CN1280973A - Low-density snow-like ammonium nitrate and its preparing process - Google Patents
Low-density snow-like ammonium nitrate and its preparing process Download PDFInfo
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- CN1280973A CN1280973A CN 00113070 CN00113070A CN1280973A CN 1280973 A CN1280973 A CN 1280973A CN 00113070 CN00113070 CN 00113070 CN 00113070 A CN00113070 A CN 00113070A CN 1280973 A CN1280973 A CN 1280973A
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- ammonium nitrate
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
A low-density snow-like ammonium nitrate used as N fertilizer or industrial explosive is prepared from crystalline ammonium nitrate and composite puffing agent containing cation and anion compounded surfactant through adding said puffing agent to 90-92% mother liquid of ammonium nitrate to obtain the product. Its advantages are simple process and high safety. The product has stack density of 0.34-0.42 g/cu.cm, high free flowability and long storage period.
Description
The present invention relates to a kind of ammonium nitrate that is used for agriculture nitrogen fertilizer and industrial explosive master composition chlorizating agent and preparation method thereof, particularly a kind of suitable preparation does not have low-density snow-like ammonium nitrate of terraced bulking ammonium nitrate explosive and preparation method thereof.This low-density snow-like ammonium nitrate is made up of crystalline powder ammonium nitrate and duplex baking powder.
That settled modern mine engineering explosion is used, by the powdery rock dynamite that ammonium nitrate (AN) and tritonal (TNT) are formed as main component, remain the principal item of current industrial explosive, and widespread use.But also have two big problems: contain the TNT of larger proportion in (1) such explosive, its toxicity is very big, both is detrimental to health in manufacturing and use, again contaminate environment.(2) main composition ammonium nitrate have easy water absorbability, with temperature morphotrophy, salt bridge recrystallization be subjected to heavily to push down physical property such as the easy concreteness of particulate, make industrial explosive easily moisture absorption, caking in storing and using, influence blast performance, even inefficacy.The problems referred to above become to be badly in need of solving and long-term unsolved technical barrier.
The eighties, Chinese patent ZL91107051.6 (1992) succeeds in developing the nothing ladder bulking ammonium nitrate explosive that contains bulk ammonium nitrate, do not contain TNT, characteristics such as low density, specific surface big (for four times of common ammonium nitrate specific surface), hole are many because bulk ammonium nitrate has, out-of-shape, low water absorbability and autosensibilization, so made the nothing ladder bulking ammonium nitrate explosive that does not contain prevented from caking in the TNT, storage period, blast performance good, low-cost (per ton save 200 yuan of costs), for a new technological approaches has been opened up in the development and the development of industrial explosive.But this technology remains in actual application in following problem and must solve: implement in industrial explosive factory (1) preparation of the bulk ammonium nitrate of low density at present, because all industrial explosive factories do not produce the production unit of this kind ammonium nitrate, so it is costly newly to design a production line of producing ten thousand tons of bulk ammonium nitrates per year, and need about 2 years found the factory and time installation.When (2) on the newly-built bulk ammonium nitrate production line of industrial explosive factory, going into operation, must adopt solid ammonium nitrate, in dissolving tank, add entry and dissolve again,, must bring defectives such as product cost height, fuels and energy consumption are big with the preparation ammonium nitrate mother liquor as raw material.Defectives such as (3) forefathers develop the bulking meterial of selecting for use, exist surfactant properties single, cost an arm and a leg, and the expanded ammonium nitrate process for making is strict, and the ammonium nitrate of puffing easily hardens, hole is few.How to solve the problem that prior art exists, accelerate the new variety industrial explosive--do not have the tempo of terraced bulking ammonium nitrate explosive, become current low-density snow-like ammonium nitrate technical field technical barrier anxious to be solved.
The objective of the invention is to overcome background technology has deficiency, and design provides a kind of low-density snow-like ammonium nitrate preparation method.Do not adopt the commodity solid ammonium nitrate to make raw material, and provide a kind of knot product ammonium nitrate that makes at storage period prevented from caking, good shatter value, production and the novel puffing material easy to use, safe of maintenance.
