CN105801244A - Environment-friendly oil-soluble anti-caking agent for compound fertilizer and preparation method thereof - Google Patents
Environment-friendly oil-soluble anti-caking agent for compound fertilizer and preparation method thereof Download PDFInfo
- Publication number
- CN105801244A CN105801244A CN201610116851.1A CN201610116851A CN105801244A CN 105801244 A CN105801244 A CN 105801244A CN 201610116851 A CN201610116851 A CN 201610116851A CN 105801244 A CN105801244 A CN 105801244A
- Authority
- CN
- China
- Prior art keywords
- compound fertilizer
- surfactant
- oil
- anticaking agent
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/20—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for preventing the fertilisers being reduced to powder; Anti-dusting additives
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to a full-biodegradable oil-soluble anti-caking agent for a compound fertilizer and a preparation method and application thereof. The anti-caking agent consists of the following raw materials: a surfactant, an acidifier, vegetable wax, waste oil and fatty acid mixture and more preferentially also comprises a nonionic surfactant and/or sodium ferrocyanide. In the invention, the prepared anti-caking agent can be completely bio-degraded in natural environment, the preparation technology is relatively simple, the cost performance is relatively high, the caking of a chemical compound fertilizer caused by dampness and extrusion can be effectively prevented, and the anti-caking rate of the most easy-to-cake potassium sulfate compound fertilizer and high-nitrogen compound fertilizer is greater than 96%, preferentially greater than 98% and more preferentially greater than 99% and approaches and even reaches 100%.
Description
Technical field
The invention belongs to compound fertilizer and use anticaking agent field and the high level chemical utilization field of surfactant (especially fatty amine cationic surfactant) and waste grease (especially animal and plant fat).It is specifically related to oil-soluble anticaking agent of a kind of all biological degradation type of compound fertilizer's use and its production and use.
Background technology
Along with people's improving constantly the understanding that applies fertilizers scientifically, compound fertilizer is reasonable due to N, P, K nutrient formula, makes consumption get more and more；But compound fertilizer is due to the problem of caking, brings many difficulties to Fertilizer application person.The fertilizer of caking must crush again and screening processes again, this thereby necessarily increases extra-pay, result also in the generation of the loss of fertilizer and dust simultaneously, the health of operator will be brought harm.It is carried out anti-caking process by application compound fertilizer anticaking agent is a necessary production link and the most simple and effective process means.
Compound fertilizer anticaking agent can be divided into following a few class according to raw material: inert powder, mainly includes zeolite powder, Pulvis Talci, silicon dioxide powder, limestone, montmorillonite, kieselguhr, bentonite, Kaolin, calcium carbonate and clay etc.；Surfactant, mainly include anionic surfactant and use more with sulfate, sulfonate, phosphate, cationic surfactant mainly has octadecylamine and its esters, and nonionic surfactant has polyethylene glycol oxide, ester, low-molecular-weight aldehyde and ketone；Inorganic salts, such as aluminum sulfate, aluminum nitrate (magnesium) or ammonium phosphate etc.；Lyophobic dust, such as machine oil, paraffin, light diesel fuel, Colophonium etc., and Compositional type inorganic agent.Adopting the anti-caking inorganic agent of two or more the composite composition of different types of material, application surface is wider, and preventing blocking effect is better.
Research about anticaking agent both at home and abroad is accompanied by the growth of compound fertilizer industry and rises.
Starting so far from the 1970's, the technique of a series of employing compound oil outer wrapping technology anti-cakings is arisen at the historic moment.Technology the earliest is on 40 DEG C of warm compound fertilizer surfaces, in the powder applying machine before packaging post, sprays the powdery such as Pulvis Talci, Gypsum Fibrosum powder lubrication cladding material, and to prevent compound fertilizer from caking, but this type of is applied powder, existence is moistureproof, preventing blocking effect is bad, serious environment pollution.
Generation France scholar L. nanowatt Si Kusi nineteen ninety (CN95118864) has invented and has adopted technology oily, that wax class fused mass processes compound fertilizer, but product particle intensity is low, and the defect of efflorescence is also solved.
The treatment technology dissolving in diamino dicarboxylic acid salt coated compound fertilizer in mineral oil has been invented by Finland T. A Ennasi (CN9619862515), although relatively satisfactory protection against the tide, preventing blocking effect can be obtained, but the raw material production cost adopted is high, production and application is inconvenient, adopt a large amount of solvent dangerous again, therefore is difficult to practical application.
Japan storehouse Tian Dusan (JP7650896) then directly uses the amides compound of 0.01%～0.1% as anticaking agent main component, but this kind of material price is sufficiently expensive.
Woods begins to join (phosphate fertilizer and compound fertilizer, 2001,05:54) and utilizes osseocolla solution to composite organic-inorganic fertilizer sprinkling pelleting.When compound fertilizer is powdery, puts it in comminutor and rotate, the osseocolla calculated is melted simultaneously, put in mixing channel, add water and stir, with ejector, osseocolla liquid mist is sprayed into pelletize in comminutor.Because osseocolla solution can make the compound fertilizer of powdery mutually bond, during particle growth, appearance has also just coated one layer of osseocolla solution, and after drying, the osseocolla on compound fertilizer surface solidifies, and can effectively stop the generation of inorganic fertilizer salt bridge.Osseocolla is a kind of fertilizer inherently, and cost is relatively low.But osseocolla is hydroaropic substance, in water, a period of time can melt, so can not meet water when fertilizer stores.
Shen Liying (Chemical Engineering and equipment, 2010,08:53) utilizes the fatty amine salt that waste lubricating oil, fatty amine and high-carbon carboxylic acid reaction generate to be primary raw material, and adds the prepared anticaking agent of compound emulsifying agent.The reaction mechanism preparing anticaking agent makes it generate salt for adding fatty amine and carboxylic acid, heating, generate amides compound, agent is become for crystalline substance with the anion surfactant of some polar group, it is aided with the moistureproof film forming matters such as wax class, add the HLB value emulsifying agent less than 4 so that it is high degree of dispersion, prepare anticaking agent.The method resource has recycled waste lubricating oil as raw material, reduces production cost, but the anticaking agent prepared is difficult to biodegradation, eventually contaminated soil.
Shi Yuanliang (CN101298400,2008-11-05) et al. hydrophobic apolar material is utilized to be combined with cationic surfactant, adopting paraffin, alkylamine, Arlacel-80, mineral oil is raw material, a kind of paste oil-soluble anticaking agent being primarily adapted for use in high-nitrogen compound fertilizer made for 20～30 minutes is stirred at 70～80 DEG C, this technology mainly utilizes the hydrophobic substances such as paraffin to wrap up at fertilizer surface, form one layer of hydrophobic membrane, hinder and between fertiliser granulates, form salt bridge, thus preventing caking from being formed.Yin Hui (CN101302128,2008-11-12) et al. prepare the method for anticaking agent for semi-refined paraffin wax granule, microgranule fully refined paraffin wax, stearic acid, octadecyl primary amine, vaseline, erucyl amide for raw material, first mineral oil is heated, adding above-mentioned raw materials, reaction was uniformly sprayed at compound fertilizer surface after 1-1.5 hour.It can be appreciated that this kind of anticaking agent is owing to employing paraffin, mineral wet goods difficult degradation raw material, thus obtained anticaking agent is also difficult to degrade.
Crown English (CN101870607A, 2010-10-27) et al. work out a kind of all biological degradation type compound fertilizer anticaking agent preparation method, primary raw material has fatty acid (stearic acid and oleic acid), anion surfactant (octadecylphenyl sodium sulfonate), cationic surfactant (18-amine. base ditallowdimethyl ammonium bromide), polyether high molecular surfactant and fatty acid [octadecyl (EO)40(PO)10Ether].First by fatty acid and anion surfactant mix homogeneously, it is warming up to 55-65 DEG C, after stirring, adds polyether high molecular surfactant, finally add fatty acid and cationic surfactant, stir 20-40 minute.Anticaking agent prepared by the method can be degradable under natural environment, and preventing blocking effect is good, but costly, it is difficult to industrialization promotion.
Desolate chess second (CN101555178, preparation method 2009-10-14) et al. devising a kind of liquid compound fertilizer anticaking agent, is directly dissolved in silicone oil emulsion prepares anticaking agent by the alkyl benzene sulphonate sodium salt of C12-C18 or potassium salt, triethanolamine, C9 fatty alcohol-polyoxyethylene ether (AEO-9).The method need not add the material of the environmental pollutions such as paraffin, and at normal temperatures, this anticaking agent is liquid, makes solvent without adding machine oil during use, cost-saved, can be painted in compound fertilizer, it is not necessary to heating.Xia Yu (CN101199921,2008.06.18) etc. with quaternary ammonium salt, anion surfactant, nonionic surfactant, polymer and water mix, make a kind of water solublity anticaking agent, this technology oriented adsorption by surfactant, form one layer of hydrophobic membrane, hinder the contact between fertiliser granulates, it is prevented that caking.But contained humidity is inherently unfavorable for anti-caking under wet environment in this kind of anticaking agent.
Sha Huaili (CN101987802A, 2011-03-23) et al. devise a kind of high tower urea-based compound fertilizer anticaking agent, primary raw material is vegetable oil, Ketohexamethylene leftover bits and pieces, mass percent is the Ketohexamethylene leftover bits and pieces of the vegetable oil of 80%-90% and 10%-20%, both mixing can be prepared by anticaking agent, and the mixture of the method vegetable oil is oil base, and environmental pollution is little, and the fusing point of vegetable oil is relatively low, in production technology, energy consumption is relatively low；Plant oil viscosity is little, and anticaking agent is good in the ductility of fertilizer surface, and consumption is few.But Ketohexamethylene leftover bits and pieces has strong pungent odor, it is commonly used for organophosphorus insecticide and the fine solvent of many similar pesticide, has carcinogenesis.With Ketohexamethylene leftover bits and pieces for the potential HSE dangerous of anticaking agent raw material.
Yang Huiping (CN102086138A, 2011-06-08) et al. is with Vegetable oil lipoprotein leftover bits and pieces for carrier, then mixes prepared a kind of ammonium nitrate fertilizer anticaking agent with alkylhydridosiloxanes tallow amine surfactant, C8-C10 fatty acid methyl ester etc..This anticaking agent can form a kind of film at ammonium nitrate fertilizer particle surface, effectively and isolated from atmosphere, can reduce the speed of particulate water absorbent, decrease intergranular inter-adhesive, it is suppressed that intergranular salt dissolves a recrystallization, so that fertilizer obtains anti-caking.
Liu Zhenmao (CN102070373A, preparation method 2011-05-25) et al. working out a kind of natural degradable compound fertilizer anticaking agent, its component and mass percent be: fatty amine or its salt 10-20%, stearic acid 20-25%, oleic acid 15-20%, refined glycerine 5-15%, recycled wood materials 20-50%, each component sum is 100%；And each component is mixed in proportion, heat to 70-85 DEG C, stirring reaction 15-30min.Compound fertilizer anticaking agent consumption is 0.5-2.0kg/t compound fertilizer, adopts the wind-cooling crystallization high-tower granulation mode of full-fusing compound fertilizer so as to mix with compound fertilizer.Liu Zhenmao (CN102070374A, 2011-05-25) et al. also investigated a kind of natural environmental-protective type compound fertilizer anticaking agent being main component with mineral material Kaolin, raw material is Kaolin, water-absorbing water-retaining agent glycerol, sodium stearate, calcium stearate, enuatrol, described filler Kaolin, water-absorbing water-retaining agent glycerol, sodium stearate, calcium stearate, enuatrol weight ratio be: 90-95:1.0-2.5:1.0-2.5:1.0-2.5:0.5-1.0；Wear into fineness after described filler Kaolin, water-absorbing water-retaining agent glycerol, sodium stearate, calcium stearate, enuatrol Homogeneous phase mixing in proportion and reach more than 800 orders, the fineness powder less than 15 μm.This anticaking agent consumption is 1.0～3.0kg/t compound fertilizer, directly sends into chilling roll with auger, is rolled by chilling roll and makes that anticaking agent and fertiliser granulates are full and uniform to be mixed, is suitable for cylinder granulation compound fertilizer production technology.Both anticaking agents are respectively suitable for the compound fertilizer production technology that high-tower granulation is two kinds different with cylinder pelletize, irreplaceable mutually, and the poor universality of technique, this is one.Its two be selected main raw material(s) glycerol be the fabulous organic compound of a kind of water absorbing and retaining properties, Hui Shi compound fertilizer is in (humidity) state of a kind of moisture moisture stable all the time, is actually and is unfavorable for moistureproof anti-caking.It three is the anticaking agent using mineral material in a large number, contained by itself, nutrient (NPK) is very micro-, for ensureing necessary compound fertilizer nutrient standard (to meet complex fertilizer product quality standard), the formulation cost of compound fertilizer will necessarily be improved, economically and uneconomical.
