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CN1192003C - Improved ammonium nitrate loosening agent - Google Patents

Improved ammonium nitrate loosening agent Download PDF

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Publication number
CN1192003C
CN1192003C CNB021135711A CN02113571A CN1192003C CN 1192003 C CN1192003 C CN 1192003C CN B021135711 A CNB021135711 A CN B021135711A CN 02113571 A CN02113571 A CN 02113571A CN 1192003 C CN1192003 C CN 1192003C
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China
Prior art keywords
agent
ammonium nitrate
sodium
raising
scorch retarder
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Expired - Fee Related
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CNB021135711A
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Chinese (zh)
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CN1374279A (en
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殷海权
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Abstract

The invention relates to an ammonium nitrate loosening agent with excellent water solubility. The method is characterized in that: the loosening agent consists of a crystal control agent, a wetting agent, an anti-scorching agent and the like. The anti-caking agent for granulating ammonium nitrate is developed by the prior people, and the anti-caking agent solves the problems of poor water solubility, easy blockage of a granulating spray head, unsafe ammonium nitrate major circulation and the like which are not solved in the actual use. The invention is characterized in that all the components are substances with excellent water solubility, so that the spray head is not blocked in the granulation process after the ammonium nitrate is mixed with molten ammonium nitrate, and the ammonium nitrate is safely used in large-cycle operation. The invention is suitable for being used as a moisture-proof anti-caking agent for preparing agricultural granular ammonium nitrate and also can be used as an effective additive for preparing porous granular ammonium nitrate with high oil absorption rate.

Description

The loosening agent for ammonium nitrate of having improved
The present invention is a kind of water-soluble loosening agent for ammonium nitrate, the moistureproof anti-hard caking agent that relates to the easy moisture absorption caking of solids such as high-efficiency nitrogen fertilizer ammonium nitrate, porous ammonium nitrate meal, mainly use the anti-hard caking agent of granulation ammonium nitrate, especially can be used as effective additive of preparation high strength, high oil absorbency ammonium nitrate as agricultural and industrial explosive.This water-soluble fluffy powder is controlled agent, raising agent, wetting agent and scorch retarder etc. by crystalline substance and is formed.
Because the raw material of ammonium nitrate is from air, have inexpensive, oxygen enrichment, burning does not have characteristics such as residue, so be widely used as the important energetic material of agrochemical and fiery explosive oxygenant, but ammonium nitrate has inherent defects such as Yi Jingbian, easily moisture absorption, easily phase transformation, salt bridge recrystallization again, use to industrial or agricultural and to bring great inconvenience and hidden danger, thereby be badly in need of seeking to change ammonium nitrate easily lump defective and service-strong loosening agent for ammonium nitrate.
Since nearly half a century, scientific and technical personnel can carry out a large amount of research work to the moistureproof agglomeration preventing performance and the brilliant sex change that improve ammonium nitrate, have invented a series of ammonium nitrate anti-hard caking agents: U.S. Mississippi chemical company adopts boric acid, ammonium sulfate mixing salt to make anti-hard caking agent; ICI Americals, Inc adopts szaibelyite and Chinese invention patent (the patent number of accepting 00130046.6,2000) to adopt inert powders such as rhombspar to make the anti-hard caking agent of ammonium nitrate, in the use because of can not effectively controlling ammonium nitrate crystal conversion DeGrain; Acetate patented technology (the JP7650898 that the eighties, Japan adopted, 1978), though can obviously change the easy anti-caking of ammonium nitrate, because of acetate solubleness in ammonium nitrate too little (0.001%), and in use need be with stimulating highly seasoned Glacial acetic acid, cost height, contaminate environment again, produce use inconvenient.Conventional art makes goods have that thermoplasticity is poor, intensity is low, heat decomposition temperature is low, can not effectively control deficiencies such as ammonium nitrate crystal conversion.
The author of modern China patent ZL 94 1 07498.6 finds: adopt the effective brilliant control agent of plane configuration anion surfactant as ammonium nitrate, be applied in the ammonium nitrate, preventing blocking effect is good.But in actual use, exist incompatible and two defectives of generation spontaneous combustion in high-temperature service with emulsifying agent, in time by Chinese patent (patent patent No. ZL99 1 14733.2,1999) author improves, high stability and high heat-proof loosening agent for ammonium nitrate have been invented, this patented technology adopts in China a lot of granulation ammonium nitrate factory, but 3 facts that had insecurity in several years in actual the use: the one, in the fluffy powder prescription that designs in forefathers' patented technology, contain insoluble silicon-dioxide inertia breeze, this class trace indissoluble material, even be provided with filter screen device at granulation process, but also often cause prilling spry to stop up, make the process material imbalance cause that easily the ammonium nitrate localized heat decomposes in the molten state ammonium nitrate storage tank, easily lead to great explosion hazard; Next is in the multi-hole nitramines production process, the defective ammonium nitrate of the particle that contains additive that obtains through vibrosieve, must be in storage tank be after mother liquor more than 95% mixes evaporation with concentration, systemic circulation is used, if the ammonium nitrate additive is water-soluble bad, trace impurity is heated medium-term and long-term stop of the pipeline of systemic circulation process, can become the unsafe factor of detonation in the production process.The 3rd is the water-soluble bad of fluffy powder itself, can often cause fluffy powder to be heated for a long time on filtering net, bonding carbonization and cause spontaneous combustion.Japanese Patent (86103193 by Kao Corp's application, 1986) and the French KT company development anti-hard caking agent attempting to address the aforementioned drawbacks, all there are the problems such as inconvenient, that material cost is high, the goods dust is big of using, all do not obtain complete success, so ammonium nitrate anticaking agent becomes the essential technical barrier that solves in the insecurity of application process.
The objective of the invention is to overcome disadvantages of background technology, must design a kind of water-soluble and high heat-proof fluffy powder, join in the molten state ammonium nitrate, the physicals of ammonium nitrate is obviously improved, and must guarantee that not producing insoluble mashed prod in use stops up prilling spry, stifled exhausted fluffy powder insolubles is bonded in carbonization on the filtering net and guarantees to contain the ammonium nitrate mother liquor systemic circulation operation of fluffy powder can be safe and reliable.
Design of the present invention: design a constituent element performance complement, with low cost, raw material sources are rich and easy to get, can solve the ammonium nitrate defective of easily luming, and have solvability and high heat-proof polynary fluffy powder system in the good water.Be intended to adopt mist projection granulating to prepare in the technological process of free-running property pelletizing nitramino or porous ammonium nitrate, the present invention can be dissolved and mix in water or in the molten state ammonium nitrate fully, eliminates in technological process to produce blocking sprayer, carbonization burning, rest in the pipeline of cycle operation hidden danger such as explosive for a long time.Therefore this fluffy powder must be cancelled insoluble inertia breeze and the easy film forming material of low melting point in the component, and this fluffy powder system must all be made up of water miscible brilliant control agent, raising agent, wetting agent, scorch retarder reconciliation flocculation agent etc.It is to make ammonium nitrate in the mist projection granulating process that raising agent in the composition mainly acts on, and obtains an amount of " microbubble " and " hole ", increases the oil absorbency of multi-hole nitramines and makes ammonium nitrate have the granularity and the free-running property of certain size; Wetting agent can reduce liquid-solid interface tension force, and when molten state ammonium nitrate or water were contacted with the powdery fluffy powder, it was very fast moistening and be dispersed in the water by water or ammonium nitrate mother liquor to quicken the fluffy powder pulvis, is easy to the even granulating of spread when mist projection granulating, plays the aid dispersion effect; Separating flocculation agent also is a kind of water-softening chemicals, plays the ion orphan from effect, can fuse to remove anhydrate middle calcium, magnesium ion, reduces surface tension, and the crystalline substance control agent in forming with protection is to the crystalline substance control effect of ammonium nitrate; Scorch retarder has the hot and anti-incipient scorch performance of anti-height, in order to improve the safety in utilization of fluffy powder in high-temperature fusion attitude ammonium nitrate (170~180 ℃); The design of the anion surfactant of graining control effect is the most key: its main effect is near the irreversible change or the slow variation of the control ammonium nitrate crystalline form ammonium nitrate transformation temperature, improve the brilliant height of ammonium nitrate, have loose stable crystalline forms to keep ammonium nitrate.
According to above-mentioned design, five yuan of powdery fluffy powder systems of a constituent element performance complement of design; Play the crystalline substance control agent of main body crystal grain effect and must adopt water-soluble, high temperature resistant, high diffusibility, and contain polar group-SO 4H ,-SO 3H ,-PO 4The plane configuration anion surfactant of H; Raising agent adopts the organic hydrazonium salt or the inorganic materials of decomposes generation gas, for example p-toluene sulfonyl hydrazide, exsiccated ammonium alum, light calcium carbonate, sodium bicarbonate etc.; Wetting agent adopts powder solid easily by water-moistened material, generally is tensio-active agent, and this class material is: saponin, sodium alkyl benzene sulfonate, polyoxyethylene groups alkyl aryl ether, various permeate agent, nonionic emulsifier, camellia oleosa seed cake powder etc.; The scorch retarder great majority are organic compound, can be divided into nitroso compound class, organic acid and sulfenamide by its chemical structure; Separate flocculation agent and often adopt phosphoric acid salt, this class material is: water-softening chemicalss such as trisodium phosphate, Sodium hexametaphosphate 99, three Sodium polymetaphosphates.
The loosening agent for ammonium nitrate that the present invention has improved is formed (quality %):
40~80 brilliant control agent: sodium lignosulfonate or fatty alcohol-polyoxyethylene ether or methylene dinaphthalene sulphur
Acid sodium or sodium polyacrylate;
16~50 raising agents: Cellmic C 121 or Weathered Sodium Sulfate or bicarbonate of ammonia or 2,4,6-three
Diazanyl-1,3,5-triazines;
2~4 wetting agents: Sodium dodecylbenzene sulfonate or sodium dibutyl naphthalene sulfonate or methylcellulose gum
Or Succinic Acid di-sec-octyl sulfonated bodies;
1.5~4 scorch retarder: phenylformic acid or benzyl naphthalene sulfonic formaldehyde condensation compound or Tetra hydro Phthalic anhydride or
N nitrosodiphenyl amine;
0.5~2 separate flocculation agent: tertiary sodium phosphate or tripoly phosphate sodium STPP or disodium pyrophosphate or SODIUM PHOSPHATE, MONOBASIC.
Best form (quality %) of the present invention is:
60 brilliant control agent: sodium lignosulfonate;
35 raising agents: Cellmic C 121;
2 wetting agents: methylcellulose gum;
2 scorch retarder: benzyl naphthalene sulfonic formaldehyde condensation compound;
1 separates flocculation agent: tripoly phosphate sodium STPP.
The present invention compared with prior art has following advantage:
1 has successfully improved brilliant control techniques and surface wettability technology the agglomeration preventing performance and the water soluble characteristic of fluffy powder effectively.
2 have cancelled the indissoluble water composition in forefathers' ammonium nitrate anticaking agent composition, thereby make the present invention's dissolving fully in water or in the molten state ammonium nitrate, can not cause in use filtering net or prilling spry being stopped up.
