CN102059140B - Carbon-based solid acid as well as preparation method and application thereof - Google Patents
Carbon-based solid acid as well as preparation method and application thereof Download PDFInfo
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- CN102059140B CN102059140B CN 201010583351 CN201010583351A CN102059140B CN 102059140 B CN102059140 B CN 102059140B CN 201010583351 CN201010583351 CN 201010583351 CN 201010583351 A CN201010583351 A CN 201010583351A CN 102059140 B CN102059140 B CN 102059140B
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Abstract
The invention discloses carbon-based solid acid as well as a preparation method and application thereof, belonging to the technical field of chemical synthesis. The preparation method is characterized in that a polyhydroxy compound is used as a raw material, isethionic acid is used as active molecules, the molar ratio of the raw material to the isethionic acid is (2:1)-(10:1), and the carbon-based solid acid is prepared through the steps of: carrying out carbonization and condensation reaction on the polyhydroxy compound and the isethionic acid at 120-400 DEG C for 2-32h, adding hot water above 80 DEG C for washing after the reaction, filtering to remove dissociative acidic substances, and drying the obtained product in a drying oven at 120 DEG C. The carbon-based solid acid has the advantages of high heat stability, high acid value, good catalytic effect, reusability and the like.
Description
Technical field:
The present invention relates to polyol and isethionic acid under the high temperature nitrogen condition, carry out the carbonization condensation and the carbon-based solid acid that is insoluble to polar solvent that obtains and above-mentioned solid acid as the purposes of solid acid catalyst.
Background technology:
Crisis occurs now in energy problem, environmental problem, do not produce unnecessary accessory substance with a spot of energy and only generate the target that the purpose product becomes the modern chemical industry pursuit effectively.Acid catalyst is absolutely necessary in the chemical in modern times industry, is widely used in the manufacturing of variety of products such as medicine, petro chemical industry product, macromolecule product, but the most liquid acid catalyst as hydrochloric acid, sulfuric acid and so on that uses at present.The liquid catalyst that uses in process of production need be neutralized by alkali, through removing the operations such as salt that generated by neutralization, from product, separates, reclaims.But removing of above-mentioned neutralization and salt consumes quite a few energy in the operation.In addition, the salt excess supply that on market, reclaims, it is the little accessory substance of availability mostly, therefore is difficult to usually handle.
With respect to above-mentioned situation; Because solid acid catalyst can not generate unnecessary accessory substance in the operation of removing of separating, do not need when reclaiming above-mentioned neutralization or salt, and energy-conservation ground manufacturing purpose product; Therefore the research of this respect has received scientific worker's concern (Ishihara, K; Hasegawa, A; Yamamoto, H.Angew.Chem.Int.Ed.2001,40,4077.).Aspect the research and development of solid acid catalyst, solid acid catalysts such as zeolite, silica-alumina, moisture niobium have become the huge achievement of chemical industry, bring very big contribution to society.In addition,, can think that the material that the polystyrene sulfonation is obtained is a solid acid, in the past always as having acid cationic ion-exchange resin as the strong acid polymer.In addition, the known Nafion (registration mark of E.I.Du Pont Company) that in the polytetrafluoroethylene (PTFE) skeleton, has sulfo group also is the extremely strong solid acid (solid super-strong acid) of possess hydrophilic property, and the super acids that known their conducts have greater than the acid strength of liquid acid works.But, the problem of selling at exorbitant prices when using is arranged in pair thermally labile, the industry.According to above-mentioned situation, consider that from aspects such as performance and costs use solid acid catalyst than using aforesaid liquid acid and more be difficult to design favourable industrial processes, nearly all now chemical industry all depends on liquid acid catalyst.In order to break this present situation, hope to appear at performance and the solid acid catalyst of cost aspect above liquid acid.
In addition, in inorganic system, with zirconia (ZrO
2) use sulfuric acid treatment; The sulfuric acid trace that obtains (sulfuric acid trace) zirconia is for having the most highly acid solid acid catalyst; But the sulfuric acid trace on surface is few, and sour point (acid point) number of per unit weight lacks a lot than liquid acid, therefore also far can not satisfy above-mentioned requirements.
Have based on this, the applicant makes the present invention.
Summary of the invention:
First aspect purpose of the present invention is to provide a kind of eco-friendly, economic carbon-based solid acid.
The present invention solves this technical problem through following technical scheme:
A kind of carbon-based solid acid is characterized in that: be raw material with the polyol, with material molar ratio be that 2: 1～10: 1 isethionic acid is a bioactive molecule; Under 120～400 ℃, carry out carbonization condensation reaction 2～32h; After reaction finished, the hot water that adds more than 80 ℃ washed, and filtered; Remove free acidic materials, products therefrom is drying to obtain carbon-based solid acid in 120 ℃ baking oven.
Carbon-based solid acid of the present invention; Be a kind of solid acid with wide range of industrial applications prospect; The present invention considers material inexpensive and that have the sulfonic group structure; This material has the stable basic framework of physical actions such as heat, is conceived to use mix with polyol and isethionic acid, at high temperature carries out carbonization and condensation.In order to reduce the excessive carbonization of material, selecting isethionic acid is gentle acid catalyst, for the more sulfonic group of introducing, selects the hydroxy functional group of isethionic acid and the hydroxyl of polyol to carry out condensation.The novel solid acid that the present invention obtains, through check, this solid acid has the acid number height, good stability, catalytic efficiency is high, synthesizes advantages such as easy.
Second aspect purpose of the present invention provides a kind of preparation method of carbon-based solid acid, it is characterized in that, may further comprise the steps:
(1), the synthetic reaction of carbon-based solid acid: with polyol and isethionic acid is after 1: 2～1: 10 ratio mixes in molar ratio; Place the quartz ampoule Muffle furnace; Logical nitrogen replacement air wherein; In nitrogen atmosphere, be heated to and carry out carbonization condensation reaction 2～32h under 120～300 ℃, obtain the solid of black;
(2), washing suction filtration and oven dry: behind the black solid cool to room temperature with step 1 preparation; The hot water that adds more than 80 ℃ washs; And filter, till filtrating clarification does not have acidity, place 120 ℃ baking oven to dry again and promptly got the carbon-based solid acid finished product in 1～2 day.
Aforesaid polyol is saccharide compound or polyvinyl alcohol etc., preferred especially glucose, sucrose, starch, shitosan or polyvinyl alcohol.
Third aspect of the invention purpose provides a kind of above-mentioned carbon-based solid acid as the application of catalyst in reactions such as catalytic esterification, condensation, alkylation, etherificate; With carbon-based solid acid of the present invention as catalyst; When being used for reaction such as catalytic esterification, condensation, alkylation, etherificate; Reaction yield reaches more than 90%, and the catalyst that reaction filters out after finishing is reusable, and activity remains unchanged basically.
The present invention compares with background technology, has following beneficial effect:
(1) the synthesis of solid acid heat stability is high, and heat decomposition temperature is more than 180 ℃;
(2) the solid acid acid number is high, and general acid number is at 1～4mmol/g;
(3) simple synthetic method;
(4) synthesis of solid acid cost is low;
(4) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. all have very high catalytic activity;
(5) catalyst can repeat repeatedly to use.
Below will do further elaboration to the present invention through concrete embodiment.
The specific embodiment:
Embodiment 1: carbon-based solid acid synthetic
(1) synthetic reaction of carbon-based solid acid: after 1mol glucose and 0.2mol isethionic acid are mixed, place the quartz ampoule Muffle furnace, in nitrogen, under 180 ℃, carry out carbonization condensation reaction 20h, obtain the solid of black;
(2) washing suction filtration and oven dry: treat that solid cooled is after room temperature; The hot water that adds more than 80 ℃ washs, and filters, until the filtrating clarification; And till the acidity; Place 120 ℃ baking oven to dry 1 day solid again, the acid number that obtains catalyst is 2.0mmol/g, and heat decomposition temperature is 200 ℃.
Embodiment 2-6:
The preparation method is identical with embodiment 1, and difference is polyol is replaced with the compound in the table 1, under 180 ℃, carries out the carbonization condensation reaction.
Product property contrast under table 1, the different polyol
| Embodiment | Polyol | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 2 | Sucrose | 2.2 | 180 |
| 3 | Starch | 3.0 | 210 |
| 4 | Cellulose | 1.9 | 220 |
| 5 | Shitosan | 4.1 | 190 |
| 6 | Polyvinyl alcohol | 5.0 | 180 |
Embodiment 7-9;
The preparation method is identical with embodiment 1, and difference is that the carbonization condensation reaction time is respectively by time of table 2.
Product property contrast under table 2, the different carbonization condensation reaction time
| Embodiment | Reaction time/h | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 7 | 16 | 2.1 | 210 |
| 8 | 24 | 2.3 | 200 |
| 9 | 32 | 2.5 | 180 |
Embodiment 10-12
The preparation method is identical with embodiment 1, and difference is that the result that influences of the consumption of different isethionic acids sees table 3.
Product property contrast under table 3, the different isethionic acid consumption
| Embodiment | Isethionic acid consumption/mmol | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 10 | 0.1 | 1.7 | 180 |
| 11 | 0.3 | 2.5 | 200 |
| 12 | 0.5 | 3.0 | 210 |
Embodiment 13-15:
The preparation method is identical with embodiment 1, and difference is that the result that influences of different carbonization setting-up points sees table 4.
Product property contrast under table 4, the different carbonization setting-up point
| Embodiment | Reaction temperature/℃ | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 13 | 200 | 2.4 | 190 |
| 14 | 220 | 3.0 | 200 |
| 15 | 300 | 2.5 | 210 |
Embodiment 16: the application of carbon-based solid acid in catalytic esterification
Catalytic esterification: having electromagnetic agitation, thermometer, reflux condensing tube; Adding 0.1mol citric acid, 0.45mol n-butanol carry out heated and stirred in the 100mL three-necked bottle of water knockout drum, treat that citric acid dissolves back sampling and measuring acidity entirely, adds the catalyst of 0.5g then; Carrying out reflux stirs; The water that reaction is produced is told from water knockout drum, reaction 4h, and calculated yield is 98.9%.
Embodiment 17-21:
Except that following difference, all the other and embodiment 16, after reaction finished, catalyst carried out filtered and recycled, behind washing with acetone, place 100 ℃ of baking oven dryings after, continue reaction, the result sees table 5.
Catalytic effect contrast under table 5, the different catalysts reuse number of times
| Embodiment | Catalyst reuse number of times | Productive rate/% |
| 17 | 0 | 98.9 |
| 18 | 1 | 98.4 |
| 19 | 2 | 98.0 |
| 20 | 3 | 97.7 |
| 21 | 4 | 97.7 |
Embodiment 22: the application of carbon-based solid acid in the catalyzing and condensing reaction
Catalyzing and condensing reaction: having electromagnetic agitation; Reflux condensing tube; Add 0.1mol cyclohexanone, 0.15mol ethylene glycol, 10ml cyclohexane and 0.1g catalyst in the 100mL three-necked bottle of water knockout drum, carry out the reflux stirring water and the entrainer azeotropic of reaction generation are steamed, about reaction 2h; Yield is that 99%. catalyst are reused 5 times, and catalytic activity does not change.
Embodiment 23: the application of carbon-based solid acid in catalytic alkylation reaction
Catalytic alkylation reaction: having electromagnetic agitation; Reflux condensing tube; Add 0.1mol catechol, the 0.15mol tert-butyl alcohol and 0.1g catalyst in the 100mL three-necked bottle of water knockout drum, carry out reflux and stir, about reaction 4h; Yield is that 92%. catalyst are reused 5 times, and catalytic activity does not change.
Embodiment 24: the application of carbon-based solid acid in the catalyst etherifying reaction
The catalyst etherifying reaction: having electromagnetic agitation, reflux condensing tube adds 0.1mol2-naphthols, 0.15mol methyl alcohol and 0.1g catalyst in the 100mL three-necked bottle of water knockout drum; Carrying out reflux stirs; About reaction 6h, yield is that 86%. catalyst are reused 5 times, and catalytic activity does not change.
Claims (5)
1. carbon-based solid acid is characterized in that: be raw material with the polyol, with material molar ratio be that 2: 1～10: 1 isethionic acid is a bioactive molecule; Under 120～400 ℃, carry out carbonization condensation reaction 2～32h; After reaction finished, the hot water that adds more than 80 ℃ washed, and filtered; Remove free acidic materials, products therefrom is drying to obtain carbon-based solid acid in 120 ℃ baking oven.
2. the preparation method of the said carbon-based solid acid of claim 1 is characterized in that, may further comprise the steps:
(1), the synthetic reaction of carbon-based solid acid: with polyol and isethionic acid is after 1: 2～1: 10 ratio mixes in molar ratio; Place the quartz ampoule Muffle furnace; Logical nitrogen replacement air wherein; In nitrogen atmosphere, be heated to and carry out carbonization condensation reaction 2～32h under 120～300 ℃, obtain the solid of black;
(2), washing suction filtration and oven dry: behind the black solid cool to room temperature with step 1 preparation; The hot water that adds more than 80 ℃ washs; And filter, till filtrating clarification does not have acidity, place 120 ℃ baking oven to dry again and promptly got the carbon-based solid acid finished product in 1～2 day.
3. the preparation method of the said carbon-based solid acid of claim 2, it is characterized in that: described polyol is saccharide compound or polyvinyl alcohol.
4. the preparation method of the said carbon-based solid acid of claim 3, it is characterized in that: described polyol is glucose, sucrose, starch or shitosan.
5. the application of the said carbon-based solid acid of claim 1～4 in catalytic esterification, condensation, alkylation, etherification reaction.
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| CN102351746A (en) * | 2011-09-08 | 2012-02-15 | 南通大学 | Method for preparing glycol sodium di-sulpho succinate di(2-methyl1-amyl) ester |
| CN102784663A (en) * | 2012-08-10 | 2012-11-21 | 绍兴文理学院 | Preparation method of high temperature-resisting carbon-based solid acid |
| CN103288643B (en) * | 2013-06-28 | 2015-12-23 | 厦门大学 | The method of ethyl levulinate is prepared based on the alcoholysis of carbon-based solid acid catalysis furfuryl alcohol |
| CN103920532B (en) * | 2014-04-16 | 2016-02-24 | 苏州元素集化学工业有限公司 | A kind of carbon-based solid acid catalyst and preparation method thereof |
| CN108080012A (en) * | 2017-11-20 | 2018-05-29 | 武梦如 | A kind of preparation method for the solid acid catalyst for being used to prepare mixed dioctyl phthalate |
| CN109627168A (en) * | 2019-01-02 | 2019-04-16 | 江苏理工学院 | A kind of preparation method of tributyl citrate |
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| CN101773860A (en) * | 2010-02-05 | 2010-07-14 | 绍兴文理学院 | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process |
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