CN102259008A - Solid acid catalyst for esterification reaction and preparation method thereof - Google Patents

Solid acid catalyst for esterification reaction and preparation method thereof Download PDF

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Publication number
CN102259008A
CN102259008A CN201110122153XA CN201110122153A CN102259008A CN 102259008 A CN102259008 A CN 102259008A CN 201110122153X A CN201110122153X A CN 201110122153XA CN 201110122153 A CN201110122153 A CN 201110122153A CN 102259008 A CN102259008 A CN 102259008A
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catalyst
zro
solid acid
acid catalyst
reaction
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CN102259008B (en
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蒋平平
郁盛健
张萍波
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Jiangnan University
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Jiangnan University
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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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a solid acid catalyst for esterification reaction and a preparation method thereof, and belongs to the technical field of fine organic chemical industry. The solid acid catalyst S2O82-/ZrO2 is prepared from zirconium oxychloride and ammonium persulfate by a solvent-free dry grinding method. The method is simple and is easy to operate, and has considerable industrial prospect; the acid content and strength of the obtained catalyst are improved obviously; when the obtained catalyst S2O82-/ZrO2 is applied to synthesis of butyl acetate and butyl oleate, the maximum conversion rate of acetic acid can reach 99.5 percent, and the conversion rate of oleic acid reaches 98.8 percent; and a product has high quality, and when the catalyst can be recycled for eight times, the maximum conversion rate of acetic acid can reach 98.6 percent.