Liu Xinzhong (CN102050679A, 2011-05-11) et al. works out a kind of straw powder-based anti-blocking agent of compound fertilizer, mass fraction form than following raw material mixed preparing: the powder of straw of 60-3000 order: 75-95；Stearic acid: 0.5-5；Stearylamine: 0.1-1；Hydramine: 0.1-0.5；White oil or hard paraffin: 0.5-5；Natural oil: 2-15, is cooled to above-mentioned powder of straw, stearic acid, stearylamine, hydramine, white oil or hard paraffin and natural oil six component room temperature, obtains anticaking agent finished product after uniform stirring 5-60 minute under 60-120 DEG C of environment.The method is mainly composed of straw, belong to pure-natural biological raw material, there is biodegradability and good environment friendly, prolonged and repeated use, soil, crops and farm environment will not be had undesirable effect, the method has efficiently, makes full use of stalk resource, does not use machine oil, environmental protection, processing is easy, cost performance is high advantage.But the addition that the powder of straw anticaking agent that this surface modification is crossed is in compound fertilizer is up to 10～15kg/t, effect is much worse than the anticaking agent containing cationic surfactants such as organic amines, and too high additive without nutrient also can improve the formulation cost of compound fertilizer, therefore the industrial application of straw anticaking agent is worth not high.
Zhao Zhuocheng (CN101450878, 2009-06-10) mineral are utilized to prepare anticaking agent, raw material is the Talcum of 80-90%, the additive of 10-20%, wherein additive is the potash feldspar of 0-10%, the attapulgite of 0-20%, the illite of 0-10%, first by feedstock purification, it is finely ground to 500-2500 order, by modified for Talcum calcining, temperature is 600-1200 DEG C, illite, potash feldspar, attapulgite is put at 80-1500 DEG C in surface modifying apparatus and is carried out surface modification, after it is mixed with compound fertilizer, this anticaking agent can select in grain process in compound and be directly added into comminutor, so as to form spray pattern, rotate through machine power, uniform fold is in compound fertilizer, after drying.But it is not the pretreatment of raw material temperature that the method is significantly high and very thin grind size, both added the cost of raw material, energy-conservation yet.The anticaking agent of this large amount of use mineral material, contained by itself, nutrient (NPK) is very micro-, for ensureing necessary compound fertilizer nutrient standard (to meet complex fertilizer product quality standard), the formulation cost of compound fertilizer will necessarily be improved, economically and uneconomical.
Summary of the invention
Summary prior art, the present inventor studies discovery, although the preparation method of the special anticaking agent of current compound fertilizer is a lot, but it is to be solved to still have many problems to have, and typical problem can be summarized to be had:
(1) inertia powder body anticaking agent is modified ultrafine powder, plays anti-caking effect by fertilizer surface carries out powder body parcel, but complex process, relatively costly.When this anticaking agent uses, Dust Capacity is big, it is easy to cause the dust pollution to air；
(2) surfactant-based anticaking agent and mineral oil mineral wax class anticaking agent are paste anticaking agent, are solid-state or paste at normal temperatures, and fusing point is high, thus need first to heat to melt before fertilizer production uses to spray to fertiliser granulates surface again.In heating process, if temperature is too high or hot-spot, its anti-caking effective ingredient being caused to run off, and the raw material used by this type of anticaking agent is mainly oil product and derivant thereof, special gas being discharged when heating, thus causing gaseous contamination；
(3) oil-soluble anticaking agent is easy to use, effective, but traditional method need to add mineral oil as solvent, and mineral oil and mineral wax etc. are not degradable, can cause the ecological pollution of farmland, fishery water system above fertilizer after being coated with anti-caking agent after application；
(4) moisture has been brought into fertilizer by water solublity anticaking agent, and moisture is the immediate cause of fertilizer agglomeration, and it is the sticky state of cream, and packaging, transport, use are all inconvenient.
On the other hand, the present inventor recognizes observantly, and along with the development of agriculture industrialization, mechanical fertilization is more and more universal, and the demand of composite no-lumping fertilizer is increased day by day.Along with the development of China's retreating chemical fertilizer and the seasonal of product consume, the yield of fertilizer and period of storage are also being continuously increased；Global warming makes environment more and more moister, more can increase the weight of caking.Market in urgent need exploitation consumption anticaking agent few, easy to use, eco-friendly.
Current domestic widely used main flow anticaking agent product pattern is " oil base+anti-caking factor ", and oil base divides mineral oil or vegetable oil, anti-caking Factor minute organic amine or organic acid.Studied discovery with keen determination by the present inventor, the by-product of a kind of commercial production surfactant has the character of mixing-in fat amine cationic surfactant, if made full use of, will reduce the production cost of anticaking agent.And for environmental issue, raw material have selected degradable vegetable wax and waste animal and vegetable oil, make product fully biodegradable, use environment all friendly anticaking agent production environment and compound fertilizer.
In sum, the defect such as relatively costly for existing oil-soluble anticaking agent, the feature of environmental protection is not good enough, the problem to be solved in the present invention is to find raw material cheap, eco-friendly, and then find a kind of suitable preparation method to synthesize the oil-soluble anticaking agent of a kind of all biological degradation type, this anticaking agent should have can degradable, preventing blocking effect good, lower-price characteristic, be applied in the compound fertilizer of easily caking.
