CN1084152A - Solid (powdery) emulsion explosive - Google Patents
Solid (powdery) emulsion explosive Download PDFInfo
- Publication number
- CN1084152A CN1084152A CN 92110219 CN92110219A CN1084152A CN 1084152 A CN1084152 A CN 1084152A CN 92110219 CN92110219 CN 92110219 CN 92110219 A CN92110219 A CN 92110219A CN 1084152 A CN1084152 A CN 1084152A
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- Prior art keywords
- explosive
- emulsion explosive
- emulsion
- emulsifying agent
- water
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Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
A kind of solid (powdery) emulsion explosive is to can be used as rock and coal mine underground explosion emulsion explosive of new generation that use, after the colloid emulsion explosive.The present invention is the water formed of main oxygenant, water and flame-cooling agent by ammonium nitrate and is that the oil phase that main fuel and specific emulsifying agent are formed forms pasty emulsion matrix through emulsification by wax, will pulverize behind this matrix cooling curing or direct spray cooling gets little yellow or deep yellow powder.The present invention has the advantage of emulsion explosive and an-tnt explosive concurrently, and has overcome their shortcoming again, is particularly suitable for developing the Permitted Detonator for Coal Mining explosive of high degree of safety, is applicable to the working face of low temperature environment and trickle simultaneously.
Description
The invention belongs to a kind of mining water-bearing explosive, exactly is a kind of emulsion explosive-solid of new generation (powdery) emulsion explosive after the colloid emulsion explosive.
According to statistics, in the gas and dust explosion accident that the colliery took place, there is considerable part to cause because of the explosive detonation.Since the seventies, new detonation tendency various water-bearing explosives (water gel explosive and colloid emulsion explosive) low, that safety performance is good are come out one after another.Wherein through tackling key problems for many years and putting into practice, its formula for a product, tooling device, technical process are perfect day by day in China for the emulsion explosive of water-in-oil-type, can be for preferably supporting.But the colloid emulsion explosive also exposes some shortcomings in production and use, though high as explosion velocity, quick-fried power is less relatively, and the coal breakage effect is relatively poor relatively, and pillar easily collapses simultaneously.In addition, induced detonation is also less relatively, is difficult to produce high safe Permitted Detonator for Coal Mining explosive kind; There is the pressurized passivation phenomenon in coal body borehole blasting, in case and after the passivation, pass performance in time and can not recover substantially; Colloid emulsion explosive form is wayward, and powder stick is yielding, behind the medicine-chest of especially packing into crimp even more serious, cause and down powder charge difficulty, overlong time, simultaneously, also easily pollute operator's clothing, and be difficult for removing.In process of production, because of the colloid emulsion explosive is a thermodynamic instability system in essence, its stability is subject to factor affecting such as processing condition, operation control and starting material, and especially emulsifying agent has the greatest impact.CN85101581A, 85103188A, 86100375A, 87101249A, 87103063A, CN1036384A, 1036942A, 1038268A, 1038269A, 1035490 etc. all are various improvement of relevant colloid emulsion explosive.It seems that from disclosed document and production practice just the technology and the prescription of colloid emulsion explosive can't process solid (powdery) emulsion explosive at present.
For overcoming the shortcoming of colloid emulsion explosive, beginning just mid-term from the eighties, the someone studies emulsion explosive-solid of new generation (powdery) emulsion explosive.USP4548059,4525225,4678524, EPA0152060,0238210 disclosed be exactly the document of relevant solid (powdery) emulsion explosive.Its method is to make fuel-displaced bag melts or oil-in-water emulsify explosive earlier, then, perhaps adds specific nucleator tetrabutyl titanate or silicic acid four butyl esters; Perhaps add siccative or tensio-active agent; Perhaps add initiator crosslinked unsaturated polyester and vinylbenzene as oil phase; Perhaps adopting dystectic oxygenant double salt to make water, dystectic fuel makes methods such as oil phase and high-molecular weight tensio-active agent the emulsion explosive that produces is in advance solidified.In order to last method product processed, or the cost height, or sensitivity is low, or processing difficulties, be difficult to apply in factory.
The objective of the invention is to produce the advantage of existing emulsion explosive, overcome its insufficient solid (powdery) emulsion explosive again by existing emulsifying process.Its thinking remains and adopts common water and oil phase, but select specific emulsifying agent for use, under emulsifying temperature, make fuel-displaced bag melts type or oil-in-water emulsify explosive with common emulsifying technology, form the uniform emulsoid that oxygenant fully contacts with fuel, cooling then, oxygenant phase microcrystallization is separated out form thermodynamically stable solid state substrate, obtain the finished product, perhaps the emulsoid spray cooling is directly obtained product through pulverizing.
The water that the present invention is made up of oxygenant, water and needed flame-cooling agent and make emulsion matrix with common emulsifying process by the oil phase that fuel, emulsifying agent are formed, its key is that selected specific compound emulsifying agent is solidified emulsion matrix in process of cooling, pulverize then and obtain product, perhaps directly obtain product through spray cooling.
Described aqueous phase, oxygenant account for 85～95%(weight percent of explosive component, down together), generally form by ammonium nitrate, nitrocalcite, SODIUMNITRATE, saltpetre, magnesium nitrate, urea etc.For ease of applying, reducing the water fusing point to the prerequisite of appropriate value (100～120 ℃), improve the consumption of ammonium nitrate as far as possible, make it account for the explosive component and be not less than 65%, surplus is other nitrate, and also available chlorine hydrochlorate or perchlorate replace above-mentioned part nitrate.Water accounts for 2～8% of explosive component, and it is unfavorable that too much water solidifies emulsion matrix, can influence the performance of explosive simultaneously.Flame-cooling agent need not add the rock type explosive, but then must add the Permitted Detonator for Coal Mining explosive, can be sodium-chlor, Repone K or mixture each other, can be other halogens or phosphorus series compound yet.Add time-division two portions, a part is added to aqueous phase, accounts for 3.5～10% of explosive component, and another part is for adding flame-cooling agent, be added in the emulsion matrix that firm emulsification comes out mix, its consumption is 10～25%, but this part amount is not counted within 100% compositional range.So for water, flame-cooling agent wherein accounts for 0～10% of explosive component.
In the described oil phase, fuel accounts for 2～7% of explosive component, should select to be the solid material under the normal temperature, and based on wax, can be paraffin, ceresine, Microcrystalline Wax, beeswax, rosin, Vaseline etc., also available machinery oil replaces the above-mentioned fuel of part.Preferably paraffin is re-dubbed compound fuel with other waxes, and ratio can be any.
In the oil phase, specific emulsifying agent accounts for 0.3～1.5% of explosive component.The compound emulsifying agent that specific emulsifying agent is made up of with the organic acid salt of amine ester.Described ester is dehydrating sorbitol monooleate, anhydrosorbitol heavy wool acid esters; The organic acid salt of described amine, organic acid wherein can be oleic acid, linolic acid, linolenic acid, lauric acid, Palmiticacid, stearic acid, eicosanoic acid and propionic acid, butyric acid, oxalic acid, pentanedioic acid, sebacic acid etc. saturated with undersaturated aliphatic acid in one or more mixed acid, its general formula is:
Saturated or the undersaturated chain of n1=1 to 18 carbon atom,
The chain of n2=0 to 10 carbon atom; Amine wherein can be one or more the mixed amine in the fatty amines such as decyl amine, lauryl amine, N, Dymanthine, di-n-propyl amine, TERTIARY BUTYL AMINE, hexanediamine, decamethylene diamine, and its general formula is:
The chain of 3=3 to 17 carbon atom of n, R1, R2 can be H or substituting groups such as methyl, propyl group, NH2-(CH2) n4-NH2, the chain of n4=6 to 10 carbon atom.Ester can be any with the compound proportion of the organic acid salt of amine, but be no less than 30% for well with the organic acid salt of amine.
The weight percent of each component is as follows:
Oxygenant 85～95%
Water 2～8%
Fuel 2～7%
Emulsifying agent 0.3～1.5%
Flame-cooling agent 0～10%
Concerning the Permitted Detonator for Coal Mining explosive, 10～25% the flame-cooling agent that adds calculates in addition.
If add emulsification promotor such as an amount of K12, Sodium dodecylbenzene sulfonate, tensio-active agents such as 6530 or clorafin, will obtain better emulsifying effectiveness, its consumption accounts for 0.05～1.0% of explosive component.
Manufacturing process of the present invention is as follows:
Prepare water and oil phase at first respectively in proportion, use common emulsifying process to produce pasty emulsion matrix then, process the Permitted Detonator for Coal Mining product in this way, should in this matrix, add and add flame-cooling agent and mix, through cooling curing, pulverize at last solid (powdery) emulsion explosive product, perhaps directly spray cooling obtains product.Specifically promptly in proportion oxygenant, water and flame-cooling agent are fused into water (A) under 100～120 ℃ of temperature, as desire to add the also adding fusing together of emulsification promotor; Fuel and emulsifying agent are fused into oil phase (B) under 80～90 ℃ of temperature.Under agitation condition, A is added to and goes among the B to mix,, add again and add flame-cooling agent and mix and obtain pasty emulsion matrix as processing Permitted Detonator for Coal Mining product.With the cooling of pasty emulsion matrix, all be cured as solid-state emulsion matrix during to 40 ℃ of left and right sides.Pulverize at last and obtain solid (powdery) emulsion explosive product, outward appearance is that little yellow or deep yellow are Powdered.Perhaps the direct spray cooling of pasty emulsion matrix is obtained product.
The present invention has at present the generally emulsion explosive of use and the advantage of an-tnt explosive concurrently, and overcome their shortcoming, show that mainly storage stability is good, powder stick is not yielding, do not have the sclerosis caking phenomenon, shockwave Sensitivity to Primary Explosion height and mechanical sensitivity is low, blasting effect is good, blasting fume is little, and is easy to use.In addition, this product low-temperature performance and water repelling property are adapted at low temperature environment and have the working face of trickle to use.
Raw material of the present invention is easy to get, and the worker is easily simple.Because the quick-fried power of product is big, induced detonation value height, explosion velocity and brisance are moderate, so be specially adapted to develop the Permitted Detonator for Coal Mining explosive of high degree of safety.
Technology sensitizations such as the also available common chemical foaming of the present invention, perlite obtain cap-sensitive solid emulsion explosive.
Embodiment:
One, the preparation of emulsifying agent:
Get above-mentioned one or both esters, get above-mentioned one or more aliphatic acid and equimolar one or more fatty amine, heat fused mixes and gets final product.Wherein, the organic acid salt of amine accounts for 30%.
Two, the preparation of solid (powdery) emulsion explosive:
To produce 100 kilograms of solids (powdery) emulsion explosive is example:
(1), rock type:
Get 80 kilograms of NH
4NO
3, 7 kilograms of NaNO
3, 6 kilograms of Ca(NO
3)
2, 2 kilograms of CO(NH
2)
2With 2 kilograms of H
2O is mixed in 110 ℃ of heat fused (A), get 2.5 kilograms of compound wax (wherein paraffin 60%, ceresine 20%, Vaseline 20%) and be mixed in 85 ℃ of heat fused (B) with 0.5 kilogram of compound emulsifying agent, under agitation condition (500 rev/mins, down with) A added mix among the B, promptly get pasty emulsion matrix (C), C is cooled to 40 ℃, promptly solidify solid-state emulsion matrix (D), with D pulverize get final product yellowish solid (powdery) emulsion explosive.
When replacing above-mentioned partial oxidation agent with other nitrate, oxymuriate or perchlorate, should guarantee NH
4NO
3Component is not less than 65%.(down together).
(2), one-level Permitted Detonator for Coal Mining:
Get 72 kilograms of NH
4NO
3, 8 kilograms of NaNO
3, 7 kilograms of Ca(NO
3)
2, 2 kilograms of CO(NH
2)
2, 3.5 kilograms of KCl are with 2 kilograms of H
2O mixes the back in 110 ℃ of heat fused (A), get 2.5 kilograms of paraffin, 2 kilograms of ceresine, 1.0 kilograms of compound emulsifying agents mixing backs in 85 ℃ of heat fused (B), under agitation condition, A added and add 10 kilograms of NaCl among the B simultaneously and mix, promptly get pasty emulsion matrix (C), the C spray cooling is promptly got product.
(3), secondary Permitted Detonator for Coal Mining:
Get 68 kilograms of NH
4NO
3, 8 kilograms of NaNO
3, 7 kilograms of Ca(NO
3)
2, 2 kilograms of CO(NH
2)
2, 7 kilograms of KCL are with 2 kilograms of H
2O mixes the back in 110 ℃ of heat fused (A), get 4.8 kilograms of compound wax (wherein paraffin 60%, rosin 20%, machinery oil 20%), 1.2 kilograms of compound emulsifying agents mixing backs in 85 ℃ of heat fused (B), under agitation condition, A added add simultaneously among the B 12 kilograms of NaCl mix (C), the same embodiment of later operation ().
(4), three grades of Permitted Detonator for Coal Mining:
Get 65 kilograms of NH
4NO
3, 8 kilograms of NaNO
3, 10 kilograms of Ca(NO
3)
2, 2 kilograms of CO(NH
2)
2, 9.5 kilograms of KCL are with 2 kilograms of H
2O mixes the back in 110 ℃ of heat fused (A), get 2 kilograms of compound wax (wherein paraffin 60%, Microcrystalline Wax 40%), 1.5 kilograms of compound emulsifying agents mixing backs in 85 ℃ of heat fused (B), under agitation condition, A added add simultaneously among the B 12 kilograms of NaCl mix (C), the same embodiment of later operation () or (two).
Product performance of the present invention are as follows:
| Performance | Rock type | One-level | Secondary | Three grades |
| Density (g/cm 3) | 0.95～1.05 | 0.95～1.05 | 0.95～1.05 | 0.95～1.05 |
| Explosion velocity (m/s) | 3000～4000 | 2900～3200 | 2900～3200 | 2700～3200 |
| Brisance (mm) | 13.5～16 | 12.5～15 | 12.5～15 | 12.5～15 |
| Quick-fried power (ml) | 325 | 298 | 296 | 240～280 |
| Toxic gas (l/Kg) | 30～60.5 | 37 | 36 | 40 |
| Store the date (moon) | >6 | >4 | >4 | >4 |
| Security (mortar big gun) | 100g,0/5 | 150g,0/5 | 450g,0/5 | |
| Induced detonation (cm) | 8～18 | 6～14 | 6～14 | 5～14 |
Claims (2)
1, a kind of solid (powdery) emulsion explosive, be the water formed of main oxygenant, water and flame-cooling agent and be that the oil phase that the fuel led and specific emulsifying agent are formed forms pasty emulsion matrix through emulsification by ammonium nitrate by wax, to pulverize behind this matrix cooling curing or direct spray cooling and getting, it is characterized in that:
(1), described specific emulsifying agent be by dehydrating sorbitol monooleate, anhydrosorbitol heavy wool acid esters with the composite compound emulsifying agent that forms of the organic acid salt of amine, the organic acid general formula is CH3 (CH2)
, the saturated or unsaturated chain of n1=1 to 18 carbon atom,
, the chain of n2=0 to 10 carbon atom, the general formula of organic amine is
, the chain of n3=3 to 17 carbon atom, R1, R2 can be H or substituting groups such as methyl, propyl group, the chain of n4-NH2n4=6 to 10 carbon atom of NH2-(CH2);
(2), the significant percentage of each component:
Oxygenant 85～95%
Water 2～8%
Flame-cooling agent 0～10%
Fuel 2～7%
Compound emulsifying agent 0.3～1.5%
(3), in the described oxygenant, ammonium nitrate accounts for the explosive component and is not less than 65%, surplus is other nitrate, oxymuriate or perchlorate and urea.
2, a kind of solid according to claim 1 (powdery) emulsion explosive, it is characterized in that: in the compound emulsifying agent, the organic acid salt of amine is no less than 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110219 CN1084152A (en) | 1992-09-17 | 1992-09-17 | Solid (powdery) emulsion explosive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110219 CN1084152A (en) | 1992-09-17 | 1992-09-17 | Solid (powdery) emulsion explosive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1084152A true CN1084152A (en) | 1994-03-23 |
Family
ID=4944685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92110219 Pending CN1084152A (en) | 1992-09-17 | 1992-09-17 | Solid (powdery) emulsion explosive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1084152A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364937C (en) * | 2005-09-06 | 2008-01-30 | 南京理工大学 | Powdery emulsified explosive preparation method |
| CN101053798B (en) * | 2007-02-13 | 2011-06-01 | 煤炭科学研究总院***技术研究所 | Double type emulsifying agent and its manufacturing method |
| CN101745340B (en) * | 2008-12-08 | 2012-01-11 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN102424643A (en) * | 2011-09-08 | 2012-04-25 | 煤炭科学研究总院***技术研究所 | High-safety emulsion explosive for coal mine |
| CN102863301A (en) * | 2012-10-11 | 2013-01-09 | 中国工程物理研究院化工材料研究所 | Explosive shock wave sensibility regulating method based on crystal orientations |
| CN104961387A (en) * | 2015-06-10 | 2015-10-07 | 北京理工大学 | Thermal expansion stone cracking agent |
| CN104961386A (en) * | 2015-06-10 | 2015-10-07 | 北京理工大学 | Preparation method of thermal expansion stone cracking agent |
-
1992
- 1992-09-17 CN CN 92110219 patent/CN1084152A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364937C (en) * | 2005-09-06 | 2008-01-30 | 南京理工大学 | Powdery emulsified explosive preparation method |
| CN101053798B (en) * | 2007-02-13 | 2011-06-01 | 煤炭科学研究总院***技术研究所 | Double type emulsifying agent and its manufacturing method |
| CN101745340B (en) * | 2008-12-08 | 2012-01-11 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN102424643A (en) * | 2011-09-08 | 2012-04-25 | 煤炭科学研究总院***技术研究所 | High-safety emulsion explosive for coal mine |
| CN102424643B (en) * | 2011-09-08 | 2013-05-15 | 煤炭科学研究总院***技术研究所 | High-safety emulsion explosive for coal mine |
| CN102863301A (en) * | 2012-10-11 | 2013-01-09 | 中国工程物理研究院化工材料研究所 | Explosive shock wave sensibility regulating method based on crystal orientations |
| CN102863301B (en) * | 2012-10-11 | 2013-11-06 | 中国工程物理研究院化工材料研究所 | Explosive shock wave sensibility regulating method based on crystal orientations |
| CN104961387A (en) * | 2015-06-10 | 2015-10-07 | 北京理工大学 | Thermal expansion stone cracking agent |
| CN104961386A (en) * | 2015-06-10 | 2015-10-07 | 北京理工大学 | Preparation method of thermal expansion stone cracking agent |
| CN104961386B (en) * | 2015-06-10 | 2017-01-18 | 北京理工大学 | Preparation method of thermal expansion stone cracking agent |
| CN104961387B (en) * | 2015-06-10 | 2017-01-25 | 北京理工大学 | Thermal expansion stone cracking agent |
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