The present invention design: in the low-density snow-like ammonium nitrate of design is formed, add by cationic and anionic surfactant and other additive compound and make performance complement, with low cost, the polynary duplex baking powder system that can solve the ammonium nitrate crystals inherent defect.At the crystalline structure and the physical property of ammonium nitrate crystals, this polynary duplex baking powder must be made up of whipping agent, dispersion agent, hydrophober, softening agent and dewatering agent.It is to make ammonium nitrate crystals in vacuum decompression crystallization process that whipping agent in the composition mainly acts on, and obtains an amount of " microbubble " and " hole ", thereby can reduce the crystalline density of ammonium nitrate significantly.The main effect of dispersion agent is to have adopted in active gene and the ammonium nitrate molecule ammonium ion similar tensio-active agent on structure and profile, thereby make ammonium nitrate from the solution that contains this material during crystallization, active group is attached on the ammonium nitrate interface, make crystal generate bulk needle-like or the crystallization of dendroid ammonium nitrate, play and improve the effect of goods shatter value; Hydrophober mainly plays moisture-proof role, prevents the intrusion of ambient moisture, and improves the outward appearance commodity of goods; The cooperation of dewatering agent, at goods in storage period, the moisture that can absorb in the ammonium nitrate forms similar Mg (NO based on it
3)
26H
2The O crystalline hydrate, this dehydration has strengthened the anti-caking ability of goods; Softening agent can reduce the efflorescence degree of goods, avoids the goods dust to discharge from the crystallizer vacuum system, and softening agent can also improve the oleophylic ability of goods, also can reduce the goods cost.Be that the design of anion surfactant of main cats product and graining control effect is the most key by playing foaming effect wherein: complexed surfactant overcomes the shortcoming of single anion type or cationic surfactant, the electrically interaction between the opposite surfaces promoting agent ion, strengthened surperficial activity, the surface energy of more effective reduction AN, make the hydrophober gene in the more intensive hydrophobic membrane of the peripheral formation of AN particle, thereby more effectively stoped the water in air molecule to enter in the AN particle, improved the anti-moisture absorption energy of goods greatly.
According to above-mentioned design, designed the polynary duplex baking powder system of a constituent element performance complement; The whipping agent that plays expanded effect must adopt the cats product of belt length alkyl group amine; The dispersion agent that plays the brilliant control effect of main body must adopt contain polar group-COOH ,-SO
4H ,-SO
3H ,-PO
4The plane configuration anion surfactant of H; Hydrophober adopts the easy film forming material of low melting point, and this material mainly is longer chain fatty acid and its esters, polyester etc.; Dewatering agent is selected the anhydrous inorganic salts that can play dehydration for use; Softening agent adopts less, the lipophilic cheap material of hydrophile-lipophile balance value (HLB value), and this class material is pitch, aromatic hydrocarbons mineral oil, alkane mineral oil, wax, vaseline etc.
It is as follows that duplex baking powder of the present invention is formed (in quality %):
50 ∽, 80 whipping agents: octadecyl primary amine or primary octadecylamine acetate or octadecyl trimethylammonium
Ammonium chloride or cetyl trimethylammonium bromide
5 ∽, 15 dispersion agents: carboxymethyl cellulose or sodium methylene bis-naphthalene sulfonate or cellulose sulfuric acid ester
Sodium salt or methylene radical benzyl naphthalene sodium sulfonate
5 ∽, 15 hydrophober: high 18 carbon stearic acid or polyester or stearic acid or cerium stearate
5 ∽, 10 softening agent: Vaseline or ceresine or microcrystalline wax or compound wax
5 ∽, 10 dewatering agents: sal epsom or nickelous nitrate or Tai-Ace S 150 or magnesium nitrate
Best composition of the present invention (in quality %) is as follows:
60 whipping agents: octadecyl trimethyl ammonium chloride
15 dispersion agents: carboxymethyl cellulose
10 hydrophober: cerium stearate
10 softening agent: microcrystalline wax
5 dewatering agents: sal epsom
The preparation method of low-density snow-like ammonium nitrate design among the present invention: adopt present fertilizer plant to produce the traditional vacuum decompression crystallizer of crystalline powder ammonium nitrate, the concentration that directly adopt on the crystallization ammonium nitrate production line, obtains from dual circulation is the ammonium nitrate mother liquor of 90% ∽ 92%, add a small amount of duplex baking powder, crystallization drying under the high vacuum reduced pressure can make low-density snow-like shape ammonium nitrate.
According to above-mentioned design, low-density snow-like ammonium nitrate preparation method and the step implementing the present invention and design are: the duplex baking powder (add-on is 0.1% ∽ 0.3% of treatment of nitric acid ammonium quality) that at first adds metering in crystallizer, inhaled concentration is the metering ammonium nitrate mother liquor of 90% ∽ 92% under negative pressure then, mixeding liquid temperature is generally 135 ℃ of 120 ∽ in the crystallizer, and release mixes and stirs 5min then; Stop at last stirring, the rapid expanded crystallization of material in the rapid vacuumizing, machine, vacuum tightness is 0.07 ∽ 0.095MPa during crystallization, crystallization time of drying is 5 ∽ 15min, promptly gets the low-density snow-like ammonium nitrate of moisture content≤0.3 (in quality %).
If (stacks density is 0.5 ∽ 0.7g/cm to make the anti-sclerosis of common loose type ammonium nitrate crystals
3), should not stop to carry out the operation of vacuum decompression crystallization under the agitation condition.
It is as follows that the present invention prepares the optimum process condition of low-density snow-like ammonium nitrate:
Batch processing ammonium nitrate mother liquor quality 800kg
Ammonium nitrate mother liquor concentration 90% ∽ 92%
Additive adds concentration 0.15%
Crystallization vacuum tightness 0.095MPa
115 ℃ of ammonium nitrate mother liquor temperature 110 ∽
120 ℃ of vacuum crystallization interior technological temperatures on opportunity
Vacuum decompression 8min time of drying
The present invention compared with prior art has the following advantages:
It is reasonable that 1 the present invention makes the process implementing technological approaches of low-density snow-like ammonium nitrate: on the ammonium nitrate crystals production line, directly adopting concentration is the ammonium nitrate mother liquor of 90% ∽ 92%, adds a small amount of duplex baking powder, makes low-density snow-like shape ammonium nitrate.This method helps industrializing implementation and production in enormous quantities, both made full use of existing installation for ammonium nitrate factory, developed the low-density snow-like ammonium nitrate of a no terraced expanded explosive demand, again for industrial explosive factory has saved investment and time, so the industrialization promotion using value is arranged.
2 successfully introduce negative and positive two class tensio-active agents raising agent simultaneously forms, and is added into auxiliary agents such as hydrophober, softening agent, makes the duplex baking powder of high comprehensive performance.
3 are applied in the ammonium nitrate crystals, have significantly improved the physicals of ammonium nitrate crystals, make that specific surface is big, hole is many, low density, free-running property are good, good heat stability and storage period long flakes ammonium nitrate.
Specific embodiments of the invention are as follows: embodiment 1
(in quality %) is as follows by optimum formula of the present invention:
99.85 ammonium nitrate crystals
0.15 duplex baking powder
Wherein duplex baking powder is formed (in quality %) enforcement by following the best:
60 whipping agents: octadecyl trimethyl ammonium chloride
15 dispersion agents: carboxymethyl cellulose
10 hydrophober: cerium stearate
10 softening agent: microcrystalline wax
5 dewatering agents: sal epsom
(1) preparation of duplex baking powder: sal epsom 50g and carboxymethyl cellulose 150g are dried by the fire 4h respectively in 100 ℃ of 90 ∽ and 70 ℃ of baking ovens of 60 ∽, cross cerium stearate 100g and the microcrystalline wax 100g of 250 μ m sieve more than 80% with octadecyl trimethyl ammonium chloride 600g and pulverizing back fineness then, add together in the double-deck double-stranded stirrer, after puddling 30 ∽ 40min, the powdery duplex baking powder is promptly made in discharging.
(2) manufacturing of the present invention: take by weighing the 1.2kg duplex baking powder, add above-mentioned metering duplex baking powder from the crystallizer charge cavity; Inhaled concentration is the ammonium nitrate mother liquor (the about 800kg of ammonium nitrate quality) of 90% ∽ 92% under negative pressure, under agitation is warming up to 120 ℃, stirs 5min, and ammonium nitrate and raising agent are mixed; Stop then stirring, rapid vacuumizing should negative pressure reach 0.09MPa in 1 ∽ 2min, the interior rapid expanded crystallization of material of crystallizer this moment, keep vacuum-drying 8min, promptly make the good flakes ammonium nitrate of low density, free-running property of water content≤0.3 (in quality %).
Utilize the performance of the low-density snow-like ammonium nitrate that above-mentioned manufacture method makes, its outward appearance is pure white, and bulk good, purity is 99.75%, moisture 0.16%, bulk density 0.40g/cm
3, it is good to store after 12 months the product appearance physical condition, and shatter value is 95%, does not lump, and is non-sclerous.
Embodiment 2
(in quality %) is as follows by prescription of the present invention:
99.90 ammonium nitrate crystals
0.10 duplex baking powder wherein duplex baking powder is implemented by following composition (in quality %):
70 whipping agents: primary octadecylamine acetate
5 dispersion agents: methylene radical benzyl naphthalene sodium sulfonate
15 hydrophober: high 18 carbon stearic acid
5 softening agent: ceresine
5 dewatering agents: nickelous nitrate
The present invention makes with reference to embodiment 1
The low-density snow-like ammonium nitrate that utilizes the present invention to make, with compounded oil, wood powder (the quality proportioning is: low-density snow-like ammonium nitrate 92.0%, compounded oil 4.0%, wood powder 4.0%), heat is mixed the performance of the nothing ladder rock expanded ammonium nitrate explosive of making in wheel roller, and test result is referring to table 1.
Table 1 goods technical feature
Embodiment 3
| Performance perameter | Make the measured value of no terraced expanded explosive by the present invention | Technical indicator |
| Moisture, % charge density, g/cm 3Explosion velocity, m/s brisance, mm gap distance, cm | ????0．18 ????0．86∽0．93 ????3802 ????15．7 ????6 | ????≤0．3 ????0．85∽0．95 ????≥3200 ????≥12 ????≥4 |
(in quality %) is as follows by prescription of the present invention:
99.80 ammonium nitrate crystals
0.20 duplex baking powder
Wherein duplex baking powder is implemented by following composition (in quality %):
50 whipping agents: octadecyl primary amine
15 dispersion agents: cellulose sulfate ester sodium salt
15 hydrophober: polyester
10 softening agent: compound wax
10 dewatering agents: Tai-Ace S 150
Manufacturing of the present invention is with reference to embodiment 1
Adopt thermal analyzer, goods of the present invention have been carried out differential scanning calorimetric analysis (DSC), studied the thermolysis collection of illustrative plates of duplex baking powder and low-density snow-like ammonium nitrate, test result is referring to table 2.
Table 2 DSC test-results
| The example classification | The sample title | Data Source | The initial heat decomposition temperature of T ℃ | The final heat decomposition temperature of T | TestDate |
| Comparative example embodiment comparative example reference example embodiment comparative example embodiment | The not expanded ammonium nitrate crystals low-density snow-like ammonium nitrate of the bulk ammonium nitrate low-density snow-like ammonium nitrate of the not expanded crystallization ammonium nitrate of leavening agent duplex baking powder duplex baking powder lightweight | ZL91 1 07051.6 goods of the present invention goods contrast test of the present invention ZL91 1 07051.6 goods control sample of the present invention goods of the present invention | ?176．35 ?199．95 ?181．5 | ?418．3 ?530．84 ?527．5 ?248．2 ?250．2 ?256．7 ?271．43 ?275．19 | ?1992 ?1998．6 ?2000．2 ?1997 ?1997 ?1997 ?2000．2 ?2000．2 |
As seen from Table 2: goods duplex baking powder of the present invention and contain the excellent heat resistance of the low-density snow-like ammonium nitrate of duplex baking powder than forefathers goods, so the technological temperature of the heat decomposition temperature of duplex baking powder when making low-density snow-like ammonium nitrate is production use safety.
Claims (6)
1 one kinds of low-density snow-like ammonium nitrates as agriculture nitrogen fertilizer or industrial explosive master composition oxygenant, this low-density snow-like ammonium nitrate is made up of crystalline powder ammonium nitrate and duplex baking powder.It is characterized in that on solid crystal ammonium nitrate production line directly adopting concentration is the ammonium nitrate mother liquor of 90% ∽ 92%, add the duplex baking powder of being made up of cationic and anionic surfactant etc., make low-density snow-like ammonium nitrate, its prescription (in quality %) is:
99.7 ∽ 99.9 ammonium nitrate crystals
0.1 ∽ 0.3 duplex baking powder
2 low-density snow-like ammonium nitrates according to claim 1 is characterized in that optimum formula (in quality %) is:
99.85 ammonium nitrate crystals
0.15 duplex baking powder
3 low-density snow-like ammonium nitrates according to claim 1 is characterized in that duplex baking powder is made up of whipping agent, dispersion agent, hydrophober, softening agent and dewatering agent.Wherein whipping agent is selected from a kind of of kiber alkyl amine or primary amine acetate or cats products such as octadecyl trimethyl ammonium chloride or double hexadecyl trimethylammonium bromide; Dispersion agent is selected from a kind of of carboxymethyl cellulose or methylene radical benzyl naphthalene sodium sulfonate or anion surfactants such as methylene-bis naphthalene acid sodium or cellulose sulfate ester sodium salt; Hydrophober is selected from a kind of of the hard ester acid of high 18 carbon or polyester or stearic acid or cerium stearate: softening agent is selected from a kind of of Vaseline or ceresine or microcrystalline wax or compound wax; Dewatering agent is selected from a kind of of sal epsom or nickelous nitrate or Tai-Ace S 150 or magnesium nitrate.Its duplex baking powder component proportioning (in quality %) is:
50 ∽, 80 whipping agents
5 ∽, 15 dispersion agents
5 ∽, 15 hydrophober
5 ∽, 10 softening agent
5 ∽, 10 dewatering agents
4 low-density snow-like ammonium nitrates according to claim 1 is characterized in that wherein a kind of composition of duplex baking powder, and each component proportioning (in quality %) is:
60 whipping agents: octadecyl trimethyl ammonium chloride
15 dispersion agents: carboxymethyl cellulose
10 hydrophober: cerium stearate
10 softening agent: microcrystalline wax
5 dewatering agents: sal epsom
5 one kinds of methods of making the described low-density snow-like ammonium nitrate of claim 1, it is characterized in that adopting fertilizer plant to produce the vacuum crystallization equipment of crystalline powder ammonium nitrate, utilize directly that concentration is the ammonium nitrate mother liquor of 90% ∽ 92% in the ammonium nitrate crystals production process, and add simultaneously by cationic and anionic surfactant compound raising agent (add-on is 0.10% ∽ 0.3% of treatment of nitric acid ammonium quality), the CONTROL PROCESS temperature is 135 ℃ of 120 ∽, expanded crystallization under vacuum decompression then, vacuum tightness is 0.070 ∽ 0.095MPa during crystallization, the explosion puffing drying time is 5 ∽ 15min, makes low density (the 0.34 ∽ 0.42g/cm of requirement thus
2), the system hole is many, the flakes ammonium nitrate of moisture content≤0.3 (in quality %).
The preparation method of 6 low-density snow-like ammonium nitrates according to claim 5 when it is characterized in that the vacuum decompression crystallization is dry, must stop stirring operation, otherwise goods are the anti-sclerosis of the loose type ammonium nitrate crystals of the similar common crystalline powder ammonium nitrate of tap density.
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|---|---|---|---|
| CN 00113070 CN1280973A (en) | 2000-06-29 | 2000-06-29 | Low-density snow-like ammonium nitrate and its preparing process |
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|---|---|---|---|
| CN 00113070 CN1280973A (en) | 2000-06-29 | 2000-06-29 | Low-density snow-like ammonium nitrate and its preparing process |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311296A (en) * | 2011-08-08 | 2012-01-11 | 殷海权 | Anti-hardener for high-stability crystal ammonium nitrate without demulsification |
| CN102336618A (en) * | 2010-07-27 | 2012-02-01 | 新时代(济南)民爆科技产业有限公司 | Liquid-mixture expander for expanded ammonium nitrate explosive |
| CN102491860A (en) * | 2011-11-24 | 2012-06-13 | 新疆天河化工有限公司 | On-site mixed and expanded ammonium nitrate explosive and production method thereof |
| CN102503741A (en) * | 2011-10-14 | 2012-06-20 | 殷海权 | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity |
| CN102515987A (en) * | 2011-12-07 | 2012-06-27 | 雅化集团三台化工有限公司 | High-performance swelling agent for expanded ammonium nitrate explosive and use method thereof |
| CN102557845A (en) * | 2010-12-31 | 2012-07-11 | 新时代(济南)民爆科技产业有限公司 | Expanded ammonium nitrate explosive and preparation process thereof |
| CN102603441A (en) * | 2012-03-15 | 2012-07-25 | 谢斌 | Swelling agent for swelling ammonium nitrate explosive |
| CN102731212A (en) * | 2012-07-10 | 2012-10-17 | 湖北富邦科技股份有限公司 | Granulation anticaking multifunctional assistant for diammonium phosphate |
| CN102924196A (en) * | 2012-12-03 | 2013-02-13 | 山东天宝化工股份有限公司 | Expanded ammonium nitrate explosive and method for preparing same |
| CN103755446A (en) * | 2013-12-21 | 2014-04-30 | 安徽颍上县汇通助剂有限公司 | Compound chemical fertilizer additive |
-
2000
- 2000-06-29 CN CN 00113070 patent/CN1280973A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336618A (en) * | 2010-07-27 | 2012-02-01 | 新时代(济南)民爆科技产业有限公司 | Liquid-mixture expander for expanded ammonium nitrate explosive |
| CN102557845A (en) * | 2010-12-31 | 2012-07-11 | 新时代(济南)民爆科技产业有限公司 | Expanded ammonium nitrate explosive and preparation process thereof |
| CN102311296A (en) * | 2011-08-08 | 2012-01-11 | 殷海权 | Anti-hardener for high-stability crystal ammonium nitrate without demulsification |
| 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 |
| CN102503741A (en) * | 2011-10-14 | 2012-06-20 | 殷海权 | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity |
| CN102491860A (en) * | 2011-11-24 | 2012-06-13 | 新疆天河化工有限公司 | On-site mixed and expanded ammonium nitrate explosive and production method thereof |
| CN102515987A (en) * | 2011-12-07 | 2012-06-27 | 雅化集团三台化工有限公司 | High-performance swelling agent for expanded ammonium nitrate explosive and use method thereof |
| CN102515987B (en) * | 2011-12-07 | 2015-03-18 | 雅化集团三台化工有限公司 | High-performance swelling agent for expanded ammonium nitrate explosive and use method thereof |
| CN102603441A (en) * | 2012-03-15 | 2012-07-25 | 谢斌 | Swelling agent for swelling ammonium nitrate explosive |
| CN102731212A (en) * | 2012-07-10 | 2012-10-17 | 湖北富邦科技股份有限公司 | Granulation anticaking multifunctional assistant for diammonium phosphate |
| CN102731212B (en) * | 2012-07-10 | 2013-11-20 | 湖北富邦科技股份有限公司 | Granulation anticaking multifunctional assistant for diammonium phosphate |
| CN102924196A (en) * | 2012-12-03 | 2013-02-13 | 山东天宝化工股份有限公司 | Expanded ammonium nitrate explosive and method for preparing same |
| CN103755446A (en) * | 2013-12-21 | 2014-04-30 | 安徽颍上县汇通助剂有限公司 | Compound chemical fertilizer additive |
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