Treatment method of white wine cellar bottom wastewater

Abstract

The invention relates to a white wine cellar bottom wastewater treatment method, which comprises: 1) taking white wine cellar bottom wastewater, and pre-treating to obtain pre-treated wastewater; 2) adjusting the pH of the pretreated wastewater to be neutral to obtain neutral wastewater; (3) inoculating the bacillus amyloliquefaciens liquid into an LB liquid culture medium, and performing activated culture to obtain a bacillus amyloliquefaciens activated solution; (4) inoculating the lactic acid bacteria liquid into an MRS liquid culture medium, and activating and culturing to obtain a lactic acid bacteria activating solution; 5) taking the bacillus amyloliquefaciens activation solution in the step 3), inoculating the neutral wastewater in the step 2), and performing fermentation treatment to obtain a material I; and (6) inoculating the lactic acid bacteria activating solution in the step (4) into the material I in the step (5), and fermenting to obtain a material II, thereby finishing the treatment. The method is simple in process, low in treatment cost and free of secondary pollution, the treated materials have economic benefits, and green and sustainable development of the Baijiu industry is achieved.

Description

Technical Field

[0001] The invention relates to the field of wastewater treatment, and in particular to a method for treating wastewater from the bottom of a liquor cellar. Background Art

[0002] Liquor cellar wastewater is an important component of industrial wastewater generated by the liquor brewing industry. According to statistics, the annual output in China is about 240 million tons, with a very high organic matter content and a COD concentration of up to 2*10 5 mg / L, high acidity (pH 3-4.5), high nitrogen and phosphorus content and color, contains some harmful substances, and is very easy to deteriorate and rot. If it cannot be effectively treated, it will have adverse effects on the environment and human body.

[0003] At present, biochemical treatment is mostly used to treat wastewater from liquor cellars. However, this method is easily affected by water quality fluctuations and cannot directly treat wastewater from liquor cellars, which in turn limits the green and sustainable development of the liquor industry.

[0004] The state encourages the use of anaerobic fermentation and biogas production technology, extraction and manufacturing of lactic acid products and other methods to treat high-concentration organic wastewater. Liquor cellar wastewater is rich in nutrients such as starch, cellulose, protein, nitrogen, and phosphorus. Bacillus amyloliquefaciens produces enzymes such as amylase, cellulase, and proteinase, which can convert starch and cellulose in wastewater into glucose, providing a sugar source for lactic acid bacteria and reducing COD in wastewater. However, the optimal growth pH of Bacillus amyloliquefaciens and lactic acid bacteria is 6-7, so using a suitable alkaline regulator to adjust the pH of cellar wastewater to neutral is a crucial step.

[0005] Patent CN110564783B discloses a method for producing polyhydroxyalkanoates by using excess sludge and liquor wastewater, Patent CN103708596B discloses a method for strengthening the removal and recovery of nitrogen and phosphorus in the traditional treatment process of liquor wastewater, and Patent CN111838405A discloses a method for preparing feed raw materials by fermenting rice wine lees with lactic acid bacteria. The above patents only consider the synthesis of products, the recovery of a very small part of the wastewater, and the addition of auxiliary materials for lactic acid bacteria to produce lactic acid, and fail to achieve the purpose of high-value comprehensive utilization and cost reduction.

[0006] Therefore, how to design a method for efficiently utilizing wastewater from liquor cellars to achieve the green and sustainable development of the liquor industry is an urgent problem to be solved by technicians in this field. Summary of the invention

[0007] The purpose of the present invention is to provide a method for treating wastewater from liquor cellar bottoms in view of the deficiencies in the prior art, which has a simple process, low treatment cost, no secondary pollution, and economic benefits for the treated materials, thereby realizing the green and sustainable development of the liquor industry.

[0008] The technical solution of the present invention is: a method for treating wastewater from liquor cellar bottom, comprising the following steps:

[0009] 1) taking wastewater from the bottom of a liquor cellar, and pre-treating it to obtain pre-treated wastewater;

[0010] 2) adjusting the pH of the pretreated wastewater to neutral to obtain neutral wastewater;

[0011] 3) taking a Bacillus amyloliquefaciens bacterial liquid and inoculating it into LB liquid culture medium for activation culture to obtain an activated Bacillus amyloliquefaciens liquid;

[0012] 4) taking the lactic acid bacteria liquid and inoculating it into the MRS liquid culture medium for activation culture to obtain the lactic acid bacteria activation liquid;

[0013] 5) taking the activated Bacillus amyloliquefaciens solution of step 3), inoculating it into the neutral wastewater of step 2), and fermenting it to obtain material I;

[0014] 6) Taking the activated lactic acid bacteria liquid from step 4), inoculating it into the material I from step 5), fermenting to obtain material II, and the treatment is completed.

