CN115518670B - Olefination catalyst, its preparation method and application - Google Patents

Olefination catalyst, its preparation method and application Download PDF

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CN115518670B
CN115518670B CN202110728275.7A CN202110728275A CN115518670B CN 115518670 B CN115518670 B CN 115518670B CN 202110728275 A CN202110728275 A CN 202110728275A CN 115518670 B CN115518670 B CN 115518670B
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catalyst
sba
molecular sieve
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CN115518670A (en
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缪长喜
危春玲
靳欢
华伟明
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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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Abstract

The invention provides an olefination catalyst, a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component, the carrier is SBA-15 molecular sieve, the active component element comprises Zn and Zr, and the small angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The diffraction peak of (2) is obvious, and the surface alkali amount of the catalyst is 0.06-0.9 mmol/g. The catalyst of the invention has good activity and stability. The catalyst is used for preparing olefin by alcohol olefination reaction, such as for preparing 1, 3-butadiene by ethanol conversion reaction, so that good reaction results are obtained, and the catalyst has high 1, 3-butadiene selectivity.

Description

Olefination catalyst, its preparation method and application
Technical Field
The invention relates to an olefination catalyst, a preparation method and application thereof.
Background
1, 3-butadiene is an important industrial raw material widely used in the production of synthetic rubber, synthetic resin and fine chemical products. The synthetic rubber prepared by using the rubber as a raw material mainly comprises polybutadiene rubber, nitrile rubber, chloroprene rubber and styrene-butadiene rubber. 1, 3-butadiene may also be copolymerized with styrene for use in the manufacture of synthetic resins, for example: acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate-butadiene-styrene copolymer resin (MBS), styrene-butadiene-styrene (SBS) copolymer resin, and the like. In addition, the 1, 3-butadiene can be used as a raw material for producing chemical raw materials such as 1, 4-butanediol, hexamethylenediamine, adiponitrile, nylon-66 and the like. With the development of industries such as national defense, military, automobiles and the like, the development of the synthetic rubber industry has important strategic significance and industrial value, so that the demand of the domestic and foreign markets for butadiene is continuously and steadily increased.
Industrial production of 1, 3-butadiene has been a history of nearly 90 years. After 1960, the technology for producing ethylene by naphtha cracking has been rapidly developed, and a series of byproducts including C4 fractions can be obtained while ethylene and propylene are produced in large quantities. At present, the global production of 1, 3-butadiene mainly comes from an ethylene cracking byproduct C4 fraction extraction process, but due to the excessive dependence of the process on petroleum resources and the serious environmental climate problems caused by the excessive dependence, a green and sustainable production process route is required to be developed. The great development of bioethanol technology, especially the rapid development of ethanol production of non-grain fuel, provides favorable conditions for the sustainable development route of synthesizing 1, 3-butadiene from bioethanol, and is paid more attention to related research.
In CN103038196a, titanium zirconium oxide containing metals such as copper, silver, gold, etc. is used as a catalyst, the ethanol conversion is 34%, and the 1, 3-butadiene is 72%, but the conversion is low although the selectivity is high.
AgO/CuO-MgO-SiO used in CN105251507A 2 The four-component composite oxide is used as a catalyst, the ethanol conversion rate is 66%, the 1, 3-butadiene is 53%, and the selectivity is low although the conversion rate is high. Dai et al dealuminate H-Beta by acid treatment and load Zn and Y bimetallic active centers, and despite the higher conversion and selectivity, the catalyst deactivated faster (ACS Catalysis, volume 7, 2017, pages 3703-3706).
The main problems of the existing one-step method for preparing 1, 3-butadiene by taking ethanol as a raw material are low activity of a catalyst and selectivity of the 1, 3-butadiene, and rapid deactivation of the catalyst, so that the method has low industrial production economy.
Disclosure of Invention
The invention aims to solve the problems of low conversion rate and selectivity and quick catalyst deactivation of an olefination reaction catalyst in the prior art, and provides the olefination reaction catalyst with high activity and strong stability.
According to a first aspect of the present invention there is provided an olefination catalyst comprising a support and an active component, the support being an SBA-15 molecular sieve and the active component element comprising Zn and Zr, the catalyst having a small angle XRD pattern which shows d 100 ，d 110 And d 200 The diffraction peak of (2) is obvious, and the surface alkali amount of the catalyst is 0.06-0.9 mmol/g.