3 Nai Gaore of the present invention, its heat decomposition temperature are more than 470 ℃, far above 170~180 ℃ of molten state ammonium nitrate temperature, and 130~160 ℃ of ammonium nitrate mother liquor temperature in the pipeline during also far above the backflow systemic circulation, thereby safe in utilization.
4 are applied in the granulation ammonium nitrate, have improved the easy caking physicals of ammonium nitrate significantly; Adopt that the water slurry method is reinforced to be applied in the multi-hole nitramines, advantage such as make goods have the oil absorbency height, lay up period keeps high free-running property physical condition, and is safe in utilization and with low cost.
Embodiment
1 forms (quality %) by following the best implements:
60 brilliant control agent: sodium lignosulfonate;
35 raising agents: Cellmic C 121;
2 wetting agents: methylcellulose gum;
2 scorch retarder: benzyl naphthalene sulfonic formaldehyde condensation compound;
1 separates flocculation agent: tripoly phosphate sodium STPP.
With tripoly phosphate sodium STPP 10g and methylcellulose gum 20g dry 4h in 80~90 ℃ and 60~70 ℃ of baking ovens respectively, cross the sodium lignosulfonate 600g of 250 μ m sieve 95% then with Cellmic C 121 350g, benzyl naphthalene sulfonic formaldehyde condensation compound 20g and pulverizing back fineness, add together in the double-deck double-stranded stirrer, puddle 30-40min, goods of the present invention are promptly made in discharging.
Utilize the present invention, adding concentration in ammonium nitrate is 0.08%~0.10% o'clock, the loose type granulation ammonium nitrate of making, and outward appearance is pure white, and shatter value is 100% after testing, and average grain intensity is the 13.0N/ particle, moisture content 0.60%, P HValue 6.0, total nitrogen content 34.88%, it is constant to store after three months the product appearance physical condition, and shatter value is 96% (high-quality product shatter value index 〉=80%), does not lump, and is non-sclerous; And do not add the granulation ammonium nitrate of goods of the present invention, store that the goods shatter value has only 10% after three months.
2 press following composition (quality %) implements:
70 brilliant control agent: fatty alcohol-polyoxyethylene ether;
23 raising agents: bicarbonate of ammonia;
3 profit agent: sodium dibutyl naphthalene sulfonate;
2.5 scorch retarder: phenylformic acid;
1.5 separate flocculation agent: tertiary sodium phosphate.
Manufacturing of the present invention is with reference to embodiment 1.
Utilize goods of the present invention, adopt the method for conventional sense pressed powder solubleness in water, detected of the present invention water-solublely, test result is referring to table 1.
Table 1 goods water soluble characteristic
Solubleness in the water, 25 ℃
Example classification sample name data source
g/100g
Comparative example anti-caking agent for ammonium nitrate ZL94107498.6 56.00
Reference example high stability and high heat-proof loosening agent for ammonium nitrate 99114733.2 58.50
Reference example KT anti-hard caking agent France KT company produces 81.02
The loosening agent for ammonium nitrate goods 94.00 of the present invention that embodiment has improved
3 press following composition (quality %) implements:
40 brilliant control agent: sodium polyacrylate;
50 raising agents: 2,4,6-three diazanyls-1,3,5-triazines;
4 wetting agents: Sodium dodecylbenzene sulfonate;
4 scorch retarder: Tetra hydro Phthalic anhydride;
2 separate flocculation agent: disodium pyrophosphate.
Manufacturing of the present invention is with reference to embodiment 1.
Utilize the present invention to prepare the ammonium nitrate performance that the ammonium oil field is used with explosive, test result is with reference to table 2.
Table 2 goods technical feature
Comparative example reference example embodiment
What the common porous grain of performance perameter contained the KT additive makes technical indicator by the present invention
The porous ammonium nitrate of shape ammonium nitrate multi-hole nitramines
Particle is pure white shaped, the hole
The rarer holes of outward appearance void content are pure white, and hole is arranged
The crack is many
Oil absorbency, % 7.50 8.00 8.80 ∽ 9.20 〉=7
Tap density, g/cm 30.84 0.80 ∽, 0.83 0.78 ∽, 0.81 0.73 ∽ 0.86
Average grain intensity, N/ particle 4.50 ∽ 5.00 6.00 ∽ 7.00 10.60 ∽ 11.70 〉=5
4 press following composition (quality %) implements:
80 brilliant control agent: sodium metnylene bis-naphthalene sulfonate;
16 raising agents: Weathered Sodium Sulfate;
2 wetting agents: Succinic Acid di-sec-octyl sulfonated bodies;
1.5 scorch retarder: N nitrosodiphenyl amine;
0.5 separate flocculation agent: SODIUM PHOSPHATE, MONOBASIC.
Adopt thermal analyzer, goods of the present invention have been carried out differential scanning calorimeter (TGA-DTA method), studied the thermolysis collection of illustrative plates of goods of the present invention, test result is referring to table 3
Table 3 goods thermal decomposition performance
Initial heat decomposition temperature, final heat decomposition temperature,
Example classification sample name data source
T 0,℃ T E,℃
Comparative example anti-caking agent for ammonium nitrate ZL94107498.6 211.30 437.80
The high heat-proof loosening agent for ammonium nitrate 99114733.2 250.00 510.20 of reference example
Reference example KT anti-hard caking agent France KT company produces 200.18 416.91
The loosening agent for ammonium nitrate combinations 251.88 513.53 of the present invention that embodiment has improved
As seen from Table 3: goods of the present invention are than forefathers' goods Nai Gaore, and its initial heat decomposition temperature is far above molten state ammonium nitrate temperature (170-180 ℃), so production use safety.

Claims (2)

1 one kinds of water-soluble loosening agent for ammonium nitrate is characterized in that this fluffy powder controls agent, raising agent, wetting agent, scorch retarder by crystalline substance and conciliate flocculation agent and form, and its component by quality % is:
40~80 brilliant control agent
16~50 raising agents
2~4 wetting agents
1.5~4 scorch retarder
0.5~2 separate flocculation agent
Wherein brilliant control agent is selected from a kind of of sodium lignosulfonate or fatty alcohol-polyoxyethylene ether or sodium metnylene bis-naphthalene sulfonate or sodium polyacrylate; Raising agent is selected from Cellmic C 121 or Weathered Sodium Sulfate or bicarbonate of ammonia or 2,4,6-three diazanyls-1,3,5-triazines a kind of; Wetting agent is selected from a kind of of Sodium dodecylbenzene sulfonate or sodium dibutyl naphthalene sulfonate or methylcellulose gum or Succinic Acid di-sec-octyl sulfonated bodies; Scorch retarder is selected from a kind of of phenylformic acid or benzyl naphthalene sulfonic formaldehyde condensation compound or Tetra hydro Phthalic anhydride or N nitrosodiphenyl amine; Separate flocculation agent and be selected from a kind of of tertiary sodium phosphate or tripoly phosphate sodium STPP or disodium pyrophosphate or SODIUM PHOSPHATE, MONOBASIC.
2 fluffy powders according to claim 1 is characterized in that its component by quality % is:
60 brilliant control agent: sodium lignosulfonate;
35 raising agents: Cellmic C 121;
2 wetting agents: methylcellulose gum;
2 scorch retarder: benzyl naphthalene sulfonic formaldehyde condensation compound;
1 separates flocculation agent: tripoly phosphate sodium STPP.
CNB021135711A 2002-04-08 2002-04-08 Improved ammonium nitrate loosening agent Expired - Fee Related CN1192003C (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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CN1192003C true CN1192003C (en) 2005-03-09

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602631B (en) * 2009-07-20 2012-05-23 殷海权 Loose agricultural explosion-proof ammonium nitrate containing water-soluble explosion-proof agent and preparation method thereof
CN102503741B (en) * 2011-10-14 2013-09-18 殷海权 Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity
CN104355827A (en) * 2014-11-05 2015-02-18 青岛锐志农业技术服务有限公司 Slowly-soluble type bio-organic chemical fertilizer and preparation method thereof
CN104591933B (en) * 2015-01-05 2017-05-03 江春华 Modified carbon powder for preparing sulfur-free micro-smoke environment-friendly propellant
CN104671989A (en) * 2015-01-28 2015-06-03 燕山大学 Water-soluble nitro-compound fertilizer anti-blocking agent as well as preparation and using method thereof
CN105254435B (en) * 2015-11-10 2019-04-19 湖北三峡职业技术学院 A kind of a great number of elements Water soluble fertilizer anticaking agent and its Preparation equipment, method and application method
CN107602204B (en) * 2016-07-12 2020-07-24 南京理工大学 A kind of anti-hygroscopic surface modification method of hexadecanol-coated ammonium nitrate
CN108002910A (en) * 2017-12-18 2018-05-08 深圳市芭田生态工程股份有限公司 Reduce the method and fertilizer of compound fertilizer from caking and dusting
CN108243859B (en) * 2017-12-30 2020-10-13 广东红树林生态科技有限公司 Method for rapidly cultivating salt-tolerant Kandelia candel
CN108012909B (en) * 2017-12-30 2020-10-13 广东红树林生态科技有限公司 Cultivation method for improving transplanting survival rate of big seedlings of bruguiera gymnorrhiza

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