Na2S and NaHS Production in the CIS

8/16/2019 Na2S and NaHS Production in the CIS

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Association of independent experts and consultant in field of mineral resources,

metallurgy and chemical industry _________________________________________________

Sodium Sulfide and

Hydrosulfide Production

Market and Forecast

in the CIS

2nd

Edition, Extended and revised

Sample PDF

Moscow

June, 2012

Internet: www.infomine.rue-mail: [email protected]


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

INFOMINE Research Group www.infomine.ru; e-mail: [email protected]; Phone: +7 (495) 988-11-23 3

Contents

Annotation .................................................................................................................... 8

Introduction ................................................................................................................ 9

1. Technology of production of sodium sulfide and sodium hydrosulfide andraw 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 inthe CIS in 2001-2011 ......................................................................................... 19 2.3. Current state of producers of sodium hydrosulfide ..................................... 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 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

hydrosulfide in RF ............................................................................................... 38 3.2. Export-import of sodium sulfide and sodium hydrosulfide in Ukraine in2001-2011 ........................................................................................................... 44 3.3. Export-import of sodium sulfide and sodium hydrosulfide in Kazakhstan in2001-2011 ........................................................................................................... 46 3.4. Import sodium sulfide and sodium hydrosulfide in other countries of theCIS ...................................................................................................................... 47

4. Prices on sodium sulfide and sodium hydrosulfide in the CIS ........................ 48 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


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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 inRussia in 2001-2011 ........................................................................................... 53

5.2. Dynamics of consumption of sodium sulfide and sodium hydrosulfide inthe CIS in 2005-2011 ......................................................................................... 55

5.3. Structure of consumption of sodium sulfide and sodium hydrosulfide inRussia ................................................................................................................. 56 5.4. The main industries-consumers of sodium sulfide and sodium hydrosulfidein 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 5.5.2. JSC "Uchalinsky GOK" ............................................................................ 75 (Republic of Bashkortostan) ................................................................................ 75

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 andsodium hydrosulfide in the CIS ................................................................................. 90


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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 2153-

296-00204168-2001 ............................................................................................ 16 Table 3. Technical characteristics of technical sodium hydrosulfide from flue gases

according to TU 2153-241-05763441-98 ............................................................. 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 596-

89 ......................................................................................................................... 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 2005-

2011, 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 tosolid) .................................................................................................................... 24

Table 10. Suppliers of liquid caustic to JSC "Permneftegazpererabotka" in 2005-2011, 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" in2005-2008, ton .................................................................................................... 31

Table 13. Foreign trade with sodium sulfide and sodium hydrosulfide in RF in2001-2011, ton .................................................................................................... 34

Table 14. Share of exports of sodium sulfide in the total volume of its production inRussia 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, % ................................................................ 36

Table 16. Main countries-consumers of Russian sodium sulfide and sodiumhydrosulfide 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


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Table 24. Main counries-suppliers of sodium sulfide and sodium hydrosulfide toKazakhstan in 2005-2011, ton ............................................................................ 47

Table 25. Annual average export-import prices on sodium sulfide and sodiumhydrosulfide 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 inRussia in 2001-2011; ton, % ............................................................................... 53

Table 28: Consumption of sodium sulfide and sodium hydrosulfide in the CIScountries 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 – consumers of sodium sulfide andsodium 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,million dm2 .......................................................................................................... 67

Table 33: Largest Russian consumers of sodium sulfide in 2005-2011, ton ............. 69 Table 34: Largest Russian consumers of sodium hydrosulfide in 2005-2011, ton* . 70

Table 35. Main production indicators of the activity of JSC "Uchalinsky GOK" in2005-2011 ........................................................................................................... 77

Table 36. Supplies of sodium hydrosulfide to JSC "Soda" and JSC "Berezniki soda plant" in 2003-2011, 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 2001-2011 (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 .............................................................................. 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 (%) in2001-2008 ........................................................................................................... 29

Figure 6. Dynamics of the production of sodium sulfide at JSC "AZKhS" (thousandton) and the share among the CIS countries (%) in 2001-2005 .......................... 33

Figure 7. Volume of production of sodium sulfide in RF and dynamics of export-import deliveries of products in RF in 2001-2011, thousand ton ....................... 34

Figure 8. Dynamics of the export-import deliveries of sodium hydrosulfide in RF in2001-2011, ton .................................................................................................... 35

Figure 9. Dynamics of import deliveries of sodium sulfide and sodium hydrosulfideto 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 ............................................................... 49

Figure 11. Export-import volumes of sodium sulfide (ton) and dynamics of export-

import prices on it ($/ton) in 2001-2011 ............................................................. 50

