CS232873B1 - Modifying the compound of mixed explosives - Google Patents

Abstract

The invention relates to the use of by-products of the process of 2-ethylhexanol oxopropene from propene and synthesis gas as a modifying component of mixed explosives. The invention can be used by manufacturers or consumers of industrial explosives.

Description

The invention relates to the use of by-products of the process of producing 2-ethylhexanol by oxosynthesis as a modifying component of mixed explosives.

The importance of mixed explosives continues to grow · Ammonium nitrate is the most widespread oxygen donor and so the most widespread mixed explosives are ammonium explosives, consisting of two main groups:

Z. mixtures of ammonium nitrate with fuel;

II. mixtures containing ammonium nitrate, water with a plasticizer or dispersant, an explosive substance, or a sensitizer.

F

Explosions of the first group can be produced by stable technological equipment, but more frequently are produced directly at the site of use, i.e. in mobile mixing equipment or directly in boreholes. Ammonium nitrate is mixed with fuel, which may be a wide variety of organic compounds. However, paraffins, oil heater or diesel fuel are most commonly used. These mixtures have approximately zero oxygen bilanoia, which corresponds to a content by weight of? % ammonium nitrate and 6 wt. diesel fuel or fuel oil in an explosive. Said fuel content will increase the value of the explosion heat from 1470 kJ.kg for ammonium nitrate to 3738 kJ.kg, which is proportional to the increase in the working ability of the explosive over ammonium nitrate alone. Explosives of this type are with us

232,873 known under the code designation DAP, similar mixtures are referred to abroad as ANDK (GDR), ANC (in Germany), Igdanite (in USSR), ANFO or ANBA (in American literature). Kenya is fuel coal dust, metal powder, etc., these mixtures are also called nitrocarbonates and are referred to as NCN code.

Ammonium line explosives of the second group are characterized by relatively simple and undemanding production technology. In our country, they are known as TPV (water-plasticized explosives); in the USA and Canada they are called Slurry Explosives for slurry consistency · At present, the most used distribution of explosives of this type is according to the method of sensitization to:

a. Slurry Explosives ”(SE) that are sensitized by an explosive additive (trinitrotoluone, hexogen, nitroesters, alkanol- or alkylamine nitrates, hydroxyalkyl nitrates, and the like);

b. Slurry Blasting Agents (SBA), which do not contain explosive additives and are sensitized by non-explosive components, most commonly aluminum dust (eg Soviet Aquanals) and / or other substance (fuel oil, fibrous cellulose, polyvinyl chloride powder, sulfur, paraffin, hexamethylenetetramine, polyols, sugars and others) or aerating additives (expanded perlite, glass pulp or hollow batter, cork, expanded polystyrene, attached ammonium nitrate, etc.) or gas-releasing substances (peroxides, nitrites) , carbonates, 1,5-endomethylene-3,7-dinitrolo-1,3,5,7-tetraazacyclooctane and others).

To prevent separation of TPV-type explosive components, the composition includes gelling agents (plasticizers, thickeners) such as guar gum and its alkyl derivatives, polyvinyl alcohol, sodium or ammonium salts of carboxymethylcellulose, hydroxyethylcellulose, polyacrylamide, and others. At the same time, these additives guarantee the flowability or plasticity of the respective compositions !.

- 4,232,873

A newer kind of Slurry explosives are the water-in-oil eraulse composition, the V / θ code in the Anglo-American literature, or the 0 / en oil-in-oil enxulsion type. These explosives have a lower content compared to conventional TPV mixtures. water (ie higher working ability) with improved flowability or plasticity ·

Its physical stability is guaranteed by dispersants, such as fatty acid salts (especially stearic or oleic acids), fatty acid esters (e.g. decaglyoerine decolate, decaglyoerine deca stearate), partially esterified with polyols with fatty acids (e.g. monoethearate, monooleate or monistalmitate, tristalmitate) mono-or di-fatty acid-forming fatty acids), further alkylarylsulfonates, soybean lecithin, ethylene oxide-propylene oxide copolymer and others. Sensitization of V / 0 or 0 / V explosives with air-entraining agents or gas-releasing additives is the most enormous technical practice.

