CN113856666B - Catalyst system and its use - Google Patents

Catalyst system and its use Download PDF

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CN113856666B
CN113856666B CN202010619832.7A CN202010619832A CN113856666B CN 113856666 B CN113856666 B CN 113856666B CN 202010619832 A CN202010619832 A CN 202010619832A CN 113856666 B CN113856666 B CN 113856666B
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catalyst
section
oxygen
oxide
carrier
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CN113856666A (en
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赵清锐
王雪
韦力
冯静
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
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts, and discloses a catalyst system and application thereof, wherein the catalyst system sequentially comprises a first catalyst section, a filling section and a second catalyst section in the direction of reactant flow, and the length of the filling section is 4-10 times of the total length of the first catalyst section and the second catalyst section in the direction of reactant flow; the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silica and/or alumina. The methane conversion rate is improved, the selectivity and the yield of the carbon dioxide are improved, and the method has good industrial application prospect.

Description

Catalyst system and its use
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst system and application thereof.
Background
In recent years, the natural gas exploration technology continuously makes a major breakthrough, a batch of large and medium-sized gas fields continuously emerge, the ascertained reserves and the ascertained yields are rapidly increased, the proportion of natural gas in primary energy sources is gradually increased, and a natural gasification industry is gradually one of the development directions of petrochemical industry. In order to reduce the dependence of olefin production from petroleum resources, the technology of producing olefin from natural gas (methane as the main component) as a carbon source has become a research hot spot in recent years. Compared with the indirect method, the technology for directly preparing olefin by methane has the advantages of short process flow, more economic energy consumption and equipment investment. Meanwhile, the technology for preparing olefin by Oxidative Coupling (OCM) of methane has more obvious advantages and industrial application prospect compared with other direct methods by considering the yield of olefin, industrialized feasibility and other factors.
The methane oxidative coupling reaction catalyst with better performance generally has good catalytic activity at the temperature of more than 700 ℃. The methane oxidative coupling reaction is a strong exothermic reaction, so that the phenomenon of temperature runaway is easy to generate, and the problems of amplification of a reactor and heat removal in the reaction process are brought. If the heat in the oxidative coupling reaction process of methane can be effectively controlled, the C2 yield can be greatly improved, the energy consumption of OCM reaction can be reduced, and the method has good application prospect in industrial application.
Disclosure of Invention
The invention aims to solve the problems that heat generated by methane oxidative coupling reaction is not easy to control and easily causes a temperature runaway phenomenon in the prior art, and provides a catalyst system and application thereof, wherein the catalyst is filled in two sections, the two sections of catalyst are separated by a filler, the length of the filler section accounts for the ratio of the total length of the first catalyst section to the total length of the second catalyst section, and the two sections of catalyst are identical or different and respectively and independently comprise 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 alkali metal to reduce the reaction temperature and disperse the reaction heat generated by the reaction system, so that the deep oxidation of methane is inhibited to a certain extent, the selectivity and the yield of the carbon dioxide are improved, and the method has good industrial application prospect.
The inventors of the present invention found in the study that the catalyst system was packed in two stages, the two stages of catalysts were separated by a filler, and the ratio of the length of the packed stage to the total length of the first catalyst stage and the second catalyst stage was controlled, and the two stages of catalysts were the same or different and each independently comprised a carrier and an active component supported on the carrier, wherein the carrier was at least one of CaO, mgO, and BaO; the active component is an oxide of alkali metal, so that the temperature of the catalytic reaction can be reduced, the deep oxidation of methane can be inhibited to a certain extent, the selectivity and the yield of the carbon dioxide can be improved, and the method has good industrial application prospect.
In order to achieve the above object, in one aspect, the present invention provides a catalyst system comprising a first catalyst section, a filling section and a second catalyst section in this order in a reactant flow direction, wherein the length of the filling section is 4 to 10 times the total length of the first catalyst section and the second catalyst section in the reactant flow direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silica and/or alumina.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 4-10 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide;
(2) Methane and oxygen are introduced into a catalytic reactor to contact the catalyst for catalytic reaction.
The method for preparing the carbon dioxide by oxidative coupling of methane has the advantages of low catalytic reaction temperature, high raw material conversion rate, less side reaction, high selectivity and yield of the carbon dioxide and easiness in large-scale production and application.
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 invention provides a catalyst system, which sequentially comprises a first catalyst section, a filling section and a second catalyst section in the direction of reactant flow, wherein the length of the filling section is 4-10 times of the total length of the first catalyst section and the second catalyst section in the direction of reactant flow;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silica and/or alumina.
In some embodiments of the invention, the length of the packed section is preferably 4.3 to 7.5 times the total length of the first and second catalyst sections. Specifically, when the length of the packed section is preferably 4.3 to 7.5 times the ratio of the total length of the first catalyst section to the second catalyst section, the yield of the carbon dioxide is further improved.
In some embodiments of the invention, the silica may be derived from commercially available silica sand, and the alumina is preferably alpha-Al 2 O 3 。
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 invention, the preparation method of the catalyst without auxiliary agent comprises the following steps: adding the precursor of the active component into deionized water, adding a carrier, stirring for 1-3 hours, then 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 method for preparing the catalyst with auxiliary agent comprises the following steps: adding the precursor of the active component into deionized water, adding a carrier, stirring for 1-3 hours, and then drying at 100-120 ℃ for 20-24 hours to obtain a solid A; then dissolving the precursor of the auxiliary agent in deionized water, adding the solid A, stirring for 1-3 hours, then drying for 20-24 hours at 100-120 ℃, and roasting for 4-6 hours at 700-750 ℃ to obtain the catalyst.
In some embodiments of the invention, the ratio of the lengths of the first catalyst section and the second catalyst section in the direction of the reactant flow is preferably from 1 to 4:1, more preferably 1-2:1.
in some embodiments of the invention, the volume ratio of the first catalyst section to the second catalyst section is preferably from 1 to 4:1, more preferably 1-2:1.
in some embodiments of the invention, the catalyst in the first catalyst stage and the catalyst in the second catalyst stage are the same or different and each independently further comprise an auxiliary, preferably at least one of an oxide of Sr, an oxide of La, an oxide of Y, and an oxide of Sm.
In some embodiments of the invention, the adjuvant is preferably present in an amount of 1 to 8g, more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the 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 present invention, a first oxygen supplementing inlet is further provided at the first catalyst section, and is used for delivering the first-section oxygen into the catalytic reactor, and may also be used as a gas raw material (methane and partial oxygen) inlet.
In some embodiments of the invention, to control the conversion degree of the catalytic reaction and improve the yield and selectivity of the product carbon dioxide, the filling section is further provided with a second oxygen supplementing inlet for delivering the second section of oxygen into the catalytic reactor.
In some embodiments of the invention, to further reduce the occurrence of side reactions, the distance of the second oxygen-compensating inlet from the cross-section of the upstream end of the second catalyst section in the reverse direction of the reactant stream is from 0.5 to 0.9 times the length of the packed section.
In a second aspect, the present invention provides a method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 4-10 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide;
(2) Methane and oxygen are introduced into a catalytic reactor to contact the catalyst for catalytic reaction.
In some embodiments of the invention, the length of the packed section is preferably 4.3 to 7.5 times the total length of the first and second catalyst sections.
In some embodiments of the present invention, the type of the catalytic reactor is not limited as long as the catalytic reaction for preparing the carbon dioxide by oxidative coupling of methane can be performed, and specifically, a batch tank reactor, a continuous tank reactor or a semi-continuous tank reactor, and preferably, the catalytic reactor is a fixed bed reactor.
