CN113856563B - Reactor and use thereof - Google Patents

Reactor and use thereof Download PDF

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Publication number
CN113856563B
CN113856563B CN202010619619.6A CN202010619619A CN113856563B CN 113856563 B CN113856563 B CN 113856563B CN 202010619619 A CN202010619619 A CN 202010619619A CN 113856563 B CN113856563 B CN 113856563B
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catalyst
spiral pipe
active component
catalyst section
reaction
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CN113856563A (en
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赵清锐
武洁花
韦力
王雪
邵芸
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
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J8/04—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 passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysis, and discloses a reactor and application thereof, wherein the reactor comprises a reaction cavity, a catalyst section filled in the reaction cavity, and a spiral pipe arranged along the outer wall of the reaction cavity in a surrounding manner, wherein an air outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 time of the length of the catalyst section; the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 And the second active component is an oxide of Mn. Thereby inhibiting the deep oxidation of methane to a certain extent, improving the methane conversion rate and the selectivity and yield of the carbon dioxide hydrocarbon, and having good industrial application prospect.

Description

Reactor and use thereof
Technical Field
The invention relates to the field of catalysis, in particular to a reactor and application thereof.
Background
In recent years, the global ethylene market has been in strong demand. The natural gas resources, particularly unconventional natural gas resources such as shale gas, biogas and the like, are rich in sources, clean and environment-friendly, and have good market prospects in the long run for preparing ethylene from natural gas. With the large-scale discovery and exploitation of global unconventional natural gas resources in the future, the production of ethylene by replacing petroleum with natural gas with relatively abundant reserves and low price becomes more and more important, and the method is worthy of arousing the attention of the industry. The technical process flow of the ethylene preparation by methane oxidative coupling is short, the energy consumption is low, the ethylene production process route which has the most development prospect, the simplest flow and the lowest raw material cost in the ethylene preparation by natural gas so far is provided, and the ethylene production cost is greatly reduced.
Methane is used as an organic gas with stable chemical properties, has high activation energy, and needs high temperature even if participating in the coupling reaction under the condition of oxygen. The high temperature and the presence of oxygen also make it possible for both methane and the resulting reaction products (ethane and ethylene, collectively carbo-hydrides) to be deeply oxidized to CO and CO x And the reaction is a strong exothermic reaction, and no effective heat transfer measure is provided, so that the temperature of a catalyst bed layer is increased too fast, the temperature of a hot spot is too high, the reaction selectivity is reduced, and the oxygen inlet amount does not reach a preset level or even a temperature runaway is caused.
Disclosure of Invention
The invention aims to solve the problems of overhigh temperature of a hot spot of a catalyst bed layer and deep oxidation of methane and an obtained reaction product in the prior art, and provides a reactor and application thereof.
The inventor of the present invention found in research that although the development of a catalyst and the research of a reaction mechanism are currently focused, the improvement of the heat removal manner of a reactor can also effectively improve the yield of the carbon dioxide hydrocarbon. Specifically, a spiral pipe is arranged on the outer wall of the reaction cavity in a surrounding mode, in the reaction process, purging gas is injected into the spiral pipe, the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is controlled to be 0.4-0.9 times of the length of the catalyst section, heat is transferred, the catalyst bed is forcibly subjected to heat transfer and temperature reduction, the hot spot temperature of the bed is reduced, the temperature runaway phenomenon is reduced, the oxygen inlet amount is increased, the deep oxidation of methane is inhibited to a certain extent, the methane conversion rate and the selectivity and the yield of carbon dioxide hydrocarbon are improved, and the method has a good industrial application prospect.
In order to achieve the above object, the present invention provides a reactor, which comprises a reaction chamber, a catalyst section filled in the reaction chamber, and a spiral pipe arranged around the outer wall of the reaction chamber, wherein the gas outlet of the spiral pipe is located at the downstream of the catalyst section, and the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 And the second active component is an oxide of Mn.
In a second aspect the present invention provides a process for the oxidative coupling of methane to produce a carbo-carburis, which process comprises:
(1) Filling a catalyst section in a reaction cavity, and arranging a spiral pipe in a surrounding manner along the outer wall of the reaction cavity, wherein an air outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times of the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
(2) Introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting a purging gas into the spiral tube during the catalytic reaction.
