CN102464519A - Powdery emulsion explosive - Google Patents
Powdery emulsion explosive Download PDFInfo
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- CN102464519A CN102464519A CN2010105357252A CN201010535725A CN102464519A CN 102464519 A CN102464519 A CN 102464519A CN 2010105357252 A CN2010105357252 A CN 2010105357252A CN 201010535725 A CN201010535725 A CN 201010535725A CN 102464519 A CN102464519 A CN 102464519A
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Abstract
The invention relates to a powdery emulsion explosive, which is prepared by the following steps: taking the raw materials of 75-85% of ammonium nitrate, 5-10% of auxiliary oxidant, 2-6% of organic oil-phase material, 0.7-1.3% of emulsifier, 1-3% of cosolvent, 1-11% of blast reducer and 1-5% of water by weight, wherein the organic oil-phase material takes decompressing cerate, petroleum wax, foots oil and polymer as basic raw materials in current technology, supplementing a phospholipid additive, introducing air under the conditions of temperature of 140-180 DEG C and an 0.1%-1.0% oxidation catalyst, and reacting for 2-10 hours. The present invention improves explosive performance, water resistance, moisture resistance, caking resistance and storage stability of the powdery emulsion explosive, and reduces the usage amount of emulsifier. The powdery emulsion explosive is subjected to industrial production under any environment, and completely eliminates harm of TNT on human and environment.
Description
Technical field
The present invention relates to a kind of powdery emulsifying explosive.
Background technology
Powdery emulsifying explosive is a kind of civil blast explosive with international most advanced level of later 1990s invention; It is by over-saturation oxidizing agent solution and oil phase under the effect of emulsifying agent, the powder type explosive that spraying drying is processed after about 140 ℃ of emulsifications.It had both had the good water repelling property of emulsion [explosive, and component does not contain TNT, and environment and human body are not had any harm; Having complied with people's blasting powders does not have the development trend of ladderization, possesses the solid form characteristic of powdery ammonium ladder detonator again, shelf-stable; Quick-fried power (capacity for work) height uses advantages such as more flexible.Powdery emulsifying explosive has not only overcome the Emulsion Explosive Stability difference but also has overcome the shortcoming of powder type explosive water resisting property difference.
Powdery emulsifying explosive has very big difference from fill a prescription production technique and emulsion [explosive and powder type explosive, moisture (weight) 12%～14% of preparation of emulsifying explosive, and 80 ℃ of emulsifying temperatures, powdery emulsifying explosive is moisture only 2%～4%, about 140 ℃ of emulsifying temperatures.Powdery emulsifying explosive is higher to the requirement of strength of emulsifying film, is convenient to spray into powder after the emulsification, and the non-caked one-tenth piece of Cheng Fenhou normal temperature.Emulsion [explosive normal temperature is paste, can not spray into powder.Powder type explosive is that Material Physics mixed grindings such as an ammonium nitrate, TNT, wood powder, oil phase form, and is all powdery with the powdery emulsifying explosive apparent condition, but its microtexture is different, and the water-in-oil particle of powdery emulsifying explosive is thinner.CN1085202A has proposed a kind of powdery emulsifying explosive and preparation method thereof, and the composition of this powdery emulsifying explosive (weight %) is: an ammonium nitrate 75～85, secondary oxidizer 5～15; Urea 1～4, organic additive 0.02～1.0, water 0～4; Organic oil phase material 2～7; Emulsifying agent (T-155) 1.5～5 becomes pulvis 1.5～4, auxiliary fuel 0～4; CN00112373.4 has proposed a kind of type powdery emulsifying explosive; It consists of: an ammonium nitrate 60～90%, SODIUMNITRATE 1～15%, nitrocalcite 1～10%, urea 0.1～2%, water 4～10%, Repone K or sodium-chlor or ammonium chloride 1～24%, paraffin 1.5～4%, ceresine 0.3～1.5%, rosin 0.3～1.5%, sorbitol monooleate 0.3～1.0%, solidifying agent high fatty amine, acid amides or cats product 0.1～0.5%; CN1336355A has proposed a kind of powdery emulsifying explosive and method of manufacture thereof, the consisting of of embodiment 2 (weight %): an ammonium nitrate 80, saltpetre 4, nitrocalcite 2, urea 1; Repone K 3, water 3, paraffin 2.0, ceresine 1.0; Rosin 0.7, Triple Pressed Stearic Acid 0.1, pitch 0.8, (T-154) 2.4.The powdery emulsifying explosive of all these reports all adopts succimide family macromolecule emulsifying agent, and the emulsifying film intensity of its formation is higher, is greatly improved with the powdery emulsifying explosive stability of its preparation.But succimide family macromolecule emulsifying agent at high temperature is prone to decompose generation nitrogen and carbonic acid gas; Reduced emulsifying power; And make and contain certain gas in the emulsifying base; Reduce the density of emulsifying base, thereby made emulsifying base have certain detonation susceptibility, influenced the safety in production of powdery emulsifying explosive.All to adopt the petroleum refinement product be the oil phase basic raw material to these patents in addition; Again blending again after making oil in the petroleum refining process/wax separation and processing corresponding paraffin, ceresine, the lubricated commercially available petroleum products of wet goods causes the waste of the unnecessary human and material resources and the energy.And the emulsifying agent large usage quantity, can reach 5% of explosive at most, or water-content is high.As everyone knows, compare with wax class material, emulsifying agent costs an arm and a leg, and therefore, reduces the emulsifying agent consumption and can obviously reduce the emulsifying agent cost.
Summary of the invention
Deficiency to prior art; The objective of the invention is to overcome above shortcoming; A large amount of unpurified cuts such as decompression slack wax and sweat oil that use are the oil phase basic material, are aided with the phosphatide additive, under suitable condition, process new organic oil phase material through oxidation technology; Reduced the emulsifying agent consumption, thus the corresponding explosive cost that reduced.Utilization of the present invention does not contain the ester family macromolecule emulsifying agent of succimide group, Heat stability is good, to reduce the emulsifying base sensitivity, improves the safety in production coefficient.
The composition of powdery emulsifying explosive of the present invention comprises (in powdery emulsifying explosive weight):
An ammonium nitrate 75%～85%
Secondary oxidizer 5%～10%
Organic oil phase material 2%～6%
Emulsifying agent 0.7%～1.3%
Solubility promoter 1%～3%
Water 1%～5%
Flame-cooling agent 1%～11%
Preferably the consisting of of powdery emulsifying explosive of the present invention (in powdery emulsifying explosive weight):
An ammonium nitrate 75%～80%
Secondary oxidizer 5%～8%
Organic oil phase material 3%～5%
Emulsifying agent 0.8%～1.2%
Solubility promoter 1%～2%
Water 2%～4%
Flame-cooling agent 3%～8%
Among the present invention, secondary oxidizer is the mixture of SODIUMNITRATE, saltpetre, nitrocalcite or these compounds.
Among the present invention, organic oil phase material weight is formed as follows:
Petroleum wax 10%～40%
Decompression slack wax 50%～85%
Sweat oil 0～20%
Polymkeric substance 0～5%
In organic oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%; Under 140～180 ℃; Feed oxygen-containing gas reaction 2～10 hours; Add in the oxidation products and account for oil phase raw material weight 0.1%～5%, be preferably 0.5%～4% phosphatide and make final powdery emulsifying explosive oil phase material.
The organic oil phase material wherein, petroleum wax is one or more mixtures in 54# SEMI-REFINED PARAFFIN WAX, 56# SEMI-REFINED PARAFFIN WAX, 58# SEMI-REFINED PARAFFIN WAX, 60# SEMI-REFINED PARAFFIN WAX, 62 SEMI-REFINED PARAFFIN WAXs, 64 SEMI-REFINED PARAFFIN WAXs, 66# SEMI-REFINED PARAFFIN WAX and the 70# mixed crystal wax.The decompression slack wax is the second line of distillation slack wax, subtracts three-way slack wax, subtracts one or more mixtures in four line slack waxs and the frivolous asphalt oil.Sweat oil be vacuum distillate or decompression slack wax through pressing the by-product oil that petroleum wax is produced in wax sweating or solvent deoiling dewaxing, the sweat oil consumption is preferably 4%～20%.Sweat oil can be regulated the spraying dispersing property in the powdery emulsifying explosive production process well, and spray process is realized smoothly.Polymkeric substance comprises that number-average molecular weight is 500～100000 oligopolymer, and like in Vilaterm (PE), Vestolen PP 7052 (PP), polyisobutene (PIB) and the ethene-vinyl acetate copolymer (EVA) etc. one or more, polymer loading is preferably 1%～5%.Polymkeric substance can improve the one-tenth membrane stability of compound wax, improves the stability in storage of powdery emulsifying explosive.
The catalyzer that organic oil phase feed oxygen process is used is permanganate, dichromate, superoxide or naphthenate; Its permanganate is potassium permanganate or sodium permanganate; The dichromic acid hydrochlorate is SRM 935a, sodium dichromate 99 or dichromic acid cobalt; Superoxide is a ydrogen peroxide 50, and naphthenate is that naphthenic acid bores or manganese naphthenate, and above-mentioned various catalyzer can use wherein a kind of wherein mixture of several kinds that also can use separately.Adopt the batch production method, the oxygen-containing gas flow is generally 15～35L/Kgh (every kilogram oil phase raw material per hour air flow), and the volume of oxygen-containing gas is in the standard state lower volume, and oxygen-containing gas can be air, oxygen-rich air or other oxygen-containing gas.Phosphatide acid number≤30mg the KOH/g that adds, the HLB value is 3～4, phosphatide can be various commercially available prod.Preferably continue reaction 0.5～3 hour after adding phosphatide.
Emulsifying agent among the present invention is the ester family macromolecule emulsifying agent that CN96100379.0 provides; Promptly by the poly-hydroxy compounds of the polyisobutenyl maleic anhydride and 10%～20% (quality) of 80%～90% (quality) ,-0.04～-0.08MPa, 150～200 ℃ of reactions made in 3～8 hours.
Solubility promoter of the present invention is a urea.
Flame-cooling agent of the present invention is sodium-chlor, Repone K, ammonium chloride or their mixture.
In the powdery emulsifying explosive of the present invention, can add other component as required, like density adjuster etc.
The preparation method of powdery emulsifying explosive of the present invention can adopt existing powdery emulsifying explosive preparation method preparation, adopts an emulsifying manner that oxygenant such as an ammonium nitrate and combustiblematerials are mixed into the latex of homogeneous, by spray pulverization technology latex is directly processed product again.
The powdery emulsifying explosive that the present invention proposes, its advantage is that with distillate and petroleum wax composition be basic material, carry out oxidizing reaction after; On raw molecule, introduce the segment polarity group,, strengthened the polarity of wax molecule like oxygen containing carboxyl and ester group etc.; And with the phosphatide thorough mixing dissolving that adds; And form stronger keying action, under the catalytic oxidation condition, possibly form the part chemical bond and combine, thereby when reducing the emulsifying agent consumption, not influence the product property of powdery emulsifying explosive; Or further improve the quality product of powdery emulsifying explosive, greatly reduce the cost of powdery emulsifying explosive.Experiment shows that when adopting the present invention to produce powdery emulsifying explosive, under the close situation of product performance, the emulsifying agent consumption can reduce more than 30%.Oil phase material makes the continuous compactness of emulsification caudacoria be able to strengthen after oxidation modification, becomes the powder better effects if, thereby has improved blast performance, water resisting property and the package stability of explosive, improves its market competitive power.Oil phase material raw material of the present invention is petroleum fractions, and participates in oxidizing reaction together, and each component compatibility is better, leave standstill for a long time under the molten state not stratified, thereby keep quality of explosive stable.The present invention has also that raw material is easy to get, advantage of simple technology in addition.
Embodiment
Specify the present invention through embodiment below.
The preparation of organic oil phase material of the present invention (wherein raw material is formed in parts by weight) sees the following form.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| 56# partly refines paraffin | 0 | 0 | 0 | 200 |
| 58# partly refines paraffin | 300 | 0 | 0 | 0 |
| 60# partly refines paraffin | 0 | 250 | 0 | 0 |
| 62# partly refines paraffin | 0 | 0 | 200 | 0 |
| Sweat oil | 80 | 90 | 120 | 160 |
| Subtract two slack waxs | 0 | 0 | 350 | 0 |
| Subtract three slack waxs | 400 | 0 | 0 | 350 |
| Subtract four slack waxs | 0 | 450 | 0 | 0 |
| The residue slack wax | 300 | 200 | 300 | 100 |
| Phosphatide | 20 | 10 | 40 | 30 |
| Vilaterm | 20 | 0 | 0 | 40 |
| Vestolen PP 7052 | 0 | 10 | 0 | 0 |
| Ethene-vinyl acetate copolymer | 0 | 0 | 30 | 0 |
| Temperature of reaction, ℃ | 160 | 170 | 150 | 140 |
| Reaction times, h | 5 | 8 | 4 | 7 |
| Catalyst levels | 1 | 10 | 4 | 8 |
| Air flow quantity, L/h | 25 | 30 | 20 | 35 |
Embodiment of the invention prescription (in powdery emulsifying explosive, weight %) sees the following form.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| The organic oil phase material | 4.5 | 4 | 5 | 3.5 |
| An ammonium nitrate | 78 | 80 | 76 | 77 |
| SODIUMNITRATE | 6 | 5 | 7 | 8 |
| Urea | 1.5 | 1 | 2 | 1.5 |
| Water | 3 | 4 | 4 | 2 |
| Emulsifying agent | 1.0 | 1.2 | 1.0 | 0.8 |
| Repone K | 6 | 4.8 | 5 | 7.2 |
Comparative example:
The powdery emulsifying explosive that adopts CN1336355A embodiment 3 to propose.
The mass percent of each component is: an ammonium nitrate 83, SODIUMNITRATE 3, urea 1, sodium-chlor 3, water 3, paraffin 1.8, ceresine 1.2, rosin 1.0, Triple Pressed Stearic Acid 0.1, pitch 0.5, emulsifying agent 2.4.
See the following form with powdery emulsifying explosive of the present invention and its performance of comparative example powdery emulsifying explosive.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Emulsifying agent consumption % | 1.0 | 1.2 | 1.0 | 0.8 | 2.4 |
| Induced detonation (cm) | 20 | 21 | 20 | 20 | 15 |
| High cold cycle (individual) | 9 | 9 | 9 | 8 | 7 |
Annotate: high cold cycle is for estimating the important indicator of emulsion [explosive, and the cycle number height representes that then Emulsion Explosive Stability is good.Its testing method is to get 50 gram emulsion [explosive samples in 50 ℃ baking oven, to place 8 hours, puts into-25 ℃ refrigerator-freezer after the taking-up again and places 16 hours as a circulation, takes out the baking oven circulation of putting into 50 ℃ again and carries out, till emulsion [explosive sample conduction.
Claims (10)
1. powdery emulsifying explosive is characterized in that forming and comprises in powdery emulsifying explosive weight:
An ammonium nitrate 75%～85%
Secondary oxidizer 5%～10%
Organic oil phase material 2%～6%
Emulsifying agent 0.7%～1.3%
Solubility promoter 1%～3%
Water 1%～5%
Flame-cooling agent 1%～11%.
2. according to the described powdery emulsifying explosive of claim 1, it is characterized in that: composition comprises in powdery emulsifying explosive weight:
An ammonium nitrate 75%～80%
Secondary oxidizer 5%～8%
Organic oil phase material 3%～5%
Emulsifying agent 0.8%～1.2%
Solubility promoter 1%～2%
Water 2%～4%
Flame-cooling agent 3%～8%.
3. according to the described powdery emulsifying explosive of claim 1, it is characterized in that: secondary oxidizer is the mixture of SODIUMNITRATE, saltpetre, nitrocalcite or these compounds.
4. according to the described powdery emulsifying explosive of claim 1, it is characterized in that: organic oil phase material weight is formed as follows:
Petroleum wax 10%～40%
Decompression slack wax 50%～85%
Sweat oil 0～20%
Polymkeric substance 0～5%
In organic oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%; Under 140～180 ℃; Feed oxygen-containing gas reaction 2～10 hours; Add in the oxidation products and account for oil phase raw material weight 0.1%～5%, be preferably 0.5%～4% phosphatide and make final powdery emulsifying explosive organic oil phase material.
5. according to the described powdery emulsifying explosive of claim 1; It is characterized in that: emulsifying agent is the ester family macromolecule emulsifying agent that CN96100379.0 provides; Promptly by the poly-hydroxy compounds of the polyisobutenyl maleic anhydride and 10%～20% (quality) of 80%～90% (quality) ,-0.04～-0.08MPa, 150～200 ℃ of reactions made in 3～8 hours.
6. according to the described powdery emulsifying explosive of claim 1, it is characterized in that: solubility promoter is a urea.
7. according to the described powdery emulsifying explosive of claim 1, it is characterized in that: flame-cooling agent is sodium-chlor, Repone K, ammonium chloride or their mixture.
8. according to the described powdery emulsifying explosive of claim 4, it is characterized in that: the petroleum wax in the organic oil phase material is one or more mixtures in 54# SEMI-REFINED PARAFFIN WAX, 56# SEMI-REFINED PARAFFIN WAX, 58# SEMI-REFINED PARAFFIN WAX, 60# SEMI-REFINED PARAFFIN WAX, 62# SEMI-REFINED PARAFFIN WAX, 64# SEMI-REFINED PARAFFIN WAX, 66# SEMI-REFINED PARAFFIN WAX and the 70# mixed crystal wax; The decompression slack wax is the second line of distillation slack wax, subtracts three-way slack wax, subtracts one or more mixtures in four line slack waxs and the frivolous asphalt oil; Sweat oil be vacuum distillate or decompression slack wax through pressing the by-product oil that petroleum wax is produced in wax sweating or solvent deoiling dewaxing, the sweat oil consumption is 4%～20%; Polymkeric substance comprises that number-average molecular weight is 500～100000 oligopolymer, and polymer loading is 1%～5%.
9. according to the described powdery emulsifying explosive of claim 4, it is characterized in that: the catalyzer that organic oil phase feed oxygen process is used is permanganate, dichromate, superoxide or naphthenate.
10. according to the described powdery emulsifying explosive of claim 4, it is characterized in that: phosphatide acid number≤30mgKOH/g, the HLB value is 3～4, adds phosphatide continued reaction 0.5～3 hour.
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| CN2010105357252A CN102464519A (en) | 2010-11-04 | 2010-11-04 | Powdery emulsion explosive |
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| CN2010105357252A CN102464519A (en) | 2010-11-04 | 2010-11-04 | Powdery emulsion explosive |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718616A (en) * | 2012-07-03 | 2012-10-10 | 保利民爆济南科技有限公司 | Three-raw-material rock type emulsion explosive matrix |
| CN103724143A (en) * | 2013-12-31 | 2014-04-16 | 宜兴市阳生化工有限公司 | Rock powdery civil emulsion explosive and production process thereof |
| CN105732240A (en) * | 2014-12-08 | 2016-07-06 | 雅化集团旺苍化工有限公司 | Emulsion explosive permissible in grade-three coal mine |
| CN105802667A (en) * | 2014-12-28 | 2016-07-27 | 中国石油化工股份有限公司 | Method for producing explosive insensitive wax |
| CN107011104A (en) * | 2017-05-03 | 2017-08-04 | 常州市润星化工有限公司 | Powdery emulsifying explosive composite oil phase and preparation method thereof |
| RU2810967C2 (en) * | 2019-08-01 | 2024-01-09 | Михаил Николаевич Оверченко | Explosive emulsion composition |
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| CN1336355A (en) * | 2000-08-02 | 2002-02-20 | 南京理工大学 | Coal mine allowable powdered emulsified explosive and its production process |
| CN1448375A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Prep. of oil phase for powered nitro-amine compound explosive |
| CN101172914A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Composite wax for powder emulsifying blasting agent |
-
2010
- 2010-11-04 CN CN2010105357252A patent/CN102464519A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336355A (en) * | 2000-08-02 | 2002-02-20 | 南京理工大学 | Coal mine allowable powdered emulsified explosive and its production process |
| CN1448375A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Prep. of oil phase for powered nitro-amine compound explosive |
| CN101172914A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Composite wax for powder emulsifying blasting agent |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718616A (en) * | 2012-07-03 | 2012-10-10 | 保利民爆济南科技有限公司 | Three-raw-material rock type emulsion explosive matrix |
| CN103724143A (en) * | 2013-12-31 | 2014-04-16 | 宜兴市阳生化工有限公司 | Rock powdery civil emulsion explosive and production process thereof |
| CN103724143B (en) * | 2013-12-31 | 2016-02-10 | 宜兴市阳生化工有限公司 | A kind of Rock powdery civil emulsion explosive and production technique thereof |
| CN105732240A (en) * | 2014-12-08 | 2016-07-06 | 雅化集团旺苍化工有限公司 | Emulsion explosive permissible in grade-three coal mine |
| CN105802667A (en) * | 2014-12-28 | 2016-07-27 | 中国石油化工股份有限公司 | Method for producing explosive insensitive wax |
| CN107011104A (en) * | 2017-05-03 | 2017-08-04 | 常州市润星化工有限公司 | Powdery emulsifying explosive composite oil phase and preparation method thereof |
| RU2810967C2 (en) * | 2019-08-01 | 2024-01-09 | Михаил Николаевич Оверченко | Explosive emulsion composition |
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Application publication date: 20120523 |