CN116651498A - Supported catalyst and method for producing 2-methallyl alcohol by catalysis of supported catalyst - Google Patents
Supported catalyst and method for producing 2-methallyl alcohol by catalysis of supported catalyst Download PDFInfo
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Abstract
The application provides a supported catalyst and a method for producing 2-methylallyl alcohol by catalysis thereof, wherein the supported catalyst is formed by loading aluminum alkoxide on a zeolite molecular sieve, and the loading amount of the aluminum alkoxide on the zeolite molecular sieve is 20% of the mass of the zeolite molecular sieve. The method for producing 2-methylallyl alcohol by using the supported catalyst comprises the following steps: the methacrolein is subjected to a reduction reaction in a solvent by using the supported catalyst. The catalyst is used for catalyzing and producing 2-methallyl alcohol, the consumption is low, the effect is good, the method for producing 2-methallyl alcohol can directly take the absorption liquid of the tail gas of the first step reaction in the process of preparing methallyl alcohol by oxidizing and hydrogenating isobutene as the raw material, and the normal-pressure hydrogenation reduction reaction is directly carried out, so that the absorption liquid of the tail gas of the reaction is not required to be rectified, the equipment and operation cost is reduced, and the safety is improved. In addition, the adopted catalyst can be directly separated, recycled and reused, so that the production cost is greatly reduced.
Description
Technical Field
The application belongs to the technical field of organic product production, and particularly relates to a supported catalyst and a method for producing 2-methallyl alcohol by catalysis.
Background
2-methylallyl alcohol (methylallyl alcohol) is a pungent colorless liquid unsaturated alcohol, an important organic intermediate, and is mainly applied to the fields of medicines, fragrances, polymers and the like, and is mainly used for mass production of methylallyl alcohol polyoxyethylene ether in China at present.
The methallyl alcohol synthesis process is divided into a chlor-alkali method and a hydrogen transfer method: the former reaction system contains various chloride byproducts, needs to be subjected to absorption post-treatment, needs to use a large amount of alkali in production, further generates a large amount of wastewater containing salt and chloride, and has the advantages that the reaction is carried out at a higher temperature, and the yield of the product methyl propenol is lower; the latter are disclosed in patents CN102167657, CN103739445, etc., mainly by H 2 The reaction requires higher pressure for reducing agent, has strict requirements on operation conditions and equipment, and is easy to leak hydrogen to cause safety accidents, and in addition, the MAC double bond is easy to hydrogenate to produce isobutanol, so the selectivity of the product is lower.
There is a relatively high-grade method for reducing methacrolein to methallyl alcohol by hydrogen transfer reduction (MPV) reaction using an alcohol reducing agent, wherein H is not directly used 2 Mild reaction and comparative operationThe two methods are simple, the requirements on instruments and equipment are low, and the possible dangers of using hydrogen are reduced. However, the method still has some problems that cannot be overcome temporarily at present, such as relatively complex production process, more steps, and the intermediate methacrolein is obtained by rectifying the isobutylene oxidized tail gas after being absorbed, and finally the methacrolein is sent to the reduction reaction part, so that the methacrolein is more lost in the process, and the reduction catalyst used later has large use amount and is difficult to recover, so that the production cost is higher.
Disclosure of Invention
Aiming at the problems of low selectivity, complex production process, incapability of recovering a catalyst, high cost and the like in the existing methallyl alcohol synthesis, the application provides a supported catalyst and a method for producing 2-methallyl alcohol by using the supported catalyst in a catalytic manner, the catalyst is low in use amount and good in effect, and the method for producing 2-methallyl alcohol can directly take an absorption liquid of a first-step reaction tail gas in the process of preparing methallyl alcohol by oxidizing and hydrogenating isobutene as a raw material to directly carry out normal-pressure hydrogenation reduction reaction without rectifying the absorption liquid of the reaction tail gas, thereby reducing equipment and operation cost and improving safety. In addition, the adopted catalyst can be directly separated, recycled and reused, so that the production cost is greatly reduced. The technical scheme of the application is as follows:
in a first aspect, the present application provides a supported catalyst, which is formed by loading aluminum alkoxide on a zeolite molecular sieve, wherein the loading amount of the aluminum alkoxide on the zeolite molecular sieve is 20% of the mass of the zeolite molecular sieve.
Further, the aluminum alkoxides include, but are not limited to, aluminum ethoxide, aluminum propoxide, aluminum isopropoxide, aluminum isobutanol, aluminum diisopropoxide, and the like.
