CN102029188A - Carbon-based solid acid catalyst with high specific surface area and preparation method thereof - Google Patents
Carbon-based solid acid catalyst with high specific surface area and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon-based solid acid catalyst with high specific surface area and a preparation method thereof. Powdery active carbon prepared by carbonizing farming and forestry residues serves as a catalyst carrier; and a sulfo group and the catalyst carrier are bonded through a covalent bond, namely a benzene sulfonic acid diazonium salt and the active carbon catalyst carrier are subjected to a diazonium salt reduction reaction to form the carbon-based solid acid catalyst with high specific surface area, which is covalently bonded from the sulfo group and the catalyst carrier. The particle size of the powdery active carbon is 0.3 to 5mm and the specific surface area is 300 to 2,000m<2>/g. In the invention, the active carbon formed by carbonizing raw materials, namely farming and forestry residual wood, straws, rice hulls, fruit husks and the like, which are low in price, serves as the catalyst carrier, so that the defect that the traditional solid acid catalyst is high in price is overcome; the farming and forestry residues are utilized with high value; and the obtained solid acid catalyst has high specific surface.
Description
Technical field
The invention belongs to the solid acid catalyst technical field, relate to high-specific surface area carbon-based solid acid catalyst and preparation method thereof.
Background technology
Liquid acid catalyst such as sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid are widely used in organic reactions such as catalytic esterification, hydrolysis, alkylation, hydration and Beckmann rearrangement, and it is acid strong, catalytic activity is high and cheap.Yet many shortcomings of liquid acid have also limited its application, and are not easily separated as catalyst and reaction system, improved energy consumption and post-processing difficulty; Liquid acid easily causes equipment corrosion, is difficult to recycling, and the discharging back produces large amount of sewage and easily causes environmental pollution etc.
Solid acid catalyst has the not available advantage of homogeneous catalyst aspect a lot, be convenient to separate as solid acid catalyst, and recyclable utilization does not more have the discharging of scrub raffinate, is convenient to realize serialization production etc.Advocating energetically under the overall background of Green Chemistry and sustainable development now, solid acid catalyst is undoubtedly best choice.
But existing solid catalyst cost is higher, complicated process of preparation, reaction temperature height, the easy inactivation of catalyst.Since 2004, Hara etc. propose notion (Hara M, et al.Angew Chem Iht Ed, 2004, the 43:2955 of carbon-based solid acid; Toda M, et al.Nature, 2005,438:178.), rise gradually through the research of charing and sulfonation Processing of Preparation charcoal base sulfonic acid catalyst by carbonaceous organic material.Domestic also some patent disclosures are arranged by the carbon-based solid acid catalyst of different material and distinct methods preparation (application number: 200610036699.2,200780008436.3,200710044614.X).The carbon-based solid acid material has mechanical strength height, Heat stability is good, acid advantage such as strong, with low cost, but its specific area (Okamura M, et al.Chem Mater, 2006,18:3039 generally on the low side; Mo X, et al.J Catal, 2008,254:332.), thereby had a strong impact on the engagement capacity of catalyst and reactant, when relating to the reaction that big molecule participates in catalytic effect relatively poor (Kitano M, et al.Catal Lett, 2009,131:242).
Summary of the invention
The problem that the present invention solves is to provide a kind of high-specific surface area carbon-based solid acid catalyst and preparation method thereof, this catalyst is as catalyst carrier with the active carbon after the agriculture and forestry organic waste material charing, as the acid site, is a kind of high-specific surface area and cheap solid acid catalyst with sulfonic group.
The present invention is achieved through the following technical solutions:
A kind of high-specific surface area carbon-based solid acid catalyst, as catalyst carrier, sulfonic group and catalyst carrier are passed through covalent bonds with the powdered active carbon after the agriculture and forestry organic waste material charing.
The particle diameter of described powdered active carbon is 0.3～5mm, and specific area is 300～2000m
2/ g.
Described agriculture and forestry organic waste material is one or more in waste wood, stalk, rice husk, the shell.
Described charing is at 300～900 ℃ of following charing 1～6h.
