CN105753691A - Method for utilizing molecular sieve supported catalyst to prepare acetic ether - Google Patents
Method for utilizing molecular sieve supported catalyst to prepare acetic ether Download PDFInfo
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- CN105753691A CN105753691A CN201610188486.5A CN201610188486A CN105753691A CN 105753691 A CN105753691 A CN 105753691A CN 201610188486 A CN201610188486 A CN 201610188486A CN 105753691 A CN105753691 A CN 105753691A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention belongs to the field of chemical synthesis processes and particularly relates to a method for utilizing a molecular sieve supported catalyst to prepare acetic ether.Ethanol, acetic acid and water are vaporized according to the volume ratio of 3-8 L to 2-3 L to 3 L, then a vaporization product is led into an esterification reaction kettle, the molecular sieve supported catalyst accounting for 5-30% of the total volume percentage of a reaction system is added, reaction is performed at the temperature of 110-115 DEG C for 15-30 minutes, condensation is performed, and the acetic ether is obtained through distillation recovery.The method utilizes the catalytic action of the molecular sieve supported catalyst to prepare the acetic ether, the acetic acid conversion rate is up to 98% or above, the acetic ether yield is 99.5% or above, an obtained esterification product is high in purity, the molecular sieve supported catalyst can be repeatedly used for 6-8 times, and the production costs are greatly reduced.
Description
Technical field
The invention belongs to chemical synthesis process field, be specifically related to a kind of method utilizing Supported on Zeolite catalyst preparing ethyl acetate, solid-carried catalyst is with molecular sieve for carrier, with heteropoly acid for catalytic active layer.
Background technology
Ethyl acetate is a kind of excellent organic solvent, and ethyl cellulose, acetylbutyrylcellulose, polystyrene, methacrylic resin, chlorinated rubber and multiple natural gum are all had good solubility property.
In traditional handicraft, ethyl acetate is esterified under sulphuric acid existent condition by acetic acid and positive ethanol and is obtained, ethanol, acetic acid and sulphuric acid are proportionally put in distillating still, it is esterified at one hundred and twenty degrees centigrade, through reflux dewatering, control acid number when being esterified below 0.5, enter in distillating still after the thick ester of gained is neutralized, carry out reflux dewatering through distillation, condensation, separation, reclaiming alcohol ester, finally below 126 degrees Celsius, distillation obtains product.Direct esterification is the production method of traditional ethyl acetate, it is generally in the presence of a catalyst, obtained by acetic acid and positive ethanol generation esterification, direct esterification is current domestic the most frequently used and accounts for leading method, in this process, the selection of catalyst is even more important, the most traditional catalyst is sulphuric acid, its advantage is that catalysis activity is high, with low cost, but owing to severe corrosive and the oxidisability of sulphuric acid make equipment corrosion serious, product colourity is poor, side reaction is more, product post processing is complicated, waste liquor contamination is serious, but owing to direct esterification technical conditions are ripe, most enterprises still adopt the method at present.Account for the 86.6% of total productive capacity, remain as main production process, therefore, it is devoted to esterification process and produces ethyl acetate technical study and exploitation, the esterification catalyst that active development is novel, and synthesis technique and equipment, improve the utilization rate of raw material and reduce production cost, doing the energy-saving and cost-reducing work of production process well, will have great significance, also it is keep one's feet in the industry simultaneously, improves the key of the market competitiveness.
Current researcheres find can replace the new catalyst for esterification of sulphuric acid and catalyst in do a lot of work, consecutive publications zeolite molecular sieve, ion exchange resin, metal sulfate, solid super acid catalyst synthesizing ethyl acetate or the article of ethyl acetate, the present invention utilizes the Supported on Zeolite catalyst of independent research to produce ethyl acetate, solves current ethyl acetate production method and prepares the problems such as conversion rate of products is low, product reaction ethyl acetate product purity incomplete, that obtain is not high.