According to a second aspect of the present invention, there is provided a process for preparing an olefination catalyst, the process comprising:
1) Soaking the SBA-15 molecular sieve in hydrogen peroxide, filtering, washing and drying to obtain the treated SBA-15 molecular sieve;
2) Dispersing the treated SBA-15 molecular sieve in water to obtain a suspension, simultaneously dropwise adding a mixed solution of a zinc source and a zirconium source and ammonia water into the suspension under the condition of maintaining constant alkaline pH value to 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is completed, filtering, washing, drying, and optionally roasting to obtain a solid catalyst;
alternatively, the process may be carried out in a single-stage,
the solid catalyst is impregnated with a source of alkaline earth metal promoters and/or a source of alkali metal promoters, and then dried and calcined.
According to a third aspect of the invention, the invention provides an olefination catalyst prepared by the preparation method; preferably the small angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The surface alkali content of the catalyst is 0.06-0.9 mmol/g, and the specific surface area of the catalyst is 480-550 m 2 And/g, pore diameter is 6-10 nm.
According to a fourth aspect of the present invention there is provided the use of an olefination catalyst according to the present invention in the manufacture of olefins by olefination of alcohols.
The catalyst solves the problems of lower activity and stability of the catalyst for olefin reaction, especially the catalyst for olefin preparation by alcohol olefin reaction in the prior art, and provides a novel catalyst for olefin reaction. The catalyst has the characteristics of good activity and stability.
The catalyst of the invention has good activity and stability. The catalyst for olefination reaction is used for olefination of alcohol to prepare olefin, for example, for reaction of ethanol conversion to prepare 1, 3-butadiene, so that good reaction results are obtained, and the selectivity of 1, 3-butadiene is high.
The active components of the catalyst prepared by the preparation method are uniformly mixed and can better interact with the carrier, the prepared catalyst has proper surface alkali amount, the mesoporous structure of the carrier is maintained, the problems in the prior art are better solved, and the catalyst can be used in industrial production of preparing olefin by alcohol olefination, particularly preparing 1, 3-butadiene by ethanol conversion.
Specifically, the catalyst prepared by the method has the advantages that the reaction performance of the catalyst is kept stable for 10 hours when the reaction temperature is 330 ℃, the catalyst dosage is 0.5g, the total flow of reaction gas is 14.4mL/min, the flow of saturated ethanol is 0.8mL/min, the flow of nitrogen is 13.6mL/min, the ethanol conversion rate is 85.8%, the selectivity of 1, 3-butadiene is 71.7%, and the better technical effect is obtained.
Drawings
FIG. 1 is a comparison of small angle XRD patterns of catalysts prepared by the constant pH precipitation-deposition method (a) of example 1 and the isovolumetric impregnation method (b) of comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides an olefination catalyst, which comprises a carrier and an active component, wherein the carrier is an SBA-15 molecular sieve, the active component element comprises Zn and Zr, and the small-angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The diffraction peak of (2) is obvious, and the surface alkali amount of the catalyst is 0.06-0.9 mmol/g.
The catalyst of the invention with the characteristics has good activity and stability. The catalyst for olefination reaction is used for olefination of alcohol to prepare olefin, for example, for reaction of ethanol conversion to prepare 1, 3-butadiene, so that good reaction results are obtained, and the selectivity of 1, 3-butadiene is high.
According to a preferred embodiment of the present invention, preferably, the Zn content is 0.1 to 10% and the Zr content is 0.5 to 15% in terms of elements based on the total mass percentage of the catalyst; whereby the activity and selectivity of the catalyst can be improved.
According to a preferred embodiment of the invention, the catalyst has a specific surface area of 480 to 550m 2 Per g, preferably 490-510m 2 And/g. Whereby the activity of the catalyst can be improved.
According to a preferred embodiment of the invention, the catalyst pore size is 6 to 10nm, preferably 7 to 8nm. Whereby the activity of the catalyst can be improved.
According to a preferred embodiment of the invention, the surface alkali amount of the catalyst is 0.15 to 0.35mmol/g.
According to a preferred embodiment of the invention, the catalyst contains an alkali metal promoter and/or an alkaline earth metal promoter. The alkali metal and alkaline earth metal species may be selected from a wide range, and common species may be used in the present invention, such as one or more of Na, K and Mg.
According to a preferred embodiment of the present invention, the catalyst contains an alkali metal promoter, more preferably the alkali metal promoter element is Na. Whereby the stability of the catalyst can be improved.
According to a preferred embodiment of the present invention, preferably, the Zn content is 0.1 to 10% in terms of elements, the Zr content is 0.5 to 15% and the auxiliary agent content is 0.1 to 2% in terms of the total mass percent of the catalyst; thereby, the activity and stability of the catalyst can be improved.
