The method of obtaining elemental sulfur

 

(57) Abstract:

The method of obtaining elemental sulfur by restoring phosphogypsum (gypsum, calcium sulphate) gaseous mixture at an elevated temperature. The new method is the use of gaseous mixtures containing natural gas-methane and water vapour in the following ratio of components, about. % : methane 0,5 - 2,1, water vapor and 97.8 - 99,5, and the restoration is carried out at 950 - S within 30 - 60 minutes the Degree of extraction of sulfur is 57.3 - sampled at 74.25% . table 1.

The invention relates to methods for sulfur.

The known method [1] sulfur from gypsum by restoring its solid or gaseous reducing agent at 800-1000aboutFor 20-120 min with intermediate receiving calcium sulfide and carbon dioxide. The resulting sulfide is treated with water and hydrogen sulphide, and the product of this processing is mixed with soda ash, resulting in a gain precipitate of calcium carbonate and a solution of sodium hydrosulfide NaHS. This solution is then blown with carbon dioxide from the stage of recovery of gypsum, while receiving the precipitate of sodium bicarbonate NaHCO3and hydrogen sulfide (H2S, which is then transferred to sulfur using the Claus process ilocandia after recovery of sulfate calcium sulfide is treated with hydrogen chloride HCl at 650-690aboutWith, and released when the hydrogen sulfide is then converted to sulfur.

The disadvantages of the above methods are the multi-stage: a) restoring the source of calcium sulfate to sulfide; b) obtaining sulphide of calcium sulfide; b) the processing of hydrogen sulfide (H2'sv sulfur; and bulkiness and complexity of the process (crushing, dissolving, filtering, large energy consumption, the presence in the exhaust gases of significant quantities of harmful HCl, SO2and H2S, which requires additional cleaning, use of hazardous to human health and causes corrosion of the equipment of the hydrogen chloride with the formation of ballast - chloride of calcium, which significantly increases the cost of production of sulfur.

The aim of the invention is to simplify the technology by conducting the process in a single stage direct receipt of sulfur, and deeper disposal of phosphogypsum, reduced consumption of reagents.

This goal is achieved by the fact that in the proposed method of obtaining sulfur by restoring phosphogypsum (gypsum, calcium sulphate) gaseous mixture at elevated temperature, according to the invention, use of a gaseous mixture containing natural gas-methane and water PA at 950-1050aboutC for 30-60 min

Comparative analysis of the proposed solutions with the prototype shows that the inventive method differs from the known fact that the composition of the gas recovery mixture includes water vapor.

Using the proposed method allows to obtain sulfur in one stage, without intermediate obtain hydrogen sulfide, and the solid residue is simultaneously formed lime (calcium oxide), which can be immediately used in the building materials industry.

The process of recovery of phosphogypsum (gypsum, calcium sulphate) indicated a mixture of features to make an educated result of the recovery process, the sulphide of calcium is immediately converted to steam. The temperature interval is chosen so as to achieve the desired degree of conversion of sulfate sulfur. The increase in temperature is undesirable due to excessive conversion of reducing methane steam and pyrolysis of CH4and the decrease in temperature will lead to incomplete recovery of calcium sulfate CaSO4. For these same reasons, it is recommended to use the mentioned interval, the duration of the process. Excess water p is p, as follows.

For sulfur used phosphogypsum of Rozdolskaja FOR "Sulfur" (Lviv region) having the following composition, wt. % (calculated on dry substance): R2ABOUT51,0-1,25; F 0,25-0,35; SiO22,5-3,5; Al2O3the 0.05-0.1; Fe2O30,05-0,1; Na2O 0,15-0,2; organic matter < 0,01, CaSO494-96; p. p. p. 14,13.

As the reductant phosphogypsum used natural gas containing about 97. % CH4.

The experiment was as follows.

A portion of phosphogypsum ( 2 g) was loaded into the boat and put her in a quartz reactor placed in an electric furnace COOL-0,25.1/12-M1. Included heat at a given temperature started feeding natural gas and water vapor. The consumption of natural gas for the recovery of phosphogypsum was calculated, assuming that the process described by the reaction equation:

CaSO4+ CH4= CaS + CO2+ 2H2O (1)

The flow of water vapor is 1.3-1.4 l/min At the end of the experience cut off supplies of gas mixture and cooled reactor. Then the solid residue after recovery of phosphogypsum were analyzed for the presence of sulfate sulfur in the chemical way (according to GOST 125-79). Exhaust gases caught in the process and analyzed iodometrically on the soda is sulfide, sulfite and sulfate sulfur after recovery of phosphogypsum.

In this series of experiments was implemented a full factorial experiment with plan type 23. Varied temperature and duration of the recovery phosphogypsum and reductant consumption of natural gas is methane, respectively, in the range 950-1050aboutC, 30-60 min and 175-290% of the consumption of CH4from the stoichiometric required standards for the equation (1). The flow rate of water vapor was not changed. The results of the experiments presented in the table.

The solid residue after recovery of phosphogypsum in addition to the chemical were subjected to x-ray phase analysis in the rays of copper Cukon the diffractometer DRON-3,0. The analysis showed that the residue contained along with the calcium sulfide (CaS line d/n - 2,85, 2,01, 1.64 and others ) also calcium hydroxide CA(Oh)2(line d/n - 2,62, 4,90, and others ) and calcium oxide Cao (line d/n - 2,40 and others ).

Was extracted and analyzed condensed after the restoration of phosphogypsum elemental sulfur. X-ray phase analysis showed that it is orthorhombic its modification (line d/n - 3,85, 3,21, 3,43, and others ). Transcript of diffraction patterns was carried out with the help of the American x-ray file cabinets ASTM.

2. USSR author's certificate 983035, CL 01 In 17/02, 1982.

The METHOD of OBTAINING SULFUR from phosphogypsum, including the restoration of its natural gas at elevated temperature, characterized in that, to simplify the process and simultaneous receipt of lime, natural gas is used in a mixture with steam at a volume ratio of 0.5 to 2.1 : of 97.8 - 99,5 respectively, and the process is conducted at 950 - 1050oC for 30 - 60 minutes

 

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