CN115518670A - Olefine reaction catalyst and its preparation method and application - Google Patents

Olefine reaction catalyst and its preparation method and application Download PDF

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CN115518670A
CN115518670A CN202110728275.7A CN202110728275A CN115518670A CN 115518670 A CN115518670 A CN 115518670A CN 202110728275 A CN202110728275 A CN 202110728275A CN 115518670 A CN115518670 A CN 115518670A
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catalyst
content
sba
molecular sieve
reaction
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CN115518670B (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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    • 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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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • 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 alkene reaction catalyst and a preparation method and application thereof, the catalyst contains a carrier and an active component, the carrier is an SBA-15 molecular sieve, the active component contains Zn and Zr, and the small-angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The diffraction peak 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 through alcohol alkylation reaction, for example, the catalyst is used for preparing 1, 3-butadiene through ethanol conversion, a better reaction result is obtained, and the catalyst has higher selectivity of 1, 3-butadiene.

Description

Olefine reaction catalyst and its preparation method and application
Technical Field
The invention relates to an alkene reaction catalyst, a preparation method and application thereof.
Background
1, 3-butadiene is an important industrial raw material widely used for the production of synthetic rubbers, synthetic resins and fine chemical products. The synthetic rubber made from the raw material mainly comprises polybutadiene rubber, nitrile rubber, chloroprene rubber and styrene butadiene rubber. 1, 3-butadiene can 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), and styrene-butadiene-styrene (SBS) copolymer resin. In addition, 1, 3-butadiene can also 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 the industries such as national defense and 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 markets at home and abroad on butadiene is continuously and stably increased.
The commercial production of 1, 3-butadiene has been known for nearly 90 years. After 1960, the technology for producing ethylene by naphtha cracking has been rapidly developed, and a series of byproducts including C4 fraction can be obtained while producing ethylene and propylene in large quantities. At present, the global production of 1, 3-butadiene mainly comes from an extraction process of ethylene cracking byproduct C4 fraction, but due to the excessive dependence of the process on petroleum resources and the more serious environmental climate problems caused by the process, people urgently need to develop a green and sustainable production process route. The vigorous development of bioethanol technology, especially the rapid development of ethanol production from non-grain fuels, provides favorable conditions for the sustainable development route of synthesizing 1, 3-butadiene from bioethanol, and the relevant research is paid more and more attention by many people.
In CN103038196A, a titanium zirconium oxide containing metals such as copper, silver, and gold is used as a catalyst, the conversion rate of ethanol is 34%, and the conversion rate of 1, 3-butadiene is 72%, although the selectivity is high, the conversion rate is low.
AgO/CuO-MgO-SiO used in CN105251507A 2 The four-component composite oxide was used as a catalyst, the conversion of ethanol was 66%, and that of 1, 3-butadiene was 53%, although the conversion was high, the selectivity was low. The acidic dealumination of H-Beta by Dai et al resulted in the loading of Zn and Y bimetallic active sites with faster catalyst deactivation despite higher conversion and selectivity (ACS Catalysis, vol.7, pp.3703-3706, 2017).
The main problems of the prior one-step method for preparing 1, 3-butadiene by taking ethanol as a raw material are that the activity of a catalyst and the selectivity of the 1, 3-butadiene are low, the catalyst is deactivated quickly, and the economic efficiency of the industrial production of the method is low.
Disclosure of Invention
The invention aims to solve the problems of low conversion rate and selectivity and quick inactivation of the catalyst in the prior art, and provides the catalyst for the alkene reaction, which has high activity and strong stability.
According to a first aspect of the present invention, there is provided an olefin reaction 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 showing d 100 ，d 110 And d 200 The diffraction peak 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 the preparation of an olefination reaction catalyst 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 containing a zinc source and a zirconium source and ammonia water into the suspension under the condition of maintaining a constant alkaline pH value of 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is finished, filtering, washing, drying, and optionally roasting to obtain a solid catalyst;
alternatively,
and (2) impregnating the solid catalyst with an alkaline earth metal auxiliary source and/or an alkali metal auxiliary source, and then drying and roasting.
According to a third aspect of the present invention, the present invention provides an olefination reaction catalyst prepared by the preparation method of the present invention; preferably the catalyst has a small angle XRD pattern showing d 100 ，d 110 And d 200 The diffraction peak of the catalyst is obvious, the surface alkali amount of the catalyst is 0.06-0.9 mmol/g, and the specific surface area of the catalyst is more preferably 480-550 m 2 G, the aperture is 6-10 nm.
