CN101112997A - Ammonii chloridum caking-proof agent and its application in preparation of caking-proof ammonii chloridum - Google Patents
Ammonii chloridum caking-proof agent and its application in preparation of caking-proof ammonii chloridum Download PDFInfo
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- CN101112997A CN101112997A CNA2007101180622A CN200710118062A CN101112997A CN 101112997 A CN101112997 A CN 101112997A CN A2007101180622 A CNA2007101180622 A CN A2007101180622A CN 200710118062 A CN200710118062 A CN 200710118062A CN 101112997 A CN101112997 A CN 101112997A
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- ammonium chloride
- caking
- caking agent
- aspartic acid
- ammonii
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to an ammonium chloride anti-caking agent and is characterized in that: the invention consists of simulating SOD and aspartic acid polymer, weight ratio of which is 1/1000-5/1000; the general formula of the simulating SOD is (C8H8O6N2M.XH2O)n), wherein, the M is chosen from Mn, Cu, Zn or any arbitrary combination thereof, the n is 5-7; the chemical general formula of the aspartic acid polymer is (C4H4O3NM)z, wherein, the z is 15-56, the M is chosen from Na, K, NH4+ or any arbitrary combination thereof. The invention also relates to the application of the anti-caking agent in preparing anti-caking ammonium chloride.
Description
Technical field
The invention belongs to the chemical fertilizer additive agent field, be specifically related to a kind of ammonium chloride anti-caking agent and the application in the anti-caking of preparation ammonium chloride thereof.
Background technology
As everyone knows, soda ash (Na2CO3) is basic raw material for chemical industry, and output is very big, about about 2,000 ten thousand tons of soda ash annual production.The production technique of soda ash mainly contains " solvay soda process ", " connection alkaline process " reaches " urao processing " three kinds of methods; Connection alkaline process also higher ammonium chloride (NH4 of nitrogen content of by-product equivalent when producing soda ash
4Cl) product, ammonium chloride are important industrial raw material and good nitrogenous fertilizer.About 7,000,000 tons of present domestic chloride yield.Ammonium chloride belongs to chloro nitrogenous fertilizer, is good nitrogen manure, contains the N amount about more than 25%.Optimum is applied to paddy rice, and is especially fairly obvious to the early rice effect of increasing production.Other crop such as wheat, cotton, oil plant, vegetables also all there is the effect that obviously raises productivity and improves the quality.
Ammonium chloride has powdery, crystalloid, form such as granular, but because of the chlorine moisture absorption very easily, so all there is agglomeration problems in the ammonium chloride of different shape, thereby gives transportation, store, use and often bring great inconvenience.The reason of ammonium chloride from caking is very complicated, major cause is that ammonium chloride has certain moisture, because the variation of factors such as outside temperature, pressure, humidity, time makes this part water produce " brilliant bridge " between crystal, " brilliant bridge " plays the mutual adhesive attraction of crystal, thereby caking phenomenon takes place.
Prevent that ammonium chloride from caking from being the technical task that must solve, scientific worker and manufacturing enterprise have proposed multiple anti-caking block method both at home and abroad, roughly are divided into following three kinds of ways:
1, desiccating method; 2, comminution granulation; 3, add additive method.
At present being used widely on agricultural ammonium chloride and being subjected to the consistent anti-hard caking agent product of praising is CN1099058A disclosed " polyacrylate " series products, it belongs to high molecular weight water soluble polymer, have anion surfactant character, preventing blocking effect can be up to state standards.But it is a kind of material of very difficult degraded, and the secondary pollution that environment is produced can't neglect, and if things go on like this, consequence is hard to predict.This kind anti-hard caking agent is just simple to solve anti-caking problem, to plant growth and improve utilization rate of fertilizer and the protection edatope without any promoter action, purpose is single.
Summary of the invention
The object of the invention is to provide a kind of ammonium chloride anti-caking agent, and it uses the biopolymer technology to solve the ammonium chloride from caking problem, improves utilization rate of fertilizer simultaneously, makes common ammonium chloride become high-effective chemical fertilizer; And eradicate because of adding anti-hard caking agent to the secondary pollution that environment produces, preserve the ecological environment, improve crop quality, for providing with fertile, the farm crop foreign exchange earning ensures.
Another object of the present invention is to provide the application of this anti-hard caking agent in the anti-caking of preparation ammonium chloride.
A kind of ammonium chloride anti-caking agent provided by the invention is characterized in that: be made up of Simulating SOD (promptly simulate superoxide dismutase, be called for short SODm) and aspartic acid polymkeric substance, their weight ratio is 1/1000-5/1000, and the general formula of described Simulating SOD is:
C
8H
8O
6N
2M·XH
2O
n
Wherein M is selected from Mn, Cu, Zn or their arbitrary combination, and n is 5-7.
The chemical general formula of described aspartic acid polymkeric substance is: (C
4H
4O
3NM) z
Wherein z is 15-56, and M is selected from Na, K, NH
4 +Or their arbitrary combination.
With polysuccinimide (being PSl) through NaOH, KOH or NH
4The OH hydrolysis forms Na, K or the NH of aspartic acid polymkeric substance
4 +Salt.In the PSI hydrolytic process, two C-N chains cause chain break on the imide ring because OH-attacks, and form the salt of α type and the coexistence of β type, and the structure of this asparagus fern radon acid polymer becomes:
α type β type
M+n=z=15-56 in the formula.
More preferably, m: n=3: 7.
M in the anti-hard caking agent in the aspartic acid polymkeric substance is Na, K or NH
4 +Any one or more than one combination.
Described Simulating SOD is synthetic according to disclosed method among the CN1803812A.
The present invention also provides the application of this anti-hard caking agent in the anti-caking of preparation ammonium chloride: anti-hard caking agent is added in the ammonium chloride after with water dissolution.The weight of anti-hard caking agent and the weight ratio of ammonium chloride are 50-600ppm: 1, can the finished product of ammonium chloride separate or packaging process in add anti-hard caking agent.
The present invention compared with prior art has the following advantages:
1, ammonium chloride anti-caking agent of the present invention is mixed by aspartic acid polymkeric substance and Simulating SOD.The aspartic acid polymkeric substance belongs to bioabsorbable polymer material; having water-soluble carboxylic acid's character, is a kind of anion surfactant, has fabulous surfactivity; easily in ammonium chloride surface diffusion, infiltration; form a kind of hydrophobic nature protective membrane, block the generation of " brilliant bridge ", thereby stoped the generation of ammonium chloride from caking; and SODm is owing to have the long-chain protein properties; belong to natural bionical material, therefore, fabulous biocompatibility and biological degradability are arranged.
2, ammonium chloride anti-caking agent of the present invention is easy to enter plant root in soil, but the nutritive element of available to plant in its enrichment and the absorption root soil, as absorption of N, P, K, S, Mn, B, Fe etc., not only can directly use, can also and fertilizer mixed applying, have and improve percentage of germination and soil moisture conservation effect.Use it both can promote plant-growth, can reduce again because the pollution that the lavishment chemical fertilizer is caused reduces agricultural cost, the purifying ecological environment.And it is nontoxic, harmless, tasteless, pollution-free and fully biodegradable to farm crop, and environment is had no adverse effects, and improves fertilizer efficiency simultaneously again, saves fertilizer.
3, ammonium chloride anti-caking agent of the present invention is used to produce when preventing caking ammonium chloride, does not influence the Production Flow Chart of original ammonium chloride, and using method is simple and practical.
4, ammonium chloride anti-caking agent of the present invention, it is a kind of anion surfactant that contains a large amount of carboxyl genes, compares with general polycarboxylate, the crystalline interface can be reduced and crystalline dissolving and recrystallization can be resisted, agglomeration resistance rate height, cost of investment is lower.
Embodiment
Below will the present invention is further elaborated by specific embodiment, still, this embodiment is only in order to illustrate the present invention rather than restriction the present invention.
Embodiment 1
Synthesizing of aspartic acid polymkeric substance
M is Na: polysuccinimide (being PSl) is added in a certain amount of water, add the solid NaOH hydrolysis half an hour of equimolar amount then, oven dry obtains poly (sodium aspartate).
M is K: with M is that the synthetic method of Na is identical, just replaces NaOH with KOH.
M is NH
4Synthetic: with M is that the synthetic method of Na is identical, just uses NH
4OH replaces NaOH.
The physical and chemical performance parameter of aspartic acid polymkeric substance:
1, state: amber color liquid
2, polymericular weight: M:2000-8000
3, density (20 ℃) g/cm: 〉=1.05-1.22
4、pH：6.0-10.0
1, biological degradability: 〉=65%30 days
Embodiment 2
According to the synthetic Mn-SOD of disclosed method among the CN1803812A, Cu, Zn-SOD.
The physical and chemical parameter of Simulating SOD compound:
1, state: amber color liquid
2, SODm specific enzyme activity: 〉=4000IU/mg
3, molecular weight: 1000-3000
6, pH value (1% aqueous solution): 8.0-10.5
7, density (20 ℃): 1.2g/cm3
8, biological degradability: 〉=65%/30 days
9, heat resisting temperature: 180 ℃
Embodiment 3
The aspartic acid polymkeric substance (wherein z is 15, and M is a potassium) of 1 kilogram SODm (wherein n is 5, and M is a manganese) and 1000 kilograms mixed promptly obtain ammonium chloride anti-caking agent 1.
Embodiment 4
The aspartic acid polymkeric substance (wherein z is 15, and M is a potassium) of 2.5 kilograms SODm mixtures (wherein n is 5, and M is copper and zinc, is 1: 1 mixed with weight ratio) and 1000 kilograms mixed promptly obtain ammonium chloride anti-caking agent 2.
Embodiment 5
(wherein z is 25, and M is sodium and NH with 2.5 kilograms SODm mixtures (wherein n is 6, and M is copper and zinc, is 1: 1 mixed with weight ratio) and 1000 kilograms aspartic acid polymkeric substance
4 +) mix and promptly to obtain ammonium chloride anti-caking agent 3.
Embodiment 6
(wherein z is 56, and M is potassium, sodium and NH4 with the aspartic acid polymkeric substance of 5 kilograms SODm mixtures (wherein n is 7, and M is copper and zinc) and 1000 kilograms
+, be 1: 1: 1 mixed with weight ratio) mix and promptly obtain ammonium chloride anti-caking agent 4.
Embodiment 7
Shop experiment
The solution of anti-hard caking agent 1 after the water dilution that obtains among the embodiment 3 is injected to spray gun in the firm isolating ammonium chloride by the difference amount, mixes then.After mixing, the ammonium chloride that is added with anti-hard caking agent is packed in 5 air-locked plastics bags of individual layer, then with plastic bag sealing, wherein every bag of weight is 500g, storage condition: 20-30 ℃ of external storage environment, humidity 60-80%.This 5 fluid-pressure moulding pocket sign indicating number is become buttress, on press the 5.4Kg weight, coexistence was put 159 days.
Detecting the caking method is: adopt the measuring method of GB2946-92 shatter value, be about to the plastics bag utilization manually from 1 meter height, freely land on the hard plane with level, pros and cons respectively falls once, the ammonium chloride in the bag is poured in the industrial screen sieved.Sieved 1 minute, and took by weighing the weight of screenings at last.Calculate caking rate with following formula, it the results are shown in Table 1.
X＝(m-m1)/m×100％
In the formula, m1 is a weight of staying the sample on the sieve after sieving;
M is the gross weight of used sample of sieving.
The table 1 caking rate test-results that the different anti-hard caking agents of measuring obtain for the ammonium chloride sample adds
Table 1
| Anti-hard caking agent amount (ppm) | Deposit fate | Check the bag number | Caking rate (%) | Remarks | |
| Embodiment 3 | 50 | 159 | 1 | 0.0 | The visual no big lump of outward appearance, hand is pinched promptly broken |
| Embodiment 3 | 80 | 159 | 1 | 0.0 | The visual no big lump of outward appearance, hand is pinched promptly broken |
| Embodiment 3 | 200 | 159 | 1 | 4.4 | The visual no big lump of outward appearance, hand is pinched promptly broken |
| Embodiment 3 | 400 | 159 | 1 | 1.2 | The visual no big lump of outward appearance, hand is pinched promptly broken |
| Embodiment 3 | 600 | 159 | 1 | 0 | The visual no big lump of outward appearance, hand is pinched promptly broken |
| Comparative Examples | 0 | 159 | 1 | 100 | Promptly harden after one day |
The detection method of Comparative Examples is the same in the table, does not just add anti-hard caking agent in the ammonium chloride.
As can be seen from Table 1, anti-hard caking agent of the present invention prevents that the ammonium chloride from caking effect is fairly obvious, and the anti-hard caking agent that adds 50ppm just can play preventing blocking effect.When surveying shatter value with screening, the sample screen overflow that has has a small amount of ammonium chloride, but hand one touches promptly and scatter, and preventing blocking effect is fine.
With identical method the anti-hard caking agent among the embodiment 4-6 is injected in the firm isolating ammonium chloride with spray gun by the difference amount and detects caking rate, the result who obtains also shows: after depositing 159 days, there is not big lump with the eyes observation, hand touches soft sensation, sample has been poured out sense of movement, loose magma touches promptly broken slightly with hand, preventing blocking effect is fine.
Embodiment 8
Shop test
Is that kinetic energy is injected to the whizzer feed opening with spray gun with the solution of anti-hard caking agent 1-4 after the water dilution that obtains among the embodiment 3-6 by difference amount pressurized air, wet ammonium chloride after the separation and vaporific anti-hard caking agent thorough mixing (wherein the weight ratio of the weight of anti-hard caking agent 1-4 and ammonium chloride is 200ppm), enter feed bin then, the computation weigh package forms on request at last.Packing bag is two-layer, and internal layer is a plastics bag, and skin is a Polywoven Bag, and internal layer is tightened with rope, outer artificial package, and every bag of 50Kg, totally 4 pile up neatly, 5 bags of every buttress, storage condition: 20-30 ℃ of external storage environment, humidity 60-80%, coexistence was put 159 days.
It is identical with embodiment 7 to detect the caking method, checks 1 bag at every turn, and it the results are shown in Table 2.
Comparative Examples: it is the same to detect step, and just ammonium chloride does not add anti-hard caking agent.
Table 2 is stacked test-results for industrial production
Table 2
| Embodiment | Take a sample test sample number of plies in buttress | Caking rate (%) | Remarks |
| 3 | 1 layer of first buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 3 | 3 layers of first buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 4 | 6 layers of first buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 4 | 1 layer of second buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 5 | 4 layers of second buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 5 | 6 layers of second buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 6 | 1 layer of the 3rd buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 6 | 3 layers of the 3rd buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| 6 | 5 layers of the 4th buttress | 0 | Screenings is zero, and outward appearance is loose slightly |
| Comparative Examples | 100 | Promptly harden after one day |
The anti-caking of industrial production test effect is better than room effect, and this is because shop experiment is to mix with hand, and shop test is with pressurized air sample to be sprayed vaporific uniformity coefficient to be higher than due to manual the stirring.
As can be seen, anti-hard caking agent of the present invention has following advantage from the foregoing description:
1, this product have simultaneously hydrophilic group because of and hydrophobic group because of; form one deck hydrophobic nature protective membrane on the ammonium chloride surface; make the chemical fertilizer surface hydrophobic of the easy moisture absorption; prevent the variation of the plane of crystal moisture that causes by a variety of causes; avoid crystallization, dissolving, recrystallize phenomenon to take place; thereby stoped the crystallization adhesion, played anti-caking effect.
2, the compound all be made up of metal ion prothetic group and protein of aspartic acid polymkeric substance and SODm has active highly, and molecular weight is little, good stability, water-soluble strong characteristics.The destruction that the accumulation of biogenic too much active oxygen and free radical simultaneously can cause plant cell structures and function, it can effectively eliminate superoxide radical, strengthens crop immunizing power and prevents advantages such as deterioration of strains.
Therefore, evidence, after agricultural ammonium chloride added product of the present invention, the product shatter value was good, and is mobile strong, and anti-caking effect is lasting, and addition means is simple and easy to do.This anti-hard caking agent itself is again a kind of fertilizer synergist, and simultaneously its non-toxic degradable does not again bring any harm to ecotope, is and environmentally friendly green product.
Claims (6)
1. ammonium chloride anti-caking agent, it is characterized in that: be made up of Simulating SOD and aspartic acid polymkeric substance, their weight ratio is 1/1000-5/1000, and the general formula of described Simulating SOD is:
C
8H
8O
6N
2M·XH
2O
n
Wherein M is selected from Mn, Cu, Zn or their arbitrary combination, and n is 5-7, and the chemical general formula of described aspartic acid polymkeric substance is: (C
4H
4O
3NM) z, wherein z is 15-56, M is selected from Na, K, NH
4 +Or their arbitrary combination.
2. anti-hard caking agent as claimed in claim 1 is characterized in that, the structural formula of aspartic acid polymkeric substance is:
α type β type
Wherein M is selected from Na, K or NH
4 +, m+n=z=15-56.
3. anti-hard caking agent as claimed in claim 2 is characterized in that m: n=3: 7.
4. the application of anti-hard caking agent as claimed in claim 1 or 2 in the anti-caking of preparation ammonium chloride is characterized in that anti-hard caking agent is added in the ammonium chloride after with water dissolution.
5. application as claimed in claim 4, it is characterized in that the finished product of ammonium chloride separate or packaging process in add anti-hard caking agent.
6. as claim 4 or 5 described application, it is characterized in that the weight of anti-hard caking agent and the weight ratio of ammonium chloride are 50-600ppm: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710118062A CN100582007C (en) | 2007-06-28 | 2007-06-28 | Ammonii chloridum caking-proof agent and its application in preparation of caking-proof ammonii chloridum |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710118062A CN100582007C (en) | 2007-06-28 | 2007-06-28 | Ammonii chloridum caking-proof agent and its application in preparation of caking-proof ammonii chloridum |
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|---|---|
| CN101112997A true CN101112997A (en) | 2008-01-30 |
| CN100582007C CN100582007C (en) | 2010-01-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746065A (en) * | 2012-07-13 | 2012-10-24 | 湖北海力化工科技有限公司 | Ammonium chloride anticaking agent and preparation method thereof |
| CN103059299A (en) * | 2013-01-22 | 2013-04-24 | 石家庄开发区德赛化工有限公司 | Compound type MSOD (Models of Superoxide Dismutase) and production process thereof |
-
2007
- 2007-06-28 CN CN200710118062A patent/CN100582007C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746065A (en) * | 2012-07-13 | 2012-10-24 | 湖北海力化工科技有限公司 | Ammonium chloride anticaking agent and preparation method thereof |
| CN102746065B (en) * | 2012-07-13 | 2013-11-06 | 湖北海力化工科技有限公司 | Ammonium chloride anticaking agent and preparation method thereof |
| CN103059299A (en) * | 2013-01-22 | 2013-04-24 | 石家庄开发区德赛化工有限公司 | Compound type MSOD (Models of Superoxide Dismutase) and production process thereof |
| CN103059299B (en) * | 2013-01-22 | 2014-01-15 | 石家庄开发区德赛化工有限公司 | Compound type MSOD (Models of Superoxide Dismutase) and production process thereof |
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| Publication number | Publication date |
|---|---|
| CN100582007C (en) | 2010-01-20 |
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