CN113856564A - Reactor provided with spiral pipe and application thereof - Google Patents

Reactor provided with spiral pipe and application thereof Download PDF

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Publication number
CN113856564A
CN113856564A CN202010621542.6A CN202010621542A CN113856564A CN 113856564 A CN113856564 A CN 113856564A CN 202010621542 A CN202010621542 A CN 202010621542A CN 113856564 A CN113856564 A CN 113856564A
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catalyst
spiral pipe
reaction
catalyst section
section
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CN113856564B (en
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赵清锐
邵芸
王雪
韦力
武洁花
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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • 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 provided with a spiral pipe and application thereof, wherein the reactor comprises a reaction cavity, a catalyst section filled in the reaction cavity and the spiral pipe arranged along the outer wall of the reaction cavity in a surrounding manner, an air outlet of the spiral pipe is positioned below 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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal. The purging gas is used as a heat carrier to remove reaction heat, the hot spot temperature of the catalyst bed layer is effectively controlled, and the temperature runaway phenomenon is reduced, so that the deep oxidation of methane is inhibited to a certain extent, the methane conversion rate and the selectivity and yield of the carbon dioxide hydrocarbon are improved, and the method has a good industrial application prospect.

Description

Reactor provided with spiral pipe and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to a reactor provided with a spiral pipe and application thereof.
Background
Natural gas is favored because of its advantages of cleanliness, abundance, wide distribution and comprehensive economy superior to other fuels, and is considered as an ideal fuel and chemical industry feedstock in the future. The natural gas reserves that have been explored far exceed the crude oil reserves. The content of methane in natural gas is about 95% generally, however, methane cannot be liquefied at normal temperature, which brings inconvenience to storage and transportation, so that the utilization of methane becomes a focus of attention.
The direct production of carbo-hydrocarbons from methane was proposed since 1986, and a large number of documents were reported on the progress of the oxidative coupling of methane during the subsequent decades. The methane oxidative coupling reaction is a strong exothermic reaction under a high-temperature condition, and the ignition temperature of the methane oxidative coupling reaction is over 600 ℃. The research on the oxidative coupling reaction of methane has advanced in theory and application after decades of exploration, but the deep oxidation to carbon oxides is inevitable because the oxidative coupling reaction of methane occurs under high temperature and oxygen exists. The deep oxidation reaction is also a strong exothermic reaction, which further aggravates the temperature rise of a methane oxidation coupling reaction bed layer, and leads the reaction temperature to be difficult to control. If the methane oxidative coupling reaction is industrialized, how to control the reaction temperature and effectively and quickly remove the heat of the reaction has important significance.
Disclosure of Invention
The invention aims to overcome the problems of overhigh temperature of a hot spot of a catalyst bed and deep oxidation of methane and obtained reaction products in the prior art, and provides a reactor provided with a spiral pipe and application thereof, wherein the spiral pipe is arranged on the outer wall of a reaction cavity in a surrounding manner, purging gas is injected into the spiral pipe, the distance between a gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is controlled to be 0.5-0.8 time of the length of the catalyst section, the catalyst section uses a catalyst with at least one of CaO, MgO and BaO as a carrier and an alkali metal oxide as an active component, the purging gas as a heat carrier to remove reaction heat, the hot spot temperature of the catalyst bed is effectively controlled, so that a reaction system is easier to control under the condition of large catalyst loading, the temperature flying phenomenon is reduced, and the deep oxidation of the methane is inhibited to a certain extent, improves the methane conversion rate and the selectivity and the yield of the carbon dioxide hydrocarbon, and has good industrial application prospect.
The inventors of the present invention have found in their studies that, although the development of a catalyst and the study of a reaction mechanism are currently focused, the improvement of the heat removal means of a reactor is effective in increasing the yield of a carbo-diimide. 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 a gas outlet of the spiral pipe and the cross section of the downstream end of the catalyst section is controlled to be 0.5-0.8 times of the length of the catalyst section, at least one of CaO, MgO and BaO is used as a carrier for the catalyst section, and a catalyst with an alkali metal oxide as an active component is used.
