U.S. patent number 3,713,919 [Application Number 05/064,580] was granted by the patent office on 1973-01-30 for chemical foaming of water-bearing explosives with n,n'-dimitrosopentamethylene-tetramine.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Ernst A. Tomic.
United States Patent |
3,713,919 |
Tomic |
January 30, 1973 |
CHEMICAL FOAMING OF WATER-BEARING EXPLOSIVES WITH
N,N'-DIMITROSOPENTAMETHYLENE-TETRAMINE
Abstract
Making foamed semisolid colloidal dispersions of water-bearing
blasting agents containing an inorganic oxidizing salt, e.g.,
ammonium nitrate, fuel, water and adding thereto the gas-generating
material N,N'-dinitrosopentamethylenetetramine that foams and
sensitizes the blasting agent.
Inventors: |
Tomic; Ernst A. (Hagerstown,
MD) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
22056921 |
Appl.
No.: |
05/064,580 |
Filed: |
August 17, 1970 |
Current U.S.
Class: |
149/47; 149/38;
149/43; 149/60; 149/41; 149/44; 149/92 |
Current CPC
Class: |
C06B
47/14 (20130101) |
Current International
Class: |
C06B
47/00 (20060101); C06B 47/14 (20060101); C06b
001/04 () |
Field of
Search: |
;149/109,43,44,46,47,38,60,41,62,92 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Lechert, Jr.; Stephen J.
Claims
I claim:
1. In a process for preparing foamed semisolid colloidal
dispersions of water-bearing blasting agents comprising mixing
inorganic oxidizing salt, fuel and water, the improvement which
comprises foaming and sensitizing the mix by incorporating into the
mix the gas-generating material
N,N'-dinitrosopentamethylenetetramine.
2. In a process for preparing foamed semisolid colloidal
dispersions of water-bearing blasting agents comprising mixing
inorganic oxidizing salt, fuel, thickener and water, the
improvement which comprises foaming and sensitizing the mix by
incorporating into the mix the gas-generating material N,N'
-dinitrosopentamethylenetetramine.
3. The process of claim 2 wherein the amount of
N,N'-dinitroso-pentamethylenetetramine added is about from 0.03 to
1 percent by weight.
4. The process of claim 2 wherein the amount of
N,N'-dinitrosopentamethylenetetramine added is about from 0.1 to
0.8 by weight.
5. The process of claim 3 wherein the thickener is
polyacrylamide.
6. The process of claim 3 wherein the thickener is guar gum.
7. The process of claim 3 wherein the inorganic oxidizing salt is
ammonium nitrate.
8. The process of claim 3 wherein the mix is at a temperature of
about from 140.degree. to 160.degree.F when the gas-generating
material is added thereto.
9. The process of claim 3 wherein aluminum is added to the mix.
10. In a process for preparing foamed semisolid colloidal
dispersions of water-bearing blasting agents comprising mixing
inorganic oxidizing salt, liquid carbonaceous fuel, emulsifying
agent and water, the improvement which comprises foaming and
sensitizing the mix by incorporating into the mix the
gas-generating material N,N' -dinitrosopentamethylenetetramine.
11. The process of claim 10 wherein the emulsifier is one that
forms a water-in-oil emulsion.
12. The process of claim 11 wherein the amount of N,N'
-dinitrosopentamethylenetetramine added is from 0.03 to 1.0 percent
by weight.
13. The process of claim 11 wherein the amount of N,N'
-dinitrosopentamethylenetetramine added is from 0.1 to 0.8 percent
by weight.
14. The process of claim 12 wherein the carbonaceous fuel is fuel
oil.
15. The process of claim 12 wherein the inorganic oxidizing salt is
ammonium nitrate.
16. The process of claim 12 wherein the mix is at a temperature of
about from 140.degree. to 160.degree.F when the gas-generating
material is added thereto.
17. The process of claim 15 wherein the inorganic oxidizing salt
contains sodium nitrate.
18. The process of claim 12 wherein the emulsifier is a stearate
salt.
Description
BACKGROUND OF THE INVENTION
Semisolid colloidal dispersions of water-bearing blasting agents
are well known. These products typically comprise an oxidizing
component, usually predominantly ammonium nitrate, a fuel component
and water. More particularly, these blasting agents are referred to
in the art as water gels or slurry explosives, and emulsion type
blasting agents. The blasting agents commonly referred to as water
gels contain, in addition to the above ingredients, a thickening
agent that gels the composition, e.g., guar gum or polyacrylamides.
In addition, the water gels may contain high explosives such as
TNT, or metallic fuels such as aluminum that function not only as
part of the fuel component of the blasting agent but also increase
explosive strength. Representative water gels of the type disclosed
hereinabove are more fully described in U.S. Pat. Nos. 3,153,606,
3,431,155 and 3,288,658. As indicated above, other water-bearing
explosive compositions that are semisolid colloidal dispersions are
known as emulsion type blasting agents. Emulsion type blasting
agents contain, at least one oxidizing agent, water, an emulsifying
agent and a fuel component that is a carbonaceous compound in
water. The carbonaceous fuel used in the process for preparing
these products is liquid during formation of the emulsion. The
emulsifying agent generally forms a water-in-oil emulsion wherein
oil is the continuous phase and water is the discontinuous phase of
the emulsion. Representative water-bearing semisolid colloidal
dispersions of emulsion type blasting agents are described in U.S.
Pat. No. 3,447,978. Furthermore, these semisolid colloidal
dispersions of waterbearing blasting agents, both the thickened
water gel and emulsion type, have been prepared in such a manner
that small gas bubbles are entrapped therein or they contain
gas-entrapping material, e.g., microballoons. The inclusion of gas
in the form of gas bubbles or in gas-entrapping material is known
to regulate the strength of the blasting agent. Methods for
preparing gas-containing water-bearing blasting agents include the
mechanical incorporation of gas and in situ chemical generation of
gas by the decomposition of certain compounds. Although these
procedures have produced satisfactory products, there is a need for
making foamed semisolid colloidal dispersions of water-bearing
blasting agents by employing a gas-generating chemical compound
that is simple to use; inexpensive; forms gas bubbles in the
blasting agent within a short period of time that remain formed
therein for extended periods of time; forms gas bubbles in the
composition that are small, generally the majority of bubbles are
not greater than about 100 micron diameter, preferably between 10
to 70 microns, for the most effective sensitivity; provides an
effective control over the amount of gas introduced into the
composition; and is applicable to water-bearing blasting agents,
e.g., water gels, and emulsion type blasting agents.
SUMMARY OF THE INVENTION
This invention provides a process for preparing foamed semisolid
colloidal dispersions of water-bearing blasting agents, especially
water gels or thickened water-bearing explosives, and emulsion type
blasting agents, which comprises mixing inorganic oxidizing salt,
fuel and water, the improvement which comprises incorporating into
the mix the gas-generating material
N,N-dinitrosopentamethylenetetramine thereby foaming and
sensitizing the blasting agent. When preparing a water gel, a
thickening agent is added to the water-bearing explosive
composition in order to thicken or gel the aqueous phase. When
emulsion type blasting agents are prepared, an emulsifying agent
and a liquid carbonaceous fuel are added to the water-bearing
explosive during preparation in order to form an emulsion between
the water and fuel. The amount of dinitrosopentamethylenetetramine
added to the mix during preparation of the blasting agent is about
0.03 to 1 percent by weight based on the weight of the total
composition.
DESCRIPTION OF PREFERRED EMBODIMENTS
The gas-generating material that is used in this process, i.e.
N,N-dinitrosopentamethylenetetramine, decomposes and gives off gas
at temperatures at which the blasting agent ingredients are
formulated to produce a foamed product that is sensitized by small
gas bubbles. The exact amount of gas-generating material used in
the process varies and the specific amount employed depends upon
the desired final density of the resulting product and the
temperature of the formulation when the gas-generating agent is
added thereto. Generally, amounts ranging about from 0.03 to 1
percent by weight, preferably about from 0.1 to 0.8 percent, are
incorporated into the mix. The gas-generating agent is added to the
composition at ordinary mixing temperatures, usually between
130.degree. to 180.degree.F. However, for optimum results, the
gas-generating agent is added to the mix when the temperature of
the mix is most favorable for decomposition of the foaming agent.
Best results are obtained when the temperature of the mix during
addition of N,N'-dinitrosopentamethylenetetramine to the mix is
from about 140.degree. to 160.degree. F. Preferably, the
gas-generating material N,N'-dinitrosopentamethylenetetramine is
added to water gel type blasting agents after the mix has
thickened, and to emulsion type blasting agents after the emulsion
has formed, so that in each case the mix is sufficiently viscous to
retain gas bubbles when the composition foams and small gas bubbles
are formed therein.
The inorganic oxidizing salts used in this invention are those
conventionally used in water-bearing blasting agents and include
ammonium, alkali metal and alkaline earth metal nitrates and
perchlorates as well as mixtures of two-or more such salts.
Representative inorganic oxidizing salts are ammonium nitrate,
sodium nitrate, potassium nitrate, magnesium nitrate, calcium
nitrate, ammonium perchlorate, sodium perchlorate, potassium
perchlorate and magnesium perchlorate. The amount of inorganic
oxidizing salt use in the water-bearing blasting agents is from
about 20 to about 75 percent by weight of the composition.
Preferably, a mixture of inorganic nitrate salt are used of which
at least about 45 percent by weight of the total composition is
ammonium nitrate and of the order of 15 to 25 percent, preferably
about 15 percent, based on the weight of the total composition, is
sodium nitrate.
As mentioned above, the foamed semisolid colloidal dispersion of
water-bearing blasting agents can contain a thickening agent to gel
the composition, thus forming the well-known blasting agents known
as water gels or slurry explosives. The amount of-thickening agent
added regulates the consistency of the blasting agent and such
thickeners are used in amounts ranging from about 0.2 to 5 percent.
Representative thickeners include galactomannans such as guar and
locust bean gum; gum arabic; starches and modified starches such as
dextrins, polyvinyl alcohol; polyacrylamides; high molecular weight
polyethylene oxides; or mixtures of two or more of the above
thickening agents. Best results are obtained when guar gum or
polyacrylamide is used as thickener with the gas-generating
agent.
In addition, as mentioned above, this invention is applicable to
the production of water and oil emulsion type water-bearing
blasting agents. These compositions contain, in addition to
inorganic oxidizing salt, water and fuel, an emulsifying agent. The
amount of emulsifying agent used is from about 0.5 to 10 percent by
weight, and preferably from about 1 to 2 percent. Larger quantities
of emulsifying agent may be added since excess emulsifying agent
merely serves as a supplemental fuel for the blasting agent.
Generally, the emulsifying agents used are those that form
water-in-oil emulsions, such as sorbitan fatty acid esters, e.g.,
sorbitan monolaurate, palmitate or oleate; polyoxyethylene sorbitol
esters and long chain fatty acids and esters thereof, so that a
water-in-oil emulsion of the blasting agent is formed. Especially
good results are obtained when the emulsifying agent is formed.
Especially a stearate salt, e.g., sodium stearate, alone or in
combination with stearic acid. Other emulsifying agents include
sodium oleate with or without oleic acid, dodecylbenzene sulfonic
acid, tall oil amides such as the tall oil amide of
tetraethylenepentamide, "EZ-Mul", manufactured by the Baroid
Division of National Lead Co.
The fuels used in thickened water gel blasting agents include
self-explosive fuels, nonexplosive fuels and metallic fuels as well
as mixtures of the aforementioned types of fuels. Representative
self-explosive fuels that can be used in the composition are
organic nitrates, nitro compounds and nitramines such as
trinitrotoluene, pentaerythritol tetranitrate,
tetra-nitro-N-methylaniline, nitrostarch, explosive grade
nitrocellulose, smokeless powder and mixtures thereof. Generally,
the amount of self-explosive fuel used is from 10 to 40 percent by
weight, based on the weight of the composition. Nonexplosive fuels
such as certain nitro aromatic hydrocarbons, for example, mono- and
dinitrobenzenes can be used, and sulfurous fuels including sulfur
itself. Carbonaceous fuels such as finely-divided coal,
hydrocarbons such as fuel oil and paraffin wax, can be added to the
composition. Metallic fuels can also be used and these include
light elements such as aluminum, magnesium, boron and silicon, both
singly and in combination. Heavier metallic compounds and alloys
including ferrophosphorus and ferrosilicon can be added to the mix.
Blasting agents of the emulsion type wherein a water and oil
emulsion is formed must contain carbonaceous fuel that is liquid
during formation of the emulsion. The carbonaceous fuel is not
soluble in water and generally forms the continuous phase of the
emulsion so that the blasting agent is in the form of a
water-in-oil emulsion. The carbonaceous fuel that is emulsified
when used in the emulsion type blasting agents can include oil
alone, a wax and oil, a wax and a polymeric material, or a wax and
a polymeric modified oil component. The fuel used thus includes
hydrocarbons such as paraffinic, olefinic and aromatic that are
saturated or unsaturated. Waxes that can be used include paraffin
wax and mineral waxes. Petroleum oil of varying viscosities can be
used as the fuel, especially No. 2 fuel oil. Polymeric materials
such as natural or synthetic rubber may be used as a carbonaceous
fuel component. Preferably, the fuel comprises oil along.
Generally, the amount of fuel used is from about 3 to 10 percent by
weight. Optionally, the emulsion type blasting agents can contain
supplementary fuels, as disclosed hereinabove, especially
particulate metals, e.g. aluminum, and finely-divided coal. In
general, the amount of fuel used in the blasting agents of the
present invention is such that the oxygen balance of the blasting
agent will be from -25 to +10 percent and preferably from -10 to +5
percent.
The amount of water used in the blasting agents of the thickened
water gel and emulsion type is from 5 to 30 percent by weight,
preferably about from 10 to 25 percent by weight water is used in
preparing thickened water gels and emulsion type blasting
agents.
Optionally, other ingredients can be incorporated in the blasting
agents. For example, nitrogen-base salts can be added to the
water-bearing blasting agents to increase their effectiveness. The
nitrogen-base salt functions, among other things, as a fuel
component and such salts that can be used in this invention are
disclosed, for example, in U.S. Pat. No. 3,431,155. Preferably, the
nitrogen-base salts used are monomethylammonium nitrate and
ethylenediammonium dinitrate. Such salts can be added to the
composition in amounts of from about 5 to 40 percent by weight. As
is conventional in the preparation of thickened water gels, the
composition can, and usually does, contain a crosslinking agent
such as an alkali metal dichromate or a soluble antimony compound,
e.g., potassium antimony tartrate, in amounts of from 0.001 to 1
percent by weight. Likewise, a crystal habit modifier for the
inorganic oxidizing salt such as Petro AG, which is a derivative of
naphthalene sulfonic acid salt, can also be added to water gel
compositions, if desired. Generally, the procedure for making
thickened water gels is as follows. The oxidizer salts and other
water-soluble materials are mixed with water usually at
temperatures between about 130.degree. to 180.degree.F to effect
maximum solubility. Then the remaining ingredients, except
thickener, crosslinking agent and gas-generating material, are
added. The addition of these ingredients cools the mix.
Subsequently, the mixture is agitated briefly and thickener added.
Mixing is continued until thickening occurs and at temperatures of
130.degree. to 180.degree.F, preferably 140.degree. to
160.degree.F, the gas-generating material
N,N'-dinitrosopentamethylenetetramine is added. The composition is
mixed for about 30 seconds and then the crosslinking agent is added
and a thickened foamed blasting agent sensitized with gas bubbles
is obtained.
A procedure for making emulsion type blasting agents involves
mixing the emulsifiable carbonaceous fuel and emulsifier at a
temperature of about 130.degree. to 180.degree.F such that the fuel
is liquified. Separately, the inorganic oxidizing salts and other
water-soluble materials are dissolved in water at about 130.degree.
to 180.degree.F, and the other materials (except for the liquid
fuel/emulsifier mix) admixed therein. To this aqueous mixture is
added the liquid fuel/emulsifier mix to form a water and oil
emulsion. Preferably at this point in the procedure the temperature
of the emulsion is usually between about 130.degree. to
180.degree.F, most preferably 140.degree. to 160.degree.F, or can
be so regulated; the emulsion begins to thicken and the
gas-generating agent is added to the thickened emulsion.
The following experiments further illustrate the invention in
detail.
Example 1
Formulation Percent by Weight 1.1 1.2 Water 17.0 17.6 Ammonium
nitrate 49.6 52.7 Sodium nitrate 16.0 16.6 Fuel 7.0(sugar) 2.5(fuel
oil) Sulfur 5.0 5.1 Coal 3.0 3.0 Thickener (guar gum) b 0.9 1.0
Crystal modifier (Petro AG) 1.0 1.0 N,N' -dinitrosopentamethylene-
0.2 0.2 tetramine (60%) Crosslinking agent, sodium 0.3 0.3
dichromate solution (5%)
The ammonium nitrate, crystal modifier Petro AG (methyl naphthalene
sulfonic acid) and the bulk of the sodium nitrate were dissolved in
the water at about 160.degree.F. Subsequently the thickener,
premixed with the sugar, when used, and the balance of the sodium
nitrate were added to the oxidizer salt solution
(155.degree.-160.degree.F). Finally the foaming agent
N,N'-dinitroso- pentamethylenetetramine premixed with the sulfur
and coal, was added to the above mixture at
140.degree.-150.degree.F. Fuel oil, when used, was admixed prior to
thickener incorporation.
The specific gravity of the resulting foamed water gel blasting
agent 1-1 containing small gas bubbles having diameters of about 10
to 100 microns was 1.1 and nine days later was still 1.1. The
material had a detonation velocity of 4118 meters/second.
Foamed water gel blasting agent formulation 1-2 had a specific
gravity of 1.1 and a velocity of 4118 meters/second. A replicate
sample shot eight weeks later had a velocity of 4233
meters/second.
Example 2
Formulation Percent by Weight 2.1 2.2 Water 18.0 18.3 Ammonium
nitrate 58.75 59.75 Sodium nitrate 15.0 14.9 Fuel oil 5.5 4.4
Sodium stearate 2.0 1.0 Stearic acid 0.9
N,N'-dinitrosopentamethylene- 0.75 0.75 tetramine (60%)
Ammonium nitrate, sodium nitrate and sodium stearate were mixed
with the water at about 170.degree.F. The fuel oil (with the
stearic acid, when used) was added thereto at
140.degree.-150.degree.F. When the mixture started to thicken the
N,N'-dinitrosopentamethylenetetramine was added and mixing
continued until a very thick mass formed. Small gas bubbles formed
having diameters of about from 10 to 100 microns in the
water-in-oil emulsion blasting agent.
Foamed emulsion formulation 2-1 had the following velocities at
40.degree.F:
diameter Velocity, meters/second 5 5640 4 5260 3 4010
Foamed emulsion blasting agent formulation 2--2 had a velocity of
5260 meters/second in 2-inch diameter at 40.degree.F confined in a
steel pipe.
Example 3
Formulation Percent by Weight Water 0.2 Ammonium nitrate (75%) 76.3
Sodium nitrate 15.0 Fuel oil 5.0 Thickener, guar gum 1.0 Aluminum
(pigment grade) 2.0 N,N' -dinitrosopentamethylene- 0.2 tetramine
(60 %) Crosslinking agent, sodium 0.3 dichromate solution (5%)
The sodium nitrate was dissolved in a solution of ammonium nitrate
at about 160.degree.F. The fuel oil and guar gum were premixed and
added to the aqueous solution, and the slurry was agitated for
about 2 minutes. Aluminum was then added and mixing continued for 1
more minute. The N,N-dinitrosopentamethylenetetramine was slurried
in the water and added to the nitrate fuel oil mixture. After about
another 30 seconds of mixing the crosslinking agent was added. The
resultant water gel had a specific gravity of 1.12 and detonated at
4646 meters/second at 40.degree.F in a 6-inch pipe.
* * * * *