CN107876037A - Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis - Google Patents
Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis Download PDFInfo
- Publication number
- CN107876037A CN107876037A CN201711297256.3A CN201711297256A CN107876037A CN 107876037 A CN107876037 A CN 107876037A CN 201711297256 A CN201711297256 A CN 201711297256A CN 107876037 A CN107876037 A CN 107876037A
- Authority
- CN
- China
- Prior art keywords
- solid base
- base catalyst
- dihydric alcohol
- butyl acetate
- diacetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The application provides a kind of solid base catalyst, its application and the method that dihydric alcohol diacetate is prepared using its catalysis.The solid base catalyst is made up of the oxide of active element and the oxide of auxiliary element, and wherein active element is selected from least one of II A races element, and auxiliary element is selected from least one of zinc and zirconium.Above-mentioned solid base catalyst is used for the catalyst of ester exchange reaction, and activity and selectivity is all higher, and binary alcohol conversion is more than 99.8%, and selectivity is more than 99.9%.And the solid catalyst has the advantages of can be easily separated, frequency of usage is more than 30 times, service life length.The method for preparing dihydric alcohol diacetate using above-mentioned solid base catalyst catalysis, technological process is simple, and reaction condition relaxes, and quantity of three wastes caused by course of reaction is few, and superior product quality, and ester content is more than 99.5%, and two ester contents are more than 95.0%.
Description
Technical field
The present invention relates to ester-exchange technology field, more particularly to a kind of solid base catalyst, its preparation method, using and
The method that dihydric alcohol diacetate is prepared using its catalysis.
Background technology
Dihydric alcohol diacetate（Such as ethylene diacetate, propylene glycol diacetate and butanediol diacetate）For nothing
Color liquid, have the advantages that smell is good, boiling range is narrow, stable components, winter quick-drying.Due to its unique structure, in same molecule both
Polarized group has non-polar group again, thus it has preferable solvability to polarity and apolar substance, and not only
Can be miscible with alcohol, ether and benzene, and possess good water solubility.Dihydric alcohol diacetate is widely used, as a kind of new
Environment protection type high-boiling-point solvent, the excellent substitute of mixed acid dimethyl, propylene glycol methyl ether acetate and cyclohexanone is not only, and
Because its hypotoxicity, environmental safety and raw material sources it is abundant the advantages that, dihydric alcohol diacetate be also widely used for ink,
The solvent of the industry such as paint, plastics, spices, medicine, as being used as deferred solvent and phenolic resin baked paint in baking finish for car
Solvent.In addition, dihydric alcohol diacetate can also substitute the glyceryl triacetate of costliness and be used as the plasticizer of vinegar fibre filter stick,
Even, important auxiliary agent of the dihydric alcohol diacetate of high-purity or cast steel etc..
At present, the synthetic method generally use of dihydric alcohol diacetate is dihydric alcohol（Ethylene glycol, propane diols, butanediol
Deng）With acetic acid direct esterification, typically using toluene as dehydrating agent, using Lewis acid as catalyst, typical catalyst has load
Molecular sieve, zinc chloride or iron chloride of iron etc..The shortcomings that this method is to use acetic acid high to equipment material requirement in course of reaction,
And water is generated in course of reaction, and product is miscible with water, and dissolved each other with unreacted raw material, formed similar in a series of boiling points altogether
Thing is boiled, product separation is difficult, need to typically be refined with multistage rectification method.
For the traditional batch direct esterification method synthesis technique of dihydric alcohol diacetate, CN104045554A discloses one kind
The fixed-bed process of ethylene diacetate is prepared, using solid acid catalyst, two-stage is carried out as raw material using ethylene glycol and acetic acid
Fixed bed esterification, 70 ~ 150 DEG C of esterification temperature, the water generated in one-level esterification need to remove through azeotropic distillation, Ran Houjin
Enter two level fixed bed reactors to continue to be esterified.By esterification reaction product rectifying, remove and reclaim unreacted acetic acid, obtain second two
Alcohol diacetate.This method can realize the continuous production of ethylene diacetate, and mode of operation is simple, significantly improve second two
The production efficiency of alcohol diacetate, its production cost is reduced, and solid pollutant and discharge of wastewater can be reduced.But due to by
The limitation of thermodynamical equilibrium, feed stock conversion and product selectivity still need further to be improved in two level esterification；In addition, by
Then acid catalysis process, the side reactions such as dehydration, polymerization, etherificate easily occurs, cause that product selectivity is low, yield is low, product matter
Measure poor.
