CN114425275B - Methane oxidative coupling reactor and application thereof - Google Patents
Methane oxidative coupling reactor and application thereof Download PDFInfo
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- CN114425275B CN114425275B CN202010986560.4A CN202010986560A CN114425275B CN 114425275 B CN114425275 B CN 114425275B CN 202010986560 A CN202010986560 A CN 202010986560A CN 114425275 B CN114425275 B CN 114425275B
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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
- B01J8/0242—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 the fluid flow within the bed being predominantly vertical
- B01J8/0257—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 the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
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- 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
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- 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
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- 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 methane oxidative coupling reactor and application thereof, wherein the methane oxidative coupling reactor comprises: 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 aperture ratio of the inner layer wall and the middle layer wall is the same or different and is not less than 60%; the inner layer wall and the middle layer wall are made of Inconel; optionally, the reactor further comprises a catalyst filled between the inner layer wall and the middle layer wall, and the catalytic reaction temperature of the catalyst is 450-700 ℃. The reactor is suitable for low-temperature reaction, can avoid side reaction, improves the conversion rate of the reaction, and improves the yield and selectivity of reaction products.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a methane oxidative coupling reactor and application thereof.
Background
Ethylene is a compound consisting of two carbon atoms and four hydrogen atoms. The two carbon atoms are connected by a double bond. Ethylene is present in certain tissues and organs of plants and is converted from methionine under conditions of sufficient oxygen supply.
Ethylene is a basic chemical raw material for synthetic fibre, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride) and synthetic alcohol (alcohol), and can be used for preparing chloroethylene, styrene, ethylene oxide, acetic acid, acetaldehyde, alcohol and explosive, etc., and can be used as ripening agent of fruit and vegetable, and is a proven plant hormone.
Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of petrochemical industry, and the ethylene product accounts for more than 75% of petrochemical products and plays an important role in national economy. Ethylene production has been worldwide used as one of the important markers for the level of petrochemical development in a country.
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 reaction is a strongly exothermic reaction, the reaction is generally carried out at a temperature of more than 800 ℃, the reaction at a high temperature has severe requirements on the operation conditions, researchers have developed researches on catalysts at low temperatures for oxidative coupling of methane, and currently, the catalysts effective at low temperatures are generally lanthanum oxide, barium oxide and the like.
From the type of the catalyst reactor reported at present, the catalyst reactor is mainly a fixed bed reactor, when the catalyst dosage of the fixed bed reactor is increased, the temperature of the catalyst bed layer is increased, and the generated carbon dioxide can be deeply oxidized under the further action of the catalyst to generate carbon monoxide and carbon dioxide, so that when the catalyst dosage is increased, how to ensure the thickness of the catalyst bed layer is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, more side reactions and large thickness change of a catalyst bed layer in the prior art of oxidative coupling of methane, and provides a methane oxidative coupling reactor and application thereof.
The inventor of the invention discovers in the research that in the three-layer sleeve type reactor, the problems of high temperature and more side reactions of methane oxidative coupling reaction 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 methane oxidative coupling 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 60%; the inner layer wall and the middle layer wall are made of Inconel;
optionally, the reactor further comprises a catalyst filled between the inner layer wall and the middle layer wall, and the catalytic reaction temperature of the catalyst is 450-700 ℃.
The methane oxidative coupling reactor provided by the invention adopts a three-layer wall 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 dosage, 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 increase of the catalyst bed layer due to the increase of the catalyst loading of the traditional fixed bed reactor is avoided, the deep oxidation of the generated carbon dioxide under the further action of the catalyst is inhibited, the materials of the inner layer wall and the middle layer wall are all Inconel, the catalyst is suitable for catalyzing the methane oxidative coupling reaction under low temperature, the conversion rate of the reaction is improved, the yield and the selectivity of the reaction product are improved, and the industrial application is easy.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
introducing methane and oxygen into a reactor to be in contact with a catalyst for catalytic reaction, wherein the reactor is the methane oxidative coupling reactor, and the catalyst is filled between the inner layer wall and the middle layer wall; the catalytic reaction temperature is 450-700 ℃.
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 methane oxidative coupling 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 60%; the inner layer wall and the middle layer wall are made of Inconel;
optionally, the reactor may further include a catalyst packed between the inner layer wall and the middle layer wall, the catalyst having a catalytic reaction temperature of 450-700 ℃. The "catalytic reaction temperature" is a reaction temperature at which the conversion of the alkane is optimal.
In some embodiments of the invention, the open porosity of the inner and middle layer walls is each independently preferably 60-85%.
In the present invention, the catalyst is selected from a lanthanide metal oxide, a lanthanide metal oxycarbide, a modified compound of a lanthanide metal oxide, or a modified compound of a lanthanide metal oxycarbide, and preferably, the catalyst is selected from at least one of lanthanum oxide, lanthanum oxycarbonate, a modified compound of lanthanum oxide, and a modified compound of lanthanum oxycarbonate.
