CN101486615A - Preparation of fertilizer coating sustained-release agent - Google Patents
Preparation of fertilizer coating sustained-release agent Download PDFInfo
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- CN101486615A CN101486615A CNA2009100144473A CN200910014447A CN101486615A CN 101486615 A CN101486615 A CN 101486615A CN A2009100144473 A CNA2009100144473 A CN A2009100144473A CN 200910014447 A CN200910014447 A CN 200910014447A CN 101486615 A CN101486615 A CN 101486615A
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- polyvinyl alcohol
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Abstract
The invention discloses a preparation method of a fertilizer envelope sustained release agent. At first, polyvinyl formal is prepared; and then the polyvinyl formal is mixed and stirred with pure acrylic emulsion, film forming assistant, polyoxyethylene nonyl phenyl ether (10) and bentonite to prepare the finished product. The use of the filming forming assistant ensures the sustained release agent is continuously formed into films and the film forming effect is good, moreover, the envelope sustained release agent is a polymeric material, and has the advantages of good sustained release performance, easy degradation, and no pollution to soil.
Description
Technical field
The present invention relates to a kind of preparation method of sustained release dosage, specifically a kind of preparation method of fertilizer coating sustained-release agent.
Background technology
At present slowly-releasing, release and release control fertilizer be because of its utilization rate of fertilizer height, season crop single-dose application, and saving of work and time, economic benefit is high and can effectively reduce advantage such as fertilising pollution on the environment and be popular fully in modern agriculture production.
Existing release-controlled coated material comprises that sulphur dressing, sulphur add resin dressing, thermosetting or thermoplastic resin dressing, coating dressing etc., its coating cracky of sulphur dressing, can not play the effect of slowly-releasing well, therefore adopt sulphur to add resin dressing or thermosetting or thermoplastic resin dressing, though can solve the damaging problem of simple sulphur dressing effectively, the higher and difficult degraded of resin of cost, degradative phase is more than 30～50 years usually, if use continuously, certainly will destroy the structure of soil; If adopt resin and sulphur coated urea, the nitrogen of urea discharges and lags behind, results back bundled slow-releasing fertilizer nitrogen has not also discharged (residual fertile core), need fertile asynchronous with crop, cause plant growth to absorb in earlier stage, still cause nitrogen loss and influence the growth of crop less than enough nitrogens.The shortcoming of coating dressing is that slow release effect is poor, and the fertilizer efficiency utilization ratio is low.
The patent No. is the production method that 200410091315.8 Chinese patent discloses a kind of water-soluble nano-submicron level PVA mixed polymer as fertilizer cementing and coating agent.Its principle is with polyvinyl alcohol dissolving, aldehyde condensation, and polyacrylamide amine solvent, two kinds of solution are mixed in proportion, emulsification, make nanometer-submicron level PVA mixed polymers by high-shear again, are used for slow release fertilizer jointing compound and coating agent.There is following defective in this patent method: use organic sodium salts such as fat alcohol polyethylene ether sodium sulfate and Sodium dodecylbenzene sulfonate among (1), the preparation technology owing to the emulsifying agent in this patent method, this fertilizer of life-time service easily causes the salinization of soil, destroy the eubiosis of soil itself, be unfavorable for environmental protection, discontented requirement that can sustainable development strategy.(2), this production method need adopt High shear device that product is sheared to make nano level material, the film-formation result of this material just can embody, complex process, tooling cost height.(3), use nanometer-submicron level PVA mixed polymers that this production method makes as the coating agent, its film-formation result can not be satisfactory.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of fertilizer slow-release formulation at the deficiencies in the prior art.Technical problem to be solved is: add film coalescence aid in preparation technology, make that the coated slow release formulation film-formation result that makes is better, sustained release performance is good; And preparation method's safety and environmental protection, finished product is easily degraded, not can to environment pollute and cost low.
In order to solve the problems of the technologies described above, the present invention has adopted following technical scheme.
