CN105801244B - A kind of compound fertilizer's environmentally friendly oil-soluble anticaking agent and preparation method thereof - Google Patents
A kind of compound fertilizer's environmentally friendly oil-soluble anticaking agent and preparation method thereof Download PDFInfo
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- CN105801244B CN105801244B CN201610116851.1A CN201610116851A CN105801244B CN 105801244 B CN105801244 B CN 105801244B CN 201610116851 A CN201610116851 A CN 201610116851A CN 105801244 B CN105801244 B CN 105801244B
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- 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
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Abstract
The present invention relates to a kind of compound fertilizer all biological degradation type oil-soluble anticaking agents and its preparation method and application, the raw material composition of the anticaking agent includes: surfactant, acidulant, vegetable wax, waste grease and fatty acid mixed, more preferably further includes nonionic surfactant and/or potassium ferrocyanide sodium salt.Anticaking agent prepared in accordance with the present invention fully biodegradable in a natural environment, preparation process is relatively easy, sexual valence is relatively high, chemically composited fertilizer can be effectively prevent to agglomerate due to moisture knot and caused by squeezing, have to the potassium sulfate compound fertilizer and high-nitrogen compound fertilizer that are easiest to agglomeration and is greater than 96%, preferably greater than 98%, more preferably greater than 99%, close to even up to 100% anti-caking rate.
Description
Technical field
The invention belongs to compound fertilizer anticaking agent field and surfactant (especially fatty amine cationic surfaces
Activating agent) and waste grease (especially animal and plant fat) high level chemical utilization field.One used more particularly to compound fertilizer
The oil-soluble anticaking agent and its preparation method and application of kind all biological degradation type.
Background technique
Continuous improvement with people to the understanding that applies fertilizers scientifically, since N, P, K nutrient formula are reasonable, usage amount is got over for compound fertilizer
Come more；But compound fertilizer brings many difficulties to Fertilizer application person due to the problem of agglomerating.The fertilizer of agglomeration must be into
Row is crushed again and screening process again, and this thereby necessarily increases extra-pays, while also resulting in the loss of fertilizer and the production of dust
It is raw, will health care belt to operator endanger.Carrying out anti-caking processing to it using compound fertilizer anticaking agent is a necessity
Production link and most simple and effective process means.
Compound fertilizer anticaking agent can be divided into following a few classes: inert powder according to raw material, mainly include zeolite powder, talcum
Powder, silicon dioxide powder, lime stone, montmorillonite, diatomite, bentonite, kaolin, calcium carbonate and clay etc.；Surfactant, it is main
To include anionic surfactant with sulfate, sulfonate, phosphate using more, cationic surfactant mainly has
Octadecylamine and its esters, nonionic surfactant have polyethylene glycol oxide, ester, low molecular weight aldehyde and ketone；Inorganic salts,
Such as aluminum sulfate, aluminum nitrate (magnesium) or ammonium phosphate；Lyophobic dust, such as machine oil, paraffin, light diesel fuel, pitch and Compositional type
Inorganic agent.Using the anti-caking inorganic agent of two or more different types of substance compounding composition, application surface is wider, prevents
Agglomeration efficiency is more preferable.
It is both at home and abroad the growth along with compound fertilizer industry about the research of anticaking agent and rises.
Since the 1970's so far, a series of techniques using technique for packing anti-caking outside compound oil are come into being.Most
Early technology is to pack in the powder applying machine before post on 40 DEG C of warm compound fertilizer surfaces, spraying the powderies such as talcum powder, land plaster
Covering material is lubricated, to prevent compound fertilizer from caking, but such face powder seriously pollutes environment there are moisture-proof, preventing blocking effect is bad.
In generation nineteen ninety France scholar L. nanowatt Si Kusi (CN95118864), has invented the fusant processing using oil, wax class
The technology of compound fertilizer, but product particle intensity is low, and the defect of dusting is not also resolved.
Finland T. A Ennasi (CN 9619862515) invented dissolved in mineral oil diamino dicarboxylic acid salt package it is compound
The processing technique of fertilizer, although relatively satisfactory moisture-proof, preventing blocking effect can be obtained, the raw material production cost used is high, produces
It is inconvenient to use, again dangerous using a large amount of solvents, therefore it is difficult to practical application.
Japanese storehouse Tian Dusan (JP7650896) then be used directly 0.01%~0.1% amides compound as anti-caking
Block agent main component, but the price is very expensive for this substance.
Woods begins to join (phosphate fertilizer and compound fertilizer, 2001,05:54) using gelatine solution to composite organic-inorganic fertilizer sprinkling pelleting.It is multiple
When Hefei is powdery, puts it into pelletizer and rotate, while the gelatine that calculates is melted, be put into mixing channel, on one side plus
Water stirs on one side, sprays into pelletizer gelatine liquid mistization with injector and is granulated.Because gelatine solution can make the compound fertilizer of powdery
Mutually bonding, when particle growth, appearance has also just coated one layer of gelatine solution, and after dry, the gelatine on compound fertilizer surface solidifies, can
Effectively prevent the generation of inorganic fertilizer salt bridge.Inherently a kind of organic fertilizer of gelatine, cost are relatively low.But gelatine is hydrophily object
Matter, a period of time can melt in water, so cannot meet water in fertilizer storage.
Shen Liying (chemical engineering and equipment, 2010,08:53) is raw using waste lubricating oil, fatty amine and high-carbon carboxylic acid reaction
At fatty amine salt be primary raw material, and be added compound emulsifying agent be made anticaking agent.Be made anticaking agent reaction mechanism be
Addition fatty amine and carboxylic acid make it generate salt, and heating generates amides compound, with the anionic surface of certain polar groups
Activating agent is brilliant change agent, is aided with the moisture-proof film forming matter such as wax class, emulsifier of the HLB value less than 4 is added, makes its high degree of dispersion, be made
Anticaking agent.This method recycling has recycled waste lubricating oil as raw material, reduces production cost, but anticaking agent obtained
It is difficult biodegrade, eventually contaminated soil.
Shi Yuanliang (CN101298400,2008-11-05) et al. utilizes hydrophobic apolar material and cation surface activating
Agent combines, and uses paraffin, alkylamine, Arlacel-80, mineral oil for raw material, stirs made of 20~30 minutes at 70~80 DEG C
A kind of paste oil-soluble anticaking agent being primarily adapted for use in high-nitrogen compound fertilizer, the technology mainly utilize the hydrophobic substances such as paraffin in fertilizer
Expect surface package, form one layer of hydrophobic membrane, hinders to form salt bridge between fertiliser granulates, to prevent agglomeration from being formed.Yin Hui
(CN101302128,2008-11-12) et al. the method for preparing anticaking agent is to refine stone with semi-refined paraffin wax particle, particle
Wax, stearic acid, octadecyl primary amine, vaseline, erucyl amide are raw material, first heat mineral oil, add above-mentioned raw materials, instead
Compound fertilizer surface is uniformly sprayed at after answering 1-1.5 hour.It can be appreciated that this kind of anticaking agent is due to having used paraffin, mineral
The raw material difficult to degrade such as oil, thus obtained anticaking agent is also to be difficult to degrade.
Crown English (CN101870607A, 2010-10-27) et al. develops a kind of all biological degradation type compound fertilizer anti-caking
Agent preparation method, primary raw material have fatty acid (stearic acid and oleic acid), anionic surfactant (octadecylphenyl sulfonic acid
Sodium), cationic surfactant (octadecylamine base ditallowdimethyl ammonium bromide), polyether high molecular surfactant and fatty acid [18
Alkyl (EO)40(PO)10Ether].First fatty acid and anionic surfactant are uniformly mixed, are warming up to 55-65 DEG C, after stirring,
Polyether high molecular surfactant is added, fatty acid and cationic surfactant are finally added, is within stirring 20-40 minutes
It can.Anticaking agent prepared by this method in a natural environment can be degradable, and preventing blocking effect is good, but cost is very high,
It is difficult to industrialization promotion.
Desolate chess secondary (CN101555178,2009-10-14) et al. devises a kind of preparation of liquid compound fertilizer anticaking agent
Method, it is directly that the alkyl benzene sulphonate sodium salt or sylvite of C12-C18, triethanolamine, C9 fatty alcohol polyoxyethylene ether (AEO-9) is molten
Anticaking agent is made in silicone oil emulsion.This method does not have to the substance of the environmental pollutions such as addition paraffin, and at normal temperature, this is anti-
Agglomeration agent is liquid, makees solvent without adding machine oil when use, cost-saved, can be painted in compound fertilizer, without plus
Heat.Xia Yu (CN101199921,2008.06.18) etc. with quaternary ammonium salt, anionic surfactant, nonionic surfactant,
Polymer and water mixing, are made a kind of water-soluble anticaking agent, which forms one layer by the oriented attachment of surfactant
Hydrophobic membrane hinders the contact between fertiliser granulates, prevents from agglomerating.But contained humidity is inherently unfavorable for tide in this kind of anticaking agent
Anti-caking under wet environment.
Sha Huaili (CN101987802A, 2011-03-23) et al. devises a kind of high tower urea-based compound fertilizer anticaking agent,
Primary raw material is vegetable oil, cyclohexanone leftover bits and pieces, and mass percent is the vegetable oil of 80%-90% and the hexamethylene of 10%-20%
Ketone leftover bits and pieces, the two, which is mixed, can be prepared by anticaking agent, and the mixture of this method vegetable oil is oil base, environmental pollution
It is small, and the fusing point of vegetable oil is lower, energy consumption is lower in production technology；The viscosity of vegetable oil is small, and anticaking agent is in fertilizer surface
Ductility it is good, dosage is few.But cyclohexanone leftover bits and pieces has strong pungent odor, is commonly used for organophosphorus insecticide and many
The fine solvent of similar pesticide, there is carcinogenesis.Using cyclohexanone leftover bits and pieces as the potential HSE dangerous of anticaking agent raw material.
Yang Huiping (CN102086138A, 2011-06-08) et al. using vegetable fat leftover bits and pieces as carrier, then with alkyl hydrogen
Change tallow amine surfactant, C8-C10 fatty acid methyl ester etc. and is mixed to prepare a kind of ammonium nitrate fertilizer anticaking agent.This anti-caking
Block agent can form a kind of film in ammonium nitrate fertilizer particle surface, effectively and isolated from atmosphere can reduce the speed of particulate water absorbent, subtract
Lack intergranular stick to each other, it is suppressed that intergranular one recrystallization of salt dissolution, so that fertilizer be made to obtain anti-caking.
Liu Zhenmao (CN102070373A, 2011-05-25) et al. develops a kind of natural degradable compound fertilizer anticaking agent
Preparation method, component and mass percent are as follows: fatty amine or its salt 10-20%, stearic acid 20-25%, oleic acid 15-
20%, refined glycerine 5-15%, recycled wood materials 20-50%, the sum of each component are 100%；And each component is mixed in proportion
It closes, is heated to 70-85 DEG C, is stirred to react 15-30min.Compound fertilizer anticaking agent dosage is 0.5-2.0kg/t compound fertilizer, is used
The wind-cooling crystallization high-tower granulation mode of fine melt melting compound fertilizers is allowed to mix with compound fertilizer.Liu Zhenmao (CN102070374A, 2011-
05-25) et al. also have investigated it is a kind of with mineral material kaolin natural environmental-protective type compound fertilizer anticaking agent as main component,
Raw material is kaolin, water-absorbing water-retaining agent glycerol, odium stearate, calcium stearate, enuatrol, and the filler kaolin, water suction are protected
Aqua glycerol, odium stearate, the weight ratio of calcium stearate, enuatrol are as follows: 90-95:1.0-2.5:1.0-2.5:1.0-2.5:
0.5-1.0；The filler kaolin, water-absorbing water-retaining agent glycerol, odium stearate, calcium stearate, enuatrol uniformly mix in proportion
Worn into after conjunction fineness up to it is more than 800 mesh, pulvis of the fineness less than 15 μm.The anticaking agent dosage is that 1.0~3.0kg/t is compound
Fertilizer is directly sent into chilling roll with auger, by chilling roll rolling make anticaking agent with fertiliser granulates are full and uniform mixes, it is suitable
Together in roller granulation compound fertilizer production technology.Both anticaking agents are respectively suitable for high-tower granulation and roller is granulated two kinds of differences
Compound fertilizer production technology, mutual irreplaceable, the poor universality of technique, this is one.The second is selected main former material
Expect that glycerol is a kind of organic compound that water absorbing and retaining properties are fabulous, compound fertilizer can be made to be in a kind of aqueous moisture stable always
(humidity) state, is actually unfavorable for moisture-proof anti-caking.The third is the anticaking agent of mineral material is largely used, due to it
Contained nutrient (NPK) itself is little, to guarantee necessary compound fertilizer's nutrient standard (to meet complex fertilizer product quality
Standard), the formulation cost of compound fertilizer will necessarily be improved, it is economically and uneconomical.
Liu Xinzhong (CN102050679A, 2011-05-11) et al. develops a kind of straw powder-based anti-blocking agent of compound fertilizer,
It is formed by the following raw material mixed preparing of mass parts ratio: the straw powder of 60-3000 mesh: 75-95；Stearic acid: 0.5-5；It is stearic
Amine: 0.1-1；Hydramine: 0.1-0.5；White oil or solid paraffin: 0.5-5；Natural oil: 2-15, by above-mentioned straw powder, tristearin
Acid, stearylamine, hydramine, white oil or solid paraffin and six component of natural oil are uniform stirring 5-60 minutes under 60-120 DEG C of environment
Afterwards, it is cooled to room temperature to get anticaking agent finished product.This method main component is stalk, belongs to pure-natural biological raw material, has biology
Degradability and good environment friendly, are repeatedly used for a long, and will not cause bad shadow to soil, crops and farm environment
Ring, this method have efficiently, make full use of stalk resource, without using high excellent of machine oil, environmentally protective, simple processing, cost performance
Point.But additive amount of the straw powder anticaking agent that was modified of this surface in compound fertilizer is up to 10~15kg/t, effect is remote
It is worse than the anticaking agent containing cationic surfactants such as organic amines, and excessively high no nutrient additive can also improve
The formulation cost of compound fertilizer, therefore the industrial application value of stalk anticaking agent is not high.
Zhao Zhuocheng (CN1 01450878,2009-06-10) prepares anticaking agent using mineral, and raw material is the cunning of 80-90%
Stone, the additive of 10-20%, wherein additive is the potassium feldspar of 0-10%, the attapulgite of 0-20%, the Erie of 0-10%
Stone, first by feedstock purification, be finely ground to 500-2500 mesh, by talcum calcine be modified, temperature be 600-1200 DEG C, illite, potassium are long
Stone, attapulgite are put into surface modifying apparatus that carry out surface modified at 80-1500 DEG C, after it mix with compound fertilizer, this
Anticaking agent can it is compound select grain during be directly added into pelletizer, be allowed to form spray pattern, be rotated through machine power, uniformly
It is covered in compound fertilizer, after drying.But the very high pretreatment of raw material temperature of this method and very thin grind size, both increased
Add the cost of raw material, it is also not energy-efficient.This large amount of anticaking agents using mineral material, the nutrient as contained by itself
(NPK) little, to guarantee necessary compound fertilizer's nutrient standard (meet complex fertilizer product quality standard), will necessarily improve
The formulation cost of compound fertilizer, it is economically and uneconomical.