Preferably, the aluminum alkoxide is aluminum isopropoxide.
Further, the zeolite molecular sieve is one or more of MCM, SBA, FSM, HMS, MSU with mesoporous structure.
Preferably, the zeolite molecular sieve is MCM.
Further, the preparation method of the supported catalyst comprises the following steps: dissolving aluminum alkoxide in a solvent, adding a zeolite molecular sieve into the aluminum alkoxide solution, stirring and adsorbing for a period of time, and then drying to remove the solvent to obtain the catalyst.
In a second aspect, the present application provides a method for producing 2-methallyl alcohol by using the supported catalyst, comprising: and (3) carrying out catalytic reduction reaction on the methacrolein by adopting the supported catalyst to obtain 2-methylallyl alcohol.
Further, a polymerization inhibitor is also added into the reduction reaction system.
Further, the method for producing 2-methylallyl alcohol by catalysis specifically comprises the following steps:
step 1, adding a polymerization inhibitor into the dehydrated methacrolein absorption liquid, and uniformly mixing;
step 2, adding the supported catalyst and further uniformly mixing;
step 3, carrying out reduction reaction after the temperature is raised to a certain level, filtering out the supported catalyst after the reaction is finished, and retaining filtrate;
step 4, recycling the filtered supported catalyst and applying the catalyst to the step 3; vacuum distilling the filtrate to obtain a fraction which is a crude 2-methallyl alcohol product, and refining the crude 2-methallyl alcohol product; the residual liquid of the reduced pressure distillation and the methacrolein absorption liquid are mixed and dehydrated, and then returned to step 1 as a starting material.
Further, the methacrolein absorption liquid is: and (3) primarily condensing tail gas from the first step of reaction in the process of preparing methallyl alcohol by oxidizing and hydrogenating isobutene, and then sending the tail gas into an absorption tower, wherein an absorption solvent is at least one of phenoxyethanol, cyclopentanol and isooctyl alcohol, and a mixed solution of the condensed tail gas and the absorption solvent is the methacrolein absorption liquid.
Preferably, the absorption solvent is cyclopentanol and phenoxyethanol with a volume ratio of 2: 3.
Further, a dehydrating agent adopted in the dehydration of the methacrolein absorption liquid is CaCl 2 One of anhydrous magnesium sulfate, 3A molecular sieve and 4A molecular sieve, preferably 4A molecular sieve.
Because a large amount of water is generated in the industrial reaction for preparing the methacrolein by oxidizing isobutene, reaction tail gas needs to be initially condensed, most of water and other byproducts are removed, and then the reaction tail gas is sent into an aldehyde absorption tower, and the absorption liquid still contains a small amount of water, so that the methacrolein absorption liquid obtained by the method needs to be dehydrated when being used in the scheme.
Further, the polymerization inhibitor is one or a mixture of more of p-benzoquinone, tetramethyl nitroxide free radical piperidinol, hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, p-tert-butyl catechol and phenothiazine, and the use amount of the polymerization inhibitor accounts for 0.01-0.2% of the mass of the methacrolein absorption liquid.
Preferably, the polymerization inhibitor is mixed by phenothiazine, hydroquinone and tetramethyl nitroxide free radical piperidinol according to the mol ratio of 2.5:1:1, and the dosage of the polymerization inhibitor is 0.1-0.15% of the mass of the methacrolein absorption liquid.
Further, the supported catalyst accounts for 20-30% of the mass of the methacrolein absorption liquid.
Preferably, the supported catalyst accounts for 20-25% of the mass of the methacrolein absorption liquid.
Further, the reduction reaction conditions in the step 3 are as follows: the reaction temperature is 50-100 ℃ at normal pressure, and the reaction time is 3-15h.
Preferably, the reduction reaction conditions in the step 3 are as follows: the reaction temperature is 70-80 ℃ at normal pressure, and the reaction time is 5-10h.
Further, in the step 4, the filtered supported catalyst is subjected to recovery treatment, which includes: washing the filtered supported catalyst for 2-5 times by adopting isooctanol, drying for 3-4 hours at 200 ℃, and then roasting for 2-3 hours at 400-500 ℃.
Further, the reduced pressure distillation temperature is controlled below 60 ℃ and the vacuum degree is-0.05 MPa.
Further, the methacrolein absorption liquid is replaced by a mixed liquid of methacrolein and at least one alcohol of phenoxyethanol, cyclopentanol and isooctanol.