According to a preferred embodiment of the present invention, more preferably, the Zn content is 0.5 to 3.5% in terms of element, the Zr content is 3 to 7% and the Na content is 0.2 to 0.4% in terms of the total mass percent of the catalyst. Thereby, the activity and stability of the catalyst can be improved.
According to a preferred embodiment of the present invention, there is provided a catalyst for the conversion of ethanol to 1, 3-butadiene, the catalyst comprising SBA-15 as a carrier, zn and Zr as active components, na as an auxiliary agent, wherein the catalyst comprises, based on the total mass percent of the catalyst, 0.1 to 10% Zn, 0.5 to 15% Zr and 0.1 to 2% Na, and the catalyst has a small angle XRD pattern of d 100 ，d 110 And d 200 The diffraction peak of (2) is obvious, and the surface alkali amount of the catalyst is 0.06-0.9 mmol/g.
According to a preferred embodiment of the invention, the zinc and zirconium active components and the sodium auxiliary agent comprise, by mass percent of the total catalyst, 0.1-10% of Zn, 0.5-15% of Zr and 0.1-2% of Na; preferably, the Zn content is 0.5 to 3.5%, preferably the Zr content is 3 to 7%, preferably the Na content is 0.2 to 0.4%.
The catalyst with the characteristics of the invention can achieve the aim of the invention, has no special requirement on the preparation method, and is preferably prepared according to the following steps:
1) Soaking the SBA-15 molecular sieve in hydrogen peroxide, filtering, washing and drying to obtain the treated SBA-15 molecular sieve;
2) Dispersing the treated SBA-15 molecular sieve in water to obtain a suspension, simultaneously dropwise adding a mixed solution of a zinc source and a zirconium source and ammonia water into the suspension under the condition of maintaining constant alkaline pH value to 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is completed, filtering, washing, drying, and optionally roasting to obtain the solid catalyst. The catalyst prepared by the method can improve the activity and selectivity of the catalyst.
According to the present invention, it is presumed that the loading of active components zinc and zirconium by a constant pH precipitation-deposition method enables the catalyst to ensure the small angle structural integrity of the SBA-15 carrier and the active components are uniformly mixed, thereby improving the activity and selectivity of the catalyst.
According to the invention, optionally, the method further comprises: the solid catalyst is impregnated with a source of alkaline earth metal promoters and/or a source of alkali metal promoters, and then dried and calcined. Whereby the stability of the catalyst can be improved. By supporting a proper amount of auxiliary agent, the alkali amount of the catalyst can be maintained in the range of 0.06-0.9 mmol/g.
According to the invention, the invention provides a preparation method of a catalyst for preparing 1, 3-butadiene by ethanol conversion, which comprises the following steps:
1) Soaking SBA-15 mesoporous molecular sieve in dilute hydrogen peroxide at room temperature, filtering, washing with deionized water, and drying;
2) Weighing SBA-15, dispersing in deionized water, simultaneously dripping a zinc source and zirconium source mixed salt solution and ammonia water into a suspension of SBA-15 under constant pH=8-9, preferably 8 and stirring, stopping dripping ammonia water after the dripping of the zinc and zirconium mixed salt solution is completed, filtering, washing with deionized water, and drying to obtain a sample;
3) And impregnating a salt solution of sodium with a required amount on the obtained sample by using an isovolumetric impregnation method, and then drying and roasting to obtain the catalyst for preparing the 1, 3-butadiene by ethanol conversion.
According to the above technical scheme, the preparation method of the catalyst for preparing 1, 3-butadiene by ethanol conversion comprises the step of selecting a zinc source from Zn (NO 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Preferably Zn (NO 3 ) 2 ·6H 2 O; the zirconium source is selected from Zr (NO) 3 ) 4 ·5H 2 O、ZrO(NO 3 ) 2 ·2H 2 O、ZrOCl 2 ·8H 2 O and ZrCl 4 Preferably ZrO (NO) 3 ) 2 ·2H 2 O; the sodium source is selected from NaNO 3 、Na 2 SO 4 And CH (CH) 3 One of COONa, preferably NaNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The drying condition is that the drying is carried out for 10 to 30 hours at the temperature of 80 to 120 ℃; the roasting condition is that roasting is carried out for 3-6 hours at 500-650 ℃ in air atmosphere.
According to the invention, the raw materials are used in such amounts that, in terms of the total mass percent of the catalyst, the Zn content is 0.1 to 10%, the Zr content is 0.5 to 15% and optionally the auxiliary content is 0.1 to 2% in terms of elements. Thereby improving the activity and stability of the catalyst.
According to the invention, the raw materials are used in such amounts that, in terms of the total mass percent of the catalyst, the Zn content is 0.5 to 3.5%, the Zr content is 3 to 7% and the Na content is 0.2 to 0.4% in terms of elements. Thereby improving the activity and stability of the catalyst.
According to the present invention, the zinc source is widely selected, and soluble zinc-containing compounds can be used in the present invention, and for the present invention, it is preferable that the zinc source is Zn (NO 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Preferably Zn (NO 3 ) 2 ·6H 2 O. Thereby improving the activity of the catalyst.
According to the present invention, the kinds of the zirconium source are wide in optional range, and the soluble zirconium-containing compound can be used in the present invention, for which it is preferable that the zirconium source is Zr (NO 3 ) 4 ·5H 2 O、ZrO(NO 3 ) 2 ·2H 2 O、ZrOCl 2 ·8H 2 O and ZrCl 4 Preferably ZrO (NO) 3 ) 2 ·2H 2 O. Whereby the selectivity of the catalyst can be improved.
According to the invention, the alkaline earth metal auxiliary source and/or the alkali metal auxiliary source is one or more of nitrate, sulfate and acetate, more preferably NaNO 3 、Na 2 SO 4 And CH (CH) 3 One of COONa, more preferably NaNO 3 . Whereby the stability of the catalyst can be improved.
According to the invention, it is preferred that the step 1) is carried out such that the surface hydroxyl group content of the resulting treated SBA-15 molecular sieve is from 5 to 6mmol/g. Thereby improving the activity and selectivity of the catalyst.
According to the invention, the concentration of hydrogen peroxide in step 1) is preferably 1% to 5% by weight. Thereby improving the activity and selectivity of the catalyst.
According to the invention, the soaking time in step 1) is preferably 10 to 30 hours. Thereby improving the activity and selectivity of the catalyst.
According to the invention, in step 1), the hydrogen peroxide is used in an amount of 10-15ml/gSBA-15 molecular sieve.
According to the invention, in step 2), the SBA-15 molecular sieve is used in an amount of 1-5g of SBA-15 molecular sieve per 100ml of water. Thereby improving the activity and selectivity of the catalyst.
In the present invention, the conventional SBA-15 can be used in the present invention, and it is preferable that the specific surface area of SBA-15 is 560-585m according to the present invention 2 And/g, pore diameter is 7.6-8.6nm. The SBA-15 molecular sieve with the technical characteristics can be selected to achieve the aim of the invention.
According to the present invention, the concentration of ammonia is not particularly limited, and for example, ammonia having a concentration of 1.0mol/L is used.
According to the invention, it is preferred that the conditions of the drying in the respective steps each include: the temperature is 80 to 120℃and the drying time is determined according to the temperature, for example, the drying time is 10 to 30 hours. Thereby improving the activity and stability of the catalyst.
According to the invention, it is preferable that the conditions of the calcination in the respective steps each include: roasting in an air atmosphere at 500-650 deg.c for 3-6 hr depending on the roasting temperature. Thereby improving the activity and stability of the catalyst.
The process of the present invention enables the preparation of catalysts having the aforementioned characteristics of the present invention.
The invention provides an olefination catalyst prepared by the preparation method; preferably the small angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The surface alkali amount of the catalyst is 0.06-0.9 mmol/g, preferably 0.15-0.35 mmol/g; more preferably the catalyst has a specific surface area of 480 to 550m 2 Preferably 490 to 510m per gram 2 /g; the pore diameter is 6 to 10nm, preferably 7 to 8nm.
The active components of the catalyst prepared by the preparation method are uniformly mixed and can better interact with the carrier, the prepared catalyst has proper surface alkali amount, the mesoporous structure of the carrier is maintained, the problems in the prior art are better solved, and the catalyst can be used in industrial production of preparing olefin by alcohol olefination, particularly preparing 1, 3-butadiene by ethanol conversion.
The invention provides application of the olefination reaction catalyst in olefination of alcohol to prepare olefin, wherein the alcohol is preferably C2-C4 alcohol, more preferably ethanol.
Specifically, the catalyst prepared by the method has the advantages that the reaction performance of the catalyst is kept stable for 10 hours when the reaction temperature is 330 ℃, the catalyst dosage is 0.5g, the total flow of reaction gas is 14.4mL/min, the flow of saturated ethanol is 0.8mL/min, the flow of nitrogen is 13.6mL/min, the ethanol conversion rate is 85.8%, the selectivity of 1, 3-butadiene is 71.7%, and the better technical effect is obtained.
In the invention, XRD pattern test is carried out on a Bruker Nanostar U type small-angle X-ray scatterometer, the current of the tube is 35mA, and the tube voltage is 40kV.
The catalyst was tested for specific surface area and pore size using a Tristar 3000 physical adsorption instrument from Micromeritics, USA, with N 2 As an adsorbate, the sample was subjected to vacuum pretreatment at 300 ℃ for 4 hours, the specific surface area of the catalyst was calculated by BET method, and the pore size of the catalyst was calculated by BJH model.
CO for surface alkali 2 TPD test, pre-treating the catalyst at 500 deg.C for 1 hr, cooling to 80 deg.C, adsorbing CO 2 Then, the temperature was raised at 10℃per minute.
Example 1
3.0g of SBA-15 molecular sieve (specific surface area 560 m) are weighed in a vessel 2 Per g, pore size of 8.5 nm), 45mL of 3 wt% hydrogen peroxide was added, immersed for 12 hours at room temperature, filtered, washed with deionized water, and then dried in an oven at 110 ℃ for 12 hours. 2.0g of the SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.8 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0033 and 0.011g/mL respectively) and 1.0mol/L ammonia water are simultaneously added into the suspension of the SBA-15 in a dropwise manner under stirring, the pH value in the whole dropwise adding process is controlled to be constant at about 8, and the dropwise adding of the ammonia water is stopped after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 110℃for 12h. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a baking oven at 110 ℃ for drying for 12 hours, and finally is baked for 4 hours in an air atmosphere in a muffle furnace at 550 ℃ to obtain the required catalyst. The Na content in the catalyst was 0.2%, the Zn content was 1.5% and the Zr content was 5%. The catalyst maintains the mesoporous structure of SBA-15 carrier, the small angle XRD spectrum is shown in figure 1 (a), the surface alkali amount is 0.21mmol/g, and the specific surface area is 503m 2 And/g, pore diameter of 8nm.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1h by introducing nitrogen at 400 ℃, the reaction temperature is 330 ℃, the catalyst dosage is 0.5g, the total flow of reaction gas is 14.4mL/min, wherein the flow of saturated ethanol is 0.8mL/min, and the flow of nitrogen is 13.6mL/min. The ethanol conversion after 1h of reaction was 85.8%, the selectivity to 1, 3-butadiene was 71.7%, the ethanol conversion after 10h of reaction was 85.7%, and the selectivity to 1, 3-butadiene was 72.1%.
Example 2
3.0g of SBA-15 molecular sieve (specific surface area 565 m) was weighed in a vessel 2 /g, pore size of 8.5 nm), 30mL of 4 wt% hydrogen peroxide is added, the mixture is soaked for 20 hours at room temperature, filtered, washed by deionized water and then put into a 100 ℃ oven for drying for 24 hours. 2.0g of the SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.8 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0033 and 0.011g/mL respectively) and 1.0mol/L ammonia water are simultaneously added into the suspension of the SBA-15 in a dropwise manner under stirring, the pH value in the whole dropwise adding process is controlled to be constant at about 8, and the dropwise adding of the ammonia water is stopped after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 100 ℃ for 24 hours. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a 100 ℃ oven for drying for 24 hours, and finally is roasted for 6 hours in an air atmosphere in a muffle furnace at 550 ℃ to obtain the required catalyst. The catalyst has Na content of 0.3%, zn content of 1.5%, zr content of 5%, and the catalyst maintains mesoporous structure of SBA-15 carrier, has small angle XRD pattern similar to that of example 1, surface alkali amount of 0.32mmol/g, and specific surface area of 501m 2 And/g, pore diameter of 8nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 82.6%, the selectivity to 1, 3-butadiene was 72.2%, the ethanol conversion after 10h of reaction was 82.9%, and the selectivity to 1, 3-butadiene was 72.1%.
Example 3
3.0g of SBA-15 molecular sieve (specific surface area 583 m) were weighed in a vessel 2 Per g, pore size 7.6 nm), 45mL of 2 wt.% hydrogen peroxide was added, immersed for 25h at room temperature, filtered, washed with deionized water, and dried in an oven at 90℃for 30h. Weighing 2.0g of SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.6 mmol/g) and dispersing in 50mL of deionized water, stirring 10mL of zinc nitrate and 10mL of zinc nitrateAnd simultaneously dropwise adding the zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0011 and 0.015g/mL respectively) and 1.0mol/L ammonia water into the SBA-15 suspension, controlling the pH value in the whole dropwise adding process to be constant at about 8.5, and stopping dropwise adding the ammonia water after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 90 ℃ for 30 hours. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a 90 ℃ oven for drying for 30 hours, and finally is roasted for 3 hours in an air atmosphere in a muffle furnace at 650 ℃ to obtain the required catalyst. The catalyst has Na content of 0.2%, zn content of 0.5%, zr content of 7%, and the catalyst maintains mesoporous structure of SBA-15 carrier, has small angle XRD pattern similar to that of example 1, surface alkali amount of 0.20mmol/g, and specific surface area of 510m 2 And/g, pore diameter of 7nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 83.4%, the selectivity for 1, 3-butadiene was 70.2%, the ethanol conversion after 10h of reaction was 83.5%, and the selectivity for 1, 3-butadiene was 70.3%.
Example 4
3.0g of SBA-15 molecular sieve (specific surface area 565 m) was weighed in a vessel 2 /g, pore size of 8.6 nm), 30mL of 5 wt% hydrogen peroxide is added, the mixture is soaked for 10 hours at room temperature, filtered, washed by deionized water and then put into a 100 ℃ oven for drying for 24 hours. 2.0g of the SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.7 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0055 and 0.011g/mL respectively) and 1.0mol/L ammonia water are simultaneously added into the suspension of the SBA-15 in a dropwise manner under stirring, the pH value in the whole dropwise adding process is controlled to be constant at about 9, and the dropwise adding of the ammonia water is stopped after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 100 ℃ for 24 hours. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a 100 ℃ oven for drying for 24 hours, and finally is roasted for 6 hours in an air atmosphere in a muffle furnace at 550 ℃ to obtain the required catalyst. The catalyst has Na content of 0.3%, zn content of 2.5%, zr content of 5%, and the catalyst maintains mesoporous structure of SBA-15 carrier, has small angle XRD pattern similar to that of example 1, surface alkali amount of 0.33mmol/g, and specific surface area of 497m 2 And/g, pore diameter of 8nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 84.8%, the selectivity to 1, 3-butadiene was 71.2%, the ethanol conversion after 10h of reaction was 84.7%, and the selectivity to 1, 3-butadiene was 71.3%.
Example 5
3.0g of SBA-15 molecular sieve (specific surface area 572 m) was weighed in a vessel 2 Per g, pore size 7.8 nm), 45mL of 1 wt% hydrogen peroxide was added, immersed for 30 hours at room temperature, filtered, washed with deionized water, and then dried in an oven at 120℃for 10 hours. 2.0g of the SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.5 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0077 and 0.015g/mL respectively) and 1.0mol/L ammonia water are simultaneously added into the suspension of the SBA-15 in a dropwise manner under stirring, the pH value in the whole dropwise adding process is controlled to be constant at about 8, and the dropwise adding of the ammonia water is stopped after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 120℃for 10h. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a baking oven at 120 ℃ for drying for 10 hours, and finally is baked for 4 hours in an air atmosphere in a muffle furnace at 550 ℃ to prepare the required catalyst. The catalyst has Na content of 0.2%, zn content of 3.5%, zr content of 7%, and the catalyst maintains mesoporous structure of SBA-15 carrier, has small angle XRD pattern similar to that of example 1, surface alkali amount of 0.23mmol/g, and specific surface area of 490m 2 And/g, pore diameter of 7nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 81.8%, the selectivity to 1, 3-butadiene was 71.2%, the ethanol conversion after 10h of reaction was 81.7%, and the selectivity to 1, 3-butadiene was 71.3%.
Example 6
3.0g of SBA-15 molecular sieve (specific surface area 569 m) are weighed in a vessel 2 Per g, pore size 7.7 nm), 45mL of 3 wt% hydrogen peroxide was added, immersed for 24 hours at room temperature, filtered, washed with deionized water, and then dried in an oven at 110 ℃ for 24 hours. Weighing 2.0g of the SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.9 mmol/g) for dispersionIn 50mL of deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentrations are 0.0033 and 0.015g/mL respectively) and 1.0mol/L ammonia water are simultaneously added into the SBA-15 suspension in a dropwise manner under stirring, the pH value in the whole dropwise adding process is controlled to be constant at about 8.5, and the dropwise adding of the ammonia water is stopped after the dropwise adding of the zinc and zirconium mixed salt solution is completed. Then filtered, washed with deionized water and dried in an oven at 110℃for 24h. The obtained sample is subjected to isovolumetric impregnation by sodium nitrate solution, then is put into a 110 ℃ oven for drying for 24 hours, and finally is roasted for 4 hours in an air atmosphere in a muffle furnace at 600 ℃ to obtain the required catalyst. The catalyst has Na content of 0.3%, zn content of 1.5%, zr content of 7%, and the catalyst maintains mesoporous structure of SBA-15 carrier, has small angle XRD pattern similar to that of example 1, surface alkali amount of 0.32mmol/g, and specific surface area of 493m 2 And/g, pore diameter of 7nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 82.6%, the selectivity to 1, 3-butadiene was 72.2%, the ethanol conversion after 10h of reaction was 82.7%, and the selectivity to 1, 3-butadiene was 72.3%.
