CN100593572C - Novel use for farming and forestry castoff such as corn straw - Google Patents
Novel use for farming and forestry castoff such as corn straw Download PDFInfo
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- CN100593572C CN100593572C CN200810019412A CN200810019412A CN100593572C CN 100593572 C CN100593572 C CN 100593572C CN 200810019412 A CN200810019412 A CN 200810019412A CN 200810019412 A CN200810019412 A CN 200810019412A CN 100593572 C CN100593572 C CN 100593572C
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- citric acid
- enzymolysis
- alkaline hydrolysis
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Abstract
A new usage for corn stalks of agricultural and forestry waste refers to applying the corn stalks of the agricultural and forestry waste in a fermentation process for preparing citric acid. The process for preparation comprises following steps: alkaline hydrolysis, enzymolysis, fermentation, separation and post-processing, The alkaline hydrolysis comprises hydrolyzing the corn stalks of the agricultural and forestry waste in diluted alkali solution1.0-2.5% at 85-95 DEG C for 2-4hours, separating, washing, and obtaining alkaline hydrolysis slag, the enzymolysis comprises enzymatically hydrolyzing the alkaline hydrolysis slag with cellulase, cellobiase and the like, transforming cellulose into dextrose, separating, washing, then fermenting enzymolysis liquid which contains the dextrose withpublic-known black aspergillus, transforming the dextrose into the citric acid, and finally obtaining water citric acid crystals whose purity >=99.8% after the post-processing. The production of citric acid per 1 ton consumes about five tons of the corn stalks, which greatly lowers the raw material cost of the citric acid.
Description
One, technical field
The present invention relates to a kind of comprehensive utilization of agriculture and forestry organic waste material, exactly is the new purposes of a kind of maize straw class agriculture and forestry organic waste material at the fermentative preparation citric acid.
Two, background technology
Citric acid has another name called Citric Acid, and English name citric acid, chemical name are 3-hydroxyl-3-carboxyl pentanedioic acid.The translucent crystal of appearance colorless, or white particle, or white crystalline powder.The citric acid crystal habit is different because of crystallization condition, and Citric Acid, usp, Anhydrous Powder C is arranged
6H
8O
7, the citric acid 2C that contains crystal water is also arranged
6H
8O
7H
2O, C
6H
8O
7H
2O or C
6H
8O
72H
2O.The commodity citric acid mainly is Citric Acid, usp, Anhydrous Powder and Citric acid monohydrate Food grade.
The production method of China's traditional mode of production citric acid is that the agricultural-food with starch-containing matter are raw material.The applicant once initiated the fermentation of corn starch legal system and was equipped with methods of citric acid (ZL95111000.4).This method is the most representative method of domestic production citric acid at present.From broadly, any amyloid agricultural-food and contain the agricultural-food and the byproduct thereof of glucose can both be as the fermentation raw material of citric acid, as corn, potato class, sugar industry byproduct etc.Basic line is: raw material pulverizing, liquefaction, fermentation production of citric acid, the common feature of these raw materials are exactly the starchiness that utilizes grain, and the production of citric acid need consume a large amount of grain, form the situation of striving grain with the people, and human existence is constituted a threat to.
China's corn annual production reaches 1.23 hundred million tons, calculate than 1: 1.2 by the paddy bar, maize straw produces 1.47 hundred million tons every year approximately, adds other agricultural crop straws, have every year about 700,000,000 tons, this is the renewable resource with great potential, and especially the starting material as the renewable energy resources and Chemicals are subjected to paying attention to widely, but at present except that the feed and development bioenergy of a part as ruminating animal, the most of burning, the waste resource, contaminate environment also constitutes a threat to aviation and road traffic.
The alleged maize straw class agriculture and forestry organic waste material of the present invention is maize straw, wheat stalk, jowar stalk, cotton seed hull, bagasse, birch sheet etc., and its main component is Mierocrystalline cellulose, xylogen etc.
Maize straw mainly is made up of plant cell wall, and main component is hemicellulose, Mierocrystalline cellulose, xylogen and ash and water etc., and wherein two kinds of main sugared sources are hemicellulose and Mierocrystalline cellulose.Hemicellulose accounts for 20%～25% of maize straw gross weight, and cellulose comprises maize straw gross weight 35%～40%.The cellulosic structure unit is by β-D-glucosyl group β-1, and the 4-glycosidic link connects the linear glucose high molecular polymer that forms, and each fiber molecule is made up of 800-1200 glucose molecule, because its crystalline texture is difficult to be degraded.Hemicellulose mainly is a wood sugar, and the complicated molecule polymkeric substance formed such as a small amount of pectinose, semi-lactosi, seminose.And xylogen is to be the polymer aromatics of fundamental unit formation with phenylpropyl alcohol alkane and derivative thereof, be a kind of phenol polymer, play the gelationus effect, Mierocrystalline cellulose and hemicellulose are linked together, be characterized in being soluble in alkali, be dissolved in the alkali lye with the xylogen sodium-salt form.Therefore, if obtain to be enough to the glucose of industrial fermentation citric acid and the wood sugar of culturing yeast, at first to purify pre-treatment and diluted alkaline processing to raw material, destroy hemicellulose and cellulosic winding arrangement, help cellulosic enzymolysis, obtain the source of glucose of fermentation production of citric acid and the wood sugar of fermented yeast.
Three, summary of the invention
The present invention is intended to fully utilize maize straw class agriculture and forestry organic waste material (being called for short stalk in the following description), and technical problem to be solved is to produce citric acid by the stalk fermentation method.
To be exactly stalk prepare application in the citric acid at fermentation method to the new purposes of the stalk that the present invention is alleged.
The stalk fermentation legal system is equipped with methods of citric acid and comprises alkaline hydrolysis, enzymolysis, fermentation, separation, washing and aftertreatment, described alkaline hydrolysis is exactly that stalk is at 1.0～2.5% (weight percents, down with) dilute alkaline soln in hydrolysis 2～4 hours under 85～95 ℃ of conditions, centrifugation then, washing, black filtrate is sent and is handled workshop section, or neutralizing treatment, or concentrate recovery alkali etc., and filter residue promptly is the alkaline hydrolysis slag, the alkaline hydrolysis slag is used to produce citric acid.
Described enzymolysis exactly with cellulase or/and the cellobiose enzyme or/and zytase carries out enzymic hydrolysis to the alkaline hydrolysis slag.Enzyme dosage is 1～3% of an alkaline hydrolysis slag, enzymolysis pH4.0～6.0,30～70 ℃ of temperature, 40～60 hours time, preferred enzymolysis pH4.5～5.5,40～60 ℃ of temperature.Enzymolysis finishes after-filtration separates washing.The enzymolysis slag mainly contains xylogen, and other carries out deep processing, and enzymolysis solution is used for the fermentative preparation citric acid after concentrating through decolouring.Mainly contain glucose in the enzymolysis solution, contain a small amount of wood sugar, pectinose etc. in addition, total sugar concentration is about about 6%, glucose concn about 3%, xylose concentration about 1.5%.
Described fermentation is carried out aerobic fermentation with black-koji mould to enzymolysis solution exactly.It is citric acid that black-koji mould makes conversion of glucose, and to no effects such as wood sugar, pectinoses.
Glucose provides carbon source for black-koji mould, need to provide other nutritive elements such as nitrogenous source in addition, just black-koji mould ferments in following enzymolysis solution: glucose 10～15%, urea 0.1～0.2%, sal epsom 0.05～0.08%, corn steep liquor 0.05～0.1%, pH5.5～6.5, black-koji mould seed liquid is inserted in above-mentioned enzymolysis solution sterilization back, in 35～38 ℃ of bottom fermentations 60～70 hours, logical sterile air between yeast phase, ventilation 0.2～0.5m
3/ min.
The fermentation ends after-filtration separates, and the washing filter residue makes citric acid residual in it clean as far as possible, and filter residue mainly contains mycelium, can process feed, and filtrate is carried out aftertreatment, with preparation-water citric acid crystal.
In the filtrate except that containing citric acid, also contain assorted sugar such as wood sugar, pectinose, seminose, pigment and a small amount of glucose, in view of carbohydrate belongs to nonelectrolyte, therefore can citric acid be separated film (electric drive membrane) partition method (also claiming electroosmose process) with carbohydrate, realize the first step purifying, neutralization makes citric acid generate the citrate of lime precipitate and separate then, realizes the second step purifying, at last the citrate of lime acidolysis is reduced into citric acid, through concentrating, obtaining-the water citric acid crystal after crystallization and the drying.
It is the new way of raw material substitution Starch Production citric acid that the present invention has started with the stalk.With the maize straw is example, and about 5 tons of maize straws are produced 1 ton of citric acid, and the raw materials cost of citric acid is reduced significantly.Resulting-water citric acid crystal purity 〉=99.9%, other every indexs all reach the standard of BP2003 version and USP28 version.
Four, embodiment
Be example with the maize straw now, non-limiting examples is described below:
1, the alkaline hydrolysis of maize straw
With the maize straw impurity elimination, clean, be ground into 3 order sizes, drop in the hydrolysis kettle, add the 1.5%NaOH dilute alkaline soln then, add-on is 3～6 times of maize straw weight, stirs, heats up, 90 ℃ of hydrolysis 3 hours.Hydrolysis finishes the back centrifugation, the washing filter residue, and filtrate is sent and is handled workshop section, and filter residue is the alkaline hydrolysis slag, is used for following processing citric acid.
2, the enzymolysis of alkaline hydrolysis slag
The tap water of alkaline hydrolysis slag and 2～3 times of amounts is dropped in the enzymolysis still, stir down and transfer pH5 with mineral acid, add the cellulase and the cellobiose enzyme (in butt) of 2% (in the acidolysis slag) then, two kinds of enzyme ratios are any, are warming up to 50 ℃, enzymolysis 50 hours.Enzymolysis finishes the back cooling, centrifuging separates, and washing.
Total sugar concentration is 6% in the enzymolysis solution, and wherein glucose concn 3%.
The enzymolysis still is the 500L glass reaction still that Shensheng Science ﹠ Tech. Co., Ltd., Shanghai produces.
Cellulase is available from biotechnology company limited of the outstanding energy in Wuxi section.
Cellobiose enzyme and zytase are all available from the auspicious imperial Bioisystech Co., Ltd in Hangzhou.
Enzymolysis solution decolouring, concentrated.The gac of pressing the long-pending adding 0.1～0.5% of enzyme liquid was in 75～80 ℃ of decolourings 0.5 hour, and filtering separation is concentrated into glucose concn 15wt% then.Adopt film (RO film) or/and vaporizer concentrates.
The RO film be triumphant can high-tech the experimental film produced of engineering (Shanghai) Co., Ltd.; Vaporizer is the 30L concentration test device that Shensheng Science ﹠ Tech. Co., Ltd., Shanghai produces.
4, enzymolysis solution fermentation
(1) preparation of seed liquor
Bacterial classification: aspergillus niger Co827.Available from
Koji: the 1000mL Erlenmeyer flask, every flask is packed into through abundant elutriation, and large stretch of wheat bran skin 38-40g of moisture content 65% sterilized 1 hour for 121 ℃, and after the cooling, access-ring aspergillus niger strain spore was cultivated 6-8 days for 37 ℃.
The seed tank culture base: enzymolysis solution 8-10%, urea 0.1%, sal epsom 0.05%, corn steep liquor 0.3%, surplus are water.
Seed tank culture condition: ventilation volume 1:0.5 (0.5m
3Sterile air/m
3Min); Temperature: 36～37 ℃; The pH nature, 30 hours cycles.
(2) enzymolysis solution fermentation
The enzymolysis solution of glucose concn 15% is dropped in the fermentor tank, stir and add urea, sal epsom and corn steep liquor down, make its concentration be followed successively by 0.15%, 0.06% and 0.06%, with adjusting PH with base to 6, seed liquor is inserted in sterilization back, and inoculum size 10% was in 36～37 ℃ of bottom fermentations 65 hours, logical sterile air between yeast phase, 0.3m
3/ min.
Fermented liquid outward appearance brown, citric acid content 9～10%, inversion rate of glucose 95%.
5, aftertreatment
(1) the fermentation ends after-filtration separates, and the washing filter residue makes citric acid residual in it clean as far as possible.
(2) purifying for the first time:
Electroosmose process separation of citric acid: filtrate is dropped into the electrodialysis separator, carry out separating of citric acid and unionization materials such as assorted sugar.Electrodialysis separator specification 400 * 600, the experimental installation of totally 80 pairs of negative and positive films.The material of freshwater room, the tap water of dense hydroecium and utmost point water circulate under the effect of pump separately, and citric acid acid group and hydrogen ion enter in the dense hydroecium by cavity block and anode membrane respectively with ionic condition.The specific conductivity of the acid solution of freshwater room is reduced to below the 100us/cm by initial 6000us/cm.Operational condition: normal temperature, normal pressure.Voltage :≤60v.Electrodialysis separation yield 98%.
(3) purifying for the second time:
During the acid solution that electrodialysis is obtained drops into and in the still, add CaCO under stirring
3Or Ca (OH)
2Neutralization makes citric acid generate calcium precipitation and separates out, and leaves standstill to make precipitation fully, separates then, obtains citrate of lime.
Acidifying: use the sulfuric acid acidation citrate of lime, obtain citric acid solution and calcium sulfate precipitation, separate obtaining citric acid solution, citric acid concentration 8～9%.In and acidolysis yield 99%.
(4) citric acid solution is dropped in the vacuum rotary evaporator concentrate, when citric acid concentration 75% left and right sides concentrated solution is dropped in the crystallization kettle, separate complete back to be crystallized, and vacuum-drying gets product-water citric acid to water content＜9%.
Claims (1)
1, a kind of new purposes of maize straw class agriculture and forestry organic waste material, it is characterized in that: the alkaline hydrolysis slag of maize straw class agriculture and forestry organic waste material after alkaline hydrolysis, centrifugation, washing prepares application in the citric acid at fermentation method, described alkaline hydrolysis is exactly the hydrolysis 2～4 hours under 85～95 ℃ of conditions in the NaOH of 1.0～2.5wt% solution of maize straw class agriculture and forestry organic waste material, obtains the alkaline hydrolysis slag through centrifugation, washing; It is exactly that alkaline hydrolysis slag elder generation enzymolysis obtains enzymolysis solution that described fermentation method prepares citric acid, then enzymolysis solution is fermented, described enzymolysis exactly with cellulase or/and the cellobiose enzyme or/and zytase carries out enzymic hydrolysis to the alkaline hydrolysis slag, enzymolysis pH4.5～5.5,40～60 ℃ of temperature, 40～60 hours time, separate after filtration, wash and obtain enzymolysis solution; Described fermentation is enzymolysis solution through decolouring, concentrate, preparation, sterilization back insert black-koji mould seed liquid, in 35～38 ℃ of bottom fermentations 60～70 hours, leads to sterile air, ventilation 0.2～0.5m between yeast phase
3/ min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810019412A CN100593572C (en) | 2008-01-04 | 2008-01-04 | Novel use for farming and forestry castoff such as corn straw |
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| CN200810019412A CN100593572C (en) | 2008-01-04 | 2008-01-04 | Novel use for farming and forestry castoff such as corn straw |
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| CN100593572C true CN100593572C (en) | 2010-03-10 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443611B (en) * | 2010-10-13 | 2014-03-05 | 中粮生物化学（安徽）股份有限公司 | Production method of citric acid |
| CN104805136B (en) * | 2014-01-24 | 2018-11-23 | 华东理工大学 | A method of citric acid is produced using lignocellulosic material |
| CN106987607A (en) * | 2017-06-06 | 2017-07-28 | 明光市裕阳农业有限公司 | A kind of method that biological fermentation process prepares citric acid |
| CN108277240B (en) * | 2018-04-26 | 2020-11-10 | 齐齐哈尔龙江阜丰生物科技有限公司 | Process for preparing citric acid by fermentation |
| CN109735578B (en) * | 2018-10-15 | 2022-05-17 | 大自然生物集团有限公司 | Method for producing citric acid by fermenting straws with aspergillus niger |
| CN113142542A (en) * | 2021-02-25 | 2021-07-23 | 仇俊鹏 | Fermented seasoning sauce using grains as raw materials, preparation method and application |
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2008
- 2008-01-04 CN CN200810019412A patent/CN100593572C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Production of Citric Acid from Corncobs by Aspergillus niger. Y.D.Hang*等.Bioresource Technology,Vol.65 No.3. 1998 * |
| Production of Citric Acid from Corncobs by Aspergillus niger.. Y. D. Hang*等.Bioresource Technology,Vol.65 No.3. 1998 |
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