A kind of method of utilizing agriculture and forestry organic waste material to prepare the high-specific surface area carbon-based solid acid catalyst may further comprise the steps:
1) agriculture and forestry organic waste material being pulverized the back is 40～60%ZnCl comprising mass fraction
2Watery hydrochloric acid in soak 8～24h, after filtration, in 300～900 ℃ of following charing 1～6h, the cooling back grinds and obtains the charing powder under nitrogen protection in dry back; Then the charing powder is heated in watery hydrochloric acid and boil 1～2h, filter, charing powder water is fully washed again, drying obtains the activated carbon catalysis agent carrier;
2) under reducing condition, make benzene sulfonic acid diazol and activated carbon catalysis agent carrier generation diazol reduction reaction, obtain the covalently bound high-specific surface area carbon-based solid acid catalyst of sulfonic group and activated carbon catalysis agent carrier.
Being prepared as of described benzene sulfonic acid diazol:
Under acid condition, be 1: 0.6～1.5 mixing in molar ratio with aminobenzenesulfonic acid and solubility nitrite, react 30～90min down at 0～5 ℃, obtain white precipitate, obtain the benzene sulfonic acid diazol after filtration, washing, the drying.
Described acid condition is that aminobenzenesulfonic acid is dissolved in hydrochloric acid, sulfuric acid or boron fluoric acid; The solubility nitrite is natrium nitrosum or potassium nitrite.
Described benzene sulfonic acid diazol and activated carbon catalysis agent carrier generation diazol reduction reaction are:
With the absolute ethyl alcohol of a certain amount of activated carbon catalysis agent carrier and 20～50 times of its quality, 20～50 times deionized water, 50～100 times mass fraction is after the benzene sulfonic acid diazol of 40～50% hypophosphorous acid and 5～10 times fully mixes, in 0～5 ℃ of reaction 30～120min; After reaction is finished, the solids of gained is used the washing of distilled water and acetone respectively, at 100～120 ℃ of down dry 8～12h, obtain the high-specific surface area carbon-based solid acid catalyst then.
Compared with prior art, the present invention has following beneficial technical effects:
1, the present invention adopt be easy to get and raw material charings such as cheap agriculture and forestry organic waste material such as waste wood, stalk, rice husk, shell after active carbon as catalyst carrier, its specific area of resulting active carbon is 300～2000m
2/ g has overcome conventional solid acid catalyst shortcoming on the high side, realized the higher value application of agricultural refuses, and the solid acid catalyst of gained has high specific area.
2, the present invention is by accurately controlling immersion and cleaning and other reaction conditions of carbonization-activation temperature, watery hydrochloric acid, can control Surface Physical Chemistry character such as specific area, pore-size distribution, hydrophilic and hydrophobic and the surface functional group etc. of catalyst preferably, make different catalysts can adapt to different reactant systems and reaction type, realize the producing in serial form and the application of carbon base catalyst.
3, the active carbon of carbon-based solid acid catalyst provided by the invention after with charing is as catalyst carrier, sulfonic group as between acid site and the acid site with covalent bonds, the mechanical strength height of formed catalyst, Heat stability is good, acid strong, catalytic efficiency is high, have high-specific surface area simultaneously, can repeatedly reuse, advantage such as with low cost and environmental protection.
The specific embodiment
The present invention is described in further detail below in conjunction with the catalytic effect of specific embodiment and carbon-based solid acid catalyst, and the explanation of the invention is not limited.
Embodiment 1:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) the 20g pine powder is immersed in contains 40% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 12h; to be deposited in after filtration, the drying and be warming up to 300 ℃ under the nitrogen protection in tube furnace, charing 3h takes out the pressed powder that grinding obtains black with it after the cooling; particle diameter is 0.3～5mm, and specific area is 300～800m
2/ g;
Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (＞80 ℃)
-1, dry 12h under 105 ℃ obtains absorbent charcoal material at last.
2) adding 0.075mol sulfanilic acid and 187mL concentration are the hydrochloric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 82mL concentration with separatory funnel in three-necked bottle is the sodium nitrite solution of 1mol/L, stirring reaction 90min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 100mL absolute ethyl alcohol, 100mL distilled water, and the hypophosphorous acid of 400mL mass fraction 50% and 12.8g benzene sulfonic acid diazol, 0～5 ℃ of reaction 60min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 105 ℃ of following dry 12h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the high-specific surface area carbon-based solid acid catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects acetate after reaction is finished is 92%.
