CN109294893A - A system and method for resource utilization of yellow water, a by-product of liquor brewing - Google Patents
A system and method for resource utilization of yellow water, a by-product of liquor brewing Download PDFInfo
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- CN109294893A CN109294893A CN201811278325.0A CN201811278325A CN109294893A CN 109294893 A CN109294893 A CN 109294893A CN 201811278325 A CN201811278325 A CN 201811278325A CN 109294893 A CN109294893 A CN 109294893A
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- yellow water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000006227 byproduct Substances 0.000 title claims abstract description 22
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 187
- 239000004310 lactic acid Substances 0.000 claims abstract description 92
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 92
- 239000002253 acid Substances 0.000 claims abstract description 66
- 238000000855 fermentation Methods 0.000 claims abstract description 55
- 230000004151 fermentation Effects 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 238000000909 electrodialysis Methods 0.000 claims abstract description 26
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 23
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 4
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- 239000003513 alkali Substances 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 34
- 239000000796 flavoring agent Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 20
- 235000019634 flavors Nutrition 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 108010089934 carbohydrase Proteins 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000003643 water by type Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- 229920002472 Starch Polymers 0.000 abstract description 11
- 239000008107 starch Substances 0.000 abstract description 11
- 235000019698 starch Nutrition 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 11
- 235000014101 wine Nutrition 0.000 description 11
- 239000000284 extract Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 159000000007 calcium salts Chemical class 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 239000008156 Ringer's lactate solution Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/26—Means for regulation, monitoring, measurement or control, e.g. flow regulation of pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/10—Separation or concentration of fermentation products
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- 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
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/56—Lactic acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/325—Nature 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Biochemistry (AREA)
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- General Health & Medical Sciences (AREA)
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- Biomedical Technology (AREA)
- Sustainable Development (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention provides the resource utilization system and method for a kind of brewed spirit by-product yellow water, the system comprises: yellow water lactic fermentation unit, bipolar membrane electrodialysis unit and supercritical CO2Extraction cells;The yellow water lactic fermentation unit includes fermentor, and the fermentor is connected with ultrafiltration apparatus, and the supernatant pipeline of the ultrafiltration apparatus connects the bipolar membrane electrodialysis unit;The bipolar membrane electrodialysis unit includes salt room, acid compartment, alkaline chamber, and the acid compartment and salt room are separated with anion-exchange membrane, and the salt room and alkaline chamber are separated with cation-exchange membrane, and the salt room connects the supercritical CO2Extraction cells;The supercritical CO2Extraction cells include rectifying column, and the tower top of rectifying column is connected with separator.Method proposed by the present invention, starch and reduced sugar in yellow water are fully used, and are converted into the higher lactic acid of utility value;The rate of recovery of lactic acid is high, and the consumption of lactic acid separating-purifying process No Assets and discharging of waste liquid, environmental benefit are high.
Description
Technical field
The invention belongs to fermentation technical fields, and in particular to a kind of the utilization method and benefit of the yellow water that liquor fermentation generates
Use system.
Background technique
Yellow water is in white spirit by solid state method brewing production process, and because fermented grain passes through the catabolism of microorganism, partial moisture is seeped
Out, a kind of brown color for depositing to pit bottom, the liquid in flow-like.General every production 1000kg white wine, about generates
300~400kg of yellow water, Luzhou-flavor liquo yield in 2017 are 985.5 ten thousand tons, then about 3,400,000 tons of annual yellow water discharge amount.According to
The conventional physicochemical property of yellow water, yellow water COD is in 135g/L~330g/L range, considerably beyond the discharge of wastewater mark of country's permission
It is quasi-.More difficult qualified discharge through anaerobic-aerobic treatment.And part brewery yellow water it is unprocessed be directly discharged into water body,
It is seriously polluted.Therefore the organic resources sufficiently in recycling yellow water are to mitigation sewage treatment load, the meaning that reduces environmental pollution weight
Greatly.
Major part brewery in China's is returned cellar fermentation or supports cellar, the artificial cellar of culture using mixing grain to the processing of yellow water at present
The methods of mud, time bottom pot distillation.It is used, is not only unable to efficent use of resources, be substantially reduced the COD discharge of yellow water, and
The best problem of complex utilization of fermentation yellow water can not fundamentally be solved.Therefore yellow water resource how is comprehensively utilized, thoroughly solved
The best problem of complex utilization of yellow water has become the key subjects that liquor industry faces.Currently, to starch in yellow water and reduction
Sugar recycling mostly together with thallus, protein through ultrafiltration membrance filter process liquid protein feed, although yellow water COD substantially under
Drop, but the utilization rate of starch and reduced sugar is low.Traditional method of the extraction of flavor substance is multistage distillation method;I.e. according to Huang
The boiling point of each component is different in flavor substance in water, carries out multistage distillation extraction, obtains the extract of different boiling;It is industrializing
In production process, since yellow water amount is big, energy consumption is very high in distillation process, and distillation efficiency is lower.In terms of preparing biological esterification liquid
Studying more is the research in enzyme preparation, and mostly thick currently with the enzyme preparation that yellow water production biological esterification liquid is utilized
Enzyme preparation, dosage is big, and it is poor to be esterified effect, and has no to the research of new and effective enzyme preparation still in experiment lab scale level
Industrialized production.The generally existing problem of Luzhou-flavor liquo is lactic acid in wine, content of ethyl lactate higher than caproic acid, ethyl hexanoate at present
Content make wine body mouthfeel bad;Lactic acid content can account for the 90% of total organic acids content in yellow water, while lactic acid has again
Great utility value;If yellow water is not extracting lactic acid first before carrying out flavor substance and extracting, in Wine blending liquid obtained, lactic acid and cream
The content of acetoacetic ester is very high, then the effect for blending Luzhou-flavor liquo is bad instead.
Existing yellow water carries out yellow water by fermentation liquid of the reduced sugar fermenting lactic acid after lactic acid separates again using calcium salt method
The extraction of flavor substance is carried out, calcium salt method is only 50% to the lactic acid rate of recovery in yellow water by fermentation liquid, and is needed in the process constantly
It consumes vast resources and discharges a large amount of waste liquids;Although other prepare yellow water esterification liquid, i.e. yellow water by-product is comprehensively utilized,
But sacrifice environmental resource and safety.Many breweries are mostly to extract flavor in yellow water to the research of utilization of yellow water simultaneously
Matter does Wine blending liquid, flavouring and yellow water esterification and prepares the distillation that esterifying liquid is back to wine.Firstly, the organic resources in yellow water are such as
Starch, reduced sugar are not efficiently used, and yellow water COD discharge amount is still very high;Secondly, the technique for extracting flavor substance in yellow water is more
For multistage distillation method, technique flavor substance extraction yield is low and energy consumption is very high.
Summary of the invention
It is insufficient in order to solve organic resources recycling in yellow water, while consumed resource during resource reclaim
Greatly, the big problem of the high and liquid and waste slag produced discharge amount of energy consumption, the present invention propose a kind of recycling benefit of brewed spirit by-product yellow water
With system, by the reduced sugar fermentation lactic acid producing in yellow water, while bipolar membrane electrodialysis technique (EDBM) separation and Extraction lactic acid is coupled;
Yellow water by fermentation liquid after lactic acid separates carries out supercritical CO again2Extraction, extracts the flavors such as alcohol, residual acid, ester and aldehyde therein
Substance does Wine blending liquid.
It is another object of the present invention to propose a kind of resource utilization method of brewed spirit by-product yellow water.
Realize the technical solution of above-mentioned purpose of the present invention are as follows:
A kind of resource utilization system of brewed spirit by-product yellow water, comprising: yellow water lactic fermentation unit, Bipolar Membrane electricity
Dialysis unit and supercritical CO2Extraction cells;
The yellow water lactic fermentation unit includes fermentor, and the fermentor is connected with ultrafiltration apparatus, the ultrafiltration apparatus
Supernatant pipeline connect the bipolar membrane electrodialysis unit, the concentrated solution outlet of the ultrafiltration apparatus passes through circulating line connection
The fermentor.
The bipolar membrane electrodialysis unit includes salt room, acid compartment, alkaline chamber, the acid compartment and salt room with anion-exchange membrane every
Open, the salt room and alkaline chamber are separated with cation-exchange membrane, the acid compartment and alkaline chamber separated with Bipolar Membrane (salt room be located at acid compartment and
Between alkaline chamber), the salt room connects the supercritical CO2Extraction cells;
The supercritical CO2Extraction cells include rectifying column, and the tower top of rectifying column is connected with separator.
