CN113797950B - Catalyst with low-temperature activity in methane oxidative coupling reaction, and preparation method and application thereof - Google Patents

Catalyst with low-temperature activity in methane oxidative coupling reaction, and preparation method and application thereof Download PDF

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CN113797950B
CN113797950B CN202010552726.1A CN202010552726A CN113797950B CN 113797950 B CN113797950 B CN 113797950B CN 202010552726 A CN202010552726 A CN 202010552726A CN 113797950 B CN113797950 B CN 113797950B
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parts
weight
carrier
supported catalyst
methane
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CN113797950A (en
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武洁花
薛伟
张明森
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20Carbon compounds
    • B01J27/232Carbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/082Decomposition and pyrolysis
    • B01J37/088Decomposition of a metal salt
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20Carbon compounds
    • C07C2527/232Carbonates
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements 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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts, and discloses a catalyst with low-temperature activity in a methane oxidative coupling reaction, and a preparation method and application thereof. Impregnating a carrier by using a precursor impregnating solution of lanthanum oxide carbonate under the condition that the pH value is 8-14, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst; wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water; wherein the carrier is halloysite; wherein the soluble carbon source is carbonate and/or bicarbonate. When the catalyst is used for the oxidative coupling reaction of methane, the catalyst still has higher reaction conversion rate and selectivity at a lower catalytic temperature.

Description

Catalyst with low-temperature activity in methane oxidative coupling reaction, and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a lanthanum oxide carbonate supported catalyst, a lanthanum oxide carbonate supported catalyst prepared by the preparation method, application of the lanthanum oxide carbonate supported catalyst in a methane oxidative coupling reaction and a method for preparing carbon two or more hydrocarbons from methane.
Background
Ethylene is a compound consisting of two carbon atoms and four hydrogen atoms. The two carbon atoms are connected by a double bond.
Ethylene is a basic chemical raw material for synthetic fibre, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride) and synthetic alcohol (alcohol), and can be used for preparing chloroethylene, styrene, ethylene oxide, acetic acid, acetaldehyde, alcohol and explosive, etc., and can be used as ripening agent of fruit and vegetable, and is a proven plant hormone.
Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of petrochemical industry, and the ethylene product accounts for more than 75% of petrochemical products and plays an important role in national economy. Ethylene production has been worldwide used as one of the important markers for the level of petrochemical development in a country.
In recent years, the discovery and exploitation of shale gas brings revolutionary promotion to the development and utilization of natural gas. Therefore, the method is also receiving more and more attention as the most direct and effective natural gas utilization method with high economic competitiveness, namely, the method for preparing ethane and ethylene by oxidative coupling of methane. Since the oxidative coupling reaction of methane is a strong exothermic reaction and is carried out at high temperature, no industrial production has been developed so far, and therefore, the development of a methane oxidative coupling catalyst with excellent performance has practical significance.
In order to improve the reaction performance of the methane oxidative coupling catalyst, researchers have made much work, such as adopting an oxide containing rare earth elements (CN 103764276: a catalyst for oxidative dehydrogenation of hydrocarbons), adopting a mesoporous molecular sieve as a catalyst carrier for modification (CN 101385982B: a mesoporous molecular sieve catalyst for preparing ethylene by oxidative coupling of methane and a preparation method thereof), adopting a defect structure to reduce the reaction temperature (CN 109569565: a preparation method and application of a defect fluorite catalyst for oxidative coupling of methane in a non-stoichiometric ratio). However, these catalysts all need to be capable of exhibiting good catalytic performance in the oxidative coupling reaction of methane at a relatively high catalytic temperature.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a lanthanum oxide carbonate supported catalyst, a preparation method of the lanthanum oxide carbonate supported catalyst, the lanthanum oxide carbonate supported catalyst prepared by the preparation method, application of the lanthanum oxide carbonate supported catalyst in methane oxidative coupling reaction and a method for preparing carbon two or more hydrocarbons from methane. When the catalyst is used for the oxidative coupling reaction of methane, the catalyst still has higher reaction conversion rate and selectivity at a lower catalytic temperature.
In order to achieve the above object, a first aspect of the present invention provides a supported catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxide carbonate;
wherein the lanthanum oxycarbonate is present in an amount of 0.5 to 18 parts by weight or 32 to 50 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis.
The second aspect of the present invention provides a method for producing a supported catalyst, comprising: impregnating a carrier by using a precursor impregnating solution of lanthanum oxide carbonate under the condition that the pH value is 8-14, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate.
In a third aspect the present invention provides a supported catalyst prepared by the method as described above.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in the oxidative coupling of methane.
In a fifth aspect, the invention provides a process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a supported catalyst is prepared as described above, and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
The sixth aspect of the invention provides the use of a supported catalyst in the oxidative coupling of methane;
the supported catalyst comprises a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxycarbonate.
The catalyst which takes halloysite as a carrier and lanthanum oxide carbonate as an active component has the following advantages:
(1) The catalyst provided by the invention takes halloysite as a carrier and lanthanum oxide carbonate as an active component, and has higher reaction conversion rate and selectivity at a lower catalytic temperature, for example, below 500 ℃ when being used for methane oxidative coupling reaction.
(2) The halloysite carrier in the catalyst provided by the invention has a hollow fiber tubular nanostructure, and has the characteristics of different charges on the surfaces of the special hollow fiber tubular nanostructure and the inner and outer tubes, so that the halloysite carrier is more beneficial to the dispersion of active components and the generation of active oxygen sites, and has good catalytic performance when being used for methane oxidative coupling reaction.
(3) The halloysite carrier in the catalyst provided by the invention has wide sources and low cost, does not need any treatment, can be directly used as a catalyst carrier, and simplifies the preparation process of the catalyst.
(4) In the preferred case, the doping element is loaded on the catalyst, so that the catalytic performance of the catalyst is further improved.
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.
Halloysite is a natural aluminosilicate clay mineral which is mainly used for researches on antibacterial, chemical templates, lithium ion batteries and the like, and has a hollow tubular nano structure, wherein the diameter is in a nano level, and the length is in a nano level to a micro level; the chemical compositions of the inner wall and the outer wall of halloysite are different, the outer wall is silicon oxide, the inner wall is aluminum oxide, the structure is unique, the surface charges of halloysite are different, the outer wall is negatively charged, and the inner wall is positively charged. The inventor of the present invention unexpectedly found that halloysite is used as a carrier for preparing a supported catalyst, lanthanum oxycarbonate is used as an active component, and the obtained catalyst is used for methane oxidative coupling reaction, and can obtain good catalytic performance at a lower temperature (below 500 ℃). Meanwhile, halloysite has high temperature resistance, and a tubular structure is kept good after being roasted at 800 ℃, so that the temperature application range of the catalyst taking halloysite as a carrier is widened.
In a first aspect, the present invention provides a supported catalyst comprising a support and an active component supported on the support, wherein the support is halloysite; the active component comprises lanthanum oxide carbonate;
wherein the lanthanum oxycarbonate is present in an amount of 0.5 to 18 parts by weight or 32 to 50 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis.
The invention has no excessive requirements on the specific size of halloysite. However, the inventors of the present invention have found that when the halloysite of the hollow tubular nanostructure has an inner diameter of 10 to 20nm (e.g., may be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and all values within the range and range of any combination), an outer diameter of 40 to 70nm (e.g., may be 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, and all values within the range and range of any combination), and a length of 200 to 1000nm (e.g., may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and all values within the range and range of any combination), the catalytic performance of the catalyst prepared therefrom can be further improved.
According to the present invention, the content of lanthanum oxycarbonate may be, for example, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, relative to 100 parts by weight of the carrier on a dry weight basis; preferably 0.8 to 17 parts by weight or 33 to 48 parts by weight, more preferably 5 to 17 parts by weight or 35 to 46 parts by weight.
According to the present invention, in order to further improve the performance of the supported catalyst, it is preferable that the supported catalyst further include a doping element supported on the carrier.
Preferably, the doping element is a metal element, a semi-metal element, a non-metal element or a combination thereof, more preferably any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof, further preferably any one of Na, K, ba and Ag or any combination thereof, and most preferably Ba.
According to the present invention, the content of the doping element in the supported catalyst may vary within a wide range, and in order to further improve the performance of the supported catalyst, it is preferable that the content of the doping element is 0.01 to 5 parts by weight, and all ranges therebetween, for example, about 0.1 to 4 parts by weight, about 1 to 3 parts by weight, and any specific value therebetween, for example, about 0.01 parts by weight, about 0.02 parts by weight, about 0.5 parts by weight, about 1 part by weight, about 2 parts by weight, about 3 parts by weight, about 4 parts by weight, or about 5 parts by weight, with respect to 100 parts by weight of the carrier.
In a second aspect, the present invention provides a method for preparing a supported catalyst, the method comprising: impregnating a carrier by using a precursor impregnating solution of lanthanum oxide carbonate under the condition that the pH value is 8-14, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate.
The inventors of the present invention found in the study that the supported catalyst, which is capable of performing a methane oxidative coupling reaction at a lower temperature while maintaining a higher catalytic performance, was obtained by impregnating halloysite as a carrier in an impregnating solution containing a lanthanum soluble salt, a carbon source (carbonate and/or bicarbonate) and water under alkaline conditions, and then sequentially drying and calcining the impregnated solid material.
According to the present invention, the soluble salt of lanthanum may be any of various existing soluble salts of lanthanum, for example, but not limited to lanthanum chloride, lanthanum chlorate and lanthanum nitrate, preferably lanthanum nitrate.
According to the present invention, the carbonate and/or bicarbonate may be any of a variety of soluble carbonates and/or bicarbonates available, for example, but not limited to, at least one of carbonate, alkali metal bicarbonate, ammonium carbonate, and ammonium bicarbonate; preferably at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate. When the carbon source selects alkali metal carbonate and/or bicarbonate, alkali metal element can be further introduced into the catalyst, so that the performance of the catalyst is further improved.
According to the invention, the pH may be 8, 9, 10, 11, 12, 13, 14, preferably 9-12, for example, 9, 9.5, 10, 10.5, 11, 11.5, 12.
According to the invention, when the added carbon source can enable the pH value of the system to reach the above level, no additional acid-base regulator can be introduced, and if the added carbon source can not enable the pH value of the system to reach the above level, the additional acid-base regulator can be further introduced to regulate the pH value.
Preferably, the hollow tubular nanostructure halloysite has an inner diameter of 10-20nm (e.g., can be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and all values within any combination and range), an outer diameter of 40-70nm (e.g., can be 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, and all values within any combination and range), and a length of 200-1000nm (e.g., can be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and all values within any combination and range).
According to the present invention, the amount of the precursor of lanthanum oxycarbonate may be selected within a wide range, and preferably, the amount thereof is such that the content of lanthanum oxycarbonate in the resultant catalyst is 0.5 to 50 parts by weight (for example, may be 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight), preferably 1 to 25 parts by weight, more preferably 2 to 15% by weight, relative to 100 parts by weight of the carrier on a dry weight basis.
According to the invention, the impregnation may be an isovolumetric impregnation or an overdose impregnation.
In accordance with the invention, the temperature and time of the impregnation may be varied within wide limits for other conditions than controlling the pH as above during the impregnation. Preferably, the temperature of the impregnation is room temperature, e.g., 20-40 ℃, e.g., 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃. Preferably, the time of the impregnation is 1 to 5 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, preferably 1.5 to 2.5 hours.
The temperature of the drying according to the invention may vary within a wide range, preferably the drying temperature is 80-180 ℃, for example 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, preferably 80-100 ℃.
The drying time may vary within wide limits, preferably is 12-24h, for example 12h, 14h, 16h, 18h, 20h, 22h, 24h, preferably 12-15h.
The temperature of the calcination may vary within a wide range according to the present invention, and preferably the temperature of the calcination is 450-600 ℃, for example, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃,500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃,500 ℃, and preferably 500-550 ℃.
The calcination time may vary within a wide range according to the invention, preferably the calcination time is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, preferably 2-6h, more preferably 2-4h.
According to the present invention, the atmosphere of the firing is not particularly limited, and is preferably an air atmosphere or a carbon dioxide atmosphere.
According to the present invention, in order to further improve the catalytic performance of the prepared supported catalyst, it is preferable that the calcination process is raised to the calcination end temperature at a temperature raising rate of 1 to 10 c/min, preferably 1 to 5 c/min, and then the calcination is performed for a predetermined time.
According to the present invention, in order to further improve the performance of the prepared supported catalyst, preferably, the method further comprises: the doping element is supported on the carrier.
Preferably, the doping element is a metal element, a semi-metal element, a non-metal element or a combination thereof, more preferably any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof, further preferably any one of Na, K, ba and Ag or any combination thereof, and most preferably Ba.
The method of supporting the doping element on the carrier is not particularly limited in the present invention, and may be performed by methods known to those skilled in the art, for example, mixing, precipitation/coprecipitation, impregnation, sol-gel, template/surface-derived metal oxide synthesis, solid state synthesis of mixed metal oxide, microemulsion technology, solvothermal synthesis, sonochemical synthesis, combustion synthesis, and the like.
The person skilled in the art can select the form of supply of the doping element according to the method of loading, for example, when loading is performed by the method of impregnation, the carrier can be impregnated with an impregnation liquid containing a soluble salt of the doping element to complete the loading, and this step can be performed together with the impregnation of the carrier with a precursor impregnation liquid of lanthanum oxycarbonate, or separately, and after all of the doping is performed on the carrier, drying and firing are sequentially performed.
The amount of the compound containing the doping element to be used according to the present invention may be selected within a wide range, and in order to further improve the performance of the supported catalyst, it is preferable that the amount thereof is such that the content of the doping element in the resulting catalyst is 0.01 to 5 parts by weight, and all ranges therebetween, for example, about 0.1 to 4 parts by weight, about 1 to 3 parts by weight, and any specific values therebetween, for example, about 0.01 parts by weight, about 0.02 parts by weight, about 0.5 parts by weight, about 1 part by weight, about 2 parts by weight, about 3 parts by weight, about 4 parts by weight, or about 5 parts by weight, relative to 100 parts by weight of the carrier on a dry weight basis.
In a third aspect, the present invention provides a supported catalyst prepared by the method as described above.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in the oxidative coupling of methane.
According to the present invention, the catalyst of the present invention may be used in a continuous flow reactor to produce c2+ hydrocarbons from methane (e.g., natural gas). The continuous flow reactor may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or an ebullated bed reactor. The catalyst may be arranged in layers in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullated bed).
In a fifth aspect, the present invention provides a process for producing carbon two or more hydrocarbons from methane, the process comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a supported catalyst is prepared as described above, and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
The method for molding the catalyst before loading the catalyst into the reaction apparatus according to the present invention is not particularly limited, and may be a conventional method in the art. Preferably, the molding condition is that the powder is crushed and sieved by a 40-60 mesh sieve after tabletting.
According to the present invention, the conditions for the oxidative coupling reaction of methane are not particularly limited and may be selected conventionally in the art, and the conditions for the oxidative coupling reaction of methane may include a reaction temperature of 400 to 750 ℃ (for example, may be 400 ℃, 430 ℃, 450 ℃, 470 ℃,500 ℃), a reaction pressure of normal pressure, and a space velocity of methane of 5000 to 100000 ml/(g.h), preferably 10000 to 80000 ml/(g.h). In order to increase the methane conversion, the molar ratio of methane to oxygen is preferably from 2 to 10:1, preferably 3-8:1.
in a sixth aspect, the invention provides the use of a supported catalyst in the oxidative coupling of methane;
the supported catalyst comprises a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxycarbonate.
According to the present invention, the method for preparing the catalyst may include: and impregnating the carrier by using a precursor impregnating solution of lanthanum oxide carbonate, and sequentially drying and roasting the impregnated solid material to obtain the supported catalyst, wherein the precursor impregnating solution of lanthanum oxide carbonate contains a soluble salt of lanthanum, a soluble carbon source and water.
According to the invention, the lanthanum oxycarbonate is preferably present in an amount of 0.5 to 50 parts by weight, preferably 1 to 25 parts by weight, relative to 100 parts by weight of the carrier on a dry weight basis.
According to the invention, preferably, the halloysite is a hollow nanotube structure, and the halloysite hollow nanotube has an inner diameter of 10-20nm, an outer diameter of 40-70nm and a length of 200-1000nm.
According to the present invention, preferably, the supported catalyst further comprises a doping element supported on the carrier.
Preferably, the doping element is a metal element, a semi-metal element, a non-metal element or a combination thereof, and more preferably any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof.
Preferably, in the supported catalyst, the doping element is contained in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A. Methane conversion and selectivity to hydrocarbons of two or more carbons including ethane, ethylene, propane, propylene, butane, butene are calculated based on the composition of the product.
Example 1
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to the lanthanum oxide carbonate load of 15 wt%, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 10.5, halloysite (with the inner diameter of 15nm, the outer diameter of 65nm and the length of 600 nm) is added into the impregnating solution, and the solution is uniformly stirred at room temperature and impregnated for 2 hours. Then heating to 80 ℃ to volatilize water, placing in a 90 ℃ oven to dry for 13.5 hours, then moving to a muffle furnace to bake, heating to 3 ℃/min, and baking in air at 550 ℃ for 2 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-1, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 2
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to the lanthanum oxide carbonate load of 10 wt%, lanthanum nitrate hexahydrate and ammonium bicarbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 9, halloysite (with the inner diameter of 10nm, the outer diameter of 40nm and the length of 1000 nm) is added into the impregnating solution, and the impregnating solution is uniformly stirred at room temperature and is impregnated for 1.5 hours. Then heating to 80 ℃ to volatilize water, placing in an 80 ℃ oven to dry for 15 hours, then moving into a muffle furnace to bake, heating up at a speed of 1 ℃/min, and baking in air at 500 ℃ for 4 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-2, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 3
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to lanthanum oxide loading of 2 wt%, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 12, halloysite (with the inner diameter of 20nm, the outer diameter of 70nm and the length of 200 nm) is added into the impregnating solution, and the impregnating solution is uniformly stirred at room temperature and impregnated for 2.5 hours. Then heating to 80 ℃ to volatilize water, placing in a 100 ℃ oven to dry for 12 hours, then moving into a muffle furnace to bake, heating at a speed of 5 ℃/min, and baking in air at 525 ℃ for 3 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-3, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 4
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-4 was prepared as in example 1, except that the halloysite inner diameter was 30nm and the lanthanum oxycarbonate loading was 20% by weight, and the catalyst had a lanthanum oxycarbonate characteristic peak as characterized by XRD.
Example 5
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-5 was prepared as in example 1 except that barium nitrate was dissolved in deionized water at a loading of 0.2 wt% of barium element, and then mixed with a precursor impregnation solution of lanthanum oxycarbonate, followed by an impregnation treatment after adjusting the pH. C2 was calcined as in example 1 and the catalyst was characterized by XRD as having a characteristic lanthanum oxycarbonate peak.
Example 6
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-6 was prepared as in example 5, except that barium nitrate was replaced with potassium nitrate, the loading of potassium element was the same as that of barium element on a molar basis, and the catalyst was characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Example 7
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-7 was prepared as in example 5, except that barium nitrate was replaced with silver nitrate, the loading of potassium element was the same as that of barium element on a molar basis, and the catalyst was characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Example 8
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-8 was prepared as in example 1 except that calcination was performed under a nitrogen atmosphere, and the catalyst was characterized by XRD as having lanthanum oxycarbonate characteristic peaks.
Example 9
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-9 was prepared as in example 1, except that the temperature was raised to the calcination temperature at a rate of 8℃per minute, and the catalyst was characterized by XRD as having a characteristic peak of lanthanum oxycarbonate.
Example 10
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-10 was prepared as in example 1, except that the calcination temperature was 750℃and the catalyst had a characteristic peak of lanthanum oxycarbonate as characterized by XRD.
Comparative example 1
This comparative example is used to illustrate the reference catalyst and its preparation method.
The preparation of catalyst Cat-D-1 was carried out in the same manner as in example 1, except that the support was replaced with diatomaceous earth during the preparation.
Comparative example 2
This comparative example is used to illustrate the reference catalyst and its preparation method.
The preparation of catalyst Cat-D-2 was carried out in the same manner as in example 1 except that the pH of the impregnation liquid was not adjusted.
Comparative example 3
This comparative example is used to illustrate the reference catalyst and its preparation method.
The catalyst Cat-D-3 was prepared as in example 1, except that ammonium carbonate was replaced with an equal amount of glycine, the pH of the impregnation solution was not adjusted, and calcination was performed under a nitrogen atmosphere.
Test example 1
This test example is used to demonstrate the catalytic performance of the catalysts of the present invention
0.2g of catalyst Cat-1 was charged into a fixed bed quartz reactor, the molar ratio of methane to oxygen was 3:1 under normal pressure, the space velocity of methane was 80000ml/gh, and the activation temperature and methane conversion of the oxidative coupling reaction of methane and the hydrocarbon selectivity of two or more carbons were as shown in Table 1.
Test examples 2 to 10
This test example is used to demonstrate the catalytic performance of the catalysts of the present invention
Ethylene ethane was produced by oxidative coupling of methane in the same manner as in test example 1, except that catalysts Cat-2 to Cat-10 were used, respectively, and the activation temperature and methane conversion of the oxidative coupling reaction of methane and the hydrocarbon selectivity of two or more carbon atoms were as shown in Table 1.
Comparative test examples 1 to 3
Ethylene ethane was produced by oxidative coupling of methane in the same manner as in test example 1, except that catalysts Cat-D-1 to Cat-D-3 were used, and the activation temperature and methane conversion of the oxidative coupling reaction of methane and hydrocarbon selectivities of two or more were as shown in Table 1.
TABLE 1
Catalyst Initial reaction temperature (. Degree. C.) Methane conversion/% Hydrocarbon selectivity of two or more carbon atoms/%
Cat-1 450 34.8 36.9
Cat-2 446 33.5 35.8
Cat-3 443 34.6 32.6
Cat-4 451 33.4 34.6
Cat-5 438 35.6 36.5
Cat-6 436 35.7 36.6
Cat-7 439 34.8 35.9
Cat-8 450 32.4 33.1
Cat-9 468 31.2 32.5
Cat-10 605 24.3 34.1
Cat-D-1 650 21.3 23.1
Cat-D-2 605 19.7 21.3
Cat-D-3 621 18.3 19.6
As can be seen from Table 1, when the catalyst prepared by the invention is used for the oxidative coupling reaction of methane, the oxidative coupling reaction of methane can obtain higher methane conversion rate and hydrocarbon selectivity of two or more carbon atoms at lower initial temperature.
As can be seen from comparing example 2 with example 4, the halloysite size is not within the preferred range and an increased amount of active component is required to achieve substantially the same catalytic effect.
Comparing example 2 with examples 5-7, it can be seen that the starting temperature of the catalyst can be further lowered and the catalytic performance of the resulting catalyst can be further improved in the case of supporting a doping element, which is most preferably barium.
Comparing example 2 with example 8, it can be seen that the starting temperature of the catalyst can be further lowered under a preferable calcination atmosphere, and the catalytic performance of the resulting catalyst can be further improved.
Comparing example 2 with examples 9 to 10, it can be seen that the starting temperature of the catalyst can be further lowered and the catalytic performance of the obtained catalyst can be further improved at the preferable firing temperature increase rate and firing temperature.
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 (23)

1. The supported catalyst is characterized by comprising a carrier and an active component supported on the carrier, wherein the carrier is halloysite, and the halloysite is of a hollow nanotube structure; the active component comprises lanthanum oxide carbonate;
wherein the lanthanum oxycarbonate is present in an amount of 0.5 to 18 parts by weight or 32 to 50 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis;
the supported catalyst further comprises a doping element supported on the carrier, wherein the doping element is any one or any combination of K, ba and Ag.
2. The supported catalyst of claim 1, wherein the halloysite hollow nanotubes have an inner diameter of 10-20nm, an outer diameter of 40-70nm, and a length of 200-1000nm.
3. The supported catalyst according to claim 1, wherein the content of the doping element is 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis in the supported catalyst.
4. A method for preparing a supported catalyst, comprising: impregnating a carrier by using a precursor impregnating solution of lanthanum oxide carbonate under the condition that the pH value is 8-14, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water; the lanthanum oxycarbonate precursor is used in an amount such that the lanthanum oxycarbonate content is 0.5 to 50 parts by weight relative to 100 parts by weight of the support on a dry weight basis in the resulting supported catalyst;
wherein the carrier is halloysite, and the halloysite is of a hollow nanotube structure;
wherein the soluble carbon source is carbonate and/or bicarbonate.
5. The method of claim 4, wherein the pH is 9-12; and/or
The soluble carbon source is at least one of alkali metal carbonate, alkali metal bicarbonate, ammonium carbonate and ammonium bicarbonate.
6. The method of claim 4, wherein the halloysite hollow nanotubes have an inner diameter of 10-20nm, an outer diameter of 40-70nm, and a length of 200-1000nm.
7. The process according to any one of claims 4 to 6, wherein the amount of the precursor of lanthanum oxycarbonate is such that the lanthanum oxycarbonate content is 1 to 25 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis in the resulting supported catalyst.
8. The method of any of claims 4-6, wherein the conditions of the impregnating further comprise: the temperature is 20-40 ℃; the time is 1-5h; and/or
The drying conditions include: the temperature is 80-180 ℃ and the time is 12-24 hours; and/or
The roasting conditions include: the temperature is 450-600 ℃ and the time is 2-8 hours, and the roasting is carried out in the atmosphere of air or carbon dioxide.
9. The method of claim 8, wherein the dried material is warmed to the firing temperature at a rate of 1-10 ℃/min.
10. The method according to any one of claims 4-6, wherein the method further comprises: the doping element is supported on the carrier.
11. The method of claim 10, wherein the doping element is a metallic element, a semi-metallic element, a non-metallic element, or a combination thereof.
12. The method of claim 10, wherein the doping element is any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof.
13. The method according to claim 10, wherein the doping element is used in such an amount that the content of the doping element is 0.01 to 5 parts by weight with respect to 100 parts by weight of the carrier on a dry weight basis in the resulting supported catalyst.
14. A supported catalyst, characterized in that it is obtainable by a process according to any one of claims 4 to 13.
15. Use of a supported catalyst according to any one of claims 1-3 and 14 in a methane oxidative coupling reaction.
16. A process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with the supported catalyst of any one of claims 1-3 and 14 in the presence of oxygen and under conditions of an oxidative coupling reaction of methane;
alternatively, a supported catalyst is prepared according to the process of any one of claims 4-13, and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
17. The method of claim 16, wherein the molar ratio of methane to oxygen is 2-10:1, a step of;
and/or, the contact temperature is 400-750 ℃; the space velocity of methane is 5000-100000 mL/(g.h).
18. The method of claim 16, wherein the molar ratio of methane to oxygen is 3-8:1.
19. The following supported catalyst is applied to the oxidative coupling reaction of methane;
the supported catalyst comprises a carrier and an active component supported on the carrier, wherein the carrier is halloysite, and the halloysite is of a hollow nanotube structure; the active component comprises lanthanum oxide carbonate, and the content of the lanthanum oxide carbonate is 0.5-50 parts by weight relative to 100 parts by weight of a carrier based on dry weight.
20. Use according to claim 19, wherein the lanthanum oxycarbonate is present in an amount of 1-25 parts by weight relative to 100 parts by weight of carrier on a dry weight basis; and/or
The halloysite hollow nanotube has an inner diameter of 10-20nm, an outer diameter of 40-70nm and a length of 200-1000nm; and/or
The supported catalyst further comprises a doping element supported on the support.
21. The use of claim 20, wherein the doping element is a metallic element, a semi-metallic element, a non-metallic element, or a combination thereof.
22. The use of claim 20, wherein the doping element is any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof.
23. Use according to claim 20, wherein the doping element is present in the supported catalyst in an amount of 0.01-5 parts by weight relative to 100 parts by weight of the support on a dry weight basis.
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