The application has the following advantages:
1. the catalyst of the application is formed by combining organic aluminum alkoxide with zeolite molecular sieve, can directly take alcohol with higher boiling point in methacrolein absorption liquid as hydrogen source to reduce aldehyde into alcohol, can be directly separated, has simple treatment process, can be recycled and reused, and greatly reduces the production cost.
2. The method can remove most of byproducts such as water, methacrylic acid, acetic acid and the like from the tail gas of the first step of reaction in the process of preparing methallyl alcohol by hydrogenating isobutene through preliminary condensation, and then send the byproducts into an absorption tower, wherein an absorption solvent is alcohol with a high boiling point, and the obtained absorption liquid is used as a raw material to carry out hydrogenation reduction reaction to produce 2-methallyl alcohol, so that waste is changed into valuables. Compared with the recovery process of directly absorbing the tail gas of the first step in the original process of preparing the methallyl alcohol by oxidizing and hydrogenating the isobutene and then obtaining the methallyl aldehyde by rectification, the absorption process is closely connected with the reduction process, so that the middle primary rectification process is reduced, the loss of the methallyl aldehyde is reduced, the production cost is greatly saved, the recovery efficiency is higher, and the environmental protection added value is higher.
Detailed Description
The methacrolein absorption liquid adopted in the embodiment of the application is as follows: the tail gas of the first step of reaction in the process of preparing methylallyl alcohol by hydrogenating isobutene is subjected to preliminary condensation and then is sent into an absorption tower, wherein the absorption solvent is cyclopentanol and phenoxyethanol according to the volume ratio of 2:3, mixing, condensing the mixed solution of tail gas and absorption solvent. The absorption liquid is used as a raw material for producing 2-methylallyl alcohol by catalysis, and aims to provide a way for changing waste into valuables for reaction tail gas of preparing methylallyl alcohol by oxidizing and hydrogenating isobutene, and the raw material is not limited to the methacrolein absorption liquid, and pure methacrolein or other raw materials containing methacrolein can be used in the application.
The methacrolein absorption liquid adopted in the embodiment of the application is dehydrated through a 4A molecular sieve before being used.
The polymerization inhibitor adopted in the embodiment of the application is formed by mixing phenothiazine, hydroquinone and tetramethyl nitroxide free radical piperidinol according to the molar ratio of 2.5:1:1.
In the description of the present application, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The present application will be described in further detail with reference to the following specific embodiments, so as to assist those skilled in the art in a more complete, accurate and thorough understanding of the inventive concept and technical solution of the present application, and the scope of the present application includes, but is not limited to, the following examples, any modifications made in the details and form of the technical solution of the present application falling within the scope of the present application without departing from the spirit and scope of the present application.
The conversion in the following examples is measured by gas chromatography for the 2-methallyl alcohol content in the crude 2-methallyl alcohol by a conventional internal standard method, the internal standard being ethylene glycol. The 2-methallyl alcohol content (product selectivity) was calculated by calculating the molar amount of methacrolein involved in the reaction (the molar amount of methacrolein varies before and after the reaction).
In the following examples, except for examples 7 and 9, cyclopentanol and phenoxyethanol were used in a volume ratio of 2:3 mixing.
Example 1
The embodiment provides a preparation method of a supported catalyst, which comprises the following steps:
6.0g of aluminum isopropoxide is dissolved in 120mL of ethanol, 30.0g of MCM-41 molecular sieve is added, and stirring is carried out for 60min, so that the aluminum isopropoxide is fully adsorbed on the surface of the molecular sieve and in the pore canal, and the mixture is dried at 50 ℃ for 5h to obtain white powdery solid which is marked as Cat-1.
Cat-1 is used for catalyzing and producing 2-methylallyl alcohol, and the method specifically comprises the following steps:
firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 50.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, stirring is uniform, 0.096g of polymerization inhibitor combination is added, 18.75g of catalyst Cat-1 is added, stirring and heating are carried out to 75 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1..
Example 2
The embodiment provides a preparation method of a supported catalyst, which comprises the following steps:
6.0g of aluminum isopropoxide is dissolved in 120mL of ethanol, 30g of SBA molecular sieve is added, and stirring is carried out for 60min, so that the aluminum isopropoxide is fully adsorbed on the surface of the molecular sieve and in the pore canal, and the mixture is dried for 3h at 50 ℃ to obtain white powdery solid which is marked as Cat-2.
Cat-2 was used for the catalytic production of 2-methallyl alcohol, differing from example 1 in that: using 80g of the dehydrated methacrolein absorption liquid, the mass content of methacrolein was about 37%, and the other procedures were the same as in example 1. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then stored (for later application).
