CN112142510A - Regulating solution for improving vitamin C content of crops and preparation method and application thereof - Google Patents
Regulating solution for improving vitamin C content of crops and preparation method and application thereof Download PDFInfo
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- CN112142510A CN112142510A CN201910588061.7A CN201910588061A CN112142510A CN 112142510 A CN112142510 A CN 112142510A CN 201910588061 A CN201910588061 A CN 201910588061A CN 112142510 A CN112142510 A CN 112142510A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic 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 relates to the technical field of resource utilization of vitamin C industrial production waste liquid and fertilizer production, in particular to a regulating liquid/fertilizer for improving the vitamin C content of crops and a preparation method and application thereof. The method is characterized in that vitamin C industrial waste gulonic acid mother liquor or/and 2-keto-L-gulonic acid are/is used as main raw materials, and the waste gulonic acid mother liquor/2-keto-L-gulonic acid and alkaline solution are subjected to acid-base reaction to obtain regulating solution with the pH value of 3.0-9.0, namely the regulating solution/fertilizer. The regulating solution/fertilizer can be independently applied or used as a regulating solution to be mixed with other chemical fertilizers and biological fertilizers in proportion to be used as a compound fertilizer for application, and can be used as a base fertilizer and an additional fertilizer for application; the fertilizer can be used as a water-soluble fertilizer for soil irrigation and can also be used as a foliar fertilizer for spraying on leaf surfaces. The invention solves the problem of treatment of waste gulonic acid mother liquor, provides a raw material rich in 2-keto-L-gulonic acid and organic acid for fertilizer production, and effectively improves the vitamin C content of crops.
Description
Technical Field
The invention relates to the technical field of fertilizer production, in particular to a technology for recycling vitamin C industrial production waste liquid, and specifically relates to a regulating liquid/fertilizer for improving the vitamin C content of crops, and a preparation method and application thereof.
Background
China is a large country for producing vitamin C (Vc), and the annual Vc production is about 16-18 ten thousand tons, wherein the export quantity is 14.8 ten thousand tons, and the vitamin C is the bulk drug with the largest export quantity in China. In the production process of vitamin C, a large amount of waste-waste gulonic acid mother liquor is discharged. About 0.45 ton of waste gulonic acid mother liquor is discharged per 1 ton of Vc produced, and the annual discharge amount in China is about 7-8 ten thousand tons. The waste gulonic acid mother liquor is the residual liquid of Vc biological fermentation liquor after the processes of ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and the like. The waste gulonic acid mother liquor mainly comprises 15-35% of 2-keto-L-gulonic acid, 1-2% of formic acid, 2-3% of oxalic acid, 1-2% of sorbose, 3-5% of protein, nucleic acid and the like, and the organic matter content of the waste gulonic acid mother liquor is as high as 50-60%. The waste gulonic acid mother liquor is brownish black and viscous, the specific gravity is 1.25-1.40, and the COD value reaches 0.5-1 multiplied by 106mg/L and pH is less than or equal to 0.5. The waste gulonic acid mother liquor can not enter a sewage treatment system for anaerobic and aerobic treatment because of extremely high COD. And if the product is used for preparing oxalic acid, more serious environmental pollution is caused. At present, no effective resource utilization way of waste gulonic acid mother liquor exists. The problem of treatment of waste gulonic acid mother liquor is the neck problem which restricts sustainable and green development of Vc production enterprises at present, and a new way of effective resource utilization is urgently needed to be developed. Meanwhile, the waste gulonic acid mother liquor mainly contains 2-keto-L-gulonic acid, and the content of the 2-keto-L-gulonic acid is as high as 15-35%. 2-keto-L-gulonic acid is a precursor substance for synthesizing vitamin C in the industrial production of vitamin C, and is finally converted into vitamin C through multi-step chemical catalytic reactions, but the vitamin C cannot be spontaneously formed at room temperature in the absence of a catalytic reagent.
The vitamin C in the plant body plays an important role in plant growth metabolism, particularly in the aspect of resisting environmental stress of the plant, and the increase of the content of the vitamin C in the crop body can improve the quality of the crop and the economic value thereof, so that the vitamin C is an important evaluation index of the quality of agricultural products. However, at present, there is no effective method for greatly increasing the vitamin C content of crops (products).
Disclosure of Invention
The invention aims to provide a fertilizer regulating solution which takes waste gulonic acid mother liquor as a main raw material and improves the content of vitamin C in crops, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a fertilizer regulating solution for increasing the content of vitamin C in crops is prepared by adjusting the pH value of waste gulonic acid mother solution/2-keto-L-gulonic acid solution to 3.0-9.0 with alkaline solution to obtain fertilizer regulating solution; meanwhile, the fertilizer can also be used as a fertilizer for crops, namely the fertilizer.
The alkaline solution is a solution with the concentration of 10-50 wt% prepared by an alkaline reagent and water; wherein the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide and liquid ammonia.
And adjusting the pH value of the fertilizer adjusting liquid to 5.5-7.5.
A preparation method of a fertilizer regulating solution for improving the vitamin C content of crops comprises the step of regulating the pH value of waste gulonic acid mother liquor/2-keto-L-gulonic acid to 3.0-9.0 by using an alkaline solution to obtain the fertilizer regulating solution.
The alkaline solution is a solution with the concentration of 10-50% prepared by an alkaline reagent and water; wherein the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide and liquid ammonia.
The application of a fertilizer regulating solution for improving the vitamin C content of crops and the application of the fertilizer regulating solution in improving the vitamin C content and yield of crops.
The regulating solution can be applied independently or mixed with one or more of chemical fertilizer, organic fertilizer, biological fertilizer, inorganic chemical fertilizer raw material and fertilizer auxiliary material.
The regulating solution can be used as a base fertilizer, an additional fertilizer, a water-soluble fertilizer or a leaf fertilizer when being applied alone or mixed with one or more of a chemical fertilizer, an organic fertilizer, a biological fertilizer, an inorganic chemical fertilizer raw material and a fertilizer auxiliary material.
The regulating solution and the base fertilizer are mixed and applied according to the mass ratio of 1: 0.1-50; the conditioning solution and the additional fertilizer are mixed and applied according to the mass ratio of 1: 0.1-50; or the regulating solution and the foliar fertilizer are mixed according to the ratio of 1: 0.1-50 and then sprayed or sprayed independently.
The fertilizer regulating solution is mixed with chemical fertilizer, organic fertilizer and biological fertilizer in proportion, and the mixing proportion is 1: 0-50: 0-50 (mass percent) as a compound fertilizer.
The fertilizer regulating solution is mixed with inorganic fertilizer raw materials and fertilizer auxiliary materials in proportion, wherein the mixing proportion is 1: 0-50: 0-50 (mass percent) as a compound fertilizer.
The fertilizer regulating solution/fertilizer can be used as a base fertilizer and an additional fertilizer, can be used as a water-soluble fertilizer for flushing soil, and can be used as a foliar fertilizer for spraying on leaf surfaces.
The crops refer to various plants cultivated in agriculture. Including grain crops (rice, corn, beans, potatoes, highland barley, broad beans, wheat and the like), oil crops (oilseed, cabbage, mustard, peanut, flax, hemp, sunflower and the like), vegetable crops (radish, cabbage, celery, leek, garlic, shallot, carrot, snake melon, lotus flower, jerusalem artichoke, sword bean, coriander, asparagus lettuce, daylily, hot pepper, cucumber, tomato, caraway and the like), fruits (pear, green plum, apple, peach, apricot, walnut, plum, cherry, strawberry, amomum tsaoko and red date), feed crops (corn, green manure, astragalus sinicus and the like), medicinal crops (ginseng, angelica, honeysuckle, mint, artemisia argyi) and the like.
The waste gulonic acid mother liquor is from a Vc production process, and is residual liquid of Vc biological fermentation liquor after the processes of ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and the like. The waste gulonic acid mother liquor mainly comprises 15-35% of gulonic acid, 3-5% of protein and nucleic acid, 1-2% of sorbose and the like. The organic matter content of the waste gulonic acid mother liquor is 40-60%, and the waste gulonic acid mother liquor contains protein, nucleic acid, micromolecular organic acid and the like. The waste gulonic acid mother liquor is brownish black and viscous, the specific gravity is 1.20-1.40, and the COD value reaches 0.5-1 multiplied by 106mg/L,pH≤0.5。
The finished products of chemical fertilizer, organic fertilizer and biological fertilizer comprise organic fertilizer and inorganic fertilizer sold in the market. The organic fertilizer comprises farmyard manure, commercial organic fertilizer, biological organic fertilizer, organic-inorganic compound fertilizer, various amino acids, protein, humic acid fertilizer and the like. The inorganic fertilizers include nitrogen fertilizers (urea, ammonium carbonate, ammonium chloride, ammonium sulfate, ammonium nitrate, etc.), phosphate fertilizers (calcium superphosphate, calcium magnesium phosphate, heavy calcium, etc.), potassium fertilizers (potassium chloride, potassium sulfate, etc.), compound fertilizers (monoammonium phosphate, diammonium phosphate, monopotassium phosphate, potassium nitrate, various ternary or binary compound fertilizers of nitrogen, phosphorus and potassium, water-soluble fertilizers, etc.), secondary element fertilizers (magnesium potassium sulfate, magnesium potassium chloride), trace element fertilizers, etc.
The inorganic fertilizer raw materials comprise large, medium and trace element fertilizer raw materials. The fertilizer raw materials of the large, medium and trace element fertilizer mainly comprise urea, ammonium chloride, ammonium nitrate, ammonium bicarbonate, calcium magnesium phosphate, calcium superphosphate, ammonium phosphate, diammonium phosphate, phosphoric acid, potassium chloride, potassium nitrate, phosphogypsum, ammonium sulfate, calcium superphosphate, magnesium sulfate, boric acid, borax, sodium decaborate, manganous sulfate monohydrate, manganese monoxide, manganous chloride tetrahydrate, manganese carbonate, manganese dioxide, ferrous sulfate, zinc chloride, zinc carbonate, zinc phosphate, ammonium molybdate tetrahydrate, ammonium molybdate dihydrate, molybdenum trioxide, copper sulfate pentahydrate, copper carbonate, copper chloride, copper oxide and cuprous oxide.
The auxiliary materials are one or more of amino acid, fertilizer synergist, biological agent, humic acid, and organic raw materials (such as turfy soil, livestock and poultry manure, cassava residue, edible fungi waste residue, cassava residue, sugar refinery filter mud, vitamin C fermentation bacteria residue, etc.).
The invention has the following advantages:
1. the method takes the waste gulonic acid mother liquor as the fertilizer raw material, not only solves the problem of resource utilization of the waste mother liquor, but also provides an organic matter raw material for fertilizer production, and realizes changing waste into valuables.
2. The waste gulonic acid mother liquor used in the invention is rich in short-chain organic acid, provides rich organic matter nutrients for crop growth, and particularly is rich in precursor substance-2-keto-L-gulonic acid synthesized by vitamin C in the waste gulonic acid mother liquor, provides sufficient framework substance for the crops to synthesize the vitamin C, promotes the synthesis of the vitamin C in the crops, improves the Vc content of agricultural products, and can realize high-value utilization of the waste gulonic acid mother liquor.
3. The invention takes waste gulonic acid mother liquor as main raw material, and can be directly applied as nutrient regulating solution in the growth process of crops after being treated; or can be prepared into compound fertilizer with finished fertilizer or organic fertilizer; or mixed with inorganic fertilizer raw materials, fertilizer auxiliary materials and the like according to a proper proportion to prepare compound fertilizer, so that the multi-raw-material and multi-formula fertilizer based on the waste gulonic acid mother liquor regulating solution is formed, and the nutrient requirements of different regions and different crops on efficiently synthesizing vitamin C are met.
4. The fertilizer regulating liquid/fertilizer obtained by the invention can be independently applied, and also can be used as a regulating liquid to be mixed with other chemical fertilizers and biological fertilizers in proportion to be used as a compound fertilizer for application. The obtained fertilizer regulating solution/fertilizer can be used as a base fertilizer and an additional fertilizer, can be used as a water-soluble fertilizer for flushing soil, and can be used as a foliar fertilizer for spraying on leaf surfaces.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The fertilizer regulating solution takes waste gulonic acid mother liquor as a raw material, and the waste gulonic acid mother liquor and an alkaline solution are subjected to acid-base reaction to obtain the regulating solution with the pH value of 3.0-9.0, so that the regulating solution is obtained. The regulating solution can be independently applied, or the regulating solution can be used as a compound fertilizer after being mixed with chemical fertilizer and biological fertilizer according to a certain proportion, or the regulating solution can be used as a compound fertilizer after being mixed with inorganic chemical fertilizer raw materials and fertilizer auxiliary materials according to a certain proportion.
Example 1
Preparing a fertilizer regulating solution:
carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 15L of 30% sodium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.32 and the gulonic acid content is 25 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to 3.0 to ensure that the solution temperature is not higher than 60 ℃ in the whole reaction process, so as to obtain a fertilizer regulating solution product 1;
example 2
Carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 17L of 48 wt% potassium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has a specific gravity of 1.25 and the gulonic acid content is 18 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to 4.0 in the whole reaction process to ensure that the solution temperature is not higher than 60 ℃, thereby obtaining a fertilizer regulating solution product 2;
example 3
Carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 18L of 25 wt% ammonia water solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.38 and the gulonic acid content is 32 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to be 6.0 by ensuring that the solution temperature is not higher than 60 ℃ in the whole reaction process, thus obtaining a fertilizer regulating solution product 3;
example 4
Carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 27L of 40% potassium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.32 and the gulonic acid content is 25 wt%), then continuously and slowly adding 8L of 10 wt% ammonia water solution into the plastic barrel, fully stirring in the adding process to prevent local overheating, ensuring that the temperature of the solution is not higher than 60 ℃ in the whole reaction process, and adjusting the pH of the reaction system to be 8.8, namely obtaining a fertilizer regulating solution product 4;
example 5
Carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 27L of 40% potassium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.40 and the gulonic acid content is 35 wt%), then continuously and slowly adding 5L of 10 wt% ammonia water solution into the plastic barrel, fully stirring in the adding process to prevent local overheating, ensuring that the temperature of the solution is not higher than 60 ℃ in the whole reaction process, and adjusting the pH value of a reaction system to 7.0 to obtain a fertilizer regulating solution product 5;
example 6
The fertilizer regulating solution product 1 in the above example 1 was used for the experiment of increasing the vitamin C content of pakchoi:
1.5kg of soil was placed in a plastic pot (15cm height. times.20 cm). Set up 2 groups of processes, the potted plant of the liquid product 1 of fertilizer regulation of applying (process group); potted plants treated with tap water (control group). Uniformly scattering 20 pakchoi seeds with the same size into each pot of soil, and thinning the pakchoi seeds in each pot of soil to 10 when the sprouts of the pakchoi sprouts to 2 cm. During the period of culturing the pakchoi, 75ml of the fertilizer regulating solution product 1 diluted by 250 times is applied to each pot of the treatment group, the application is carried out twice a week, the application is carried out for 10 times totally, tap water is used for replacing the control group, and other conditions are consistent. After 70 days of pot experiment, the pakchoi in each pot is harvested, washed, dried and weighed. And (4) crushing the root parts uniformly, and then measuring the vitamin C content of the pakchoi. Vc content determination adopts 2, 6-dichlorophenol indophenol titration method. The results show that the treatment group significantly increased the yield of pakchoi (9.74 g per pot significantly increased to 12.48g), with an increase of up to 28.13%. The content of the vitamin C is obviously improved by 55.6 percent (from 85.6mg/Kg to 133.2mg/Kg), which shows that the quality of the pakchoi is obviously improved under the action of the treated waste gulonic acid mother liquor.
Example 7
The experiment of increasing the content of cucumber vitamin C with the waste gulonic acid mother liquor was carried out using the fertilizer conditioner product 2 of example 2 above:
1.5kg of soil was placed in a plastic pot (15cm height. times.20 cm). 3 sets of treatments were set: (1) pot treated with conditioning liquid product 2 (treatment group 1); (2) tap water treated potted plants (control); (3) 2-keto-L-gulonic acid solution treated pots (treatment group 2). 4 cucumber seeds with the same size are uniformly scattered in each pot of soil, and when the cucumber sprouts to 2cm, the cucumber in each pot of soil is thinned to 2 pieces. During the culture period, 75ml of conditioning fluid product 2 diluted by 300 times is poured into each pot of the treatment group 1, twice a week and 10 times in total; pouring 75ml of a gulonic acid solution (the content of the 2-keto-L-gulonic acid is 30 wt%) diluted by 300 times into each basin of the 2-keto-L-gulonic acid solution treatment group, performing pouring twice a week and performing pouring 10 times in total; the control group was replaced with tap water, and the other conditions were the same. After 60d pot experiment, the cucumbers produced in each pot are harvested, cleaned, dried and weighed. The cucumber is sampled and crushed uniformly, and then the content of vitamin C in the cucumber is measured. The content of the vitamin C is measured by adopting a 2, 6-dichlorophenol indophenol titration method.
The results show that compared with the control group, the treatment group 1 remarkably increases the cucumber yield by 10.5%, and the vitamin C content is remarkably improved by 20.1%; the content of the cucumber vitamin C in the treatment group 1 is not obviously different from that in the treatment group 2, which shows that the 2-keto-L-gulonic acid can obviously promote the content of the cucumber vitamin C to be increased.
Example 8
A test for increasing the vitamin C content of apples was carried out using the conditioning solution product 3 obtained in example 3 above:
set 3 sets of treatments: (1) pot treated with conditioning liquid product 3 (treatment group 1); (2) tap water treated potted plants (control); (3) potted plant treated with 2-keto-L-gulonic acid solution (treatment group 2) apple trees 4 years old fruit trees were selected, each of 5 fruit trees. After the fruit trees bloom, 50L of the treated waste gulonic acid mother liquor diluted by 400 times is applied to each fruit tree of the treatment group 1, 1 time per month and 5 times in total; applying 50L of gulonic acid solution (the content of 2-keto-L-gulonic acid is 25 wt%) diluted by 400 times to each fruit tree in the 2-keto-L-gulonic acid solution treatment group, wherein the spraying is performed for 1 time per month and 5 times in total; the control group was replaced with tap water, and the other conditions were the same. After 5 months of field experiments, the apples of each treatment group are harvested, weighed and the vitamin C content is determined. The content of the vitamin C is measured by adopting a 2, 6-dichlorophenol indophenol titration method.
The results show that compared with the control group, the treatment group 1 increases the weight of a single apple, the average weight of the apple is increased by 16g, and the content of the vitamin C is obviously increased by 10.1%; the vitamin C content of the apples in the treatment group 1 and the treatment group 2 is not obviously different, which shows that the 2-keto-L-gulonic acid can obviously promote the vitamin C content of the apples to be increased.
Example 9
The compound fertilizer is prepared by mixing the regulating solution obtained in the example 1 and inorganic fertilizer raw materials:
carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
and slowly adding 15L of 30% sodium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.32 and the gulonic acid content is 25 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to be 3.0 by ensuring that the solution temperature is not higher than 60 ℃ in the whole reaction process to obtain the fertilizer regulating solution.
Mixing 10L of fertilizer regulating solution with an inorganic fertilizer, wherein the weight ratio of the fertilizer regulating solution to the inorganic fertilizer is 1: 0.46, fully and uniformly mixing, and drying in a 60 ℃ oven until the water content is reduced to 10 percent to obtain a solid fertilizer product A, namely the organic-inorganic compound fertilizer.
