CS250016B1 - Flotation agent and / or component - Google Patents

Abstract

A flotation agent and/or a component of a flotation agent based on oxygenated organic compounds, which form at least one of the three by-products from the cyclohexanone production plant by oxidizing cyclohexane. Thus, it consists of 20 to 100 masses. part of the liquid untreated by-product — distillation residue from the step of de-detoxing residual cyclohexanol oxidation mixture cyclohexanol — cyclohexanone and/or 50 to 100 wt. part of the organic residue from the boiling point of the hydrolyzation column after separating part of the water and 5 to 50 wt. part of the leading alcoholic by-product isolated from the rectification of a predominantly cyclohexanol — cyclohexanone mixture. The flotation agent or component of the flotation agent is suitable for the flotation of coal, ore and other non-ore raw materials.

Description

250016

BACKGROUND OF THE INVENTION The present invention relates to a flotation agent and / or to a flotation agent component or to a floatation agent based on defined side-chain oxygenated organic products based on an oxidation process.

It is known that floatation agents are an important factor in the process of flotation as a result of the process. A distinctive feature of the basic agents used in flotation in small amounts is the selectivity of their effect on interfacial surfaces: liquid-solid (water-mineral) and liquid-gas (water-air). Thus, saflotting agents according to their basic design are generally divided into three large groups: 1. pantographs or collectors; 2. foaming agents or foaming agents; and 3. regulators or modifiers.

Typically, the collectors are organic substances which are preferably adsorbed at the interface of the liquid-solid, i.e. at the surface of the mineral particles. The collectors provide for the hydrophobization of the mineral surface, thus reducing the wettability of the mineral surface, which ultimately adds to the addition of air bubbles. In this way, the typical collector molecules consist of two parts, polar and non-polar.

The polar part attacks the mineral, allowing binding, respectively. adsorption of the mineral surface molecule collector. Typically, the non-polar portion is a hydrocarbon chain of varying length, water-oriented, with only a very weak "watering" of the water molecules, ensuring hydrophobicity of the mineral surface.

Typical collectors are most often (Tuturina VV, Slavin GP: Organicheskajachimia and flotoreagents. Gosudarstvennoenaucno-issledovatefskoe litera-literary after the gun, Moscow / 1962 /) from oil and oil fractions, aliphatic acids, compounds containing polar molar they have bivalent sulfur, sulfo, other nitrogen and phosphorus. At the same time, each type of collector is extremely effective in flotation-specific minerals.

Typically, the foaming agents form a polopolymeric substance which is most frequently adsorbed on the interfacial surface by the liquid gas and which ensures the desirable dispersion of the air bubbles and the stability of the foam. However, the excess foaming agent strongly reduces the foam stability.

Thereafter, the regulators are particularly important for priselective flotation, which, for example, increases wetting in the case of a single plant, while others decrease it. Usually, these are electrolytes, which have the physico-chemical state and properties of the collectors and the surface condition of the mineral particles.

Thus, from flotation agents, typical collectors include butylxanthate, amylxanate; to foaming agents cresols, xylenols, phenol and alcohols and to carbon monoxide regulators, calcium oxide and the like. (Glembockij, V.A., Klassen, V.I., Plaskin, I.N., Flotation, Gostop-techizdat, 1961).

Many substances have a multifunctional effect. Sodium lauryl sulphate used in the flotation of non-sulphide minerals has a foaming, collecting and wetting effect; Naphthenic acids, usually used in the flotation of dense salts, barites and imagensite, have a potent and harvesting effect. In addition to these effects, a depressant, alkali, peptizing, flocculating and emulsifying effect is still required from the flotation agent.

Thus, for flotation purposes, flotation agents or components of flotation agents include alkyl sulfates, alkyl sulfonates, alkyl arylsulfonates, higher fatty alcohols, phenoxy, carboxylic acids, amines, xanthogenic salts, mercaptans, dialkyldithio-phosphates (Abram AA, Leonov SB, Soro-kin M M .: Chimija flotacionnych sistem.Izd Motherhood Nedra, Moscow (1982); Duden-kov SV (ed.): Osnovy teorii i praktikaprimenenija flotacionnych reagentov. Izda-tefstvo Nedra, Moskva / 1969 /). However, many of the flotation agents used have been technically demanding, possibly toxic, so that they strongly contaminate the waste water.

