CN110683908B - Amino acid slow-release fertilizer prepared from fermentation waste - Google Patents
Amino acid slow-release fertilizer prepared from fermentation waste Download PDFInfo
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- CN110683908B CN110683908B CN201911052018.5A CN201911052018A CN110683908B CN 110683908 B CN110683908 B CN 110683908B CN 201911052018 A CN201911052018 A CN 201911052018A CN 110683908 B CN110683908 B CN 110683908B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
Abstract
The invention belongs to the technical field of environmental protection of amino acid waste treatment, and discloses an amino acid slow release fertilizer prepared from fermentation waste, which is characterized by being prepared according to the following steps: step 1) separating amino acid fermentation liquor; step 2) preparing amino acid metal chelating liquid; step 3) preparing carbonized particles; and 4) spraying, stirring and packaging. The slow release fertilizer prepared by the invention has low cost, high nutritional value and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental protection of amino acid waste treatment, and particularly relates to an amino acid slow-release fertilizer prepared by utilizing fermentation waste.
Background
The amino acid in the amino acid fertilizer can be directly used by crops to synthesize protein, nucleic acid and individual endogenous hormone, so that the amino acid fertilizer is a good fertilizer with quick response and good effect, can replace part of nitrogen fertilizer, enhances photosynthesis, and turns dark green in leaf color. The different amino acid types function differently, wherein aspartic acid enhances seed germination, protein synthesis, and nitrogen supply during stressed growth; isoleucine and leucine can improve salt stress resistance, pollen activity and germination, and aromatic precursor; the phenylalanine can increase lignification, tip control and anthocyanin of the plant; arginine can enhance root development, is a precursor for synthesizing plant endogenous hormone polyamine, and can improve the salt stress resistance of crops; the alanine is added to synthesize chlorophyll, so that the stomata are regulated and opened, and the resistance to pathogenic bacteria is realized; the glycine has a unique effect on the photosynthesis of crops, is beneficial to the growth of the crops and increases the sugar content of the crops; tryptophan is a precursor for synthesis of indole acetic acid, an endogenous hormone, and improves synthesis of aromatic compounds; histidine regulates stomatal opening and provides a precursor for carbon skeleton hormones, a catalytic enzyme for cytokinin synthesis; lysine can enhance chlorophyll synthesis and increase drought tolerance; tyrosine can increase drought tolerance and improve pollen germination; glutamic acid can stimulate plant growth and improve resistance to adverse climatic conditions.
Amino acid can produce a large amount of mycoprotein in the fermentation process, the prior art generally prepares the mycoprotein into feed, and the applicant further studies the utilization of mycoprotein, including preparing nitrogen source components of culture medium or amino acid fertilizer, for example, chinese patent "CN 201410519206", a fertilizer prepared by threonine fermentation waste "treats mycoprotein for preparing amino acid chelated fertilizer, wherein, the method for preparing amino acid chelate is as follows: drying mycoprotein, crushing the mycoprotein into powder by a crusher, then placing the powder into a reaction kettle, adding 6-8mol/L hydrochloric acid, stirring and hydrolyzing the raw materials at 60 ℃ for 12-15 hours at a stirring speed of 100 r/min, neutralizing residual hydrochloric acid by potassium hydroxide after the reaction is finished to obtain an amino acid aqueous solution, and then adding a catalyst into the reaction kettle according to a molar ratio of amino acid to metal ions of 3: 1, adding metal ions at the temperature of 40 ℃, for 30min and at the pH of 7.0, carrying out a chelation reaction, and finally concentrating, drying and crushing a chelated product to obtain an amino acid chelate; the method adopts acid hydrolysis to obtain L-amino acid, but tryptophan is completely destroyed by boiling acid; a small portion of amino acids containing hydroxyl groups such as serine or threonine is cleaved; the amide groups of the asparagine and glutamine side chains are hydrolyzed to carboxyl groups. The products of the prior art which adopts alkaline hydrolysis are D-type amino acid and L-type amino acid, and because many amino acids are damaged in different degrees in the hydrolysis process, the yield is not high. Therefore, the obtained free amino acid part belongs to right helix by hydrolyzing the mycoprotein with strong acid and alkali, the activity is poor, the absorption by plants is not facilitated, and tryptophan used for synthesizing the plant growth hormone is damaged.
However, various L-amino acids can be produced by using the biological enzyme technology, but the enzyme preparation is needed, so that the cost is high and the enterprise is difficult to bear.
Disclosure of Invention
The invention aims to solve the technical problem of providing an amino acid slow-release fertilizer prepared by utilizing fermentation waste.
The invention is realized by the following technical scheme.
The amino acid slow release fertilizer prepared from fermentation waste is characterized by being prepared according to the following steps:
step 1) separating amino acid fermentation liquor;
step 2) preparing amino acid metal chelating liquid;
step 3) preparing carbonized particles;
and 4) spraying, stirring and packaging.
Further, the amino acid slow release fertilizer is prepared according to the following steps:
step 1) separating amino acid fermentation liquor: separating amino acid fermentation liquor, collecting mycoprotein and liquid, extracting amino acid from the liquid, and reserving fermentation wastewater generated in the extraction process for later use;
step 2) preparing amino acid metal chelating solution: drying mycoprotein at 80 ℃, grinding, sieving with a 50-100 mesh sieve, adding an aqueous solution containing calcium salt, manganese salt and zinc salt, keeping the mycoprotein content at 40-100g/L, treating by ultrasonic waves for 8-10min, shearing in a high-speed shearing machine at 10000rpm for 60-80s, stopping shearing, adding neutral protease and papain, keeping the temperature at 50 ℃ and the time at 8 h; then heating to 60 ℃, and preserving heat for 1-2 hours to obtain amino acid metal chelating liquid;
step 3) preparing carbonized particles: crushing crop straws to obtain straw powder, sequentially adding the straw powder and bentonite into fermentation wastewater, uniformly mixing, standing for 12 hours, then placing the mixture into a granulator for granulation, placing the granules into a tubular furnace, carbonizing the granules in a nitrogen atmosphere at the temperature of 500 ℃ for 30min, taking out, and naturally cooling to obtain carbonized granules;
step 4), spraying, stirring and packaging: spraying the amino acid metal chelating solution obtained in the step 2) to the carbonized particles obtained in the step 3), uniformly stirring, drying at 55-65 ℃, and packaging to obtain the amino acid metal chelating agent.
Preferably, the concentrations of the calcium salt, the manganese salt and the zinc salt are all 0.03-0.05 mol/L.
Preferably, the calcium salt is selected from calcium nitrate, calcium chloride or a mixture of the two.
Preferably, the manganese salt is manganese sulfate, manganese nitrate or a mixture of the manganese sulfate and the manganese nitrate.
Preferably, the zinc salt is zinc sulfate, zinc nitrate or a mixture of the two.
Preferably, the addition amount of the neutral protease is 1200U/L, and the addition amount of the papain is 1000U/L.
Preferably, the ratio of the amino acid metal chelating solution to the carbonized particles is 1L:4-5 kg.
Preferably, the fermentation wastewater: straw powder: bentonite = 1L: 200-300 g: 150- & ltwbr/& gt 200g.
Preferably, the frequency of the ultrasonic wave is 20-25 kHz.
Compared with the prior art, the invention has the advantages that the following aspects are mainly included but not limited:
the invention adopts ultrasonic treatment and high-speed shearing treatment, can fully crush the cell walls of the thalli, and simultaneously leads partial protein peptide bonds to be broken, thereby being beneficial to the subsequent enzymolysis reaction; according to the invention, firstly, the metal salt is added into the mycoprotein solution, so that the osmotic pressure is improved, the thallus cracking is promoted, the enzyme activity is improved, the metal salt can be used as metal ions for amino acid chelation for preparing amino acid chelates, a plurality of technical problems are solved, the enzymolysis and the chelation are carried out simultaneously, and the cost and the operation flow are saved; experiments show that the hydrolysis rate and the amino acid yield can be improved by the compatibility of the neutral protease and the papain.
The method has the advantages that the amino acid wastewater is difficult to treat, the investment cost of enterprises is high, the traditional stacking and burning disposal mode is improved by utilizing the process, the negative influence on the environment is reduced, and the nutrient substances contained in the amino acid wastewater are fully utilized; the carbonized particles prepared by the invention utilize waste water and agricultural wastes, the adsorption effect is enhanced by adding bentonite, amino acid chelates can be adsorbed by coordination, hydrogen bonds, coulomb force and other modes, the defects of amino acid loss and too fast release along with water are avoided, and the carbonized particles can be finally and fully utilized by plants to provide nutrients for the plants.
Drawings
FIG. 1: influence of enzymolysis temperature on amino acid content;
FIG. 2: influence of enzymolysis time on amino acid content.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the present application will be clearly and completely described below with reference to specific embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The amino acid slow release fertilizer prepared from the fermentation waste is prepared according to the following steps:
preparing glutamic acid fermentation liquor by utilizing corynebacterium glutamicum fermentation, centrifuging the fermentation liquor, collecting mycoprotein and filtrate, using the filtrate for extracting glutamic acid, and reserving fermentation wastewater generated in the extraction process for later use;
drying mycoprotein at 80 ℃, grinding, sieving with a 100-mesh sieve, adding an aqueous solution containing calcium salt, manganese salt and zinc salt, keeping the mycoprotein content at 70g/L, processing by adopting 20kHz ultrasonic waves for 10min, then placing in a high-speed shearing machine to shear for 80s at the speed of 10000rpm, stopping shearing, adding neutral protease (12 ten thousand U/g) and papain (10 ten thousand U/g), wherein the adding amounts are 1200U/L and 1000U/L respectively, the temperature is 50 ℃, and the time is 8 h; then heating to 60 ℃, and preserving heat for 1h to obtain amino acid metal chelating liquid;
the concentrations of the calcium salt, the manganese salt and the zinc salt are all 0.05mol/L;
calcium salt is calcium nitrate; manganese sulfate is selected as manganese salt; zinc salt is zinc sulfate;
smashing corn stalk and obtaining straw powder, then adding straw powder and bentonite in proper order into waste water, the addition is waste water: straw powder: bentonite = 1L: 300 g: 200g, uniformly mixing, standing for 12h, then placing in a granulator for granulation (the particle size is 1 mm), placing the granules in a tube furnace, carbonizing in a nitrogen atmosphere at 500 ℃ for 30min, taking out, and naturally cooling to obtain carbonized granules;
spraying amino acid metal chelate liquid onto the carbonized particles, stirring uniformly, drying at 60 ℃, and packaging to obtain the product; the ratio of the amino acid metal chelating solution to the carbonized particles is 1L:5 kg.
Example 2
The amino acid slow release fertilizer prepared from the fermentation waste is prepared according to the following steps:
preparing threonine fermentation liquor by utilizing Brevibacterium flavum through fermentation according to a conventional fermentation mode, separating the fermentation liquor, collecting mycoprotein and liquid, using the liquid for extracting threonine, and reserving fermentation wastewater generated in the extraction process for later use;
baking mycoprotein at 85 ℃, grinding, sieving with a 50-mesh sieve, adding an aqueous solution containing calcium salt, manganese salt and zinc salt, keeping the mycoprotein content at 60g/L, treating with 25kHz ultrasonic waves for 8min, shearing in a high-speed shearing machine at 10000rpm for 70s, stopping shearing, adding neutral protease (12 ten thousand U/g) and papain (10 ten thousand U/g), wherein the adding amounts are 1000U/L and 800U/L respectively, the temperature is 50 ℃, and the time is 8 h; then heating to 60 ℃, and preserving heat for 2 hours to obtain amino acid metal chelating liquid;
the concentrations of the calcium salt, the manganese salt and the zinc salt are all 0.04 mol/L;
calcium salt is calcium chloride; manganese nitrate is selected as the manganese salt; zinc salt is zinc nitrate;
smashing corn stalk and obtaining straw powder, then adding straw powder and bentonite in proper order into waste water, the addition is waste water: straw powder: bentonite = 1L: 250 g: 150g, uniformly mixing, standing for 12h, then placing in a granulator for granulation (the particle size is 2 mm), placing the granules in a tube furnace, carbonizing in a nitrogen atmosphere at 550 ℃ for 20min, taking out, and naturally cooling to obtain carbonized granules;
spraying amino acid metal chelate liquid onto the carbonized particles, stirring uniformly, drying at 65 ℃, and packaging to obtain the product; the ratio of the amino acid metal chelating solution to the carbonized particles is 1L:4 kg.
Example 3
And (3) testing the performance of the amino acid metal chelating solution:
chelation rate (%) = (W1-W0) × 100/Wl;
w1: the total metal ion content;
w0: content of free metal ions.
Grouping:
experimental groups: example 1;
comparative group 1: only neutral protease is used, and the addition amount is 2200U/L;
comparative group 2: only using papain, and the adding amount is 2200U/L;
comparative group 3: ultrasonic and high speed shearing treatments are not used.
See table 1 for details.
TABLE 1
| 1. Index (I) | 2. Chelate ratio (%) | 3. Amino acid content g/ |
| 4. The invention | 5. 91.4 | 6. 3.35 |
| 7. |
8. 86.9 | 9. 2.31 |
| 10. |
11. 88.5 | 12. 2.74 |
| 13. |
14. 75.8 | 15. 1.77 |
As shown in Table 1, compared with the comparison groups 1-3, the experimental group of the present invention has significantly improved chelating ratio and amino acid content. The invention adopts ultrasonic treatment and high-speed shearing treatment in sequence, can fully crush the cell walls of the thalli, and simultaneously breaks partial protein peptide bonds, thereby being beneficial to the subsequent enzymolysis reaction; according to the invention, calcium salt, manganese salt and zinc salt are added into the mycoprotein solution, so that the osmotic pressure is improved, the cracking of thalli is promoted, the enzyme activity is improved, the mycoprotein solution can be used as metal ions for amino acid chelation to prepare amino acid chelate, the enzymolysis and the chelation are carried out simultaneously, and the cost and the operation flow are saved; the invention adopts the compatibility of neutral protease and papain to improve the hydrolysis rate and the amino acid yield.
Example 4
The influence of the enzymolysis temperature and time on the amino acid content.
As shown in figure 1-2, the enzymolysis temperature is selected to be 45-50 deg.C, the highest amino acid content, considering that the formation of amino acid chelate needs higher temperature (60 deg.C is the best), the enzyme activity and the chelating temperature are combined for consideration, and 50 deg.C is selected as the best temperature. The content of amino acid is continuously increased along with the increase of the enzymolysis time, the amino acid is close to the peak value after about 8 hours of enzymolysis, the enzymolysis time is continuously increased, the content of the amino acid is not obviously improved, but the chelating time and the required temperature of the amino acid and metal ions are comprehensively considered, after the enzymolysis reaction is basically finished, the temperature is raised to 60 ℃, and the heat is preserved for 1 hour, so that the chelating rate is improved.
Example 5
The fertilizer efficiency test of the invention takes winter wheat as an example.
Setting fertilizer groups:
group 1: no fertilizer is applied;
group 2: 7kg of nitrogen-phosphorus-potassium ternary fertilizer (the content ratio of nitrogen, phosphorus and potassium is 15:14: 12) and 1kg of amino acid slow-release fertilizer are applied to each cell;
group 3: 8kg of nitrogen, phosphorus and potassium ternary fertilizer is applied to each cell;
9 cells are set, and each cell has an area of 100m2Each group was planted 3 times in duplicate and distributed completely at random.
