CN110586062A - Si-Mg-Zr-Zn composite metal oxide catalyst and preparation method and application thereof - Google Patents
Si-Mg-Zr-Zn composite metal oxide catalyst and preparation method and application thereof Download PDFInfo
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- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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Abstract
The invention discloses multifunctional MgaZrbZncSidOeA composite metal oxide catalyst, a preparation method thereof and application thereof in preparing enol compounds. The multifunctional MgaZrbZncSidOeThe composite metal oxide catalyst is obtained by adding a Si source into the original Mg-Zr-Zn composite metal oxide catalyst. The catalyst ensures the catalytic activity, and the reaction activity is hardly reduced after 800 hours; and by adopting the original Mg-Zr-Zn composite metal oxide catalyst (CN107398264A), under the same condition, after 800 hours, the conversion rate of the reaction raw material is reduced to less than 5% from 18% at the beginning, and the selectivity of the allyl alcohol in the reaction product is also reduced to 32% from 87% at the beginning. Show thatBy adding the Si component, the stability of the catalyst in the reaction process can be obviously improved.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a multi-component Si-Mg-Zr-Zn composite metal oxide catalyst and application thereof in preparation of an enol compound.
Background
The enol contains double bond and hydroxyl functional groups in its molecular structure, and can participate in oxidation, reduction, esterification, etherification, coupling, polymerization and other reactions to synthesize a series of downstream products with wide application, which are widely used in synthesizing perfume, resin and the like, and are important fine chemical raw materials and organic synthesis intermediates. Common alkenols mainly include: allyl alcohol, isobutenol, crotyl alcohol, and the like. For example, isobutenol, also known as 2-methallyl alcohol, is a colorless transparent liquid, boiling point: at the temperature of 114.5 ℃, isobutene alcohol and ethylene oxide are used as raw materials to synthesize methyl allyl polyoxyethylene ether (TPEG) which is used for a new generation of high-performance concrete water reducing agent. Allyl alcohol, also known as allyl alcohol, is a raw material for producing diallyl phthalate resin and bis (2, 3-dibromopropyl) fumarate.
For example, the industrial production method of isobutylene alcohol mainly includes isobutylene chlorination hydrolysis and oxidation. A plurality of domestic enterprises adopt an isobutene chlorination hydrolysis method, isobutene is subjected to two-step reaction, namely, isobutene reacts with chlorine gas in the first step to generate chlorinated isobutene, and hydrogen chloride is a byproduct; and in the second step, the chloro isobutylene is hydrolyzed under the action of sodium hydroxide and a catalyst to generate the isobutylene alcohol, and simultaneously, a large amount of salt-containing oily wastewater is generated. The oxidation method generally uses isobutene as a raw material to synthesize methallyl aldehyde through oxidation, and the methallyl aldehyde is hydrogenated to generate methallyl alcohol (isobutenol). The existing production process of propylene alcohol comprises methods such as propylene oxide isomerization, acrolein selective reduction, chloropropene hydrolysis, allyl acetate hydrolysis and the like, and catalysts or additives such as acid, alkali and the like are required.
The method has the defects of complicated operation steps, high energy consumption, heavy pollution, difficult treatment of byproducts and the like. Therefore, the development of a novel process for preparing enol products is urgent. Aiming at the current process situation, in a Chinese invention patent (CN107398264A) previously filed by the applicant, a Mg-Zr-Zn composite metal oxide catalyst and a preparation method thereof are disclosed, and the Mg-Zr-Zn composite metal oxide catalyst is applied to the reaction of taking methanol and n-propanol as raw materials to generate the isobutenol. However, although the catalyst disclosed in the patent publication (CN107398264A) can show better stability within 200 hours, the conversion rate of the reaction raw material and the distribution of the products do not change greatly. However, in the case of longer-term applications, for example, extended periods of time up to 400 hours or more, the deactivation of the catalyst becomes more pronounced, which is manifested by a reduction in the conversion of the starting material and a reduction in the selectivity for the isobutenol. The long-term stability of the catalyst is very important for the actual production process. In response to this problem in the aforementioned patent, the present invention discloses a method for improving the stability of a catalyst.
In the invention, Si source is added into the original Mg-Zr-Zn composite metal oxide catalyst to form multifunctional Si-MgxZryZnzO composite metal oxide catalyst. Taking the reaction process for preparing the propenol as an example, the specific reaction step is that methanol and ethanol are added into multifunctional Si-Mg on a fixed bed reactorxZryZnzAnd quickly dehydrogenating, aldol cross-condensing and hydrogenating under the action of the O composite metal oxide catalyst to finally generate the allyl alcohol. After a Si source is introduced into the Mg-Zr-Zn composite metal oxide, the stability of the catalyst can be greatly improved and the service life can be prolonged while the high selectivity of the allyl alcohol is ensured.
Disclosure of Invention
In view of the problems of the aforementioned patent invention, it is an object of the present application to provide a multifunctional Si-MgaZrbZncOdThe composite metal oxide catalyst can obviously improve the stability of the prepared catalyst by adding the Si component as an auxiliary agent. In the presence of MgaZrbZncSidOeIn the composite oxide catalyst, a, b, c and d are respectively the molar ratio of Mg, Zr, Zn and Si active components, and e is the stoichiometric ratio of O atoms, wherein the ratio of Mg, Zr, Zn and Si is 0.1-10: 0.01-1, and preferably 0.1-10: 0.1-1: 0.01-01:0.1 to 1, more preferably 1 to 10:0.1 to 1:0.01 to 0.1:0.1 to 1.
According to another aspect of the present invention, there is provided a multicomponent MgaZrbZncSidOeA method for preparing a composite metal oxide catalyst, the method comprising the steps of:
(1) adding metal salt, metal oxide or metal hydroxide containing metal active components Mg, Zr and Zn into a solvent for dissolving and/or dispersing, and stirring for fully mixing, wherein the total concentration of the metal precursor mixed solution is 1-3 mol.L-1And heating and refluxing;
(2) adding a compound containing Si into the mixed solution obtained in the step (1), continuously stirring until the mixture is fully mixed, and heating and refluxing;
(3) removing the solvent from the mixed solution obtained in the step (2) by rotary evaporation, drying and roasting at high temperature to obtain the multicomponent MgaZrbZncSidOeA composite metal oxide catalyst.
Preferably, the active ingredient metal salt in step (1) is selected from at least one of nitrate, carbonate, bicarbonate, chloride, acetate, sulfate, lower metal alkoxide. Wherein the lower metal alkoxide represents an alkoxy organometallic compound formed by substituting hydroxyl hydrogen of an alcohol molecule with a metal, and the alcohol may be at least one of ethanol, propanol or butanol.
Preferably, the metal oxide and the metal hydroxide in the step (1) can be commercial products and can be directly used without any pretreatment.
Preferably, the solvent in step (1) is water, or a mixed solvent of water and a unit lower alcohol selected from at least one of methanol, ethanol, propanol and butanol, preferably at least one selected from methanol, ethanol and propanol. The volume percentage of the unit lower alcohol in the composite solvent is 1-50%, and preferably 20-50%.
Preferably, the heating reflux temperature of the active component mixed solution in the step (1) is 50-90 ℃, and the reflux time is not less than 2 hours. More preferably, the heating reflux time in the step (1) is 2 to 8 hours.
Preferably, the Si-containing compound in step (2) is selected from silica powder or an organosilicon monomer.
Further preferably, the Si-containing compound in step (2) is selected from tetraethyl orthosilicate and tetrabutyl orthosilicate.
Further preferably, the Si-containing compound in step (2) is silica powder having a particle size of 10 to 100 micrometers.
Preferably, when the Si-containing compound in step (2) is an organosilicon monomer selected from tetraethyl orthosilicate and tetrabutyl orthosilicate, the Si-containing compound is added to the mixed solution of step (1) in a gradually dropwise manner.
Preferably, when the Si-containing compound in step (2) is silica powder, the silica powder is added to the mixed solution in step (1) in a batch manner.
Preferably, the temperature of the solvent removed by rotary evaporation in the step (3) is 50-90 ℃, the drying temperature is 100-150 ℃, and the drying time is 4-12 hours, preferably 6-10 hours; the roasting temperature is 400-800 ℃, and the roasting time is 1-12 hours, preferably 2-8 hours.
According to another aspect of the present invention, there is provided a use of the multifunctional Mg-Zr-Zn-Si composite metal oxide catalyst in the preparation of an enol compound. The enolic compounds prepared may include: at least one of allyl alcohol, crotyl alcohol, isobutenol, 2-ethyl-allyl alcohol, 2-propyl-allyl alcohol and 2-butyl-allyl alcohol.
According to another aspect of the present invention, there is provided a process for the direct preparation of an enol compound from monoalcohols, said process employing a fixed-bed reactor charged with said Mg according to the present inventionaZrbZncSidOeThe composite metal oxide catalyst is loaded with one or more unit lower alcohols through nitrogen to react to prepare an enol compound, wherein the using amount of the catalyst is 0.1-10 g, and the sample injection rate is 0.1-5 mL.h-1The temperature is 150-350 ℃, and the pressure is 0.1-2 MPa.
The unit lower alcohols include: methanol, ethanol, propanol, butanol, pentanol, hexanol, phenethyl alcohol, phenylpropyl alcohol, etc., and preferably methanol, ethanol, propanol, butanol, pentanol, hexanol.
When the unit lower alcohol is a mixed solution of methanol and other unit lower alcohols, the mass percentage of the other unit lower alcohols is 1-50%, preferably, the mass percentage of the other unit lower alcohols is 2-20%.
Advantageous effects
In the invention, Si source is added into the original Mg-Zr-Zn composite metal oxide catalyst to form multi-component MgaZrbZncSidOeA composite metal oxide catalyst. The catalyst ensures the catalytic activity, and the reaction activity is hardly reduced after 800 hours; and by adopting the original Mg-Zr-Zn composite metal oxide catalyst (CN107398264A), under the same condition, after 800 hours, the conversion rate of the reaction raw material is reduced to less than 5% from 18% at the beginning, and the selectivity of the allyl alcohol in the reaction product is also reduced to 32% from 87% at the beginning. The stability of the catalyst in the reaction process can be obviously improved by adding the Si component.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The key point of the invention is that Si element substances are doped in the previously developed multifunctional Mg-Zr-Zn composite oxide catalyst, so that the long-term use stability of the catalyst is successfully improvedAnd (5) performing qualitative determination. The inventors of the present invention have found that when three metals, Mg-Zr-Zn and Si, are used as catalyst active components in a specific ratio, the long-term use stability of the catalyst can be greatly improved while achieving high selectivity in converting a lower alcohol into an enol compound. Multicomponent Mg prepared according to the inventionaZrbZncSidOeIn the composite oxide catalyst, a, b, c and d are respectively the molar ratio of Mg, Zr, Zn and Si active components, and e is the stoichiometric ratio of O atoms, wherein the ratio of Mg, Zr, Zn and Si is 0.1-10: 0.01-1, preferably 0.1-10: 0.1-1: 0.01-0.1: 0.1-1, and more preferably 1-10: 0.1-1: 0.01-0.1: 0.1-1.
Wherein the Si-containing substance is added differently from the other three metal elements in the multicomponent Mg according to the inventionaZrbZncSidOeIn the preparation method of the composite oxide catalyst, precursors containing Mg, Zr and Zn are mixed in the step (1), and are heated and refluxed to fully mix the precursors of the three elements, and then a Si-containing substance is added.
Particularly when the Si-containing substance added is an organosilicon monomer selected from the group consisting of tetraethyl orthosilicate and tetrabutyl orthosilicate, a slow dropwise addition operation is required. So that the organosilicon monomer can be fully flocculated and simultaneously mixed with the precursors of other three metal elements. If the organic silicon monomer is added at one time, partial flocculation is easy to be serious, and the final catalyst product has uneven performance.
The inventors of the present invention have surprisingly found that the object of improving the long-term stability of the catalyst can be achieved when the molar ratio of the elements in the four is controlled within the range specified in the present invention and at the same time the preparation is carried out using specific preparation steps.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1 to example 5: preparation of catalysts CAT-1 to CAT-5
Mg, Zr, Zn metal salts in the amounts calculated in Table 1 below were dissolved and dispersed in 50mL of an alkaline hydroalcoholic mixed solution, vigorously stirred at 35 ℃ for 15 minutes, continuously stirred for 30 minutes, and then Si source was selectively added according to Table 1 below. Stirring is continued, and heating and refluxing are carried out at 70 ℃. And (4) roasting the washed and dried catalyst at high temperature, and sealing for later use.
The numbers of the obtained samples and the corresponding preparation conditions are shown in table 1.
Table 1: preparation of CAT-1-CAT-5 catalysts
Comparative examples 1 and 2: preparation of CAT-6 and CAT-7 catalysts
The Mg, Zr and Zn metal salts, calculated as in Table 2 below, were dissolved and dispersed in 50mL of an alkaline hydroalcoholic mixed solution, vigorously stirred at 35 ℃ for 15 minutes, further stirred for 30 minutes, and heated under reflux at 70 ℃. And (4) roasting the washed and dried catalyst at high temperature, and sealing for later use.
The numbers of the obtained samples and the corresponding preparation conditions are shown in table 2.
Table 2: preparation of CAT-6 and CAT-7 catalysts
Test example 1: multifunctional MgaZrbZncSidEvaluation of catalytic performance of O composite oxide catalyst in preparation of propenol directly from methanol and ethanol
The catalysts prepared in examples 1 to 5 and comparative examples 1 and 2 were tabletted and sieved, and 20 to 60 mesh granules were taken for use. Respectively filling 2g of catalyst into a fixed bed reactor with an inner diameter of 10mm, taking a mixed solution of methanol and ethanol as a reaction raw material, taking the mass concentration of the ethanol as 10 percent, taking nitrogen as a carrier gas, and feeding the sample at a rate of 1.2 mL.h-1The reaction temperature is 300 ℃, and the pressure of carrier gasThe reaction was carried out under a pressure of 1.5 MPa. The collected reaction solution was quantitatively detected by gas chromatography (equipped with FID detector, Rtx-WAX column, 30 m.times.0.25 μm.times.0.32 mm), and the resultant product was qualitatively analyzed by GC-MS apparatus. The initial reactivity of the different catalysts is shown in table 2; after the reaction is continuously operated for 800h, the reaction product is detected and analyzed to test the stability of the catalyst, and the test result after 800h is shown in Table 3.
Table 2: multifunctional MgaZrbZncSidEvaluation of catalytic performance of O composite oxide catalyst in preparation of propenol
| Catalyst and process for preparing same | Ethanol conversion (%) | Propenol selectivity (%) |
| CAT-1 | 23 | 86 |
| CAT-2 | 25 | 85 |
| CAT-3 | 22 | 85 |
| CAT-4 | 26 | 90 |
| CAT-5 | 22 | 87 |
| CAT-6 | 19 | 85 |
| CAT-7 | 18 | 87 |
As can be seen from the data in Table 2, the multifunctional Mg according to the present inventionaZrbZncSidThe initial reaction activity of the O composite oxide catalyst is not much different from that of the composite oxide catalyst without Si, so that the high selectivity of the allyl alcohol can be realized, and the conversion rate of the ethanol is slightly improved.
Table 3: multifunctional MgaZrbZncSidPerformance evaluation of O composite oxide catalyst after 800h reaction
| Catalyst and process for preparing same | Ethanol conversion (%) | Propenol selectivity (%) |
| CAT-1 | 22 | 85 |
| CAT-2 | 26 | 85 |
| CAT-3 | 21 | 86 |
| CAT-4 | 25 | 89 |
| CAT-5 | 21 | 87 |
| CAT-6 | 4 | 30 |
| CAT-7 | 4 | 32 |
However, as can be seen from the data in Table 3, the multifunctional Mg according to the present inventionaZrbZncSidAfter the continuous operation of the O composite oxide catalyst for 800 hours, the selectivity of propylene alcohol and the conversion rate of ethanol are not greatly different from the initial reaction activity. However, after the composite oxide catalyst without Si is continuously operated for 800 hours, the selectivity of the allyl alcohol and the conversion rate of the ethanol are obviously reduced. Thus the multifunctional Mg prepared according to the inventionaZrbZncSidThe O composite oxide catalyst has more excellent long-term use stability.
The above examples do not limit the present invention in any way, and although the examples of the present invention only disclose the application of the mixture of methanol and ethanol in the catalytic conversion of the mixture to prepare the propenol compound, the application of the prepared catalyst in the catalysis of lower alcohol or the mixture of methanol and lower alcohol in the preparation of the enol compound is not limited by the examples. Any person skilled in the art can also realize the equivalent embodiments by changing the technical details without departing from the scope of the invention.
Claims (10)
1. Multifunctional MgaZrbZncSidOeThe composite metal oxide catalyst comprises a, b, c and d which are molar ratios of active components Mg, Zr, Zn and Si respectively, and e which is a stoichiometric ratio of O atoms, wherein the ratio of Mg, Zr, Zn and Si is 0.1-10: 0.01-1, preferably 0.1-10: 0.1-1: 0.01-0.1: 0.1-1, and more preferably 1-10: 0.1-1: 0.01-0.1: 0.1-1.
