CN102259008B - Solid acid catalyst for esterification reaction and preparation method thereof - Google Patents
Solid acid catalyst for esterification reaction and preparation method thereof Download PDFInfo
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- CN102259008B CN102259008B CN201110122153A CN201110122153A CN102259008B CN 102259008 B CN102259008 B CN 102259008B CN 201110122153 A CN201110122153 A CN 201110122153A CN 201110122153 A CN201110122153 A CN 201110122153A CN 102259008 B CN102259008 B CN 102259008B
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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
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, 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 commercial 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.The solid super-strong acid acid strength is high, selectivity is good, high temperature resistant, can use repeatedly, and preparation is convenient, 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, 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 are not seen bibliographical information at present as yet.
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, filtrating neutralization washing back distillation dewaters, 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, filtrating neutralization washing back distillation dewaters, 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 is high, 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 superior to 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 is high, and 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, reaction efficiency is high, reacts 1 hour acetic acid conversion ratio and can reach 97.2%, and the acetic acid conversion ratio reaches as high as 99.5%.Reaction temperature is low simultaneously, and the products obtained therefrom quality is high, color and luster is 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
Following embodiment is to further elaboration of the present invention, but the invention is not restricted to this.
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.
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.
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.
Take by weighing a certain amount of glacial acetic acid and n-butanol, glacial acetic acid and n-butanol be according to mol ratio 1:4, and then add 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, filtrating is divided water with buck and warm water washing back distillation respectively, obtains transparent oily product butyl acetate.
Take by weighing a certain amount of glacial acetic acid and n-butanol, glacial acetic acid and n-butanol be according to mol ratio 1:4, and then add 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, filtrating 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 be according to mol ratio 1:4, and then add 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, filtrating 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 be according to mol ratio 1:4, and then add 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, filtrating 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 be according to mol ratio 1:4, and then add 1% (raw material gross mass meter) catalyst, stirs, and stable control reaction temperature is increased to 120 ℃, reflux water-dividing, reaction 2h.Filter, filtrating 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 | |
| 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 following:
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. the solid acid catalyst S for preparing with the said method 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 filtrating neutralization washing back distillation dewaters, and obtains water white transparency oily product butyl acetate.
3. the solid acid catalyst S for preparing with the said method 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 filtrating neutralization washing back distillation dewaters, and obtains light yellow oily product butyl oleate.
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| CN102259008B true CN102259008B (en) | 2012-10-10 |
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| 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 |
| CN113024376B (en) * | 2021-03-12 | 2022-12-23 | 润泰化学（泰兴）有限公司 | Production process of hexadecanediester |
| CN113416528B (en) * | 2021-06-22 | 2022-10-28 | 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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| CN101708470A (en) * | 2009-11-18 | 2010-05-19 | 广西科学院 | Method for preparing magnetic solid acid catalyst for production of biodiesel |
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Non-Patent Citations (2)
| Title |
|---|
| 奚洪民等.纳米固体超强酸S2O82-/ZrO2催化剂的改性研究.《东北师大学报（自然科学版）》.2006,第38卷(第3期),第77-81页. * |
| 尹燕磊等.Ce4+- S2O82--SBA-15催化剂合成乙酸正丁酯.《齐齐哈尔大学学报》.2008,第24卷(第1期),第4-7页. * |
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Application publication date: 20111130 Assignee: JIANGSU XIXIN VITAMIN Co.,Ltd. Assignor: Jiangnan University Contract record no.: 2013320000523 Denomination of invention: Solid acid catalyst for esterification reaction and preparation method thereof Granted publication date: 20121010 License type: Exclusive License Record date: 20130606 |
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