CN101786015A - Hydrothermal preparation method of carbon-based solid sulfoacid - Google Patents
Hydrothermal preparation method of carbon-based solid sulfoacid Download PDFInfo
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Abstract
The invention discloses a hydrothermal preparation method of carbon-based solid sulfoacid, which comprises the following steps that: polysaccharide water solution is subject to the carbonization reaction for 8 to 48 hours at the temperature of 140 to 180 DEG C, then is cooled to the room temperature, and is washed with water and is vacuum filtered to obtain the black brown carbonized product; inorganic strong acid with the liquid-solid ratio of 8 to 25 ml/g is added into a reaction kettle which is provided with the above product to be heated and mixed, at the same time, inertia gas is introduced into the reaction kettle to protect the reaction, and the product is subject to the sulfonation reaction for 8 to 30 hours at the temperature of 120 to 200 DEG C to obtain reaction liquid, the reaction liquid is poured into the water after being cooled to the room temperature and is vacuum filtered, and then the reaction liquid is washed with the hot water at the temperature of 80 to 100 DEG C to obtain the black solid substance, i.e. the carbon-based solid sulfoacid. The product of the preparation method has the advantages of high heat stability and high acidity; the source of the raw material is wide, the cost is low, and the catalyzing effect is good; the granularity distribution is uniform, and metal ions can be well solid borne; and the product can be repeatedly recycled to use.
Description
Technical field
The present invention relates to the preparation method of solid acid catalyst, be specifically related to the hydrothermal preparing process of carbon-based solid sulfoacid.
Background technology
In the modern chemical industry field, acid catalyst is indispensable, is widely used in the manufacturing of various products such as medicine, petrochemical industry, Polymer Synthesizing, biomass energy, and its most of acid catalysts are liquid acid as sulfuric acid, nitric acid, acetate etc.Liquid acid causes product and acid catalyst separation difficulty, can't reuse; Shortcomings such as equipment corrosion is serious make the acid catalysis utilization ratio reduce greatly, have increased carrying capacity of environment and economic load.For the solid acid catalyst of present existence, exist cost an arm and a leg, the shortcomings such as sour trace deficiency on poor heat resistance, surface; Recently research is the carbon-based solid sulfoacid of heat, the carbon back sulfonic acid acid number that with the naphthalene is feedstock production is higher, but it belongs to flexible material, and the aromatic hydrocarbon molecule on surface runs off in liquid phase reactor easily, and when being surfactant, can lose catalytic activity fully with the high fatty acid; The carbon back sulfonic acid that snead process makes need be realized in high temperature more than 400 ℃ under the protection of inert gas, and its carbonization yield is below 15%, and not only process condition is comparatively harsh, and its course of reaction produces a large amount of waste water and gas serious environment pollutions.
With respect to the direct carbonisation of high temperature, the hydrothermal carbonization condition is comparatively gentle, is easy to realize control, only need carry out under the condition of about 150 ℃ of thermal and hydric environments.Therefore, the present invention adopts hydro-thermal method to prepare carbon-based solid sulfoacid.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, a kind of hydrothermal preparing process of carbon-based solid sulfoacid is provided.Reaction condition of the present invention is easy to realization, and raw material sources are extensive, and are with low cost, and acid number is higher, better heat stability, and environmental friendliness overcomes existing low in economic efficiency, the deficiencies such as acid pollution is serious, realization condition harshness of acid catalyst.Realize that technical scheme of the present invention is as follows.
A kind of hydrothermal preparing process of carbon-based solid sulfoacid comprises the steps:
(1) with polysaccharide aqueous solution carburizing reagent 8～48h under 140～180 ℃ of temperature, be cooled to room temperature, water flushing, suction filtration obtain the pitchy carbonized product, again with this product oven dry;
(2) in the reactor that the material with carbon element that step (1) oven dry obtains is housed; add inorganic acid according to liquid-solid ratio 8～25ml/g; add thermal agitation, feed inert gas protection simultaneously, 120～200 ℃ of following sulfonating reaction 8～30h get reactant liquor in temperature; after being cooled to room temperature; in reactant liquor impouring water, suction filtration, the hot water of following with 80～100 ℃ washs; with the black solid material that obtains, i.e. carbon-based solid sulfoacid.
Above-mentioned preparation method, the temperature temperature that oven dry is adopted described in the step (1) is 80～120 ℃, drying time is 24～72h.
Above-mentioned preparation method, be cooled to room temperature described in the step (1) after, with distilled water wash repeatedly, suction filtration, until filtrate clarification, obtain the pitchy carbonized product.
Above-mentioned preparation method carried out stripping 15～60min with inert gas to the carbohydrate aqueous solution in the step (1) before reaction.
Above-mentioned preparation method, washing described in the step (2) is that washing is clarified until filtrate, does not have the inorganic acid radical ion to be detected, the black solid material that obtains.
Above-mentioned preparation method, the described black solid material that will obtain in the step (2) is 80～120 ℃ in temperature, oven dry 24～72h gets carbon-based solid sulfoacid.
Above-mentioned preparation method, the described polysaccharide of step (1) is cellulose, carbohydrate, starch or plasm; Described inert gas is argon gas or nitrogen.
Above-mentioned preparation method, in the step (2), described inorganic acid is sulfuric acid, nitric acid, hydrochloric acid; Described inert gas is argon gas or nitrogen.
Above-mentioned preparation method, the concentration of the described polysaccharide aqueous solution of step (1) is 0.5～5mol/L.
Above-mentioned preparation method, step (2) is described be cooled to room temperature after, in reactant liquor impouring distilled water, suction filtration then washs with 80～100 ℃ hot water, and the black solid material that obtains is dried, and obtains carbon-based solid sulfoacid.
Hydrothermal preparing process of the present invention mainly be divided into two the step carry out, at first adopt the hydrothermal carbonization method to carry out incomplete carbonization, the degree of carbonization is bigger to the carbon-based solid sulfoacid influential effect that makes, if carbonizing degree is too high, can cause follow-up sulfonation process to introduce sulfonic acid group; If the degree of carbonization is not enough, in follow-up sulfonation process, oxidation can take place and generate accessory substance in carbide, thereby the catalyst of formation can be mixed with water isopolarity solvent, does not reach the purpose of solid acid catalyst.Carbonisation at first is that a certain amount of sugar is soluble in water, be mixed with mixed dissolution, under 140～180 ℃ temperature, carry out hydro-thermal reaction 8～48h then, under the effect of high-temperature high pressure water, the continuous condensation of saccharide compound, along with the carrying out of reaction, sugar constantly aggregates into corresponding carbon, thereby finishes whole carbonisation.Then carbonized product is carried out sulfonation, in 120～200 ℃; Sulfonation 8～30h makes sulfonic acid group carburet thing generation crosslinked action.The carbon-based solid sulfoacid load that obtains at last-OH ,-COOH ,-SO
3The H group has highdensity acid number.
Compared with prior art, the present invention has the following advantages:
(1) carbonization of the present invention is that hydro-thermal is synthetic, condition is easy to realize, reduced energy consumption, hydro-thermal is synthetic synthetic with respect to high temperature simultaneously, on the one hand the glycogen material is caused very little loss, not exclusively the carbonized product rate of recovery is higher, produces seldom waste liquid and waste gas on the other hand, has avoided the pollution to environment.
(2) carbon-based solid sulfoacid that synthesizes of the present invention, equal globulate before and after the material with carbon element sulfonation, particle diameter is more even, takes place crosslinkedly between the carbon ball each other, is easy to supported metal ion, realizes the loading effect of co-catalyst.
(3) the carbon-based solid sulfoacid acid number that synthesizes of the present invention is bigger, generally at 1～2mmolNaOH/g; Hydrothermal stability is better, more than 160 ℃; The big 3.208m of specific area
2/ g.
(4) carbohydrate, starch, cellulose, plasm are raw material to the carbon-based solid sulfoacid that synthesizes of the present invention to originate widely, and the carbonization yield has good economic benefits between 30～50%; This catalyst is a solid catalyst simultaneously, can realize separating of product and catalyst, realizes catalyst recycling, has vast market prospect.
The specific embodiment
Below in conjunction with case study on implementation concrete enforcement of the present invention is described further.Following discloses only be preferable case study on implementation of the present invention, should not limit enforcement of the present invention and protection domain with this.
Present case is with the preparation raw material of polysaccharide (starch, glucose, sucrose) as carbon-based solid sulfoacid, with the glucose solution that is mixed with 0.5～5mol/L soluble in water, for future use.
Embodiment 1
The 1st step hydrothermal carbonization
The D/W of preparation 2mol/L uses N
2To D/W stripping 40min, react 15h down for 150 ℃ in temperature, obtain the incomplete carbonized product of brown-black.
The 2nd step washing suction filtration
Carbonized product is washed, and suction filtration becomes clarification until filtrate, places 105 ℃ of baking ovens to dry 24h again, obtains the bronzing carbide.
The carbide sulfonation of the 3rd step
Add the concentrated sulfuric acid of 2g carbide, 20ml98% in having the 50ml there-necked flask of electromagnetic agitation, thermometer, reflux condensing tube, (see Table 1) the sulfonating reaction 15h time under different temperatures, gained carbon-based solid sulfoacid acid number adopts NaOH to carry out titration.Acid number such as table 1 under the different temperatures.
Hydrothermal preparation carbon-based solid sulfoacid effect contrast under table 1 different temperatures
The 4th step washing suction filtration
To the carbon back sulfonic acid that obtains wash, suction filtration, until the existence that detects less than sulfate ion, place 105 ℃ of baking ovens oven dry 24 hours again, promptly obtain carbon-based solid sulfoacid.
Embodiment 2
Except for the following differences, the stripping time is 60min, and bake out temperature is 120 ℃, and other step is identical with case 1; React different time, gained acid number such as table 2 down in 150 ℃.
Hydrothermal preparation carbon-based solid sulfoacid effect contrast under table 2 different time
Embodiment 3
Except for the following differences, other step is identical with case 1; React 15h, gained acid number such as table 3 down in 150 ℃.
Hydrothermal preparation carbon-based solid sulfoacid effect contrast under the different sulfuric acid additions of table 3
Embodiment 4
To the hydrolysis of string, it is miscible that OCC fragment, carbon back sulfonic acid catalyst are added to the water according to certain concentration, reacts the different time down in 150 ℃.Filter hydrolyzate, a gained filtrate part is used to produce glycan analysis, and a part is used for the hydrolyzate fermentation, and filter residue is used for circulating and recovering.
Carbon-based solid sulfoacid is to the hydrolysis effect contrast of OCC under table 4 different time
Table 5 reuse number of times is to the influence of hydrolysis effect
As can be seen from Table 4, carbon-based solid sulfoacid can be finished the hydrolysis to string, along with the variation of time, sugared yield reaches maximum 24.07%, subsequently along with the time from 8～12h, the sugar yield has reduced by 7.61%, explanation is under the thermal and hydric environment of gentleness, and this catalyst has very high selectivity to sugar, and sugar further is converted into accessory substance seldom, the carrying out that helps follow-up fermentation, residue are filtered and are used for next batch.As can be seen from Table 5 along with the increase of reuse number of times, the sugar slip is respectively 5.29%, 16.84%, 1.10%, illustrate that carbon-based solid sulfoacid has only the loss of fraction, under high thermal and hydric environment, still have good stability and catalytic, can satisfy the requirement of reuse.
Claims (10)
1. the hydrothermal preparing process of a carbon-based solid sulfoacid is characterized in that comprising the steps:
(1) with polysaccharide aqueous solution carburizing reagent 8～48h under 140～180 ℃ of temperature, be cooled to room temperature, water flushing, suction filtration obtain the pitchy carbonized product, again with this product oven dry;
(2) in the reactor that the product that step (1) oven dry obtains is housed; add inorganic acid according to liquid-solid ratio 8～25ml/g; add thermal agitation, feed inert gas protection simultaneously, 120～200 ℃ of following sulfonating reaction 8～30h get reactant liquor in temperature; after being cooled to room temperature; in reactant liquor impouring water, suction filtration, the hot water of following with 80～100 ℃ washs; with the black solid material that obtains, i.e. carbon-based solid sulfoacid.
2. preparation method according to claim 1 is characterized in that the temperature temperature that oven dry is adopted described in the step (1) is 80～120 ℃, and drying time is 24～72h.
3. preparation method according to claim 1, after it is characterized in that being cooled to room temperature described in the step (1), with distilled water wash repeatedly, suction filtration, until filtrate clarification, obtain the pitchy carbonized product.
4. preparation method according to claim 1 is characterized in that with inert gas the carbohydrate aqueous solution being carried out stripping 15～60min in the step (1) before reaction.
5. preparation method according to claim 1 is characterized in that washing described in the step (2) is that washing is clarified until filtrate, does not have the inorganic acid radical ion to be detected, the black solid material that obtains.
6. preparation method according to claim 1 is characterized in that the described black solid material that will obtain in the step (2) is 80～120 ℃ in temperature, and oven dry 24～72h gets carbon-based solid sulfoacid.
7. preparation method according to claim 1 is characterized in that: the described polysaccharide of step (1) is cellulose, carbohydrate, starch or plasm; Described inert gas is argon gas or nitrogen.
8. preparation method according to claim 1 is characterized in that: in the step (2), described inorganic acid is sulfuric acid, nitric acid, hydrochloric acid; Described inert gas is argon gas or nitrogen.
9. according to each described preparation method of claim 1～8, it is characterized in that the concentration of the described polysaccharide aqueous solution of step (1) is 0.5～5mol/L.
10. preparation method according to claim 9 is after it is characterized in that step (2) is described and being cooled to room temperature, in reactant liquor impouring distilled water, suction filtration, the hot water of following with 80～100 ℃ washs, and the black solid material oven dry with obtaining obtains carbon-based solid sulfoacid.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489316A (en) * | 2011-12-02 | 2012-06-13 | 南开大学 | Preparation of glycosyl microsphere catalyst and process for hydrolyzing cellulose |
| CN103084188A (en) * | 2012-12-20 | 2013-05-08 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN106824226A (en) * | 2017-01-14 | 2017-06-13 | 江苏理工学院 | A kind of preparation method and its usage of carbon-based solid acid |
| CN106847532A (en) * | 2017-04-07 | 2017-06-13 | 苏州海凌达电子科技有限公司 | A kind of preparation method of the high performance material for ultracapacitor |
| CN106981372A (en) * | 2017-04-14 | 2017-07-25 | 苏州海凌达电子科技有限公司 | A kind of carbon electrode material preparation method applied to ultracapacitor |
| CN107045946A (en) * | 2017-04-01 | 2017-08-15 | 苏州海凌达电子科技有限公司 | A kind of preparation method and applications of modified calcite complex carbon material |
| CN108940327A (en) * | 2018-06-02 | 2018-12-07 | 太原理工大学 | A kind of preparation method of sulphur carbon-based solid acid catalyst |
| CN110860274A (en) * | 2019-11-19 | 2020-03-06 | 南京工程学院 | Method for preparing adsorption coke by using waste lile pillow |
| CN111893219A (en) * | 2020-07-14 | 2020-11-06 | 江苏理工学院 | Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst |
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| CN101400443A (en) * | 2006-03-10 | 2009-04-01 | 新日本石油株式会社 | Carbon-based solid acid, catalyst comprising the solid acid, and reaction using the solid acid as catalyst |
| CN101670299A (en) * | 2009-10-16 | 2010-03-17 | 青岛生物能源与过程研究所 | Preparation method of nanometer carbon-based solid acid |
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| CN101400443A (en) * | 2006-03-10 | 2009-04-01 | 新日本石油株式会社 | Carbon-based solid acid, catalyst comprising the solid acid, and reaction using the solid acid as catalyst |
| CN101670299A (en) * | 2009-10-16 | 2010-03-17 | 青岛生物能源与过程研究所 | Preparation method of nanometer carbon-based solid acid |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489316A (en) * | 2011-12-02 | 2012-06-13 | 南开大学 | Preparation of glycosyl microsphere catalyst and process for hydrolyzing cellulose |
| CN103084188A (en) * | 2012-12-20 | 2013-05-08 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN103084188B (en) * | 2012-12-20 | 2015-03-11 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN106824226A (en) * | 2017-01-14 | 2017-06-13 | 江苏理工学院 | A kind of preparation method and its usage of carbon-based solid acid |
| CN106824226B (en) * | 2017-01-14 | 2020-01-07 | 江苏理工学院 | Preparation method and application of carbon-based solid acid |
| CN107045946A (en) * | 2017-04-01 | 2017-08-15 | 苏州海凌达电子科技有限公司 | A kind of preparation method and applications of modified calcite complex carbon material |
| CN106847532A (en) * | 2017-04-07 | 2017-06-13 | 苏州海凌达电子科技有限公司 | A kind of preparation method of the high performance material for ultracapacitor |
| CN106981372A (en) * | 2017-04-14 | 2017-07-25 | 苏州海凌达电子科技有限公司 | A kind of carbon electrode material preparation method applied to ultracapacitor |
| CN108940327A (en) * | 2018-06-02 | 2018-12-07 | 太原理工大学 | A kind of preparation method of sulphur carbon-based solid acid catalyst |
| CN108940327B (en) * | 2018-06-02 | 2021-08-31 | 太原理工大学 | Preparation method of sulfur-carbon-based solid acid catalyst |
| CN110860274A (en) * | 2019-11-19 | 2020-03-06 | 南京工程学院 | Method for preparing adsorption coke by using waste lile pillow |
| CN110860274B (en) * | 2019-11-19 | 2022-06-17 | 南京工程学院 | Method for preparing adsorption coke by using waste lile pillow |
| CN111893219A (en) * | 2020-07-14 | 2020-11-06 | 江苏理工学院 | Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst |
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Application publication date: 20100728 |