CN1432574A - Biomass hydrolyzing process of preparing reductive monosaccharide - Google Patents
Biomass hydrolyzing process of preparing reductive monosaccharide Download PDFInfo
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- CN1432574A CN1432574A CN 02145150 CN02145150A CN1432574A CN 1432574 A CN1432574 A CN 1432574A CN 02145150 CN02145150 CN 02145150 CN 02145150 A CN02145150 A CN 02145150A CN 1432574 A CN1432574 A CN 1432574A
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Abstract
In the biomass hydrolyzing process of preparing reductive monosaccharide, biomass material is hydrolyzed at 100-200 deg.c in the dilute acid catalyst, and the hydrolysate stays in the reactor for 5-40 min. The hydrolysate is divided into three parts based on dydrolysis order and hdyrolysate concentration and the three parts are used as the hydrolysis product and acid solution for the next batch of material to hydrolyze. The partial circulation of the hydrolysate can raise the concentration of monosaccharide in the hydrolysate from 4% to 6% and reduce acid consumption.
Description
Technical field
The present invention relates to a kind of method of reductive monosaccharide preparation, particularly a kind of is raw material prepares reductive monosaccharide through hydrolysis method with biomass.
Background technology
The energy and environmental problem have become the focus that the whole world is paid close attention to.Along with industrialized progress, the mankind have consumed a large amount of fossil class energy, cause petering out of these resources, have brought the serious environmental pollution on the other hand again, and a large amount of dischargings of carbonic acid gas have caused Greenhouse effect.People begin to seek substitute energy for this reason, and biomass cause people's interest just day by day as a kind of important renewable energy.
Biomass are meant based on terrestrial plant of xylogen, Mierocrystalline cellulose, hemicellulose and other organic matters (timber, yule logs, stalk etc.) and waterplant etc., are a kind of stable renewable energy source resources.It is compared with fossil energies such as coal and oil, and not only sulphur, nitrogen, ash are low, and the source is abundant, and only China's agricultural crop straw output is about 700,000,000 tons every year, and the stock number that can be used as the energy is hundred million tons of 2.8-3.5; The year rational exploitation amount of yule logs is about 1.58 hundred million tons, also has a large amount of waterplant in addition.Therefore biomass are called the green energy resource of instant utilization.
After the last century oil crisis, it is the technology of feedstock production fuel alcohol that people begin to pay attention to by biomass.Promptly be that raw material obtains reductive monosaccharide through hydrolysis, as wood sugar, glucose etc., just by fermentation, can obtain fuel alcohol after the rectifying with reductive monosaccharide with biomass.Wherein to prepare reductive monosaccharide be a comparatively crucial step to biomass by hydrolyzation, because gained reductive monosaccharide content and purity will directly influence fuel alcohol output and quality after the hydrolysis.Be that raw material can be divided into two big class---enzyme hydrolysis method and acid-hydrolysis methods through the method that hydrolysis prepares reductive monosaccharide with biomass at present, existing division is as follows:
1, enzyme hydrolysis method
Enzymic hydrolysis is a biochemical reaction, and what add hydrolysis reactor is the cellulase of microorganisms.Katalysis by enzyme can be cellulose hydrolysis a monose.Only generate by product seldom in this hydrolytic process, purification process is simple relatively, has also avoided pollution.But raw material in this technology---biomass need pre-treatment, and the production cost height of enzyme, and the hydrolysis cycle is long, thereby cause the enzyme hydrolysis method process cost too high.
2, acid-hydrolysis method
In acid-hydrolysis method, divide concentrated acid hydrolysis and dilute acid hydrolysis again
(1) concentrated acid hydrolysis
Its flow process of concentrated acid hydrolysis is: the biomass material of flush away dirt is dried to moisture about 10%, and is crushed to about 3-5mm.The sulfuric acid of this raw material and 70-77% is mixed, and to destroy cellulosic crystalline structure, best acid solution and solid weight ratio are 1.25: 1 (is benchmark with bright sulfur acid).Treatment temp 60-80 ℃.Then acid concentration is diluted to 20-30%, and is heated to 80-100 ℃, under normal pressure hydrolysis 40-480 minute.After finishing, hydrolysis carries out liquid-solid separation with filter press technique.The weak point of this method is that its hydrolysis cycle is long, and the necessary recovery of acid, and the cost of acid recovery at present is higher.Therefore many investigators forward sight on the dilute acid hydrolysis to.
(2) dilute acid hydrolysis
Traditional dilute acid hydrolysis flow process adopts an one-step hydrolysis diafiltration, the similar fixed bed of reactor that this method adopts.The solid biologic raw material is filled in the reactor, acid solution Continuous Flow mistake.Its characteristics mainly contain the sugar of generation and can in time discharge, and have reduced sugared decomposition; Can operate under lower liquid-solid ratio, liquid flows out by the strainer tube in the reactor, and liquid-solid separation is finished naturally, needn't use other liquid-solid separation equipments; Reactor is controlled easily.
In sum, no matter disclosed at present biomass by hydrolyzation method is acid-hydrolysis method or enzyme hydrolysis method, because it all adopts the hydrolysis of single still single stage method, therefore, causes its ubiquity the low shortcoming of sugared concentration in the product.This ethanol concn that just makes fermentation obtain is low, has caused shortcomings such as subsequent handling energy consumptions such as fermentation, rectifying are big, facility investment is big.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of method that improves sugared concentration in the biomass by hydrolyzation product, solve the defective that prior art exists with this.
Design of the present invention:
Biomass by hydrolyzation process just Mierocrystalline cellulose, hemicellulose is degraded to the process of glucose and wood sugar.But glucose and wood sugar are also unstable, also can further be degraded to materials such as furfural and hydroxymethylfurfural, and these byproducts all have certain damaging effect for microbial fermentation, should reduce their generation in the hydrolytic process in the concentration that improves sugar as far as possible.
Compare the easier generation DeR of wood sugar with glucose.For this reason, in each hydrolytic process, we collect hydrolyzed solution earlier under 100-130 ℃ of condition, and mainly contain wood sugar in the hydrolyzed solution this moment.Improve temperature then and collect hydrolyzed solution once more to 140-200 ℃, mainly contain glucose in the hydrolyzed solution this moment, this partial hydrolysis liquid participated in the hydrolysis of next batch biomass as circulation fluid.Circulation is hydrolyzed according to this, thereby reaches the purpose that improves sugared concentration in the hydrolyzed solution.
The present invention adopts many still series connection, and the method for hydrolysis that partial hydrolysis liquid recycles carries out biomass by hydrolyzation, thereby reaches the purpose that improves sugared concentration in the biomass by hydrolyzation product.
Technical scheme:
The key step of biomass by hydrolyzation method of the present invention is:
Biomass material is added in the hydrolysis reactor, and the aqueous solution that with the concentration expressed in percentage by weight is 0.25-5%HCl is that hydrolyzed solution adds in the hydrolysis reactor, and its add-on is 4-15 a times of biomass material weight.Be warming up to 100-130 ℃, begin to collect hydrolyzed solution, stop to collect when adding the 30-50% of hydrolyzed solution gross weight to the weight of the hydrolyzed solution of collecting, gained solution is labeled as I.Continue to be warmed up to 140-200 ℃, collect hydrolyzed solution once more and arranged to the hydrolyzed solution in the hydrolysis reactor, gained solution is labeled as II.Finished 5-40 consuming time minute from beginning to collect solution I to solution II collection.Add water washing in hydrolysis reactor, the add-on of water is biomass material weight 5-8 times, and the gained washings is labeled as III.Mark I solution is as the product of this hydrolysis; The washings of mark II solution and mark III is as the hydrolysis of circulation fluid participation next batch biomass material, and the feeding quantity of second batch of hydrolysis is identical with first with hydrolysis method, so carries out 3-5 hydrolysis and promptly gets desired product.
For making the more effective hydrolysis of biomass, adding weight percent concentration before each hydrolysis in the above-mentioned HCL aqueous solution is 0.25-3%FeCl
2The aqueous solution, its add-on are 4-15 times of biomass material weight.
The present invention compares with the method that present biomass by hydrolyzation prepares reductive monosaccharide, not only can improve the concentration of sugar in the hydrolyzed solution, make its concentration 4% (weight percent) bring up to 6% (weight percent) from present sugar, thereby improved the content of alcohol in the fermented liquid, reduced the expense of power and equipment (as fermentor tank, rectifying tower etc.), and, can reduce demand to acid by the recycling of acid solution.
Description of drawings
The series connection of the many stills of Fig. 1, the biomass by hydrolyzation schematic flow sheet that partial hydrolysis liquid recycles be wherein: 1-one-stage hydrolysis reactor; 2-secondary hydrolysis reactor; 3-three grades of hydrolysis reactors; 4-level Four hydrolysis reactor
Specific implementation method:
The invention will be further described below by embodiment, but it does not influence protection scope of the present invention:
Embodiment 1
Biomass material 400 grams are added in the hydrolysis reactor; 3wt%HCl and 1wt%FeCl with 2000ml
2The aqueous solution is hydrolyzed solution, and it is joined in the acid tank, is pressed in the hydrolysis reactor by high pressure nitrogen, utilizes the mode of external electric to be heated to 110 ℃ for the hydrolysis reactor, begins to collect, and gained solution is labeled as I, and volume is 1620ml.The temperature of reaction to 160 that raises then ℃ is collected for the second time, and gained solution is labeled as II, and volume is 3130ml.The washings of collecting behind the washing hydrolytic residue is labeled as III, and volume is 1960ml.Hydrolysis time arrives 110 ℃ from heating up, and finishing to the second section collection is 20 minutes consuming time.Solution I is as the product of this hydrolysis, and its sugared concentration is 3.5wt%.Solution II and cleaning solution II I participate in the next batch biomass by hydrolyzation as circulation fluid.
