The chlor- alkali industry is the industry that chlorine(Cl2) and alkali, sodium hydroxide(NAOH)or hydroxide(KOH),by electrolysis of a salt solution. produces potassium

The main technologies applied for chlor-alkali production are mercury, diaphragm and membrane cell electrolysis.

History of Chlor-alkali Industry
The diaphragm cell process and the mercury cell process were both introduced in late 1800s. The membrane cell process was developed much more recently (1970).
Each of these processes represents a different method of keeping chlorine produced at the anode separate from caustic soda and hydrogen produced at the cathode.

Currently 95% of world chlorine production is obtained by chloralkali process. The geographic distribution of chlor-alkali processes world-wide differs appreciably: Western Europe, predominance of mercury cell process (June 2000):55% United States, predominance of diaphragm cell process: 75% Japan predominance of membrane cell process: >90%

The chlor-alkali sector in Europe has developed over time and is scattered geographically. Europe is approximately balance in chlorine, and has traditionally been the world’s second largest exporter of caustic.

and the process became known as Weldon process . chlorine.  It was made by reacting manganese dioxide with hydrochloric acid.During the last half of 19th century. Recycling of manganese improved the overall process economics.used almost exclusively in the textile and paper industry.

.SODA ASH  Soda Ash also known as sodium carbonate. is a sodium salt of carbonic acid.  It is synthetically produced in large quantities from salt (sodium chloride) and limestone by a method known as the Solvay process. Na2CO3.  It can be extracted from the ashes of many plants or seaweed.  Sodium carbonate is domestically well known for its everyday use as a water softener.

. which is used for the detergent market and certain chemical intermediates.  The raw material of this process is found every where in the world. also called ammonia soda process.  The Solvay process produces “light soda ash”. uses salt (NaCl) and limestone (CaCO3) as raw materials.MANUFACTURING OF SODA ASH SOLVAY PROCES  The Solvay process.  Recrytasllization of light soda ash produce dense “soda ash”.

NaCl + H2O + NH3  NaCl + NH4OH 2 NH4OH + CO2 (NH4)2 CO3 + H2O (NH4)2CO3 + CO2 + H2O 2 NH4HCO3 2 NH4HCO3 + 2 NaCl 2 NaHCO3 ↓ + 2 NH4Cl (1) (2) (3) (4) . 2 NaCl + CaCO3 → Na2CO3 + CaCl2 In practice this direct way is not possible and it needs the participation of other substances and many different process steps to get the final product: soda ash.MAIN CHEMICAL REACTIONS The two main components: sodium chloride and calcium carbonate.

sodium bicarbonate is decomposed thermally into sodium carbonate.Sodium bicarbonate crystals are separated from the mother liquor by filtration. 2 NaHCO3 → Na2CO3 + H2O + CO2 (5) The ammonium chloride filtrate (4) is reacted with alkali. followed by steam stripping to recover free gaseous ammonia: 2 NH4Cl + Ca(OH)2 → CaCl2 + 2 NH3 ↗ + 2 H2O (6) . generally milk of lime (6). water and carbon dioxide (5).

→ Mg(OH)2 ↓ (9) (10) . If not removed they would react with alkali and carbon dioxide to produce insoluble salts contributing to scale formation inside equipment.→ CaCO3 ↓ Mg2+ + 2 OH.Carbon dioxide and calcium hydroxide originate from limestone calcination (7) CaCO3 → CaO + CO2 ↗ (7) CaO + H2O → Ca(OH)2 (8) Brine (NaCl) has to be treated before the input in the process to remove impurities : calcium and magnesium. Ca2+ + CO3 2.

by adding water (equation 11) then followed by drying (equation 12). A subsequent operation called densification enables this value to be doubled by crystallisation into sodium monohydrate.z Na2CO3 + H2O -------.H2O --------. Final product is "dense soda".H2O Na2CO3.Sodium carbonate formed (equation 5) is called "light soda ash" because its bulk density is approximately 0.> Na2CO3.5 t/m3.> Na2CO3 + H2O ↗ (12) (11) .

ADVANTAGES OF SOLVAY PROCESS      Can use low-grade brine Less electric power Less corrosion problems No co-products to dispose of Does not require ammonia plant investment DISADVANTAGES OF SOLVAY PROCESS  Higher salt consumption  Higher investment in ammonia recovery unit verses crystallization units for ammonium chloride  Waste disposal of calcium chloride brine stream  More steam consumption  Higher capacity plant for economic break-even operation  With current fertilizer shortage. so co-product disposal no problem. . all of the ammonium chloride will be used as a mixed chemical fertilizer ingredient.

Storage: Store in a cool. or gas.HANDLING AND STORAGE  Handling: Do not breathe dust. or on clothing. on skin. mist.  . dry place. vapor. Store in a tightly closed container. Use only in a chemical fume hood. Do not get in eyes.