Embodiment 2:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) the 30g pine powder is immersed in contains 60%ZnCl
2The HCl solution of 120mL 1mol/L at room temperature react 8h, filter, filter, will be deposited in after the drying and in tube furnace, be warming up to 600 ℃ under the nitrogen protection; charing 2h; after the cooling it is taken out the pressed powder that grinding obtains black, particle diameter is 0.3～3mm, and specific area is 1000～2000m
2/ g;
Put it in the HCl solution of 100mL 1mol/L heating then and boil 2h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (85 ℃)
-1, dry 12h under 120 ℃ obtains absorbent charcoal material at last.
2) adding 0.1mol sulfanilic acid and 100mL, concentration are the HCl of 1mol/L in three-necked bottle, the electromagnetic agitation mixing, with ice-water bath temperature of reaction system is controlled at 0～5 ℃, slowly adding 120mL, concentration are the sodium nitrite solution of 1mol/L in reaction system with separatory funnel, stirring reaction 60min, obtain white depositions, i.e. benzene sulfonic acid diazol is with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) prepared active carbon is taken by weighing 2.0g and put into three-necked bottle, add hypophosphorous acid and the 10.8g benzene sulfonic acid diazol of 40mL absolute ethyl alcohol, 40mL distilled water, 400mL 40wt%, the benzene sulfonic acid diazol that makes, 0～2 ℃ of reaction 120min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 120 ℃ of following dry 8h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the caproic acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 80%.
Embodiment 3:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) the 20g maize straw is immersed in contains 50% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 16h; to be deposited in after filtration, the drying and be warming up to 700 ℃ under the nitrogen protection in tube furnace, charing 4h takes out the pressed powder that grinding obtains black with it after the cooling; particle diameter is 0.3～2mm, and specific area is 500～1200m
2/ g
Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (90 ℃)
-1, dry 10h under 115 ℃ obtains absorbent charcoal material at last.
2) adding 0.1mol sulfanilic acid and 200mL concentration are the hydrochloric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 80mL concentration with separatory funnel in three-necked bottle is the sodium nitrite solution of 1mol/L, stirring reaction 50min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 80mL absolute ethyl alcohol, 60mL distilled water, and the hypophosphorous acid of 500mL mass fraction 50% and 20g benzene sulfonic acid diazol, 0～5 ℃ of reaction 60min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 105 ℃ of following dry 12h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the capric acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 90%.
Embodiment 4:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) the 20g wheat stalk is immersed in contains 40% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 24h, filter, will be deposited in after the drying and in tube furnace, be warming up to 900 ℃ under the nitrogen protection, charing 1h after the cooling takes out it and grinds the pressed powder that obtains black; Particle diameter is 0.3～5mm, and specific area is 300～2000m
2/ g
Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (95 ℃)
-1, dry 10h under 115 ℃ obtains absorbent charcoal material at last.
2) adding 0.15mol sulfanilic acid and 200mL concentration are the boron fluoric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 90mL concentration with separatory funnel in three-necked bottle is the sodium nitrite solution of 1mol/L, stirring reaction 80min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 100mL absolute ethyl alcohol, 100mL distilled water, and the hypophosphorous acid of 200mL mass fraction 50% and 10g benzene sulfonic acid diazol, 0～5 ℃ of reaction 100min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 105 ℃ of following dry 12h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the oleic acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 85%.
Embodiment 5:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) the 20g walnut shell powder is immersed in contains 40% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 10h, filter, will be deposited in after the drying and in tube furnace, be warming up to 300 ℃ under the nitrogen protection, charing 3h after the cooling takes out it and grinds the pressed powder that obtains black;
Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (95 ℃)
-1, dry 12h under 105 ℃ obtains absorbent charcoal material at last.
2) adding 0.075mol sulfanilic acid and 187mL concentration are the sulfuric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 82.5mL concentration with separatory funnel in three-necked bottle is the sodium nitrite solution of 1mol/L, stirring reaction 90min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 50mL absolute ethyl alcohol, 40mL distilled water, and the hypophosphorous acid of 300mL mass fraction 50% and 15g benzene sulfonic acid diazol, 0～5 ℃ of reaction 30min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 105 ℃ of following dry 8h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the stearic acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 80%.
