CN110526800B - Preparation method of isobutenol - Google Patents
Preparation method of isobutenol Download PDFInfo
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- CN110526800B CN110526800B CN201910971254.0A CN201910971254A CN110526800B CN 110526800 B CN110526800 B CN 110526800B CN 201910971254 A CN201910971254 A CN 201910971254A CN 110526800 B CN110526800 B CN 110526800B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—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 without formation of -OH groups
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Abstract
The invention discloses a method for preparing isobutenol from methanol and propanol, which adopts multicomponent MgaZrbZncSidOeThe composite metal oxide catalyst and formaldehyde are used as initiators to synthesize the isobutenol efficiently. The method for preparing the isobutenol can greatly improve the conversion rate of the propanol and the selectivity of the isobutenol. In the whole reaction process, the selectivity of the isobutylene alcohol is over 90 percent, and the single pass conversion rate of the n-propanol is more than 30 percent. The preparation process of the isobutenol is more environment-friendly, saves the cost and has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing isobutenol from methanol and propanol.
Background
Isobutenol, also known as 2-methallyl alcohol, is a colorless transparent liquid, boiling point: 114.5 ℃, can participate in a series of chemical reactions due to the specificity of enol structure, is widely applied to the fields of medicines, pesticides, spices, resins and the like, and is an important fine chemical raw material and an organic synthesis intermediate. Wherein, 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 reducer.
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 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 producing methacrylol is urgent. In the 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 generating the isobutenol by taking methanol and n-propanol as raw materials.
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 longer applications, for example, up to 400 hours or more, catalyst deactivation becomes more pronounced, which is manifested by a reduction in the conversion of the starting material and a reduction in the allyl alcohol selectivity. Meanwhile, the utilization rate of the reaction raw materials is not high.
Therefore, the invention adds Si source into the original Mg-Zr-Zn composite metal oxide catalyst to form multifunctional Si-MgxZryZnzThe O composite metal oxide catalyst adopts formaldehyde as an initiator, realizes the preparation of the isobutenol from the methanol and the propanol with high conversion rate, and improves the utilization rate of raw materials and the production efficiency. The novel Si-MgxZryZnzThe O composite metal oxide catalyst is additionally filed at the same time.
Disclosure of Invention
In view of the problems presented in the aforementioned invention patent (CN107398264A), an object of the present application is to provide a process for producing methacrolein from methanol and propanol, which process efficiently synthesizes methacrolein using a multicomponent Si-Mg-Zr-Zn composite metal oxide catalyst and formaldehyde as an initiator, said process comprising the steps of: charging of Mg in a fixed bed reactoraZrbZncSidOeThe composite metal oxide catalyst has pre-prepared reaction liquid containing AThe methanol and propanol solutions of aldehyde are carried into the mixed solution for reaction by taking nitrogen as a carrier gas. Wherein the volume airspeed of the sample injection is 0.1-1 h-1The temperature is 150-350 ℃, and the pressure is 0.1-2 MPa.
Adding propanol and formaldehyde with specific mass fractions into a methanol solution, uniformly mixing, preparing a reaction solution, and conveying the reaction solution into a fixed bed reactor by using a sample injection pump.
Preferably, the reaction temperature is 230-270 ℃.
Preferably, the methanol serves as a reaction raw material and also as a solvent.
Preferably, the mass percentage of the propanol is 2-20%, preferably 5-15%, based on the mass of the total reaction solution.
Preferably, the mass percentage of the initiator formaldehyde is 0.1-10%, preferably 0.1-5%, based on the mass of the total reaction liquid.
Preferably, the formaldehyde may be selected from aqueous formaldehyde, trioxymethylene or paraformaldehyde.
Preferably, said MgaZrbZncSidOeIn the composite metal 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.
The MgaZrbZncSidOeThe composite metal oxide catalyst is obtained according to the following preparation method, which comprises the following steps:
(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 lower alcohol in the mixed solvent is 1-50%, 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 said MgaZrbZncSidOeUse of a composite metal oxide catalyst in a process for the preparation of isobutenol from methanol and propanol.
