CN101096689A - Method for hydrolyzing straw by glucurolactone production waste liquid and application in ethanol production by saccharomycete fermentation - Google Patents
Method for hydrolyzing straw by glucurolactone production waste liquid and application in ethanol production by saccharomycete fermentation Download PDFInfo
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- CN101096689A CN101096689A CNA2007101187602A CN200710118760A CN101096689A CN 101096689 A CN101096689 A CN 101096689A CN A2007101187602 A CNA2007101187602 A CN A2007101187602A CN 200710118760 A CN200710118760 A CN 200710118760A CN 101096689 A CN101096689 A CN 101096689A
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- waste liquid
- glucurolactone
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- ethanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for hydrolyzing the straw with glucurolactone production waste liquid for fermenting the alcohol with yeast in the industry waste water biological treatment field. The invention applies the effective treatment and recovering method, which doesn't have the bibliographical information in china. The invention is characterized by the following: hydrolyzing the straw with strong acid of glucurolactone production waste liquid; treating the hydrolyzing liquid by adding Ca (oH)2 or Cao; centrifuging and removing the deposit; adding the liquid as the unique carbon source or the nutrient; fermenting the alcohol with yeast. The invention achieves the treatment of glucurolactone production waste liquid, which recovers the acid of the waste liquid and the sugar substance in the waste liquid, and protects the environment and the resources.
Description
Technical field
This paper relates to a kind of method of utilizing glucurolactone production waste liquid hydrolyzing straw and being used for the saccharomycetes to make fermentation producing and ethanol.This technology is mainly used in the processing and the utilization of glucurolactone being produced waste liquid, belongs to biological process and handles the trade effluent field.
Background technology
China is the major country of production of glucurolactone (having another name called glucuronic acid) in the world, but existing manufacturing technique exist energy consumption big, pollute drawbacks such as big, that waste is big, industrial chain is single.10 tons of starch of generalized case produce 1 ton of glucurolactone.Can produce a large amount of waste liquids in the production process of glucurolactone, wherein contain a large amount of glucides and acid, directly discharging not only can cause serious pollution to environment, still is to the serious waste of resource.Therefore waste liquid is handled and utilized significantly again, but at present domesticly also do not have a relevant report.
With starch producing and ethanol in next life is the traditional technology of development alcohol fuel industry, but present worldwide staple food supply is still big a problem, particularly developing country, therefore, will be restricted for the raw material production alcohol fuel with grain.Solve the basic outlet of fermentation alcohol raw material, be to utilize fibrous material to replace grain, therefore the research of the transformation technology of the lignocellulose relevant with fermentative Production ethanol becomes one of focus of domestic and international concern thereupon.China is large agricultural country, all can produce a large amount of stalks behind the annual crop harvesting, and the main component of stalk is a lignocellulose.Lignocellulose has constituted the cell walls of plant, and pair cell plays provide protection.It mainly is made up of Mierocrystalline cellulose, hemicellulose and xylogen three parts, account for 70%~75% of biomass dry weight, wherein Mierocrystalline cellulose and hemicellulose can obtain monose or polysaccharide such as glucose, seminose, semi-lactosi, wood sugar by hydrolysis, can be used for the microbial fermentation producing and ethanol.But reality is that most of stalk all directly burns or as animal-feed, owing to reasons such as technology and costs, having only very, small portion is used to producing and ethanol.Therefore, research lignocellulose producing and ethanol is significant.
At present, hydrolysis to lignocellulose mainly contains enzyme hydrolysis method and acid-hydrolysis method, in acid-hydrolysis method, be divided into concentrated acid hydrolysis method and dilute acid hydrolysis method again, the concentrated acid hydrolysis promptly proposed in 19th century, its principle is that crystalline cellulose can be dissolved under lower temperature in the phosphoric acid of 72% sulfuric acid, 42% hydrochloric acid and 77%~83% fully, causes cellulosic homogeneous hydrolysis.The vitriol oil is hydrolyzed to most popular method, and its major advantage is the rate of recovery height of sugar, and nearly 90% the hemicellulose and the sugar of cellulose conversion are recovered, but concentrated acid is a major issue to the corrosive nature of hydrolysis reactor.Dilute acid hydrolysis process is simpler, is the most ancient method that lignocellulosic material is produced alcohol, also is comparatively sophisticated method.The productive rate of sugar is lower in the dilute acid hydrolysis process, is generally about 50%, and can generates the deleterious byproduct that ferments in the hydrolytic process.Reported the cellulosic diluted acid Research on degradation of wheat stalk in " Degrading plant cellulose by thin acid " (2005 the 20th the 2nd phases of volume of people's " Anhui University of Engineering Science ﹠ Technology's journal " such as Hang Zhixi), investigated of the influence of factors such as temperature, massfraction, reaction times the cellulosic acid degraded.Adopt orthogonal experiment to inquire into the cellulosic optimum reaction conditions of diluted acid degrading plant such as acetate, hydrochloric acid. main experimentation is: sample after will at every turn handling and acid solution are all by pack at 1: 4 triangular flask of 100mL of solid-liquid ratio, leave standstill in the water bath with thermostatic control, every 10min rocks once.Degraded product separates with medical centrifuge, and clear liquid is an acid degradation liquid, waits until the sugar amount of surveying.The result shows and uses the acetate degraded cellulose, and transformation efficiency can reach 41.2%, uses the hydrochloric acid degraded cellulose, and transformation efficiency can reach 44.3%.