The preparation method of fertilizer coating sustained-release agent is characterized in that preparation technology is as follows:
1), in reactor, add industrial water purification, and be heated to 94～98 ℃, add the polyvinyl alcohol of quality 9%～11%, stir 1.5～2h and make polyvinyl alcohol solution to the polyvinyl alcohol dissolving; Be cooled to 80～85 ℃ then; Adding hydrochloric acid soln adjusting pH value in reactor is 2～3;
2), in reactor, add the 1st) used quality 4%～7% of step, content is 37% formaldehyde solution, maintains the temperature at 80～85 ℃, stirring reaction 30～35 minutes; Adding ammonia soln, to regulate pH value be 7～8, adds the 1st) urea reaction of used quality 2%～4% of step 20～30 minutes, make urea and unnecessary formaldehyde reaction;
3), in reactor, adding the 1st) pure-acrylic emulsion of 1.5～2 times of step gained polyvinyl alcohol solution quality stirred 20～30 minutes, was cooled to 40～50 ℃; Add earlier polyvinyl alcohol solution and the film coalescence aid of pure-acrylic emulsion total mass 4 ‰～6 ‰ and Nonyl pheno (10) ether of polyvinyl alcohol solution and pure-acrylic emulsion total mass 0.5 ‰～1 ‰, 8%～12% the wilkinite that the back adds polyvinyl alcohol solution and pure-acrylic emulsion total mass stirred 20～30 minutes;
Described film coalescence aid is propylene glycol phenylate or 12 carbon alcohol esters or 2,2,4-trimethylammonium-1, a kind of in the 3-pentanediol mono isobutyrate.
Positively effect of the present invention is:
(1), this preparation technology is simple, cost is low, adopts film coalescence aid, makes film more continuous, need not to adopt High shear device, the film-formation result of finished product just can meet the demands, with the material that does not add the film forming auxiliary agent relatively, the film forming continuity can improve more than 30%.
(2), material choice do not relate to the sodium salt class and becomes the strain organic materials, degradable own, degradative phase six months～a year can not cause untoward reaction to soil again, the ecological environment security performance is good.The process of material degraded itself just can play the effect of chessom, and the ethene that produces in the degradation process has dematuration, and other degraded products can also discharge phosphorus by crop with Phosphorus inorganic salt reaction and absorb, and improve chemical fertilizer utilization ratio.
(3), crop early stage required fertilizer discharge the ammonia-state nitrogen supply by coated slow release formulation itself, the required nutrient of crop late growing stage is satisfied by the acyl ammonia-state nitrogen of fertilizer, therefore, can satisfy the crop nutrient in little seedling stage, the crop seedling is looked, and the later stage is not taken off fertilizer again, satisfies the demand of crop this season.
(4), finished product produce fringe cost low, be compared as follows with existing coated fertilizer: 700 yuan of-800 yuan/t of sulphur coated urea material fringe cost, 800 yuan of-1000 yuan/t of resin coated urea material fringe cost; 50 yuan of-150 yuan/t of this technologic material fringe cost are 1/10-1/20. of sulphur and resin coated urea fringe cost
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment one:
Preparation technology is as follows:
1), in reactor, add 1 ton of industrial water purification, and be heated to 94 ℃, add the polyvinyl alcohol of quality 9%, stir 1.5h and make polyvinyl alcohol solution to the polyvinyl alcohol dissolving; Be cooled to 80 ℃ then; Be that 30% concentrated hydrochloric acid is diluted with water to dilute hydrochloric acid solution according to volume ratio 1:1 with mass concentration, it is 3 that the dilute hydrochloric acid solution that adds polyvinyl alcohol solution quality 1% in reactor is regulated pH value;
2), in reactor, add the 1st) used quality 4% of step, content is 37% formaldehyde solution, maintains the temperature at 80 ℃, stirring reaction 30 minutes; The mass concentration that adds polyvinyl alcohol solution quality 1% be 25% ammonia soln to regulate pH value be 7, add the 1st) urea reaction of used quality 2% of step 20 minutes, make urea and unnecessary formaldehyde reaction;
3), in reactor, adding the 1st) pure-acrylic emulsion of 1.5 times of step gained polyvinyl alcohol solution quality stirred 20 minutes, was cooled to 40 ℃; Add earlier polyvinyl alcohol solution and the 12 carbon alcohol esters of pure-acrylic emulsion total mass 4 ‰ and Nonyl pheno (10) ether of polyvinyl alcohol solution and pure-acrylic emulsion total mass 0.5 ‰, 8% the wilkinite that the back adds polyvinyl alcohol solution and pure-acrylic emulsion total mass stirred 20 minutes.
Described pure-acrylic emulsion is the abbreviation of methyl acrylic ester, esters of acrylic acid and vinylformic acid ternary copolymer emulsion.
Embodiment two:
1), in reactor, add 1 ton of industrial water purification, and be heated to 98 ℃, add the polyvinyl alcohol of quality 11%, stir 2h and make polyvinyl alcohol solution to the polyvinyl alcohol dissolving; Be cooled to 85 ℃ then; Be that 30% concentrated hydrochloric acid is diluted with water to dilute hydrochloric acid solution according to volume ratio 1:1 with mass concentration, it is 2 that the dilute hydrochloric acid solution that adds polyvinyl alcohol solution quality 2% in reactor is regulated pH value;
2), in reactor, add the 1st) used quality 7% of step, content is 37% formaldehyde solution, maintains the temperature at 85 ℃, stirring reaction 35 minutes; The mass concentration that adds polyvinyl alcohol solution quality 2% be 25% ammonia soln to regulate pH value be 8, add the 1st) urea reaction of used quality 4% of step 30 minutes, make urea and unnecessary formaldehyde reaction;
3), in reactor, adding the 1st) pure-acrylic emulsion of 2 times of step gained polyvinyl alcohol solution quality stirred 30 minutes, was cooled to 50 ℃; Add earlier polyvinyl alcohol solution and the propylene glycol phenylate of pure-acrylic emulsion total mass 6 ‰ and Nonyl pheno (10) ether of polyvinyl alcohol solution and pure-acrylic emulsion total mass 1 ‰, 12% the wilkinite that the back adds polyvinyl alcohol solution and pure-acrylic emulsion total mass stirred 30 minutes.
Embodiment three:
1), in reactor, add 1 ton of industrial water purification, and be heated to 96 ℃, add the polyvinyl alcohol of quality 10%, stir 1.8h and make polyvinyl alcohol solution to the polyvinyl alcohol dissolving; Be cooled to 83 ℃ then; Be that 30% concentrated hydrochloric acid is diluted with water to dilute hydrochloric acid solution according to volume ratio 1:1 with mass concentration, it is 2.5 that the dilute hydrochloric acid solution that adds polyvinyl alcohol solution quality 1.5% in reactor is regulated pH value;
2), in reactor, add the 1st) used quality 5.5% of step, content is 37% formaldehyde solution, maintains the temperature at 85 ℃, stirring reaction 33 minutes; The mass concentration that adds polyvinyl alcohol solution quality 1.5% be 25% ammonia soln to regulate pH value be 7.5, add the 1st) urea reaction of used quality 3% of step 25 minutes, make urea and unnecessary formaldehyde reaction;
3), in reactor, adding the 1st) pure-acrylic emulsion of 1.7 times of step gained polyvinyl alcohol solution quality stirred 25 minutes, was cooled to 45 ℃; Add 2 of polyvinyl alcohol solution and pure-acrylic emulsion total mass 5 ‰ earlier, 2,4-trimethylammonium-1, the Nonyl pheno of 3-pentanediol mono isobutyrate and polyvinyl alcohol solution and pure-acrylic emulsion total mass 1.7 ‰ (10) ether, afterwards 10% of adding polyvinyl alcohol solution and pure-acrylic emulsion total mass wilkinite stirred 25 minutes.
The use of fertilizer coating sustained-release agent:
1, starts the cylinder encapsulation tool, use travelling belt to add fertilizer (particle diameter 2.0～4.0mm) on one side from charging opening, by material lifting flights fertiliser granulates is kicked up, using pressurised metered pump that fertilizer coating sustained-release agent is vaporific by nozzle on one side is sprayed on the fertiliser granulates, fertilizer is kicked up, is fallen in the fog-zone of coated slow release formulation, this operation repeatedly, thus make fertilizer superscribe one deck coated slow release formulation, and the consumption of sustained release dosage is 1%～1.5% of a fertilizer quality.
2, (6～8r/min), the fertiliser granulates that is wrapped enters 90～95 ℃ of hot blast districts, oven dry along with the rotation of coating tube.
3, the coated fertilizer of being dried enters the cooling cylinder cooling by travelling belt.
4, packing.
