CN102718598A - Slow release type biodegradable caking-proof film coating material used for fertilizer and application thereof - Google Patents
Slow release type biodegradable caking-proof film coating material used for fertilizer and application thereof Download PDFInfo
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- CN102718598A CN102718598A CN2012102288033A CN201210228803A CN102718598A CN 102718598 A CN102718598 A CN 102718598A CN 2012102288033 A CN2012102288033 A CN 2012102288033A CN 201210228803 A CN201210228803 A CN 201210228803A CN 102718598 A CN102718598 A CN 102718598A
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Abstract
The invention provides a slow release type biodegradable caking-proof film coating material used for fertilizer and an application thereof. The film coating material is mainly prepared from a main ingredient and an additive at a mass ratio of 1:(0-50%), wherein the main ingredient is prepared from aliphatic polyester, copolyester, surfactant and light calcium carbonate at a certain ratio. The film coating material provided by the invention has the advantages of small use adding amount in chemical fertilizer, good slow release effect, no pollution on the environment, simple preparation technology and low cost, and is especially suitable for industrial production, and the problem that the fertilizer is easily caked can be solved.
Description
Technical field
The present invention relates to a kind of coated fertilizer and application thereof, be specifically related to of coated fertilizer and the application thereof of a kind of fertilizer with the biodegradable anti-caking of slow release type.
Technical background
China is a large agricultural country; Chemical fertilizer is used widely in proportion of crop planting, but because nitrogen utilization efficiency hangs down the loss that causes fertilizer, has caused the serious waste and the enormous economic loss of resource; And for a long time because utilizing of fertilizer is improper; Caused serious pollution for human body, animal, atmosphere, soil, water quality, grain, even seriously hindered the productive rate of grain, the nutrient of soil has also been had very big harm.Therefore, how to improve fertilizer utilization ratio, organically combine, day by day become the focus of fertilizer expert research for protection and sustainable development with the organising of the raising the output of effective utilization of fertilizer and grain, soil, environment.
Be accompanied by the fast development of China's agricultural modernization, the demand of composite fertilizer is very big, and the consumption of various chemical fertilizer is at 5000x10
4Can about t/a, the mechanized application of arising at the historic moment be more and more, keep the requirement of good flowability also increasingly high to composite fertilizer.Fertilizer caking is not only very inconvenient in use but also to transportation, storage brings very big trouble.Can bring huge economic benefit for agriculture prodn so develop a kind of composite fertilizer that soil is not had an anti-caking of slow release type degradable of injury.
At present both at home and abroad main slow release type coating mainly contains inorganic coated fertilizer and two big types of organic polymer coatings: the inorganics coated fertilizer is domestic main with ground phosphate rock, sulphur, talcum powder, terra alba, flyash, the organic and inorganic cementitious material material as coating.The organic polymer coated fertilizer both at home and abroad mainly with thermoset and thermoplastic resin as the coated slow-release material.
US3295950 discloses a kind of sulfur-coated urea of representative that is in the prior art; Though price is not high; But do not play the anti-caking effect of fertilizer, main is that this coating material contains the easy oxidation of sulphur coating, fragmentation, also is unfavorable for that transportation and a large amount of sulphur shell are caused soil acidification by the microbiological degradation long-term application in soil.CN100457694C, CN101037368 disclose one type of biological biodegradable self-control slow-releasing fertilizer and preparation method thereof; Introduced with high molecular polymer such as Mierocrystalline cellulose, epoxy resin, polymkeric substance such as Z 150PH are the solution-type slow-release material of main body; This material can biological degradation; It is expensive but the price reduction of this human subject material is all compared to reduce environmental pollution, increases cost burden, and can not effectively solve the problem of fertilizer caking.CN100575317C discloses a kind of slow released agglomeration resistant compound fertilizer and working method thereof; But owing to its employed anti-hard caking agent is mixed and made into by alkylammonium salt, sulfonated alkylbenzene and gets than the consumption that is 225230:600 is mixed with the composite fertilizer massfraction; The large usage quantity of anti-hard caking agent has obviously increased the production cost of fertilizer; Bring economical load to the peasant, be unfavorable for suitability for industrialized production.
For solving above-mentioned price height and the problem that can not prevent luming; The present invention provides a kind of fertilizer with having slow-releasing and biodegradable anti-caking coated fertilizer; Technology is simply with low cost, had good sustained release effect, good, the environmentally safe of agglomeration preventing performance; Can secularly be applied to the fertilising of food crop, very help suitability for industrialized production.