For this, the present invention is realized by such technology path: by the acidifying of Surfactant (especially fatty amine cationic surfactant), forms fatty amine salt；Add vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt；Add fatty acid mixed and waste grease (such as animal and plant fat), namely obtain the oil-soluble anticaking agent of a kind of all biological degradation type, thus completing the present invention.
Therefore, the invention provides the oil-soluble anticaking agent of a kind of all biological degradation type, it is made up of cheap combination of raw materials, and specifically, it includes following raw material composition: surfactant, acidulant, vegetable wax, waste grease and fatty acid.
According to the preferred embodiment of the present invention, this compound fertilizer forms with the raw material of oil-soluble anticaking agent and also includes nonionic surfactant and/or potassium ferrocyanide sodium salt.
According to the present invention, wherein each raw material composition and respective quality proportioning are:
Surfactant, 30～70 parts, it is preferable that 40～65 parts, more preferably 45～60 parts,
Acidulant, 1～10 part, it is preferable that 1～5 part, more preferably 2～4 parts,
Vegetable wax, 20～50 parts, it is preferable that 30～50 parts, more preferably 35～45 parts,
Waste grease, 200～600 parts, it is preferable that 300～500 parts, more preferably 350～450 parts,
Fatty acid, 300～700 parts, it is preferable that 400～600 parts, more preferably 450～550 parts,
Preferred nonionic surfactant, 1～20 part, it is preferable that 5～15 parts, more preferably 8～12 parts,
Preferred potassium ferrocyanide sodium salt, 1～20 part, it is preferable that 5～15 parts, more preferably 10～15 parts.
According to the preferred embodiment of the present invention, wherein:
Described surfactant is cationic surfactant, it is preferred to fatty amine cationic surfactant, more preferably the by-product in Surfactant Industry production.
Described acidulant is the mixture of one or both or the two or more composition in the acid mineral reagent such as concentrated hydrochloric acid, acetic acid.
Described vegetable wax is the mixture of one or both or the two or more composition in rice bran wax, sugarcane wax, palm wax etc..
In the present invention, vegetable wax is lyophobic dust, it is possible to improve preventing blocking effect, it is also possible to improve the hardness of anticaking agent, it is simple to produces and uses.
Described waste grease is the mixture of one or both or the two or more composition in waste oil, swill oil, animal and plant fat etc., it is preferred to animal and plant fat.
Described fatty acid is Palmic acid, stearic acid, or the mixture of the two.
In the present invention, above-mentioned fatty acid and waste grease both can improve the hardness of anticaking agent, were also lyophobic dusts simultaneously, played an important role in anticaking agent.
Described nonionic surfactant is fatty alcohol polyethenoxy ether class, it is preferred to the mixture of one or both or two or more composition in AEO-7, AEO-9 etc..
In the present invention, the existence of nonionic surfactant has blocked the diffusion path of salt, is distributed on each alternate interface, and its water-wet side is towards the stronger component of water absorption, them are made not easily to be diffused into particle surface and contact area and the crystalline solid prevented from caking again formed.
Described potassium ferrocyanide sodium salt is technical grade potassium ferrocyanide sodium salt, potassium ferrocyanide potassium salt, or the mixture of the two.
In the present invention, potassium ferrocyanide sodium salt or potassium salt can effectively block the formation of multicomponent crystallization salt bridge, and the crystallization inhibitory action being similar to compound fertilizer's such multicomponent salt is significant.
The present invention also invents and provides a kind of method of oil-soluble anticaking agent preparing above-mentioned all biological degradation type further, and its each raw material forms and quality proportioning is:
Surfactant, 30～70 parts, it is preferable that 40～65 parts, more preferably 45～60 parts,
Acidulant, 1～10 part, it is preferable that 1～5 part, more preferably 2～4 parts,
Vegetable wax, 20～50 parts, it is preferable that 30～50 parts, more preferably 35～45 parts,
Waste grease, 200～600 parts, it is preferable that 300～500 parts, more preferably 350～450 parts,
Fatty acid, 300～700 parts, it is preferable that 400～600 parts, more preferably 450～550 parts,
Preferred nonionic surfactant, 1～20 part, it is preferable that 5～15 parts, more preferably 8～12 parts,
Preferred potassium ferrocyanide sodium salt, 1～20 part, it is preferable that 5～15 parts, more preferably 10～15 parts.
Described preparation method comprises the following steps:
1) pre-treatment of raw material, by surfactant, it is preferable that cationic surfactant, and more preferably the precipitated impurities in fatty amine cationic surfactant filters,
2) weigh pretreated surfactant and acidulant, and mix, obtain solution,
3) weigh vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt, join step 2) in the solution that obtains, heating, stirring,
4) weigh step 3) solution that obtains, fatty acid, join in waste grease (preferred animal and plant fat), heating, stirring, be completely dissolved,
5) optional by step 4) the solution cooling that obtains.
Concrete technology of preparing scheme is as described below:
1) pre-treatment of raw material: surfactant (preferred cationic surfactant, more preferably fatty amine cationic surfactant) raw material carries out primary election, removes the block impurity of the inside so that it is in homogeneous solution, standby；
2) pretreated surfactant and acidulant are weighed by proportioning, mix homogeneously,
3) vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt are weighed by proportioning, it is dissolved in step 2) in the solution prepared, heating, it is warming up to 70～120 DEG C, preferably 80～110 DEG C, more preferably 90～100 DEG C, stirring, it is preferable that 8～20min, more preferably 10～15min, such as 12min, to obtaining uniform solution
4) said ratio 3 is weighed) solution that obtains and fatty acid, join in waste grease (preferred animal and plant fat), heating, it is warming up to 50～90 DEG C, preferably 60～80 DEG C, more preferably 65～75 DEG C, stirring, 10～20min, preferably 12～18min, it is completely dissolved, obtains uniform solution
5) optional by step 4) solution that obtains is cooled to solid-state.