Description

A kind of solid acid catalyst that is used for esterification and preparation method thereof
Technical field
The present invention relates to the preparation method of a kind of esterification, be equipped with S with solvent-free dry grinding legal system with novel solid acid 2O 8 2-/ ZrO 2Solid acid catalyst belongs to meticulous field of chemical technology.
Background technology
Butyl acetate is the organic solvent of function admirable, is widely used in making fields such as paint industry, coatings industry, PETROLEUM PROCESSING and pharmacy, is a kind of important meticulous Organic Chemicals.Therefore butyl acetate is a colourless transparent oil liquid, has fruit aroma, and toxicity is very low, also is applied to perfume industry and as the deodorant tune of drinks.Butyl oleate is the light amber transparent oily liquid, and little scent of can be used as plasticizer such as solvent, lubricant, waterproofing agent, ethyl cellulose.The prior synthesizing method of butyl acetate and butyl oleate, be that acetate, oleic acid obtain with the direct dehydration of n-butanol respectively under sulphuric acid catalysis, though concentrated sulfuric acid catalytic activity is higher, cheap, but as esterification catalyst, still have very big deficiency: at first, have reactions such as esterification, oxidation, etherificate in the reaction simultaneously, accessory substance is more, increases the difficulty of raw material recovery and product purification; Secondly, the concentrated sulfuric acid can not be recycled, contaminated environment; Once more, etching apparatus increases the industrial production cost.Therefore, searching can replace the new catalyst for esterification of the concentrated sulfuric acid to become current research and hot of research and development.
The synthetic for the first time SO of Hino in 1979 and Arata 4 2-/ ZrO 2Solid super acid catalyst [M.Hino, K.Arata, J.Am.Chem.Soc., 101 (21) 6439 (1979)], its acid strength is up to 10,000 times of 100% concentrated sulfuric acid.Solid super-strong acid acid strength height, selectivity be good, high temperature resistant, can use repeatedly, and easy to prepare, etching apparatus not, and the application in esterification is also more and more widely.The research of present domestic solid super acid catalyst mainly concentrates on SO 4 2-Be the promoter aspect, have document to point out S recently 2O 8 2-Facilitation to solid acid obviously is better than SO 4 2-(Zhang, a state in the Zhou Dywnasty tin is medium, Journal of Molecular Catalysis, and 2002,16(1): 65-68; Ma Xuedan etc., high chemical journal, 2006,20(2): 239-244).Therefore, need be to the further development and application of this type of solid super acid catalyst.
At present, S 2O 8 2-/ M xO yThe research of type solid super acid catalyst is still in the starting stage, and the present invention adopts solvent-free dry grinding legal system to get S 2O 8 2-/ ZrO 2Solid acid catalyst Synthesis of n-Butyl Acetate and butyl oleate, this method has not yet to see bibliographical information.
Summary of the invention
The present invention be directed to conventional solid acid catalyst preparation method's deficiency, provide that a kind of technology is simple, easy and simple to handle, catalyst activity is high, the preparation S of good reproducibility 2O 8 2-/ ZrO 2The method of solid acid catalyst, and be applied to catalysis Synthesis of n-Butyl Acetate and butyl oleate, obtain good effect.
Technical scheme of the present invention: with the ammonium persulfate is promoter, adopts solvent-free dry grinding method to prepare a kind of novel solid acid catalyst S 2O 8 2-/ ZrO 2Method, may further comprise the steps:
Taking by weighing a certain amount of zirconium oxychloride and ammonium persulfate, is 1:1 ~ 1:6 by zirconium oxychloride and ammonium persulfate mol ratio, mixes; Grind 30min under the room temperature, place 6-48h, the solid acid presoma after grinding at 400 ~ 800 ℃ of following roasting 1 ~ 10h, is obtained S 2O 8 2-/ ZrO 2Nano solid acid catalyst.
The method of catalysis Synthesis of n-Butyl Acetate of the present invention may further comprise the steps:
With glacial acetic acid and n-butanol is the raw material Synthesis of n-Butyl Acetate, and sour and pure mol ratio 1:4 adds 0.05% ~ 2%(raw material gross mass meter) catalyst S 2O 8 2-/ ZrO 2, stirring, reaction temperature is increased to 100 ~ 150 ℃, reflux water-dividing, reaction 0.5 ~ 8h.Filter, in the filtrate and washing back is distilled and is dewatered, and obtains water white transparency oily product butyl acetate.
The method of catalysis artificial oil acid butyl ester of the present invention may further comprise the steps:
With oleic acid and n-butanol is raw material artificial oil acid butyl ester, and sour and pure mol ratio 1:4 adds 0.05% ~ 2%(raw material gross mass meter) catalyst S 2O 8 2-/ ZrO 2, stirring, reaction temperature is increased to 100 ~ 150 ℃, reflux water-dividing, reaction 0.5 ~ 8h.Filter, in the filtrate and washing back is distilled and is dewatered, and obtains light yellow oily product butyl oleate.
Compared with prior art, advantage of the present invention is:
1, method for preparing catalyst is simple: the solvent-free dry grinding legal system that the present invention adopts is equipped with solid acid catalyst S 2O 8 2-/ ZrO 2, method is simple, and weak point consuming time is easy and simple to handle, is applicable to large-scale industrialization production.
