A method for preparing plant growth regulating solid based on S-inducible production residual liquid

Abstract

This invention relates to the technical field of plant growth regulators and specifically discloses a method for preparing a plant growth regulator solid based on residual liquid from the production of S-absorbent. The S-absorbent residual liquid comprises a first crystallization mother liquor and / or a second crystallization mother liquor; the second crystallization mother liquor undergoes a first pretreatment to obtain an S-absorbent aqueous solution; the first crystallization mother liquor and / or the S-absorbent aqueous solution undergo a second pretreatment to obtain a mother powder; and agriculturally acceptable adjuvants are added to the mother powder to prepare a plant growth regulator solid containing 0.1-10% S-absorbent. The solid includes, but is not limited to, soluble powders, wettable powders, and granules. The implementation of this invention can improve the production efficiency and economic benefits of S-absorbent, reduce pollution and waste, and achieve the goals of waste utilization, energy conservation, and emission reduction.

Description

Technical Field

[0001] The present invention relates to the technical field of plant growth regulators, and in particular to a method for preparing a plant growth regulator solid by recycling S-absorbent production residual liquid, a by-product in the S-absorbent production process. Background Art

[0002] Currently, most plant growth regulators on the domestic market are produced primarily through chemical synthesis, with only a little over ten derived through microbial fermentation. S-abscisic acid, also known as abscisic acid, is one of the five major plant hormones. It is produced using a bio-fermentation-chemical extraction process. During the post-extraction process, a large amount of residual liquid is generated. This residual liquid serves as the mother liquor for crystallization. The fermentation broth undergoes plate and frame filtration, membrane filtration, and salting-out crystallization. The resulting mother liquor is then filtered to obtain the first mother liquor for crystallization. During the crude S-abscisic acid refining process, the second mother liquor is obtained through concentration, crystallization, and filtration. This mother liquor is a byproduct of S-abscisic acid production and contains a high content of active ingredients, accounting for approximately 30-40% of the extraction yield. Failure to utilize this residual liquid results in significant economic losses.

[0003] The mother liquor from the first crystallization of S-absorbent is typically extracted, concentrated, and crystallized to obtain the S-absorbent product, or directly evaporated and concentrated to obtain an S-absorbent concentrate, which is then formulated into the desired dosage form by adding surfactants and stabilizers. The first method suffers from low production efficiency and extraction yield. The second method consumes a lot of energy.

[0004] The second crystallization mother liquor of S-inducer is viscous and contains high levels of impurities and organic solvents. These impurities and organic solvents become obstacles to the direct utilization of the mother liquor and have a great impact on the preparation of preparations. Application to crops may cause side effects or phytotoxicity. Furthermore, it is very expensive to have a professional organization handle the waste liquid.

[0005] Regarding the issue of recycling and reusing by-products in the production of S-absorbent, domestic patent documents have been published. For example, the invention application with publication number CN 107047552A discloses a method for recycling by-products in the production of S-absorbent. The recycling method comprises the following steps: (1) filtering the fermentation broth containing S-absorbent through a plate and frame filter to obtain a first by-product and a filtrate, and drying, crushing, and compounding the first by-product to obtain a first by-product; (2) filtering the filtrate in step (1) through a membrane filter and acid precipitation to obtain a second by-product and an acid precipitation product, and concentrating and compounding the second by-product to obtain a second by-product; (3) extracting, concentrating, crystallizing, and recrystallizing the acid precipitation product in step (2) to obtain a third by-product and S-absorbent crystals, and back-extracting, drying, and compounding the third by-product to obtain a third by-product. This patented technology appears to recycle the first, second, and third by-products. However, since the second by-product needs to be concentrated and compounded to obtain the second by-product, the recovery energy consumption is high. The recovery of the third by-product does not take into account its viscous state and high content of impurities and organic solvents. The third by-product is obtained only through back-extraction, drying, and compounding. The third by-product is a powder, which is particularly easy to absorb moisture and stick together. It is not only easy to inactivate and has a short shelf life, but also has poor fluidity, which brings great inconvenience to users during use. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to address the shortcomings and deficiencies of current technologies for recycling and reusing the S-absorbent residual liquid, a byproduct of the S-absorbent production process. By doing so, a method is provided for preparing a plant growth regulator solid based on the S-absorbent production residual liquid. This method recycles the S-absorbent first and second crystallization mother liquors. Through pretreatment, the addition of an anti-hygroscopic agent, adsorption with a carrier, and the addition of agriculturally acceptable adjuvants, a plant growth regulator solid containing 0.1-10% S-absorbent and exhibiting good fluidity and moisture absorption resistance is prepared. Alternatively, a plant growth regulator liquid containing 0.01-1% S-absorbent can be directly prepared. Implementation of the present invention can improve the production efficiency and economic benefits of S-absorbent, reduce pollution and waste, and achieve the goals of waste utilization, energy conservation, and emission reduction.

[0007] The present invention achieves the purpose of the invention through the following technical solutions.

[0008] A method for preparing a plant growth regulating solid based on the residual liquid produced by S-inducible hormone production.

[0009] The S-absorbent residual liquid of the method includes a first crystallization mother liquor and / or a second crystallization mother liquor; the second crystallization mother liquor is subjected to a first pretreatment to obtain an S-absorbent aqueous solution; the first crystallization mother liquor and / or the S-absorbent aqueous solution are subjected to a second pretreatment to obtain a mother powder, and then an agriculturally acceptable adjuvant is added to the mother powder as a basis to prepare a plant growth regulating solid containing 0.1-10% of S-absorbent; the solid includes but is not limited to a soluble powder, a wettable powder, and a granule.

[0010] The present invention can directly prepare the first crystallization mother liquor of S-inducer by adding agriculturally acceptable adjuvants to prepare a liquid agent without pretreatment, thereby simplifying the process flow and improving production efficiency. The first crystallization mother liquor of S-inducer can also be subjected to a second pretreatment to obtain a mother powder, and then based on the mother powder, agriculturally acceptable adjuvants are added to prepare a plant growth regulating solid containing 0.1-10% of S-inducer. The plant growth regulating solid has good fluidity and moisture absorption resistance, solves the problem of easy moisture absorption and adhesion that has long been wanted to be solved but has not been solved, and ensures the quality of the solid product.

[0011] The present invention addresses the problem of the second crystallization mother liquor of S-inducible protein, which is viscous and contains high levels of impurities and organic solvents. This makes it unusable directly and requires a first pretreatment to convert it into an S-inducible protein aqueous solution, a water-based raw material, for recycling. The resulting S-inducible protein aqueous solution can be directly formulated into a liquid product. However, if the first crystallization mother liquor and / or the S-inducible protein aqueous solution are to be formulated into a solid product, a second pretreatment process, such as carrier adsorption and / or the addition of an anti-moisture absorption agent, is required to address the solid product's tendency to deteriorate due to moisture resorption and adhere to production and packaging equipment. This ensures that the formulated solid product exhibits good fluidity and moisture absorption resistance, meeting product quality requirements.

[0012] Furthermore, the first crystallization mother liquor is obtained by filtering the S-absorbent fermentation liquor through plate and frame filtration, membrane filtration, and then salting out crystallization, and filtering to obtain the crystallization mother liquor.

[0013] Furthermore, the second crystallization mother liquor is the crystallization mother liquor obtained through extraction, concentration, crystallization and filtration during the purification process of crude S-absorbent.

[0014] Furthermore, the first pretreatment method is: according to the volume ratio of mother liquor, water and liquid alkali of 1:0.3-0.4:0.25-0.45, the second crystallization mother liquor is first dissolved and diluted with water, and then liquid alkali is slowly added under stirring conditions to convert all the S-absorbent contained in the second crystallization mother liquor into sodium salt and enter the aqueous phase. The temperature of the mixed liquid is controlled below 35°C, and then it is allowed to stand to allow the back-extraction aqueous phase and the organic phase to be fully separated. Finally, the lower back-extraction aqueous phase obtained is the S-absorbent aqueous solution.

[0015] Preferably, the dilution method with water is to slowly add the second crystallization mother liquor into water while stirring.

[0016] Preferably, the concentration of the liquid caustic soda is 30-32%.

[0017] Due to different contents of the second crystallization mother liquor in different batches, the S-absorbent content of the S-absorbent aqueous solution after the first pretreatment is determined to be 2.0-7.0%, and the solid content of the S-absorbent aqueous solution is 25-40% (m / v).

[0018] Furthermore, the second pretreatment method is: adding an anti-moisture absorption agent and / or adsorbing with a carrier to the first crystallization mother liquor and / or the S-abductin aqueous solution, and drying-crushing-sieving to obtain a mother powder.

[0019] The present invention adopts a carrier adsorption pretreatment process for the first crystallization mother liquor and / or the S-abductin aqueous solution, which has low requirements on equipment, is simple to operate, and has good moisture-proof effect on the product.

[0020] The present invention adopts a pretreatment process of adding an anti-moisture absorption agent to the first crystallization mother liquor and / or the S-absorbent aqueous solution, which belongs to the internal addition method of adding the anti-moisture absorption agent, dissolving and mixing evenly, and after spray drying, the surface of the S-absorbent is evenly covered with an anti-moisture absorption film. Then, fillers and auxiliary agents are added, which belongs to the external addition method. The fillers also have a certain anti-moisture absorption effect. After mixing, the exposed specific surface area of ​​the S-absorbent is reduced, and the fluidity and anti-moisture absorption properties of the product are further increased.

[0021] Preferably, the first crystallization mother liquor and / or S-absorbent aqueous solution, in addition to adding the anti-moisture absorption agent by the internal addition method to make the dissolution and mixing uniform, can also add fillers during boiling granulation and drying to obtain fine granular S-absorbent mother powder particles coated with S-absorbent, anti-moisture absorption agent and filler, thereby achieving better moisture absorption resistance and improving product stability.

[0022] The boiling granulator has both granulation and drying functions. The boiling granulator can lift the filler from the bottom of the tank through hot air, and simultaneously spray the mother liquor or aqueous solution dissolved with the anti-hygroscopic agent. By controlling the spray speed, air volume and other parameters, fine particles are obtained.

[0023] Preferably, the amount of the anti-moisture absorption agent added is the first crystallization mother liquor and / or S-inducible aqueous solution: anti-moisture absorption agent = 100: 5-20 (v: m);

[0024] Preferably, the amount of the carrier adsorption is the first crystallization mother liquor and / or S-abductin aqueous solution: carrier = 100:15-50 (v:m), and the solid content in the first crystallization mother liquor and / or S-abductin aqueous solution: carrier is controlled to be ≤1.5:1 (m:m); wherein the optimal ratio of solid content in the aqueous solution: carrier is =1.5:1 (m:m);

[0025] Preferably, the drying is vacuum drying, spray drying or boiling granulation drying.

[0026] Depending on the solid content, the adsorption and drying operations can be performed once or repeatedly. The aforementioned repeated operations involve dividing the first crystallization mother liquor and / or the S-abductin aqueous solution into 2-4 batches, and repeating the adsorption and drying operations 2-4 times using the same batch of carrier. The carrier is added in full the first time, and the subsequent 2-4 adsorptions are repeated. During the first adsorption, the ratio of the first crystallization mother liquor and / or the S-inducing agent aqueous solution to the carrier is less than 2.25:1 (v:m); during the second adsorption, the ratio of the first crystallization mother liquor and / or the S-inducing agent aqueous solution to the carrier is less than 1.8:1 (v:m); during the third adsorption, the ratio of the first crystallization mother liquor and / or the S-inducing agent aqueous solution to the carrier is less than 1.2:1 (v:m); during the fourth adsorption, the ratio of the first crystallization mother liquor and / or the S-inducing agent aqueous solution to the carrier is less than 0.8:1 (v:m); finally, the mass ratio of solid content in the first crystallization mother liquor and / or the S-inducing agent aqueous solution to the carrier is controlled to be ≤1.5:1 (m:m).

