CN112409057A - Method for preparing organic fertilizer by using amino acid fermentation waste - Google Patents
Method for preparing organic fertilizer by using amino acid fermentation waste Download PDFInfo
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- CN112409057A CN112409057A CN202011600506.8A CN202011600506A CN112409057A CN 112409057 A CN112409057 A CN 112409057A CN 202011600506 A CN202011600506 A CN 202011600506A CN 112409057 A CN112409057 A CN 112409057A
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- 150000008575 L-amino acids Chemical class 0.000 description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The invention belongs to the technical field of amino acid fermentation, and discloses a method for preparing an organic fertilizer by using amino acid fermentation waste, which comprises the following steps: collecting mycoprotein in the amino acid fermentation waste, drying, grinding, sieving, adding an aqueous solution containing copper salt, manganese salt and zinc salt, treating by ultrasonic waves, shearing by a high-speed shearing machine, adding phosphoric acid to adjust the pH value to 4.0-4.5, adding glucose to control the glucose concentration to be 20-40g/L, inoculating the composite bacterial liquid according to the inoculation amount of 4-8%, biologically treating for 8-12h at the temperature of 30 ℃, centrifuging for 3min at 500rpm, and collecting a supernatant; then heating to 60 ℃, and preserving heat for 1h to obtain the amino acid metal chelating solution.
Description
Technical Field
The invention belongs to the technical field of amino acid fermentation, and relates to a method for preparing an organic fertilizer by using amino acid fermentation waste.
Background
Amino acid exists in the fertilizer as the minimum molecule of the protein, and has the characteristic of being easily absorbed by crops; also has the functions of improving disease resistance of the fertilization objects and improving the quality of the fertilization crops. Supplementing essential amino acids, stimulating and regulating plant growth, promoting plant growth, and promoting nutrient absorption. The metabolism function of the plant is enhanced, the photosynthesis is improved, the development of the root system of the plant is promoted, and the growth and the propagation of the plant are accelerated. The fertilizer containing an amino acid is a fertilizer containing a specific amount of an amino acid-based substance. When applied to soil, amino acid-containing fertilizers have the functions of improving disease resistance of fertilization targets and improving quality of fertilization crops. At present, most of fertilizers containing amino acid are prepared by hydrochloric acid, but the preparation method by hydrochloric acid needs severer production conditions and has high production cost, so that the biological fertilizer containing amino acid is not easy to popularize.
Amino acid can produce a large amount of mycoprotein in the fermentation process, the prior art generally prepares the mycoprotein into feed, the application value is low, the application channel is narrow, the applicant further studies the utilization of the mycoprotein, the utilization of the mycoprotein comprises nitrogen source components or amino acid fertilizers prepared into culture media, for example, Chinese patent ' CN201410519206 ', a fertilizer prepared by threonine fermentation waste ' treats the mycoprotein for preparing amino acid chelated fertilizers, wherein the method for preparing the amino acid chelate comprises the following steps: 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. The existing literature adopts hydrochloric acid with higher concentration to treat mycoprotein, which is easy to damage amino acid, and results in lower nutritive value of hydrolysate.
In contrast, the patent technology CN201911052018 discloses a method for preparing amino acid metal chelating liquid, comprising 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 with ultrasonic waves for 8-10min, shearing in a high-speed shearing machine at 10000rpm for 60-80s, stopping shearing, adding neutral protease and papain, at 50 ℃ for 8 h; then heating to 60 ℃, and preserving heat for 1-2 hours to obtain amino acid metal chelating liquid; the method can produce diversified L-amino acids by adopting a biological enzyme technology, but needs an enzyme preparation, has higher cost and is difficult to bear by enterprises.
Disclosure of Invention
On the basis of the prior art, the invention provides a method for preparing an organic fertilizer by using amino acid fermentation waste in order to improve the product quality and save the enterprise cost.
The invention is realized by the following technical scheme:
the method for preparing the organic fertilizer by utilizing the amino acid fermentation waste comprises the following steps:
collecting mycoprotein in the amino acid fermentation waste, drying at 80 ℃, grinding, sieving with a 100-mesh sieve, adding an aqueous solution containing copper salt, manganese salt and zinc salt, keeping the mycoprotein content at 60-80g/L, treating with 20kHz ultrasonic waves for 10min, placing in a high-speed shearing machine, shearing at 10000rpm for 80s, stopping shearing, adding phosphoric acid to adjust the pH to 4.0-4.5, adding glucose to control the glucose concentration to be 20-40g/L, inoculating a compound bacterial liquid according to an inoculation amount of 4-8%, biologically treating at 30 ℃ for 8-12h, centrifuging at 500rpm for 3min, and collecting a supernatant; then heating to 60 ℃, and preserving heat for 1h to obtain amino acid metal chelating liquid;
the amino acid metal chelate fertilizer is used for preparing the organic fertilizer.
Specifically, the specific steps of preparing the amino acid metal chelate fertilizer into the organic fertilizer are as follows:
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 12 hours, then placing in a granulator for granulation, placing the granules in a tube furnace, carbonizing at 500 ℃ in a nitrogen atmosphere 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.
Preferably, the composition of the compound bacterial liquid is as follows: aspergillus oryzae seed liquid: lactobacillus acidophilus seed liquid = 2: 1, in a volume ratio.
Preferably, the composition of the compound bacterial liquid is as follows: aspergillus oryzae seed liquid: lactobacillus acidophilus seed liquid = 1: 1, in a volume ratio.
Preferably, the copper salt is copper sulfate, the manganese salt is manganese sulfate, and the zinc salt is zinc sulfate.
Preferably, phosphoric acid is added to adjust the pH to 4.0.
Preferably, glucose is added to control the glucose concentration to 30 g/L.
Preferably, the biological treatment is carried out at a temperature of 30 ℃ for 10 h.
More preferably, the concentration of the copper salt, the manganese salt and the zinc salt is 0.05 mol/L.
Compared with the prior art, the invention has the advantages that the following aspects are mainly included but not limited:
the method for preparing the organic fertilizer continues to use the technology of CN201911052018, and is different in that the treatment process of mycoprotein is improved, so that the method aims to avoid using an industrial enzyme preparation and reduce the cost of enterprises.
According to the invention, the pH value suitable for the growth of the strain to produce the enzyme is adjusted by adding phosphoric acid, both aspergillus oryzae and lactobacillus acidophilus can proliferate in a weakly acidic environment, and the strain has good symbiotic synergistic performance, the capability of producing acid protease and neutral protease is greatly improved compared with that of a single strain, and metal ions such as copper, manganese, zinc and the like are added in the biological enzymolysis treatment process, so that the strain not only serves as heavy metal ions for chelating fertilizer, but also can promote the enzyme production of aspergillus oryzae and lactobacillus acidophilus. The invention carries out biological enzymolysis and chelation simultaneously, thus saving cost and operation flow.
Detailed Description
Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the products and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications, or appropriate alterations and combinations, of the products and methods described herein may be made and utilized without departing from the spirit, scope, and spirit of the invention. For a further understanding of the present invention, reference will now be made in detail to the following examples.
The specific strains selected by the invention are Aspergillus oryzae ATCC 42149 and Lactobacillus acidophilus ATCC 4356, and the concentration of the strains is 10 according to the conventional culture mode respectively9cfu/ml of seed solution.
Example 1
The method for preparing the organic fertilizer by utilizing the amino acid fermentation waste comprises the following steps:
baking mycoprotein at 80 ℃, grinding, sieving with a 100-mesh sieve, adding an aqueous solution containing copper salt, manganese salt and zinc salt, keeping the mycoprotein content at 80g/L, processing by adopting 20kHz ultrasonic wave for 10min, then placing in a high-speed shearing machine, shearing at 10000rpm for 80s, stopping shearing, adding phosphoric acid to adjust the pH to 4.0, adding glucose to control the glucose concentration in the solution to be 30g/L, then inoculating a compound bacterial liquid (an aspergillus oryzae seed liquid: lactobacillus acidophilus seed liquid = 2: 1 in volume ratio) according to an inoculum concentration of 5 percent, biologically treating for 10h at the temperature of 30 ℃, then centrifuging at 500rpm for 3min, and collecting a supernatant; then heating to 60 ℃, and preserving heat for 1h to obtain amino acid metal chelating liquid;
the concentrations of the copper salt, the manganese salt and the zinc salt are all 0.05 mol/L;
copper sulfate is selected as the copper salt; 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 method for preparing the organic fertilizer by utilizing the amino acid fermentation waste comprises the following steps:
baking mycoprotein at 80 ℃, grinding, sieving with a 100-mesh sieve, adding an aqueous solution containing copper salt, manganese salt and zinc salt, keeping the mycoprotein content at 80g/L, processing by adopting 20kHz ultrasonic waves for 10min, then placing in a high-speed shearing machine, shearing at 10000rpm for 80s, stopping shearing, adding phosphoric acid to adjust the pH to 4.5, adding glucose to control the glucose concentration to be 35g/L, then inoculating a compound bacterial liquid (an Aspergillus oryzae seed liquid: a Lactobacillus acidophilus seed liquid = 1: 1 in volume ratio) according to an inoculum size of 6%, biologically treating at 30 ℃ for 8h, then centrifuging at 500rpm for 4min, and collecting supernatant and precipitate (the supernatant and the precipitate can be applied to animal feed proteins after sterilization); then heating the supernatant to 60 ℃, and preserving heat for 1h to obtain amino acid metal chelating solution;
the concentrations of the copper salt, the manganese salt and the zinc salt are all 0.05 mol/L;
copper sulfate is selected as the copper salt; 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.
Comparative 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 copper salt, manganese salt and zinc salt, keeping the mycoprotein content at 80g/L, processing by adopting 20kHz ultrasonic wave 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 copper salt, the manganese salt and the zinc salt are all 0.05 mol/L;
copper sulfate is selected as the copper salt; 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 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.
Comparing enzymatic hydrolysis and biological enzymatic hydrolysis of the enzyme preparation:
group 1: example 1;
group 2: the same procedure as in example 1 was repeated except that Aspergillus oryzae alone was used;
group 3: using only lactobacillus acidophilus, the rest of the procedure was the same as in example 1;
group 4: comparative example 1.
The specific chelating ratio and amino acid content are shown in table 1:
TABLE 1
| Group of | Chelate ratio (%) | Amino acid content g/L |
| Group 1 | 92.5 | 3.66 |
| Group 2 | 87.1 | 2.97 |
| Group 3 | 84.6 | 2.82 |
| Group 4 | 92.6 | 3.53 |
As shown in Table 1, the group 1 adopts a method of mixed enzymolysis of Aspergillus oryzae and Lactobacillus acidophilus, the enzymolysis effect is slightly better than that of the group 4 adopting a combination mode of neutral protease and papain, and the metal chelation rate is not obviously different; the group 2 and the group 3 adopt single aspergillus oryzae or lactobacillus acidophilus for enzymolysis, and the two indexes of the chelation rate and the amino acid content are obviously reduced compared with the group 1.
The invention also detects the composition of each main functional amino acid in the total amino acid, and the composition is specifically shown in the following table 2:
TABLE 2
| Name of major amino acid | Example 1 | Comparative example 1 |
| Phenylalanine | 5.29 | 5.71 |
| Leucine | 6.89 | 6.32 |
| Isoleucine | 5.13 | 4.89 |
| Aspartic acid | 7.87 | 8.21 |
| Arginine | 6.26 | 5.78 |
| Alanine | 3.71 | 4.03 |
| Glycine | 4.39 | 3.96 |
| Tryptophan | 3.87 | 4.05 |
| Histidine | 4.92 | 5.12 |
As can be seen from Table 2, the amino acid components obtained by hydrolyzing mycoprotein with the complex enzyme preparation and the complex microbial inoculum are relatively complete in variety and have small integral difference.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The method for preparing the organic fertilizer by utilizing the amino acid fermentation waste comprises the following steps:
collecting mycoprotein in the amino acid fermentation waste, drying at 80 ℃, grinding, sieving with a 100-mesh sieve, adding an aqueous solution containing copper salt, manganese salt and zinc salt, keeping the mycoprotein content at 60-80g/L, treating with 20kHz ultrasonic waves for 10min, placing in a high-speed shearing machine, shearing at 10000rpm for 80s, stopping shearing, adding phosphoric acid to adjust the pH to 4.0-4.5, adding glucose, controlling the glucose concentration in the solution to be 20-40g/L, inoculating a compound bacterial solution according to an inoculation amount of 4-8%, biologically treating at 30 ℃ for 8-12h, centrifuging at 500rpm for 3min, and collecting a supernatant; then heating to 60 ℃, and preserving heat for 1h to obtain amino acid metal chelating liquid;
the amino acid metal chelate fertilizer is used for preparing the organic fertilizer.
2. The process according to claim 1, wherein the specific steps of preparing the organic fertilizer from the amino acid metal chelate fertilizer are as follows:
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 12 hours, then placing in a granulator for granulation, placing the granules in a tube furnace, carbonizing at 500 ℃ in a nitrogen atmosphere 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.
3. The process of claim 1, wherein the composition of the composite bacterial liquid is as follows: aspergillus oryzae seed liquid: lactobacillus acidophilus seed liquid = 2: 1, in a volume ratio.
4. The process of claim 1, wherein the composition of the composite bacterial liquid is as follows: aspergillus oryzae seed liquid: lactobacillus acidophilus seed liquid = 1: 1, in a volume ratio.
5. The process of claim 1, wherein the copper salt is copper sulfate, the manganese salt is manganese sulfate, and the zinc salt is zinc sulfate.
6. The process of claim 1, wherein the pH is adjusted to 4.0 by the addition of phosphoric acid.
7. The process of claim 1, wherein the glucose is added to control the glucose concentration to 30 g/L.
8. The process according to claim 1, characterized in that the biological treatment is carried out at a temperature of 30 ℃ for 10 h.
9. The process according to claim 5, wherein the concentrations of the copper, manganese and zinc salts are 0.05 mol/L.
10. An organic fertilizer prepared by the process of any one of claims 1-9.
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