The inorganic fertilizer comprises 3400g of urea, 900g of ammonium dihydrogen phosphate and 1780g of potassium chloride.
Detection of the obtained Compound fertilizers, N-P2O5-K2The proportion of O is 15-5-10, the total nutrient is more than or equal to 30 percent, and the organic matter content is more than or equal to 30 percent; it meets the national standard of organic-inorganic compound fertilizer (GB 18877-2009).
Example 10
And (3) mixing the regulating solution obtained after the treatment in the embodiment with an organic fertilizer to prepare a compound fertilizer:
carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 17L of 48 wt% potassium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has a specific gravity of 1.25 and the gulonic acid content is 18 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to 4.0 in the whole reaction process to ensure that the solution temperature is not higher than 60 ℃, thereby obtaining a fertilizer regulating solution product 2;
mixing a fertilizer regulating solution and an organic fertilizer according to the proportion of 1: 5, fully and uniformly mixing, and drying in a 60 ℃ oven until the water content is reduced to 25 percent to obtain a solid organic fertilizer product, namely the compound fertilizer.
The organic fertilizer is a commercial organic fertilizer, adopts high-quality organic raw materials such as biogas residue, tobacco mud, starch residue, sesame cake, mushroom residue, livestock and poultry manure, bone meal and the like, and mainly comprises the following components: organic matter content is greater than or equal to 45%, N + P2O5+ K2O is more than or equal to 12%, pH is 6.0-8.0, and water content is less than or equal to 30%.
Detection of the obtained Compound fertilizers, N-P2O5-K2The proportion of O is 5-3-3, the total nutrient is more than or equal to 10 percent, and the organic matter content is more than or equal to 45 percent; it meets the national standard of organic fertilizer (NY 525-2009).
Example 11
Mixing the waste gulonic acid mother liquor conditioning solution treated by the embodiment with a water soluble fertilizer to prepare a compound fertilizer:
carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 18L of 25 wt% ammonia water solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has a specific gravity of 1.38 and the gulonic acid content is 32 wt%), fully stirring in the adding process to prevent local overheating, and adjusting the pH of a reaction system to be 6.0 by ensuring that the solution temperature is not higher than 60 ℃ in the whole reaction process to obtain a fertilizer regulating solution product;
mixing a fertilizer regulating solution with a water-soluble fertilizer, wherein the fertilizer regulating solution and the water-soluble fertilizer are mixed according to the proportion of 1: 4, fully and uniformly mixing, and drying in a 60 ℃ oven until the water content is reduced to 10 percent to obtain a solid fertilizer product, namely the organic-inorganic compound fertilizer.
The water-soluble fertilizer is a commercial product, N-P2O5-K2The proportion of O is 20-20-20.
Detection of the obtained Compound fertilizers, N-P2O5-K2The proportion of O is 18-18-18, the total nutrient is more than or equal to 50 percent, the organic matter content is more than or equal to 5 percent, and the water content is less than or equal to 12 percent.
Example 12
Mixing the regulating solution obtained after the treatment by the embodiment with inorganic fertilizer raw materials and fertilizer auxiliary materials to prepare a compound fertilizer:
carrying out ultrafiltration separation, ion exchange, triple effect evaporation, concentration, gulonic acid crystallization and other steps on Vc biological fermentation liquor, and then taking residual liquid as waste gulonic acid mother liquor as a raw material;
slowly adding 27L of 40% potassium hydroxide solution into a 100L plastic barrel containing 50L of waste gulonic acid mother liquor (the mother liquor has the specific gravity of 1.40 and the gulonic acid content is 35 wt%), then continuously and slowly adding 5L of 10 wt% ammonia water solution into the plastic barrel, fully stirring in the adding process to prevent local overheating, ensuring that the temperature of the solution is not higher than 60 ℃ in the whole reaction process, and adjusting the pH value of a reaction system to 7.0 to obtain a fertilizer regulating solution product 5;
mixing 10L of fertilizer regulating solution with inorganic fertilizer raw materials and fertilizer auxiliary materials, wherein the three are mixed according to the proportion of 1: and (3) mixing at a ratio of 5:0.5, and fully and uniformly mixing to obtain a liquid organic fertilizer product, namely the compound fertilizer.
