CN111203283A - Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane - Google Patents

Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane Download PDF

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Publication number
CN111203283A
CN111203283A CN201811399475.7A CN201811399475A CN111203283A CN 111203283 A CN111203283 A CN 111203283A CN 201811399475 A CN201811399475 A CN 201811399475A CN 111203283 A CN111203283 A CN 111203283A
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methane
carrier
catalyst
oxidative coupling
nitrate
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赵清锐
张明森
柯丽
韦力
武洁花
冯静
邵芸
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of catalysts, and discloses a supported methane oxidative coupling reaction catalyst, and a preparation method and application thereof. Wherein the methane oxidative coupling reaction catalyst comprises a carrier and Na loaded on the carrier2WO4A component, a Mn component and an M component, wherein the carrier is SiO2M is metal Y or Sr, and the Na is based on the total weight of the carrier2WO4The content of the component is 2-8 wt%, the content of the Mn component is 1-5 wt%, and the content of M is 1-4 wt%. The new technology for preparing the methane oxidative coupling reaction catalyst by adopting the one-step impregnation method provided by the invention has simple operationThe method avoids the operation of twice impregnation, reduces the preparation steps, has excellent catalyst performance, and saves a large amount of manpower, material resources and time.

Description

Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane
Technical Field
The invention relates to the field of catalysts, in particular to a supported catalyst and a preparation method thereof, and a method for preparing olefin by oxidative coupling of methane.
Background
In recent years, with the discovery of a large amount of natural gas, research on the source of chemical raw materials is gradually shifted from the petroleum route to the natural gas utilization route, and among them, research on the reaction for preparing ethylene by oxidative coupling of methane is a key issue for completing the shift.
Over the years of research, scientists have screened thousands of catalysts for the oxidative coupling of methane. But in the existing Na2WO4-Mn/SiO2In the preparation report of the similar catalyst, the raw materials of sodium tungstate and manganese nitrate are mixed to form precipitates during impregnation, so that the impregnation effect is influenced, and the similar catalyst is prepared by a step impregnation method. However, the distributed impregnation method requires at least two impregnation operations, and the preparation process is complicated, thereby wasting a lot of manpower, material resources and time.
Thus, how to prepare SiO with Na, W, Mn, Y and/or Sr as active components2Supported catalysts that are carriers also need to be researched and developed.
Disclosure of Invention
The invention aims to overcome the defect that the step-by-step impregnation method is adopted to prepare Na in the prior art2WO4-Mn/SiO2The preparation process of the catalyst is complex, and a large amount of manpower and material resources are wastedThe new technology for preparing the catalyst for methane oxidation coupling reaction by adopting the one-step impregnation method provided by the invention has the advantages of simple operation, avoidance of operation of twice impregnation, reduction of preparation steps, excellent performance of the prepared catalyst and saving of a large amount of manpower, material resources and time.
The invention provides a preparation method of a supported catalyst in a first aspect, wherein the method comprises the following steps:
(1) SiO carrier2Dipping in an aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate;
(2) and (2) roasting the solid obtained in the step (1).
The invention provides a supported catalyst prepared by the method, wherein the supported catalyst comprises a carrier and Na, W, Mn, Y and/or Sr loaded on the carrier, wherein the carrier is SiO2And on the basis of the total weight of the carrier, the content of Na element is 0.3-1.2 wt%, the content of W element is 1.2-4.8%, the content of Mn element is 1-5%, and the content of yttrium and/or strontium element is 1-4%.
In a third aspect, the present invention provides a process for preparing olefins by oxidative coupling of methane, the process comprising: methane and oxygen are subjected to a methane oxidative coupling reaction in the presence of the aforementioned catalyst. By adopting the technical scheme of the invention, Na, W, Mn, Sr and/or Y are loaded on a carrier SiO as active components by adopting a one-step impregnation method2In addition, due to the synergistic effect of multiple components, the performance is excellent, so that the catalytic activity of the prepared supported methane oxidative coupling reaction catalyst is improved, and the conversion of methane is facilitated.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
As indicated above, the first aspect of the present invention provides a method for preparing a supported catalyst, wherein the method comprises the steps of:
(1) SiO carrier2Dipping in an aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate;
(2) and (2) roasting the solid obtained in the step (1).