CN103183609A discloses a kind of ethylene diacetate new synthetic method, using sec-butyl acetate and ethylene glycol
For raw material, in base catalyst KOH, K2CO3、NaOH、CH3ONa or C2H5Ester exchange reaction occurs in the presence of ONa to be prepared
Ethylene glycol monoacetate and ethylene diacetate.Due to the ethylene glycol monoacetate in reaction product, ethylene diacetate
Approached with unreacted ethylene glycol three boiling point, and ethylene glycol monoacetate and ethylene glycol, ethylene diacetate and ethylene glycol
Azeotropic can be produced, is difficult to separate product using conventional rectification method, this method obtains toluene and second two using toluene extract and separate
The mixture of alcohol monoacetate, ethylene diacetate, mixture must be first through separation of methylbenzene and ethylene glycol monoacetate after extraction
Azeotropic mixture, then with rectification under vacuum separation of methylbenzene and ethylene glycol monoacetate.It is higher separation process length, energy consumption to be present in this method
Defect, industrially practical application difficulty is bigger；Not enough, conversion ratio is relatively low, after causing for the solid base catalyst activity of use
Continuous separation is difficult；Most of all, the separation of such base catalyst is difficult and compared with easy in inactivation, a large amount of solid pollutants are produced.
The content of the invention
Based on this, it is necessary to separate difficult, raw material conversion for product in existing dihydric alcohol diacetate synthetic method
Rate is low, product selectivity is low, yield is low, and product quality is poor, and catalyst activity is not high enough and service life is short and reacts
The technical problems such as a large amount of three wastes are produced in journey, there is provided a kind of solid base catalyst and prepare dihydric alcohol diacetate using its catalysis
Method, the catalyst shows high activity, and service life is long, the characteristics of being easily isolated, and dihydric alcohol two is prepared using its catalysis
Acetate, feed stock conversion, product selectivity and yield are all higher, and product separation is simple, obtained dihydric alcohol diacetate production
Quality is good.
A kind of solid base catalyst, it is made up of the oxide of active element and the oxide of auxiliary element, the activity member
For element selected from least one of beryllium, magnesium, calcium, strontium, barium, radium, the auxiliary element is selected from least one of zinc and zirconium.
In one of the embodiments, the oxide of the active element account for the solid base catalyst quality 30% ~
90%, surplus is the oxide of auxiliary element.
Application of the solid base catalyst in ester exchange reaction as catalyst described in any of the above-described.
A kind of method that solid base catalyst catalysis using described in any of the above-described prepares dihydric alcohol diacetate, including
Following steps：
Dihydric alcohol and butyl acetate are subjected to ester exchange reaction in the presence of the solid base catalyst, obtain the vinegar of dihydric alcohol two
Acid esters.
In one of the embodiments, the ester exchange reaction is carried out in catalytic distillation tower, the ester exchange reaction tool
Body comprises the following steps：
Dihydric alcohol, butyl acetate and solid base catalyst are well mixed in catalytic distillation tower, are heated to seething with excitement, azeotropic steams
The azeotropic mixture of butanol and butyl acetate；
After tower top temperature reaches the boiling point of butyl acetate, tower bottoms is discharged；
The tower bottoms is isolated and purified, obtains dihydric alcohol diacetate.
In one of the embodiments, the azeotropic steams the step of azeotropic mixture of butanol and butyl acetate and is specially:
Reaction reaches the azeotropic point of butanol and butyl acetate to tower top temperature under conditions of infinite reflux；
It is 2 in reflux ratio:~8:Under conditions of 1, azeotropic steams the azeotropic mixture of butanol and butyl acetate.
In one of the embodiments, the dihydric alcohol is selected from least one of C2 ~ C4 dihydric alcohol；The acetic acid fourth
Ester is selected from least one of n-butyl acetate, isobutyl acetate, tert-butyl acetate and sec-Butyl Acetate.
In one of the embodiments, the mol ratio of the butyl acetate and dihydric alcohol is 2.5 ~ 10:1.
In one of the embodiments, the addition of the solid base catalyst is the dihydric alcohol, butyl acetate and consolidated
The 0.1% ~ 10% of body base catalyst gross mass.
The preparation method of solid base catalyst described in any of the above-described, comprises the following steps：
Water soluble compound containing the active element and the water soluble compound containing the auxiliary element are dissolved in deionized water
In, it is configured to solution；
Precipitating reagent and the solvent are contacted, obtain suspension；
The suspension is filtered and washed in neutrality, dries, be calcined, obtaining the solid base catalyst.
In carbonate of the precipitating reagent selected from alkali metal, the bicarbonate of alkali metal and the hydroxide of alkali metal extremely
Few one kind.
Above-mentioned solid base catalyst is used for the catalyst of ester exchange reaction, and activity and selectivity is all higher, dihydric alcohol conversion
Rate is more than 99.8%, and selectivity is more than 99.9%.And the solid catalyst has the advantages of can be easily separated, frequency of usage is more than 30
It is secondary, service life length.
The method for preparing dihydric alcohol diacetate using above-mentioned solid base catalyst catalysis, technological process is simple, reacts bar
Part relaxes, and quantity of three wastes caused by course of reaction is few, and one of reaction product butanol is constantly steamed in the form of azeotropic mixture, promotes reaction
It is constantly positive to carry out, significantly shorten the reaction time, improve production efficiency, superior product quality, ester content is more than 99.5%, and diester contains
Amount is more than 95.0%.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below to the specific reality of the present invention
The mode of applying is described in detail.Many details are elaborated in the following description in order to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
A kind of solid base catalyst, it is made up of the oxide of active element and the oxide of auxiliary element, wherein activity member
Element is selected from II A races element（Beryllium, magnesium, calcium, strontium, barium, radium）At least one of, auxiliary element in zinc and zirconium at least one
Kind.
It is appreciated that the oxide of active element is selected from beryllium oxide（BeO）, magnesia（MgO）, calcium oxide（CaO）, oxygen
Change strontium（SrO）, barium monoxide（BaO）And radium oxide（RaO）At least one of.
The oxide of auxiliary element is selected from zinc oxide（ZnO）And zirconium oxide（ZrO2）At least one of.
Wherein, the oxide of active element accounts for the 30% ~ 90% of solid base catalyst quality, and surplus is the oxidation of auxiliary element
Thing.
Preferably, the oxide of active element accounts for the 50% ~ 80% of solid base catalyst quality, and surplus is the oxygen of auxiliary element
Compound.
Above-mentioned solid base catalyst is prepared by following methods：
（1）Water soluble compound containing active element and the water soluble compound containing auxiliary element are dissolved in deionized water, matched somebody with somebody
Solution is made；
Wherein, the water soluble compound containing active element and the water soluble compound containing auxiliary element are not particularly limited.It is preferred that
, in the nitrate of chlorate and active element of the above-mentioned water soluble compound containing active element selected from active element at least
It is a kind of.In the nitrate of chlorate and auxiliary element of the above-mentioned water soluble compound containing auxiliary element selected from auxiliary element extremely
Few one kind.
For example, active element is Mg, auxiliary element Zn, then the water soluble compound containing active element can be selected from
MgCl2And Mg（NO3）2At least one of, the water soluble compound containing auxiliary element can be selected from ZnCl2And Zn（NO3）2In
It is at least one.
（2）Precipitating reagent is contacted with above-mentioned solution, obtains suspension.
Wherein, in carbonate of the precipitating reagent selected from alkali metal, the bicarbonate of alkali metal and the hydroxide of alkali metal
It is at least one.
Preferably, the mixture that precipitating reagent forms for the carbonate of alkali metal and the hydroxide of alkali metal, the mixture
The mol ratio of the carbonate of middle alkali metal and the hydroxide of alkali metal is 0.5 ~ 5:1.
In the present embodiment, the condition of contact is：40 DEG C ~ 70 DEG C of temperature, pH value are 8 ~ 11.
（3）Above-mentioned suspension is filtered and washed to filtrate in neutrality, dries, obtain the catalyzed by solid base after roasting
Agent.
Wherein, drying can be dried under normal conditions, to remove solvent therein.
In the present embodiment, drying is carried out at a temperature of 80 DEG C ~ 150 DEG C.Preferably, dry at 90 DEG C ~ 120 DEG C
At a temperature of carry out.
The dry duration can be selected according to the temperature being dried, with can be by solvent removal therein or base
This removing is defined.
In the present embodiment, the dry duration is 8 ~ 24 hours.Preferably, the dry duration is 12 ~ 20
Hour.
The temperature of roasting is 600 DEG C ~ 900 DEG C, and the time of roasting is 3 ~ 10 hours.
Above-mentioned solid base catalyst is used as catalyst in ester exchange reaction, has higher base strength and high activity position
Point, show higher catalytic activity.And the catalyst of ester exchange reaction, course of reaction are used as by the use of above-mentioned solid base catalyst
Produced without Bronsted acid, avoid the generation of many side reactions, show high selectivity.Especially enter in alcohol with acetate for raw material
In capable ester exchange reaction, above-mentioned solid base catalyst shows high catalytic activity and high selectivity.
The present invention provides a kind of method for preparing dihydric alcohol diacetate using above-mentioned solid base catalyst catalysis, including following step
Suddenly：
Dihydric alcohol and butyl acetate are subjected to ester exchange reaction in the presence of above-mentioned solid base catalyst, obtain the vinegar of dihydric alcohol two
Acid esters.
Wherein, dihydric alcohol is selected from C2 ~ C4 at least one of dihydric alcohol, such as ethylene glycol, 1,2-PD, 1,3- the third two
Alcohol, 1,2- butanediols, 1,4- butanediols, 2,3- butanediols etc..
Butyl acetate is selected from least one of n-butyl acetate, isobutyl acetate, tert-butyl acetate and sec-Butyl Acetate.
In the present embodiment, the mol ratio of butyl acetate and dihydric alcohol is 2.5 ~ 10:1.Preferably, butyl acetate and two
The mol ratio of first alcohol is 3 ~ 5:1.
In order to obtain preferable catalytic effect, the addition of above-mentioned solid base catalyst is above-mentioned dihydric alcohol, butyl acetate
With the 0.1% ~ 10% of solid base catalyst gross mass.Preferably, the addition of above-mentioned solid base catalyst is above-mentioned dihydric alcohol, vinegar
The 1.0% ~ 5.0% of acid butyl ester and solid base catalyst gross mass.
In the present embodiment, the temperature of above-mentioned ester exchange reaction is 100 DEG C ~ 160 DEG C.Preferably, above-mentioned ester exchange is anti-
The temperature answered is 120 DEG C ~ 140 DEG C.
Specifically, above-mentioned ester exchange reaction is carried out in catalytic distillation tower.
The ester exchange reaction specifically includes following steps：
S110, the dihydric alcohol by catalytic distillation tower, butyl acetate and solid base catalyst are heated to seething with excitement, and azeotropic steams butanol
With the azeotropic mixture of butyl acetate.
Wherein, azeotropic steams the step of azeotropic mixture of butanol and butyl acetate and is specially：
React under total reflux conditions to tower top temperature and reach the azeotropic point of butanol and butyl acetate；
It is 2 ~ 8 in reflux ratio:Under conditions of 1, azeotropic steams the azeotropic mixture of butanol and butyl acetate.
It is appreciated that tower top here is the tower top of catalytic distillation tower.
Dihydric alcohol and butyl acetate in the catalytic distillation tower successive reaction under the catalytic action of solid base catalyst, complete
Reaction reaches the azeotropic point of butanol and butyl acetate to tower top temperature under counterflow condition, is then 2 ~ 8 in reflux ratio:1 condition
Under, azeotropic steams the azeotropic mixture of butanol and butyl acetate.
S120, after tower top temperature reaches the boiling point of butyl acetate, tower bottoms is discharged.
It is appreciated that tower top here is similarly the tower top of catalytic distillation tower.
After tower top temperature reaches the boiling point of butyl acetate, that is, show to react the butanol generated in the form of azeotropic mixture
Steam completely, i.e., dihydric alcohol has completely reacted, the binary that only the complete butyl acetate of remaining unreacted and reaction generate in system
Alkoxide compound.
S130, above-mentioned tower bottoms is isolated and purified, obtain dihydric alcohol diacetate.
