CN112871152A - Methane oxidative coupling catalyst, preparation method thereof and method for preparing ethylene by methane oxidative coupling - Google Patents
Methane oxidative coupling catalyst, preparation method thereof and method for preparing ethylene by methane oxidative coupling Download PDFInfo
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- CN112871152A CN112871152A CN201911202018.9A CN201911202018A CN112871152A CN 112871152 A CN112871152 A CN 112871152A CN 201911202018 A CN201911202018 A CN 201911202018A CN 112871152 A CN112871152 A CN 112871152A
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/34—Manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention relates to the field of natural gas utilization, and discloses a methane oxidative coupling catalyst, a preparation method thereof and a method for preparing ethylene by methane oxidative coupling. The methane oxidative coupling catalyst comprises cristobalite and an active component loaded on the cristobalite; wherein the active set comprises sodium tungstate, oxides of manganese, and gallium oxide; in the catalyst, based on the weight of the cristobalite, the content of sodium tungstate is 0.9-15 wt%, the content of manganese oxide is 0.4-6.5 wt% calculated by manganese, and the content of gallium oxide is 0.01-8 wt%. The catalyst can effectively promote the methane oxidation coupling reaction at high temperature to generate carbon and above hydrocarbons such as ethylene. The method for preparing the catalyst has simple steps, and the catalyst has higher industrial application prospect.
Description
Technical Field
The invention relates to the field of natural gas utilization, in particular to a methane oxidative coupling catalyst, a preparation method thereof and a method for preparing ethylene by methane oxidative coupling.
Background
Ethylene is the most important basic organic chemical raw material, and the production of ethylene depends on a petroleum cracking route for a long time, so that the problems of environmental pollution and the like caused by the ethylene are more and more serious. In recent years, the price of crude oil is continuously rising to cause the price of ethylene cracking raw materials to rise, and the phenomenon of short supply and short demand of the ethylene cracking raw materials is also very prominent.
As an important energy source, the natural gas provides good guarantee for the utilization of the natural gas in the chemical industry. Meanwhile, in order to meet the requirement of global energy and petrochemical raw material structure transformation internationally, the synthesis of olefin by substituting natural gas for petroleum is one of important research directions. At present, the processes for the production of ethylene starting from natural gas include direct processes and indirect processes. The direct method is specifically divided into oxidative coupling, chlorination coupling and direct dehydrogenation; the indirect method is to convert natural gas into synthesis gas and then prepare olefin from the synthesis gas, and specifically comprises the methods of preparing olefin by an improved F-T method and methanol cracking.
From natural gas, the ethylene is prepared by adopting a three-step method (POM/GTM/MTO) of preparing synthesis gas/methanol from synthesis gas/methanol to olefin from partial oxidation, so that the reaction steps are various, and oxygen atoms are inserted and then taken out, so that the non-atomic economic reaction is realized; from the aspects of technology, resource utilization, environmental protection and the like, the multi-step method is not an economical and reasonable choice.
Natural gas, i.e., oxidative coupling of methane to produce ethylene (OCM)) is the most direct method, and therefore OCM has been the focus of research by scientists throughout the world for decades. Since UCC corporation of America published the first research report on OCM in 1982, up to 2000 or more catalysts have been studied. At present, the catalytic system with better reaction performance is mainly focused on alkaline combinationThe catalyst system comprises a catalyst system of a single-phase oxide, an alkali metal and an alkaline earth metal supported by an oxide, a transition metal oxide supported by an alkali metal ion, a halogen ion modified oxide and a solid super acid. One of the best systems is a supported catalyst with silica as the carrier and sodium tungstate and manganese as the active components (see Li, S. (2003). "Reaction Chemistry of W-Mn/SiO2(ii) Catalyst for the Oxidative Coupling of methane. "Journal of Natural Gas Chemistry (01): 1-9.); in addition, CN101385982A provides a method for assembling the catalyst active component into the mesoporous molecular sieve SBA-15; CN1067831A preparation of catalyst for converting methane into higher hydrocarbon (ethylene and ethane) by impregnation method and slurry mixing method, the catalyst is made of SiO2Or Al2O3The pellet is used as carrier.
The oxidative coupling of methane is an exothermic reaction, the reaction temperature is very high, generally at 750-.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a methane oxidative coupling catalyst, a preparation method thereof and a method for preparing ethylene by oxidative coupling of methane. The catalyst provided by the invention can improve the conversion rate of methane and the hydrocarbon (C) of carbon two or more in the high-temperature methane coupling oxidation reaction2+Hydrocarbon) selectivity.
In a first aspect, the present invention provides a methane oxidative coupling catalyst comprising cristobalite and an active component supported on the cristobalite; wherein the active set comprises sodium tungstate, oxides of manganese, and gallium oxide; in the catalyst, based on the weight of the cristobalite, the content of sodium tungstate is 0.9-15 wt%, the content of manganese oxide is 0.4-6.5 wt% calculated by manganese, and the content of gallium oxide is 0.01-8 wt%.
In a second aspect, the present invention provides a process for preparing a methane oxidation coupling catalyst, the process comprising: in the presence of water, contacting the cristobalite with sodium tungstate, soluble salts of manganese and soluble salts of gallium, drying and roasting to load oxides of the sodium tungstate and the manganese and gallium oxide on the cristobalite; wherein the amount of the cristobalite, sodium tungstate, soluble salts of manganese and soluble salts of gallium is such that the catalyst contains sodium tungstate in an amount of 0.9 to 15 wt%, manganese oxide in an amount of 0.4 to 6.5 wt% and gallium oxide in an amount of 0.01 to 8 wt%, based on the weight of the cristobalite.
In a third aspect, the present invention provides a methane oxidative coupling catalyst prepared by the process of the second aspect of the present invention.
In a fourth aspect, the present invention provides a method for preparing ethylene by oxidative coupling of methane, which comprises: in the presence of the methane oxidative coupling catalyst of the present invention, methane and oxygen are subjected to a methane oxidative coupling reaction.
The catalyst of the invention takes cristobalite as a carrier, combines a certain amount of sodium tungstate, manganese oxide and gallium oxide as active components, and can effectively promote methane oxidation coupling reaction at high temperature to generate carbon dioxide and above hydrocarbons such as ethylene; in addition, the introduction of gallium oxide improves the catalyst activity. The method for preparing the catalyst provided by the invention has simple steps, and the catalyst has higher industrial application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a methane oxidative coupling catalyst comprising cristobalite and an active component supported on the cristobalite, wherein the active component comprises sodium tungstate, an oxide of manganese and gallium oxide.
In the methane oxidative coupling catalyst of the present invention, sodium tungstate (Na) is added based on the weight of the cristobalite2WO4) 0.9-15 wt%, manganese oxide 0.4-6.5 wt%, calculated as manganese, gallium oxide (Ga)2O3) Is contained in an amount of 0.01 to 8 wt%.
Preferably, the catalyst has a sodium tungstate content of 3 to 10 wt%, more preferably 3 to 6 wt%, based on the weight of the cristobalite; the content of manganese oxide is 1 to 5% by weight, preferably 2 to 4% by weight, based on manganese; the content of gallium oxide is 0.05 to 5.5% by weight, more preferably 0.1 to 5% by weight. Thus, the synergistic effect of the active components and the cristobalite can be further exerted, the catalytic activity is improved, and the conversion of methane into C is facilitated2+A hydrocarbon.
The content of each component in the catalyst is calculated according to the feeding amount. It should be understood that commercially available sodium tungstate is typically sodium tungstate hydrate. The sodium tungstate used in the present invention is, unless otherwise specified, Na in the same amount as that in the present invention2WO4The content and the amount of the compound (A).
According to a second aspect of the present invention, there is provided a process for the preparation of a methane oxidation coupling catalyst, the process comprising: in the presence of water, contacting the cristobalite with sodium tungstate, soluble salts of manganese and soluble salts of gallium, drying and roasting to enable oxides of the sodium tungstate, the manganese and the gallium oxide to be loaded on the cristobalite.
In the preparation method of the catalyst, the cristobalite used as the carrier has the characteristics of high-temperature structure and stable performance, and the cristobalite can be obtained by commercial purchase or by roasting amorphous silicon dioxide.
In the preparation method of the catalyst, the cristobalite, the sodium tungstate, the soluble salt of manganese and the soluble salt of gallium are used in amounts such that the content of sodium tungstate is 0.9-15 wt%, the content of manganese oxide is 0.4-6.5 wt% and the content of gallium oxide is 0.01-8 wt% based on the weight of the cristobalite in the prepared catalyst.
Preferably, the amount of cristobalite, sodium tungstate, soluble salts of manganese and soluble salts of gallium is such that the catalyst is prepared with a sodium tungstate content of 3 to 10 wt.%, more preferably 3 to 6 wt.%, based on the weight of cristobalite; the content of the oxide of manganese is 1 to 5% by weight, more preferably 2 to 4% by weight, in terms of manganese; the content of gallium oxide is 0.05 to 5.5% by weight, more preferably 0.1 to 5% by weight.
In the catalyst preparation method of the present invention, the calcination temperature may be, for example, 500-850 ℃, and the calcination time may be, for example, 2-10 hours. Preferably, the roasting process comprises: the dried product is heated up to 600-850 deg.C (more preferably to 650-850 deg.C) at a constant rate of 3-15 deg.C/min (more preferably 5-10 deg.C/min) and held for 2-10 hours (more preferably 4-8 hours).
In the preparation method of the catalyst, the soluble salt of manganese and the soluble salt of gallium can be various precursors of active components dissolved in water, and only need to be capable of respectively forming various oxides of manganese and gallium oxide by roasting. The soluble salt of manganese is preferably manganese nitrate and the soluble salt of gallium is preferably gallium nitrate. The gallium nitrate is typically present as its hydrate.
According to the preparation method, each active component is loaded on the cristobalite carrier through an impregnation method to form the catalyst. The cristobalite can be impregnated by sodium tungstate, soluble salt of manganese and soluble salt of gallium step by step to load the active component on the carrier (the step impregnation can be to impregnate the cristobalite by one or two salts in advance), or the active component can be loaded on the carrier by synchronous impregnation. It will be understood that when the aqueous solution containing the precursors of the respective active components is impregnated into the support in succession, each impregnation comprises contacting and drying operations, the final impregnation being followed by the calcination. The synchronous impregnation refers to that the carrier is simultaneously impregnated with the aqueous solution containing the precursors of the active components, and then dried and roasted.
Preferably, the drying is carried out in two stages,
the first stage is as follows: rotary evaporating the contact product at 70-90 deg.C for 0.5-3 hr;
and a second stage: the product obtained by evaporation was dried at 110-180 ℃ for 1-6 hours.
Typically, each contacting is carried out under agitation, which may be at a temperature of 20 to 90 ℃ for a period of 1 to 2 hours.
According to a particular embodiment, the process for preparing the catalyst comprises the following steps: and respectively contacting the water solution containing sodium tungstate, the water solution containing soluble salt of manganese and the water solution containing soluble salt of gallium with the cristobalite, and drying the obtained product after each contact.
According to another specific embodiment, the process for preparing the catalyst comprises the steps of:
1) in the presence of water, contacting the cristobalite with soluble salt containing manganese and sodium tungstate, and then drying to obtain cristobalite impregnated with manganese and sodium tungstate;
2) and contacting the cristobalite impregnated with manganese and sodium tungstate with a soluble salt aqueous solution containing gallium, and then drying and roasting.
In the step 1), the carrier may be impregnated with an aqueous solution of a soluble salt of manganese and an aqueous solution of sodium tungstate, or may be impregnated with an aqueous solution of a soluble salt of manganese and an aqueous solution of sodium tungstate. The contact is effected by stirring, which may be at room temperature (20-45 ℃ C.), for example.
In step 2), the contact is carried out with stirring, the temperature of the stirring being, for example, from 30 to 90 DEG C
In the catalyst preparation method of the present invention, in each aqueous salt solution used for impregnating the carrier, the concentration of the soluble salt of manganese may be, for example, 1 to 30% by weight, the concentration of sodium tungstate may be, for example, 1 to 10% by weight, and the concentration of the soluble salt of gallium may be, for example, 0.01 to 15% by weight.
In order to obtain a catalyst product with a certain particle size distribution, the method for preparing the catalyst of the invention can further comprise the following steps: and tabletting, crushing and sieving the roasted product.
According to a third aspect of the present invention there is provided a methane oxidative coupling catalyst prepared by the process of the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a process for the oxidative coupling of methane to ethylene, the process comprising: in the presence of the methane oxidative coupling catalyst of the present invention, methane and oxygen are subjected to a methane oxidative coupling reaction.
In the method for preparing ethylene by oxidative coupling of methane, methane and an oxygen source can be directly introduced for reaction, or natural gas and the oxygen source can be reacted. The oxygen source may be oxygen gas, or a mixed gas containing oxygen gas, such as air.
The methane oxidative coupling catalyst can be used in any form of reactor, such as a fixed bed reactor (e.g., a fixed bed quartz tube reactor), a fluidized bed reactor, and the like.
The conditions of the oxidative coupling of methane reaction may include: the reaction temperature is 700-850 ℃, the molar ratio of the methane to the oxygen is (1-10) to 1, and the reaction space velocity is 10000-60000 mL/(g.h).
Preferably, in the methane oxidation coupling reaction, the reaction temperature is 750-850 ℃, and more preferably 800-850 ℃; the molar ratio of the methane to the oxygen is (1-5) to 1, and the molar ratio is more preferably (2-5) to 1; the reaction space velocity is 10000-50000 mL/(g.h), more preferably 30000-50000 mL/(g.h); this allows higher methane conversion and C2+A hydrocarbon selectivity.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
amorphous silica was purchased from Qingdao ocean chemical Co., Ltd;
cristobalite was purchased from national drug group chemical agents ltd;
manganese nitrate solution (50 wt% aqueous solution), sodium tungstate dihydrate (Na)2WO4·2H2O) were purchased from national pharmaceutical group chemical agents, Inc.;
gallium nitrate hydrate (Ga (NO)3)3·9H2O) was purchased from ALFA corporation.
Example 1
Dissolving 7.03g of manganese nitrate solution in 35mL of water, adding 18g of cristobalite carrier, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 110 ℃ for 3h to obtain manganese-impregnated cristobalite.
Dissolving 0.20g of sodium tungstate dihydrate in 20mL of water, adding the manganese-impregnated cristobalite, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 3h, and drying at 120 ℃ for 2h to obtain the manganese-and sodium tungstate-impregnated cristobalite.
Dissolving gallium nitrate hydrate 0.05g in water 20mL, adding cristobalite impregnated with manganese and sodium tungstate, stirring at 50 deg.C for 1.5h, rotary evaporating at 80 deg.C for 2h, drying at 110 deg.C for 3h, heating to 800 deg.C at a rate of 5 deg.C/min in air, and calcining for 5 h. After cooling to room temperature, catalyst A1 (Na) was obtained2WO4-Mn-Ga2O3Cristobalite); wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO41.0%, Mn oxide (Mn) 6.0%, Ga2O3 0.1％。
Comparative example 1
Dissolving 7.03g of manganese nitrate solution in 35mL of water, adding 18g of amorphous silica carrier, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 110 ℃ for 3h to obtain the manganese-impregnated carrier.
Dissolving 0.20g of sodium tungstate dihydrate in 20mL of water, adding a carrier for impregnating manganese, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 3h, drying at 120 ℃ for 2h, heating to 800 ℃ at the speed of 5 ℃/min in the air, and roasting for 5h to obtain a catalyst D1; wherein, in the catalyst D1, based on the weight of amorphous silicon dioxide, the mass percentage of active components is as follows: na (Na)2WO41.0%, and the oxide of Mn is 6.0% in terms of Mn.
Comparative example 2
Dissolving 7.03g of manganese nitrate solution in 35mL of water, adding 18g of amorphous silica carrier, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 110 ℃ for 3h to obtain the manganese-impregnated carrier.
Dissolving 0.20g of sodium tungstate dihydrate in 20mL of water, adding the carrier impregnated with manganese, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 3h, and drying at 120 ℃ for 2h to obtain the carrier impregnated with manganese and sodium tungstate.
Dissolving 0.05g of gallium nitrate hydrate in 20mL of water, adding a carrier for impregnating manganese and sodium tungstate, stirring for 1.5h at 50 ℃, then rotationally evaporating for 2h at 80 ℃, drying for 2h at 120 ℃, then heating to 800 ℃ in air at the speed of 5 ℃/min, roasting for 5h, and cooling to room temperature to obtain a catalyst D2; wherein based on the weight of the amorphous silicon dioxide, the mass content of the active components is as follows: na (Na)2WO41.0%, Mn oxide (Mn) 6.0%, Ga2O30.1％。
Example 2
4.68g of manganese nitrate solution was dissolved in 30mL of water, 18g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary-evaporated at 80 ℃ for 2 hours, and dried at 150 ℃ for 5 hours to obtain manganese-impregnated cristobalite.
Dissolving 1.21g of sodium tungstate dihydrate in 25mL of water, adding the manganese-impregnated cristobalite, stirring at room temperature for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 180 ℃ for 2h to obtain the manganese-and sodium tungstate-impregnated cristobalite.
Dissolving gallium nitrate hydrate 0.005g in water 20mL, adding cristobalite impregnated with manganese and sodium tungstate, stirring at 40 deg.C for 1h, rotary evaporating at 80 deg.C for 2h, drying at 150 deg.C for 2h, heating to 850 deg.C in air at a rate of 5 deg.C/min, and calcining for 8 h. After cooling to room temperature, catalyst A2 (Na) was obtained2WO4-Mn-Ga2O3Cristobalite); wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO46.0%, Mn oxide (calculated as Mn) 4.0%, Ga2O30.01 wt%.
Example 3
2.34g of manganese nitrate solution was dissolved in 30mL of water, 18g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary-evaporated at 80 ℃ for 2 hours, and dried at 120 ℃ for 2 hours to obtain manganese-impregnated cristobalite.
Dissolving 1.96g of gallium nitrate in 20mL of water, adding the manganese-impregnated cristobalite, stirring at 60 ℃ for 1h, performing rotary evaporation at 80 ℃ for 2h, and drying at 120 ℃ for 2h to obtain the manganese-and gallium-impregnated cristobalite.
Mixing the two liquidsDissolving sodium tungstate 0.61g in water 40mL, adding above cristobalite impregnated with manganese and gallium, stirring at room temperature for 1h, rotary evaporating at 80 deg.C for 2h, drying at 150 deg.C for 5h, heating to 650 deg.C in air at a rate of 5 deg.C/min, and calcining for 5 h. After cooling to room temperature, catalyst A3 (Na) was obtained2WO4-Mn-Ga2O3Cristobalite); wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO43.0%, Mn oxide 2.0% in terms of Mn, Ga2O32.0% by weight.
Example 4
2.02g of sodium tungstate was dissolved in 15mL of water, 0.58g of manganese nitrate solution was dissolved in 20mL of water, mixed and added to 18g of cristobalite, stirred at room temperature for 1 hour, rotary evaporated at 80 ℃ for 2 hours, and dried at 120 ℃ for 3 hours to obtain cristobalite impregnated with manganese and sodium tungstate.
Dissolving gallium nitrate 0.93g in water 20mL, adding cristobalite impregnated with manganese and sodium tungstate, stirring at 40 deg.C for 1h, rotary evaporating at 80 deg.C for 2h, drying at 120 deg.C for 2h, heating to 650 deg.C in air at a rate of 10 deg.C/min, and calcining for 5 h. After cooling to room temperature, catalyst A4 (Na) was obtained2WO4-Mn-Ga2O3Cristobalite); wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO410.0%, Mn oxide (calculated as Mn) 0.5%, Ga2O32.0% by weight.
Comparative example 3
2.02g of sodium tungstate is dissolved in 15mL of water, 0.58g of manganese nitrate solution is dissolved in 20mL of water, the mixture is added into 18g of cristobalite, the mixture is stirred for 1h at room temperature, rotary evaporation is carried out at 80 ℃ for 2h, drying is carried out at 120 ℃ for 3h, and then the mixture is heated to 650 ℃ at the speed of 10 ℃/min in air and roasted for 5 h. After cooling to room temperature, catalyst D3 was obtained; wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO410.0%, Mn oxide is 0.5% in terms of Mn.
Example 5
2.34g of manganese nitrate solution was dissolved in 30mL of water, 18g of cristobalite carrier was added, stirred at room temperature for 1 hour, rotary-evaporated at 80 ℃ for 2 hours, and dried at 120 ℃ for 2 hours to obtain manganese-impregnated cristobalite.
2.4g of sodium tungstate dihydrate is dissolved in 50mL of water, added with cristobalite impregnated with manganese, stirred at room temperature for 1h, rotary evaporated at 80 ℃ for 3h, and dried at 150 ℃ for 4h to obtain the cristobalite impregnated with manganese and sodium tungstate.
Dissolving gallium nitrate hydrate 3.8g in 50mL of water, adding cristobalite impregnated with manganese and sodium tungstate, stirring at 50 ℃ for 1h, performing rotary evaporation at 80 ℃ for 2h, drying at 170 ℃ for 5h, and heating to 800 ℃ in air at the rate of 5 ℃/min to bake for 5 h. After cooling to room temperature, catalyst A5 (Na) was obtained2WO4-Mn-Ga2O3Cristobalite); wherein based on the weight of the cristobalite, the mass percentage of the active components is as follows: na (Na)2WO412.0%, Mn oxide 2.0% in terms of Mn, Ga2O38.0％。
Test example
The catalyst A1-A5 and the catalyst D1-D3 are respectively tableted, crushed and sieved, and the part between 40 meshes and 60 meshes is used for the following methane oxidative coupling reaction.
In a fixed bed quartz tube reactor (inner diameter 8mm), 0.2g of the above catalyst was charged, and quartz sand (20-40 mesh) was filled up and down with the catalyst, respectively. Then methane and oxygen are injected into the reactor to carry out the oxidative coupling reaction of methane under the set operating conditions. The reaction results were analyzed by Agilent 7890A gas chromatography, in which hydrocarbons were detected by FID detector, alumina capillary chromatography column and methane, carbon monoxide and carbon dioxide by TCD detector. During the operation, the catalytic performance of the catalyst under the reaction conditions (reaction temperature, reaction space velocity and alkylene oxide ratio) shown in Table 1 was evaluated in sequence as CH4Conversion, C2+Selectivity and C2+The yield is shown in Table 1.
TABLE 1
Note: ' CH4/O2"means aMolar ratio of alkane to oxygen.
In combination with the results of Table 1, it is understood that the methane conversion rate and C in the oxidative coupling reaction of methane can be improved by the methane conversion catalysts prepared in examples 1 to 5, as compared with comparative examples 1 to 32+High yield and high application value.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A methane oxidative coupling catalyst, which comprises cristobalite and an active component supported on the cristobalite; wherein the active set comprises sodium tungstate, oxides of manganese, and gallium oxide; in the catalyst, based on the weight of the cristobalite, the content of sodium tungstate is 0.9-15 wt%, the content of manganese oxide is 0.4-6.5 wt% calculated by manganese, and the content of gallium oxide is 0.01-8 wt%.
2. The oxidative coupling catalyst for methane according to claim 1, wherein the sodium tungstate is present in the catalyst in an amount of 3 to 10 wt.%, preferably 3 to 6 wt.%, based on the weight of the cristobalite; the content of manganese oxide is 1 to 5% by weight, preferably 2 to 4% by weight, based on manganese; the content of gallium oxide is 0.05 to 5.5% by weight, more preferably 0.1 to 5% by weight.
3. A process for preparing a methane oxidation coupling catalyst, the process comprising: in the presence of water, contacting the cristobalite with sodium tungstate, soluble salts of manganese and soluble salts of gallium, drying and roasting to load oxides of the sodium tungstate and the manganese and gallium oxide on the cristobalite; wherein the content of the first and second substances,
the amounts of the cristobalite, sodium tungstate, soluble salts of manganese and soluble salts of gallium are such that the catalyst prepared contains, based on the weight of the cristobalite, 0.9 to 15 wt% of sodium tungstate, 0.4 to 6.5 wt% of manganese oxide and 0.01 to 8 wt% of gallium oxide.
4. A process according to claim 3, wherein the amount of cristobalite, sodium tungstate, soluble salts of manganese, soluble salts of gallium is such that the catalyst is prepared with a sodium tungstate content of 3 to 10 wt.%, preferably 3 to 6 wt.%, based on the weight of cristobalite; the content of manganese oxide is 1 to 5% by weight, preferably 2 to 4% by weight, based on manganese; the content of gallium oxide is 0.05 to 5.5% by weight, more preferably 0.1 to 5% by weight.
5. The production method according to claim 3, wherein the soluble salt of manganese is manganese nitrate and the soluble salt of gallium is gallium nitrate;
preferably, the roasting process comprises: the dried product is heated to 600-850 ℃ at a constant rate of 3-15 ℃/min and is kept warm for 2-10 hours.
6. A process according to claim 3, wherein the drying is carried out in two stages,
the first stage is as follows: rotary evaporating the contact product at 70-90 deg.C for 0.5-3 hr;
and a second stage: the product obtained by evaporation was dried at 110-180 ℃ for 1-6 hours.
7. The method according to any of claims 3-6, wherein the method comprises the steps of: and respectively contacting the water solution containing sodium tungstate, the water solution containing soluble salt of manganese and the water solution containing soluble salt of gallium with the cristobalite, and drying the obtained product after each contact.
8. The method according to any of claims 3-6, wherein the method comprises the steps of:
1) in the presence of water, contacting the cristobalite with soluble salt containing manganese and sodium tungstate, and then drying to obtain cristobalite impregnated with manganese and sodium tungstate;
2) and contacting the cristobalite impregnated with manganese and sodium tungstate with a soluble salt aqueous solution containing gallium, and then drying and roasting.
9. The process according to claim 7 or 8, wherein the contacting is carried out under stirring at a temperature of 20-90 ℃ for a period of 1-2 hours.
10. The method of any of claims 3-9, wherein the method further comprises: and tabletting, crushing and sieving the product obtained by roasting.
11. An oxidative coupling catalyst for methane, prepared by the process of any one of claims 3 to 10.
12. A method for preparing ethylene by oxidative coupling of methane comprises the following steps: subjecting methane and oxygen to an oxidative coupling reaction of methane in the presence of the oxidative coupling catalyst for methane as defined in any one of claims 1 to 2 and 11.
13. The method of claim 12, wherein the conditions of the oxidative coupling of methane reaction comprise: the reaction temperature is 700-850 ℃, preferably 750-850 ℃; the molar ratio of the methane to the oxygen is (1-10) to 1, preferably (1-5) to 1; the reaction space velocity is 10000-60000 mL/(g.h), preferably 10000-50000 mL/(g.h).
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| CN115703075A (en) * | 2021-08-16 | 2023-02-17 | 中国石油化工股份有限公司 | Methane oxidative coupling catalyst, preparation method and application thereof, and method for preparing carbo-dylic hydrocarbon |
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