CN101773860A - Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process - Google Patents
Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process Download PDFInfo
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- CN101773860A CN101773860A CN201010109149A CN201010109149A CN101773860A CN 101773860 A CN101773860 A CN 101773860A CN 201010109149 A CN201010109149 A CN 201010109149A CN 201010109149 A CN201010109149 A CN 201010109149A CN 101773860 A CN101773860 A CN 101773860A
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Abstract
The invention discloses a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, belonging to the technical field of chemical synthesis. In the invention, carbonizable compounds and sulfo-containing functional molecules are prepared into aqueous solution, placed in an autoclave, heated at 150-200 DEG C for 4-10 hours in a baking oven, cooled to room temperature, filtered after opening the autoclave, washed and dried to obtain a novel carbon-based solid acid catalyst. The solid acid has the following advantages: the synthesis process is simple and convenient, which can be finished in one step; synthesis cost is low; catalytic effect is good, and the solid acid catalyst has higher catalytic activity to general acid catalyzed reactions such as esterification, condensation, alkylation, etherification, ester exchange and the like; and the catalyst can be used repeatedly.
Description
Technical field
The present invention relates to an a kind of carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, belong to the organic chemistry synthesis technical field.
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 modern chemistry industry, is widely used in the manufacturing of variety of products such as medicine, petro chemical industry product, macromolecule product, but the liquid acid catalyst that mostly is hydrochloric acid, sulfuric acid and so on greatly that uses at present.The liquid catalyst of Shi Yonging need be neutralized by alkali in process of production, by removing the operations such as salt that generated by neutralization, separates from product, 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 mostly is the little accessory substance of availability greatly, 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 been subjected to 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 has sulfo group in the polytetrafluoroethylene (PTFE) skeleton 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 pair thermally labile, industrial use are arranged.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.Carbon-based solid acid catalyst is as a class new catalyst, and it synthesizes and application has all obtained paying attention to widely.But the building-up process of this class material is loaded down with trivial details, needs to carry out under high-temperature and high-pressure conditions earlier carbonization, and generally more than 400 degree, the time surpasses 15 hours to temperature, can produce a large amount of harmful substances such as discarded waste liquid in this course.Secondly, need the sulfonation process through the concentrated sulfuric acid, because the material with carbon element that generates previously is more stable, sulfonation process also need carry out under exacting terms.At last, need isolate product from the solution of a large amount of concentrated sulfuric acids, this process also is very loaded down with trivial details.
In order to address the above problem, and provide a kind of solid acid catalyst that industrial prospect is arranged, the present invention considers to prepare the carbon-based solid acid material by a step hydrothermal synthesis method.By with the compound of some easy carbonizations with to contain sulfonic functional compound be that 10～100: 1 ratio is made into the aqueous solution in the ratio of amount, place autoclave then, in 150～200 ℃ baking oven, heated 4～10 hours, cool to room temperature, open autoclave, filter, washing, oven dry promptly gets novel carbon-based solid acid catalyst.In addition, using the solid acid that obtains, during reactions such as trial catalytic esterification, condensation, alkylation, etherificate, can significantly promote above-mentioned reaction, is useful as solid acid catalyst therefore, can solve above-mentioned problem.
Summary of the invention
The object of the present invention is to provide an a kind of eco-friendly carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, to solve the existing problem of background technology.
The present invention solves this technical problem by the following technical programs, one carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, it is characterized in that: with the compound of easy carbonization with to contain sulfonic functional compound be that 10～100: 1 ratio is made into the aqueous solution in the ratio of amount, place autoclave then, in 150～200 ℃ baking oven, heated 4～10 hours, cool to room temperature, open autoclave, filter, washing, oven dry promptly gets carbon-based solid acid catalyst.
The present invention further is provided with as follows:
The compound of described easy carbonization is saccharide compound and derivative thereof, preferably from sucrose, and glucose, furtural, any one of polyvinyl alcohol etc.;
The concentration of readily carbonizable substance matter is generally between 3%～20% in the described aqueous solution;
Describedly contain sulfonic functional compound and be meant the compound that contains a sulfonate functional groups and other active groups at least, preferably from the 2-isethionic acid, vinyl sulfonic acid, benzene sulfonic acid, p-hydroxybenzenyl sulfonate, 1, any one of 4-butane sultone etc.;
The present invention further is provided with as follows: a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, it is characterized in that, and may further comprise the steps:
1, the preparation of carbon-based solid acid catalyst: by with the compound of some easy carbonizations with to contain sulfonic functional compound be that 10～100: 1 ratio is made into the aqueous solution in the ratio of amount, place autoclave then, in 150～200 ℃ baking oven, heated 4～10 hours, cool to room temperature, open autoclave, filter, washing, oven dry promptly gets carbon-based solid acid catalyst;
2, the investigation of the catalytic performance of catalyst: with the solid acid catalyst of above-mentioned preparation, be used for reactions such as esterification, condensation, alkylation, etherificate, and its catalytic performance is investigated;
3, catalyst is reused: catalyst carries out centrifugal separatory and reclaims, and is directly used in reaction next time.
Beneficial effect of the present invention:
Adopt method of the present invention to prepare carbon-based solid acid catalyst, compare with background technology and have the following advantages:
(1) building-up process is easy, only needs a step;
(2) synthetic method green, the waste liquid discharge amount of exhaust gas is few;
(3) acid number height, its acid number is more than 1～4mmol/g;
(4) He Cheng cost is low;
(5) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate, ester exchange etc. have very high catalytic activity;
(6) catalyst can repeat repeatedly to use;
(7) solid acid catalyst of the present invention's preparation is with a wide range of applications.
Below will the present invention is further elaborated by specific embodiment.
The specific embodiment
Synthesizing of embodiment 1, novel carbon-based solid acid:
Furtural with 5g, the 2-isethionic acid base of 2g and the water of 80g place the autoclave of 100ml, carry out stirring and dissolving, autoclave tightened heat 4 hours in the baking oven that is placed on 180 ℃ after, cool to room temperature is opened autoclave, filter, washing, oven dry, the acid number that promptly gets novel carbon-based solid acid catalyst is 2.3mmol/g.
Embodiment 2-4
Except for the following differences, all the other are identical with embodiment 1, heat at the furtural of 5g, carry out carbonization under 180 ℃, and the 2-isethionic acid reacted 4 hours in the ratio consumption of table 1.
Table 1
| Embodiment | 2-isethionic acid (gram) | Acid number/mmol/g |
| ??2 | ??1 | ??1.7 |
| ??3 | ??3 | ??2.5 |
| ??4 | ??5 | ??2.8 |
Embodiment 5-12
Except for the following differences, all the other and embodiment 1, the influence of differential responses thing the results are shown in Table 2.
Table 2
| Embodiment | The compound of easy carbonization | Contain sulfonic functional compound | Acid number/mmol/g |
| ??5 | Sucrose | The 2-isethionic acid | ??1.5 |
| ??6 | Glucose | Vinyl sulfonic acid | ??1.7 |
| ??7 | Polyvinyl alcohol | Benzene sulfonic acid | ??1.1 |
| ??8 | Sucrose | P-hydroxybenzenyl sulfonate | ??2.1 |
| ??9 | Glucose | 1, the 4-butane sultone | ??1.7 |
| ??10 | Polyvinyl alcohol | 1, the 4-butane sultone | ??2.0 |
| ??11 | Furtural | P-hydroxybenzenyl sulfonate | ??2.5 |
| ??12 | Polyvinyl alcohol | Vinyl sulfonic acid | ??2.3 |
Embodiment 13
Catalytic esterification: having electromagnetic agitation, thermometer, reflux condensing tube, adding 0.1mol citric acid, 0.45mol n-butanol add thermal agitation in the 100mL three-necked bottle of water knockout drum, treat the complete molten back of citric acid sampling and measuring acidity, add the catalyst of 0.5g then, adding hot reflux stirs, the water that reaction is produced is told from water knockout drum, reaction 4h, and calculated yield is 99.0%.
Embodiment 14-18
Except for the following differences, all the other and embodiment 11, after reaction finished, catalyst carried out centrifugal separatory and reclaims,, continue reaction, the results are shown in Table 3.
Table 3
| Embodiment | Catalyst reuse number of times | Productive rate/% |
| ??14 | ??0 | ??99.0 |
| ??15 | ??1 | ??98.7 |
| ??16 | ??2 | ??99.0 |
| ??17 | ??3 | ??98.4 |
| ??18 | ??4 | ??98.5 |
Embodiment 19
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, adding the hot reflux stirring steams the water and the entrainer azeotropic of reaction generation, about reaction 2h, yield is that 99%. catalyst are reused 5 times, and catalytic activity does not change.
Embodiment 20
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, adding hot reflux stirs, about reaction 4h, yield is that 95%. catalyst are reused 5 times, and catalytic activity does not change.
Embodiment 21
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, adding hot reflux stirs, about reaction 6h, yield is that 93%. catalyst are reused 5 times, and catalytic activity does not change.
Embodiment 22
Having electromagnetic agitation, thermometer, adding 5g rapeseed oil, 1.2g methyl alcohol, 0.1g catalyst add about hot reflux stirring 8h in the 100mL three-necked bottle of reflux condensing tube, centrifugal separatory is reclaimed catalyst can be directly used in down secondary response, and upper strata product adding mass fraction is 5～10% NaHCO
3Solution 80ml washing to remove unreacted free fatty, is told upper organic phase with separatory funnel, with anhydrous MgSO then to neutral
4Drying removes by filter drier, and decompression distillation can obtain nearly light yellow transparent product and be biological rape oil.Yield is 95.2%.
Claims (6)
1. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process, it is characterized in that: with the compound of easy carbonization with to contain sulfonic functional compound be that 10～100: 1 ratio is made into the aqueous solution in the ratio of amount, place autoclave then, heated in 150～200 ℃ baking oven 4～10 hours, cool to room temperature is opened autoclave, filter, washing, oven dry promptly gets carbon-based solid acid catalyst.
2. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process according to claim 1 is characterized in that: the compound of described easy carbonization is saccharide compound and derivative thereof.
3. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process according to claim 2 is characterized in that: the compound of described easy carbonization is selected from sucrose, glucose, furtural, any one of polyvinyl alcohol.
4. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process according to claim 1 is characterized in that: the concentration of readily carbonizable substance matter is 3%～20% in the described aqueous solution.
5. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process according to claim 1 is characterized in that: describedly contain sulfonic functional compound and be meant the compound that contains a sulfonate functional groups and other active groups at least.
6. a carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process according to claim 5 is characterized in that: describedly contain sulfonic functional compound and be selected from 2-isethionic acid, vinyl sulfonic acid, benzene sulfonic acid, p-hydroxybenzenyl sulfonate, 1, any one of 4-butane sultone etc.
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Application publication date: 20100714 |