CN101654387B - Liquid anti-caking agent for compound fertilizer - Google Patents
Liquid anti-caking agent for compound fertilizer Download PDFInfo
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- CN101654387B CN101654387B CN 200810147497 CN200810147497A CN101654387B CN 101654387 B CN101654387 B CN 101654387B CN 200810147497 CN200810147497 CN 200810147497 CN 200810147497 A CN200810147497 A CN 200810147497A CN 101654387 B CN101654387 B CN 101654387B
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Abstract
The invention relates to a liquid anti-caking agent for a compound fertilizer, which consists of 1 to 50 weight percent of aqueous polymer, 1 to 50 weight percent of surfactant, and the balance of water. The surfactant is one or combination of any of an anionic surfactant, a non-ionic surfactant, a cationic surfactant and an amphoteric surfactant. Optionally, one ore more additives which are selected from a defoaming agent, a preservative, a dye and a pigment can also be added into the liquid anti-caking agent for the compound fertilizer; and the consumption of the defoaming agent is 0 to 5 weight percent, the consumption of the preservative is 0 to 5 weight percent and the total consumption of the dye and the pigment is 0 to 50 weight percent. The liquid anti-caking agent for the compound fertilizer can effectively solve the caking problem of a compound fertilizer product, particularly the caking problem of a compound fertilizer with high nutrient content such as a high nitrogen compound fertilizer which is difficult to solve by present enterprises producing compound fertilizers, and ensures that the compound fertilizer product has the characteristics of green fertilizers.
Description
Technical field
The present invention relates to the chemical fertilizer additive, be specifically related to a kind of liquid anti-caking agent for compound fertilizer.
Background technology
Complex fertilizer product all has certain water absorbability, just exists the difference of severity between the different varieties.Because change of external conditions such as the humidity in production, packing and the storage and transport process, temperature, extruding, the powdery that a part is loose, granular, globular solids will lose flowability, and form hard and block that be difficult to fragmentation.Compound fertilizer from caking has just destroyed its free-flowing, not only give to use and bring great inconvenience, also can affect the product fertilizer efficiency, when serious even inefficacy, increase and use cost and amount of application, cause user's financial loss, simultaneously also can widen marketing channel to composite fertilizer manufacturing enterprise, increase sales volume, set up brand negative impact is arranged.
The factor that affects compound fertilizer from caking is a lot,, material matching overheated such as Moisture high UCL, when packing not science, particle is little, powder is many, high pressure stacking etc., enterprise can take targetedly to strengthen product granularity control, with the science agglomeration technique, improve the measure such as storage requirement and avoid.But domestic and international a large amount of scientific research and industrialization actual production sufficient proof: by adding anti-hard caking agent, improving plane of crystal character, is effective, most scientific, the easiest and the most most economical a kind of method that prevents compound fertilizer from caking.
Compound fertilizer anticaking agent commonly used can be divided at present: 1) inert powder, and this type of is such as kaolin, silicon-dioxide, diatomite and talcum powder etc.; 2) non-surface active organic compound is such as paraffin, machine oil etc.; 3) tensio-active agent can be anionic, cationic and nonionic surface active agent.Utilize inert powder as compound fertilizer anticaking agent, addition is generally larger, quality product is affected greatly, and owing to the anti-caking ability owes to be eliminated lastingly and gradually.On-surface-active class organic compound only makes composite fertilizer prevent caking by the mechanical isolation effect, the anti-caking function singleness, and result of use is general.Surfactant-based anti-hard caking agent can effectively reduce the surface tension of particle surface solution, and the kapillary adsorptive power is reduced, and is also adsorbable in plane of crystal formation hydrophobic layer, hinders the exchange of moisture of crystal and atmosphere, thereby plays preventing blocking effect.Nearest studies show that: use merely tensio-active agent as anti-hard caking agent, although can reduce the water absorbability of object, its mechanical isolation effect is not strong, can not prevent muchly the formation of intercrystalline point of contact.
