CN1951563A - Method for preparing solid sulphoacid by catalyzing carbohydrate - Google Patents
Method for preparing solid sulphoacid by catalyzing carbohydrate Download PDFInfo
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- CN1951563A CN1951563A CNA2006100325526A CN200610032552A CN1951563A CN 1951563 A CN1951563 A CN 1951563A CN A2006100325526 A CNA2006100325526 A CN A2006100325526A CN 200610032552 A CN200610032552 A CN 200610032552A CN 1951563 A CN1951563 A CN 1951563A
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- sulphoacid
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- sulfuric acid
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Abstract
The invention relates to a method for using carbohydrate catalyst to produce solid sulfonic acid. Wherein, it comprises that, in the 65-95% sulfuric acid, mixing sulfuric acid and carbohydrate at 3-20:1, adding carbohydrate material, mixing and carbonizing at 40-200Deg. C; cooling and adding deionized water; washing and filtering until it is neutral; drying, shaping to obtain carbonized particles; adding sulphonating agent while the ratio between sulphonating agent and carbonized particles is 3-15:1, sulphonating for 1-20h at 30-150Deg. C; cooling and using boiled deionized water to wash the product and filtering until there is no sulphuric acid, drying to obtain the solid sulfonic acid. The invention uses sulphuric acid carbonization method, to shorten the reaction period and reduce energy consumption, while the product has high stability.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts method, be specifically related to the preparation method of solid sulfoacid.
Background technology
Carbohydrate is the abundantest organic matter of occurring in nature, and it mainly is present in the plant, accounts for 50～80% of plant proportion.Can be divided three classes: monose, as glucose, fructose, galactolipin, mannose; Oligosaccharides, (seeing so that disaccharide more) is as sucrose, maltose, lactose, cellobiose; Polysaccharide is as starch, dextrin, glycogen, cellulose, hemicellulose and pectin etc.Carbohydrate is the main energy supply nutrient of human body, is the necessary composition that constitutes cell and tissue, can keep the normal function of brain cell.Its physiological action is known by people, and it is mainly used also is in medicine, health care, food, daily use chemicals industrial aspect, does not also relate to the application of catalysis industrial circle.
In the catalysis industrial circle, Preparation of catalysts is eternal technological challenge.Along with chemical industry production develops to greenization, the application of solid catalyst is more and more wider.From the viewpoint of sustainable development, seek renewable raw materials and replace the oil mineral raw material to be used for the preparation of solid catalyst, be the important channel that environmental protection is moved towards in catalyst industry.Existing solid sulfoacid catalyst such as p-methyl benzenesulfonic acid, sulfamic acid, sulfonate resin etc., its preparation raw material all be unable to do without mineral resources such as non-reproducible coal and oil, and this shortcoming will limit the production and the application in their futures.In recent years there is Japanese seminar to propose saccharide raw material and prepares solid sulfoacid, for carbohydrate provides possibility in the application of catalytic field through high temperature pyrolysis, sulfonation.However, the required energy consumption height of its preparation process, the time is long, haves much room for improvement.
Summary of the invention
For solving above-mentioned existing in prior technology problem, the invention provides a kind of less energy consumption, the cycle is short, and carbohydrate is applied to catalytic field, meets the method for preparing peracid amount solid sulfoacid that Green Chemistry requires.
The principle of the inventive method is: carbohydrate raw material obtains having the solid carbon material of polycyclic aromatic hydrocarbon structure through the sulfuric acid catalysis dehydration carbonization, and then introduces sulfonic group and prepare solid sulfoacid on aromatic ring.
The inventive method is achieved by the following technical programs.
A. in mass percent is 65～95% sulfuric acid, add carbohydrate raw material while stirring by sulfuric acid and carbohydrate raw material mass ratio 3～20: 1,40～200 ℃ are stirred charings, and the reaction time is 1～10h;
B. adding deionized water cyclic washing and suction filtration after the above-mentioned final reacting product cooling, is neutral until filtrate, oven dry, and moulding gets the charing particle;
C. above-mentioned charing particle adds sulfonating agent, 30～150 ℃ of sulfonation, and the time is 1～20h, described sulfonating agent is 3～15: 1 with charing granular mass ratio, the cooling back does not have sulfuric acid with the deionized water cyclic washing product and the suction filtration of boiling in filtrate, oven dry obtains solid sulfoacid.
Carbohydrate raw material is any one or its composition in monose, oligosaccharides, the polysaccharide among the described step a, described monose is glucose, fructose, described oligosaccharides is sucrose, maltose, lactose, described polysaccharide is starch, dextrin, glycogen, cellulose, hemicellulose, sulfuric acid and raw material mass ratio are preferably 6～12: 1, stir carbonization temperature and be preferably 60～120 ℃, carbonization time is preferably 1～3h; Sulfonation temperature is preferably 60～120 ℃ among the described step c, and the sulfonation time is preferably 2～6h, and sulfonating agent is preferably 3～9: 1 with charing granular mass ratio, and sulfonating agent is oleum, the concentrated sulfuric acid or chlorosulfonic acid.
The advantage of the inventive method is: (1). to nature by photosynthesis and a large amount of carbohydrate resource that exists provides a kind of new application approach, carbohydrate is achieved in the application of catalytic field, suitability for industrialized production becomes possibility, has also developed a kind of new technology for preparing solid sulfoacid simultaneously.(2). adopt the sulfuric acid catalysis charring among the step a, shortened reaction time, reduced energy dissipation.(3). the solid acid catalyst acid amount with the method preparation is higher, good hydrothermal stability.
Description of drawings
Fig. 1 is the infrared spectrogram (FT-IR) of solid sulfoacid.
Wherein a is a grape sugar charcoal type solid sulfoacid, and b is a sucrose charcoal type solid sulfoacid, and c is a starch charcoal type solid sulfoacid.
The specific embodiment
Embodiment 1:
In the sulfuric acid solution of 100kg 80% (mass percent), stir adding glucose 10kg, 80 ℃ of isothermal reaction 3h add deionized water cyclic washing and suction filtration after the cooling, be neutral until filtrate, and 100 ℃ of oven dry obtain product grape sugar charcoal 3.9kg.Get gained grape sugar charcoal 3.9kg, add chlorosulfonic acid 27.3kg, 60 ℃ of constant temperature sulfonation 4h, the cooling back is with the deionized water cyclic washing product and the suction filtration of boiling, until using BaCl
2Solution detects filtrate does not have BaSO
4White precipitate does not promptly have sulfuric acid in the filtrate, 100 ℃ dry grape sugar charcoal type solid sulfoacid 5.76kg, titration gets its acid amount and is 2.50mmolg
-1
Above-mentioned products therefrom grape sugar charcoal type solid sulfoacid is defined as containing the solid sulfoacid of sulfonic acid group through infrared spectrum analysis (FT-IR) and elementary analysis.Infrared spectrum analysis is carried out on AVATAR370 FT-IR infrared spectrometer, and the S elementary analysis is carried out on U.S. ANTEK7000 element instrument.(see Fig. 1 a) as can be known: 1400cm from gained FT-IR collection of illustrative plates
-1～1622cm
-1There is tangible aromatic ring structure eigen vibration, illustrates and contain aromatic ring structure in the product; Be present in 1178cm
-1And 1032cm
-1Asymmetric and the symmetrical stretching vibration peak of the two keys of the S=O at place is with 645cm
-1The eigen vibration of the C-S of place singly-bound has illustrated the existence that sulfonic acid group is all arranged in the product structure.The above-mentioned gained grape of elementary analysis sugar charcoal type solid sulfoacid sample records sulfur content and reaches 4.77%, and illustrating equally has a certain amount of sulfonic acid group to exist in the product.
Esterification with this catalyst n-butanol and acetate, reaction condition is, n-butanol: acetate=0.05: 0.15 (mol ratio), catalyst amount is 0.1 gram, and reaction temperature is 106 ℃, and the reaction time is 1h, gas chromatographic detection reaction back mixed liquor, obtaining the n-butanol conversion ratio is 90.8%, and the catalyst activity height is described, effective.
Embodiment 2:
Add sucrose 10kg in the sulfuric acid solution of 63.2kg 95% (mass percent), 120 ℃ of constant temperature stirring reaction 3h add deionized water cyclic washing and suction filtration after the cooling, are neutral until filtrate, and 100 ℃ of oven dry obtain sucrose charcoal 5.9kg.Get gained sucrose charcoal 5.9kg, add concentrated sulfuric acid 41.3kg, 80 ℃ of sulfonation 2h, the cooling back is with the deionized water cyclic washing product and the suction filtration of boiling, until using BaCl
2Solution detects filtrate does not have BaSO
4White precipitate does not promptly have sulfuric acid in the filtrate, and 100 ℃ of oven dry obtain sucrose charcoal type solid sulfoacid 7.15kg.Titration gets this sulfonic acid acid amount and is 2.53mmolg
-1
Above-mentioned products therefrom sucrose charcoal type solid sulfoacid is defined as containing the solid sulfoacid of sulfonic acid group through infrared spectrum analysis (FT-IR) and elementary analysis.Used instrument, method be with embodiment 1, and product structure and embodiment 1 product structure are similar as can be known from gained FT-IR collection of illustrative plates (seeing b Fig. 1), and the sulfonic acid group characteristic peak is obvious; Detect as can be known through elementary analysis, sulfur content reaches 4.94% in the sucrose charcoal type solid sulfoacid, and the existence of a certain amount of sulfonic acid group in the product is described.
With the esterification of this catalyst n-butanol and acetate, reaction condition is with embodiment 1, and the gas-chromatography conversion ratio that obtains n-butanol is 93.9%.
Embodiment 3:
Get starch 10kg, add the sulfuric acid solution 107kg of 75% (mass percent), 80 ℃ of constant temperature stirring reaction 3h add deionized water cyclic washing and suction filtration after the cooling, are neutral until filtrate, and 100 ℃ of oven dry obtain starch charcoal 4.6kg.Get gained starch charcoal 4.6kg, add 50% (mass percent) oleum 23.0kg, 120 ℃ of sulfonation 2h, the cooling back is with the deionized water cyclic washing product and the suction filtration of boiling, until using BaCl
2Solution detects filtrate does not have BaSO
4White precipitate does not promptly have sulfuric acid in the filtrate, 100 ℃ dry starch charcoal type solid sulfoacid 5.71kg.The starch charcoal type solid sulfoacid acid amount that titration obtains is 2.12mmolg
-1
Above-mentioned products therefrom starch charcoal type solid sulfoacid is defined as containing the solid sulfoacid of sulfonic acid group through infrared spectrum analysis (FT-IR) and elementary analysis.Used instrument, method be with embodiment 1, and product structure and embodiment 1 product structure are similar as can be known from gained FT-IR collection of illustrative plates (seeing c Fig. 1), and the sulfonic acid group characteristic peak is obvious; Detect as can be known through elementary analysis, sulfur content reaches 3.97% in the starch charcoal type solid sulfoacid, and the existence of a certain amount of sulfonic acid group in the product is described.
With the esterification of this catalyst n-butanol and acetate, reaction condition is with embodiment 1, and the gas-chromatography conversion ratio that obtains n-butanol is 93.0%.
Above embodiment is intended to illustrate the present invention rather than limitation of the invention.
Claims (10)
1, a kind of method of preparing solid sulphoacid by catalyzing carbohydrate is characterized in that, may further comprise the steps:
A. in mass percent is 65～95% sulfuric acid, add carbohydrate raw material while stirring by sulfuric acid and carbohydrate raw material mass ratio 3～20: 1,40～200 ℃ are stirred charings, and the reaction time is 1～10h;
B. adding deionized water cyclic washing and suction filtration after the above-mentioned final reacting product cooling, is neutral until filtrate, oven dry, and moulding gets the charing particle;
C. above-mentioned charing particle adds sulfonating agent, 30～150 ℃ of sulfonation, and the time is 1～20h, described sulfonating agent is 3～15: 1 with charing granular mass ratio, the cooling back does not have sulfuric acid with the deionized water cyclic washing product and the suction filtration of boiling in filtrate, oven dry obtains solid sulfoacid.
According to the described method of claim 1, it is characterized in that 2, carbohydrate raw material is any one or its composition in monose, oligosaccharides, the polysaccharide among the described step a from preparing solid sulphoacid by catalyzing carbohydrate.
3, according to claim 1 or 2 described methods, it is characterized in that sulfuric acid and raw material mass ratio are 6～12: 1 among the described step a from preparing solid sulphoacid by catalyzing carbohydrate.
4, according to claim 1 or 2 described methods, it is characterized in that carbonization temperature is 60～120 ℃ among the described step a from preparing solid sulphoacid by catalyzing carbohydrate.
5, according to claim 1 or 2 described methods, it is characterized in that carbonization time is 1～3h among the described step a from preparing solid sulphoacid by catalyzing carbohydrate.
According to claim 1 or 2 described methods, it is characterized in that 6, among the described step c, sulfonation temperature is 60～120 ℃ from preparing solid sulphoacid by catalyzing carbohydrate.
According to claim 1 or 2 described methods, it is characterized in that 7, the sulfonation time is 2～6h among the described step c from preparing solid sulphoacid by catalyzing carbohydrate.
According to claim 1 or 2 described methods, it is characterized in that 8, sulfonating agent is 3～9: 1 with charing granular mass ratio among the described step c from preparing solid sulphoacid by catalyzing carbohydrate.
9, according to claim 1 or 2 described methods, it is characterized in that sulfonating agent is oleum, the concentrated sulfuric acid or chlorosulfonic acid among the described step c from carbohydrate catalytic preparation circle sulfonic acid.
10, according to the described method of claim 2 from preparing solid sulphoacid by catalyzing carbohydrate, it is characterized in that, described monose is glucose, fructose, and described oligosaccharides is sucrose, maltose, lactose, and described polysaccharide is starch, dextrin, glycogen, cellulose, hemicellulose.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617347A (en) * | 2012-03-13 | 2012-08-01 | 湖北远成药业有限公司 | Method for preparing isoamyl cinnamate |
| CN105536818A (en) * | 2016-01-26 | 2016-05-04 | 裴卿 | Preparation method for sulfonic acid type solid acid and method for utilizing waste plastic to prepare fuel oil |
| CN109289870A (en) * | 2018-09-21 | 2019-02-01 | 陕西科技大学 | A kind of sulfonation charcoal and its preparation method and application |
| CN109289871A (en) * | 2018-10-31 | 2019-02-01 | 湖南师范大学 | A kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct |
| CN109482199A (en) * | 2018-12-05 | 2019-03-19 | 中国制浆造纸研究院有限公司 | A method of preextraction hemicellulose and its hydrolysis and saccharification efficiency are improved using biomass carbon based solid acid catalyst |
| CN112076801A (en) * | 2020-08-31 | 2020-12-15 | 江苏大学 | Carbon microsphere catalyst, preparation method and application |
| CN112717953A (en) * | 2020-12-23 | 2021-04-30 | 浙江大学 | Carbon-based solid acid catalyst, preparation method and method for applying carbon-based solid acid catalyst to biomass hydrothermal conversion |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1022180C (en) * | 1990-06-06 | 1993-09-22 | 河北省石油化学工业研究所 | Process for preparing solid decolorizer |
| JP4041409B2 (en) * | 2003-02-05 | 2008-01-30 | 独立行政法人科学技術振興機構 | Polycyclic aromatic carbon-based solid strong acid |
| CN100580818C (en) * | 2003-09-16 | 2010-01-13 | 国立大学法人东京工业大学 | Proton conductibility material, sulfonic amorphous carbon and preparation method thereof |
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2006
- 2006-11-10 CN CNB2006100325526A patent/CN100421793C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617347A (en) * | 2012-03-13 | 2012-08-01 | 湖北远成药业有限公司 | Method for preparing isoamyl cinnamate |
| CN105536818A (en) * | 2016-01-26 | 2016-05-04 | 裴卿 | Preparation method for sulfonic acid type solid acid and method for utilizing waste plastic to prepare fuel oil |
| CN109289870A (en) * | 2018-09-21 | 2019-02-01 | 陕西科技大学 | A kind of sulfonation charcoal and its preparation method and application |
| CN109289870B (en) * | 2018-09-21 | 2021-03-30 | 陕西科技大学 | Sulfonated carbon and preparation method and application thereof |
| CN109289871A (en) * | 2018-10-31 | 2019-02-01 | 湖南师范大学 | A kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct |
| CN109482199A (en) * | 2018-12-05 | 2019-03-19 | 中国制浆造纸研究院有限公司 | A method of preextraction hemicellulose and its hydrolysis and saccharification efficiency are improved using biomass carbon based solid acid catalyst |
| CN112076801A (en) * | 2020-08-31 | 2020-12-15 | 江苏大学 | Carbon microsphere catalyst, preparation method and application |
| CN112076801B (en) * | 2020-08-31 | 2023-04-07 | 江苏大学 | Carbon microsphere catalyst, preparation method and application |
| CN112717953A (en) * | 2020-12-23 | 2021-04-30 | 浙江大学 | Carbon-based solid acid catalyst, preparation method and method for applying carbon-based solid acid catalyst to biomass hydrothermal conversion |
| CN112717953B (en) * | 2020-12-23 | 2022-01-18 | 浙江大学 | Carbon-based solid acid catalyst, preparation method and method for applying carbon-based solid acid catalyst to biomass hydrothermal conversion |
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Assignee: Hubei Yuhua Chemical Group Co., Ltd. Assignor: Hunan Normal University Contract fulfillment period: 2009.10.11 to 2015.10.10 contract change Contract record no.: 2009430000183 Denomination of invention: Method for preparing solid sulphoacid by catalyzing carbohydrate Granted publication date: 20081001 License type: Exclusive license Record date: 2009.11.5 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.10.11 TO 2015.10.10; CHANGE OF CONTRACT Name of requester: HUNAN YUHUA CHEMICAL INDUSTRY GROUP CO.,LTD. Effective date: 20091105 |
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