Advantageous effects
The invention adopts novel MgaZrbZncSidOeThe composite metal oxide catalyst adopts formaldehyde as an initiator, so that the conversion rate of the propanol is greatly improved, and the selectivity of the isobutenol is stably improved. In the whole reaction process, the selectivity of the isobutylene alcohol is over 90 percent, and the single pass conversion rate of the n-propanol is more than 30 percent. The preparation process of the isobutenol is more environment-friendly, saves the cost and has good industrial application prospect.
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 to form the catalystThe work improves the long-term use stability of the catalyst. The inventor of the invention finds that when three metals Mg-Zr-Zn and Si are adopted as the active components of the catalyst in a specific ratio, the catalyst can greatly improve the long-term use stability of the catalyst while realizing the conversion of methanol and ethanol into propenol with high selectivity. 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 step (1), and heating and refluxing are carried out, so that the precursors of the three elements are fully mixed. Then the 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.
On the other hand, the preparation method provided by the invention adopts formaldehyde as an initiator, so that the utilization rate of the propanol can be obviously improved. The dehydrogenation step of methanol and propanol in the reaction feed is the initial step of the overall catalytic reaction process, wherein the dehydrogenation activation energy for converting methanol to formaldehyde is 84kJ/mol and the dehydrogenation activation energy for converting propanol to propionaldehyde is 45 kJ/mol. In a reaction system without a formaldehyde auxiliary agent, methanol is required to be dehydrogenated firstly to generate formaldehyde, and then subsequent reaction is carried out; in the reaction system containing formaldehyde, a large amount of methanol is not needed for dehydrogenation, so that more active sites are provided for propanol dehydrogenation, and the reaction rate is greatly accelerated.
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.
Preparation example 1: mg (magnesium)aZrbZncSidOePreparation of composite metal oxide catalyst
(1) 10.24g of Mg (NO)3)2·6H2O，2.41g ZrO(NO3)2And 0.2g Zn (NO)3)2·6H2Dissolving O in water to obtain a metal precursor mixed solution with a total concentration of 5 mol.L-1And heating and refluxing;
(2) adding 0.03mol (SiO) of ethyl orthosilicate into the mixed solution obtained in the step (1)2Meter), stirring continuously until fully mixed, and heating to reflux at 70 ℃ for 5 hours;
(3) removing the solvent from the mixed solution obtained in the step (2) by rotary evaporation, drying, and then roasting at the high temperature of 550 ℃ for 5 hours to obtain multi-component MgaZrbZncSidOeA composite metal oxide catalyst.
Example 1
Preparing a reaction solution: adding propanol into a proper amount of methanol liquid, uniformly mixing to form a reaction liquid, and sealing for later use, wherein the mass percentage of the propanol is 10% based on the mass of the total reaction liquid.
2.0g of Mg obtained in production example 1aZrbZncSidOeThe composite metal oxide catalyst was loaded into a fixed bed reaction tube, and the formaldehyde-free mixture of methanol and propanol was fed into the reaction tube using nitrogen as a carrier gas, while the temperature in the reactor was controlled at 230 ℃, the reaction pressure at 1.0MPa, and the sample injection rate at 0.02mL/min, and after the temperature and pressure in the reaction tube were stabilized, samples were taken at intervals of 4 hours, and the conversion of propanol and the yield of isobutenol were shown in table 1 by gas chromatography analysis.
Example 2
Preparing a reaction solution: adding propanol into a proper amount of methanol solution, then adding formaldehyde, uniformly mixing, and sealing for later use, wherein the mass percent of the propanol is 10% and the mass percent of the formaldehyde is 5 wt% based on the mass of the total reaction solution.
2.0g of Mg obtained in production example 1aZrbZncSidOeThe composite metal oxide catalyst was loaded into a fixed bed reaction tube, and a mixture of 5 wt% formaldehyde in methyl propanol was introduced into the reaction tube using nitrogen as a carrier gas, the temperature in the reactor was controlled at 230 ℃, the reaction pressure was 1.0MPa, the sample introduction rate was 0.02mL/min, samples were taken every 4 hours after the temperature and pressure in the reaction tube were stabilized, and the conversion of propanol and the yield of isobutenol were shown in table 1 by gas chromatography.
