples. In the examples and comparative examples, the reagents used were all commercially available analytical reagents. Quartz sand was purchased from Qingdao ocean chemical Co. Alumina is available from nodulizer fillers, ltd.
Preparation example 1
Catalyst Na2WO4-Mn/SiO2The preparation of (1):
adding manganese nitrate into deionized water at 60 ℃ and 25g, adding a carrier, stirring for 4 hours, and drying at 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 for 12 hours at 120 ℃ to obtain a solid B; then calcined at 550 ℃ for 5 hours, and then calcined at 850 ℃ at a rate of 5 ℃/min to obtain the catalyst used in the examples.
Example 1
The thickness of reactor inlayer wall is 2mm, the thickness of intermediate wall is 6mm, the material is quartz, the bottom is provided with the feed gas entry, open the round hole that the diameter is 250 microns on inlayer wall and the intermediate wall, wherein the aperture ratio of inlayer wall is 55%, the aperture ratio of intermediate wall is 65%, outer wall is the quartz capsule, the thickness of outer wall is 5mm, the card that passes through of inlayer wall and intermediate wall (namely block the card on inlayer wall and intermediate wall through the draw-in groove) swing joint to adjust the length of inlayer along axial direction (also be the volume of the cavity that inlayer wall and intermediate wall formed). The catalyst is filled between the inner wall and the middle wall, the average grain diameter of the catalyst is 300 microns, the inert material quartz sand is filled between the middle wall and the outer wall, the average grain diameter of the quartz sand is 300 microns, and two ends of the reactor are sealed by stainless steel flanges. The material outlet is 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 the mixing preheating heating furnace, react through the catalyst bed layer and are discharged out of the reactor through the gas outlet.
1g of the catalyst obtained in production example 1 was packed between the middle wall and the inner wall, the distance between the inner wall and the middle wall (i.e., the catalyst thickness) was 5mm in the radial direction, the card was adjusted so that the packing 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, the raw material gas passes through an inlet of the reactor, is reacted by a catalyst bed layer, passes through an inert material zone, is collected from an outlet, and is reacted for 1 hour, and then a reaction product is collected.
Example 2
The thickness of reactor inlayer wall is 5mm, the thickness of intermediate lamella wall is 1mm, the material is quartz, the bottom is provided with the feed gas entry, open the round hole that the diameter is 350 microns on inlayer wall and the intermediate lamella wall, wherein the aperture ratio of inlayer wall is 65%, the aperture ratio of intermediate lamella wall is 55%, the outer wall is alumina pipe, the thickness of outer wall is 3mm, the card that passes through of inlayer wall and intermediate lamella wall (namely block the card on inlayer wall and intermediate lamella wall through the draw-in groove) swing joint, the both ends of inlayer wall are through card swing joint to adjust the length of inlayer along axial direction (also be the volume of the cavity that inlayer wall and intermediate lamella wall formed). The catalyst is filled between the inner wall and the middle wall, the average grain diameter of the catalyst is 400 microns, the inert material alumina is filled between the middle wall and the outer wall, the average grain diameter of the alumina is 400 microns, and two ends of the reactor are sealed by stainless steel flanges. The material outlet is 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 the mixing preheating heating furnace, react through the catalyst bed layer and are discharged out of the reactor through the gas outlet.
5g of the catalyst obtained in production example 1 was packed 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 packing height of the catalyst was 18mm, the reaction gas hourly space velocity 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 passes through an inlet of the reactor, passes through a catalyst bed layer for reaction, passes through an inert material zone, is collected from an outlet, and is collected after the reaction for 1 hour.
Example 3
The thickness of the inner wall of the reactor is 2mm, the thickness of the middle wall is 10mm, the material is quartz, the bottom of the reactor is provided with a raw material gas inlet, round holes with the diameter of 400 microns are formed in the inner wall and the middle wall, the aperture ratio of the inner wall is 75%, the aperture ratio of the middle wall is 80%, the outer wall is an alumina tube, the thickness of the outer wall is 6mm, and the inner wall and the middle wall are movably connected through a clamping piece (namely the clamping piece is clamped on the inner wall and the middle 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 wall and the middle wall). The catalyst is filled between the inner wall and the middle wall, the average grain diameter of the catalyst is 450 microns, the inert material alumina is filled between the middle wall and the outer wall, the average grain diameter of the alumina is 450 microns, and two ends of the reactor are sealed by stainless steel flanges. The material outlet is 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 the mixing preheating heating furnace, react through the catalyst bed layer and are discharged out of the reactor through the gas outlet.
10g of the catalyst obtained in production example 1 was packed 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 packing height of the catalyst was 30mm, the reaction gas hourly space velocity 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 passes through an inlet of the reactor, passes through an inert material zone after the reaction of a catalyst bed layer, is collected from an outlet, and is collected after the reaction is carried out for 0.5 hour.
Example 4
The reaction for producing hydrocarbons by oxidative coupling of methane was carried out in the same manner as in example 1, except that the distance between the inner wall and the intermediate wall was 8mm in the radial direction and the length of the inner wall was 2mm in the axial direction.
Example 5
The reaction for producing hydrocarbons 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 were formed with circular holes having a diameter of 600 μm.
Example 6
A reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that the amount of the catalyst charged was 10g and the height of the catalyst charged was 40 mm.
Example 7
A reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 2, except that the amount of the catalyst charged was 15g and the height of the catalyst charged was 54 mm.
Example 8
A reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 3, except that the amount of the catalyst charged was 20g and the height of the catalyst charged was 60 mm.
Comparative example 1
The reaction for preparing the carbon-dioxide hydrocarbon by methane oxidative coupling 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 a 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 hydrocarbons by oxidative coupling of methane was carried out in accordance with the method of comparative example 1, except that the loading of the catalyst was 5g and the thickness of the catalyst bed was 35 mm.
Comparative example 3
The reaction for producing hydrocarbons 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 made of 316L stainless steel.
Comparative example 4
A reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that the inner wall had an open porosity of 40% and the intermediate wall had an open porosity of 45%.
Test example 1
The reaction product components obtained in the examples and comparative examples were measured on a gas chromatograph available from Agilent under the model number 7890A. The product is measured by a double detection channel triple valve four-column system, wherein the FID detector is connected with an alumina column and is used for analyzing CH4、C2H6、C2H4、C3H8、C3H6、C4H10、C4H8、CnHmEqual-component TCD detector mainly used for detecting CO and CO2、N2、O2、CH4。
The methane conversion and the like are calculated as follows:
methane conversion ═ amount of methane consumed by the reaction/initial amount of methane × 100%
Ethylene selectivity is the amount of methane consumed by ethylene produced/total consumption of methane × 100%
Ethane selectivity is the amount of methane consumed by ethane produced/total consumption of methane × 100%
Carbo-carb selectivity ═ ethane selectivity + ethylene selectivity
COx(CO+CO2) Selectivity to CO and CO formed2The amount of co-consumed methane/total consumption of methane X100%
Yield of carbo-carb ═ methane conversion x (ethane selectivity + ethylene selectivity) x 100%
The results obtained are shown in table 1.
TABLE 1
Figure BDA0002690243050000121
As can be seen from Table 1, the reactors of examples 1 to 8 each had an opening ratio of the inner wall and the middle wall of not less than 50%, and the reactors of examples 1 to 8 were used in the oxidative coupling reaction of methane with a higher methane conversion and selectivity for hydrocarbons over two carbons, as compared with examples 1 and 5, examples 2 and 7, and examples 3 and 8, in which the catalyst loading was increased, the thickness of the catalyst bed (i.e., the distance between the middle wall and the inner wall in the radial direction) was not changed, the methane conversion and selectivity for hydrocarbons over two carbons were not substantially changed and side reactions were less in the reaction products collected after the same time of reaction, while the reactors of comparative examples 3 to 4 did not employ the technical means of the present invention, and the opening ratio of the inner wall of comparative example 4 was 40%, the opening ratio of the middle wall of 45%, below 50%, the methane conversion and the selectivity for hydrocarbons over carbon two were lower and the side reactions were more, and it can be seen from table 1 that the methane conversion and the selectivity for hydrocarbons over carbon two were higher and the side reactions were less in comparative example 1, because the material of the reactor used in comparative example 1 was quartz, and the catalyst loading was the same and the catalyst bed thickness was the same as in example 1, the effect of comparative example 1 was not much different from that of example 1 in terms of the catalytic effect. However, as compared with comparative example 2, it can be seen that the catalyst bed thickness becomes thicker as the loading of the catalyst increases, the conversion of methane and the selectivity of hydrocarbon over carbon are lower, and the number of side reactions is large, indicating that the change in the catalyst bed thickness has a great influence on the oxidative coupling reaction of methane. When the loading of the catalyst is increased, the thickness of the catalyst bed (namely, the distance between the middle-layer wall and the inner-layer wall along the radial direction) is not changed, so that the method is favorable for the oxidative coupling reaction of methane, the methane conversion rate and the selectivity of hydrocarbon above carbon are higher, and the side reaction is less, so that the method is favorable for industrial amplification production.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A reactor, characterized in that it comprises:
the inner layer wall is provided with a first opening;
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 inner layer wall and the middle layer wall have the same or different opening rate and are not less than 50%; the inner wall and the middle wall are made of the same or different materials and are respectively and independently selected from at least one of quartz, alumina and ceramics.
2. The reactor of claim 1 wherein the inner wall and the middle wall each independently have an open cell content of 50-80%;
and/or the first and second apertures are the same or different in shape and are each independently of the other a regular or irregular shape;
preferably, the first opening and the second opening are the same in shape and are both circular;
more preferably, the diameter of the first and second openings is not more than 500 microns, even more preferably 50-500 microns.
3. The reactor of claim 1 or 2 wherein said intermediate wall is spaced coaxially around said inner wall;
and/or the outer layer wall is coaxially sleeved outside the middle layer wall at intervals.
4. The reactor according to any one of claims 1-3, wherein the ratio of the thickness of the inner wall and the middle wall is 1: 0.2 to 5;
preferably, the thickness of the inner wall is 2-5 mm.
5. The reactor according to any of claims 1-4, wherein the distance between the inner wall and the middle wall in radial direction is 1-10 mm.
6. The reactor as claimed in any one of claims 1 to 5, wherein the inner wall and the middle wall are oppositely provided with at least two pairs of structures for fixing a card, 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.
7. A method for preparing a carbo-hydrocarbon by oxidative coupling of methane, the method comprising: introducing methane and oxygen into a reactor to contact with a catalyst to perform a catalytic reaction, wherein the reactor is the reactor of any one of claims 1-6, and the catalyst is filled between the inner wall and the middle wall.
8. The process according to claim 7, wherein, in using the above reactor, the ratio of the distance between the inner wall and the middle wall in the radial direction to the packing height of the catalyst in the axial direction is 1: 0.25 to 10, preferably 1: 1 to 9;
and/or inert materials are filled between the middle layer wall and the outer layer wall;
preferably, the inert material is selected from at least one of quartz sand, ceramic, and alumina.
9. The process of claim 7, wherein the catalyst has an average particle size of 300-500 microns;
and/or the molar ratio of the methane to the oxygen is 1-10: 1, preferably 2-5: 1.
10. The method of claim 9, 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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