Preferably, the concentrated solution outlet of the ultrafiltration apparatus connects the fermentor by circulating line.The fermentor
On be provided with ferment control device.Wherein, the bipolar membrane electrodialysis unit is 2~100 duplicate units, and each unit parallel connection is set
It sets.
A kind of optional scheme of the present invention are as follows: membrane stack specification 800mm × 400mm, the unit weight of every 1000L (processing water)
Plural number is 5 groups.
Wherein, the alkaline chamber connects alkali storage tank by alkali outlet pipe line, and the alkali storage tank is connected to the fermentor;More preferably
Ground, the alkali storage tank connect the alkaline chamber by alkali reflux pipeline.
Wherein, the acid compartment is connected with lactic acid storage tank by going out acid tube line, and the lactic acid storage tank is connected with condensing crystallizing dress
It sets;Preferably, the lactic acid storage tank connects the acid compartment by lactic acid reflux pipeline.
Wherein, the supercritical CO2Extraction cells include rectifying column, and the tower top of rectifying column is connected with the first separator,
Two separators.
A kind of resource utilization method of brewed spirit by-product yellow water, including operation:
1) after yellow water enters in fermentor, carbohydrase and lactic acid bacteria is added, carries out anaerobic fermentation, after fermentation, fermentation
Liquid is filtered by ultrafiltration apparatus, removes thallus residue;
2) supernatant that ultrafiltration apparatus is isolated enters the salt room of bipolar membrane electrodialysis unit, under DC Electric Field,
HLa-Acid compartment is migrated into, when acid compartment concentration reaches the 60~85% of salt room concentration, isolated lactic acid is stored in acid storage tank
Lactic acid finished product is made using condensing crystallizing;OH-Into alkaline chamber, when alkaline chamber concentration reaches the 60~85% of salt room concentration, point
Alkali storage is separated out in alkali storage tank (needing supplement that deionized water is added later);
3) the salt room water outlet of the bipolar membrane electrodialysis unit is the remaining yellow water after separating lactic acid, is pumped into overcritical dioxy
Change the extraction that carbon rectifying column carries out flavor substance.
Beneficial microbe rich in, genus lactubacillus account for 15.9% in yellow water, are superiority bacteria spp, to reduce yellow water COD
It discharges, the carbohydrate in yellow water has the potentiality of fermentation lactic acid producing.
Lactic fermentation is that lactic acid bacteria will restore the process that glycolysis is lactic acid under anaerobic.Lactic fermentation is divided into homotype
Lactic fermentation and heterolactic fermentation.In lactic homofermentation, 1C6H12O6→2C3H6O3, it is newborn that 1 molecule glucose generates 2 molecules
Acid, i.e. 1g glucose fermentation generate 1g lactic acid, and glucose theoretical yield is 100%.When lactic acid carries out heterofermentation,
1C6H12O6→1C3H6O3,1C2H5OH(or 1.5CH3COOH), 1 molecule glucose generates 1 molecule lactic acid, and theoretical yield is
50%.
However the key constraints of reduced sugar fermentation lactic acid producing are yellow water pH and product inhibition in yellow water.Yellow water
PH range is 2.8~4.6, and the pH value that can reach genus lactubacillus fermentation is adjusted through pH value between 5~7.Meanwhile it is organic in yellow water
Sour COD content accounts for total COD about 1/3, and wherein lactic acid accounts for the 90% of total organic acids COD content, therefore the cream of fermentation liquid middle and high concentration
Acid can also inhibit yellow water to carry out lactic fermentation.The yellow water lactic fermentation that this method uses couples EDBM lactic acid separating technology, can be real
The separation and fermentation in situ of existing lactic acid.The high-purity lye that bipolar membrane electrodialysis generates can be used to adjust the perseverance of pH in fermentation process
It is fixed, and improve the conversion ratio of reduced sugar fermentation lactic acid producing.
Further, in the concentrate that fermentation liquid is obtained by ultrafiltration apparatus, 90~99% thallus is recovered, 1~
10% thallus is discharged.
For example 95% thallus is recovered, 5% thallus is discharged.
Wherein, in step 1), NaOH is added into fermentor and/or is adjusted with the lye that bipolar membrane electrodialysis unit generates
Yellow water pH value carries out anaerobic fermentation after being 5.8~6.2.
Wherein, lactic acid from acid compartment import acid storage tank, NaOH from alkaline chamber import alkali storage tank after, (add into equal volume go from
While sub- water), the lactic acid moieties of acid compartment separation flow back into acid compartment, the alkali partial reflux of the alkaline chamber separation to alkaline chamber,
To maintain the concentration in acid compartment and alkaline chamber to be not less than 0.2mol/L.
Wherein, it in the step 3), is extracted with supercritical carbon dioxide rectifying column, with separator separate fraction, is divided
Separate out the fraction of acid, ester, alcohol, aldehyde.Wherein first separator controls 7~10MPa of separating pressure, and 40~50 DEG C of separation temperature,
Main separation of the esters product;Second separator controls 5~6MPa of separating pressure, 30~50 DEG C of separation temperature, separation alcohol, organic
Acid, aldehyde product.
Main organic pollutant in yellow water is carbohydrate (starch, reduced sugar) and fragrance matter similar with liquor flavor:
Organic acid, alcohol, ester, aldehyde.Wherein carbohydrate, lactic acid and remaining flavor substance about respectively account for the 1/3 of yellow water COD.Carbohydrate returns in yellow water
Receive can by under the action of carbohydrase and lactic acid bacteria microbe conversion be lactic acid;The recycling of lactic acid passes through bipolar membrane electrodialysis technique
(EDBM) it is separated;The recycling of flavor substance carries out supercritical CO by the remaining yellow water by fermentation liquid after lactic acid extracts2
Extraction is recycled.So that organic resources in yellow water is fully recycled, farthest reduces the COD row of yellow water
It puts.
System and method provided by the invention first carries out yellow water in fermentor starch sugar and reduced sugar fermentation, together
When coupling bipolar membrane electrodialysis (EDBM) technique the lactic acid generated during yellow water by fermentation is separated;Remaining yellow water hair later
Zymotic fluid is pumped into supercritical carbon dioxide extraction apparatus and extracts to the flavor substance in remaining yellow water by fermentation liquid, is repeatedly recycled
Wine blending liquid is made in extraction, extract liquor, and kettle liquid is discharged into sewage treatment plant;Isolated lactic acid can be further purified be made lactic acid at
Product.Maximize resource recycling, environmental benefit highest, be suitable in, large-scale brewery.
Method proposed by the present invention has the advantage that
(1) starch in yellow water and reduced sugar are fully used, and are converted into the higher lactic acid of utility value;
(2) rate of recovery of lactic acid is high, and the consumption of lactic acid separating-purifying process No Assets and discharging of waste liquid, environmental benefit are high;
(3) supercritical CO is harvested2Technique extracts the flavor substance in remaining yellow water, and extraction yield is high, the extraction to organic acid
Rate can realize whole extractions up to 90% or more, to flavor substances such as alcohol, ester, aldehyde substantially, and extract liquor can do high-quality Wine blending liquid.And institute
Lactic acid, content of ethyl lactate are no longer the main flavors in Wine blending liquid in the Wine blending liquid obtained, for blending oneself cream ratio imbalance
Common white spirit effect it is fine.
Detailed description of the invention
Fig. 1 is the resource utilization system structure diagram of brewed spirit by-product yellow water of the present invention.
The corresponding relationship of component and number in figure are as follows:
Yellow water enters pipeline 101, and pH value adjusts pipeline 102, fermentor 103, ultrafiltration apparatus 104, circulating line 105, row
The outlet 106 of thallus residue out, salt room 201, acid compartment 202, alkaline chamber 203, alkali storage tank 204, lactic acid storage tank 205, condensing crystallizing dress
Set 206, remaining yellow water pipeline 207, lactic acid reflux pipeline 208, rectifying column 301, the first separator 302, the second separator 303,
Kettle liquid collector 304, discharging of waste liquid pipeline 305.
Fig. 2 is the flow chart of the resource utilization method of brewed spirit by-product yellow water of the present invention.
Specific embodiment
Technical solution of the present invention is further illustrated with specific embodiment below.Those skilled in the art should know real
It applies example and is merely to illustrate the present invention, be not used in and limit the scope of the invention.
In embodiment, unless otherwise instructed, technological means used is this field conventional technology.
Embodiment 1:
Referring to Fig. 1, a kind of resource utilization system of brewed spirit by-product yellow water, comprising: yellow water lactic fermentation unit,
Bipolar membrane electrodialysis unit and supercritical CO2Extraction cells;
The yellow water lactic fermentation unit includes fermentor 103, and the top of fermentor 103 has yellow water to enter pipeline 101, pH
Value adjusts pipeline 102, and the fermentor is connected with ultrafiltration apparatus 104, described in the supernatant pipeline connection of the ultrafiltration apparatus 104
Bipolar membrane electrodialysis unit;
The bipolar membrane electrodialysis unit includes salt room 201, acid compartment 202, alkaline chamber 203, the acid compartment 202 and salt room 201
It is separated with anion-exchange membrane (am), the salt room 201 and alkaline chamber 203 are separated with cation-exchange membrane (cm), acid compartment 202 and alkali
Room 203 is separated with Bipolar Membrane (bm), and the remaining yellow water pipeline 207 at 201 top of salt room is connected to the supercritical CO2Extraction is single
Member;
Duplicate unit is using form in parallel.In specific the present embodiment, membrane stack specification chooses 0.4m × 0.8m, and membrane stack is matched
10 groups of group (unit repeat number), (Fig. 1 shows a unit, is outlined with dotted line).Membrane stack specification 800mm × 400mm, every 1000L
The unit repeat number for handling water is 5 groups.
The supercritical CO2Extraction cells include rectifying column 301, and the tower top of rectifying column 301 is connected with the first separator 302
With the second separator 303.Tower bottom of rectifying tower connects kettle liquid collector 304.Kettle liquid collector 304 is provided with discharging of waste liquid pipeline
305。
The concentrated solution outlet of the ultrafiltration apparatus is connected on fermentor described in the fermentor 103 by circulating line 105
It is provided with ferment control device.Concentrated solution outlet is also connected with the outlet 106 of discharge thallus residue.
Alkaline chamber 203 connects alkali storage tank 204 by alkali outlet pipe line, and the alkali storage tank is connected to the pH value tune on the fermentor
Length of tubing 102;The alkali storage tank connects the alkaline chamber by alkali reflux pipeline.
Acid compartment 202 is connected with lactic acid storage tank 205 by the acid tube line that goes out of bottom, and the lactic acid storage tank is connected with condensing crystallizing
Device 206;The lactic acid storage tank connects the acid compartment by lactic acid reflux pipeline 208.It is arranged in 206 bottom of concentration and crystallization device
Lactic acid product outlet.
Embodiment 2
The system of Application Example 1, a kind of resource utilization method of brewed spirit by-product yellow water, process referring to fig. 2,
Including operation:
1) after yellow water enters in fermentor, carbohydrase and lactic acid bacteria is added, carries out anaerobic fermentation, after fermentation, fermentation
Liquid is filtered by ultrafiltration apparatus;The larger molecular organics such as thallus residue, humus and protein are removed, fermentation liquid is filled by ultrafiltration
In the concentrate set, part thallus is recycled into fermentor;Specifically 95% thallus is recovered, and 5% thallus is arranged
Out.NaOH is added when initial launch into fermentor;Yellow water pH is adjusted with the lye that bipolar membrane electrodialysis unit generates in operation
Value is 6.0, carries out anaerobic fermentation.
2) supernatant that ultrafiltration apparatus is isolated enters the salt room of bipolar membrane electrodialysis unit, under DC Electric Field,
HLa-Acid compartment is migrated into, lactic acid finished product is made by condensing crystallizing in isolated lactic acid;OH-Into alkaline chamber, and isolate lye
It is stored in alkali storage tank.When acid compartment and alkaline chamber concentration increase, the lactic acid in acid compartment is imported into acid storage tank respectively, the NaOH in alkaline chamber
Alkali storage tank is imported, fills into the deionized water of same volume later, while the lactic acid moieties of acid compartment separation flow back into acid compartment, the alkali
For the alkali partial reflux of room separation to alkaline chamber, maintaining the concentration difference between salt room and acid compartment and alkaline chamber is to guarantee in acid compartment and alkaline chamber
Concentration be not less than 0.2mol/L.
3) the salt room water outlet of the bipolar membrane electrodialysis unit is the remaining yellow water after separating lactic acid, is pumped into overcritical dioxy
Change the extraction that carbon rectifying column carries out flavor substance, is extracted with supercritical carbon dioxide rectifying column, isolate alcohol, acid, ester, aldehyde
Fraction.In the present embodiment, the first separator controls 7~10MPa of separating pressure, and separation temperature is 40~50 DEG C or so, mainly
Separation of the esters product;Second separator controls 5~6MPa of separating pressure, and 30~50 DEG C of separation temperature or so, separation alcohol, organic
Acid, aldehyde product.
The present embodiment provides the compositional datas of one group of yellow water, are shown in Table 1.Table 1 also lists ingredient (table 1 after fermented tank fermentation
" yellow water by fermentation liquid "), the yellow water ingredient (table 1 its " yellow water by fermentation liquid after extracting lactic acid ") being discharged through salt room, discharging of waste liquid pipe
The waste component that road 305 is discharged.
Main content of organics in each process in 1 yellow water resource utilization scheme of table
In the EDBM technique of the present embodiment, the current density 50mA/cm of application2, concentration between salt room, acid compartment and alkaline chamber
It is 1.2mol/L for sodium lactate solution concentration in salt room, every time when the NaOH concentration accumulation in acid compartment in lactic acid concn and alkaline chamber is arrived
When 1.0mol/L, lactic acid is imported in acid storage tank, NaOH is imported into alkali storage tank;Same volume is added into acid compartment, alkaline chamber respectively again
Deionized water, while part lactic acid and NaOH pass back into acid compartment from lactic acid tank, guarantee that lactic acid concn is not less than 0.2mol/L, to cream
The rate of recovery of acid is 85.4% (rate of recovery through bipolar film process).
Lactic acid content is in terms of 30g/L in raw material, and content of starch is 40g/L in yellow water, and reduced sugar 50g/L, starch is with theory
Conversion ratio 111% is counted, and conversion rate of reducing sugar is in terms of 82.7%, and for lactic acid separation rate in terms of 85%, remaining yellow water carries out supercritical CO2
Extraction, organic acid extraction yield are 90%, and alcohol, ester, aldehyde extraction yield are 95%.After the program, 1t yellow water can produce lactic acid
92kg, Wine blending liquid 30kg, yellow water COD reduce discharge about 96.7%, the basic full recycling for realizing yellow water organic resources.
Embodiment 2
The process conditions of the present embodiment are substantially with embodiment 1, the difference is that lactic acid content is 40g/L in yellow water, starch contains
Measuring is 30g/L, in reduced sugar 30g/L, EDBM technique, the current density 60mA/cm of application2, conversion rate of reducing sugar (lactic acid yield
Coefficient) it is 78.5%;Fermentation process lactic acid production is 90g/L.Concentration between acid compartment and alkaline chamber is that acid compartment concentration is 73g/L,
Alkaline chamber NaOH concentration is 32.4g/L, and the rate of recovery to lactic acid is 81.22%.
Embodiment 3
The process conditions of the present embodiment are substantially with embodiment 1, the difference is that lactic acid content is 25g/L in yellow water, starch contains
Amount is about 20g/L, and reduced sugar is about 30g/L, and conversion rate of reducing sugar is 80% in fermentation process, lactic acid production 66.76g/L.
In EDBM technique, the current density 50mA/cm of application2, the concentration between acid compartment and alkaline chamber is that acid compartment concentration is 52.3g/L, alkali
Room NaOH concentration is 23.2g/Lg/L, and the rate of recovery to lactic acid is 78.3%.
Comparative example 1
Ion exchange resin technique separation and Extraction lactic acid, raw material and embodiment 1 are identical.Institute's spent ion exchange resin is D315
Ion exchange resin.
2 D315 resin of table extracts lactic acid MaterialBalance Computation
Note: industry does not introduce other impurities cation during elution, chooses quality herein to obtain molecular state lactic acid
The H that score is 5%2SO4Do eluent;In order to which remaining yellow water by fermentation liquid is carrying out supercritical CO2SO is not introduced when extraction4 2-, choosing
Select the NaOH regenerated liquid that mass fraction is 4%.
Comparative example 2
Calcium salt method handles raw material and embodiment 1 is identical.Due to needing multiple condensing crystallizing and filtering, each process lactic acid equal
Loss is had, lactic acid recovery rate is lower than 60%.Compared with calcium salt method and ion-exchange-resin process, EDBM technique extracts the ring of lactic acid
Border benefit is best.Table 1,2 is respectively the resource consumption of every production pure lactic acid of 1t from yellow water using calcium salt method and ion-exchange
Amount and waste discharge amount.
3 calcium salt method of table extracts yellow water lactic acid MaterialBalance Computation
Note: this table does not calculate ion exchange process removal SO4 2-、Ca2+Acid, alkali and the water of equal zwitterions consumption;Activity
Charcoal dosage is the 25% of 80% lactic acid output.
EDBM technique is in the case that Bipolar Membrane can not be by outer acid adding, alkali under extra electric field, and wherein interbed is by water power
HLa and NaOH is generated in conjunction with La- and Na+ from acid compartment and alkaline chamber is respectively enterd at H+ and OH-.The dissociation of water does not generate any gas
Body, energy consumption are very low;The water in solution can continuously be fallen again into the middle layer of Bipolar Membrane with supplementing electrolysis simultaneously
Water.Theoretically realize waste " zero-emission ".EDBM process energy consumption is lower, and energy consumption is at 0.8~1.2kWh (kgHLa)-1
Range.Ion-exchange resin does not have energy consumption;The energy consumption of calcium salt method is higher, because being to prevent cream in filtering, acid hemolysis process
Sour calcium crystallization, needs continuous high temperature.
Above embodiment be only a specific embodiment of the invention is described, not to the scope of the present invention into
Row limits, and those skilled in the art can also do numerous modifications and variations on the basis of existing technology, set not departing from the present invention
Under the premise of meter spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of resource utilization system of brewed spirit by-product yellow water characterized by comprising yellow water lactic fermentation list
Member, bipolar membrane electrodialysis unit and supercritical CO2Extraction cells;
The yellow water lactic fermentation unit includes fermentor, and the fermentor is connected with ultrafiltration apparatus, the ultrafiltration apparatus it is upper
Clear liquid pipeline connects the bipolar membrane electrodialysis unit, and the concentrated solution outlet of the ultrafiltration apparatus passes through described in circulating line connection
Fermentor;
The bipolar membrane electrodialysis unit includes salt room, acid compartment, alkaline chamber, and the acid compartment and salt room are separated with anion-exchange membrane,
The salt room and alkaline chamber are separated with cation-exchange membrane, and the acid compartment and alkaline chamber are separated with Bipolar Membrane, described in the salt room connection
Supercritical CO2Extraction cells;
The supercritical CO2Extraction cells include rectifying column, and the tower top of rectifying column is connected with separator.
2. the resource utilization system of brewed spirit by-product yellow water according to claim 1, which is characterized in that described double
Pole membrane electrodialysis unit is 2~100 duplicate units, and each unit is arranged in parallel.
3. the resource utilization system of brewed spirit by-product yellow water according to claim 1, which is characterized in that the alkali
Room connects alkali storage tank by alkali outlet pipe line, and the alkali storage tank is connected to the fermentor;Preferably, the alkali storage tank is returned by alkali
Flow tube line connects the alkaline chamber.
4. the resource utilization system of brewed spirit by-product yellow water according to claim 1, which is characterized in that the acid
Room is connected with lactic acid storage tank by going out acid tube line, and the lactic acid storage tank is connected with concentration and crystallization device;Preferably, the lactic acid storage
Tank connects the acid compartment by lactic acid reflux pipeline.
5. the resource utilization system of brewed spirit by-product yellow water according to any one of claims 1 to 4, feature exist
In the supercritical CO2Extraction cells include rectifying column, and the tower top of rectifying column is connected with the first separator and the second separator.