According to the invention, in the aqueous solution, SiO is supported on the carrier2The total weight of the composite is taken as a reference, the mass concentration of the ammonium metatungstate counted by W element is 1.2-4.8 wt%, the mass concentration of the manganese nitrate counted by Mn element is 1-5 wt%, the mass concentration of the sodium nitrate counted by Na element is 0.3-1.2 wt%, and the mass concentration of the yttrium nitrate and/or strontium nitrate counted by Y and/or Sr element is 1-4 wt%; according to the present invention, although the mass concentrations of ammonium metatungstate, manganese nitrate and sodium nitrate are limited to the above-mentioned ranges, excellent catalytic effects can be obtained, but it is preferable that the mass concentration of ammonium metatungstate in terms of W element is 2.4 to 3.6% by weight, the mass concentration of manganese nitrate in terms of Mn element is 1.5 to 3% by weight, the mass concentration of sodium nitrate in terms of Na element is 0.6 to 0.9% by weight, and the mass concentration of yttrium nitrate and/or strontium nitrate in terms of Y and/or Sr element is 2 to 3% by weight, based on the total weight of the carrier.
Preferably, the carrier has a saturated water absorption of 3 to 4g/g, that is, in the present invention, SiO equivalent to 1g in mass of the carrier2The amount of water in the aqueous solution is preferably 3 to 4g, i.e., in the range of the saturated water absorption capacity of the carrier defined above, the impregnation is preferably saturated impregnation, so that not only is the amount of water containedThe active component in the prepared catalyst can be loaded on the carrier, and the cost can be saved.
According to the invention, the method further comprises the step of SiO the carrier2Before dipping the carrier in the aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate, dropwise adding the aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate to the SiO carrier2The above. In the present invention, the dropping rate may be 0.2 to 1ml/s, preferably 0.4 to 0.6ml/s, for obtaining a good effect. In the present invention, in order to obtain a better effect, an aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate is added dropwise to the SiO carrier2In the above, in order to improve the uniformity of impregnation, it is preferable to stir the impregnated mixture, wherein the stirring rate may be 50 to 100 rpm, preferably 60 to 80 rpm.
According to the invention, an aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate is added dropwise to the SiO support2And (3) performing impregnation after the above, wherein in the present invention, when the impregnation method is used, the temperature of the aqueous solution is controlled within a certain range, which is advantageous for improving the solubility of the solute. In the present invention, the temperature of the aqueous solution is preferably controlled to 50 to 100 ℃, more preferably 60 to 80 ℃, and the dipping time may be 4 to 24 hours, more preferably 6 to 12 hours. The amount of water to be used for forming the aqueous solution can be selected within a wide range according to actual needs by those skilled in the art, and is preferably 3 to 4g/g in terms of the saturated water absorption of the carrier, which corresponds to 1g of SiO as the carrier in the present invention2The amount of water in the aqueous solution is 3-4 g.
According to the invention, in the step (2), the method further comprises the step of drying the solid obtained after the step (1) before roasting the solid, wherein the drying conditions comprise: the temperature is 80-120 ℃ and the time is 2-12 hours.
According to the invention, in the step (2), the roasting comprises a first roasting and a second roasting which are sequentially carried out; preferably, the temperature of the first roasting is 450-550 ℃ for 1-5 hours, and the temperature of the second roasting is 750-850 ℃ for 5-8 hours. In the present invention, the temperature increase rate and the state after the first firing and before the second firing are not particularly limited as long as the above-described conditions defined by the first firing and the second firing are satisfied, and it is preferable that the temperature increase rate is increased after the first firing and then the second firing is performed.
The second aspect of the present invention provides a supported catalyst prepared by the method, wherein the supported catalyst comprises a carrier and Na, W, Mn, Y and/or Sr supported on the carrier, wherein the carrier is SiO2And based on the total weight of the carrier, the content of Na element is 0.3-1.2 wt%, the content of W element is 1.2-4.8 wt%, the content of Mn element is 1-5 wt%, and the content of yttrium and/or strontium element is 1-4 wt%.
According to the present invention, although the supported catalyst comprises the above-mentioned carrier and active components and the content of each active component is within the above-mentioned range to obtain an excellent catalytic effect, it is preferable that the effect is more excellent when the content of Na element is 0.6 to 0.9 wt%, the content of W element is 2.4 to 3.6 wt%, the content of Mn element is 1.5 to 3 wt%, and the content of yttrium and/or strontium element is 2 to 3 wt% based on the total weight of the carrier.
In a third aspect, the present invention provides a process for preparing olefins by oxidative coupling of methane, the process comprising: methane and oxygen are subjected to a methane oxidative coupling reaction in the presence of the aforementioned catalyst. The method for preparing the olefin by the oxidative coupling reaction of the methane comprises the following steps: the method is carried out on a normal-pressure miniature fixed bed reaction device, and methane oxidative coupling reaction is carried out in the presence of a catalyst, methane and oxygen, wherein the catalyst is the supported methane oxidative coupling reaction catalyst or the supported methane oxidative coupling reaction catalyst prepared by the method.
According to the invention, the volume ratio of methane to oxygen may be (2-10): 1, preferably (2.2-4): 1;
preferably, the conditions of the oxidative coupling reaction of methane comprise: the reaction temperature is 750-830 ℃, the reaction time is 0.5-8h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000mlg-1h-1To 20000mlg-1h-1In the present invention, the unit "mlg-1h-1"is the amount (ml) of the total gas of methane and oxygen at a time of 1 hour with respect to 1g of the supported catalyst by mass.
In the present invention, the reactants and products are analyzed on-line using a gas chromatograph, thereby obtaining the conversion of methane and the selectivity of C2 hydrocarbon.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, ammonium metatungstate, manganese nitrate and sodium nitrate are commercially available, for example, ammonium metatungstate hydrate is available from mclin, manganese nitrate is available from west Longscience, and sodium nitrate is available from Alfa.
In the following examples and comparative examples, the active component loading of the methane oxidative coupling catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, model Axios-Advanced, available from PANALYtic, Netherlands; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
Example 1
This example illustrates a supported catalyst for oxidative coupling of methane and a method for preparing the same according to the present invention.
Preparation of 0.77 wt% Na-3 wt% W-2 wt% Mn-1 wt% Sr/SiO2Catalyst and process for preparing same
0.17g of ammonium metatungstate, 0.52g of Mn (NO)3)2(50% by weight) aqueous solution, 0.11g of NaNO3And 0.10g of strontium nitrate were added to 14g of distilled water at 20 ℃ and dissolved completely, and 4g of SiO was added2Stirring for 2 hours, drying for 2 hours at 120 ℃, then roasting for 5 hours at 550 ℃, and then heating to 850 ℃ and roasting for 5 hours to obtain a catalyst; wherein the carrierThe saturated water absorption of (2) was 3.5 g/g.
The catalyst is used for the reaction of preparing olefin by oxidative coupling of methane, the reaction is carried out on a continuous flow fixed bed, the reactor is a quartz tube with the inner diameter of 10mm and the length of 530mm, the loading amount of the catalyst is 0.2g, the reaction pressure is the pressure generated by the raw material, the reaction temperature is 830 ℃, the alkane-oxygen ratio is 2.2, the hourly space velocity of reaction gas calculated by methane and oxygen is 20000ml/gh, and the evaluation results of the catalyst performance of the catalyst for the reaction of preparing ethylene by oxidative coupling of methane after 1 hour are listed in Table 1.
Example 2
This example illustrates a supported catalyst for oxidative coupling of methane and a method for preparing the same according to the present invention.
Preparation of 0.3 wt% Na-1.2 wt% W-5 wt% Mn-3 wt% Sr/SiO2Catalyst and process for preparing same
0.07g of ammonium metatungstate, 1.30g of Mn (NO)3)2(50% by weight) aqueous solution, 0.04g NaNO3Adding 0.30g of strontium nitrate into 12g of distilled water at 20 ℃, and after completely dissolving, adding 4g of SiO2Stirring for 2 hours, drying for 12 hours at 80 ℃, then roasting for 2 hours at 550 ℃, and then heating to 750 ℃ and roasting for 8 hours to obtain a catalyst; wherein the saturated water absorption capacity of the carrier is 3 g/g.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the procedure of example 1, except that the reaction temperature was 750 ℃, the ratio of alkane to oxygen was 3, the hourly space velocity of the reaction gas in terms of methane and oxygen was 10000ml/gh, and the evaluation results after 1 hour of the reaction were shown in Table 1.
Example 3
This example illustrates a supported catalyst for oxidative coupling of methane and a method for preparing the same according to the present invention.
Preparation of 1.2 wt% Na-4.8 wt% W-1 wt% Mn-2 wt% Y/SiO2Catalyst and process for preparing same
0.28g of ammonium metatungstate, 0.26g of Mn (NO)3)2(50% by weight) aqueous solution, 0.17g NaNO3And 0.34g of yttrium nitrate were added to 16g of distilled water at 20 ℃ and dissolved completely, and 4g of SiO was added2Stirred for 2 hours, dried at 100 ℃ for 10 hours, and then calcined at 450 ℃ for 1 hourThen heating to 850 ℃ and roasting for 8 hours to obtain a catalyst; wherein the saturated water absorption capacity of the carrier is 4 g/g.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the procedure of example 1, except that the reaction temperature was 810 ℃, the alkylene oxide ratio was 4, the hourly space velocity of the reaction gas in terms of methane and oxygen was 12000ml/gh, and the evaluation results after 1 hour of the reaction were shown in Table 1.
Example 4
This example illustrates a supported catalyst for oxidative coupling of methane and a method for preparing the same according to the present invention.
Preparation of 0.9 wt% Na-3.6 wt% W-4 wt% Mn-4 wt% Y/SiO2Catalyst and process for preparing same
0.21g of ammonium metatungstate, 1.04g of Mn (NO)3)2(50% by weight) aqueous solution, 0.13g NaNO3And 0.69g of yttrium nitrate were added to 15.2g of distilled water at 20 ℃ to completely dissolve the yttrium nitrate, and 4g of SiO was added thereto2Stirring for 2 hours, drying for 10 hours at 100 ℃, then roasting for 2 hours at 500 ℃, and then heating to 800 ℃ and roasting for 8 hours to obtain a catalyst; wherein the saturated water absorption capacity of the carrier is 3.8 g/g.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the procedure of example 1, except that the reaction temperature was 800 ℃, the alkylene oxide ratio was 3, the hourly space velocity of the reaction gas in terms of methane and oxygen was 15000ml/gh, and the evaluation results after 1 hour of the reaction are shown in Table 1.
Comparative example 1
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 1, except that: without addition of ammonium metatungstate and NaNO3And sodium tungstate is added, namely, the supported methane oxidative coupling reaction catalyst is prepared by adopting the distributed impregnation of the sodium tungstate and the manganese nitrate.
Preparation of 0.77 wt% Na-3 wt% W-2 wt% Mn-1 wt% Sr/SiO2Catalyst and process for preparing same
Adding 0.22g sodium tungstate into 14g distilled water at 80 ℃, after completely dissolving, adding 4g SiO2Stirred for 2 hours, dried at 120 ℃ for 2 hours, and then 0.52g of Mn (NO) was added3)2(50% by weight) aqueous solution and 0.10gAdding strontium nitrate into distilled water of 80 ℃ and 14g, after completely dissolving, adding the SiO loaded with sodium tungstate2Stirring for 2 hours, drying at 120 ℃ for 2 hours, then roasting at 550 ℃ for 5 hours, and then heating to 850 ℃ for 8 hours to obtain the catalyst.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the method of example 1 at a reaction temperature of 830 ℃, an alkane-oxygen ratio of 2.2, and a reaction gas hourly space velocity in terms of methane and oxygen of 20000ml/gh, and the evaluation results after 1 hour of the reaction are shown in Table 1.
Comparative example 2
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 2, except that: without addition of ammonium metatungstate and NaNO3And sodium tungstate is added, namely, the supported methane oxidative coupling reaction catalyst is prepared by adopting the distributed impregnation of the sodium tungstate and the manganese nitrate.
Preparation of 0.3 wt% Na-1.2 wt% W-5 wt% Mn-3 wt% Sr/SiO2Catalyst and process for preparing same
Adding 0.09g sodium tungstate into 12g distilled water at 50 deg.C, completely dissolving, adding 4g SiO2Stirred for 2 hours, dried at 80 ℃ for 5 hours, and then 1.30g of Mn (NO) was added3)2(50 wt%) of the aqueous solution and 0.30g of strontium nitrate were added to 12g of distilled water at 50 ℃ and, after complete dissolution, the above SiO supported sodium tungstate was added2Stirring for 2 hours, drying at 80 ℃ for 12 hours, then roasting at 550 ℃ for 2 hours, and then heating to 750 ℃ and roasting for 8 hours to obtain the catalyst.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the method of example 2 at a reaction temperature of 750 ℃ and an alkane-oxygen ratio of 3, and a reaction gas hourly space velocity in terms of methane and oxygen was 10000ml/gh, and the evaluation results after 1 hour of the reaction are shown in Table 1.
Comparative example 3
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 3, except that: without addition of ammonium metatungstate and NaNO3And sodium tungstate is added, namely, the supported methane oxidative coupling reaction catalyst is prepared by adopting the distributed impregnation of the sodium tungstate and the manganese nitrate.
Preparation of 1.2 wt% Na-4.8 wt% W-1 wt% Mn-2 wt% Y/SiO2Catalyst and process for preparing same
Adding 0.35g sodium tungstate into distilled water of 16g at 90 ℃, after completely dissolving, adding 4g SiO2Stirred for 2 hours, dried at 120 ℃ for 10 hours, and then 0.26g of Mn (NO) was added3)2(50 wt%) of the aqueous solution and 0.34g of yttrium nitrate were added to distilled water (16 g) at 60 ℃ and dissolved completely, and then the SiO supported with sodium tungstate was added2Stirring for 2 hours, drying at 100 ℃ for 5 hours, then roasting at 450 ℃ for 1 hour, and then heating to 850 ℃ for 8 hours to obtain the catalyst.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the method of example 3 at a reaction temperature of 810 ℃ and an alkane-oxygen ratio of 4, and at a reaction gas hourly space velocity in terms of methane and oxygen of 12000ml/gh, and the evaluation results after 1 hour of the reaction are shown in Table 1.
Comparative example 4
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 4, except that: without addition of ammonium metatungstate and NaNO3And sodium tungstate is added, namely, the supported methane oxidative coupling reaction catalyst is prepared by adopting the distributed impregnation of the sodium tungstate and the manganese nitrate.
Preparation of 0.9 wt% Na-3.6 wt% W-4 wt% Mn-4 wt% Y/SiO2Catalyst and process for preparing same
Adding 0.26g sodium tungstate into 15.2g distilled water at 90 deg.C, completely dissolving, adding 4g SiO2Stirred for 2 hours, dried at 120 ℃ for 10 hours, and then 1.04g of Mn (NO) was added3)2(50 wt%) of the aqueous solution and 0.69g of yttrium nitrate were added to distilled water at 90 ℃ and 15.2g, and after complete dissolution, the above SiO supported with sodium tungstate was added2Stirring for 2 hours, drying at 100 ℃ for 10 hours, then roasting at 500 ℃ for 2 hours, and then heating to 800 ℃ for 8 hours to obtain the catalyst.
The catalyst was used in the reaction for producing ethylene by oxidative coupling of methane according to the method of example 4 at a reaction temperature of 830 ℃, an alkylene oxide ratio of 4, and a reaction gas hourly space velocity in terms of methane and oxygen of 15000ml/gh, and the evaluation results after 1 hour of the reaction are shown in Table 1.
Comparative example 5
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 1 and used in the reaction for oxidative coupling of methane to ethylene in the same manner as in example 1, except that: the dosage of ammonium tungstate, manganese nitrate, sodium nitrate and strontium nitrate makes the prepared supported methane oxidative coupling reaction catalyst D2 be: 0.2 wt% Na-1 wt% W-0.5 wt% Mn-0.5 wt% Sr/SiO2The catalyst, wherein the evaluation results are shown in table 1.
Comparative example 6
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 1 and used in the reaction for oxidative coupling of methane to ethylene in the same manner as in example 1, except that: strontium nitrate is replaced by yttrium nitrate, and the dosage of ammonium tungstate, manganese nitrate, sodium nitrate and yttrium nitrate is such that the prepared supported methane oxidative coupling reaction catalyst D3 is: 3 wt% Na-9 wt% W-6 wt% Mn-5 wt% Y/SiO2A catalyst; the evaluation results are shown in Table 1.
Comparative example 7
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 1 and used in the reaction for oxidative coupling of methane to ethylene in the same manner as in example 1, except that: strontium nitrate and manganese nitrate are not contained, and the dosage of ammonium tungstate and sodium nitrate is such that the prepared supported methane oxidative coupling reaction catalyst D4 is as follows: 0.77 wt% Na-3 wt% W/SiO2The catalyst and evaluation results are shown in Table 1.
Comparative example 8
A supported catalyst for oxidative coupling of methane was prepared in the same manner as in example 1 and used in the reaction for oxidative coupling of methane to ethylene in the same manner as in example 1, except that: strontium nitrate, ammonium tungstate and sodium nitrate are not used, and the dosage of the manganese nitrate is such that the prepared supported methane oxidative coupling reaction catalyst D5 is as follows: 2 wt% Mn/SiO2The catalyst and evaluation results are shown in Table 1.
TABLE 1
Figure BDA0001875999390000111
From the data in table 1, it can be seen that: the catalyst for the oxidative coupling reaction of methane prepared by the one-step dipping method provided by the invention, such as examples 1-4, has the advantages of uniform particle size of the active component of the supported catalyst, good dispersibility, and good methane conversion rate and selectivity of carbon dioxide when being applied to the oxidative coupling reaction of methane; in addition, the invention provides a new technology, the operation is simple, the operation of twice impregnation is avoided, the preparation steps are reduced, a large amount of manpower, material resources and time are saved, and the catalyst prepared in the embodiment 1 to 4 is used for the reaction of preparing ethylene by oxidative coupling of methane, namely CH4Conversion rate is up to 51.1%, C2The selectivity is as high as 74.3 percent; the catalyst prepared by the preparation method of the invention has excellent performance.
While comparative examples 1 to 4 do not adopt the primary impregnation method of the present invention, but adopt the secondary impregnation method, so that the catalysts prepared in comparative examples 1 to 4 are used for the reaction of oxidative coupling of methane to produce ethylene, CH4Conversion was only 47.2% at the highest, C2The selectivity is only 68.6 percent at most; it is shown that the catalysts prepared by the methods of comparative examples 1 to 4 are less effective than the catalysts prepared by the method of the present invention.
In addition, the contents of active components in the catalysts prepared in comparative examples 5 to 6 were not within the range defined by the present invention, and CH4Conversion rates were 22.1% and 28.1%, respectively, C2The selectivity was 34.2% and 31.8%, respectively; the active component in the catalyst prepared in comparative example 7 contained only Na element and W element, CH4Conversion was only 8.2%, C2The selectivity was only 27.5%; the active component in the catalyst prepared in comparative example 8 contains only Mn element, CH4Conversion was only 4.6%, C2The selectivity was only 29.8%; the results show that the catalysts prepared by the methods of comparative examples 5-8 are less effective than the catalysts prepared by the method of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method of preparing a supported catalyst, the method comprising:
(1) SiO carrier2Dipping in an aqueous solution containing ammonium metatungstate, manganese nitrate, sodium nitrate, strontium nitrate and/or yttrium nitrate;
(2) and (2) roasting the solid obtained in the step (1).
2. The method of claim 1, wherein the carrier is SiO2The total weight of the composite is taken as a reference, the mass concentration of the ammonium metatungstate counted by W element is 1.2-4.8 wt%, the mass concentration of the manganese nitrate counted by Mn element is 1-5 wt%, the mass concentration of the sodium nitrate counted by Na element is 0.3-1.2 wt%, and the mass concentration of the yttrium nitrate and/or strontium nitrate counted by Y and/or Sr element is 1-4 wt%;
preferably, the carrier has a saturated water absorption capacity of 3 to 4 g/g.
3. The process according to claim 1 or 2, wherein in step (1) the temperature of the aqueous solution is 50-100 ℃, preferably 60-80 ℃.
4. The method of claim 1, wherein in step (2), the method further comprises drying the solid before calcining the solid, wherein the drying conditions comprise: the temperature is 80-120 ℃ and the time is 2-12 hours.
5. The method as claimed in claim 1 or 4, wherein, in the step (2), the firing includes a first firing and a second firing which are sequentially performed; preferably, the temperature of the first roasting is 450-550 ℃ for 1-5 hours, and the temperature of the second roasting is 750-850 ℃ for 5-8 hours.
6. The supported catalyst prepared by the method of any one of claims 1-5, wherein the supported catalyst comprises a carrier and Na, W, Mn, Y and/or Sr supported on the carrier, wherein the carrier is SiO2And based on the total weight of the carrier, the content of Na element is 0.3-1.2 wt%, the content of W element is 1.2-4.8 wt%, the content of Mn element is 1-5 wt%, and the content of yttrium and/or strontium element is 1-4 wt%.
7. The catalyst according to claim 6, wherein the content of Na element is 0.6-0.9 wt%, the content of W element is 2.4-3.6 wt%, the content of Mn element is 1.5-3 wt%, and the content of yttrium and/or strontium element is 2-3 wt%, based on the total weight of the carrier.
8. A method for preparing olefins by oxidative coupling of methane, the method comprising: subjecting methane and oxygen to an oxidative coupling reaction of methane in the presence of the catalyst of claim 6 or 7.
9. The method of claim 8, wherein the volume ratio of methane to oxygen is (2-10): 1.
10. the method of claim 8, wherein the conditions of the oxidative coupling of methane reaction comprise: the reaction temperature is 750-830 ℃, the reaction time is 0.5-8h, and the hourly space velocity of the reaction gas calculated by methane and oxygen is 10000mlg-1h-1To 20000mlg-1h-1。
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