By the oil-soluble anticaking agent of foregoing compound fertilizer all biological degradation type obtained by said method of the present invention, it is possible to improve the shatter value of compound fertilizer, good preventing blocking effect can be obtained.
Therefore, comparing existing oil-soluble anticaking agent on market, the oil-soluble anticaking agent of compound fertilizer's all biological degradation type of the present invention has the advantage that
1, raw material sources are extensive, and cost is comparatively cheap；
2, the surfactant (such as mixing-in fat amine cationic surfactant) of by-product and waste grease (such as animal and plant fat) are carried out higher value application, and make it be transformed into the product with certain added value, both economically and environmentally beneficial；
3, the formation to multicomponent crystallization salt bridge that adds of potassium ferrocyanide sodium salt has very strong inhibitory action, so that this anticaking agent has the wider scope of application, the compound fertilizer of various formula is all had good preventing blocking effect；
4, with natural degradable raw material for main constituent, the anticaking agent of synthesis can be degradable in natural environment, agricultural land soil and aquatic ecosystem will not be caused potential pollution, is environmentally friendly product；
5, the chemically composited fertilizer of various formula is all had good agglomeration preventing performance by the product of the present invention, temperature range 14～36 DEG C, air humidity more than 60%, 10～20 layer stack 60 days storage times of buttress, the shatter value of compound fertilizer generally can reach more than 99%, for instance has more than 96%, it is preferable that more than 98%, more preferably greater than 99%, close to even up to 100% anti-caking rate.
Accompanying drawing explanation
Fig. 1 is the oil-soluble anticaking agent preparation technology flow chart of all biological degradation type of the present invention.
Detailed description of the invention
Further explain and describe present invention by the following examples.But the embodiment provided is understood not to scope is construed as limiting.
Agglomeration preventing performance is evaluated
(1) laboratory sample performance test
Use seed-coating machine that anticaking agent is uniformly dispersed in the surface of compound fertilizer granules, compound fertilizer is contained in small plastic bag, airtight sealing, every bag of 200g, it is overlapped being positioned in climatic chamber, compound fertilizer's sample is put the dumbbell weight stack of 10kg, set certain humidity and temperature (higher temperature and humidity), every morning opens instrument, close instrument in the evening, it is made quickly to lump, through presetting test natural law (such as 7 days, 20 days, 30 days or 60 days) take out measuring samples, test sample is freely dropped into ground from 1 meter of height level, positive and negative each once, then style in bag is sieved, employment horizontal hunting frequency about 50 times, sieving time is 1min, survey the caking rate of corresponding standing time.
(2) field performance test is used
The Bag fertilizer of spray coated anticaking agent 40 bags, total amount is 2 tons, and stacking is 8 layers, 5 bags every layer, extra applying pressure 2 tons, stack presetting test natural law (such as 7 days, 20 days, 30 days or 60 days), from top to bottom, every layer takes 2 bags and carries out shatter value test.Artificially from 1 meter of height level test sample being freely dropped into ground, positive and negative each is once then sieved by sample in bag, by artificial horizontal hunting frequency 50 ± 5 times, sieving time is 1min, the caking rate of survey correspondence standing time.
(3) mensuration of caking rate
W: caking rate；
M: the quality of sample before sieving；
M ＇: the quality of sample after sieving
Embodiment raw materials
Fatty amine cationic surfactant selects the mixture of the Long carbon chain fatty amine cationic surfactant containing fatty alcohol, fatty acid and wide molecular weight distribution of by-product in fatty amine cationic surfactant production process, its carbon number distribution is generally C12～C22, better than the fatty amine cationic surfactant cost performance of commercial single composition for preparing anticaking agent, purchased from Shandong Boxing Huarun Grease Chemical Co., Ltd, the self-control adjustment of softened point uses after processing.
The industrial by-products deviate from rice bran wax system Rice bran crude oil refining process, purchased from Cangzhou forest La Ye company, the self-control adjustment of softened point uses after processing.
Fatty alcohol polyethenoxy ether class (AEO-7) is technical grade, purchased from TaiWan, China east connection chemistry limited company (OUCC) Nanjing company.
Potassium ferrocyanide sodium salt or potassium ferrocyanide potassium salt are technical grade, purchased from Hebei sincerity chemical company.
The animal and plant fat of waste animal and vegetable oil system kitchen industry and food-processing industry by-product, purchased from Shandong biodiesel group company.
The conventional chemical reagent such as hydrochloric acid, stearic acid is analytical pure level (AR), is that buying is from Beijing Chemical Plant.
Potassium sulfate compound fertilizer (the N:P being easiest to caking selected by compound fertilizer's sample2O5: K2And high-nitrogen compound fertilizer (N:P O=15:15:15)2O5: K2O=28:6:6), by energy-conservation Jin Feng agricultural science and technology company limited provide.
Embodiment
Embodiment 1:
Weigh pretreated fatty amine cationic surfactant 0.44g, add acidulant concentrated hydrochloric acid 0.02g, stir, add the rice bran wax of 0.34g, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 12g, the animal and plant fat of 7.2g, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 1 being tested according to above laboratory sample performance test methods, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15).The agglomeration preventing performance testing result of embodiment 1 shows, the shatter value after 7 days is 96%.
Embodiment 2:
Weigh pretreated fatty amine cationic surfactant 5.56g, add acidulant concentrated hydrochloric acid 0.27g, stir, add the rice bran wax of 4.17g, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 10g, the animal and plant fat of 8g, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 2 being tested according to above laboratory sample performance test methods, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15).The agglomeration preventing performance testing result of embodiment 2 shows, the shatter value after 7 days is 97%.
Embodiment 3:
Weigh pretreated fatty amine cationic surfactant 0.56kg, add acidulant concentrated hydrochloric acid 0.02kg, stir, add the rice bran wax of 0.42kg, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 18kg, the animal and plant fat of 11kg, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 3 being tested according to field performance method of testing used above, compound fertilizer is high nitrogen fertilizer (N:P2O5: K2O=28:6:6), pilling up time is 20 days.The agglomeration preventing performance testing result of embodiment 3 shows, the shatter value after 20 days is 100%.