The second catalytic production of 2-methallyl alcohol (using the same batch of methacrolein absorbing solution) was performed under the same conditions.
The reaction results of this example are shown in Table 1.
Example 3
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
Firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 30.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, stirring is uniform, 0.072g of polymerization inhibitor combination is added, 18.75g of catalyst Cat-1 is added, stirring and heating are carried out, the temperature is raised to 75 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1..
Example 4
The embodiment provides a preparation method of a supported catalyst, which comprises the following steps:
6.0g of aluminum isopropoxide is dissolved in 60mL of ethanol, 30.0g of MCM-41 molecular sieve is added, and stirring is carried out for 60min, so that the aluminum isopropoxide is fully adsorbed on the surface of the molecular sieve and in the pore canal, and the mixture is dried at 50 ℃ for 5h to obtain white powdery solid which is marked as Cat-3.
Cat-3 was used for the catalytic production of 2-methallyl alcohol, differing from example 1 in that: using 80g of the dehydrated methacrolein absorption liquid, the mass content of methacrolein was about 37%, and the other procedures were the same as in example 1.. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then stored (for later application).
The second catalytic production of 2-methallyl alcohol (using the same batch of methacrolein absorbing solution) was performed under the same conditions.
The reaction results of this example are shown in Table 1.
Example 5
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
Firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 50.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, stirring is uniform, 0.096g of polymerization inhibitor combination is added, 18.75g of catalyst Cat-1 is added, stirring and heating are carried out to 65 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
Example 6
The embodiment provides a method for producing 2-methylallyl alcohol by aluminum isopropoxide catalysis, which comprises the following steps:
firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 50.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, the mixture is stirred uniformly, 0.096g of polymerization inhibitor combination is added, 3.75g of catalyst aluminum isopropoxide is added, the mixture is stirred and heated to 75 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
Example 7
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
50 phenoxyethanol and 30g of methacrolein were placed in a 250ml four-necked flask, and the other steps were the same as in example 1, and the mixture was stirred and heated to 75℃to conduct a reflux reaction for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly phenoxyethanol) of reduced pressure distillation is dehydrated, phenoxyethanol is added until the mass is 50g, the reaction is returned to the process as a starting material, and the second catalytic production of 2-methylallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
Example 8
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
Firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 50.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, the mixture is stirred uniformly, 0.096g of polymerization inhibitor combination is added, 18.75g of catalyst Cat-1 is added, the mixture is stirred and heated to 85 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
Example 9
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
Firstly, raw materials of methacrolein and cyclopentanol are dehydrated by a 4A molecular sieve, 50.0g of cyclopentanol is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, the mixture is stirred uniformly, 0.096g of polymerization inhibitor combination is added, 18.75g of catalyst Cat-1 is added, the mixture is stirred and heated to 75 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentanol) of reduced pressure distillation is dehydrated, cyclopentanol is added to the mass of 50g, the reaction is returned to the process as a starting material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
Example 10
The present example provides a method for producing 2-methallyl alcohol using supported catalyst, comprising the steps of:
the catalyst preparation was the same as in example 1.
Firstly, raw materials of methacrolein, cyclopentanol and phenoxyethanol are subjected to 4A molecular sieve dehydration treatment, 50.0g of phenoxyethanol and cyclopentanol mixed solution is placed in a 250ml four-neck flask, 30.0g of methacrolein is added, stirring is uniform, 0.096g of polymerization inhibitor combination is added, 16.00g of catalyst Cat-1 is added, stirring and heating are carried out to 75 ℃, and condensation reflux reaction is carried out for 5 hours. And after the reaction is finished, the catalyst is obtained by pressurized filtration, the filtered supported catalyst is washed for 5 times by adopting isooctanol, dried for 3 hours at 200 ℃, then baked for 3 hours at 450 ℃, and sleeved for the second catalytic production of 2-methallyl alcohol.
Performing reduced pressure distillation on the filtrate, wherein the reduced pressure distillation temperature is controlled below 60 ℃, the vacuum degree is-0.05 MPa, and the fraction is the crude product of 2-methylallyl alcohol; and measuring the content of the crude 2-methylallyl alcohol product, counting the conversion rate, and then entering a refining process.
The residual liquid (mainly cyclopentene alcohol and phenoxyethanol) after reduced pressure distillation is dehydrated and then mixed with the phenoxyethanol and cyclopentanol mixed solution until the total mass is 50g, the mixture is returned to the process as the initial raw material, and the second catalytic production of 2-methallyl alcohol is carried out according to the same conditions.