2. Mg of claim 1aZrbZncSidOeA method for preparing a composite metal oxide catalyst, the method comprising the steps of:
(1) adding metal salt, metal oxide or metal hydroxide containing metal active components Mg, Zr and Zn into a solvent for dissolving and/or dispersing, and stirring for fully mixing, wherein the total concentration of the metal precursor mixed solution is 1-3 mol.L-1And heating and refluxing;
(2) adding a compound containing Si into the mixed solution obtained in the step (1), continuously stirring until the mixture is fully mixed, and heating and refluxing;
(3) removing the solvent from the mixed solution obtained in the step (2) by rotary evaporation, drying and roasting at high temperature to obtain the multicomponent MgaZrbZncSidOeA composite metal oxide catalyst.
3. The production method according to claim 2, wherein the active ingredient metal salt in the step (1) is at least one selected from the group consisting of nitrate, carbonate, bicarbonate, chloride, acetate, sulfate, and lower metal alkoxide; wherein the lower metal alkoxide represents an alkoxy organometallic compound formed by substituting a hydroxyl hydrogen of an alcohol molecule with a metal, and the alcohol is at least one of ethanol, propanol or butanol.
4. The method according to claim 2, wherein the metal oxide or metal hydroxide in step (1) is a commercial product and is used without any pretreatment.
5. The production method according to claim 2, wherein the solvent in step (1) is water, or a mixed solvent of water and a unit lower alcohol selected from at least one of methanol, ethanol, propanol and butanol, preferably at least one selected from methanol, ethanol and propanol; the volume percentage of the unit lower alcohol in the composite solvent is 1-50%, and preferably 20-50%.
6. The preparation method according to claim 2, wherein the heating reflux temperature of the active component mixed solution in the step (1) is 50 to 90 ℃, and the reflux time is not less than 2 hours; more preferably, the heating reflux time in the step (1) is 2 to 8 hours.
7. The method according to claim 2, wherein the Si-containing compound in step (2) is selected from silica powder or an organosilicon monomer;
further preferably, the Si-containing compound in step (2) is selected from tetraethyl orthosilicate and tetrabutyl orthosilicate;
further preferably, the Si-containing compound in step (2) is silica powder having a particle size of 10 to 100 micrometers;
further preferably, when the Si-containing compound in step (2) is an organosilicon monomer selected from tetraethyl orthosilicate and tetrabutyl orthosilicate, the Si-containing compound is added to the mixed solution in step (1) in a gradually dropwise manner;
preferably, when the Si-containing compound in step (2) is silica powder, the silica powder is added to the mixed solution in step (1) in a batch manner.
8. The preparation method according to claim 2, wherein the temperature of the solvent removed by rotary evaporation in the step (3) is 50-90 ℃, the drying temperature is 100-150 ℃, and the drying time is 4-12 hours, preferably 6-10 hours; the roasting temperature is 400-800 ℃, and the roasting time is 1-12 hours, preferably 2-8 hours.
9. Mg of claim 1aZrbZncSidOeUse of a composite metal oxide catalyst in the preparation of an enol compound, the enol compound comprising: at least one of allyl alcohol, crotyl alcohol, isobutenol, 2-ethyl-allyl alcohol, 2-propyl-allyl alcohol and 2-butyl-allyl alcohol.
10. A process for the direct preparation of an enol compound from monoalcohols, said process employing a fixed bed reactor charged with Mg according to claim 1aZrbZncSidOeThe composite metal oxide catalyst is loaded with one or more unit lower alcohols through nitrogen to react to prepare an enol compound, wherein the using amount of the catalyst is 0.1-10 g, and the sample injection rate is 0.1-5 mL.h-1The temperature is 150-350 ℃, and the pressure is 0.1-2 MPa;
preferably, the mono-lower alcohols include: methanol, ethanol, propanol, butanol, pentanol, hexanol, phenethyl alcohol, phenylpropyl alcohol, etc., preferably methanol, ethanol, propanol, butanol, pentanol, hexanol;
preferably, when the unit lower alcohol is a mixed solution of methanol and other unit lower alcohols, the mass percentage of the other unit lower alcohols is 1-50%, and more preferably, the mass percentage of the other unit lower alcohols is 2-20%.
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| CN112958074A (en) * | 2021-02-04 | 2021-06-15 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing 3-hydroxypropionaldehyde and preparation method and application thereof |
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