Embodiment 4:
Different from embodiment 3 it is in that: the kind of compound fertilizer.Weigh pretreated fatty amine cationic surfactant 0.56kg, add acidulant concentrated hydrochloric acid 0.02kg, stir, add the rice bran wax of 0.42kg, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 18kg, the animal and plant fat of 11kg, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 4 being tested according to field performance method of testing used above, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time respectively 7 days, 20 days, 30 days and 60 days.Detection data are in Table 1.
Table 1: the agglomeration preventing performance testing result of embodiment 4
| Pilling up time (my god) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 95 | 95 | 90 |
Embodiment 5:
Different from embodiment 4 it is in that: whether nonionic surfactant adds.Weigh pretreated fatty amine cationic surfactant 1.5kg, add acidulant concentrated hydrochloric acid 0.075kg, stir, add the rice bran wax of 1.125kg, the fatty alcohol polyethenoxy ether class (AEO-7) of 0.3kg, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 15kg, the animal and plant fat of 12kg, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 5 being tested according to field performance method of testing used above, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time respectively 7 days, 20 days, 30 days and 60 days.Detection data are in Table 2.
Table 2: the agglomeration preventing performance testing result of embodiment 5
| Pilling up time (my god) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 99 | 99 | 98 |
Embodiment 6:
Different from embodiment 4 it is in that: whether potassium ferrocyanide sodium salt adds.Weigh pretreated fatty amine cationic surfactant 1.5kg, add acidulant concentrated hydrochloric acid 0.075kg, stir, add the rice bran wax of 1.125kg, the potassium ferrocyanide sodium salt of 0.6kg, heating, it is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 15kg, the animal and plant fat of 12kg, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 6 being tested according to field performance method of testing used above, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time respectively 7 days, 20 days, 30 days and 60 days.Detection data are in Table 3.
Table 3: the agglomeration preventing performance testing result of embodiment 6
| Pilling up time (my god) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 96 | 95 | 93 |
Embodiment 7:
Different from embodiment 4 it is in that: whether nonionic surfactant and potassium ferrocyanide sodium salt add.As shown in Figure 1: weigh pretreated fatty amine cationic surfactant 1.5kg, add acidulant concentrated hydrochloric acid 0.075kg, stir, add the rice bran wax of 1.125kg, the fatty alcohol polyethenoxy ether class (AEO-7) of 0.3kg, the potassium ferrocyanide sodium salt of 0.5kg, heating, is warming up to 100 DEG C, stirring, 10min, to uniform solution.Add the stearic acid of 15kg, the animal and plant fat of 12kg, heating, it is warming up to 80 DEG C, stirring, 15min, obtain uniform solution.After cooling, obtain sample.Embodiment 7 being tested according to field performance method of testing used above, compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time respectively 7 days, 20 days, 30 days and 60 days.Detection data are in Table 4.
Table 4: the agglomeration preventing performance testing result of embodiment 7
| Pilling up time (my god) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 100 | 100 | 100 |
By examples detailed above it can be seen that the oil-soluble anticaking agent performance of all biological degradation type prepared by the present invention is generally better, can be applicable in the fertilizer of various easy caking, and under field conditions (factors) can be degradable, very environmental protection.
According to the above embodiments, the present invention is described in detail.It should be noted that, above embodiments is just to illustrating the present invention.Under the premise of the spirit and essence that not necessarily depart from the present invention, those skilled in the art can be designed that multiple alternative and the improvement project of the present invention, and it all should be interpreted within protection scope of the present invention.
Claims (10)
1. compound fertilizer's all biological degradation type oil-soluble anticaking agent, it is characterised in that its raw material composition includes surfactant, acidulant, vegetable wax, waste grease and fatty acid.
2. compound fertilizer according to claim 1 oil-soluble anticaking agent, it is characterised in that its raw material forms and respective quality proportioning is:
3. compound fertilizer according to claim 1 and 2 oil-soluble anticaking agent, it is characterised in that its raw material composition also includes nonionic surfactant and/or potassium ferrocyanide sodium salt, it is preferable that
Nonionic surfactant 1～20 part, it is preferable that 5～15 parts, and/or
Potassium ferrocyanide sodium salt 1～20 part, it is preferable that 5～15 parts.
4. according to the oil-soluble anticaking agent of the compound fertilizer one of claims 1 to 3 Suo Shu, it is characterised in that its each raw material forms and respective quality proportioning is:
5. according to the oil-soluble anticaking agent of the compound fertilizer one of Claims 1-4 Suo Shu, it is characterised in that:
Described surfactant is cationic surfactant, it is preferred to fatty amine cationic surfactant, more preferably the by-product in Surfactant Industry production, and/or
Described acidulant is the mixture of one or both or the two or more composition in the acid mineral reagent such as concentrated hydrochloric acid, acetic acid, and/or
Described vegetable wax is the mixture of one or both or the two or more composition in rice bran wax, sugarcane wax, palm wax etc., and/or
Described waste grease is the mixture of one or both or the two or more composition in waste oil, swill oil, animal and plant fat etc., it is preferred to animal and plant fat, and/or
Described fatty acid is Palmic acid, stearic acid, or the mixture of the two, and/or
Described nonionic surfactant is fatty alcohol polyethenoxy ether class, it is preferred to the mixture of one or both or two or more composition in AEO-7, AEO-9 etc., and/or
Described potassium ferrocyanide sodium salt is technical grade potassium ferrocyanide sodium salt, potassium ferrocyanide potassium salt, or its mixture.
6. preparation is according to the method with oil-soluble anticaking agent of the compound fertilizer one of claim 1 to 5 Suo Shu, it is characterised in that the method comprises the following steps:
1) pre-treatment of raw material, by surfactant, it is preferable that cationic surfactant, and more preferably the precipitated impurities in fatty amine cationic surfactant filters,
2) weigh pretreated surfactant and acidulant, and mix, obtain solution,
3) weigh vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt, join step 2) in the solution that obtains, heating, stirring,
4) weigh step 3) solution that obtains, fatty acid, join in waste grease (preferred animal and plant fat), heating, stirring, be completely dissolved,
5) optional by step 4) the solution cooling that obtains.
7. preparation method according to claim 6, it is characterised in that this comprises the following steps:
1) pre-treatment of raw material: surfactant (preferred cationic surfactant, more preferably fatty amine cationic surfactant) raw material carries out primary election, removes the block impurity of the inside so that it is in homogeneous solution, standby；
2) pretreated surfactant and acidulant are weighed by proportioning, mix homogeneously,
3) vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt are weighed by proportioning, it is dissolved in step 2) in the solution prepared, heating, is warming up to 70～120 DEG C, it is preferable that 80～110 DEG C, stirring, preferably 8～20min, more preferably 10～15min, for instance 12min, to obtaining uniform solution
4) said ratio 3 is weighed) solution that obtains and fatty acid, join in waste grease (preferred animal and plant fat), heating, it is warming up to 50～90 DEG C, preferably 60～80 DEG C, stirring, 10～20min, it is preferable that 12～18min, it is completely dissolved, obtains uniform solution
5) optional by step 4) solution that obtains is cooled to solid-state.
8. the preparation method according to claim 6 or 7, it is characterised in that
Step 3) in constant temperature control at 90～100 DEG C, and/or
Step 4) in temperature control at 65～75 DEG C.
9. the compound fertilizer's oil-soluble anticaking agent prepared according to the preparation method one of claim 6 to 8 Suo Shu, it is all biological degradation type oil-soluble anticaking agent, preferably in temperature range 14～36 DEG C, air humidity more than 60%, 10～20 layer stack 60 days storage times of buttress, the shatter value of compound fertilizer can reach more than 99%.
10. the purposes according to one of claim 1 to 5 or anticaking agent according to claim 9, it is as compound fertilizer's oil-soluble anticaking agent, it is preferable that can improve the shatter value of compound fertilizer, obtains good agglomeration preventing performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610116851.1A CN105801244B (en) | 2016-03-02 | 2016-03-02 | A kind of compound fertilizer's environmentally friendly oil-soluble anticaking agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610116851.1A CN105801244B (en) | 2016-03-02 | 2016-03-02 | A kind of compound fertilizer's environmentally friendly oil-soluble anticaking agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801244A true CN105801244A (en) | 2016-07-27 |
| CN105801244B CN105801244B (en) | 2019-08-02 |
Family
ID=56466040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610116851.1A Active CN105801244B (en) | 2016-03-02 | 2016-03-02 | A kind of compound fertilizer's environmentally friendly oil-soluble anticaking agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801244B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093290A (en) * | 2016-07-27 | 2016-11-09 | 湖北富邦科技股份有限公司 | A kind of qualitative determination method that anti-caking agent dispensing is the most correct |
| CN106242803A (en) * | 2016-08-17 | 2016-12-21 | 湖北富邦科技股份有限公司 | The inorganic pigment type colour oily fertilizer anti-caking agent of high temperature resistant plant |
| CN106380321A (en) * | 2016-09-06 | 2017-02-08 | 中南林业科技大学 | Compound fertilizer antiblocking agent, and preparation and application methods thereof |
| CN106748159A (en) * | 2016-12-25 | 2017-05-31 | 吴迪 | A kind of preparation method of Environment-friendlypaste paste anticaking agent |
| CN107963925A (en) * | 2017-11-24 | 2018-04-27 | 湖北富邦科技股份有限公司 | A kind of high phosphorus compound fertilizer anticaking agent and preparation method thereof |
| CN108424259A (en) * | 2018-05-16 | 2018-08-21 | 芜湖市创源新材料有限公司 | A kind of preparation method for the slow-release compound fertilizer being coated with anticaking agent |
| CN108794206A (en) * | 2018-08-22 | 2018-11-13 | 苏州丰倍生物科技有限公司 | A kind of micro-emulsion type Water soluble fertilizer anticaking agent and preparation method thereof |
| CN109251105A (en) * | 2018-11-20 | 2019-01-22 | 四川中农众和农业科技有限公司 | It is a kind of to utilize natural oil production degradable compound fertilizer anticaking agent and preparation method |
| CN109896894A (en) * | 2019-03-27 | 2019-06-18 | 广东博科实业有限公司 | A kind of anticaking agent and preparation method thereof for full water soluble fertilizer |
| CN110903127A (en) * | 2019-11-19 | 2020-03-24 | 山东聊城鲁西硝基复肥有限公司 | Anti-caking agent, preparation method thereof, anti-caking compound fertilizer and preparation method thereof |
| CN114988955A (en) * | 2022-07-06 | 2022-09-02 | 安徽富瑞雪化工科技股份有限公司 | Preparation method of oil for chemical fertilizer anti-caking agent and chemical fertilizer anti-caking agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376653A (en) * | 2001-11-08 | 2002-10-30 | 宁国市中化司尔特化肥有限公司 | Anti-coagulating agent for composite fertilizer |
| CN101372318A (en) * | 2008-08-21 | 2009-02-25 | 陶华西 | Anti-caking treatment method for potassium monopersulfate composite salt |
| CN102070373A (en) * | 2010-12-02 | 2011-05-25 | 福建达安能源实业有限责任公司 | Preparation method of naturally-degradable compound fertilizer anti-blocking agent and application thereof |
| CN103232296A (en) * | 2013-05-14 | 2013-08-07 | 衡水晨辉化学助剂有限公司 | Environment-friendly anti-blocking agent for compound fertilizer and processing method for same |
| CN104151075A (en) * | 2014-08-15 | 2014-11-19 | 苏州丰倍生物科技有限公司 | Process method for producing chemical fertilizer anti-caking agent by using oleochemical industry by-product |
| CN104355819A (en) * | 2014-10-30 | 2015-02-18 | 郭武侠 | Degradable compound fertilizer anti-blocking agent, preparation method and application thereof |
-
2016
- 2016-03-02 CN CN201610116851.1A patent/CN105801244B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376653A (en) * | 2001-11-08 | 2002-10-30 | 宁国市中化司尔特化肥有限公司 | Anti-coagulating agent for composite fertilizer |