In some embodiments of the invention, the ratio of the length of the first catalyst section to the length of the second catalyst section is preferably from 1 to 4:1, more preferably 1-2:1.
in some embodiments of the invention, the volume ratio of the first catalyst section to the second catalyst section is preferably from 1 to 4:1, more preferably 1-2:1.
in some embodiments of the invention, the catalyst in the first catalyst stage and the catalyst in the second catalyst stage are the same or different and each independently further comprise an auxiliary, preferably at least one of an oxide of Sr, an oxide of La, an oxide of Y, and an oxide of Sm.
In some embodiments of the invention, the adjuvant is preferably present in an amount of 1 to 8g, more preferably 2 to 4g, based on 100g of the carrier.
In some embodiments of the 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, a first supplemental oxygen inlet is also provided at the first catalyst section to introduce methane and a first section of oxygen into the catalytic reactor.
In some embodiments of the invention, to control the conversion of the catalytic reaction and to increase the yield and selectivity of the product carbon dioxide, the packing segment is further provided with a second oxygen make-up inlet to introduce a second segment of oxygen into the catalytic reactor.
In some embodiments of the invention, to further reduce the occurrence of side reactions, the distance of the second oxygen-compensating inlet from the cross-section of the upstream end of the second catalyst section in the reverse direction of the reactant stream is preferably from 0.5 to 0.9 times the length of the packed section.
In some embodiments of the present invention, the temperature of the oxygen inlet point of the second stage oxygen is preferably 680-750deg.C, more preferably 700-750deg.C;
in some embodiments of the invention, the volume ratio of the first stage oxygen to the second stage oxygen is preferably 1-10:1, more preferably 4-10:1. the inventor of the invention discovers that oxygen matched with each section of bed layer after the sectional oxygen feeding is smaller than that of the single section of oxygen feeding, thereby controlling the temperature rise of the catalyst bed layer, modulating the methane conversion rate and selectivity of the reaction, further inhibiting the occurrence of side reaction and further improving the yield and selectivity of the product carbon dioxide.
In some embodiments of the invention, the volume ratio of methane to total oxygen fed to the catalytic reactor is preferably between 2 and 6:1, more preferably 2.2-4:1.
in some embodiments of the invention, the conditions of the catalytic reaction include: the reaction temperature is preferably 680 to 800 ℃, more preferably 700 to 750 ℃. The catalytic reaction pressure is 0-0.02MPa. The catalytic reaction time is 0.5-8h. The reaction gas hourly space velocity in terms of methane and oxygen is 5000-25000 mL/(g.h). Specifically, the reaction temperature refers to a temperature 1cm above the first stage catalyst bed.
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. SiO (SiO) 2 Derived from quartzSand, quartz sand was purchased from Qingdao ocean chemical Co. Alumina is purchased from world chemical filler limited. The method for measuring the element composition of the catalyst is an X-ray fluorescence method, and specific detection is referred to GB/T30905-2014.
Preparation example 1
The preparation method of the catalyst without the auxiliary agent comprises the following steps: the precursor of the active component was added to 50℃and 25g of deionized water, the carrier was added, stirred for 2 hours, dried at 120℃for 24 hours, and then calcined at 750℃for 6 hours, to obtain the catalyst used in the examples.
Preparation example 2
The preparation method of the catalyst with the auxiliary agent comprises the following steps: adding the 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, and drying at the temperature of 120 ℃ for 24 hours to obtain a solid A; then, the precursor of the auxiliary agent was dissolved in 50℃and 25g of deionized water, and solid A was added thereto, stirred for 2 hours, dried at 120℃for 24 hours, and then calcined at 750℃for 6 hours to obtain the catalyst used in the examples.
The precursors of the active components and the precursors of the auxiliary agents in the preparation examples are nitrate, and the use amount of each component is such that the content of the active components and the auxiliary agents in the catalyst is shown in table 1:
TABLE 1
Note that: the content of each component in the catalyst is based on 100g of carrier;
"/" indicates that no promoter is present in the catalyst.