The size of the catalyst particles in the present invention is not limited as long as it does not affect the progress of the catalytic reaction, and preferably the catalyst has a particle size of 1 to 2mm.
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 compact material, and more preferably at least one of stainless steel, ceramic, inconel, and alumina.
In the present invention, the type of inconel is not particularly limited, and inconel625 or inconel825 may be used.
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 not more than 1mm, more preferably 600-800 micrometers.
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 distance between the inner layer wall and the middle layer wall in the radial direction is preferably 1-15mm.
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 clamping grooves for fixing the card 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 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 1-5mm. The thickness of the outer wall is 1-10mm, preferably 2-5mm.
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 a material inlet, a catalyst bed layer and the temperature of a 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:
introducing methane and oxygen into a reactor to be in contact with a catalyst for catalytic reaction, wherein the reactor is the methane oxidative coupling reactor, and the catalyst is filled between the inner layer wall and the middle layer wall; the catalytic reaction temperature is 450-700 ℃.
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 1:1 to 100, more preferably 1 to 16.
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 1-2mm.
In some embodiments of the invention, the catalyst preferably has an average particle size of 1-2mm.
In the present invention, the catalyst used is a lanthanide metal oxide, a lanthanide metal oxycarbide, a modified compound of a lanthanide metal oxide, or a modified compound of a lanthanide metal oxycarbide, and preferably, the catalyst is at least one selected from lanthanum oxide, lanthanum oxycarbonate, a modified compound of lanthanum oxide, and a modified compound of lanthanum oxycarbonate.
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:
dissolving lanthanum precursor in water (preferably deionized water), regulating the pH value of the solution to 10-13.5 by an alkaline solution, standing for 5-30min, then carrying out ultrasonic treatment for 30-90min at 20-100Hz, then maintaining for 12-120h at 120-180 ℃, separating, filtering, washing, drying, and roasting to obtain the nano lanthanum oxide catalyst. Wherein the lanthanum precursor is preferably a water-soluble lanthanum salt, more preferably selected from lanthanum nitrate or lanthanum chloride. The alkaline substance in the alkaline solution is at least one of ammonia, sodium hydroxide or potassium hydroxide.
In some embodiments of the invention, the molar ratio of methane to oxygen is preferably 1-10:1, more preferably 2-6:1.
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, for example, 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 according to the amount of the catalyst used, so as to realize the control of the catalyst bed thickness.
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 in the range from 1000 to 100000 mL/(g.multidot.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. Inconel625 is available as Inconel nickel.
Preparation example 1
6g of lanthanum nitrate hexahydrate is dissolved in 300ml of deionized water, the pH value of the solution is regulated to be 12 by 1mol/L NaOH solution, the solution is kept stand for 30min, the solution is placed in an ultrasonic reactor for ultrasonic treatment at 80Hz for 60min, the solution is placed in a hydrothermal kettle and maintained for 24h at 170 ℃, and the solution is dried at 80 ℃ for 12h and baked at 500 ℃ for 4h after separation, filtration and washing, so that the nano lanthanum oxide catalyst is prepared.
Example 1
The thickness of the inner layer wall of the reactor is 1mm, the thickness of the middle layer wall is 5mm, the material is Inconel, the bottom is provided with a raw material gas inlet, round holes with the diameter of 600 microns are formed in the inner layer wall and the middle layer wall, the opening ratio of the inner layer wall is 60%, the opening ratio of the middle layer wall is 75%, the outer layer wall is Inconel, the thickness of the outer layer wall is 2mm, 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 1mm, 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 1mm, 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 4mm in the radial direction, the card was adjusted so that the charging height of the catalyst was 5mm, the hourly space velocity of the reaction gas in terms of methane and oxygen was 40000 mL/(g.h), and the molar ratio of methane to oxygen was 5:1, the catalytic reaction temperature is 550 ℃, 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 0.5 hour of reaction.
Example 2
The thickness of the inner layer wall of the reactor is 2mm, the thickness of the middle layer wall is 6mm, the material is Inconel, the bottom is provided with a raw material gas inlet, round holes with the diameter of 700 microns are formed in the inner layer wall and the middle layer wall, the opening ratio of the inner layer wall is 75%, the opening ratio of the middle layer wall is 60%, the outer layer wall is Inconel, 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 1.5mm, 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 1.5mm, 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.
4g of the catalyst obtained in preparation 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 4mm in the radial direction, the card was adjusted so that the packing height of the catalyst was 15mm, the hourly space velocity of the reaction gas in terms of methane and oxygen was 1000 mL/(g.h), and the molar ratio of methane to oxygen was 2:1, the catalytic reaction temperature is 500 ℃, the reaction pressure is 0.01MPa, 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 0.5 hour of reaction.