The method for preparing the carbo-dydrocarbon by oxidative coupling of the methane has the advantages of low temperature of catalytic reaction, high conversion rate of raw materials, less side reaction, high selectivity and yield of the carbo-dydrocarbon, and easy large-scale production and application.
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.
The invention provides a reactor, which comprises a catalyst section, and comprises a reaction cavity, the catalyst section filled in the reaction cavity and a spiral pipe arranged along the outer wall of the reaction cavity in a surrounding way, wherein the gas outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times of the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 And the second active component is an oxide of Mn.
In some embodiments of the invention, the outlet of the spiral tube is spaced from the cross-section of the downstream end of the catalyst section by a distance of from 0.4 to 0.9 times the length of the catalyst section. Specifically, the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is less than 0.9 times of the length of the catalyst section, otherwise the catalyst is easy to deactivate in the reaction, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is more than 0.4 times of the length of the catalyst section, otherwise the reaction heat is not suitable to transfer.
In some embodiments of the present invention, the distance between the outlet of the spiral tube and the cross section of the downstream end of the catalyst section is preferably 0.7 to 0.9 times the length of the catalyst section, in order to further remove heat generated by the reaction, suppress the occurrence of side reactions, and improve the carbon dioxide yield.
In some embodiments of the present invention, the catalyst is packed in a single stage, and the reactor may include a first packed stage, a catalyst stage, and a second packed stage in this order in the reactant flow direction, and the packing in the first packed stage and the second packed stage is the same or different and is each independently selected from silica and/or alumina; preferably, the silica is derived from quartz sand.
In some embodiments of the present invention, the catalyst is filled in a multi-stage (two-stage) manner, in the direction of the reactant flow, the reactor may sequentially comprise a first catalyst stage, a filling stage and a second catalyst stage, and the filling material in the filling stage is selected from silica and/or alumina; preferably, the silica is derived from quartz sand. The catalysts of the first catalyst section and the second catalyst section can be the same or different and respectively and independently comprise a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate, the active component comprises a first active component and a second active component, and the first active component is Na 2 WO 4 And/or K 2 WO 4 And the second active component is MnAn oxide of (2).
In some embodiments of the invention, the position of the gas inlet of the spiral tube is not limited, preferably, the gas inlet of the spiral tube is disposed upstream of the gas outlet of the spiral tube in the direction of reactant flow; preferably, the air inlet of the spiral duct is disposed upstream of the catalyst section. Preferably, the length of the helical tube is 5 to 20 times, more preferably 8 to 15 times the length of the catalyst section. Specifically, the distance between the air inlet of the spiral tube and the air outlet of the spiral tube along the direction of reactant flow is the length of the spiral tube.
In some embodiments of the invention, the catalyst used is commercially available or prepared by methods known in the art.
According to one embodiment of the present invention, the catalyst is prepared by: adding manganese nitrate into deionized water, adding a carrier, stirring for 2-4 hours, and drying at 100-120 ℃ for 22-24 hours to obtain solid A; then dissolving sodium tungstate/potassium tungstate in deionized water, adding the solid A, stirring for 2-4 hours, and drying at 100-120 ℃ for 22-24 hours to obtain a solid B; and dissolving a precursor of the auxiliary agent in deionized water, adding the solid B, stirring for 2-4 hours, drying at 100-120 ℃ for 22-24 hours, roasting at 500-550 ℃ for 4-5 hours, and heating to 850-880 ℃ for roasting for 4-5 hours to obtain the catalyst.
In some embodiments of the present invention, preferably, the catalyst in the catalyst section further contains an auxiliary agent, preferably at least one selected from the oxides of Ce, la, sr, sm and Y. More preferably, the content of the auxiliary is 0.2 to 4g, and still more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the present invention, the content of the first active ingredient is preferably 1 to 20g, and more preferably 5 to 15g, based on 100g of the carrier. The content of the second active ingredient is preferably 1 to 10g, and more preferably 3 to 6g.