Embodiment 6:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) 10g pine powder and 10g maize straw are immersed in contain 40% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 24h, filter, will be deposited in after the drying and in tube furnace, be warming up to 500 ℃ under the nitrogen protection, charing 2h after the cooling takes out it and grinds the pressed powder that obtains black;
Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (95 ℃)
-1, dry 12h under 105 ℃ obtains absorbent charcoal material at last.
2) adding 0.075mol sulfanilic acid and 187mL concentration are the sulfuric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 100mL concentration with separatory funnel in three-necked bottle is the potassium nitrite solution of 1mol/L, stirring reaction 90min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 80mL absolute ethyl alcohol, 80mL distilled water, and the hypophosphorous acid of 600mL mass fraction 50% and 12.8g benzene sulfonic acid diazol, 0～5 ℃ of reaction 120min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 100 ℃ of following dry 12h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the n-capric acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 80%.
Embodiment 7:
The preparation of high-specific surface area carbon-based solid acid catalyst specifically may further comprise the steps:
1) 10g poplar powder and 10g rice husk are immersed in contain 40% (mass fraction) ZnCl
2100mL hydrochloric acid at room temperature soak reaction 12h, filter, will be deposited in after the drying and in tube furnace, be warming up to 500 ℃ under the nitrogen protection, charing 1h after the cooling takes out it and grinds the pressed powder that obtains black; Put it in the HCl solution of 100mL 1mol/L heating then and boil 1h, filter,, detect less than Cl up to flushing liquor with fully washing of pressed powder reusable heat distilled water (95 ℃)
-1, dry 12h under 105 ℃ obtains absorbent charcoal material at last.
2) adding 0.1mol sulfanilic acid and 200mL concentration are the boron fluoric acid of 1mol/L in three-necked bottle, the electromagnetic agitation mixing; Under the ice-water bath condition, temperature of reaction system is controlled at 0～5 ℃, slowly adding 120mL concentration with separatory funnel in three-necked bottle is the potassium nitrite solution of 1mol/L, stirring reaction 90min, obtain white precipitate, be the benzene sulfonic acid diazol, with the washing of gained benzene sulfonic acid diazol, filtration, drying.
3) take by weighing the 2.0g active carbon and put into three-necked bottle, add 100mL absolute ethyl alcohol, 100mL distilled water, and the hypophosphorous acid of 300mL mass fraction 50% and 18g benzene sulfonic acid diazol, 0～5 ℃ of reaction 120min.After reaction was finished, with the solids usefulness distilled water and the acetone washing respectively of gained, 120 ℃ of following dry 8h in baking oven obtained the high-specific surface area carbon-based solid acid catalyst then.
The catalytic effect of high-specific surface area carbon-based solid acid catalyst detects:
In round-bottomed flask, add the n-capric acid of 0.1mol, the absolute ethyl alcohol of 1mol, the Pd/carbon catalyst of 0.2g, reaction 10h under 85 ℃, the conversion ratio that detects caproic acid after reaction is finished is 84%.
Claims (8)
1. a high-specific surface area carbon-based solid acid catalyst is characterized in that, as catalyst carrier, sulfonic group and catalyst carrier are passed through covalent bonds with the powdered active carbon after the agriculture and forestry organic waste material charing.
2. high-specific surface area carbon-based solid acid catalyst as claimed in claim 1 is characterized in that, the particle diameter of powdered active carbon is 0.3～5mm, and specific area is 300～2000m
2/ g.
3. high-specific surface area carbon-based solid acid catalyst as claimed in claim 1 is characterized in that, described agriculture and forestry organic waste material is one or more in waste wood, stalk, rice husk, the shell.
4. high-specific surface area carbon-based solid acid catalyst as claimed in claim 1 is characterized in that, described charing is at 300～900 ℃ of following charing 3～6h.
5. a method of utilizing agriculture and forestry organic waste material to prepare the high-specific surface area carbon-based solid acid catalyst is characterized in that, may further comprise the steps:
1) agriculture and forestry organic waste material being pulverized the back is 40～60%ZnCl comprising mass fraction
2Watery hydrochloric acid in soak 8～24h, after filtration, in 300～900 ℃ of following charing 1～6h, the cooling back grinds and obtains the charing powder under nitrogen protection in dry back; Then the charing powder is heated in watery hydrochloric acid and boil 1～2h, filter, charing powder water is fully washed again, drying obtains the activated carbon catalysis agent carrier;
2) under reducing condition, make benzene sulfonic acid diazol and activated carbon catalysis agent carrier generation diazol reduction reaction, obtain the covalently bound high-specific surface area carbon-based solid acid catalyst of sulfonic group and activated carbon catalysis agent carrier.
6. the method for utilizing agriculture and forestry organic waste material to prepare the high-specific surface area carbon-based solid acid catalyst as claimed in claim 5 is characterized in that, being prepared as of described benzene sulfonic acid diazol:
Under acid condition, be 1: 0.6～1.5 mixing in molar ratio with aminobenzenesulfonic acid and solubility nitrite, react 30～90min down at 0～5 ℃, obtain white precipitate, obtain the benzene sulfonic acid diazol after filtration, washing, the drying.
7. the method for utilizing agriculture and forestry organic waste material to prepare the high-specific surface area carbon-based solid acid catalyst as claimed in claim 6 is characterized in that, described acid condition is that aminobenzenesulfonic acid is dissolved in hydrochloric acid, sulfuric acid or boron fluoric acid; The solubility nitrite is natrium nitrosum or potassium nitrite.
8. the method for utilizing agriculture and forestry organic waste material to prepare the high-specific surface area carbon-based solid acid catalyst as claimed in claim 5 is characterized in that, benzene sulfonic acid diazol and activated carbon catalysis agent carrier generation diazol reduction reaction are:
With the absolute ethyl alcohol of activated carbon catalysis agent carrier and 20～50 times of its quality, 20～50 times deionized water, 50～100 times mass fraction is after the benzene sulfonic acid diazol of 40～50% hypophosphorous acid and 5～10 times fully mixes, in 0～5 ℃ of reaction 30～120min; After reaction is finished, the solids of gained is used the washing of distilled water and acetone respectively, at 100～120 ℃ of down dry 8～12h, obtain the high-specific surface area carbon-based solid acid catalyst then.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104525252A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Immobilized ionic liquid solid acid catalyst and preparation method thereof |
| US9504992B2 (en) * | 2014-10-17 | 2016-11-29 | Hyundai Motor Company | Solid acid catalyst for preparing a monosaccharide and method of preparing a monosaccharide from seaweed using the same |
| CN109603905A (en) * | 2018-12-05 | 2019-04-12 | 福州大学 | A kind of Jujun grasses porous charcoal base solid catalyst and preparation method thereof |
| CN115518656A (en) * | 2022-10-25 | 2022-12-27 | 陕西科技大学 | Lignin-PVC carbon-based solid acid and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618341A (en) * | 2009-07-27 | 2010-01-06 | 西北农林科技大学 | Carbon-based solid acid catalyst and preparation method thereof |
-
2010
- 2010-11-15 CN CN 201010544184 patent/CN102029188A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618341A (en) * | 2009-07-27 | 2010-01-06 | 西北农林科技大学 | Carbon-based solid acid catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《广西轻工业》 20100331 徐泽龙 等 农业废弃物制备活性炭及其应用进展 65-67 1-8 , 第3期 2 * |
| 《河北工业科技》 20100731 焦其帅 等 氯化锌活化法制备棉花秸秆活性炭的研究 232-235 5-8 第27卷, 第4期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US9504992B2 (en) * | 2014-10-17 | 2016-11-29 | Hyundai Motor Company | Solid acid catalyst for preparing a monosaccharide and method of preparing a monosaccharide from seaweed using the same |
| CN104525252A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Immobilized ionic liquid solid acid catalyst and preparation method thereof |
| CN109603905A (en) * | 2018-12-05 | 2019-04-12 | 福州大学 | A kind of Jujun grasses porous charcoal base solid catalyst and preparation method thereof |
| CN109603905B (en) * | 2018-12-05 | 2022-03-25 | 福州大学 | Pennisetum hydridum porous carbon-based solid catalyst and preparation method thereof |
| CN115518656A (en) * | 2022-10-25 | 2022-12-27 | 陕西科技大学 | Lignin-PVC carbon-based solid acid and preparation method and application thereof |
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