[0027] For the S-absorbent aqueous solution with a relatively high solid content, the solid content of the S-absorbent aqueous solution is about 25-40%, and the solvent is relatively small, so the carrier cannot be too much, otherwise when preparing the soluble powder, the solubility and wettability indicators of the soluble powder will be unqualified. Therefore, combined with the adsorption capacity of the carrier, after multiple experimental verifications, it was concluded that the optimal ratio of solid content: carrier in the S-absorbent aqueous solution is =1.5:1 (m:m); and the first crystallization mother liquor has a low solid content of about 2-5%, and relatively more solvent. Therefore, during the adsorption-drying operation, in addition to repeated multiple times, a larger proportion but still lower total amount of carrier is required to adsorb and dry the first crystallization mother liquor, and the solid content: carrier of the first crystallization mother liquor is controlled to be <1.5:1 (m:m).

[0028] Preferably, the anti-moisture absorption agent is at least one selected from soybean dietary fiber, maltodextrin, polyethylene glycol-6000, water-soluble starch, microcrystalline cellulose, mannitol, and sodium alginate.

[0029] Preferably, the carrier is selected from one of white carbon black, talc, kaolin, bentonite, attapulgite and diatomaceous earth.

[0030] Furthermore, the preparation method of the wettable powder or soluble powder is: based on the first crystallization mother liquor and / or S-absorbent aqueous solution, 0.1-5% wetting agent, 0-5% dispersant, 0-2% pH regulator, and the remainder as filler are added to prepare a plant growth regulating wettable powder or soluble powder containing 0.1-10% S-absorbent.

[0031] Preferably, the dispersant is selected from any one of 2-naphthalenesulfonic acid formaldehyde polymer sodium salt (NNO), alkylnaphthalenesulfonic acid polycondensate sodium salt (Morwet D-425), D8916, D8986, sodium tripolyphosphate, and sodium carboxymethyl cellulose;

[0032] Preferably, the filler is selected from one or two of white carbon black, talc, kaolin, bentonite, water-soluble starch, sodium sulfate, white sugar, lactose, and sodium citrate;

[0033] Preferably, the wetting agent is selected from any one of sodium octyl sulfosuccinate, sodium diisooctyl sulfosuccinate, sodium lauryl sulfate, naphthalenesulfonate phenolsulfonate, sodium N-oleoyl-N-methyl taurate, Morwet EFW, and anionic sulfonates;

[0034] Preferably, the pH adjuster is selected from one or two of citric acid, oxalic acid and tartaric acid.

[0035] Furthermore, the granules are prepared by adding 0.8-1.2% binder, 0.1-3% wetting agent, 40-65% acid-base regulator, and the remainder as filler to the first crystallization mother liquor and / or S-absorbent aqueous solution, based on the weight ratio of the prepared granules. Granulation is performed using an extrusion granulator or a boiling granulator, and drying is performed in a boiling dryer to produce plant growth regulating granules containing 0.1-10% S-absorbent. The boiling granulator is selected because it has both granulation and drying functions.

[0036] Preferably, an anti-moisture absorption agent may be added to the first crystallization mother liquor and / or the S-abductin aqueous solution in a ratio of 100:5-10 (v:m);

[0037] Preferably, the adhesive is selected from one or two of water-soluble starch, polyvinyl pyrrolidone, and maltodextrin;

[0038] Preferably, the acid-base regulator is selected from one or two of citric acid, sodium carbonate, potassium carbonate, adipic acid, and tartaric acid.

[0039] In addition, the S-abductin aqueous solution obtained by subjecting the second crystallization mother liquor to the first pretreatment and / or the first crystallization mother liquor can be directly formulated into a liquid formulation without undergoing the second pretreatment.

[0040] The preparation method of the liquid is as follows: based on the S-absorbent aqueous solution and / or the first crystallization mother liquor, 3-10% solvent, 0-10% stabilizer, 5-15% emulsifier, 0-0.1% antioxidant, 0-0.1% preservative are added, and the balance is water to prepare a plant growth regulating liquid containing 0.01-1% S-absorbent.

[0041] Preferably, the solvent is selected from any one or two of ethanol, isopropanol, ethylene glycol, propylene glycol, diethylene glycol butyl ether, dimethyl sulfoxide, and N-methylpyrrolidone.

[0042] Preferably, the stabilizer is selected from any one of propylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, and triethyl phosphate.

[0043] Preferably, the emulsifier is selected from any one of Tween-20, Tween-80, polyethylene glycol-400, polyethylene glycol-200, castor oil polyoxyethylene ether-80, isomeric tridecyl alcohol polyoxyethylene ether, alkyl diphenyl ether disulfonate, and methylcyclohexane and ethylene oxide monoether polymer.

[0044] Preferably, the antioxidant is selected from any one of propyl gallate and vitamin C.

[0045] Preferably, the preservative is sodium benzoate or kasone.

[0046] The first crystallization mother liquor and / or the S-abductin aqueous solution can also be mixed with a certain proportion of fertilizer to prepare medicinal fertilizer.

[0047] Beneficial effects of the present invention:

[0048] (1) The method for recycling and reusing S-absorbent waste liquor described in the present invention can recycle both the first and second crystallization mother liquors of S-absorbent and prepare a plant growth regulator solid containing 0.1-10% S-absorbent or a plant growth regulator liquid containing 0.01-1% S-absorbent. The resulting plant growth regulator solid has good fluidity and moisture absorption resistance, solving the long-standing problem of moisture absorption and adhesion, ensuring the quality of the solid product and gaining widespread popularity and praise. The implementation of the present invention can improve the production efficiency and economic benefits of S-absorbent, reduce pollution and waste, and achieve the goals of waste utilization, energy conservation, and emission reduction.

[0049] (2) The present invention can directly prepare the first crystallization mother liquor of S-inducer by adding agriculturally acceptable adjuvants to prepare a liquid agent without pretreatment, thereby simplifying the process flow and improving production efficiency. The first crystallization mother liquor of S-inducer can also be subjected to a second pretreatment to obtain a mother powder, and then based on the mother powder, agriculturally acceptable adjuvants are added to prepare a plant growth regulating solid containing 0.1-10% of S-inducer. The plant growth regulating solid has good fluidity and moisture absorption resistance, solves the problem of easy moisture absorption and adhesion that has long been wanted to be solved but has not been solved, and ensures the quality of the solid product.

[0050] (3) The present invention is directed to the second crystallization mother liquor of S-absorbent, which is viscous and contains high levels of impurities and organic solvents. It cannot be directly used and must undergo a first pretreatment process to be converted into an S-absorbent aqueous solution, a water-based raw material, before it can be recycled. The obtained S-absorbent aqueous solution can be directly formulated into a liquid preparation.

[0051] (4) The present invention addresses the characteristics and shortcomings of the solid product prepared by adding auxiliary materials after the first crystallization mother liquor and / or S-inducing agent aqueous solution is directly dried, and the product is very easy to regain moisture and easily adhere to the production and packaging equipment. In order to make the prepared solid product meet the product quality requirements, the present invention adopts a second pretreatment process of carrier adsorption and / or addition of an anti-moisture absorption agent to the first crystallization mother liquor and / or S-inducing agent aqueous solution, which can make the product have a good moisture-proof effect and the quality of the prepared product meets the requirements.

[0052] (5) The present invention adopts a carrier adsorption pretreatment process for the first crystallization mother liquor and / or the S-inducible protein aqueous solution, which has low requirements for equipment, is easy to operate, and has good moisture-proof effect on the product.

[0053] (6) The present invention adopts a pretreatment process of adding an anti-moisture absorption agent to the first crystallization mother liquor and / or the S-absorbent aqueous solution, which belongs to the internal addition method of adding the anti-moisture absorption agent. The solution is dissolved and mixed uniformly. After spray drying, the surface of the S-absorbent is evenly covered with an anti-moisture absorption film. Fillers and auxiliary agents are then added, which belongs to the external addition method. The fillers also have a certain anti-moisture absorption effect. After mixing, the exposed specific surface area of ​​the S-absorbent is reduced, further increasing the fluidity and anti-moisture absorption properties of the product. In addition to using the internal addition method to add the anti-moisture absorption agent to the first crystallization mother liquor and / or the S-absorbent aqueous solution to achieve uniform dissolution and mixing, fillers can also be added during boiling granulation drying to obtain fine granular S-absorbent mother powder particles coated with layers of S-absorbent, anti-moisture absorption agent and fillers, thereby achieving better anti-moisture absorption properties and improving product stability. DETAILED DESCRIPTION

[0054] The present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. The raw materials described are commercially available unless otherwise specified. The data listed in the following examples and comparative examples were obtained during the same period of preparation and testing.

[0055] Example 1: Pretreatment of the Second Crystallization Mother Liquor

[0056] The second crystallization mother liquor was first diluted with water in a volume ratio of 1:0.35:0.28 for mother liquor, water, and liquid caustic soda. The dilution method was to slowly add the second crystallization mother liquor to water while stirring. Then, liquid caustic soda at a concentration of 30-32% was slowly added while stirring. The temperature of the mixed liquid was controlled below 35°C. The addition of liquid caustic soda was stopped when the pH value reached 7.5-8.0, so that all the S-absorbin in the second crystallization mother liquor was converted to sodium salt and entered the aqueous phase. The solution was then allowed to stand to allow the stripping aqueous phase and the organic phase to fully separate. The resulting lower stripping aqueous phase was an S-absorbin aqueous solution. The S-absorbin content of the aqueous solution was determined to be 6.6% and the solids content was 30% (m / v).

[0057] Example 2: Preparation of 0.4% S-absorbent wettable powder (first crystallization mother liquor + carrier adsorption 1 time)

[0058] (1) The first crystallization mother liquor is made into mother powder through carrier adsorption:

[0059] A. The amount of carrier adsorption is: mother liquor: carrier = 100: 50 (v:m);

[0060] B. Carrier (white carbon black) adsorption to obtain mother powder: that is, take 100 parts by volume of the first crystallization mother liquor (solid content is 4.5%, inducible content is 0.35%), use 50 parts by mass of white carbon black for adsorption, and obtain mother powder containing S-inducible through vacuum drying and sieving. After testing, the mother powder contains 0.6% S-inducible.

[0061] (2) Preparation of 0.4% S-antibiotic wettable powder:

[0062] Raw material ratio (based on 100 parts by mass): 67 parts of mother powder (containing 0.6% of S-inducible), 1 part of sodium octyl sulfosuccinate (wetting agent), and the balance is talc (filler);

[0063] Preparation process: In a preparation container equipped with a stirring device, weigh the above raw materials in order according to the above raw material ratio and add them, make up to 100 parts by mass with talc powder, turn on the stirring device until the mixture is uniform, and pack after testing to obtain 0.4% S-absorbent wettable powder. Example 3: Preparation of 0.2% S-absorbent soluble powder (first crystallization mother liquor + carrier adsorption 3 times)

[0064] (1) The first crystallization mother liquor is made into mother powder through carrier adsorption:

[0065] A. The amount of carrier adsorption is: mother liquor: carrier = 100:25 (v:m);

[0066] B. Carrier (white carbon black) adsorption to obtain mother powder: that is, 100 parts by volume of the first crystallization mother liquor (solid content of 4.5%, abductin content of 0.35%) was taken and repeatedly adsorbed with 25 parts by mass of white carbon black three times. The first adsorption was carried out according to the weight ratio of the first crystallization mother liquor to the carrier of 2:1. That is, 50 parts by volume of the first crystallization mother liquor was taken and 25 parts by mass of white carbon black was added for adsorption. The first adsorption mother powder was obtained by vacuum drying and sieving.

[0067] Second adsorption: Adsorption is carried out according to the weight ratio of the first crystallization mother liquor to the carrier of 1.5:1, that is, 37.5 parts by volume of the first crystallization mother liquor are added to the first adsorption mother powder for adsorption, and the second adsorption mother powder is obtained by vacuum drying and sieving;

[0068] Third adsorption: Take 12.5 parts by volume of the first crystallization mother liquor, add the second adsorption mother powder for adsorption, and vacuum dry and sieve to obtain a mother powder containing 1.15% of S-absorbent; (2) Prepare 0.2% S-absorbent soluble powder:

[0069] Raw material ratio (based on 100 parts by mass): 17.5 parts of mother powder (containing 1.15% of S-inducible), 1 part of sodium diisooctyl sulfosuccinate (wetting agent), 1 part of sodium tripolyphosphate (dispersant), and the balance is white sugar (filler);

[0070] Preparation process: In a preparation container equipped with a stirring device, weigh the above raw materials in order according to the above raw material ratio and add them, make up to 100 parts by mass with white sugar, turn on the stirring device until the mixture is uniform, and pack after testing to obtain 0.2% S-absorbent soluble powder. Example 4: Preparation of 8% S-absorbent soluble powder (S-absorbent aqueous solution + carrier adsorption 4 times)

[0071] (1) The S-abductin aqueous solution obtained in Example 1 was prepared into a mother powder by carrier adsorption:

[0072] A. Calculation of carrier adsorption dosage: Since the solid content of the S-abducin aqueous solution obtained in Example 1 is 30% (m / v), according to the requirement that the optimal ratio of solid content: carrier in the S-abducin aqueous solution is 1.5:1 (m:m), the carrier adsorption dosage is calculated to be: aqueous solution: carrier = 100:20 (v:m), that is, 100 parts by volume of the S-abducin aqueous solution (obtained in Example 1) requires 20 parts by mass of the carrier for adsorption.

[0073] B. The carrier (white carbon black) is adsorbed with the aqueous solution several times to obtain the mother powder:

[0074] First adsorption: adsorption was performed according to a weight ratio of aqueous solution to carrier of 2:1, i.e., 40 parts by volume of the S-absorbent aqueous solution obtained in Example 1 was added with 20 parts by mass of white carbon black for adsorption, and the first adsorption mother powder was obtained by spray drying;

[0075] Second adsorption: adsorption was performed at a weight ratio of aqueous solution to carrier of 1.5:1. 30 parts by volume of the S-absorbent aqueous solution obtained in Example 1 was added to the first adsorption master powder for adsorption, and spray-dried to obtain the second adsorption master powder;

[0076] The third adsorption: adsorption was carried out according to the weight ratio of aqueous solution to carrier of 1:1, that is, 20 parts by volume of the S-absorbent aqueous solution obtained in Example 1 was added to the second adsorption master powder for adsorption, and the third adsorption master powder was obtained by spray drying;

[0077] Fourth adsorption: The 10 parts by volume of the S-absorbent aqueous solution obtained in Example 1 remaining after the three adsorptions were added to the third adsorption mother powder for adsorption. After vacuum drying, the powder was crushed and sieved to obtain the fourth adsorption mother powder. The fourth adsorption mother powder was found to contain 13.1% S-absorbent.

[0078] (2) Preparation of 8% S-inducible soluble powder:

[0079] Raw material ratio (based on 100 parts by mass): 61 parts of fourth adsorption masterbatch (containing 13.1% S-inducible), 1.5 parts of anionic sulfonate (wetting agent), 2 parts of sodium tripolyphosphate (dispersant), 1.5 parts of citric acid (pH adjuster), 15 parts of sodium citrate (filler), and the balance is white sugar (filler);

[0080] Preparation process: In a preparation container equipped with a stirring device, weigh the above raw materials in sequence according to the above raw material ratio and add them, make up to 100 parts by mass with white sugar, turn on the stirring device until stirring is uniform, and package after testing to obtain 8% S-inducing agent soluble powder (using carrier adsorption technology).

[0081] Example 5: Preparation of 8% S-absorbent soluble powder (S-absorbent aqueous solution + anti-moisture absorption agent)

[0082] (1) The S-absorbent aqueous solution obtained in Example 1 was added with an anti-hygroscopic agent and the mixture was spray-dried to obtain a mother powder.

[0083] According to the ratio of aqueous solution: anti-moisture absorption agent = 100:10-20 (v:m), 100 parts by volume of the S-absorbent aqueous solution obtained in Example 1 were added with 10 parts by mass of maltodextrin (anti-moisture absorption agent 1) and 0.5 parts by mass of polyethylene glycol-6000 (anti-moisture absorption agent 2). The mixture was stirred and dissolved, spray-dried, crushed and sieved to obtain a mother powder containing the anti-moisture absorption agent. Testing showed that the mother powder containing the anti-moisture absorption agent contained 15.6% of S-absorbent.

[0084] (2) Preparation of 8% S-inducible soluble powder:

[0085] Raw material ratio (based on 100 parts by mass): 51.3 parts of the above-mentioned mother powder containing anti-moisture absorption agent (containing 15.6% of S-inducible), 0.5 parts of anionic sulfonate (wetting agent), 2 parts of sodium tripolyphosphate (dispersant), 1.5 parts of citric acid (pH adjuster), 15 parts of sodium citrate (filler), and the balance is white granulated sugar (filler);

[0086] Preparation process: In a preparation container equipped with a stirring device, weigh the above raw materials in order according to the above raw material ratio and add them, make up to 100 parts by mass with white sugar, turn on the stirring device until stirring is uniform, and pack after testing to obtain 8% S-inducible soluble powder.

[0087] Example 6: Preparation of 10% S-absorbent soluble powder (S-absorbent aqueous solution + anti-moisture absorption agent)

[0088] Raw material ratio (based on 100 parts by mass): 64 parts of the mother powder containing the anti-moisture absorption agent of Example 5 (containing 15.6% of S-inducible), 0.5 parts of anionic sulfonate (wetting agent), 2 parts of sodium tripolyphosphate (dispersant), 1.0 parts of citric acid (pH adjuster), and the balance is white sugar (filler);

[0089] According to the preparation process of Example 5, 10% S-absorbent soluble powder was obtained (using the process of adding an anti-hygroscopic agent).

[0090] Example 7: Preparation of 8% S-absorbent soluble powder (S-absorbent aqueous solution + anti-moisture absorption agent + carrier adsorption 4 times)

[0091] (1) The S-absorbent aqueous solution obtained in Example 1 was prepared into a mother powder by adding an anti-moisture absorption agent and a carrier for adsorption:

[0092] A. Adding an anti-moisture absorption agent: Add 10 parts by mass of maltodextrin (anti-moisture absorption agent 1) and 0.5 parts by mass of polyethylene glycol-6000 (anti-moisture absorption agent 2) to 100 parts by volume of the S-absorbent aqueous solution obtained in Example 1 according to the ratio of aqueous solution: anti-moisture absorption agent = 100:10-20 (v:m). After dissolving and stirring evenly, an S-absorbent aqueous solution containing the anti-moisture absorption agent is obtained.

[0093] B. The carrier (white carbon black) is adsorbed with the aqueous solution containing the anti-moisture absorption agent several times to obtain the mother powder:

[0094] After testing, the solid content of the S-absorbent aqueous solution obtained in Example 1 was 30%. According to the requirement that the optimal ratio of solid content in the S-absorbent aqueous solution to carrier is 1.5:1 (m:m), the amount of carrier adsorption was calculated to be: aqueous solution: carrier = 100:20 (v:m);

[0095] First adsorption: adsorption is carried out according to the weight ratio of aqueous solution to carrier of 2:1, that is, 40 parts by volume of the above-mentioned S-absorbent aqueous solution with the anti-moisture absorption agent added thereto is added with 20 parts by mass of white carbon black for adsorption, and the first adsorption masterbatch is obtained by vacuum drying and sieving;

[0096] Second adsorption: Adsorption is carried out according to the weight ratio of aqueous solution to carrier of 1.5:1, that is, 30 parts by volume of the above-mentioned S-absorbent aqueous solution with the anti-moisture absorption agent added are added to the first adsorption master powder for adsorption, and the second adsorption master powder is obtained by vacuum drying and sieving;

[0097] The third adsorption: adsorption is carried out according to the weight ratio of aqueous solution to carrier of 1:1, that is, 20 parts by volume of the above-mentioned S-absorbent aqueous solution with the addition of the anti-moisture absorption agent are added to the second adsorption master powder for adsorption, and the third adsorption master powder is obtained by vacuum drying and sieving;

[0098] Fourth adsorption: Take 10 parts by volume of the remaining S-absorbent aqueous solution with the anti-moisture absorption agent added, add the third adsorption master powder for adsorption, vacuum dry and sieve to obtain the fourth adsorption master powder. The fourth adsorption master powder was tested to contain 10.5% S-absorbent.

[0099] (2) Preparation of 8% S-inducible soluble powder:

[0100] Raw material ratio (based on 100 parts by mass): 76.5 parts of fourth adsorption masterbatch (containing 10.5% S-inducible), 0.5 parts of anionic sulfonate (wetting agent), 2 parts of sodium tripolyphosphate (dispersant), 1.5 parts of citric acid (pH adjuster), 15 parts of sodium citrate (filler), and the balance is white sugar (filler);

[0101] Preparation process: In a preparation container equipped with a stirring device, weigh the above raw materials in order according to the above raw material ratio and add them, make up to 100 parts by mass with white sugar, turn on the stirring device until stirring is uniform, and pack after testing to obtain 8% S-inducible soluble powder.

[0102] Example 8: Preparation of 5% S-absorbent granules (S-absorbent aqueous solution + anti-moisture absorption agent)

[0103] (1) Adding an anti-moisture absorption agent: Add an anti-moisture absorption agent to the S-absorbent aqueous solution obtained in Example 1, and follow the same steps as in Example 5. After stirring and dissolving uniformly, an S-absorbent aqueous solution containing the anti-moisture absorption agent is obtained.

[0104] (2) Preparation of 5% S-inducible granules:

[0105] Raw material ratio (based on 100 parts by mass): 85 parts of an aqueous solution of S-inducible containing an anti-moisture absorption agent (containing 5.9% S-inducible), 1 part of anionic sulfonate (wetting agent), 32 parts of citric acid (acid-base regulator 1), 27 parts of sodium carbonate (acid-base regulator 2), no additional binder is required (the maltodextrin in the anti-moisture absorption agent 1 also has a binding effect), and the balance is white sugar (filler);

[0106] Preparation process: Weigh the above solid raw materials in sequence and pour all the raw materials into the material cart of the boiling granulation dryer. Use a spray gun to spray the S-inducing agent aqueous solution containing anti-moisture absorption agent into the boiling granulation dryer, granulate, dry, test and package to obtain 5% S-inducing agent granules.

[0107] Example 9: Preparation of 0.03% S-abductin soluble solution

[0108] Raw material ratio (based on 100 parts by volume): 8.6 parts of the first crystallization mother liquor (containing 0.35% of S-inducible protein, 4 parts of isopropyl alcohol (solvent), 6 parts of Tween-80 (emulsifier), 0.05 parts of propyl gallate (antioxidant), 0.1 parts of kasone (preservative), and the balance is water;

[0109] Preparation process: In a preparation container equipped with a stirring device, according to the above raw material ratio, measure or weigh the above raw materials in sequence and add them, add water to 100 parts by volume, turn on the stirring device until the mixture is evenly stirred, and package after testing to obtain 0.03% S-inducible soluble solution.

[0110] Example 10: Preparation of 0.03% S-inducible soluble solution

[0111] Raw material ratio (based on 100 parts by volume): Different batches of second crystallization mother liquor were pretreated according to the method of Example 1 to obtain an S-abducin aqueous solution, and 1 part of the S-abducin aqueous solution (containing 3.0% S-abducin) was added to 4 parts of ethanol (solvent), 5 parts of Tween-20 (emulsifier), and the balance was water;

[0112] Preparation process: In a preparation container equipped with a stirring device, according to the above raw material ratio, measure or weigh the above raw materials in sequence and add them, add water to 100 parts by volume, turn on the stirring device until the mixture is evenly stirred, and package after testing to obtain 0.03% S-inducible soluble solution.

[0113] Example 11: Preparation of 0.1% S-abductin soluble solution

[0114] Raw material ratio (based on 100 parts by volume): Different batches of second crystallization mother liquor were pretreated according to the method of Example 1 to obtain an S-absin aqueous solution, 2.5 parts of the S-absin aqueous solution (containing 4.0% S-absin), 4 parts of ethanol (solvent), 5 parts of a polymer of methylcyclohexane and ethylene oxide monoether (emulsifier), 6 parts of propylene glycol (stabilizer), 0.05 parts of propyl gallate (antioxidant), and the balance was water;

[0115] Preparation process: In a preparation container equipped with a stirring device, according to the above raw material ratio, measure or weigh the above raw materials in sequence and add them, make up to 100 parts by volume with water, turn on the stirring device until the mixture is evenly stirred, and package after testing to obtain 0.1% S-inducible soluble solution.

[0116] Example 12: Preparation of 1% S-inducible soluble solution

[0117] Raw material ratio (based on 100 parts by volume): The second crystallization mother liquor is pretreated according to the method of Example 1 to obtain an S-absin aqueous solution, 15.2 parts of the S-absin aqueous solution (containing 6.6% S-absin), 8 parts of N-methylpyrrolidone (solvent), 15 parts of a polymer of methylcyclohexane and ethylene oxide monoether (emulsifier), 10 parts of propylene glycol (stabilizer), 0.05 parts of propyl gallate (antioxidant), and the balance is water;

[0118] Preparation process: In a preparation container equipped with a stirring device, according to the above raw material ratio, measure or weigh the above raw materials in sequence and add them, add water to 100 parts by volume, turn on the stirring device until the mixture is evenly stirred, and package after testing to obtain 1% S-inducible soluble solution.

[0119] Comparative Example 1:

[0120] Except for the different mother powder, the other preparation steps were the same as those in Example 5, and the obtained product was 8% S-inducible soluble powder.

[0121] The mother powder is obtained by spray drying the S-absorbent aqueous solution obtained in Example 1 (the second crystallization mother solution has undergone the first pretreatment) without undergoing the second pretreatment (adsorption of an anti-hygroscopic agent and / or a carrier).

[0122] Comparative Example 2:

[0123] Except for the different mother powder, the other preparation steps were the same as those in Example 5, and the obtained product was 8% S-inducible soluble powder.

[0124] This mother powder was directly spray-dried with the second crystallization mother liquor. It did not undergo the first pretreatment (i.e., it was not converted into an S-absorbent aqueous solution) nor the second pretreatment (i.e., it did not use an anti-hygroscopic agent and / or carrier adsorption). The 8% S-absorbent soluble powder obtained in Comparative Example 2 was prepared using a mother powder directly sprayed with the second crystallization mother liquor without either the second or first pretreatment. Although constant temperature dehumidification, timely preparation, and tight packaging were employed during preparation, moisture absorption and adhesion began to occur during the packaging process, resulting in adhesion to packaging equipment or product packaging bags. After one month of storage, it showed severe moisture absorption, with some portions already in a syrupy state.

[0125] Storage test example:

[0126] The plant growth regulator solids prepared in the same period in Examples 2 to 8 and Comparative Example 1 were sealed and stored at room temperature for 12 months, and their fluidity and S-absorbent content were tested.

[0127] To test for fluidity, first inspect the appearance for signs of agglomeration. Flow rate: The rate at which a powder flows out of a hole or tube of a certain diameter per unit time. Generally, a faster flow rate indicates better fluidity. A funnel (11cm diameter, 4cm neck, 1.1cm inner diameter) is plugged at the bottom. Pour 20g of sample into the funnel, then open the bottom. Observe the fluidity and speed of the sample flow, and record the time it takes for each sample to flow out. The results are tabulated below:

[0128]

[0129] The storage test results above show that Example 4, Example 5, Example 7, and Comparative Example 1, all 8% S-absorbent soluble powders, all contain identical additives during preparation, differing only in their masterbatch preparation processes. Their fluidity and moisture absorption resistance differ significantly, with flow rates of 70 seconds, 71 seconds, and 63 seconds, respectively, and the order of flow rates from fastest to slowest being Example 7 > Example 4 ≈ Example 5 > Comparative Example 1. Note: The masterbatch prepared using an S-absorbent aqueous solution + moisture absorption inhibitor + carrier adsorption process (Example 7) exhibits the best fluidity (63 seconds), while the masterbatch prepared using an S-absorbent aqueous solution + moisture absorption inhibitor or carrier adsorption processes exhibits the second-best fluidity (Example 5 using an moisture absorption inhibitor process, 71 seconds, and Example 4 using a carrier adsorption process, 70 seconds). The masterbatch not subjected to the second pretreatment (Comparative Example 1) exhibits significant moisture absorption and agglomeration, with some even absorbing moisture to the point of syrup. It is described that the second crystallization mother liquor is subjected to a first pretreatment to obtain an S-inducing agent aqueous solution, and the S-inducing agent aqueous solution is further subjected to a second pretreatment (anti-moisture absorption agent and / or carrier adsorption) to prepare a mother powder, which is then used to formulate a solid agent, which completely solves the problems of previous solid agent products being extremely prone to moisture and deterioration, and easy to adhere to production and packaging equipment, so that the formulated solid agent product has good fluidity and moisture absorption resistance, and fully meets the product quality requirements.

