CN104592018B - A kind of method of reaction-reaction strengthening synthesis of acetic acid isopropyl ester - Google Patents
A kind of method of reaction-reaction strengthening synthesis of acetic acid isopropyl ester Download PDFInfo
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- CN104592018B CN104592018B CN201510003359.9A CN201510003359A CN104592018B CN 104592018 B CN104592018 B CN 104592018B CN 201510003359 A CN201510003359 A CN 201510003359A CN 104592018 B CN104592018 B CN 104592018B
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Abstract
The invention belongs to reaction reinforcement technique field, relate to the synthesis of isopropyl acetate, the method particularly relating to a kind of reaction-reaction strengthening synthesis of acetic acid isopropyl ester, acetic acid, concentrated sulphuric acid and isopropanol being joined in homogeneous reaction still, the acetic acid in homogeneous reaction still and isopropanol react generation isopropyl acetate and water under concentrated sulphuric acid effect；In fixed bed reactors, the acetic acid of unreacted isopropanol completely and acetic acid steam and internal reflux continues reaction under catalyst action, generates isopropyl acetate and water, and isopropyl acetate and the azeotropic mixture of water enter interior cooler condensation；Synthetic product enters water and oil separator, and aqueous phase enters waste water tank, and oil phase enters thick products pot, obtains isopropyl acetate crude product, to be purified refining.The preparation method of the present invention makes feed stock conversion high, and product is easily separated, and catalyst concentrated sulphuric acid and the alumina load polystyrolsulfon acid resin catalysts cycle of operation of use are long, recyclable reuse, technique is simple, operates safe and stable, and system capacity consumption is few.
Description
Technical field
The invention belongs to reaction reinforcement technique field, relate to the synthesis of isopropyl acetate, the method particularly relating to a kind of reaction-reaction strengthening synthesis of acetic acid isopropyl ester.
Background technology
Isopropyl acetate, also known as isopropyl acetate, is a kind of transparence liquid, there is fruital taste, volatile, it is slightly soluble in water, with the immiscible organic solvent such as alcohol, ketone, ethers, can ethyl cellulose dissolved and celluloid, polystyrene, lucite and chlorinated rubber etc., have the title of " alembroth ".Isopropyl acetate is also a kind of important organic intermediate, component as the raw material of synthetic resin and surface coating or some spice, as extractant for pharmaceutical synthesis, it is used for the production of printing-ink, coating as solvent, is used for the separating and dehydrating of synthetic product as dehydrant.Therefore, isopropyl acetate is a kind of broad-spectrum carboxylic acid ester compound.
The main method producing isopropyl acetate is alcohol acid system, and traditional method is to be catalyst with concentrated sulphuric acid, isopropyl acetate is synthesized with acetic acid and isopropanol for primary raw material.The subject matter that the method exists is the equipment corrosion that brings of concentrated sulphuric acid and problem of environmental pollution, next to that raw material converts the problems such as the product separation process not exclusively brought is complicated, equipment investment is big, energy consumption is high.
For above-mentioned conventional production methods Problems existing, patent CN1446791A discloses a kind of reactive distillation method being catalyst with concentrated sulphuric acid, the conversion ratio making isopropanol reaches 98%, even can reach 100%, but the method has the drawback that: it is poor that tower bottoms circulates the operational stability brought between tower reactor and conversion zone, and under high temperature, concentrated sulphuric acid circulates the problems such as the equipment corrosion brought and security maintenance between tower reactor and conversion zone.Patent CN1837183A discloses a kind of with modified 001 × 7 hydro-strong acidic cation exchange resin for catalyst, adopt reactive distillation method synthesis of acetic acid isopropyl ester, avoid the problem using concentrated sulfuric acid catalyst to bring in traditional method, but there is the problem that the iso-propanol conversion rate of the method is not high enough, be unfavorable for product separation.Patent CN1785955A discloses a kind of with metallic aluminium for catalyst, aluminum chloride is initiator, with propanol, isopropanol and ethyl acetate are the method that raw material prepares propyl acetate and isopropyl acetate, patent CN102773118A discloses a kind of method that reaction, extraction method being catalyst with ionic liquid prepares organic ester, patent CN103254067A discloses a kind of method that compressive reaction rectification method prepares isopropyl acetate, traditional method has been carried out linguistic term from replacement concentrated sulfuric acid catalyst and raising conversion ratio aspect by the preparation method of above-mentioned patent disclosure respectively, but all not up to the effect obtaining raw material high conversion with non-concentrated sulfuric acid catalyst, or it is few to use concentrated sulfuric acid catalyst to obtain by etching apparatus, operation safety, stable effect.
