A method and system for treating distiller's grains

Abstract

The present invention relates to a method for treating vinasse, wherein dilute acid is added to vinasse until the pH range of the vinasse is 0.5-1 for acid hydrolysis, and a first filtrate and residual dregs after acid hydrolysis are obtained; dilute alkali is added to the residual dregs after acid hydrolysis until the pH range of the residual dregs after acid hydrolysis is 11-12 for alkaline hydrolysis, and a second filtrate and residual dregs after alkaline hydrolysis are obtained; the residual dregs after alkaline hydrolysis are enzymatically hydrolyzed to obtain a third filtrate and residual dregs after enzymatic hydrolysis; and total sugar solution is obtained: the first filtrate, the second filtrate and the third filtrate are mixed. Different from the single acid hydrolysis, alkaline hydrolysis, steam explosion and other methods for treating vinasse commonly used in the prior art, the present invention is directed to winemaking waste dregs with a water content of 50-60%, and is treated in an acid-base-enzyme combined manner. The treatment method for winemaking waste dregs has mild conditions (no need to set up high pressure or high temperature control equipment additionally), few by-products such as furfural, low cost, and easy process control.

Description

Technical Field

[0001] The invention relates to the technical field of distiller's grains fermentation, and in particular to a distiller's grains processing method and system. Background Art

[0002] Wine lees are the main waste from liquor brewing. According to the solid-state liquor production process, about 3 tons of lees are produced for 1 ton of liquor. The most promising high-value utilization method of lees is to enzymatically hydrolyze the waste wine lees and then ferment them into high-value-added products.

[0003] During the winemaking process, under the fermentation of a large number of microorganisms, the starch of the winemaking raw materials is degraded and consumed in large quantities, and the protein, fat, cellulose, minerals and other components contained in it are retained while generating alcohol, ester, acid, ketone and other substances. The water content of winemaking waste is as high as 50%-60%, the pH is about 4, and it is rich in nutrients. After drying, it generally contains 8%-12% starch, 10%-12% protein, 3%-5% fat, 30%-35% cellulose, 15%-20% hemicellulose and about 6% ash. The total amount of carbohydrates including starch, hemicellulose and cellulose is 55%-60%, which has a high utilization value.

[0004] In the prior art, there are more and more ways to treat wine lees, and common methods include adding it as feed and using it in fertilizer production. However, since wine lees contain a high amount of free lactic acid and acetic acid, it is easy to become moldy and rancid during storage, causing fungal poisoning in livestock and poultry and inducing other diseases. In addition, it also has the disadvantages of limited addition amount and difficulty in transportation. These disadvantages greatly limit the application of wine lees as feed addition and fertilizer production.

[0005] In the existing technology, many scholars have carried out research on high-temperature pyrolysis gasification of grains and utilization of biochar. Although the pyrolysis gas has a high energy utilization value, it can only barely meet the energy demand of grains drying with a water content of 60% and other links. In addition, the nitrogen and sulfur oxides in the cracking gas need to be specially treated, which does not have significant economic benefits.

[0006] Acid hydrolysis is a widely used method for hydrolyzing wood fiber. It has the advantages of high efficiency, low cost and simple operation, but it has high requirements on equipment materials and is prone to produce fermentation inhibitors such as furfural. Acid hydrolysis is divided into two methods: dilute acid hydrolysis and concentrated acid hydrolysis. Dilute acid hydrolysis is the earliest method for hydrolyzing wood fiber. Generally, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc. are used as catalysts. The acid concentration of dilute acid hydrolysis is generally 0.4-10%. It needs to be carried out under high temperature and high pressure conditions. Wood fiber is heated to 100 °C. +Catalytic degradation produces fermentable sugars such as hexose and pentose. Dilute acid hydrolysis can be completed at high temperature (180℃-240℃), high pressure and short time (1-10min), or at slightly lower temperature (100℃-140℃) and long time (30-120min). Hemicellulose is easier to hydrolyze than cellulose, and the pentose produced is more easily hydrolyzed at high temperature and H + Under the action of 2% HCl, side reactions occur to produce fermentation inhibitors such as furfural, 5-hydroxymethylfurfural (HMF) and levulinic acid (LA). Therefore, the dilute acid method often uses a two-step process to reduce the further degradation of sugar in the sugar production process and increase the production of sugar. Tan Li et al. investigated the two-step dilute acid hydrolysis of liquor waste using dilute hydrochloric acid as a catalyst. The optimal solid-liquid ratio was 1:8. The first step of acid hydrolysis was hydrolyzed with 1% dilute hydrochloric acid at 120°C for 0.5h, and the second step was hydrolyzed with 2% dilute hydrochloric acid at 120°C for 3h. Under this condition, the reducing sugar yield was 0.34g / g (dry waste). Liu Gaomei et al. studied the effect of preparing HCl and H with the same mass concentration on the reducing sugar yield. 3 PO 4 The process of preparing xylose by mixed acid hydrolysis of liquor waste was 61.24% at a temperature of 110°C, a solid-liquid ratio of 1:12, a mixed acid concentration of 1.5%, and a time of 145 min. Liu Yuehong et al. studied the preparation of degradable sugar by degrading liquor waste with concentrated sulfuric acid. Using 70% (m / m) H 2 SO 4 , solid-liquid ratio 7:5, gelatinize for 30 minutes, add water to dilute H 2 SO 4 The concentration was 22% (m / m), and the degradation rate of dry waste grains could reach 0.35 g / g after hydrolysis at 85 °C for 1 h. Ren Haiwei et al. used reducing sugar concentration and furfural production as indicators to explore the effect of preparing HCl and H with the same mass concentration. 3 PO 4 Effect of mixed acid on hydrolysis of liquor lees: temperature 100℃, solid-liquid ratio 1:12, mixed acid concentration 2.5%, time 120min, reducing sugar 59.32g / L can be obtained, and the inhibitor furfural production is only 8.37g / L. Furfural inhibitors can significantly inhibit the growth of microorganisms when the concentration is higher than 1g / L. In the past decade, the adaptability of fermentation fungi to furfural has increased, and the tolerance of bacteria to furfural has also increased. When the furfural concentration is greater than 0.6g / L, many fungi can also tolerate it, such as hydrogen-producing microorganisms (yeast C.saccharolyticus and T.neapolitana), alcohol-producing microorganisms (Saccharomyces cerevisiae, Pichia stipitis and Zymomonas mobilis), but the furfural concentration should be avoided to be higher than 1g / L.