In order to achieve the above object, the present invention provides a reactor provided with a spiral pipe, the reactor comprising 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 below 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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting a sweeping gas into the spiral tube in the reverse catalysis process.
The method for preparing the carbon dioxide hydrocarbon by the oxidative coupling of the methane can remove reaction heat in time, effectively control the hot spot temperature of a catalyst bed layer, reduce the temperature runaway phenomenon without influencing the conversion rate of the methane and the yield of the carbon dioxide hydrocarbon, and is easy for 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 provided with a spiral pipe, which comprises a reaction cavity, a catalyst section filled in the reaction cavity and the spiral pipe arranged along the outer wall of the reaction cavity in a surrounding way, wherein an air outlet of the spiral pipe is positioned below 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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
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 0.5 to 0.8 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 0.8 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 0.5 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 0.6 to 0.8 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.
According to a preferred embodiment of the present invention, the catalyst is packed in a single stage, and the reactor may sequentially include a first packed stage, a catalyst stage and a second packed stage 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 independently selected from silica and/or alumina; preferably, the silica is derived from quartz sand.
According to another preferred embodiment of the present invention, the catalyst is packed in multiple stages (two stages), the reactor may sequentially include a first catalyst stage, a packed stage and a second catalyst stage in the reactant flow direction, and the packing in the packed 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 may be the same or different and each independently include a carrier and an active component supported on the carrier, wherein the carrier is at least one of CaO, MgO, and BaO; the active component is an oxide of an alkali metal.
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 10 to 30 times, more preferably 10 to 20 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 a preferred embodiment of the present invention, the catalyst without promoter is prepared by: adding a precursor of the active component into deionized water, adding a carrier, stirring for 1-3 hours, drying at 100-120 ℃ for 20-24 hours, and roasting at 700-750 ℃ for 4-6 hours to obtain the catalyst.
According to another preferred embodiment of the present invention, the promoted catalyst is prepared by: adding a precursor of an active component into deionized water, adding a carrier, stirring for 1-3 hours, and then drying at the temperature of 100-120 ℃ for 20-24 hours to obtain a solid A; and then dissolving the precursor of the auxiliary agent in deionized water, adding the solid A, stirring for 1-3 hours, drying at the temperature of 100-750 ℃ for 20-24 hours, and roasting at the temperature of 700-750 ℃ for 4-6 hours to obtain the catalyst.
In some embodiments of the present invention, preferably, the catalyst in the catalyst section further contains an auxiliary agent, the auxiliary agent preferably being at least one selected from Sr oxide, La oxide, Y oxide, Sn oxide, and Ce oxide. More preferably, the adjuvant is present in an amount of 1 to 8g, preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the present invention, the active component is preferably at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb.
In some embodiments of the invention, the active ingredient is preferably present in an amount of 1 to 25g, more preferably 3 to 20g, based on 100g of the carrier.
In some embodiments of the invention, the ratio between the outside diameter of the spiral pipe and the inside diameter of the spiral pipe is preferably 1: 0.3-0.62, more preferably 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 BDA0002563192650000051
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: 1.2-2.5, more preferably 1: 1.5-2.
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: 2-6, more preferably 1: 4-6.
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 6mm, more preferably 0 to 4 mm.
In some embodiments of the present invention, the material of the spiral tube is preferably stainless steel, glass or ceramic, and more 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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting a sweeping gas into the spiral tube in the reverse catalysis process.
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 0.5 to 0.8 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 0.8 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 0.5 times of the length of the catalyst section, otherwise the reaction heat is not suitable to transfer.
In some embodiments of the present invention, in order to further remove heat generated by the reaction, suppress the occurrence of side reaction, and increase the carbon dioxide yield, the distance between the gas outlet of the spiral tube and the cross section of the downstream end of the catalyst section is preferably 0.6 to 0.8 times the length of the catalyst section.
In some embodiments of the invention, the catalyst in the catalyst section further contains a promoter, preferably at least one selected from the group consisting of Sr oxide, La oxide, Y oxide, Sn oxide and Ce oxide. More preferably, the adjuvant is present in an amount of preferably 1 to 8g, more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the present invention, the active component is preferably at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb. More preferably, the active ingredient is contained in an amount of 1 to 25g, and still more preferably 3 to 20g, based on 100g of the carrier.
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 500 mL/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 preferably 2-4: 1, more preferably 2 to 3: 1.
in some embodiments of the invention, the conditions of the catalytic reaction include: the reaction temperature is preferably 700 ℃ to 850 ℃, more preferably 700 ℃ to 800 ℃. The reaction pressure for the catalytic reaction is preferably 0.001 to 0.02 MPa. The catalytic reaction time is preferably 0.5 to 8 hours. The hourly space velocity of the reaction gas in terms of methane and oxygen is preferably 5000-. Specifically, the reaction temperature refers to 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. SiO 22Is derived from quartz sand, and the quartz sand is purchased from Qingdao ocean chemical industry Co. Alumina is available from nodulizer fillers, ltd. 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
The preparation method of the catalyst without the auxiliary agent comprises the following steps: adding a precursor of the active component into deionized water with the temperature of 50 ℃ and the weight of 25g, adding a carrier, stirring for 2 hours, drying for 24 hours at the temperature of 120 ℃, and then roasting for 6 hours at the temperature of 750 ℃ to obtain the catalyst used in the embodiment.
Preparation example 2
The preparation method of the catalyst with the auxiliary agent comprises the following steps: adding a precursor of the active component into deionized water at 50 ℃ and 25g, adding a carrier, stirring for 2 hours, and drying at 120 ℃ for 24 hours to obtain a solid A; then dissolving the precursor of the auxiliary agent in deionized water with the temperature of 50 ℃ and the weight of 25g, adding the solid A, stirring for 2 hours, drying for 24 hours at the temperature of 120 ℃, and then roasting for 6 hours at the temperature of 750 ℃ to obtain the catalyst used in the embodiment.
In the preparation examples, the precursor of the active component and the precursor of the auxiliary agent both refer to nitrate, and the usage amount of each component is such that the content of the active component and the auxiliary agent in the catalyst is shown in table 1:
TABLE 1
Figure BDA0002563192650000081
Figure BDA0002563192650000091
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 reaction cavity with the inner diameter of 10mm and the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 10mm, a spiral pipe with the outer diameter of 2mm is sleeved from the upper part of the reactor, the inner diameter of the spiral pipe is 1mm, the length of the spiral pipe is 20cm, the distance from the outer wall of the spiral pipe to the outer wall of the reaction cavity is 0mm, the screw pitch of the spiral pipe is 3mm, the distance from the air outlet of the spiral pipe to the cross section of the downstream end of the catalyst section is 8mm, nitrogen enters from the air inlet of the spiral pipe and is discharged from the air outlet of the spiral pipe, the nitrogen temperature is 30 ℃, and the nitrogen flow is 200 mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.011MPa, the reaction temperature is 750 ℃, the volume ratio of methane to oxygen is 2.2, the hourly space velocity of the 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 reaction cavity with the inner diameter of 8mm and the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 16mm, a spiral pipe with the outer diameter of 2mm is sleeved from the upper part of the reactor, the inner diameter of the spiral pipe is 1mm, the length of the spiral pipe is 16cm, the distance from the outer wall of the spiral pipe to the outer wall of the reaction cavity is 3mm, the screw pitch of the spiral pipe is 4mm, the distance from the air outlet of the spiral pipe to the cross section of the downstream end of the catalyst section is 10mm, nitrogen enters from the air inlet of the spiral pipe and is discharged from the air outlet of the spiral pipe, the nitrogen temperature is 10 ℃, and the nitrogen flow is 50 mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.008MPa, the reaction temperature is 700 ℃, the volume ratio of methane to oxygen is 2, the hourly space velocity of the reaction gas calculated by methane and oxygen is 5000 mL/(g.h), and the reaction product is collected after 1 hour of reaction.
Example 3
The reactor is a reaction cavity with the inner diameter of 12mm and a quartz tube with the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 7mm, 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 10cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 1mm, the thread pitch of the spiral tube is 3.5mm, the distance from the air outlet of the spiral tube to the cross section of the downstream end of the catalyst section is 5mm, 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 500 mL/min. The reaction pressure is the pressure generated by the raw material, namely 0.018MPa, 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 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 11mm, 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 1mm, the length of the spiral tube is 25cm, 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 5.5mm, 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 flow of the nitrogen is 400 mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 820 ℃, the volume ratio of methane to oxygen is 4, the hourly space velocity of reaction gas calculated by methane and oxygen is 20000 mL/(g.h), and the reaction products are 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 catalyst loading amount is 1g, the length of the catalyst section reaches 11mm, a spiral tube with the outer diameter of 4mm is sleeved from the upper part of the reactor, the inner diameter of the spiral tube is 2.5mm, the length of the spiral tube is 33cm, the distance from the outer wall of the spiral tube to the outer wall of the reaction cavity is 6mm, 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 6.5mm, 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 10 ℃, and the flow of the nitrogen is 300 mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.013MPa, the reaction temperature is 850 ℃, the volume ratio of methane to oxygen is 3.5, the hourly space velocity of reaction gas calculated by methane and oxygen is 15000 mL/(g.h), and the reaction products are collected after 1 hour of reaction.
Example 6
The reactor is a reaction cavity with the inner diameter of 10mm and a quartz tube with the length of 530mm, the total catalyst loading amount is 1g, the length of the catalyst section reaches 10mm, 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 10cm, 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 7mm, 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 12 ℃, and the nitrogen flow is 400 mL/min. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the reaction temperature is 780 ℃, the volume ratio of methane to oxygen is 4, the hourly space velocity of reaction gas calculated by methane and oxygen is 20000 mL/(g.h), and the reaction products are collected after 1 hour of reaction.
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 10 mm. The reaction pressure is the pressure generated by the raw materials, namely 0.011MPa, the reaction temperature is 750 ℃, the volume ratio of methane to oxygen is 2.2, the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000 mL/(g.h), 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 0.4 cm.
Comparative example 3
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 4 cm.
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
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)
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 within the catalyst bed was measured during the reaction using a thermocouple. The point at which the temperature in the catalyst bed was the highest, i.e., the hot spot temperature, gave the results shown in Table 2.
TABLE 2
Figure BDA0002563192650000131
As can be seen from Table 2, when the distance between the outlet of the spiral duct and the cross-section of the downstream end of the catalyst section is 0.5 to 0.8 times the length of the catalyst section, the methane conversion ratio is higher, the carbon-dioxide selectivity is higher, the carbon-dioxide yield is higher, and the CO is higher in examples 1 to 6 than in comparative examples 1 to 4xThe selectivity is relatively low, and the hot spot temperature is relatively low, which indicates that the deep oxidation of methane is inhibited and the occurrence of side reactions is reduced when the catalyst system is used for preparing the carbon dioxide hydrocarbons by methane oxidative coupling. 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 (10)

1. A reactor provided with a spiral pipe is characterized in that the reactor comprises a reaction cavity, a catalyst section filled in the reaction cavity and the 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 below 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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal.
2. The reactor according to claim 1, wherein the catalyst in the catalyst section further contains a promoter, preferably selected from at least one of Sr oxide, La oxide, Y oxide, Sn oxide and Ce oxide;
preferably, the content of the auxiliary agent is 1 to 8g, preferably 2 to 4g, based on 100g of the carrier.