Example 7
The procedure of example 1 was followed except that the sodium nitrate solution was replaced with a potassium nitrate solution.
The catalyst maintains the mesoporous structure of SBA-15 carrier, the small angle XRD spectrum is shown in figure 1 (a), the surface alkali amount is 0.16mmol/g, and the specific surface area is 505m 2 And/g, pore diameter of 8nm.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 86.2%, the selectivity to 1, 3-butadiene was 70.8%, the ethanol conversion after 10h of reaction was 83.8%, and the selectivity to 1, 3-butadiene was 71.0%.
Example 8
3.0g of SBA-15 molecular sieve (specific surface area 560 m) are weighed in a vessel 2 Per g, pore size of 8.5 nm), 45mL of 3 wt% hydrogen peroxide was added, immersed for 12 hours at room temperature, filtered, washed with deionized water, and then dried in an oven at 110 ℃ for 12 hours. Weighing 2.0g of SBA-15 carrier treated by the hydrogen peroxide (the surface hydroxyl content is 5.8 mmol/g) and dispersing in 50mL of deionized water, and stirring to obtain 10mL of zinc nitrate and oxygen nitrateThe mixed solution of zirconium (Zn and Zr with the concentration of 0.0033 and 0.011g/mL respectively) and 1.0mol/L ammonia water are added into the suspension of SBA-15 at the same time, the pH value of the whole adding process is controlled to be about 8, and the adding of the ammonia water is stopped after the adding of the mixed salt solution of zinc and zirconium is completed. And then filtering, washing with deionized water, drying in a 110 ℃ oven for 12 hours, and finally roasting in an air atmosphere in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The Zn content in the catalyst was 1.5% and the Zr content was 5%. The amount of base in the catalyst was 0.02mmol/g.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 87.6%, the selectivity to 1, 3-butadiene was 70.5%, the ethanol conversion after 10h of reaction was 67.5%, and the selectivity to 1, 3-butadiene was 67.9%.
It can be seen that the stability of the catalyst is poor.
Comparative example 1
2.0g of SBA-15 molecular sieve which is not treated by hydrogen peroxide (the property is the same as that of example 1) is weighed, the mixed solution of zinc nitrate, zirconyl nitrate and sodium nitrate is used for carrying out equal volume impregnation, then the mixture is put into a 110 ℃ oven for drying for 12 hours, and finally the mixture is roasted for 4 hours in an air atmosphere in a muffle furnace at 550 ℃ to prepare the required catalyst. The Na content in the catalyst was 0.2%, the Zn content was 1.5% and the Zr content was 5%. The small angle XRD pattern of the catalyst is shown in figure 1 (b), and the intensity of diffraction peak is greatly reduced, which shows that the mesoporous structure of the SBA-15 carrier is seriously damaged.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 65.6%, the selectivity to 1, 3-butadiene was 65.5%, the ethanol conversion after 10h of reaction was 64.5%, and the selectivity to 1, 3-butadiene was 64.9%.
Comparative example 2
The procedure of example 1 was followed, except that the SBA molecular sieve of step 1) was composed of an equivalent amount of molecular sieve TS-1 of MFI structure (commercially available, tiO 2 /SiO 2 Molar ratio of 0.04).
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 68.3%, the selectivity to 1, 3-butadiene was 65.4%, the ethanol conversion after 10h of reaction was 65.4%, and the selectivity to 1, 3-butadiene was 65.7%.
Comparative example 3
The procedure of example 1 was followed except that the zinc nitrate of step 1) was replaced with copper nitrate of the same copper element as zinc.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 70.3%, the selectivity to 1, 3-butadiene was 64.3%, the ethanol conversion after 10h of reaction was 67.4%, and the selectivity to 1, 3-butadiene was 64.6%.
Comparative example 4
The procedure of example 1 was followed except that zirconyl nitrate of step 1) was replaced with hafnium chloride of the same hafnium element as zinc.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 74.3%, the selectivity to 1, 3-butadiene was 64.3%, the ethanol conversion after 10h of reaction was 70.7%, and the selectivity to 1, 3-butadiene was 64.7%.
Comparative example 5
The procedure of example 1 was followed, except that the pH in step 1) was about 12.