Calcium nitrate (especially in liquid formulations) or sodium hypochlorite is sometimes used as oxygen donors in Slurry explosives - the second mainly in aluminized compositions. Low production costs, high production and handling safety and the possibility of meohanizáo blasting washing are characterized by explosive mixtures ammonium nitrate base · This is the main reason why in technical practice exploitation of explosives of DAJP, TPV type and now of V / θ and O / tf types prevails over exploitation of other types of industrial explosives. military purposes (aluained aqueous ammonium nitrate gels are, for example, laboratory in some types of aviation bombs, trinitrotoluane is replaced by more powerful liquid compositions based on aqueous solutions of hydrazine nitrate, etc.) ·

232 873

Many of the components mixed. explosives are themselves becoming increasingly important and economically more attractive for use in various sectors of the national economy (eg diesel, fuel oils, ethylene glycol and others); on the other hand, some traditional sensitizers for toxicological and / or safety reasons (trinitrotoluene and nitroesters) are, however, dispensed with. • The resulting gap can be filled with * suitable, in particular by-products of the chemical industry which further chemical processing is still a problem. This also applies to by-products from the production of 2-ethyl hexanol by oxoprooeside from propene, carbon monoxide and hydrogen. These products consist, firstly, of rectal fractions of crude 2-ethylhexanol, forming a colorless to yellowish liquid consisting of 20 to 90% by weight 5 to 30% by weight of 2-ethylhexanol and 5 to 35% by weight of a mixture of other oxygen-containing and optionally hydrocarbon-containing organic compounds. Thereafter, from the heavy fractions of oil consistency, the mixture is up to 38% by weight. % Of 2-ethylhexanol, up to 48 wt. dodecyl alcohol diols up to 1 wt.

The α-ethers and the remainder are esters of Οθ and C C-alcohols with and / or C 8 -acids.

In terms of physicochemical properties, said composition is a potenoic phlegmatizer, plasticizer and / or fuel of mixed explosives, in particular ammonium nitrate based explosives. Taking into account the content of higher alcohols, respectively. diols, this mixture may also act as a sensitizer in compositions characterized by good sensitivity to detonator initiation (sensitization in this sense by aliphatic alcohols 8 C Ϊ 12 see eg Jap · pat. No. 78-47 509), good patronity, good physical properties. stability and water resistance. Given that polyhydric alcohols such as 1,6-hexanediol, also applied as DAP-type antistatic agents (eg Jap. Pat. No. 80-56 088), there is a potential possibility of analogy application to by-products as well.

- 6,232,873 for the production of 2-ethylhexanol, optionally treated so that the diol predominates in niobium

According to the present invention, the by-products of the process of producing 2-ethylhexanol by oxoprooeses from propene and synthesis gas useful as modifying the mixed explosive component in an amount of 0.5 to 20% by weight, preferably in an amount of 5.55 to 15.00% by weight . calculated on the weight of the resulting composition.

An advantage of the present invention is the technical and economic availability of the modifier. The use of the by-products of the production of 2-ethylhexanol by oxoprooes in this invention contributes to increasing the economic efficiency of this production, at the same time being a potential source of economical savings in petro-chemical products in blend explosives and last but not least.

. The by-products from the production of 2-ethylhexanol can be applied to the production of explosives according to the invention in such a form that after separation of the gaseous components the process results or by physico-chemical operations it is possible to obtain fractions satisfactory for that particular application. (e.g. frakoia enriched diol C for _l2-type antistatic treatment composition DA.P etc.) ·

Explosives containing by-products of the production of 2-ethylhexanol are aluminizable. Xoh physical stability can be increased by conventional means: for example, for D1P compositions, application of the attached ammonium nitrate and / or the addition of wood meal and / or the addition of another suitable adsorbent, for TPV explosives, the application of a suitable gelling agent.

The application according to the invention in addition to the particularly difficult products from the production of 2-ethylhexanol by oxoprooeses from propene and synthesis gas has not been known so far, is documented by the following examples, which in no way preclude the possible variability of application methods.

- 7 Example 1

232 873 £ available! are the heavier by-products of the process of producing 2-ethylhexanol by oxoprooes from propene, carbon monoxide and hydrogen, characterized by the following quality parameters:

hydroxy group content ($ w / w) 12,28 content of called aldehydes (wt w / w) 0 content of glacial aldehydes ($ w / w) O bromine number (g of bromine per 100 g of sample) 1.28 water content (% by weight) 0.078 density at 20 ° C (g.om -1) 0.9019 refractive index (η ^ θ) 1.4530 acid number (mg potassium hydroxide) 1.10

Saponification number (mg of potassium hydroxide per 100 g vz) 14,46 flash point (° C) 94 flash point (° C) 246 per sec danger class III combustion heat (kJ.kg ¹ ) 39 174,79

Next available! industrial ammonium nitrate, of a content by weight of 1% water. A mixture of paste-like consistency of 84.15 wt. ammonium nitrate,

0.85 wt. water and 15.0 wt. by-products of 2-ethylhexanol production. Said mixture is characterized by: to data:

oxygen balance -32.0 $ explosion heat max. (kJ.kg “ ¹ ) 3 860 explosion heat (kJ.kg ~ ^) for charge density 1000 kg.m ^ 3 240 complete ideal explosion threshold (kJ.kg” ¹ ) 2 970

232 873 explosion gas volume (l.kg “ ¹ ) 970 detonation speed (km.s“ ¹ ) 2,8 - 3,0

Said mixture is particularly suitable for application as an intermediate in the production of mixed explosives.

Example 2

A bulk mixture of the following composition is prepared from the raw materials and the procedure of Example 1; 93.4 wt. ammonium nitrate, 0.9 wt.%, water and 5.7 wt. by-products of 2-ethylhexanol production. This mixture is characterized by data:

oxygen balance + 5 $ explosion heat max. (kJ.kg ¹ ) 3708 explosion heat (kJ.kg ” ¹ ) over charge mass' 1000 kg.m“ ^ 3 395 complete ideal explosion work (kJ.kg “ ¹ ) 3 055 explosion gas volume (l.kg ” ¹ ) 980 detonation velocity (km.s“ ¹ ) for charge specific gravity '1000 kg.m ”^ 2,8

Example 3

From a raw material as in Example 1, but with dried ammonium nitrate and aluminum dust having a specific surface area of about 0.7 m .g, a free-flowing mixture of 91-52% by weight is prepared by a malaxer process at atmospheric pressure. % ammonium nitrate, 5.55 wt. % by-products of 2-ethylhexanol and 2.93 wt. of aluminum.

This mixture is characterized by:

oxygen balance - 2% explosive heat max. (kJ.kg ” ¹ ) 5 3θ3 explosion heat (kJ.kg“ ¹ ) for charge weight '1000 kg.m ”^ 4 7θθ complete ideal explosion work (kJ.kg ¹ ) 4 270 volume of explosive fumes (l.kg ') 8ló

232 873 detonation velocity (km.s ^-1 ) for a charge density of 1000 kg.m 3.8

Example 4

Using a non-isothermal differential thermal analysis (DTA) flowing at a linear temperature rise rate of 5 K »ain * \ sample weights of 0.08 to 0.09 g, at a measuring range of 1mV, the temperature difference recorder results in production by-products for mixtures with application 2 -ethylhexanol the following parameters (Table i):

Table 1

Composition Data from differential thermal analysis Beginning of melting (K) Melting peak (K) Beginning of exotherm (K) Starting ammonium nitrate 431.6 437.1 460.1 According to Example 1 424.6 433.1 442.6 According to example 2 424.6 431.6 440.1

It is apparent from the tabular overview that the side-by-side heavier fracoxes from the production of 2-ethylhexanol activate thermolysis of ammonium nitrate, which corresponds to the general knowledge of the effect of alcohols and / or polyols on thermal stability and / or sensitivity of ammonium nitrate.

Claims (1)

OBJECT OF THE INVENTION 232 873 Use of by-products of the process for the preparation of 2-ethylhexanol by oxoproeae from propene and synthesis gas as a modifier of the mixed explosive component in an amount of 0.5 to 20% by weight, preferably in an amount of 5.55 to 15.00% by weight of the resulting composition.