Example 1
The catalyst corresponding to example 1 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into upper and lower stages, the charge amounts of both stages were 0.4g, the length of the first stage catalyst was 4mm, the length of the second stage catalyst was 4mm, the space between the two stages catalyst was filled with quartz sand, and the length of the filled stage was 3.5cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 750 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 3cm, and the temperature of the oxygen inlet point of the second section is 700 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.011MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 2.2, the volume ratio of the first section of oxygen to the second section of oxygen is 10, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 12000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 2
The catalyst corresponding to example 2 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into an upper and a lower stages, the loading of the first stage was 0.6g, the loading of the second stage was 0.2g, the length of the first stage was 6mm, the length of the second stage was 2mm, the space between the two stages was filled with alumina, and the length of the filled stage was 6cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 700 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 4cm, and the temperature of the oxygen inlet point of the second section is 750 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.008MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 3, the volume ratio of the first section of oxygen to the second section of oxygen is 4, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 5000 mL/(g.h), and the reaction product is collected after the reaction for 1 hour.
Example 3
The catalyst corresponding to example 3 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into upper and lower stages, wherein the first stage had a loading of 0.55g and the second stage had a loading of 0.25g, the first stage had a length of 5.5mm and the second stage had a length of 2.5mm, and alumina was filled between the two stages, and the length of the filled stage was 4cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 730 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 2cm, and the temperature of the oxygen inlet point of the second section is 720 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.018MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 4, the volume ratio of the first stage oxygen to the second stage oxygen is 6, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 25000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 4
The catalyst corresponding to example 4 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into upper and lower stages, wherein the first stage had a loading of 0.64g and the second stage had a loading of 0.16g, the first stage had a length of 6.4mm and the second stage had a length of 1.6mm, and the space between the two stages was filled with quartz sand, and the length of the filled stage was 5cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 680 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 4cm, and the temperature of the oxygen inlet point of the second section is 680 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 6, the volume ratio of the first section of oxygen to the second section of oxygen is 4, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 20000 mL/(g.h), and the reaction product is collected after the reaction for 1 hour.
Example 5
The catalyst corresponding to example 5 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into upper and lower stages, the charge amounts of both stages were 0.4g, the length of the first stage catalyst was 4mm, the length of the second stage catalyst was 4mm, the space between the two stages catalyst was filled with quartz sand, and the length of the filled stage was 6cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 800 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 5cm, and the temperature of the oxygen inlet point of the second section is 750 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.012MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 2, the volume ratio of the first section of oxygen to the second section of oxygen is 3, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 10000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Example 6
The catalyst corresponding to example 6 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, and the catalyst was divided into upper and lower stages, the charge amounts of both stages were 0.4g, the length of the first stage catalyst was 4mm, the length of the second stage catalyst was 4mm, the space between the two stages catalyst was filled with quartz sand, and the length of the filled stage was 8cm. The mixed gas of methane and the first-stage oxygen is continuously introduced into the first-stage catalyst bed, and the reaction temperature is 700 ℃. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 4cm, and the temperature of the oxygen inlet point of the second section is 720 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.013MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 6, the volume ratio of the first section of oxygen to the second section of oxygen is 1, the hourly space velocity of the reaction gas calculated by the methane and the oxygen is 20000 mL/(g.h), and the reaction product is collected after the reaction is carried out for 1 hour.
Comparative example 1
The catalyst corresponding to comparative example 1 described in Table 1 was charged into a quartz reactor having an inner diameter of 8mm and a length of 530mm, the catalyst was charged in a single stage in an amount of 0.8g, the catalyst length was 8mm, and the upper and lower sides of the catalyst were filled with quartz sand. The mixed gas of methane and oxygen is continuously introduced into the catalyst bed layer, and the reaction temperature is 680 ℃. The reaction pressure is the pressure generated by the raw materials, namely 0.015MPa, the volume ratio of methane to the total oxygen input into the catalytic reactor is 6, the hourly space velocity of the reaction gas based on the methane and the oxygen is 20000 mL/(g.h), and the reaction product is collected after the reaction for 1 hour.