[0015] Furthermore, in step 1), the pH of the wastewater from the liquor cellar is 3-5, and the COD is greater than 1.5×10 5 mg / L, TN is 1×10 3 -2×10 3 mg / L, TP is 4×10 3 -5×10 3 mg / L.

[0016] Furthermore, the pretreatment in step 1) is a photocatalytic treatment, and the photocatalyst used in the photocatalytic treatment is any one or more of titanium dioxide, graphite carbon nitride, and graphene oxide, wherein the amount of titanium dioxide added is 0.2-0.5 g / L, the amount of graphite carbon nitride added is 0.1-5 g / L, the amount of graphene oxide added is 0.1-5 g / L, the photocatalytic treatment time is 0.5-3 h, and the temperature is 30-50 ° C.

[0017] Preferably, in step 2), an ammonium carbonate solution is used to adjust the pH, and the concentration of the ammonium carbonate solution is 1-3 wt %.

[0018] Furthermore, in step 3), the LB liquid culture medium is an aqueous solution of tryptone, yeast extract, and sodium chloride, with contents of 10 g / L, 5 g / L, and 10 g / L, respectively, and a pH value of 7.0-7.2.

[0019] Further, in step 3), inoculation is carried out under a sterile environment, 0.5-1.5 mL of Bacillus amyloliquefaciens bacterial solution is inoculated into 150-250 mL of LB liquid culture medium, and activation culture is carried out at 30-40° C. with shaking at 100-200 r / min for 20-30 h.

[0020] Further, step 4) MRS liquid culture medium is an aqueous solution of peptone, beef extract, yeast extract, glucose, dipotassium hydrogen phosphate, triammonium citrate, sodium acetate, Tween-80, magnesium sulfate, and manganese sulfate, with contents of 10 g / L, 5 g / L, 4 g / L, 20 g / L, 2 g / L, 2 g / L, 5 g / L, 1 mL / L, 0.2 g / L, and 0.05 g / L, respectively, and a pH value of 6.2-6.4.

[0021] Further, step 4) is inoculated under anaerobic and aseptic conditions, the lactic acid bacteria are one or more of Lactobacillus plantarum, Lactobacillus bulgaricus, Lactobacillus acidophilus, and Bifidobacterium bifidum, 0.5-1.5 mL of lactic acid bacteria liquid is inoculated into 150-250 mL of MRS liquid culture medium, and the activation culture is performed at 35-40° C. and the shaking table is shaken at 50-100 r / min for 20-30 hours.

[0022] Furthermore, in step 5), the amount of Bacillus amyloliquefaciens activated liquid added to the neutral wastewater is 0.04-0.4wt%, and the fermentation is carried out on a shaker at 100-200r / min at 30-40°C. In step 6), the amount of lactic acid bacteria liquid added to material I is 0.5-5wt%, and the fermentation is carried out on a shaker at 100-200r / min at 30-40°C.

[0023] The present invention also provides the use of the material II as a feed additive.

[0024] The above technical solution has the following beneficial effects:

[0025] 1. The present invention first performs photocatalytic treatment on the wastewater from the bottom of the liquor cellar, oxidizes and removes the difficult-to-degrade organic matter and toxic substances such as tannin, etc., to ensure the normal growth and fermentation of the functional bacteria used in the subsequent process; at the same time, the treatment can sterilize the wastewater, effectively reduce the adverse effects of miscellaneous bacteria, improve the lactic acid conversion efficiency and reduce the cost of additional sterilization. Adding ammonium carbonate to the wastewater treated with photocatalysis to adjust the pH can achieve the purpose of low concentration and high efficiency. If other alkalis are used, it is not conducive to the growth and fermentation of microorganisms. After the pH is adjusted, active Bacillus amyloliquefaciens is added to produce enzymes such as amylase, cellulase and protease, and decompose organic matter such as starch and cellulose in the treated wastewater into glucose as a carbon source, while preliminarily reducing the COD value in the wastewater. Finally, active lactic acid bacteria are added to use the generated glucose and nitrogen and phosphorus compounds in the wastewater to ferment and produce lactic acid, and reduce the COD value in the wastewater. The COD removal rate in the final material reaches 71.4±2.57%, and the lactic acid content reaches 51.53±1.46g / L. The number of live bacteria and metal indicators in material II are up to standard. Lactic acid can be used as a pharmaceutical intermediate, biodegradable material and feed additive, which effectively improves the utilization value of wastewater from the bottom of the liquor cellar without generating any three wastes.