The slow release effect of coated slow release fertilizer:
1, water wash effect
1.1 coated slow-release urea
67.12%, 3 accumulative total of the elementary solubility rate of urea solubility rate 99.01%;
Coated slow-release urea: 12.40%, 18 accumulative total of elementary solubility rate solubility rate 95.46%.
1.2 coated slow-release compound fertilizer
47.6%, 5 cumulative leaching rate 97.7% of the fertile elementary solubility rate of nitrogen of common compound.
31.88%, 20 cumulative leaching rate 83.98% of the fertile elementary solubility rate of nitrogen of coated slow-release compound.
Europe resin and sulfur coating urea proposed standard regulation: elementary solubility rate≤15%; The U.S. and Japanese resin coated urea proposed standard regulation: elementary solubility rate≤40%; Japan's fertilizer law (1996) is stipulated elementary nitrogen solubility rate＜50% to field crop.From the drip washing result, the effect of this sustained release dosage coated carbamide and compound fertilizer is fine.
2, field crops fertilizer efficiency
2.1 test site and soil
Retired village Zhen Dong cross board at the rear of an ancient carriage Ge Zhuan village experimental field in the Laishan District, Yantai City, soil type is a moisture soil, middle loamy texture ground, fertility is even, and irrigation condition is good, does not do fertilizer test.Soil organism 9.6g/kg, alkali-hydrolyzable nitrogen 83mg/kg, organophosphorus 32mg/kg, available potassium 76mg/kg, pH value are 6.5; Wheat breed: the tobacco grower 15.
2.2 test method
Three processing are established in test, and 12 sub-districts are established in 4 repetitions altogether, and the sub-district area is 5 * 6=30m
2, each sub-district random alignment.Handle the contrast (ck) of not applying fertilizer of 1 blank; Handle 2 conventional fertilizer applications (potassium sulfate compound fertilizer N+P
2O
5+ K
2O 〉=45%, N-P
2O
5-K
2O is 24-10-11), base is executed 30kg/ mu, and 20kg/ mu topdresses before the jointing; Handle 3 coated slow-release compound fertilizer (N+P
2O
5+ K
2O 〉=45%, N-P
2O
5-K
2O is 22-9-9), usage and dosage is with handling 2 conventional fertilizer applications.
2.3, test results and analysis
2.3.1 different treatment bearing status investigation
Each handles the investigation of fertility proterties table one
As can be seen from Table I, using the fertile blank basic seedling of coated slow-release compound increases by 0.22 ten thousand/mu, and tiller increases by 4.05 ten thousand/mu before the winter, spring, the highest tiller increased by 5.9 ten thousand/mu, the mu spike number increases by 5.85 ten thousand, and grain number per spike increases by 4.6, and investigating thousand seed weight during results increases by 2.29 grams; Increase by 0.15 ten thousand/mu than the basic seedling of conventional processing, tiller increases by 0.9 ten thousand/mu before the winter, and spring, the highest tiller increased by 1.1 ten thousand/mu, and the mu spike number increases by 1.03 ten thousand, and grain number per spike increases by 1, and investigating thousand seed weight during results increases by 0.49 gram.
2.3.2 different fertilization is to the influence of wheat yield
Test is once gathered, the single receipts in each sub-district, single title, single note product, and yield result sees Table two.
Table two wheat yield is table as a result
Annotate: the mean number multiple comparisons of series, mark little numerical tabular and be shown with utmost point significant difference with letter.
Find out that from table two processing 3 is used coated slow-release compound fertilizer and increased wheat 125.61kg than blank mu, volume increase 32.07%; Conventional fertilizer application increases wheat 94.13kg than blank mu, volume increase 24.03%; Coated slow-release compound fertilizer increases wheat 31.48kg than conventional fertilizer application mu, volume increase 6.5%.
Through variance analysis F=176.679〉F0.01=27.34 difference is extremely remarkable, by multiple comparisons, handle 1, handle 2, handle 3 between difference reach utmost point conspicuous level.Blank that coated slow-release compound fertilizer does not more apply fertilizer and conventional fertilizer application all have extremely significant production-increasing function.