Example 3
Preparing a reaction solution: adding propanol into a proper amount of methanol solution, then adding trioxymethylene, mixing uniformly, and sealing for later use, wherein the mass percent of the propanol is 10% and the mass percent of the trioxymethylene is 3 wt% based on the mass of the total reaction solution.
The reaction conditions and procedure were the same as in example 2. The conversion of propanol and yield of isobutenol are shown in Table 1.
TABLE 1 Effect of Formaldehyde adjuvant in the reaction feed
| Serial number | Reaction solution | Conversion rate of propanol% | (ii) isobutylene alcohol Selectivity% |
| Example 1 | Methanol and propanol | 16.5 | 80.4 |
| Example 2 | 5% Formaldehyde-methanol and propanol | 55 | 98 |
| Example 3 | 3% trioxymethylene-methanol and propanol | 58 | 96 |
As can be seen from the data in Table 1, neither the conversion of propanol nor the selectivity to iso-butenol is ideal in the absence of formaldehyde as initiator. When a small amount of formaldehyde is used, the conversion rate of propanol can be increased by about 3.5 times, and the selectivity of the isobutylene can also reach more than 96%.
Examples 4 to 6
The test was carried out in the same manner as in example 2 except that the reaction temperature was changed. The propylene alcohol conversion and the isobutylene alcohol yield by gas chromatography are shown in Table 2.
TABLE 2 Effect of reaction temperature
| Serial number | Reaction temperature/. degree.C | Conversion rate of propanol% | (ii) isobutylene alcohol Selectivity% |
| Example 4 | 230 | 55 | 98 |
| Example 5 | 250 | 67 | 86 |
| Example 6 | 270 | 88 | 69 |
As can be seen from the data in Table 2, increasing the reaction temperature favors the increase in the conversion of propylene alcohol, but too high a reaction temperature causes other side reactions to progress and the selectivity to isobutylene alcohol to decrease.
Examples 7 to 9
The test was carried out in the same manner as in example 2 except that the reaction pressure was varied. The propylene alcohol conversion and the isobutylene alcohol selectivity by gas chromatography are shown in Table 3.
TABLE 3 Effect of reaction pressure
| Serial number | Reaction pressure/MPa | Conversion rate of propanol% | (ii) isobutylene alcohol Selectivity% |
| Example 7 | 0.1 | 31 | 97 |
| Example 8 | 0.5 | 38 | 96 |
| Example 9 | 1.0 | 55 | 98 |
As can be seen from the data in Table 3, the increase in reaction pressure is helpful in increasing the conversion of propylene alcohol, but has little influence on the selectivity for isobutylene alcohol, so that the pressure in the process for producing isobutylene alcohol according to the present invention is 0.1 to 2 MPa.
The above examples do not limit the present invention in any way, and although the examples of the present invention disclose only the application of the methanol-n-propanol mixture and the methanol-n-butanol mixture in the preparation of the enolate compound by catalytic conversion, the application of the prepared catalyst in the preparation of the enolate compound by catalyzing lower alcohol or methanol and lower alcohol 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 (16)
1. A process for preparing isobutenol from methanol and propanol features use of multicomponent Si-Mg-Zr-Zn composite metal oxide catalyst and formaldehyde as catalystAn initiator, the method comprising the steps of: charging of Mg in a fixed bed reactoraZrbZncSidOeThe composite metal oxide catalyst comprises a reaction solution, a nitrogen gas and a mixed solution, wherein the reaction solution is a methanol and propanol solution which is prepared in advance and contains formaldehyde, the nitrogen gas is used as a carrier gas, and the mixed solution is loaded for reaction, wherein the volume space velocity of sample injection is 0.1-1 h-1The temperature is 230 to 270 DEG CoC, the pressure is 0.5-2 MPa; the reaction liquid is conveyed into the fixed bed reactor through a sample injection pump, and the methanol is used as a reaction raw material and a solvent.
2. The method of claim 1, wherein the reaction temperature is 230 to 270%oC; based on the mass of the total reaction liquid, the mass percentage of the propanol is 2-20%.
3. The method according to claim 2, wherein the mass percentage of the propanol is 5-15% based on the mass of the total reaction solution.
4. The method according to claim 1, wherein the mass percentage of the initiator formaldehyde is 0.1-10% based on the mass of the total reaction solution; the formaldehyde is selected from aqueous formaldehyde solution, trioxymethylene or paraformaldehyde.