Additionally, existing homogeneous reaction is due to Equilibrium limit, the limit of feed stock conversion is exactly equilibrium conversion." reacting while separating " of reactive distillation method, makes conversion ratio breach the restriction of equilibrium conversion, but the existence of azeotropic thing (Phase Equilibria) constrains the further raising of conversion ratio.Therefore, although inhomogeneous reaction and catalytic distillation solve catalyst and reclaim and Equilibrium limit problem, but Phase Equilibria yet suffers from.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, it is provided that the method for a kind of reaction-reaction strengthening synthesis of acetic acid isopropyl ester.
The method that the technical scheme is that a kind of reaction-reaction strengthening synthesis of acetic acid isopropyl ester, step is as follows:
(1) acetic acid is joined in homogeneous reaction still, till when addition is for reaching homogeneous reaction still 50% liquid level；Adding concentrated sulphuric acid, addition is the 1～4% of acetic acid volume；Add isopropanol, till when addition is for making mixed liquor in homogeneous reaction still reach 60% liquid level；
(2) when homogeneous reaction still is heated to the boiling of its internal mix material, opening the cooling water of interior cooler, the acetic acid in homogeneous reaction still and isopropanol react generation isopropyl acetate and water under concentrated sulphuric acid effect；
(3) what control homogeneous reaction still adds heat, the isopropyl acetate generated in homogeneous reaction still is made to enter into the fixed bed reactors equipped with catalyst with water, the azeotropic mixture of isopropanol and the azeotropic mixture of isopropanol and water and acetic acid steam, the acetic acid of unreacted isopropanol completely and acetic acid steam and internal reflux continues reaction under catalyst action, generating isopropyl acetate and water, isopropyl acetate and the azeotropic mixture of water enter interior cooler condensation；
(4) when the temperature of homogeneous reaction still reach 115～120 DEG C, fixed bed reactors outlet temperature reach 77 DEG C time, again in homogeneous reaction still, it is continuously added to acetic acid and isopropanol, the addition mol ratio of acetic acid and isopropanol is 1:1, and controlling homogeneous reaction still temperature is 115～125 DEG C；
(5) keeping fixed bed reactors outlet temperature is 77 DEG C, cooler material outlet valve in opening, and synthetic product enters water and oil separator, and aqueous phase enters waste water tank, and oil phase enters thick products pot, obtains isopropyl acetate crude product, to be purified refining.
The invention has the beneficial effects as follows:
1, iso-propanol conversion rate is high: the present invention utilizes reaction-reaction intensifying method, directly it is connected with homogeneous reaction still by fixed bed reactors, make in homogeneous reaction still unconverted, the isopropanol existed as an azeotrope enters in fixed bed reactors, reaction is continued under the effect of catalyst, the packing type catalyst loaded in fixed bed reactors, existing catalytic action has again separation function, the isopropanol entered in fixed bed reactors can not only be carried out catalytic reaction, reaction can be produced simultaneously, and the acetic acid product isopropyl ester entered from homogeneous reaction still and water are with the isolated in form of azeotropic mixture out, raw acetic acid and isopropanol are stayed all the time and reacts in systems, the conversion ratio making raw material isopropanol can reach more than 98%.
2, product is easily separated: in preparation process of the present invention, completely or nearly converting completely and point phase dehydration of product of isopropanol, make final synthetic crude product composition simple, only it is made up of minor amount of water, isopropanol and acetic acid product isopropyl ester, creates advantage for the simple flow of product separation, minimizing investment and reduction energy consumption.
3, catalyst recoverable: the present invention utilizes reaction-reaction intensifying method, although use concentrated sulphuric acid as catalyst, but concentrated sulphuric acid can be accumulated in homogeneous reaction still, does not need outer row, and consumption is few, to equipment almost without corrosion；The alumina load polystyrolsulfon acid resin catalysts cycle of operation used is long, recyclable reuses.
4, operation safety and stability: in preparation process of the present invention, only homogeneous reaction still contact concentrated sulphuric acid, and need not circulate in systems, therefore technique is simple, operates safe and stable.
5, energy consumption is low: the homogeneous reaction heat of the present invention and inhomogeneous reaction heat are utilized by product in homogeneous reaction still reaction product and fixed bed reactors respectively, and system capacity consumption is few；It addition, the composition of synthetic crude product simplifies, the energy consumption that product separates is made to be greatly lowered.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described homogeneous reaction still is enamel reaction still；Described fixed bed reactors and inner member thereof are acidproof material, and fixed bed reactors are adiabatic reactor；Described interior cooler is tubular heat exchanger, passes into cooling water in tube side.
Further, the solid catalyst loaded in described fixed bed reactors is alumina load polystyrolsulfon acid resin, and catalyst particle size is 3～5mm, and granule strength is more than 40N, and specific surface area is 300m2/ g, exchange capacity is 5.35mmol/g.
Further, in preparation process, remaining that in homogeneous reaction still, liquid level is 60%, in homogeneous reaction still, temperature of charge is lower than 125 DEG C；If liquid level is lower than 60%, supplement acetic acid in time, if liquid level is higher than 75%, unnecessary material is discharged from homogeneous reaction bottom portion, and supplementary acetic acid and concentrated sulphuric acid continue reaction.
Further, after reaction stops, can continue to after the alumina load polystyrolsulfon acid resin catalysts drying of use, screening, load active component use.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention；
In figure, 1, homogeneous reaction still；2, fixed bed reactors；3, interior cooler；4, water and oil separator；5, waste water tank；6, thick products pot；7, isopropanol charge pump；8, acetic acid charge pump；9, isopropanol head tank；10, acetic acid raw material tank；11, concentrated sulphuric acid charging aperture.
Detailed description of the invention
Below in conjunction with example and accompanying drawing, principles of the invention and feature being described, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Embodiment 1
A kind of method of reaction-reaction strengthening synthesis of acetic acid isopropyl ester, method is as follows:
In conjunction with Fig. 1, wherein, fixed bed reactors 2 are arranged on homogeneous reaction still 1 top, it is joined directly together with homogeneous reaction still 1, it is filled with solid catalyst in fixed bed reactors 2, interior cooler 3 is arranged on fixed bed reactors 2, it is joined directly together with fixed bed reactors 2 top, water and oil separator 4 is connected with interior cooler 3 by pipeline, waste water tank 5, thick products pot 6 is connected with water and oil separator 4 respectively by pipeline, acetic acid raw material tank 10, isopropanol head tank 9 is respectively through acetic acid charge pump 8, isopropanol charge pump 7 is connected to homogeneous reaction still 1, pipeline dypass between described acetic acid feed tank 10 and acetic acid charge pump 8 is concentrated sulphuric acid charging aperture 11.
Homogeneous reaction still is 250ml there-necked flask, side thermometric, opposite side charging, fixed bed reactors are Φ 20*500mm glass tubing, and outer wall is coated with heat insulating conductive film, built-in alumina load polystyrolsulfon acid resin catalysts, loading is highly 300mm, all the other highly load Φ 2*2mm porcelain ring, and catalyst particle size is 1-3mm, and exchange capacity is 5.35mmol/g.