Therefore, the effort is used for flotation of ores and non-ore raw materials such as coal and so on. products as cheap as possible. Such include butanol, high-boiling and 2-ethylhexanol oxosynthesis, as well as by-products from the production of alkyl polyglycol ethers by oxyethylation alcohols in admixture with mineral oil such as polyethylene glycols and polypropylene glycol in the production of ethylene glycol and propylene glycol (U.S. Pat. No. 205,769 and No. 203 716). However, their sources are limited, so there is an effort to find further technically-economically available flotation agents. Such compounds include, according to the present invention, a floatation agent and / or a flotation agent component, or an oxygen organic compound reagent, which comprises 20 to 100 wt. parts of the original untreated product of the cyclohexanone production by oxidation of cyclohexane, an alcohol distillation residue from the separation step of the residual cyclohexanol of the cyclohexanol-cyclohexanone oxidation mixture at a density of 20 ° C in the range of 960 to 980 kg. m-3, an acid number of 0.3 to 3 mg KOH / g, a bromine number of 180 to 280 g Br / 100 g, an ihydroxy content of 2.0 to 10% by weight. and a carbonyl group content of 3.5 to 14% by weight. and / or 50 to 100 wt. parts of the organic residue from the binder of the hydrolysis column after separation of water at a density of 20 ° C of 10 to 1115 kg · m-3, acid number 150 to 290 mg KOH / g, saponification number 250 to 480 mg KOH / g g, bromine number 18 to 55 g Br / 100 g, content

2.5 O and 1 B hydroxyl groups 3.5 to 7.5 wt. 5 to 50 wt. parts of a first alcoholic by-product isolated from the rectification of predominantly cyclohexanol-cyclohexanone mixture, characterized by a number of 0.01 to 5 mg KOH / g, a saponification number of 10 to 60 mg KOH / g, a bromine number of 8 to 38 mg KOH / g, hydroxyl groups 8-22% wt. and carbonyl groups 2 to 8 wt. The advantage of the flotation agent and / or the component of the flotation agent, or the mixture of the agents of the present invention, is the technical availability, since the separate streams of the by-products of the cyclohexanone product are catalytic oxidation cyclohexane, good flotation efficiency and hygenic harmlessness, or only low text. Because it is practically three separate streams of low-tech-economically evaluated by-products, differing in carbonate composition by its technical composition, or by the diverse flotation efficiency of the ores, by other non-metallic raw materials, a high selectivity and efficiency for the flotated builder can be utilized by a suitable combination .

This is the predominant alcoholic by-product, isolated from the rectification (from column FK-102) of the predominantly cyclohexanol-cyclohexanone mixture. The density of this colorless liquid at 20 ° C is in the range of 840 to 865 kg. m-3 and 95% in the range of 92 to 142 ° C // 101 kPa; an acid number of 0.01 to 5 mg KOH / g; saponification number 10 to 60 mg KOH / g; bromine number 8 to 38 mgKOH / g; hydroxyl groups of 8 to 22% by weight; the carbonyl group contains 2 to 8% by weight, usually containing 48 to 53% amyl alcohol, 8 to 10% n-butanol; 5 to 7% isobutanol; 1-2% sec-butyl alcohol; 3-5% isoamyl alcohol; 18-20% cyclohexanone; 8 to 10% cyclopentanol, about 5% cyclopentanone and about 2% water. The admixtures of cyclohexane, cyclohexene and cyclohexanol are about 1%. Further, the distillation residue from the step of separating the residual cyclohexanol of the cyclohexanol-cyclohexanone oxidation mixture (heavy particles from FK-105), having a density in the range of 960 to 980 kg at 20 ° C. nr 3 and 95% distances between 150 and 263 ° C / 101 kPa; an acid number of 0.3 to 3 mg KOH / g; bromine numbers 180-280 g Br / 100 g; obslah of hydroxyl groups of 2 to 10% by weight; % carbonyl groups of 3.5 to 14 wt.

The amount of organic residue from the hydrolysis column cooker after separation of a generally substantial portion of the water (e.g., D 110 column) having a density at 20 ° C of 1010 to 1115 kg. m-3; a water content of 4 to 10% by weight, an acid number of 150 to 290 mg KOH / g; saponification number 250 to 480 mg KOH / g; bromine number 18 to 55 g Br / 100 g; hydroxyl content of 3.5 to 7.5 wt. It consists of mixtures of monocarboxylic and dicarboxylic acids of hydroxy- and ketoacids, their cyclohexyl esters. Furthermore, lactones are present in the monomeric form, but also dimers and polymers. Monocarboxylic groups (butyric, capric, valeric, dicarboxylic acids (succinic, glutaric, adipic and hydroxyl acids (delta-hydroxybutyric acid, delta-hydroxyvaleric acid; ε-hydroxycaproic acid) were identified. esters of the foregoing and other acids (cyclohexyl valerate, cyclohexylcaprenate; dicyclohexyl glutarate, cyclohexyl adi-pianate), and mixtures of cobalt, iron, nickel, titanium and zinc compounds.

The flotation agent according to the invention can also be combined with known flotation agents or components of the cleaning agents. A more detailed characterization and additional advantages of the flotation agent and / or the flotation component of the present invention are apparent from the examples. Example 1

As a flotation agent for the flotation of angular sludge with a grain size of 0.1 to 0.5 mm in a Denver 2.7 liter laboratory flotator, a mixture of by-products from the cyclohexanone product was used by oxidation of cyclohexane, while the mixture was 75% by weight. . organic residue from the brewing hydrolysis column after separation of a portion of the water, otherwise determined by combustion utilization and 25% by weight of the by-product by-product of the rectification of the oxidation mixture (substantially about 60% cyclohexanol and about 30 ° C on cyclohexanone) from the rectification column ( FK-102).

The organic residue from the brewing hydrolysis column after separation of the water has the following characteristics: yellow to dark brown liquid; dynamic viscosity at 20 ° C = 268.9 mPa · s; density at 20 ° C = 1106 µg / cm 3; ohsiah water = 6.9 wt%; acid value = 256.3 mg KOH. g-1; saponification number = 412.8 mg KOH. g-1; bromine number = 23.1 g Br / 100 g; hydroxyl content = 4.7% by weight. The column by-product of the present invention (FK-102) has the following characteristics: a colorless to slightly yellow liquid of 95%. distilling at 92 to 142 degrees C; .250016 densely at 20 ° C = 855 kg. m 3; kinematic viscosity at 20 ° C = 3.86 mm 2. s-1; water content = 3.6% by weight; acid value = 0.95 mg KOH / g-1; saponification number = 21.00 mg KOH. g-1; bromine number = 27.8 g Br / 100 g; OH = 14.3%; CHO = 4.50%; mole. weight = 109.4 g. mole-1; it contains 51.9% of n-amyl alcohol from the identified components; 3.7% isoamyl alcohol; 5.6% isobutanol; 9.7% n-butanol; 19.7% cyclohexanone / 4-methyl-1-pentanol; 1.1% sec.-butanol and 0.2% isopropyl-alcol.

The presence of esecyclopentanol, cyclopentanone, cyclohexane, cyclohexene and cyclohexanol is found qualitatively.

The flotation tests are carried out by feeding the flotation agent in an amount of 1.3 kg / l of dry matter. The flotation efficiency evaluated by the ash content of the concentrate at both the graded and the purified flotation is also compared to the flotation efficiency of the commercially successfully used flotation agent FNX. The results obtained also with the floatation agent specified in this example as well as in Examples 2 and 3 are shown in Table 1. The results show that the activity of these flotation agents is similar to the high as well as the commercial flotation agent FNX. Example 2

In a similar manner to Example 1, flocculant was screened as a flocculent by-product from the cyclohexanone manufacturing plant - after separation of the cyclohexanone and residual cyclohexanol, the trone distillation residue (FK-105) having this characteristic: dark brown to brownish black a liquid; a fraction of from 150 to 263 ° C / kPa is 95 ° / o; density at 20 ° C = 970 kg. m-3; kinematic viscosity at 20 ° C = 12.1 mm 2 .. s-1; average mole. mass = 173.5 g mol-1; water - 0.01 wt%; acid value = 0.9 mg KOH / g; saponification number = 43.2 mg KOH / g; OH = 4.51% by weight; CHO = 8.28 wt.

The favorable result obtained is in Table 1; the flotation agent is comparable to a high-quality commercial FNX flocculating agent.

Table 1

Effect of flotation agents to achieve ashiness of slurry concentrates

Flotation Agent Ash Content in Concentrate (% w / w) Flotation Gradual Flotation Purified Flotation Agent FNX 6.7 10.7 Flotation Agent Example 1 6.7 10.6 Flotation Agent Example 2 6.9 10.3 Flotation Example Example 3 9.7 10.7

Claims (1)

The flotation agent and / or components of the flotation agent or agents based on oxygen-containing organic compounds, characterized in that it consists of 20 to 100 wt. parts of the untreated by-product from the cyclohexanone production plant by oxidation of cyclohexane as the distillation residue from the residual cyclohexanol separation step of the cyclohexanol-cyclohexanone mixture having a density at 20 ° C in the range of 960 to 980 kg. . m ^-3 , acid value 0.3 to 3 mg KOH / g, bromine number 180 to 280 g Br / 100 g, hydroxyl group content 2.0 to 10 wt. % and a carbonyl group content of 3.5 to 14 wt. and / or 50 to 100 wt. parts of an orga Example 4 The procedure is similar to that of Example 2, except that 20% by weight of the fluxing agent, as described in Example 2, is added. a front alcoholic by-product (from the FK-102 column) characterized in Example 1. The ash content of the gradual flotation concentrate was 6.6% by weight. and flotation purified 10.6 wt. BACKGROUND OF THE INVENTION Nickel residue from the hydrolysis column after separation of a portion of water having a density at 20 ° C of 1,010 to 1,115 kg. m ^-3 , acid number 150 to 290 mg KOH / g, saponification number 250 to 480 mg KOH / g, bromine number 18 to 55 g Br / 100 g, hydroxyl group content 3.5 to 7.5 wt. and 5 to 50 wt. parts of the front alcoholic by-product isolated from rectification of a predominantly cyclohexanol-cyclohexanone mixture, characterized by an acid number of 0.01 to 5 mg KOH / g, a saponification number of 10 to 60 mg KOH / g, a bromine number of 8 to 38 mg KOH / g, % hydroxyl groups 8 to 22 wt. % and carbonyl groups of 2 to 8 wt.