CN107262149A - A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst - Google Patents
A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst Download PDFInfo
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- CN107262149A CN107262149A CN201710504991.0A CN201710504991A CN107262149A CN 107262149 A CN107262149 A CN 107262149A CN 201710504991 A CN201710504991 A CN 201710504991A CN 107262149 A CN107262149 A CN 107262149A
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- acid catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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Abstract
The invention discloses a kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst, the present invention prepares carbon-based solid acid catalyst using hydro-thermal charing sulfonation method, without hydrolyzing straw under catalysts conditions, carbonize to form spherical carbon core by carbon source of its hydrolyzate, with huge specific surface area, afterwards sulfonated processing, area load has sulfonic group, phenolic hydroxyl group and carboxyl, group produces cooperative effect each other, enhances the acidity and stability of catalyst；And bigger serface is during catalyzing hydrolysis cellulose, decentralization of the catalyst in heterogeneous system can not only be improved, and catalytic activity group can be made fully to be contacted with reactant, and it is high with catalytic reaction substrate affinity, so that with higher catalytic activity.
Description
Technical field
The present invention relates to natural plant fibre technical field of comprehensive utilization, and in particular to a kind of cellulose hydrolysis biomass
The preparation method of carbon-based solid acid catalyst.
Background technology
Petroleum resources are replaced to produce important fine chemical product using widely distributed and cheap wood fibre resource
One of study hotspot as domestic and international resource and energy field.The Nomenclature Composition and Structure of Complexes of wood fibre is complicated, how efficiently to urge
Change wood fibre be converted into grain and fine chemicals, to meet human social development the need for be key point.
Using aromatic compound and saccharide compound as raw material, it is made through not exclusively charing and sulfonation and contains sulfonic charcoal base
The higher catalytic activity that solid acid catalyst is shown, causes the extensive concern of domestic and foreign scholars.Biomass carbon sulfonic acid catalyst
Have product easily separated in the hydrolysis of catalysis wood fibre, operation is simple, the advantage such as catalyst is cheap, but catalyst deposits
Catalytic activity it is not high and recycle the shortcomings of performance is poor.
The content of the invention
The present invention provides a kind of cellulose hydrolysis preparation method of biomass carbon based solid acid catalyst, preparation condition phase
To gentle, and required reaction temperature is relatively low, can reduce the energy consumption of catalyst preparation process, and make by this method
Standby catalyst activity is high, and stability is good.
The present invention is achieved by the following technical solutions：
A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst, including step in detail below：
（1）Pretreatment：
By the length of 50-70 parts by weight well cuttings in the NaOH solution that 1-3cm agricultural crop straw is placed in 200-400 parts of 2wt%
Immersion 2-3 hours, then takes out, and is washed with distilled water to neutrality, removes the wax on stalk surface and the impurity of other attachments, puts
In dry, pulverize in 70-85 DEG C of baking oven and cross 100 mesh sieves, it is stored in drier, it is standby；
（2）Hydrolysis：
Then the stalk after sieving is mixed by certain solid-to-liquid ratio with water, magnetic agitation shifted mixed liquor after 20-40 minutes
Into stainless steel cauldron, reactor is placed in the electric heating constant-temperature blowing drying box that temperature is 180-200 DEG C, hydrolysis 1-2 is small
When, after the product after hydrolysis is centrifuged, it is transferred to stainless steel cauldron；
（3）Carbonization treatment：
By step（2）Reactor equipped with clear liquid is placed in the baking oven that temperature is 170-190 DEG C, carries out carbonization treatment, continues charcoal
Change 5-9 hours, reaction takes out reactor after terminating, and naturally cools to room temperature, after carbonized product is centrifuged, second is used respectively
Alcohol, deionized water are washed for several times, then after drying, grind into powder；
（4）Sulfonation is handled：
By step（3）Carbon carrier powder is added into stainless steel water heating kettle, under magnetic stirring, adds a certain amount of 98% dense sulphur
Acid is well mixed, is heated at 110-150 DEG C, sulfonation 5-9 hours under nitrogen protection, naturally cools to after room temperature, will mix
The concentrated sulfuric acid is recovered by filtration in thing, and filter cake, in neutrality, is placed in 100-110 DEG C of baking oven and dried, produced with boiling water cyclic washing to filtrate
To carbon-based solid acid catalyst.
Wherein, described agricultural crop straw refers to one or more kinds of in rice straw, wheat stalk, cotton stalk
Mixture.
Wherein, described step（2）The solid-to-liquid ratio of middle stalk and water is 1:30-50.
Wherein, the ratio of described carbon carrier and 98% concentrated sulfuric acid is 1g/20ml.
Compared with prior art, the present invention has advantages below：
The present invention prepares carbon-based solid acid catalyst using hydro-thermal charing-sulfonation method, without hydrolyzing straw under catalysts conditions, with
Its hydrolyzate is that carbon source carbonizes to form spherical carbon core, and with huge specific surface area, afterwards sulfonated processing, area load has sulphur
Acidic group, phenolic hydroxyl group and carboxyl, and bigger serface can not only improve catalyst non-equal during catalyzing hydrolysis cellulose
Decentralization in phase system, and catalytic activity group can be made fully to be contacted with reactant, with catalytic reaction substrate affinity
Height, so that with higher catalytic activity；Other phenolic hydroxyl group is that crystalline sites are conciliate in absorption, has solution to crystallize and inhale to reaction substrate
Reactant, can be adsorbed onto around catalyst by attached effect, reach sulfonic sphere of action, and collaboration effect is produced each other
Should, enhance the acidity and stability of catalyst.
Embodiment
A kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst, including step in detail below：
（1）Pretreatment：
The length of 70 parts by weight well cuttings is soaked in the NaOH solution that 1-3cm agricultural crop straw is placed in 360 parts of 2wt% to 2 small
When, then take out, be washed with distilled water to neutrality, remove the wax on stalk surface and the impurity of other attachments, be placed in 80 DEG C
It dry, pulverize in baking oven and cross 100 mesh sieves, be stored in drier, it is standby；
（2）Hydrolysis：
Then the stalk after sieving is mixed by certain solid-to-liquid ratio with water, mixed liquor is transferred to by magnetic agitation after 40 minutes
In stainless steel cauldron, reactor is placed in the electric heating constant-temperature blowing drying box that temperature is 190 DEG C, hydrolyzed 1.5 hours, hydrolysis
After product afterwards is centrifuged, stainless steel cauldron is transferred to；
（3）Carbonization treatment：
By step（2）Reactor equipped with clear liquid is placed in the baking oven that temperature is 180 DEG C, carries out carbonization treatment, persistently carbonizes 8 small
When, reaction terminate after reactor is taken out, naturally cool to room temperature, after carbonized product is centrifuged, respectively with ethanol, go from
Sub- water washing for several times, then after drying, grind into powder；
（4）Sulfonation is handled：
By step（3）Carbon carrier powder is added into stainless steel water heating kettle, under magnetic stirring, adds a certain amount of 98% dense sulphur
Acid is well mixed, is heated at 130 DEG C, sulfonation 7 hours, are naturally cooled to after room temperature under nitrogen protection, and mixture is filtered
The concentrated sulfuric acid is reclaimed, filter cake, in neutrality, is placed in 105 DEG C of baking ovens and dried, that is, obtain carbon-based solid with boiling water cyclic washing to filtrate
Acid catalyst.
Wherein, described agricultural crop straw refers to one or more kinds of in rice straw, wheat stalk, cotton stalk
Mixture.
Wherein, described step（2）The solid-to-liquid ratio of middle stalk and water is 1:40.
Wherein, the ratio of described carbon carrier and 98% concentrated sulfuric acid is 1g/20ml.
Claims (4)
1. a kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst, it is characterised in that including following tool
Body step：
（1）Pretreatment：
By the length of 50-70 parts by weight well cuttings in the NaOH solution that 1-3cm agricultural crop straw is placed in 200-400 parts of 2wt%
Immersion 2-3 hours, then takes out, and is washed with distilled water to neutrality, removes the wax on stalk surface and the impurity of other attachments, puts
In dry, pulverize in 70-85 DEG C of baking oven and cross 100 mesh sieves, it is stored in drier, it is standby；
（2）Hydrolysis：
Then the stalk after sieving is mixed by certain solid-to-liquid ratio with water, magnetic agitation shifted mixed liquor after 20-40 minutes
Into stainless steel cauldron, reactor is placed in the electric heating constant-temperature blowing drying box that temperature is 180-200 DEG C, hydrolysis 1-2 is small
When, after the product after hydrolysis is centrifuged, it is transferred to stainless steel cauldron；
（3）Carbonization treatment：
By step（2）Reactor equipped with clear liquid is placed in the baking oven that temperature is 170-190 DEG C, carries out carbonization treatment, continues charcoal
Change 5-9 hours, reaction takes out reactor after terminating, and naturally cools to room temperature, after carbonized product is centrifuged, second is used respectively
Alcohol, deionized water are washed for several times, then after drying, grind into powder；
（4）Sulfonation is handled：
By step（3）Carbon carrier powder is added into stainless steel water heating kettle, under magnetic stirring, adds a certain amount of 98% dense sulphur
Acid is well mixed, is heated at 110-150 DEG C, sulfonation 5-9 hours under nitrogen protection, naturally cools to after room temperature, will mix
The concentrated sulfuric acid is recovered by filtration in thing, and filter cake, in neutrality, is placed in 100-110 DEG C of baking oven and dried, produced with boiling water cyclic washing to filtrate
To carbon-based solid acid catalyst.