Any residue that cannot be swept up should be diluted with large amounts of water  Fires – Sodium carbonate is not flammable or combustible.Exposures can occur at a sodium carbonate (soda ash) manufacturing facility or a manufacturing. sampling and testing activities.  Environmental releases.Spills of sodium carbonate should be contained and isolated from waterways and sewers or drains. packaging or storage facility that handles soda ash. Spills should be swept up and placed in a compatible container. Exposure may also occur in the event of a transportation incident.EXPOSURE POTENTIAL  Workplace exposure . or in the loading and unloading of sodium carbonate containers are at greater risk of exposure. . Persons involved in maintenance.

Sodium carbonate can produce the following adverse health effects:  Contact . irreversible eye damage may result. Repeated or prolonged exposures may cause sore throat or nosebleeds. nausea.HEALTH INFORMATION Sodium carbonate typically found in consumer products may pose a risk of symptoms due to skin or inhalation exposure.The ingestion of sodium carbonate may cause severe irritation of the mouth and throat.  Ingestion . tearing or severe eye irritation. . abdominal irritation and diarrhea.  Other Effects .The inhalation of sodium carbonate dusts can cause nose and throat irritation or coughing. In severe exposures.The International Agency for Research on Cancer (IARC) has not classified sodium carbonate as a carcinogen (cancer causing). Eye exposure to sodium carbonate may result in redness.  Inhalation .Skin exposures can cause symptoms ranging from minor skin irritation or itching to redness and swelling. vomiting.

and produces chlorine and sodium hydroxide through the electrolysis of table salt (NaCl). This produces NaClO3.CHLOR-ALKALI INDUSTRY PROCESSES The chlorine-alkali (chlor-alkali) industry is an important part of the chemical industry. NaClO.  Cl and NaOH can be produced through a number of different reactions  When Cl and NaOH are produced together  Cl combines with the NaOH to form ClO and Cl ions. . a component of household bleach.

1892)  The Membrane Cell (1970) .TYPES OF CELLS IN ELECTRYLOSIS Three industrial processes and all three methods involve electrolytic cells:  The Diaphragm Cell (Griesheim cell. 1885)  The Mercury Cell (Castner–Kellner cell.

RAW MATERIAL  Brine which is a saturated solution of sodium chloride (NaCl) that is obtained from natural salt deposits.  Electricity  Water .




PRIMARY ELECTROLYSER NaCl Na+ + Cl- DECOMPOSER 2Na/Hg + 2 H2O 2 Na+ + 2OH.+ H2 (g) + 2Hg .

reducing the level of impurities of (NaClO). oxygen and (NaClO3). along with a little oxygen.  Efficient separation of chlorine. generally can be used without further purification.  The products are extremely pure. .ADVANTAGES  If brine leaving the cell is saturated with chlorine and so is first dechlorinated and then purified by a precipitation-filtration process. The chlorine.

DRAW BACK  Only produces a fraction of the chlorine and sodium hydroxide  Mercury is expensive and toxic  In the past effluent was released into lakes and rivers  About 100 to 200 g mercury were lost for each 1000 kg chlorine produced. .  Today. the brine is treated before it is discharged so that the environmental impact is lower.

 In North America.THE DIAPHRAGM PROCESS FOR ELECTROLYSIS OF BRINE  The diaphragm process was developed in the 1880s in the USA . diaphragm cells are still the primary technology. accounting for roughly 70% of all USA production. .

. and the hydrogen and caustic soda produced directly at the cathode. All reactions take place within one cell.  The chlorine liberated at the anode.  Certain practical problems that are needed to be addressed in the diaphragm cell.

+ H2 (g) 2Na+ + 2Cl-+ 2H2O → 2Na+ + 2OH.(aq) → Cl2 (g) + 2eReaction at cathode: 2 H2O (l) + 2e.+ H2 + Cl2 The complete ionic equation with neutral species is as follows: 2NaCl (aq) + 2H2O (l) → 2NaOH (aq) + H2 (g) + Cl2 (g) .→ 2OH.CHEMICAL REACTIONS IN DIAPHRAGM CELL Reaction at anode: 2Cl.

Flow Sheet for the whole process of production of NaOH and Cl gas by electrolysis of brine with the help of diaphragm cell .


at reasonable costs .ADVANTAGES AND DISADVANTAGES OF DIAPHARGM PROCESS  The advantage of this process is that large quantities of sodium hydroxide can be produced and chlorine. . which are two highdemand industrial chemicals.

. a strong oxidant.The disadvantages are:  A small amount of chloride in the NaOH produced. in the waste brine solution.  There are health and environmental problems with small losses of asbestos in making and using diaphragms.  There may be hypochlorite.


the development of ion-exchange membranes enabled a new technology to produce chlorine: the membrane electrolysis process.THE MEMBRANE PROCESS FOR ELECTROLYSIS OF BRINE  In the 1970s. .  The first industrial membrane plant was installed in Japan in 1975 due to the pressure of Japanese environmental regulations.  Non-chlor-alkali related mercury pollution in Minamata drove the authorities to prohibit all mercury processes.