Summary of the invention
The corrosivity that it is an object of the invention to overcome existing catalyst to bring is relatively strong, environmental pollution is serious, preparation technology is loaded down with trivial details, product purpose is not pointed, and the current production method of ethyl acetate product prepares, and conversion rate of products is low, product reaction ethyl acetate product purity incomplete, that obtain is not high, there is provided a kind of and make the method utilizing Supported on Zeolite catalyst preparing ethyl acetate simple, that be easily achieved, solid-carried catalyst is with molecular sieve for carrier, with heteropoly acid for catalytic active layer.
The solution of the present invention is by being achieved in that: a kind of method utilizing Supported on Zeolite catalyst preparing ethyl acetate, it is characterized in that, ethanol, acetic acid, water three are vaporized according to the ratio that volume is 3 ~ 8L:2 ~ 3L:3L, again the vaporizer of three is passed in reaction kettle of the esterification, and input accounts for the Supported on Zeolite catalyst that reaction system volume toatl proportion is 5 ~ 30%, condensation after temperature is react 15 ~ 30min under 110 ~ 115 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
Further restriction as the present invention, this Supported on Zeolite catalyst is made up of carrier and catalyst, the mass ratio of carrier and catalyst is 1:8 ~ 10, catalyst is covered on carrier and forms the active layer containing active constituent, and described carrier is ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve with microcellular structure；Described catalyst is a kind of or their compositions in 12 phosphotungstic acids, 12 silico-tungstic acids, 12 phosphomolybdate.
As the further restriction of the present invention, this Supported on Zeolite method for preparing catalyst comprises the following steps:
null1) prepared by carrier: be dissolved in the deionized water of 150-250mol in the aluminum source of 2-5mol silicon source and 0.01-0.05mol，Strong stirring 10-20min，Both are made fully to dissolve，Add the template of 0.4-0.8mol，Sulfuric acid regulation solution pH=10-15 is used after stirring 20-30min，Add the auxiliary agent that mass fraction is 2-3%，Gained mixed solution is obtained concentrated gel material as evaporation 5-10h in baking oven 100-120 DEG C，Concentrated gel material is sealed，Crystallization 10-24h in 150-180 DEG C of crystallizing kettle，Sample is filtered washing and dry，550-650 DEG C of roasting 5-8h，Obtain ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve carrier with microcellular structure；
2) load of catalyst activity component: catalyst and carrier are that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved according to mass ratio, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 3-5h is activated, thus preparing the solid-carried catalyst of ethyl acetate at 180-250 DEG C.
As the further restriction of Supported on Zeolite method for preparing catalyst of the present invention, described silicon source is any one in silica gel or waterglass；Described aluminum source is any one in aluminum sulfate or sodium metaaluminate.
As the further restriction of Supported on Zeolite method for preparing catalyst of the present invention, described template is any one in n-butylamine, ethylenediamine, triethylamine and ethanolamine or their combination in any.
As the further restriction of Supported on Zeolite method for preparing catalyst of the present invention, described auxiliary agent is any one in Lanthanum (III) nitrate, cobalt acetate, magnesium acetate.
The know-why that the present invention realizes is: the solid acid catalyst catalyst of the present invention is be made up of carrier and catalysis active ingredient immobilized, with molecular sieve for catalyst carrier, with heteropoly acid for catalyst active component, this new structure has bigger voidage and specific surface area, the efficiency of catalyst can be given full play to, enough gas liquid interfacial area are provided for reaction, be conducive to the mass transfer between gas-liquid two-phase, it is high that this catalyst has catalysis activity, free from environmental pollution, not etching apparatus, ester yield is higher, the advantages such as renewable recycling use, being covered securely by catalyst activity component invests on carrier, avoid the loss of catalysis active constituent；Make active constituent be uniformly distributed in component, improve the geometrical surface of catalyst；Improving wearability and the heat stability of catalyst, increasing the antitoxin performance of catalyst, thus extending the life-span of catalyst.It is prepared ethyl acetate by the catalytic action of Supported on Zeolite catalyst, the process efficiency of reaction is greatly improved, acetic acid conversion ratio reaches more than 98%, ethyl acetate yield is more than 99.5%, the esterification products purity obtained is high, decrease the pressure of rectification purification, and Supported on Zeolite catalyst of the present invention can be reused 6 ~ 8 times, makes production cost greatly be reduced.
