CN101148458A - Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass - Google Patents
Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass Download PDFInfo
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- CN101148458A CN101148458A CN 200710121441 CN200710121441A CN101148458A CN 101148458 A CN101148458 A CN 101148458A CN 200710121441 CN200710121441 CN 200710121441 CN 200710121441 A CN200710121441 A CN 200710121441A CN 101148458 A CN101148458 A CN 101148458A
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Abstract
The present invention is process of co-producing sugar and levulic acid solution with lignocellulose material, and belongs to the field of biomass resource utilizing technology. Agricultural and forestry waste as reaction material is dilute acid hydrolyzed in a two-step process at certain temperature and in the presence of 0.01-0.2 mol concentration hydrochloric acid solution, hydroiodic acid solution, sulfuric acid solution or other inorganic acid solution as catalyst to produce both sugar solution and levulic acid solution in the total conversion rate over 20 wt%. The present invention provides one new way for utilizing lignocellulose comprehensively.
Description
Technical field
The invention belongs to biomass as resources and utilize technical field, relate to the method that a kind of lignocellulose-like biomass prepares sugar and levulinic acid.
Technical background
The main component of lignocellulose-like biomass comprises hemicellulose, Mierocrystalline cellulose and xylogen.Effectively the carbohydrate in the trans-utilization agriculture and forestry organic waste material partly replaces petroleum chemicals, is one of important research direction of current renewable energy source.The trans-utilization agriculture and forestry organic waste material mainly contains methods such as direct burning, pyrolysis, gasification, fermentation, enzymolysis and acid hydrolysis at present.Wherein acid hydrolysis is divided into dilute acid hydrolysis and concentrated acid hydrolysis again.The concentrated acid hydrolysis is used and is restricted owing to consuming a large amount of mineral acids.Dilute acid hydrolysis mainly is to be purpose to obtain hydrolysis of hemicellulose sugar.For example, Chinese patent (application number: 200310121806.8 and 96101585.3) disclose a kind of method of utilizing the stalk dilute acid hydrolysis to produce wood sugar and glucose solution respectively.Yet dilute acid hydrolysis has mainly transformed the hemicellulose part of lignocellulose, and Mierocrystalline cellulose partly transforms less.The present invention can obtain the higher levulinic acid of transformation efficiency with (160-220 ℃) the further hydrolysis under comparatively high temps of remaining Mierocrystalline cellulose part, has improved the comprehensive transformation efficiency of lignocellulose greatly.
Summary of the invention
The present invention is raw material with the lignocellulose-like biomass, to be 0.01mol/L carry out dilute acid hydrolysis under the mineral acid (example hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, phosphoric acid, sulfuric acid etc.) of 0.2mol/L and the certain temperature condition produces sugar and levulinic acid solution in concentration, can further ferment producing and ethanol or transform product such as preparation Xylitol of sugar soln, levulinic acid solution can further be converted into the diesel-dope of ester class or the preparation levulinic acid of purifying.This method principal feature is as follows: 1. agriculture and forestry organic waste material is a raw material, and raw materials cost is low, belongs to renewable resources; 2. diluted mineral acid is a catalyzer, and aftertreatment is simple; 3. via continuous two-step reaction: the first step, in the anaerobic encloses container, lower temperature (about 110 ℃) is reaction down, helps hydrolysis conversion hemicellulose and is corresponding sugar, and impurity in products content is few; Second step, use the filtration residue of the first step to be raw material, in the anaerobic encloses container, higher temperature (about 180 ℃) reaction down, helping cellulose conversion is levulinic acid, the productive rate height.This method is stepwise reaction in diluted acid with hemicellulose in the lignocellulose-like biomass and Mierocrystalline cellulose, raw material is made full use of, and main component content height in the product, help the carrying out of subsequent disposal, technology is simple, has higher industrialized developing and is worth.The sugar soln of gained can be used as the carbon source of microbial fermentation, further is converted into high value added products such as ethanol, Xylitol, and levulinic acid solution can further be converted into the ester class as procetane.Therefore this method provides a new way for effective trans-utilization lignocellulose-like biomass.
Lignocellulose method for transformation of the present invention thes contents are as follows:
1. the used lignocellulose-like biomass of the present invention comprises agricultural waste material (as: stalk, bagasse etc.), also comprises forestry waste (as: wood chip, branch, sawdust etc.).
2. the mass ratio of biomass material and dilute acid soln is between 1: 5 to 1: 20.
3. the conversion operation method is as follows: carry out two-step reaction by 2 described proportioning raw materials: the first step, and in the anaerobic encloses container, temperature is between 90 ℃ to 140 ℃, reaction 10min obtains sugar soln to 200min; Second step, use the filtration residue of the first step to be raw material, in the anaerobic encloses container, temperature is between 160 ℃ to 220 ℃, reaction 10min obtains levulinic acid solution to 300min.
4. be 0.01mol/L to the diluted mineral acid of 0.2mol/L all by 3 described two-step reactions be catalyzer with concentration.
5. be mineral acid by 2 described diluted acids, comprise: hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, phosphoric acid, sulfuric acid etc.
6. by the filter residue that obtains behind the 3 described two-step reactions, be mainly xylogen and charcoal, can be used as propellant of high energy and replace coal-fired the use, also can be used as soil improvement agent.
Embodiment 1: cotton stalk coproduction sugar and levulinic acid
The cotton stalk and the 0.01mol/L dilute hydrochloric acid solution of precomminution are put into reactor in the ratio of 100kg and 500L, stirring and evenly mixing, be heated to 90 ℃, stir, be incubated 30 minutes, centrifuging, solid-liquid separation, collect filter residue and solution respectively, filter residue merges in the filtrate with an amount of water washing, washings, promptly obtain sugar soln, sugared content 11kg (in wood sugar and glucose quality) in the solution.This solution can add the cotton stalk that 100kg pulverizes again, repeats above-mentioned steps.
Every crowd of about 70kg of remaining filter residue (dry weight), the dilute hydrochloric acid solution 350L that adds 0.01mol/L, put into autoclave, stirring and evenly mixing, be heated to 160 ℃, stir, be incubated 100 minutes, cold filtration, filter residue merges in the filtrate with an amount of water washing, washings, promptly obtain levulinic acid solution, levulinic acid content 7kg in the solution (in the levulinic acid quality), the about 30kg of filter residue (dry weight) is mainly xylogen and charcoal, can be used as propellant of high energy and replace coal-fired the use, also can be used as soil improvement agent.
Embodiment 2: maize straw coproduction sugar and levulinic acid solution
The maize straw (the consisting of 40%, 28%, 11% of Mierocrystalline cellulose, hemicellulose and xylogen) of precomminution is put into reactor with the 0.2mol/L dilute hydrochloric acid solution in the ratio of 100kg and 1000L, stirring and evenly mixing, be heated to 110 ℃, stir, be incubated 10 minutes, centrifuging, solid-liquid separation, collect filter residue and solution respectively, filter residue merges in the filtrate with an amount of water washing, washings, promptly obtain sugar soln, sugared content 13kg (in wood sugar and glucose quality) in the solution.
Remain 65 kilograms of filter residues (dry weight), add the dilute hydrochloric acid solution 650L of 0.2mol/L, put into autoclave, stirring and evenly mixing is heated to 2000 ℃, is incubated 10 minutes, cold filtration, filter residue merges in the filtrate with an amount of water washing, washings, promptly obtain levulinic acid solution, levulinic acid content 6kg in the solution (in the levulinic acid quality), filter residue 26kg (dry weight) is mainly xylogen and charcoal, can be used as propellant of high energy and replace coal-fired the use, also can be used as soil improvement agent.
Claims (6)
- With lignocellulose-like biomass as reaction raw materials, be catalyzer with the diluted mineral acid, carry out continuously under the certain temperature condition two the step dilute acid hydrolysis can obtain sugar soln and levulinic acid solution.
- 2. in 1 described method of claim the, lignocellulose-like biomass is agricultural waste material, forestry waste.
- 3. in 1 described method of claim the, mineral acid is hydrochloric acid, hydroiodic acid HI, Hydrogen bromide, phosphoric acid, sulfuric acid.
- 4. in 1 described method of claim the, the concentration of diluted mineral acid is the 0.01-0.2 mol.
- 5. in 1 described method of claim the, the mass ratio of raw material and dilute inorganic acid solution is 1: 5-1: 20.
- 6. in 1 described method of claim the, continuous two one-step hydrolysis are the hydrolysis reaction under 90-140 ℃ and 160-220 ℃ of two differing temps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200710121441 CN101148458A (en) | 2007-09-06 | 2007-09-06 | Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass |
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| CN 200710121441 CN101148458A (en) | 2007-09-06 | 2007-09-06 | Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285106B (en) * | 2008-06-10 | 2010-08-18 | 南京工业大学 | Process for preparing multicomponent liquid glucose and lignose while effectively hydrolyzing lignocellulosic biomass |
| CN101381351B (en) * | 2008-10-21 | 2011-05-11 | 华南理工大学 | Method for coproduction of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid |
| CN102112432A (en) * | 2008-06-26 | 2011-06-29 | 波利玛利欧洲股份公司 | Process for production of esters of levulinic acid from biomasses |
| CN101691326B (en) * | 2009-09-28 | 2012-10-03 | 黑龙江省科学院自然与生态研究所 | Acid-adjusting hydrolysis process for preparing levulinic acid |
| US9073841B2 (en) | 2012-11-05 | 2015-07-07 | Segetis, Inc. | Process to prepare levulinic acid |
| CN104945446A (en) * | 2015-05-20 | 2015-09-30 | 中国科学院广州能源研究所 | Method for preparing formate, acetate and levulinate from straw biomass |
| CN107973709A (en) * | 2017-11-23 | 2018-05-01 | 莫祖勇 | A kind of biomass-based method for preparing methyl ester levulinate |
| CN108114746A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of lignin-base acidic catalyst |
| US10202312B2 (en) | 2012-03-05 | 2019-02-12 | Iogen Energy Corporation | Process for producing a fuel from lignocellulosic feedstock |
| US10618864B2 (en) | 2011-11-23 | 2020-04-14 | Gfbiochemicals Ip Assets B.V. | Process to prepare levulinic acid |
-
2007
- 2007-09-06 CN CN 200710121441 patent/CN101148458A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285106B (en) * | 2008-06-10 | 2010-08-18 | 南京工业大学 | Process for preparing multicomponent liquid glucose and lignose while effectively hydrolyzing lignocellulosic biomass |
| CN102112432A (en) * | 2008-06-26 | 2011-06-29 | 波利玛利欧洲股份公司 | Process for production of esters of levulinic acid from biomasses |
| CN101381351B (en) * | 2008-10-21 | 2011-05-11 | 华南理工大学 | Method for coproduction of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid |
| CN101691326B (en) * | 2009-09-28 | 2012-10-03 | 黑龙江省科学院自然与生态研究所 | Acid-adjusting hydrolysis process for preparing levulinic acid |
| US10618864B2 (en) | 2011-11-23 | 2020-04-14 | Gfbiochemicals Ip Assets B.V. | Process to prepare levulinic acid |
| US10202312B2 (en) | 2012-03-05 | 2019-02-12 | Iogen Energy Corporation | Process for producing a fuel from lignocellulosic feedstock |
| US10766826B2 (en) | 2012-03-05 | 2020-09-08 | Iogen Energy Corporation | Process for producing a fuel from lignocellulosic feedstock |
| US9598341B2 (en) | 2012-11-05 | 2017-03-21 | Gfbiochemicals Limited | Process to prepare levulinic acid |
| US9073841B2 (en) | 2012-11-05 | 2015-07-07 | Segetis, Inc. | Process to prepare levulinic acid |
| CN104945446B (en) * | 2015-05-20 | 2017-11-14 | 中国科学院广州能源研究所 | A kind of method that formic acid esters, acetic acid esters, levulinate are prepared using stalk biomass |
| CN104945446A (en) * | 2015-05-20 | 2015-09-30 | 中国科学院广州能源研究所 | Method for preparing formate, acetate and levulinate from straw biomass |
| CN108114746A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of lignin-base acidic catalyst |
| CN107973709A (en) * | 2017-11-23 | 2018-05-01 | 莫祖勇 | A kind of biomass-based method for preparing methyl ester levulinate |
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