CS230081B1 - Mixed explosive fuel - Google Patents

Abstract

The invention relates to the use of by-products of the production of cyclohexanol from benzene as fuel in the production of mixed explosives. The amount of by-products applied in the explosive ranges from 2 to 20% by mass. to the weight of the resulting explosive. The invention can be used in companies producing industrial explosives or directly by users of explosives.

Description

X 230 081

BACKGROUND OF THE INVENTION The present invention relates to the use of Cyclohexanone byproducts from bison as fuel in the manufacture of a mixed blasting agent. The importance of mixed explosives is increasing in both civilian and military applications. The most widely distributed oxygen donor in them is ammonium nitrate - hence the most common mixed gases are ammonolite explosives, consisting of a dozen main groups; I. Ammonium nitrate mixtures with fuel. mixtures of ammonium nitrate, water with a plasticizer, and substances of an explosive nature, or sensitizer.

The first group explosives can be produced in stable technology plants, but are more likely to be produced at the site of use / t. j. in mobile mixing devices or directly in boreholes /. Ammonium nitrate is mixed with a fuel that can be a wide variety of organic compounds, but paraffins, fuel oils, and diesel are most commonly used. These mixtures have an approximate zero oxygen balance corresponding to 94% by weight. ammonium nitrate and 6% w / w of fuel or oil in the blasting content indicated above will increase the explosion heat of 1470 kJ / kg for ammonium nitrate at 3738 kJ / kg, which is proportionally increased in the blasting performance versus ammonium nitrate alone. Markets of this type are known in the Czech Republic under the code name DAP, abroad they have similar mixtures labeled ANDK / in NDR /, ANC / in NSR /, Igdanite / in USSR /, ANFO or ANBA / in Anglo-American literature /. When the dust in the explosive is dust, metal dust, etc., these mixtures are also referred to as NCNs.

Amonoliad explosives of the second group characterized by a relatively simple and uncomplicated production technology. Known as TPV / water plasticized explosives / j - 2 - 230 081 in the US and Canada, they are called "SlurryExplosives" for the pulpy consistency. Currently, the most usable distribution of the abovementioned type is according to the method of sensitization, namely: " Slurry Explosives " (SE), which are sensitized by the explosive nature / trinitrotoluene, hexogen, nitroesters, nitrates of alkanol or alkylamines, hydroxialkyl nitrates and the like. /; b. "Slurry Blasting Agents" (SBA), which do not contain any explosive-type component and are sensitized by an explosion-proof additive, most commonly aluminum dust. Soviet Akvanals / and / or other substance / fuel oil, fibrous cellulose, polyvinyl chloride powder, sulfur, paraffin, hexamethylenetetramine, polyols, sugars and others /, respectively, aerating additives / perlite, glass pulp, cork, polystyrene, rubber ammonium nitrate and the like /, or gas / peroxide releasing substances, nitrites, carbonates, 1,5-endomethylene-3,7-di-nitroso-1,3,5,7-tetraazacycloctane and the like.

The pixation of the physical stability of these Slurrytravine subgroups, i.e. avoiding the separation of components while maintaining fluidity or plasticity of the composition, is accomplished by a gel-forming additive, such as, e.g. guar gum, polyvinyl alcohol, sodium or ammonium salts of carboximethylcellulose, oxiethylcellulose, polyacrylamide, and others. Calcium nitrate and sodium perchlorate are sometimes also used as oxygen donors in water-plasticized blasting agents, especially in aluminized compositions. However, by low production costs, high production safety and handling and the possibility of blasting mechanization, explosive mixtures based on ammonium nitrate are mainly characterized. The main reason why the exploitation of the DAP and TPV type changes in technical practice is dominated by the exploitation of other types of industrial explosives.