Figure 12. Volumes of export-import of sodium hydrosulfide (ton) and dynamics ofexport-import prices on it ($/ton) in 2001-2011 ................................................. 51

Figure 13. Dynamics of export-import prices on sodium sulfide and sodiumhydrosulfide in 2005-2011, $/ton ........................................................................ 52

Figure 14. Dynamics of consumption of sodium sulfide and sodium hydrosulfide inRussia in 2001-2011, thousand ton ..................................................................... 54

Figure 15. Structure of consumption of sodium sulfide in RF in 2011, % ................ 56 Figure 16. Changes in the structure of consumption of sodium sulfide in RF in 2005-

2011, %................................................................................................................ 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 in2005-2011, % ...................................................................................................... 58

Figure 19. The production of the molybdenum concentrate at the Sorsky andZhirekensky 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 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


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Annotation

This study focuses on the analysis of the market of sodium sulfide andhydrosulfide 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. Multiplesources of information were analyzed, particularly data of state bodies - FederalService of State Statistics of Russia (Rosstat), JSC "RZD" (statistics of railtransportation), Federal Customs Service (data on foreign trade operations). Alsohave been involved the customs statistics of Ukraine and Kazakhstan, data ofcompanies, a database of "InfoMine", media materials and the Internet.

It should be noted that not all companies provide to the state bodies thestatistics data on the production of this product. Therefore, data on productionvolumes were estimated by experts of "InfoMine" based on the statistics of domestic

rail transport, export statistics and fragmentary data of the enterprises, "leaked" tothe 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, and their characteristics. Also in thissection there are detaila of the technology of production. In addition, data on themain suppliers of raw materials, directions and volumes of supplies are given.

The second chapter is devoted to the production in the CIS countries. Thissection 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, are described.

The third chapter of the report presents data on foreign trade with sodiumsulfide and hydrosulfide in Russia and Ukraine in 2001-2011, as well as inKazakhstan and other CIS countries in 2005-2011.

The fourth chapter presents data on prices of Russian producers on sodiumhydrosulfide in the domestic market. In addition, the analysis of data on export andimport 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 sulfideand sodium hydrosulfide in Russia. This section provides a balance of the production - consumption of the product, the sectoral structure of consumption, themain consumers, as well as the current state and prospects of development of thelargest enterprises-consumers. It also provides a brief overview of the consumers inother CIS countries.

The sixth chapter presents a forecast of the development of the Russianmarket of sodium sulfide and hydrosulfide for the period up to 2020.

The Appendices present addresses and contact information of enterprises

producing and consuming sodium sulfide and hydrosulfide in the CIS countries.


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Introduction

Sodium sulfide is colorless or slightly yellow crystals of the cubic system.The density of anhydrous sulfide is 1.856 g/cm3, the melting temperatureTm=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, itssolubility in water increases with increasing temperature (grams per 100 g): 12.4 (at0°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 iseasily oxidized by an atmospheric oxygen to thiosulfate, and then to sulfite andsulfate 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 isa 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 sodiumhydroxide. Aqueous solutions of sodium sulfide dissolve sulfur to form polysulfides Na2Sx.

Sodium hydrosulfide NaHS is colorless or yellow crystals. The meltingtemperature 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 beoxidized by an atmospheric oxygen. It is more stable in solutions, which are slowlyoxidized in air. Sodium hydrosulfide lliberates H2S (hydrogen sulfide) when heated,at the hydrolysis, under the action of acids; it is a reducing agent. Sodiumhydrosulfide is prepared by reacting H2S with solutions of Na2S and NaOH.

The main physico-chemical properties of sodium sulfide and sodiumhydrosulfide are given in Table 1.

Table 1. Physico-chemical properties of

sodium sulfide and sodium hydrosulfide

Property DesignationSodium

sulfide

Sodium

hydrosulfide

Chemical formula Na2S NaHS

Molecular mass MM 78.01 56.06

Temperature of melting, оС Tm 1180 350

Density, g/cm3 ρ 1.856 1.790Source: "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 threemethods 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 industrialscale the method of the thermal reduction of sodium sulfate by solid carbonaceousmaterials 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 sulfatethe side reactions occur, associated with the oxidation and carbonization of sodiumsulfide. Side processes lead to the increased consumption of raw materials and acontamination of products with ballast salts.

Throughout the lifetime of the production of sodium sulfide in the CIS thehardware design of the high-temperature process of the sodium sulfate reduction bysolid carbonaceous materials (coal, coke) changed. Initially, those were the hearthfurnaces, and then rotating drum furnaces, and finally, shaft furnaces of continuousaction. Hearth furnaces were characterized by low indicators: the removal of themelt - 0.5-0.8 tons/day, the coefficient of the utilization of heat - 15%, of calendartime - 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 calendar-

time - 74-78%, the rate of utilization of heat was almost twice higher. At the sametime it was possible to implemente the process of hot leaching of the melt, providinga more complete extraction of sodium sulfide from the furnace melt.