Summary of the invention
To the deficiency of prior art, the present invention has set forth a kind of release-controlled coated material of biodegradable preventing blocking effect and in Application in Fertilizer.
For realizing the object of the invention, adopt the preparation technology of following technology as coated fertilizer:
A kind of fertilizer comprises main body composition and additive with the coated fertilizer of the biodegradable anti-caking of slow release type, and the mass ratio of described main body composition and additive is 1 ︰ 0-50%, wherein,
Said main body composition comprises and a) gathers barkite, or its copolyesters, or its blending polyester; B) tensio-active agent; C) lime carbonate
Said additive is a powdered, comprises organic amine, metal carboxylate and salt thereof, gypsum, clay, acidic phosphorus mine powder, straw burning ash, urea, starch or MOX; Or the mixture of two or more described additive arbitrarily.
The described barkite that gathers is 20～60 parts, preferred 25～50 parts; Tensio-active agent is 0.01～15 part, preferred 0.1～5 part; Lime carbonate is 30～60 parts, preferred 35～60 parts; 0.1～10 part of additive, preferred 0.1～5 part.
Described tensio-active agent comprises Triple Pressed Stearic Acid, X 2073, oleic acid, quaternary ammonium compound or glyceryl ester; Preferred Triple Pressed Stearic Acid, oleic acid and X 2073.Described lime carbonate comprises light calcium carbonate or water-ground limestone; The particle of affiliated light calcium carbonate is the 100-3000 order, preferred 250-2500 order.
Wherein, the described molecular weight that gathers the oxalic acid glycol ester is 500-35000, is preferably 5000-20000.
Said to gather barkite blending polyester or copolyesters be other polyester with gather barkite blend or copolyester compound, and wherein the consumption of other polyester is 0.1～5% mol ratios of gathering barkite.Wherein said other polyester are PGTA, Sodium bromoacetate homopolymer, SRU methyl esters, polylactide, poly (glycolide-lactide), poly butylene succinate, polyethylene glycol succinate, gather oxalic acid glycol ether ester, gather oxalic acid Tetraglycol 99 ester, gather the inferior diester of suberic acid, gather the inferior diester of certain herbaceous plants with big flowers diacid, gather certain herbaceous plants with big flowers diacid Aden ester, polyethylene glycol adipate, poly adipate succinic acid ester, polyethylene terephthalate, polybutylene terephthalate, gather and make into naphthalic acid terepthaloyl moietie.
Another object of the present invention is to provide the biodegradable anti-caking block manure of a kind of slow release type material, said fertilizer contains above-mentioned coated fertilizer and urea or the common fertilizer that mass ratio is 0.1～20%:1.The mass ratio of described coated fertilizer and fertilizer preferably is preferably 0.1～10% ︰ 1.
The mode that the biodegradable anti-caking block manure of described slow release type material can those of ordinary skills be known prepares, and for example, adopts encapsulation tool that described coated fertilizer is carried out dressing to fertilizer.
Said encapsulation tool is preferably rotary drum, disk granulation or fluidized-bed.
Another object of the present invention provides a kind of method for preparing coated fertilizer of the present invention:
1) get in the aqueous solution of sodium hydroxide that 0.01～15 part in tensio-active agent adds certain content and stir, after the dissolving, add 20～80 parts of combinations of lime carbonate fully, stir mashed prod;
2) get 20～60 parts of aliphatic polyesters, be dissolved in chloroform or the ethylene dichloride, stir, add again in the mashed prod of step 1);
3) get 0.1～10 part of one or more compsn that are selected from organic amine, metal carboxylate and salt thereof, gypsum, clay, acidic phosphorus mine powder, straw burning ash, urea, starch, the MOX simultaneously; Add step 2 to) mashed prod in; Stir, in 20～100 ℃ of waters bath with thermostatic control, stir 10～80min, suction filtration reclaims solvent; Drying, the preparation and coated fertilizer.
The preferred Triple Pressed Stearic Acid of tensio-active agent described in the described step 1) or oleic acid or X 2073, shared umber are 0.01～15 part, preferred 0.1～5 part; Lime carbonate is preferably light calcium carbonate, and 20～80 parts of umbers are preferably 35～60 parts.
Additive is preferred 0.1～5 part in the step 3); The time of water bath with thermostatic control is preferably 35～70min; The temperature of water bath with thermostatic control is preferably 40～80 ℃.
