CN102452864B - Preparation method of powdery emulsion explosive oil phase material - Google Patents
Preparation method of powdery emulsion explosive oil phase material Download PDFInfo
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Abstract
The invention discloses a preparation method of a powdery emulsion explosive oil phase material. The oil phase material comprises 10-40% of petroleum wax, 50-85% of vacuum cerate, 0-20% of foots oil and 0-5% of a polymer. According to the weight of the oil phase, 0.1-1.0% of a catalyst is added to the oil phase; under a temperature of 130-180 DEG C, oxygen-containing gas is delivered into the oil phase, and the mixture is subject to a reaction for 2-10 hours; according to the weight of the oil phase, 0.1-5% of phosphatide is added to the oxidation product, such that the powdery emulsion explosive oil phase material is finally prepared. According to the invention, when the oil phase material is used for preparing the powdery emulsion explosive, the dosage of an emulsifying agent can be reduced to 1.0%, and the stability of the powdery emulsion explosive can be further improved.
Description
Technical field
The present invention relates to a kind of preparation method of the oil phase material for 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 be by over-saturation oxidizing agent solution and oil phase under the effect of emulsifying agent, the dry powder type explosive of making of spraying after 140 DEG C of emulsification.It had both had the good water repelling property of emulsion explosive, component is not containing TNT, to environment and human body without harm, meet the development trend of people's blasting powders without ladder, possesses again the solid form feature of powdered TNT-free explosive, shelf-stable, quick-fried power (capacity for work) height, uses the advantages such as more flexible.It is poor but also overcome the poor shortcoming of powder type explosive water resisting property that powdery emulsifying explosive had not only overcome Emulsion Explosive Stability.
Powdery emulsifying explosive has very large difference from fill a prescription production technique and emulsion explosive and powder type explosive, moisture (weight) 12%～14% of preparation of emulsifying explosive, 80 DEG C of emulsifying temperatures, powdery emulsifying explosive is moisture only 2%～4%, 140 DEG C of left and right of emulsifying temperature.Its production unit technique also has larger difference, although the effect of Wax special is all foreign minister, the emulsifying film requirement of strength that powdery emulsifying explosive forms Wax special is higher, is convenient to spray into powder after 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 the Material Physics mixed grindings such as ammonium nitrate, TNT, wood powder, oil phase form, Wax special forms coating layer on ammonium nitrate granule surface, be all powdery with powdery emulsifying explosive apparent condition, but its microtexture difference, the water-in-oil particle of powdery emulsifying explosive is thinner, and reductive agent (Wax special) contacts tightr with oxygenant.Because powdery emulsifying explosive is completely different from character and the production process of emulsion explosive and powder type explosive, therefore, the character of oil phase is required also to difference completely, can not be used for powdery emulsifying explosive for the oil phase material (as CN96106444.7, CN96106443.9, CN96106442.0, CN1174182A etc.) of emulsion explosive with for the oil phase material (as CN99113309.9, CN99113308.0, CN99113295.5, CN99113294.7, CN02109421.7 etc.) of powder type explosive.
The MF Series Special Compound Wax for Emulsion Explosives that Fushun Petrochemical Research Institute succeeds in developing and DT type firer Wax special is respectively used to emulsion explosive and powder type explosive is all obtained better result of use, but can not meet powdery emulsifying explosive requirement.CN91107080.X has proposed a kind of powder emulsified ammoniumnitrate explosives for engineering explosion, and its oil phase feature consists of: 1.5～2.0 (T-155 emulsifying agents), 1.0～1.5 rosin, 0.75～1.0 paraffin, 0.75～1.0 ceresine; CN00112373.4 has proposed a kind of Permitted Detonator for Coal Mining powdery emulsifying explosive, its oil phase is characterised in that and consists of: 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%.The oil phase of above prior art is the compositions such as paraffin, ceresine, rosin.The powdery emulsifying explosive of all these reports is all taking petroleum refinement product as oil phase basic raw material, and cost is higher.CN101172914A has proposed a kind of compound wax for powdery emulsifying explosive, form as basic material is composite taking petroleum wax, decompression slack wax and the sweat oil produced in petroleum refining process, effectively reduced powdery emulsifying explosive cost, on the consumption of emulsifying agent in powdery emulsifying explosive production process without any impact.
As everyone knows, compared with wax class material, emulsifying agent is expensive, and especially macromolecule emulsifier price is more expensive.At present, the consumption of emulsifying agent accounts for 1.5%～5% of powdery emulsifying explosive.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of lower-cost powdery emulsifying explosive Wax special composition, when the oil phase that the inventive method obtains is produced for powdery emulsifying explosive, can obviously reduce the consumption of emulsifying agent, ensure the quality of powdery emulsifying explosive simultaneously.
The preparation method of powdery emulsion explosive oil phase material of the present invention comprises following content:
Oil phase raw material contains (by weight):
Petroleum wax 10%～40%
Decompression slack wax 50%～85%
Sweat oil 0～20%
Polymkeric substance 0～5%
In oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%, at 130～180 DEG C, pass into oxygen-containing gas reaction 2～10 hours, in oxidation products, add and account for oil phase raw material weight 0.1%～5%, be preferably 0.5%～4% phosphatide and make final powdery emulsion explosive 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 WAX, 64# SEMI-REFINED PARAFFIN WAX, 66# SEMI-REFINED PARAFFIN WAX and 70# mixed crystal wax.
Wherein, decompression slack wax is second line of distillation slack wax, subtracts three line slack waxs, subtracts one or more mixtures in four line slack waxs and frivolous asphalt oil.
Wherein, sweat oil is vacuum distillate or decompression slack wax are produced petroleum wax by-product oil through squeezing wax sweating or solvent dewaxing and deoiling, and sweat oil consumption is preferably 4%～20%.Sweat oil can regulate the spraying dispersing property in powdery emulsifying explosive production process well, and spray process is realized smoothly.
Wherein, polymkeric substance comprises that number-average molecular weight is 500～100000 oligopolymer, as one or more in polyethylene (PE), polypropylene (PP), polyisobutene (PIB) and ethene-vinyl acetate copolymer (EVA) etc., polymer loading is preferably 1%～5%.Polymkeric substance can improve the film forming stability of compound wax, improves the stability in storage of powdery emulsifying explosive.
Wherein, the catalyzer using is permanganate, dichromate, superoxide or naphthenate, its permanganate is potassium permanganate or sodium permanganate, dichromic acid hydrochlorate is potassium bichromate, sodium dichromate 99 or dichromic acid cobalt, superoxide is hydrogen peroxide, naphthenate is that naphthenic acid bores or manganese naphthenate, and above-mentioned various catalyzer can use wherein independent a kind of wherein several mixture that also can use.
The inventive method adopts batch production method, oxygen-containing gas flow is generally 15～35L/Kgh (every kilogram of oil phase raw material air flow per hour), the volume of oxygen-containing gas is in standard state lower volume, and oxygen-containing gas can be air, oxygen-rich air or other oxygen-containing gas.
In the present invention, the phosphatide acid number≤30mg KOH/g adding, HLB value is 3～4, phosphatide can be various commercially available prod.After adding phosphatide, preferably continue reaction 0.5～3 hour.
Powdery emulsion explosive oil phase material prepared by the inventive method application in powdery emulsifying explosive, emulsifier accounts for 0.7%～1.3% of powdery emulsifying explosive weight.Emulsifying agent is emulsifying agent conventional in this area, as succimide macromolecule emulsifier etc.
The preparation method of the powdery emulsion explosive oil phase material that the present invention proposes, its advantage is taking distillate and petroleum wax composition as basic material, carry out after oxidizing reaction, introducing portion polar group on raw molecule, as oxygen containing carboxyl and ester group etc., strengthen the polarity of wax molecule, and with the abundant mixed dissolution of the phosphatide adding, and the stronger keying action of formation, under catalytic oxidation condition, may form part chemical bonds, thereby in reducing emulsifier, do not affect 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, adopts oil phase material of the present invention, and while producing powdery emulsifying explosive, in the situation that product performance are close, emulsifier can reduce more than 30%.Oil phase material, after oxidation modification, is strengthened the continuous compactness of emulsification caudacoria, becomes powder better effects if, thereby has improved blast performance, water resisting property and the package stability of explosive, improves its market competitiveness.Oil phase material raw material of the present invention is petroleum fractions, and participates in oxidizing reaction together, and each component compatibility is better, long-time standing not stratified under molten state, thereby keeps quality of explosive stable.The present invention also has that raw material is easy to get, the simple advantage of technique in addition.
Embodiment
Illustrate the present invention below by embodiment.
Embodiment 1
By 58# SEMI-REFINED PARAFFIN WAX 200g, subtract three line slack wax 400g, residual oil slack wax 300g, sweat oil 80g, PE20g and 1g naphthenic acid and bore after heating mixes, pour reactor into, pass into air reaction 5 hours at 160 DEG C, air flow quantity is 25L/h, after oxidation, add phosphatidase 12 0g, continue reaction 1 hour.
Embodiment 2
By 60# SEMI-REFINED PARAFFIN WAX 250g, subtract four line slack wax 450g, residual oil slack wax 200g, sweat oil 90g, PP20g heating and mix after, pour reactor into, slowly add 10g hydrogen peroxide, pass into air reaction 8 hours at 170 DEG C, air flow quantity is 30L/h, oxidation adds phosphatidase 11 0g, continues reaction 0.5 hour.
Embodiment 3
After 62# SEMI-REFINED PARAFFIN WAX 200g, second line of distillation slack wax 350g, residual oil slack wax 300g, sweat oil 120g, EVA30g and the heating of 4g potassium permanganate are mixed, pour reactor into, pass into air reaction 4 hours at 150 DEG C, air flow quantity is 20L/h, after oxidation, add phosphatidase 14 0g, continue reaction 2 hours.
Embodiment 4
By 56# SEMI-REFINED PARAFFIN WAX 350g, subtract three line slack wax 350g, residual oil slack wax 100g, sweat oil 160g, PE40g and the heating of 8g potassium bichromate and mix after, pour reactor into, pass into air reaction 7 hours at 140 DEG C, air flow quantity is 35L/h, adds phosphatidase 13 0g after oxidation.
Comparative example 1
Adopt the oil phase material formula (parts by weight) of CN101172914A embodiment 1
56# SEMI-REFINED PARAFFIN WAX 5,64# SEMI-REFINED PARAFFIN WAX 5, subtracts three line slack waxs 40, subtracts four line slack waxs 30, frivolous asphalt oil 10, sweat oil 5, PE 5.
Under the condition of 1700 revs/min, 135 DEG C, carry out powdery emulsifying explosive application test with oil phase material of the present invention and comparative example oil phase material, its performance sees the following form.Under the constant condition of other powdery emulsifying explosive component, the detonation property of prepared powdery emulsifying explosive improves to some extent compared with comparative example with stability, and emulsifier significantly reduces, and emulsifying agent is polyisobutene succinimide.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Emulsifier % | 1.0 | 1.0 | 1.0 | 1.0 | 1.5 |
| Induced detonation (cm) | 20 | 21 | 20 | 20 | 18 |
| High cold cycle (individual) | 9 | 9 | 9 | 8 | 7 |
Note: high cold cycle is the important indicator of evaluating emulsion explosive, and cycle number height represents that Emulsion Explosive Stability is good.Its testing method is to get 50 grams of emulsion explosive samples in the baking oven of 50 DEG C, to place 8 hours, puts into the refrigerator-freezer of-25 DEG C again and place 16 hours as a circulation after taking-up, takes out to put into the baking oven of 50 DEG C again and loop, until emulsion explosive sample conduction.
Claims (10)
1. a preparation method for powdery emulsion explosive oil phase material, comprises following content:
Oil phase raw material contains by weight:
In oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%, at 130～180 DEG C, pass into oxygen-containing gas reaction 2～10 hours, in oxidation products, add the phosphatide that accounts for oil phase raw material weight 0.1%～5%, after adding phosphatide, continue reaction 0.5～3 hour, make final powdery emulsion explosive oil phase material.
2. it is characterized in that in accordance with the method for claim 1: 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 WAX, 64# SEMI-REFINED PARAFFIN WAX, 66# SEMI-REFINED PARAFFIN WAX and 70# mixed crystal wax; Decompression slack wax is second line of distillation slack wax, subtracts three line slack waxs, subtracts one or more mixtures in four line slack waxs and frivolous asphalt oil; Sweat oil is vacuum distillate or decompression slack wax are produced petroleum wax by-product oil through squeezing wax sweating or solvent dewaxing and deoiling; Polymkeric substance comprises that number-average molecular weight is 500～100000 oligopolymer.
3. it is characterized in that in accordance with the method for claim 1: sweat oil consumption is 4%～20%.
4. it is characterized in that in accordance with the method for claim 1: polymkeric substance is one or more in polyethylene, polypropylene, polyisobutene and ethene-vinyl acetate copolymer.
5. it is characterized in that in accordance with the method for claim 1: polymer loading is 1%～5%.
6. it is characterized in that in accordance with the method for claim 1: catalyzer is permanganate, dichromate, superoxide or naphthenate; Oxygen-containing gas flow is 15～35L/Kgh, and oxygen-containing gas is air, oxygen-rich air or other oxygen-containing gas.
7. in accordance with the method for claim 6, it is characterized in that: permanganate is potassium permanganate or sodium permanganate, dichromic acid hydrochlorate is potassium bichromate, sodium dichromate 99 or dichromic acid cobalt, superoxide is hydrogen peroxide, naphthenate is that naphthenic acid bores or manganese naphthenate, above-mentioned various catalyzer uses wherein a kind of separately, or uses wherein several mixtures.
8. in accordance with the method for claim 1, it is characterized in that: add acid number≤30mg KOH/g of phosphatide, HLB value is 3～4.
9. it is characterized in that in accordance with the method for claim 1: in oxidation products, add the phosphatide that accounts for oil phase raw material weight 0.5%～4%.
10. the application of the powdery emulsion explosive oil phase material that described in the arbitrary claim of claim 1 to 9 prepared by method in powdery emulsifying explosive, emulsifier accounts for 0.7%～1.3% of powdery emulsifying explosive weight.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105802667B (en) * | 2014-12-28 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of production method of explosive insensitiveness wax |
| CN105294369B (en) * | 2015-07-23 | 2017-10-13 | 浏阳金科新材料有限公司 | A kind of water-resistant type composite oil phase for being exclusively used in the mixing expanded explosive production technology of liquid |
| CN107513406B (en) * | 2016-06-17 | 2019-05-21 | 中国石油化工股份有限公司 | The method for preparing hydro carbons phase-change material |
| 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 |
| CN111378505B (en) * | 2018-12-31 | 2024-05-07 | 中国石油化工股份有限公司 | Oxidation method of petroleum wax |
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| CN1174182A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Compound wax for emulsified explosive |
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| 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 |
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| US4840687A (en) * | 1986-11-14 | 1989-06-20 | The Lubrizol Corporation | Explosive compositions |
| CN1225916A (en) * | 1998-02-10 | 1999-08-18 | 帝国化学工业印度有限公司 | Non-incendive water-in oil emulsive explosion composition |
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| US4594118A (en) * | 1984-04-19 | 1986-06-10 | Ici Australia Limited | Explosive composition with bubble enhancer |
| CN1174182A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Compound wax for emulsified explosive |
| 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 |
| CN1597646A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Preparation method of emulsifier aid for eulsified 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 |
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