3, field crops fertilizer efficiency
3.1 test site and soil
Experimental field in the interplanting corn ground of Longkou, Yantai City seed multiplication farm, soil type is damp cinnamon soil, and the top layer quality is light earth, the fertility one-level.Fertility is even, and irrigation condition is good, does not do fertilizer test.The conventional per mu yield 550～600kg of corn.The soil nutrient result of laboratory test is that alkali-hydrolyzable nitrogen 98mg/kg, available potassium 120mg/kg, pH value are 6.5; Corn variety: west jade three, spacing in the rows 25cm, line-spacing 70cm, several 3810 strains of mu strain.
3.2 test method
Three processing are established in test, 3 repetitions.Handle 1: the contrast of not applying fertilizer (ck); Handle 2: conventional fertilizer application, mu is executed potassium sulfate compound fertilizer (15-9-21) 50kg, and base is executed 25kg/ mu, the typhon mouth phase 20kg/ mu that topdresses; Handle 3: grant the coated slow-release urea 17.05kg of 2 amounts such as nitrogen such as grade of processing, wait the general calcium 37.5kg of phosphorus amount, wait the vitriolate of tartar 21kg of potassium amount, base is executed 50% of total amount, and the typhon mouth phase imposes 50% of total amount.More than each is handled except that test fertilizer difference, field management method is all consistent with agronomic measures.
3.3 test-results and analysis
3.3.1 this tests disposable results, respectively gets 20 fringes and carry out the proterties investigation after drying, and the results are shown in Table one
Each proterties of table one is investigated table as a result
By table one as can be seen, use the processing cob of coated slow-release urea than handling the thick 0.43cm of 1 (ck), than handling 2 thick 0.19cm; Average spike length is than handling 1 long 2.3cm, than handling 2 long 0.7cm; Bald than handling 1 short 1.57cm, than handling 2 short 0.29cm; Grain number per spike is Duoed 36.1 and 3 than contrast of not applying fertilizer and conventional fertilizer application respectively; Thousand seed weight increases 55.3g and 29.5g respectively; The processing mealie that is to say coated slow-release urea is thick.Spike length, bald weak point, grain number per spike is many, thousand seed weight is heavy.
3.3.2 output is investigated at each test site results 30m
2, real receipts, yield result sees Table two.
Table two corn yield is table as a result
As can be seen from Table II, the processing output of using coated slow-release urea increases 150.7kg and 61.99kg than blank and conventional fertilizer application respectively, stimulation ratio is respectively 27.2% and 9.6%, according to 1.4 yuan of calculating of per kilogram corn, use the coated slow-release urea processing and increase income 241.12 yuan, than 99.18 yuan of conventional fertilizer application mu volume increase than the blank mu that does not apply fertilizer.
Through variance analysis, F=525.83〉F0.01=99.36 difference is extremely remarkable, by multiple comparisons, handle 1, handle 2, handle 3 between difference reach utmost point conspicuous level.Blank that coated slow-release urea does not more apply fertilizer and conventional fertilizer application all have extremely significant production-increasing function.
Claims (2)
1, a kind of preparation method of fertilizer coating sustained-release agent is characterized in that preparation technology is as follows:
1), in reactor, add industrial water purification, and be heated to 94～98 ℃, add the polyvinyl alcohol of quality 9%～11%, stir 1.5～2h and make polyvinyl alcohol solution to the polyvinyl alcohol dissolving; Be cooled to 80～85 ℃ then; Adding hydrochloric acid soln adjusting pH value in reactor is 2～3;
2), in reactor, add the 1st) used quality 4%～7% of step, content is 37% formaldehyde solution, maintains the temperature at 80～85 ℃, stirring reaction 30～35 minutes; Adding ammonia soln, to regulate pH value be 7～8, adds the 1st) urea reaction of used quality 2%～4% of step 20～30 minutes, make urea and unnecessary formaldehyde reaction;
3), in reactor, adding the 1st) pure-acrylic emulsion of 1.5～2 times of step gained polyvinyl alcohol solution quality stirred 20～30 minutes, was cooled to 40～50 ℃; Add earlier polyvinyl alcohol solution and the film coalescence aid of pure-acrylic emulsion total mass 4 ‰～6 ‰ and Nonyl pheno (10) ether of polyvinyl alcohol solution and pure-acrylic emulsion total mass 0.5 ‰～1 ‰, 8%～12% the wilkinite that the back adds polyvinyl alcohol solution and pure-acrylic emulsion total mass stirred 20～30 minutes.