In some embodiments of the invention, the ratio between the outside diameter of the helical pipe and the inside diameter of the helical pipe is preferredIs 1:0.3-0.5. Specifically, the outside diameter of the spiral pipe refers to the diameter of the outer circle of the spiral pipe, usually measured with a vernier caliper, and is designated by the symbol Φ. The diameter of the inner circle of the spiral tube is called the inner diameter, and is usually measured directly by a micrometer or a vernier caliper with the symbol of
Figure BDA0002562587800000051
In some embodiments of the invention, the ratio between the outside diameter of the helical pipe and the pitch of the helical pipe is preferably 1:1.1-3, more preferably 1:1.25-1.6.
In some embodiments of the invention, the ratio between the outer diameter of the spiral tube and the inner diameter of the reaction chamber is preferably 1:2-5, more preferably 1:2.6-5.
In some embodiments of the invention, the distance between the outer wall of the spiral tube and the outer wall of the reaction chamber is preferably 0 to 5mm.
In some embodiments of the present invention, the material of the spiral tube is preferably stainless steel, glass or ceramic, and is preferably stainless steel.
In the present invention, the reaction chamber may be various containers capable of containing a catalyst, such as a quartz tube.
In a second aspect the present invention provides a process for the oxidative coupling of methane to produce a carbo-carburis, which process comprises:
(1) Filling a catalyst section in a reaction cavity, and arranging a spiral pipe in a surrounding manner along the outer wall of the reaction cavity, wherein an air outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times of the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
(2) Introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting a purging gas into the spiral tube during the catalytic reaction.
In some embodiments of the invention, the outlet of the spiral tube is spaced from the cross-section of the downstream end of the catalyst section by a distance of from 0.4 to 0.9 times the length of the catalyst section. Specifically, the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is less than 0.9 times the length of the catalyst section, otherwise the catalyst is easily deactivated in the reaction, and the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is more than 0.4 times the length of the catalyst section, otherwise the reaction heat is not suitable to be transferred.
In some embodiments of the present invention, in order to further remove the heat generated by the reaction, suppress the occurrence of side reaction, and increase the carbon dioxide yield, the distance between the outlet of the spiral tube and the cross section of the downstream end of the catalyst section is preferably 0.7 to 0.9 times the length of the catalyst section.
In some embodiments of the present invention, preferably, the catalyst in the catalyst section further contains an auxiliary agent, the auxiliary agent preferably being selected from at least one of oxides of Ce, la, sr, sm and Y. More preferably, the content of the auxiliary is 0.2 to 4g based on 100g of the carrier.
In some embodiments of the present invention, the first active ingredient is preferably present in an amount of 1 to 20g, based on 100g of the carrier. The content of the second active ingredient is preferably 1 to 10g.
In the present invention, the description of the structure of the spiral duct, as mentioned above, is omitted.
In the present invention, the reaction chamber may be various containers capable of containing a catalyst, such as a quartz tube.
In some embodiments of the invention, the temperature of the purge gas is preferably 0-30 ℃.
In some embodiments of the invention, the volume flow rate of the purge gas is preferably 50 to 500mL/min.
In some embodiments of the present invention, the type of purge gas is not limited, but for cost savings, the purge gas is preferably nitrogen and/or air. In some embodiments of the invention, the volume ratio of methane to oxygen is from 2 to 6:1, preferably 2 to 4:1.
in some embodiments of the invention, the conditions of the catalytic reaction include: the reaction temperature is preferably 800 to 900 deg.C, more preferably 800 to 850 deg.C. The reaction pressure for the catalytic reaction is preferably 0 to 0.02MPa. The catalytic reaction time is preferably 0.5 to 8 hours. The reaction gas hourly space velocity in terms of methane and oxygen is preferably 8000-25000 mL/(g.h). Specifically, the reaction temperature means a temperature 1cm above the bed of the catalyst section.
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. The method for measuring the element composition of the catalyst is an X-ray fluorescence method, and the specific detection refers to GB/T30905-2014.
Preparation example 1
Adding manganese nitrate into deionized water at 20 ℃ and 25g, adding a carrier, stirring for 4 hours, and drying at 120 ℃ for 24 hours to obtain a solid A; then dissolving sodium tungstate in 25g of deionized water at 20 ℃, adding the solid A, stirring for 4 hours, and drying for 24 hours at 120 ℃ to obtain a solid B; then dissolving the precursor of the auxiliary agent in deionized water with the temperature of 50 ℃ and the weight of 25g, adding the solid B, stirring for 2 hours, drying for 24 hours at the temperature of 120 ℃, roasting for 5 hours at the temperature of 550 ℃, and then heating to 850 ℃ for roasting for 5 hours to obtain the catalyst used in the embodiment.
The precursors of the auxiliary agents all refer to nitrate, and the using amount of each component enables the contents of active components and the auxiliary agents in the catalyst to be shown in the table 1:
TABLE 1
Figure BDA0002562587800000081
Note: the content of each component in the catalyst is based on 100g of carrier;
"/" indicates no promoter is present in the catalyst.
Example 1
The reactor is a quartz tube with the inner diameter of a reaction cavity of 10mm and the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 48mm, a spiral tube with the outer diameter of 2mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 1mm, the length of the spiral tube is 50cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 0mm, the thread pitch of the spiral tube is 2.5mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 3.4cm, nitrogen enters from the air inlet of the spiral tube and is discharged from the air outlet of the spiral tube, the temperature of the nitrogen is 20 ℃, and the nitrogen flow is 200mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 830 ℃, the volume ratio of methane to oxygen is 2, the hourly space velocity of reaction gas calculated by methane and oxygen is 10000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 2
The reactor is a quartz tube with the inner diameter of a reaction cavity being 8mm and the length being 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 70mm, a spiral tube with the outer diameter being 3mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 1mm, the length of the spiral tube is 60cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 5mm, the screw pitch of the spiral tube is 5mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 6cm, nitrogen enters from the air inlet of the spiral tube and is discharged from the air outlet of the spiral tube, the nitrogen temperature is 30 ℃, and the nitrogen flow is 50mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.012MPa, the reaction temperature is 800 ℃, the volume ratio of methane to oxygen is 3, the hourly space velocity of the reaction gas calculated by methane and oxygen is 25000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 3
The reactor is a quartz tube with the inner diameter of a reaction cavity of 12mm and the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 33mm, a spiral tube with the outer diameter of 6mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 3mm, the length of the spiral tube is 49cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 2mm, the thread pitch of the spiral tube is 8mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 2.3cm, nitrogen enters from the air inlet of the spiral tube and is discharged from the air outlet of the spiral tube, the temperature of the nitrogen is 14 ℃, and the flow of the nitrogen is 500mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.02MPa, the reaction temperature is 850 ℃, the volume ratio of methane to oxygen is 4, the hourly space velocity of the reaction gas calculated by methane and oxygen is 8000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 4
The reactor is a quartz tube with the inner diameter of a reaction cavity of 10mm and the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 47mm, a spiral tube with the outer diameter of 2mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 1mm, the length of the spiral tube is 24cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 3mm, the thread pitch of the spiral tube is 5mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 2cm, nitrogen enters from the air inlet of the spiral tube and is discharged from the air outlet of the spiral tube, the nitrogen temperature is 20 ℃, and the nitrogen flow is 400mL/min. The reaction pressure is the pressure generated by the raw material, namely 0.010MPa, the reaction temperature is 880 ℃, the volume ratio of methane to oxygen is 6, the hourly space velocity of the reaction gas calculated by methane and oxygen is 15000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 5
The reactor is a quartz tube with the inner diameter of a reaction cavity of 10mm and the length of 530mm, the total loading amount of the catalyst is 1g, the length of the catalyst section reaches 45mm, a spiral tube with the outer diameter of 3mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 1.2mm, the length of the spiral tube is 90cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 5mm, the pitch of the spiral tube is 6mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 2.7cm, nitrogen enters from the air inlet of the spiral tube and is discharged from the air outlet of the spiral tube, the temperature of the nitrogen is 5 ℃, and the flow of the nitrogen is 300mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.08MPa, the reaction temperature is 900 ℃, the volume ratio of methane to oxygen is 2, the hourly space velocity of reaction gas calculated by methane and oxygen is 10000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 6
The reaction for producing a dihydrocarbane by oxidative coupling of methane was carried out in the same manner as in example 1, except that the composition of the catalyst used was as shown in Table 1.
