CN115595335A - Method for producing biodegradable plastic by using wine-making wastewater - Google Patents
Method for producing biodegradable plastic by using wine-making wastewater Download PDFInfo
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- CN115595335A CN115595335A CN202211350730.5A CN202211350730A CN115595335A CN 115595335 A CN115595335 A CN 115595335A CN 202211350730 A CN202211350730 A CN 202211350730A CN 115595335 A CN115595335 A CN 115595335A
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- succinic acid
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/44—Polycarboxylic acids
- C12P7/46—Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
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Abstract
The invention discloses a method for producing biodegradable plastic by using brewing wastewater, which comprises the following steps: 1) Filtering the brewing wastewater, and separating filter residue and filtrate; 2) Separating water from the filtrate by ultrafiltration membrane equipment, and concentrating; 3) Adding filter residues into the concentrated filtrate, mixing, and respectively and intensively discharging into two fermentation tanks; 4) Respectively adding succinic acid fermentation microorganisms and butanediol fermentation microorganisms into the two fermentation tanks; 5) Separating succinic acid and butanediol in the fermentation tank; 6) PBS was synthesized from succinic acid and butanediol. The invention researches out a method for producing biodegradable plastics by using the brewing wastewater, produces the raw material of PBS by using the brewing wastewater through a microbial fermentation method, and then synthesizes the raw material into the PBS, thereby not only solving the problem of treating a large amount of brewing wastewater, but also generating additional economic benefit.
Description
Technical Field
The invention relates to a method for recycling waste water, in particular to a method for producing biodegradable plastics by using wine-making waste water.
Background
The brewing of white spirit mostly takes sorghum, wheat, corn and the like as raw and auxiliary materials, and is brewed by adopting basic procedures of artificial culture and old cellar, fermentation, distillation, graded storage, elaborate blending and the like. The pot-bottom water, yellow water, grain soaking water and the like generated in the white spirit brewing process are rich in residual starch, protein, saccharides and other organic matters, and the biodegradability of sewage is good.
However, in the prior art, a good utilization mode for brewing wastewater is lacked, and the wastewater is generally directly discharged after being subjected to microbial fermentation treatment to decompose organic matters and reaching the discharge standard.
In fact, organic matters such as starch, protein, sugar and the like in the wastewater can be used for producing degradable plastics by a reasonable method, but an effective method is lacked at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing biodegradable plastics by using wine-making wastewater, so that a large amount of organic matters in the wine-making wastewater can be reasonably used for producing the biodegradable plastics.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for producing biodegradable plastics by using brewing wastewater comprises the following steps:
(1) Filtering the brewing wastewater, and separating filter residue and filtrate;
(2) Separating water from the filtrate by ultrafiltration membrane equipment, and concentrating;
(3) Adding filter residues into the concentrated filtrate, mixing, and respectively and intensively discharging into two fermentation tanks;
(4) Respectively adding succinic acid fermentation microorganisms and butanediol fermentation microorganisms into the two fermentation tanks;
(5) Separating succinic acid and butanediol in the fermentation tank;
(6) PBS was synthesized from succinic acid and butanediol.
Further, the butanediol fermenting microorganisms of step 4 include Klebsiella, bacillus, aeromonas, pseudomonas and Serratia.
Further, the butanediol fermenting microorganism in the step 4 is actinobacillus succinogenes.
Further, the purification of the succinic acid comprises the following steps:
(1) Filtering the fermentation liquor, centrifuging to remove thallus cells and insoluble solid particle impurities, and taking supernatant fermentation liquor;
(2) Adding urea into the supernatant, and co-crystallizing at 6-25 ℃ to separate out an adduct of succinic acid-urea;
(3) Dissolving the succinic acid-urea adduct in alcohol, adding NaOH alcohol solution, mixing to separate out sodium succinate, filtering and drying to obtain sodium succinate;
(4) Sodium succinate is exchanged by strong acid cation exchange resin, effluent liquid with pH of 2-6 is collected, and the effluent liquid is decompressed, evaporated and dried to obtain the succinic acid.
Furthermore, the addition amount of the urea is 3-7 times of the mass of the succinic acid in the fermentation liquor, and the cocrystallization time is 5-18 h.
Further, in the step 5, the butanediol fermentation liquor is sequentially subjected to conventional desalting, distillation and vacuum rectification steps for separation.
Further, the succinic acid and the butanediol are synthesized into the PBS by a direct esterification method, an ester exchange method or a chain extension method.
The invention has the advantages that:
the invention researches out a method for producing biodegradable plastics by using wine-making wastewater, produces PBS (phosphate buffer solution) by using the wine-making wastewater through a microbial fermentation method, and synthesizes the PBS from the raw materials, thereby not only solving the problem of treatment of a large amount of wine-making wastewater, but also generating additional economic benefit.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
PBS, chinese name: polybutylene succinate; alias: polybutylene succinate; the molecular formula is as follows: HO- (CO- (CH 2) 2-CO-O- (CH 2) 4-O) n-H; PBS is polybutylene succinate which is formed by condensation polymerization of succinic acid and butanediol and belongs to aliphatic polyester biodegradable plastics. PBS is a degradable plastic variety with the best comprehensive performance which is generally recognized in the world at present, and the product can be completely biodegraded into carbon dioxide and water, belonging to a novel environment-friendly material.
The brewing wastewater is rich in residual starch, protein, saccharides and other organic matters, and the wastewater amount is large.
The specific scheme is as follows:
firstly, filtering the brewing wastewater, separating filter residue and filtrate, wherein the separation of the filter residue is mainly used for preparing for subsequent osmotic separation, and after separation, the filtrate is subjected to water separation by ultrafiltration membrane equipment and concentration treatment; the ultrafiltration membrane equipment only allows water to pass through, while organic matters generally have large molecular weight and are difficult to pass through, and the filtrate is sequentially concentrated.
Adding filter residues into the concentrated filtrate for mixing, then respectively and intensively discharging the mixture into two fermentation tanks, and respectively adding succinic acid fermentation microorganisms and butanediol fermentation microorganisms into the two fermentation tanks for carrying out microbial fermentation production of succinic acid and butanediol, wherein the butanediol fermentation microorganisms can adopt Klebsiella, bacillus, aeromonas, pseudomonas, serratia and the like, the bacteria can metabolize butanediol, and the Bacillus has the capability of producing amylase and xylanase, so that starch substances can be directly used as substrates, but the amount of metabolic byproducts is large, and the conversion rate of target products is low; although the Klebsiella lacks the capability of directly saccharifying starch, the range of a substrate recipe is wider, such as glucose, xylose, fructose, arabinose and the like are good carbon sources, the fermentation is more thorough, the utilization rate of the substrate is high, the amount of a byproduct ethanol is less, and the yield of butanediol is higher, so the Klebsiella is a strain with better prospect for industrially producing butanediol.
As for the fermentation microorganism of succinic acid, actinobacillus succinogenes is most suitable, and succinic acid is an important intermediate product of metabolism of a plurality of strict anaerobes and facultative anaerobes. It has now been found that various microorganisms can produce succinic acid (also known as succinic acid) by fermentation, with studies mainly focused on actinobacillus succinogenes and escherichia coli. In addition, succinic acid can be produced in a small amount by mannheimia succiniciproducens, anaerobiospirillum succiniciproducens, lactic acid bacteria, propionic acid-producing bacteria, fungi, and the like. Among many succinic acid-producing microorganisms, actinobacillus succinogenes is capable of fermentation using various carbon sources (glucose, xylose, arabinose, lactose, etc.) and can tolerate concentrations of glucose and succinic acid as high as 158g/l and 104g/l, respectively. Therefore, the strain has the advantages of high succinic acid yield, strong tolerance and the like, and becomes one of the most industrialized production strains of succinic acid at present.
After fermentation is finished, succinic acid and butanediol in a fermentation tank are separated, and the succinic acid can be purified by adopting the following method: 1) Filtering the fermentation liquor, centrifuging to remove thallus cells and insoluble solid particle impurities, and taking supernatant fermentation liquor; 2) Adding urea into the supernatant, and co-crystallizing at 6-25 ℃ to separate out an adduct of succinic acid-urea, wherein the addition amount of the urea is 3-7 times of the mass of the succinic acid in the fermentation broth, and the co-crystallization time is 5-18 h; 3) Dissolving the succinic acid-urea adduct in alcohol, adding NaOH alcohol solution, mixing to separate out sodium succinate, filtering, and drying to obtain sodium succinate; 4) Sodium succinate is exchanged by strong acid cation exchange resin, effluent liquid with pH of 2-6 is collected, and the effluent liquid is decompressed, evaporated and dried to obtain the succinic acid.
As for butanediol, the butanediol fermentation liquor is separated by sequentially carrying out conventional desalting, distillation and vacuum rectification steps, and the steps of extraction are mature and are not described in detail.
After butanediol and succinic acid are separated and purified, PBS can be synthesized according to the existing synthesis process, such as a direct esterification method, an ester exchange method or a chain extension method.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (7)
1. A method for producing biodegradable plastics by using brewing wastewater is characterized by comprising the following steps:
(1) Filtering the brewing wastewater, and separating filter residue and filtrate;
(2) Separating water from the filtrate by ultrafiltration membrane equipment, and concentrating;
(3) Adding the filter residue into the concentrated filtrate, mixing, and respectively and intensively discharging into two fermentation tanks;
(4) Respectively adding succinic acid fermentation microorganisms and butanediol fermentation microorganisms into the two fermentation tanks;
(5) Separating succinic acid and butanediol in the fermentation tank;
(6) PBS was synthesized from succinic acid and butanediol.
2. The method for producing biodegradable plastic by using brewery wastewater according to claim 1, wherein: the butanediol-fermenting microorganisms of step 4 include Klebsiella, bacillus, aeromonas, pseudomonas and Serratia.
3. The method for producing biodegradable plastic by using brewery wastewater according to claim 1, wherein: the succinic acid fermentation microorganism in the step 4 adopts actinobacillus succinogenes.
4. The method for producing biodegradable plastic by using brewery wastewater according to claim 1, wherein: the purification of succinic acid comprises the following steps:
(1) Filtering the fermentation liquor, centrifuging to remove thallus cells and insoluble solid particle impurities, and taking supernatant fermentation liquor;
(2) Adding urea into the supernatant, and co-crystallizing at 6-25 ℃ to separate out an adduct of succinic acid-urea;
(3) Dissolving the succinic acid-urea adduct in alcohol, adding NaOH alcohol solution, mixing to separate out sodium succinate, filtering, and drying to obtain sodium succinate;
(4) Exchanging sodium succinate with strong acid cation exchange resin, collecting effluent liquid with pH of 2-6, and evaporating and drying under reduced pressure to obtain succinic acid.
5. The method for producing biodegradable plastics by using brewery wastewater according to claim 4, wherein: the addition amount of urea is 3-7 times of the mass of succinic acid in the fermentation liquor, and the cocrystallization time is 5-18 h.
6. The method for producing biodegradable plastic by using brewery wastewater according to claim 1, wherein: in the step 5, the butanediol fermentation liquor is separated through conventional desalting, distillation and vacuum rectification steps in sequence.
7. The method for producing biodegradable plastic by using brewery wastewater according to claim 1, wherein: the succinic acid and the butanediol are synthesized into the PBS by a direct esterification method, an ester exchange method or a chain extension method.
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