2, the preparation method of fertilizer coating sustained-release agent as claimed in claim 1 is characterized in that: film coalescence aid is propylene glycol phenylate or 12 carbon alcohol esters or 2,2,4-trimethylammonium-1, a kind of in the 3-pentanediol mono isobutyrate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093143A (en) * | 2009-12-15 | 2011-06-15 | 黑龙江金事达农业科技开发有限公司 | Sustained-release sulfur-containing nitrogen fertilizer |
| CN102267841A (en) * | 2011-06-22 | 2011-12-07 | 北京市农林科学院 | Slightly water-soluble fertilizer and preparation method thereof |
| CN102838413A (en) * | 2012-08-22 | 2012-12-26 | 中国农业科学院农业资源与农业区划研究所 | Ternary slow-release compound fertilizer and preparation method thereof |
| CN102924176A (en) * | 2012-11-20 | 2013-02-13 | 中南林业科技大学 | Sustained oxygen release fertilizer and preparation method thereof |
| CN103288564A (en) * | 2012-02-28 | 2013-09-11 | 五洲丰农业科技有限公司 | Production method of encapsulated sustained release agent specially for urea or compound fertilizer |
| CN107162803A (en) * | 2017-07-12 | 2017-09-15 | 烟台市昊星晟信息技术有限公司 | A kind of preparation method of fertilizer anti-caking agents |
| CN107619339A (en) * | 2017-09-12 | 2018-01-23 | 湖北富邦科技股份有限公司 | One kind is rich in micro-element nutrition synergist and its application in sulphur zinc |
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| CN1208289C (en) * | 2003-10-16 | 2005-06-29 | 华东理工大学 | Coating agent for slow release fertilizer |
| CN100554329C (en) * | 2004-11-22 | 2009-10-28 | 中国农业科学院土壤肥料研究所 | The nanometer-submicron level PVA mixed polymer as fertilizer cementing coating agent preparation method |
| CN100457694C (en) * | 2007-02-12 | 2009-02-04 | 山东省农业科学院土壤肥料研究所 | Biological biodegradable self-control slow-releasing fertilizer and preparation method thereof |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093143A (en) * | 2009-12-15 | 2011-06-15 | 黑龙江金事达农业科技开发有限公司 | Sustained-release sulfur-containing nitrogen fertilizer |
| CN102267841A (en) * | 2011-06-22 | 2011-12-07 | 北京市农林科学院 | Slightly water-soluble fertilizer and preparation method thereof |
| CN102267841B (en) * | 2011-06-22 | 2013-04-17 | 北京市农林科学院 | Slightly water-soluble fertilizer and preparation method thereof |
| CN103288564A (en) * | 2012-02-28 | 2013-09-11 | 五洲丰农业科技有限公司 | Production method of encapsulated sustained release agent specially for urea or compound fertilizer |
| CN103288564B (en) * | 2012-02-28 | 2014-05-07 | 五洲丰农业科技有限公司 | Production method of encapsulated sustained release agent specially for urea or compound fertilizer |
| CN102838413A (en) * | 2012-08-22 | 2012-12-26 | 中国农业科学院农业资源与农业区划研究所 | Ternary slow-release compound fertilizer and preparation method thereof |
| CN102838413B (en) * | 2012-08-22 | 2014-03-26 | 中国农业科学院农业资源与农业区划研究所 | Ternary slow-release compound fertilizer and preparation method thereof |
| CN102924176A (en) * | 2012-11-20 | 2013-02-13 | 中南林业科技大学 | Sustained oxygen release fertilizer and preparation method thereof |
| CN107162803A (en) * | 2017-07-12 | 2017-09-15 | 烟台市昊星晟信息技术有限公司 | A kind of preparation method of fertilizer anti-caking agents |
| CN107619339A (en) * | 2017-09-12 | 2018-01-23 | 湖北富邦科技股份有限公司 | One kind is rich in micro-element nutrition synergist and its application in sulphur zinc |
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Denomination of invention: Preparation of coated slow release fertilizer Effective date of registration: 20201126 Granted publication date: 20120125 Pledgee: SINOAGRI HOLDING Co.,Ltd. Pledgor: WUZHOUFENG AGRICULTURAL SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2020980008490 |