Comparative example 1
The reactor is a quartz tube with the inner diameter of a reaction cavity of 10mm and the length of 530mm, the total loading amount of the catalyst is 1g, and the length of the catalyst section reaches 48mm. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 830 ℃, the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000 mL/(g.h), when the volume ratio of methane to oxygen is 2, the hot spot temperature is 961 ℃, and the temperature of the reaction system is very easy to fly. Therefore, the oxygen feed amount can only be reduced, the volume ratio of methane to oxygen is 2.2, and the reaction product is collected after 1 hour of reaction.
Comparative example 2
The reaction for oxidative coupling of methane to produce dihydrocarbons was carried out in accordance with example 1, except that the distance between the outlet of the spiral tube and the cross-section of the downstream end of the catalyst section was 0.2cm.
Comparative example 3
The oxidative coupling of methane to produce hydrocarbons was carried out in accordance with example 1, except that the outlet of the spiral tube was spaced 4.5cm from the cross-sectional area of the downstream end of the catalyst section.
Comparative example 4
The reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in example 1, except that the catalyst was replaced with another catalyst, as shown in Table 1.
Comparative example 5
The reaction for producing a hydrocarbon by oxidative coupling of methane was carried out in the same manner as in comparative example 1, except that the catalyst used in comparative example 4 was used.
Test example 1
For instance, a pair of fruitsThe 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 CH 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 Equal-component TCD detector mainly used for detecting CO and CO 2 、N 2 、O 2 、CH 4 。
The methane conversion and the like are calculated as follows:
methane conversion = amount of methane consumed by reaction/initial amount of methane × 100%
Ethylene selectivity = amount of methane consumed by ethylene produced/total consumption of methane × 100%
Ethane selectivity = amount of methane consumed by ethane produced/total consumption of methane × 100%
Carbo-carb selectivity = ethane selectivity + ethylene selectivity
CO x (CO+CO 2 ) Selectivity = CO and CO generated 2 The amount of co-consumed methane/total consumption of methane X100%
Yield of carbo-dehydes = methane conversion x (ethane selectivity + ethylene selectivity)
The results obtained are shown in Table 2.
Test example 2
The index of the removed heat investigation is judged by the temperature of the hot spot. The temperature in the catalyst bed was measured by a thermocouple during the reaction, and the point at which the temperature in the catalyst bed was the highest, i.e., the hot spot temperature, and the obtained results are shown in table 2.
TABLE 2
Figure BDA0002562587800000131
The test results show that, as can be seen from table 2, compared to comparative examples 1 to 4,when the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times of the length of the catalyst section, the methane conversion rate of the embodiments 1-6 is higher, the selectivity of the carbon dioxide is higher, the yield of the carbon dioxide is higher, and CO is higher x The selectivity is relatively low, the temperature of the hot spot is relatively low, which shows that the deep oxidation of methane is inhibited when the catalyst system is used for preparing the carbo-dihydrocarb through the oxidative coupling of the methane, the occurrence of side reaction is reduced, and the oxygen inlet amount is increased in the example 1 compared with the comparative example 1. The methane conversion, the selectivity to the carbon dioxide, and the yield of the carbon dioxide were all higher in examples 1-6 relative to comparative examples 4-5 (the carriers were all SiC), and the effect of using the spiral tube in comparative example 4 was similar to that of using no spiral tube in comparative example 5, indicating that superior catalytic effect could be obtained only by removing the heat generated by the reaction with the spiral tube for a particular catalyst.
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 (17)

1. A reactor is characterized by comprising a reaction cavity, a catalyst section filled in the reaction cavity and a spiral pipe arranged along the outer wall of the reaction cavity in a surrounding manner, wherein an air outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 time of the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is MnAn oxide;
wherein the catalyst in the catalyst section further comprises an auxiliary agent, and the auxiliary agent is at least one selected from Ce oxide, la oxide, sr oxide, sm oxide and Y oxide.
2. The reactor according to claim 1, wherein the content of the auxiliary is 0.2 to 4g based on 100g of the carrier.
3. A reactor as claimed in claim 2, wherein the adjuvant is present in an amount of 2 to 4g, based on 100g of the support.
4. The reactor according to claim 1, wherein the first active component is present in an amount of 1 to 20g, based on 100g of the carrier; the content of the second active component is 1-10g.
