CN113244909A - Catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, preparation method and application thereof - Google Patents

Catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, preparation method and application thereof Download PDF

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CN113244909A
CN113244909A CN202110496147.4A CN202110496147A CN113244909A CN 113244909 A CN113244909 A CN 113244909A CN 202110496147 A CN202110496147 A CN 202110496147A CN 113244909 A CN113244909 A CN 113244909A
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catalyst
reaction
preparing
methane
hydrocarbon
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CN113244909B (en
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张清德
闫丽娜
谭猗生
韩怡卓
杨彩虹
宋法恩
解红娟
潘俊轩
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • 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
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • 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 Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, a preparation method and application thereof. The catalyst comprises Mo species and tin oxide species, the Mo species of the catalyst is MoOxUniformly dispersed on the surface of the catalyst in the form of Na as a tin oxide species2SnO3And SnO2Two structures exist; wherein the molar ratio of the Mo element to the Sn element is 1:30-2: 1. The preparation process of the catalyst is simple and easy to operate, and the catalyst components are simple(ii) a The catalyst has low reaction temperature and can effectively inhibit deep oxidation of methane into COxThe catalyst is converted into C2 hydrocarbon with high selectivity, has better stability, obviously reduces carbon emission, greatly reduces the production cost of C2 hydrocarbon, and has very important significance in the oxidative coupling reaction of methane.

Description

Catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, which has high C2 hydrocarbon selectivity and can effectively inhibit deep oxidation, and a preparation method and application thereof, and belongs to the technical field of catalyst preparation.
Background
In recent years, with the increase of social demands and the improvement of industrialization degree, the restriction of energy utilization on the development of human economy and society and the influence on the environment become more and more obvious. The reasonable utilization of clean energy with rich reserves, the reduction of carbon emission and the realization of carbon peak reaching and carbon neutralization are important measures for guaranteeing the national energy safety. With the continuous improvement of exploration technology, energy sources such as natural gas, shale gas, combustible ice and coal bed gas are developed in a large quantity, and if methane serving as a main component of the natural gas, shale gas, combustible ice and coal bed gas can be efficiently utilized and converted into chemical products with high added values, the high-value utilization of the natural gas, shale gas, combustible ice and coal bed gas can be revolutionarily promoted.
Much work has been done so far on the study of methane, which can be converted into synthesis gas (CO and H)2) Aromatic compounds, C2 hydrocarbons, methanol, and the like. Indirect conversion of methane to CO and H2The process route has high energy consumption and high COxThe method has the advantages of low energy consumption, short process flow, low cost and the like, and therefore, the method has potential economic value by adopting a direct method to efficiently utilize methane. The direct methane conversion technology is mainly divided into two modes of aerobic methane conversion and anaerobic methane conversion. Among them, the reaction research of preparing C2 hydrocarbon by oxidative coupling of methane is more and has attracted much attention in the field of catalysis, and has been one of the research hotspots of which researchers have paid extensive attention.
For the oxidative coupling reaction of methane, the molecular structure of methane is extremely stable, the harsh condition for activating C-H bonds is required, and ethane and ethylene are easy to activate than methane, so that the oxidative coupling reaction of methane always has the following problems: high reaction temperature, low C2 hydrocarbon selectivity and easy deep oxidation of methane into COxAnd the like. The number of catalysts for the reaction of preparing C2 hydrocarbon by methane oxidative coupling in domestic and foreign research is over 2000, and the four main catalysts are alkaline earth/alkali metal oxides, rare earth metal oxides, transition metal oxides, composite salt oxide catalysts and the like. In which a transition metal oxide catalyst Na is used2WO4-Mn/SiO2Has better performance, such as Y/Sr-Na reported by Chinese patent CN111203283A2WO4-Mn/SiO2The catalyst and the Mn-Na-W-Si composite oxide catalyst containing Ti or not containing Ti reported by the Chinese patent CN104759291A have the problems of high reaction temperature, complex catalyst components and the like, the reaction temperature is between 750-830 ℃, the minimum reaction temperature is 750 ℃, the methane conversion rate is 31.7 percent, the C2 hydrocarbon selectivity is 74.3 percent, and the like; mn of China patent CN106964341A2O3、Na2WO4And MnTiO3Three active components and SiO2The catalyst consists of carrier, the reaction temperature is between 620 ℃ and 700 ℃, the conversion rate of methane is 14.8 percent, the selectivity of C2 hydrocarbon is 45.7 percent, and the CO content is lower than the reaction temperaturexThe selectivity of (a) was 49.5%; although the reaction temperature is lower than 700 ℃, the selectivity of C2 hydrocarbon is low, and methane is still easy to deeply oxidize into COxComplex catalyst components, complex preparation process and the like. Coated catalyst B invented by Chinese patent CN109529799AbOy-AaOx@ S (A is La, Ce and Mg, B is Li, Na, K, Ca, Sr and Ba) has better low-temperature performance, the lowest reaction temperature is 500 ℃, the methane conversion rate is 32.1 percent, the C2 hydrocarbon selectivity is 58.38 percent, and CO is introduced under normal pressurexThe selectivity of (A) is 41.62%, the selectivity of C2 hydrocarbon is low, and the preparation process of the catalyst is complicated. The Sm-Li/MgO catalyst reported in Chinese patent CN1145824A has high methane conversion rate and stability only at 800 ℃, but the C2 hydrocarbon has low selectivity and still existsIn the deep oxidation of methane. At present, most of catalysts for oxidative coupling of methane have high reaction temperature (>700 ℃) and methane is easily deeply oxidized into COxComplex catalyst components, complicated catalyst preparation process and the like. Therefore, the development of the methane oxidative coupling catalyst which has simple components, low temperature, high C2 hydrocarbon selectivity and can effectively inhibit deep oxidation is of great significance.
Disclosure of Invention
The invention aims to provide a catalyst which has high C2 hydrocarbon selectivity and can effectively inhibit deep oxidation for preparing C2 hydrocarbon by methane oxidative coupling, and a preparation method and application thereof.
The invention provides a catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, which comprises Mo species and tin oxide species, wherein the Mo species of the catalyst is MoOxUniformly dispersed on the surface of the catalyst in the form of Na as a tin oxide species2SnO3And SnO2Two structures exist, wherein the molar ratio of the Mo element to the Sn element is 1:30-2: 1. In MoOx、Na2SnO3And SnO2Under the mutual synergistic effect of the three components, the catalyst has a proper amount of medium-strong basic sites and active oxygen species, so that the catalyst can effectively inhibit CO at a relatively low reaction temperaturexWith high selectivity to form C2 hydrocarbons.
The invention provides a preparation method of the Mo-Sn catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, which is synthesized by a hydrothermal method and comprises the following steps:
(1) preparing a mixed solution: according to the molar ratio of molybdenum element to tin element in the raw materials of 1:30-2:1, weighing tin salt or tin dioxide and molybdenum salt, sequentially adding the tin salt or tin dioxide and molybdenum salt into a reaction kettle, adding a solvent, stirring, dissolving, and heating in a water bath at 60 ℃ for 1 h;
(2) hydrothermal reaction: placing the reaction kettle filled with the mixed solution in a homogeneous reactor, heating at 80-200 ℃ for 20-26 h to ensure that the molybdenum salt and the tin salt fully react;
(3) and (3) drying: centrifuging the obtained suspension, washing, and drying at 80-110 deg.C for 12 hr;
(4) roasting: and putting the dried sample into a tubular furnace, heating to 650-700 ℃ at the heating rate of 2 ℃ per minute, roasting for 4-8 h in a protective atmosphere, and naturally cooling to room temperature to obtain the Mo-Sn catalyst.
The tin source used for preparing the catalyst is tin dioxide or tin salt, and the tin salt comprises one of tin tetrachloride pentahydrate, sodium stannate trihydrate, stannous chloride dihydrate, anhydrous stannous chloride, stannous sulfate and stannous fluoride.
The molybdenum source is one of ammonium molybdate tetrahydrate, ammonium molybdate dihydrate, sodium molybdate dihydrate and potassium molybdate.
The hydrothermal solvent is one or two of deionized water, absolute ethyl alcohol or N, N-dimethylformamide. Wherein when two solvents are selected, the volume ratio of the two solvents is 5: 1-1: 5.
the protective atmosphere during roasting is one of oxygen, air, nitrogen or argon.
The invention provides an application of the Mo-Sn catalyst for preparing C2 hydrocarbon by methane oxidative coupling at relatively low temperature: reaction is carried out in a fixed bed reactor, and reaction gas CH4：O2：N2Is 19: 1: 20-9: 1: 10, N2 For the equilibrium gas, the space velocity of the reaction is: 7200 25000 h-1The reaction temperature is 550-700 ℃, and the reaction pressure is normal pressure.
The invention has the beneficial effects that:
(1) the invention develops a novel catalyst for preparing C2 hydrocarbon by oxidative coupling of methane, the preparation process of the catalyst is simple and easy to operate, and the catalyst component is simple;
(2) compared with most catalysts, the catalyst has lower reaction temperature and can effectively inhibit deep oxidation of methane into COxHigh selectivity is converted into C2 hydrocarbon, the stability is better, and the carbon emission is obviously reduced;
(3) when the catalyst is used for preparing C2 through oxidative coupling of methane, the process flow is simple, the reaction temperature is relatively low, the energy consumption can be obviously reduced, the production cost of C2 hydrocarbon is greatly reduced, and the catalyst has very important significance in the oxidative coupling of methane.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
Placing a polytetrafluoroethylene-lined reaction kettle filled with deionized water in a water bath kettle at 60 ℃, respectively weighing 13.748 g of sodium stannate trihydrate and 2.972 g of ammonium molybdate tetrahydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1, continuously heating in a water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 160 ℃ for 20 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 80 deg.C for 12 hr in a forced air drying oven; roasting for 8 hours at 650 ℃ in an oxygen atmosphere to obtain the Mo1Sn3 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 19: 1: 20, N2 The reaction space velocity is 25000 h for equilibrium gas-1The reaction temperature is 580 ℃, the reaction pressure is normal pressure, and the reaction time is 4.5 h. The conversion of methane was 8.9%, the selectivity to C2 hydrocarbons was 97.7%, and CO was2The selectivity was 1.5%.
Example 2
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 15.81 g of sodium stannate trihydrate and 2.051 g of ammonium molybdate tetrahydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 2:1, continuously heating in a water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 120 ℃ for 26 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying in a forced air drying oven at 100 deg.C for 12 hr; roasting for 8 hours at 650 ℃ in an oxygen atmosphere to obtain the Mo1Sn5 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 14: 1: 15, N2 The reaction space velocity is 14000 h for balanced gas-1The reaction temperature is 630 ℃, the reaction pressure is normal pressure, and the reaction time is 5.5 h. The conversion of methane was 11.2%, the selectivity of C2 hydrocarbons was 98.3%, and CO was2The selectivity was 0.6%.
Example 3
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 16.498 g of sodium stannate trihydrate and 0.4811 g of potassium molybdate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring N, N-dimethylformamide into the reaction kettle, wherein the volume ratio of the deionized water to the N, N-dimethylformamide is 5: 1, continuously heating in a water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 180 ℃ for 24 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 80 deg.C for 12 hr in a forced air drying oven; roasting for 6 h at 650 ℃ in an argon atmosphere to obtain the Mo1Sn30 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 9: 1: 10, N2 The reaction space velocity is 7200 h for balancing gas-1The reaction temperature is 700 ℃, the reaction pressure is normal pressure, and the reaction time is 3.5 h. The conversion of methane was 15.2%, the selectivity to C2 hydrocarbons was 84.1%, and CO was2The selectivity was 13.1%.
Example 4
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 14.458 g of stannic chloride pentahydrate and 4.8623 g of sodium molybdate dihydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3, continuously heating in the water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 180 ℃ for 24 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 80 deg.C for 12 hr in a forced air drying oven; roasting for 8 hours at 700 ℃ in air atmosphere to obtain the Mo1Sn2 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 18: 1: 19, N2 The reaction space velocity is 23000 h for equilibrium gas-1The reaction temperature is 610 ℃, the reaction pressure is normal pressure, and the reaction time is 2.5 h. Methane conversion 9.8%, C2 hydrocarbon selectivity 96.7%, CO2The selectivity of (a) was 2.3%.
Example 5
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 15.178 g of sodium stannate trihydrate and 0.799 g of ammonium molybdate dihydrate, and sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 4: 1, continuously heating in a water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 140 ℃ for 20 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 110 deg.C for 12 hr; roasting for 8 hours at 650 ℃ in an oxygen atmosphere to obtain the Mo1Sn12 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 13: 1: 14, N2 The reaction space velocity is 13000 h for the balance gas-1The reaction temperature is 660 ℃, the reaction pressure is normal pressure, and the reaction time is 6.5 h. The conversion of methane was 11.7%, the selectivity of C2 hydrocarbons was 92.2%, and CO was2The selectivity was 6.8%.
Example 6
Placing a reaction kettle containing absolute ethyl alcohol in a water bath kettle at 60 ℃, respectively weighing 15.278 g of sodium stannate trihydrate and 0.991 g of ammonium molybdate tetrahydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; after the mixed solution is completely dissolved, placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction for 20 hours at 160 ℃; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 110 deg.C for 12 hr; roasting for 6 h at 700 ℃ in a nitrogen atmosphere to obtain the Mo1Sn9 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 15: 1: 16, N2 The reaction space velocity is 15000 h for balancing gas-1The reaction temperature is 650 ℃, the reaction pressure is normal pressure, and the reaction time is 6.5 h. The conversion of methane was 11%, the selectivity of C2 hydrocarbons was 93.2%, and CO2The selectivity was 6.3%.
Example 7
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 15.961 g of anhydrous stannous chloride and 4.073 g of sodium molybdate dihydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; after the mixed solution is completely dissolved, placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 120 ℃ for 24 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 110 deg.C for 12 hr; roasting for 4 hours at 650 ℃ in air atmosphere to obtain the Mo1Sn5 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 17: 1: 18, N2 The reaction space velocity is 19000 h for equilibrium gas-1The reaction temperature is 630 ℃, the reaction pressure is normal pressure, and the reaction time is 5.5 h. The conversion of methane was 10%, the selectivity of C2 hydrocarbons was 93.3%, and CO2The selectivity was 4.8%.
Example 8
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 15.712 g of sodium stannate trihydrate and 1.019 g of ammonium molybdate tetrahydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 5, continuously heating in the water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 200 ℃ for 24 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 90 deg.C for 12 hr in a forced air drying oven; roasting for 4 hours at 700 ℃ in an oxygen atmosphere to obtain the Mo1Sn10 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 16: 1: 17, N2 The reaction space velocity is 17000 h for equilibrium gas-1The reaction temperature is 640 ℃, the reaction pressure is normal pressure, and the reaction time is 6.5 h. The conversion of methane was 10.8%, the selectivity to C2 hydrocarbons was 94.1%, and CO was2The selectivity was 5.1%.
Example 9
Placing a reaction kettle filled with deionized water in a water bath kettle at 60 ℃, respectively weighing 15.071 g of tin dioxide and 0.955 g of potassium molybdate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; after the mixed solution is completely dissolved, placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction for 26 hours at the temperature of 150 ℃; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 110 deg.C for 12 hr; roasting for 7 h at 700 ℃ in a nitrogen atmosphere to obtain the Mo1Sn25 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 10: 1: 11, N2 The reaction space velocity is 9000 h for equilibrium gas-1The reaction temperature is 690 ℃, the reaction pressure is normal pressure, and the reaction time is 4.5 h. The conversion of methane was 13.6%, the selectivity to C2 hydrocarbons was 89.4%, and CO was2The selectivity was 11%.
Example 10
Placing a reaction kettle containing N, N-dimethylformamide in a water bath kettle at 60 ℃, respectively weighing 14.407 g of stannous sulfate and 0.859 g of potassium molybdate, sequentially placing the stannous sulfate and the potassium molybdate in the reaction kettle for water bath heating and magnetic stirring; after the mixed solution is completely dissolved, placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction for 26 hours at the temperature of 100 ℃; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying in a forced air drying oven at 100 deg.C for 12 hr; roasting for 4 hours at 650 ℃ in an argon atmosphere to obtain the Mo1Sn20 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 11: 1: 12, N2 The reaction space velocity is 11000 h for equilibrium gas-1The reaction temperature is 680 ℃, the reaction pressure is normal pressure, and the reaction time is 3.5 h. The conversion of methane was 13.2%, the selectivity of C2 hydrocarbons was 90.1%, and CO was2The selectivity was 8.9%.
Example 11
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 15.1945 g of stannous chloride dihydrate and 4.073 g of sodium molybdate dihydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 2, continuously heating in the water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 120 ℃ for 24 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 80 deg.C for 12 hr in a forced air drying oven; roasting for 4 hours at 650 ℃ in an oxygen atmosphere to obtain the Mo1Sn4 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 18: 1: 19, N2 The reaction space velocity is 21000 h for balancing gas-1The reaction temperature is 620 ℃, the reaction pressure is normal pressure, and the reaction time is 4.5 h. Conversion of methane was 9.5%, selectivity of C2 hydrocarbons was 95.5%, and CO was2The selectivity was 3.5%.
Example 12
Placing a reaction kettle containing deionized water in a water bath kettle at 60 ℃, respectively weighing 14.839 g of stannous fluoride and 1.527 g of sodium molybdate dihydrate, sequentially placing the materials in the reaction kettle for water bath heating and magnetic stirring; and after the mixture is completely dissolved, pouring absolute ethyl alcohol into the reaction kettle, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 4, continuously heating in the water bath and uniformly stirring; placing the reaction kettle filled with the mixed solution in a homogeneous reactor for reaction at 140 ℃ for 20 hours; pouring the prepared suspension into a centrifuge tube, centrifuging and washing for several times; drying at 90 deg.C for 12 hr in a forced air drying oven; roasting for 4 hours at 650 ℃ in an oxygen atmosphere to obtain the Mo1Sn15 catalyst.
The reaction is carried out in a continuous-flow fixed-bed reactor, the reaction gas CH4：O2：N2Is 12: 1: 13, N2 The reaction space velocity is 12000 h for equilibrium gas-1The reaction temperature is 670 ℃, the reaction pressure is normal pressure, and the reaction time is 5.5 h. The conversion of methane was 12.5% and the selectivity of C2 hydrocarbons was 90.5%，CO2The selectivity was 8.5%.

Claims (7)

1. A catalyst for preparing C2 hydrocarbon by oxidative coupling of methane is characterized in that: comprising Mo species and Sn-O species, the Mo species of the catalyst being MoOxUniformly dispersed on the surface of the catalyst in the form of Na as a tin oxide species2SnO3And SnO2Two structures exist; wherein the molar ratio of the Mo element to the Sn element is 1:30-2: 1.
2. The preparation method of the catalyst for preparing C2 hydrocarbon by oxidative coupling of methane according to claim 1, which is synthesized by a hydrothermal method, and is characterized by comprising the following steps:
(1) preparing a mixed solution: weighing tin salt or tin dioxide and molybdenum salt, sequentially adding the tin salt or tin dioxide and molybdenum salt into a reaction kettle according to the molar ratio of molybdenum element to tin element in the raw materials of 1:30-2:1, adding a solvent, stirring, dissolving, and heating in water bath at 60 ℃ for 1 h;
(2) hydrothermal reaction: placing the reaction kettle filled with the mixed solution in a homogeneous reactor, heating at 80-200 ℃ for 20-26 h to ensure that the molybdenum salt and the tin salt fully react;
(3) and (3) drying: centrifuging the obtained suspension, washing, and drying at 80-110 deg.C for 12 hr;
(4) roasting: and putting the dried sample into a tubular furnace, heating to 650-700 ℃ at the heating rate of 2 ℃ per minute, roasting for 4-8 h in a protective atmosphere, and naturally cooling to room temperature to obtain the Mo-Sn catalyst.
3. The method for preparing the catalyst for preparing C2 hydrocarbon by oxidative coupling of methane according to claim 2, wherein: the tin source is tin dioxide or tin salt, and the tin salt comprises one of tin tetrachloride pentahydrate, sodium stannate trihydrate, stannous chloride dihydrate, anhydrous stannous chloride, stannous sulfate and stannous fluoride.
4. The method for preparing the catalyst for preparing C2 hydrocarbon by oxidative coupling of methane according to claim 2, wherein: the molybdenum source is one of ammonium molybdate tetrahydrate, ammonium molybdate dihydrate, sodium molybdate dihydrate and potassium molybdate.
5. The method for preparing the catalyst for preparing C2 hydrocarbon by oxidative coupling of methane according to claim 2, wherein: the hydrothermal solvent is one or two of deionized water, absolute ethyl alcohol or N, N-dimethylformamide; wherein when two solvents are selected, the volume ratio of the two solvents is 5: 1-1: 5.
6. the method for preparing the catalyst for preparing C2 hydrocarbon by oxidative coupling of methane according to claim 2, wherein: the protective atmosphere during roasting is one of oxygen, air, nitrogen or argon.
7. The use of the catalyst for oxidative coupling of methane to produce C2 hydrocarbons, as claimed in claim 1, wherein: reaction is carried out in a fixed bed reactor, and reaction gas CH4：O2：N2Is 19: 1: 20-9: 1: 10, N2 For the equilibrium gas, the space velocity of the reaction is: 7200 25000 h-1The reaction temperature is 550-700 ℃, and the reaction pressure is normal pressure.
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