2. a kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst according to claims 1,
Characterized in that, described agricultural crop straw refer to it is one or more kinds of mixed in rice straw, wheat stalk, cotton stalk
Compound.
3. a kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst according to claims 1,
Characterized in that, described step（2）The solid-to-liquid ratio of middle stalk and water is 1:30-50.
4. a kind of preparation method of cellulose hydrolysis biomass carbon based solid acid catalyst according to claims 1,
Characterized in that, described carbon carrier and the ratio of 98% concentrated sulfuric acid are 1g/20ml.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165330A (en) * | 2018-01-30 | 2018-06-15 | 中山大学 | A kind of method of one step recycling of plant and energy after soil remediation |
| CN109092370A (en) * | 2018-08-03 | 2018-12-28 | 华南农业大学 | A kind of rice silicon source magnetic solid acid catalyst and preparation method thereof and the application in reduced sugar is prepared in catalysis corncob |
| CN109289870A (en) * | 2018-09-21 | 2019-02-01 | 陕西科技大学 | A kind of sulfonation charcoal and its preparation method and application |
| CN109482197A (en) * | 2018-10-30 | 2019-03-19 | 陕西中医药大学 | Magnetic solid acid catalyst SO3H-CBC@M preparation method and application |
| CN111118066A (en) * | 2020-01-22 | 2020-05-08 | 广东省石油与精细化工研究院 | Method for producing biogas through biochar solid acid reinforced two-phase anaerobic fermentation |
| CN111303220A (en) * | 2020-03-27 | 2020-06-19 | 安徽银创生物科技股份有限公司 | Preparation method of D-glucosamine sulfate |
| CN112264051A (en) * | 2020-10-16 | 2021-01-26 | 湖南三五二环保科技有限公司 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
| CN112517061A (en) * | 2020-12-03 | 2021-03-19 | 北方民族大学 | Sulfonic acid type solid acid catalyst and preparation method thereof |
| CN112844409A (en) * | 2021-01-22 | 2021-05-28 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890364A (en) * | 2010-06-25 | 2010-11-24 | 西北农林科技大学 | Method of using agricultural and forestry waste to prepare solid-acid catalyst |
| CN103303899A (en) * | 2013-05-21 | 2013-09-18 | 新乡学院 | Carbon microsphere prepared by adopting green technology by utilizing wheat straws as carbon source and preparation technology |
-
2017
- 2017-06-28 CN CN201710504991.0A patent/CN107262149A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890364A (en) * | 2010-06-25 | 2010-11-24 | 西北农林科技大学 | Method of using agricultural and forestry waste to prepare solid-acid catalyst |
| CN103303899A (en) * | 2013-05-21 | 2013-09-18 | 新乡学院 | Carbon microsphere prepared by adopting green technology by utilizing wheat straws as carbon source and preparation technology |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165330A (en) * | 2018-01-30 | 2018-06-15 | 中山大学 | A kind of method of one step recycling of plant and energy after soil remediation |
| CN109092370A (en) * | 2018-08-03 | 2018-12-28 | 华南农业大学 | A kind of rice silicon source magnetic solid acid catalyst and preparation method thereof and the application in reduced sugar is prepared in catalysis corncob |
| CN109289870A (en) * | 2018-09-21 | 2019-02-01 | 陕西科技大学 | A kind of sulfonation charcoal and its preparation method and application |
| CN109289870B (en) * | 2018-09-21 | 2021-03-30 | 陕西科技大学 | Sulfonated carbon and preparation method and application thereof |
| CN109482197A (en) * | 2018-10-30 | 2019-03-19 | 陕西中医药大学 | Magnetic solid acid catalyst SO3H-CBC@M preparation method and application |
| CN111118066A (en) * | 2020-01-22 | 2020-05-08 | 广东省石油与精细化工研究院 | Method for producing biogas through biochar solid acid reinforced two-phase anaerobic fermentation |
| CN111303220A (en) * | 2020-03-27 | 2020-06-19 | 安徽银创生物科技股份有限公司 | Preparation method of D-glucosamine sulfate |
| CN112264051A (en) * | 2020-10-16 | 2021-01-26 | 湖南三五二环保科技有限公司 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
| CN112264051B (en) * | 2020-10-16 | 2022-11-18 | 德安县塑丽龙纺织有限公司 | Preparation method of solid acid catalyst for cellulose hydrolysis and product thereof |
| CN112517061A (en) * | 2020-12-03 | 2021-03-19 | 北方民族大学 | Sulfonic acid type solid acid catalyst and preparation method thereof |
| CN112844409A (en) * | 2021-01-22 | 2021-05-28 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
| CN112844409B (en) * | 2021-01-22 | 2023-06-23 | 江苏省农业科学院 | Preparation method and application of biomass straw-based magnetic solid acid catalyst |
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Application publication date: 20171020 |