SU1112029A1 - Method for preparing sulfonium methylsulfates - Google Patents

Abstract

METHOD FOR OBTAINING METHYL SULFIGATE SULPHONY, characterized in that the diesel fraction of sulfur oil with a boiling point. 190-360 C is subjected to alkylation dimethylsulfa-. volume at a ratio of 1-1.8 mol of dimethyl sulfate per 1 mol of sulfur sulfide at 85-100s for 5-12 hours

Description

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The invention relates to the preparation of a new mixture of sulfonium methyl sulfates based on a diesel fraction of sulfur oil, which can be used as a flotation reagent, for example, in the preparation of copper concentrates from tin-copper mine chips.

A known method for producing dioxyaryl thiacyclanedylsulfonium salts is that quinone is reacted with organic sulfidamide, for example, a fraction of petroleum sulfides, in the presence of a mineral or strong organic acid at an acid: sulfide molar ratio of 0.8-1.05 :,

with rp;

The obtained salts are interesting as flotation reagents, however, there are no specific digital data confirming this statement. In addition, the method of obtaining these salts is rather complicated using acid, maintaining a certain ratio of initial reagents and low process temperature,

In industry, the most common I and photoreagents are alkali metal xanthates, for example, sulphate KALIUM (BKK) D2.1.

A disadvantage of the known flotation reagent is that its use requires an additional stage (selection), in which the content of the mouse is reduced with the help of special reagents and the concentrate is brought to marketable conditions, i.e. the concentrate obtained using a known flotation reagent is not of the best quality.

The aim of the invention is to develop a method for producing a new fleet of reagent, based on sulfonium salts, with the help of which high quality copper concentrates.

This goal is achieved by the described method of producing sulfonium methyl sulfates (MFDT), in that the diesel fraction of sulfur oil with a boiling point. 190-ZbO C is subjected to alkylation with dimethyl sulfate at a ratio of 1-1.8 mol of dimethyl sulfate to 1 mol of sulfide sulfur at 85-100 ° С for 5-12 h.

While 46-71% (depending on the process conditions) sulfides, containing

20292

 in the oil fraction, is converted to sulfonate methyl sulfates. The selection of the latter from the reaction mixture

can be carried out by settling or. by centrifugation. In order to more quickly and completely release sulfonium methyl sulfates, water can be added to the reaction mixture in an amount of 20-35% of the alkylate product obtained, and the mixture is stirred for 20-30 minutes, followed by separation of sulfonium methyl sulfate in the form of a 50-80% aqueous solution.

The resulting mixture of methyl sulfates, J5 sulfonium, contains mainly compounds in which a positively charged sulfur atom enters thiophane rings, some of which are condensed with one or two saturated necks with 20 membered rings. The presence of these structures is confirmed by the IR spectrum of the product (i3855 1460, 2875, 2950 cm bands, due to the presence of saturated hydrocarbons, stripes 750, 1010, doublet 1220-1250 cm, due to the presence of methyl sulfate anion). The molecular weight of the product is 330-340.

The oil fractions remaining after separation of the mixture of sulfonium sulphate methyl sulphates are partially (by about 30-40%) desalted oil and can be used, in particular, as a high calorific fuel.

An increase in temperature in excess of 100 ° C is impractical, since at 104-109 decomposition of sulfonium methyl sulfates begins, as indicated by thermal analysis and visual observations. Lowering the temperature below causes a decrease in yield.

An increase in the excess of dimethyl sulfate over 80% and the duration of alkylation in excess of 12 hours leads to an improvement in the quality of MHRDS.

Example 1. A reactor with a capacity of 630 l is loaded with 299 kg (350 l) of the Arlan oil fraction, boiling at 190-360 ° С and containing 1, t3% sulfide sulfur. The diesel fraction is heated to 100 ° C, and 26.6 kg of technical dimethyl sulfate (1.8 mol per mole of sulfide sulfur) are charged to the reactor. The temperature at the same time decreases to 94 ° C. The mixture is heated in the reactor to 100 ° C and stirred I at 95-100 ° C for 12 hours. Cool the contents of the reactor before and pour 12 liters of water there. Stir the mixture for 1 hour, settle for 4 hours. Separate the lower layer (54.4 kg), which is a concentrated aqueous solution of sulfonium methyl sulfate, and separate. This technical product contains. 1, 37-10 mol / g (60%) of the basic substance and 17% of water. Example 2. In a flask with a capacity of 250 ml, equipped with a stirrer, a thermometer and a return chiller with a calcium chloride tube, 110 g (128 ml) of the Arlano oil fraction boiling at 190-360 C and containing 1.1 % sulfide sulfur. 5.4 g of technical dimethyl sulfate containing 96% of the basic substance (1.1 mol of dimethyl sulfate per 1 mol of sulfide sulfur) are added, the mixture is heated on a water bath to 85-90 ° C and stirred at this temperature for 5 h. The reaction mixture is cooled to 50-60 ° C, poured into a separating funnel and allowed to stand for 2 hours. Lower layer — black viscous liquid is separated; 10.1 g of alkylation product is obtained. The product is washed with ether (5 ml x 15 times), the ether extract is separated, and the ether residues from the raffinate are distilled off on a rotary evaporator. Obtain 8.1 g of a mixture of purified sulfonate methyl sulfates containing 2.55 Yu mol / l (85%) of the basic substance. Content of total sulfur is 19%. The product contains 8% sulfuric acid and t, 7% methyl sulfuric acid, 0.6% water and 0.4% dimethyl sulfate. PrimerZ, In a 250 ml flask equipped with a thermometer, a stirrer and a reverse water cooling; NIKOM, pour 110 g (128 ml) of the Arlan oil fraction, boiling away at 190–360 ° C and containing 0.8% sulfur sulfide. 3.55 g of technical dimethyl sulfate (1.0 mol per mol of sulfur sulfide) is added to the flask. Stir the mixture at 85-90 ° C for 9 hours, cool to 50-60 ° C, and pour into laboratory centrifuge cups. Treat the emulsion for 10 minutes at a separation factor of 1900 hours. The upper bright layer of the oil fraction (105) is removed with a pipette, the sulfide sulfur content in it is 0.4%. The mass of the lower layer of the alkylation product is 6.0 g. It contains 2.13 10 mol / g (71%) of a mixture of sulfonium methyl sulfates. EXAMPLE 4 A mixture of 110 g of petroleum fraction and 3.9 g of technical dimethyl sulfate used in Example 3 is heated, stirring, at 85-90 ° C for 5 hours. After cooling the reaction mixture, it is discharged from the flask using the siphon, the bulk of the waste oil, and 2 ml of water is added to the residue. Stir the mixture for 25 minutes and pour into a separatory funnel. Set up the emulsion for 0.5 hour. Separate the lower layer (7.7 g), which is an aqueous solution of sulfonium methyl sulfate. This technical product contains 1.4610 mol / g (50%) of the basic substance and 26% of water. In tab. Tables 1 and 2 show comparative data for the preparation of copper concentrate from tin mono-mouse ores using the known flotation reagent butyl xanthate (BPC) and MFDT. Copper extraction using MFDS can be enhanced by adding a blowing agent. Since, when using CCBs, a special stage of selection is required to obtain a content-suitable concentrate concentrate, the total copper recovery with this collector will still be lower than with the new MFDT. For sample ore 82, the use of MFDS instead of BPC dramatically improves the quality of the concentrate almost without reducing the recovery of copper, even if MFDG is used without foaming agent. The data table. 1 and 2 show that the replacement of xanthate with the MFSDT flotation reagent makes it possible to obtain a copper concentrate, containing 1–7% more copper, and 2.3–7.1 times less mnp. When MSSDT is used, the main flotation is enough to get by the mouse, and for the 82 grade ore, also by the copper of the commercial product. When using xanthate, as already mentioned, an additional step (selection) is needed, where the amount of mice is reduced by special reagents and the concentrate is brought to commercial conditions (18% copper, 5% mouse). Simplification of flotation technology saves reagents. time, labor, reduces copper loss. In addition, processing at concentrate copper smelters. containing by 5%, more copper by 1.5-2.5% and less mSa, which prevents the technology and reduces the risk of environmental pollution. Data on copper concentrate, obtained using BPC and MSSDT from the ore of the sample 80, are given in table. 1 Table 1

Data on copper concentrate obtained using BPC and

30 MSDT from ore of sample 82 are presented in Table 2.

Table 2

Claims (1)

METHOD FOR PRODUCING SULFONIL METHYL SULPHATES, characterized in that the diesel fraction of sulphurous oil with so on. 190-360 ° C is alkylated with dimethyl sulfate at a ratio of 1-1.8 mol per 1 mol of dimethyl sulphate sulphide sulfur ^is, at 85-100 C for 5-12 hours.