The reaction results of this example are shown in Table 1.
TABLE 1 reaction results of the methallyl alcohol production from the methylpropenes obtained in examples 1 to 10
Note that: 1) The catalyst recovery rate is the ratio of the mass of the catalyst obtained after recovery and drying to the mass of the catalyst originally put into the reactor; 2) MAL represents methacrolein.
The data in Table 1 show that the conversion rate of the methacrolein can reach more than 50% by adopting the supported catalyst of the application to catalyze and produce 2-methallyl alcohol, the highest selectivity of the 2-methallyl alcohol product can reach 94.6%, the supported catalyst is recovered and then is reused, the conversion rate of the methacrolein and the selectivity of the 2-methallyl alcohol product are not greatly changed, and the recovery rate of the catalyst can also reach more than 98%. Compared with the case of catalyzing and producing 2-methylallyl alcohol by using aluminum isopropoxide as a catalyst, although the conversion rate of the methylacrolein can reach 76.3 percent and the product selectivity can reach 95.3 percent, the catalyst is recycled for secondary application, and the conversion rate of the methylacrolein is reduced to 2.6 percent because the recovery rate of the catalyst is only 3.2 percent.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. A supported catalyst characterized by: the catalyst is formed by loading aluminum alkoxide on a zeolite molecular sieve, wherein the loading amount of the aluminum alkoxide on the zeolite molecular sieve is 20% of the mass of the zeolite molecular sieve.
2. A supported catalyst according to claim 1, characterized in that: the zeolite molecular sieve is one or more of MCM, SBA, FSM, HMS, MSU with mesoporous structure.
3. A supported catalyst according to claim 1, characterized in that: dissolving aluminum alkoxide in a solvent, adding a zeolite molecular sieve into the aluminum alkoxide solution, stirring and adsorbing for a period of time, and then drying to remove the solvent to obtain the catalyst.
4. A process for the catalytic production of 2-methallyl alcohol using a supported catalyst as claimed in any one of claims 1 to 3, characterised in that: comprising the following steps: and (3) carrying out catalytic reduction reaction on the methacrolein by adopting the supported catalyst.
5. The method for producing 2-methallyl alcohol by using the supported catalyst according to claim 4, wherein: and a polymerization inhibitor is also added into the reaction system.
6. The method for producing 2-methallyl alcohol by using the supported catalyst according to claim 5, wherein: the method for producing 2-methylallyl alcohol by catalysis specifically comprises the following steps:
step 1, adding a polymerization inhibitor into the dehydrated methacrolein absorption liquid, and uniformly mixing;
step 2, adding the supported catalyst and further uniformly mixing;
step 3, carrying out reduction reaction after the temperature is raised to a certain level, filtering out the supported catalyst after the reaction is finished, and retaining filtrate;
step 4, recycling the filtered supported catalyst and applying the catalyst to the step 3; vacuum distilling the filtrate to obtain a fraction which is a crude 2-methallyl alcohol product, and refining the crude 2-methallyl alcohol product; the residual liquid of the reduced pressure distillation and the methacrolein absorption liquid are mixed and dehydrated, and then returned to step 1 as a starting material.
7. The method for producing 2-methallyl alcohol by using the supported catalyst according to claim 5, wherein: the methacrolein absorption liquid comprises: and (3) primarily condensing tail gas from the first step of reaction in the process of preparing methallyl alcohol by oxidizing and hydrogenating isobutene, and then sending the tail gas into an absorption tower, wherein an absorption solvent is at least one of phenoxyethanol, cyclopentanol and isooctyl alcohol, and a mixed solution of the condensed tail gas and the absorption solvent is the methacrolein absorption liquid.
8. The method for producing 2-methallyl alcohol by using the supported catalyst according to claim 6, wherein: the polymerization inhibitor is one or a mixture of more of p-benzoquinone, tetramethyl nitroxide free radical piperidinol, hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, p-tert-butyl catechol and phenothiazine, and the use amount of the polymerization inhibitor accounts for 0.01-0.2% of the mass of the methacrolein absorption liquid.
9. The method for producing 2-methallyl alcohol by using the supported catalyst according to claim 5, wherein: the supported catalyst accounts for 20-30% of the mass of the methacrolein absorption liquid.
10. The method for producing 2-methallyl alcohol by catalysis of a supported catalyst according to any one of claims 4 to 9, wherein: the methacrolein absorption liquid is replaced by a mixed liquid of methacrolein and at least one alcohol of phenoxyethanol, cyclopentanol and isooctanol.
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