Na2S and NaHS Production in the CIS

As so ci ati on of in dep end ent exp ert s an d c on su lt ant in fi eld of mi ner al r eso ur ces , metallurgy and chemical industry

_________________________ ____________ __________________________ ________________________ ___________

Sodium Sulfide and Hydrosulfide Production Market and Forecast in the CIS nd

2 Edition, Extended and revised

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Moscow June, 2012 Internet: www.infomine www.infomine.ru .ru e-mail: info@infomine [email protected] .ru

Sodium Sulfide and Hydrosulfide Production, Market and Forecast in the CIS

Contents Annotation .................................................................................................................... 8 Introduction ................................................................................................................ 9 1. Technology of production of sodium sulfide and sodium hydrosulfide and raw materials used ................................................................................................... 10 1.1. Methods of production of sodium sulfide ................................................... 10 1.2. Methods of production of sodium hydrosulfide .............................. .............. ............................ ............ 14 1.3. Raw material for the production of sodium sulfide and sodium hydrosulfide ............................................................................................................................ 15 2. Production of sodium sulfide and sodium hydrosulfide in the CIS countries 16 2.1. Quality of products ...................................................................................... 16 2.2. The volume of production of sodium sulfide and sodium hydrosulfide in the CIS in 2001-2011 ......................................................................................... 19 2.3. Current state st ate of producers of sodium hydrosulfide hydrosulf ide............................. .............. ....................... ........ 22 2.3.1. JSC "Volzhsky Orgsintez" (Volzhsky, Volgograd region, RF) ................. 22 2.3.2. LLC "Lukoil-Permneftegazpererabotka" (Perm, RF).................... ............................... ........... 26 2.4. Companies that have discontinued the production of sodium sulfide ........ 29 2.4.1. JSC "Kuchuksulfat" (the settlement Stepnoe Ozero, Altai Territory, RF) 29 2.4.2. JSC " Aktobe plant of chromium compounds" (Aktobe, Kazakhstan) ...... ...... 33 3. Export-import of sodium sulfide and sodium hydrosulfide in the CIS .......... 34 3.1. Export-import of sodium sulfide sulf ide and sodium hydrosulfide in RF .............. ............ .. 34 3.1.1. Volumes of export-import of sodium sulfide and sodium hydrosulfide in RF in 2001-2011 ................................................................................................. 34 3.1.2. Tendencies and features of export deliveries of sodium sulfide and sodium hydrosulfide in RF ............................................................................................... ............................................................................................... 36 3.1.3. Main destination of export-import deliveries of sodium sulfide and sodium ............................................................................................... 38 hydrosulfide in RF ............................................................................................... 3.2. Export-import of sodium sulfide and sodium hydrosulfide in Ukraine in 2001-2011 ........................................................................................................... 44 3.3. Export-import of sodium sulfide and sodium hydrosulfide in Kazakhstan in 2001-2011 ........................................................................................................... 46 3.4. Import sodium sulfide and sodium hydrosulfide in other countries of the CIS ...................................................................................................................... 47

.............. .......... 48 4. Prices on sodium sulfide and sodium hydrosulfide in the CIS ........................ 4.1. Prices on sodium sulfide and sodium hydrosulfide in RF .......................... 48 4.1.1. Domestic prices on sodium hydrosulfide in RF .............................. .............. .......................... .......... 48 4.1.2. Dynamics of export-import prices on sodium sulfide and sodium hydrosulfide in RF in 2001-2011 ........................................................................ 49 4.2. Prices on sodium sulfide and sodium hydrosulfide in the CIS ................... 52 INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23

