CN110267929A - Improved explosive compositions - Google Patents
Improved explosive compositions Download PDFInfo
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- CN110267929A CN110267929A CN201780086179.9A CN201780086179A CN110267929A CN 110267929 A CN110267929 A CN 110267929A CN 201780086179 A CN201780086179 A CN 201780086179A CN 110267929 A CN110267929 A CN 110267929A
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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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
- C06B23/003—Porous or hollow inert particles
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/285—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with fuel oil, e.g. ANFO-compositions
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
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Abstract
The present invention provides explosive compositions, and one or more other oxidants of up to about 90%w/w are arrived it includes about 2 to about 25%w/w hydrogen peroxide, greater than 0.The present invention also provides the methods for preparing explosive compositions and explosive compositions of the invention in such as mining is crushed and the purposes of mobile ground.
Description
This application claims Australian Provisional Patent Application the 2016905130th priority on December 12nd, 2016
And equity, it is integrally incorporated by reference herein.
Invention field
The present invention relates to improved explosive compositions.More particularly it relates to comprising hydrogen peroxide (HP) and a kind of
Or the explosive compositions of a variety of other oxidant combinations.
Main application of the invention is used as combining used in mining application based on the explosion of hydrogen peroxide/nitrate
Object is described below in reference to the application.It is to be understood, however, that the present invention is not limited to this specific application fields.
Background of invention
To the discussion of the prior art to place this invention into technical background appropriate and obtain its advantage below providing
It is more fully understood by.It will be appreciated, however, that throughout the specification any discussion of the prior art is not construed as expressing or
Hint recognizes that this prior art is well-known or is formed a part of general knowledge known in this field.
The nearly all business and minelite used in the world at present is all based on ammonium nitrate (AN) or AN and on a small quantity its
The mixture of its alkali metal and/or alkaline earth nitrate, such as sodium nitrate (SN) or calcium nitrate (CN).AN is strong oxidizer,
The basis of business explosive was at least had been used as in past 50 to 60 years.Such most of explosives are by nitrogen in explosive
The energy response of compound provides necessary explosive force.
Initially, mining company oneself uses AN as explosive.However, they readily recognize that the addition of diesel oil increases energy
Amount output, without cost (ammonium nitrate-fuel oil, now commonly referred to as " ANFO ") is significantly increased.However, ANFO's is water-fast
Property is very poor, and which has limited its uses in wet blast hole.In order to improve the problem, slurry and hydrogel are developed.Slurry is logical
It often include the AN of dissolution/dispersion in water, other salts such as calcium nitrate, sodium nitrate, amine nitrate, perchlorate etc., Qi Tatian
Add agent such as guar gum (as thickener) and water-soluble or insoluble fuel (glycerol, MMAN, diesel oil etc.).According to by fried ground
Characteristic, they can also be mixed with ANFO.Slurry usually also includes solid sensitizer (aluminium and high explosives, such as TNT, RDX
Deng), it miss-fires so that slurry explodes and reduces to the maximum extent.Hydrogel has composition similar with slurry, however, it is possible to add
Crosslinking agent improves the water resistance of product.
The shortcomings that hydrogel and slurry first is that the AN that can be mixed in solution is limited.The development of water-in-oil emulsion overcomes this
Disadvantage.When lotion manufactures at high temperature, these lotions can the AN containing high concentration (see U.S. Patent No. 3,447,978
Number).Water-in-oil emulsion (is made of) group by the heated aqueous phase being dispersed in organic-fuel AN, other nitrate, perchlorate etc.
At.Stablize aqueous-organic mixture by using emulsifier.Lotion can also be mixed with the ANFO of different proportion, therefore suitable
Close ground blasting.
However, although developing AN lotion, AN slurry and hydrogel, it is still desirable to improved explosive is developed, and it is existing
Explosive compositions compare, it is suitably more cost effective, and can mass production with meet industry high demand.It is being formulated
It is middle to be advantageous using less AN, and use the use of other types of nitrate substitution AN.In addition, this substitute is answered
When it is preferably safer, with relatively low carbon footprint, near point of use manufacture to minimize the transport on public way, energy
Enough manufactures on demand are to minimize storage requirements and improve safety, allow to produce using existing conveying equipment, and/or in explosion time
Raw less amount (or not generating) toxic nitrogen oxide smoke (NOx) etc..If there is no heavy supervision to want this substitute
It asks to reduce management cost, and ideal.Explosive compositions can be further preferably cross-linked in situ, viscous under blast hole to increase
Degree.
Although being improved by the type of composition of ammonium nitrate manufacture, disadvantage first is that in blast process, due to
There are nitrogen compound (coming from nitrate) in explosive compositions, NO can be generatedxSmog.These NOxSmog is toxic, will affect mining area
The health of personnel.Therefore, NO after explosionxThe discharge of smog is a safety problem, and in countries such as Australia, now with
Strict supervision control measure manage this discharge.It is issued for example, with reference to Queensland, Australia regulatory agency in 2011
" Queensland Guidance Note:Management of oxides of nitrogen in open cut
Blasting (Queensland state teachings: the management of nitrogen oxides in surface blasting) ".Equally, Australian explosive manufacture
Quotient has also issued NO after a management explosionxBusiness norms (AEISG Code of Practice, Prevention of gas
And Management of Blast Generated NOx Gases in Surface Blasting, Australian explosive
Industry security group: the NO for generation of exploding in earth's surface explosionxThe prevention and management business specification of gas, 2011).Therefore, it needs
NO can be substantially reduced by findingxThe explosive compositions of generation.
Hydrogen peroxide (HP) is also a kind of oxidant, can at least be able to satisfy some of them demand.
International PCT discloses WO 2013/013272 explosive compositions described comprising HP and sensitizer, wherein quick
Agent includes the compressible material with one or more gas-filled spaces and/or bubble.WO 2013/013272 also describes
The method of explosive compositions and the purposes of the explosive compositions are prepared, wherein the preparation method includes by hydrogen peroxide
It is mixed with sensitizer, the sensitizer includes compressible material and/or bubble.Composition in WO 2013/013272 can
HP containing very high concentration.Despite the presence of the prior art example of HP base explosive, however, there remains develop improved explosion
Composition.In particular, need to develop the improved explosive compositions made of HP and one or more other oxidants, it is described quick-fried
Fried composition can control the conveying of susceptibility, density, rate of detonation and energy.
The purpose of the present invention is overcoming or improve one or more disadvantages of the prior art, or at least provide useful replace
For scheme.
Summary of the invention
The present invention relates to for business, building, civilian, agriculture, mining and similar field explosive.It will be appreciated, however, that
The present invention can be used for other related fieldss.
The preferred purpose of embodiment of the present invention is to provide the explosive compositions for meeting following one or more purposes: preparation
It is convenient, have that improved stability, a large amount of sustainable fuel can be used, and (it reduce fried in situ over time
The carbon footprint of medicine) and can be used a large amount of nitrate in addition to AN (it reduce the dependences to AN).
In a first aspect, the present invention provides explosive compositions, it includes:
A. about 2% to about 25%w/w hydrogen peroxide；With
B. it is greater than the 0 one or more other oxidants for arriving up to about 90%w/w.
In one embodiment, explosive compositions are provided, it includes:
About 2% to about 25%w/w hydrogen peroxide；With
One or more other oxidants of up to about 90%w/w are arrived greater than 0；With
About 15% to about 25%w/w fuel, preferably sustainable fuel.
According to preferred embodiment, the present invention provides explosive compositions, it includes:
About 2% to about 25%w/w hydrogen peroxide；
One or more other oxidants of up to about 90%w/w are arrived greater than 0；
Fuel phase；
Thickener and/or crosslinking agent；
Secondary fuel；With
Sensitizer.
Preferably, the composition includes about 5% to about 25%w/w hydrogen peroxide.Preferably, one or more other oxygen
Agent is selected from the group of nitrate, perchlorate, peroxide salt or nitric acid composition.For example, one or more other oxidants can
With the group formed selected from nitrate, perchlorate, sodium peroxide, potassium peroxide and optional nitric acid.Perchlorate can be selected from height
Ammonium chlorate and sodium perchlorate.Preferably, salt be selected from ammonium nitrate (AN), calcium nitrate (CN), calcium ammonium nitrate (CAN), sodium nitrate (SN),
NH4ClO4、NaClO4、Na2O2、K2O2Or mixtures thereof.For example, nitrate can be selected from ammonium nitrate, calcium nitrate and sodium nitrate.Make
For other examples, nitrate can be selected from calcium ammonium nitrate, calcium nitrate and sodium nitrate.In one embodiment, explosive compositions are not
Containing AN.One of explosive compositions or a variety of other oxidants can be selected from calcium nitrate and sodium nitrate.Preferably, explosion combination
Object includes 0.1 to 75%w/w one or more other oxidants.In one embodiment, explosive compositions contain 0.1 to
The dissolving salt of 75%w/w.In preferred embodiments, at least some of of at least one of one or more other oxidants does not have
It is dissolved completely in explosive compositions, but exists in the form of solid oxidizer, such as the form of powder or particle.At this
In the embodiment of sample, at least partly in solid form existing one or more other oxidants can selected from AN, SN, CN,
The group of or mixtures thereof CAN composition.The composition may include solid nitric acid salt oxidizing agent, such as content is 0.1 to 70%w/
w.The composition can wrap aqueous.Solid nitric acid salt oxidizing agent can be selected from the group of or mixtures thereof AN, SN, CAN composition.
Preferably, the composition include 50%w/w or less water or 30%w/w or less water or 25%w/w or
Less water.Explosive compositions also may include one or more selected from sensitizer, fuel, secondary fuel, water, thickener, crosslinking
Agent, emulsifier, energy dilution agent and optional other additives the other groups of groups being grouped as.
Preferably, explosive compositions include sensitizer.Preferably, sensitizer includes compressible material and/or bubble, or
Material comprising retaining gas.Bubble can be formed in situ, and by N2、O2、CO2, NO or H2Or mixtures thereof bubble composition.
The material of retention gas can be selected from glass microsphere, ceramic microsphere, plastic microsphere or EPS that partial size is less than 2mm.Explosive compositions are excellent
The density that there is the sensitizer by adding sufficient amount to control is selected, so that the composition is sensitive to explosion.Density can control
About 0.3 to 1.4g/cm3, or can be formulated as about 0.3 to 1.4g/cm3。
The composition may include fuel or it may include fuel and secondary fuel.Fuel can be water-soluble combustion
Material.Water soluble fuel can be selected from or mixtures thereof amine nitrate or urea.Explosive compositions containing 0.1 to 30%w/w water
Dissolubility fuel.The composition may include the fuel phase of 13-25%w/w.Preferably, fuel mutually include it is one or more selected from glue,
The group that the group of or mixtures thereof glycerol, ethylene glycol, propylene glycol, molasses, formamide is grouped as.For example, fuel mutually may include one
The group that kind or a variety of groups selected from or mixtures thereof glue, glycerol, ethylene glycol, propylene glycol, formamide are grouped as.The composition can be with
Include sustainable fuel.The content of sustainable fuel in the composition can be 15% between 25%w/w.
Preferably, the composition is hydrogel composition, and in this case, the composition may include thickener or crosslinking
Agent.The composition can be the hydrogel composition comprising thickener and crosslinking agent.Thickener can be suspended in fuel.Thickening
Agent can be selected from the group of guar gum, xanthan gum, sodium alginate, polyacrylamide and polyvinyl alcohol composition.The composition may include
The group of crosslinking agent composition selected from or mixtures thereof antimonic salt, chromic salts, phosphoric acid.Fuel mutually may include one or more water-insolubles
Fuel, the group selected from or mixtures thereof diesel oil, oil, vegetable oil composition.Therefore, explosive compositions can be configured to lotion,
In this case, it may include emulsifier.Emulsifier may be combined in fuel.Emulsifier can be selected from PIBSA- amine derivative,
The group of or mixtures thereof SMO, lecithin composition.
Preferably, the composition is formulated into the oxygen balance between+10 to -10, for example, the composition can be with
With the oxygen balance between+5 to -5.Explosive compositions can energy reducing agents (the i.e. dilution material containing 1-800%v/v
Material).Energy dilution material can be selected from EPS, waste rubber tire, puffed rice and plastic bead.Hydrogen peroxide, one or more other oxygen
Agent and fuel containing thickener can mix, until forming viscosity 5 to the viscous material between 50Pa*s.The composition
It can have 5 to 50Pa*s viscosity.
The creative explosive compositions instructed herein produce many advantages.For example, compared with existing explosive compositions,
Certain formulas of the present composition may be more convenient for preparation, it is more cost effective, produce and store safer, and/or person's energy
Enough mass productions are to meet the needs of mining industry.Additional safety is provided by using for example relatively high concentration of CAN,
It is well known that CAN is lower than ammonium nitrate to the susceptibility of accidental explosion.This in formula SN using equally applicable.Therefore, this hair
Bright is the major progress of this field.That explosive compositions of the invention utilize is HP, and HP is the material of sustainable production, with ability
Other types of oxidant used in domain is compared, and carbon footprint is relatively low.Sustainable fuel also can be used in the composition,
It is opposite with technology currently used in mining industry.In order to explain this point, current explosive compositions use the fuel of low concentration,
This fuel is usually from petrochemical industry.On the contrary, present invention disclosed herein explosive compositions can be incorporated to it is commercially available or existing
There is technology explosion composition compared to relatively a greater amount of sustainable fuel.Therefore, the dependence of the fuel of petrochemical industry is reduced
It is the major progress of this field.In addition, the increase of sustainable fuel means that the amount of oxidizer materials in formula can in formula
It reduces but does not influence explosion property.
The present invention is opposite with the common sense of this field.In order to explain, it is now recognized that, it is impossible to or very difficult ignite has relatively
The composition of the nitrate of high concentration such as CAN.However, it is surprising that the present invention provides ignite containing up to 30%w/
W, it is even as high as the ability of the composition of 65%w/w.This respect of the invention is the marked improvement of this field.The present invention also provides
The ability of relatively great amount of nitrate is incorporated to by manufacture hydrogel or lotion, the hydrogel or lotion wrap in water phase
The solid nitric acid salt phase of nitrate containing HP/ and particle form.It can be to entire composition using the oxidant of solid form
Density carries out certain controls, therefore provides certain controls to VOD, this is discussed below.
Explosive compositions of the invention can also be configured to emulsion form.It is also understood that inventive combination of the invention
Object can produce a small amount of NOx, and NO is not generated in certain forms of the inventionx。
Composition of the invention is considered to provide several advantages better than the prior art, such as compares over time
Explosive compositions comprising higher percent HP have better stability.This is all advantageous in terms of safety and storage.More
Specifically, " dormancy time " (i.e. time for deteriorating in situ of explosive so that the explosive compositions with rock contact
When, rate of detonation is reduced to the defined useful limit or less) it is estimated greater than the explosive containing higher HP content.For example,
CAN/HP composition of the invention has been prepared for it, and it was found that the composition has the application phase with viable commercial product
When/compatible dormancy time, such as more than 24 hours or longer dormancy time.Thus, it can be assumed that bigger explosion is
It is possible, because can have longer time (such as several days) before the explosive that first time loads becomes unstable in hole
Explosive is loaded into many holes.Therefore, more holes can be loaded before explosion.
Another advantage is that when using CAN, these compositions can explode.This is unexpected, because CAN is non-explosive
It is fried.Accordingly, it is considered to which inventor thinks the base with addition CN and SN to the explosion tendency (compared with ammonium nitrate) of CAN relative reduction
It is compared in the explosive of ammonium nitrate, there are security advantages using the combination of CAN and CAN/SN.In view of CAN characteristic not easy to explode
(compared with AN), inventor think to use CAN's and CAN/SN compared with using the explosive based on AN added with CN and SN
Combination has security advantages.
Second aspect, the present invention provides the methods of the explosive compositions of preparation first aspect, and this method includes by peroxide
Change hydrogen and one or more other oxidant mixing, optionally further comprising the sensitization of composition.Preferably, by hydrogen peroxide, its
Its oxidant and fuel mixing, until forming viscosity about 5 to the viscous material between 50Pa*s.Preferably, pass through addition foot
The sensitizer enough measured carrys out the density of control composition, so that composition is sensitive to explosion.
The third aspect, the present invention provides the explosive compositions of first aspect in such as mining is crushed and movably
Purposes in face.
Definition
When the present invention is described and claimed as, following term will be used according to definition given below.It should also be understood that
The term used herein specific embodiment of the invention just for the sake of description, rather than in order to limit.Unless otherwise defined,
All technical and scientific terms used herein has normally understood identical as those skilled in the art
Meaning.
Unless context clearly indicates otherwise, otherwise in entire disclosure and claims, word " includes
(comprise, comprising) " etc. is interpreted as including property meaning, rather than exclusiveness or exhaustive meaning；That is,
It is the meaning of " including but not limited to ".
In addition in the embodiment of implementation, or in the place indicated, all expression components as used herein or reaction item
The number of the quantity of part is understood to be modified by term " about " in all cases.Embodiment is not limited to of the invention
Range.Hereinafter, unless otherwise stated, " % " will imply that " %w/w ", and " ratio " will imply that " w/w ", and " part " will be anticipated
Taste " parts by weight ".
Unless context clearly indicates otherwise, otherwise refer to organize timesharing existing for a certain %w/w, is relative to entire
For explosive compositions.For example, the explosive compositions comprising 2-25%w/w hydrogen peroxide refer to every 100g explosive compositions packet
The explosive compositions of the hydrogen peroxide containing 2-25g.
Term HP is the abbreviation of hydrogen peroxide.
Term AN means ammonium nitrate.
CN means calcium nitrate tetrahydrate.
CAN means calcium ammonium nitrate
SN is the abbreviation of sodium nitrate.
ANFO is the abbreviation of ammonium nitrate fuel oil.
Amine nitrate is the abbreviation of monomethyl amine or ethamine or propylamine nitrate.
Sensitizer means the additive for introducing gap in the composition.Sensitizer can increase the sensitivity of energetic material explosion
Property.Sensitizer can be chemistry generation gap (bubble), or can close or retain gas (example include ceramics/glass
Glass microballoon, expanded polystyrene (EPS) and polyurethane foam).
GMB is the abbreviation of glass microsphere.
EPS is the abbreviation of expanded polystyrene (EPS).
TNT means trinitrotoluene.
HMX means four oxazoline of octahydro -1,3,5,7- tetranitro -1,3,5,7-.
RDX means 1,3,5- trinitro- hydrogen -1,3,5- triazine.
VOD system refers to the rate of detonation as unit of m/s.
OB means oxygen balance.
Term g/cm3Meaning it is identical as g/ml.
It term " preferred ", " preferably " and " suitably " means this hair of certain benefits can be provided in some cases
Bright embodiment.However, other embodiments are also likely to be preferred in identical or other situations.In addition, reference one
Or multiple preferred embodiments be not meant to other embodiments be it is useless, do not mean that yet and exclude other embodiments
Except the scope of the present invention.
Unless expressly stated otherwise, term " a ", " an " and " the " refers to " one or more ".Term " embodiment (an
Embodiment) ", " embodiment (embodiment) ", " embodiment (embodiments) ", " embodiment (the
Embodiment) ", " embodiment (the embodiments) ", " embodiment (an embodiment) ", " certain implementations
Scheme ", " exemplary implementation scheme ", " an at least embodiment ", " one or more embodiments " and " embodiment " are
Refer to " one or more of the invention (but be not necessarily all have) embodiment ", unless expressly stated otherwise,.
The prior art mentioned in this specification is incorporated herein by reference.
Brief Description Of Drawings
Fig. 1 is in the pipeline that diameter is 50mm, and the VOD of the CAN/ fuel based gel of about 20% HP and about 40% is to close
The curve graph of degree.Sensitized treatment is a kind of HP to be resolved into O by adding2The gas generating agent of bubble is realized.
Fig. 2 is the CAN/ fuel based gel and CAN particle of about 6% HP and about 65% in the pipeline that diameter is 102mm
With the VOD of the manufactured mixture of ratio of 45:55 (gel: particle) to the curve graph of density.Sensitized treatment is to pass through addition
It is a kind of HP to be resolved into O2The gas generating agent of bubble is realized.
Fig. 3 is VOD pairs of the SN/ fuel based gel of about 30% HP and about 24% in the pipeline that diameter is 50mm
The curve graph of density.Sensitized treatment is a kind of HP to be resolved into O by adding2The gas generating agent of bubble is realized.
Fig. 4 is the SN/ fuel based gel and SN particle of about 16% HP and about 44% in the pipeline that diameter is 102mm
With the VOD of mixture made of the ratio of 70:30 (gel: particle) to the curve graph of density.Sensitized treatment is by addition one
HP can be resolved into O by kind2The gas generating agent of bubble is realized.
Detailed description of the invention
In a first aspect, the present invention provides explosive compositions, it includes:
About 2% to about 25%w/w hydrogen peroxide；With
One or more other oxidants of up to about 90%w/w are arrived greater than 0.
Suitably, the composition also includes one or more as discussed further below selected from sensitizer, fuel, other
Fuel, water, thickener, crosslinking agent, emulsifier, energy dilution agent and optional other additives the other groups of groups being grouped as.
Hydrogen peroxide (HP)
The concentration of HP is about 2% between 25%w/w in the present composition.
Suitably, the HP concentration in composition is about 0.5,0.8,1,2,5,6,10,12,13,15,20 or 25%w/w.Example
Such as, the HP concentration in composition can be in about 0.5,0.8,1,2,5,6,10,12,13,15 or 20 between 25%w/w.For example, group
2% can be perhaps greater than but be less than 25%w/w or can be greater than greater than 1% but less than 25% by closing the HP concentration in object
5% but be less than 25%w/w.Therefore, suitably, the HP concentration in composition is about 1 to 5,2 to 5,1 to 10,5 to 10,5 to 6,6
To 10,5 to 15,10 to 12,12 to 13,13 to 15,2 to 20,5 to 20,15 to 25,15 to 20 or 2 to 25,5 to 25 or 20 to
Between 25%w/w.For example, the HP concentration in composition can be 2 to 10%w/w or 12 to 25%w/w or 10 to 20%w/
w。
It should be appreciated that the %w/w of hydrogen peroxide present in composition means the amount of pure hydrogen peroxide.Due to hydrogen peroxide
It is provided in the form of aqueous solution of the HP concentration less than 100%, such as HP concentration is 50%w/w or 35%w/w or 30%w/w,
Therefore the person skilled in the art will easily understand can be by adjusting the required amount for diluting HP solution to ensure explosion of the invention
Composition needs summing mode to 25%w/w HP comprising 2.To avoid query, for example, if composition of the invention contains
There is the HP solution of 20% 50%w/w, then the composition contains the HP of 10%w/w.It will also be appreciated by those of skill in the art that 2
HP concentration to 25%w/w is the final HP concentration in explosive compositions, it is therefore necessary to which consideration is added to group in process for preparation
Close the dilution effect of any other component (such as fuel, oxidant, thickener etc.) in object.
Other oxidants
Composition as described herein includes one or more other materials for being suitable as explosive material in itself or substance
Mixture.
Specifically, explosive compositions of the invention include one or more other oxidants (such as a kind of other oxidants,
Such as two kinds of other oxidants).Any suitable oxidant can be used.For example, one or more other oxidants are suitably
The group formed selected from nitrate, perchlorate, sodium peroxide and potassium peroxide and optional nitric acid.
Nitrate can be selected from ammonium nitrate, sodium nitrate, calcium ammonium nitrate, calcium nitrate, potassium nitrate, barium nitrate and magnesium nitrate composition
Group.
Perchlorate can be selected from ammonium perchlorate, sodium perchlorate, potassium hyperchlorate, barium perchlorate, magnesium perchlorate and Calcium perchlorate
The group of (such as ammonium perchlorate and sodium perchlorate) composition.
In one embodiment, one or more other oxidants are selected from the group that nitrate and perchlorate form.One
In embodiment, one or more other oxidants are selected from nitrate.In one embodiment, one or more other oxidants
Group selected from AN, CAN and SN composition.In one embodiment, one or more other oxidants are formed selected from CAN, CN and SN
Group.In one embodiment, one or more other oxidants are selected from the group that CAN and SN is formed.In one embodiment, separately
A kind of oxidant is CAN.In one embodiment, another oxidant is SN.In one embodiment, another oxidant is
CN.In one embodiment, one or more other oxidants do not include AN.In other words, in one embodiment, explosion group
It closes object and is free of ammonium nitrate.
Composition of the invention includes to be greater than the 0 one or more other oxidants for arriving up to about 90%w/w, for example, about
0.1% to about 75%w/w.For example, composition of the invention may include greater than 0,0.1%, 1%, 10%, 20%, 30%,
40%, one or more other oxidants of 50% or 60%w/w to 90%w/w, for example, composition of the invention may include
1 to 20%, 20 to 40%, 15 to 35%, 35 to 55%, 30 to 70%, 40 to 70% or 50 to 80%w/w it is one or more
Other oxidants.For example, composition of the invention may include up to 90%, 80%, 75%, 70%, 65%, 60%, 50%,
40%, 30%, one or more other oxidants of 20%w/w etc., or may include about 90%, 80%, 75%, 70%,
65%, one or more other oxidants of 60%, 55%, 50%, 45%, 40%, 30% or 20%w/w.It should be appreciated that this
In explosive compositions in total include one or more oxidants according to aforementioned quantities or range, therefore, when use more than one
Oxidant when, every kind of oxidant can be in aforementioned quantities or range with the presence of any suitable amount, so that the gross mass of oxidant
Add up the amount or range for reaching specified.
It should be appreciated that oxidant can be the form of solid and liquid mixture.In order to explain, when oxidant is with relatively
Low concentration in use, would generally be dissolved in water, if there is concentration be higher than the solubility of oxidant, then oxidant can be molten
Xie Bingcheng solid form.In certain embodiments, oxidant is completely dissolved (or substantially completely dissolving) in the composition.At this
It, can be with the solid oxidizer of such as particle form of excessive addition in the embodiment of sample.In other embodiments, oxidant
It is only partly dissolved in the composition, in this case, solid oxidizer (for example, in the form of solid particle) can add before explosion
Add, so that particle does not have time enough sufficiently to dissolve.Oxidant can be 100:0 to the liquid between 20:80: solid ratio
Example, and any ratio therebetween.For example, the ratio of liquid and solid can between 100:0 and 70:30, or in 80:20 and
Between 60:40, perhaps between 70:30 and 40:60 perhaps between 50:50 and 30:70 or in 100:0,70:30,60:
40, between 50:50,45:55,40:60；Or 20:80.
The present invention also includes many institutes of one or more such as trinitrotoluenes, nitroglycerine or pentaerythrite Tetranitrate
Another Explosives of the known explosive material as the composition.
Water
Explosive compositions described herein can wrap aqueous.In one embodiment, explosive compositions may include being less than
The water or 40%w/w or less water or 30%w/w of 50%w/w or less water, such as 25%w/w or less, 20%w/w
Or less, 15%w/w or less or 10%w/w or less.In one embodiment, explosive compositions may include 5%w/w or
More water, such as 10%w/w or more.Therefore, the composition may include 5 to 50%w/w water or 5 to 20%w/w's
Water or 15 to 30%w/w water or 10 to 40%w/w water or 50,45,40,35,30,25,20,15,10,5 or 1%w/w
Water.
Sensitizer
Explosive compositions of the invention, which may include, is dispersed in one of composition or a variety of sensitizers, is improved with generating
The gap for sensibility of exploding.In addition, HP itself can function simultaneously as sensitizer and oxidant.Alternatively, HP itself can serve as it is quick
Agent is without the use of other sensitizers.
Suitably, explosive compositions of the invention are suitable for for sensitizer being maintained in substantially homogeneous dispersion (for example, dividing
Not in the case where hydrogel or lotion, pass through thickener or emulsifier).It should be appreciated that as discussed further below, it can be with
The characteristic is realized using multiple technologies.
It suitably, include the sensitizer of Cmin in composition, to make it have explosivity.Suitably, comprising explosion
The sensitizer of sensitive concentration or amount.Sensitizer also suitably keeps sensitive dispersion/distribution of exploding in entire composition.Suitably
Ground, the final densities of composition are controlled in preferred predetermined explosive range.Suitably, final densities are controlled with sensitizer
About 0.3 to 1.4g/cm3.Suitably, the density of composition be configured to about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,
1.1,1.2,1.3 or 1.4g/cm3.Suitably, the final densities of composition are configured to about 0.3 to 0.4,0.4 to 0.5,0.5
To 0.6,0.6 to 0.7,0.7 to 0.8,0.8 to 0.9,0.9 to 1.0,1.0 to 1.1,1.1 to 1.2,1.2 to 1.3 or 1.3 to
1.4g/cm3。
It will be understood to those of skill in the art that by ceramic/glass/plastic microsphere weight or the chemistry to be decomposed for bubble
The volume (for bubble) that the amount of substance is converted into specific density needs mathematics to convert.However, regardless of sensitization type such as
What, it should be understood that final densities are controlled to predetermined value, to generate explosive compositions, to control above-mentioned parameter.
Once explosive is sensitized, so that it may easily be detonated by primer, as understood by the skilled person, primer is to generate
Then high blast pressure ignites the explosive of sensitization.
It can (voids when passing through mixing, pass through note at the bubble generated by using in-situ chemical by various technologies
Emanate bubble, or composition mixed with the gas material of retention) gap is introduced into composition, these technologies are suitable for this
Invention.
In one embodiment, bubble can be " trapped " during preparing explosive compositions by mechanical mixture.Beauty
State's patent the 3,400,026th describes using protein solution (albumin, collagen, soybean protein etc.) and promotes bubble
Formation and its stability formula.U.S. Patent No. 3,582,411 describe aqueous gels formula, contain and are changed by hydroxyl
The Guar glue-type foaming agent of property.U.S. Patent No. 3,678,140 describe the side that air is incorporated to by using protein solution
A series of method, by making composition introduce air by openings, while by injector under 40 to 200psi pressure.
The in-situ preparation of bubble is wherein provided by the decomposition of compound, decomposition suitably generates O2、CO2、N2、H2、NO
Or combinations thereof.
The gas of various bubble forms has been used for being sensitized blasting agent, such as nitrogen is (referring to U.S. Patent No. 3,713,919
Number, No. 3,886,010, No. 4,875,951, No. 4,305,766 and No. 3,390,030), carbon dioxide is (referring to beauty
State's patent No. 3,288,658 and No. 3,390,032), oxygen (referring to U.S. Patent No. 3,706,607, the 3,790th,
No. 415, No. 5,397,399, No. 4,081,299 and No. 3,617,401) and hydrogen (referring to U.S. Patent No. 3,711,
No. 345).
Include HP itself for the Suitable chemical species in situ for generating bubble, manganese (Mn) salt, yeast, iodide can be used
Salt etc. decomposes；Nitrilo compound, such as nitrosamine, such as N, N '-dinitropentamethylenetetramine；Boron-based compounds, such as boron
Sodium hydride；Carbonate, such as sodium carbonate.
The discontinuous phase of minute bubbles can pass through the composition that gas injection/bubbling is incorporated herein by composition
In.It is well known (for example, see U.S. Patent No. 6,537,399, that air or gas, which is directly injected into explosive mixture,
No. 3,582,411 and No. 3,642,547).
The gas for being suitble to injection includes air, oxygen, nitrogen, carbon dioxide, hydrogen, NO and inert gas (such as argon gas).
Alternatively, the gas of injection is suitble to include the compressible particle of hollow inflation, such as microballoon, porous particle or hair
Or mixtures thereof foamed polystyrene (EPS).In the relevant embodiments, compressible material is specific gravity < 1.0g/cm3It is any low
Density material.In brief, the example of glass marble can be found in U.S. Patent No. 4,326, No. 900 and the 3rd, 447, No. 978, plastics
Microballoon can be found in U.S. Patent No. No. 4,820,361 and No. 4,547,234.These ball general diameters are 0.05mm, are accumulated close
Degree is 100g/l.For example, the use of expanded polystyrene (EPS) can be found in U.S. Patent No. 5,470, No. 407 and the 5th, 271, No. 779.
In one embodiment, compressible material is inflation, and selected from ceramics, glass or resin material or porous material
The small tiny balloon and combinations thereof of material, such as perlite or flyash.
Suitably, microsphere/microballoon includes gas, such as pentane etc..Suitably, the size of microsphere is about 20 to 2000
Between micron, and there is the bulk density less than 100g/l.
In an alternate embodiment, compressible material is porous material, such as expanded polystyrene (EPS) (EPS), polyurethane foam
Foam, cottonseed, expansion puffed rice, shell and combinations thereof.
The example of suitable hollow particle includes the small hollow microspheres of ceramics, glass and resin material, such as phenol-first
Aldehyde, poly- (vinylidene chloride)/poly- (acrylonitrile) copolymer and ureaformaldehyde.The example of suitable hollow bead include Q-Cel,3M、Deng.Porous material
Example include expansion mineral, such as perlite, flyash.Other examples of porous material are as Coal fired power station byproduct
Hollow particle.
Typically, enough bubbles and/or hollow particle and/or porous particle are used in the present compositions, with
Density is obtained 0.3 to 1.4g/cm3Explosive compositions in range.
For example, explosive compositions of the invention can have up to 1.4g/cm3, up to 1.3g/cm3, up to 1.2g/cm3、
Up to 1.1g/cm3, up to 1.0g/cm3Deng density.Explosive compositions of the invention can have 0.3g/cm3、0.4g/cm3、
0.5g/cm3Deng density.Being there is provided bubble in emulsification explosive compositions using conventional mixing techniques and would generally generated has centainly
The bubble of range bubble size.For example, the diameter of bubble is often up to 2000 microns, mean air bubble diameter is less than 300 microns
It is very common.By selecting suitable surfactant, smaller or larger-diameter bubble can produce.Therefore, by selecting the phase
The suitable surfactant for hoping concentration, can control the mean air bubble diameter in discontinuous gas phase, and 50 to 300 microns of gas
Bubble is possible.For emulsion, density range is preferably in about 0.60-1.30g/cm3, for hydrogel, density range preferably exists
0.2-1.40g/cm3Between.In emulsifying systems, bubble is suitably 10 to 100 times bigger than dispersed phase drop.Oily phase may be with gas
Bubble contact, and do not contacted with oxidant (or discontinuous phase).
Other types of sensitized material, such as TNT, HMX, RDX, aluminium powder and silicon can be used in the present compositions
Powder and combinations thereof (such as TNT, HMX, RDX and aluminium powder and combinations thereof).
Hydrogel fuel
Explosive compositions of the invention may include one or more fuel.
HP based aquagel can use water miscibility or water unmixability preparation of fuel.
It will be understood by those skilled in the art that there are many options that can be used as fuel.For example, according to their source, fuel
It can be the product of plant origin, such as sugar, molasses, vegetable oil or alcohol.Such fuel can be considered sustainable fuel.It is other
Fuel can come from petrochemical industry, such as diesel oil, paraffin oil or mineral oil, organic acid, ether, ester, amine nitrate, urea, hexamine
Deng.Other fuel can be silicone oil etc..Fuel suitable for the present composition be glycerol, sugar, syrup, alcohol, carbon, cleaned coal,
Wax, oil, such as corn oil, cottonseed oil, olive oil, peanut oil or fatty acid oil.Suitable for the present composition is held
Afterflame material may include molasses, vegetable oil, alcohol, oily such as corn oil, cottonseed oil, olive oil, peanut oil or fatty acid oil, or
Glue.Other fuel can be selected from ethylene glycol, glycerol, propylene glycol and/or formamide.Preferably, sustainable fuel is glycerol.The combination
Object may include the sustainable fuel of 15-25%w/w, such as 15 to 20% or 20 to 25%w/w.Alternatively, the composition may include
Less than 40%w/w, the sustainable fuel less than 30%, less than 25% or less than 20%w/w, for example, 5%, 10%, 15%,
20%, the sustainable fuel of 25%, 30%, 35% or 40%w/w.Alternatively, above-mentioned fuel can also be divided into water-soluble and water not
Dissolubility fuel.Water miscibility fuel for use in the present invention can be selected from glycerol, sugar, amine nitrate (such as monomethyl amine nitrate or
Nitric acid ethanol amine), hexamine and urea composition group.
Fuel unmixing with water for use in the present invention can be selected from: including be in a liquid state at a temperature of formula aliphatic,
The group that alicyclic and aromatic compound and its mixture form.Suitable organic-fuel can be selected from fuel oil, diesel oil, distillate
Object, naphtha, wax (such as microwax, paraffin and slack wax), paraffin oil, benzene,toluene,xylene, asphalt material, gathers kerosene
Close the oil such as low-molecular weight polymer of alkene, vegetable oil, animal oil, fish oil and other mineral oil, hydrocarbon or fat oil and its mixing
Object.Suitable organic-fuel is the liquid hydrocarbon of commonly referred to as petroleum distillate, such as gasoline, kerosene, fuel oil, paraffin oil and plant
Or mixtures thereof object oil.
In general, the water miscibility or water unmixability fuel of subject hydrogel compositions account for the 5-30%w/ of total composition
W is suitably 10-25%w/w.Suitably, the concentration of fuel be about 5,7,8,10,12,15,20,25,30,35,40,45 or
50%w/w.Suitably, the concentration of fuel be about 5 to 10,10 to 15,5 to 20,15 to 20,15 to 25,20 to 25,25 to 30,
20 to 40,30 to 35,35 to 40,40 to 45 or 45 to 50w/w.
In one embodiment, the unmixing fuel of water accounts for the 7% to 25%w/w of total composition.
In one embodiment, water miscibility fuel accounts for the 8% to 25%w/w of total composition.
Emulsion fuel
Explosive compositions of the invention may include one or more fuel.
HP base emulsion can use preparation of fuel unmixing with water.
Fuel can be any fuel, such as diesel oil.Alternatively, it can be paraffin oil, mineral oil, alkene oil, naphthenic oil,
Animal oil, vegetable oil, fish oil and silicone oil.Other types of fuel has benzene,toluene,xylene, asphalt material etc..Fuel can be
Sustainable fuel.Suitable sustainable fuel may include vegetable oil, such as corn oil, cottonseed oil, olive used in lotion
Oil, peanut oil or fatty acid oil.The composition may include 15 to 25%w/w sustainable fuel, for example, 15 to 20% or 20 to
25%w/w.The composition alternatively may include less than 40%w/w, less than 30%, less than 25%, or less than 20%w/w can
Continuous fuel, such as the sustainable fuel of 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%w/w.
The unmixing organic phase component of the water of the present composition includes continuous " oil " phase of water-in-oil emulsion, and is combustion
Material.Suitable organic-fuel includes aliphatic, alicyclic and aromatic compound and its mixing being in a liquid state at a temperature of being formulated
Object.Suitable organic-fuel can be selected from fuel oil, diesel oil, distillate, kerosene, naphtha, wax and (such as microwax, paraffin and dredge
Loose wax), paraffin oil, benzene,toluene,xylene, asphalt material, the low-molecular weight polymer of godied oil such as alkene, vegetable oil, animal
Oil, fish oil and other mineral oil, hydrocarbon or fat oil and its mixture.Suitable organic-fuel is commonly referred to as petroleum distillate
Or mixtures thereof liquid hydrocarbon, such as gasoline, kerosene, fuel oil, paraffin oil and vegetable oil.
In general, the organic-fuel or continuous phase of HP base emulsion composition of the invention account for the 2 to 20%w/w of total composition,
The 3 to 20%w/w of total composition is suitably accounted for, such as accounts for the 7 to 12%w/w of total composition.Suitably, the concentration of organic-fuel
About 2,4,6,8,10,12,14,16,18 or 20%w/w.Suitably, the concentration of organic-fuel is about 2 to 4,4 to 6,6 to 8,8
To 10,10 to 12,12 to 14,14 to 16,16 to 18 or 18 to 20%w/w.
The secondary fuel of hydrogel and lotion
If desired, other optional fuel materials of hereinafter referred to as secondary fuel can be added to composition of the invention
In.
The example of this secondary fuel includes solid fine crushing.The example of secondary fuel includes sulphur, aluminium, pitch, crushing
Coke or charcoal, carbon black, abietic acid, glucose or dextrose, starch, nut powder, grain dust, wood pulp etc. and combinations thereof.Secondary combustion
The example of material further includes recycled plastic waste.
In general, the optional secondary fuel component of the present composition account for the 0 to 20%w/w of total composition, such as 0.1 to
12%w/w.
The ratio of component
In one embodiment, explosive compositions may include the HP of 100:1 to 30:70: one or more other oxidations
Agent.
In one embodiment, explosive compositions may include HP (or the one or more oxidations of HP+ of 87:13 to 64:36
Agent): fuel.
In one embodiment, explosive compositions may include the HP of 60:20:20 to 72:24:4 (or HP+ be a kind of or more
Kind oxidant): fuel: water.
Thickener
Explosive compositions of the invention may include one or more thickeners.More specifically, hydrogel of the invention is quick-fried
Fried composition may include one or more thickeners.
Because the material of bubble and confining gas has relatively low density, if the viscosity of HP base explosive compositions cannot
Sensitized material is kept to be uniformly distributed therein, they will tend to surface migration to explosive column.Sensitized material is moved to surface
Shifting is undesirable, because it may make explosive excessively insensitive to detonating, explosive compositions may not be able to produce as required
Energy and gas needed for raw broken and mobile rock, or worse, explosive may miss-fire.Improve this problem
A kind of method is that explosive compositions are configured to hydrogel.The composition of these types can be configured to have by using thickener
There is the viscosity of different level.Different viscosities be can choose so that sensitized material generally maintains evenly dispersed in entire composition
State.
If desired, the aqueous solution of the present composition may include optionally crosslinkable thickener.The present invention can
To use any Conventional thickeners.When suitably, in for composition of the invention, thickener is polymeric material, especially
Using galactomannan gum as the glue material of representative, such as locust bean gum or xanthan gum or guar gum or derivatives thereof, such as hydroxypropyl
Guar gum.Thickener can be selected from the glue including natural gum such as guar gum, xanthan gum, sodium alginate, carboxymethyl cellulose, first
Base cellulose etc..Other useful but less preferred glue is so-called biological polymer glue, such as passes through carbohydrate materials
Microorganism conversion and the heteroglycan prepared, such as take campestris (Xanthomonas campestris) as the Huang of representative
Zygosaccharomyces (genus Xanthomonas) phytopathogen handles glucose.Other useful thickeners include synthesized polymer
The synthetic polymeric material that material, especially at least part are derived from monomeric acrylamide.The example of synthetic thickening agent is polypropylene
Amide.Also inorganic thickening agent, such as fumed silica, clay and carbon silicon adsorbent (carbosil) or its group can be used
It closes.Suitably, thickener is selected from locust bean gum, guar gum, hydroxypropyl guar gum, sodium alginate and heteroglycan and combinations thereof.
In general, the thickener component of the present composition accounts for the 0 to 5%w/w of total composition, such as account for total composition
0.5 to 5%w/w, such as the 0 to 2%w/w of total composition is accounted for, such as account for the 0.1 to 2%w/w of total composition.
Crosslinking agent
Crosslinking agent can be used for the present invention.
The water resistance and mechanical strength of explosive can be improved in thickener combination crosslinking agent.For this purpose, using conventional crosslinking
Agent such as zinc chromate or bichromate are convenient, the redox body as the component of individual entity or redox system
The mixture of system e.g. potassium bichromate and potassium antimony tartrate.The salt of Ca, Ti, Sb are also used as crosslinking agent.In an embodiment party
In case, crosslinking agent is selected from the salt containing zinc, calcium, titanium, antimony, chromium, borate and bichromate and combinations thereof.
In general, the crosslinker component of the present composition accounts for the 0 to 3%w/w of total composition, such as 0 to 0.1%w/w, example
As total composition 0.1 to 1%w/w, the 1 to 2%w/w of such as total composition, such as total composition 2 to 3%w/w.
Emulsifier/stabilizer
When being prepared into emulsion form, explosive compositions of the invention may include one or more emulsifying agents.
HP base emulsion composition is made of the discontinuous phase of oxidation material, and the oxidation material is in one or more emulsifying agents
In the presence of be dispersed in the continuous phase of organic-fuel.Adjustment or selection emulsifier are to keep mutually separating.
The emulsifier component of the present composition can be used to prepare Water-In-Oil emulsification explosion group selected from known in the art
Close the various emulsifiers of object.The example of the grade emulsifiers includes the polyisobutylene succinic anhydride (PIBSA) reacted with amine；Other creams
The example of agent is PIB- lactone and its aminoderivative, alcohol alkoxide, phenol alkoxide, poly- (oxyalkylene) glycol, poly- (oxygen
Change alkene) aliphatic ester, amine alkoxide, the aliphatic ester of sorbierite and glycerol, fatty acid salt, Isosorbide Dinitrate, poly- (oxidation
Alkene) Isosorbide Dinitrate, fatty amine alkoxylates, poly- (oxyalkylene) diol ester, fatty acid amide, fatty acid amide alkoxide
Object, fatty amine, quaternary ammonium, alkylated oxazoline quinoline, alkenyl oxazoline, imidazoline, alkyl sulfonic ester, alkyl aryl sulfonate, alkyl phosphorus
The copolymer of acid esters, alkenyl phosphate, phosphate, lecithin, poly- (oxyalkylene) two pure and mild poly- (12- hydroxy stearic acid) and its mixed
Close object.
Preferred emulsifier be 2- alkyl-and bis- (methylol) oxazolines of 2- alkenyl -4,4 ' -, sorbierite aliphatic ester,
The copolymer and its mixture of lecithin, poly- (oxyalkylene) two pure and mild poly- (12- hydroxy stearic acid), especially sorbitan
Monoleate, NOFABLE SO-992,2- alkenyl -4,4 '-bis- (methylol) oxazoline, sorbitan sesquialter
Mixture, lecithin and the poly- (copolymer and its mixture of oxidative olefinic diols and poly- (12- hydroxy stearic acid) of oleate.
Typically, the emulsifier component of the present composition accounts for the up to 5%w/w of total composition.Higher ratio can be used
The emulsifier of example, and may be used as the supplement fuel of composition, but it is not usually required to the emulsifier that addition is more than 5%w/w
To reach desired effect.The advantages of present composition first is that the emulsifier that low relative levels can be used formed it is stable
Lotion, and for economic reason, the dosage of emulsifier is preferably maintained to minimum needed for reaching desired effects.Emulsification
The appropriate level of agent is the 0.1 to 2.0%w/w of total composition.
Energy dilution agent
Explosive compositions of the invention can optional include one or more energy dilution agent.
In the context of the present invention, energy dilution agent is inert material, the tribute as sensitization means to blast process
Minimum is offered, but it can be used for the part energetic material in substitute composition, therefore the energy for reducing hydrogen peroxide-based explosive is defeated
Out.
In some cases, these energy dilution agent can increase, reduce or do not change the density of HP base composition.At certain
In a little situations, these energy dilution agent can reduce the density of HP base composition, without increasing susceptibility.
The example of these diluent materials is polystyrene (partial size is greater than 2mm), particle/crumb (from tire), cotton
Seed, sawdust, shell, extruding puffed rice, plastic bead, wool powder, bagasse, peanut and shood, peanut shell etc..U.S. Patent No.
No. 5,409,556 describe certain examples of these energy dilution agent.In one embodiment, energy dilution agent be selected from particle/
Broken tire, rubber, puffed rice, extruding puffed rice, extruded wheat and combinations thereof.For the performance of hydrogen peroxide-based explosive,
These materials can also be used in combination with sensitizer, to provide greater flexibility (such as U.S. Patent No. 5,470, No. 407 institutes
Show).Therefore, another advantage of HP base explosive is that the performance characteristics of explosive can change, the characteristics of to adapt to demolition site.
The HP base explosive compositions of hydrogel or Water-In-Oil prepared in accordance with the present invention include concentration in 0 to 800% volume
The energy dilution agent of ratio.Therefore, the use of additive (sensitizer and energy dilution agent) provide to by the density on explosion ground,
The more preferable control of VOD and energy conveying.Therefore, another advantage of HP base explosive is that it can be in 0.3g/cm3To 1.4g/cm3It is close
It spends in range and uses.
The density of explosive compositions
Suitably, final densities are controlled with sensitizer about 0.3 to 1.4g/cm3.Suitably, the density of composition is matched
It is made as about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3 or 1.4g/cm3.Suitably, composition is final
Density is configured to about 0.3 to 0.4,0.4 to 0.5,0.5 to 0.6,0.6 to 0.7,0.7 to 0.8,0.8 to 0.9,0.9 to 1.0,
1.0 to 1.1,1.1 to 1.2,1.2 to 1.3 or 1.3 to 1.4g/cm3.In certain embodiments, by selecting composition component
Ratio by density domination in scheduled target value.For example, reducing density by the concentration of equilibrium composition, component is for example hollow micro-
Ball and component such as nitrate granules with relative high density.
The pH of explosive compositions
The pH of emulsification explosive compositions of the invention is not stringent crucial.However, in general, pH between 0 to 8,
Suitably pH is between 1 to 6, and can be controlled by being properly added conventional additives, for example, inorganic acid or organic acid and
Salt.
The viscosity of explosive compositions
The viscosity of explosive compositions (hydrogel or emulsion-type) will be discussed with apparent viscosity.Term used herein
" apparent viscosity " refers to using Brookfield RVT viscosimeter, with 50r.p.m, the viscosity of #7 rotor measurement.
In the method for the invention, the explosive compositions of preferably water-in-oil emulsion explosive particle have before voids
Greater than the apparent viscosity of 10Pa*s (Pascal * seconds).Apparent viscosity is more suitable in the range of 5 to 50Pa*s.It is mixed by machinery
The more preferable range of viscosities of the bubble entrapment of conjunction is 10 to 35Pa*s.10 to 25Pa*s are provided through the most effective of mechanical mixture
Bubble entrapment.
Suitably, explosive compositions of the invention can be pumped easily.
The oxygen balance of explosive compositions
" oxygen balance " (OB) is a term of this field, for indicating the degree of oxidation of explosive.When preparing mining explosive,
The OB close to zero is preferred, it is just excessive without reactant in this way in blast process, it is therefore contemplated that product be nitrogen gas and water and
Carbon dioxide.If oxygen balance is far from zero, certain reactive materials will not react, on the contrary, those unreacted substances are from explosion
Absorption/convergence heat, it is bad to instead result in explosive property in reaction.For example, the composition discomfort combination burning of certain prior arts,
Because they lack fuel (therefore OB numerical value is too high) and composition cannot burn.
The amount of fuel material can be suitably adjusted in explosive compositions, so that the composition has between+10 to -10,
Such as the final oxygen balance between+5 to -5.
The preparation of explosive compositions
Second aspect, the present invention provides the methods of the explosive compositions of preparation first aspect, and this method includes by peroxide
Change hydrogen and one or more other oxidant mixing.
Explosive compositions of the invention can be prepared by a variety of methods.For emulsifying the skill of explosive compositions preparation field
For art personnel, the possibility variation of this general operation is obvious.
This method may include the step of the composition is configured to hydrogel or lotion.
This method can also include the steps that the addition fuel that water is unmixing or water is miscible.
This method can also include the steps that adding thickener or emulsifier.
This method can also include the steps that adding secondary fuel.
This method can also include the steps that adding energy dilution agent.
This method can also include sensitising step.
This method can also include the steps that adding crosslinking agent.
In a suitable manufacturing method, explosion aquogel type composition can be prepared as follows:
It is made by mixing hydrogen peroxide with one or more other oxidants and one or more water soluble fuels
Standby oxidant phase, then
It is (such as gummy by adding one or more water miscibility fuel (such as glycerol) and one or more thickeners
Such as guar gum) and mix (such as stirring) fuel phase is prepared with suspension thickener；
Fuel combination phase and oxidant phase；
Optionally, add and mix other oxidants (itself and the oxygen of one or more solid forms such as powder or particle
One or more other oxidants of agent phase are identical or different)；
It adds and mixes secondary fuel；
Add simultaneously mixed tensor diluent；
The sensitizer that will be sensitized the amount of the composition is mixed into the composition (for example, in mixing 2 to 5
After minute, gas generating agent is added)；
Mixed cross-linker is to be converted to gel for composition.
In a suitable manufacturing method, explosive emulsion type composition can be prepared as follows:
Oxidant phase is prepared by dissolving one or more oxidants with hydrogen peroxide；Then
By add one or more water-insoluble fuel (such as diesel oil) and one or more emulsifying agents (such as based on
PIBSA or SMO) and mix (such as stirring) fuel phase is prepared with suspension thickener；
Fuel is mutually added in oxidant phase and is mixed；
Optionally, add and mix other oxidants (itself and the oxygen of one or more solid forms such as powder or particle
One or more other oxidants of agent phase are identical or different)；And
The sensitizer that will be sensitized the amount of the lotion is mixed into the composition.
The purposes of composition
It should be appreciated that composition of the invention can be used for many purposes, especially for broken in mining and
Mobile ground.
Therefore, the third aspect, the present invention provides the explosive compositions of first aspect in such as mining be crushed and
The purposes of mobile ground.
Suitably, explosive compositions are introduced into (such as passing through pumping) into the blast hole for being placed with detonator.Mining
The ignition in operation borehole blasting hole is well known to the skilled person.
The preferred embodiments of the invention
Many embodiments are described in the present patent application, and these implementations are given merely for illustrative purpose
Scheme.Described embodiment is limited in any sense unintentionally.Such as from this disclosure it will be apparent that originally
Invention can be widely applied to many embodiments.
In one embodiment, the present invention includes or substantially by hydrogen peroxide, one or more other oxidants, combustion
Material, thickener, sensitizer, crosslinking agent, auxiliary fuel and energy dilution agent form, in the other oxidants of one or more of them
It is at least one at least some (such as powder, particle) to be present in composition in solid form.In other embodiments
In, the present invention include or substantially by hydrogen peroxide, one or more other oxidants, fuel, surfactants/emulsifiers,
Sensitizer, secondary fuel and energy dilution agent composition, at least the one of at least one of other oxidants of one or more of them
(such as powder, particle) is present in composition in solid form a bit.In such embodiments, the final oxygen of mixture is flat
Weighing apparatus is preferably between -5 to+5.
The present invention relates to be suitble to be prepared into peroxide-nitrate/fuel base explosion group of hydrogel or water-in-oil emulsion
Object is closed, solid oxidizer can be contained or not contain and be sensitized.Table 1 lists the usual component of every kind of explosive technology.
Table 1: for every kind of explosive technology, usual component of the invention
Table 2 lists the component for the explosive compositions being discussed herein, and provides the usual range of each component.
Table 2: the component of explosive compositions described herein and the usual range of each component
Note: it should be appreciated that volume can increase separately 8 times (*) and 3 times (* *).
Embodiment
The present invention can be used for various forms of explosives, certainly on condition that abiding by the principle of invention described herein.Ginseng
It examines the following embodiment being described in detail in table 3 and further illustrates the present invention.
Table 3: example of the invention
Exploding test
The selected composition of test is to measure explosion.Diameter 50mm, length 600mm, the pvc pipe of one end sealing is for coagulating
Glue.Diameter is 102mm, length 600mm, one end sealing polyvinyl chloride pipe be used for the composition made of gel and particle.
VOD is using the VOD apparatus measures for being based on time domain reflectometry (TRD).
Embodiment 1 to 4 (corresponding respectively to Fig. 1 to 4) in table 3 above shows that the mixing of HP and nitrate can be one
It is ignited in fixed density range, and a certain range of rate of detonation is provided.
It can be seen from the figure that explosive compositions, for example, HP-CAN/ fuel based gel mixture as described herein and
CAN particle can be ignited with low concentration HP, such as 5.4%w/w or lower.Embodiment is also in the composition containing relatively great amount of
Nitrate.Evidence suggests high-caliber CAN or SN can be used for the water base explosive compositions of different densities in the prior art.
Although the present invention is described referring to specific example, however, those skilled in the art should understand that, the present invention can be with
A variety of other forms embody.Especially, the feature of any instance can be provided with any combination in any other examples.
It will be understood by those skilled in the art that embodiment disclosed herein and feature and disclosed embodiment and spy
All combinations and/or displacement of sign are all contained in the present invention.
Claims (59)
1. explosive compositions, it includes:
A. about 2% to about 25%w/w hydrogen peroxide；With
B. it is greater than the 0 one or more other oxidants for arriving up to about 90%w/w.
2. explosive compositions according to claim 1, wherein one or more other oxidants are selected from nitrate, height
The group of chlorate, sodium peroxide, potassium peroxide and optional nitric acid composition.
3. explosive compositions according to claim 2, wherein nitrate is selected from ammonium nitrate, calcium ammonium nitrate, calcium nitrate and sodium nitrate.
4. according to claim 1 to explosive compositions described in any claim in 3, wherein the explosive compositions are free of nitre
Sour ammonium.
5. according to claim 1 to explosive compositions described in any claim in 4, wherein one or more other oxygen
Agent is selected from calcium nitrate, calcium ammonium nitrate and sodium nitrate.
6. according to claim 1 to explosive compositions described in any claim in 4, wherein the perchlorate is selected from high chlorine
Sour ammonium and sodium perchlorate.
7. according to claim 1 to explosive compositions described in any claim in 6, it includes water, preferably 50%w/w or more
Few water.
8. it includes 25%w/w or less water according to claim 1 to explosive compositions described in any claim in 7.
9. it includes about 5 to about 25%w/w mistakes according to claim 1 to explosive compositions described in any claim in 8
Hydrogen oxide.
10. it includes about 0.1 to about 75%w/w according to claim 1 to explosive compositions described in any claim in 9
One or more other oxidants.
11. also including one or more other according to claim 1 to explosive compositions described in any claim in 10
Component, described one or more other groups be selected from sensitizer, fuel, secondary fuel, water, thickener, crosslinking agent, emulsifier,
The group of energy dilution agent and optional other additive compositions.
12. explosive compositions according to any one of the preceding claims, wherein the composition includes sensitization
Agent.
13. explosive compositions according to claim 12, wherein the sensitizer includes compressible material and/or bubble.
14. according to claim 12 or claim 13 described in explosive compositions, wherein the density of the composition is by adding
The sensitizer of sufficient amount is added to control, so that the composition is sensitive to explosion.
15. explosive compositions according to claim 14, wherein the density is controlled in about 0.3 to 1.4g/cm3。
16. explosive compositions according to any one of the preceding claims, wherein the composition includes fuel.
17. explosive compositions according to any one of the preceding claims, wherein the composition also includes two
Secondary fuel.
18. explosive compositions according to any one of the preceding claims, wherein the composition include 15 to
The sustainable fuel of 25%w/w.
19. explosive compositions according to any one of the preceding claims, wherein the composition is comprising one
The hydrogel composition of kind or a variety of thickeners.
20. explosive compositions according to any one of the preceding claims, wherein the composition is comprising one
The hydrogel composition of kind or a variety of crosslinking agents.
21. according to claim 1 to explosive compositions described in any claim in 18, wherein the composition is comprising one
The emulsion compositions of kind or numerous emulsifiers.
22. explosive compositions according to any one of the preceding claims, wherein the composition includes one kind
Or multiple kinds of energy diluent.
23. explosive compositions according to any one of the preceding claims, wherein the composition includes other
Additive.
24. explosive compositions according to any one of the preceding claims, oxygen balance between+10 to -10 it
Between.
25. explosive compositions according to any one of the preceding claims, viscosity is 5 to 50Pa*s.
26. explosive compositions, it includes
A. about 2% to about 25%w/w hydrogen peroxide；
B. it is greater than 0% to up to 90% one or more other oxidants；
C. fuel phase；
D. thickener and/or crosslinking agent；
E. secondary fuel；With
F. sensitizer.
27. explosive compositions according to claim 26, it includes about 5% to about 25%w/w hydrogen peroxide.
28. the explosive compositions according to claim 26 or 27, wherein one or more other oxidants are to be selected from
Salt or the sour group formed of nitrate, perchlorate, peroxide salt or nitric acid.
29. explosive compositions according to claim 28, wherein the salt is selected from AN, CN, SN, CAN, NH4ClO4、
NaClO4、Na2O2、K2O2Or mixtures thereof.
30. the explosive compositions according to any claim in claim 26 to 28, wherein the composition is free of AN.
31. the explosive compositions according to any claim in claim 28 to 30, wherein the explosive compositions packet
Containing 0.1 to 75%w/w dissolving salt.
32. the explosive compositions according to any claim in claim 26 to 31, wherein the explosive compositions packet
Containing water-soluble fuel.
33. according to the explosive compositions of claim 32, wherein the water soluble fuel is selected from ammonium nitrate or urea or its mixing
Object.
34. explosive compositions according to claim 33, it includes 30%w/w or less water.
35. the explosive compositions according to any claim in claim 32 to 34, wherein the explosive compositions packet
Containing 0.1 to 30%w/w water soluble fuel.
36. the explosive compositions according to any claim in claim 26 to 35, wherein the fuel mutually includes one
Kind or the group of a variety of fuel compositions selected from or mixtures thereof glue, glycerol, ethylene glycol, propylene glycol, molasses, formamide.
37. wherein thickener is suspended in the fuel according to the explosive compositions of claim 36.
38. according to the explosive compositions of claim 37, wherein the thickener is selected from guar gum, xanthan gum, sodium alginate, gathers
The group of acrylamide, polyvinyl alcohol composition.
39. the explosive compositions according to any claim in claim 26 to 38, wherein the composition includes choosing
The group formed from the crosslinking agent of or mixtures thereof antimonic salt, chromic salts, phosphoric acid.
40. the explosive compositions according to any claim in claim 26 to 39, wherein the fuel mutually includes one
Kind or a variety of water-insoluble fuel, the water-insoluble fuel are selected from the group of or mixtures thereof diesel oil, oil, vegetable oil composition.
41. wherein emulsifier is blended in the fuel according to the explosive compositions of claim 40.
42. explosive compositions according to claim 41, wherein the emulsifier is selected from PIBSA- amine derivative, SMO, ovum
The group of or mixtures thereof phosphatide composition.
43. the explosive compositions according to any claim in claim 26 to 42, wherein by the hydrogen peroxide, one
Kind or a variety of other oxidants and the fuel mixing containing thickener, until forming viscous material of the viscosity 5 to 50pa*s.
44. the explosive compositions according to any claim in claim 26 to 43, wherein the composition includes 13-
The fuel phase of 25%w/w.
45. the explosive compositions according to any claim in claim 26 to 44, wherein solid nitric acid salt oxidizing agent
It is mixed with the composition.
46. explosive compositions according to claim 45, wherein the explosive compositions include 0.1 to 70%w/w to consolidate
Body nitrate oxidizer.
47. wherein solid nitric acid salt oxidizing agent is selected from ammonium nitrate, sodium nitrate, nitric acid according to the explosive compositions of claim 46
The group of or mixtures thereof ammonium calcium composition.
48. the explosive compositions according to any claim in claim 26 to 47, wherein the explosive compositions packet
Containing 1 to 800%v/v energy reducing agents (diluent materials).
49. explosive compositions according to claim 48, wherein the energy dilution agent material is selected from EPS, scrap rubber wheel
The group of tire, puffed rice and plastic bead composition.
50. the explosive compositions according to any claim in claim 26 to 49, wherein the sensitizer includes gas
Or mixtures thereof the material of bubble or retention gas.
51. explosive compositions according to claim 51, wherein the bubble is formed in situ, and by N2、O2、CO2、
NO、H2Or mixtures thereof bubble composition.
52. explosive compositions according to claim 50, wherein the material of the retention gas is selected from partial size less than 2mm's
Glass microsphere, ceramic microsphere, plastic microsphere or EPS.
53. according to the explosive compositions of claim 51 or 52, wherein the density of the composition is by being added the quick of sufficient amount
Agent controls, so that the composition is sensitive to explosion.
54. explosive compositions according to claim 53, wherein the density is configured to about 0.3 to 1.4g/cm3。
55. according to the explosive compositions of claim 54, wherein the density is controlled in about 0.3 to 1.4g/cm3。
56. the explosive compositions according to any claim in claim 26 to 55, oxygen balance between+5 to -5 it
Between.
57. the method for preparing explosive compositions described in any claim in preceding claims, the method includes by mistake
Hydrogen oxide and one or more other oxidant mixing.
58. further including sensitising step according to the method for claim 57.
59. purposes of the explosive compositions described in any claim in broken and mobile ground in claim 1 to 56.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2016905130A AU2016905130A0 (en) | 2016-12-12 | Improved explosive composition | |
| AU2016905130 | 2016-12-12 | ||
| PCT/AU2017/051368 WO2018107213A1 (en) | 2016-12-12 | 2017-12-12 | Improved explosive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110267929A true CN110267929A (en) | 2019-09-20 |
Family
ID=62557765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780086179.9A Pending CN110267929A (en) | 2016-12-12 | 2017-12-12 | Improved explosive compositions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20200002241A1 (en) |
| EP (1) | EP3551597A4 (en) |
| CN (1) | CN110267929A (en) |
| AU (1) | AU2017376827A1 (en) |
| BR (1) | BR112019011806A2 (en) |
| CA (1) | CA3046538A1 (en) |
| CL (1) | CL2019001524A1 (en) |
| WO (1) | WO2018107213A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230148505A (en) | 2022-04-18 | 2023-10-25 | 주식회사 한화 | Emulsion explosive composition based on hydrogen peroxide and nitrate |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2019396127A1 (en) * | 2018-12-11 | 2021-06-24 | STT-Surfex Technology & Trading Pty Ltd | A water-based explosive |
| EP4086237A1 (en) * | 2021-05-05 | 2022-11-09 | Hypex Bio Explosives Technology AB | Composition for forming a hydrogen peroxide based emulsion explosive |
| USD1032928S1 (en) | 2021-10-19 | 2024-06-25 | Wellness Insight Technologies, Inc. | Vaporizer device |
| CN115057753B (en) * | 2022-07-20 | 2023-04-07 | 中国矿业大学 | Liquid explosive for low-permeability oil field in-situ combustion and explosion fracturing and application thereof |
| CN115160092B (en) * | 2022-07-29 | 2024-01-26 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Metallized emulsion explosive containing boron-magnesium mixed powder and preparation method thereof |
| WO2024030815A1 (en) * | 2022-08-03 | 2024-02-08 | Locus Solutions Ipco, Llc | Emulsion explosive compositions and methods of use |
| WO2024098118A1 (en) * | 2022-11-11 | 2024-05-16 | Proactive Ground Solutions Pty Ltd | Explosive additive |
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| CN86102842A (en) * | 1986-04-15 | 1987-10-28 | 包钢矿山研究所 | Normal temperature pumpable emulsion explosive loading car |
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| WO2013013272A1 (en) * | 2011-07-27 | 2013-01-31 | Cmte Development Limited | Ιμproved explosive composition |
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| US3047441A (en) * | 1946-04-08 | 1962-07-31 | American Cyanamid Co | Hydrogen peroxide explosives |
| US2452074A (en) * | 1947-01-29 | 1948-10-26 | Buffalo Electro Chem Co | Peroxide-glycerol explosive |
| US3790415A (en) * | 1970-08-18 | 1974-02-05 | Du Pont | Chemical foaming and sensitizing of water-bearing explosives with hydrogen peroxide |
| US3808062A (en) * | 1972-12-08 | 1974-04-30 | Nippon Kayaku Kk | Liquid explosive compositions of hydrogen peroxide and an aromatic sulforic acid and process for the preparation thereof |
| US6165295A (en) * | 1999-11-23 | 2000-12-26 | Wagaman; Kerry L. | Gas-generating liquid compositions (PERSOL 1) |
| US20080190525A1 (en) * | 2007-02-12 | 2008-08-14 | Kerry Lee Wagaman | Inorganic nitrate-hydrogen peroxide adducts and methods for their preparation |
-
2017
- 2017-12-12 AU AU2017376827A patent/AU2017376827A1/en not_active Abandoned
- 2017-12-12 EP EP17882170.8A patent/EP3551597A4/en not_active Withdrawn
- 2017-12-12 WO PCT/AU2017/051368 patent/WO2018107213A1/en active Application Filing
- 2017-12-12 CA CA3046538A patent/CA3046538A1/en active Pending
- 2017-12-12 US US16/468,137 patent/US20200002241A1/en not_active Abandoned
- 2017-12-12 CN CN201780086179.9A patent/CN110267929A/en active Pending
- 2017-12-12 BR BR112019011806-3A patent/BR112019011806A2/en not_active Application Discontinuation
-
2019
- 2019-06-05 CL CL2019001524A patent/CL2019001524A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102842A (en) * | 1986-04-15 | 1987-10-28 | 包钢矿山研究所 | Normal temperature pumpable emulsion explosive loading car |
| CN1434009A (en) * | 2003-02-28 | 2003-08-06 | 汪石成 | Safety type oxidant |
| WO2013013272A1 (en) * | 2011-07-27 | 2013-01-31 | Cmte Development Limited | Ιμproved explosive composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230148505A (en) | 2022-04-18 | 2023-10-25 | 주식회사 한화 | Emulsion explosive composition based on hydrogen peroxide and nitrate |
Also Published As
| Publication number | Publication date |
|---|---|
| US20200002241A1 (en) | 2020-01-02 |
| AU2017376827A1 (en) | 2019-07-25 |
| EP3551597A4 (en) | 2020-09-02 |
| CL2019001524A1 (en) | 2019-08-23 |
| CA3046538A1 (en) | 2018-06-21 |
| EP3551597A1 (en) | 2019-10-16 |
| BR112019011806A2 (en) | 2019-10-29 |
| WO2018107213A1 (en) | 2018-06-21 |
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Application publication date: 20190920 |