[0026] 2. The photocatalyst used in the photocatalytic treatment of the present invention is any one or more of titanium dioxide, graphite carbon nitride, and graphene oxide.

[0027] Among them, under light conditions, titanium dioxide can be excited to generate electrons (e - ) and holes (h + ). The electrons and holes migrate to the surface of the catalyst respectively, and the electrons and holes undergo redox reactions with the oxygen and organic matter in the water. Holes have strong oxidizing properties and can oxidize water molecules into hydroxyl radicals (·OH), while electrons can reduce oxygen into superoxide anions (O2 -·). Hydroxyl radicals (·OH) are very strong oxidants that can indiscriminately attack organic pollutants in wastewater and degrade them into harmless small molecules, such as H2O and CO2. Photocatalytic reactions can also produce a certain amount of ozone (O3), which has a disinfecting effect and can kill bacteria and viruses in wastewater. Titanium dioxide, as a photocatalyst, is not consumed during the reaction process, so it does not produce secondary pollution. If the amount of titanium dioxide added is too large, firstly, too much catalyst will increase the treatment cost and cause waste of resources. Secondly, excessive titanium dioxide will cause the dispersion of the catalyst in the wastewater to deteriorate, forming agglomerations, resulting in a decrease in the active surface area of ​​the catalyst, thereby reducing the photocatalytic efficiency. Furthermore, a large number of catalyst particles will increase the difficulty of subsequent filtration of wastewater treatment, causing clogging of filtration equipment and increasing maintenance costs. Finally, although titanium dioxide itself is relatively harmless to the environment, excessive addition may leave more catalyst particles in the treated wastewater, requiring further treatment to meet emission standards. If the amount added is too small, firstly, the amount of photocatalyst is insufficient, resulting in fewer active centers for the photocatalytic reaction, which cannot fully absorb light energy, low treatment efficiency, and difficulty in effectively degrading organic pollutants in wastewater. Secondly, insufficient catalyst dosage may lead to unstable photocatalytic reaction and large fluctuations in treatment effect, making it difficult to meet the needs of continuous and stable wastewater treatment. Finally, due to insufficient catalyst dosage, it takes longer to complete the degradation of pollutants, which will increase the energy consumption and operating costs of the treatment process.

[0028] Among them, graphite phase carbon nitride absorbs light energy, excites electrons to jump from the valence band to the conduction band, and generates electron-hole pairs. Electrons and holes participate in different reactions on the catalyst surface. Holes can react with water molecules or hydroxide ions to generate hydroxyl radicals (·OH), while electrons can react with oxygen to generate superoxide anions (·O2 - ), which is further converted into hydrogen peroxide (H2O2) and singlet oxygen ( 1 O2). Hydroxyl radical (·OH) and singlet oxygen ( 1 O2) and other reactive oxygen species have very high reactivity, they can attack the cell membrane of bacteria, destroy its lipid structure, and cause the cell membrane permeability to increase. Reactive oxygen species can also enter bacterial cells, react with proteins and DNA, cause protein oxidation inactivation and DNA chain breakage, and affect the life activities of bacteria. The destruction of cell membrane and the damage of intracellular macromolecules can cause metabolic disorders of bacteria, and then affect its growth and reproduction ability, and finally cause bacterial death. If the addition amount of graphite phase carbon nitride is too much, it will occupy reactive sites, reduce effective heterojunction interface, be unfavorable for charge transfer, inhibit photocatalytic reaction, and cause the waste of catalyst. If the addition amount is too low, it is impossible to form a sufficient number of highly active heterojunction interfaces, which affects the separation efficiency of photogenerated electron-hole pairs, thereby reducing the photocatalytic performance.