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5. Consumption of sodium sulfide and sodium hydrosulfide in the CIS ............ 53 5.1. Balance of consumption of sodium sulfide and sodium hydrosulfide in Russia in 2001-2011 ........................................................................................... 53 5.2. Dynamics of consumption of sodium sulfide and sodium hydrosulfide in the CIS in 2005-2011 ......................................................................................... 55 5.3. Structure of consumption of sodium sulfide and sodium hydrosulfide in Russia ................................................................................................................. 56 5.4. The main industries-consumers of sodium sulfide and sodium hydrosulfide in Russia ............................................................................................................. 59 5.4.1. Non-ferrous metallurgy ............................................................................. 60 5.4.2. Chemical industry ..................................................................................... 64 5.4.3. Light industry ............................................................................................ 67 5.5. Main Russian company-consumers, their projects ..................................... 68 5.5.1. CJSC "UK "Soyuzmetallresurs" .............................. .............. ................................ ................................ .................. .. 71 ............................................................................ 75 5.5.2. JSC "Uchalinsky GOK" ............................................................................ .............. ................................ ................................ ................................ .................. .. 75 (Republic of Bashkortostan) .............................. 5.5.3. JSC “Soda” (Sterlitamak, Republic of Bashkortostan) JSC "Berezniki soda plant" (Berezniki, Perm Territory) ............................................................. 78 5.6. Consumers in the CIS .................................................................................. 82 6. Forecast of development of the Russian market of sodium sulfide und sodium hydrosulfide until 2020 ............................................................................................ 87

Appendix 1: Address directory of the enterprises-producesrs of sodium hydrosulfide in Russia ..................................................................................................................... 89 Appendix 2: Address directory of enterprises-consumers of sodium sulfide and sodium hydrosulfide in the CIS ................................................................................. 90

INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23

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List of Tables Table 1. Physico-chemical properties of sodium sulfide and sodium hydrosulfide ... 9 Table 2. Technical characteristics of sodium hydrosulfide according to TU 2153296-00204168-2001 ............................................................................................ 16 Table 3. Technical characteristics characteris tics of technical sodium hydrosulfide from flue flue gase gasess according to TU 215 2153-2 3-24141-057 057634 6344141-98 98 .............................. .............. ................................ ............................... ............... 16 Table 4. Technical characteristics of solid sodium hydrosulfide .............................. 17 Table 5. Grades and applications of sodium sulfide .................................................. 17 Table 6. Technical characteristics of sodium sulfide in accordance with GOST 59689 ......................................................................................................................... 18 Table 7. Production of sodium sulfide and sodium hydrosulfide in the CIS by enterprises in 2001-2011, thousand ton .............................................................. 19 Table 8. Suppliers of liquid caustic soda to JSC "Volzhsky Orgsintez" in 20052011, ton .............................................................................................................. 23 Table 9. Supplies of sodium hydrosulfide produced by JSC "Volzhsky Orgsintez" to the domestic and foreign markets in 2002-2011, thousand ton, (recalculated to solid) .................................................................................................................... 24 Table 10. Suppliers of liquid caustic to JSC "Permneftegazpererabotka" in 20052011, ton .............................................................................................................. 27 Table 11. Supplies of sodium hydrosulfide of the production of LLC "Permneftegazpererabotka" to the domestic and foreign markets in 2005-2011, thousand ton ........................................................................................................ 28 Table 12. Consumers of sodium sulfide of the production of JSC Kuchuksulfat" in 2005-2008, ton .................................................................................................... 31 Table 13. Foreign trade with sodium sulfide and sodium hydrosulfide in RF in 2001-2011, ton .................................................................................................... 34 Table 14. Share of exports of sodium sulfide in the total volume of its production in Russia in 2001-2008, % ...................................................................................... 36 Table 15. The share of exports of sodium hydrosulfide in the total volume of its production in Russia in 2001-2011, 2001-20 11, % ............................. .............. ............................... ............................... ................... .... 36 Table 16. Main countries-consumers of Russian sodium sulfide and sodium hydrosulfide in 2001-2011, ton ........................................................................... 38 Table 17. Countries-suppliers of sodium sulfide and sodium hydrosulfide to Russia in 2001-2011, ton ................................................................................................ 39 Table 18. Main suppliers of sodium sulfide and sodium hydrosulfide to Russia in 2005-2011, ton .................................................................................................... 40 Table 19. Main Russian buyers of imported sodium sulfide and sodium hydrosulfide in 2005-2011, ton ................................................................................................ 42 Table 20. Foreign trade in sodium sulfide and sodium hydrosulfide in Ukraine in 2001-2011, ton .................................................................................................... 44 Table 21. Countries-suppliers of sodium sulfide and sodium hydrosulfide to Ukraine in 2001-2011, ton ................................................................................................ 45 Table 22. Countries-consumers of Kazakhstan sodium sulfide in 2000-2005, ton ... 46 Table 23. Main countries-suppliers of sodium sulfide and sodium hydrosulfide to Kazakhstan in 2001-2011, ton ............................................................................ 46 INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23

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Table 24. Main counries-suppliers of sodium sulfide and sodium hydrosulfide to Kazakhstan in 2005-2011, ton ............................................................................ 47 Table 25. Annual average export-import prices on sodium sulfide and sodium hydrosulfide in Russia in 2001-2011, $/ton ........................................................ 50 Table 26. Main countries-suppliers of sodium sulfide and sodium hydrosulfide in Russia in 2005-2011 and prices for imported products, $/ton ............................ ............... ............. 51 Table 27: Indicators of consumption of sodium sulfide and sodium hydrosulfide in Russia in 2001-2011; ton, % ............................................................................... 53 Table 28: Consumption of sodium sulfide and sodium hydrosulfide in the CIS countries in 2005-2011; ton ................................................................................ 55 Table 29. Consumption of sodium sulfide and sodium hydrosulfide in RF in 2011, ton, % .................................................................................................................. 59 Table 30: Enterprises of non-ferrous metallurgy metallurgy – consumers of sodium sulfide and sodium hydrosulfide in 2008-2011, ton .............................................................. 60 Table 31: Chemical enterprises-consumers of sodium hydrosulfide in 2005-2011, ton ........................................................................................................................ 64 Table 32. Dynamics of the production of leather products in Russia in 2001-2011, 2 million dm .......................................................................................................... 67 Table 33: Largest Russian consumers of sodium sulfide in 2005-2011, ton............. ........... .. 69 Table 34: Largest Russian consumers of sodium hydrosulfide hydrosulf ide in 2005-2011, ton* . 70 Table 35. Main production indicators of the activity of JSC "Uchalinsky GOK" in 2005-2011 ........................................................................................................... 77 Table 36. Supplies of sodium hydrosulfide to JSC "Soda" and JSC "Berezniki soda plant" in 2003-2011, ton.................... ton..... ............................... ............................... ............................... ............................... ................... .... 79