5. The reactor according to claim 4, wherein the first active component is present in an amount of 5 to 15g, based on 100g of the carrier; the content of the second active component is 3-6g.
6. The reactor of claim 1 wherein the ratio between the outside diameter of the spiral tube, the inside diameter of the spiral tube, the pitch of the spiral tube and the inside diameter of the reaction chamber is 1:0.3-0.5:1.1-3:2-5;
and/or the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.7-0.9 times of the length of the catalyst section;
and/or the distance between the outer wall of the spiral pipe and the outer wall of the reaction cavity is 0-5mm;
and/or the length of the spiral tube is 5-20 times of the length of the catalyst section;
and/or the spiral pipe is made of stainless steel, glass or ceramic.
7. The reactor of claim 6 wherein the ratio between the outside diameter of the spiral tube, the inside diameter of the spiral tube, the pitch of the spiral tube and the inside diameter of the reaction chamber is 1:0.3-0.5:1.25-1.6:2.6-5;
and/or the length of the spiral pipe is 8-15 times of the length of the catalyst section;
and/or the spiral pipe is made of stainless steel.
8. A method for preparing carbo-diimides by oxidative coupling of methane, which comprises:
(1) Filling a catalyst section in a reaction cavity, and arranging a spiral pipe in a surrounding manner along the outer wall of the reaction cavity, wherein an air outlet of the spiral pipe is positioned at the downstream of the catalyst section, and the distance between the air outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.4-0.9 times of the length of the catalyst section;
the catalyst in the catalyst section comprises a carrier and an active component loaded on the carrier, wherein the carrier is selected from silicon dioxide and/or barium titanate; the active components comprise a first active component and a second active component, wherein the first active component is Na 2 WO 4 And/or K 2 WO 4 The second active component is an oxide of Mn;
wherein the catalyst in the catalyst section further comprises an auxiliary agent, and the auxiliary agent is selected from at least one of Ce oxide, la oxide, sr oxide, sm oxide and Y oxide;
(2) Introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting sweeping gas into the spiral pipe during the catalytic reaction at 800-900 ℃.
9. The method according to claim 8, wherein the adjuvant is contained in an amount of 0.2 to 4g based on 100g of the carrier.
10. The method according to claim 9, wherein the adjuvant is present in an amount of 2-4g based on 100g of the carrier.
11. The method according to claim 8, wherein the first active ingredient is contained in an amount of 1 to 20g based on 100g of the carrier; the content of the second active component is 1-10g.
12. The method according to claim 11, wherein the first active ingredient is present in an amount of 5-15g, based on 100g of the carrier; the content of the second active component is 3-6g.
13. The method of claim 8, wherein a ratio between an outer diameter of the spiral pipe, an inner diameter of the spiral pipe, a pitch of the spiral pipe, and an inner diameter of the reaction chamber is 1:0.3-0.5:1.1-3:2-5;
and/or the distance between the gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is 0.7-0.9 times of the length of the catalyst section;
and/or the distance between the outer wall of the spiral pipe and the outer wall of the reaction cavity is 0-5mm;
and/or the length of the spiral tube is 5-20 times of the length of the catalyst section;
and/or the spiral pipe is made of stainless steel, glass or ceramic.
14. The method of claim 13, wherein a ratio between an outer diameter of the spiral pipe, an inner diameter of the spiral pipe, a pitch of the spiral pipe, and an inner diameter of the reaction chamber is 1:0.3-0.5:1.25-1.6:2.6-5;
and/or the length of the spiral pipe is 8-15 times of the length of the catalyst section;
and/or the spiral pipe is made of stainless steel.
15. The method of claim 8, wherein the temperature of the purge gas is 0-30 ℃;
and/or the volume flow of the purge gas is 50-500mL/min;
and/or the purge gas is nitrogen and/or air;
and/or the volume ratio of the methane to the oxygen is 2-6:1.
16. the method of claim 15, wherein the volume ratio of methane to oxygen is 2-4:1.
17. the method of claim 8, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 800-850 ℃, the reaction pressure is 0-0.02MPa, the reaction time is 0.5-8h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 8000-25000 mL/(g.h).
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