[0029] Among them, the photocatalysts graphene oxide (GO) and graphite carbon nitride (g-C3N4) have essentially similar sterilization mechanisms in the photocatalytic treatment process, both of which are based on the generation of reactive oxygen species (ROS) by photocatalytic reactions to destroy bacterial cell structures. However, due to differences in their structures and properties, there are some differences in the specific manifestations of their sterilization mechanisms:

[0030] Formation of Reactive Oxygen Species:

[0031] Graphene oxide: The oxygen-containing functional groups on its surface can serve as active sites and promote the formation of reactive oxygen species, especially hydroxyl radicals (·OH).

[0032] Graphitic carbon nitride: Its photocatalytic activity mainly comes from its unique electronic structure and surface properties, which can promote the superoxide anion (·O2 - ) and singlet oxygen ( 1 O2) formation.

[0033] Cell membrane disruption and intracellular damage:

[0034] Graphene oxide: Due to its large specific surface area and good dispersibility, graphene oxide has more contact points with bacterial cells, thus destroying the cell membrane more effectively.

[0035] Graphitic carbon nitride: Its stable structure and good photocatalytic performance may make the active oxygen species more stable on the catalyst surface, thereby causing continuous damage to bacterial cells.

[0036] In addition, if the amount of graphene oxide added is too low, it cannot fully play its role as a photocatalyst, affecting the photocatalytic efficiency. If the amount added is too large, it will compete with the reactants, making it impossible to fully utilize the reactants.

[0037] 3. Active Bacillus amyloliquefaciens is first added to the neutral wastewater of the present invention. The purpose of adding Bacillus amyloliquefaciens first is: ① converting substances such as starch, cellulose and protein in the wastewater into glucose to provide a carbon source for lactic acid bacteria; ② improving the wastewater environment. The bacteria can produce some organic acids and metabolites during the fermentation process, and these substances help to improve its microecological environment; ③ inhibiting harmful microorganisms. The bacteria can produce some substances with antibacterial effects during the fermentation process. These substances can inhibit the growth and reproduction of other harmful microorganisms in the wastewater, thereby reducing their interference and competition with lactic acid bacteria fermentation. By controlling its addition amount within the specified range, the fermentation process can be optimized and the cost can be reduced. In addition, ecological imbalance can be avoided. If the addition amount is too small, the starch in the wastewater may not be effectively decomposed, resulting in the lack of sufficient carbon source for lactic acid bacteria to ferment, which will affect the yield and fermentation efficiency of lactic acid. If the addition amount is too much, too many metabolites and organic acids may be produced, resulting in a decrease in the pH value of the wastewater or an imbalance in the microecological environment, which will affect the growth and fermentation of lactic acid bacteria and may even lead to fermentation failure. In addition, too much Bacillus amyloliquefaciens may increase the difficulty and cost of wastewater treatment.

[0038] The following is a further description in conjunction with specific implementation methods. DETAILED DESCRIPTION

[0039] In the present invention, the materials used in the MBR culture medium are: peptone (Beijing Aoboxing Biotechnology Co., Ltd.); beef extract and yeast extract (Shanghai Bowei Microbiology Technology Co., Ltd.); glucose, dipotassium hydrogen phosphate, Tween-80, magnesium sulfate and manganese sulfate (Tianjin Komiou Chemical Reagent Co., Ltd.); triammonium citrate and sodium acetate (Chengdu Jinshan Chemical Reagent Co., Ltd.); the purity is analytical grade.

[0040] Four lactic acid bacteria (Xi’an Mixianer Biotechnology Co., Ltd.).

[0041] The sources of materials used in the preparation of LB medium include: tryptone (purchased from Biosharp, purity: total nitrogen ≥ 12.5%, amino nitrogen ≥ 2.5%), yeast extract (purchased from Millipore), and sodium chloride (Guangdong Guanghua Technology Co., Ltd., analytical grade).

[0042] Bacillus amyloliquefaciens (ATCC).

[0043] Photocatalyst: titanium dioxide and graphite carbon nitride (Jiangsu Xianfeng Nanomaterial Technology Co., Ltd., purity > 99%), graphene oxide (Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.)

[0044] Ammonium carbonate: (Tianjin Komiou Chemical Reagent Co., Ltd.).

[0045] The wastewater from the bottom of the liquor cellar comes from Xishui County, Zunyi City, Guizhou Province.