Comparative example 2
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 length of the packed section was 12cm. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 1cm.
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 2, except that the length of the packed section was 2cm. The distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 0.2cm.
Comparative example 4
The reaction for oxidative coupling of methane to make carbon dioxide was performed as in example 4, except that the catalyst was replaced with another catalyst as shown in table 1.
Comparative example 5
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 of comparative example 4 was used.
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
Yield of carbon diolefms = methane conversion x (ethane selectivity + ethylene selectivity)
The results obtained are shown in Table 2.
TABLE 2
The test results show that, as can be seen from Table 2, the relativeIn comparative examples 1-5, where the length of the packed section is 4-10 times the total length of the first and second catalyst sections, examples 1-6 have higher methane conversion, higher selectivity to carbon dioxide, higher yield of carbon dioxide, and CO x The selectivity is relatively low, so that the deep oxidation of methane is inhibited and side reactions are reduced when the catalyst system is adopted for preparing the carbon dioxide through methane oxidative coupling, and the side surfaces illustrate that the heat generated by the methane oxidative coupling reaction can be effectively controlled and the temperature flying phenomenon is reduced by adopting the technical scheme. The methane conversion, selectivity to carbon dioxide, and yield to carbon dioxide were all higher for examples 1-6 than for comparative examples 4-5 (SiC as the support), and the effect of the multi-stage loading for comparative example 4 was similar to that of the single-stage loading for comparative example 5, indicating that superior catalytic effect could be obtained only for the specific catalyst by the multi-stage loading.
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 (26)

1. A catalyst system comprising, in the direction of the reactant flow, a first catalyst section, a packing section and a second catalyst section in that order, wherein the length of the packing section in the direction of the reactant flow is 4-10 times the total length of the first and second catalyst sections;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silica and/or alumina.
2. The catalyst system of claim 1, wherein the ratio of the lengths of the first catalyst section and the second catalyst section is from 1 to 4:1, a step of;
and/or the volume ratio of the first catalyst section to the second catalyst section is 1-4:1, a step of;
and/or the length of the filling section is 4.3-7.5 times of the total length of the first catalyst section and the second catalyst section.
3. The catalyst system of claim 1 or 2, wherein the ratio of the lengths of the first catalyst section and the second catalyst section is from 1 to 2:1, a step of;
and/or the volume ratio of the first catalyst section to the second catalyst section is 1-2:1.
4. the catalyst system of claim 1 or 2, wherein the catalyst in the first catalyst stage and the catalyst in the second catalyst stage are the same or different and each independently further comprise an adjunct that is at least one of an oxide of Sr, an oxide of La, an oxide of Y, and an oxide of Sm.
5. The catalyst system according to claim 4, wherein the promoter is present in an amount of 1 to 8g based on 100g of the support.
6. The catalyst system according to claim 5, wherein the promoter is present in an amount of 2 to 4g based on 100g of the support.
7. The catalyst system of claim 1, 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.
8. The catalyst system according to claim 1, wherein the active component is present in an amount of 1 to 25g based on 100g of the support.
9. The catalyst system of claim 8, wherein the active component is present in an amount of 3 to 20g based on 100g of the support.
10. The catalyst system of claim 1, wherein the first catalyst section is further provided with a first oxygen make-up inlet;
and/or the filling section is provided with a second oxygen supplementing inlet;
and/or, in the reverse direction of the reactant stream, the distance between the second oxygen-supplementing inlet and the cross section of the upstream end of the second catalyst section is 0.5-0.9 times the length of the filling section.
11. A method for preparing a carbon dioxide by oxidative coupling of methane, the method comprising:
(1) Sequentially filling a catalyst and a filler in a catalytic reactor along the reverse direction of a reactant stream to form a catalyst system comprising a second catalyst section, a filling section and a first catalyst section, wherein the length of the filling section is 4-10 times of the total length of the first catalyst section and the second catalyst section in the reactant stream direction;
the catalyst in the first catalyst section and the catalyst in the second catalyst section are the same or different and each independently comprise 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 alkali metal; the filler in the filling section is selected from silicon dioxide and/or aluminum oxide;
(2) Methane and oxygen are introduced into a catalytic reactor to contact the catalyst for catalytic reaction.
12. The method of claim 11, wherein the first catalyst section and the second catalyst section have a length ratio of 1-4:1, a step of;
and/or the volume ratio of the first catalyst section to the second catalyst section is 1-4:1, a step of;
and/or the length of the filling section is 4.3-7.5 times of the total length of the first catalyst section and the second catalyst section.
13. The method of claim 11 or 12, wherein the ratio of the lengths of the first catalyst section and the second catalyst section is 1-2:1, a step of;
and/or the volume ratio of the first catalyst section to the second catalyst section is 1-2:1.
14. the method of claim 11 or 12, wherein the catalyst in the first catalyst stage and the catalyst in the second catalyst stage are the same or different and each independently further comprise an adjunct that is at least one of an oxide of Sr, an oxide of La, an oxide of Y, and an oxide of Sm.
15. The process according to claim 14, wherein the adjuvant is present in an amount of 1-8g based on 100g of the carrier.
16. The process according to claim 15, wherein the adjuvant is present in an amount of 2-4g based on 100g of the carrier.
17. The method of claim 11, 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.
18. A method according to claim 11 or 12, wherein the active ingredient is present in an amount of 1-25g based on 100g of the carrier.
19. The method according to claim 18, wherein the active ingredient is contained in an amount of 3 to 20g based on 100g of the carrier.
20. The method of claim 11, wherein a first supplemental oxygen inlet is further provided at the first catalyst section to introduce methane and a first section of oxygen into the catalytic reactor;
and/or the filling section is provided with a second oxygen supplementing inlet for introducing second-section oxygen into the catalytic reactor;
and/or, the distance between the second oxygen supplementing inlet and the cross section of the upstream end of the second catalyst section is 0.5-0.9 times of the length of the filling section along the reverse direction of the reactant flow.
21. The method of claim 20, wherein the temperature of the oxygen inlet point of the second stage oxygen is 680-750 ℃;
and/or the volume ratio of the first section of oxygen to the second section of oxygen is 1-10:1.
22. the method of claim 20 or 21, wherein the temperature of the oxygen inlet point of the second stage oxygen is 700-750 ℃;
and/or the volume ratio of the first section of oxygen to the second section of oxygen is 4-10:1.
23. the method of claim 11 or 21, wherein the volume ratio of methane to total oxygen input to the catalytic reactor is 2-6:1.
24. the method of claim 23, wherein the volume ratio of methane to total oxygen input to the catalytic reactor is from 2.2 to 4:1.
25. the method of claim 11, wherein the conditions of the catalytic reaction comprise: the reaction temperature is 680-800 ℃; 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 5000-25000 mL/(g.h).
26. The method of claim 25, wherein the catalytic reaction is at a temperature of 700-750 ℃.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659500A (en) * 2012-05-16 2012-09-12 北京化工大学 Method for producing ethylene and ethane and catalytic reactor
CN103657640A (en) * 2012-09-10 2014-03-26 中国石油化工股份有限公司 Load catalyst and preparation method and application thereof as well as method for preparing low carbon olefin by methane oxidative coupling
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
CN109201031A (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
CN109201033A (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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659500A (en) * 2012-05-16 2012-09-12 北京化工大学 Method for producing ethylene and ethane and catalytic reactor
CN103657640A (en) * 2012-09-10 2014-03-26 中国石油化工股份有限公司 Load catalyst and preparation method and application thereof as well as method for preparing low carbon olefin by methane oxidative coupling
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
CN109201031A (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
CN109201033A (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

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