Example 3
The thickness of the inner layer wall of the reactor is 5mm, the thickness of the middle layer wall is 1mm, the material is Inconel, the bottom is provided with a raw material gas inlet, round holes with the diameter of 800 microns are formed in the inner layer wall and the middle layer wall, the opening ratio of the inner layer wall is 80%, the opening ratio of the middle layer wall is 85%, the outer layer wall is Inconel, 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 2mm, 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 2mm, 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 4mm in the radial direction, the card was adjusted so that the charging height of the catalyst was 32mm, the length of the inner layer wall in the axial direction was 45mm, 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 6:1, the catalytic reaction temperature is 700 ℃, the reaction pressure is 0.05MPa, 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 0.5 hour of reaction.
Example 4
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 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 3, except that the inner and middle walls were provided with circular holes having a diameter of 1000 microns.
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 50mm.
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 57mm.
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 64mm.
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 4mm, 1g of the catalyst obtained in the preparation example 1 is filled in the reactor, the thickness of the catalyst bed layer is 5mm, the space velocity of methane is 4000 mL/(g.h), and the molar ratio of methane to oxygen is 5:1, the catalytic reaction temperature is 550 ℃, the reaction pressure is 0.001MPa, and the reaction product is collected after 0.5 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 4g and the catalyst bed thickness was 20mm.
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 60%, the material was Yinkang nickel, the reaction temperature was lower when the reactors of examples 1 to 8 were used for the oxidative coupling reaction of methane, but the selectivity of hydrocarbons of more than two carbon atoms was higher, the opening ratio of the inner wall was 40%, the opening ratio of the middle wall was 45%, the selectivity of hydrocarbons of less than 50%, the methane conversion and side reactions were lower, and the side reactions were higher in the reaction products collected after the same time, in examples 3 to 4, compared with example 7, example 2 and example 3, the thickness of the catalyst bed (i.e., the distance between the middle and inner walls in the radial direction) was unchanged. In addition, as can be seen from table 1, the methane conversion and the selectivity of hydrocarbons of more than two carbon atoms were high and the side reactions were less, because the reactor used in comparative example 1 was made of quartz, the catalyst loading was the same as that in example 1, and the catalyst bed thickness was the same, so that the effect of comparative example 1 was not greatly different from that of example 1 in terms of catalytic effect. 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 (10)
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 lanthanum oxide; the average particle diameter of the catalyst is 1-2mm, wherein the catalyst is filled between the inner layer wall and the middle layer wall; the methane oxidative coupling 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 aperture ratio of the inner layer wall and the middle layer wall is the same or different and is not less than 60%; the inner layer wall and the middle layer wall are made of Inconel; an inert material is filled between the middle layer wall and the outer layer wall, the inert material is at least one selected from quartz sand, ceramic and alumina, and the average particle size of the inert material is 1-2mm;
the catalytic reaction temperature of the catalyst is 450-700 ℃;
the first and second openings have diameters of 600-800 microns.
2. The method of claim 1, wherein the open cell content of the inner and middle layer walls is each independently 60-85%;
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 thickness ratio of the inner layer wall and the middle layer wall is 1:0.2-5.
5. The method of claim 1, wherein the inner layer wall has a thickness of 1-5mm.
6. The method according to claim 1, wherein, in using the above 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 1:1-100.
7. The process according to claim 1, wherein the ratio of the distance between the inner and middle walls in the radial direction to the filling height of the catalyst in the axial direction is 1-16 when using the above reactor.
8. The method of any of claims 1-7, wherein the volume ratio of methane to oxygen is 1-10:1.
9. the method of any of claims 1-7, wherein the volume ratio of methane to oxygen is from 2 to 6:1.
10. the method of any one of claims 1-7, wherein the conditions of the catalytic reaction comprise: the reaction pressure is 0.001-0.05MPa, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 1000-100000 mL/(g.h).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1103606A (en) * | 1993-12-11 | 1995-06-14 | 中国科学院大连化学物理研究所 | Methane-oxidizing and -coupling radial fixed-bed reactor |
| CN1119431A (en) * | 1993-03-24 | 1996-03-27 | 帝国化学工业公司 | Production of difluoromethanen |
| CN102056657A (en) * | 2008-04-09 | 2011-05-11 | 万罗赛斯公司 | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
| CN108472611A (en) * | 2015-12-15 | 2018-08-31 | 沙特阿拉伯石油公司 | Supercritical reaction device system and technique for oil upgrading |
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| US10047020B2 (en) * | 2013-11-27 | 2018-08-14 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
| US9433911B2 (en) * | 2015-02-05 | 2016-09-06 | Institute Of Nuclear Energy Research, Atomic Energy Council | Reactor with honeycomb catalyst for fuel reformation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1119431A (en) * | 1993-03-24 | 1996-03-27 | 帝国化学工业公司 | Production of difluoromethanen |
| CN1103606A (en) * | 1993-12-11 | 1995-06-14 | 中国科学院大连化学物理研究所 | Methane-oxidizing and -coupling radial fixed-bed reactor |
| CN102056657A (en) * | 2008-04-09 | 2011-05-11 | 万罗赛斯公司 | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
| CN108472611A (en) * | 2015-12-15 | 2018-08-31 | 沙特阿拉伯石油公司 | Supercritical reaction device system and technique for oil upgrading |
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