[0046] Example 1

[0047] The method for efficiently treating wastewater from liquor cellar bottom in a resource-efficient manner comprises the following steps:

[0048] 1) Pretreatment of liquor cellar wastewater: Photocatalysis (catalytic conditions: titanium dioxide dosage 0.35 g / L, reaction time 1.5 h, reaction temperature 45 ° C) was used to remove the refractory organic matter and toxic substances such as tannin in the wastewater; then 2% alkaline regulator ammonium carbonate was added to the liquor cellar wastewater, stirred evenly, and allowed to stand for 10 min. The pH of the liquor cellar wastewater was measured to be 6.70;

[0049] 2) Preparation of Bacillus amyloliquefaciens bacterial solution: In a sterile environment, take a 250 mL conical flask, measure 250 mL of LB liquid culture medium and place it in it, add 1.5 mL of Bacillus amyloliquefaciens bacterial solution, and culture it at a temperature of 37°C and 180 r / min for 20 h;

[0050] 3) Preparation of lactic acid bacteria liquid: Take a 250 mL conical flask, measure 250 mL of MRS liquid culture medium and place it therein, add 1.5 mL of Lactobacillus acidophilus liquid, seal the mouth of the conical flask with a sterile sealing film to ensure an anaerobic state and minimize the influence of other bacteria, put it in a shaker and set the temperature to 37°C, ferment for 20 h, and shake at a speed of 50 r / min to obtain the activated lactic acid bacteria liquid, which is stored in a -2°C refrigerator.

[0051] 4) Fermentation of liquor cellar wastewater: First, inoculate the 0.2% amyloliquefaciens solution prepared in step 2) into a 250mL conical flask containing the wastewater treated in step 1), and shake and ferment at 37°C and 180r / min to obtain material I with a pH of 6.5; secondly, after an interval of 4h, add the 2% Lactobacillus acidophilus solution prepared in step 3) to material I, and ferment and culture at 40°C and 150r / min for 2d to obtain material II. The COD utilization rate in material II reaches 75%, the TP consumption rate reaches 83%, the TN consumption rate is 30%, and the NH3 + The consumption rate of -N was 28%, and the lactic acid production was about 51g / L. In addition, the number of live Lactobacillus acidophilus in the fermentation broth (2.9×10 9 (CFU / g)) and metal ion (Pb, Hg, Cd) concentrations can meet the standards of feed additives.

[0052] Example 2

[0053] The method for efficiently treating wastewater from liquor cellar bottom in a resource-efficient manner comprises the following steps:

[0054] 1) Pretreatment of liquor cellar wastewater: Photocatalysis (catalytic conditions: titanium dioxide dosage 0.25 g / L, reaction time 1.0 h, reaction temperature 35° C.) was used to remove the refractory organic matter and toxic substances such as tannin in the wastewater; 3% alkaline regulator ammonium carbonate was added to the liquor cellar wastewater, stirred evenly, and allowed to stand for 10 min. The pH of the liquor cellar wastewater was measured to be 7.10;

[0055] 2) Preparation of Bacillus amyloliquefaciens bacterial solution: the same as in Example 1;

[0056] 3) Preparation of lactic acid bacteria liquid: Take 4 250 ml conical flasks, measure 250 ml of MRS liquid culture medium respectively and place them therein, add 1.5 ml of Lactobacillus plantarum, Lactobacillus bulgaricus, Lactobacillus acidophilus and Bifidobacterium bifidum to each of the four conical flasks, seal the conical flask mouths with sterile sealing films to ensure anaerobic state and minimize the influence of other bacteria, put them into a shaker and set the temperature to 37 ° C, ferment for 20 h, and shake at a speed of 50 r / min to obtain the four lactic acid bacteria liquids after activation, which are stored in a -2 ° C refrigerator.

[0057] 4) Fermentation of liquor cellar wastewater: First, inoculate the 0.2% amyloliquefaciens bacterial solution prepared in step 2) into a 250mL conical flask containing the wastewater treated in step 1), and shake and ferment at 37°C and 180r / min to obtain material I with a pH of 6.8; secondly, after an interval of 4 hours, add the plant lactobacillus, bulgaricus, lactobacillus acidophilus and bifidobacterium prepared in step 3) to material I in a mass ratio of 1:1:1:1, and the total inoculation amount of the four bacterial solutions is 3% of the mass ratio of material I. Ferment and culture at 35°C and 200r / min for 3 days to obtain material II. The COD utilization rate of material II reaches 70%, the TP consumption rate reaches 78%, the TN consumption rate is 27%, and the NH3 + The consumption rate of -N was 27%, and the lactic acid production was about 46g / L. In addition, the number of live lactic acid bacteria in the fermentation broth (7.2×10 8 (CFU / g)) and metal ion (Pb, Hg, Cd) concentrations can meet the standards of feed additives.

[0058] Example 3

[0059] The method for efficiently treating wastewater from liquor cellar bottom in a resource-efficient manner comprises the following steps:

[0060] 1) Pretreatment of liquor cellar wastewater: consistent with Example 1;

[0061] 2) Preparation of Bacillus amyloliquefaciens bacterial solution: the same as in Example 1;

[0062] 3) Preparation of lactic acid bacteria liquid: Take two 250 ml conical flasks, measure 250 ml of MRS liquid culture medium respectively and place them therein, add 1.5 ml of Lactobacillus plantarum and Lactobacillus acidophilus respectively to the two conical flasks, seal the mouths of the conical flasks with sterile sealing films to ensure anaerobic state and minimize the influence of other bacteria, put them into a shaker and set the temperature to 37 ° C, ferment for 20 h, and shake at a speed of 50 r / min to obtain the two lactic acid bacteria liquids after activation, which are stored in a -2 ° C refrigerator.

[0063] 4) Fermentation of liquor cellar wastewater: First, inoculate the 0.1% amyloliquefaciens solution prepared in step 2) into a 250mL conical flask containing the solution treated in step 1), and ferment at 37°C and 180r / min to obtain material I with a pH of 6.8; secondly, after an interval of 2h, add the plant lactobacillus and acidophilus solutions prepared in step 3) to material I in a mass ratio of 1:1, and the total inoculation amount of the two solutions is 5% of the mass ratio of material I, and ferment and culture at 37°C and 100r / min for 4 days to obtain material II. The COD utilization rate in material II reaches 65%, the TP consumption rate reaches 76%, the TN consumption rate is 25%, and the NH3 + The consumption rate of -N was 23%, and the lactic acid production was about 43g / L. In addition, the number of live lactic acid bacteria in the fermentation broth (1.4×10 8 (CFU / g)) and metal ion (Pb, Hg, Cd) concentrations can meet the standards of feed additives.

[0064] Example 4

[0065] The method for efficiently treating wastewater from liquor cellar bottom in a resource-efficient manner comprises the following steps:

[0066] 1) Pretreatment of liquor cellar wastewater: Photocatalysis (catalytic conditions: graphite phase carbon nitride g-C3N4: dosage 5g / L, reaction time 1.5h, reaction temperature 45°C) was used to remove the refractory organic matter and toxic substances such as tannin in the wastewater; then 5% alkaline regulator ammonium carbonate was added to the liquor cellar wastewater, stirred evenly, and allowed to stand for 10 minutes. The pH of the liquor cellar wastewater was measured to be 6.90;

[0067] 2) Preparation of Bacillus amyloliquefaciens bacterial solution: the same as in Example 1;

[0068] 3) Preparation of lactic acid bacteria liquid: Take a 150 mL conical flask, measure 150 mL of MRS liquid culture medium and place it therein, add 1.0 mL of Bifidobacterium bifidum liquid, seal the mouth of the conical flask with a sterile sealing film to ensure anaerobic state and minimize the influence of other bacteria, put it in a shaker and set the temperature to 32°C, ferment for 30 h, and shake at a speed of 200 r / min to obtain the activated lactic acid bacteria liquid, which is stored in a -2°C refrigerator.

[0069] 4) Fermentation of liquor cellar wastewater: First, inoculate the 0.08% amyloliquefaciens solution prepared in step 2) into a 150mL conical flask containing the wastewater treated in step 1), and shake and ferment at 34°C and 150r / min to obtain material I with a pH of 6.6; secondly, after an interval of 2h, add the 5% Bifidobacterium bifidum solution prepared in step 3) to material I, and ferment and culture at 36°C and 170r / min for 4d to obtain material II. The COD utilization rate in material II reaches 67%, the TP consumption rate reaches 72%, the TN consumption rate is 21%, and the NH3 + The consumption rate of -N was 28%, and the lactic acid production was about 42 g / L. In addition, the number of live bacteria of Bifidobacterium bifidum in the fermentation broth (5.2×10 7 (CFU / g)), which does not meet the standards for feed additives.

[0070] Example 5

[0071] The method for efficiently treating wastewater from liquor cellar bottom in a resource-efficient manner comprises the following steps:

[0072] 1) Pretreatment of liquor cellar wastewater: Photocatalysis (catalytic conditions: graphene oxide: dosage 2 g / L, reaction time 1 h, reaction temperature 35 ° C) was used to remove the refractory organic matter and toxic substances such as tannin in the wastewater; then 3% alkaline regulator ammonium carbonate was added to the liquor cellar wastewater, stirred evenly, and allowed to stand for 10 min. The pH of the liquor cellar wastewater was measured to be 6.80;

[0073] 2) Preparation of Bacillus amyloliquefaciens bacterial solution: the same as in Example 1;

[0074] 3) Preparation of lactic acid bacteria liquid: Take a 250 mL conical flask, measure 250 mL of MRS liquid culture medium and place it therein, add 0.5 mL of Lactobacillus acidophilus liquid, seal the mouth of the conical flask with a sterile sealing film to ensure an anaerobic state and minimize the influence of other bacteria, put it in a shaker and set the temperature to 35°C, ferment for 25 h, and shake at a speed of 75 r / min to obtain the activated lactic acid bacteria liquid, which is stored in a -2°C refrigerator.

[0075] 4) Fermentation of liquor cellar wastewater: First, inoculate the 0.08% amyloliquefaciens solution prepared in step 2) into a 150mL conical flask containing the solution treated in step 1), and shake and ferment at 34°C and 150r / min to obtain material I with a pH of 6.7; secondly, after an interval of 2h, add the 3% Lactobacillus acidophilus solution prepared in step 3) to material I, and ferment and culture at 40°C and 150r / min for 2d to obtain material II. The COD utilization rate in material II reaches 72%, the TP consumption rate reaches 78%, the TN consumption rate is 27%, and the NH3 +The consumption rate of -N was 26%, and the lactic acid production was about 46g / L. In addition, the number of live Lactobacillus acidophilus in the fermentation broth (8.6×10 8 (CFU / g)) and metal ion (Pb, Hg, Cd) concentrations can meet the standards of feed additives.

[0076] Comparative Example 1

[0077] Same as Example 1, except that the alkaline regulator added in step 1) is sodium hydroxide.

[0078] The COD utilization rate in material II reaches 61%, the TP consumption rate reaches 67%, the TN consumption rate is 20%, and the NH3 + The consumption rate of -N was 17%, and the lactic acid production was about 34g / L. In addition, the number of live Lactobacillus acidophilus in the fermentation broth (3.8×10 7 (CFU / g)), which does not meet the standards for feed additives.

[0079] Comparative Example 2

[0080] The same as Example 1, except that the alkaline regulator added in step 1) is calcium carbonate.

[0081] The COD utilization rate in material II reaches 57%, the TP consumption rate reaches 62%, the TN consumption rate is 17%, and the NH3 + The consumption rate of -N was 15%, and the lactic acid production was about 31g / L. In addition, the number of live Lactobacillus acidophilus in the fermentation broth (8.1×10 6 (CFU / g)), which does not meet the standards for feed additives.

[0082] Comparative Example 3

[0083] The same as Example 1, except that in step 4), the Lactobacillus acidophilus bacterial solution is added first, and then the Bacillus amyloliquefaciens bacterial solution is added.

[0084] The COD utilization rate in material II reaches 67%, the TP consumption rate reaches 73%, the TN consumption rate is 25%, and the NH3 + The consumption rate of -N was 21%, and the lactic acid production was about 45g / L. In addition, the number of live Lactobacillus acidophilus in the fermentation broth (1.1×10 8 (CFU / g)) and metal ion (Pb, Hg, Cd) concentrations can meet the standards of feed additives.

[0085] Comparative Example 4

[0086] Same as Example 1, except that Bacillus amyloliquefaciens is not added, the lactic acid bacteria are Lactobacillus plantarum, Lactobacillus bulgaricus and Bifidobacterium bifidum (mass ratio is 1:2:3), and the total inoculation amount of the three bacterial liquids is 2% of the mass ratio of the wastewater treated in step 1).