2, catalytic activity height, good reproducibility: the solid acid catalyst of the present invention's preparation adopts ammonium persulfate as promoter, and the catalyst acid intensity for preparing than traditional sulfuric acid, ammonium sulfate is significantly improved; And good reaction selectivity, product yield and quality obviously are better than the product of sulphuric acid catalysis; The good reproducibility of catalyst is reused 8 acetic acid conversion ratios and still can be reached 98.6% simultaneously.
3, esterification efficient height, product color is good: adopt the solid acid catalyst catalysis Synthesis of n-Butyl Acetate and the butyl oleate of the present invention's preparation, the reaction efficiency height reacts 1 hour acetic acid conversion ratio and can reach 97.2%, and the acetic acid conversion ratio reaches as high as 99.5%.Simultaneously reaction temperature is low, and products obtained therefrom quality height, color and luster are good, and butyl acetate is a colourless transparent liquid, and butyl oleate is light yellow oily liquid.
Description of drawings
The solid acid catalyst S of Fig. 1 the present invention preparation 2O 8 2-/ ZrO 2Infrared figure, 1,400 ℃ of calcining heats, 2,500 ℃ of calcining heats, 3,600 ℃ of calcining heats, 4,700 ℃ of calcining heats, 5,800 ℃ of calcining heats.
The solid acid catalyst S of Fig. 2 the present invention preparation 2O 8 2-/ ZrO 2XRD figure, 1,400 ℃ of calcining heats, 2,500 ℃ of calcining heats, 3,600 ℃ of calcining heats, 4,700 ℃ of calcining heats, 5,800 ℃ of calcining heats.
The specific embodiment
The following examples are to further elaboration of the present invention, but the invention is not restricted to this.
Embodiment 1
Taking by weighing a certain amount of zirconium oxychloride and ammonium persulfate, is 1 ︰ 4 by zirconium oxychloride and ammonium persulfate mol ratio, mixes; Grind 30min under the room temperature, place 6h, the catalyst precursor after grinding at 400 ℃ of following roasting 1h, is obtained S 2O 8 2-/ ZrO 2Solid acid catalyst.
Embodiment 2
Taking by weighing a certain amount of zirconium oxychloride and ammonium persulfate, is 1 ︰ 4 by zirconium oxychloride and ammonium persulfate mol ratio, mixes; Grind 30min under the room temperature, place 12h, the catalyst precursor after grinding at 600 ℃ of following roasting 2h, is obtained S 2O 8 2-/ ZrO 2Solid acid catalyst.
Embodiment 3
Taking by weighing a certain amount of zirconium oxychloride and ammonium persulfate, is 1 ︰ 6 by zirconium oxychloride and ammonium persulfate mol ratio, mixes; Grind 30min under the room temperature, place 48h, the catalyst precursor after grinding at 800 ℃ of following roasting 4h, is obtained S 2O 8 2-/ ZrO 2Solid acid catalyst.
Embodiment 4
Take by weighing a certain amount of glacial acetic acid and n-butanol, glacial acetic acid and n-butanol are according to mol ratio 1:4, and then adding 1%(raw material gross mass meter) S 2O 8 2-/ ZrO 2Solid acid catalyst stirs, and stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 2h.Filter, filtrate is divided water with buck and warm water washing back distillation respectively, obtains transparent oily product butyl acetate.
Embodiment 5
Take by weighing a certain amount of glacial acetic acid and n-butanol, glacial acetic acid and n-butanol are according to mol ratio 1:4, and then adding 2%(raw material gross mass meter) S 2O 8 2-/ ZrO 2Solid acid catalyst stirs, and stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 8h.Filter, filtrate is divided water with buck and warm water washing back distillation respectively, obtains transparent oily product butyl acetate.
Embodiment 6
Take by weighing a certain amount of oleic acid and n-butanol, oleic acid and n-butanol are according to mol ratio 1:4, and then adding 0.5%(raw material gross mass meter) S 2O 8 2-/ ZrO 2Solid acid catalyst stirs, and stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 2h.Filter, filtrate is divided water with buck and warm water washing back distillation respectively, obtains light yellow oily product butyl oleate.
Embodiment 7
Take by weighing a certain amount of oleic acid and n-butanol, oleic acid and n-butanol are according to mol ratio 1:4, and then adding 2%(raw material gross mass meter) S 2O 8 2-/ ZrO 2Solid acid catalyst stirs, and stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 8h.Filter, filtrate is divided water with buck and warm water washing back distillation respectively, obtains light yellow oily product butyl oleate.
Comparative example 1-2
Take by weighing a certain amount of glacial acetic acid and n-butanol, glacial acetic acid and n-butanol are according to mol ratio 1:4, and then adding 1%(raw material gross mass meter) catalyst, stir, stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 2h.Filter, filtrate is divided water with buck and warm water washing back distillation respectively, obtains transparent oily product butyl acetate.Use different catalysts, obtain product-related data such as following table 1.
Table 1 embodiment and comparative example related data are relatively
? Comparative example 1 Comparative example 2 Embodiment 4
Catalyst type Sulfuric acid (98%) Ammonium persulfate S 2O 8 2-/ZrO 2
Catalyst amount (raw material gross mass meter) 1% 1% 1%
Acetic acid conversion ratio (reaction 1h) 92.6% 91.2% 96.5%
Acetic acid conversion ratio (reaction 2h) 95.2% 96.0% 97.1%

Claims (3)

1. a preparation method who is used for the solid acid catalyst of esterification is characterized in that: adopt ammonium persulfate to be promoter and to control zirconium oxychloride and the mol ratio of ammonium persulfate, adopt solvent-free dry grinding legal system to be equipped with solid acid catalyst S 2O 8 2-/ ZrO 2, preparation process is as follows:
Take by weighing a certain amount of zirconium oxychloride and ammonium persulfate, by zirconium oxychloride and ammonium persulfate mol ratio be: 1:1 ~ 1:6 mixes; Grind 30min under the room temperature, place 6-48h; Catalyst precursor after grinding at 400 ~ 800 ℃ of following roasting 1 ~ 10h, is obtained S 2O 8 2-/ ZrO 2Solid acid catalyst.
2. use the solid acid catalyst S of the described method preparation of claim 1 2O 8 2-/ ZrO 2Application, it is characterized in that: being used for the reaction of catalysis Synthesis of n-Butyl Acetate, is the raw material Synthesis of n-Butyl Acetate with glacial acetic acid and n-butanol, sour and pure mol ratio 1:4 adds the catalyst S of raw material gross mass meter 0.05% ~ 2% 2O 8 2-/ ZrO 2, stirring, reaction temperature is increased to 100 ~ 150 ℃, reflux water-dividing, reaction 0.5 ~ 8h filters, and dewaters with the distillation of washing back in the filtrate, obtains water white transparency oily product butyl acetate.
3. use the solid acid catalyst S of the described method preparation of claim 1 2O 8 2-/ ZrO 2Application, it is characterized in that: being used for the reaction of catalysis artificial oil acid butyl ester, is raw material artificial oil acid butyl ester with oleic acid and n-butanol, sour and pure mol ratio 1:4 adds the catalyst S of raw material gross mass meter 0.05% ~ 2% 2O 8 2-/ ZrO 2, stirring, reaction temperature is increased to 100 ~ 150 ℃, reflux water-dividing, reaction 0.5 ~ 8h filters, and dewaters with the distillation of washing back in the filtrate, obtains light yellow oily product butyl oleate.
CN201110122153A 2011-05-12 2011-05-12 Solid acid catalyst for esterification reaction and preparation method thereof Expired - Fee Related CN102259008B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268938A (en) * 2016-08-03 2017-01-04 江南大学 A kind of bisgallic acid position solid-carrying type ionic-liquid catalyst of biodiesel synthesis and preparation method thereof
CN113024376A (en) * 2021-03-12 2021-06-25 润泰化学（泰兴）有限公司 Production process of hexadecanediester
CN113416528A (en) * 2021-06-22 2021-09-21 西南石油大学 Organic/inorganic nano composite gel plugging agent and oil-based drilling fluid
CN114602513A (en) * 2022-03-29 2022-06-10 江南大学 Mesoporous solid acid catalyst for esterification reaction and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293209A (en) * 2007-04-29 2008-10-29 华中农业大学 Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof
CN101708470A (en) * 2009-11-18 2010-05-19 广西科学院 Method for preparing magnetic solid acid catalyst for production of biodiesel

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293209A (en) * 2007-04-29 2008-10-29 华中农业大学 Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof
CN101708470A (en) * 2009-11-18 2010-05-19 广西科学院 Method for preparing magnetic solid acid catalyst for production of biodiesel

Non-Patent Citations (2)

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Title
《东北师大学报（自然科学版）》 20060930 奚洪民等 纳米固体超强酸S2O82-/ZrO2催化剂的改性研究 第77-81页 1-3 第38卷, 第3期 *
《齐齐哈尔大学学报》 20080131 尹燕磊等 Ce4+- S2O82--SBA-15催化剂合成乙酸正丁酯 第4-7页 1-3 第24卷, 第1期 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268938A (en) * 2016-08-03 2017-01-04 江南大学 A kind of bisgallic acid position solid-carrying type ionic-liquid catalyst of biodiesel synthesis and preparation method thereof
CN106268938B (en) * 2016-08-03 2018-09-28 江南大学 A kind of bisgallic acid position solid-carrying type ionic-liquid catalyst of biodiesel synthesis and preparation method thereof
CN113024376A (en) * 2021-03-12 2021-06-25 润泰化学（泰兴）有限公司 Production process of hexadecanediester
CN113416528A (en) * 2021-06-22 2021-09-21 西南石油大学 Organic/inorganic nano composite gel plugging agent and oil-based drilling fluid
CN114602513A (en) * 2022-03-29 2022-06-10 江南大学 Mesoporous solid acid catalyst for esterification reaction and preparation method thereof

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