The present invention possesses following good result:
(1) the solid-carried catalyst granule of the present invention can be put in the interlayer of porous container component and wavy metal silk screen and flat bed screen or the interlayer of two panels ripple silk net and the interlayer of porous sheet frame thus being placed in ethyl acetate catalytic rectifying tower conversion zone.
(2) present invention is with heteropoly acid for catalyst active component, has that catalysis activity is high, free from environmental pollution, etching apparatus, ester yield are not higher, the advantage such as renewable recycling use；Simultaneously catalyst combines with carrier, can be covered securely by catalyst activity component and invest on carrier, it is to avoid the loss of catalysis active constituent.
(3) catalyst activity component of the present invention is uniformly distributed in component, improve the geometrical surface of catalyst, catalyst is made to have higher utilization rate, catalytic efficiency is more traditional improves 10 ~ 25%, acetic acid conversion ratio reaches more than 98%, ethyl acetate yield is more than 99.5%, and the esterification products purity obtained is high, decreases the pressure of rectification purification；Carried catalyst has bigger voidage and specific surface area, and pressure drop reduces, and mass-and heat-transfer efficiency is improved, and heat transfer efficiency is up to more than 85%.And Supported on Zeolite catalyst of the present invention can be reused 6 ~ 8 times, makes production cost greatly be reduced.
Detailed description of the invention
Describing, below in conjunction with embodiment, the method that the present invention utilizes Supported on Zeolite catalyst preparing ethyl acetate, these descriptions are not that present invention is further limited.
Embodiment 1
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the aluminum sulfate of 2mol waterglass and 0.01mol, strong stirring 10min, it is made fully to dissolve, add the n-butylamine of 0.4mol, stirring 20min, use sulfuric acid regulation solution pH=10, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, is filtered washing and dry, 550 DEG C of roasting 5h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 400g and make it be completely dissolved, be subsequently adding carrier vector 40g, stir 1-2 hour, impregnate 24 hours, then dry moisture, activate 3.5h at 250 DEG C, thus preparing solid-carried catalyst ZSM-5, prepare ethyl acetate with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 3L:2L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 20%, condensation after temperature is react 20min under 110 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 98%, and ethyl acetate yield is 99.5%, and Supported on Zeolite catalyst can reuse 6 times.
Embodiment 2
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the sodium metaaluminate of 3mol waterglass and 0.03mol, strong stirring 10min, it is made fully to dissolve, add the ethylenediamine of 0.6mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, is filtered washing and dry, 600 DEG C of roasting 6h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 500g and make it be completely dissolved, be subsequently adding carrier vector 50g, stir 1 hour, impregnate 24 hours, then dry moisture, activate 4h at 200 DEG C, thus preparing solid-carried catalyst MCM-22, prepare ethyl acetate with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 8L:3L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 15%, condensation after temperature is react 15min under 115 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 98.5%, and ethyl acetate yield is 99.8%, and Supported on Zeolite catalyst can reuse 8 times.
Embodiment 3
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the sodium metaaluminate of 4mol waterglass and 0.05mol, strong stirring 20min, it is made fully to dissolve, add n-butylamine and the ethylenediamine (molal quantity 1:1) of 0.6mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, sample is filtered washing and dry, 600 DEG C of roasting 6h.Take 12 phosphotungstic acid 5g to put into stirring in the water of 600g and make it be completely dissolved, be subsequently adding carrier vector 60g, stir 1 hour, impregnate 24 hours, then dry moisture, activate 3h at 200 DEG C, thus preparing solid-carried catalyst HZSM-5, prepare ethyl acetate with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 5L:1.5L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 30%, condensation after temperature is react 30min under 110 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 98.5%, and ethyl acetate yield is 99.6%, and Supported on Zeolite catalyst can reuse 7 times.