Summary of the invention
The present invention utilizes glucurolactone to produce the waste liquid hydrolyzing straw and obtains ethanol with saccharomycetes to make fermentation, is that glucurolactone is produced the feasible method that waste liquid is handled and utilize again.
The present invention is characterised in that, may further comprise the steps:
1) produce waste liquid hydrolysis agricultural crop straw slag with glucurolactone, according to solid-to-liquid ratio m: v1: 8~1: 20 ratio is mixed, and isothermal reaction is 10~120 minutes in 60~120 ℃ water-baths or oil bath pan, isolates solid residue by the physics method;
2) will isolate hydrolyzed solution behind the solid residue by adding Ca (OH)
2Or the CaO method handles, and regulates pH value to 8, the centrifugal precipitation of removing;
3) with gac and the centrifugal liquid of removing post precipitation according to solid-to-liquid ratio m: v1: 20 mix, and carry out whip attachment at 50 ℃, adsorb 60 minutes, and vacuumizing filtration is removed gac; The liquid that removes by filter behind the gac is used for the thalline fermentation as carbon source, adopts existing stream addition and batch fermentation producing and ethanol.
It is acid solution that the glucurolactone that the present invention uses is produced waste liquid, and acidity height in the waste liquid contains a large amount of nitric acid and acetate, belongs to compound acid.Advantage of the present invention is to have utilized waste liquid tart characteristics, has further excavated the effective value of waste liquid, and has obtained the sugared source of available fermentation simultaneously by hydrolysis crop material slag, has promoted the effective rate of utilization of stalk.
Stalk of the present invention adopts sorghum stalk, maize straw, wheat straw stalk, rice straw etc.Can be with water-bath or oil bath in when reaction of being hydrolyzed, wherein oil can be soya-bean oil, silicone oil.The available physical method is separated when filtering the hydrolysis solid residue, such as using multilayer filtered through gauze, mechanical expression, standing demix.
The present invention Ca (OH)
2Or CaO handles the hydrolyzed solution of isolating behind the solid residue, and regulates pH value to 8, and the acetate in the hydrolyzed solution can generate calcium acetate indissoluble thing, and objectionable impuritiess such as furfural and heavy metal can both precipitate removes.
The present invention will remove the liquid that post precipitation obtains, with gac according to solid-to-liquid ratio m: v1: 20 mix, and carry out whip attachment at 50 ℃, adsorb 60 minutes, and vacuumizing filtration is removed gac.The liquid that removes by filter behind the gac is used for the thalline fermentation as carbon source, adopts existing stream addition and batch fermentation producing and ethanol.
The present invention is adsorbed with gac, and assorted sugar of macromole and the objectionable impurities in the hydrolyzed solution removed in absorption, purifies the thalli growth environment.
The present invention is fermented by yeast and is utilized sugar in the hydrolyzed solution, as glucose, seminose, semi-lactosi, and the part nitrate radical.The sugar that glucurolactone is produced in the waste liquid obtains utilizing, and has realized the doulbe-sides' victory that glucurolactone is produced the improvement of waste liquid and utilized.
Embodiment:
Percent hydrolysis account form: (C1-C0) * V/m*100%
Wherein: C1 is a waste liquid sugar content (g/L) after the hydrolysis, and C0 is a waste liquid sugar content (g/L) before the hydrolysis, the add-on of waste liquid (L) when V is hydrolysis, and m is for adding stalk slag weight (g).
Seed liquor substratum: glucose concn 20g/L, yeast extract paste 3g/L, peptone 5g/L
After inserting yeast in the seed liquor substratum, cultivated 20 hours for 30 ℃, as seed liquor.
Embodiment 1
1) glucurolactone is produced waste liquid and sorghum stalk slag according to solid-to-liquid ratio m: v1: 12 mixed, reaction is 60 minutes in 100 ℃ of water-baths, and stirs, and uses the multilayer filtered through gauze, isolates solid residue, and measuring its sorghum stalk percent hydrolysis is 40%.
2) hydrolyzed solution that will isolate behind the solid residue adds Ca (OH)
2Regulate pH value to 8, the centrifugal precipitation of removing.Afterwards, in the liquid that obtains after centrifugal according to solid-to-liquid ratio m: v1: 20 ratio adds gac, and absorption is 1 hour in 50 ℃ of constant temperature blender with magnetic force, and vacuumizing filtration is removed gac.
3) hydrolyzed solution that will remove behind the gac carries out batch fermentation as sole carbon source, and in the seed liquor that inserts volume ratio 5% and after cultivating 10 hours, initial glucose concentration is in the substratum of 20g/l, and its final ethanol content is 12g/l.
Embodiment 2
1) glucurolactone is produced waste liquid and sorghum stalk slag according to solid-to-liquid ratio m: v1: 8 mixed, reaction is 120 minutes in 60 ℃ of water-baths, and stirs, and uses the multilayer filtered through gauze, isolates solid residue, and measuring its sorghum stalk percent hydrolysis is 48%.
2) with embodiment 1 step 2
3) hydrolyzed solution that will remove behind the gac adopts the stream addition to carry out the saccharomycetes to make fermentation experiment.The preparation starting point concentration is the dextrose culture-medium of 40g/l, and after adding volume ratio 5% seed liquor and cultivating 10 hours, ethanol content is 23g/L, adds the hydrolyzed solution of volume ratio 20% afterwards and cultivates 8 hours, and its ethanol content is 35g/L.
Embodiment 3
1) glucurolactone is produced waste liquid and sorghum stalk slag according to solid-to-liquid ratio m: v1: 20 mixed, reaction is 10 minutes in 120 ℃ of silicone oil baths, and stirs, and uses the multilayer filtered through gauze, isolates solid residue, and measuring its sorghum stalk percent hydrolysis is 33%.
2) with embodiment 1 step 2
3) hydrolyzed solution that will remove behind the gac adopts the stream addition to carry out the saccharomycetes to make fermentation experiment.The preparation starting point concentration is the dextrose culture-medium of 40g/l, and after adding volume ratio 5% seed liquor and cultivating 10 hours, ethanol content is 25g/L, adds the hydrolyzed solution of volume ratio 20% afterwards and cultivates 8 hours, and its ethanol content is 30g/L.
Embodiment 4
1) glucurolactone is produced waste liquid and maize straw slag according to solid-to-liquid ratio m: v1: 12 mixed, reaction is 60 minutes in 100 ℃ of water-baths, and stirs, and filters with mechanical expression, isolates solid residue, measures its sorghum stalk percent hydrolysis 45%.
2) with embodiment 1 step 2
3) hydrolyzed solution that will remove behind the gac adopts the stream addition to carry out the saccharomycetes to make fermentation experiment.The preparation starting point concentration is the dextrose culture-medium of 40g/l, and after adding volume ratio 5% seed liquor and cultivating 10 hours, ethanol content is 30g/L, adds the hydrolyzed solution of volume ratio 20% afterwards and cultivates 8 hours, and its ethanol content is 40g/L.
Claims (2)
1. the method utilizing glucurolactone production waste liquid hydrolyzing straw and be used for the saccharomycetes to make fermentation producing and ethanol is characterized in that, may further comprise the steps:
1) produce waste liquid hydrolysis agricultural crop straw slag with glucurolactone, according to solid-to-liquid ratio m: v1: 8~1: 20 ratio is mixed, and isothermal reaction is 10~120 minutes in 60~120 ℃ water-baths or oil bath pan, isolates solid residue by the physics method;
2) will isolate hydrolyzed solution behind the solid residue by adding Ca (OH)
2Or the CaO method handles, and regulates pH value to 8, the centrifugal precipitation of removing;
3) with gac and the centrifugal liquid of removing post precipitation according to solid-to-liquid ratio m: v1: 20 mix, and carry out whip attachment at 50 ℃, adsorb 60 minutes, and vacuumizing filtration is removed gac; The liquid that removes by filter behind the gac is used for the thalline fermentation as carbon source, adopts existing stream addition and batch fermentation producing and ethanol.
2. method according to claim 1 is characterized in that, used stalk can adopt sorghum stalk, maize straw, wheat straw stalk, rice straw.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101429111B (en) * | 2008-12-17 | 2011-10-12 | 安徽富博医药化工股份有限公司 | Comprehensive processing method and apparatus for mother solution in production of glucurolactone |
CN104830942A (en) * | 2015-05-11 | 2015-08-12 | 汪周启 | Biological alcohol production technique of organic sewage |
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2007
- 2007-07-13 CN CNA2007101187602A patent/CN101096689A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101429111B (en) * | 2008-12-17 | 2011-10-12 | 安徽富博医药化工股份有限公司 | Comprehensive processing method and apparatus for mother solution in production of glucurolactone |
CN104830942A (en) * | 2015-05-11 | 2015-08-12 | 汪周启 | Biological alcohol production technique of organic sewage |
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