[0087] After fermentation, the COD utilization rate in the wastewater reaches 63%, the TP consumption rate reaches 69%, the TN consumption rate reaches 22%, and the NH3 + The consumption rate of -N was 18%, and the lactic acid production was about 39g / L. In addition, the number of live lactic acid bacteria in the fermentation broth (7.4×10 7 (CFU / g)), which does not meet the standards for feed additives.

Claims

1. A method for treating wastewater from liquor cellars, characterized in that: The following steps are involved: 1) taking wastewater from the bottom of a liquor cellar, and pre-treating it to obtain pre-treated wastewater; 2) adjusting the pH of the pretreated wastewater to neutral to obtain neutral wastewater; 3) taking a Bacillus amyloliquefaciens bacterial liquid and inoculating it into LB liquid culture medium for activation culture to obtain an activated Bacillus amyloliquefaciens liquid; 4) taking the lactic acid bacteria liquid and inoculating it into the MRS liquid culture medium for activation culture to obtain the lactic acid bacteria activation liquid; 5) taking the activated Bacillus amyloliquefaciens solution of step 3), inoculating it into the neutral wastewater of step 2), and fermenting it to obtain material I; 6) Taking the activated lactic acid bacteria liquid of step 4), inoculating it into the material I of step 5), fermenting to obtain material II, and the treatment is completed.

2. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: Step 1) The pH of the wastewater from the liquor cellar is 3-5, and the COD is greater than 1.5×10 5 mg / L, TN is 1×10 3 -3×10 3 mg / L, TP is 4×10 3 -6×10 3 mg / L.

3. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: The pretreatment in step 1) is a photocatalytic treatment, and the photocatalyst used in the photocatalytic treatment is any one or more of titanium dioxide, graphite carbon nitride, and graphene oxide, wherein the addition amount of titanium dioxide is 0.2-0.5 g / L, the addition amount of graphite carbon nitride is 0.1-5 g / L, and the addition amount of graphene oxide is 0.1-5 g / L. The photocatalytic treatment time is 0.5-3 h and the temperature is 30-50 ° C.

4. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: Step 2) using an ammonium carbonate solution to adjust the pH, the concentration of the ammonium carbonate solution is 1-3 wt%.

5. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: Step 3) LB liquid culture medium is an aqueous solution of tryptone, yeast extract, and sodium chloride, with contents of 10 g / L, 5 g / L, and 10 g / L, respectively, and a pH value of 7.0-7.

2.

6. The method for treating liquor cellar wastewater according to claim 1 or 5, characterized in that: Step 3) Inoculate in a sterile environment, inoculate 0.5-1.5 mL of Bacillus amyloliquefaciens culture liquid into 150-250 mL of LB liquid culture medium, and activate the culture by shaking at 100-200 r / min at 30-40° C. for 20-30 hours.

7. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: Step 4) MRS liquid culture medium is an aqueous solution of peptone, beef extract, yeast extract, glucose, dipotassium hydrogen phosphate, triammonium citrate, sodium acetate, Tween-80, magnesium sulfate, and manganese sulfate, with contents of 10 g / L, 5 g / L, 4 g / L, 20 g / L, 2 g / L, 2 g / L, 5 g / L, 1 mL / L, 0.2 g / L, and 0.05 g / L, respectively, and a pH value of 6.2-6.

4.

8. The method for treating liquor cellar wastewater according to claim 1 or 7, characterized in that: Step 4) inoculating under anaerobic and aseptic conditions, wherein the lactic acid bacteria are one or more of Lactobacillus plantarum, Lactobacillus bulgaricus, Lactobacillus acidophilus, and Bifidobacterium bifidum, and 0.5-1.5 mL of the lactic acid bacteria liquid is inoculated into 150-250 mL of MRS liquid culture medium, and the activation culture is performed at 35-40° C. and the activation is performed on a shaker at 50-100 r / min for 20-30 h.

9. The method for treating wastewater from liquor cellars according to claim 1, characterized in that: Step 5) The amount of Bacillus amyloliquefaciens activated liquid added to the neutral wastewater is 0.04-0.4wt%, and the fermentation is carried out on a shaker at 100-200r / min at 30-40°C. Step 6) The amount of lactic acid bacteria liquid added to material I is 0.5-5wt%, and the fermentation is carried out on a shaker at 100-200r / min at 30-40°C.

10. Use of the material II according to claim 1 as a feed additive.