The inorganic fertilizer comprises 21Kg of urea, 16Kg of ammonium dihydrogen phosphate, 21Kg of potassium nitrate, 5Kg of magnesium sulfate, 6Kg of calcium superphosphate, 0.2Kg of manganous chloride tetrahydrate, 0.2Kg of ferrous sulfate, 0.2Kg of zinc sulfate, 0.2Kg of ammonium molybdate dihydrate and 0.2Kg of copper sulfate pentahydrate.
Detection of the obtained Compound fertilizers, N-P2O5-K2The proportion of O is 11-11-11, the total nutrient is more than or equal to 30 percent, and the organic matter content is more than or equal to 5 percent.
Application example 1
Tomato tests were applied with conditioning liquors produced from spent gulonic acid mother liquor.
The test method comprises the following steps: there were 2 treatments in total, with 3 replicates of each treatment. The area of each cell is 4 square meters, and 80 tomatoes are planted. The treatment 1 is conventional fertilization and pure inorganic fertilizer, 20 kg of urea, 30 kg of calcium magnesium phosphate fertilizer and 15 kg of potassium chloride are applied to a base fertilizer mu, wherein 60% of a nitrogen fertilizer is applied to the base fertilizer, and 40% of the nitrogen fertilizer is used as an additional fertilizer. Treatment 2 is the conditioning solution product 5 of example 1 diluted 400 times applied every 10 days after tomato seedling transplantation on the basis of the conventional fertilization of treatment 1. And (5) measuring the vitamin C content of the fruits after the fruits are ripe.
The results show that the conditioning solution (conditioning solution product 5 of example 1) promotes the growth of tomatoes and increases the vitamin C content of tomatoes by 12%.
Application example 2
The regulating solution produced by the waste gulonic acid mother solution is used as a foliar fertilizer to be sprayed on the apples for a test.
The test method comprises the following steps: there were 2 treatments, each of 10 4-year old apple trees. The treatment 1 is conventional fertilization of fruit trees, 80 kg of urea, 30 kg of calcium magnesium phosphate fertilizer and 60 kg of potassium sulfate are applied to each mu, wherein 50% of nitrogen fertilizer is applied as a base fertilizer, 40% of potassium fertilizer is applied as a top dressing, and 50% of potassium fertilizer is applied as a base fertilizer and 50% of the top dressing. Treatment 2 is to spray the 600-fold diluted regulating solution product 5 of example 1 on the leaf surface every 10 days in the full bearing period of the apples on the basis of the conventional fertilization of treatment 1. As a control, treatment 1 sprayed the foliage with an equal amount of tap water. And (5) measuring the vitamin C content of the fruits after the fruits are ripe.
The results show that the sprayed regulating solution (regulating solution product 5 of example 1) has smooth leaf surfaces and dark green color, and the vitamin C content in the apples is increased by 10%.
Application example 3
The test is carried out by mixing the regulating solution produced by the waste gulonic acid mother solution with the inorganic fertilizer raw material and applying the mixture as compound fertilizer.
The test method comprises the following steps: the total number of the treatments is 2, and the sowing area of the crowndaisy chrysanthemum of each treatment is 3m multiplied by 3 m. Treatment 1 was a control group and treatment 2 was a compound fertilizer group based on waste gulonic acid mother liquor. The fertilizer components and the proportion of the two groups are completely the same, and the application mode is that the fertilizer is applied after being diluted by 200 times of water solution. And (4) measuring the content of the vitamin C in the stems of the crowndaisy chrysanthemum after the crowndaisy chrysanthemum is harvested.
The results show that the crowndaisy chrysanthemum treated by the method 2 grows fast, and the content of the vitamin C in the stems is averagely improved by 18 percent.