Many of the components applied in mixed explosives, such as sensitizers and fuels, find themselves more significant and economically more attractive to be used in various industries. however, diesel, fuel oils and the like on the other hand, slowly releasing some sensitizers and fuels from the toxicological and / or safety of the Oxygen / Trinitrotoluene, nitroesters. The resulting gap can be filled with suitable, especially by-products of the chemical industry whose further processing is viable. This also applies to the by-products of cyclohexane oxidation to cyclohexanol and cyclohexanone in the benzene production of cyclohexanone. Said by-products, referred to in PIR and MEK, are mixtures of free and esterified. acid hydroxycaproic acid, adipic acid, glutaric acid, succinic acid and other organic substances also containing up to 10 wt. water, and having a pour point in the temperature range of -26 to -28 ° C, flash point 130 ° C, specific gravity 1.09 g.cm "3 at gQ ° q) viscosity 45 cP at 60 ° C and 15 cP at 100 ° C.

According to the invention, the mixtures of free and esterified acids of the MEK type are applied in particular as a mixed explosive fuel in an amount of 2 to 20% by weight, preferably 9 to 16% by weight. to the resulting composition. An advantage of the present invention is the technical and economical availability of the MEK mixture. The use of these by-products in the sense of the present invention contributes to increasing the economy of the cyclohexanone production process from benzene. Since the MEK blend contains chemically bound oxygen, it contains an approximate zero oxygen balance of the multi-organic component (i.e., less ammonium nitrate) than the saturated hydrocarbon-based fuel in the DAP type. the value of the ideal ideal explosion work is enhanced for the MEK composition. Since the cost of production of DAP compositions is predominantly determined by the price of ammonium nitrate, it is a further advantage of the present invention to provide it with the above stated purpose. Although the by-products of the MEK type contain a certain amount of water, I am acting as a distinctive hydrophobic liquid, which in the "dry" ammonia explosives has a beneficial effect on their waterproofing and agglomeration of the composition grain.

The by-products of the production of cyclohexanone from benzene can be applied to produce explosives in such form as, for example, for combustion, or they can be back-loaded with the gelling agent and used as modifying components of plasticized water. MEK explosives are - 4 - 230 0B1 aluminizable. The physical stability of DAP type explosives with hom can be increased in conventional ways, such as for example. by the application of admixed ammonium nitrate and / or by the addition of wood chips and / or by the addition of other suitable adsorbent / water-soluble urea-formaldehyde condensates, high dispersion silicon dioxide with chemosorbed methyl groups - modified Aerosil and the like /.

The use of cyclohexanone byproducts of benzene from benzene in the present invention has not been described in the literature to date and is exemplified by the following examples. EXAMPLE 1 Cyclohexanone cyclohexanol and cyclohexanone oxidation products are available, characterized by the following data: elemental analysis ... 59.4 wt. % carbon; % 32.6 wt. oxygen

gross calorific value .......... »28 12Q kJ.kg '' ^ '' 'specific heat« 2,51 kJ. 6.40% w / w otjsstd popols «» «** ** 0.19% w / w acidity. 269 mg of potassium hydroxide per saponification ... 416 mg of potassium hydroxide per liter of bromine ... 20.9 g of bromine per 100 g content , hydroxi-groups ... 5.7% solidification e ............... below +10 ° C slurry consistency, solidification at -26 to -29 ° C specific gravity '......... 1,1374 g.cm' 3 at 20 ° G 1,1177 g.cm "3 at 50 ° G dynamic viscosity ... 0, 6268 Pa.s for 30 ° C

0.1209 Pa.s for 50 ° C - 5 - 230 081 Next available! technical ammonium nitrate with a content of 0,4% by weight moisture content and grain size of 94% by weight, from 0.6 to 3.0 mm. A mixture of DAP type explosives is prepared from these raw materials under atmospheric pressure. The standard DAP sample results from the mixing of the above-mentioned ammonium nitrate with diesel fuel,

The composition of the individual mixtures, the respective oxygen balance values (OB), the explosion heat (Q-g), the explosion volume of the flue gases (V), the ideal explosion work (W) and other characteristics are presented in Table 1.

Table 1.

Components and Indicators Composites Type DAP A B C Standard Mass Composition /: Ammonium Nitrate 93.63 89.52 86.70 94, & diesel oil - - 5,5 MEK 5,62 9,46 12,10 - water 0,75 1,02 1,20 max. 0,5 Consistency a: semi-loose half paste loose powder Calculated values: OB /% / +15, 30 +0.03 - 8.80 +0.12 Qe /kJ.kg"1/ 3765 3640 3535 3790 V /liter.kg"1/ 980 955 950 980 W /kj.kg*1/ 3365 3240 3145 3160

Experimental values - - 3 bulk density / g. cm "V 0.75 _ - 0.80 detonation velocity for the charge density of 0.95 to 1.10g.cm-3 / in krn.s" 1 / 2.6-2.8 2.4-2, 7 2,0-2,4 2,2-2 / 230 081 - 6 - It can be seen from Table 1 that the composition C and the value of the ideal ideal explosion work / W / near the standard mixture DAP that from the application of MEK in mixed explosives of the DAP and / or TPV type, there is a potential for saving ammonium nitrate.

Using a non-isothermal differential thermal analysis (DTA), working with 0.08 to 0.09 g sample weight, a linear temperature rise rate of 5 µm -1 · 1 and a differential temperature recorder with a 0.5 mV range data were presented in Table 2 for the standard DAP and Composition A compositions.

Table 2.

Type of data from DTA Composition A Standard. DAP melting point / ° C / 151.0 154.2 melting peak / ° C / 155.0 160.5 exo-decomposition onset / ° G / 174-176 177.0 For comparison, the DTA method for starting ammonium nitrate provides;

melting point ....... 154,3 ° C

melting peak ......... 160.0 ° C

exo-decomposition number ....... 184.0 ° C Example 2

The aluminum powder / aluminum puddle incorporated in the composition A of Example 1 is added and incorporated therein to produce a mixture of 90.9% by weight. ammonium nitrate, 5.45 wt. MEK, 0.73 wt. water and 2.92 wt. allium. For a charge density of 1 g.cnT, this mixture is characterized by: oxygen balance / OB, in% / ............... +4.15 explosion heat / 0 ™ , in kJ.kg “^ / ............. 5440" —i volume of explosion fumes / V, in l.kg / .... 900 - 7 - complete 'ideal blast work / W, in kj.kg “* 1 / .................. detonation speed /km.s” ^ / ............. bulk density / / g cm in ............. 230 081 3800 3.8 0.73 to 0.77

DTA method as in example 1 heater start / ° C / ........... melting peak / 0 / * ·· .. »· · · · · · · exo-decomposition / ° C / I is found in this mixture: 149.5156.2172.2 Example 3 In 30 wt. parts of MEK of Example 1 are suspended in 2 wt. parts of gel-forming substance "guar-gum". Of the 21 parts by weight of this relatively stable suspension, 85 wt. sodium perchlorate monohydrate and 3 wt. a dense gel with a composition (% w / w) of sodium perchlorate, 16.97% MEK, 10.92% water, 1.38% guar is prepared by the atmospheric pressure malaxing method in an aluminum powder / aluminum puddle. -gum and 2.75% aluminum. For charge density5.7 g.cm 3, this gel is characterized by values; In the case of a mica balance / OS, in $ & / ...... ·. —9.06 Explosion Heat / Qg, in kJ.kg * ^ / 5600 Explosion Outflow Volume / V, in l.kg "'1 / .... 508 Complete Ideal Explosion Work / W, in kJ.kg' '^ ^ / ....................... 3900 detonation velocity /km.s. .. 2.4

Claims (1)

OBJECT OF THE INVENTION 230 081 The use of by-products of the production of cyclohexanone from benzene as fuel in the production of a mixed explosive in an amount of 2 to 20% by weight, preferably in an amount of 5.45 to 16.97% by weight. these by-products to the weight of the resulting explosive.