. Most promising and fast-developing technique for the production of chlor-alkali .This can be deduced from the fact that since 1987 practically 100% of the new chlor-alkali plants world-wide apply the membrane process.

CHEMICAL REACTIONS IN MEMBRANE CELL  A membrane cell is a diaphragm cell with an improved diaphragm called a ‘membrane’. This is made from polytetrafluoroethylene (PTFE). .

+ H2 (g) • The overall equation is as follows: .Reaction at anode: Reaction at cathode: 2 H2O (l) + 2e.→ 2OH.

Flow Sheet for the whole process of production of NaOH and Cl gas by electrolysis of brine with the help of membrane cell .


ADVANTAGES OF MEMBRANE CELL  Pure sodium hydroxide (only contains about 0. .02% of sodium chloride at most) being produced  No contamination by chloride  No oxidant in the spent brine  There is no working hazard of working with asbestos or mercury.



whereas. sodium hypochlorite. Caustic Soda (Sodium Hydroxide. bleaching earth. chlorinated paraffin.CHLOR ALKALI INDUSTRY IN ECONOMY OF PAKISTAN  Chemical industry plays a vital role in the economic development of Pakistan. hydrochloric acid. .NaOH) is the key product of this sector.  The chlor-alkali business can be described as a subsector of the chemical industry which produces liquid chlorine.

000 MT of caustic soda and chlor alkali based products. there 4 major players in the market with a production capacity of more than 500. Presently. NIMIR produces caustic soda for its internal usage only . However. These plants are  SCIL  Ittehad Chemicals Limited (ICL)  Engro Polymers Chemicals Limited (EPCL)  NIMIR Industrial Chemicals Limited (NIMIR).

. as well as an intermediate in manufacturing other substances where it is not contained in the final product. agrochemicals and pharmaceuticals.Uses of products form in chlor alkali industry  Chlorine Disinfectant and purifier. solvents. in plastics and polymers. bleach.

It is able to kill bacteria and algae.  Chlorine is used in pools and drinking water because it is a great disinfectant. among other things . Chlorine is used worldwide to purify water supply as the ultimate defense against waterborne microbiological infection.

Combustion generates plenty of energy .HYDROGEN Hydrogen and Fuel Cells  The element is often used as fuel because of its high calorific value.

scientists are able to use it with weather balloons. Because hydrogen is light. hydrochloric acids and an assortment of bases .  Other uses of hydrogen are in the fertilizer and paint industries. Apart from ammonia. It can be used to make fertilizers. hydrogen can be harnessed in other ways. It is also used in the food and chemical industries  This element is used for producing several chemical compounds.

Sodium hydroxide .

 Energy in the form of fuels or steam is used primarily for evaporation of the sodium hydroxide solution to a useable state.DISADVANTAGES Electricity Is the Largest Energy Source  Electricity fuels the electrolysis process and represents the primary energy source.  Among the three types of chlorine cells. with electricity requirements of nearly 3600 kWhr per metric ton of chlorine. . the mercury cell is the most energy-intensive.

source reduction. and programs to monitor such leaks . Air emissions from brine electrolysis include chlorine gas and freon emissions (both fugitive and point source) and other vapors  These emissions are controlled through leak-resistant equipment modifications.Air Emissions  Chlorine Gas and Freon Are Primary Air Emissions from Brine Electrolysis.

chlorine drying.Effluents  Wastewater Is Treated To Remove Chlorine and Acids Prior to Discharge Wastewater from diaphragm and membrane cells originates from caustic evaporation. and from purification of salt recovered from evaporators. . washing of the ion-exchange resin.

The sludge or brine mud containing these impurities must be disposed of in a landfill . one of the largest waste streams from the chlor-alkali industry  The brine mud contains a variety of compounds. typically magnesium hydroxide and calcium carbonate formed during the addition of compounds to purify the brine.Hazardous Wastes and Byproducts  Brine Mud Constitutes the Largest Solid Waste Stream from Chlor-Alkali Production Brine purification results in brine mud.

renal. thyroid. gastrointestinal. hematologic. reproductive. sensory and genotoxic disorders has been associated with mercury exposure . A wide variety of respiratory. dermal. immunologic. hepatic. cardiovascular. musculoskeletal.Health effect  The chlor-alkali industry is also a major source of industrial mercury pollution  The central nervous system is considered the critical organ for mercury toxicity.

Environmental Issues Within the Chlor/Alkali Industry  There are several environmental concerns that have made a significant impact on the growth of the chlor-alkali industry. and the associated "chemophobia" is likely to adversely affect the chlorine consumption profile in the future . These issues are highly debated.

 • Scrub chlorine tail gases to reduce chlorine discharges and to produce hypochlorite. .  • Resaturate brine in closed vessels to reduce the generation of salt sprays.  • Use noncontact condensers to reduce process wastewater quantities.  • Recycle condensates and waste process water to the brine system. if possible.Pollution Prevention and Control  • Use metal rather than graphite anodes to reduce lead and chlorinated organics.