Chemical Fact Sheet

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Other names
Soda ash Carbonate acid, disodium salt Dry alkali

Molecular formula
Na -CO 2 3

Physical properties
Specific Gravity: 2.53 Solubility in water (22C): 22g/100ml Melting Point: 851.0C Boiling Point: Decomposes before melting pH (1% aq. soln.): 11.5 Sodium carbonate is an odourless, opaque white, crystalline or granular solid. It is soluble in water and insoluble in alcohol, acetone, and ether. Sodium carbonate reacts exothermically with strong acids evolving carbon dioxide. It corrodes aluminium, lead and iron.

End uses
Sodium carbonate is used as an intermediate in the production of other chemicals and in the manufacture of finished consumer goods. The major uses are as follows: Glass The glass industry is the largest user of sodium carbonate. The product acts as a flux reducing the melting point of sand, the major raw material of glass. The main glass markets are container glass (jars, bottles, glasses etc) flat glass (windows) and fibreglass which is generally used for insulation and reinforced plastics. Detergents & soaps Sodium carbonate is a major raw material in the manufacture of sodium phosphates and sodium silicates which are important components of domestic and industrial cleaners. Sodium carbonate is also added to these detergents to produce formulations for heavy duty laundering and other specialised detergents manufacture. Sodium carbonate may also be used for neutralising fatty acids in the production of soap. Metals and mining Sodium carbonate is used for the production of metals in both the refining and smelting stages. It is often used for producing a metal carbonate which can later be converted to the oxide prior to smelting. Paper and pulp Sodium carbonate solution is used for the production of sodium sulphite or bisulphite for the manufacture of paper pulp by various sulphite processes.

Sodium Carbonate

Chemicals Sodium carbonate is used extensively in the production of sodium compounds such as phosphates, silicates and sulphites. Textiles Sodium carbonate is widely used in the preparation of fibres and textiles. In wool processing it is used during scouring and carbonising to remove grease and dirt from wool. It is also used as a neutraliser after treatment with acids.

Production process
Synthetic sodium carbonate is produced in Australia (at Penrice Soda Products, Osborne, South Australia) using the Solvay or Ammonia Soda process. The manufacturing process consists of several discrete operations, each comprising a plant area: calcination of limestone in kilns and the production of CO2 and milk of lime brine purification absorption of ammonia into purified brine carbonation of the ammoniated brine with CO2 to produce sodium bicarbonate recovery of the ammonia using milk of lime calcination of sodium bicarbonate to form sodium carbonate (light ash) densification of sodium carbonate to form dense ash The two raw materials are salt and limestone and the overall reaction which is slightly endothermic can be given as follows; 2 NaCl + CaCO ----> CaCl + Na CO 3 2 2 3 Limestone is decomposed by heating to give lime and carbon dioxide. The decomposition is highly endothermic but ample chemical energy can be stored inside the lime and carbon dioxide and released later in the process. Mixed feed vertical shaft kilns burning coke are chosen for their ability to produce a high CO2 concentration and their excellent energy efficiency. However they are more sensitive to the effects of raw material than for example a rotary kiln used principally to produce only lime. In some factories, the lime is used in its unslaked form (CaO) later in the process, but more usually it is slaked and slurried in water to form milk of lime. Lime is only slightly soluble in water, so at the concentrations required for the process, the bulk of the lime exists as a suspension of Ca(OH)2 crystals in water. Crude brine received from the saltfields is treated to remove any impurities. These impurities are removed prior to further processing by precipitationcalcium with recycled sodium carbonate and magnesium with sodium hydroxide. The purified brine produced is required near to saturation in order to obtain the greatest possible conversion of salt with minimum energy. Recycled ammonia gas is absorbed into the purified brine, forming a highly alkaline solution. A lot of heat is generated and this must be removed by cooling the solution to allow the absorption of ammonia to proceed. Some carbon dioxide is also recycled with the ammonia. Being an acidic gas, CO2 is absorbed readily into the alkaline ammoniated brine, although it is not particularly soluble in brine. Carbonation occurs in two stages. The first stage absorbs 40 vol% CO2 gas from the kilns into the ammoniated brine stream from the absorbers, and proceeds to the point where most of the CO2 in the solution exists as carbonate ions.