Removing and adding 83ml concentration through the complex acid groove again in by embodiment 1 gained circulation fluid is 9.86mol/LHCl and 10ml13wt%FeCl
2Outside the aqueous solution, other processing condition are identical with embodiment 1, and the concentration of sugar is 5.5wt% in the products obtained therefrom.
Removing and adding 83ml concentration through the complex acid groove again in by embodiment 2 gained circulation fluids is 9.86mol/LHCl and 9ml13wt%FeCl
2Outside the aqueous solution, other processing condition are identical with embodiment 1, and sugared concentration is 6.1wt% in the products obtained therefrom.
Removing and adding 82ml concentration through the complex acid groove again in by embodiment 3 gained circulation fluids is 9.86mol/LHCl and 9ml13wt%FeCl
2Outside the aqueous solution, other processing condition are identical with embodiment 1, and the concentration of sugar is 6.0wt% in the products obtained therefrom.
The comparative example
Biomass material 1600 grams are added in the hydrolysis reactor, and the catalyst solution volume is 16000ml, and the washings volume is 8000ml, carries out single still operation, and the I that collects, volume are 8500ml; II, volume are 6450ml; III, volume are 7850m.Other conditions are with identical with embodiment 1, and (I, II) mean concns of middle sugar is 3.3% to the product that obtains in this hydrolytic process.
Claims (2)
1, a kind of method for preparing reductive monosaccharide by biomass by hydrolyzation, the key step of described method is: biomass material is added in the hydrolysis reactor, the aqueous solution that with the concentration expressed in percentage by weight is 0.25-5%HCl is that hydrolyzed solution adds in the hydrolysis reactor, its add-on is 4-15 a times of biomass material weight, hydrolysis under 100-200 ℃ of condition, it is characterized in that described hydrolysis reactor connects with series system, the part hydrolyzed solution recycles in hydrolytic process.
2, the method for claim 1, it is characterized in that, biomass material is added in the hydrolysis reactor, the aqueous solution that with the concentration expressed in percentage by weight is 0.25-5%HCl is that hydrolyzed solution adds in the hydrolysis reactor, its add-on is 4-15 a times of biomass material weight, is warming up to 100-130 ℃, begins to collect hydrolyzed solution, stop to collect when adding the 30-50% of hydrolyzed solution gross weight to the weight of the hydrolyzed solution of collecting, gained solution is labeled as I; Continue to be warmed up to 140-200 ℃, collect hydrolyzed solution once more and arranged to the hydrolyzed solution in the hydrolysis reactor, gained solution is labeled as II; Finished 5-40 consuming time minute from beginning to collect solution I to solution II collection, add water washing in hydrolysis reactor, the add-on of water is biomass material weight 5-8 times, and the gained washings is labeled as III; Mark I solution is as the product of this hydrolysis, the washings of mark II solution and mark III participates in the hydrolysis of next batch biomass material as circulation fluid, the feeding quantity of second batch of hydrolysis is identical with first with hydrolysis method, so carries out 3-5 hydrolysis and promptly gets desired product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021252A (en) * | 2010-12-21 | 2011-04-20 | 山东省鲁洲食品集团有限公司 | Method and device for continuously hydrolyzing corn bran |
| CN102260229A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethylfurfural and 5-alkoxymethylfurfural |
| CN104480229A (en) * | 2014-12-01 | 2015-04-01 | 天津大学 | Method for preparing high-concentration pentaglucose solution from lignocellulose |
| CN114276885A (en) * | 2022-01-05 | 2022-04-05 | 湖南华诚生物资源股份有限公司 | Method for preparing ethanol from fresh momordica grosvenori |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235605B (en) * | 2008-02-28 | 2010-07-21 | 中国石油化工股份有限公司 | Lignocellulose pretreatment method and system with acid recovery |
-
2002
- 2002-11-08 CN CNB021451508A patent/CN1177854C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260229A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethylfurfural and 5-alkoxymethylfurfural |
| CN102021252A (en) * | 2010-12-21 | 2011-04-20 | 山东省鲁洲食品集团有限公司 | Method and device for continuously hydrolyzing corn bran |
| CN102021252B (en) * | 2010-12-21 | 2013-02-27 | 山东省鲁洲食品集团有限公司 | Method and device for continuously hydrolyzing corn bran |
| CN104480229A (en) * | 2014-12-01 | 2015-04-01 | 天津大学 | Method for preparing high-concentration pentaglucose solution from lignocellulose |
| CN114276885A (en) * | 2022-01-05 | 2022-04-05 | 湖南华诚生物资源股份有限公司 | Method for preparing ethanol from fresh momordica grosvenori |
| CN114276885B (en) * | 2022-01-05 | 2024-05-17 | 江西海富生物工程有限公司 | Method for preparing ethanol from fresh fructus momordicae |
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