Embodiment 4
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the aluminum sulfate of 5mol waterglass and 0.05mol, strong stirring 20min, it is made fully to dissolve, add the ethanolamine of 0.8mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the magnesium acetate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 120 DEG C of evaporation 10h, concentrated gel material is sealed, crystallization 24h in 180 DEG C of crystallizing kettles, is filtered washing and dry, 650 DEG C of roasting 8h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 500g and make it be completely dissolved, be subsequently adding carrier vector 50g, stir 2 hours, impregnate 24 hours, then dry moisture, activate 5h at 230 DEG C, thus preparing solid-carried catalyst ZSM-5, prepare ethyl acetate with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 5.5L:2.5L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 5%, condensation after temperature is react 15min under 125 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches more than 99.5%, and ethyl acetate yield is more than 99.5%, and Supported on Zeolite catalyst can reuse 6 times..
Embodiment 5
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 150mol by the aluminum sulfate of 4.5mol silica gel and 0.04mol, strong stirring 15min, both are made fully to dissolve, add the n-butylamine of 0.6mol, triethylamine and ethanolamine (molal quantity 1:1:1), sulfuric acid regulation solution pH=10 is used after stirring 20min, add the cobalt acetate that mass fraction is 3%, gained mixed solution is obtained concentrated gel material as evaporation 10h in baking oven 110 DEG C, concentrated gel material is sealed, crystallization 18h in 180 DEG C of crystallizing kettles, sample is filtered washing and dry, 550 DEG C of roasting 8h, obtain the MCM-22 type molecular sieve carrier with microcellular structure；
Taking catalyst and carrier according to mass ratio is that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 5h is activated, thus preparing reactive distillation coupled method to produce the solid-carried catalyst of ethyl acetate at 180 DEG C.Ethyl acetate is prepared with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 4L:2L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 10%, condensation after temperature is react 20min under 115 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 99.2%, and ethyl acetate yield is 99.8%, and Supported on Zeolite catalyst can reuse 7 times..
Embodiment 6
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 200mol by the sodium metaaluminate of 2.5mol silica gel and 0.02mol, strong stirring 10min, both are made fully to dissolve, add the template of 0.4mol, sulfuric acid regulation solution pH=12 is used after stirring 25min, add the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is obtained concentrated gel material as evaporation 10h in baking oven 120 DEG C, concentrated gel material is sealed, crystallization 10h in 180 DEG C of crystallizing kettles, sample is filtered washing and dry, 650 DEG C of roasting 5h, obtain the HZSM-5 type molecular sieve carrier with microcellular structure；
Taking catalyst and carrier according to mass ratio is that 5g:40g puts into stirring in purified water and makes it be completely dissolved, carrier and purified water mass ratio are 40g:400g, rear dipping 24 hours, dry moisture, 3h is activated, thus preparing reactive distillation coupled method to produce the solid-carried catalyst of ethyl acetate at 200 DEG C.Ethyl acetate is prepared with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 6L:3L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 25%, condensation after temperature is react 30min under 112 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 98%, and ethyl acetate yield is 99.6%, and Supported on Zeolite catalyst can reuse 6 times.