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List of Figures Figure 1. Principal schematic flow diagram of the production of sodium sulfide .... 12 Figure 2. Dynamics of the production of sodium sulfide and sodium hydrosulfide in the CIS in 2001-2011, thousand ton ................................................................... 20 Figure 3. Dynamics of the production of sodium hydrosulfide at JSC "Volzhsky Orgsintez" (thousand ton) and its share in the domestic production (%) in 20012011 (recalculated to solid) ................................................................................. 23 Figure 4. Dynamics of the production of sodium hydrosulfide at LLC "Permneftegazpererabotka" (thousand ton) and its share in the domestic production (%) in 2005-2011 2005-201 1 ............................... ............... ................................ ................................ ............................... ............... 27 Figure 5. Dynamics of the production of sodium sulfide at JSC "Kuchuksulfat" (thousand ton) and its share among the enterprises of the CIS countries (%) in 2001-2008 ........................................................................................................... 29 Figure 6. Dynamics of the production of sodium sulfide at JSC "AZKhS" (thousand ton) and the share among the CIS countries (%) (% ) in 2001-2005 .......................... .............. ............ 33 Figure 7. Volume of production of sodium sulfide in RF and dynamics of exportimport deliveries of products in RF in 2001-2011, thousand ton ....................... 34 Figure 8. Dynamics of the export-import deliveries of sodium hydrosulfide in RF in 2001-2011, ton .................................................................................................... 35 Figure 9. Dynamics of import deliveries of sodium sulfide and sodium hydrosulfide to Ukraine in 2001-2011, ton .............................................................................. 44 Figure 10. Quarterly dynamics of prices on sodium sulfide and sodium hydrosulfide, supplied to Russia in 2006-2011, $/ton $/t on............................... ................ ............................... ............................... ................. 49 Figure 11. Export-import volumes of sodium sulfide (ton) and dynamics of exportimport prices on it ($/ton) in 2001-2011 ............................................................. 50 Figure 12. Volumes of export-import of sodium hydrosulfide (ton) and dynamics of export-import prices on it ($/ton) in 2001-2011 ................................................. 51 Figure 13. Dynamics of export-import prices on sodium sulfide and sodium hydrosulfide in 2005-2011, $/ton ........................................................................ 52 Figure 14. Dynamics of consumption of sodium sulfide and sodium hydrosulfide in Russia in 2001-2011, thousand ton ..................................................................... 54 Figure 15. Structure Struct ure of consumption consumpti on of sodium sulfide in RF in 2011, % ................ ........... ..... 56 Figure 16. Changes in the structure of consumption of sodium sulfide in RF in 20052011, %................................................................................................................ 56 Figure 17. Structure of the consumption of sodium hydrosulfide in RF in 2011, % 57 Figure 18. Changes in the structure of consumption of sodium hydrosulfide in RF in 2005-2011, % ...................................................................................................... 58 Figure 19. The production of the molybdenum molybdenum concentrate at the Sorsky and Zhirekensky enterprises and supplies of sodium sulfide in 2001-2011, kt......... 73 Figure 20: Dynamics of the production of soda ash at JSC "Soda" and JSC "Berezniki soda plant" in 2001-2011, thousand ton ........................................... 78 Figure 21. Dynamics of the production of the molybdenum and the zinc concentrates in Armenia and supplies of sulfides sul fides in 2004-2011, thousand ton ....................... .............. ......... 82 Figure 22: Forecast of the production and consumption of sodium sulfide and sodium hydrosulfide in RF until 2020, thousand ton ............................ ............. ............................. .............. 88 INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23

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Annotation This study focuses on the analysis of the market of sodium sulfide and hydrosulfide in the CIS. The report consists of 6 Sections, contains 91 pages, including 22 figure, 36 tables, and two Appendices. Methodologically, the work done in the form of a "desk" research. Multiple sources of information were analyzed, particularly data of state bodies - Federal Service of State Statistics of Russia (Rosstat), JSC "RZD" (statistics of rail transportation), Federal Customs Service (data on foreign trade operations). Also have been involved the customs statistics of Ukraine and Kazakhstan, data of companies, a database of "InfoMine", media materials and the Internet. It should be noted that not all companies provide to the state bodies the statistics data on the production of this product. Therefore, data on production volumes were estimated by experts of "InfoMine" based on the statistics of domestic rail transport, export statistics and fragmentary data of the enterprises, "leaked" to the media. All this has allowed the experts of "InfoMine" to reveal a picture of the market of sodium sulfide and hydrosulfide in the CIS and its prospects. The first chapter of the report presents data on resources required for the production of sodium sulfide and hydrosulfide, hydrosulf ide, and their characteristics. Also in i n this section there are detaila of the technology of production. In addition, data on the main suppliers of raw materials, directions and volumes of supplies are given. The second chapter is devoted to the production in the CIS countries. This section of the report presents data on volumes of production in Russia and Kazakhstan. In addition, the quality data of the products are presented. The current producers of sodium hydrosulfide, and the companies that recently ceased the production of sodium sulfide, sulfide , are described. The third chapter of the report presents data on foreign trade with sodium sulfide and hydrosulfide in Russia and Ukraine in 2001-2011, as well as in Kazakhstan and other CIS countries in 2005-2011. The fourth chapter presents data on prices of Russian producers on sodium hydrosulfide in the domestic market. In addition, the analysis of data on export and import prices for sodium sulfide and hydrosulfide in Russia, and import prices in other CIS countries are given. The fifth chapter of the report describes the consumption of sodium sulfide and sodium hydrosulfide in Russia. This section provides a balance of the production - consumption of the product, the sectoral structure of consumption, the main consumers, as well as the current state and prospects of development of the largest enterprises-consumers. It also provides a brief overview of the consumers in other CIS countries. The sixth chapter presents a forecast of the development of the Russian market of sodium sulfide and hydrosulfide for the period up to 2020. The Appendices present addresses and contact information of enterprises producing and consuming sodium sodi um sulfide and hydrosulfide in the CIS countries.


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Introduction Sodium sulfide is colorless or slightly yellow crystals of the cubic system. 3 The density of anhydrous sulfide is 1.856 g/cm , the melting temperature Tm=1180°C (1453 K), and by the chemical composition it is a salt of the general formula Na2S·nH2O (n=1.9-2.4). Sodium sulfide is strongly hygroscopic, its solubility in water increases with increasing temperature (grams per 100 g): 12.4 (at 0°C), 18.6 (at 20°C), 39.1 (at 60°C); 45.0 (at 97.5°C), it forms crystallohydrates. Sodium sulfide in contact with acids liberates hydrogen sulfide, sodium sulfide is easily oxidized by an atmospheric oxygen to thiosulfate, and then to sulfite and sulfate of sodium, and also forms polythionic acids. It is soluble in lower alcohols (methanol, ethanol), which is used in practice to obtain pure sodium sulfide. Na2S is a strong reducing agent: dilute HNO3 (nitric acid) oxidizes sodium sulfide to S (sulfur), concentrated HNO3 - to Na2SO4 (sodium sulfate). Sodium sulfide reacts with hydrohalic acids and dilute H2SO4 with the release of H2S and sodium hydroxide. Aqueous solutions of sodium sulfide dissolve sulfur to form polysulfides Na2Sx. Sodium hydrosulfide NaHS is colorless or yellow crystals. The melting temperature is 350°C. It is easily soluble in water (43 wt% at 20°C) and in alcohol. Its solutions have an alkaline reaction. Two of its crystallohydrates are known: NaHS·2H2O, NaHS·3H2O. Solid sodium hydrosulfide is hygroscopic and can be oxidized by an atmospheric oxygen. It is more stable in solutions, which are slowly oxidized in air. Sodium hydrosulfide lliberates H2S (hydrogen sulfide) when heated, at the hydrolysis, under the action of acids; it is a reducing agent. Sodium hydrosulfide is prepared by reacting H2S with solutions of Na2S and NaOH. The main physico-chemical properties of sodium sulfide and sodium hydrosulfide are given in Table 1. Table 1. Physico-chemical properties of sodium sulfide and sodium hydrosulfide Sodium Designation Property sulfide Chemical formula Na2S Molecular mass MM 78.01 о Temperature of melting, С Tm 1180 3 Density, g/cm ρ 1.856

Sodium hydrosulfide NaHS 56.06 350 1.790

Source: "Handbook of Inorganic Chemistry", ed. R.A. Lidin


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1. Technology of production of sodium sulfide and sodium hydrosulfide and raw materials used 1.1. Methods of production of sodium sulfide

Sodium sulfide is produced by the following methods: 1. the reduction of sodium sulfate by solid carbonaceous materials; 2. the reduction of sodium sulfate by gaseous reducing agents; 3. the absorption of hydrogen sulfide by sodium hydroxide; 4. the exchange decomposition of barium sulfide with sodium sulfate, carbonate, and hydroxide; 5. the electrolytic (amalgam) method. Due to the fact that in the CIS for the production of sodium sulfide three methods were used (1, 3 and 4), this review will consider only these methods. Other ways of producing commercial sodium sulfide in Russia have not been applied. They are found at enterprises of USA, Canada, Poland, Germany, Italy, France, Spain, etc. Reduction of sodium sulfate by solid carbonaceous materials Traditionally in the CIS for the sodium sulfide production on an industrial scale the method of the thermal reduction of sodium sulfate by solid carbonaceous materials was used. The chemistry of the process is expressed by the following basic equations:

Na2SO4 + 2C → Na2S + 2CO2↑, Na2SO4 + 4CO → Na2S + 4CO2↑, CO2 + C → 2CO↑ Along with the main reactions in the process of reduction of sodium sulfate the side reactions occur, associated with the oxidation and carbonization of sodium sulfide. Side processes lead to the increased consumption of raw materials and a contamination of products with ballast salts. Throughout the lifetime of the production of sodium sulfide in the CIS the hardware design of the high-temperature process of the sodium sulfate reduction by solid carbonaceous materials (coal, coke) changed. Initially, those were the hearth furnaces, and then rotating drum furnaces, and finally, shaft furnaces of continuous action. Hearth furnaces were characterized by low indicators: the removal of the melt - 0.5-0.8 tons/day, the coefficient of the utilization of heat - 15%, of calendar time - 60-65%, the degree of conversion of sodium sulfate - 70-77%. Somewhat higher was the performance of the rotating drum furnaces of periodic action. The capacity of furnaces reached 11 tons/day, the use the calendartime - 74-78%, the rate of utilization of heat was almost twice higher. At the same time it was possible to implemente the process of hot leaching of the melt, providing a more complete extraction of sodium sulfide from the furnace melt. INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23

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In the factories of organic synthesis the experimental-industrial cyclone furnace was tested (D = 2,600 mm, L = 2,300 mm) using natural gas as fuel. The 3 removal of the melt from 1 m of the oven volume was significantly higher than that of the rotary furnace. The content of Na2S in the melt was 70-74%. The continuous operation of the furnace provided an easy hot leaching of the melt. However, the effective use of the cyclone furnace is possible at the condition of utilization of the heat of high-temperature exhaust gases (1200-1250°C). This possibility appears when as the feedstock sulfate-containing industrial effluents are used. For obtaining of the melt of sodium sulfide in the last few years of its production in the CIS shaft furnaces were used. The shaft furnace was first tested in Kazakhstan at the Balkhash mining-andmetallurgical company. As a raw material mirabilite of the Karachaganak deposit, containing 51.8% of H2O, was used. From this mirabilite sodium sulfate with a low water content was obtained by drying. As a reducing agent and the fuel the metallurgical coke was used with sizes of pieces of 30-100 mm. The dosage of coke was ~ 35-40% from the weight of natural sodium sulfate. For 1 ton of 63% Na2S 2 tons of natural sodium sulfate and 0.7 tons of coke were consumed. According to the factory data, the average content of Na2S in the melt was 66.1%, and the productivity of the furnace - 24.1 tons/day. In the initial period of operation of the shaft furnaces a relatively highquality lump sodium sulfate was supplied. In the last years of the operation of the shaft furnace at the Balkhash mining-and-metallurgical company it worked in extremely unfavorable conditions in connection with the exhaustion of reserves of lump sodium sulfate. The content of insoluble residue in sodium sulfate amounted to 4-10%, and of moisture - to 30%. The content of fine materials and dust in the charge significantly increased, sometimes accounting for 40% or more. All this led to a sharp drop in the furnace productivity and the reduction of the quality of the melt. As a result, the production was halted. Figure 1 shows a schematic flow diagram of the production of sodium sulfide. The production process includes the following stages: - Briquetting of sodium sulfate - Preparation of the charge - Smelting reduction of sodium sulfate - Cleaning of furnace f urnace gases - Leaching of the furnace melt - Filtering of the pulp slurry - Evaporation of productional solutions - Granulation (flaking) of the product


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Figure 1. Principal schematic flow diagram of the production of sodium sulfide Sodium sulfate

To atmosphere

Crushing

Water

Dust

Wetting

Dedusting

Briquetting Sieving Preparation of the charge

Coke

Screening Charge Flue gases

Reduction Melt Leaching

Separation

1st filtration

Filtrate

Coke

Filtrate

Evaporation

Slurry Repulping

Flaking

Granulation

2nd filtration Slud e Repulping

Prepared product Na 2S

To the slurry tank


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In many industries wastes, containing sodium sulfate, are produced in large quantities. By-product sodium sulfate appears in the production of sodium dichromate. Typically, this is a low-grade sodium sulphate, and consequently it has a limited distribution. Therefore, sodium sulfate obtained in the production of sodium dichromate is traditionally converted to sodium sulfide due to the inability of its other uses because it contains highly toxic hexavalent chromium. The process of the reduction of sodium sulfate by solid carbonaceous materials has been implemented at many Soviet enterprises. This method, implemented on an industrial scale in the mid-60s and being progressive at that time, is now obsolete. It does not provide a compliance with the increasing demands of environmental protection and is uncompetitive with the foreign processes, both in technical and economic indicators, and by the quality of the product. This led to the cessation of the production of sodium sulfide. For example, in 1994 due to lack of demand and the unfavorable ecological situation a shop for the production of sodium sulfide with the capacity of 42 thousand tons at JSC "Russian chromium 1915" has been closed. The production at "Novotroitsk plant of chromium compounds" was also stopped, where an industrial unit for obtaining fused sodium sulfide from wastes worked from 1964 to 2001. In 2005 the production was also stopped at "Aktobe plant of chromium compounds". compoun ds". In the early 2000s, the possibility of recycling of industrial sulfate-containing fluids by the conversion method without forming a solid sodium sulfate was considered. The technology was developed, pilot-scale tests have been performed, but at conditions of the fierce competition with the foreign product, the process on an industrial scale has not been implemented. Exchange decomposition of barium sulfide

Sodium sulfide is also obtained as a byproduct in the production of barium carbonate (JSC "Soda"), but it was an intermediate product, since for its own consumption "Soda" required sodium hydrosulfide. In this process, BaSO4 is fired with coal at a temperature of 750-1000°C in a rotary furnace: BaSO4 + 4C = BaS + 4CO. The melt is leached with water to form a slurry of barium sulfide (15-18% of BaS). The clarified solution is treated with a 30% solution of soda ash: BaS + Na2CO3 = BaCO3 + Na2S. A solution of sodium sulfide is filtered off. At this stage it is possible to stop and obtain sodium sulfide by evaporation of the solution. At JSC "Soda" from the intermediate product sodium hydrosulfide NaHS was obtained.


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1.2. Methods of production of sodium hydrosulfide. Absorption of hydrogen sulfide with sodium hydroxide

The main method for obtaining sodium hydrosulfide is the absorption of hydrogen sulfide with sodium hydroxide: NaOH + H2S = NaHS + H2O In Russia, this method is used quite extensively. At this, if as a raw material pure hydrogen sulfide is used, which is obtained by the interaction between hydrogen and sulfur, then the method provides a high quality product, suitable for use in the production of dyes, synthetic fibers, leather processing. In Russia, by this way sodium hydrosulfide is obtained at JSC "Volzhsky Orgsintez". Sodium hydrosulfide of lower quality is obtained by using hydrogen sulfide a byproduct in the process of oil and gas processing, organic synthesis and others. At refineries and petrochemical plants one of the major environmental issues is associated with the need to neutralize or dispose wastes contaminated with sulfur compounds of alkaline solutions. They are formed during the purification of pyrolysis gases from hydrogen sulfide and carbon dioxide in the production of lower olefins, at the alkaline treatment of liquefied gas, gasoline and kerosene fractions in the refining processes. In the units of primary oil refining, catalytic cracking, delayed coking, etc., where in the process steam is used, water condensates are contaminated with hydrogen sulfide. For the purification of exhaust gases caustic solutions of 5-20% concentration are used. Then sulfurous effluents are evaporated to a concentration of 65-70%. Together with steam about 70% of organic impurities are carried away, and the fused product, which is a mixture of sodium sulfide and sodium hydrosulfide, contains up to 0.5% of phenols and up to 0.2% of mercaptans. The presence of phenols and mercaptans prevents the utilization of alkaline wastes of refineries with the production of sodium hydrosulfide. In 2005 an installation was commissioned for the disposal of acid gases at LLC "Lukoil-Permneftegazpererabotka". This unit is used to obtain the 30-35% solution of sodium hydrosulfide and the solid product with the content the valuable substance of 70-72%. Small amounts of technical sodium hydrosulfide are obtained from the flue gases of organic synthesis at JSC "Khimprom", Novocheboksarsk. By passing gases containing hydrogen sulfide through sodium sulfide the Kemerovo JSC "Azot" obtained up to 1.5 thousand tons of sodium hydrosulfide per year.


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Na2S and NaHS Production in the CIS

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