CN113278659A - Recycling method of lactic acid fermentation acid-containing wastewater - Google Patents

Recycling method of lactic acid fermentation acid-containing wastewater Download PDF

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CN113278659A
CN113278659A CN202110589297.XA CN202110589297A CN113278659A CN 113278659 A CN113278659 A CN 113278659A CN 202110589297 A CN202110589297 A CN 202110589297A CN 113278659 A CN113278659 A CN 113278659A
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lactic acid
reverse osmosis
wastewater
fermentation
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张标
吴健
熊德彬
王皓磊
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Zhengzhou Operation And Maintenance Biotechnology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/56Lactic acid
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/06Nutrients for stimulating the growth of microorganisms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used

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Abstract

The invention discloses a method for recycling acid-containing wastewater generated in lactic acid fermentation, which comprises the following steps: (1) uniformly mixing the corn starch and the reverse osmosis wastewater, and mixing the slurry; (2) dissolving the corn starch which is mixed with the pulp, performing enzymolysis for two times, and filtering by a plate frame to obtain liquefied sugar clear liquid; (3) respectively supplementing reverse osmosis wastewater with liquefied sugar clear liquid and nutrients such as ammonium sulfate and yeast powder to adjust concentration, continuously sterilizing to obtain a microbial culture medium, and performing strain fermentation; (4) after fermentation, solid-liquid separation is carried out to remove thalli, lactic acid is obtained through acidolysis, the concentration of the lactic acid is improved through concentration of an evaporator, and a large amount of lactic acid-containing wastewater is generated in the evaporation process; (5) neutralizing the waste water containing lactic acid with calcium hydroxide to produce calcium lactate, and allowing the calcium lactate solution to permeate through a reverse osmosis membrane to obtain a calcium lactate concentrated solution and reverse osmosis waste water; the generated wastewater returns to the step (1) and the step (3), and the circulation is carried out. The invention relatively saves the sewage treatment cost, improves the recovery rate of the lactic acid, and has important environmental benefit and economic benefit.

Description

Recycling method of lactic acid fermentation acid-containing wastewater
Technical Field
The invention relates to the field of lactic acid fermentation processes, in particular to a recycling method of lactic acid fermentation acid-containing wastewater.
Technical Field
With the development of society, especially the progress of science and technology, the rapid development of social productivity is greatly promoted, and the living standard of people is greatly improved; people enjoy the happiness brought by social progress, and can reasonably utilize and pay more attention to the living environment, particularly whether the discharge of the produced and domestic sewage reaches the standard or not.
Lactic acid, an important natural organic acid, is known under the name 2-hydroxypropionic acid and has a relative molecular mass of 90.08. Lactic acid contains one chiral carbon atom in its molecule, so that it has optical activity, and has two optical active configurations, including L-lactic acid and D-lactic acid. Lactic acid is a biological metabolite or metabolic intermediate widely existing in animals, plants and microorganisms, and only L-lactate dehydrogenase capable of metabolizing L-lactic acid exists in human and animal bodies, so that the configuration of lactic acid is very important from the nutritional point of view, and thus L-lactic acid is required to replace D-lactic acid when used in the fields of food and medicine. L-lactic acid is the output raw material of the biodegradable material PLA, and the PLA is the biodegradable material with the most application potential at present.
The microbial fermentation method is a main method for producing lactic acid in the prior art, and a large amount of waste water is generated in the extraction process of the prior art. If the waste water is not properly treated, not only is serious environmental pollution caused, but also a large amount of water resources are wasted, and the production cost of enterprises is increased. Therefore, how to effectively realize energy conservation and emission reduction and reduce the cost is a major subject of healthy development of the lactic acid industry. The wastewater in the lactic acid production process is simply treated and recycled, and has great significance for solving the problem of sewage treatment.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the method for recycling the waste water generated in the lactic acid production, which saves the process water consumption, saves the sewage treatment cost, improves the recovery rate of the lactic acid and has important environmental and economic benefits compared with the traditional process.
The purpose of the invention is realized as follows:
a method for recycling acid-containing wastewater generated in lactic acid fermentation comprises the following steps:
(1) under the condition that the temperature of corn starch and reverse osmosis wastewater is 40-60 ℃, regulating starch milk to 32% in a slurry regulating tank, regulating the pH of slurry to 5.8-6.0 by using calcium hydroxide, and then adding high-temperature alpha-amylase, wherein the dosage of the amylase is 0.03-0.05%;
(2) carrying out two-step enzymolysis treatment on the mixed solution obtained in the step (1): pumping starch slurry into a jet liquefier by a pump, controlling the temperature at 110-; then carrying out secondary spraying, controlling the temperature at 120-130 ℃, maintaining the temperature in a high-temperature maintaining tank for 3-5 minutes to thoroughly kill the high-temperature-resistant a-starch, further cooling to 60 ℃ under the condition that the iodine test is qualified, simultaneously adjusting the pH value to 4.2, adding saccharifying enzyme, carrying out heat preservation and saccharification for 45-55 hours to reach a saccharification end point, pumping the liquefied sugar solution into a plate frame for filtration to obtain a liquefied sugar clear solution;
(3) adding nutrients such as ammonium sulfate and yeast powder into the liquefied sugar clear liquid obtained in the step (2), supplementing reverse osmosis wastewater, adjusting the concentration, and enabling the obtained mixed liquid total sugar to be 220g/L-250 g/L; sterilizing to obtain a microbial culture medium, and performing strain fermentation;
(4) after fermentation is finished, removing thalli through solid-liquid separation, obtaining lactic acid through acidolysis, concentrating through an evaporator to improve the concentration of the lactic acid, and generating a large amount of lactic acid-containing wastewater in the evaporation process;
(5) and (3) neutralizing the lactic acid-containing wastewater obtained in the step (4) to pH 6.5-7.5 by using a calcium hydroxide solution to produce a calcium lactate solution, and allowing the calcium lactate solution to permeate a reverse osmosis membrane to obtain a calcium lactate concentrated solution and reverse osmosis wastewater.
The strain used for lactic acid fermentation in the step (3) is bacillus coagulans; the total sugar content of the mixed liquid was 235 g/L.
The lactic acid-containing wastewater in the step (4) refers to steam condensate water generated in the processes of an evaporator and short-path distillation of a lactic acid solution.
The temperature of the solution containing calcium lactate and permeating through the reverse osmosis membrane in the step (5) is 40-60 ℃;
and (3) neutralizing the waste water containing the lactic acid in the step (4) by using a calcium hydroxide solution, wherein the pH value is 7.2, producing a calcium lactate solution, and allowing the calcium lactate solution to permeate a reverse osmosis membrane at the temperature of 50 ℃ to obtain a calcium lactate concentrated solution and reverse osmosis waste water.
Has the positive and beneficial effects that: the fermentation temperature of the invention is equivalent to the technical level of the traditional process, the process water consumption is saved, the sewage treatment cost is saved, the recovery rate of lactic acid is improved, and the invention has important environmental benefit and economic benefit.
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and specific embodiments:
examples
As shown in figure 1, 300kg of corn starch and 637.5kg of lactic acid reverse osmosis wastewater are uniformly mixed in a size mixing tank at 50 ℃, calcium hydroxide is added to adjust the pH value to 6.0, and 150g of high temperature resistant alpha-amylase with the enzyme activity unit of 20000U/g is added. Performing secondary spray liquefaction, wherein the primary spray temperature is 97 ℃, keeping the temperature for 60min, the secondary spray temperature is 110 ℃, maintaining the high temperature for 5min, performing vacuum flash evaporation cooling to 95 ℃, cooling to 60 ℃, adding 60g of 1000000U/g saccharifying enzyme, adjusting the pH to 4.8 by using lactic acid, keeping the temperature for 60h, and filtering sugar liquor by using a plate frame after saccharification.
Adding lactic acid reverse osmosis wastewater into the sugar clear liquid, adding 235g/L of mixed liquid total sugar, and adding 0.2% of ammonium sulfate and 0.05% of yeast powder; sterilizing at 115 deg.C for 30min, inoculating lactobacillus, fermenting at 50 deg.C until the lactic acid concentration is 152g/L, fermenting for 36h, and residual sugar is 0.36%.
Adjusting pH of the fermentation broth to 9.0 with calcium hydroxide, heating to 85 deg.C, maintaining the temperature for 6 hr, and filtering with plate-frame filter to remove mycelium; adding 98% sulfuric acid into the filtrate until calcium lactate is completely converted into calcium sulfate, keeping the temperature at 85 ℃ for 6h, performing solid-liquid separation, and removing calcium sulfate crystals.
The purity of the concentration of the lactic acid solution is improved by 10 percent of low-concentration lactic acid through an evaporator and a short-path distillation process, a large amount of steam condensate water is generated, and the steam condensate water is mixed, wherein the content of the lactic acid is 2 percent.
The pH value of the steam condensate water is adjusted to 7.2 by calcium hydroxide, the steam condensate water is filtered and concentrated by a reverse osmosis membrane at the temperature of 50 ℃, the rejection rate of calcium lactate of the reverse osmosis membrane is about 90 percent, and as a result, 83 percent of water in the steam condensate water is removed, the concentration of a calcium lactate concentrate reaches 10.6 percent, the generated reverse osmosis wastewater and the calcium lactate concentrate enter a lactic acid extraction process, and the recovery rate of lactic acid is increased.
300kg of corn starch and 637.5kg of lactic acid reverse osmosis wastewater are recycled, the materials are uniformly mixed in a size mixing tank at 50 ℃, calcium hydroxide is added to adjust the pH value to 6.0, 150g of high temperature resistant alpha-amylase with the enzyme activity unit of 20000U/g is added, secondary injection liquefaction is carried out, wherein the primary injection temperature is 97 ℃, the temperature is kept for 60min, the secondary injection temperature is 110 ℃, the high temperature is kept for 5min, vacuum flash evaporation cooling is carried out to 95 ℃, the temperature is reduced to 60 ℃, 60g of glucoamylase with 1000000U/g is added, the pH value is adjusted to 4.8 by lactic acid, the liquid glucose is filtered by a plate frame after the temperature is kept for 60 h.
Adding lactic acid reverse osmosis wastewater into the sugar clear liquid, adding 235g/L of mixed liquid total sugar, supplementing water shortage by using tap water, adding 0.2% of ammonium sulfate and 0.05% of yeast powder, sterilizing at 115 ℃ for 30min, inoculating lactic acid bacteria for fermentation, wherein the culture temperature is 50 ℃, the lactic acid concentration is 152g/L after fermentation, the fermentation period is 36h, and the residual sugar is 0.36%.
Adjusting pH of the fermentation broth to 9.0 with calcium hydroxide, heating to 85 deg.C, maintaining the temperature for 6h, filtering with plate frame to remove mycelium, adding 98% sulfuric acid into the filtrate until calcium lactate is completely converted into calcium sulfate, maintaining the temperature at 85 deg.C for 6h, separating solid and liquid, and removing calcium sulfate crystal.
The purity of the concentration of the lactic acid solution is improved by 10 percent of low-concentration lactic acid through an evaporator and a short-path distillation process, a large amount of steam condensate water is generated, and the steam condensate water is mixed, wherein the content of the lactic acid is 2 percent.
The pH value of the steam condensate water is adjusted to 7.2 by calcium hydroxide, the steam condensate water is filtered and concentrated by a reverse osmosis membrane at the temperature of 50 ℃, the rejection rate of calcium lactate of the reverse osmosis membrane is about 90 percent, and as a result, 83 percent of water in the steam condensate water is removed, the concentration of a calcium lactate concentrate reaches 10.6 percent, the generated reverse osmosis wastewater and the calcium lactate concentrate enter a lactic acid extraction process, and the recovery rate of lactic acid is increased.
And (3) taking the reverse osmosis wastewater as process water, adding corn starch and sugar clear liquid for recycling, repeating the steps for 9 times, and performing normal lactic acid fermentation.
Figure 824948DEST_PATH_IMAGE002
The fermentation acid production of the invention is equivalent to the technical level of the traditional process, saves the process water consumption, saves the sewage treatment cost, improves the recovery rate of the lactic acid, and has important environmental benefit and economic benefit.
The above are only preferred embodiments of the present invention, and are not intended to limit the present invention, and the present invention is related to the field
The invention is susceptible to various modifications and alternative forms, all as would be apparent to persons skilled in the art. All coming within the spirit and principle of the invention
Any modification, equivalent replacement, improvement and the like made by the method are all included in the protection scope of the invention.

Claims (5)

1. A method for recycling acid-containing wastewater generated in lactic acid fermentation is characterized by comprising the following steps:
(1) uniformly mixing the corn starch and the reverse osmosis wastewater, and mixing the slurry; (2) dissolving the corn starch which is mixed with the pulp, performing enzymolysis for two times, and filtering by a plate frame to obtain liquefied sugar clear liquid; (3) respectively supplementing reverse osmosis wastewater with liquefied sugar clear liquid and nutrients such as ammonium sulfate and yeast powder to adjust concentration, continuously sterilizing to obtain a microbial culture medium, and performing strain fermentation; (4) after fermentation, solid-liquid separation is carried out to remove thalli, lactic acid is obtained through acidolysis, the concentration of the lactic acid is improved through concentration of an evaporator, and a large amount of lactic acid-containing wastewater is generated in the evaporation process; (5) neutralizing the waste water containing lactic acid with calcium hydroxide to produce calcium lactate, and allowing the calcium lactate solution to permeate through a reverse osmosis membrane to obtain a calcium lactate concentrated solution and reverse osmosis waste water; the produced wastewater is returned to the step (1) and the step (3).
2. The recycling method of lactic acid fermentation acid-containing wastewater according to claim 1, characterized by comprising the following steps:
(1) under the condition that the temperature of corn starch and reverse osmosis wastewater is 40-60 ℃, regulating starch milk to 32% in a slurry regulating tank, regulating the pH of slurry to 5.8-6.0 by using calcium hydroxide, and then adding high-temperature alpha-amylase, wherein the dosage of the amylase is 0.03-0.05%;
(2) carrying out two-step enzymolysis treatment on the mixed solution obtained in the step (1): pumping starch slurry into a jet liquefier by a pump, controlling the temperature at 110-; then carrying out secondary spraying, controlling the temperature at 120-130 ℃, maintaining the temperature in a high-temperature maintaining tank for 3-5 minutes to thoroughly kill the high-temperature-resistant a-starch, further cooling to 60 ℃ under the condition that the iodine test is qualified, simultaneously adjusting the pH value to 4.2, adding saccharifying enzyme, carrying out heat preservation and saccharification for 45-55 hours to reach a saccharification end point, pumping the liquefied sugar solution into a plate frame for filtration to obtain a liquefied sugar clear solution;
(3) adding nutrients such as ammonium sulfate and yeast powder into the liquefied sugar clear liquid obtained in the step (2), supplementing reverse osmosis wastewater, adjusting the concentration, and enabling the obtained mixed liquid total sugar to be 220g/L-250 g/L; sterilizing to obtain a microbial culture medium, and performing strain fermentation;
(4) after fermentation is finished, removing thalli through solid-liquid separation, obtaining lactic acid through acidolysis, concentrating through an evaporator to improve the concentration of the lactic acid, and generating a large amount of lactic acid-containing wastewater in the evaporation process;
(5) and (3) neutralizing the lactic acid-containing wastewater obtained in the step (4) to pH 6.5-7.5 by using a calcium hydroxide solution to produce a calcium lactate solution, and allowing the calcium lactate solution to permeate a reverse osmosis membrane to obtain a calcium lactate concentrated solution and reverse osmosis wastewater.
3. The recycling method of lactic acid fermentation acid-containing wastewater according to claim 1 or 2, characterized in that: the strain used in the lactic acid fermentation in the step (3) is bacillus coagulans.
4. The recycling method of lactic acid fermentation acid-containing wastewater according to claim 1 or 2, characterized in that: the lactic acid-containing wastewater in the step (4) refers to steam condensate water generated in the processes of an evaporator and short-path distillation of a lactic acid solution.
5. The recycling method of lactic acid fermentation acid-containing wastewater according to claim 1 or 2, characterized in that: the temperature of the solution containing calcium lactate permeating the reverse osmosis membrane in the step (5) is 40-60 ℃.
CN202110589297.XA 2021-05-28 2021-05-28 Recycling method of lactic acid fermentation acid-containing wastewater Pending CN113278659A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110210001A1 (en) * 2008-11-10 2011-09-01 Nanjing University Of Technology Cleaning process of producing lactic acid
CN102952831A (en) * 2011-08-24 2013-03-06 株式会社日立工业设备技术 Manufacturing process of purified lactic acid
CN104109697A (en) * 2014-07-08 2014-10-22 江南大学 Method for producing citric acid by citric acid wastewater reflux fermentation
CN106086093A (en) * 2016-07-29 2016-11-09 河南金丹乳酸科技股份有限公司 The method that lactate fermentation thalline slag preprocess method and circulating fermentation produce lactic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110210001A1 (en) * 2008-11-10 2011-09-01 Nanjing University Of Technology Cleaning process of producing lactic acid
CN102952831A (en) * 2011-08-24 2013-03-06 株式会社日立工业设备技术 Manufacturing process of purified lactic acid
CN104109697A (en) * 2014-07-08 2014-10-22 江南大学 Method for producing citric acid by citric acid wastewater reflux fermentation
CN106086093A (en) * 2016-07-29 2016-11-09 河南金丹乳酸科技股份有限公司 The method that lactate fermentation thalline slag preprocess method and circulating fermentation produce lactic acid

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