Embodiment 7
The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 200mol by the sodium metaaluminate of 3mol waterglass and 0.05mol, strong stirring 18min, both are made fully to dissolve, add the template of 0.8mol, sulfuric acid regulation solution pH=15 is used after stirring 30min, add the Lanthanum (III) nitrate that mass fraction is 2.5%, gained mixed solution is obtained concentrated gel material as evaporation 8h in baking oven 100 DEG C, concentrated gel material is sealed, crystallization 24h in 250 DEG C of crystallizing kettles, sample is filtered washing and dry, 600 DEG C of roasting 6h, obtain the type ZSM 5 molecular sieve carrier with microcellular structure；
Taking catalyst and carrier according to mass ratio is that 5g:50 puts into stirring in purified water and makes it be completely dissolved, carrier and purified water mass ratio are 5g:500g, rear dipping 24 hours, dry moisture, 4h is activated, thus preparing reactive distillation coupled method to produce the solid-carried catalyst of ethyl acetate at 250 DEG C.Ethyl acetate is prepared with this catalyst reaction.
Ethanol, acetic acid, water three are added in reaction kettle of the esterification according to the ratio that volume is 3L:3L:3L, and input accounts for the present embodiment Supported on Zeolite catalyst that reaction system volume toatl proportion is 25%, condensation after temperature is react 20min under 115 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
The present embodiment, acetic acid conversion ratio reaches 98.9%, and ethyl acetate yield is 99.7%, and Supported on Zeolite catalyst can reuse 8 times.
The above embodiment of the present invention scheme is only the description of the invention and can not limit the present invention, claim indicates the scope of product constituent of the present invention, component ratio, preparation method parameter, and the scope of parameter of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all will be understood that in the scope being included in claims.
Claims (6)
1. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate, it is characterized in that, ethanol, acetic acid, water three are vaporized according to the ratio that volume is 3 ~ 8L:2 ~ 3L:3L, again the vaporizer of three is passed in reaction kettle of the esterification, and input accounts for the Supported on Zeolite catalyst that reaction system volume toatl proportion is 5 ~ 30%, condensation after temperature is react 15 ~ 30min under 110 ~ 115 DEG C of conditions, rectification is reclaimed and is obtained ethyl acetate.
2. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate according to claim 1, it is characterized in that, described Supported on Zeolite catalyst is made up of carrier and catalyst, the mass ratio of carrier and catalyst is 1:8 ~ 10, catalyst is covered on carrier and forms the active layer containing active constituent, and described carrier is ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve with microcellular structure；Described catalyst is a kind of or their compositions in 12 phosphotungstic acids, 12 silico-tungstic acids, 12 phosphomolybdate.
3. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate according to claim 1, it is characterised in that this Supported on Zeolite method for preparing catalyst comprises the following steps:
null1) prepared by carrier: be dissolved in the deionized water of 150-250mol in the aluminum source of 2-5mol silicon source and 0.01-0.05mol，Strong stirring 10-20min，Both are made fully to dissolve，Add the template of 0.4-0.8mol，Sulfuric acid regulation solution pH=10-15 is used after stirring 20-30min，Add the auxiliary agent that mass fraction is 2-3%，Gained mixed solution is obtained concentrated gel material as evaporation 5-10h in baking oven 100-120 DEG C，Concentrated gel material is sealed，Crystallization 10-24h in 150-180 DEG C of crystallizing kettle，Sample is filtered washing and dry，550-650 DEG C of roasting 5-8h，Obtain ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve carrier with microcellular structure；
2) load of catalyst activity component: catalyst and carrier are that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved according to mass ratio, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 3-5h is activated, thus preparing the solid-carried catalyst of ethyl acetate at 180-250 DEG C.
4. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate according to claim 3, it is characterised in that described silicon source is any one in silica gel or waterglass；Described aluminum source is any one in aluminum sulfate or sodium metaaluminate.
5. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate according to claim 3, it is characterised in that described template is any one in n-butylamine, ethylenediamine, triethylamine and ethanolamine or their combination in any.
6. the method utilizing Supported on Zeolite catalyst preparing ethyl acetate according to claim 3, it is characterised in that described auxiliary agent is any one in Lanthanum (III) nitrate, cobalt acetate, magnesium acetate.
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|---|---|---|---|---|
| CN114956995A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of acetate |
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