CN109294893B - Resource utilization system and method for white spirit brewing byproduct yellow water - Google Patents

Resource utilization system and method for white spirit brewing byproduct yellow water Download PDF

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CN109294893B
CN109294893B CN201811278325.0A CN201811278325A CN109294893B CN 109294893 B CN109294893 B CN 109294893B CN 201811278325 A CN201811278325 A CN 201811278325A CN 109294893 B CN109294893 B CN 109294893B
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chamber
alkali
lactic acid
acid
yellow water
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CN109294893A (en
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许萍
白鹏凯
王湘晋
欧玉民
陈梓豪
张雅君
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Beijing University of Civil Engineering and Architecture
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M41/00Means for regulation, monitoring, measurement or control, e.g. flow regulation
    • C12M41/26Means for regulation, monitoring, measurement or control, e.g. flow regulation of pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M47/00Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
    • C12M47/10Separation or concentration of fermentation products
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/26Treatment of water, waste water, or sewage by extraction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/325Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
    • 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention provides a resource utilization system and a resource utilization method of white spirit brewing byproduct yellow water, wherein the system comprises the following steps: yellow water lactic acid fermentation unit, bipolar membrane electrodialysis unit and supercritical CO 2 An extraction unit; the yellow water lactic acid fermentation unit comprises a fermentation tank, wherein the fermentation tank is connected with an ultrafiltration device, and a supernatant pipeline of the ultrafiltration device is connected with the bipolar membrane electrodialysis unit; the bipolar membrane electrodialysis unit comprises a salt chamber, an acid chamber and a base chamber, wherein the acid chamber and the salt chamber are separated by an anion exchange membrane, the salt chamber and the base chamber are separated by a cation exchange membrane, and the salt chamber is connected with the supercritical CO 2 An extraction unit; the supercritical CO 2 The extraction unit comprises a rectifying tower, and the top of the rectifying tower is connected with a separator. According to the method provided by the invention, starch and reducing sugar in yellow water are fully utilized and converted into lactic acid with higher utilization value; the recovery rate of the lactic acid is high, the lactic acid separation and purification process has no resource consumption and waste liquid discharge, and the environmental benefit is high.

Description

Resource utilization system and method for white spirit brewing byproduct yellow water
Technical Field
The invention belongs to the technical field of fermentation, and particularly relates to a utilization method and a utilization system of yellow water generated by white spirit fermentation.
Background
Yellow water is a brown yellow fluid liquid deposited at the bottom of a pit because part of water exudes due to the catabolism of the fermented grains by microorganisms in the process of brewing and producing white spirit by a solid state method. Generally, about 300-400 kg of yellow water is produced per 1000kg of white spirit, and the yield of the strong aromatic white spirit in 2017 is 985.5 ten thousand tons, so that the emission of yellow water per year is about 340 ten thousand tons. According to the conventional physicochemical properties of yellow water, the COD of the yellow water is in the range of 135g/L to 330g/L, which is far more than the national allowable wastewater discharge standard. Even through anaerobic-aerobic treatment, the waste water is difficult to reach the standard for discharge. And part of yellow water of winery is directly discharged into water body without treatment, so that the pollution is serious. Therefore, the method for fully recycling the organic matter resources in the yellow water is significant for reducing the sewage treatment load and reducing the environmental pollution.
At present, most wineries in China treat yellow water by adopting methods of vinasse mixing and pit returning fermentation or pit raising, artificial pit mud culturing, bottom returning pot distillation and the like. The method can not only effectively utilize resources and fully reduce COD discharge of the yellow water, but also can not fundamentally solve the problem of optimal comprehensive utilization of the fermented yellow water. Therefore, how to comprehensively utilize the yellow water resource thoroughly solves the problem of optimal comprehensive utilization of the yellow water, and becomes a great subject faced by the white spirit industry. At present, most of the recycling of starch and reducing sugar in yellow water is carried out through ultrafiltration membrane filtration together with thalli and protein to process liquid protein feed, and the utilization rate of starch and reducing sugar is low although COD of yellow water is greatly reduced. The traditional method for extracting flavor substances is a multi-stage distillation method; according to the difference of boiling points of all components in flavor substances in yellow water, carrying out multistage distillation extraction to obtain extracts with different boiling points; in the industrial production process, the energy consumption in the distillation process is high and the distillation efficiency is low due to the large yellow water quantity. The preparation of biological esterified liquid is more studied on enzyme preparations, but the enzyme preparations used by the existing yellow water biological esterified liquid are mostly coarse enzyme preparations, the dosage is large, the esterification effect is poor, and the novel efficient enzyme preparations are still studied at the level of experimental laboratory tests, and industrial production is not seen. At present, the strong aromatic white spirit has the common problem that the content of lactic acid and ethyl lactate in the white spirit is higher than that of caproic acid and ethyl caproate, so that the taste of the white spirit body is poor; the content of lactic acid in the yellow water can be 90% of the total organic acid content, and meanwhile, the lactic acid has great utilization value; if the yellow water does not extract lactic acid before extracting the flavor substances, the content of lactic acid and ethyl lactate in the prepared liquor is very high, and the effect of blending the strong aromatic white spirit is poor.
The existing yellow water is subjected to reducing sugar fermentation by using a calcium salt method to produce the yellow water fermentation liquor after lactic acid is separated, and then flavor substances are extracted, wherein the recovery rate of the calcium salt method to the lactic acid in the yellow water fermentation liquor is only 50%, and a large amount of resources are required to be continuously consumed and a large amount of waste liquid is required to be discharged in the process; other yellow Shui Zhihua liquid preparation methods, namely yellow water byproducts are comprehensively utilized, but environmental resources and safety are sacrificed. And meanwhile, many winery researches on recycling of yellow water are mostly carried out by extracting flavor substances in the yellow water to prepare liquor, seasonings and esterifying the yellow water to prepare esterified liquor for distillation of wine. Firstly, organic materials such as starch and reducing sugar in the yellow water are not fully utilized, and the COD discharge amount of the yellow water is still high; secondly, most of the processes for extracting flavor substances in yellow water are multistage distillation, and the process has low extraction rate of the flavor substances and high energy consumption.
Disclosure of Invention
In order to solve the problems of insufficient recycling of organic materials in the yellow water, high resource consumption, high energy consumption and high discharge of waste liquid and waste residues in the resource recycling process, the invention provides a recycling system of the yellow water which is a byproduct of white spirit brewing, which is used for recycling the yellow waterFermenting the reducing sugar in water to produce lactic acid, and simultaneously separating and extracting the lactic acid by coupling a bipolar membrane electrodialysis process (EDBM); supercritical CO is carried out on the yellow water fermentation liquor after lactic acid separation 2 Extracting to obtain flavoring agent such as alcohol, residual acid, ester and aldehyde.
The invention further aims to provide a resource utilization method of yellow water which is a byproduct of white spirit brewing.
The technical scheme for realizing the purposes of the invention is as follows:
a recycling system of byproduct yellow water in white spirit brewing comprises: yellow water lactic acid fermentation unit, bipolar membrane electrodialysis unit and supercritical CO 2 An extraction unit;
the yellow water lactic acid fermentation unit comprises a fermentation tank, the fermentation tank is connected with an ultrafiltration device, a supernatant pipe of the ultrafiltration device is connected with the bipolar membrane electrodialysis unit, and a concentrated solution outlet of the ultrafiltration device is connected with the fermentation tank through a circulating pipe.
The bipolar membrane electrodialysis unit comprises a salt chamber, an acid chamber and a base chamber, wherein the acid chamber and the salt chamber are separated by an anion exchange membrane, the salt chamber and the base chamber are separated by a cation exchange membrane, the acid chamber and the base chamber are separated by a bipolar membrane (the salt chamber is positioned between the acid chamber and the base chamber), and the salt chamber is connected with the supercritical CO 2 An extraction unit;
the supercritical CO 2 The extraction unit comprises a rectifying tower, and the top of the rectifying tower is connected with a separator.
Preferably, the concentrate outlet of the ultrafiltration device is connected to the fermenter via a circulation line. And a fermentation controller is arranged on the fermentation tank. Wherein the bipolar membrane electrodialysis units are 2-100 repeated units, and the units are arranged in parallel.
The invention has the following optional scheme: the membrane stack specification was 800mm×400mm, and the number of unit repetitions per 1000L (treated water amount) was 5 groups.
Wherein the alkali chamber is connected with an alkali storage tank through an alkali outlet pipeline, and the alkali storage tank is connected with the fermentation tank; more preferably, the alkali storage tank is connected to the alkali chamber by an alkali return line.
The acid chamber is connected with a lactic acid storage tank through an acid outlet pipeline, and the lactic acid storage tank is connected with a concentration crystallization device; preferably, the lactic acid tank is connected to the acid chamber by a lactic acid return line.
Wherein the supercritical CO 2 The extraction unit comprises a rectifying tower, and the top of the rectifying tower is connected with a first separator and a second separator.
A resource utilization method of white spirit brewing byproduct yellow water comprises the following steps:
1) Adding saccharifying enzyme and lactobacillus into yellow water into a fermentation tank for anaerobic fermentation, and filtering fermentation liquor by an ultrafiltration device after fermentation is completed to remove thallus residues;
2) Supernatant separated by the ultrafiltration device enters a salt chamber of a bipolar membrane electrodialysis unit, and HLa is carried out under the action of an external electric field - Transferring the lactic acid into an acid chamber, and when the concentration of the acid chamber reaches 60-85% of the concentration of a salt chamber, separating to obtain lactic acid, storing the lactic acid in an acid storage tank, and concentrating and crystallizing to obtain a lactic acid finished product; OH (OH) - Entering an alkali chamber, and when the concentration of the alkali chamber reaches 60-85% of the concentration of the salt chamber, separating alkali liquor and storing the alkali liquor in an alkali storage tank (after which deionized water is added in a supplementary way);
3) And the salt chamber effluent of the bipolar membrane electrodialysis unit is residual yellow water after lactic acid is separated, and the residual yellow water is pumped into a supercritical carbon dioxide rectifying tower to extract flavor substances.
The yellow water contains abundant beneficial microorganisms, the lactobacillus accounts for 15.9 percent, is dominant bacteria, and has the potential of producing lactic acid by fermentation for reducing COD emission of the yellow water.
Lactic acid fermentation is the process by which lactic acid bacteria under anaerobic conditions ferment reduced sugars to lactic acid. Lactic acid fermentation is classified into homolactic fermentation and heterolactic fermentation. In homotype fermentation of lactic acid, 1C 6 H 12 O 6 →2C 3 H 6 O 3 1 molecule of glucose generates 2 molecules of lactic acid, namely 1g of glucose is fermented to generate 1g of lactic acid, and the theoretical conversion rate of glucose is 100%. 1C when lactic acid is subjected to abnormal fermentation 6 H 12 O 6 →1C 3 H 6 O 3 ,1C 2 H 5 OH(or 1.5CH 3 COOH), 1 molecule of glucose produced 1 molecule of lactic acid, with a theoretical conversion of 50%.
However, the main limiting factors for the fermentation of reducing sugars in yellow water to produce lactic acid are yellow water pH and product inhibition. The pH range of the yellow water is 2.8-4.6, and the pH value of the lactobacillus fermentation can be adjusted to be 5-7. Meanwhile, the COD content of the organic acid in the yellow water is about 1/3 of the total COD, wherein the COD content of the lactic acid is 90%, so that the lactic acid with high concentration in the fermentation liquid can inhibit the yellow water from lactic acid fermentation. The yellow Shui Rusuan fermentation coupling EDBM lactic acid separation process adopted by the method can realize in-situ separation fermentation of lactic acid. The high-purity alkali liquor generated by bipolar membrane electrodialysis can be used for regulating the pH constant in the fermentation process, and the conversion rate of lactic acid produced by reducing sugar fermentation is improved.
Further, 90 to 99% of the cells in the concentrated solution obtained by passing the fermentation broth through the ultrafiltration device are recovered, and 1 to 10% of the cells are discharged.
For example, 95% of the cells are recovered and 5% of the cells are discharged.
In the step 1), naOH and/or alkali liquor generated by a bipolar membrane electrodialysis unit is added into a fermentation tank to adjust the pH value of yellow water to 5.8-6.2, and anaerobic fermentation is carried out.
After the lactic acid is introduced into the acid storage tank from the acid chamber and the NaOH is introduced into the alkali storage tank from the alkali chamber, (when the same volume of deionized water is added), the lactic acid separated from the acid chamber partially flows back to the acid chamber, and the alkali separated from the alkali chamber partially flows back to the alkali chamber, so that the concentration in the acid chamber and the alkali chamber is maintained to be not lower than 0.2mol/L.
Wherein in the step 3), the supercritical carbon dioxide rectifying tower is used for extraction, and a separator is used for separating fractions, and the fractions of acid, ester, alcohol and aldehyde are separated. Wherein the first separator controls the separation pressure to be 7-10 MPa, the separation temperature to be 40-50 ℃, and mainly separates ester products; the second separator controls the separation pressure to be 5-6 MPa, the separation temperature to be 30-50 ℃ and separates alcohol, organic acid and aldehyde products.
The main organic pollutants in the yellow water are saccharides (starch and reducing sugar) and fragrant substances similar to the flavor of white wine:organic acids, alcohols, esters, aldehydes. Wherein the sugar, lactic acid and residual flavor substances each account for about 1/3 of COD of yellow water. The recovery of saccharides in yellow water can be converted into lactic acid by fermentation under the action of saccharifying enzyme and lactobacillus; the recovery of lactic acid is separated by bipolar membrane Electrodialysis (EDBM); the recovery of flavor substances depends on supercritical CO of residual yellow water fermentation liquor after lactic acid extraction 2 And (5) extracting and recycling. The organic material in the yellow water is fully recycled, and the COD emission of the yellow water is reduced to the greatest extent.
The system and the method provided by the invention are characterized in that the yellow water is firstly subjected to starch saccharification and reducing sugar fermentation in a fermentation tank, and meanwhile, the lactic acid generated in the yellow water fermentation process is separated by coupling with a bipolar membrane Electrodialysis (EDBM) process; pumping the residual yellow water fermentation liquor into a supercritical carbon dioxide extraction device to extract flavor substances in the residual yellow water fermentation liquor, performing multiple-cycle extraction, preparing an extract liquor into a liquor mixing liquid, and discharging the liquor into a sewage treatment plant; the separated lactic acid can be further purified to prepare a lactic acid finished product. The resource recycling is maximized, the environmental effect is highest, and the method is suitable for medium and large wineries.
The method provided by the invention has the following advantages:
(1) Starch and reducing sugar in the yellow water are fully utilized and converted into lactic acid with higher utilization value;
(2) The recovery rate of the lactic acid is high, the lactic acid separation and purification process has no resource consumption and waste liquid discharge, and the environmental benefit is high;
(3) Harvesting supercritical CO 2 The process is high in extraction rate, the extraction rate of the organic acid is more than 90%, the total extraction of the flavor substances such as alcohol, ester and aldehyde can be basically realized, and the extract can be used as a high-quality liquor. And the content of lactic acid and ethyl lactate in the obtained liquor is no longer the main flavor substance in the liquor, and the liquor has good effect when being used for blending common white spirit with deregulation of the ratio of the breast milk.
Drawings
FIG. 1 is a schematic diagram of a system for recycling yellow water, a byproduct of brewing white spirit.
The corresponding relation between the parts and the numbers in the figure is as follows:
yellow water enters the pipeline 101, the pH value adjusting pipeline 102, the fermentation tank 103, the ultrafiltration device 104, the circulation pipeline 105, the outlet 106 for discharging bacterial residues, the salt chamber 201, the acid chamber 202, the alkali chamber 203, the alkali storage tank 204, the lactic acid storage tank 205, the concentration crystallization device 206, the residual yellow water pipeline 207, the lactic acid reflux pipeline 208, the rectifying tower 301, the first separator 302, the second separator 303, the kettle liquid collector 304 and the waste liquid discharge pipeline 305.
FIG. 2 is a flow chart of the method for recycling yellow water, a byproduct of brewing white spirit, in the invention.
Detailed Description
The technical scheme of the invention is further described in the following specific examples. It will be appreciated by those skilled in the art that the examples are provided for illustration only and are not intended to limit the scope of the present invention.
In the examples, the technical means used are conventional technical means in the art unless otherwise specified.
Example 1:
referring to fig. 1, a system for recycling yellow water, which is a byproduct of brewing white spirit, comprises: yellow water lactic acid fermentation unit, bipolar membrane electrodialysis unit and supercritical CO 2 An extraction unit;
the yellow water lactic acid fermentation unit comprises a fermentation tank 103, wherein a yellow water inlet pipeline 101 and a pH value adjusting pipeline 102 are arranged at the top of the fermentation tank 103, the fermentation tank is connected with an ultrafiltration device 104, and a supernatant pipeline of the ultrafiltration device 104 is connected with the bipolar membrane electrodialysis unit;
the bipolar membrane electrodialysis unit comprises a salt chamber 201, an acid chamber 202 and a base chamber 203, wherein the acid chamber 202 and the salt chamber 201 are separated by an anion exchange membrane (am), the salt chamber 201 and the base chamber 203 are separated by a cation exchange membrane (cm), the acid chamber 202 and the base chamber 203 are separated by a bipolar membrane (bm), and a residual yellow water pipeline 207 at the top of the salt chamber 201 is connected to the supercritical CO 2 An extraction unit;
the repeating units take the form of parallel connections. In the present embodiment, the membrane stack specification is selected from 0.4mx0.8m, and 10 membrane stack assembly groups (the number of unit repetitions) (fig. 1 shows one unit, and is outlined by a dotted line). The membrane stack specification is 800mm×400mm, and the number of unit repetitions per 1000L of the treated water is 5 groups.
The supercritical CO 2 The extraction unit comprises a rectifying tower 301, and a first separator 302 and a second separator 303 are connected to the top of the rectifying tower 301. The rectifying tower kettle is connected with a kettle liquid collector 304. The tank liquid collector 304 is provided with a waste liquid discharge pipe 305.
The concentrated solution outlet of the ultrafiltration device is connected with the fermentation tank 103 through a circulating pipeline 105, and a fermentation controller is arranged on the fermentation tank. The concentrated solution outlet is also connected to an outlet 106 for discharging the bacterial cell residue.
The alkali chamber 203 is connected with an alkali storage tank 204 through an alkali outlet pipeline, and the alkali storage tank is connected with a pH value adjusting pipeline 102 on the fermentation tank; the alkali storage tank is connected with the alkali chamber through an alkali reflux pipeline.
The acid chamber 202 is connected with a lactic acid storage tank 205 through an acid outlet pipeline at the bottom, and the lactic acid storage tank is connected with a concentration crystallization device 206; the lactic acid tank is connected to the acid chamber by a lactic acid return line 208. A lactic acid product outlet is provided at the bottom of the concentrating crystallization device 206.
Example 2
By applying the system of the embodiment 1, a method for recycling yellow water as a byproduct of brewing white spirit, the flow of which is shown in fig. 2, comprises the following operations:
1) Adding saccharifying enzyme and lactobacillus into yellow water after entering a fermentation tank, carrying out anaerobic fermentation, and filtering fermentation liquor by an ultrafiltration device after fermentation is completed; removing macromolecular organic matters such as thallus residues, humus, proteins and the like, and recycling part of thallus in concentrated solution obtained by passing fermentation liquor through an ultrafiltration device into a fermentation tank; specifically, 95% of the cells were recovered and 5% of the cells were discharged. NaOH is added into the fermentation tank during initial operation; and in the operation, the pH value of yellow water is regulated to 6.0 by alkali liquor generated by the bipolar membrane electrodialysis unit, and anaerobic fermentation is carried out.
2) Supernatant separated by the ultrafiltration device enters a salt chamber of a bipolar membrane electrodialysis unit, and HLa is carried out under the action of an external electric field - Transferring into an acid chamber, separating to obtain lactic acid, concentrating and crystallizing to obtain lactic acid finished product; OH (OH) - Enters an alkali chamber and is separated outThe alkali liquor is stored in an alkali storage tank. When the concentration of the acid chamber and the alkali chamber is increased, lactic acid in the acid chamber is respectively led into an acid storage tank, naOH in the alkali chamber is led into an alkali storage tank, then deionized water with the same volume is supplemented, meanwhile, the lactic acid separated from the acid chamber partially flows back to the acid chamber, the alkali separated from the alkali chamber partially flows back to the alkali chamber, and the concentration difference between the salt chamber and the acid chamber and the alkali chamber is maintained to ensure that the concentration in the acid chamber and the alkali chamber is not lower than 0.2mol/L.
3) And the salt chamber effluent of the bipolar membrane electrodialysis unit is residual yellow water after lactic acid is separated, the residual yellow water is pumped into a supercritical carbon dioxide rectifying tower for extracting flavor substances, and the supercritical carbon dioxide rectifying tower is used for extracting, so that fractions of alcohol, acid, ester and aldehyde are separated. In the embodiment, the first separator controls the separation pressure to be 7-10 MPa, the separation temperature is about 40-50 ℃, and the ester products are mainly separated; the second separator controls the separation pressure to be 5-6 MPa, the separation temperature is about 30-50 ℃, and the alcohol, the organic acid and the aldehyde products are separated.
The present example provides a set of yellow water composition data, as shown in Table 1. Table 1 also shows the components after fermentation in the fermenter (Table 1, "yellow water fermentation broth"), the yellow water components discharged from the salt chamber (Table 1, "yellow water fermentation broth after lactic acid extraction"), and the waste water components discharged from the waste liquid discharge line 305.
TABLE 1 Main organic content in each flow in yellow Water resource utilization scheme
In the EDBM process of the present embodiment, the applied current density is 50mA/cm 2 The concentration among the salt chamber, the acid chamber and the alkali chamber is 1.2mol/L of sodium lactate solution in the salt chamber, and each time the concentration of lactic acid in the acid chamber and the concentration of NaOH in the alkali chamber are accumulated to 1.0mol/L, lactic acid is led into the acid storage tank, and NaOH is led into the alkali storage tank; adding the same body into the acid chamber and the alkali chamber respectivelyAnd (3) accumulating deionized water, and simultaneously, refluxing part of lactic acid and NaOH from a lactic acid tank into an acid chamber, so that the concentration of the lactic acid is not lower than 0.2mol/L, and the recovery rate of the lactic acid is 85.4 percent (the recovery rate after bipolar membrane treatment).
The lactic acid content in the raw materials is calculated by 30g/L, the starch content in the yellow water is 40g/L, the reducing sugar content is 50g/L, the starch conversion rate is calculated by 111% of theory, the reducing sugar conversion rate is calculated by 82.7%, the lactic acid separation rate is calculated by 85%, and the residual yellow water is subjected to supercritical CO 2 The extraction rate of the organic acid is 90%, and the extraction rate of the alcohol, the ester and the aldehyde is 95%. After the scheme is utilized, 92kg of lactic acid can be produced by 1t of yellow water, 30kg of liquor is regulated, the COD of the yellow water is reduced by about 96.7%, and the full recycling of organic matters of the yellow water is basically realized.
Example 2
The process conditions of this example were substantially the same as those of example 1, except that the lactic acid content in the yellow water was 40g/L, the starch content was 30g/L, the reducing sugar was 30g/L, and the applied current density was 60mA/cm in the EDBM process 2 The conversion of reducing sugars (lactic acid yield coefficient) was 78.5%; the lactic acid yield during fermentation was 90g/L. The concentration between the acid chamber and the alkali chamber is 73g/L, the concentration of NaOH in the alkali chamber is 32.4g/L, and the recovery rate of lactic acid is 81.22%.
Example 3
The process conditions of this example were substantially the same as in example 1, except that the lactic acid content in the yellow water was 25g/L, the starch content was about 20g/L, the reducing sugar content was about 30g/L, the reducing sugar conversion rate during fermentation was 80%, and the lactic acid yield was 66.76g/L. In EDBM process, the applied current density is 50mA/cm 2 The concentration between the acid chamber and the alkali chamber is 52.3g/L, the concentration of NaOH in the alkali chamber is 23.2g/Lg/L, and the recovery rate of lactic acid is 78.3%.
Comparative example 1
The separation and extraction of lactic acid by ion exchange resin process was carried out, and the raw material was the same as in example 1. The ion exchange resin used was D315 ion exchange resin.
TABLE 2 calculation of lactic acid Material balance by extraction of D315 resin
Note that: in order to obtain molecular lactic acid in industry, no other impurity cations are introduced during the elution process, and H with the mass fraction of 5% is selected 2 SO 4 Preparing eluent; supercritical CO for residual yellow water fermentation liquor 2 No SO is introduced during extraction 4 2- NaOH regeneration solution with mass fraction of 4% is selected.
Comparative example 2
The calcium salt method was used to treat the same starting material as in example 1. Because of the need of concentration crystallization and filtration for multiple times, the lactic acid is lost in each process, and the lactic acid extraction rate is lower than 60 percent. Compared with the calcium salt method and the ion exchange resin method, the EDBM process for extracting lactic acid has the best environmental benefit. Tables 1 and 2 show the resource consumption and waste discharge per 1t of pure lactic acid produced from yellow water by the calcium salt method and the ion exchange method, respectively.
Table 3 calculation of material balance for extracting yellow Shui Rusuan by calcium salt method
Note that: the table does not calculate SO removal during ion exchange 4 2- 、Ca 2+ Acid, alkali and water consumed by the plasma; the amount of the activated carbon is 25% of the amount of the finished product of 80% lactic acid.
In the EDBM technology, under the condition of an external electric field and without the help of external acid and alkali, the bipolar membrane ionizes water into H+ and OH-by an intermediate layer, and the H+ and the OH-enter an acid chamber and an alkali chamber respectively to be combined with La-and Na+ to generate HLa and NaOH. The dissociation of water does not generate any gas, and the energy consumption is low; at the same time, water in the solution continuously enters the middle layer of the bipolar membrane to supplement water consumed by electrolysis. The zero emission of waste is realized in theory. The energy consumption of the EDBM process is lower, and the energy consumption is 0.8-1.2 kW.h. (kgHLa) -1 Range. The ion exchange resin has no energy consumption; the calcium salt method has high energy consumption because a continuous high temperature is required to prevent calcium lactate from crystallizing during the filtration and acidolysis.
The above embodiments are merely illustrative of specific embodiments of the present invention, and not intended to limit the scope of the invention, and those skilled in the art may make various modifications and changes on the basis of the prior art, which should fall within the scope of protection defined in the claims of the present invention.

Claims (7)

1. A recycling system of white spirit brewing byproduct yellow water is characterized by comprising: yellow water lactic acid fermentation unit, bipolar membrane electrodialysis unit and supercritical CO 2 An extraction unit;
the yellow water lactic acid fermentation unit comprises a fermentation tank, wherein the fermentation tank is connected with an ultrafiltration device, a supernatant pipeline of the ultrafiltration device is connected with the bipolar membrane electrodialysis unit, and a concentrated solution outlet of the ultrafiltration device is connected with the fermentation tank through a circulating pipeline; adding saccharifying enzyme and lactobacillus into yellow water into a fermentation tank for anaerobic fermentation, and filtering fermentation liquor by an ultrafiltration device after fermentation is completed to remove thallus residues;
the bipolar membrane electrodialysis unit comprises a salt chamber, an acid chamber and a base chamber, wherein the acid chamber and the salt chamber are separated by an anion exchange membrane, the salt chamber and the base chamber are separated by a cation exchange membrane, the acid chamber and the base chamber are separated by a bipolar membrane, and the salt chamber is connected with the supercritical CO 2 An extraction unit;
the supercritical CO 2 The extraction unit comprises a rectifying tower, and the top of the rectifying tower is connected with a first separator and a second separator; supercritical CO is carried out on the yellow water fermentation liquor after lactic acid separation 2 Extracting, namely extracting alcohol, residual acid, ester and aldehyde in the extract to obtain liquor;
the alkali chamber is connected with an alkali storage tank through an alkali outlet pipeline, and the alkali storage tank is connected with the fermentation tank; the alkali storage tank is connected with the alkali chamber through an alkali reflux pipeline; the acid chamber is connected with a lactic acid storage tank through an acid outlet pipeline, and the lactic acid storage tank is connected with a concentration crystallization device; the lactic acid storage tank is connected with the acid chamber through a lactic acid reflux pipeline;
after lactic acid is introduced from the acid chamber into the lactic acid storage tank and NaOH is introduced from the alkali chamber into the alkali storage tank, a lactic acid portion separated from the acid chamber is refluxed to the acid chamber, and an alkali portion separated from the alkali chamber is refluxed to the alkali chamber, so that the concentration of both lactic acid in the acid chamber and alkali in the alkali chamber is maintained at not less than 0.2mol/L.
2. The recycling system of yellow water as a byproduct of brewing white spirit according to claim 1, wherein the bipolar membrane electrodialysis units are 2-100 repeated units, and each unit is arranged in parallel.
3. The method for recycling the byproduct yellow water in the brewing of the white spirit is characterized by adopting the recycling system as claimed in claim 1 or 2, and comprises the following operations:
1) Adding saccharifying enzyme and lactobacillus into yellow water after entering a fermentation tank, carrying out anaerobic fermentation, and filtering fermentation liquor by an ultrafiltration device after fermentation is completed; the residue of the bacteria is removed and the bacteria are removed,
2) Supernatant separated by the ultrafiltration device enters a salt chamber of a bipolar membrane electrodialysis unit, and La is treated by an external electric field - Transferring the lactic acid into an acid chamber, separating to obtain lactic acid, storing the lactic acid in an acid storage tank, and concentrating and crystallizing to obtain a lactic acid finished product when the concentration of the lactic acid in the acid chamber reaches 60-85% of the concentration of sodium lactate in a salt chamber; OH (OH) - Entering an alkali chamber, and separating alkali liquor and storing the alkali liquor in an alkali storage tank when the alkali concentration in the alkali chamber reaches 60-85% of the sodium lactate concentration in the salt chamber;
3) And the salt chamber effluent of the bipolar membrane electrodialysis unit is residual yellow water after lactic acid is separated, and the residual yellow water is pumped into a supercritical carbon dioxide rectifying tower to extract flavor substances.
4. The method for recycling yellow water, which is a byproduct of brewing white spirit, according to claim 3, wherein 90-99% of the cells are recovered and 1-10% of the cells are discharged from the concentrate obtained by passing the fermentation broth through an ultrafiltration device.
5. The method for recycling yellow water as a byproduct in brewing white spirit according to claim 3, wherein in the step 1), naOH and/or alkali liquor generated by a bipolar membrane electrodialysis unit is added into a fermentation tank to adjust the pH value of the yellow water to 5.8-6.2, and anaerobic fermentation is performed.
6. The method for recycling yellow water, which is a byproduct of brewing white spirit, according to claim 3, wherein after lactic acid is introduced into the acid storage tank from the acid chamber and NaOH is introduced into the alkali storage tank from the alkali chamber, a part of lactic acid separated from the acid chamber flows back to the acid chamber, and a part of alkali separated from the alkali chamber flows back to the alkali chamber, so that the concentration of lactic acid in the acid chamber and the concentration of alkali in the alkali chamber are maintained to be not lower than 0.2mol/L.
7. The method for recycling yellow water as a byproduct in brewing white spirit according to any one of claims 3 to 6, wherein in the step 3), the supercritical carbon dioxide rectifying tower is used for extraction, and a separator is used for separating the fraction, and the fractions of acid, ester, alcohol and aldehyde are separated; wherein the first separator controls the separation pressure to be 7-10 MPa, the separation temperature to be 40-50 ℃, and mainly separates the ester products; the second separator controls the separation pressure to be 5-6 MPa, the separation temperature to be 30-50 ℃, and the alcohol, organic acid and aldehyde products are separated.
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