Summary of the invention
In summary the prior art, though the present inventor is the study found that the preparation method of compound fertilizer dedicated anticaking agent at present
It is so very much, but still have to be solved there are many problem, typical problem, which can be summarized, to be had:
(1) inertia powder anticaking agent is modified ultrafine powder, plays anti-caking by carrying out powder package to fertilizer surface
Effect, but complex process, higher cost.Dust Capacity is big when the anticaking agent uses, and be easy to cause pollution of the dust to air；
(2) surfactant-based anticaking agent and mineral oil mineral wax class anticaking agent are paste anticaking agent, in room temperature
It is down solid-state or paste, fusing point is high, thus sprays to fertiliser granulates surface again using preceding needing first to heat fusing in fertilizer production.
During heating, if temperature is excessively high or hot-spot, the loss of its anti-caking effective component, and such anticaking agent institute be will cause
Raw material are mainly oil product and its derivative, can release special gas when heated, to cause gaseous contamination；
(3) oil-soluble anticaking agent is easy to use, and effect is good, but mineral oil need to be added as solvent, mine in conventional method
Object oil and mineral wax etc. is not degradable, will cause farmland, the water-based ecology of fishery after application after coating anti-caking agent above fertilizer
Pollution；
(4) water-soluble anticaking agent has brought moisture into fertilizer, and moisture is the immediate cause of fertilizer agglomeration, and it is in cream
The sticky state of oil, packaging, use all inconveniences at transport.
On the other hand, the present inventor observantly recognizes, with the development of agriculture industrialization, mechanical fertilization is more and more general
And the demand to composite no-lumping fertilizer increasingly increases.As the development of China's retreating chemical fertilizer and the seasonal of product are consumed,
The yield and period of storage of fertilizer are also being continuously increased；Global warming makes environment more and more moister, but will aggravate to agglomerate.
Few, easy to use, the environmental-friendly anticaking agent of dosage is developed in market in urgent need.
Domestic widely used mainstream anticaking agent product pattern is " oil base+anti-caking factor " at present, and oil base divides mineral oil
Or vegetable oil, anti-caking Factor minute organic amine or organic acid.People's sharp study is found through the invention, and a kind of industrial production surface is living
Property agent by-product have mixing-in fat amine cation surfactant property will reduce anti-caking if made full use of
The production cost of block agent.And it is directed to environmental issue, degradable vegetable wax and waste animal and vegetable oil has been selected on raw material, has made
Product fully biodegradable, it is friendly to anticaking agent production environment and compound fertilizer's use environment.
In conclusion for existing oil-soluble anticaking agent higher cost, the feature of environmental protection is not good enough the defects of, the invention solves
The problem of be to find cheap, environmental-friendly raw material, and then find a kind of suitable preparation method to synthesize a kind of full biology
The oil-soluble anticaking agent of degradation-type, the anticaking agent should have can it is degradable, preventing blocking effect is good, the spies such as cheap
Point, applied in the compound fertilizer easily agglomerated.
For this purpose, the present invention is that technology path in this way is realized: passing through Surfactant (especially fatty amine sun
Ionic surface active agent) acidification, formed fatty amine salt；Add vegetable wax, preferred nonionic surfactant and/or more
Preferred potassium ferrocyanide sodium salt；Fatty acid mixed and waste grease (such as animal and plant fat) are added, that is, obtain a kind of full biology
The oil-soluble anticaking agent of degradation-type, so as to complete the present invention.
Therefore, the present invention provides a kind of oil-soluble anticaking agents of all biological degradation type, by cheap former material
Material combination is made, specifically comprising following raw material composition: surfactant, acidulant, vegetable wax, waste grease and
Fatty acid.
Preferred embodiment according to the present invention, compound fertilizer oil-soluble anticaking agent raw material composition further include it is non-from
Sub- surfactant and/or potassium ferrocyanide sodium salt.
According to the present invention, wherein each raw material composition and respective quality proportioning are as follows:
Surfactant, 30~70 parts, preferably 40~65 parts, more preferable 45~60 parts,
Acidulant, 1~10 part, preferably 1~5 part, more preferable 2~4 parts,
Vegetable wax, 20~50 parts, preferably 30~50 parts, more preferable 35~45 parts,
Waste grease, 200~600 parts, preferably 300~500 parts, more preferable 350~450 parts,
Fatty acid, 300~700 parts, preferably 400~600 parts, more preferable 450~550 parts,
Preferred nonionic surfactant, 1~20 part, preferably 5~15 parts, more preferable 8~12 parts,
Preferred potassium ferrocyanide sodium salt, 1~20 part, preferably 5~15 parts, more preferable 10~15 parts.
Preferred embodiment according to the present invention, in which:
The surfactant is cationic surfactant, preferably fatty amine cationic surfactant, more preferably
For the by-product in Surfactant Industry production.
The acidulant is the mixed of one or both of acid minerals reagent such as concentrated hydrochloric acid, acetic acid or two or more compositions
Close object.
The vegetable wax is the mixing of one or both of rice bran wax, sugarcane wax, palm wax etc. or two or more compositions
Object.
In the present invention, vegetable wax is lyophobic dust, and preventing blocking effect can be improved, and can also improve the hard of anticaking agent
Degree, easy to produce and use.
The waste grease is one or both of gutter oil, swill oil, animal and plant fat etc. or two or more compositions
Mixture, preferably animal and plant fat.
The fatty acid be palmitinic acid, stearic acid, or both mixture.
In the present invention, the hardness of anticaking agent had both been can be improved in above-mentioned fatty acid and waste grease, while being also hydrophobicity
Substance plays an important role in anticaking agent.
The nonionic surfactant is fatty alcohol polyethenoxy ether class, preferably one of AEO-7, AEO-9 etc.
Or the mixture of two or more composition.
In the present invention, the presence of nonionic surfactant has blocked the diffusion path of salt, is distributed to each alternate boundary
On face, water-wet side makes them be not easy to be diffused into particle surface and contact zone towards the stronger component of water imbibition, and shape again
At crystalline solid it is prevented from caking.
The potassium ferrocyanide sodium salt be technical grade potassium ferrocyanide sodium salt, potassium ferrocyanide sylvite, or both mixture.
In the present invention, potassium ferrocyanide sodium salt or sylvite can effectively block the formation of multicomponent crystallization salt bridge, compound to being similar to
The crystallization inhibiting effect of multicomponent salt as fertilizer is of great significance.
The present invention also further invents and provides a kind of oil-soluble anticaking agent for preparing above-mentioned all biological degradation type
Method, each raw material composition and its quality proportioning are as follows:
Surfactant, 30~70 parts, preferably 40~65 parts, more preferable 45~60 parts,
Acidulant, 1~10 part, preferably 1~5 part, more preferable 2~4 parts,
Vegetable wax, 20~50 parts, preferably 30~50 parts, more preferable 35~45 parts,
Waste grease, 200~600 parts, preferably 300~500 parts, more preferable 350~450 parts,
Fatty acid, 300~700 parts, preferably 400~600 parts, more preferable 450~550 parts,
Preferred nonionic surfactant, 1~20 part, preferably 5~15 parts, more preferable 8~12 parts,
Preferred potassium ferrocyanide sodium salt, 1~20 part, preferably 5~15 parts, more preferable 10~15 parts.
The preparation method comprises the following steps:
1) pre-treatment of raw material, by surfactant, preferred cationic surfactant, more preferable fatty amine cation form
Precipitated impurities filtering in the activating agent of face,
2) pretreated surfactant and acidulant are weighed, and is mixed, solution is obtained,
3) vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt are weighed, step is added to
2) it in the solution obtained, heats, stirring,
4) solution, the fatty acid that step 3) obtains are weighed, is added in waste grease (preferably animal and plant fat), is heated,
Stirring, is completely dissolved,
5) solution for optionally obtaining step 4) is cooling.
Specific technology of preparing scheme is as described below:
1) pre-treatment of raw material: by surfactant (preferred cationic surfactant, more preferable fatty amine cation form
Face activating agent) raw material progress primary election, the blocky impurity of the inside is removed, makes it in homogeneous solution, it is spare；
2) pretreated surfactant and acidulant are weighed according to the ratio, are uniformly mixed,
3) vegetable wax, preferred nonionic surfactant and/or preferred potassium ferrocyanide sodium salt are weighed according to the ratio, are dissolved
In the solution that step 2) is prepared, heating is warming up to 70~120 DEG C, preferably 80~110 DEG C, more preferable 90~100 DEG C, stirs,
It is preferred that 8~20min, more preferable 10~15min, such as 12min, until uniform solution is obtained,
4) said ratio 3 is weighed) obtained solution and fatty acid, it is added in waste grease (preferably animal and plant fat),
Heating is warming up to 50~90 DEG C, preferably 60~80 DEG C, more preferable 65~75 DEG C, stirs, 10~20min, preferably 12~18min,
It is completely dissolved, obtains uniform solution,
5) solution for optionally obtaining step 4) is cooled to solid-state.
The oil-soluble anti-caking of foregoing compound fertilizer all biological degradation type obtained by the above method through the invention
Agent can improve the shatter value of compound fertilizer, can obtain preferable preventing blocking effect.
Therefore, compared to existing oil-soluble anticaking agent in the market, the oil of compound fertilizer's all biological degradation type of the invention
Dissolubility anticaking agent has the advantage that
1, raw material sources are extensive, and cost is more cheap；
2, (such as dynamic to the surfactant of by-product (such as mixing-in fat amine cation surfactant) and waste grease
Vegetable fat) higher value application is carried out, and it is made to be transformed into the product with certain added value, it is both economically and environmentally beneficial；
3, the addition of potassium ferrocyanide sodium salt has very strong inhibiting effect to the formation of multicomponent crystallization salt bridge, to keep this anti-
Agglomeration agent has the wider scope of application, all has preferable preventing blocking effect to the compound fertilizer of various formulas；
4, using natural degradable raw material as principal component, the anticaking agent of synthesis in the natural environment can be degradable, no
Potential pollution can be caused to agricultural land soil and aquatic ecosystem, be environmentally friendly product；
5, product of the invention all has preferable agglomeration preventing performance to the chemically composited fertilizer of various formulas, in temperature model
14~36 DEG C are enclosed, 60% or more air humidity, 10~20 layer heap pile storage times 60 days, the shatter value of compound fertilizer generally can reach
99% or more, such as with being greater than 96%, preferably greater than 98%, more preferably greater than 99%, close to even up to 100% anti-caking
Block rate.
Detailed description of the invention
Fig. 1 is the oil-soluble anticaking agent preparation technology flow chart of all biological degradation type of the present invention.
Specific embodiment
It is further explained and described the content of present invention by the following examples.But provided embodiment is not understood that
To be construed as limiting to the scope of the present invention.
Agglomeration preventing performance evaluation
(1) laboratory sample performance test
Anticaking agent is uniformly dispersed in the surface of compound fertilizer granules using seed-coating machine, compound fertilizer is mounted in small plastic bag
In, closed sealing, every bag of 200g is overlapped and is placed in climatic chamber, and the dumbbell that 10kg is put on compound fertilizer's sample is matched
Weight piece sets certain humidity and temperature (higher temperature and humidity), opens instrument every morning, close instrument at night,
So that it is quickly agglomerated, takes out measurement sample by presetting test number of days (such as 7 days, 20 days, 30 days or 60 days), will test
Sample is freely dropped into ground from 1 meter of height level, positive and negative each primary, then will wrap interior style and sieve, employment horizontal hunting
Frequency 50 times or so, sieving time 1min, survey the caking rate of corresponding standing time.
(2) use site performance test
40 bags of the Bag fertilizer of spray coated anticaking agent, total amount are 2 tons, and stacking is 8 layers, 5 bags every layer, additionally applies pressure
2 tons, presetting test number of days (such as 7 days, 20 days, 30 days or 60 days) are stacked, from top to bottom, every layer takes 2 packets to carry out loosely
Degree test.Test sample is artificially freely dropped into ground from 1 meter of height level, it is positive and negative each primary, it then will wrap interior sample and carry out
Screening, manually horizontal hunting frequency 50 ± 5 times, sieving time 1min survey the caking rate of corresponding standing time.
(3) measurement of caking rate
W: caking rate；
M: the quality of sample before being sieved；
M ': the quality of sample after sieving
Embodiment raw materials
By-product contains in fatty amine cationic surfactant selection fatty amine cationic surfactant production process
The mixture of the Long carbon chain fatty amine cationic surfactant of fatty alcohol, fatty acid and wide range of molecular weight distributions, carbon
Number distribution is generally C12~C22, is used to prepare fatty amine cation surface activating of the anticaking agent than the single composition of commercialization
Agent cost performance is more preferable, is purchased from Shandong Boxing Huarun Grease Chemical Co., Ltd, uses after softened point self-control adjusting processing.
The industrial by-products deviate from rice bran wax system Rice bran crude oil refining process are purchased from Cangzhou forest La Ye company,
It is used after softened point self-control adjusting processing.
Fatty alcohol polyethenoxy ether class (AEO-7) is technical grade, joins chemical limited liability company purchased from TaiWan, China east
(OUCC) Nanjing company.
Potassium ferrocyanide sodium salt or potassium ferrocyanide sylvite are technical grade, are 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 is purchased from Shandong biology bavin
Oily group company.
The common chemical reagent such as hydrochloric acid, stearic acid is the pure grade (AR) of analysis, is to purchase from Beijing Chemical Plant.
Compound fertilizer's sample selects the potassium sulfate compound fertilizer (N:P for being easiest to agglomeration2O5: K2O=15:15:15) and high nitrogen is multiple
Hefei (N:P2O5: K2O=28:6:6), provided by middle energy conservation Jin Feng agricultural science and technology Co., Ltd.
Embodiment
Embodiment 1:
Pretreated fatty amine cationic surfactant 0.44g is weighed, acidulant concentrated hydrochloric acid 0.02g, stirring is added
Uniformly, the rice bran wax of 0.34g is added, is heated, is warming up to 100 DEG C, is stirred, 10min, until uniform solution.Add the hard of 12g
Resin acid, the animal and plant fat of 7.2g, heating are warming up to 80 DEG C, and stirring, 15min obtains uniform solution.To get sample after cooling
Product.Embodiment 1 is tested according to the above laboratory sample performance test methods, compound fertilizer is potassium sulfate type (N:P2O5: K2O
=15:15:15).Shatter value after the agglomeration preventing performance testing result of embodiment 1 shows 7 days is 96%.
Embodiment 2:
Pretreated fatty amine cationic surfactant 5.56g is weighed, acidulant concentrated hydrochloric acid 0.27g, stirring is added
Uniformly, the rice bran wax of 4.17g is added, is heated, is warming up to 100 DEG C, is stirred, 10min, until uniform solution.Add the hard of 10g
Resin acid, the animal and plant fat of 8g, heating are warming up to 80 DEG C, and stirring, 15min obtains uniform solution.To get sample after cooling.
Embodiment 2 is tested according to the above laboratory sample performance test methods, compound fertilizer is potassium sulfate type (N:P2O5: K2O=
15:15:15).Shatter value after the agglomeration preventing performance testing result of embodiment 2 shows 7 days is 97%.
Embodiment 3:
Pretreated fatty amine cationic surfactant 0.56kg is weighed, acidulant concentrated hydrochloric acid 0.02kg is added, stirs
It mixes uniformly, adds the rice bran wax of 0.42kg, heat, be warming up to 100 DEG C, stir, 10min, until uniform solution.Add 18kg
Stearic acid, the animal and plant fat of 11kg, heating is warming up to 80 DEG C, and stirring, 15min obtains uniform solution.After cooling to get
Sample.Embodiment 3 is tested according to apparatus potential assessment method used above, compound fertilizer is high nitrogen fertilizer (N:P2O5: K2O=
28:6:6), pilling up time is 20 days.Shatter value after the agglomeration preventing performance testing result of embodiment 3 shows 20 days is 100%.
Embodiment 4:
It is with 3 difference of embodiment: the type of compound fertilizer.Weigh pretreated fatty amine cationic surfactant
0.56kg is added acidulant concentrated hydrochloric acid 0.02kg, stirs evenly, add the rice bran wax of 0.42kg, heats, is warming up to 100 DEG C,
Stirring, 10min, until uniform solution.The stearic acid of 18kg, the animal and plant fat of 11kg are added, heating is warming up to 80 DEG C, stirs
It mixes, 15min obtains uniform solution.To get sample after cooling.By embodiment 4 according to apparatus potential assessment method used above into
Row test, compound fertilizer are potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time is respectively 7 days, 20 days, 30 days and 60
It.Detection data is shown in Table 1.
Table 1: the agglomeration preventing performance testing result of embodiment 4
| Pilling up time (day) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 95 | 95 | 90 |
Embodiment 5:
It is with 4 difference of embodiment: whether nonionic surfactant is added.Weigh pretreated fatty amine cation
Surfactant 1.5kg is added acidulant concentrated hydrochloric acid 0.075kg, stirs evenly, add the rice bran wax of 1.125kg, 0.3kg
Fatty alcohol polyethenoxy ether class (AEO-7), heating is warming up to 100 DEG C, stirring, 10min, until uniform solution.It adds
The stearic acid of 15kg, the animal and plant fat of 12kg, heating are warming up to 80 DEG C, and stirring, 15min obtains uniform solution.After cooling,
Up to sample.Embodiment 5 is tested according to apparatus potential assessment method used above, compound fertilizer be potassium sulfate type (N:
P2O5: K2O=15:15:15), pilling up time is respectively 7 days, 20 days, 30 days and 60 days.Detection data is shown in Table 2.
Table 2: the agglomeration preventing performance testing result of embodiment 5
| Pilling up time (day) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 99 | 99 | 98 |
Embodiment 6:
It is with 4 difference of embodiment: whether potassium ferrocyanide sodium salt is added.It is living to weigh pretreated fatty amine cationic surface
Property agent 1.5kg, be added acidulant concentrated hydrochloric acid 0.075kg, stir evenly, add the rice bran wax of 1.125kg, the yellow blood of 0.6kg
Salt sodium salt, heating are warming up to 100 DEG C, stir, 10min, until uniform solution.Add the stearic acid of 15kg, the animals and plants of 12kg
Grease, heating are warming up to 80 DEG C, and stirring, 15min obtains uniform solution.To get sample after cooling.By embodiment 6 according to
Upper use site performance test methods are tested, and 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 is shown in Table 3.
Table 3: the agglomeration preventing performance testing result of embodiment 6
| Pilling up time (day) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 96 | 95 | 93 |
Embodiment 7:
It is with 4 difference of embodiment: whether nonionic surfactant and potassium ferrocyanide sodium salt are added.It is as shown in Fig. 1: to claim
Pretreated fatty amine cationic surfactant 1.5kg is taken, acidulant concentrated hydrochloric acid 0.075kg is added, stirs evenly, then plus
Enter 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 heats, and rises
Temperature is to 100 DEG C, stirring, 10min, until uniform solution.The stearic acid of 15kg is added, the animal and plant fat of 12kg heats, heating
To 80 DEG C, stirring, 15min obtains uniform solution.To get sample after cooling.By embodiment 7 according to field performance used above
Test method is tested, and compound fertilizer is potassium sulfate type (N:P2O5: K2O=15:15:15), pilling up time is respectively 7 days, 20
It, 30 days and 60 days.Detection data is shown in Table 4.
Table 4: the agglomeration preventing performance testing result of embodiment 7
| Pilling up time (day) | 7 | 20 | 30 | 60 |
| Shatter value (%) | 100 | 100 | 100 | 100 |
The oil-soluble anticaking agent performance of all biological degradation type prepared by the present invention it can be seen from examples detailed above is universal
Preferably, it can be applied in the various fertilizer easily to agglomerate, and under field conditions (factors) can be degradable, it is very environmentally friendly.
The present invention is described in detail according to the above embodiments.It should be noted that above embodiment just to
It illustrates the present invention.Under the premise of without departing from spirit and substance of the present invention, those skilled in the art can be designed
A variety of alternatives and improvement project of the invention out, should all be interpreted within protection scope of the present invention.
Claims (12)
1. a kind of compound fertilizer all biological degradation type oil-soluble anticaking agent, which is characterized in that its raw material composition includes that surface is living
Property agent, acidulant, vegetable wax, waste grease, fatty acid and nonionic surfactant, raw material composition and respective quality
Proportion are as follows:
The surfactant is fatty amine cationic surfactant, which selects fatty amine
By-product is living containing fatty alcohol, fatty acid and Long carbon chain fatty amine cationic surface in cationic surfactant production process
The mixture of property agent,
The acidulant be one or both of concentrated hydrochloric acid, acetic acid,
The waste grease is the mixing of one or both of gutter oil, swill oil, animal and plant fat or two or more compositions
Object,
The fatty acid is the mixture of palmitinic acid, stearic acid or the two,
The nonionic surfactant is fatty alcohol polyethenoxy ether class.
2. compound fertilizer according to claim 1 oil-soluble anticaking agent, which is characterized in that its raw material composition and it is respective
Quality proportioning are as follows:
The acidulant be one or both of concentrated hydrochloric acid, acetic acid,
The vegetable wax is the mixture of one or both of rice bran wax, sugarcane wax, palm wax or two or more compositions,
The waste grease is animal and plant fat,
The nonionic surfactant is the mixture of one or both of AEO-7, AEO-9 composition.
3. compound fertilizer according to claim 2 oil-soluble anticaking agent, which is characterized in that its raw material composition further includes Huang
Blood salt sodium salt,
1~20 part of potassium ferrocyanide sodium salt.
4. compound fertilizer according to claim 3 oil-soluble anticaking agent, which is characterized in that 5~15 parts of potassium ferrocyanide sodium salt,
The potassium ferrocyanide sodium salt be technical grade potassium ferrocyanide sodium salt, potassium ferrocyanide sylvite, or mixtures thereof.
5. compound fertilizer according to claim 4 oil-soluble anticaking agent, which is characterized in that its each raw material composition and respectively
Quality proportioning are as follows:
6. preparing the compound fertilizer according to claim 1 or 2 method of oil-soluble anticaking agent, which is characterized in that the party
Method the following steps are included:
1) pre-treatment of raw material filters the precipitated impurities in fatty amine cationic surfactant,
2) pretreated surfactant and acidulant are weighed, and is mixed, solution is obtained,
3) vegetable wax, nonionic surfactant are weighed, is added in the solution that step 2) obtains, is heated, stirring,
4) solution, the fatty acid that step 3) obtains are weighed, is added in waste grease, is heated, stirring is completely dissolved,
5) solution for optionally obtaining step 4) is cooling.
7. preparing the compound fertilizer according to claim 6 method of oil-soluble anticaking agent, which is characterized in that in step 3)
Potassium ferrocyanide sodium salt can also be added.
8. preparation method according to claim 7, which is characterized in that should the following steps are included:
1) pre-treatment of raw material: carrying out primary election for fatty amine cationic surfactant raw material, remove the blocky impurity of the inside,
Make it in homogeneous solution, it is spare；
2) pretreated surfactant and acidulant are weighed according to the ratio, are uniformly mixed,
3) vegetable wax, nonionic surfactant and potassium ferrocyanide sodium salt are weighed according to the ratio, are dissolved in the solution of step 2) preparation,
Heating is warming up to 70~120 DEG C, stirs, 8~20min, until uniform solution is obtained,
4) said ratio 3 is weighed) obtained solution and fatty acid, it is added in waste grease, heats, be warming up to 50~90 DEG C,
Stirring, 10~20min are completely dissolved, and obtain uniform solution,
5) solution for optionally obtaining step 4) is cooled to solid-state.
9. preparation method according to claim 8, which is characterized in that
Constant temperature control is at 80~110 DEG C in step 3), 10~15min
Temperature control is at 60~80 DEG C in step 4), 12~18min.
10. preparation method according to claim 9, which is characterized in that
Constant temperature is controlled at 90~100 DEG C in step 3), and/or
Temperature control is at 65~75 DEG C in step 4).
11. the oil-soluble anticaking agent of compound fertilizer made from the preparation method according to one of claim 9 to 10, is complete
Biodegradable oil-soluble anticaking agent, at 14~36 DEG C of temperature range, 60% or more air humidity, 10~20 layer heap piles are stored
Time 60 days, the shatter value of compound fertilizer can achieve 99% or more.
12. being used as compound fertilizer to one of 5 or the purposes of anticaking agent according to claim 11 according to claim 1
With oil-soluble anticaking agent, the shatter value of compound fertilizer can be improved, obtain preferable agglomeration preventing performance.
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| CN106380321B (en) * | 2016-09-06 | 2019-06-21 | 中南林业科技大学 | A kind of compound fertilizer anticaking agent and its preparation, application method |
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| 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 |
| 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 |
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