According to a fourth aspect of the present invention, there is provided the use of the catalyst for olefin alkylation according to the present invention in the preparation of olefins by olefin alkylation of alcohols.
The catalyst solves the problems of low activity and stability of the catalyst for the alkene alkylation reaction in the prior art, particularly low activity and stability of the catalyst for preparing the alkene by the alcohol alkylation reaction, and provides a novel catalyst for the alkene alkylation reaction. The catalyst has the characteristics of good activity and stability.
The catalyst of the invention has good activity and stability. The invention uses the catalyst for the olefin alkylation reaction to prepare the olefin, such as the reaction for preparing the 1, 3-butadiene by converting ethanol, obtains better reaction result and has higher selectivity of the 1, 3-butadiene.
The active components of the catalyst prepared by the preparation method of the invention 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 of the prior art are better solved, and the method can be used for the industrial production of preparing olefin by alcohol alkylation, particularly preparing 1, 3-butadiene by ethanol conversion.
Specifically, when the reaction temperature of the catalyst prepared by the method is 330 ℃, the dosage of the catalyst is 0.5g, the total flow of reaction gas is 14.4mL/min, the flow of ethanol saturated gas is 0.8mL/min, the flow of nitrogen is 13.6mL/min, the conversion rate of ethanol is 85.8%, the selectivity of 1, 3-butadiene is 71.7%, the reaction performance of the catalyst is kept stable after 10h of reaction, and a better technical effect is achieved.
Drawings
FIG. 1 is a comparison of the small angle XRD patterns of the catalysts prepared by the pH-constant precipitation-deposition method (a) of example 1 and the equivalent volume impregnation method (b) of comparative example 1.
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.
The invention provides an olefin reaction catalyst, which comprises a carrier and an active component, wherein the carrier is an SBA-15 molecular sieve, the active component element contains Zn and Zr, and the small-angle XRD (X-ray diffraction) spectrum of the catalyst shows d 100 ，d 110 And d 200 The diffraction peak is obvious, and the surface alkali amount of the catalyst is 0.06-0.9 mmol/g.
The catalyst of the present invention having the aforementioned characteristics is excellent in activity and stability. The invention uses the catalyst for the olefin alkylation reaction to prepare the olefin, such as the reaction for preparing the 1, 3-butadiene by converting ethanol, obtains better reaction result and has higher selectivity of the 1, 3-butadiene.
According to a preferred embodiment of the present invention, the Zn content is preferably 0.1 to 10% and the Zr content is preferably 0.5 to 15% in terms of elements, based on the total mass percentage content of the catalyst; thereby improving the activity and selectivity of the catalyst.
According to a preferred embodiment of the invention, the specific surface area of the catalyst is between 480 and 550m 2 Per g, preferably 490 to 510m 2 (iv) g. Whereby the activity of the catalyst can be improved.
According to a preferred embodiment of the invention, the catalyst pore size is between 6 and 10nm, preferably between 7 and 8nm. Whereby the activity of the catalyst can be improved.
According to a preferred embodiment of the invention, the amount of surface base of the catalyst is between 0.15 and 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 may be selected from a wide range, and a general species such as one or more of Na, K and Mg may be used in the present invention.
According to a preferred embodiment of the present invention, the catalyst contains an alkali metal promoter, and more preferably the alkali metal promoter element is Na. This can improve the stability of the catalyst.
According to a preferred embodiment of the present invention, preferably, the Zn content is 0.1 to 10%, the Zr content is 0.5 to 15%, and the promoter content is 0.1 to 2% by element in terms of the total mass percentage content of the catalyst; thereby improving the activity and stability of the catalyst.
According to a preferred embodiment of the present invention, more preferably, 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, based on the total mass% content of the catalyst. Thereby improving the activity and stability of the catalyst.