5. The method according to claim 4, wherein the mass percentage of the initiator formaldehyde is 0.1-5% based on the mass of the total reaction solution.
6. The method of claim 1, wherein the Mg is presentaZrbZncSidOeIn the composite metal 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 Mg, Zr, Zn and Si = 0.1-10: 0.01-1;
the MgaZrbZncSidOeThe composite metal oxide catalyst is obtained according to the following preparation method, which comprises the following steps:
(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.
7. The method of claim 6, wherein the MgaZrbZncSidOeIn the composite metal oxide catalyst, the ratio of Mg, Zr, Zn and Si is 0.1-10: 0.1-1: 0.01-0.1: 0.1-1.
8. The method of claim 7, wherein said MgaZrbZncSidOeIn the composite metal oxide catalyst, the ratio of Mg, Zr, Zn and Si is 1-10: 0.1-1: 0.01-0.1: 0.1-1.
9. The method of claim 6, wherein said Mg is present in a bath of MgaZrbZncSidOeIn the preparation method of the composite metal oxide catalyst, in the step (1), the active component metal salt is selected from at least one of nitrate, carbonate, bicarbonate, chloride, acetate, sulfate and lower metal alkoxide, wherein the lower metal alkoxide represents an alkoxy organic metal compound generated by replacing hydroxyl hydrogen of an alcohol molecule with metal, and the alcohol can be at least one of ethanol, propanol or butanol;
the metal oxide and the metal hydroxide in the step (1) can be commercial products, and can be directly used without any pretreatment;
the solvent in the step (1) is water or a mixed solvent of water and unit lower alcohol, the unit lower alcohol is at least one selected from methanol, ethanol, propanol and butanol, and the volume percentage of the unit lower alcohol in the mixed solvent is 1-50%;
the heating reflux temperature of the active component mixed liquid in the step (1) is 50-90 DEGoC, refluxing for not less than 2 hours.
10. The method according to claim 9, wherein the unit lower alcohol in step (1) is at least one selected from the group consisting of methanol, ethanol and propanol, and the volume percentage of the unit lower alcohol in the mixed solvent is 20 to 50%.
11. The method according to claim 9, wherein the heating reflux time in step (1) is 2 to 8 hours.
12. The method according to claim 6, wherein the Si-containing compound in step (2) is selected from silica powder or an organosilicon monomer, and when the Si-containing compound is silica powder, the silica powder is added to the mixed solution in step (1) in a batch manner.
13. The method according to claim 12, wherein the Si-containing compound in step (2) is a silica powder having a particle size of 10 to 100 μm.
14. The method of claim 6 wherein in step (2) the Si-containing compound is selected from the group consisting of tetraethyl orthosilicate and tetrabutyl orthosilicate; and (2) when the Si-containing compound is an organosilicon monomer selected from tetraethyl orthosilicate and tetrabutyl orthosilicate, adding the Si-containing compound into the mixed solution obtained in the step (1) in a gradually dropwise manner.
15. The method according to claim 6, wherein the temperature of the solvent spin-off in the step (3) is 50 to 90 ℃oC, the drying temperature is 100-150 DEG CoC, drying for 4-12 hours; the roasting temperature is 400-800 DEG CoAnd C, roasting for 1-12 hours.
16. The method according to claim 15, wherein the drying time in the step (3) is 6 to 10 hours; the roasting time is 2-8 hours.
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| CN103288594A (en) * | 2013-06-04 | 2013-09-11 | 临海市联盛化学有限公司 | Method for preparing methanol and ethanol by methyl acetate by way of hydrogenation |
| CN107398264A (en) * | 2017-08-21 | 2017-11-28 | 中国科学院青岛生物能源与过程研究所 | A kind of Mg Zr Zn O composite metallic oxide catalysts and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288594A (en) * | 2013-06-04 | 2013-09-11 | 临海市联盛化学有限公司 | Method for preparing methanol and ethanol by methyl acetate by way of hydrogenation |
| CN107398264A (en) * | 2017-08-21 | 2017-11-28 | 中国科学院青岛生物能源与过程研究所 | A kind of Mg Zr Zn O composite metallic oxide catalysts and its preparation method and application |
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