Sodium Carbonate

The second stage of carbonation occurs in the Solvay towers. More kiln gas, and a recycled stream of up to 90 vol% CO2, are used to convert carbonate ions to bicarbonate ions. More heat is liberated, and cooling of the tower contents is necessary to assist absorption and to control crystallisation of sodium bicarbonate. At the bottom of the Solvay towers, where the stronger CO2 stream enters, the pressure is approximately three atmospheres, giving maximum CO2 absorption.

NaCl + H O + NH + 2 3 salt water ammonia

CO )))))))> NH Cl + NaHCO 2 4 3 carbon ammonium sodium dioxide chloride bicarbonate

The temperature profile of the Solvay tower is carefully controlled to give sodium bicarbonate crystals of the required size and to maximise bicarbonate yield. If the crystal size is too small, filtration of the product is more difficult and other problems arise at the calcining stage. The precipitated bicarbonate is separated using rotary vacuum drum filters. The filtrate, sucked through the filter cloth on the drum, is fed to the ammonia recovery plant. The solid bicarbonate is washed and dried, by drawing air through the cake, before discharge from the drum. The filtrate contains mainly ammonium chloride (coproduced with sodium bicarbonate) along with substantial quantities of unreacted salt, ammonia and carbon dioxide. Only 7075 per cent of the salt entering the factory as brine reacts to form sodium bicarbonate. In the distillation plant, the carbon dioxide and ammonia are recovered from the filtrate. The carbon dioxide and unreacted ammonia are stripped from the liquor in the top section of a column by a hot stream of ammonia and steam passing up from the bottom section. After removing the CO2, milk of lime can be added to react with the ammonium chloride and free the ammonia. 2NH Cl + Ca(OH) ---> 2NH + 2H O + CaCl 4 2 3 2 2 The resulting mixture is returned to the column, where the ammonia is stripped out using low pressure steam. This process uses large amounts of energy in the form of steam in order to recover all the ammonia possible; its efficient operation is critical to the economic performance of the factory. The gas leaving the distillers is cooled to condense out as much water as possible before being recycled to the absorbers to prevent dilution of the brine. The gas is primarily ammonia (55vol%), carbon dioxide (33vol%) and water vapour (12vol%). The solid sodium bicarbonate is then fed into a rotating calciner or dryer where it is heated, by contact with steam heated tubes, to give the light ash grade of sodium carbonate: heat 2NaHCO ))))))> Na CO + 3 2 3 Sodium Bicarbonate Sodium carbonate

H O + CO 2 2 Water Carbon Dioxide

As the reaction is endothermic, heat is required to decompose the bicarbonate. Part of this heat is represented by the chemical energy in the carbon dioxide released and, since it is recycled, this energy is retained in the process. Much of the heat in the gas is also recovered by heat exchangers. To produce dense ash, with particle size and bulk density to match those of the glassmaker's sand, light ash is first reacted with water to give sodium carbonate monohydrate crystals. These are then dehydrated by heating in a rotary drier or fluid bed drier.

Sodium Carbonate

Waste management during manufacture

The effect of waste on the environment has been a key issue in the manufacture of sodium carbonate for nearly 200 years. The Le Blanc process, which pre-dated the current Solvay or Ammonia Soda process, was heavily integrated with a number of other processes which produced feedstocks or byproducts. The development of equipment and processes for treating the wastes and byproducts of the Le Blanc process is perhaps the earliest example of a successful waste management program designed to protect the environment by conversion of waste material into commercial products. In the Solvay process, the raw materials, products and byproducts of the Ammonia Soda process are naturally occurring chemicals, present in almost any environment. As a result, the potential for damage to the environment is small provided good management practices are observed. There is only one significant waste produced directly by the Solvay process, calcium chloride. This is apparent from an examination of the overall equation for the process: 2NaCl + CaCO ---> Na CO + CaCl 3 2 3 2 The calcium chloride is produced as a solution of 1015wt% together with unreacted salt, some residual lime and some fine limestone in suspension. It is discharged from the bottom of the distiller in the ammonia recovery operation. Approximately 8 cubic metres of solution is produced per tonne of ash. Where a substantial market exists for calcium chloride, some of the distiller waste stream may be processed to commercial calcium chloride after settling the solids. The market for calcium chloride in Australia is however rarely of sufficient magnitude to utilise more than a small fraction of this waste stream. The balance can be safely discharged to marine waters, where any residual alkalinity is quickly neutralised by the strong buffering capacity of bicarbonate ions in sea water. Major excursions in pH must of course be prevented. Inert solids such as calcium carbonate and calcium sulphate may need to be dredged to keep navigation channels clear. The soluble salts are all present in sea water in large concentrations, and apart from a local elevation in salinity, have no adverse impact. Sodium carbonate manufacturing plants operating away from the sea must take more care in the disposal of distiller waste. Land disposal may pollute groundwater with undesirable levels of chloride ions. Disposal to inland waterways is generally not permitted if the resulting increase in salinity cannot be tolerated. Treatment by settling prior to discharge is the minimum requirement. Ammonia, whilst participating in the Solvay process, is not consumed. The unreacted ammonia, and ammonium chloride produced in the towers reaction, must be stripped from the filter liquor with the greatest possible efficiency, both to prevent discharge of ammonia to the environment in distiller waste, and to ensure economic operation of the process. Tight control of lime and steam addition to the distillation process is required to achieve maximum ammonia recovery at minimum cost. Another impact on the environment is the low grade energy discharged by ammonia soda plants. The waste discharged from the distillers is at nearly 100C and large amounts of cooling water are required to remove the heat of reaction from a number of process streams. Energy is recovered wherever economically and technically feasible, but substantial amounts of energy must inevitably be discharged to the environment. The thermal impact of cooling water and distiller waste on receiving waters is usually not a problem; the warm outfall is often used by marine life as an ideal breeding or feeding area. The fraction of limestone passing uncalcined through the lime kilns can be sold either to the construction industry for fill or as a stable founding material or to farmers who can take advantage of residual lime values to remediate acid soils.

Quality control during manufacture

Because the main raw materials for the Solvay Process are naturally occurring minerals, variations in quality must be expected over time. Careful quality control checks must be performed to ensure that these variations are detected and corrected before they can affect the process.

Sodium Carbonate

Penrice uses a limestone analyser developed by AMDEL in South Australia, to determine the level of impurities (mainly silica, alumina, iron and magnesium) in its limestone supply. The analyser contains a small radioactive source, and uses neutron excitation to determine the limestone composition. Impurities can react and melt together to form "clinker", which can block kilns if it solidifies on the walls. Brine strength is important to maintaining good plant efficiency. A simple density test is usually sufficient for quick checks. A chemical analysis is performed regularly to confirm the salt concentration, and to test for calcium and magnesium ion concentration. High levels of Ca and Mg lead to excessive consumption of the chemicals needed to purify the brine. Process streams are analysed at each stage in the process to ensure that the final product will be within specification. Process parameters (temperatures, pressures, flows etc) must be tightly controlled for the same reason. The product itself must then be subjected to a range of tests to confirm that it falls within the specification limits agreed with customers. Typical analyses include particle size, colour, chloride and iron concentration and moisture content. Much of the analysis is performed using modern instrumentation methods: for example, atomic absorption spectrophotometry, gas chromatography and automatic titration for many solutions. However, traditional "wet chemistry", distillation, titration etc is still used for many analyses.