Application example 4
The rice test is directly applied with the conditioning solution produced by the waste gulonic acid mother liquor.
The test method comprises the following steps: the total of 2 treatments were set, and the rice planting area of each treatment was 3m × 3m, 5 replicates. Treatment 1 was a control group, treatment 2 was a conditioning solution group based on a mother liquor of waste gulonic acid, and the conditioning solution used was conditioning solution product 2 of example 1. The application components and proportion, application time and application mode of the organic fertilizer and the inorganic fertilizer of the two treatment groups are completely the same. Treatment 2 is applied every 20 days in the growth period of rice after being diluted by 200 times of water solution, and 10L is applied per mu. And after the rice is harvested, measuring the content of the vitamin C in the threshed rice.
The results show that the rice after the treatment 2 is applied has good growth vigor and lodging resistance, and the vitamin C content is averagely improved by 11 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, which falls into the protection scope of the present invention.
Claims (9)
1. A fertilizer regulating solution for improving the vitamin C content of crops is characterized in that: the pH value of the waste gulonic acid mother liquor/2-keto-L-gulonic acid solution is adjusted to 3.0-9.0 by the alkaline solution to form the fertilizer adjusting solution.
2. The fertilizer conditioner for increasing the vitamin C content of crops as claimed in claim 1, wherein: the alkaline solution is a solution with the concentration of 10-50 wt% prepared by an alkaline reagent and water; wherein the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide and liquid ammonia.
3. The fertilizer conditioner for increasing the vitamin C content of crops as claimed in claim 1, wherein: and adjusting the pH value of the fertilizer adjusting liquid to 5.5-7.5.
4. A method for preparing a fertilizer conditioning fluid for increasing the vitamin C content of crops, which is characterized by comprising the following steps: and adjusting the pH value of the waste gulonic acid mother liquor/2-keto-L-gulonic acid to 3.0-9.0 by using an alkaline solution to obtain the fertilizer adjusting solution.
5. A method for preparing a fertilizer conditioner for increasing the vitamin C content of crops according to claim 4, which is characterized in that: the alkaline solution is a solution with the concentration of 10-50% prepared by an alkaline reagent and water; wherein the alkaline reagent is one or more of sodium hydroxide, potassium hydroxide and liquid ammonia.
6. The use of a fertilizer conditioner according to claim 1 for increasing the vitamin C content of crops, characterized in that: the fertilizer regulating solution is applied to improving the content and yield of vitamin C in crops.
7. The use of a fertilizer conditioner for increasing vitamin C content in crops as claimed in claim 6, characterized in that: the regulating solution can be applied independently or mixed with one or more of chemical fertilizer, organic fertilizer, biological fertilizer, inorganic chemical fertilizer raw material and fertilizer auxiliary material.
8. The use of a fertilizer conditioner according to claim 7 for increasing the vitamin C content of crops, characterized in that: the regulating solution can be used as a base fertilizer, an additional fertilizer, a water-soluble fertilizer or a leaf fertilizer when being applied alone or mixed with one or more of a chemical fertilizer, an organic fertilizer, a biological fertilizer, an inorganic chemical fertilizer raw material and a fertilizer auxiliary material.
9. Use of a fertilizer conditioner according to claim 7 or 8 for increasing the vitamin C content of crops, characterized in that: the regulating solution and the base fertilizer are mixed and applied according to the mass ratio of 1: 0.1-50; the conditioning solution and the additional fertilizer are mixed and applied according to the mass ratio of 1: 0.1-50; or the regulating solution and the foliar fertilizer are mixed according to the ratio of 1: 0.1-50 and then sprayed or sprayed independently.
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PCT/CN2020/092068 WO2021000665A1 (en) | 2019-07-02 | 2020-05-25 | Conditioning solution for increasing vitamin c content in plants, conditioners for fertilizer and soil, preparation therefor and application thereof |
US17/597,330 US20220315504A1 (en) | 2019-07-02 | 2020-05-25 | Regulating solution, fertilizer and soil conditioner for increasing vitamin c content of plants as well as preparation and application thereof |
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