The evaluation conditions were the same as in example 1, and the results were as follows: the ethanol conversion after 1h of reaction was 65.0%, the selectivity for 1, 3-butadiene was 67.0%, the ethanol conversion after 10h of reaction was 64.9%, and the selectivity for 1, 3-butadiene was 67.2%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (15)

1. A catalyst for olefination reaction is characterized by comprising a carrier and an active component, wherein the carrier is SBA-15 molecular sieve, the active component element comprises Zn and Zr, and the small angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 Is obvious in diffraction peak of (C) and the table of catalystThe amount of the surface alkali is 0.06-0.9 mmol/g, and the specific surface area of the catalyst is 480-550 m 2 /g；
Wherein the catalyst contains an alkali metal auxiliary agent and/or an alkaline earth metal auxiliary agent; based on the total mass percent of the catalyst, the content of Zn is 0.1-10%, the content of Zr is 0.5-15% and the content of auxiliary agent is 0.1-2% calculated by elements;
the preparation method of the catalyst comprises the following steps:
1) Soaking the SBA-15 molecular sieve in hydrogen peroxide, filtering, washing and drying to obtain the treated SBA-15 molecular sieve;
2) Dispersing the treated SBA-15 molecular sieve in water to obtain a suspension, simultaneously dropwise adding a mixed solution of a zinc source and a zirconium source and ammonia water into the suspension under the condition of maintaining constant alkaline pH value to be 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is completed, filtering, washing, drying and roasting to obtain a solid catalyst;
impregnating the solid catalyst with an alkaline earth metal auxiliary source and/or an alkali metal auxiliary source, and then drying and roasting;
and step 1), after the treatment, the surface hydroxyl content of the obtained treated SBA-15 molecular sieve is 5-6 mmol/g.
2. The catalyst according to claim 1, wherein,
the specific surface area of the catalyst is 490-510m 2 /g; the aperture is 6-10 nm.
3. The catalyst of claim 2, wherein the pore size is 7-8nm.
4. The catalyst according to claim 1, wherein the surface alkali amount of the catalyst is 0.15 to 0.35mmol/g.
5. The catalyst according to claim 1, wherein,
the catalyst contains an alkali metal auxiliary agent, wherein the alkali metal auxiliary agent element is Na;
calculated by the total mass percent of the catalyst, the Zn content is 0.5 to 3.5 percent, the Zr content is 3 to 7 percent, and the Na content is 0.2 to 0.4 percent.
6. The catalyst according to claim 1, wherein,
the zinc source is Zn (NO) 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Is one of (a);
the zirconium source is Zr (NO) 3 ) 4 ·5H 2 O、ZrO(NO 3 ) 2 ·2H 2 O、ZrOCl 2 ·8H 2 O and ZrCl 4 Is one of (a);
the alkaline earth metal auxiliary source and/or the alkali metal auxiliary source is one or more of nitrate, sulfate and acetate.
7. The catalyst according to claim 6, wherein,
the zinc source is Zn (NO) 3 ) 2 ·6H 2 O；
The zirconium source is ZrO (NO) 3 ) 2 ·2H 2 O；
The alkaline earth metal auxiliary source and/or the alkali metal auxiliary source is NaNO 3 、Na 2 SO 4 And CH (CH) 3 One of COONa.
8. The catalyst of claim 7, wherein the alkaline earth metal promoter source and/or alkali metal promoter source is NaNO 3 。
9. The catalyst according to claim 1, wherein in step 1),
the specific surface area of the SBA-15 molecular sieve is 560-585m 2 And/g, pore diameter is 7.6-8.6nm.
10. The catalyst according to claim 1, wherein,
the concentration of hydrogen peroxide in the step 1) is 1-5 wt%, and the soaking time is 10-30 h; the dosage of the hydrogen peroxide is 10-15ml/g SBA-15 molecular sieve.
11. The catalyst according to claim 1, wherein,
in step 2), the SBA-15 molecular sieve is used in an amount of 1-5g of SBA-15 molecular sieve per 100ml of water.
12. The catalyst according to claim 1, wherein,
the drying conditions of each step each include: the temperature is 80-120 ℃ and the time is 10-30 h; and/or
The conditions of the calcination in each step each include: roasting for 3-6 h at 500-650 ℃ in air atmosphere.
13. Use of the olefination catalyst of any one of claims 1 to 12 in the production of olefins by alcohol olefination.
14. The use according to claim 13, wherein the alcohol is a C2-C4 alcohol.
15. The use according to claim 14, wherein the alcohol is ethanol.
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