The soil is brown soil, winter wheat is planted, and planting conditions of all communities are completely the same; see table 2 for details.
TABLE 2
| 16. Group of | 17. Cell output kg | 18. Ear length cm | 19. Height cm of plant | 20. Grain number per ear | 21. Protein content% |
| 22. |
23. 26.2 | 24. 6.3 | 25. 75.3 | 26. 27.8 | 27. 20.9 |
| 28. |
29. 49.6 | 30. 7.2 | 31. 89.5 | 32. 38.1 | 33. 23.4 |
| 34. |
35. 43.1 | 36. 7.0 | 37. 86.4 | 38. 35.9 | 39. 22.7 |
And (4) conclusion: the amino acid slow release fertilizer is adopted to replace part of nitrogen, phosphorus and potassium ternary fertilizer, so that the cost is saved, and various indexes of crop planting are improved. The amino acid slow release fertilizer can improve the chlorophyll content of the leaves, enhance the photosynthetic capacity and increase the grain weight, thereby improving the yield; compared with the group 3 only using the compound fertilizer, the group 2 uses the amino acid slow release fertilizer to partially replace the nitrogen-phosphorus-potassium ternary fertilizer, so that the biological properties of the wheat are improved, the ear length, the plant height and the grain number per ear are improved, and the protein content and the yield of wheat grains can be improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. The amino acid slow release fertilizer prepared from fermentation waste is characterized by being prepared according to the following steps:
step 1) separating amino acid fermentation liquor: separating amino acid fermentation liquor, collecting mycoprotein and liquid, extracting amino acid from the liquid, and reserving fermentation wastewater generated in the extraction process for later use;
step 2) preparing amino acid metal chelating solution: drying mycoprotein at 80 ℃, grinding, sieving with a 50-100 mesh sieve, adding an aqueous solution containing calcium salt, manganese salt and zinc salt, keeping the mycoprotein content at 40-100g/L, treating by ultrasonic waves for 8-10min, shearing in a high-speed shearing machine at 10000rpm for 60-80s, stopping shearing, adding neutral protease and papain, keeping the temperature at 50 ℃ and the time at 8-9 h; then heating to 60 ℃, and preserving heat for 1-2 hours to obtain amino acid metal chelating liquid;
the concentrations of the calcium salt, the manganese salt and the zinc salt are all 0.03-0.05mol/L;
the calcium salt is selected from calcium nitrate, calcium chloride or a mixture of the calcium nitrate and the calcium chloride;
the manganese salt is manganese sulfate, manganese nitrate or a mixture of the manganese sulfate and the manganese nitrate;
the zinc salt is zinc sulfate, zinc nitrate or a mixture of the zinc sulfate and the zinc nitrate;
the addition amount of the neutral protease is 1200U/L, and the addition amount of the papain is 1000U/L;
step 3) preparing carbonized particles: crushing crop straws to obtain straw powder, sequentially adding the straw powder and bentonite into fermentation wastewater, uniformly mixing, standing for 12 hours, then placing the mixture into a granulator for granulation, placing the granules into a tubular furnace, carbonizing the granules in a nitrogen atmosphere at the temperature of 500 ℃ for 30min, taking out, and naturally cooling to obtain carbonized granules;
the fermentation wastewater: straw powder: bentonite = 1L: 200-300 g: 150-200 g;
step 4), spraying, stirring and packaging: spraying the amino acid metal chelating solution obtained in the step 2) to the carbonized particles obtained in the step 3), uniformly stirring, drying at 55-65 ℃, and packaging to obtain the amino acid metal chelating solution;
the ratio of the amino acid metal chelating solution to the carbonized particles is 1L:4-5 kg.
2. The amino acid slow release fertilizer according to claim 1, wherein the frequency of the ultrasonic waves is 20-25 kHz.
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