CN101618341B - Carbon-based solid acid catalyst and preparation method thereof - Google Patents
Carbon-based solid acid catalyst and preparation method thereof Download PDFInfo
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- CN101618341B CN101618341B CN2009100234287A CN200910023428A CN101618341B CN 101618341 B CN101618341 B CN 101618341B CN 2009100234287 A CN2009100234287 A CN 2009100234287A CN 200910023428 A CN200910023428 A CN 200910023428A CN 101618341 B CN101618341 B CN 101618341B
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Abstract
The invention discloses a carbon-based solid acid catalyst and a preparation method thereof. The prepared catalyst adopts activated carbon as carrier and benzenesulfonic acid as acid site which are combined through firm carbon-carbon covalent bond. The preparation method comprises the following steps: first adopting aminobenzene sulfonic acid to perform diazotization process, obtaining diazosalt of sulfanilic acid, then using hypophosphorous acid as reductant to react with diazosalt of sulfanilic acid on activated carbon, and finally filtrating, washing and drying the products after finishing the reaction to obtain the carbon-based solid acid catalyst. The carbon-based solid acid catalyst has the advantage of stable structure, strong acidity, low cost, good catalytic effect and environmental-friendliness and can be reproducible and reused.
Description
Technical field
The present invention relates to a kind of catalyst and preparation thereof, particularly a kind of carbon-based solid acid catalyst and preparation method thereof.
Background technology
Traditional homogeneous acid catalyst such as sulfuric acid, phosphoric acid, alchlor etc. are widely used in chemical process such as alkylation, esterification, hydrolysis, hydration; Annual sulfuric acid as catalyst consumption just surpasses 1,500 ten thousand tons of (Hara; M; Et al.Angew Chem Int Ed, 2004,43:2955-2958).The advantage of these homogeneous acids is that cost is low, acid by force, catalytic efficiency is high, but also has many shortcomings, as is prone to cause equipment corrosion, and catalyst is difficult to separate with reaction system, is difficult to recycling, is prone to cause environmental pollution etc.
Under the current overall background of advocating Green Chemistry and sustainable development, the high and eco-friendly solid-acid material of catalytic efficiency becomes the catalytic science hot research fields.Solid-acid material comprises zeolite molecular sieve, acidic oxide, heteropoly acid, phosphate and ion exchange resin etc.At present some solid acid catalysts have been realized commercialization production, be applied in 180 kinds of chemical process such as oil catalytic pyrolysis (Okuhara, T.Chem Rev, 2006,106:4044-4098).The result shows that these solid acid catalysis activity are higher, the easily separated and clean environment firendly of product, its weak point be acidity a little less than, and cost is higher.
Summary of the invention
Defective or deficiency to existing acid catalyst exists the objective of the invention is to, and a kind of with low cost and novel carbon-based solid acid catalyst that catalytic activity is high and preparation method thereof is provided.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of carbon-based solid acid catalyst is characterized in that, the carrier of this catalyst that makes is an active carbon, and the acid site is a benzene sulfonic acid, between charcoal carrier and the acid site with the carbon-to-carbon covalent bonds.
The preparation method of above-mentioned carbon-based solid acid catalyst; It is characterized in that, at first aminobenzenesulfonic acid is carried out diazotising and handle, obtain the benzene sulfonic acid diazol; Then with hypophosphorous acid as reducing agent; Make the benzene sulfonic acid diazol that reduction reaction take place on active carbon, after reaction finishes, active carbon is promptly got carbon-based solid acid catalyst after filtering, wash and drying.
Concrete steps are following:
The first step, the preparation of benzene sulfonic acid diazol:
In three-necked bottle, add sulfanilic acid and dilute acid soln, fully stir, the temperature of reaction system is controlled at 0-5 ℃, dropwise add the solubility nitrite, stirred again after dripping off 30-90 minute with ice-water bath, white solid, be the benzene sulfonic acid diazol.
Second step, reduction reaction
In three-necked bottle, add the benzene sulfonic acid diazol that makes in active carbon, distilled water, absolute ethyl alcohol and the first step, open electromagnetic agitation, add hypophosphorous acid and carry out reduction reaction, temperature is controlled at 0-5 ℃ in the course of reaction.Reaction is used distilled water and washing with acetone active carbon after finishing successively, and dry 6h～18h under 120 ℃ obtains carbon-based solid acid catalyst in baking oven.
Said active carbon is to comprise the merchandise active carbon that various timber, bamboo, coal, shell or synthetic high polymer etc. obtain for raw material by various carbon sources, and its specific area is at 500-3000m
2/ g.
Said dilute acid soln is hydrochloric acid, sulfuric acid or boron fluoric acid.
Said solubility nitrite solution is natrium nitrosum or potassium nitrite.
The carbon-based solid acid catalyst that the present invention makes has advantage:
(1) carrier active carbon mechanical strength height, Heat stability is good, specific area is big and aperture structure is abundant, and is and cheap.
(2) combine with firm covalent bond between carrier active carbon and the acid site benzene sulfonic acid; And be the simple physics suction-operated unlike general loaded catalyst that kind; Thereby catalyst Heat stability is good; Used carbon-based solid acid catalyst is through after simple filtering washing and the drying, and is promptly renewable and repeat use.
(3) used raw material active carbon, ethanol, hydrochloric acid, sulfanilic acid and hypophosphorous acid etc. are common agents, and are cheap and easy to get, so production cost is very low, has overcome conventional solid acid catalyst shortcoming on the high side, is expected to realize commercialization production.
(4) excellent catalytic effect and applied widely all has very high catalytic activity for general acid catalyzed reaction such as esterification, ester exchange, alkylation and hydration reaction etc.
The specific embodiment
Below through concrete embodiment the present invention is done further elaboration, need to prove that following embodiment is that the present invention is not limited to these embodiment for those skilled in the art better understands the present invention.
Embodiment 1:
In three-necked bottle, add the hydrochloric acid of 0.075mol sulfanilic acid and 187ml, 1mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at 4 ℃, in reaction system, slowly adds the sodium nitrite solution of 80ml, 1mol/l, stirring reaction 30min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.
The chemical equation of reaction system is following:
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 90min.
The chemical equation of reduction reaction is following:
With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, in 70 ℃ of refluxed, reaction 6h, the acetate conversion ratio is 92%.
Embodiment 2:
In three-necked bottle, add the hydrochloric acid of 0.075mol sulfanilic acid and 187ml, 1mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at 2 ℃, with separatory funnel slow sodium nitrite solution that adds 80ml, 1mol/l in reaction system, stirring reaction 60min; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 90min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, in 70 ℃ of refluxed, reaction 6h, the acetate conversion ratio is 94%.
Embodiment 3:
In three-necked bottle, add the sulfuric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at 2 ℃, in reaction system, slowly adds 80ml, 1mol/l potassium nitrite solution, stirring reaction 90min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 2.0g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, in 70 ℃ of refluxed, reaction 6h, the acetate conversion ratio is 92%.
Embodiment 4:
In three-necked bottle, add the sulfuric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the oleic acid of 28.2g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the catalyst of 1.0g, in 80 ℃ of refluxed, reaction 8h, the oleic acid conversion ratio is 89%.
Embodiment 5:
In three-necked bottle, add the sulfuric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the palmitic acid of 25.6g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the carbon-based solid acid catalyst of 1.0g, in 80 ℃ of refluxed, reaction 8h, esterification yield is 91%.
Embodiment 6:
In three-necked bottle, add the hydrochloric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at about 4 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the palmitic acid of 25.6g (0.1mol), the methyl alcohol of 41ml (1mol), the catalyst of 1.0g, in 80 ℃ of refluxed, reaction 8h, esterification yield is 91%.
Embodiment 7:
In three-necked bottle, add the hydrochloric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the stearic acid of 28.4g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the carbon-based solid acid catalyst of 1.0g, in 80 ℃ of refluxed, reaction 8h, esterification yield is 89%.
Embodiment 8:
In three-necked bottle, add the hydrochloric acid of 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system is opened electromagnetic agitation; With ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90 minutes with separatory funnel; Obtain white depositions; Be the benzene sulfonic acid diazol,, filter subsequent use with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and 400ml, the hypophosphorous acid of 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and washing with acetone active carbon, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the stearic acid of 28.4g (0.1mol), the methyl alcohol of 41ml (1mol), the carbon-based solid acid catalyst of 1.0g, in 80 ℃ of refluxed, reaction 8h, esterification yield is 91%.
Claims (3)
1. the preparation method of a carbon-based solid acid catalyst; It is characterized in that, at first sulfanilic acid is carried out diazotising and handle, obtain the benzene sulfonic acid diazol; Then with hypophosphorous acid as reducing agent; Make the benzene sulfonic acid diazol that reduction reaction take place on active carbon, after reaction finishes, active carbon is promptly got carbon-based solid acid catalyst after filtering, wash and drying; The carrier of this carbon-based solid acid catalyst is an active carbon, and the acid site is a benzene sulfonic acid, between charcoal carrier and the acid site with the carbon-to-carbon covalent bonds; Concrete steps are following:
The first step, the preparation of benzene sulfonic acid diazol:
In flask, add sulfanilic acid and dilute acid soln, fully stir, make temperature of reaction system remain on 0 ~ 5 ℃ with ice-water bath; Under agitation drip an amount of solubility nitrite solution; Reaction 30min～90 min obtain white precipitate, i.e. the benzene sulfonic acid diazol;
To the filtration of benzene sulfonic acid diazol, washing, the drying that obtains;
Second step, reduction reaction:
In flask, adding the benzene sulfonic acid diazol that makes in active carbon, distilled water, absolute ethyl alcohol and the first step, is reducing agent with the hypophosphorous acid, reacts 30 min～120 min down at 0 ~ 5 ℃;
Reaction is used distilled water and washing with acetone active carbon after finishing successively, and dry 6h ~ 18h under 120 ℃ promptly obtains carbon-based solid acid catalyst in baking oven;
Described active carbon is to be the extensive stock active carbon that raw material obtains by timber or bamboo or coal or shell, and its specific area is at 500m
2/ g ~ 3000m
2/ g.
2. the method for claim 1 is characterized in that, described dilute acid soln is hydrochloric acid or sulfuric acid.
3. the method for claim 1 is characterized in that, described solubility nitrite is natrium nitrosum or potassium nitrite.
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| CN102029188A (en) * | 2010-11-15 | 2011-04-27 | 西北农林科技大学 | Carbon-based solid acid catalyst with high specific surface area and preparation method thereof |
| CN102491322A (en) * | 2011-12-12 | 2012-06-13 | 福建农林大学 | Preparation method of active carbon fixed with organic functional group on surface |
| CN102600893B (en) * | 2012-03-02 | 2014-05-07 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN103084187B (en) * | 2012-12-17 | 2015-07-01 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103878025B (en) * | 2014-03-31 | 2015-12-02 | 福建农林大学 | A kind of absorbent charcoal based solid acid catalyst and preparation method thereof |
| CN105130783B (en) * | 2015-09-24 | 2018-01-30 | 中国科学技术大学 | A kind of preparation method of succinic acid |
| CN105289722B (en) * | 2015-11-04 | 2017-08-01 | 常州大学 | It is a kind of for catalyst of ester exchange Catalysts of Preparing Methyl Ethyl Carbonate and preparation method thereof |
| CN108786738A (en) * | 2018-07-03 | 2018-11-13 | 西北农林科技大学 | A kind of magnesium salts modification biological charcoal and its application |
| CN109777896A (en) * | 2019-02-27 | 2019-05-21 | 天津大学 | The method that magnetic solid acid catalyzing cellulose hydrolysis prepares glucose |
| CN110190290A (en) * | 2019-06-12 | 2019-08-30 | 浙江科技学院 | The preparation method of sulfonated platinum carbon catalyst |
| CN115304480A (en) * | 2022-08-12 | 2022-11-08 | 浙江嘉澳环保科技股份有限公司 | Preparation method of tributyl citrate and acetyl tributyl citrate |
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