CN102503741B - Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity - Google Patents
Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity Download PDFInfo
- Publication number
- CN102503741B CN102503741B CN 201110311198 CN201110311198A CN102503741B CN 102503741 B CN102503741 B CN 102503741B CN 201110311198 CN201110311198 CN 201110311198 CN 201110311198 A CN201110311198 A CN 201110311198A CN 102503741 B CN102503741 B CN 102503741B
- Authority
- CN
- China
- Prior art keywords
- ammonium nitrate
- agents
- agent
- sodium
- forming agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Edible Oils And Fats (AREA)
- Glanulating (AREA)
Abstract
The invention relates to a water-soluble pore-forming agent for improving performances of porous granular ammonium nitrate and is characterized in that the pore-forming agent is composed of foaming agents, penetrating agents, reinforcing agents, dispersing agents, heat resistance agents and solubilizing agents. The invention aims to solve the problems in the prior art that the porous granular ammonium nitrate additive has poor oil absorptivity during practical use, the granulation sprayer is liable to be blocked during production process, the additive deposits on the filter screen are carbonized to cause spontaneous combustion, the imported raw materials have high cost, and the wrapping agent is inconvenient to use. The invention has the following characteristics: all the components of the pore-forming agent dissolve completely in water, which prevents the sprayer from being blocked during granulation process after the pore-forming agent is mixed with molten ammonium nitrate and ensures safety in ammonium nitrate mother liquid large-loop operation. The pore-forming agent is used as an effective additive for preparation of bulky porous granular ammonium nitrate with high oil absorptivity, and is also used as a moisture-proofing and anti-caking additive for preparation of bulky granular ammonium nitrate, bulky crystal ammonium nitrate and bulky nitrates. The amount of addition of the pore-forming agent is 0.08% to 0.12%.
Description
Technical field
The present invention relates to a kind of tensio-active agent be used to improving ammonium nitrate-fuel oil mixture principal constituent oxygenant ammonium nitrate, especially a kind of water-soluble pore former for preparing high oil absorbency free-running property ammonium nitrate.This pore former is comprised of whipping agent, permeate agent, toughener, dispersion agent, heat-resistant agent and solubilizing agent.
Technical background
Ammonium nitrate is a kind of form of industrial ammonium nitrate.Because it has the characteristic of higher oil absorbency and low bulk density, so be widely used as ammonium nitrate-fuel oil mixture and without the main body oxygenant of the low explosive of high explosive composition, be better than emulsification and powder breast explosive based on its economy, handiness and security again, thus modern age ammonium nitrate output in state-owned alarming development.According to incompletely statistics: its output is produced several ten thousand tons per year and is brought up to 2011 and can reach millions of tons from the whole nation of the nineties; And according to China " 12 " planning to greatly develop on-site mixed explosive, make the market of ammonium nitrate that larger development be arranged.But multi-hole nitramines has the inherent defects such as Yi Jingbian, easily moisture absorption, easily phase transformation, salt bridge recrystallization equally, bring great inconvenience and hidden danger, particularly industry and market in urgent need to seek a kind of energy high oil absorbency free-running property ammonium nitrate of preparation and service-strong pore former new technology to the industrial or agricultural use.
Since nearly half a century, scientific and technical personnel had once carried out a large amount of research work to the moistureproof agglomeration preventing performance that improves ammonium nitrate and the pore former of developing ammonium nitrate: 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 the inert powders such as rhombspar to make the anti-hard caking agent of ammonium nitrate, in the use because can not effectively controlling ammonium nitrate crystal conversion DeGrain; Rise the eighties, China's longer-term adopts the acetate patented technology (JP7650898 of Japan, 1978) produce 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 is high, contaminate environment again, and production and application is inconvenient.So conventional art makes goods have that thermoplasticity is poor, granule strength is low, heat decomposition temperature is low, can not effectively control the deficiencies such as ammonium nitrate crystal conversion.The author of modern China patent ZL 94107498.6 finds: adopt the plane configuration anion surfactant as the effective brilliant control agent of ammonium nitrate, be applied in the ammonium nitrate, preventing blocking effect is good.But in actual use, exist incompatible with emulsifying agent and two defectives of generation spontaneous combustion in high-temperature service, in time by Chinese patent (patent No. ZL99114733.2,1999) author improves, high stability and high heat-proof loosening agent for ammonium nitrate have been invented, this patented technology adopts in China many production granulations ammonium nitrate factory, but in actual use in several years, find to exist and easily stop up prilling spry, the systemic circulation process is dangerous and fluffy powder itself is water-soluble bad, and can often cause fluffy powder to be heated for a long time on filtering net can the bonding carbonization and cause the defective such as spontaneous combustion; France KT company has developed the interior interpolation external parcel composite anticaking piece agent of attempting to address the aforementioned drawbacks, also exist to use the problems such as inconvenient, that material cost is high, the goods dust is large, oil absorbency is low, therefore explore provide a kind of can solve security and carry again high performance new pore-forming material become the further technical barrier of solution.
Summary of the invention
The object of the invention is to overcome the deficiency of background technology, must design a kind of in water fully dissolving, Nai Gaore and can improve the pore former of ammonium nitrate oil absorbency, join in the molten state ammonium nitrate, the physicals of multi-hole nitramines is obviously improved, guarantee that again not producing insoluble mashed prod in use procedure stops up prilling spry, stifled exhausted pore former insolubles is bonded in carbonization on the filtering net, and the ammonium nitrate mother liquor big cirle job of guaranteeing to contain pore former can be safe and reliable; In addition, energy substituting import one whipping agent reduces production costs.
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 easily lump defective and improve oil absorbency of multi-hole nitramines, and can be in water fully dissolving and high heat-proof polynary pore former system.Be intended to adopt mist projection granulating to prepare the free-running property pelletizing nitramino or adopt from the water slurry method technique of the multi-hole nitramines of external introduction, make the present invention and in water or in the molten state ammonium nitrate, can dissolve fully and mix, eliminate in technological process producing blocking sprayer, carbonization burning, resting in the pipeline of cycle operation the hidden danger such as easy firing for a long time.Therefore this pore former must be cancelled insoluble inertia breeze and the easy film forming material of low melting point in forefathers' additive component, and this pore former system must all be comprised of water-soluble whipping agent, permeate agent, toughener, dispersion agent, heat-resistant agent and solubilizing agent.The Main Function of the toughener in the composition is to make it and the fused eutectic of ammonium nitrate obtain the crystal of lattice densification, makes goods reduce dust, improves granule strength, reduces goods and is subjected to Transport Vibration to cause the breakage rate of spheroid; Dispersion agent can reduce liquid-solid interface tension force, when molten state ammonium nitrate or water are contacted with pore former, accelerates pore former very fast moistening and be dispersed in water by water or ammonium nitrate mother liquor, is easy to the even granulating of spread when mist projection granulating, plays the aid dispersion effect; Heat-resistant agent has the hot and anti-carbonation properties of anti-height, in order to improve the safety in utilization of pore former in high-temperature molten-state ammonium nitrate (170～180 ℃); The emulsification of solubilizer acts system, increase the effect of the speed of dissolving each other; Wherein the design of whipping agent and permeate agent is the most key: the Main Function of the permeate agent of graining control effect is near irreversible change or the slow variation of the control ammonium nitrate crystalline form porous ammonium nitrate transformation temperature, improve the brilliant height of ammonium nitrate, have loose stable crystalline forms to keep multi-hole nitramines; The keying action of whipping agent is to make ammonium nitrate in the mist projection granulating process, obtains an amount of " microbubble " and " hole ", increases the oil absorbency of multi-hole nitramines and makes ammonium nitrate have granularity and the free-running property of certain size.
According to above-mentioned design, the polynary complete water-soluble powdery pore former system of a constituent element performance complement of design; Whipping agent adopts organic hydrazonium salt or the inorganic materials of decomposes generation gas, such as p-toluene sulfonyl hydrazide, exsiccated ammonium alum, light calcium carbonate, sodium bicarbonate etc.; The permeate agent of graining control effect must adopt water-soluble, high temperature resistant, high diffusibility, and contains polar group-SO
4H ,-SO
3H ,-PO
4The plane configuration anion surfactant of H; Toughener adopts water soluble inorganic substance, and this type of material is: muriate, vitriol and inorganic phosphate; Dispersion 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, camellia oleosa seed cake powder etc.; The heat-resistant agent great majority can be divided into nitroso compound class, organic acid and sulfenamide for having the functionalization auxiliary agent of high heat capacity, difficult to burn by its chemical structure; Solubilizing agent generally adopts nonionic surface active agent, the emulsifying agents soluble in water such as Span-80, Tween-40 and polyethers commonly used.
The composition of the water-soluble pore former of the present invention by quality % is:
30～80 whipping agents: Weathered Sodium Sulfate or sodium bicarbonate or bicarbonate of ammonia or exsiccated ammonium alum
10～40 permeate agents: sodium metnylene bis-naphthalene sulfonate or sodium polyacrylate or dioctyl succinate sodium sulfate or methyl sodiosul foaliphatate
5～15 tougheners: Tai-Ace S 150 or ammonium sulfate or ammonium chloride or phosphoric acid one hydrogen two ammoniums
2～6 dispersion agents: Sodium dodecylbenzene sulfonate or sodium dibutyl naphthalene sulfonate or carboxymethyl cellulose or alkyl phosphate sodium
2～6 heat-resistant agents: Whitfield's ointment or adjacent sour front three phenyl ester or contain halophosphate or decabromodiphenyl oxide
1～3 solubilizing agent: sorbitan monooleate or polyethers L31 or modified soybean phosphide or fatty alcohol-polyoxyethylene ether
Best composition of the present invention by quality % is:
50 whipping agents: Weathered Sodium Sulfate;
30 permeate agents: sodium metnylene bis-naphthalene sulfonate;
10 tougheners: Tai-Ace S 150;
4 dispersion agents: Sodium dodecylbenzene sulfonate;
4 heat-resistant agents: Whitfield's ointment;
2 solubilizing agent: fatty alcohol-polyoxyethylene ether.
Preparation method's design of the present invention: at first with heat-resistant agent, dispersion agent and solubilizing agent oven dry, after whipping agent is crushed to the regulation fineness in ball mill or pulverizer, then in the quality % ratio that forms, whipping agent, permeate agent, toughener, dispersion agent, heat-resistant agent and solubilizing agent with metering, add in the stirrer together and puddle, can make pulverulent water-soluble pore former of the present invention.
The present invention compared with prior art has advantages of as follows:
1 successfully introduces the permeate agent of inorganic materials whipping agent and graining control effect in the pore former component, has effectively improved the shatter value of ammonium nitrate within storage period and has improved the goods oil absorbency.
2 have cancelled the indissoluble water composition of forefathers' multi-hole nitramines additive in forming, thereby the fully dissolving in water or in the molten state ammonium nitrate that makes the present invention, can not cause in use procedure filtering net or prilling spry being stopped up.
3 Nai Gaore of the present invention, its initial heat decomposition temperature are more than 270 ℃, 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 production and application safety.
4 the present invention add concentration little (0.1%), can cancel the external parcel operation, make to produce easy and low production cost.
Embodiment
1 forms (quality %) by following the best implements:
50 whipping agents: Weathered Sodium Sulfate
30 permeate agents: sodium metnylene bis-naphthalene sulfonate
10 tougheners: Tai-Ace S 150
4 dispersion agents: Sodium dodecylbenzene sulfonate
4 heat-resistant agents: Whitfield's ointment
2 solubilizing agent: fatty alcohol-polyoxyethylene ether
Preparation of the present invention: with Whitfield's ointment 40g, Sodium dodecylbenzene sulfonate 40g and fatty alcohol-polyoxyethylene ether 20g dry 4h in 60～70 ℃ of baking ovens respectively, then fineness after sodium metnylene bis-naphthalene sulfonate 300g, Tai-Ace S 150 100g and the pulverizing is crossed the Weathered Sodium Sulfate 500g of 250 μ m sieve 95%, add together in the stirrer of double-layer double spiral structure, puddle 25～30min, goods of the present invention are namely made in discharging.
Utilize the present invention, adopt the high tower atomizing granulating technology, when interpolation concentration is 0.08%～0.12% in molten state ammonium nitrate, the common granulation ammonium nitrate of the loose type of making, outward appearance is pure white, presses the GB2945-89 technological standard, detecting shatter value is 100%, and average grain intensity is the 13.0N/ particle, moisture content 0.60%, pH value 6.2, total nitrogen content 34.88% is stored after three months the product appearance physical condition constant, and shatter value is 97% (high-quality product shatter value index 〉=80%), do not lump, non-sclerous;
2 press following composition (quality %) implements:
80 whipping agents: sodium bicarbonate
10 permeate agents: sodium polyacrylate
5 tougheners: ammonium sulfate
2 dispersion agents: sodium dibutyl naphthalene sulfonate
2 heat-resistant agents: adjacent sour front three phenyl ester
1 solubilizing agent: sorbitan monooleate
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
3 press following composition (quality %) implements:
30 whipping agents: bicarbonate of ammonia
40 permeate agents: dioctyl succinate sodium sulfate
15 tougheners: ammonium chloride
6 dispersion agents: carboxymethyl cellulose
6 heat-resistant agents: contain halophosphate
3 solubilizing agent: polyethers L31
Manufacturing of the present invention is with reference to embodiment 1.
Utilize the present invention, the technical process that the high tower mist projection granulating that adopts French KT company to provide prepares ammonium nitrate, the present invention and water are mixed with 35% water slurry solution, with 95% molten state ammonium nitrate mother liquor, behind prilling tower top slot mixing, through mist projection granulating, not outer coated coating agent, drying, obtain mining ammonium nitrate-fuel oil mixture by screening with the pure white ammonium nitrate of outward appearance, press ZB G21007-90 technological standard, the test performance result is referring to table 2.
Table 2 goods technical feature
4 press following composition (quality %) implements:
60 whipping agents: exsiccated ammonium alum
20 permeate agents: methyl sodiosul foaliphatate
8 tougheners: phosphoric acid one hydrogen two ammoniums
5 dispersion agents: alkyl phosphate sodium
4.5 heat-resistant agent: decabromodiphenyl oxide
2.5 solubilizing agent: modified soybean phosphide
Adopt the linkage analysis (TGA-DTA method) of the thermogravimetric analysis of Q600 type differential scanning calorimetric, studied the kinetics of thermal decomposition of goods of the present invention, the heat decomposition temperature detected result is referring to table 3.
Table 3 goods thermal decomposition performance
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 ℃), therefore the production and application process safety.
Claims (2)
1. the water-soluble pore former of porous and granular ammonium nitrate is characterized in that this pore former is comprised of whipping agent, permeate agent, toughener, dispersion agent, heat-resistant agent and solubilizing agent, and its component by quality % is:
30～80 whipping agents: Weathered Sodium Sulfate or sodium bicarbonate or bicarbonate of ammonia or exsiccated ammonium alum;
10～40 permeate agents: sodium metnylene bis-naphthalene sulfonate or sodium polyacrylate or dioctyl succinate sodium sulfate or methyl sodiosul foaliphatate;
5～15 tougheners: Tai-Ace S 150 or ammonium sulfate or ammonium chloride or phosphoric acid one hydrogen two ammoniums;
2～6 dispersion agents: Sodium dodecylbenzene sulfonate or sodium dibutyl naphthalene sulfonate or carboxymethyl cellulose or alkyl phosphate sodium;
2～6 heat-resistant agents: Whitfield's ointment or adjacent sour front three phenyl ester or contain halophosphate or decabromodiphenyl oxide;
1～3 solubilizing agent: sorbitan monooleate or polyethers L31 or modified soybean phosphide or fatty alcohol-polyoxyethylene ether.
2. pore former according to claim 1 is characterized in that its component by quality % is:
50 whipping agents: Weathered Sodium Sulfate;
30 permeate agents: sodium metnylene bis-naphthalene sulfonate;
10 tougheners: Tai-Ace S 150;
4 dispersion agents: Sodium dodecylbenzene sulfonate;
4 heat-resistant agents: Whitfield's ointment;
2 solubilizing agent: fatty alcohol-polyoxyethylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110311198 CN102503741B (en) | 2011-10-14 | 2011-10-14 | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110311198 CN102503741B (en) | 2011-10-14 | 2011-10-14 | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102503741A CN102503741A (en) | 2012-06-20 |
| CN102503741B true CN102503741B (en) | 2013-09-18 |
Family
ID=46215892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110311198 Expired - Fee Related CN102503741B (en) | 2011-10-14 | 2011-10-14 | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102503741B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113173B (en) * | 2013-03-14 | 2015-04-15 | 太原海力丰科技发展有限公司 | Composite additive for high-strength high temperature and high moisture resisting porous granular nitramine |
| RU2738268C1 (en) * | 2020-06-18 | 2020-12-11 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method for production of mixed explosive substance |
| CN113045368A (en) * | 2021-03-31 | 2021-06-29 | 神华准格尔能源有限责任公司 | Ammonium nitrate fuel oil explosive containing water-melting active additive and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233607A (en) * | 1999-03-25 | 1999-11-03 | 蔡剑斌 | Loosening agent for ammonium nitrate with high stability and high thermal stability |
| CN1280973A (en) * | 2000-06-29 | 2001-01-24 | 蔡剑斌 | Low-density snow-like ammonium nitrate and its preparing process |
| CN1289718A (en) * | 2000-10-12 | 2001-04-04 | 蔡剑斌 | Free-particles loosening agent for ammonium nitrate |
| CN1374279A (en) * | 2002-04-08 | 2002-10-16 | 殷海权 | Improved ammonium nitrate loosening agent |
| CN1443732A (en) * | 2003-04-28 | 2003-09-24 | 殷海权 | Improved ammonium nitrate leavening agent |
| CN101948363A (en) * | 2010-09-29 | 2011-01-19 | 殷海权 | High-looseness high-sensitivity ammonium nitrate fuel oil explosive for explosion welding and preparation method thereof |
-
2011
- 2011-10-14 CN CN 201110311198 patent/CN102503741B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233607A (en) * | 1999-03-25 | 1999-11-03 | 蔡剑斌 | Loosening agent for ammonium nitrate with high stability and high thermal stability |
| CN1280973A (en) * | 2000-06-29 | 2001-01-24 | 蔡剑斌 | Low-density snow-like ammonium nitrate and its preparing process |
| CN1289718A (en) * | 2000-10-12 | 2001-04-04 | 蔡剑斌 | Free-particles loosening agent for ammonium nitrate |
| CN1374279A (en) * | 2002-04-08 | 2002-10-16 | 殷海权 | Improved ammonium nitrate loosening agent |
| CN1443732A (en) * | 2003-04-28 | 2003-09-24 | 殷海权 | Improved ammonium nitrate leavening agent |
| CN101948363A (en) * | 2010-09-29 | 2011-01-19 | 殷海权 | High-looseness high-sensitivity ammonium nitrate fuel oil explosive for explosion welding and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102503741A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113173B (en) | Composite additive for high-strength high temperature and high moisture resisting porous granular nitramine | |
| CN101659581A (en) | Anti-caking additive with slow release effect | |
| CN102503741B (en) | Water-soluble pore-forming agent used for bulky porous granular ammonium nitrate with high oil absorptivity | |
| US2590054A (en) | Process of producing ammonium nitrate-containing composition | |
| CN103896682A (en) | Instant macroelement water-soluble fertilizer and preparation method thereof | |
| ES2674718T3 (en) | Ammonium nitrate granule and method for preparing it | |
| CN1192003C (en) | Improved ammonium nitrate loosening agent | |
| CN100572343C (en) | Ammonium nitrate modifier and preparation method thereof | |
| CN101417909B (en) | Powdery ammonium nitrate explosives and preparation method thereof | |
| RU2650162C2 (en) | Raw material of composite pellets used in kiln phosphoric acid process and forming method therefor | |
| CN1107663C (en) | Loosening agent for ammonium nitrate with high stability and high thermal stability | |
| CN100425580C (en) | Method and equipment for preparing powder explosive | |
| CN107417407A (en) | A kind of powdery potassium nitrate anticaking agent and preparation method thereof | |
| CN101857516A (en) | Micro-pore firework powder capable with improved fire ignition and transfer properties and preparation method thereof | |
| CN1137071C (en) | Process for preparing loose ammonium nitrate crystals using anti-hardening agent | |
| CN102603441A (en) | Swelling agent for swelling ammonium nitrate explosive | |
| CN102850150B (en) | The powder porous ammonium nitrate explosive of ternary component and manufacture method thereof and using method | |
| CN102115352B (en) | Ammonium nitrate modifier | |
| CN102428921A (en) | Clodinafop-propargyl water dispersible granule and preparation method thereof | |
| CN101328098B (en) | Solution state modified ammonium nitrate fuel explosive and preparation thereof | |
| CN1321949C (en) | Rocky powdery ammonium nitrate explosive with no stibium, and preparation method | |
| CN107551444A (en) | A kind of powder extinguishing agent and preparation method thereof | |
| CN102311296B (en) | Anti-hardener for high-stability crystal ammonium nitrate without demulsification | |
| CN103787800A (en) | Method for preparing ammonium nitrate composite explosive by using organic waste | |
| CN103210912B (en) | Ring worm hydrazides water dispersible granules and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130918 Termination date: 20181014 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |