CN101787400A - Method for hydrolyzing vegetable fibre by solid acid - Google Patents
Method for hydrolyzing vegetable fibre by solid acid Download PDFInfo
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- CN101787400A CN101787400A CN 201010139111 CN201010139111A CN101787400A CN 101787400 A CN101787400 A CN 101787400A CN 201010139111 CN201010139111 CN 201010139111 CN 201010139111 A CN201010139111 A CN 201010139111A CN 101787400 A CN101787400 A CN 101787400A
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- vegetable fibre
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Abstract
The invention discloses a method for hydrolyzing vegetable fibre by solid acid, comprising the following steps: (1) adding smashed vegetable fibre and a solid-acid catalyst into water, mixing and dissolving; (2) carrying out hydro-thermal reaction at the temperature of 140-180DEG C for 6-10 hours after the smashed vegetable fibre and the solid-acid catalyst are evenly mixed and dissolved, and obtaining hydrolysate after the reaction; and (3) filtering the hydrolysate so as to separate target objects and the solid-acid catalyst, drying filter residues so as to be directly reused, and regulating the pH value of filter liquor to be within 6-8. The invention adopts solid sulfoacid with better hydrothermal stability and larger acid value to replace liquid acid, realizes the hydrolyzation of the cellulose under the moderate condition and solves the problem that the tradition catalyst is difficult to be separated from products; and after separation, the catalyst can be recycled, thereby avoiding lower economic benefit and acid contamination caused by the loss of liquid-acid catalysts.
Description
Technical field
The invention belongs to the vegetable fibre acid hydrolysis and produce the method for sugar, be specifically related to the method for hydrolysis that solid sulfoacid is used for vegetable fibre.
Background technology
Utilizing biomass resource to produce liquid fuel and Chemicals, is that cellulose hydrolysis is become carbohydrate, as oligosaccharides, monose etc., utilizes microorganism (candiyeast, yeast saccharomyces cerevisiae etc.) production fluid fluid fuel in next life and Chemicals then.The cellulose hydrolysis method for saccharifying mainly contains diluted acid method, concentrated acid method, enzyme process and comparatively popular extremely low acids hydrolysis and the supercritical water hydrolysis of research now.
Traditional acid hydrolysis process is concentrated acid hydrolysis and dilute acid hydrolysis, dilute acid hydrolysis is higher to the conditional request of technology, energy consumption is excessive in the existence reaction, sugar transformation efficiency lower (being about 25%) easily produces a large amount of harmful intermediate product shortcomings such as (as furfural, organic acids) that suppress microorganism growth in the reaction process; Though and the transformation efficiency higher (more than 90%) of concentrated acid hydrolysis sugar, it is too serious that the catalyzer concentrated acid runs off, acid consumption is bigger, and the erosion resistance of equipment is had relatively high expectations, production cost is higher; Though cellulase is higher to cellulosic hydrolysis process transformation efficiency, the zymin cost is higher, and pre-processing device is bigger, and running cost is higher, and reaction time is longer; Extremely low acids hydrolysis and supercritical water hydrolysis need be reacted under high temperature, high pressure exacting terms, and operation and the difficult control of process easily produce degradation product, influence follow-up fermentation.Therefore, invention is a kind of can realize the saccharification of Mierocrystalline cellulose effectively hydrolyzing simultaneously catalyzer is can recycle necessary under the condition of gentleness.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, a kind of method of hydrolyzing vegetable fibre by solid acid is provided, reaction conditions gentleness of the present invention, sugar transformation efficiency height, acid catalyst can recycle, objectionable impurities produces fewly in the hydrolysis reaction, has environmentally friendly and is worth than large economy.The present invention is achieved through the following technical solutions:
A kind of method of hydrolyzing vegetable fibre by solid acid, vegetable fibre hydrolysis under the effect of solid acid catalyst, saccharification specifically comprises the steps:
(1) vegetable fibre after the pulverization process and solid acid catalyst are added to the water carry out miscible;
(2) 6～10h hydro-thermal reaction is carried out at 140～180 ℃ in miscible even back, and reaction finishes to make hydrolyzed solution;
(3) target product is separated the hydrolyzed solution filtration with solid acid catalyst, filter residue oven dry back direct reuse, filtrate is adjusted pH value to 6～8.
The method of above-mentioned hydrolyzing vegetable fibre by solid acid, the mass percent that the described vegetable fibre of step (1) accounts for water is 0.2～2%; The mass percent that described solid acid catalyst accounts for water is 0.2～2%.
The method of above-mentioned hydrolyzing vegetable fibre by solid acid, the described vegetable fibre of step (1) comprises one or both in thallophyta fiber, the aftergrowth fiber.
The method of above-mentioned hydrolyzing vegetable fibre by solid acid, the described solid acid catalyst of step (1) comprises carbon-based solid sulfoacid, SO
4 2-/ ZrO
2In one or both.
Compared with prior art, the present invention has the following advantages:
(1) the present invention has realized the hydrolysis that carbon-based solid acid substitution liquid acid catalyst carries out vegetable fibre, and this invention reaction conditions gentleness has reduced energy consumption; The sugar of having avoided simultaneously generating further is degraded into by product, suppresses the carrying out of follow-up fermentation.
(2) carbon-based solid sulfoacid hydrolyzing plant fiber temperature, pressure are lower, and thermally-stabilised in water simultaneously better the pH value of hydrolyzed solution is 3～4, and is therefore less demanding to the corrodibility of equipment, is easy to realize, reduced production cost, improved economic benefit.
(3) carbon-based solid sulfoacid that the present invention adopts can be realized catalyzer and product separation, and catalyzer can recycle and regeneration, and the almost not influence of output to sugar has met the requirement of cleaner production.
(4) the present invention can the phytoplasm of rich cellulose be a raw material to originate widely, can produce the alcoholic acid substrate for fermentation, overcomes the low in economic efficiency deficiency of traditional liquid acid catalyst hydrolysis.
Embodiment
Specifically be described further of the present invention below in conjunction with case study on implementation.Following discloses only be preferable case study on implementation of the present invention, concrete enforcement of the present invention and protection domain are not limited thereto.
With the hydrolysis material of old corrugated container board (OCC) as the carbon-based solid sulfoacid catalyzer, utilize the plant pulverizer to copy OCC and fragmentate, be put in that oven dry 12h is stored in the sealing bag, for future use in 105 ℃ the baking oven.
Embodiment 1
It is miscible that OCC fragment, carbon back sulfonic acid catalyst are added to the water according to the mass percent that accounts for water (as table 1), reacts 12h under different temperature.Filter hydrolyzed solution, a gained filtrate part is used to produce glycan analysis, and a part is as fermentation substrate, and filter residue is used for cyclically utilizing.
Carbon-based solid sulfoacid is to the hydrolysis effect contrast of OCC under table 1 differing temps
Table 2 reuse number of times is to the influence of hydrolysis effect
As can be seen from Table 1, along with variation of temperature, the taking the lead in of sugar increases the back and reduces, and when 150 ℃ of temperature, sugared yield reaches maximum value 22.16%, compares very approaching with traditional dilute sulphuric acid hydrolysis (sugared yield maximum 25%); When 180 ℃ of temperature, sugared yield 11.50% illustrates that under thermal and hydric environment, the part carbohydrate begins to be converted into by product, and the hydrolysed filtrate residue is used for the next batch hydrolysis.Along with the increase of reuse number of times, sugared decrement is respectively 14.13%, 8.62%, 7.08% as can be seen from Table 2, illustrates that carbon-based solid sulfoacid has the loss of small portion, has good stability under the high-temperature water thermal environment, can satisfy the requirement of reuse fully.
Embodiment 2
It is miscible that OCC fragment, carbon back sulfonic acid catalyst are added to the water according to the mass percent that accounts for water (as table 3), reacts the different time down in 150 ℃.Filter hydrolyzed solution, a gained filtrate part is used to produce glycan analysis, and a part is used for the hydrolyzed solution fermentation, and filter residue is used for cyclically utilizing.
Carbon-based solid sulfoacid is to the hydrolysis effect contrast of OCC under table 3 different time
Table 4 reuse number of times is to the influence of hydrolysis effect
As can be seen from Table 3, along with the variation of time, sugaredly must take the lead in increasing the back and reduce, when 8h, the sugar yield reaches maximum value 24.07%, subsequently along with the time from 8～12h, sugared yield has reduced by 7.61%, illustrates under the thermal and hydric environment of gentleness, this catalyzer has very high selectivity to sugar, sugar further is converted into by product seldom, helps the carrying out of follow-up fermentation, and residue filters and is used for next batch.Along with the increase of reuse number of times, sugared decrement is respectively 13.30%, 9.83%, 7.71% as can be seen from Table 4, illustrates that carbon-based solid sulfoacid has the loss of small portion, has good stability under the high-temperature water thermal environment, can satisfy the requirement of reuse fully.
Embodiment 3
It is miscible that the OCC fragment is added to the water according to the mass percent that accounts for water (as table 5), and the carbon-based solid sulfoacid catalyzer is added to the water miscible according to different concentration, reacts 8h down in 150 ℃.Filter hydrolyzed solution, a gained filtrate part is used to produce glycan analysis, and a part is used for the hydrolyzed solution fermentation, and filter residue is used for cyclically utilizing.
Table 5 different concns carbon-based solid sulfoacid is to the hydrolysis effect contrast of OCC
The different carbon-based solid sulfoacid reuse of table 6 number of times is to the influence of hydrolysis effect
As can be seen from Table 5, along with the variation of catalyzer add-on, sugaredly must take the lead in increasing the back and reduce, when 1.2% add-on, the sugar yield reaches maximum value 26.44%, and subsequently along with the increase of catalyzer add-on, reduction has appearred in sugared yield, mainly be because sugar further transforms for furfural, acetate etc., from whole sugared yield, catalyzer comparatively relaxes the hydrolysis of vegetable fibre, illustrates under the thermal and hydric environment of gentleness, this catalyzer has very high selectivity to sugar, and residue filters and is used for next batch.Along with the increase of reuse number of times, sugared decrement is respectively 12.14%, 8.23%, 7.09% as can be seen from Table 6, illustrates that carbon-based solid sulfoacid has the loss of small portion, has good stability under the high-temperature water thermal environment, can satisfy the requirement of reuse fully.
Claims (5)
1. the method for a hydrolyzing vegetable fibre by solid acid is characterized in that comprising the steps:
(1) vegetable fibre after the pulverization process and solid acid catalyst are added to the water carry out miscible;
(2) 6～10h hydro-thermal reaction is carried out at 140～180 ℃ in miscible even back, and reaction finishes to make hydrolyzed solution;
(3) target product is separated the hydrolyzed solution filtration with solid acid catalyst, filter residue oven dry back direct reuse, filtrate is adjusted pH value to 6～8.
2. the method for hydrolyzing vegetable fibre by solid acid according to claim 1, it is characterized in that: the mass percent that the described vegetable fibre of step (1) accounts for water is 0.2～2%; The mass percent that described solid acid catalyst accounts for water is 0.2～2%.
3. the method for hydrolyzing vegetable fibre by solid acid according to claim 1 is characterized in that the described vegetable fibre of step (1) comprises one or both in thallophyta fiber, the aftergrowth fiber.
4. according to the method for each described hydrolyzing vegetable fibre by solid acid of claim 1～3, it is characterized in that the described solid acid catalyst of step (1) comprises carbon-based solid sulfoacid, SO
4 2-/ ZrO
2In one or both.
5. the method for hydrolyzing vegetable fibre by solid acid according to claim 4 is characterized in that the described reuse of step (3) is that reaction residues is directly used in next time described hydro-thermal reaction.
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| CN 201010139111 CN101787400A (en) | 2010-03-31 | 2010-03-31 | Method for hydrolyzing vegetable fibre by solid acid |
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| CN 201010139111 CN101787400A (en) | 2010-03-31 | 2010-03-31 | Method for hydrolyzing vegetable fibre by solid acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504028A (en) * | 2011-10-11 | 2012-06-20 | 常茂生物化学工程股份有限公司 | Method for preparing organic cellulose acid ester by solid acid catalysts |
| CN103189526A (en) * | 2010-11-05 | 2013-07-03 | 国际壳牌研究有限公司 | Treating biomass to produce materials useful for biofuels |
| CN104395478A (en) * | 2012-05-07 | 2015-03-04 | 国际壳牌研究有限公司 | Continuous or semi-continuous process for treating biomass to produce materials useful for biofuels |
| CN104894298A (en) * | 2015-05-06 | 2015-09-09 | 重庆大学 | Method used for degrading lignocellulose with solid acid catalyst |
| EP2871246A4 (en) * | 2012-07-03 | 2016-03-09 | Showa Denko Kk | Method for decomposing plant biomass, and method for producing glucose |
| CN112661376A (en) * | 2020-12-30 | 2021-04-16 | 广东省科学院化工研究所 | Municipal sludge pretreatment method and application thereof |
| CN115558001A (en) * | 2022-09-26 | 2023-01-03 | 南开大学 | Method for decomposing polaroid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
-
2010
- 2010-03-31 CN CN 201010139111 patent/CN101787400A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103189526A (en) * | 2010-11-05 | 2013-07-03 | 国际壳牌研究有限公司 | Treating biomass to produce materials useful for biofuels |
| CN104651539A (en) * | 2010-11-05 | 2015-05-27 | 国际壳牌研究有限公司 | Treating Biomass To Produce Materials Useful For Biofuels |
| CN103189526B (en) * | 2010-11-05 | 2015-07-08 | 国际壳牌研究有限公司 | Treating biomass to produce materials useful for biofuels |
| CN104651539B (en) * | 2010-11-05 | 2018-09-28 | 国际壳牌研究有限公司 | Biomass is handled to generate the material that can be used for bio-fuel |
| CN102504028A (en) * | 2011-10-11 | 2012-06-20 | 常茂生物化学工程股份有限公司 | Method for preparing organic cellulose acid ester by solid acid catalysts |
| CN104395478A (en) * | 2012-05-07 | 2015-03-04 | 国际壳牌研究有限公司 | Continuous or semi-continuous process for treating biomass to produce materials useful for biofuels |
| CN104395478B (en) * | 2012-05-07 | 2017-07-28 | 国际壳牌研究有限公司 | Biomass is handled to produce the continuously or semi-continuously method for the material that can be used for bio-fuel |
| EP2871246A4 (en) * | 2012-07-03 | 2016-03-09 | Showa Denko Kk | Method for decomposing plant biomass, and method for producing glucose |
| CN104894298A (en) * | 2015-05-06 | 2015-09-09 | 重庆大学 | Method used for degrading lignocellulose with solid acid catalyst |
| CN112661376A (en) * | 2020-12-30 | 2021-04-16 | 广东省科学院化工研究所 | Municipal sludge pretreatment method and application thereof |
| CN112661376B (en) * | 2020-12-30 | 2023-01-24 | 广东省科学院化工研究所 | Municipal sludge pretreatment method and application thereof |
| CN115558001A (en) * | 2022-09-26 | 2023-01-03 | 南开大学 | Method for decomposing polaroid |
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Application publication date: 20100728 |