CN103183609B - Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate - Google Patents
Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate Download PDFInfo
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- CN103183609B CN103183609B CN201110459655.1A CN201110459655A CN103183609B CN 103183609 B CN103183609 B CN 103183609B CN 201110459655 A CN201110459655 A CN 201110459655A CN 103183609 B CN103183609 B CN 103183609B
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- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 88
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 76
- 238000004821 distillation Methods 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000010533 azeotropic distillation Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 7
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
- 238000012856 packing Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- 238000010025 steaming Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- -1 acetoxyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- GQKZRWSUJHVIPE-UHFFFAOYSA-N sec-amyl acetate Natural products CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of ethylene glycol monoacetate and ethylene glycol diacetate. The preparation method is to take sec-butyl acetate and ethylene glycol as raw materials, perform transesterification in the presence of a base catalyst to prepare ethylene glycol monoacetate and ethylene glycol diacetate, and comprises the specific steps of primary transesterification, chemical reaction equilibrium breaking of transesterification, final-phase transesterification, separation and purification of the products ethylene glycol monoacetate and ethylene glycol diacetate, and the like. The preparation method of ethylene glycol monoacetate and ethylene glycol diacetate is high in product yield, quick in reaction speed, low in power consumption, easy to separate and purify the products, low in cost and simple in technique. In addition, the synthesis method provided by the invention can prepare an important common solvent sec-butyl alcohol. The products are all required by application, so that the utilization ratio of the products is high, the three wastes are less, and the preparation method is green and environment-friendly.
Description
Technical field
The present invention relates to the synthesis field of organic compound, particularly relate to a kind of method applied ester-interchange method and prepare ethylene glycol acetate and glycol diacetate simultaneously.
Background technology
Glycol diacetate (EGDA) is the high boiling point environment-friendly type strong solvent of a new generation, have that smell is good, boiling range is narrow, stable components, winter quick-drying advantage.It can not only be miscible with alcohol, ether and benzene, and possess well water-soluble, and it is various organic resin particularly nitrocellulosic fine solvent, and its Chang Zuowei nitro in paint sprays paint, the solvent of printing-ink, cellulose ester, fluorescent coating.The same with EGDA, ethylene glycol acetate is also a kind of important nuisanceless high boiling solvent of non-optical class, and it is slightly soluble in water, and being dissolved in ethanol, ether, benzene class material, is very important paint remover.
Because EGDA has very wide purposes, so be a very active problem for its preparation research.In the preparation process of EGDA, after a hydroxyl in ethylene glycol and the carboxyl in a molecular acid shrink, generating glycol monoacetate, due to sterically hindered much bigger than hydroxyl of acetoxyl group sterically hindered, this shrinks into the difficulty of ester further with regard to the hydroxyl in increase ethylene glycol acetate and the carboxyl in another molecular acid, and therefore the preparation of EGDA is much more complicated than the esterification of monocarboxylic acid, monohydroxy-alcohol, much more difficult.At present, EGDA synthetic method has acetate esterification process, oxyethane and acetic acid catalysis additive process, ethylene glycol and acetic acid direct esterification.Acetate esterification process adopts glycol dibromide and potassium acetate to react, with pyridine, second acid as catalyst.The method productive rate is low, long reaction time, and cost of material is high, and toxicity is large, is unfavorable for suitability for industrialized production.In oxyethane and acetic acid catalysis additive process, reaction process neither generates water and does not also generate alcohol, reaction mixture composition is simple, product separation and control are also easier to, but the catalyzer that exploitation activity and selectivity of still needing is good, and oxyethane is dangerous large, reaction need be carried out under comparatively high temps and pressure condition, the poor stability of reaction.Ethylene glycol and acetic acid direct esterification are conventional synthetic methods, are generally dewatering agent with toluene, adopt Lewis acid to make catalyzer, and typical catalyzer has the molecular sieve of load iron, zinc chloride or iron(ic) chloride etc.The shortcoming of the method is water generation reaction, and object product and water dissolve each other, and dissolve each other again with unreacted raw material, form the azeotrope that a series of boiling point is close, and product separation difficulty, generally need refine by multistage rectification method.General ethylene glycol acetate can add and obtain in the preparation process of EGDA.
Summary of the invention
The technical problem to be solved in the present invention is: provide that a kind of product yield is high, speed of response is fast, energy consumption is low, and product separation is purified easily, the method for the simple ethylene glycol acetate of with low cost, technique and glycol diacetate.Another kind of product of the present invention is important common solvent sec-butyl alcohol in addition, and make the product of product all required for application in the present invention, product utilization rate is high, and the three wastes are few, environmental protection.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
1, a kind of method preparing ethylene glycol acetate and glycol diacetate, with sec-butyl acetate and ethylene glycol for raw material, under basic catalyst exist, carry out transesterification reaction be prepared into ethylene glycol acetate and glycol diacetate, specifically comprise the following steps:
1) preliminary transesterification reaction: under basic catalyst existence condition, sec-butyl acetate and ethylene glycol carry out preliminary transesterification reaction, wherein, the mol ratio of basic catalyst, ethylene glycol, sec-butyl acetate is 0.01 ~ 0.08: 1: 0.9 ~ 1.5, this step reaction response temperature is 90 ~ 140 DEG C, and the reaction times is 1 ~ 15h;
2) transesterify chemical reaction equilibrium is broken: complete 1) maintain the temperature at 90 ~ 140 DEG C after step, distill out step 1) the middle sec-butyl alcohol generated, detect the amount of the sec-butyl acetate contained in the mixture distilled out in batches, and sec-butyl acetate is added in former reaction system, the amount of substance of the sec-butyl acetate at every turn added is the amount of substance 1 ~ 4 times of the sec-butyl acetate at every turn distilled out, and the time that this step continues is 4 ~ 20h;
3) latter stage transesterification reaction: in step 2) in add for the last time and add sec-butyl acetate after, maintain 90 ~ 140 DEG C of temperature and proceed transesterification reaction 1 ~ 6h;
4) separating-purifying of glycol product monoacetate and glycol diacetate: air distillation goes out the sec-butyl alcohol that in reaction vessel, unreacted sec-butyl acetate produces very much under 125 ~ 135 DEG C of conditions, mixture remaining in reaction vessel is extracted successively, extraction liquid azeotropic distillation, underpressure distillation operation separating-purifying obtain need ethylene glycol acetate and glycol diacetate.
Preferably, described step 4) in, the mixing that the extraction agent that extracting operation uses is one or more in benzene,toluene,xylene, the volume of extraction agent is 1 ~ 4 times of reaction solution cumulative volume; Get upper layer of extraction liquid body after extraction and carry out normal pressure azeotropic distillation, normal pressure azeotropic distillation temperature is 120 ~ 130 DEG C, and the mixture that normal pressure azeotropic distillation steams carries out underpressure distillation further and obtains product ethylene glycol acetate; The mixture do not distilled out in normal pressure azeotropic distillation carries out underpressure distillation and obtains product glycol diacetate.
Preferably, the extraction agent used in described extracting operation process is toluene.
Preferably, further comprising the steps of: the separating-purifying of product sec-butyl alcohol: to step 2) and step 3) in distill out carry out rectification and purification containing the mixture of sec-butyl alcohol and obtain sec-butyl alcohol.
Preferably, described basic catalyst is KOH, K
2cO
3, NaOH, CH
3oNa, C
2h
5one or more combination in ONa.
Preferably, described basic catalyst is K
2cO
3.
Preferably, the mol ratio of basic catalyst, ethylene glycol, sec-butyl acetate is 0.02: 1: 1.
Preferably, the described preliminary transesterification reaction time is 5 ~ 7h, and temperature is 110 ~ 120 DEG C.
Preferably, described in break temperature of reaction in transesterify chemical reaction equilibrium step be 110 ~ 120 DEG C, the amount of substance of the sec-butyl acetate added is the amount of substance 2 times of the sec-butyl acetate distilled out, and the reaction times is 10 ~ 15h.
Preferably, the reaction times of described last transesterification reaction is 2 ~ 3h, and temperature of reaction is 110 ~ 120 DEG C.
Method of the present invention also can be applicable to glycerol, primary isoamyl alcohol, hexanol, 2-Ethylhexyl Alcohol, hexalin, phenol and benzylalcohol and reacts to 2-butyl acetate and prepare corresponding acetic ester.
The invention has the beneficial effects as follows: the present invention adopts sec-butyl acetate and ethylene glycol under the effect of basic catalyst, carry out transesterification reaction and obtains ethylene glycol acetate and glycol diacetate and sec-butyl alcohol, use sec-butyl acetate to replace acetic acid in traditional ester-interchange method as raw material.Make the present invention can also obtain another conventional important solvent sec-butyl alcohol except can obtaining ethylene glycol acetate and glycol diacetate, relative to the secondary butyl ester of raw acetic acid and ethylene glycol, the value of product is high, the product of product of the present invention all needed for application, make product utilization rate high, combined coefficient is high, and the three wastes are few, environmental protection.Do not have water to produce in addition in the present invention, product and the few azeotropic of reactant, make separating-purifying convenient.In synthesis technique of the present invention, by distilling out product sec-butyl alcohol and hand in the chemical equilibrium that reactant sec-butyl acetate breaks transesterification reaction retroactively, make product yield high, and in the present invention temperature of reaction and reaction times control rationally, technique is simple, and speed of response is fast, energy consumption is low.Finally, the cheap and recoverable of catalyzer in synthetic method of the present invention.
Embodiment
Below by concrete embodiment, the invention will be further elaborated.
Embodiment one
(1) preliminary transesterification reaction
400g (6.451mol) ethylene glycol is added in the four-hole boiling flask of band separator column, reflux exchanger, thermometer, add 15g (0.2674mol) KOH, add 1000g (8.621mol) sec-butyl acetate, temperature is elevated to 110 DEG C and carries out reaction 2h.
(2) transesterify chemical reaction equilibrium is broken
After previous step has been reacted, maintain the temperature at 110 DEG C, the sec-butyl alcohol of generation is steamed (wherein containing a small amount of sec-butyl acetate and ethylene glycol acetate), the content of sec-butyl acetate in the mixture steamed by gas chromatographic analysis at interval of 2h, calculate the amount of the sec-butyl acetate steamed in this period of timed interval, and sec-butyl acetate is added in reaction system, the amount of the sec-butyl acetate at every turn added is 2 times of the amount of sec-butyl acetate of steaming.This time distilling out that sec-butyl alcohol adds the process lasts of sec-butyl acetate is 8h, adds altogether sec-butyl acetate 700g (6.034mol).
(3) latter stage transesterification reaction
After adding sec-butyl acetate the last time, continue transesterification reaction 2 hours, temperature of reaction is 110 DEG C.Be glycol diacetate, ethylene glycol acetate, sec-butyl alcohol, the sec-butyl acetate not participating in reaction and ethylene glycol in flask.
(4) the steaming and being separated of sec-butyl acetate
To the material air distillation in flask, distillation temperature is 125 ~ 135 DEG C, sec-butyl alcohol and unreacted sec-butyl acetate can be steamed, and is ethylene glycol acetate, glycol diacetate and unreacted ethylene glycol in bottle.
(5) sec-butyl alcohol-sec-butyl acetate is separated:
Sec-butyl alcohol-sec-butyl acetate knockout tower is a diameter 300mm, the packing tower of high 16000mm, in-built structured packing, and number of theoretical plate is 100 pieces.Sec-butyl alcohol-sec-butyl acetate enters the middle and lower part of knockout tower, tower reactor reboiler is provided by outer heat and is separated whole energy, trim the top of column is than 5, tower top temperature 105 ~ 110 DEG C, bottom temperature 120-125 DEG C, working pressure is normal pressure, tower top can obtain sec-butyl alcohol product, product introduction finished pot, tower reactor is the mixed solution of sec-butyl acetate, sec-butyl alcohol, can be used as Matter Transfer and uses.
(6) ethylene glycol acetate, glycol diacetate are separated with ethylene glycol
A, toluene extracting and separating:
Add toluene in material in flask after transesterification reaction, the add-on of toluene is 2 times of material total amount in bottle, stratification after stirring, and lower floor is unreacted ethylene glycol, and upper strata is the mixed solution of toluene, ethylene glycol acetate and glycol diacetate.
The separation of upper strata mixed solution after B, extraction
1. being separated (azeotropic method) of glycol diacetate and ethylene glycol acetate and toluene:
Upper strata mixed solution azeotropic when toluene is extracted, controlling reflux ratio is 3, temperature is 120 ~ 130 DEG C, the cut distilled out is toluene and ethylene glycol acetate mixed solution, complete to remaining liq underpressure distillation in bottle, wherein distillation condition is: 1330Pa pressure, 150 DEG C steam be glycol diacetate.
2. being separated of ethylene glycol acetate and toluene
To ethylene glycol acetate and toluene mixture liquid underpressure distillation, toluene and ethylene glycol acetate can be obtained.Wherein the distillation condition of ethylene glycol acetate is: vacuum tightness is 10mm mercury column, i.e. 1330Pa, 140 DEG C.
(7) product detects
The detection of product purity adopts vapor-phase chromatography to detect:
Testing conditions is: Agilent 7820A, capillary chromatographic column, fid detector, injector temperature 300 DEG C, the highest column temperature 300 DEG C, detected temperatures 300 DEG C, H2 flow: 30mL/min, air flow quantity: 300mL/min, N
2flow: 25mL/min.
Detect through chromatogram, the purity of product ethylene glycol acetate is 97.8%, the purity of Ethylene glycol acetate is 98%, and the purity of sec-butyl alcohol is 99.0%.
Embodiment two
150L stainless steel cauldron scale up test.Reactions steps is similar to embodiment one.
(1) preliminary transesterification reaction:
Drop into raw material ethylene glycol 40kg (655.7mol), sec-butyl acetate 100kg (862mol) and 1.5kg (26.7mol) KOH in clean, dry reactive distillation column, start and stir and heat up, 120 DEG C are warmed up in 2 hours, transesterification reaction starts, 120 DEG C of insulation 2h, transesterification reaction reaches balance;
(2) transesterify chemical reaction equilibrium is broken:
A, preliminary transesterification reaction are after 2 hours, slowly be warming up to backflow, controlling reflux ratio is 3, from overhead extraction sec-butyl alcohol crude product (sec-butyl acetate with having neither part nor lot in reaction a little), along with sec-butyl alcohol is constantly separated, transesterification reaction balance moves to right, along with the carrying out of reaction, the content steamed shared by the sec-butyl alcohol steamed in material reduces gradually (when just having started to steam, the content of sec-butyl alcohol is more than 80%), and the reaction times is 10 hours.
B, while steaming sec-butyl alcohol, add sec-butyl acetate, the sec-butyl acetate added is 1.5 times of the quality of the sec-butyl acetate steamed with propyl carbinol, adds altogether sec-butyl acetate 70kg.
(3) latter stage transesterification reaction
Transesterification reaction is continued 3 hours after adding sec-butyl acetate the last time, now the temperature of material in reactor is 125 DEG C, in whole process, the top temperature of reflux column is less than 100 DEG C, is a small amount of glycol diacetate, ethylene glycol acetate, sec-butyl alcohol, the sec-butyl acetate not participating in reaction and ethylene glycol in reactor.
(4) the steaming of sec-butyl alcohol and sec-butyl acetate
To the material distillation in reactor, distillation temperature is 125 ~ 135 DEG C, sec-butyl alcohol and unreacted sec-butyl acetate can be steamed, and is ethylene glycol acetate, glycol diacetate and unreacted ethylene glycol in still.
(5) sec-butyl alcohol-sec-butyl acetate is separated
Feed liquid from reactor directly enters the middle and lower part of sec-butyl alcohol-sec-butyl acetate knockout tower, tower reactor reboiler is provided by outer heat and is separated whole energy, trim the top of column is than 5, tower top temperature 105 ~ 110 DEG C, bottom temperature 120 ~ 125 DEG C, working pressure is normal pressure, and tower top can obtain sec-butyl alcohol finished product, and tower reactor can obtain the mixture of sec-butyl acetate, sec-butyl alcohol.
(6) separation of materials at bottom of tower
A, toluene extracting and separating:
Toluene is added in material after transesterification reaction at the bottom of tower, the add-on of toluene is 2 times of all material total amounts at the bottom of tower, stratification after stirring, lower floor is unreacted ethylene glycol (purity is 98%), load the raw material that storage tank does lower secondary response, upper strata is that the mixed solution of toluene, ethylene glycol acetate and EGDA is directly placed in.
The separation of B, extraction upper strata mixed solution
1. being separated (azeotropic method) of glycol diacetate and ethylene glycol acetate and toluene:
Upper strata mixed solution azeotropic when toluene is extracted, controlling reflux ratio is 3, temperature is 120 ~ 130 DEG C, the cut distilled out is toluene and ethylene glycol acetate mixed solution, complete to liquid pressure-reducing distillation in still, wherein distillation condition is: vacuum tightness is 10mm mercury column, i.e. 1330Pa, 150 DEG C steam be glycol diacetate.
2. being separated of ethylene glycol acetate and toluene
To ethylene glycol acetate and toluene mixture liquid underpressure distillation, toluene and ethylene glycol acetate can be obtained.Wherein distillation condition is: vacuum tightness is 10mm mercury column, i.e. 1330Pa, and the condition that steams of toluene is: still temperature 60 DEG C, and gas phase temperature is 40 DEG C, and the condition that steams of ethylene glycol acetate is: 140 DEG C.
(7) product detects
The detection of product purity adopts vapor-phase chromatography to detect:
Testing conditions is: Agilent 7820A, capillary chromatographic column, fid detector, injector temperature 300 DEG C, the highest column temperature 325 DEG C, detected temperatures 300 DEG C, H2 flow: 30mL/min, air flow quantity: 300mL/min, N
2flow: 25mL/min.
Detect through chromatogram, the purity of product ethylene glycol acetate is 98.8%, the purity of glycol diacetate is 98.7%, and the purity of sec-butyl alcohol is 99.0%.
Embodiment three
1m
3stainless steel cauldron is produced, and the operation steps in this step and embodiment one is similar.
Equipment used is for being an intermittent reaction rectifying tower and a sec-butyl alcohol-sec-butyl acetate knockout tower composition, and test set is Agilent 7820A gas chromatographic detection instrument.
Intermittent reaction rectifying tower is a diameter 0.3m, the packing tower of high 2m, the screen waviness packings that interior filling 1m is high, number of theoretical plate 7 pieces.
Sec-butyl alcohol-sec-butyl acetate knockout tower is a diameter 300mm, the packing tower of high 16000mm, in-built structured packing, and number of theoretical plate is 100 pieces.
(1) preliminary transesterification reaction
Drop into raw material ethylene glycol 300kg (4838.7mol), sec-butyl acetate 700kg (6034.5mol) and 2.7kg KOH (213.9mol) in clean, dry reactive distillation column, start and stir and heat up, 110 DEG C are warmed up in 3 hours, transesterification reaction starts, 110 DEG C of insulation 4h, namely transesterification reaction reaches balance;
(2) transesterify chemical reaction equilibrium is broken:
A, preliminary transesterification reaction are after 2 hours, slowly be warming up to backflow, controlling reflux ratio is 3, from overhead extraction sec-butyl alcohol crude product (sec-butyl acetate with having neither part nor lot in reaction a little), along with sec-butyl alcohol is constantly separated, transesterification reaction balance moves to right, along with the carrying out of reaction, the content steamed shared by the sec-butyl alcohol steamed in material reduces gradually (when just having started to steam, the content of sec-butyl alcohol is more than 80%), and the reaction times is 8-15 hour.
B, while steaming sec-butyl alcohol, add sec-butyl acetate, the sec-butyl acetate added is 2 times of the quality of the sec-butyl acetate steamed with propyl carbinol, adds altogether sec-butyl acetate 300kg (2586.2mol).
(3) latter stage transesterification reaction
Transesterification reaction is continued 5 hours after adding sec-butyl acetate the last time, now the temperature of material in reactor is 125 DEG C, in whole process, the top temperature of reflux column is less than 100 DEG C, is a small amount of glycol diacetate, ethylene glycol acetate, sec-butyl alcohol, the sec-butyl acetate not participating in reaction and ethylene glycol in reactor.
(4) the steaming of sec-butyl alcohol and sec-butyl acetate
To the material distillation in reactor, distillation temperature is 125-135 DEG C, sec-butyl alcohol and unreacted sec-butyl acetate can be steamed, and is ethylene glycol acetate, glycol diacetate and unreacted ethylene glycol in still.
(5) sec-butyl alcohol-sec-butyl acetate is separated:
With the step (5) in embodiment one;
(6) separation of materials at bottom of tower
With the step (6) in embodiment one;
(7) product detects:
With the step (7) in embodiment one;
Detect through chromatogram, the purity of product ethylene glycol acetate is 99.2%, the purity of ethylene glycol acetate is 99.1%, and the purity of sec-butyl alcohol is 99.0%.
Embodiment four
6m
3stainless steel cauldron is produced.
Equipment used is for being made up of an intermittent reaction rectifying tower and a sec-butyl alcohol-sec-butyl acetate knockout tower, and test set is Agilent 7820A gas chromatographic detection instrument.
Intermittent reaction rectifying tower is a diameter 0.5m, the packing tower of high 20m, the screen waviness packings that interior filling 12m is high, number of theoretical plate 120 pieces.
Sec-butyl alcohol-sec-butyl acetate knockout tower is a diameter 0.3m, the packing tower of high 16m, in-built structured packing, and number of theoretical plate is 100 pieces.
(1) preliminary transesterification reaction:
Drop into raw material ethylene glycol 1.5 tons (24.2kmol), sec-butyl acetate 3 tons (25.8kmol) and 21.1kg CH
3oNa (0.39kmol) is in clean, dry reactive distillation column, and start and stir and heat up, be warmed up to 130 DEG C in 3 hours, transesterification reaction starts, 130 DEG C of insulation 3h, and namely transesterification reaction reaches balance;
(2) transesterify chemical reaction equilibrium is broken
A, preliminary transesterification reaction are after 3 hours, slowly be warming up to backflow, controlling reflux ratio is 3, from overhead extraction sec-butyl alcohol crude product (sec-butyl acetate with having neither part nor lot in reaction a little), along with sec-butyl alcohol is constantly separated, transesterification reaction balance moves to right, along with the carrying out of reaction, the content steamed shared by the sec-butyl alcohol steamed in material reduces gradually, and the reaction times is 12 hours.
B, while steaming sec-butyl alcohol, add sec-butyl acetate, the sec-butyl acetate added is 2 times of the quality of the sec-butyl acetate steamed with propyl carbinol, adds altogether sec-butyl acetate 2.8 tons.
(3) latter stage transesterification reaction
Transesterification reaction is continued 5 hours after adding sec-butyl acetate the last time, now the temperature of material in reactor is 125 DEG C, is a small amount of glycol diacetate, Ethylene glycol acetate, sec-butyl alcohol, the sec-butyl acetate not participating in reaction and ethylene glycol in reactor.
(4) the steaming of sec-butyl alcohol and sec-butyl acetate
With the step (4) in embodiment one;
(5) sec-butyl alcohol-sec-butyl acetate is separated
With the step (5) in embodiment one;
(6) separation of materials at bottom of tower:
With the step (6) in embodiment one, obtain glycol diacetate 1.7 tons, ethylene glycol acetate 1.25 tons.
(7) product detects:
Step (7) in same embodiment (2);
Detect through chromatogram, the purity of product ethylene glycol acetate is 99.4%, the purity of glycol diacetate is 99%, and the purity of sec-butyl alcohol is 99.0%.
Equivalence explanation
Above prepared by the clear the present invention of describing of specific descriptions of the present invention to the method product yield of ethylene glycol acetate and glycol diacetate is high, speed of response is fast, energy consumption is low, product separation is purified easily, with low cost, technique is simple, product utilization rate advantages of higher.Although specific embodiment here describes in detail, this only as the explanation of technical solution problem of the present invention, and does not limit the scope of claims to the claims in the present invention.Particularly point out, inventor is through careful consideration, and the replacement that the present invention is different, change do not depart from the connotation and extension that the claims in the present invention define.
Claims (10)
1. prepare the method for ethylene glycol acetate and glycol diacetate for one kind, it is characterized in that: with sec-butyl acetate and ethylene glycol for raw material, under basic catalyst exist, carry out transesterification reaction be prepared into ethylene glycol acetate and glycol diacetate, specifically comprise the following steps:
1) preliminary transesterification reaction: under basic catalyst existence condition, sec-butyl acetate and ethylene glycol carry out preliminary transesterification reaction, wherein, the mol ratio of basic catalyst, ethylene glycol, sec-butyl acetate is 0.01 ~ 0.08: 1: 0.9 ~ 1.5, this step reaction response temperature is 90 ~ 140 DEG C, and the reaction times is 1 ~ 15h;
2) transesterify chemical reaction equilibrium is broken: complete 1) maintain the temperature at 90 ~ 140 DEG C after step, distill out step 1) the middle sec-butyl alcohol generated, detect the amount of the sec-butyl acetate contained in the mixture distilled out in batches, and sec-butyl acetate is added in former reaction system, the amount of substance of the sec-butyl acetate at every turn added is the amount of substance 1 ~ 4 times of the sec-butyl acetate at every turn distilled out, and the time that this step continues is 4 ~ 20h;
3) latter stage transesterification reaction: in step 2) in add sec-butyl acetate for the last time after, maintain 90 ~ 140 DEG C of temperature and proceed transesterification reaction 1 ~ 6h;
4) separating-purifying of glycol product monoacetate and glycol diacetate: air distillation goes out the sec-butyl alcohol of unreacted sec-butyl acetate and generation in reaction vessel under 125 ~ 135 DEG C of conditions, mixture remaining in reaction vessel is extracted successively, extraction liquid azeotropic distillation, underpressure distillation operation separating-purifying obtain need ethylene glycol acetate and glycol diacetate.
2. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: described step 4) in,
The mixing that the extraction agent that extracting operation uses is one or more in benzene,toluene,xylene, the volume of extraction agent is 1 ~ 4 times of reaction solution cumulative volume;
Get upper layer of extraction liquid body after extraction and carry out normal pressure azeotropic distillation, normal pressure azeotropic distillation temperature is 120 ~ 130 DEG C, and the mixture that normal pressure azeotropic distillation steams carries out underpressure distillation further and obtains product ethylene glycol acetate; The mixture do not distilled out in normal pressure azeotropic distillation carries out underpressure distillation and obtains product glycol diacetate.
3. the method preparing ethylene glycol acetate and glycol diacetate according to claim 2, is characterized in that: the extraction agent used in described extracting operation process is toluene.
4. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: further comprising the steps of:
The separating-purifying of product sec-butyl alcohol: to step 2) and step 3) in distill out carry out rectification and purification containing the mixture of sec-butyl alcohol and obtain sec-butyl alcohol.
5. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: described basic catalyst is KOH, K
2cO
3, NaOH, CH
3oNa, C
2h
5one or more combination in ONa.
6. the method preparing ethylene glycol acetate and glycol diacetate according to claim 5, is characterized in that: described basic catalyst is K
2cO
3.
7. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: the mol ratio of basic catalyst, ethylene glycol, sec-butyl acetate is 0.02: 1: 1.
8. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: the described preliminary transesterification reaction time is 5 ~ 7h, and temperature is 110 ~ 120 DEG C.
9. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, it is characterized in that: described in break temperature of reaction in transesterify chemical reaction equilibrium step be 110 ~ 120 DEG C, the amount of substance of the sec-butyl acetate added is the amount of substance 2 times of the sec-butyl acetate distilled out, and the reaction times is 10 ~ 15h.
10. the method preparing ethylene glycol acetate and glycol diacetate according to claim 1, is characterized in that: the reaction times of described last transesterification reaction is 2 ~ 3h, and temperature of reaction is 110 ~ 120 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| CN1197790A (en) * | 1997-04-30 | 1998-11-04 | 石伟 | Preparation of acetate product |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
-
2011
- 2011-12-31 CN CN201110459655.1A patent/CN103183609B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| CN1197790A (en) * | 1997-04-30 | 1998-11-04 | 石伟 | Preparation of acetate product |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
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