According to a preferred embodiment of the invention, the invention provides a catalyst for preparing 1, 3-butadiene by ethanol conversion, the catalyst comprises SBA-15 as a carrier, zn and Zr as active components and Na as an auxiliary agent, the Zn content is 0.1-10%, the Zr content is 0.5-15% and the Na content is 0.1-2% in percentage by mass of the total mass of the catalyst, and the small-angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 The diffraction peak of the catalyst is obvious, and the surface alkali amount of the catalyst is 0.06-0.9mmol/g。
According to a preferred embodiment of the invention, the zinc and zirconium active components and the sodium promoter have a Zn content of 0.1-10%, a Zr content of 0.5-15% and a Na content of 0.1-2% in terms of the total mass percentage of the catalyst; 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 having the aforementioned characteristics of the present invention can achieve the object of the present invention, and there is no particular requirement for the preparation method thereof, and in accordance with the present invention, it is preferred that the catalyst is prepared by the steps of:
1) Soaking the SBA-15 molecular sieve by using 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 containing a zinc source and a zirconium source and ammonia water into the suspension under the condition of maintaining a constant alkaline pH value of 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is finished, and then 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 invention, the constant pH precipitation-deposition method is supposed to be used for loading the active components of zinc and zirconium, so that the catalyst can ensure that the small-angle structure of the SBA-15 carrier is complete, and the active components are uniformly mixed, thereby improving the activity and the selectivity of the catalyst.
According to the invention, optionally, the method further comprises: and (2) impregnating the solid catalyst with an alkaline earth metal auxiliary source and/or an alkali metal auxiliary source, and then drying and roasting. The stability of the catalyst can thereby be improved. The amount of the base of the catalyst can be maintained in the range of 0.06-0.9 mmol/g by loading a proper amount of the auxiliary agent.
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, dripping a zinc source and zirconium source mixed salt solution and ammonia water into a suspension of the SBA-15 at the same time under the conditions of constant pH =8-9, preferably 8 and stirring, stopping dripping the ammonia water after the dripping of the zinc and zirconium mixed salt solution is finished, then filtering, washing with the deionized water, and drying to obtain a sample;
3) And (3) impregnating the required amount of sodium salt solution on the obtained sample by using an equal-volume impregnation method, and then drying and roasting to obtain the catalyst for preparing 1, 3-butadiene through ethanol conversion.
According to the invention, in the technical scheme, the preparation method of the catalyst for preparing 1, 3-butadiene by ethanol conversion is adopted, and the zinc source is selected from Zn (NO) 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Is preferably Zn (NO) 3 ) 2 ·6H 2 O; the source of zirconium 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 Is preferably ZrO (NO) 3 ) 2 ·2H 2 O; the sodium source is selected from NaNO 3 、Na 2 SO 4 And CH 3 One of COONa, preferably NaNO 3 (ii) a The drying condition is drying for 10 to 30 hours at a temperature of between 80 and 120 ℃; the roasting condition is roasting for 3-6 h at 500-650 ℃ in air atmosphere.
According to the invention, the raw materials are used in such amounts that, calculated as element, the Zn content is 0.1 to 10%, the Zr content is 0.5 to 15%, optionally the promoter content is 0.1 to 2%, based on the total mass percentage content of the catalyst. Thereby improving the activity and stability of the catalyst.
According to the invention, the raw materials are used in such amounts that, calculated as the elements, the Zn content is 0.5-3.5%, the Zr content is 3-7%, and the Na content is 0.2-0.4%, based on the total mass percentage content of the catalyst. Thereby improving the activity and stability of the catalyst.
According to the invention, the zinc source can be selected from a wide range, soluble zinc-containing compounds can be used in the invention, and for the invention, the zinc source is preferably Zn (NO) 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Is preferably Zn (NO) 3 ) 2 ·6H 2 And (O). The activity of the catalyst can thereby be increased.
According to the invention, the zirconium source can be selected from a wide range of types, and soluble zirconium-containing compounds can be used in the invention, and for the invention, the preferred 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 preferably ZrO (NO) 3 ) 2 ·2H 2 And (O). Thereby increasing the selectivity of the catalyst.
According to the invention, the alkaline earth metal promoter source and/or the alkali metal promoter source is one or more of nitrate, sulfate and acetate, and is more preferably NaNO 3 、Na 2 SO 4 And CH 3 One of COONa, more preferably NaNO 3 . The stability of the catalyst can thereby be improved.
According to the invention, the treatment of the step 1) is preferably carried out so that the surface hydroxyl content of the SBA-15 molecular sieve after treatment is 5-6 mmol/g. Thereby improving the activity and selectivity of the catalyst.
According to the invention, the concentration of the hydrogen peroxide in the step 1) is preferably 1-5 wt%. Thereby improving the activity and selectivity of the catalyst.
According to the invention, the soaking time in the step 1) is preferably 10-30 h. Thereby improving the activity and selectivity of the catalyst.
According to the invention, in the step 1), the dosage of hydrogen peroxide is 10-15ml/g SBA-15 molecular sieve.
According to the invention, in step 2), the amount of SBA-15 molecular sieve is 1-5g of SBA-15 molecular sieve per 100ml of water. Thereby improving the activity and selectivity of the catalyst.
In the present invention, SBA-15 which is conventionally used may be used in the present invention, and according to the present invention, it is preferable that the SBA-15 has a specific surface area of 560 to 585m 2 G, the pore diameter is 7.6-8.6nm. The object of the invention can be achieved by selecting the SBA-15 molecular sieve with the technical characteristics.
According to the present invention, the concentration of the aqueous ammonia is not particularly limited, and for example, aqueous ammonia having a concentration of 1.0mol/L is used.
According to the present invention, it is preferable that the drying conditions of each step each include: the temperature is 80-120 ℃, and the drying time is determined according to the temperature, for example, the drying time is 10-30 h. Thereby improving the activity and stability of the catalyst.
According to the present invention, it is preferable that the conditions of the calcination in each step each include: roasting at 500-650 deg.c in air atmosphere for 3-6 hr. 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 reaction catalyst prepared by the preparation method; preferably the catalyst has a small angle XRD pattern showing d 100 ，d 110 And d 200 The diffraction peak of the catalyst is obvious, the surface alkali amount of the catalyst is 0.06-0.9 mmol/g, preferably 0.15-0.35 mmol/g; more preferably, the specific surface area of the catalyst is 480 to 550m 2 Per g, preferably 490 to 510m 2 (ii)/g; the pore diameter is 6-10 nm, preferably 7-8nm.
The active components of the catalyst prepared by the preparation method of the invention 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 of the prior art are better solved, and the method can be used for the industrial production of preparing olefin by alcohol alkylation, particularly preparing 1, 3-butadiene by ethanol conversion.
The invention provides application of the olefin alkylation reaction catalyst in olefin preparation by alcohol alkylation, more preferably, the alcohol is C2-C4 alcohol, and more preferably ethanol.
Specifically, when the reaction temperature of the catalyst prepared by the method is 330 ℃, the dosage of the catalyst is 0.5g, the total flow of reaction gas is 14.4mL/min, the flow of ethanol saturated gas is 0.8mL/min, the flow of nitrogen is 13.6mL/min, the conversion rate of ethanol is 85.8%, the selectivity of 1, 3-butadiene is 71.7%, the reaction performance of the catalyst is kept stable after 10h of reaction, and a better technical effect is achieved.
In the present invention, the XRD pattern test was performed on a Bruker Nanostat U-type small angle X-ray scatterometer using a tube current of 35mA and a tube pressure of 40kV.
The specific surface area and pore diameter of the catalyst were measured by using Tristar 3000 type physical adsorption apparatus from Micromeritics, USA, and N was used 2 As adsorbates, samples were subjected to vacuum pretreatment at 300 ℃ for 4h, the specific surface area of the catalyst was calculated by the BET method, and the pore diameter of the catalyst was calculated by the BJH model.
CO for surface alkali amount 2 TPD test, pretreatment of the catalyst at 500 ℃ for 1h before the test, cooling to 80 ℃ to adsorb 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) was weighed into a container 2 Per g, the aperture is 8.5 nm), 45mL of 3 wt% hydrogen peroxide is added, the mixture is soaked for 12 hours at room temperature, then filtered and washed by deionized water, and then the mixture is dried for 12 hours in a 110 ℃ oven. 2.0g of the hydrogen peroxide treated SBA-15 carrier (the surface hydroxyl content is 5.8 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of a mixed solution of zinc nitrate and zirconyl nitrate (the concentrations of Zn and Zr are 0.0033 and 0.011g/mL respectively) and 1.0mol/L of ammonia water are simultaneously dripped into the suspension of the SBA-15 under stirring, the pH value is controlled to be about 8 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the mixed salt solution of zinc and zirconium is finished. Then filtered, washed with deionized water and dried in an oven at 110 ℃ for 12h. And (3) soaking the obtained sample in sodium nitrate solution in the same volume, drying in a drying oven at 110 ℃ for 12 hours, and finally roasting in a muffle furnace at 550 ℃ for 4 hours in air atmosphere to obtain the required catalyst. In the catalyst, the Na content was 0.2%, the Zn content was 1.5%, and the Zr content was 5%. The catalyst maintains the mesoporous structure of the SBA-15 carrier, the small-angle XRD pattern of the catalyst is shown in figure 1 (a), the surface alkali amount is 0.21mmol/g, and the specific surface area is 503m 2 G, pore diameter of 8nm.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: before reaction, 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, the flow of ethanol saturated gas is 0.8mL/min, and the flow of nitrogen is 13.6mL/min. The conversion of ethanol after 1 hour of reaction was 85.8%, the selectivity for 1, 3-butadiene was 71.7%, the conversion of ethanol after 10 hours of reaction was 85.7%, and the selectivity for 1, 3-butadiene was 72.1%.
Example 2
3.0g of SBA-15 molecular sieve (specific surface area 565 m) was weighed into a vessel 2 Per gram, the aperture is 8.5 nm), 30mL of 4 wt% hydrogen peroxide is added, the mixture is soaked for 20 hours at room temperature, then filtered, washed by deionized water and dried in an oven at 100 ℃ for 24 hours. 2.0g of the SBA-15 carrier (with the surface hydroxyl content of 5.8 mmol/g) treated by the hydrogen peroxide is weighed and dispersed in 50mL of deionized water, 10mL of mixed solution of zinc nitrate and zirconyl nitrate (with the Zn and Zr concentrations of 0.0033 and 0.011g/mL respectively) and 1.0mol/L of ammonia water are simultaneously dripped into the suspension of the SBA-15 under stirring, the pH value is controlled to be about 8 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the mixed salt solution of the zinc and the zirconium is finished. Then filtered, washed with deionized water and dried in an oven at 100 ℃ for 24h. And (3) soaking the obtained sample in sodium nitrate solution in an equal volume, drying in a 100 ℃ oven for 24h, and finally roasting in a muffle furnace at 550 ℃ for 6h under an air atmosphere to obtain the required catalyst. The catalyst has Na content of 0.3%, zn content of 1.5% and Zr content of 5%, and retains the mesoporous structure of SBA-15 carrier, and its small-angle XRD pattern is similar to that of example 1, surface alkali amount is 0.32mmol/g, and specific surface area is 501m 2 G, pore diameter of 8nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 82.6%, the selectivity for 1, 3-butadiene was 72.2%, the conversion of ethanol after 10 hours of reaction was 82.9%, and the selectivity for 1, 3-butadiene was 72.1%.
Example 3
3.0g of SBA-15 molecular sieve (specific surface area 583 m) was weighed into a vessel 2 Per g, the aperture is 7.6 nm), 45mL of 2 wt% hydrogen peroxide is added, the mixture is soaked for 25 hours at room temperature, then filtered and washed by deionized water, and then the mixture is dried for 30 hours in a 90 ℃ oven. 2.0g of SBA-15 carrier (surface hydroxyl content is 5.6 mmol/g) treated by hydrogen peroxide is weighed and dispersed in 50mL of deionized water,10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentration is 0.0011 and 0.015g/mL respectively) and 1.0mol/L of ammonia water are simultaneously dripped into the SBA-15 suspension under stirring, the pH value is controlled to be constant at about 8.5 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the zinc and zirconium mixed salt solution is finished. Then filtered, washed with deionized water and dried in an oven at 90 ℃ for 30h. And (3) soaking the obtained sample in sodium nitrate solution in the same volume, drying the sample in a 90 ℃ oven for 30 hours, and finally roasting the sample in a 650 ℃ muffle furnace for 3 hours in air atmosphere to obtain the required catalyst. The Na content of the catalyst is 0.2 percent, the Zn content is 0.5 percent, the Zr content is 7 percent, the catalyst maintains the mesoporous structure of the SBA-15 carrier, the small-angle XRD pattern is similar to that of example 1, the surface alkali amount is 0.20mmol/g, and the specific surface area is 510m 2 G, pore diameter of 7nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 83.4%, the selectivity for 1, 3-butadiene was 70.2%, the conversion of ethanol after 10 hours 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 into a vessel 2 Per gram, the aperture is 8.6 nm), 30mL of 5 wt% hydrogen peroxide is added, the mixture is soaked for 10 hours at room temperature, then filtered, washed by deionized water and dried in an oven at 100 ℃ for 24 hours. 2.0g of the SBA-15 carrier (with the surface hydroxyl group content of 5.7 mmol/g) treated by the hydrogen peroxide is weighed and dispersed in 50mL of deionized water, 10mL of mixed solution of zinc nitrate and zirconyl nitrate (with the Zn and Zr concentrations of 0.0055 and 0.011g/mL respectively) and 1.0mol/L of ammonia water are simultaneously dripped into the suspension of the SBA-15 under stirring, the pH value is controlled to be about 9 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the mixed salt solution of the zinc and the zirconium is finished. Then filtered, washed with deionized water and dried in an oven at 100 ℃ for 24h. And (3) soaking the obtained sample in sodium nitrate solution in an equal volume, drying in a 100 ℃ oven for 24h, and finally roasting in a muffle furnace at 550 ℃ for 6h under an air atmosphere to obtain the required catalyst. The Na content of the catalyst is 0.3 percent, the Zn content is 2.5 percent, the Zr content is 5 percent, the catalyst keeps the mesoporous structure of the SBA-15 carrier, the small-angle XRD pattern is similar to that of example 1, and the surface alkali content is 0.33mmol/g, specific surface area 497m 2 G, pore diameter of 8nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 84.8%, the selectivity for 1, 3-butadiene was 71.2%, the conversion of ethanol after 10 hours of reaction was 84.7%, and the selectivity for 1, 3-butadiene was 71.3%.
Example 5
3.0g of SBA-15 molecular sieve (specific surface area: 572 m) was weighed into a container 2 Per g, the aperture is 7.8 nm), 45mL of 1 weight percent hydrogen peroxide is added, the mixture is soaked for 30 hours at room temperature, then filtered and washed by deionized water, and then the mixture is dried for 10 hours in a 120 ℃ oven. 2.0g of the hydrogen peroxide treated SBA-15 carrier (surface hydroxyl content of 5.5 mmol/g) is weighed and dispersed in 50mL of deionized water, 10mL of a mixed solution of zinc nitrate and zirconyl nitrate (Zn and Zr concentrations are 0.0077 and 0.015g/mL respectively) and 1.0mol/L of ammonia water are simultaneously dripped into the suspension of the SBA-15 under stirring, the pH value is controlled to be about 8 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the mixed salt solution of zinc and zirconium is finished. Then filtered, washed with deionized water and dried in an oven at 120 ℃ for 10h. And (3) soaking the obtained sample in sodium nitrate solution in the same volume, drying in a 120 ℃ oven for 10h, and finally roasting in a muffle furnace at 550 ℃ for 4h under the air atmosphere to obtain the required catalyst. The Na content of the catalyst is 0.2 percent, the Zn content is 3.5 percent, the Zr content is 7 percent, the catalyst keeps the mesoporous structure of the SBA-15 carrier, the small-angle XRD pattern is similar to that of example 1, the surface alkali amount is 0.23mmol/g, and the specific surface area is 490m 2 G, pore diameter of 7nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 81.8%, the selectivity for 1, 3-butadiene was 71.2%, the conversion of ethanol after 10 hours of reaction was 81.7%, and the selectivity for 1, 3-butadiene was 71.3%.
Example 6
3.0g of SBA-15 molecular sieve (specific surface area 569 m) was weighed into a container 2 Per g, the aperture is 7.7 nm), 45mL of 3 wt% hydrogen peroxide is added, the mixture is soaked for 24 hours at room temperature, then filtered and washed by deionized water, and then the mixture is put into a 110 ℃ oven to be dried for 24 hours. The above SBA-15 carrier (surface hydroxyl group containing) treated with hydrogen peroxide was weighedThe amount is 5.9 mmol/g) 2.0g is dispersed in 50mL deionized water, 10mL of zinc nitrate and zirconyl nitrate mixed solution (the concentrations of Zn and Zr are 0.0033 and 0.015g/mL respectively) and 1.0mol/L ammonia water are simultaneously dripped into the suspension of SBA-15 under stirring, the pH value is controlled to be constant at about 8.5 in the whole dripping process, and the dripping of the ammonia water is stopped after the dripping of the zinc and zirconium mixed salt solution is finished. Then filtered, washed with deionized water and dried in an oven at 110 ℃ for 24h. And (3) soaking the obtained sample in sodium nitrate solution in the same volume, drying in a drying oven at 110 ℃ for 24h, and finally roasting in a muffle furnace at 600 ℃ for 4h in air atmosphere to obtain the required catalyst. The Na content of the catalyst is 0.3 percent, the Zn content is 1.5 percent, the Zr content is 7 percent, the catalyst maintains the mesoporous structure of the SBA-15 carrier, the small-angle XRD pattern is similar to that of example 1, the surface alkali amount is 0.32mmol/g, and the specific surface area is 493m 2 G, pore diameter of 7nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 82.6%, the selectivity for 1, 3-butadiene was 72.2%, the conversion of ethanol after 10 hours of reaction was 82.7%, and the selectivity for 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 the SBA-15 carrier, the small-angle XRD pattern of the catalyst is shown in figure 1 (a), the surface alkali amount is 0.16mmol/g, and the specific surface area is 505m 2 G, pore diameter of 8nm.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 86.2%, the selectivity for 1, 3-butadiene was 70.8%, the conversion of ethanol after 10 hours of reaction was 83.8%, and the selectivity for 1, 3-butadiene was 71.0%.
Example 8
3.0g of SBA-15 molecular sieve (specific surface area 560 m) was weighed into a container 2 Per g, the aperture is 8.5 nm), 45mL of 3 wt% hydrogen peroxide is added, the mixture is soaked for 12 hours at room temperature, then filtered and washed by deionized water, and then the mixture is dried for 12 hours in a 110 ℃ oven. 2.0g of SBA-15 carrier (surface hydroxyl content is 5.8 mmol/g) treated by hydrogen peroxide is weighed and dispersed in 50mL of deionized water, and stirredDripping 10mL of zinc nitrate and zirconyl nitrate mixed solution (Zn and Zr concentration is 0.0033 and 0.011g/mL respectively) and 1.0mol/L of ammonia water into the SBA-15 suspension at the same time, controlling the pH value to be constant at about 8 in the whole dripping process, and stopping dripping the ammonia water after the dripping of the zinc and zirconium mixed salt solution is finished. Then filtering, washing with deionized water, drying in an oven at 110 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 4h under air atmosphere 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 [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 87.6%, the selectivity for 1, 3-butadiene was 70.5%, the conversion of ethanol after 10 hours of reaction was 67.5%, and the selectivity for 1, 3-butadiene was 67.9%.
It can be seen that the catalyst has poor stability.
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 the example 1) is weighed, the mixed solution of zinc nitrate, zirconyl nitrate and sodium nitrate is used for soaking in the same volume, then the obtained product is put into a 110 ℃ oven to be dried for 12 hours, and finally the obtained product is roasted in a muffle furnace at 550 ℃ for 4 hours in air atmosphere to obtain the required catalyst. In the catalyst, the Na content 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 diffraction peak intensity is greatly weakened, which indicates that the mesoporous structure of the SBA-15 carrier is seriously damaged.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion rate of ethanol after 1 hour of reaction was 65.6%, the selectivity of 1, 3-butadiene was 65.5%, the conversion rate of ethanol after 10 hours of reaction was 64.5%, and the selectivity of 1, 3-butadiene was 64.9%.
Comparative example 2
The procedure of example 1 is followed except that the SBA molecular sieve of step 1) is prepared from an equivalent amount of molecular sieve TS-1 of MFI structure (commercially available, tiO) 2 /SiO 2 The molar ratio of (3) is 0.04).
The evaluation conditions were the same as in [ example 1], and the results were as follows: the conversion rate of ethanol after 1 hour of reaction was 68.3%, the selectivity of 1, 3-butadiene was 65.4%, the conversion rate of ethanol after 10 hours of reaction was 65.4%, and the selectivity of 1, 3-butadiene was 65.7%.
Comparative example 3
The procedure is as in example 1, except that the zinc nitrate of step 1) is replaced by copper nitrate of the same copper element as the zinc.
The evaluation conditions were the same as [ example 1], and the results were as follows: the conversion of ethanol after 1 hour of reaction was 70.3%, the selectivity for 1, 3-butadiene was 64.3%, the conversion of ethanol after 10 hours of reaction was 67.4%, and the selectivity for 1, 3-butadiene was 64.6%.
Comparative example 4
The procedure is as in example 1, except that the zirconyl nitrate of step 1) is replaced by 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 conversion of ethanol after 1 hour of reaction was 74.3%, the selectivity for 1, 3-butadiene was 64.3%, the conversion of ethanol after 10 hours of reaction was 70.7%, and the selectivity for 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 conversion of ethanol after 1 hour of reaction was 65.0%, the selectivity of 1, 3-butadiene was 67.0%, the conversion of ethanol after 10 hours of reaction was 64.9%, and the selectivity of 1, 3-butadiene was 67.2%.
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. The alkene reaction catalyst is characterized by comprising a carrier and an active component, wherein the carrier is an SBA-15 molecular sieve, the active component element contains Zn and Zr, and the small-angle XRD pattern of the catalyst shows d 100 ，d 110 And d 200 Diffraction peak of (2)Obviously, the surface alkali amount of the catalyst is 0.06-0.9 mmol/g.
2. The catalyst according to claim 1, wherein,
calculated by the total mass percentage of the catalyst, calculated by elements, the Zn content is 0.1-10%, and the Zr content is 0.5-15%; and/or
The specific surface area of the catalyst is between 480 and 550m 2 Per g, preferably 490 to 510m 2 (ii)/g; the aperture is 6-10 nm, preferably 7-8nm; and/or
The surface alkali amount of the catalyst is 0.15-0.35 mmol/g.
3. The catalyst of claim 1 or 2, wherein,
the catalyst contains an alkali metal auxiliary agent and/or an alkaline earth metal auxiliary agent, preferably contains an alkali metal auxiliary agent, and more preferably, the alkali metal auxiliary agent element is Na; and/or
Preferably, the Zn content is 0.1-10%, the Zr content is 0.5-15%, and the auxiliary agent content is 0.1-2% by element in terms of the total mass percentage content of the catalyst; and/or
More preferably, 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, based on the total mass percentage content of the catalyst.
4. A method of preparing an olefination reaction catalyst, the method 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 containing a zinc source and a zirconium source and ammonia water into the suspension under the condition of keeping constant alkaline pH of 8-9, stopping dropwise adding the ammonia water after the dropwise adding of the mixed solution is finished, and then filtering, washing, drying and optionally roasting to obtain a solid catalyst;
alternatively,
and (2) impregnating the solid catalyst with an alkaline earth metal auxiliary source and/or an alkali metal auxiliary source, and then drying and roasting.
5. The production method according to claim 4, wherein the respective raw materials are used in such amounts that,
calculated by the total mass percentage of the catalyst and calculated by elements, the Zn content is 0.1 to 10 percent, the Zr content is 0.5 to 15 percent, and optionally the auxiliary agent content is 0.1 to 2 percent;
more preferably still, the first and second liquid crystal compositions are,
calculated by the total mass percentage of the catalyst, the Zn content is 0.5-3.5%, the Zr content is 3-7%, and the Na content is 0.2-0.4%.
6. The production method according to claim 4 or 5,
the zinc source is Zn (NO) 3 ) 2 ·6H 2 O、ZnSO 4 ·7H 2 O and ZnCl 2 Is preferably Zn (NO) 3 ) 2 ·6H 2 O; and/or
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 preferably ZrO (NO) 3 ) 2 ·2H 2 O; and/or
The alkaline earth metal auxiliary source and/or the alkali metal auxiliary source is/are one or more of nitrate, sulfate and acetate, and is preferably NaNO 3 、Na 2 SO 4 And CH 3 One of COONa, more preferably NaNO 3 (ii) a And/or
The specific surface area of the SBA-15 molecular sieve is 560-585m 2 G, the pore diameter is 7.6-8.6nm.
7. The preparation method of any one of claims 4 to 6, wherein the treatment of step 1) is carried out so that the surface hydroxyl content of the treated SBA-15 molecular sieve is 5-6 mmol/g.
8. The production method according to any one of claims 4 to 7,
in the step 1), the concentration of hydrogen peroxide is 1 to 5 weight percent, and the soaking time is 10 to 30 hours; and/or
In the step 1), the dosage of hydrogen peroxide is 10-15ml/g SBA-15 molecular sieve; and/or
In the step 2), the dosage of the SBA-15 molecular sieve is 1-5g of the SBA-15 molecular sieve per 100ml of water; and/or
The drying conditions in each step each include: the temperature is 80-120 ℃, and/or the time is 10-30 h; and/or
The roasting conditions in each step respectively comprise: roasting for 3-6 h at 500-650 ℃ in air atmosphere.
9. An olefination reaction catalyst produced by the production method according to any one of claims 4 to 8; preferably the catalyst has a small angle XRD pattern showing d 100 ，d 110 And d 200 The diffraction peak of (2) is obvious, the surface alkali amount of the catalyst is 0.06-0.9 mmol/g, and the specific surface area of the catalyst is more preferably 480-550 m 2 G, the aperture is 6-10 nm.
10. Use of the catalyst of claims 1-3 and 9 for the olefin alkylation reaction in the preparation of an olefin by the olefin alkylation reaction of an alcohol, more preferably the alcohol is a C2-C4 alcohol, more preferably ethanol.
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