CN1011964B - Using compound surface active agent composition for raising emulsive rate - Google Patents
Using compound surface active agent composition for raising emulsive rateInfo
- Publication number
- CN1011964B CN1011964B CN 85101928 CN85101928A CN1011964B CN 1011964 B CN1011964 B CN 1011964B CN 85101928 CN85101928 CN 85101928 CN 85101928 A CN85101928 A CN 85101928A CN 1011964 B CN1011964 B CN 1011964B
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- Prior art keywords
- amine
- sorbitan
- nitrogen
- emulsion
- emulsifying agent
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- Colloid Chemistry (AREA)
Abstract
The present invention adopts the composition of some surface active agents for simplifying the preparation method of inverse water-in-oil emulsion blasting agents and improving the stability thereof, and relates to a corresponding formulation.
Description
The present invention relates to the method for a kind of inverted emulsion blasting agent and this blasting agent of manufacturing.
The people knows, and in US Patent specification 4,141, discloses use " anti-phase " pulpous state blasting agent composition in 767.They contain a kind of water-fast liquid organic-fuel (normally a kind of hydrocarbon) as external phase, and the emulsified soln of a kind of inorganic oxidising salt such as ammonium nitrate (AN) is as discontinuous phase and a kind of emulsifying agent.
There is shortcoming in this " ANFO " (ammonium nitrate-fuel oil) composition.In the darker or moist place of eyelet of planning to bore, the easy reducing sensitivity of this prescription, and need to adopt proprietary waterproof packing material or expensive ammonium nitrate coating, or adopt stable proprietary viscosifying agent or gelifying agent to be protected.And because the tap density of " ANFO " is little, its blasting energy has certain limit.
The United States Patent (USP) 3 of Egly, 161,551 disclose a kind of anti-water blasting agent, solid inorganic salt wherein (as ammonium nitrate) is handled with 50～70% ammonium nitrate solution, form a kind of aqueous inverted emulsion, it contains a kind of oil fuel and a kind of longer chain fatty acid or derivatives thereof as the successive hydrophobic mutually.
The composition of Egly has sizable anti-outlet capacity, because this water-in-oil emulsion is filled in the natural hole of most solid nitric acid salt component, and water is difficult for forcing it to pass through the outside hydrophobic phase continuously of emulsion.But when the explosion deep hole, sensitivity problem still exists.
The United States Patent (USP) 3 of BLuhm, 447,978 have described the water-in-oil emulsion blasting agent, it is made up of a kind of discrete ammonium nitrate water in a kind of external phase, external phase is made up of the carbonaceous fuel that has predetermined maintenance gas consistency under 21 ℃ and normal pressure, and contains a kind of water-in-oil emulsifier of standard.
Though the composition of BLuhm can be avoided those above-mentioned problems to dark and moist eyelet, preparation is inconvenient at the scene.
According to above-mentioned US Patent specification 3,161,551 and 3,447,978 and also according to US Patent specification 3,765,964 and 4,110,134 with british patent specification 1,306,546, it is superior that sorbitan fatty ester (as the sorbitan oleic acid ester) is used to obtain stable inverted emulsion, although their effect is very slow.Other the emulsifying agent that is used for contrary water-in-oil emulsion blasting agent comprises nitrogen-containing surfactants, as United States Patent (USP) 4,141; disclosed fatty acid amine and ammonium salt thereof in 767 and 4,216,040; with United States Patent (USP) 4; disclosed undersaturated fatty two (hydroxyethyl) oxazoline is at United States Patent (USP) 4 in 216,040; 315; disclosed 1-hydroxyethyl-2-imidazolidine derivatives and N-methyl in 784-N-alkyl (tallow)-Sodium taurine salt (for example United States Patent (USP) 4,315,787).Yet existing knowledge is to the sorbitan fatty ester and unconfirmed any advantage arranged, and (it participates in the effect of tensio-active agent, in order to make the emulsifying agent of inverted emulsion) is particularly because it may reduce desirable emulsion stability.In fact, United States Patent (USP) 4,315,784 point out, the inverted emulsion blasting agent of " nearly all " all adopts the emulsifying agent different with sorbitan ester, its poor stability, explosivity and detonation property are bad.
The slow speed of fatty acid ester and need pressure and water resisting property matter to show must have long-time and violent frequent stirring frequency, could form a kind of stable inverted emulsion.This has just limited the ability that comprises the control of density particle on the contrary, as glass sphere in whipping process or agglomerating microballoon, because such prescription when being subjected to sizable shearing force, can cause the instability of physics and chemical property.
Thereby be desirable to provide stable inverted emulsion blasting agent, promptly its emulsive rate will be higher than the emulsive rate of fatty acid ester widely, and fabulous stability is arranged, and can adopt simple device context manufacturing; It also needs in use, particularly to dark and moist eyelet, avoids taking place the problems referred to above when still allowing to add as the glass sphere of density-controlling agent or the similar additive of keeping hole.
According to the present invention, a kind of method that is used for making a kind of inverted emulsion blasting agent is that the combination by following material realizes: (1) contain a kind of in hydrocarbon solvent the oil phase of sorbitan fatty acid esters emulsifying agent and the water that (2) contain a kind of water miscible inorganic oxidant salt at least.The method is characterized in that, the sorbitan ester emulsifying agent is to combine with nitrogen-containing surfactants in advance, nitrogen-containing surfactants is one or more fatty acid amides, a kind of fatty amine, or the salt of a kind of fatty acid amide or fatty amine, wherein alkyl is a kind of straight-chain alkyl of about 10-20 carbon atom.
In addition, according to the present invention, prepared inverted emulsion blasting agent comprises: (1) contains a kind of oil phase of the emulsifying agent in hydrocarbon solvent, and (2) contain the water of at least a water-soluble inorganic oxidizer salt.This blasting agent is characterised in that, emulsifying agent is the composition of the nitrogen-containing surfactants of a kind of sorbitan ester and 0.1-10 times of weight, nitrogen-containing surfactants is one or more fatty acid amides, a kind of fatty amine, or the salt of a kind of fatty acid amide or a kind of fatty amine, wherein alkyl is a kind of straight-chain alkyl of about 10-20 carbon atom.
Preferably, the sorbitan fatty acid esters emulsifying agent is NOFABLE SO-992, sorbitan laurate esters, sorbitan oleic acid ester, dehydrated sorbitol palmitate, sorbitan stearate, comprises single and polysubstituted two kinds of derivative of fatty acid.The 0.5-5%(that its preferred working concentration is about the emulsion total amount is heavy).
Preferred nitrogen-containing surfactants is tallow amine, lauryl amine, oleyl amine, coconut amine, coconut single ethanol amide, coconut diethanolamide, linolic acid diglycollic amide, oleic acid diethyl amide or the Stearic acid diethanolamine salt of hydrogenation or a kind of salt in them.The 0.1%(that its preferred concentration is not less than the emulsion total amount is heavy) about.
In addition, the total content of emulsifying agent preferably is about the 0.6-7.0%(weight of emulsion total amount).
The emulsive rate that sorbitan fatty ester and nitrogen-containing surfactants component (all not having high emulsive rate and the utmost point advantages of excellent stability when both use separately) provide good package stability and increased greatly.For example use the conventional required preparation time of rotor one stator homogenizer, can be reduced to 4-60 second from 80-180 second or bigger cycle commonly used.
The 3-20%(that the oil phase hydrocarbon solvent is generally the emulsion total amount is heavy) about, it is heavy to be preferably 5-10%().According to the present invention, be used as the suitable oil phase hydro carbons of emulsion, be aliphatic hydrocarbon, naphthenic hydrocarbon or the aromatic hydrocarbon of positive structure or side chain, they can be saturated or undersaturated, if two kinds of components that can dissolved emulsifier, and when preparation, keep liquid.This material can comprise benzene, nitro benzene,toluene,xylene, petroleum fractions and byproduct, as gasoline, kerosene and diesel oil (comprising Number 2 fuel oil), and Yatall MA, paraffin, wax oil or their mixture.
It is heavy that water of the present invention generally contains the 5-30%(that has an appointment) water, best moisture 10-20%(is heavy) (all to the emulsion total amount), it is heavy to contain 50-95%() at least a oxidizer salt; The latter can be one or more ammonium nitrate, sodium chlorate, sodium perchlorate, nitrocalcite, calcium chlorate, cross calcium chlorate, saltpetre, Potcrate, potassium perchlorate, ammonium chlorate, ammonium perchlorate, lithium nitrate, lithium chlorate, lithium perchlorate, magnesium nitrate, magnesium chlorate, aluminum chlorate, nitrate of baryta, barium chlorate, barium perchlorate, zinc nitrate, zinc chlorate and cross zinc chlorate.
Because oil phase and water the time need keep liquid in preparation, so emulsification is preferably in about 50-90 ℃ the temperature range to be carried out.Though method of the present invention can be used simple device at the scene, thereby greatly facilitate the preparation of inverted emulsion blasting agent, preferably select suitable opportunity, under condition for validity, prepare.
Method of the present invention can be used common equipment, as propeller stirrer, rotor-stator homogenizer, rubber mill, or similar whipping appts.Under the close situation of other condition, when the preparation time is limited at independent use fatty acid ester usually 1/2 to 1/10 of desired normal time.When the weighting agent that forms hole, as Microperl TM GT-25* or other glass, when perlite or plastic microsphere are made the additive of control of density, wish the shortening cycle especially, because fatty acid ester has a sensitivity problem under vigorous stirring.
The following examples further specify concrete feature of the present invention.All percentage are all represented with weight.
Embodiment 1
Hereinafter identify the emulsion test specimens S-1～S-10 of usefulness and to C-1～C-4 in the same old way, be by with Number 2 fuel oil with as the NOFABLE SO-992 pre-mixing of emulsifying agent, and under essentially identical stirring and temperature (77 ℃) condition with the nitrogen-containing surfactants of different amounts in conjunction with and preparation obtains.Under essentially identical stirring * * and temperature control condition, hot ammonium nitrate (83%) is added in this solution, observation forms the required time of emulsion, and be recorded in the table 1 right-hand, as the direct tolerance of used emulsifier/surfactant system validity.
Embodiment 2
The emulsion test specimens S-11～S-13 that is used for identifying and to C-5 in the same old way, be to make organic solvent and quite a large amount of NOFABLE SO-992 is made emulsifying agent with Number 2 fuel oil, and the industry oil ammonium and the acid amides that add specified amount make tensio-active agent, and adopting at a slow speed, propellar mixer * * * preparation gets.
* the trade mark of Grefco company
The Tekmar Suoer Dispax homogenizer (SD-45) of * Tekmar company, speed location 65
The Jiffy mixer model ES of * * Jiffy mixing tank company
In this embodiment, water is made up of the solution * of ammonium nitrate, SODIUMNITRATE and the water of a kind of stirring heating (82 ℃).The aqueous solution that in premixed oil phase, adds about 1/3 capacity, and under per minute 400 changes, stirred 1 minute, then change rotating speed, under per minute 200 changes, stirred 3 minutes, and under per minute 600 changes, stirred 1 minute, up to thickening significantly occurring.After forming emulsion, under changeing, per minute 600 adds remaining aqueous solution, then under changeing, stirred 10 minutes per minute 700, to reach suitable granularity.
The required time record of emulsion right-hand in table 2 will be begun to form.
Embodiment 3
To mix according to sample 13 and the 153 Microperl TM GT 25** perlites that restrain that embodiment 2 obtains, and be contained in the polyethylene bag, stored 85 days down at 40 °F (4.4 ℃), at 40 following pentolite blasting cap initiations, obtain detonate speed and 8.2 * 10 of 5400 meter per seconds then with 500 grams
5Foot-pound/pound (588 card/gram) than energy content value.The minimum ignition agent of said composition is 25 Ke Taian under 40,150 restrains pentolites down at 0 °F.
Embodiment 4
Three kinds of test specimens S-14, C-6 and C-7 prepare in embodiment 1 and get, and C-6 and C-7 sample are the check samples that uses coconut amine and NOFABLE SO-992 emulsifier component respectively, and they are combined as the emulsifying agent of S-14.Write down the emulsion formation time in each case and adopted the relative stability of the emulsion that the penetrometer * * * of taper records after seven days, two kinds of results all are recorded in right-hand in the table 3.
* 4420 restrain NH
4OH, 1331 gram NaNO
3, 1402 gram H
2O
The trade mark of * Grefco company
* * exact science company
Claims (10)
1, a kind of method that adopts the following component of common emulsification to make the inverted emulsion blasting agent, said composition is: (1) contains a kind of oil phase of the sorbitan fatty acid esters emulsifying agent in hydrocarbon solvent, (2) contain the water of at least a water-soluble inorganic oxidizer salt, the method is characterized in that, the sorbitan ester emulsifying agent is to combine with nitrogen-containing surfactants in advance, nitrogen-containing surfactants is a kind of fatty acid amide, a kind of fatty amine, or the salt of a kind of fatty acid amide or fatty amine, wherein alkyl is the straight-chain alkyl of a kind of 10-20 of containing carbon atom.
2, according to the method for claim 1, it is further characterized in that, the sorbitan fatty acid esters emulsifying agent is NOFABLE SO-992, sorbitan laurate esters, sorbitan oleic acid ester, dehydrated sorbitol palmitate, or the sorbitan stearate.
3, according to the method for claim 1, it is further characterized in that, uses the 0.5-5%(weight of the concentration of emulsifying agent as the emulsion total amount).
4, according to the method for claim 1, it is further characterized in that the emulsifying agent total content is the 0.6-7.0%(weight of emulsion total amount), and the nitrogen-containing surfactants component is not less than the 0.1%(weight of emulsion total amount).
5, according to the method for above-mentioned each claim, it is further characterized in that, nitrogen-containing surfactants is tallow amine, lauryl amine, oleyl amine, coconut amine, coconut single ethanol amide, coconut diethanolamide, linolenic acid diglycollic amide, the oleic acid diethyl amide of hydrogenation, or Stearic acid diethanolamine salt, or their salt.
6, a kind of inverted emulsion blasting agent, this blasting agent comprises: (1) contains a kind of oil phase of the emulsifying agent in hydrocarbon solvent, (2) contain the water of at least a water-soluble inorganic oxidizer salt, it is characterized in that, this emulsifying agent is the composition of the nitrogen-containing surfactants of a kind of sorbitan ester and 0.1-10 times of weight, nitrogen-containing surfactants is the salt of a kind of fatty acid amide, a kind of fatty amine or a kind of fatty acid amide or fatty amine, and wherein alkyl is the straight-chain alkyl of a kind of 10-20 of containing carbon atom.
7, according to the inverted emulsion blasting agent of claim 6, it is further characterized in that, the sorbitan fatty acid esters emulsifying agent is NOFABLE SO-992, sorbitan laurate esters, sorbitan oleic acid ester, dehydrated sorbitol palmitate, or the sorbitan stearate.
8, according to the inverted emulsion blasting agent of claim 6, it is further characterized in that used emulsifier concentration is that the 0.5-5%(of emulsion total amount is heavy).
9, according to the inverted emulsion blasting agent of claim 6, it is further characterized in that the emulsifying agent total content is the 0.6-0.7%(weight of emulsion total amount), and the nitrogen-containing surfactants component is not less than the 0.1%(weight of emulsion total amount).
10, according to each inverted emulsion blasting agent among the claim 6-9, it is further characterized in that, nitrogen-containing surfactants is tallow amine, lauryl amine, oleyl amine, coconut amine, coconut single ethanol amide, coconut diethanolamide, linolenic acid diglycollic amide, the oleic acid diethyl amide of hydrogenation, or Stearic acid diethanolamine salt, or their salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101928 CN1011964B (en) | 1984-08-06 | 1985-04-01 | Using compound surface active agent composition for raising emulsive rate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/638,334 US4523967A (en) | 1984-08-06 | 1984-08-06 | Invert emulsion explosives containing a one-component oil phase |
| CN 85101928 CN1011964B (en) | 1984-08-06 | 1985-04-01 | Using compound surface active agent composition for raising emulsive rate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101928A CN85101928A (en) | 1987-01-17 |
| CN1011964B true CN1011964B (en) | 1991-03-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101928 Expired CN1011964B (en) | 1984-08-06 | 1985-04-01 | Using compound surface active agent composition for raising emulsive rate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011964B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022346B (en) * | 2016-11-15 | 2021-03-02 | 陕西邦希化工有限公司 | Composite surfactant system with high emulsifying performance and preparation method thereof |
| CN108165301B (en) * | 2017-11-17 | 2020-12-25 | 南京尚易环保科技有限公司 | Water removing agent for diesel oil |
-
1985
- 1985-04-01 CN CN 85101928 patent/CN1011964B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101928A (en) | 1987-01-17 |
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