What at present domestic and international composite fertilizer producer was the most frequently used is machinery oil, Wax and surfactant-based composite anti-hard caking agent, mentioned a kind of compound fertilizer anticaking agent such as patent of invention PL171121, it contains the primary amine of 5wt%～20wt%, and 12～22 carbon are arranged on the alkyl chain of this amine; The tertiary amine and the reaction product that contains the lipid acid of 12～22 carbon that also contain 1wt%～20wt%; The methyl-silicone oil of 0.01wt%～2wt%; Secondary aliphatic amide less than 5% (containing 11～22 carbon); Remainder is mineral oil, paraffin or their mixture.Patent of invention CN1376653 relates to a kind of anti-caking preparation of composite fertilizer, raw material by following consumption proportion is made: stearic acid 10wt%～15wt%, hydrogenated tallow amine 10wt%～15wt%, crystal wax 5wt%～10wt%, machine oil 60wt%～70wt%, feed intake by above-mentioned prescription, with steam heat fusing, stir finished product.Patent of invention CN1342628 has introduced a kind of compound fertilizer anticaking agent, comprises the water-resisting agent of 10wt%～60wt%, a kind of in the following material that has drawn from: Palmiticacid, stearic acid, sodium stearate, lipid acid; The anti-looseness agent of 15wt%～30wt%, a kind of in the following material that has drawn from: Stearyl Amine, dialkyl acid amides, laurylamide; The non-blushing thinner of 20wt%～40wt% is taken from a kind of in the following material: wax, paraffin and blended wax; The lubricant of 4wt%～15wt% is taken from a kind of in the following material: silicone oil, Vaseline, whiteruss and glycerine; The anti-caking agent of 1wt%～5wt% is taken from a kind of in the following material: octadecylene acid amides, Mierocrystalline cellulose carboxylic acid sodium, N, N-dimethyl Stearyl Amine and two lauramides.Contain mineral oil, paraffin or their mixture among the PL171121; Relate to crystal wax 5wt%～10wt%, machine oil 60wt%～70wt% in the CN1376653 prescription; The non-blushing thinner of 80wt%～40wt% among the CN134262 is taken from wax, paraffin and blended wax, and the lubricant of 4wt%～15wt% is taken from silicone oil, Vaseline, whiteruss and glycerine.
This class is absorbed by chemical fertilizer granule after machine oil overflows by machine oil, Wax and surfactant-based composite anti-hard caking agent, machine oil has serious harm to crop germination, root system, the seedling root system is then die with gently then withered, heavy after machine oil contacts, the visible water surface has the vestige of greasy dirt behind the paddy field fertilizing, not only rice seedling is injured, water quality and environment have also been produced pollution, and life-time service is especially serious to the pollution of environment.Thereby need to a kind of new compound fertilizer anticaking agent that does not contain machine oil and Wax in this area.
Summary of the invention
The object of the present invention is to provide a kind of novel liquid anti-caking agent for compound fertilizer.
According to the present invention, a kind of liquid anti-caking agent for compound fertilizer is provided, its water by 1wt%～50wt% aqueous high molecular, 1wt%～50wt% tensio-active agent and surplus forms.
According to the present invention, also can add applicable any other additive in this area in the described liquid anti-caking agent for compound fertilizer, described additive comprises but is not limited to: the conventional additives such as defoamer, sanitas and dyestuff or pigment.Therefore, according to one embodiment of the invention, also optionally add a kind of or any one the above additive that is selected from defoamer, sanitas, dyestuff, the pigment in the described liquid anti-caking agent for compound fertilizer, consumption is defoamer 0wt%～5wt%, 0.001wt%～5wt% for example, sanitas 0wt%～5wt%, for example 0.001wt%～5wt%, total consumption of dyestuff and pigment is 0wt%～50wt%, for example 0.001wt%～50wt%.
Certainly, the high-content that it will be understood by those skilled in the art that above-mentioned each component all may be subjected to the restriction of its solubleness.
According to the present invention, described aqueous high molecular can be the water-soluble polymer that can dissolve in water, also can be the polymer water miscible liquid that can be dispersed in water, its content range be 1wt%～50wt%, and the preferred content scope is 1wt%～40wt%, more preferably 1wt%～30wt%, 1wt%～25wt% for example, 2wt%～30wt%, 5wt%～25wt%, 10wt%～25wt%, 15wt%～25wt%.Any intermediate value in 1wt%～50wt% scope all is applicable to the present invention, and these intermediate values include but not limited to: 0.1,2,3,4,5,6,7,8,9,10,12,15,18,20,25,33,35,40,45 etc.The specific examples of described aqueous high molecular comprises polyvinyl acetate (PVA), polyvinylpyrrolidone, polymaleic anhydride, polyacrylic acid and salt thereof, polyacrylate emulsion, polymethyl acrylic acid and salt thereof, polyacrylamide, polyvinyl sulfuric acid and salt thereof, polyvinyl alcohol, polyvinyl acetal solution, polyvinyl methyl ethermaleic anhydride, polyoxyethylene glycol, polyoxyethylene, carboxymethyl cellulose, Natvosol, methylcellulose gum, polyamine, quaternary ammonium polymer, Resins, epoxy, urea-formaldehyde resin, aminoresin, Synolac, urethane resin, polymeric amide, urea-formaldehyde resin, chitin, xanthan gum, in the starch any one or arbitrarily two or more being mixed, any two is above when being mixed, and its proportioning is any proportioning, or the modification derivant of above-mentioned substance, described modification derivant is water-based, and is namely water-soluble aqueous or emulsification is aqueous.Preferred aqueous high molecular comprises, molecular weight is that 20,000～200,000 polyvinyl acetate (PVA), molecular weight are that 5000～700000 polyvinylpyrrolidone, molecular weight are that 1000～1,000,000 polyacrylate, solid content are that 10%～50% polyacrylate emulsion, molecular weight are that 100～5,000,000 polyacrylamide, molecular weight are that 500～300,000 polyvinyl alcohol, molecular weight are that 200～20000 polyoxyethylene glycol, molecular weight are 1000～10000 urethane resin.Described salt can be any applicable salt, comprises sodium salt, sylvite, ammonium salt.
Above-mentioned water-based polymer comprises the derivative through chemical modification, for example (but being not limited to this example),
Polyacrylamide can be through chemical modification, for example: Partially hydrolyzed polyacrylamide, methylolation polyacrylamide, sulfomethylation polyacrylamide, Mannich reaction generate dimethylin N methacrylamide polymkeric substance, become cationic polymine through the hoffman degradation reaction thing.
Polyvinyl alcohol can be through chemical modification, such as the product after processing through etherificate, esterification, acetalation etc.The etherification product of polyvinyl alcohol comprises that polyvinyl alcohol and reacting ethylene oxide generation hydroxyethylation compound, polyvinyl alcohol and acrylonitrile reactor obtain cyano ethyl ether compound, polyvinyl alcohol and acrylamide reaction and obtain amido formylation product; The esterification products of polyvinyl alcohol comprises that polyvinyl alcohol and organic acid and inorganic acid reaction generate corresponding organic acid acetic and inorganic acid ester; The acetalation product of polyvinyl alcohol comprises that polyvinyl alcohol and carbonyl compound reaction generate acetal compound, and applicable aldehydes comprises saturated aldehyde (formaldehyde, acetaldehyde, butyraldehyde, oxalic dialdehyde etc.), unsaturated aldehyde (propenal, crotonic aldehyde), aromatic aldehyde etc.
Chitin and derivative thereof can be through chemical modifications, such as the product of acylations, hydroxylation, carboxylated, cyano group, acidifying.
According to the present invention, the content range that adds tensio-active agent is 1wt%～50wt%, and the preferred content scope is 1wt%～40wt%, more preferably 1wt%～30wt%, 1wt%～25wt% for example, 2wt%～30wt%, 5wt%～25wt%, 10wt%～25wt%, 15wt%～25wt%.Any intermediate value in 1wt%～50wt% scope all is applicable to the present invention, and these intermediate values include but not limited to: 0.1,2,3,4,5,6,7,8,9,10,12,15,18,20,25,33,35,40,45 etc.Described tensio-active agent can be a kind of in anion surfactant, nonionogenic tenside, cats product and the amphoterics or any multiple arbitrary combination, and condition is that each material is mixed in together and can precipitate.Should be appreciated that " multiple arbitrarily " comprises any two kinds in " arbitrarily multiple arbitrary combination ", " arbitrary combination " comprises that various materials are with arbitrarily proportioning combination or mixed situation; And comprise for example a kind of or any multiple situation that mixes or make up of the tensio-active agent of a kind of or any multiple and other type of nonionogenic tenside, vice versa.
According to the present invention, described anion surfactant can be a kind of or any multiple arbitrary combination in lipid acid and salt, organic sulfonic acid and its esters, organo-sulfate or salt, organophosphate or the salt etc.Organic sulfonic acid and its esters comprise alkylsulphonic acid and salt thereof, alkyl substituted benzene or naphthene sulfonic acid and salt thereof, olefin sulfonic acid and salt thereof; Organo-sulfate or salt comprise alkylsurfuric acid and salt thereof, alkylamine sulfuric acid and salt thereof, fatty alcohol sulphuric acid and salt thereof, fatty alcohol-polyoxyethylene ether sulfuric acid and salt thereof, alkylphenol polyoxyethylene sulfuric acid and salt thereof; Organophosphate or salt comprise Fatty Alcohol(C12-C14 and C12-C18) phosphoric acid and salt thereof, fatty alcohol-polyoxyethylene ether phosphoric acid and salt thereof, alkylphenol polyoxyethylene phosphoric acid and salt thereof etc.Preferably, described anion surfactant is: lipid acid and salt thereof such as stearic acid, Sodium pentadecanecarboxylate, sodium oleate, alkyl substituted benzene or naphthene sulfonic acid and salt thereof such as sodium butylnaphthalenesulfonate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, alkylsurfuric acid and salt thereof such as sodium lauryl sulphate, alkylamine sulfuric acid and salt thereof, fatty alcohol sulphuric acid and salt thereof, fatty alcohol-polyoxyethylene ether phosphoric acid and salt thereof.Described salt can be any applicable salt, comprises sodium salt, sylvite, ammonium salt.
According to the present invention, described nonionogenic tenside can be a kind of or any multiple arbitrary combination in Determination of Polyoxyethylene Non-ionic Surfactants, polyol esters of fatty acids type nonionogenic tenside, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan mono fatty acid ester, the alkyl glycoside etc.Determination of Polyoxyethylene Non-ionic Surfactants comprises fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene fatty acid ester, polyox-yethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl amine etc.; Polyol esters of fatty acids type ionic surfactant pack is drawn together glycerin fatty acid ester, fatty acid pentaerythritol ester, sorbitan-fatty acid ester, sorbitan fatty acid ester; Alkyl glycoside comprises sugar ester.Preferably, described nonionogenic tenside is: the alkylphenol polyoxyethylene of the fatty alcohol-polyoxyethylene ether of 6～22 carbon, 6～22 carbon, polyox-yethylene-polyoxypropylene block copolymer, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan mono fatty acid ester.
According to the present invention, described cats product comprises in alkylamine and salt thereof, quaternary amine, the polyoxyethylene alkyl amine etc. any one or arbitrarily two or more being mixed, and any two is above when being mixed, and its proportioning is any proportioning.Preferably, described cats product is alkylamine and salt thereof, quaternary ammonium salt.
According to the present invention, described amphoterics can be any one or arbitrarily two or more being mixed in amphoteric imidazoline, surfactivity trimethyl-glycine, the amino acid surfactant etc., and any two is above when being mixed, and its proportioning is any proportioning.Amphoteric imidazoline comprises carboxyl tetrahydroglyoxaline, sulfonic group tetrahydroglyoxaline, phosphoimidazole quinoline; The surfactivity trimethyl-glycine comprises that carboxybetaine, sultaine, sulfatobetaine sulfoniobetaine, Phosphonium base trimethyl-glycine, amino acid comprise aminocarboxylic acid, thionamic acid.Preferably, described amphoterics is sulfonic group tetrahydroglyoxaline, carboxybetaine, aminocarboxylic acid.
According to the present invention, described sanitas can be the applicable any sanitas in this area, include but not limited in phenylformic acid, Sodium Benzoate, Morpan BB, trichloro-butyl alcohol, phenol, cresylol, phenylcarbinol, methyl alcohol, formaldehyde, the Whitfield's ointment etc. any one, or any two above being mixed, any two is above when being mixed, and its proportioning is any proportioning.Preferably, described sanitas is: Sodium Benzoate, phenol, formaldehyde, Whitfield's ointment.The preferable amount of described sanitas is 0.01wt%～5wt%, 0.05wt%～4.5wt% for example, and 0.05wt%～3.5wt%, 0.05wt%～3wt%, 0.5wt%～2wt%,
According to the present invention, described defoamer can be the applicable any defoamer in this area, include but not limited in ethanol, octanol, enanthol, Virahol, methyl isobutyl carbinol, dimethyl silicone oil, hydroxy silicon oil, organic silicon emulsion, tributyl phosphate, sulfated castor oil, shrink Sorbitol Powder lauric acid monoester, shrink Sorbitol Powder lauric acid three esters etc. any one, or any two above being mixed, any two is above when being mixed, and its proportioning is any proportioning.Preferably, described defoamer is: octanol, enanthol, Virahol, dimethyl silicone oil, organic silicon emulsion, tributyl phosphate.The preferable amount of described defoamer is 0.01wt%～5wt%, 0.05wt%～4.5wt% for example, and 0.05wt%～3.5wt%, 0.05wt%～3wt%, 0.5wt%～2wt%,
According to the present invention, in liquid anti-caking agent for compound fertilizer, can also randomly add other applicable additive, for example, versicolor dyestuff and/or pigment.The example of described dyestuff includes but not limited to, matching stain, glacial dye, basic dyestuff, dispersed dye, substantive dyestuff, mordant dyes, reactive dyestuffs, thioxine dyes and vat dyes etc.; The example of described pigment includes but not limited to, the oxide compound of mineral dye such as various metals, salt and the carbon blacks such as sulfide, vitriol, chromic salt, molybdate, pigment dyestuff such as azo (comprising two kinds of monoazo, tetrazos), phthalocyanines, condensed ring ketone (comprising isoindoline ketone, perylene class, quinophthalone class etc.), triarylmethane compound pigment and the pigment that from plant, extracts.Total amount ranges of described dyestuff and pigment is 0wt%～50wt%, and preferred amount ranges is 0wt%～30wt%, 2wt%～30wt% for example, 5wt%～25wt%, 10wt%～25wt%, 15wt%～25wt%.Any intermediate value in 1wt%～50wt% scope all is applicable to the present invention, and these intermediate values include but not limited to: 0.1,2,3,4,5,6,7,8,9,10,12,15,18,20,25,33,35,40,45 etc.
Aqueous high molecular described in the invention and tensio-active agent can be miscible easily.In addition, those skilled in the art will know that, easy precipitation and cause no longer including activity when polymer and negatively charged ion and cats product are miscible, can produce precipitation during such as polyacrylic ester and positively charged ion mixing, therefore when selecting tensio-active agent of the present invention, avoid being mixed in the situation that a time-out can produce precipitation, this selection is apparent to those skilled in the art.
Liquid anti-caking agent for compound fertilizer of the present invention is when using, and the addition of anti-hard caking agent (take solid content meter wherein) is the 0.005wt%～0.5wt% of composite fertilizer's weight, preferred 0.01wt%～0.1wt%.
New type compound fertilizer liquid anti-caking agent of the present invention can continue and effectively reduce the caking of composite fertilizer for a long time, again not to the negative effect of environment.And, the preventing blocking effect of liquid anti-caking agent for compound fertilizer of the present invention is compared with the like product of existing market and is had significant improvement, solved well the easily defectives such as caking, adhesion, dust formation of composite fertilizer, especially more remarkable on the preventing blocking effect of high nutrient composite fertilizer such as high-nitrogen compound fertilizer.In addition, it also has good chemical stability and lasting anti-caking ability, be liquid under its normal temperature, do not need machinery oil as carrier, overcome the oil pollution that the fertile anti-hard caking agent of conventional composite brings to the farmland water system, and had nutrient composition that fertilizer discharges and the characteristics easy to use of not changing.Anti-hard caking agent of the present invention is applicable to all granular composite fertilizer and Chemical Mixed Fertilizers, and other has the fertilizer of similarity.In addition, to those skilled in the art, after reading this specification sheets, remaining advantage of the present invention and feature also are apparent.
Description of drawings
Fig. 1 uses composite fertilizer by before the liquid anti-caking agent for compound fertilizer processing of the present invention by embodiment 15, and its particle surface amplifies 3000 times scanning electronic microscope (SEM) figure; And
Fig. 2 uses composite fertilizer by after the liquid anti-caking agent for compound fertilizer processing of the present invention by embodiment 15, and its particle surface amplifies 3000 times scanning electron microscope diagram.
Embodiment
Hereinafter describe the present invention in detail with reference to specific embodiment.Should be appreciated that those skilled in the art can carry out various various modifications and the improvement that do not depart from the spirit and scope of the invention to the present invention based on content disclosed herein, they should all drop in the scope of patent protection of claim definition of the present patent application.In addition, should be appreciated that embodiment provided herein only is used for purpose of the present invention is described, and should not be construed as limitation of the present invention.
Embodiment 1
The about 30000 polyacrylic acid sodium water solution 1mL of average molecular weight Mw (weight-average molecular weight) that add solid content 30wt% in the 60mL water, the about 30000 sodium polymethacrylate 1mL of the molecular weight Mw of 30wt%, polyvinylpyrrolidone 0.4g, dodecyl sodium naphthalene sulfonate 8g, α-sodium olefin sulfonate 5g, polyoxyethylene sorbitan fatty acid ester (T-40) 10g, polyoxyethylene octylphenol ether 4.5g, fatty alcohol-polyoxyethylene ether (AEO-7) 2.5g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-5-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Be the embodiment 1 of the Chinese invention patent of CN1376653A by publication number, prescription is: stearic acid 13wt%, hydrogenated tallow amine 12wt%, crystal wax 5wt%, machine oil 70wt%, feed intake by this prescription, with steam heat fusing, stir anti-hard caking agent finished product (hereinafter referred reference substance).This anti-hard caking agent of weighing 0.15g evenly is coated in the above-mentioned composite fertilizer of 100g, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=Σ, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 34%, and the average caking rate of the composite fertilizer of reference substance coating is 45%.
Embodiment 2
The polyoxyethylene glycol 29g that adds molecular weight 12000～15000 in the 67mL water, hydroxyethyl replaces the Natvosol 0.3g of (MS1.8), methylcellulose gum (substitution value 2.0, molecular weight about 90000) 0.2g, T-80 1g, Ethylene Glycol Distearate 1g, palmityl trimethyl ammonium chloride (1631 chlorine type) 1.8g, alkyl glycoside (50%) 0.5g, octadecyl trimethyl ammonium chloride (1831) 2.4g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 28-10-10, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 40%, and the average caking rate of the composite fertilizer of reference substance coating is 48%.
Embodiment 3
The urea-formaldehyde resin 10g that adds molecular-weight average about 10000 in the 55mL water, polyox-yethylene-polyoxypropylene block copolymer 4.2g, Natvosol (MS1.8) 1.3g, C12～C18 sodium alkyl sulfate 2.1g, C8～C18 fatty alcohol sulphuric acid triethanolamine salt 3.2g, polyoxyethylene (15) lauryl alcohol 4.2g, sorbitan fatty acid ester 5.1g, sodium xylene sulfonate 4.1g, sodium oleate 4.0g, octanol 0.2g, hydroxy silicon oil 0.4g, Whitfield's ointment 1.0g, phenol 0.5g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 28-12-10, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 37%, and the average caking rate of the composite fertilizer of reference substance coating is 44%.
Embodiment 4
Adding solid content in the 55mL water is the aqueous polyvinyl acetate emulsion 20mL of 48wt%, polymaleic anhydride 3g, polyoxyethylene 1.1g, sodium polyoxyethelene lauryl alcohol sulfate 4.3g, polyoxyethylenated alcohol sodium sulfate 7.2g, sodium xylene sulfonate 1.0g, polyoxyethylene carboxylate (SE-10) 1.5g, polyoxyethylene nonylphenol ether (NP-10) 5.1g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 15-15-15, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 31%, and the average caking rate of the composite fertilizer of reference substance coating is 39%.
Embodiment 5
Adding the polymerization degree in the 60mL water is 25000, alcoholysis degree is 87% polyvinyl alcohol 8.1g, the polyoxyethylene glycol 3.1g of molecular weight 2000, imidazoline quaternary ammonium salt 0.4g, polyoxyethylene octylphenol ether 1.4g, carboxymethyl tetrahydroglyoxaline 1.3g, fatty alcohol-polyoxyethylene ether (SA-20) 5.1g, castor oil polyoxyethylene ether (EL-20) 1.5g, aliphatic amine polyoxyethylene ether (AC1820) 1.6g, alkylphenol polyoxyethylene (OP-7) 2.1g, phosphoric acid ester (AEO-3) 2.3g, CH3-(CH2)13N(CH3)2-O (active matter content 25%) 2.1g, stearyl dimethyl benzyl ammonium chloride 1.1g, Varion CDG-K (active matter content 30%) 2.4g, AMONYL 380LC 2.0g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 18-18-18, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=Σ, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 39%, and the average caking rate of the composite fertilizer of reference substance coating is 47%.
Embodiment 6
In 80mL water, add molecular weight 5000 polyoxyethylene glycol 1.3g, hydroxyethyl replaces 1.8 carboxymethyl cellulose 0.2g, ethoxylated alkyl sulfate 2.3g, polyoxyethylene aliphatic alcohol ether sodium sulfate (C12～14+nEO, n=5) 3.1g, polyoxyethylene carboxylate (SE-10) 1.8g, sorbitan stearate (S-60) 2.4g, phthalocyanine green 1.5g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-5-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=5 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 41%, and the average caking rate of the composite fertilizer of reference substance coating is 52%.
Embodiment 7
In 75mL water, add molecular weight 1 * 10
6Polyacrylamide 5g, Xylo-Mucine (butt 96%) 0.2g, average molecular weight Mw 175000 Polyvinyl sulfate sylvite 2.1g, polyvinyl methyl ethermaleic anhydride 3.2g, sodium lignosulfonate 4.5g, C12-15-fatty alcohol phosphate ammonium salt 3.1g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 18-18-18, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 36%, and the average caking rate of the composite fertilizer of reference substance coating is 48%.
Embodiment 8
Polyacrylate emulsion (bc-98N) 40g that adds solid content 39% in the 40mL water, average molecular weight Mw 5000, solid content 29.8% water soluble polyurethane resin 10g, petroleum sodium sulfonate 6.2g, Phosphate of Polyoxyethylene Isooctyl Ether sodium salt 2.1g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 25-6-9, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 32%, and the average caking rate of the composite fertilizer of reference substance coating is 47%.
Embodiment 9
In 40mL water, add Polyquaternium-10 10g, solid content 35% melamine resin 15g, solid content 12.5% Polyamide-Polyamsne-Epichlorohydrin 10g, stearyl dimethyl benzyl ammonium chloride 5g, polyoxyethylene nonylphenol ether (NP-21) 2g, polyoxyethylene carboxylate (SE-10) 5g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-0-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 35%, and the average caking rate of the composite fertilizer of reference substance coating is 51%.
Embodiment 10
Get solid content 60% Resins, epoxy (E560) 30g, 30% polymine 15g, xanthan gum 5g, sorbitan stearate (S-60) 6g, T-80 (T-60) 6g, active matter content 50% alkyl glycoside 7g, polyoxyethylene sorbitan fatty acid ester 4g, average molecular weight Mw 175000 Polyvinyl sulfate sylvite 4g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 28-10-12, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=Σ, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 30%, and the average caking rate of the composite fertilizer of reference substance coating is 45%.
Embodiment 11
Get solid content 55% water-soluble urea-formaldehyde resin 19g, with in the triethylamine and solid content 75% water soluble alkyd resin (phthalic acid glycerine ester) 12g that crosses, 30% chitin carboxyl methylation derivant 4g, water-soluble amylopectin 1g, polyoxyethylene carboxylate (SE-10) 8g, alkylphenol polyoxyethylene (OP-7) 9g, actives 96% isomerous tridecanol polyoxyethylene ether phosphoric acid ester 3g, C12～C18 sodium alkyl sulfate 6g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-5-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 35%, and the average caking rate of the composite fertilizer of reference substance coating is 52%.
Embodiment 12
Get solid content 55% water-soluble urea-formaldehyde resin 90g, alkylphenol polyoxyethylene (OP-7) 0.4g, polyoxyethylene carboxylate (SE-10) 0.3g, alkylphenol polyoxyethylene (OP-7) 1.1g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-0-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=∑, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 36%, and the average caking rate of the composite fertilizer of reference substance coating is 50%.
Embodiment 13
Get α-sodium olefin sulfonate (AOS) 20g of active matter content 40%, the polyoxyethylenated alcohol sodium sulfate of active matter content 70% (AES) 60g, the polyoxyethylene glycol 2g of molecular weight 12000～15000, polyox-yethylene-polyoxypropylene block copolymer 1.2g, sodium xylene sulfonate 0.2g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 30-5-5, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=Σ, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 38%, and the average caking rate of the composite fertilizer of reference substance coating is 58%.
Embodiment 14
The polyoxyethylene glycol 9g that adds molecular weight 12000～15000 in the 10mL water, T-80 2.1g, Ethylene Glycol Distearate 1.1g, sodium polyoxyethelene lauryl alcohol sulfate 3.2g, polyoxyethylenated alcohol sodium sulfate 5.2g, sodium xylene sulfonate 1.5g, polyoxyethylene carboxylate (SE-10) 2g, 85% water soluble fluorescence yellow dye 40g.
The water constant volume stirs behind 100mL after the dissolving, makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 28-5-10, stirs evenly mixedly, and makes its drying, puts into the moisture absorption apparatus moisture absorption sealing bag of after 10 hours composite fertilizer being packed into again, puts into 70 ℃ baking oven heating 72 hours, after the taking-up, at room temperature cools off 3 hours.Sealing bag is being put down eminence free-falling from 50cm, falling on the cement flooring, the composite fertilizer in the sealing bag is taken out, and telling caking and the composite fertilizer of caking not, weighing is calculated average caking rate according to following formula.
Same weighing 0.15g embodiment 1 described reference substance evenly is coated in the 100g composite fertilizer, and other operation is the same.As a comparison sample.
Caking rate=(caking composite fertilizer quality/total composite fertilizer quality) * 100%
Average each sample caking rate/n of caking rate=Σ, n=4 in this example
The average caking rate that calculates the composite fertilizer of liquid anti-caking agent coating of the present invention is 37%, and the average caking rate of the composite fertilizer of reference substance coating is 58%.
Embodiment 15
With the polyvinylpyrrolidone aqueous solution 75g of 40wt%, the ethylene glycol monobutyl ether phosphoric acid ester aqueous solution 10g of 4wt%, the petroleum sodium sulfonate 0.6g of active matter content 24% mixes and makes liquid anti-caking agent for compound fertilizer.This anti-hard caking agent of weighing 0.15g evenly is coated in 100g, N-P
2O
5-K
2The O mass ratio is in the composite fertilizer of 25-6-9, will not be coated with the composite fertilizer (N-P of (blank sample) and coating liquid anti-hard caking agent
2O
5-K
2The O mass ratio is 25-6-9) composite fertilizer's sample of (consumption of concrete operation step and anti-hard caking agent is with embodiment 1) has been done electron-microscope scanning with scanning electronic microscope respectively after the dry and cooling, and the result is as depicted in figs. 1 and 2.
From stereoscan photograph illustrated in figures 1 and 2, the crystalline form of compound fertilizer granules surface particle surface before and after the spraying liquid anti-caking agent for compound fertilizer has obvious difference.Blank particle surface crystallization is looser, particle surface crystallization after the processing is intensive, fertiliser granulates its surface compressed after treatment is described, particle surface is more regular mellow and full, can reduce like this particle and intergranular contact area, thereby reduce the formation of brilliant bridge and reduce the kapillary adsorptive power, play the effect that suppresses caking.
Claims (8)
1. liquid anti-caking agent for compound fertilizer, the tensio-active agent of its aqueous high molecular by 1wt%～50wt%, 1wt%～50wt% and the water of surplus form, described aqueous high molecular is selected from any two or more being mixed in polymaleic anhydride, polyoxyethylene, urethane resin, Resins, epoxy, polymine, xanthan gum, chitin, the starch, and arbitrarily its proportioning is any proportioning during two or more being mixed.
2. liquid anti-caking agent for compound fertilizer according to claim 1, it is characterized in that: described tensio-active agent is a kind of in anion surfactant, nonionogenic tenside, cats product and the amphoterics or any multiple arbitrary combination, and condition is that each material is mixed in together and can precipitate.
3. liquid anti-caking agent for compound fertilizer according to claim 2 is characterized in that: described anion surfactant is a kind of in lipid acid and salt, organic sulfonic acid and its esters, organo-sulfate or salt, organophosphate or the salt or any multiple arbitrary combination.
4. liquid anti-caking agent for compound fertilizer according to claim 2 is characterized in that: described nonionogenic tenside is a kind of in Determination of Polyoxyethylene Non-ionic Surfactants, polyol esters of fatty acids type nonionogenic tenside, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan mono fatty acid ester, the alkyl glycoside or any multiple arbitrary combination.
5. liquid anti-caking agent for compound fertilizer according to claim 2 is characterized in that: described cats product is selected from a kind of in alkylamine and salt thereof, quaternary ammonium salt, the polyoxyethylene alkyl amine or any multiple arbitrary combination.
6. liquid anti-caking agent for compound fertilizer according to claim 2 is characterized in that: described amphoterics is selected from a kind of in amphoteric imidazoline, surfactivity trimethyl-glycine, the amino acid surfactant or any multiple arbitrary combination.
7. each described liquid anti-caking agent for compound fertilizer according to claim 1 ~ 6, it is characterized in that: described liquid anti-caking agent for compound fertilizer is comprised of the aqueous high molecular of 1wt%～30wt%, the tensio-active agent of 1wt%～30wt% and the water of surplus.
8. liquid anti-caking agent for compound fertilizer, comprise according to claim 1～7 each described liquid anti-caking agent for compound fertilizer and one or more additives that are selected from defoamer, sanitas, dyestuff or the pigment, consumption is defoamer 0wt%～5wt%, sanitas 0wt%～5wt%, total consumption of dyestuff and pigment is 0wt%～50wt%.
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| CN113929535A (en) * | 2021-12-02 | 2022-01-14 | 安徽富瑞雪化工科技股份有限公司 | Environment-friendly anti-blocking agent for compound fertilizer and preparation method thereof |
| WO2023209761A1 (en) * | 2022-04-25 | 2023-11-02 | 花王株式会社 | Anti-caking agent composition for fertilizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373109A (en) * | 2002-04-08 | 2002-10-09 | 殷海权 | Loose compound fertilizer containing loosening agent and its preparing process |
| CN1648110A (en) * | 2004-12-14 | 2005-08-03 | 中国地质大学（武汉） | Anti-powdering and anti-caking agent for urea |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1109665A (en) * | 1965-03-29 | 1968-04-10 | Kao Corp | Method of preventing the caking of substancesapt to cake |
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2008
- 2008-08-21 CN CN 200810147497 patent/CN101654387B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373109A (en) * | 2002-04-08 | 2002-10-09 | 殷海权 | Loose compound fertilizer containing loosening agent and its preparing process |
| CN1648110A (en) * | 2004-12-14 | 2005-08-03 | 中国地质大学（武汉） | Anti-powdering and anti-caking agent for urea |
Non-Patent Citations (1)
| Title |
|---|
| 庞宝才等.国内外化肥防结块剂的开发概况.《精细石油化工》.1994,(第6期),第56-60页. * |
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| Publication number | Publication date |
|---|---|
| CN101654387A (en) | 2010-02-24 |
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