3. The reactor of claim 1 or 2, wherein the active component is at least one of an oxide of Li, an oxide of Na, an oxide of K, and an oxide of Rb;
and/or the content of the active component is 1 to 25g, preferably 3 to 20g based on 100g of the carrier.
4. 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: 0.3-0.62: 1.2-2.5: 2-6, preferably 1: 0.3-0.5: 1.5-2: 4-6;
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 0.6-0.8 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 0-6 mm; preferably 0-4 mm;
and/or the length of the spiral tube is 10-30 times, preferably 10-20 times, the length of the catalyst section;
and/or the spiral pipe is made of stainless steel, glass or ceramic, preferably stainless steel.
5. A method for preparing a carbo-hydrocarbon by oxidative coupling of methane, the method comprising:
(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 0.5-0.8 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 at least one of CaO, MgO and BaO; the active component is an oxide of an alkali metal;
(2) introducing methane and oxygen into the reaction cavity to contact with the catalyst for catalytic reaction, and injecting a sweeping gas into the spiral tube in the reverse catalysis process.
6. The process according to claim 5, wherein the catalyst in the catalyst section further contains a promoter, preferably at least one selected from the group consisting of oxides of Sr, La, Y, Sn and Ce;
preferably, the content of the auxiliary agent is 1 to 8g, preferably 2 to 4g, based on 100g of the carrier.
7. The method according to claim 5 or 6, wherein the active component is at least one of an oxide of Li, an oxide of Na, an oxide of K and an oxide of Rb;
and/or the content of the active component is 1 to 25g, preferably 3 to 20g based on 100g of the carrier.
8. The method of claim 5, 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: 0.3-0.62: 1.2-2.5: 2-6, preferably 1: 0.3-0.5: 1.5-2: 4-6;
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 0.6-0.8 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 0-6mm, preferably 0-4 mm;
and/or the length of the spiral tube is 10-30 times, preferably 10-20 times, the length of the catalyst section;
and/or the spiral pipe is made of stainless steel, glass or ceramic, preferably stainless steel.
9. The method of claim 5 or 8, wherein the temperature of the purge gas is 0-30 ℃;
and/or the volume flow of the purge gas is 50-500 mL/min;
and/or the purge gas is nitrogen and/or air;
and/or the volume ratio of the methane to the oxygen is 2-4: 1, preferably 2 to 3: 1.
10. the method of claim 5, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 700-850 ℃, preferably 700-800 ℃, the reaction pressure is 0.001-0.02MPa, the reaction time is 0.5-8h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 5000-30000 mL/(g.h).
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109201032A (en) * 2017-07-03 2019-01-15 中国石油化工股份有限公司 The method that methane oxidative coupling catalyst and preparation method thereof and methane oxidation coupling prepare ethylene
CN210065594U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Fluidized bed reaction device for methane oxidative coupling reaction
CN210065595U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Device for oxidative coupling of methane
CN210058196U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Fixed bed reactor for producing hydrocarbons
RU2018145511A (en) * 2017-12-22 2020-06-22 Аксенс SPIRAL HEAT EXCHANGER FOR HYDRAULIC PROCESSING OR HYDROCONVERSION

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109201032A (en) * 2017-07-03 2019-01-15 中国石油化工股份有限公司 The method that methane oxidative coupling catalyst and preparation method thereof and methane oxidation coupling prepare ethylene
RU2018145511A (en) * 2017-12-22 2020-06-22 Аксенс SPIRAL HEAT EXCHANGER FOR HYDRAULIC PROCESSING OR HYDROCONVERSION
CN210065594U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Fluidized bed reaction device for methane oxidative coupling reaction
CN210065595U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Device for oxidative coupling of methane
CN210058196U (en) * 2019-03-27 2020-02-14 中国石油化工股份有限公司 Fixed bed reactor for producing hydrocarbons

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