| CN101372318A (en) * | 2008-08-21 | 2009-02-25 | 陶华西 | Anti-caking treatment method for potassium monopersulfate composite salt |
| CN102070373A (en) * | 2010-12-02 | 2011-05-25 | 福建达安能源实业有限责任公司 | Preparation method of naturally-degradable compound fertilizer anti-blocking agent and application thereof |
| CN103232296A (en) * | 2013-05-14 | 2013-08-07 | 衡水晨辉化学助剂有限公司 | Environment-friendly anti-blocking agent for compound fertilizer and processing method for same |
| CN104151075A (en) * | 2014-08-15 | 2014-11-19 | 苏州丰倍生物科技有限公司 | Process method for producing chemical fertilizer anti-caking agent by using oleochemical industry by-product |
| CN104355819A (en) * | 2014-10-30 | 2015-02-18 | 郭武侠 | Degradable compound fertilizer anti-blocking agent, preparation method and application thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106093290A (en) * | 2016-07-27 | 2016-11-09 | 湖北富邦科技股份有限公司 | A kind of qualitative determination method that anti-caking agent dispensing is the most correct |
| CN106242803A (en) * | 2016-08-17 | 2016-12-21 | 湖北富邦科技股份有限公司 | The inorganic pigment type colour oily fertilizer anti-caking agent of high temperature resistant plant |
| CN106380321A (en) * | 2016-09-06 | 2017-02-08 | 中南林业科技大学 | Compound fertilizer antiblocking agent, and preparation and application methods thereof |
| CN106748159A (en) * | 2016-12-25 | 2017-05-31 | 吴迪 | A kind of preparation method of Environment-friendlypaste paste anticaking agent |
| CN107963925A (en) * | 2017-11-24 | 2018-04-27 | 湖北富邦科技股份有限公司 | A kind of high phosphorus compound fertilizer anticaking agent and preparation method thereof |
| CN108424259A (en) * | 2018-05-16 | 2018-08-21 | 芜湖市创源新材料有限公司 | A kind of preparation method for the slow-release compound fertilizer being coated with anticaking agent |
| CN108794206A (en) * | 2018-08-22 | 2018-11-13 | 苏州丰倍生物科技有限公司 | A kind of micro-emulsion type Water soluble fertilizer anticaking agent and preparation method thereof |
| CN109251105A (en) * | 2018-11-20 | 2019-01-22 | 四川中农众和农业科技有限公司 | It is a kind of to utilize natural oil production degradable compound fertilizer anticaking agent and preparation method |
| CN109896894A (en) * | 2019-03-27 | 2019-06-18 | 广东博科实业有限公司 | A kind of anticaking agent and preparation method thereof for full water soluble fertilizer |
| CN110903127A (en) * | 2019-11-19 | 2020-03-24 | 山东聊城鲁西硝基复肥有限公司 | Anti-caking agent, preparation method thereof, anti-caking compound fertilizer and preparation method thereof |
| CN114988955A (en) * | 2022-07-06 | 2022-09-02 | 安徽富瑞雪化工科技股份有限公司 | Preparation method of oil for chemical fertilizer anti-caking agent and chemical fertilizer anti-caking agent |
| CN114988955B (en) * | 2022-07-06 | 2023-11-21 | 安徽富瑞雪化工科技股份有限公司 | Preparation method of oil for chemical fertilizer anti-caking agent and chemical fertilizer anti-caking agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801244B (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105801244A (en) | Environment-friendly oil-soluble anti-caking agent for compound fertilizer and preparation method thereof | |
| AU2015212412B2 (en) | Fertilizer capsule comprising one or more cores and method of making same | |
| CN103539573B (en) | Water-soluble polysaccharide environment-friendly anti-caking agent for composite fertilizer and application thereof in composite fertilizer | |
| CN102050679B (en) | Straw powder-based anti-blocking agent of compound fertilizer | |
| CN103159550B (en) | Environment-friendly slow-release sulfur-based nitrogen potassium compound fertilizer | |
| CN101781134A (en) | Tower-smelt organic-inorganic compound fertilizer and preparation method thereof | |
| CN104030854B (en) | A kind of phase-change material temperature-control slow-release fertilizer and preparation method thereof | |
| CN106380321A (en) | Compound fertilizer antiblocking agent, and preparation and application methods thereof | |
| CN103435425A (en) | Hierarchical slow release multielement fertilizer and manufacturing process thereof | |
| CN107721603A (en) | A kind of environment-friendly type compound fertilizer anticaking agent pulvis and its preparation method and application | |
| EP3245177B1 (en) | Flowable mixture including elemental sulfur and hydrated clay and method for producing the same | |
| CN104230571A (en) | Dispersible biological compound fertilizer made from gutter oil, and preparation method thereof | |
| WO2014101265A1 (en) | Slow-release compound fertilizer applicable to plantation of corn | |
| CN103664376A (en) | Preparation method of coated controlled-release compound fertilizer | |
| CN101638345A (en) | High-efficiency nitrogen-phosphorus-potassium fertilizer containing silicon and calcium and preparation method thereof | |
| CN102786366B (en) | Endoplasmic slow release composite fertilizer and its preparation method | |
| CN102807415A (en) | Manufacturing method of environment-friendly type controlled-release compound mixed fertilizer | |
| CN1184174C (en) | Loose compound fertilizer containing internally added loosening agent and preparation method thereof | |
| CN1255362C (en) | Manufacturing method of nitrogen phosphorus potassium cmposite fertilizer rich in nitrogen and potassium | |
| CN104844368B (en) | A kind of manufacture craft of banana fertilizer | |
| CN103159549A (en) | Preparation method of slow-release long-acting sulfur-based nitrogen potassium compound fertilizer | |
| CN113173819A (en) | Potash fertilizer with strong water retention property | |
| CN106565308A (en) | Anti-caking fast-dissolving nitro-compound fertilizer and preparation method thereof | |
| CN102030585A (en) | Corn special fertilizer in case of returning all straws to field in Huanghuai Plain and preparation method thereof | |
| CN101293666B (en) | Calcium magnesium phosphor potassium fertilizer particle balling preparation technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |