FI59387C - SPRAENGAEMNESKOMPOSITION - Google Patents

Description

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Patent · And register held · __________________ ______ ..._ PMH »OCh ri | lmi1tywllH '' AmMcm ocfc« cUkrtfMn puMiurad 30.0U.8l (32X33X31) Pn * «« r »oHimm l <W» rtorfct 30.ll.7i

England-England (GB) 55 ^ 95/71 (71) Canadian Industries Limited, P.0. Box 10, Montreal 101, Quebec,

Canada (CA) (72) Errol Linton Falconer, Mont Saint-Hillaire, Quebec, Harold William Holden, Mont Saint-Hillaire, Quebec, Leo Joseph Francis Saulnier, Beloeil, Quebec, Canada (CA) (7U) Qy Kolster Ab (5U) The present invention relates to an explosive composition which may be in the form of a pumpable aqueous slurry, an extrudable gel, a sealable cohesive semi-gel or a dry free-flowing mixture containing 20 to 95% by weight of water inorganic nitrate. , 0-15 weight # carbon-containing fuel, 0-10 weight # gel extender, 0-5 weight # thickener and 5-U0 weight # liquid sensitizer.

There has long been a desire in the explosives industry to invent a safe, economical and practical substitute for nitroglycerin and ethylene glycol dinitrate, commonly referred to as NG and EGD, respectively. Because NG and / or EGD are hazardous to prepare and formulate into useful explosive mixtures, and because NG and / or EGD vapors often cause undesirable physiological effects on those who come in contact with them, their use poses ongoing problems for the explosives industry. It was expected that a non-toxic aqueous sludge explosive consisting of a mixture of oxidant salt-fuel-2 59387 in an aqueous base would replace most NG / EGD-based explosives. Although this has been done to a substantial extent, it has not been economically possible to produce sludge explosives which are suitably sensitive and strong in small diameters without the addition of expensive sensitizers. A particular disadvantage has been that known useful sludge sensitizers, such as particulate organic explosives, such as TNT, or particulate energy-containing metals, are not soluble or fully compatible with the aqueous base and thus do not function optimally during the blasting process.

Ideally, an explosive sensitizer, especially a sensitizer for aqueous oxidizing salt slurry explosives, should have the economy and potency of conventional nitroglycerin / ethylene glycol dinitrate without the associated hazards and toxicity, and should be fully compatible with the solvent.

The explosive composition according to the invention is characterized in that the sensitizer is ethylene glycol mononitrate, propylene glycol mononitrate or hydroxychloropropyl nitrate or mixtures thereof.

The preparation of hydroxyalkyl nitrates (HÄN) is carried out industrially by reacting an oxirane ring compound with an aqueous solution of ammonium nitrate and nitric acid. For example, ethylene oxide reacts to form ethylene glycol and EGMN in a dilute solution of nitric acid and ammonium nitrate. Other nitrate salts such as sodium nitrate and calcium nitrate may be added to the reaction mixture. The reaction product containing EGMN can be subjected to an extraction treatment to obtain substantially pure EGMN. Alternatively, the final product can be used as such as part of a sludge explosive mixture with increased sensitivity.

The invention is illustrated by the following examples, which do not limit its scope. The percentages are weight percentages in all examples.

Example 1

Preparation of ethylene glycol mononitrate (EGMN) 1 mole (1 + U g) of ethylene oxide was introduced as a gas into a solution containing 220 g of ammonium nitrate, ho g of sodium nitrate, 80 g of 98% nitric acid and 1U0 g of water, and the mixture was cooled in an ice bath. The reaction was exothermic with increasing temperature from 8 ° C to 20 ° C with the addition of oxide. When the oxide addition ceased, the temperature dropped rapidly and no ethylene oxide evolved from the reaction vessel. This showed a very rapid reaction. The EGMN formed did not separate from the aqueous solution, not even upon neutralization and saturation with ammonium nitrate / 59387 sodium nitrate. The aqueous solution was extracted with methylene chloride to give a 50-35 $> EGMN yield. This yield was quite low and did not represent the actual reaction yield, but was the result of a simple distribution of the product between the two phases into which it was completely miscible.

The isolated EGMN was shown by thin layer chromatography and gas-liquid chromatography to consist mainly of EGMN and small amounts of ethylene glycol, ethylene glycol dinitrate and diethylene glycol mononitrate. Example 2

Second Preparation of Ethylene Glycol Mononitrate (EGMN) Ethylene oxide was introduced into a solution containing 500 g of ammonium nitrate, 80 g of sodium nitrate, 160 g of $ 98 nitric acid and 280 g of water. The reaction temperature was kept below 35 ° C by external cooling. The rate of oxide addition to the solution was adjusted to 1.2 l / min. and at the same time 160 g of $ 98 nitric acid was added dropwise over 57 minutes, which time was required for the addition of 3 moles of oxide. An additional 6 moles of ethylene oxide and 320 g of $ 98 nitric acid were added in the same manner, after which an additional 4 moles of oxide were introduced into the system to neutralize the excess nitric acid. Typically, after a total of 13 moles of oxide had been absorbed, 2 ml of 28-6 ammonium hydroxide solution (d-0.90) was needed to bring the final solution to pH 7 → 0. Calculation of the material balance of the reaction products showed approximately the following composition: ammonium nitrate $ 24.1 sodium nitrate 3 $ 19> water $ 11.5> ethylene glycol mononitrate 51 »4 $ ethylene glycol 9» 1 #

Examples 4-8 Preparation of EGMN

The following EGMN fluids were produced in the pilot-plant reaction process of Example 2. The amounts shown are by weight.

Example: 4 5678 ammonium nitrate 25 »4 22.0 24» 7 25.9 28.8 sodium nitrate 4 »2 4» 2 3.8 3.8 410 water 12.8 15.7 11.9 11.5 15.3 EGMN1 54.2 51.3 54.7 55.8 52.4 Ethylene glycol 5.4 6.8 4.8 5.0 5.5

Additions of ethylene oxide and concentrated nitric acid can be repeated to obtain even higher EGMN concentrations (e.g., 70 #).

4 59387

Examples 9-11 Continuous Preparation of EGMN A continuous process was used to prepare EGMN. The three vessels were connected in one series and formed a mixing tank, a nitration tank, and a neutralization tank. The vessels were equipped with mixing devices, cooling devices and inlet and outlet openings. An acidic aqueous solution containing 26 to 33 parts by weight of ammonium nitrate, 46 to 52 parts by weight of concentrated $ 98 nitric acid and 15 to 25 parts by weight of water was prepared in a mixing tank. This solution was pumped into a nitration tank where it was contacted with ethylene oxide gas. The solution and gas feed rates were adjusted to maintain the reaction temperature at about 30 to about 60 ° C, which reduced the formation of by-products such as ethylene glycol or ethylene glycol dinitrate. The composition of the desired nitration product by weight is 1 to 12 nitric acid, 18 to 25 ammonium nitrate, 10 to 15 water, 2 to 10 ethylene glycol and 30 to 60 EGMN. The crude product flowed continuously from the nitration tank to the neutralization tank, where ammonia gas was uniformly dispersed in the stirred reaction mixture by means of a gas atomizer. The pH was adjusted to 6.2 to 6.5. At this point, 2 to 15 wt% more ammonium nitrate was formed in the reaction between ammonia gas and residual nitric acid. The liquid flowing from the neutralization tank through the outlet was the desired end product, which normally contained 40 to 60 wt.% EGMN, 2 to 8 wt.% Ethylene glycol, 25 to 35 wt.% Ammonium nitrate, and 10 to 25 wt.% Water. The following EGMN fluids were prepared by a continuous process.

Example 9 10 11 ammonium nitrate 27.5 29.2 25.9 water 15.0 16.1 22.4 EGMN. 53.6 49.4 46.8 ethylene glycol 3.8 5.5 4.9

Example 12

Sensitivity of ethylene glycol mononitrate (EGMN)

The impact sensitivity of nitroglycerin (NG) and EGMN was compared in a drop weight impact test by absorbing both substances in a base containing $ 25 wood chips, $ 25 sodium nitrate, and $ 50 ammonium nitrate. A mixture of 60 and NG / 40 io of base mass exploded when 5 kg was dropped to 57.5 cm. However, a mixture of $ 70 EGMN and 30 base masses did not explode when 5 kg was dropped 137.5 cm.

Examples 13-21 Preparation of PGMNs and HCPN

Doses of propylene glycol mononitrate and hydroxychloropropyl nitrate were prepared by a method similar to Example 2. However, it was found that the high initial concentration of ammonium nitrate caused it to crystallize as the reaction continued and that the presence of sodium nitrate caused liquid-liquid phase separation during the reaction. Typically, 50 S of ammonium nitrate and 65 ml of 70% nitric acid were used as starting material. Propylene oxide or epichlorohydrin and $ 70 nitric acid were added through separate inlets in the same molar ratio until 16 to 30 moles of acid were added, followed by an excess of $ 5 to $ 17 in propylene oxide or epichlorohydrin. Additional ammonium nitrate can be added dissolved in nitric acid to maintain a high nitrate concentration. Up to 470 g of ammonium nitrate remained in solution. Neutralization of the excess acid with liquid ammonia in the synthesis of propylene glycol mononitrate resulted in the separation of the liquid-liquid phases, with a more concentrated solution of the desired product, PGMN, in the upper layer. It was found that in both syntheses, saturation of the system with sodium nitrate or calcium nitrate resulted in more efficient separation, with the layer containing most of the mononitrate ester containing relatively little water. Preferred compositions fed to the reactor can be used in the preparations by the continuous method of Examples 9 ** H.

The analyzes of representative batch reaction products are summarized below:

Example 13 14 15 16 17 18 19 20 21

Analysis: H 2 O 14.1 12.7 12.6 8.8 14.5 5.7 11.3 H, 6 5.8 ammonium 12.9 12.4 13.5 7.7 14.3 4.1 9.5 8.3 5.5 nitrate sodium - - - 1.7 ~ 0.33 “- 0.74 nitrate propylene 7.3 7.3 7.7 7.4 7.8 - glycol propylene glycol 65 .7 67.7 66.2 74.5 63.4 - - limononitrate chlorohydrin - - 9.2 8.6 9.3 9.1 hydroxychloro- ----- 80.7 70.6 70.8 78, 9 propyl nitrate

Note: In Examples 13, 14 and 15, the products were obtained by separating the main liquid layer after neutralization with ammonia.

The product of Example 16 was obtained from Example 15 by impregnating the system with sodium nitrate and retaining the sensitizer-rich layer.

In Examples 19 and 20, the reaction product was obtained as a single-phase product after neutralization with ammonia.

6 59387

The product of Example 21 was obtained from the example by impregnating the system with sodium nitrate and retaining the sensitizer-rich layer.

Example 22

The slurry blasting explosive composition

The EGMN prepared in Example 1 was used in the preparation of the following slurry explosive composition in a laboratory apparatus. ammonium nitrate 45 »2 i ° sodium nitrate 10.0 i zinc nitrate 0.17 i> water 12.0 io EGMII 30.0 gilsonite 1.0 i> thickener (guar gum) 0.6 $ ethylene glycol 1.0 i crosslinker ) 0.03 ys ° density lt44 g / cm 2

The above composition exploded in a 5.1 cm diameter cartridge using 20 g of pentolite for initial ignition.

Example 23

The slurry blasting explosive composition

A slurry having the following composition was prepared in a laboratory using the reaction product of Example 2.

EGMN 30.0 io ethylene glycol 5 »3 i ammonium nitrate 54» 0 fo sodium nitrate 10.1 io water 12.0 i aluminum 5 »0 i thickener (guar gum) 2.6 i surfactant 1.0 i density 1.10 g / cm 2

The above composition exploded in a J.8 cm diameter cartridge using a Euro-powered detonator cap for initial ignition.

Example 24

The slurry blasting explosive composition

The following slurry was prepared in the laboratory using the reaction product of Example 2.

EGMII 12.0 i ethylene glycol 4.2 i> ammonium nitrate 51.68 io sodium nitrate 12.4 i 7 59387 water 14 »6 $ sodium lignosulfonate 3.0 fumaric acid 0.02 $ zinc nitrate 0.2 thickener (guar gum) 1.2 ^ crosslinker 0.7 i ° density 1.3 g / cm 2

The above composition exploded in a 10.2 cm diameter cartridge using a 110 g cast pentolite detonator for initial ignition.

Example 25

Slurry Explosive Composition EGMJT, prepared by extraction with methylene chloride, was used in the laboratory to prepare the following slurry: ammonium nitrate 39.5 ^ sodium nitrate 10.0 fo water 12.0 'fo aluminum 5.0 ^ EGMN $ 30.0> thickener (guar gum) 1, 5 $ ethylene glycol 1.0 $ surfactant 1.0 ^ density 1.12 g / cm 2

The above composition exploded in a 3.5 cm diameter cartridge using a high-powered detonator cap for initial ignition.

Examples 26-29 Sludge Explosive Composition

A series of aqueous high diameter slurry coolant compositions of low density were prepared in amounts of 45 kg in a belt mixer. The mixing methods used were chosen to resemble a typical mixing operation in a Pulkki mixer connected to a mobile wagon so that the products would be suitable for use in this manner. Thus, most of the dry substances were mixed in a mixer before the addition of water, the guar thickener was added dispersed in glycol, and the temperature was adjusted to 1Θ to 24 ° C; EGMN liquid was added after stirring the guar gum for 5 minutes; after stirring for an additional 5 minutes, about half of the ammonium nitrate (25.0% of the total composition) was added as porous pieces to mix the air into the slurry; finally, the crosslinking solution was added only after the slurry had stood for one day.

The crosslinking solution was prepared from equal parts by weight of sodium dichromate, ferrin nitrate and water.

8 59387

The following is a summary of the results for slurries showing increasing sensitivity as the proportion of ethylene glycol mononitrate increases. The sensitizing effect of aluminum has also been shown to be used in combination with the EGMN sensitizer. The ratios shown are by weight.

Example 26 27 28 29

Ingredients (added) ammonium nitrate (in pieces) 45 »8 50.48 52.18 45» 7 sodium nitrate 11 * 50 11.80 11 * 90 11 * 9 sodium lignosulphonate 5 * 00 5 * 00 5 * 00 5 * 0 zinc nitrate 0.20 0.20 0.20 0.2 fumaric acid 0.02 0.02 0.02 ~ gilsonite 0.90 1.60 2.60 water 11.80 13.10 15.40 15.7 guar thickener 1.00 1 .00 1.00 1 * 0 glycol 3 * 00 5 * 40 3 * 40 4.2 EGMN liquid 22.101 14.801 11.702 11.72 aluminum powder - - - 10.0 crosslinking solution 0.60 0.60 0.60 0 «6 100.00 100.00 100.00 100.0

Total amounts of main constituents ammonium nitrate 50.1 54.0 46.3 46.4 sodium nitrate 12.4 12.4 12.4 12.4 ethylene glycol 4 * 2 4 * 2 4.2 5 * 0 EGMN 12.0 8, 0 6.0 6.0

Water 14.8 15.2 15.4 15.7 Aluminum powder - - 10.0 Other 6.5 6.2 15.7 4.5 Density after crosslinking 1.25 1.25 1.17 After 1.25 nan Explosion resultsBet plastic cartridge 15.2 cm 10.2 om 15.2 om 8.9 cm diameter blasting used 80 g 450 g 450 g 450 g (pentolite)

slurry temperature 4.4 ° C 4.4 ° C 5.5 ° C 4.4 C

in the explosion

X54.2 $> EGMN 251.5 1 ° EGMN

example 4 example 8 9 59387

Examples 30-32 Sludge Explosive Compositions

High density explosive compositions of a type suitable for large diameter were prepared. The dry salts were first stirred, then EGMN liquid was added and stirred, adjusting the temperature to 18-24 ° C and pH 4 → 0-5 ° C. The finely divided metal contained in the composition, aluminum powder, was added at this stage, followed by modified guar gum and crosslinkers dispersed in glycol. After a thickening time of 2-4 minutes, the blends did not segregate and were packaged in polyethylene lined fiberboard cylinders. Explosion tests were performed on the compositions using a 320 g molded pentolite detonator, and the results and material ratios in weight are shown in the table below.

Example 30 31 32

Ingredients (added) ammonium nitrate (in pieces) 43 »9 41.9 34.8 sodium nitrate 10.0 10.0 10.0 zinc nitrate 0.2 0.2 0.2 EGMN liquid (eg II) 42.0 42, 0 42.0 aluminum powder - - 10.0 sulfur - 3 »0 gilsonite 1.0 - - ethylene glycol 1.93 1» 93 1 »93 guar thickener 1.00 1.00 1.00 potassium pyrantimonate 0.07 0.07 0.07 cross-linking 100 .00 100.00 100.00 density 1.43 1 »42 1.57

Total amounts of main components ammonium nitrate 54 »7 52.7 45» 7 sodium nitrate 10.0 10.0 10.0 ethylene glycol 4f0 4 »0 4» 0 EGMN 19.7 19.7 19.7 water 9> 4 9 »4 9.4 aluminum - - 10.0 cartridge size (om) 15 »2 x 58.4 15» 2 x 59.4 15> 2 x 59.4

slurry temperature 1.7 ° C 6 ° C 24 ° C

The result exploded exploded exploded 10 59387

Examples 33-35 Slurry Explosive Compositions

A series of aqueous small diameter fits were prepared, i. Explosive, sludge explosive compositions with a diameter of 5.1 cm or less. Teddy-sensitive compositions are provided in which additional sensitization is achieved by incorporating air bubbles stabilized in the thickened slurry with surfactants. In these systems, the dry ingredients were mixed together, then liquids were added and thickened. The ratios shown are reported as weight swimmers.

Example 33 34 35

Ingredients (added) ammonium nitrate (in pieces) 32.025 25.925 23.625 sodium nitrate (synthetic) 10.2 15 »0 12.9 zinc nitrate 0.2 - 0.2 with nitro cotton (dynamite grade) 0.5 thickener (modified guar) 1.5 1.5 lt5 crosslinking solution 0.075 0.075 0.075 zinc chromate 0.5 O »5 - 50 nen sodium dichromate - - 0.5 solution surfactant 1.0 ^ 1.0 ^ 1.0 ^ water 6.5 6.6 5.5 EGMN liquid 47.5 ^ 49.4 ^ 54.7 ^ 100.00 100.00 100.00 density 1.18 1.05 1.17

Total amounts of main constituents ammonium nitrate 43 * 3 39 »5 40.1 sodium nitrate 12.0 15 * 0 15.25 ethylene glycol 2.4 1.9 2.6 EGMN 26.5 26.5 30.0 water 12.0 14.0 12.0

Successful detonations of the primary nucleus No: 8 No: 6 No: 5

P / C detonator P / C detonator p / c detonator temperature 4 * 4 ° C 4 * 4 ° C 22 ° C

polyethylene lined cartridge diameter 1 "1" 1 «measured explosion rate 2.8 3 * 2 3f0 (km / sec) n 59387 1GAP" Cedepol '* SA-406 (registered trademark) 2GAF "Cedepon" LT-40 "" ^ example 7 4 .

example 9 5 • 'example θ

Examples 36-37 Slurry Explosive Compositions

High density slurries were also prepared on a laboratory scale from propylene glycol mononitrate and hydroxychloropropyl nitrate. Their explosiveness was later tested by the "lead crushing" method described after Examples 57-64. The compositions and results are shown below, the ratios are by weight in $.

1 2

Example 36 36

Total amounts of ingredients ammonium nitrate 42.3 35 »5 sodium nitrate 18» 7 15 »0 water 15» 1 5> 7 propylene glycol mononitrate 16.3 propylene glycol 3 »4 hydroxychloropropyl nitrate - 35» 3 chlorohydrin - 4 * 3 guar thickener 1.9 1 * 9 hydroxyethylcellulose package 1.9 1 * 9 sunscreen potassium pyrantimonate crosslinkers 0.1 0.1 zinc chromate 0.1 0.1 fumaric acid 0.2 0.2 density 1.41 1.54 tested charge 10.2 cm φ x 1 kg 10, 2 cm φ x 1 kg explosion primer 20 g pentolite 60 g pentolite Prepared from both layers of the reaction product as described in Examples 13-21 2 nCPN liquid concentrated from Example 20 by impregnation with sodium nitrate Examples 38-40 Slurry Explosive Compositions

A series of aqueous slurry compositions were prepared in which additional sensitization was achieved by incorporating glass microbubbles containing air into the composition. In these systems, liquids to which a dose of ammonium-12 59387 sodium nitrate had been added were pre-thickened before the remaining dry ingredients and crosslinker were added. The ratios shown are by weight.

Example 38 39 40

Ingredients (added) EGMN liquid 57.31 57.31 34.42 ammonium nitrate (in pieces) 8.0 8.0 15.0 water 1.2 1.2 3.4 ethylene glycol - - 0.7 thickener (modified guar) 1.0 1.0 0.4 glass microbubbles 1.0 2.0 2.0 ammonium nitrate (powder) - - 14.08 "" (porous pieces) 18.65 17.65 13.0 sodium nitrate (synthetic) 12.7 12.7 13.0 gilsonite - - 2.0 crosslinking solution 0.05 0.05 0.02 zinc chromate 0.1 0.1 - 100.0 100.0 100.0 density 1.19 1.12 1.18

Total amounts of main components ammonium nitrate 39.8 38.8 52.1 sodium nitrate 15.0 15.0 13.0 ethylene glycol 3.2 3.2 2.5 EGMN 30.0 30.0 17.0 water 10.0 10 .0 11.0 glass microbubbles 1.0 2.0 2.0

Successful detonations polyethylene lined cartridge diameter, om 3.2 2.5 2.5 primary igniter No. 8 No. 6 high-power * "Anodet" detonator

temperature 4.4 ° C 5.5 ° C 4.4 ° C

explosion rate (km / sec) 3.0 3.6 3.2 ^ example 8 2 example 9 registered trademark

II

13 59387

Slurry explosive compositions such as Examples 22-1 + 0 may also advantageously contain additional sensitizers such as metal particles, ethanolamine nitrate, ethylene glycol dinitrate, nitroglycerin, Pentaerythritol tetranitrate, dinitrotoluene, alkylamine nitrate and ammonium perchlorate. The addition of such known explosive sensitizers provides compositions with rare sensitivity, especially for use in small diameters. For example, a slurry having a density of 1.15 g / cm and containing only 12.5% EGMN, 10% ethanolamine nitrate, 12.1% water and 0.8% preferred surfactant (see e.g. 33), exploded at a speed of 2.6 km / sec in a 2.5 cm diameter polyethylene cartridge with initial ignition of No. 8 F / C with a detonator at 6.7 ° C.

The preparation of hydroxyalkyl nitrate (HÄN) compositions analogous to conventional high performance explosives based on nitroglycerin, ethylene glycol dinitrate, or mixtures thereof involves the isolation of substantially anhydrous HAN from its aqueous liquids. In the present sense, this can be done by extracting the EGMN from the reactor liquid with methylene chloride, which is then evaporated in an evaporation unit.

Example 1 + 1

Gelled explosive composition

The gelled explosive composition was prepared from a liquid phase containing ethylene glycol mononitrate with about 3% ethylene glycol. This mixture quickly and efficiently gelled dynamite-grade nitro cotton, and the resulting gel was resistant to disintegration when immersed in water. The following composition was prepared on a laboratory scale by mixing methods well known in the art; the ratios shown are by weight $.

EGMN / EG 26.0 Nitrocellulose (dynamite grade) 0.7 Ammonium nitrate (powder mixture) 55 »5 Sodium nitrate (Chile) 16.0 Vegetable flour 0.5 Wood chips 0.5 Sulfur 0.1+ Calcium carbonate (lime) 0.1+ 100 0

A very well extrudable, full explosive composition was obtained which exploded (3.2 x 20.3 cm cartridge) upon initial ignition with either a 50% dynamite detonator or a high power electric ball at a speed of 2.57 km / sec. The cartridge did not ignite with No. 6 electric detonator. This represents an explosive with a controlled decrease in sensitivity compared to a nitroglycerin gel with a similar strength.

Although the toxic properties of ethylene glycol mononitrate are not fully known, i4 59387 has been reported to be much less toxic than nitroglycerin. Its vapor pressure is quite similar to that of ethylene glycol dinitrate, which is the volatile and predominant component of all nitroglycerins currently on the market. In any case, both under the controlled effect of EGMK and during prolonged work with it, no typical "NG headaches" caused by dinitrate vapors were experienced. Thus, additional features of EGMN-made explosives include the absence of typical headache-producing properties caused by TG explosives.

Nitroglycerin was found to have significant and unexpected solubility properties with respect to EGMN fluids. When nitroglycerin prepared from starting materials with $ 15 glycerin and $ 85 ethylene glycol was mixed with the EGMN liquid of Example 13, no phase separation up to $ 12 occurred with NG, despite the fact that the system contained about 14 i »water and 24 i ° dissolved salts. Higher nitroglycerin levels resulted in pure, efficient layer separation, and good extraction of EGMN predominantly into the organic layer. Further dehydration of this layer could be performed by adding water-immiscible compounds. Dinitrotoluene or molten trinitrotoluene was found to be effective extractants for the hydroxyalkyl nitrate components from the reactor liquid.

Examples 42 to 46

Gelled Explosive Compositions Concentrated solutions of EGMNs were prepared by mixing reactor fluid with explosive components that promote phase separation as described above. From these solutions, jelly-type compositions were prepared by methods well known in the art; the results of these are summarized in the following table, where the ratios are by weight - $: and.

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The mixture of Example 42 had a density of 1.47 g / cm 2 and a soft consistency that made it easy and neat to extrude into cartridges. The composition was still soft after 23 days of storage in an environment where the temperature varied daily from + 35.5 to -32 ° C.

These examples are further examples of explosives with progressively variable sensitivity. Estimated nitroglycerin content ranges from $ 15 to $ 7. ·

Examples 47 to 48

Jelly-type explosive compositions

Jelly-type explosives with somewhat lower sensitivity were prepared from propylene glycol mononitrate and hydroxychloropropyl nitrate liquids. Concentrated liquids with low water content swelled nitrocellulose, but were found to be more effective when a small amount of high molecular weight hydroxyethylcellulose was first added and swollen.

Example 47 48 liquid 33.01 33.01 hydroxyethylcellulose 0.3 0.3 with nitro cotton 1.3 1.3 sodium nitrate 35.0 35.0 ammonium nitrate 28.5 28.5 wood chips 0.8 0.8 wheat flour 0.7 0.7 lime 0.4 0.4 (contains about $ 25 (contains about $ 26 propylene glycol hydroxychloropropyl mononitrate and linitrate and about 2.9 io water) 1.9 ° already water) Explosion tests free

Polyethylene cartridge diameter 10.2 om 10.2 o · Explosive (pentolite) 60 g 60 g

Results exploded exploded ^ liquid concentrated from the product of Example 17 by impregnation with sodium nitrate

Example 21 17 59387

Examples 49-52

Gelatinized explosive compositions

Sensitizing fluids were prepared by mixing low water fluids such as those obtained in Examples 16 and 21 with standard EGMN fluids such as the products of Examples 9-11 and saturating with salt. For example, 100 parts of PGMN liquid and 200 parts of EGMN liquid were mixed with sodium nitrate; a sensitizer-rich layer (209 parts) was present, containing only $ 11 of water and 15 ° of ammonium nitrate.

The low water contents achieved in the liquid concentrates were advantageous in preparing gelatinized compositions containing nitroglycerin without the need for further liquid separation operations of the type described in Examples 42-46. These are illustrated in Examples 49-51, where the compositions are expressed as weight.

Semi - jelly types Jelly types

Eg 49 Example 50 Example 51 Example 52 liquid 101 102 155 154 nitroglycerin 10 10 15 15 with nitro cotton 0,5 0,5 0,8 0,8 ammonium nitrate 75 »9 75» 9 53 »9 65,0 (powder mixture ) sodium nitrate - - 12,0 vegetable stock 2,5 2,5 2,5 2,0 sulfur 0,3 0,3 0,3 0,3 stearic acid 0,5 0,5 lime 0,3 0,3 0,5 0.5 Blasting tests (free in 3 * 2 om diameter polyethylene cartridges) primary igniter No. 2 No. 4 No. 6 No. 4

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A

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Example 53

Substantially dry dynamite-type explosive composition

Low nitroglycerin compositions typically use about $ 9 nitroglycerin. A typical EGMN fluid used at a level of 59387 instead of about 15-20 io nitroglycerin and formulated with conventional oxygen donating salts and base mass as dynamite would take 2-5 ° / ° water and 8-11 $ ethylene glycol mononitrate into the composition. These water contents were found to be acceptable, and thus drying the EGMN fluid would not be necessary prior to use in such a composition. The composition was prepared by the following combination: EGMK liquid (Example 9) 18.0 ° /> ammonium nitrate (powder) 63.3 sodium nitrate (Chilean) 10.0 vegetable powder 2.0 wood chips 2.0 wheat flour 1.5 Tamarind flour 3 * 0 calcium carbonate 0.2 100.0

The composition was moist, cohesive and typical of conventional dynamite in consistency. When filled into a 10.2 cm diameter cartridge, this composition gave a strong explosion at 21 ° C using a large detonator cap for initial ignition.

Examples 54 to 56

Substantially dry, dynamite-type explosive compositions

The following table provides examples of explosive compositions containing relatively large amounts of liquid hydroxyalkyl nitrate sensitizer thickened with nitrocellulose and made relatively dry in consistency by the addition of pulp. 100 parts of HCPN liquid (which according to the analysis contains 5 »7 ° water, 4» 1 ° / ° ammonium nitrate, 0.33 sodium nitrate, 9 * 2 fo chlorohydrin) and 200 parts of EGMN liquid (14 * 5 ° / a water, 14 * 3 ammonium nitrate, 63.4 ° / ° ethylene glycol mononitrate) was mixed and saturated with sodium nitrate; the more organic phase separated, containing 11.2 l of water, 12.6 fo ammonium nitrate and mixtures of two glycols and two hydroxyalkyl nitrates. This liquid was used in the preparation of Example 56.

Example 54 55 56 12¾ hydroxyalkyl nitrate liquid 45 * 0 45 * 0 50.0 'hydroxyethylcellulose 0.2 0.2 0.2 with nitro cotton 1.2 1.2 1.5 sodium nitrate 46.2 46.2 40.9 pulp 7 * 0 7 * 0 7 * 0 lime 0.4 0.4 0.4 19 59387 Blasting tests (free) polyethylene cartridge 7 # 6 7.6 5 * 1 diameter * cm blaster (pentolite) 60 g 60 g 60 g explosion rate (km / sec) 2.4 2.4 2.6 1Liquid, concentrated from the product of Example 17 by impregnation with sodium nitrate 2

Example 21 EGMN-HCPN Liquid Mixture Examples 57-64

Dry blasting agent compositions

Examples of dry blasting agents normally used in dry boreholes, especially in open pit mines and guarrying operations, are ammonium nitrate fuel oil (ANFO) compositions.

ANFO has proven to be both economical and safe, but still suffers from substantial insensitivity, which is why special measures are needed for the initial ignition and progress of the input. It has been found that by adding hydroxyalkyl nitrate (HÄN) liquid to typical ANFO compositions, their sensitivity can be increased. The solubility of nitroglycerin in HAN can also be utilized to introduce small amounts of NG into dry explosives to prepare compositions of exceptional sensitivity. Because NG is soluble and dissolved, it is evenly distributed throughout the dry composition in a very dilute form.

The detonation tests of the dry explosive compositions shown below were performed by placing the explosive in a 10 cm diameter knee-vein sinus with a steel plate supported by a lead rod bent into a circular shape with a cross-section of 3.5 χ 0.6 cm. A strong explosion greatly rectified this rod.

All of the products in the examples are demonstrably more sensitive than the control, a standard ammonium nitrate / fuel oil explosive made from porous bodies. The standard ANFO normally requires a No. 6 EB detonator cap + five No. 8 blasting caps for a strong explosion. The ratios shown are weight-based.

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