It is appreciated that in the tower bottoms containing dihydric alcohol diacetate, dihydric alcohol monoacetate, butyl acetate and trace not
The dihydric alcohol of reaction.
Above-mentioned tower bottoms isolates and purifies, and conventional distillation or rectificating method can be used to be isolated and purified.
In the present embodiment, the above-mentioned temperature isolated and purified is 80 DEG C ~ 200 DEG C.
Above-mentioned solid base catalyst is used for the catalyst of ester exchange reaction, and activity and selectivity is all higher, dihydric alcohol conversion
Rate is more than 99.8%, and selectivity is more than 99.9%.And the solid catalyst has the advantages of can be easily separated, frequency of usage is more than 30
It is secondary, service life length.
The method for preparing dihydric alcohol diacetate using above-mentioned solid base catalyst catalysis, technological process is simple, reacts bar
Part relaxes, and quantity of three wastes caused by course of reaction is few, and one of reaction product butanol is constantly steamed in the form of azeotropic mixture, promotes reaction
It is constantly positive to carry out, significantly shorten the reaction time, improve production efficiency, superior product quality, ester content is more than 99.5%, and diester contains
Amount is more than 95.0%.
It is specific embodiment below
Embodiment 1
Solid base catalyst is made up of the oxide of the oxide of calcium, the oxide of magnesium and zirconium, is designated as CaO-MgO-ZrO2, wherein
CaO content is 50%, content of MgO 20%, ZrO2Content is 30%, is prepared by following methods：
（1）By Ca (NO3)2、Mg(NO3)2With ZrO (NO3)2It is dissolved in by proportioning in deionized water, is configured to solution.
（2）It is 2 by mol ratio:1 Na2CO3Contacted with the precipitating reagent of NaOH compositions with above-mentioned solution, obtain suspension.
（3）Above-mentioned suspension is filtered and washed to filtrate in neutrality, dries, obtain above-mentioned catalyzed by solid base after roasting
Agent.
Ethylene glycol is catalyzed using above-mentioned solid base catalyst and sec-Butyl Acetate prepares ethylene diacetate, its specific mistake
Journey is as follows：
176.0g ethylene glycol, 980.0g sec-Butyl Acetates and 14.0g solid base catalysts are well mixed in catalytic distillation tower,
It is heated to seething with excitement, after reacting to tower top temperature 100 DEG C of azeotropic point for reaching sec-butyl alcohol and sec-Butyl Acetate under total reflux conditions,
It is 10 in reflux ratio:Azeotropic steams the azeotropic mixture of sec-butyl alcohol and sec-Butyl Acetate under conditions of 2, and it is secondary to treat that tower top temperature reaches acetic acid
After the boiling point of butyl ester, tower bottoms is discharged.
Gained tower bottoms is subjected to chromatography, its result is as follows：Ethylene glycol reforming is 99.9%, selectivity of product 100%,
Wherein, ethylene diacetate is selectively 97.0%, and the selectivity of ethylene glycol monoacetate is 3.0%.
Above-mentioned tower bottoms is isolated and purified, in obtained product, ester content 99.6%, ethylene diacetate contains
Measure as 96.8%.
Embodiment 2
Solid base catalyst is made up of the oxide of the oxide of calcium, the oxide of strontium and zinc, is designated as CaO-SrO-ZnO, wherein
CaO content is 80%, SrO contents are 10%, ZnO content 10%.
1,2-PD is catalyzed using above-mentioned solid base catalyst and sec-Butyl Acetate prepares 1,2-PD diacetate,
Its detailed process is as follows：
500.0g1,2- propane diols, 3000.0g sec-Butyl Acetates and 60.0g solid base catalysts are mixed in catalytic distillation tower
Uniformly, it is heated to seething with excitement, reacts under total reflux conditions to tower top temperature and reach the azeotropic point 100 of sec-butyl alcohol and sec-Butyl Acetate
It is 10 in reflux ratio after DEG C:Azeotropic steams the azeotropic mixture of sec-butyl alcohol and sec-Butyl Acetate under conditions of 4, treats that tower top temperature reaches
After the boiling point of sec-Butyl Acetate, tower bottoms is discharged.
Gained tower bottoms is subjected to chromatography, its result is as follows：1,2-PD is converted into 99.99%, selectivity of product
100%, wherein, 1,2-PD diacetate is selectively 98.0%, and the selectivity of 1,2-PD monoacetate is 2.0%.
Above-mentioned tower bottoms is isolated and purified, in obtained product, ester content 99.9%, the acetic acid of 1,2-PD two
Ester content is 98.0%.
Embodiment 3
Solid base catalyst is made up of the oxide of the oxide of calcium, the oxide of barium and zirconium, is designated as CaO-BaO-ZrO2, wherein
CaO content is 70%, BaO contents are 20%, ZrO2Content 10%.
BDO is catalyzed using above-mentioned solid base catalyst and n-butyl acetate prepares BDO diacetate,
Its detailed process is as follows：
400.0g1,4- butanediols, 2980.0g n-butyl acetates and 80.0g solid base catalysts are mixed in catalytic distillation tower
Uniformly, it is heated to seething with excitement, reacts under total reflux conditions to tower top temperature and reach the azeotropic point 116 of n-butanol and n-butyl acetate
It is 10 in reflux ratio after DEG C:Azeotropic steams the azeotropic mixture of n-butanol and n-butyl acetate under conditions of 4, treats that tower top temperature reaches
After the boiling point of n-butyl acetate, tower bottoms is discharged.
Gained tower bottoms is subjected to chromatography, its result is as follows：BDO is converted into 99.99%, selectivity of product
100%, wherein, BDO diacetate is selectively 97.5%, and the selectivity of BDO monoacetate is 2.5%.
Above-mentioned tower bottoms is isolated and purified, in obtained product, ester content 99.9%, ethylene diacetate contains
Measure as 97.0%.
Embodiment 4
Solid base catalyst is made up of the oxide of the oxide of calcium, the oxide of magnesium and zirconium, is designated as CaO-MgO-ZrO2, wherein
CaO content is 50%, content of MgO 20%, ZrO2Content is 30%.
1,3-PD is catalyzed using above-mentioned solid base catalyst and sec-Butyl Acetate prepares 1,3-PD diacetate,
Its detailed process is as follows：
500.0g1,3- propane diols, 3053.0g sec-Butyl Acetates and 72.5g solid base catalysts are mixed in catalytic distillation tower
Uniformly, it is heated to seething with excitement, reacts under total reflux conditions to tower top temperature and reach the azeotropic point 100 of sec-butyl alcohol and sec-Butyl Acetate
It is 10 in reflux ratio after DEG C:Azeotropic steams the azeotropic mixture of sec-butyl alcohol and sec-Butyl Acetate under conditions of 4, treats that tower top temperature reaches
After the boiling point of sec-Butyl Acetate, tower bottoms is discharged.
Gained tower bottoms is subjected to chromatography, its result is as follows：1,3-PD is converted into 99.99%, selectivity of product
99.99%, wherein, 1,3-PD diacetate is selectively 98.0%, and the selectivity of 1,3-PD monoacetate is 2.0%.
Above-mentioned tower bottoms is isolated and purified, in obtained product, ester content 99.9%, the acetic acid of 1,3-PD two
Ester content is 98.0%.
The present embodiment catalyst is used to repeat to test, its reaction result is shown in Table 1.
The catalytic performance of the solid base catalyst of table 1
| Frequency of usage | 1,3-PD conversion ratio, % | Selectivity of product, % | 1,3-PD diacetate selectivity, % |
| 1 | 99.99 | 99.99 | 98.0 |
| 3 | 99.99 | 100 | 97.8 |
| 5 | 100 | 100 | 98.2 |
| 7 | 99.99 | 99.98 | 97.8 |
| 15 | 99.98 | 99.99 | 97.9 |
| 18 | 99.92 | 99.99 | 97.8 |
| 20 | 99.90 | 100 | 97.6 |
| 24 | 99.85 | 100 | 97.3 |
| 26 | 99.83 | 100 | 97.0 |
| 28 | 99.81 | 99.99 | 96.7 |
| 30 | 99.8 | 100 | 95.7 |
| 32 | 99.4 | 100 | 92.9 |
Above-mentioned solid base catalyst is after using 32 times it can be seen from table, still with preferable reactivity and selection
Property.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (12)
1. a kind of solid base catalyst, it is characterised in that be made up of the oxide of active element and the oxide of auxiliary element, institute
State active element and be selected from beryllium, magnesium, calcium, strontium, barium, at least one of radium, the auxiliary element in zinc and zirconium at least one
Kind.