[0007] Enzymatic hydrolysis has mild conditions, low energy consumption, and low equipment requirements, but it has the disadvantages of high enzyme production costs and slow reaction rates. Enzymatic hydrolysis refers to the process of converting biomass into fermentable sugars using enzymes produced by microorganisms. Enzymatic hydrolysis is a biological process with the characteristics of mild conditions, strong specificity, and environmental friendliness. Cellulase is composed of three complex enzymes, including endoglucanase (EG), cellobiohydrolase (CBH), and β-glucosidase (BG). The three enzymes each have enzyme specificity, but have good synergistic effects with each other. Before enzymatic hydrolysis, pretreatment is often required to break the complex structure of lignin-polysaccharide polymers, change their physicochemical properties, overcome the anti-degradation barrier, and increase the accessibility of polysaccharides to enzymes, thereby improving the efficiency of polysaccharides converted into monosaccharides for subsequent fermentation. Cheng Chi et al. studied the effect of composite bacteria producing cellulase on liquor spent grains. Compared with single strains, the composite bacterial system composed of four bacteria had significantly improved the hydrolysis ability and carboxymethyl cellulase activity of spent grains, reaching 37.54% and 41.30U, which were 15.87% and 15.20U higher than the optimal single bacteria fermentation. Chen Zhe et al. pretreated brewing grains with NaOH-peracetic acid and used a multi-enzyme combination to hydrolyze the pretreated dry grains. Based on cellulase NS22086, they supplemented with complex enzymes NS22119, NS22002, β-glucosidase NS22118, xylanase NS22083 and glucoamylase NS22035. After 48 hours of saccharification and hydrolysis, the reducing sugar concentration, glucose and xylose concentrations in the hydrolyzate were 107.30 g / L, 57.44 g / L and 16.53 g / L, respectively. At this time, the total sugar, glucose and xylose yields were 659.13 mg / g, 317.22 mg / g and 96.01 mg / g, respectively (dry grains after pretreatment). Yang Jian et al. studied the effect of NaOH pretreatment on the cellulose degradation of liquor lees. After 48 hours of cellulase saccharification, the concentrations of reducing sugar, glucose and xylose in the hydrolyzate of the treated liquor lees reached 91.33 g / L, 61.72 g / L and 13.88 g / L, respectively, and the corresponding sugar yields were 565.41 mg / g, 379.44 mg / g and 84.55 mg / g (dry lees after pretreatment). Ren Haiwei et al. studied the effects of four pretreatment methods, namely acid-ultrasonic coupling, liquid ammonia, alkaline hydrogen peroxide and acidic bisulfite, on the cellulose retention, hemicellulose and lignin removal, structural characteristics and enzymatic hydrolysis yield of wine lees. The study showed that the use of H 2 SO 4 Dosage 0.2%, NaHSO 3The cellulose and hemicellulose retention rates in wine lees were the highest at 3% dosage, 1:3 (g / ml) solid-liquid ratio, 130℃, and 20 minutes of treatment, which were 84.59% and 84.87% respectively; the cellulose enzymatic hydrolysis yields of the four pretreatment methods increased by 49.12% (acid-ultrasound), 55.48% (liquid ammonia), 92.79% (alkaline hydrogen peroxide) and 99.15% (acidic bisulfite). SEM and XRD showed that the surface structure of wine lees changed significantly after different pretreatments, the network structure was destroyed, the surface showed irregular or different shapes of puffy state, the grooves were obvious, the porosity increased, the specific surface area increased, which was conducive to improving the activity of hydrolytic enzymes. Yang Jian et al. studied the pretreatment of wine lees by NaOH-peracetic acid and prepared fermentable sugar solution by cellulase hydrolysis. When the NaOH concentration was 1%, the solid-liquid ratio was 1:10, the time was 60min, and the temperature was 75℃, the mass concentrations of reducing sugar, glucose and xylose in the enzymatic hydrolyzate reached 91.33g / L, 61.72g / L, and 13.88g / L, and the corresponding sugar yields were 565.41mg / g, 379.44mg / g and 84.55mg / g, respectively, which was 2 times higher than the direct enzymatic saccharification concentration and yield. Chen Zhe et al. investigated the NaOH-peracetic acid combined pretreatment of liquor waste. Under the conditions of peracetic acid concentration of 2%, solid-liquid ratio of 1:8, temperature of 85℃, and time of 90min, 96.20% of cellulose in the waste was retained and 71.90% of lignin was removed. Wang Lizhi investigated the effects of different combinations of temperature (37℃, 38℃, 39℃), time (8d, 9d, 10d), water content (55%, 60%, 65%) and inoculation amount (10%, 20%, 30% by V / W) on the degradation of lignin in white wine lees by Phanerochaete chrysosporium in the article "Factors affecting the degradation of lignin in white wine lees by Phanerochaete chrysosporium". The study showed that when the inoculation amount was 10%, the water content was 60%, and the fermentation was carried out at 39℃ for 10d, the degradation rate of lignin in white wine lees could reach 5.93%; the order of the influence of the four factors on the degradation of lignin in white wine lees by Phanerochaete chrysosporium was: time>water content>inoculation amount; the optimal fermentation combination under the experimental conditions was: time of 10d, inoculation amount of 10%, temperature of 38℃, and water content of 65%. Zhang Xichao et al. investigated the effects of different pretreatment methods on the degradation and structural changes of liquor waste grains. 2 SO 4 , NaOH and H 2 O 2 ), physical methods (microwave and ultrasound) and biological methods (Trichoderma viride, Phanerochaete chrysosporium and Aspergillus oryzae) were used to treat liquor waste. The results showed that chemical treatment reduced the hemicellulose content, of which 30% H 2 SO 4The treatment removed all hemicellulose, while the cellulose content continued to increase; microwave treatment reduced the lignin content, and the cellulose content first increased and then decreased; the treatment with Phanerochaete chrysosporium reduced the lignin content from 27.71% to 15.27%, while the treatment with Trichoderma viride and Aspergillus oryzae continued to increase the lignin content. The highest specific surface area of ​​the chemical and microwave treatment waste was 32.13-36.85m 2 With the increase of solvent concentration, the crystallinity of chemically treated fiber continued to increase. 2 SO 4 , 25% NaOH and 10% H 2 O 2 The crystallinity of the fiber tended to be stable during treatment; the crystallinity of the fiber decreased from 27.52% to 23.45% after ultrasonic treatment, while it increased to 37.03% after microwave treatment; the crystallinity of the fiber increased first and then decreased after the treatment with Trichoderma viride and Aspergillus oryzae, and continued to increase after the treatment with Phanerochaete chrysosporium.

[0008] Traditional pretreatment of wine lees before enzymatic hydrolysis often uses single acid hydrolysis, alkaline hydrolysis, steam explosion and other methods. However, in order to achieve good treatment effects, the pretreatment reaction conditions are often drastic and difficult to control, and the equipment investment and chemical dosage are large, resulting in high costs. Acid-enzyme combined hydrolysis can fully utilize the advantages of the two hydrolysis methods, improve the hydrolysis effect, avoid the loss of reducing sugars caused by the pretreatment process before enzymatic hydrolysis of wine lees, and reduce the formation of fermentation inhibitors. Ren Haiwei et al. conducted a study on the acid-enzyme combined hydrolysis and saccharification of liquor lees. The results showed that the acid-enzyme combined hydrolysis and saccharification of liquor lees were saccharified at a temperature of 100°C, a solid-liquid ratio of 1:12, and a mixed acid (HCl and H 3 PO 4 Under the conditions of 2.0% concentration and 120min of preparation with the same mass concentration, 59.32g / L reducing sugar and 6.49g / L xylose can be obtained. The solid content analysis shows that the mass fraction of cellulose is reduced from 33.6% to 12.6%, the mass fraction of hemicellulose is reduced from 8.4% to 1.8%, and the mass fraction of lignin is reduced from 22.2% to 12.6%. The residue after acid hydrolysis is enzymatically hydrolyzed. Under the conditions of 4000U / g enzyme, 45℃, pH value 4.8 and 2.5h, 13.27g / L reducing sugar can be obtained. The mass fractions of cellulose, hemicellulose and lignin in the residue are 10.53%, 1.61% and 12.23% respectively. The cellulose conversion rate in the enzymatic hydrolysis stage is 44.45%, and the enzymatic hydrolysis rate reaches 90.73%.

[0009] At the same time, a Chinese patent with patent publication number CN105256081B discloses a method for preparing xylose using liquor lees. The invention method includes pretreatment of liquor lees, acid hydrolysis of liquor lees, alkaline hydrolysis of liquor lees, adjustment of filtrate pH, low-temperature enzymatic hydrolysis, neutralization treatment, activated carbon decolorization, decolorization liquid impurity removal, ultrafiltration and nanofiltration, and concentration and drying steps. The present invention comprehensively utilizes cellulose substances in liquor lees, can process and convert hemicellulose in liquor lees into xylose, obtains xylose products with high market value, effectively manages liquor lees in liquor production, and effectively utilizes solid waste materials in the production process of liquor enterprises.

[0010] However, based on the research on the efficient decomposition of vinasse by alkaline hydrolysis, acid hydrolysis or enzymatic hydrolysis, most of the existing technologies achieve the purpose of improving efficiency through a simple stacking hydrolysis step. Based on this, the present invention provides a method for treating vinasse, which adopts acid-base-enzyme combined enzymatic hydrolysis, combines the advantages of acid hydrolysis, alkaline hydrolysis and enzymatic hydrolysis, and achieves the purpose of efficiently recovering sugar from vinasse and enriching the nitrogen source in the residual dregs.

[0011] In addition, on the one hand, there are differences in understanding among those skilled in the art; on the other hand, the applicant studied a large number of documents and patents when making the present invention, but due to space limitations, not all details and contents are listed in detail. However, this does not mean that the present invention does not have the characteristics of these prior arts. On the contrary, the present invention already has all the characteristics of the prior art, and the applicant reserves the right to add relevant prior art to the background technology. Summary of the invention

[0012] The present invention provides a method for treating distiller's grains, which at least comprises the following steps:

[0013] Add dilute acid to the lees until the pH of the lees is in the range of 0.5-1 for acid hydrolysis, and obtain a first filtrate and residual lees after acid hydrolysis; add dilute alkali to the residual lees after acid hydrolysis until the pH of the residual lees after acid hydrolysis is in the range of 11-12 for alkaline hydrolysis, and obtain a second filtrate and residual lees after alkaline hydrolysis; enzymatically hydrolyze the residual lees after alkaline hydrolysis, and obtain a third filtrate and residual lees after enzymatic hydrolysis; obtain a total sugar solution by mixing the first filtrate, the second filtrate and the third filtrate; obtain a total sugar solution by mixing the first filtrate, the second filtrate and the third filtrate.

[0014] According to a preferred embodiment, a dilute acid with a mass fraction of 0.5%-4% is added to the lees, and the solid-liquid ratio of the lees to the dilute acid is 1:3-8, so that the pH range of the lees is 0.5-1. Preferably, the mass fraction of the dilute acid is 1.5%, and the solid-liquid ratio of the lees to the dilute acid solution is 1:6. Preferably, the dilute acid is dilute sulfuric acid.

[0015] According to a preferred embodiment, a dilute alkali having a mass fraction of 3% to 20% is added to the residual grains after acid hydrolysis, and the solid-liquid ratio of the grains to the dilute alkali is 1:4-8, so that the pH range of the grains is 11-12. Preferably, the mass fraction of the ammonia water is 12%, and the solid-liquid ratio of the grains to the ammonia solution is 1:6. Preferably, the dilute alkali is ammonia water.

[0016] According to a preferred embodiment, a dilute acid with a mass fraction of 0.5%-4% is added to the lees for acid hydrolysis, and the solid-liquid ratio of the lees to the dilute acid solution is 1:3-8, so as to obtain a first filtrate and residual lees after acid hydrolysis; an ammonia solution with a mass fraction of 3%-20% is added to the residual lees after acid hydrolysis for alkaline hydrolysis, and the solid-liquid ratio of the lees to the ammonia solution is 1:4-8, so as to obtain a second filtrate and residual lees after alkaline hydrolysis; the residual lees after alkaline hydrolysis is enzymatically hydrolyzed to obtain a third filtrate and residual lees after enzymatic hydrolysis; and the total sugar solution is obtained by mixing the first filtrate, the second filtrate and the third filtrate.

[0017] In the process of acid-base-enzyme combined treatment, the present application unexpectedly found that the combination of dilute sulfuric acid, ammonia water and cellulase in the treatment process can specifically increase the reducing sugar yield of vinasse. In particular, the vinasse treatment with the content ratio disclosed in Example 1 of the present application can make the reducing sugar yield reach 512 mg / g.

[0018] According to a preferred embodiment, the enzyme used in the enzymatic hydrolysis comprises at least cellulase.

[0019] According to a preferred embodiment, obtaining the first filtrate further comprises the following step: mechanically filtering the vinasse treated under acidic conditions.

[0020] According to a preferred embodiment, obtaining the second filtrate further comprises the following step: mechanically filtering the vinasse treated under alkaline conditions.

[0021] The lees or winemaking lees involved in the present invention refer to the lees formed in the solid-state liquor brewing production process.

[0022] The present invention provides a method for treating vinasse, such as Figure 1 The processing method includes at least the following steps:

[0023] directly adding dilute sulfuric acid to the waste dregs, and subjecting the waste dregs mixed with the dilute sulfuric acid to acid hydrolysis under the first reaction conditions;

[0024] Mechanical filtration to collect the acid hydrolyzed sugar solution;

[0025] Ammonia solution is added to the acid hydrolysis residue to perform alkaline hydrolysis under the second reaction condition;

[0026] Mechanical filtration to collect alkaline hydrolyzed sugar solution;

[0027] Adding cellulase to the alkaline hydrolysis residue to perform enzymolysis under the third reaction condition;

[0028] Mechanical filtration, collection of enzymatic sugar solution, and subsequent treatment of residual dregs;

[0029] The acid hydrolysis sugar solution, alkaline hydrolysis sugar solution and enzymatic hydrolysis sugar solution are mixed to obtain the total sugar solution.

[0030] According to a preferred embodiment, the first reaction condition comprises a reaction temperature of 90-120°C. Preferably, the reaction temperature is 100-110°C. Particularly preferably, the reaction temperature is 100°C. The reaction temperature is 105°C. The reaction temperature is 110°C.

[0031] According to a preferred embodiment, the first reaction condition comprises a reaction time of 30-120 min. Preferably, the reaction time is 45-90 min. Particularly preferably, the reaction time is 45 min. The reaction time is 60 min. The reaction time is 90 min.

[0032] According to a preferred embodiment, the first reaction condition comprises a solid-liquid ratio of brewing lees mass (water content 50-60%) / dilute acid solution volume. The solid-liquid ratio is 1:3-8. Preferably, the solid-liquid ratio is 1:4-6. Particularly preferably, the solid-liquid ratio is 1:4. The solid-liquid ratio is 1:6.

[0033] According to a preferred embodiment, the dilute sulfuric acid added to the dregs during acidolysis can be a dilute sulfuric acid with a mass fraction of 0.5%-4%. Preferably, the dilute sulfuric acid added to the dregs during acidolysis can be a dilute sulfuric acid with a mass fraction of 0.75%-2%. Particularly preferably, the dilute sulfuric acid added to the dregs during acidolysis can be a dilute sulfuric acid with a mass fraction of 0.75%. The dilute sulfuric acid added to the dregs during acidolysis can be a dilute sulfuric acid with a mass fraction of 2%. The dilute sulfuric acid added to the dregs during acidolysis can be a dilute sulfuric acid with a mass fraction of 1.5%.

[0034] According to a preferred embodiment, the second reaction condition comprises a reaction temperature of 60-100°C. Preferably, the reaction temperature is 75-90°C. Particularly preferably, the reaction temperature is 85°C. The reaction temperature is 90°C. The reaction temperature is 75°C.

[0035] According to a preferred embodiment, the second reaction condition comprises a reaction time of 50-100 min. Preferably, the reaction time is 60-90 min. Particularly preferably, the reaction time is 75 min. The reaction time is 90 min. The reaction time is 60 min.

[0036] According to a preferred embodiment, the second reaction condition comprises a solid-liquid ratio of the mass of wine lees (water content 50-60%) / volume of dilute alkali solution. The solid-liquid ratio is 1:4-8. Preferably, the solid-liquid ratio is 1:5-7. Particularly preferably, the solid-liquid ratio is 1:6. The solid-liquid ratio is 1:5. The solid-liquid ratio is 1:7.

[0037] According to a preferred embodiment, the diluted alkali added to the spent grains during alkaline hydrolysis can be ammonia water with a mass fraction of 3%-20%. Preferably, the diluted alkali added to the spent grains during alkaline hydrolysis can be ammonia water with a mass fraction of 5%-15%. Particularly preferably, the diluted alkali added to the spent grains during alkaline hydrolysis can be ammonia water with a mass fraction of 5%. The diluted alkali added to the spent grains during alkaline hydrolysis can be ammonia water with a mass fraction of 12%. The diluted alkali added to the spent grains during alkaline hydrolysis can be ammonia water with a mass fraction of 15%.

[0038] According to a preferred embodiment, the third reaction condition comprises a reaction temperature of 45-60°C. Preferably, the reaction temperature is 45-50°C. Particularly preferably, the reaction temperature is 50°C. The reaction temperature is 45°C. The reaction temperature is 48°C.

[0039] According to a preferred embodiment, the third reaction condition comprises a reaction time of 12-84 hours. Preferably, the reaction time is 24-72 hours. Particularly preferably, the reaction time is 24 hours. The reaction time is 48 hours. The reaction time is 72 hours.

[0040] According to a preferred embodiment, the third reaction condition comprises a solid-liquid ratio of brewing grains mass (water content 50-60%) / enzyme solution volume. The solid-liquid ratio is 1:4-8. Preferably, the solid-liquid ratio is 1:5-7. Particularly preferably, the solid-liquid ratio is 1:6. The solid-liquid ratio is 1:5. The solid-liquid ratio is 1:7.

[0041] According to a preferred embodiment, the third reaction condition comprises a pH of 4-6. Preferably, the pH is between 4.8-5.2. Particularly preferably, the pH is 4.8. The pH is 5.0. The pH is 5.2.

[0042] According to a preferred embodiment, the third reaction condition comprises that the filter paper enzyme activity (FPU) of the cellulase is between 5-10 IU / ml. Preferably, the filter paper enzyme activity of the cellulase is 10 IU / ml. The filter paper enzyme activity of the cellulase is 5 IU / ml.

[0043] According to a preferred embodiment, the third reaction condition comprises that the β-glucosidase activity of the cellulase is between 10-15 IU / ml. Preferably, the β-glucosidase activity of the cellulase is 15 IU / ml. The β-glucosidase activity of the cellulose is 12 IU / ml.

[0044] Beneficial effects of this technical solution:

[0045] 1. Different from the single acid hydrolysis, alkaline hydrolysis, steam explosion and other methods commonly used in the prior art to treat wine lees, the present invention uses an acid-base-enzyme combination method to treat wine lees with a water content of 50-60%. The treatment method for wine lees has mild conditions (no need to set up additional high-pressure or high-temperature control equipment), less by-products such as furfural, low cost, and easy process control.

[0046] Specifically, the maximum reaction intensity (acid concentration 2%, temperature 110°C, time 90 min) of this experiment is less than 1.2, and the furfural content is less than 1. Compared with the furfural concentration in the lees treatment products in the industry, the furfural concentration of the product in this application is reduced and is much lower than the furfural concentration under similar acid hydrolysis reaction conditions in the industry.

[0047] Aldehydes are byproducts produced during the fermentation of distiller's grains, especially when high concentrations of acid are used, the furfural content will increase significantly. Furfural is a type of substance that has adverse effects on humans or animals. When consumed in high amounts, it can cause symptoms such as dizziness and hypoxia.

[0048] Furfural can seriously inhibit the growth of microorganisms and the subsequent fermentation process, thus affecting the fermentation efficiency. According to the articles published by Liu et al in 2004, Martínet al in 2007, and Almeida et al in 2007, the adaptability of fermentation fungi to furfural has increased in the past decade, and the tolerance of bacteria to furfural has also increased. When the furfural concentration is greater than 0.6g / L, many fungi can also tolerate it, such as hydrogen-producing microorganisms (yeast C.saccharolyticus and T.neapolitana) and alcohol-producing microorganisms (Saccharomyces cerevisiae, Pichia stipitis, Zymomonas mobilis), but the furfural concentration still needs to be avoided above 1g / L.

[0049] According to existing research on the effect of furfural concentration on microbial fermentation, the furfural concentration produced in this experiment has little effect on subsequent microbial fermentation.

[0050] 2. Both acid hydrolysis and alkaline hydrolysis are carried out at a relatively low reaction intensity, without involving high temperature and high pressure. Under acid hydrolysis conditions, hemicellulose and starch can be fully hydrolyzed, and under alkaline conditions, the structure of lignin can be effectively destroyed, so that the cellulose in the lees after acid-base pretreatment (need to participate in the enzymatic reaction) is fully exposed, which is conducive to the improvement of subsequent enzymatic hydrolysis efficiency and saving the cost of the enzymatic hydrolysis process.

[0051] 3. In the pretreatment process, the acid hydrolysis and alkaline hydrolysis methods used in the prior art will cause the products after acid hydrolysis and alkaline hydrolysis to contain a large amount of harmful substances, and the recovered products of acid hydrolysis and alkaline hydrolysis are ignored. The present technical solution recovers the products of each hydrolysis step to reduce the loss of nutrients, and the products recovered by the hydrolysis method proposed in the present application will not produce toxic and harmful substances after mixing, which will cause the total sugar solution obtained after mixing to be unusable. At the same time, the recovered products after alkaline hydrolysis and acid hydrolysis involved in the present application not only contain sugar solution, but also contain some amino acid components (according to the test results, the protein content in the residue is 8%-12%), making the culture medium more nutritious.

[0052] 4. This application is based on the mixed treatment of the acid hydrolysis solution and the alkaline hydrolysis solution to neutralize each other. This treatment method reduces the input of chemical reagents and thus reduces the cost. 2 SO 4 The ammonium sulfate formed after neutralization with ammonia water can be used as a nitrogen source for the fermentation medium. Through the use of the sugar solution in the culture medium shown in the implementation case, it can be seen that the sugar solution obtained based on the above method has greatly reduced substances (such as furfural) that are not conducive to biological growth after neutralization, and can be directly used in industrial production without direct treatment.

[0053] 5. Compared with the reducing sugar yield of 400-470 mg / g in Examples 2-5, the present application found that the high yield of reducing sugar (512 mg / g) was unexpectedly obtained by treating the lees with the extraction conditions set in Example 1. Therefore, the process method involved in Example 1 can greatly improve the reducing sugar yield.

[0054] Preferably, the ammonium sulfate-rich sugar solution can be used for the production of ethanol and L-lactic acid fermentation.

[0055] The present invention provides a system for treating lees. The treatment system comprises an acid treatment module for mixing lees and dilute acid, an alkali treatment module for mixing lees and ammonia water, an enzymatic treatment module and a mixing tank for receiving the products obtained after the treatment. The enzymatic treatment module receives the residual lees after the acid treatment module and the alkali treatment module are treated, and provides enzymatic conditions for the residual lees, wherein the residual lees refers to the product obtained by separating the filtrate after the lees are treated with acid and alkali, wherein the acid treatment module obtains the first filtrate after the lees are treated with acid, the alkali treatment module obtains the second filtrate after the lees are treated with alkali, and the enzymatic treatment module obtains the third filtrate after the residual lees are treated with enzymes, and the mixing tank receives and mixes the first filtrate, the second filtrate and the third filtrate.

[0056] According to a preferred embodiment, the acid treatment module and the alkali treatment module at least partially collide to form a first heat exchange area, and the alkali treatment module and the enzymatic treatment module at least partially collide to form a second heat exchange area, wherein the first heat exchange area is arranged inside the second heat exchange area, so that the heat generated by the acid treatment described in the treatment method described in this application is transferred to the space where the alkali treatment or enzyme treatment with lower reaction temperature requirements than the acid treatment is located. Reaction temperature requirements refer to

[0057] Beneficial effects of this technical solution:

[0058] In the method for treating lees involved in the present application, the reaction temperature of acid hydrolysis is in the range of 90-120°C, the reaction temperature of alkaline hydrolysis is in the range of 60-100°C, and the reaction temperature of enzymatic hydrolysis is in the range of 45-60°C.

[0059] This also means that the waste heat generated during acid hydrolysis is higher, followed by the waste heat generated during alkaline hydrolysis. In actual production, a fermentation mode as shown in Implementation Case 4 is often adopted, that is, each fermentation tank is connected by a pipeline and has no influence on each other. At the same time, the material of the reaction device is generally metal with good thermal conductivity, which also means that the heat generated by acid hydrolysis or alkaline hydrolysis will be quickly transferred to the environment by the reaction device, but not used, resulting in more heat waste in the fermentation process.

[0060] This application designs a wine lees processing system that matches the wine lees processing method proposed in this application.

[0061] The present application separates the treatments of acid hydrolysis, alkaline hydrolysis and enzymatic hydrolysis so that the liquids obtained by filtration in each treatment process can be collected. At the same time, the devices used for treating acid hydrolysis, alkaline hydrolysis and enzymatic hydrolysis in the present application at least partially conflict with each other, thereby forming a heat transfer area, so that the waste heat generated by the acid hydrolysis with a higher reaction temperature is at least partially transferred to the alkaline hydrolysis device, so as to reduce the additional heat required in the alkaline hydrolysis process, thereby reducing the consumption of heat resources.

[0062] Similarly, since the reaction temperature of alkaline hydrolysis is higher than that of enzymatic hydrolysis, the waste heat generated by alkaline hydrolysis is at least partially transmitted to the enzymatic hydrolysis device to reduce the additional heat required during the enzymatic hydrolysis process, thereby reducing the consumption of heat resources.

[0063] Since the reaction temperature difference between acid hydrolysis and enzymatic hydrolysis is the largest and too high an enzymatic hydrolysis reaction temperature will lead to enzyme inactivation, the acid hydrolysis reaction device and the enzymatic hydrolysis reaction device will not be in direct contact, and the alkaline hydrolysis device is set between the two to form a temperature buffer, which can save resource consumption while ensuring the stability of the enzymatic hydrolysis environment.

[0064] According to a preferred embodiment, the second heat exchange area is provided with a heat exchanger plate, wherein, based on the heat transfer direction, the flow pipeline of the heat carrier of the heat exchanger plate is respectively provided with flow outlets in the acid treatment module, the alkali treatment module and the enzymatic treatment module, so that when the temperature of the alkali treatment module / enzymatic treatment module reaches a preset reaction temperature, the heat carrier flowing out of the acid treatment module can flow out from the opening of the acid treatment module / alkali treatment module.

[0065] Based on the heat transfer direction, the heat medium flow pipeline of the heat exchanger plate is provided with a double-port valve in the acid treatment module, so that the heat exchanger plate can control the flow path of the heat medium based on the heat demand of the alkali treatment module and / or the enzymatic treatment module. The flow path of the heat medium includes: from the acid treatment module to the alkali treatment module; from the acid treatment module to the alkali treatment module and the enzyme treatment module in sequence; from the acid treatment module to the alkali treatment module.

[0066] Beneficial effects of this technical solution:

[0067] In the lees processing method involved in this application, the reaction temperature of acid hydrolysis is in the range of 90-120°C, the reaction temperature of alkaline hydrolysis is in the range of 60-100°C, and the reaction temperature of enzymatic hydrolysis is in the range of 45-60°C. The temperature difference of the three treatments is quite different. In particular, when the reaction temperature of acid hydrolysis reaches 120°C, the sustainable heat output can reach 67.2KJ / L·s (taking water as an example). Even if it is partially reduced due to loss during the transmission process, the reaction temperature of alkaline hydrolysis will exceed the maximum threshold (100°C) of its reaction temperature range. For enzymatic hydrolysis, when the temperature exceeds 60°C, the enzyme in the enzyme treatment module will die on a large scale due to the high temperature, causing the enzymatic hydrolysis reaction to fail.

[0068] The technical solution sets a heat exchanger plate suitable for the treatment method involved in the present application in the second heat exchange area. The heat exchanger plate is arranged with a flow pipeline for guiding the flow of the heat medium, so that the heat medium can absorb heat from the acid treatment module with the highest temperature, and then flow through the alkaline treatment module and the enzymatic treatment module in sequence.

[0069] According to a preferred embodiment, the flow pipeline arranged in the acid treatment module is provided with a double-port valve connected to the flow pipelines arranged in the alkali treatment module and the enzymatic treatment module respectively, so that the heat carrier medium of the acid treatment module can flow directly from the acid treatment module to the enzymatic treatment module without passing through the alkali treatment module.

[0070] According to a preferred embodiment, the acid treatment module is arranged inside the alkali treatment module, and the alkali treatment module is arranged inside the enzymatic treatment module.

[0071] Beneficial effects of this technical solution:

[0072] 1. Increase the heat transfer area. This setting can provide the acid treatment module with the maximum area for heat dissipation to the alkali treatment module, thereby increasing the heat transfer effect. Similarly, this setting also provides the alkali treatment module with the maximum area for heat dissipation to the enzyme treatment module.

[0073] 2. Based on the processing flow involved in this application, reduce the complexity of pipeline arrangement, thereby reducing the valves that need to be operated. Since the three processing modules are interconnected, when treating the lees based on the processing method involved in this application, the acid treatment module is provided with a pipeline for receiving the lees and the enzyme treatment module is provided with a pipeline for discharging the treated lees. Only one-way discharge channels and valves need to be provided between different processing modules, so that the lees move from the inside to the outside in sequence and undergo acid hydrolysis, alkaline hydrolysis and enzymolysis respectively.

[0074] According to a preferred embodiment, the acid treatment module is connected to the alkali treatment module, so that the vinasse enters the alkali treatment unit for alkali hydrolysis after the acid treatment unit acid hydrolysis or enters the acid treatment unit for acid hydrolysis after the alkali treatment unit alkali hydrolysis. Preferably, since the time of enzymatic hydrolysis (24-72h) is longer than that of alkali hydrolysis (60-90min) and acid hydrolysis (45-90min), the space capacity of the enzymatic treatment module should be greater than the sum of the space capacities of the acid treatment module and the alkali treatment module, so that the vinasse treated with multiple acid treatments and alkali treatments can be accommodated by the alkali treatment module at the same time.

[0075] According to a preferred embodiment, the treatment system also includes a filtration module capable of performing solid-liquid separation on the products treated by the acid treatment module, the alkali treatment module or the enzymatic treatment module, wherein the filtration module includes a first filtration unit arranged between the acid treatment module and the alkali treatment module and a second filtration unit arranged between the alkali treatment module and the enzymatic treatment module. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 This is a processing flow chart of winemaking waste provided by the present invention;

[0077] Figure 2 is the furfural detection result provided by the present invention;

[0078] Figure 3 This is an implementation of the device for processing wine waste provided by the present invention;

[0079] Figure 4 It is an embodiment of the socket connection of the alkali treatment module, the acid treatment module and the enzyme treatment module provided by the present invention;

[0080] Figure 5 It is a double-layer plate diagram of the growth of lactic acid bacteria cultivated with hydrolyzed sugar solution rich in ammonium sulfate provided by the present invention;

[0081] Figure 6 This is a statistical chart of the lactic acid bacteria yield cultivated based on the hydrolyzed sugar solution rich in ammonium sulfate provided by the present application.

[0082] Reference numerals list

[0083] 100: acid treatment module; 200: alkali treatment module; 300: enzymatic treatment module; 400: filtration module; 500: mixing tank. DETAILED DESCRIPTION

[0084] The following is a detailed description with reference to the accompanying drawings.

[0085] Implementation Case 1

[0086] The invention provides a method for preparing sugar by utilizing winemaking waste.

[0087] The method comprises the following process steps:

[0088] (1) Pretreatment of winemaking waste

[0089] The water content of the wine spent grains is adjusted to 50-60% (water content by weight).

[0090] (2) Acid hydrolysis of winemaking waste

[0091] The pretreated wine-making spent grains were hydrolyzed in dilute sulfuric acid with a mass fraction of 1.5%, a solid-liquid ratio (mass of wine-making spent grains / volume of dilute acid solution, g / ml) of 1:6, an acid hydrolysis temperature of 110°C, and an acid hydrolysis time of 60 min.

[0092] (3) Filter

[0093] The acid hydrolysis residue and the first filtrate are obtained by filtration.

[0094] (4) Alkaline hydrolysis of the residue after acid hydrolysis

[0095] The residue after acid hydrolysis was hydrolyzed in the presence of 12% ammonia water, a solid-liquid ratio (mass of the residue after acid hydrolysis / volume of ammonia water solution, g / ml) of 1:6, an alkaline hydrolysis temperature of 85°C, and an alkaline hydrolysis time of 75 min.

[0096] (5) Filter

[0097] The residue after alkaline hydrolysis and the second filtrate are obtained by filtration.

[0098] (6) Enzymatic hydrolysis

[0099] The cellulase used in this implementation case is a strain with high filter paper enzyme activity screened in the laboratory in the early stage and a strain screened by alkaline hydrolysis of residual dregs, which is the same as the cellulase involved in the Chinese patent with publication number CN113621674B. The enzyme solution is a composite enzyme obtained from the laboratory or purchased by Novozymes.

[0100] The filter paper enzyme activity (FPU) of the cellulase solution is 10 IU / ml, and the β-glucosidase activity is 15 IU / ml.

[0101] The residue after alkaline hydrolysis was hydrolyzed in the presence of cellulase solution, reaction pH of 5.0, solid-liquid ratio (mass of residue after alkaline hydrolysis / volume of enzyme solution, g / ml) of 1:7, hydrolysis temperature of 50°C, and hydrolysis time of 48h.

[0102] (7) Filtering

[0103] Filtration was performed to obtain the residue and the third filtrate.

[0104] (8) Mixing

[0105] The first filtrate, the second filtrate and the third filtrate are mixed to obtain a total sugar solution.

[0106] Detect the reducing sugar content of the total sugar solution.

[0107] Experimental results:

[0108] The yield of total reducing sugars was 512 mg / g (60°C oven-dried distiller's grains).

[0109] Implementation Case 2

[0110] The invention provides a method for preparing sugar by utilizing winemaking waste.

[0111] The method comprises the following process steps:

[0112] (1) Pretreatment of winemaking waste

[0113] Adjust the water content of wine spent grains to 50-60%.

[0114] (2) Acid hydrolysis of winemaking waste

[0115] The pretreated wine lees were hydrolyzed in dilute sulfuric acid with a mass fraction of 0.75%, a solid-liquid ratio (mass of wine lees / volume of dilute acid solution, g / ml) of 1:6, an acid hydrolysis temperature of 110°C, and an acid hydrolysis time of 90 min.

[0116] (3) Filter

[0117] The acid hydrolysis residue and the first filtrate are obtained by filtration.

[0118] (4) Alkaline hydrolysis of the residue after acid hydrolysis

[0119] The residue after acid hydrolysis was hydrolyzed in the presence of 15% ammonia water by mass, a solid-liquid ratio (mass of the residue after acid hydrolysis / volume of ammonia water solution, g / ml) of 1:5, an alkaline hydrolysis temperature of 90° C., and an alkaline hydrolysis time of 90 min.

[0120] (5) Filter

[0121] The residue after alkaline hydrolysis and the second filtrate are obtained by filtration.

[0122] (6) Enzymatic hydrolysis

[0123] The cellulase used in this implementation case is a strain with high filter paper enzyme activity screened in the laboratory in the early stage and a strain screened by alkaline hydrolysis of residual dregs, which is the same as the cellulase involved in the Chinese patent with publication number CN113621674B. The enzyme solution is a composite enzyme obtained from the laboratory or purchased by Novozymes.

[0124] The filter paper enzyme activity (FPU) of the cellulase solution is 5 IU / ml, and the β-glucosidase activity is 10 IU / ml.

[0125] The residue after alkaline hydrolysis was hydrolyzed in the presence of cellulase solution, reaction pH of 5.2, solid-liquid ratio (mass of residue after alkaline hydrolysis / volume of enzyme solution, g / ml) of 1:5, hydrolysis temperature of 45°C, and hydrolysis time of 72h.

[0126] (7) Filter

[0127] Filtration was performed to obtain the residue and the third filtrate.

[0128] (8) Mixing

[0129] The first filtrate, the second filtrate and the third filtrate are mixed to obtain a total sugar solution.

[0130] Detect the reducing sugar content of the total sugar solution.

[0131] Experimental results:

[0132] The yield of total reducing sugars was 419 mg / g (dry grains).

[0133] Implementation Case 3

[0134] The invention provides a method for preparing sugar by utilizing winemaking waste.

[0135] The method comprises the following process steps:

[0136] (1) Pretreatment of winemaking waste

[0137] Adjust the water content of wine spent grains to 50-60%.

[0138] (2) Acid hydrolysis of winemaking waste

[0139] The pretreated wine lees were hydrolyzed in dilute sulfuric acid with a mass fraction of 2%, a solid-liquid ratio (mass of wine lees / volume of dilute acid solution, g / ml) of 1:4, an acid hydrolysis temperature of 100°C, and an acid hydrolysis time of 45 minutes.

[0140] (3) Filter

[0141] The acid hydrolysis residue and the first filtrate are obtained by filtration.

[0142] (4) Alkaline hydrolysis of the residue after acid hydrolysis

[0143] The residue after acid hydrolysis was hydrolyzed in the presence of 5% ammonia water, a solid-liquid ratio (mass of the residue after acid hydrolysis / volume of ammonia water solution, g / ml) of 1:7, an alkaline hydrolysis temperature of 75°C, and an alkaline hydrolysis time of 60 min.

[0144] (5) Filter

[0145] The residue after alkaline hydrolysis and the second filtrate are obtained by filtration.

[0146] (6) Enzymatic hydrolysis

[0147] The cellulase used in this implementation case is a strain with high filter paper enzyme activity screened in the laboratory in the early stage and a strain screened by alkaline hydrolysis of residual dregs, which is the same as the cellulase involved in the Chinese patent with publication number CN113621674B. The enzyme solution is a composite enzyme obtained from the laboratory or purchased by Novozymes.

[0148] The filter paper enzyme activity (FPU) of the cellulase solution is 10 IU / ml, and the β-glucosidase activity is 12 IU / ml.

[0149] The residue after alkaline hydrolysis was enzymolyzed in the presence of cellulase solution, reaction pH of 4.8, solid-liquid ratio (mass of residue after alkaline hydrolysis / volume of enzyme solution, g / ml) of 1:6, enzymolysis temperature of 48°C, and enzymolysis time of 24h.

[0150] (7) Filtering

[0151] Filtration was performed to obtain the residue and the third filtrate.

[0152] (8) Mixing

[0153] The first filtrate, the second filtrate and the third filtrate are mixed to obtain a total sugar solution.

[0154] Detect the reducing sugar content of the total sugar solution.

[0155] Experimental results:

[0156] The yield of total reducing sugars was 402 mg / g (dry grains).

[0157] Implementation Case 4

[0158] Based on the optimization of the extraction method steps for extracting reducing sugars from distiller's grains, this implementation case adjusts the acid hydrolysis process, and the extraction method includes the following steps:

[0159] (1) Pretreatment of winemaking waste

[0160] Adjust the water content of wine spent grains to 50-60%.

[0161] (2) Acid hydrolysis of winemaking waste

[0162] The pretreated wine lees were hydrolyzed in dilute sulfuric acid with a mass fraction of 1%, a solid-liquid ratio (mass of wine lees / volume of dilute acid solution, g / ml) of 1:5, an acid hydrolysis temperature of 100°C, and an acid hydrolysis time of 90 min.

[0163] (3) Filter

[0164] The acid hydrolysis residue and the first filtrate are obtained by filtration.

[0165] (4) Alkaline hydrolysis of the residue after acid hydrolysis

[0166] The residue after acid hydrolysis was hydrolyzed in the presence of 12% ammonia water, a solid-liquid ratio (mass of the residue after acid hydrolysis / volume of ammonia water solution, g / ml) of 1:6, an alkaline hydrolysis temperature of 85°C, and an alkaline hydrolysis time of 75 min.

[0167] (5) Filter

[0168] The residue after alkaline hydrolysis and the second filtrate are obtained by filtration.

[0169] (6) Enzymatic hydrolysis

[0170] The cellulase used in this implementation case is a strain with high filter paper enzyme activity screened in the laboratory in the early stage and a strain screened by alkaline hydrolysis of residual dregs, which is the same as the cellulase involved in the Chinese patent with publication number CN113621674B. The enzyme solution is a composite enzyme obtained from the laboratory or purchased by Novozymes.

[0171] The filter paper enzyme activity (FPU) of the cellulase solution is 10 IU / ml, and the β-glucosidase activity is 15 IU / ml.

[0172] The residue after alkaline hydrolysis was hydrolyzed in the presence of cellulase solution, reaction pH of 5.0, solid-liquid ratio (mass of residue after alkaline hydrolysis / volume of enzyme solution, g / ml) of 1:7, hydrolysis temperature of 50°C, and hydrolysis time of 48h.

[0173] (7) Filter

[0174] Filtration was performed to obtain the residue and the third filtrate.

[0175] (8) Mixing

[0176] The first filtrate, the second filtrate and the third filtrate are mixed to obtain a total sugar solution.

[0177] Detect the reducing sugar content of the total sugar solution.

[0178] Experimental results:

[0179] The yield of total reducing sugars was 456 mg / g (60°C oven-dried distiller's grains).

[0180] Implementation Case 5

[0181] Based on the optimization of the extraction method steps for extracting reducing sugars from distiller's grains, this implementation case adjusts the alkaline hydrolysis process, and the extraction method includes the following steps:

[0182] (1) Pretreatment of winemaking waste

[0183] Adjust the water content of wine spent grains to 50-60%.

[0184] (2) Acid hydrolysis of winemaking waste

[0185] The pretreated wine-making spent grains were hydrolyzed in dilute sulfuric acid with a mass fraction of 1.5%, a solid-liquid ratio (mass of wine-making spent grains / volume of dilute acid solution, g / ml) of 1:6, an acid hydrolysis temperature of 110°C, and an acid hydrolysis time of 60 min.

[0186] (3) Filter

[0187] The acid hydrolysis residue and the first filtrate are obtained by filtration.

[0188] (4) Alkaline hydrolysis of the residue after acid hydrolysis

[0189] The residue after acid hydrolysis was hydrolyzed in the presence of 10% ammonia water, a solid-liquid ratio (mass of the residue after acid hydrolysis / volume of ammonia water solution, g / ml) of 1:5, an alkaline hydrolysis temperature of 90° C., and an alkaline hydrolysis time of 60 min.

[0190] (5) Filter

[0191] The residue after alkaline hydrolysis and the second filtrate are obtained by filtration.

[0192] (6) Enzymatic hydrolysis

[0193] The cellulase used in this implementation case is a strain with high filter paper enzyme activity screened in the laboratory in the early stage and a strain screened by alkaline hydrolysis of residual dregs, which is the same as the cellulase involved in the Chinese patent with publication number CN113621674B. The enzyme solution is a composite enzyme obtained from the laboratory or purchased by Novozymes.

[0194] The filter paper enzyme activity (FPU) of the cellulase solution is 10 IU / ml, and the β-glucosidase activity is 15 IU / ml.

[0195] The residue after alkaline hydrolysis was hydrolyzed in the presence of cellulase solution, reaction pH of 5.0, solid-liquid ratio (mass of residue after alkaline hydrolysis / volume of enzyme solution, g / ml) of 1:7, hydrolysis temperature of 50°C, and hydrolysis time of 48h.

[0196] (7) Filtering

[0197] Filtration was performed to obtain the residue and the third filtrate.

[0198] (8) Mixing

[0199] The first filtrate, the second filtrate and the third filtrate are mixed to obtain a total sugar solution.

[0200] Detect the reducing sugar content of the total sugar solution.

[0201] Experimental results:

[0202] The yield of total reducing sugars was 472 mg / g (60°C oven-dried distiller's grains).

[0203] Implementation Case 6

[0204] The present application provides a method for detecting furfural components in acid-treated vinasse.

[0205] The furfural components in the lees were detected at different reaction intensities.

[0206] Reaction intensity = logRo-pH

[0207] Ro=[t*exp(TH–TR) / 14.75]

[0208] The calculation method of Ro was proposed by Overend and Chornet (1987), where TH is the acid treatment temperature, TR is usually 100°C, and t is the acid treatment time. The reaction intensity is positively correlated with the temperature, time, and pH of the biomass acid hydrolysis process.

[0209] The results are as follows Figure 2 As shown, when the reaction intensity is 1.2, the furfural concentration is 0.8g / L. When the reaction intensity is 1.4, the furfural concentration is 1.4g / L. When the reaction intensity is 1.6, the furfural concentration is 1.8g / L. When the reaction intensity is 1.8, the furfural concentration is 2.3g / L.

[0210] According to the acid concentration and temperature reported in the literature of the prior art, the furfural concentration generated by the reaction intensity involved in the prior art is above 2 g / L.

[0211] The maximum reaction intensity of this experiment (acid concentration 2%, temperature 110°C, time 90 min) was less than 1.2, and the furfural content was less than 1 g / L, which was much lower than the furfural concentration under similar acid hydrolysis reaction conditions in the industry.

[0212] According to existing research on the effect of furfural concentration on microbial fermentation, the furfural concentration produced in this experiment has little effect on subsequent microbial fermentation.

[0213] Implementation Case 7

[0214] This embodiment provides a culture medium component suitable for L-lactic acid. A sugar solution is obtained based on the preparation method of embodiment 1, and the sugar solution is used to prepare a culture medium for cultivating L-lactic acid.

[0215] The L-lactic acid fermentation medium of the experimental group was prepared as follows:

[0216] The sugar solution obtained in Example 1 was adjusted to a hydrolyzed sugar solution with 6% reducing sugar, and 1000 mL of the hydrolyzed sugar solution (i.e., the sugar solution obtained in Example 1) was mixed with 6 g of yeast powder, 10 g of peptone, and K 2 HPO 4 2g, glucose 20g, adjusted to pH 7.0, added CaCO 3 60g, sterilize at 100℃ for 20min.

[0217] The L-lactic acid fermentation medium of the control group was prepared as follows:

[0218] Mix 1000 mL of 6% reducing sugar hydrolyzate, 6 g of yeast powder, 10 g of peptone, and K 2 HPO 4 2g, glucose 20g, adjusted to pH 7.0, added CaCO 3 60g, sterilize at 100℃ for 20min.

[0219] Figure 5 The experimental results shown are plate images of L-lactic acid cultured in the culture medium configured in the above method. The colonies are round and no foreign bacteria grow, indicating that the sugar solution is pure.

[0220] Figure 6 The experimental results shown are the L-lactic acid yield results of the experimental group and the control group. After 24 hours of cultivation, the L-lactic acid in the experimental group was 39g / L, and the L-lactic acid in the control group was 34g / L. After 36 hours of cultivation, the L-lactic acid in the experimental group was 46g / L, and the L-lactic acid in the control group was 43g / L. After 48 hours of cultivation, the L-lactic acid in the experimental group was 51g / L, and the L-lactic acid in the control group was 50g / L. After 60 hours of cultivation, the L-lactic acid in the experimental group was 50g / L, and the L-lactic acid in the control group was 49g / L.

[0221] According to the experimental results shown in the present application, compared with the L-lactic acid fermentation medium in the prior art, the L-lactic acid fermentation medium provided by the present invention can also achieve the same culture effect, and the culture effect in the early stage of cultivation is better.

[0222] Implementation Case 8

[0223] The present invention provides a system for recovering sugar products from vinasse. The present invention provides a system for fermenting vinasse.

[0224] The system comprises an acid treatment module 100, an alkali treatment module 200 and an enzymatic treatment module 300. The acid treatment module 100 and the alkali treatment module 200 are connected in series. The alkali treatment module 200 and the enzymatic treatment module 300 are connected in series. The vinasse that has been acid-hydrolyzed in the acid treatment module 100 can be transferred to the alkali treatment module 200 after the filtrate is recovered, and the vinasse that has been alkaline-hydrolyzed in the alkali treatment module 200 can be transferred to the enzymatic treatment module 300 after the filtrate is recovered, such as Figure 3 shown.

[0225] The acid treatment module 100 receives the lees, and the acid treatment module 100 can mix dilute sulfuric acid into the lees, and the alkali treatment module 200 can mix ammonia water into the lees.

[0226] According to a preferred embodiment, the acid treatment module 100 is a hydrolysis tank having a filling pipe connected to the outside. The alkali treatment module 200 is a hydrolysis tank having a filling pipe connected to the outside. Particularly preferably, the acid treatment module 100 is provided with at least two hydrolysis tanks connected in series. The alkali treatment module 200 is provided with at least two hydrolysis tanks connected in series. The system is capable of transferring the residue after hydrolysis and filtration in the acid treatment module 100 to the alkali treatment module 200.

[0227] According to a preferred embodiment, the filtration module 400 can separate the solid and liquid of the product treated by the acid treatment module 100, the alkali treatment module 200 or the enzymatic treatment module 300. Preferably, the filtration module 400 is a mechanical press. Particularly preferably, a mechanical press is arranged between the alkali treatment module 200 and the acid treatment module 100. The first hydrolyzed lees pass through the mechanical press during the transmission process, and the hydrolyzed sugar solution is recovered, and the pressed lees are further transmitted to the next unit for hydrolyzing the lees. A mechanical press is arranged between the acid treatment module 100, the alkali treatment module 200 and the enzymatic treatment module 300, so that the hydrolyzed lees can be separated from the solid and liquid for a second time when flowing to the enzymatic treatment module 300.

[0228] The enzymatic hydrolysis treatment module 300 receives the slag treated by the alkali treatment module 200 and provides enzymatic hydrolysis conditions for the slag treated by the acid and alkali. Preferably, the enzymatic hydrolysis treatment module 300 is a fermentation tank having a filling pipe connected to the outside.

[0229] According to a preferred embodiment, the hydrolysis tank involved in the present invention has the functions of controlling temperature, timing, and automatically adding set materials into the tank. The fermentation tank involved in the present invention has the functions of controlling temperature, detecting pH value, timing, and automatically adding set materials into the tank. Preferably, both the hydrolysis tank and the fermentation tank are provided with observation windows. Both the hydrolysis tank and the fermentation tank are provided with sampling ports to facilitate sampling and detection of the current hydrolysis or fermentation state.

[0230] According to a preferred embodiment, the system is further provided with a mixing tank 500 or a mixing tank. The sugar solution obtained by the acid-base-enzyme combination method is transferred to the mixing tank 500 or the mixing tank, and the total sugar solution neutralized by acid and base is obtained after being stirred evenly. In the present application, the mixing tank 500 is an open container, and the mixing tank is a closed container.

[0231] Implementation Case 9

[0232] This embodiment provides a fermentation reaction device.

[0233] The device comprises an acid treatment module 100 for mixing vinasse and dilute sulfuric acid, an alkali treatment module 200 for mixing vinasse and ammonia water, and an enzymatic treatment module 300.

[0234] The acid treatment module 100 includes an acid treatment fermentation tank. The alkali treatment module 200 includes an alkali treatment fermentation tank. The enzyme treatment module 100 includes an enzyme treatment fermentation tank.

[0235] like Figure 4 As shown, an alkali treatment fermentation tank is arranged inside the enzyme treatment fermentation tank. Figure 4 As shown, an acid treatment fermentation tank is arranged inside the alkali treatment fermentation tank. Preferably, a plurality of alkali treatment fermentation tanks are arranged inside the enzyme treatment fermentation tank.

[0236] The waste heat continuously diffused outward from the acid treatment fermentation tank can provide heat support for the alkaline hydrolysis reaction in the alkali treatment fermentation tank. The waste heat continuously diffused outward from the alkali treatment fermentation tank can provide heat support for the enzymatic hydrolysis reaction in the enzyme treatment fermentation tank.

[0237] According to a preferred embodiment, the acid treatment module 100 and the alkali treatment module 200 at least partially conflict with each other to form a first heat exchange area, and the alkali treatment module 200 and the enzymatic treatment module at least partially conflict with each other to form a second heat exchange area, wherein the first heat exchange area is arranged inside the second heat exchange area, so that the heat generated by the acid treatment described in the treatment method described in the present application is transferred to the space where the alkali treatment or enzyme treatment having a lower reaction temperature requirement than the acid treatment is located.

[0238] According to a preferred embodiment, the second heat exchange area is provided with a heat exchanger plate, wherein, based on the heat transfer direction, the flow pipeline of the heat carrier medium of the heat exchanger plate is provided with flow outlets in the acid treatment module 100, the alkali treatment module 200 and the enzymatic treatment module, respectively, so that when the temperature of the alkali treatment module 200 / enzymatic treatment module reaches the preset reaction temperature, the heat carrier medium flowing out of the acid treatment module 100 can flow out from the flow outlet of the acid treatment module 100 / alkali treatment module 200. According to a preferred embodiment, the flow pipeline arranged in the acid treatment module 100 is provided with a double-port valve connected to the flow pipelines arranged in the alkali treatment module 200 and the enzymatic treatment module, respectively, so that the heat carrier medium of the acid treatment module 100 can flow directly from the acid treatment module 100 to the enzymatic treatment module without passing through the alkali treatment module 200.

[0239] Preferably, the dual-port valve and the flow outlet are controlled by a remotely-set server. The acid treatment module 100, the alkali treatment module 200 and the enzymatic treatment module are each provided with at least one temperature detection unit.

[0240] When the temperature of the alkali treatment module 200 is higher than a preset threshold value (e.g., 100°C) and the temperature of the alkali treatment module 200 is higher than a preset threshold value (e.g., 60°C), the server controls the flow outlet set in the acid treatment module 100 to open, so that the heat carrier medium can flow out directly from the flow outlet or does not enter the acid treatment module 100.

[0241] When the temperature of the alkali treatment module 200 is higher than a preset threshold (for example, 100°C) and the temperature of the alkali treatment module 200 is lower than a preset threshold (for example, 45°C), the server controls the double-port valve provided in the acid treatment module 100 and the flow outlet of the enzyme treatment module 300 to open, so that the flow pipeline of the acid treatment module 100 is directly connected to the flow pipeline of the enzyme treatment module 300, and the heat carrier can flow from the acid treatment module 100 to the enzyme treatment module 300 without flowing through the alkali treatment module 200.

[0242] When the temperature of the alkali treatment module 200 is lower than a preset threshold value (for example, 90°C) and the temperature of the alkali treatment module 200 is lower than a preset threshold value (for example, 45°C), the server controls the double-port valve set in the acid treatment module 100 and the flow outlet of the enzyme treatment module 300 to open, so that the heat carrier can flow from the acid treatment module 100 to the alkali treatment module 200 and the enzyme treatment module 300 sequentially.

[0243] When the temperature of the alkali treatment module 200 is lower than a preset threshold (for example, 90°C) and the temperature of the alkali treatment module 200 is higher than a preset threshold (for example, 60°C), the server controls the double-port valve provided in the acid treatment module 100 and the flow outlet of the alkali treatment module 200 to open, so that the heat carrier can flow from the acid treatment module 100 to the alkali treatment module 200 without flowing through the enzyme treatment module 300.

[0244] The structure of the heat exchanger plate involved in the present application is similar to the structure of CN101191116B, and on this basis, a controllable flow outlet and a double-port valve for controlling the flow direction of the pipeline are adapted.

[0245] It should be noted that the above-mentioned specific embodiments are exemplary, and those skilled in the art can come up with various solutions inspired by the disclosure of the present invention, and these solutions also belong to the disclosure scope of the present invention and fall within the protection scope of the present invention. Those skilled in the art should understand that the present invention specification and its drawings are illustrative and do not constitute a limitation of the claims. The scope of protection of the present invention is defined by the claims and their equivalents. The present invention specification contains multiple inventive concepts, such as "preferably", "according to a preferred embodiment" or "optionally", all of which indicate that the corresponding paragraph discloses an independent concept, and the applicant reserves the right to file a divisional application based on each inventive concept. Throughout the text, the features guided by "preferably" are only an optional method and should not be understood as being required. Therefore, the applicant reserves the right to abandon or delete the relevant preferred features at any time.

Claims

1. A method for treating distiller's grains, characterized in that: At least the following steps are included: Add dilute acid to the lees until the pH of the lees is in the range of 0.5-1 for acid hydrolysis to obtain a first filtrate and residual lees after acid hydrolysis. The dilute acid is dilute sulfuric acid, the mass concentration range of which is 0.75-2%, the ratio of the mass of the lees to the volume of the dilute sulfuric acid solution is 1:(4-6), the acidolysis temperature is 100-110°C, and the acidolysis time is 45-90 min; Adding dilute alkali to the acid hydrolysis residue until the pH of the acid hydrolysis residue is in the range of 11-12 to perform alkaline hydrolysis to obtain a second filtrate and the alkaline hydrolysis residue, The dilute alkali is ammonia water, the mass concentration of which ranges from 5 to 12%, the ratio of the mass of the lees to the volume of the ammonia solution is 1:(5 to 7), the alkaline hydrolysis temperature is 75 to 90°C, and the alkaline hydrolysis time is 60 to 90 min; enzymatically hydrolyzing the residual dregs after alkaline hydrolysis to obtain a third filtrate and residual dregs after enzymatic hydrolysis; Obtaining total sugar solution: mixing the first filtrate, the second filtrate and the third filtrate, The enzyme solution used in the enzymatic hydrolysis step is a composite enzyme. Among them, the filter paper enzyme activity of the cellulase solution was 10 IU / ml, and the β-glucosidase enzyme activity was 15 IU / ml.

2. A distiller's grains processing system, characterized in that: The treatment system comprises an acid treatment module (100) for mixing wine lees and dilute acid, an alkali treatment module (200) for mixing wine lees and ammonia water, an enzymatic treatment module (300) and a mixing tank (500) for receiving the product obtained after the treatment. The enzymatic hydrolysis treatment module (300) receives the residual grains after treatment by the acid treatment module (100) and the alkali treatment module (200), and provides enzymatic hydrolysis conditions for the residual grains, wherein the residual grains refer to the product obtained by separating the filtrate from the wine grains after the acid treatment and the alkali treatment, wherein: The acid treatment module (100) obtains a first filtrate after acid treatment of the lees, the alkali treatment module (200) obtains a second filtrate after alkali treatment of the lees after acid hydrolysis and recovery of the filtrate, and the enzymatic treatment module (300) obtains a third filtrate after enzymatic treatment of the residual lees. The mixing tank (500) receives and mixes the first filtrate, the second filtrate and the third filtrate, The acid treatment module (100) and the alkali treatment module (200) at least partially collide to form a first heat exchange region, and the alkali treatment module (200) and the enzymatic treatment module (300) at least partially collide to form a second heat exchange region, wherein the first heat exchange region is arranged inside the second heat exchange region, so that the heat generated by the acid hydrolysis is transferred to the space where the alkali treatment or enzyme treatment having a lower reaction temperature requirement than the acid hydrolysis is located.

3. The processing system according to claim 2, characterized in that The second heat exchange region is provided with a heat exchanger plate, wherein, based on the heat transfer direction, a flow pipeline of the heat carrier medium of the heat exchanger plate is provided with a double-port valve in the acid treatment module (100), so that the heat exchanger plate can control the flow path of the heat carrier medium based on the heat demand of the alkali treatment module (200) and / or the enzymatic treatment module (300).

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