(1) 50.1g acetic acid is joined in homogeneous reaction still, add 2ml concentrated sulphuric acid and 10.2g isopropanol；
(2) when homogeneous reaction still is heated to the boiling of its internal mix material, opening the cooling water of interior cooler, the acetic acid in homogeneous reaction still and isopropanol react generation isopropyl acetate and water under concentrated sulphuric acid effect；
(3) what control homogeneous reaction still adds heat, the isopropyl acetate generated in homogeneous reaction still is made to enter into the fixed bed reactors equipped with catalyst with water, the azeotropic mixture of isopropanol and the azeotropic mixture of isopropanol and water and acetic acid steam, the acetic acid of unreacted isopropanol completely and acetic acid steam and internal reflux continues reaction under catalyst action, generating isopropyl acetate and water, isopropyl acetate and the azeotropic mixture of water enter interior cooler condensation；
(4) when the temperature of homogeneous reaction still reach 115～120 DEG C, fixed bed reactors outlet temperature reach 77 DEG C time, again in homogeneous reaction still, be continuously added to acetic acid and isopropanol, accumulative in course of reaction add acetic acid 1315.4g, isopropanol 1136.8g,；
(5) keeping fixed bed reactors outlet temperature is 77 DEG C, cooler material outlet valve in opening, synthetic product enters water and oil separator, aqueous phase enters waste water tank, oil phase enters thick products pot, obtaining isopropyl acetate crude product 1964.6g, isopropyl acetate ester content 97.36wt% in the thick product of gas chromatographic analysis synthesis, the conversion ratio calculating raw material isopropanol reaches 98.97%..
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (1)
1. the method for reaction-reaction strengthening synthesis of acetic acid isopropyl ester, it is characterised in that step is as follows:
(1) acetic acid is joined in homogeneous reaction still, till when addition is for reaching homogeneous reaction still 50% liquid level；Adding concentrated sulphuric acid, addition is the 1～4% of acetic acid volume；Add isopropanol, till when addition is for making mixed liquor in homogeneous reaction still reach 60% liquid level；
(2) when homogeneous reaction still is heated to the boiling of its internal mix material, opening the cooling water of interior cooler, the acetic acid in homogeneous reaction still and isopropanol react generation isopropyl acetate and water under concentrated sulphuric acid effect；
(3) what control homogeneous reaction still adds heat, the isopropyl acetate generated in homogeneous reaction still is made to enter into the fixed bed reactors equipped with catalyst with water, the azeotropic mixture of isopropanol and the azeotropic mixture of isopropanol and water and acetic acid steam, the acetic acid of unreacted isopropanol completely and acetic acid steam and internal reflux continues reaction under catalyst action, generating isopropyl acetate and water, isopropyl acetate and the azeotropic mixture of water enter interior cooler condensation；
(4) when the temperature of homogeneous reaction still reach 115～120 DEG C, fixed bed reactors outlet temperature reach 77 DEG C time, again in homogeneous reaction still, it is continuously added to acetic acid and isopropanol, the addition mol ratio of acetic acid and isopropanol is 1:1, and controlling homogeneous reaction still temperature is 115～125 DEG C；
(5) keeping fixed bed reactors outlet temperature is 77 DEG C, cooler material outlet valve in opening, and synthetic product enters water and oil separator, and aqueous phase enters waste water tank, and oil phase enters thick products pot, obtains isopropyl acetate crude product, to be purified refining；
Catalyst described in step (3) is alumina load polystyrolsulfon acid resin, and catalyst particle size is 3～5mm, and granule strength is more than 40N, and specific surface area is 300m2/ g, exchange capacity is 5.35mmol/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510003359.9A CN104592018B (en) | 2015-01-04 | 2015-01-04 | A kind of method of reaction-reaction strengthening synthesis of acetic acid isopropyl ester |
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| CN201510003359.9A CN104592018B (en) | 2015-01-04 | 2015-01-04 | A kind of method of reaction-reaction strengthening synthesis of acetic acid isopropyl ester |
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| CN104592018A CN104592018A (en) | 2015-05-06 |
| CN104592018B true CN104592018B (en) | 2016-06-29 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US1808155A (en) * | 1926-11-24 | 1931-06-02 | Standard Oil Dev Co | Process of making isopropyl acetate |
| CN100402485C (en) * | 2006-04-19 | 2008-07-16 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
| CN103214367B (en) * | 2013-05-09 | 2015-06-10 | 江苏瑞佳化学有限公司 | Continuous production device and method for isopropyl acetate |
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Effective date of registration: 20170627 Address after: Laishan District of Shandong city of Yantai province Zhen Road 264003 No. 66 Patentee after: Yantai Hongtai Chemical Industry Co., Ltd. Address before: 264000 Sheng Quan Industrial Park, Laishan District, Shandong, Yantai Patentee before: YANTAI SITONG RUBBER CO., LTD. |
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Granted publication date: 20160629 Termination date: 20210104 |