2. solid base catalyst according to claim 1, it is characterised in that the oxide of the active element accounts for described solid
The 30% ~ 90% of body base catalyst quality, surplus are the oxide of auxiliary element.
A kind of 3. application of the solid base catalyst described in claim 1 or 2 in ester exchange reaction as catalyst.
4. a kind of method that catalyzed by solid base using described in claim 1 or 2 prepares dihydric alcohol diacetate, its feature exists
In comprising the following steps：
Dihydric alcohol and butyl acetate are subjected to ester exchange reaction in the presence of the solid base catalyst, obtain the vinegar of dihydric alcohol two
Acid esters.
5. the method according to claim 4 that dihydric alcohol diacetate is prepared using solid base catalyst catalysis, its feature
It is, the ester exchange reaction is carried out in catalytic distillation tower, and the ester exchange reaction specifically includes following steps：
Dihydric alcohol, butyl acetate and solid base catalyst are well mixed in catalytic distillation tower, are heated to seething with excitement, azeotropic steams
The azeotropic mixture of butanol and butyl acetate；
After tower top temperature reaches the boiling point of butyl acetate, tower bottoms is discharged；
The tower bottoms is isolated and purified, obtains dihydric alcohol diacetate.
6. the method according to claim 5 that dihydric alcohol diacetate is prepared using solid base catalyst catalysis, its feature
It is, the step of azeotropic steams the azeotropic mixture of butanol and butyl acetate is specially：
React under total reflux conditions to tower top temperature and reach the azeotropic point of butanol and butyl acetate；
It is 2 ~ 8 in reflux ratio:Under conditions of 1, azeotropic steams the azeotropic mixture of butanol and butyl acetate.
7. the method according to claim 4 that dihydric alcohol diacetate is prepared using solid base catalyst, it is characterised in that
The dihydric alcohol is selected from least one of C2 ~ C4 dihydric alcohol；The butyl acetate is selected from n-butyl acetate, i-butyl
At least one of ester, tert-butyl acetate and sec-Butyl Acetate.
8. the method according to claim 4 that dihydric alcohol diacetate is prepared using solid base catalyst, it is characterised in that
The mol ratio of the butyl acetate and dihydric alcohol is 2.5 ~ 10:1.
9. the method according to claim 4 that dihydric alcohol diacetate is prepared using solid base catalyst catalysis, its feature
Be, the addition of the solid catalyst is the dihydric alcohol, butyl acetate and solid base catalyst gross mass 0.1% ~
10%。
10. the method according to claim 4 that dihydric alcohol diacetate is prepared using solid base catalyst catalysis, its feature
It is, the transesterification reaction temperature is 100 DEG C ~ 160 DEG C.
11. the preparation method of the solid base catalyst described in a kind of claim 1 or 2, it is characterised in that comprise the following steps：
Water soluble compound containing the active element and the water soluble compound containing the auxiliary element are dissolved in deionized water
In, it is configured to solution；
Precipitating reagent and the solution are contacted, obtain suspension；
The suspension is filtered and washed to filtrate in neutrality, dries, roasting, obtains the solid base catalyst.
12. the preparation method of solid base catalyst according to claim 11, it is characterised in that the precipitating reagent is selected from alkali
At least one of hydroxide of the carbonate of metal, the bicarbonate of alkali metal and alkali metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711297256.3A CN107876037A (en) | 2017-12-08 | 2017-12-08 | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711297256.3A CN107876037A (en) | 2017-12-08 | 2017-12-08 | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107876037A true CN107876037A (en) | 2018-04-06 |
Family
ID=61773524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711297256.3A Pending CN107876037A (en) | 2017-12-08 | 2017-12-08 | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107876037A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206315A (en) * | 2018-08-31 | 2019-01-15 | 江苏华伦化工有限公司 | The method of separating propylene glycol acetate from propylene glycol methyl ether acetate heavy constituent |
| CN113996280A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Solid base catalyst for hydrolyzing TDI tar residue and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768927A (en) * | 2005-10-12 | 2006-05-10 | 中国科学院山西煤炭化学研究所 | A kind of catalyst for multi-phase catalytic synthesis of methyl carbonate and method for making thereof and application |
| CN102172521A (en) * | 2011-03-04 | 2011-09-07 | 北京林业大学 | Solid basic catalyst and preparation method and application thereof |
| CN104355996A (en) * | 2014-09-30 | 2015-02-18 | 天津中昊天久工程技术有限公司 | Method for synthesizing ethylene glycol diacetate by adopting transesterification method |
| US20160297737A1 (en) * | 2013-12-04 | 2016-10-13 | Greenyug, Llc | Production of Butyl Acetate from Ethanol |
-
2017
- 2017-12-08 CN CN201711297256.3A patent/CN107876037A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768927A (en) * | 2005-10-12 | 2006-05-10 | 中国科学院山西煤炭化学研究所 | A kind of catalyst for multi-phase catalytic synthesis of methyl carbonate and method for making thereof and application |
| CN102172521A (en) * | 2011-03-04 | 2011-09-07 | 北京林业大学 | Solid basic catalyst and preparation method and application thereof |
| US20160297737A1 (en) * | 2013-12-04 | 2016-10-13 | Greenyug, Llc | Production of Butyl Acetate from Ethanol |
| CN104355996A (en) * | 2014-09-30 | 2015-02-18 | 天津中昊天久工程技术有限公司 | Method for synthesizing ethylene glycol diacetate by adopting transesterification method |
Non-Patent Citations (1)
| Title |
|---|
| CHAWALIT NGAMCHARUSSRIVICHAI ET AL.: "Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernel oil", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206315A (en) * | 2018-08-31 | 2019-01-15 | 江苏华伦化工有限公司 | The method of separating propylene glycol acetate from propylene glycol methyl ether acetate heavy constituent |
| CN113996280A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Solid base catalyst for hydrolyzing TDI tar residue and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2011224044B2 (en) | Conversion of 2,5- (hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor | |
| US20080103340A1 (en) | Applications of biobased glycol compositions | |
| TWI677577B (en) | Method for producing 1,4-butanediol | |
| KR101441268B1 (en) | Method for the synthesis of bioresourced acrylic acid esters | |
| CN101318901A (en) | Novel synthesis process for dimethyl fumarate | |
| CN101717327B (en) | Method for producing propylene glycol mono-methyl ether with energy conservation | |
| CN107876037A (en) | Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis | |
| CN103209951A (en) | Ketocarboxylic acids, ketocarboxylic esters, methods of manufacture and uses thereof | |
| CN101381283A (en) | Method for continuously preparing 3-methyl-2-butenol | |
| CN101717338A (en) | Method for preparing carbonic acid glyceride by catalytic reaction-azeotropic reification coupling | |
| CN110143876A (en) | A kind of method that can continuously prepare propylene glycol diacetate | |
| CN102093212A (en) | Synthesis method of aliphatic alkoxy oxethyl dibasic acid ethyl ester | |
| CN107899612A (en) | A kind of more acids ionic-liquid catalysts of functionalization, preparation method and catalyze and synthesize the method for compounding acetic isoborneol ester with it | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| CN111138278B (en) | Preparation method of butanediol caprylate | |
| RU2605094C2 (en) | Improved method for epoxidation of fatty acids, esters thereof and mixtures thereof | |
| CN108047171A (en) | The method that formic acid transfer hydrogenation levulic acid based on heterogeneous catalyst prepares gamma-valerolactone | |
| CN1479707A (en) | Method for production of tetrahydrofuran | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN105646223B (en) | A kind of method that levulic acid catalysis oxidation esterification prepares succinate | |
| CN102285883B (en) | Method for synthesizing tributyl citrate (TBC) by adopting composite ionic liquid catalyst | |
| CN110143878B (en) | Preparation method of methyl p-methoxycinnamate | |
| CN1063427C (en) | Technology for preparing propylene-glycol monoalky lether carboxylic ester by catalytic distillation | |
| CN1224621C (en) | Tetrahydrofuran refining process | |
| CN114805064A (en) | Method for synthesizing alpha-hydroxy carboxylic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180406 |