Personnel
There are a range of careers associated with the production of soda ash. These include; Production Quarry operators Salt field operators Chemical plant operators Skilled/semi skilled process workers Production Support Engineering: chemical, mechanical, electrical, civil, mining Laboratory: laboratory technicians, chemists Administration: general management, quality management, accounting, purchasing, human resource management, safety officer, occupational health nurse, typing and secretarial, computing, training. Maintenance: mechanical/electrical trades, instrument technicians. Transport/stores: drivers, storemen Sales/marketing Sales representatives marketing officers Some of these jobs may be provided by "contract" labour, consultants etc depending upon the complexity, duration and extent of the work to be performed.

Sodium Carbonate

Handling
Storage and transport Sodium carbonate is not defined as a dangerous good by the Australian code for the transport of dangerous goods by road and rail. The product should be stored in a cool, dry place and out of direct sunlight. Store away from acids and keep containers closed at all times to prevent absorption of moisture and carbon dioxide from air. Spills Wear protective equipment to prevent skin and eye contamination and inhalation of dust. Sweep up, but avoid generating dust. Collect and seal in properly labelled containers for disposal. Wash area down with excess water. Disposal Sodium carbonate is normally suitable for disposal at approved land waste sites. Fire/explosion hazard The product is not combustible.

Safety data Health effects

Skin Contact with skin may result in mild to moderate irritation, particularly if skin is wet or moist due to sweating. Solutions are severely irritant to the skin due to its alkaline nature. Eyes Sodium carbonate is severe eye irritant. Contamination of eyes can result in permanent injury. Inhalation Inhalation of dust will result in respiratory irritation. Symptoms may include coughing, sneezing and difficulty in breathing. Ingestion Swallowing can result in burning of the mouth, throat and stomach, resulting in cramps, vomiting, diarrhoea, and at higher levels (2030 g), possible circulatory effects and death. As with any chemical, ingestion, inhalation, and prolonged or repeated skin contact should be avoided by good occupational work practice.

First aid
Skin Immediately wash contaminated skin with plenty of water. Remove contaminated clothing and wash before re-use. If irritation occurs seek medical advice. Eyes Immediately irrigate with copious quantities of water for at least 15 minutes. Eyelids to be held open. Remove clothing if contaminated and wash skin. Seek immediate medical assistance. Inhalation Remove victim from exposureavoid becoming a casualty. Keep the patient at rest until fully recovered. Seek medical advice if effects persist.

Sodium Carbonate
Ingestion Immediately rinse mouth with water. Give water to drink. DO NOT induce vomiting. If vomiting occurs give further water to achieve effective dilution. Seek medical assistance.

Attachment
Sodium carbonate production process. Orica Limited January 1999 Copyright 19921999 Orica Limited, ACN 004 145 868.

SODIUM CARBONATE: PROCESS FLOW DIAGRAM

Limestone (CaCO3 )

Coke (C)

Brine
Heat Exchanger

CO2

NH3 , CO2 , H2 O

Recycle Gases

Waste Gases CO2

Lime Kiln Air

Milk of Lime Ca(OH)2

CARBONATOR

ABSORBER

DISTILLER

Coolers

Compressors

Lime CaO

NH3 Makeup Steam

Cooling Water

CO2
Water Condenser

H2O

Slaker

Calcium Chloride Grit

Rotary Vacuum Drum Filter

Conveyor

Filterate (NH4Cl Liquor) Solid Sodium Bicarbonate (NaHCO3)

Conveyor

CO2 + H2 O

Water Steam

Mixer

Fluidised Bed Dryer

Air & Moisture

Steam

Conveyor

Steam Heated Calciner

Air
Conveyor

Conveyor

Cooler
Light Ash
Conveyor

Dense Ash

-To Storage & Packing -Transport By: -Sea -Road -Rail