[0130] In addition, it can be seen from the above storage test results that the products obtained in Example 3 / Example 2 / Example 4 / Example 6 are all S-absorbent soluble powder products, and all use anti-moisture absorption agents and / or carrier adsorption processes to prepare mother powders. However, due to the different S-absorbent content in the soluble powders after preparation, the S-absorbent content in Example 3 / Example 2 / Example 4 / Example 6 is 0.2% / 0.4% / 8% / 10% respectively, and the flow speeds are ranked from fast to slow as 61 seconds / 62 seconds / 70 seconds / 75 seconds, indicating that the higher the S-absorbent content in the soluble powder, the slower the flow speed will be.

[0131] While the specific embodiments of the present invention have been described in detail above, these are merely exemplary and the present invention is not limited thereto. It will be apparent to those skilled in the art that any equivalent modifications and substitutions to the present invention fall within the scope of the present invention. Therefore, any equivalent changes and modifications made without departing from the spirit and scope of the present invention are encompassed within the scope of the present invention.

Claims

1. A method for preparing a plant growth regulator solid based on the residual liquid produced by S-inducible production, characterized in that: The S-absorbent residual solution comprises a first crystallization mother liquor and a second crystallization mother liquor; the second crystallization mother liquor is subjected to a first pretreatment to obtain an S-absorbent aqueous solution; the first crystallization mother liquor and / or the S-absorbent aqueous solution is subjected to a second pretreatment to obtain a mother powder, and an agriculturally acceptable adjuvant is added to the mother powder as a basis to prepare a plant growth regulator solid containing 0.1-10% S-absorbent; the solid includes a soluble powder, a wettable powder, and a granular agent; The first crystallization mother liquor is obtained by filtering the S-absorbent fermentation liquor through plate and frame filtration, membrane filtration, salting out crystallization, and filtering to obtain the crystallization mother liquor; The second crystallization mother liquor is the crystallization mother liquor obtained by extraction, concentration, crystallization and filtration during the purification process of the crude S-absorbent; The first pretreatment method comprises: first dissolving and diluting the second crystallization mother liquor with water in a volume ratio of 1:0.3-0.4:0.25-0.45 between mother liquor, water, and liquid alkali; then slowly adding liquid alkali under stirring conditions to convert all S-absorbent contained in the second crystallization mother liquor into sodium salt and enter the aqueous phase; controlling the temperature of the mixed liquid below 35°C; then standing to allow the back-extraction aqueous phase and the organic phase to fully separate; and finally obtaining the lower back-extraction aqueous phase as an S-absorbent aqueous solution; the water dissolution and dilution method comprises slowly adding the second crystallization mother liquor into water while stirring; and the concentration of the liquid alkali is 30-32%; The second pretreatment method is: adding an anti-moisture absorption agent and / or adsorbing with a carrier to the first crystallization mother liquor and / or S-inducing agent aqueous solution, and drying-crushing-sieving to obtain a mother powder; the amount of the anti-moisture absorption agent added is the first crystallization mother liquor and / or S-inducing agent aqueous solution: anti-moisture absorption agent = 100: 5-20 (v: m); the amount of the carrier adsorption is the first crystallization mother liquor and / or S-inducing agent aqueous solution: carrier = 100: 15-50 (v: m), and the solid content: carrier mass ratio in the first crystallization mother liquor and / or S-inducing agent aqueous solution is controlled to be ≤1.5:1 (m: m); the drying is vacuum drying, spray drying, or boiling granulation drying.

2. The method for preparing a plant growth regulator solid based on the residual liquid produced by S-inducing agent according to claim 1, characterized in that: The anti-moisture absorption agent is selected from at least one of soybean dietary fiber, maltodextrin, polyethylene glycol-6000, water-soluble starch, microcrystalline cellulose, mannitol, and sodium alginate; and the carrier is selected from one of white carbon black, talc, kaolin, bentonite, attapulgite, and diatomaceous earth.

3. The method for preparing a plant growth regulating solid based on the residual liquid of S-inducing agent production according to claim 1, characterized in that: The preparation method of the wettable powder or soluble powder is as follows: based on mother powder, 0.1-5% wetting agent, 0-5% dispersant, 0-2% pH regulator and the balance as filler are added to prepare a plant growth regulating wettable powder or soluble powder containing 0.1-10% S-inducer.

4. The method for preparing a plant growth regulator solid based on the residual liquid produced by S-inducing agent according to claim 3, characterized in that: The dispersant is selected from any one of 2-naphthalenesulfonic acid formaldehyde polymer sodium salt, alkylnaphthalenesulfonic acid condensation product sodium salt, D8916, D8986, sodium tripolyphosphate, and sodium carboxymethyl cellulose; the filler is selected from one or two of white carbon black, talc, kaolin, bentonite, water-soluble starch, sodium sulfate, white sugar, lactose, and sodium citrate; the wetting agent is selected from any one of sodium octyl sulfosuccinate, sodium diisooctyl sulfosuccinate, sodium lauryl sulfate, naphthalenesulfonate phenolsulfonate, sodium N-oleoyl-N-methyltaurate, Morwet EFW, and anionic sulfonates; and the pH adjuster is selected from one or two of citric acid, oxalic acid, and tartaric acid.

5. The method for preparing a plant growth regulating solid based on the residual liquid of S-inducing agent production according to claim 1, characterized in that: The preparation method of the granules is as follows: based on the first crystallization mother liquor and / or the S-absorbent aqueous solution, 0.8-1.2% of a binder, 0.1-3% of a wetting agent, 40-65% of a pH regulator, and the remainder as filler are added according to the weight ratio of the prepared granule product, granulation is carried out using an extrusion granulator or a boiling granulator, and drying is carried out using a boiling dryer to prepare plant growth regulating granules containing 0.1-10% of S-absorbent.

6. The method for preparing a plant growth regulator solid based on the residual liquid produced by S-absorbent according to claim 5, characterized in that: An anti-moisture absorption agent may also be added to the first crystallization mother liquor and / or the S-abductin aqueous solution in a ratio of 100:5-10 (v:m); the adhesive is selected from one or two of water-soluble starch, polyvinyl pyrrolidone, and maltodextrin; and the acid-base regulator is selected from one or two of citric acid, sodium carbonate, potassium carbonate, adipic acid, and tartaric acid.

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