6. a kind of resource utilization method of brewed spirit by-product yellow water, which is characterized in that including operation:
1) after yellow water enters in fermentor, carbohydrase and lactic acid bacteria is added, carries out anaerobic fermentation, after fermentation, fermentation liquid is logical
Cross ultrafiltration apparatus filtering;Thallus residue is removed,
2) supernatant that ultrafiltration apparatus is isolated enters the salt room of bipolar membrane electrodialysis unit, under DC Electric Field, HLa-It moves
Move up into acid compartment, when acid compartment concentration reaches the 60~85% of salt room concentration, isolated lactic acid be stored in acid storage tank using
Lactic acid finished product is made in condensing crystallizing;OH-Alkali is isolated when alkaline chamber concentration reaches the 60~85% of salt room concentration into alkaline chamber
Liquid is stored in alkali storage tank;
3) the salt room water outlet of the bipolar membrane electrodialysis unit is the remaining yellow water after separating lactic acid, is pumped into supercritical carbon dioxide
The extraction of rectifying column progress flavor substance.
7. the resource utilization method of brewed spirit by-product yellow water according to claim 6, which is characterized in that fermentation liquid
In the concentrate obtained by ultrafiltration apparatus, 90~99% thallus is recovered, and 1~10% thallus is discharged.
8. the resource utilization method of brewed spirit by-product yellow water according to claim 6, which is characterized in that step 1)
In, it is 5.8~6.2 that NaOH is added into fermentor and/or adjusts yellow water pH value with the lye that bipolar membrane electrodialysis unit generates
After carry out anaerobic fermentation.
9. the resource utilization method of brewed spirit by-product yellow water according to claim 6, which is characterized in that in lactic acid
Acid storage tank, NaOH are imported after alkaline chamber importing alkali storage tank from acid compartment, and the lactic acid moieties of the acid compartment separation flow back into acid compartment, described
The alkali partial reflux of alkaline chamber separation is to alkaline chamber, to maintain the concentration in acid compartment and alkaline chamber to be not less than 0.2mol/L.
10. according to the resource utilization method of the described in any item brewed spirit by-product yellow waters of claim 6~9, feature
Be, in the step 3), extracted with supercritical carbon dioxide rectifying column, with separator separate fraction, isolate acid,
Ester, alcohol, aldehyde fraction;Wherein first separator controls 7~10MPa of separating pressure, 40~50 DEG C of separation temperature, main to separate
Esters product;Second separator controls 5~6MPa of separating pressure, 30~50 DEG C of separation temperature, separates alcohol, organic acid, aldehydes
Product.
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CN110643487A (en) * | 2019-09-26 | 2020-01-03 | 南京华创环境技术研究院有限公司 | Fermentation device and system for producing caproic acid by utilizing yellow water by-product of liquor brewing |
CN113373182A (en) * | 2021-06-17 | 2021-09-10 | 四川剑南春(集团)有限责任公司 | Method for recovering caproic acid in biological fermentation liquid |
CN114477579A (en) * | 2022-01-24 | 2022-05-13 | 四川绵竹剑南春酒厂有限公司 | Process for treating waste liquid after production of wine seasoning liquid |
CN114517142A (en) * | 2022-02-28 | 2022-05-20 | 四川绵竹剑南春酒厂有限公司 | Wine additive preparation process and formula |
CN114890888A (en) * | 2022-06-20 | 2022-08-12 | 安徽瑞思威尔科技有限公司 | Method for extracting ultrahigh-concentration lactic acid from yellow wine brewing water based on tangential flow membrane technology |
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CN110643487A (en) * | 2019-09-26 | 2020-01-03 | 南京华创环境技术研究院有限公司 | Fermentation device and system for producing caproic acid by utilizing yellow water by-product of liquor brewing |
CN110643487B (en) * | 2019-09-26 | 2024-11-08 | 南京华创环境技术研究院有限公司 | A fermentation device and a system for producing caproic acid using yellow water as a byproduct of liquor brewing |
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CN114477579A (en) * | 2022-01-24 | 2022-05-13 | 四川绵竹剑南春酒厂有限公司 | Process for treating waste liquid after production of wine seasoning liquid |
CN114517142A (en) * | 2022-02-28 | 2022-05-20 | 四川绵竹剑南春酒厂有限公司 | Wine additive preparation process and formula |
CN114890888A (en) * | 2022-06-20 | 2022-08-12 | 安徽瑞思威尔科技有限公司 | Method for extracting ultrahigh-concentration lactic acid from yellow wine brewing water based on tangential flow membrane technology |
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