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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. Theremoval of the melt from 1 m3 of the oven volume was significantly higher than thatof the rotary furnace. The content of Na2S in the melt was 70-74%. The continuousoperation 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 theheat of high-temperature exhaust gases (1200-1250°C). This possibility appearswhen 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-and-metallurgical company. As a raw material mirabilite of the Karachaganak deposit,containing 51.8% of H2O, was used. From this mirabilite sodium sulfate with a lowwater content was obtained by drying. As a reducing agent and the fuel themetallurgical coke was used with sizes of pieces of 30-100 mm. The dosage of cokewas ~ 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 cokewere consumed. According to the factory data, the average content of Na2S in themelt 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 high-quality lump sodium sulfate was supplied. In the last years of the operation of theshaft furnace at the Balkhash mining-and-metallurgical company it worked inextremely unfavorable conditions in connection with the exhaustion of reserves oflump 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 thecharge significantly increased, sometimes accounting for 40% or more. All this ledto a sharp drop in the furnace productivity and the reduction of the quality of themelt. As a result, the production was halted.

Figure 1 shows a schematic flow diagram of the production of sodiumsulfide.

The production process includes the following stages:- Briquetting of sodium sulfate

- Preparation of the charge

- Smelting reduction of sodium sulfate- Cleaning of furnace 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

Crushing

Wetting

Water

DustDedusting

To atmosphere

Briquetting

Preparation of the chargeCoke

Screening

Sieving

Reduction

Charge

Leaching

Melt

Separation Coke

Flue gases

1st filtration

Repulping

Slurry

2nd filtration

Repulping

Slud e

To the slurry tank

Filtrate Filtrate Evaporation

Flaking Granulation

Prepared product

Na 2S


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In many industries wastes, containing sodium sulfate, are produced in largequantities. By-product sodium sulfate appears in the production of sodiumdichromate. Typically, this is a low-grade sodium sulphate, and consequently it has alimited distribution. Therefore, sodium sulfate obtained in the production of sodiumdichromate is traditionally converted to sodium sulfide due to the inability of its

other uses because it contains highly toxic hexavalent chromium. The process of thereduction of sodium sulfate by solid carbonaceous materials has been implementedat 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 theincreasing demands of environmental protection and is uncompetitive with theforeign processes, both in technical and economic indicators, and by the quality ofthe product. This led to the cessation of the production of sodium sulfide. Forexample, in 1994 due to lack of demand and the unfavorable ecological situation ashop for the production of sodium sulfide with the capacity of 42 thousand tons atJSC "Russian chromium 1915" has been closed.

The production at "Novotroitsk plant of chromium compounds" was alsostopped, where an industrial unit for obtaining fused sodium sulfide from wastesworked from 1964 to 2001. In 2005 the production was also stopped at "Aktobe plant of chromium compounds".

In the early 2000s, the possibility of recycling of industrial sulfate-containingfluids by the conversion method without forming a solid sodium sulfate wasconsidered. 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 bariumcarbonate (JSC "Soda"), but it was an intermediate product, since for its ownconsumption "Soda" required sodium hydrosulfide. In this process, BaSO4 is firedwith 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% ofBaS). 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 stopand obtain sodium sulfide by evaporation of the solution. At JSC "Soda" from theintermediate 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 ofhydrogen 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 betweenhydrogen and sulfur, then the method provides a high quality product, suitable foruse in the production of dyes, synthetic fibers, leather processing. In Russia, by thisway 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 issuesis associated with the need to neutralize or dispose wastes contaminated with sulfurcompounds of alkaline solutions. They are formed during the purification of pyrolysis gases from hydrogen sulfide and carbon dioxide in the production of lowerolefins, at the alkaline treatment of liquefied gas, gasoline and kerosene fractions inthe refining processes. In the units of primary oil refining, catalytic cracking,delayed coking, etc., where in the process steam is used, water condensates arecontaminated with hydrogen sulfide.

For the purification of exhaust gases caustic solutions of 5-20% concentrationare used. Then sulfurous effluents are evaporated to a concentration of 65-70%.Together with steam about 70% of organic impurities are carried away, and thefused 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 withthe 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 valuablesubstance of 70-72%.

Small amounts of technical sodium hydrosulfide are obtained from the fluegases 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 peryear.

Na2S and NaHS Production in the CIS

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