Its advantage of coated fertilizer of the biodegradable anti-caking of this slow release type provided by the invention is, can add in the various chemical fertilizer, can effectively be adsorbed on the surface of chemical fertilizer; Form layer protective layer; This resist both can play the separant of chemical fertilizer granule, can be used as the sorbent material of the organic coated material of carrier again, more help the isolation between the chemical fertilizer granule; The coated fertilizer of absorption has the biodegradable performance; Play the effect of real slowly-releasing, improving fertilizer utilization ratio and this anti-caking coated fertilizer can biological degradation be water and carbonic acid gas, and soil is not had injury effect.Compare with existing similar release-controlled coated material, have that starting material are cheap, cost is low, preparation technology is simple, few, the had good sustained release effect of addition, an environmentally safe in the chemical fertilizer, the more important thing is to solve the problem that existing fertilizer is prone to caking.
Embodiment
In order to make technique effect of the present invention more clear, easy to understand will be enumerated embodiment below, the present invention further explained, but be not in order to limit scope of the present invention.
Embodiment one
Get Triple Pressed Stearic Acid 5g, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 200 order powder 48g lime carbonate stir mashed prod; Get and gather oxalic acid glycol ester 50g (the weight average relative molecular weight is 500) and be dissolved in the 100ml chloroformic solution, stir 10min, change in the above-mentioned mashed prod; Stir, add acidic phosphorus mine powder 5g again, while stirring 80 ℃ of water bath with thermostatic control 60min; Precipitation liquid reclaims solvent, and is dry, grind to form powdery, is finished product.
Getting the 2g coated fertilizer and join coating in the 100g urea (40～60 order), in the accelerated test, is under 50% the environment, not have caking phenomenon after 5 days in 1.5 times normal atmosphere, humidity, and the release period of urea is 7 days.
Embodiment two
Get X 2073 5g, add in 0.7% the aqueous sodium hydroxide solution of 100m and stir, add again 200 order powder 30g lime carbonate stir mashed prod; Get and gather oxalic acid glycol ester 40g (the weight average relative molecular weight is 2500) and be dissolved in the 100ml dichloroethane solution, stir 8min, change in the above-mentioned mashed prod; Stir, add straw burning ash 5g and urea 5g, 85 ℃ of water bath with thermostatic control 70min while stirring again; Precipitation liquid reclaims solvent, and is dry, grind to form powdery, is finished product.
Getting the 5g coated fertilizer and join coating in the 100g urea (40～60 order), in the accelerated test, is under 50% the environment, not have caking phenomenon after 7 days in 2 times normal atmosphere, humidity, and the release period of urea is 10 days.
Embodiment three
Get oleic acid 5g, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 200 order powder 35g lime carbonate stir mashed prod; Get and gather oxalic acid glycol ester 60g (the weight average relative molecular weight is 5000) and be dissolved in the 100ml dichloroethane solution, stir 10min, change in the above-mentioned mashed prod; Stir, add gypsum, clay, each 2g of acidic phosphorus mine powder again, while stirring 90 ℃ of water bath with thermostatic control 50min; Precipitation liquid reclaims solvent, and is dry, grind to form powdery, is finished product.
Getting the 8g coated fertilizer and join coating in the 100g urea (40～60 order), in the accelerated test, is under 50% the environment, not have caking phenomenon after 10 days in 2 times normal atmosphere, humidity, and the release period of urea is 20 days.
Embodiment four
Get X 2073 5g, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 2500 order powder 45g silicon oxide stir mashed prod; Get and gather oxalic acid glycol ester 60g (the weight average relative molecular weight is 15000) and be dissolved in the 100ml chloroformic solution, stir 5min, change in the above-mentioned mashed prod; Stir, add clay, each 5g of starch again, while stirring 60 ℃ of water bath with thermostatic control 80min; Precipitation liquid reclaims solvent, and is dry, grind to form powdery, is finished product.
Get the 2g coated fertilizer and join coating in the 100g urea (40～60 order), stacked 180 days under the natural condition, do not have caking and take place, the release period of urea is 80 days.
Embodiment five
Get oleic acid 15g, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 2500 order powder 45g silicon oxide stir mashed prod; Get and gather oxalic acid glycol ester 35g (the weight average relative molecular weight is 13000) and be dissolved in the 100ml chloroformic solution, stir 10min, change in the above-mentioned mashed prod; Stir, add clay, each 5g of starch again, while stirring 65 ℃ of water bath with thermostatic control 70min; Precipitation liquid reclaims solvent, and is dry, grind to form powdery, is finished product.
