CN102452864A - 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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- CN102452864A CN102452864A CN2010105137411A CN201010513741A CN102452864A CN 102452864 A CN102452864 A CN 102452864A CN 2010105137411 A CN2010105137411 A CN 2010105137411A CN 201010513741 A CN201010513741 A CN 201010513741A CN 102452864 A CN102452864 A CN 102452864A
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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 who is used for the oil phase material 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 be 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 140 ℃ of emulsification.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 harm; Meeting people's blasting powders does not have the development trend of ladderization, possesses the solid form characteristic of powdered TNT-free explosive 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.Its production unit technology also has than big-difference, though the effect of Wax special is all the foreign minister, powdery emulsifying explosive is higher to the emulsifying film requirement of strength that Wax special forms, and 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; Wax special forms coating layer on the ammonium nitrate granule surface; Be 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, and reductive agent (Wax special) contacts tightr with oxygenant.Because powdery emulsifying explosive is different fully with the character and the production process of emulsion [explosive and powder type explosive; Therefore; The character of oil phase is required also different fully, the oil phase material (like CN99113309.9, CN99113308.0, CN99113295.5, CN99113294.7, CN02109421.7 etc.) that is used for the oil phase material (like CN96106444.7, CN96106443.9, CN96106442.0, CN1174182A etc.) of emulsion [explosive and is used for powder type explosive can not be used for powdery emulsifying explosive.
MF that Fushun Petrochemical Research Institute succeeds in developing series emulsion [explosive specific complex wax and DT type firer Wax special is respectively applied for emulsion [explosive and powder type explosive is all obtained better result of use, but can not satisfy the powdery emulsifying explosive requirement.CN91107080.X has proposed a kind of powder emulsified ammoniumnitrate explosives that is used for engineering explosion, and its oil phase characteristic 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 compositions such as paraffin, ceresine, rosin.The powdery emulsifying explosive of all these reports is the oil phase basic raw material with the petroleum refinement product all, and cost is higher.CN101172914A has proposed a kind of compound wax that is used for powdery emulsifying explosive; Being that basic material is composite with the petroleum wax produced in the petroleum refining process, decompression slack wax and sweat oil forms; Reduced the powdery emulsifying explosive cost effectively, the consumption of emulsifying agent in the powdery emulsifying explosive production process has been had no influence.
As everyone knows, compare with wax class material, emulsifying agent costs an arm and a leg, and especially the 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
Deficiency to prior art; The present invention provides a kind of lower-cost powdery emulsifying explosive with Wax special preparation of compositions method; When the oil phase that the inventive method obtains is used for powdery emulsifying explosive production, can obviously reduce the consumption of emulsifying agent, guarantee the quality of powdery emulsifying explosive simultaneously.
The preparation method of powdery emulsifying explosive oil phase material of the present invention comprises following content:
The 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 the oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%; Under 130～180 ℃; 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.
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 the 70# mixed crystal wax.
Wherein, 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.
Wherein, 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.
Wherein, 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.
Wherein, Employed catalyzer is permanganate, dichromate, superoxide or naphthenate; Its permanganate is potassium permanganate or sodium permanganate, and the dichromic acid hydrochlorate is SRM 935a, sodium dichromate 99 or dichromic acid cobalt, and superoxide is a ydrogen peroxide 50; 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.
The inventive method adopts the batch production method; The oxygen-containing gas flow is generally 15～35L/Kgh (every kilogram oil phase raw material per hour air flow); 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.
Among the present invention, the phosphatide of adding acid number≤30mg KOH/g, the HLB value is 3～4, phosphatide can be various commercially available prod.Preferably continue reaction 0.5～3 hour after adding phosphatide.
The application of powdery emulsifying explosive oil phase material in powdery emulsifying explosive of the inventive method preparation, the emulsifying agent consumption accounts for 0.7%～1.3% of powdery emulsifying explosive weight.Emulsifying agent is an emulsifying agent commonly used in this area, like the succimide macromolecule emulsifier etc.
The preparation method of the powdery emulsifying explosive oil phase material 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, adopts oil phase material of the present invention, and when producing 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 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, 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.
Embodiment 1
With 58# SEMI-REFINED PARAFFIN WAX 200g, subtract three-way slack wax 400g, residual oil slack wax 300g, sweat oil 80g, PE20g and 1g naphthenic acid and bore after heating mixes; Pour reactor drum into, 160 ℃ of bubbling air reactions 5 hours, air flow quantity was 25L/h; Add phosphatidase 12 0g after the oxidation, continue reaction 1 hour.
Embodiment 2
With 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 drum into; Slowly add the 10g ydrogen peroxide 50,170 ℃ of bubbling air reactions 8 hours, air flow quantity was 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 4g potassium permanganate heating mixing; Pour reactor drum into, 150 ℃ of bubbling air reactions 4 hours, air flow quantity was 20L/h; Add phosphatidase 14 0g after the oxidation, continue reaction 2 hours.
Embodiment 4
With 56# SEMI-REFINED PARAFFIN WAX 350g, subtract three-way slack wax 350g, residual oil slack wax 100g, sweat oil 160g, PE40g and the heating of 8g SRM 935a and mix after; Pour reactor drum into; 140 ℃ of bubbling air reactions 7 hours, air flow quantity was 35L/h, added phosphatidase 13 0g after the oxidation.
Comparative example 1
Adopt the oil phase material prescription (parts by weight) of CN101172914A embodiment 1
56# SEMI-REFINED PARAFFIN WAX 5,64# SEMI-REFINED PARAFFIN WAX 5 subtracts three-way slack wax 40, subtracts four line slack waxs 30, frivolous asphalt oil 10, sweat oil 5, PE 5.
Under 1700 rev/mins, 135 ℃ condition, carry out the 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 is compared with comparative example with stability and is improved to some extent, and the emulsifying agent consumption reduces significantly, and emulsifying agent is a polyisobutene succinimide.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Emulsifying agent consumption % | 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 |
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. the preparation method of a powdery emulsifying explosive oil phase material comprises following content:
The 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 the oil phase raw material, add the catalyzer that accounts for oil phase raw material weight 0.1%～1.0%; Under 130～180 ℃; 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.
2. according to the described method of claim 1, it is characterized in that: 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 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 is vacuum distillate or decompression slack wax are produced petroleum wax through press for extracting juice wax sweating or solvent deoiling dewaxing a by-product oil; Polymkeric substance comprises that number-average molecular weight is 500～100000 oligopolymer.
3. according to the described method of claim 1, it is characterized in that: the sweat oil consumption is 4%～20%.
4. according to the described method of claim 1, it is characterized in that: polymkeric substance is Vilaterm, Vestolen PP 7052, gather and differ from alkene and the ethene-vinyl acetate copolymer one or more.
5. according to the described method of claim 1, it is characterized in that: polymer loading is 1%～5%.
6. according to the described method of claim 1, it is characterized in that: catalyzer is permanganate, dichromate, superoxide or naphthenate; The oxygen-containing gas flow is 15～35L/Kgh, and oxygen-containing gas is air, oxygen-rich air or other oxygen-containing gas.
7. according to the described method of claim 6; It is characterized in that: permanganate is potassium permanganate or sodium permanganate; The dichromic acid hydrochlorate is SRM 935a, sodium dichromate 99 or dichromic acid cobalt, and superoxide is a ydrogen peroxide 50, and naphthenate is that naphthenic acid bores or manganese naphthenate; Above-mentioned various catalyzer uses wherein a kind of separately, perhaps uses wherein several kinds mixture.
8. according to the described method of claim 1, it is characterized in that: add the acid number≤30mgKOH/g of phosphatide, the HLB value is 3～4.
9. according to claim 1 or 8 described methods, it is characterized in that: add phosphatide continued reaction 0.5～3 hour.
10. the application of powdery emulsifying explosive oil phase material in powdery emulsifying explosive of the said method preparation of the arbitrary claim of claim 1 to 9, the emulsifying agent consumption accounts for 0.7%～1.3% of powdery emulsifying explosive weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294369A (en) * | 2015-07-23 | 2016-02-03 | 浏阳金科新材料有限公司 | Water-resistant composite oil phase special for liquid mixed type expanded explosive production process |
| 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 |
| CN107513406A (en) * | 2016-06-17 | 2017-12-26 | 中国石油化工股份有限公司 | The method for preparing hydro carbons phase-change material |
| CN111378505A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Oxidation method of petroleum wax |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111378505A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Oxidation method of petroleum wax |
| 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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