Continuous production process for preparing fertilizer from histidine fermentation waste liquid

Abstract

The invention discloses a continuous production process for preparing a fertilizer from histidine fermentation waste liquid, and relates to the technical field of fertilizer preparation. The continuous production process has the advantages that a mixture composed of nanoscale zeolite and modified lignocellulose is added into the histidine fermentation waste liquid; nanoscale zeolite has a rich microporous structure and strong ion exchange capacity, and micropores of the nanoscale zeolite can capture heavy metal ions in waste liquid, so that the content of the heavy metal ions in the waste liquid is effectively reduced, and carboxyl functional groups of modified lignocellulose have very strong complexing capacity, so that the heavy metal ions in the waste liquid are effectively reduced. The lignocellulose can be subjected to complex reaction with heavy metal ions such as lead ions, cadmium ions and mercury ions in the waste liquid to form a stable complex, and ester functional groups can adsorb small organic molecules such as methanol, ethanol and acetic acid in the waste liquid to the surface of the lignocellulose through Van der Waals force, so that the pollution of the waste liquid to the environment is greatly reduced, and the environmental pollution is reduced. Purer raw materials are provided for subsequent fertilizer preparation, so that the quality of the fertilizer is improved.

Description

Technical Field

[0001] The invention relates to the technical field of fertilizer preparation, in particular to a continuous production process for preparing fertilizer from histidine fermentation waste liquid. Background Art

[0002] With the rapid development of the global biotechnology industry, the scale of histidine fermentation production, as one of the main ways to obtain this important amino acid, has been continuously expanded. However, it is accompanied by the generation of a large amount of histidine fermentation waste liquid. These waste liquids contain multiple components. If they are directly discharged, they will bring many serious harms to the ecological environment, and also mean the loss of precious resources. Therefore, how to properly treat histidine fermentation waste liquid and realize its resource conversion has become a focus of common concern in the current biotechnology and environmental protection fields. The fermentation production of histidine usually adopts microbial fermentation. During the fermentation process, microorganisms use nutrients in the culture medium to grow and metabolize to produce histidine and other metabolites. At the same time, a large amount of waste liquid will also be generated. These waste liquids mainly include unused culture medium components, microbial metabolites, bacterial cells, etc. The existing technology has certain defects. First, it is difficult to efficiently remove heavy metals and organic impurities in histidine fermentation waste liquid, which affects the quality of fertilizer and the environment. Secondly, there is a lack of specific methods for extracting histidine, resulting in low extraction efficiency and purity, and limited resource utilization. Furthermore, the existing technology does not fully utilize the nutrients in the waste liquid to generate multifunctional complexes, and the waste liquid treatment is not environmentally friendly and costly. For this reason, we propose a continuous production process for preparing fertilizer from histidine fermentation waste liquid. Summary of the invention

[0003] The purpose of the present invention is to provide a continuous production process for preparing fertilizer from histidine fermentation waste liquid.

[0004] In order to solve the problems raised in the above background technology, the present invention provides the following technical solution: a continuous production process for preparing fertilizer from histidine fermentation waste liquid, the production process specifically comprising the following steps: Step 1, collecting histidine fermentation waste liquid, adding a mixture of nano-zeolite and modified cellulose to the waste liquid, wherein the nano-zeolite has rich microporous structure and ion exchange capacity, and can effectively adsorb heavy metal ions and some organic impurities in the waste liquid, and the modified cellulose has two active functional groups, namely carboxyl and ester groups, and the carboxyl functional group can react with lead ions, cadmium ions and mercury ions of heavy metal ions in the waste liquid to form a stable complex, thereby achieving the removal of heavy metal ions, and the ester functional group can react with methanol, ethanol and acetic acid of organic small molecules in the waste liquid to adsorb these organic small molecules on the surface of cellulose through van der Waals force, thereby achieving the purpose of removing organic impurities, and stirring for a period of time to mix evenly, thereby achieving efficient impurity removal, and after the reaction is completed, centrifugally separating the composite adsorption material and the waste liquid; Step 2: Preparation of specific polymer materials: dissolving a monomer containing a carboxyl group and a benzene ring structure in a dimethyl sulfoxide solvent, adding an azobisisobutyronitrile initiator to carry out a polymerization reaction, and preparing a polymer containing a carboxyl group and a benzene ring structure; adding the polymer to the waste liquid that has been preliminarily removed from impurities, stirring the reaction, and centrifugally separating the polymer and the waste liquid after the reaction is completed; and then eluting the bound histidine with an acidic eluent, and purifying and concentrating the polymer; Step 3: adding lysine solution, glutamic acid solution and vitamin B6 solution to the purified and concentrated histidine solution, stirring and reacting for a period of time to generate a new complex substance containing multiple amino acids and vitamins; Step 4: Collect the secondary waste liquid generated in the above treatment process, filter and remove impurities, add adsorbent to the secondary waste liquid to adsorb residual organic matter and heavy metal ions, add neutralizer to adjust pH after adsorption, and finally, mix the treated secondary waste liquid with the new composite material and conventional fertilizer ingredients, stir evenly to make liquid fertilizer.

[0005] As a further scheme of the present invention: in the step 1, the cellulose is modified by the following method: the cellulose is reacted with acetic anhydride under the action of pyridine catalyst, so that the hydroxyl groups in the cellulose molecules are acetylated, thereby introducing ester functional groups, and at the same time, the cellulose is oxidized by an oxidant to generate carboxyl functional groups on its surface, so that the modified cellulose has two active functional groups, namely carboxyl and ester groups.

[0006] As a further solution of the present invention: in the step 1, the fermentation waste liquid and the mixture are fully reacted at a temperature of 25°C-30°C and a stirring speed of 20r / min-25r / min for 1h-1.5h.

[0007] As a further scheme of the present invention: in the step 2, the monomer containing carboxyl and benzene ring structure is p-carboxyl styrene, and the mass ratio of p-carboxyl styrene and azobisisobutyronitrile initiator added is 3-5:1-1.2, the polymerization reaction temperature is controlled at 50°C-60°C, and the reaction time is 1.0h-1.5h.

[0008] As a further solution of the present invention: in the step 2, a high molecular polymer is added to the waste liquid after preliminary impurity removal, the stirring speed is controlled to be 30r / min-40r / min, the temperature is 30℃-35℃, the reaction time is 2h-3h, and after centrifugation, the bound histidine is eluted with an acidic eluent with a pH value of 4.0-5.0.

[0009] As a further scheme of the present invention: in the step three, the concentration of lysine solution is 0.1 mol / L, the concentration of glutamic acid solution is 0.05 mol / L, the concentration of vitamin B6 solution is 0.01 mol / L, and the addition ratio of histidine solution, lysine solution, glutamic acid solution and vitamin B6 solution is 9-11:1.2-1.5:0.6-0.8:2.1-2.6.

[0010] As a further solution of the present invention: in the step three, the reaction temperature is 40°C-45°C, the stirring speed is 20r / min-25r / min, and the reaction time is 1h-1.5h.

[0011] As a further solution of the present invention: in the step 4, the adsorbent is attapulgite adsorbent, the adsorption temperature is 20°C-25°C, the adsorption time is 1h-2h, the neutralizer is sodium bicarbonate, and the adjusted pH value is 6.5-7.5.

[0012] As a further scheme of the present invention: in the step four, the conventional fertilizer ingredients include potassium dihydrogen phosphate, urea and potassium sulfate, the mass ratio of the treated secondary waste liquid: the new composite substance: potassium dihydrogen phosphate: urea: potassium sulfate is 0.8-1.0: 1.0-1.2: 0.3-0.5: 0.5-0.8: 0.2-0.4, the stirring speed is controlled to 15r / min-20r / min, and the stirring time is 2h-3h.

[0013] By adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are: 1. The present invention adds a mixture of nano-zeolite and modified lignocellulose to the histidine fermentation waste liquid. The nano-zeolite has a rich microporous structure and a strong ion exchange capacity. The micropores can capture heavy metal ions in the waste liquid, thereby effectively reducing the content of heavy metal ions in the waste liquid. The carboxyl functional group of the modified lignocellulose has a strong complexing ability and can react with heavy metal ions such as lead ions, cadmium ions, and mercury ions in the waste liquid to form a stable complex. The ester functional group can adsorb organic small molecules such as methanol, ethanol, and acetic acid in the waste liquid on the surface of the lignocellulose through van der Waals force, so that organic impurities can be removed. The two act synergistically to significantly reduce the content of heavy metal ions and organic impurities in the waste liquid, which not only greatly reduces the pollution of the waste liquid to the environment, but also provides a purer raw material for subsequent fertilizer preparation, thereby improving the quality of the fertilizer; 2. The present invention prepares a high molecular polymer by dissolving a monomer containing a carboxyl group and a benzene ring structure in a dimethyl sulfoxide solvent and performing a polymerization reaction under the action of an azobisisobutyronitrile initiator, and then reacting the monomer with a preliminarily impurity-removed waste liquid, and finally eluting and purifying and concentrating histidine with an acidic eluent. In this process, the prepared high molecular polymer containing a carboxyl group and a benzene ring structure can specifically bind to histidine in the waste liquid. The synergistic effect of the carboxyl group and the benzene ring structure, the carboxyl group has a certain chemical activity, and can form a chemical bond and a strong interaction with the amino group on the histidine molecule, and the benzene ring structure provides a certain steric hindrance and electronic effect, so that the combination is selective and can specifically identify and bind to histidine. Through this specific combination, histidine is efficiently and accurately separated from the waste liquid, and the extraction efficiency and purity of histidine are significantly improved. After eluting with an acidic eluent and combining with the purification and concentration steps, a high-purity histidine solution is successfully obtained, which effectively improves the resource utilization rate of the entire fertilizer production process; 3. The present invention adds a specific concentration of lysine solution, glutamic acid solution and vitamin B6 solution to the purified and concentrated histidine solution and stirs the reaction, thereby promoting the interaction between multiple amino acids and vitamins to generate a new complex substance rich in multiple essential amino acids, organic acids and vitamins. The structure of this new complex substance is connected by peptide bonds between amino acids and interacts with vitamin molecules to form a molecular combination with a specific spatial structure and function, which provides comprehensive and balanced nutritional support for plant growth, promotes plant growth and development, enhances stress resistance, and improves crop yield and quality. Then, the secondary waste liquid generated in the treatment process is collected and filtered to remove impurities, the residual organic matter and heavy metal ions are adsorbed by attapulgite, and the pH is adjusted by sodium bicarbonate. Then, it is mixed with the new complex substance and conventional fertilizer ingredients to form a nutrient-rich and environmentally friendly liquid fertilizer. In this process, the attapulgite adsorbent purifies the raw materials and the sodium bicarbonate stabilizes the fertilizer properties to facilitate absorption, ultimately realizing the resource utilization of the waste liquid throughout the entire process and reducing waste emissions and production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 A schematic diagram of a process flow in an embodiment of the present invention; Figure 2 Schematic diagram of performance comparison of embodiments of the present invention. DETAILED DESCRIPTION

[0015] The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention.

[0016] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0017] Please refer to the attached Figure 1 -Attached Figure 2 The present invention provides a continuous production process for preparing fertilizer from histidine fermentation waste liquid, and the production process specifically comprises the following steps: Step 1, collecting histidine fermentation waste liquid, adding a mixture of nano-zeolite and modified cellulose to the waste liquid, wherein the nano-zeolite has rich microporous structure and ion exchange capacity, and can effectively adsorb heavy metal ions and some organic impurities in the waste liquid, and the modified cellulose has two active functional groups, namely carboxyl and ester groups, and the carboxyl functional group can react with lead ions, cadmium ions and mercury ions of heavy metal ions in the waste liquid to form a stable complex, thereby achieving the removal of heavy metal ions, and the ester functional group can react with methanol, ethanol and acetic acid of organic small molecules in the waste liquid to adsorb these organic small molecules on the surface of cellulose through van der Waals force, thereby achieving the purpose of removing organic impurities, and stirring for a period of time to mix evenly, thereby achieving efficient impurity removal, and after the reaction is completed, centrifugally separating the composite adsorption material and the waste liquid; Step 2: Preparation of specific polymer materials: dissolving a monomer containing a carboxyl group and a benzene ring structure in a dimethyl sulfoxide solvent, adding an azobisisobutyronitrile initiator to carry out a polymerization reaction, and preparing a polymer containing a carboxyl group and a benzene ring structure; adding the polymer to the waste liquid that has been preliminarily removed from impurities, stirring the reaction, and centrifugally separating the polymer and the waste liquid after the reaction is completed; and then eluting the bound histidine with an acidic eluent, and purifying and concentrating the polymer; Step 3: adding lysine solution, glutamic acid solution and vitamin B6 solution to the purified and concentrated histidine solution, stirring and reacting for a period of time to generate a new complex substance containing multiple amino acids and vitamins; Step 4: Collect the secondary waste liquid generated in the above treatment process, filter and remove impurities, add adsorbent to the secondary waste liquid to adsorb residual organic matter and heavy metal ions, add neutralizer to adjust pH after adsorption, and finally, mix the treated secondary waste liquid with the new composite material and conventional fertilizer ingredients, stir evenly to make liquid fertilizer.

[0018] In one embodiment of the present invention: in step 1, the following modification method is used for lignocellulose: lignocellulose is reacted with acetic anhydride in the presence of a pyridine catalyst so that the hydroxyl groups in the lignocellulose molecules are acetylated, thereby introducing ester functional groups; at the same time, the lignocellulose is oxidized with an oxidant to generate carboxyl functional groups on its surface, so that the modified lignocellulose has two active functional groups, namely, carboxyl and ester groups.

[0019] In one embodiment of the present invention: in step 1, the fermentation waste liquid and the mixture are fully reacted at a temperature of 25°C-30°C and a stirring speed of 20r / min-25r / min for 1h-1.5h.

[0020] In one embodiment of the present invention: in step 2, the monomer containing carboxyl and benzene ring structure is p-carboxyl styrene, and the mass ratio of p-carboxyl styrene and azobisisobutyronitrile initiator added is 3-5:1-1.2, the temperature of the polymerization reaction is controlled at 50°C-60°C, and the reaction time is 1.0h-1.5h.

[0021] In one embodiment of the present invention: in step 2, a high molecular polymer is added to the waste liquid that has been preliminarily cleaned of impurities, the stirring speed is controlled to be 30r / min-40r / min, the temperature is 30°C-35°C, the reaction time is 2h-3h, and after centrifugation, the bound histidine is eluted with an acidic eluent with a pH value of 4.0-5.0.

[0022] In one embodiment of the present invention: in step three, the concentration of lysine solution is 0.1 mol / L, the concentration of glutamic acid solution is 0.05 mol / L, the concentration of vitamin B6 solution is 0.01 mol / L, and the addition ratio of histidine solution, lysine solution, glutamic acid solution and vitamin B6 solution is 9-11:1.2-1.5:0.6-0.8:2.1-2.6.

[0023] In one embodiment of the present invention: in step three, the reaction temperature is 40°C-45°C, the stirring speed is 20r / min-25r / min, and the reaction time is 1h-1.5h.

[0024] In one embodiment of the present invention: in step 4, the adsorbent is attapulgite adsorbent, the adsorption temperature is 20°C-25°C, the adsorption time is 1h-2h, the neutralizer is sodium bicarbonate, and the adjusted pH value is 6.5-7.5.

[0025] In one embodiment of the present invention: in step four, conventional fertilizer ingredients include potassium dihydrogen phosphate, urea and potassium sulfate, the mass ratio of treated secondary waste liquid: new composite material: potassium dihydrogen phosphate: urea: potassium sulfate is 0.8-1.0: 1.0-1.2: 0.3-0.5: 0.5-0.8: 0.2-0.4, the stirring speed is controlled to 15r / min-20r / min, and the stirring time is 2h-3h.

[0026] In one embodiment of the present invention: before the modified lignocellulose reacts with acetic anhydride, it is first pretreated to crush the lignocellulose to a particle size of 50μm-100μm, and then dried at a temperature of 80μm-100°C for 2h-3h. This pretreatment can increase the specific surface area of ​​lignocellulose, make it more fully contact with acetic anhydride, improve the efficiency of introducing ester functional groups, enhance the adsorption capacity of organic impurities, and thus improve the impurity removal effect of the entire process.

[0027] In one embodiment of the present invention: microbial agents are added to the treated secondary waste liquid, the microbial agents include Bacillus subtilis, Bacillus licheniformis and Bacillus megaterium, and the added amount is 0.1%-0.3% of the mass of the secondary waste liquid. These microbial agents can decompose residual organic matter and convert it into small molecules that are easily absorbed by plants, while activating heavy metal ions and reducing their toxicity, thereby further improving the quality of fertilizers and environmental friendliness.

[0028] In one embodiment of the present invention: after the polymerization reaction is completed, the obtained high molecular polymer is post-treated by using ultrasonic dispersion technology and treating it at a frequency of 20kHz-40kHz for 15min-30min to make the polymer particles more evenly dispersed, and then dialyzed with a dialysis bag for 24h-48h to remove unreacted monomers and small molecule impurities, improve the purity of the polymer, enhance its specific binding ability to histidine, and optimize the histidine extraction effect.

[0029] In one embodiment of the present invention: when the treated secondary waste liquid is mixed with the new composite material and conventional fertilizer components, a chelating agent disodium ethylenediaminetetraacetate (EDTA-2Na) is added in an amount of 0.05%-0.1% of the total mass. EDTA-2Na can form a stable chelate with residual heavy metal ions, reduce the activity of heavy metals, prevent their accumulation in the soil and cause harm to plants, and at the same time improve the effectiveness of trace elements in fertilizers and promote plant absorption.

[0030] Example 1, please refer to the attached Figure 1 -Attached Figure 2 First, the histidine fermentation waste liquid was collected and a mixture of nano-zeolite and modified wood cellulose was added thereto. The nano-zeolite, with its rich microporous structure and ion exchange capacity, adsorbed heavy metal ions (lead ions, cadmium ions, mercury ions, etc.) and some organic impurities in the waste liquid. The modified wood cellulose complexed with heavy metal ions through its carboxyl functional group, and adsorbed small organic molecules (methanol, ethanol, acetic acid, etc.) through its ester functional group. After fully reacting for 1.5 hours at a temperature of 30°C and a stirring speed of 25r / min, the composite adsorption material was separated by centrifugation. Then, p-carboxy styrene as a monomer containing a carboxyl group and a benzene ring structure is dissolved in a dimethyl sulfoxide solvent, azobisisobutyronitrile initiator is added in a ratio of p-carboxy styrene to azobisisobutyronitrile initiator of 5:1 by mass, and then a polymerization reaction is carried out at a temperature of 60° C. for 1.5 hours to prepare a high molecular polymer, and the polymer is added to the waste liquid after preliminary impurity removal, and the reaction is stirred for 3 hours at a temperature of 35° C. and a stirring speed of 40 r / min. After the reaction is completed, the high molecular polymer and the waste liquid are separated by centrifugation, and then the polymer is separated by stirring with p The bound histidine was eluted with an acidic eluent having an H value of 5.0, and then purified and concentrated. Then, a lysine solution with a concentration of 0.1 mol / L, a glutamic acid solution with a concentration of 0.05 mol / L, and a vitamin B6 solution with a concentration of 0.01 mol / L were added to the purified and concentrated histidine solution. The addition ratio of the histidine solution, the lysine solution, the glutamic acid solution, and the vitamin B6 solution was 9:1.5:0.8:2.6. The reaction was stirred at a temperature of 45°C and a stirring speed of 25 r / min for 1.5 hours to generate a solution containing various amino acids and vitamins. After that, the secondary waste liquid generated in the treatment process was collected, filtered to remove impurities, and then added with attapulgite adsorbent for adsorption at 25°C for 2 hours to remove residual organic matter and heavy metal ions. Sodium bicarbonate was used as a neutralizer to adjust the pH value to 7.0. Finally, the components were mixed in the ratio of 1.0:1.2:0.3:0.8:0.2 of the treated secondary waste liquid: new composite substance: potassium dihydrogen phosphate: urea: potassium sulfate, and stirred for 3 hours at a stirring speed of 20r / min to make liquid fertilizer.

[0031] Example 2, please refer to the attached Figure 1 -Attached Figure 2First, the histidine fermentation waste liquid was collected and a mixture of nano-zeolite and modified chitosan was added thereto. The nano-zeolite, with its rich microporous structure and ion exchange capacity, adsorbed heavy metal ions (lead ions, cadmium ions, mercury ions, etc.) and some organic impurities in the waste liquid. The modified chitosan complexed with heavy metal ions through its carboxyl functional group, and adsorbed small organic molecules (methanol, ethanol, acetic acid, etc.) through its ester functional group. After fully reacting for 1.5 hours at a temperature of 30°C and a stirring speed of 25 r / min, the composite adsorption material and the modified chitosan were separated by centrifugation. Then, p-carboxy styrene as a monomer containing a carboxyl group and a benzene ring structure is dissolved in a dimethyl sulfoxide solvent, and benzoyl peroxide initiator is added in a mass ratio of p-carboxy styrene to benzoyl peroxide initiator of 5:1, and then a polymerization reaction is carried out at a temperature of 60° C. for 1.5 hours to prepare a high molecular polymer, and the polymer is added to the waste liquid after preliminary impurity removal, and the reaction is stirred for 3 hours at a temperature of 35° C. and a stirring speed of 40 r / min. After the reaction is completed, the high molecular polymer and the waste liquid are separated by centrifugation, and then pH The bound histidine was eluted with an acidic eluent with a value of 5.0, and purified and concentrated. Then, 0.1 mol / L arginine solution, 0.05 mol / L glutamic acid solution and 0.01 mol / L vitamin B6 solution were added to the purified and concentrated histidine solution. The addition ratio of histidine solution, arginine solution, glutamic acid solution and vitamin B6 solution was 9:1.5:0.8:2.6. The reaction was stirred for 1.5 hours at a temperature of 45°C and a stirring speed of 25 r / min to generate a mixture containing various amino acids and vitamins. After that, the secondary waste liquid generated in the treatment process was collected, filtered to remove impurities, and then activated carbon adsorbent was added to adsorb for 2 hours at 25°C to remove residual organic matter and heavy metal ions. Sodium carbonate was used as a neutralizer to adjust the pH value to 7.0. Finally, the components were mixed in the ratio of 1.0:1.2:0.3:0.8:0.2 of the treated secondary waste liquid: new composite substance: potassium dihydrogen phosphate: urea: potassium sulfate, and stirred for 3 hours at a stirring speed of 20r / min to make liquid fertilizer.

[0032] Example 3, please refer to the attached Figure 1 -Attached Figure 2First, the histidine fermentation waste liquid was collected and a mixture of nano-zeolite and modified wood cellulose was added thereto. The nano-zeolite, with its rich microporous structure and ion exchange capacity, adsorbed heavy metal ions (lead ions, cadmium ions, mercury ions, etc.) and some organic impurities in the waste liquid. The modified wood cellulose complexed with heavy metal ions through its carboxyl functional group, and adsorbed organic small molecules (methanol, ethanol, acetic acid, etc.) through its ester functional group. After fully reacting for 1 hour at a temperature of 25°C and a stirring speed of 25r / min, the composite adsorption material was separated by centrifugation. and waste liquid, then, dissolving p-carboxystyrene as a monomer containing carboxyl and benzene ring structure in dimethyl sulfoxide solvent, adding azobisisobutyronitrile initiator in a mass ratio of p-carboxystyrene to azobisisobutyronitrile initiator of 3:1, and then carrying out polymerization reaction at a temperature of 60°C for 1 hour to prepare a high molecular polymer, adding the polymer to the waste liquid after preliminary impurity removal, stirring and reacting for 2 hours at a temperature of 30°C and a stirring speed of 40r / min, and separating the high molecular polymer and the waste liquid by centrifugation after the reaction, and then using pH value The bound histidine was eluted with an acidic eluent of 5.0, and purified and concentrated. Then, a lysine solution with a concentration of 0.1 mol / L, a glutamic acid solution with a concentration of 0.05 mol / L, and a vitamin B6 solution with a concentration of 0.01 mol / L were added to the purified and concentrated histidine solution. The addition ratio of the histidine solution, the lysine solution, the glutamic acid solution, and the vitamin B6 solution was 10:1.2:0.8:2.3. The reaction was stirred at a temperature of 45°C and a stirring speed of 25 r / min for 1 hour to generate a complex containing multiple amino acids and vitamins. After that, the secondary waste liquid generated in the treatment process was collected, filtered to remove impurities, and then added with attapulgite adsorbent for adsorption at 20°C for 2 hours to remove residual organic matter and heavy metal ions. Sodium bicarbonate was used as a neutralizer to adjust the pH value to 6.5. Finally, the components were mixed in the ratio of 1.0:1.2:0.3:0.8:0.2 of the treated secondary waste liquid: new complex substance: potassium dihydrogen phosphate: urea: potassium sulfate, and stirred for 3 hours at a stirring speed of 20r / min to make liquid fertilizer.

[0033] Experimental design: Experimental materials and equipment Several portions of histidine fermentation waste liquid (make sure that each example uses the same source of waste liquid), nano-zeolite, modified lignocellulose, modified chitin, p-carboxylstyrene, azobisisobutyronitrile, benzoyl peroxide, dimethyl sulfoxide, arginine, lysine, glutamic acid, vitamin B6, potassium dihydrogen phosphate, urea, potassium sulfate, sodium bicarbonate, sodium carbonate, attapulgite adsorbent, activated carbon adsorbent, pH meter, centrifuge, magnetic stirrer, high performance liquid chromatograph (for detecting the purity of histidine), atomic absorption spectrometer (for detecting the content of heavy metal ions), plant cultivation equipment and several plant seeds suitable for planting.

[0034] Experimental procedures Waste liquid treatment and material preparation stage: the histidine fermentation waste liquid was treated according to the methods of Example 1, Example 2 and Example 3 respectively. During the treatment process, the initial concentration of heavy metal ions (lead ions, cadmium ions, mercury ions, etc.) and small organic molecules (methanol, ethanol, acetic acid, etc.) in the waste liquid during the stage of adding composite adsorption materials to adsorb impurities and the concentration after treatment were accurately recorded in each example, and the removal rate was calculated. At the same time, in the stage of preparing a specific high molecular polymer to react with the waste liquid to extract histidine, the content of histidine in the waste liquid before extraction, as well as the amount and purity of the histidine extracted after treatment by the methods of each example were recorded; Fertilizer preparation and plant cultivation stage: After completing the above steps, liquid fertilizer is prepared according to the methods of each embodiment, tomato seeds with similar growth conditions are selected, and the liquid fertilizers prepared in the three embodiments are used for irrigation and cultivation respectively. 10 groups of repeated experiments are set to ensure the accuracy of the experimental data. During the growth of tomatoes, other environmental conditions (light, temperature, humidity, etc.) are controlled to be consistent, the growth of tomatoes is observed regularly, and the growth indicators such as plant height, stem thickness, number of leaves, and leaf color changes of the plants are recorded. After the tomato growth cycle is over, the yield of the plants (such as fruit weight, seed weight, etc.) and the resistance of tomatoes to diseases and pests (expressed as the incidence of diseases and pests) are counted; Heavy metal ion removal rate calculation formula Formula: Heavy metal ion removal rate = (C 0 -C 1 ) / C 0 ×100%, where C 0 is the heavy metal ion concentration in the initial wastewater (mg / L), C 1 is the concentration of heavy metal ions in the treated wastewater (mg / L); Organic small molecule removal rate calculation formula Formula: Organic small molecule removal rate = (M 0 -M 1 ) / M 0 ×100%, where M 0is the total concentration of small organic molecules (methanol, ethanol, acetic acid, etc.) in the initial wastewater (mg / L), M 1 is the total concentration of small organic molecules in the treated wastewater (mg / L); Histidine extraction rate calculation formula Formula: Histidine extraction rate = W 1 / W 0 ×100%, where W 0 is the initial histidine content in the wastewater (g), W 1 is the amount of histidine extracted (g); Histidine purity calculation formula The high performance liquid chromatography was used for detection and the peak area was calculated based on the chromatographic peak area. Assuming that the histidine peak area obtained by chromatographic analysis is A 1 , the sum of the impurity peak areas is A 2 , then the purity of histidine is A 1 / (A 1 +A 2 )×100%; Plant growth index calculation and explanation The growth of plant height, stem thickness and leaf number are the differences between the treatment group (irrigated with the corresponding example fertilizer) and the control group (irrigated with ordinary water) at the end of the experiment.

[0035] As attached Figure 2 As shown, Example 1 performs best in many aspects. In terms of reducing waste liquid impurities, the removal rate of heavy metal ions and small organic molecules is high. In terms of histidine extraction, the extraction rate and purity are excellent. After being used for tomato planting, the plant height, stem thickness, number of leaves, yield, etc. increase significantly, and the incidence of diseases and insect pests is low. In comparison, Examples 2 and 3 perform slightly worse in various indicators. This fully proves that the process of Example 1 has significant advantages in waste liquid treatment, resource recycling and fertilizer growth-promoting effects.

[0036] Although the present invention is disclosed as above in terms of preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art may make possible changes and modifications without departing from the spirit and scope of the present invention. Therefore, any modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall fall within the scope of protection defined by the claims of the present invention.

Claims

1. A continuous production process for preparing fertilizer from histidine fermentation waste liquid, characterized in that: The production process specifically comprises the following steps: Step 1: collecting histidine fermentation waste liquid, adding a mixture of nano-zeolite and modified wood cellulose to the waste liquid, stirring for a period of time to mix and react evenly, and after the reaction is completed, centrifugally separating the composite adsorption material and the waste liquid; Step 2: Preparation of specific polymer materials: dissolving a monomer containing a carboxyl group and a benzene ring structure in a dimethyl sulfoxide solvent, adding an azobisisobutyronitrile initiator to carry out a polymerization reaction, and preparing a polymer containing a carboxyl group and a benzene ring structure; adding the polymer to the waste liquid that has been preliminarily removed from impurities, stirring the reaction, and centrifugally separating the polymer and the waste liquid after the reaction is completed; and then eluting the bound histidine with an acidic eluent, and purifying and concentrating the polymer; Step 3: adding lysine solution, glutamic acid solution and vitamin B6 solution to the purified and concentrated histidine solution, stirring and reacting for a period of time to generate a new complex substance containing multiple amino acids and vitamins; Step 4: Collect the secondary waste liquid generated in the above treatment process, filter and remove impurities, add adsorbent to the secondary waste liquid to adsorb residual organic matter and heavy metal ions, add neutralizer to adjust pH after adsorption, and finally, mix the treated secondary waste liquid with the new composite material and conventional fertilizer ingredients, stir evenly to make liquid fertilizer.

2. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 1, the following modification method is used for the lignocellulose: the lignocellulose is reacted with acetic anhydride under the action of pyridine catalyst to introduce ester functional groups, and at the same time, the lignocellulose is oxidized by an oxidant to generate carboxyl functional groups on its surface, so that the modified lignocellulose has two active functional groups, namely carboxyl and ester groups.

3. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 1, the fermentation waste liquid and the mixture are fully reacted for 1 h to 1.5 h at a temperature of 25° C. to 30° C. and a stirring speed of 20 r / min to 25 r / min.

4. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 2, the monomer containing carboxyl and benzene ring structure is p-carboxyl styrene, and the mass ratio of p-carboxyl styrene and azobisisobutyronitrile initiator added is 3-5:1-1.2, the polymerization reaction temperature is controlled at 50°C-60°C, and the reaction time is 1.0h-1.5h.

5. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 2, a high molecular weight polymer is added to the waste liquid after preliminary impurity removal, the stirring speed is controlled to be 30 r / min-40 r / min, the temperature is 30° C.-35° C., the reaction time is 2 h-3 h, and after centrifugation, the bound histidine is eluted with an acidic eluent with a pH value of 4.0-5.

0.

6. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step three, the concentration of the lysine solution is 0.1 mol / L, the concentration of the glutamic acid solution is 0.05 mol / L, the concentration of the vitamin B6 solution is 0.01 mol / L, and the addition ratio of the histidine solution, the lysine solution, the glutamic acid solution and the vitamin B6 solution is 9-11:1.2-1.5:0.6-0.8:2.1-2.

6.

7. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 3, the reaction temperature is 40°C-45°C, the stirring speed is 20r / min-25r / min, and the reaction time is 1h-1.5h.

8. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 4, the adsorbent is attapulgite adsorbent, the adsorption temperature is 20°C-25°C, the adsorption time is 1h-2h, the neutralizer is sodium bicarbonate, and the adjusted pH value is 6.5-7.

5.

9. The continuous production process for preparing fertilizer from histidine fermentation waste liquid according to claim 1, characterized in that: In the step 4, conventional fertilizer ingredients include potassium dihydrogen phosphate, urea and potassium sulfate, and the mass ratio of the treated secondary waste liquid: the new composite substance: potassium dihydrogen phosphate: urea: potassium sulfate is 0.8-1.0: 1.0-1.2: 0.3-0.5: 0.5-0.8: 0.2-0.4, the stirring speed is controlled to 15r / min-20r / min, and the stirring time is 2h-3h.

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