Get the 5g coated fertilizer and join coating in the 100g urea (40～60 order), stacked 360 days under the natural condition, do not have caking and take place, the release period of urea is 78 days.
Embodiment six
Get each 5g of Triple Pressed Stearic Acid and X 2073, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 2500 order powder 32g silicon oxide stir mashed prod; Get and gather oxalic acid glycol ester 60g (the weight average relative molecular weight is 13000) and be dissolved in the 100ml dichloroethane solution, stir 5min, change in the above-mentioned mashed prod; Stir; Add gypsum, urea, each 5g of starch again, 80 ℃ of water bath with thermostatic control 80min while stirring, precipitation liquid reclaims solvent; Dry, grind to form powdery, be finished product.
Get the 12g coated fertilizer and join coating in the 100g urea (40～60 order), stacked 180 days under the natural condition, do not have caking and take place, the release period of urea is 100 days.
Embodiment seven
Get each 5g of oleic acid and X 2073, add in 0.7% the aqueous sodium hydroxide solution of 100ml and stir, add again 2500 order powder 32g silicon oxide stir mashed prod; Get and gather oxalic acid glycol ester 60g (the weight average relative molecular weight is 13000) and be dissolved in the 100ml dichloroethane solution, stir 7min, change in the above-mentioned mashed prod; Stir; Add gypsum, urea, each 5g of starch again, 80 ℃ of water bath with thermostatic control 75min while stirring, precipitation liquid reclaims solvent; Dry, grind to form powdery, be finished product.
Get the 10g coated fertilizer and join coating in the 100g urea (40～60 order), stacked 90 days under the natural condition, do not have caking and take place, the release period of urea is 110 days.
Claims (13)
1. a fertilizer comprises main body composition and additive with the coated fertilizer of the biodegradable anti-caking of slow release type, and the mass ratio of described main body composition and additive is 1:0-50%, wherein,
Said main body composition comprises and a) gathers barkite, or its copolyesters, or its blending polyester; B) tensio-active agent; C) lime carbonate;
Said additive is a powdered, comprises organic amine, metal carboxylate and salt thereof, gypsum, clay, acidic phosphorus mine powder, straw burning ash, urea, starch or MOX; Or the mixture of two or more described additive arbitrarily.
2. according to the said coated fertilizer of claim 1, it is characterized in that described tensio-active agent comprises: Triple Pressed Stearic Acid, X 2073, oleic acid, quaternary ammonium compound or glyceryl ester.
3. coated fertilizer according to claim 2 is characterized in that described tensio-active agent is oleic acid and/or Triple Pressed Stearic Acid and/or X 2073.
4. coated fertilizer according to claim 1 is characterized in that described polyester is for gathering the oxalic acid glycol ester.
5. coated fertilizer according to claim 4 is characterized in that the described oxalic acid glycol ester molecular weight that gathers is 500-35000.
6. coated fertilizer according to claim 5 is characterized in that the described oxalic acid glycol ester molecular weight that gathers is 5000-20000.
7. coated fertilizer according to claim 1 is characterized in that described lime carbonate is light calcium carbonate or water-ground limestone.
8. coated fertilizer according to claim 1; It is characterized in that described to gather barkite blending polyester or copolyesters be other polyester with gather barkite blend or copolyester compound, wherein the consumption of other polyester is 0.1～5% mol ratios of gathering barkite; Wherein said other polyester are PGTA, Sodium bromoacetate homopolymer, SRU methyl esters, polylactide, poly (glycolide-lactide), poly butylene succinate, polyethylene glycol succinate, gather oxalic acid glycol ether ester, gather oxalic acid Tetraglycol 99 ester, gather the inferior diester of suberic acid, gather the inferior diester of certain herbaceous plants with big flowers diacid, gather certain herbaceous plants with big flowers diacid Aden ester, polyethylene glycol adipate, poly adipate succinic acid ester, polyethylene terephthalate, polybutylene terephthalate, gather naphthalic acid terepthaloyl moietie, can select wherein a kind of or two or more polyester arbitrarily.
9. coated fertilizer according to claim 1 is characterized in that the described barkite that gathers is 20～60 parts; Tensio-active agent is 0.01～15 part; Lime carbonate is 20～80 parts; Additive is 0.1～10 part.
10. coated fertilizer according to claim 9 is characterized in that described aliphatic polyester is 25～50 parts; Preferred 0.1～5 part of tensio-active agent; Preferred 35～60 parts of lime carbonate; Preferred 0.1～5 part of other additives.
11. the fertilizer of the biodegradable anti-caking of slow release type is characterized in that said fertilizer contains any described coated fertilizer of claim 1-10 and urea or the common fertilizer that mass ratio is 0.1～20% ︰ 1.
12. one kind prepare fertilizer with the biodegradable anti-caking of slow release type the method for coated fertilizer, comprising:
1) get in the aqueous solution of sodium hydroxide that 0.01～15 part in tensio-active agent adds certain content and stir, after the dissolving, add 20～80 parts of combinations of lime carbonate fully, stir mashed prod;
2) get 20～60 parts of aliphatic polyesters, be dissolved in chloroform or the ethylene dichloride, stir, add again in the mashed prod of step 1);
3) get 0.1～10 part of one or more compsn that are selected from organic amine, metal carboxylate and salt thereof, gypsum, clay, acidic phosphorus mine powder, straw burning ash, urea, starch, the MOX simultaneously; Add step 2 to) mashed prod in; Stir, in 20～100 ℃ of waters bath with thermostatic control, stir 10～80min, suction filtration reclaims solvent; Drying, the preparation and coated fertilizer.
13. method according to claim 12 is characterized in that described bath temperature is 40-80 ℃, churning time is 30-75min.
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Cited By (6)
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| CN103833479A (en) * | 2014-03-21 | 2014-06-04 | 润禾泰华生物科技（北京）有限公司 | Special liquid medicine fertilizer for increasing production, killing pests and reducing residues of rice and preparation method thereof |
| CN103833476A (en) * | 2014-03-21 | 2014-06-04 | 润禾泰华生物科技（北京）有限公司 | Special liquid fertilizer for increasing yield of strawberry, killing insects and degrading pesticide residues and preparation method thereof |
| CN107954778A (en) * | 2017-11-27 | 2018-04-24 | 岳西县天泰化工有限责任公司 | A kind of production method of foliar fertilizer |
| CN108164334A (en) * | 2018-01-26 | 2018-06-15 | 宜州市横山泰顺种养专业合作社 | A kind of high-yield planting method of selenium-rich sugar orange fertilizer and sugar orange |
| WO2018149421A1 (en) * | 2017-08-10 | 2018-08-23 | 阜阳富瑞雪化工科技有限公司 | Humic acid fertiliser anti-caking agent having fertiliser synergistic function, and preparation method therefor |
| CN108752088A (en) * | 2018-05-29 | 2018-11-06 | 贵州紫云月华新材料有限公司 | A kind of dedicated modified calcium carbonate of chemical fertilizer anti-caking and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833479A (en) * | 2014-03-21 | 2014-06-04 | 润禾泰华生物科技（北京）有限公司 | Special liquid medicine fertilizer for increasing production, killing pests and reducing residues of rice and preparation method thereof |
| CN103833476A (en) * | 2014-03-21 | 2014-06-04 | 润禾泰华生物科技（北京）有限公司 | Special liquid fertilizer for increasing yield of strawberry, killing insects and degrading pesticide residues and preparation method thereof |
| CN103833476B (en) * | 2014-03-21 | 2015-09-09 | 润禾泰华生物科技（北京）有限公司 | Residual Special-purpose liquid pesticide-containing fertilizer of a kind of strawberry volume increase desinsection degraded agriculture and preparation method thereof |
| WO2018149421A1 (en) * | 2017-08-10 | 2018-08-23 | 阜阳富瑞雪化工科技有限公司 | Humic acid fertiliser anti-caking agent having fertiliser synergistic function, and preparation method therefor |
| CN107954778A (en) * | 2017-11-27 | 2018-04-24 | 岳西县天泰化工有限责任公司 | A kind of production method of foliar fertilizer |
| CN108164334A (en) * | 2018-01-26 | 2018-06-15 | 宜州市横山泰顺种养专业合作社 | A kind of high-yield planting method of selenium-rich sugar orange fertilizer and sugar orange |
| CN108752088A (en) * | 2018-05-29 | 2018-11-06 | 贵州紫云月华新材料有限公司 | A kind of dedicated modified calcium carbonate of chemical fertilizer anti-caking and preparation method thereof |
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| CN102718598B (en) | 2015-01-14 |
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Effective date of registration: 20201201 Address after: 226000 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee after: Nantong Yaoxiang Technology Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |