Overview of Chlor-Alkali Industry

Chlorine and co-product, caustic soda, fundamental building-block chemicals - Used in over 50% of all industrial chemical processes - Basic manufacturing chemical so products utilized in numerous industries and applications

Essential to numerous products and services - Critical role in water disinfection and water delivery - 85% of all pharmaceuticals - 95% of crop protection chemicals

MANUFACTURE OF SODIUM CARBONATE

TYPES OF PROCESS
Solvay or ammonia soda (accounts for of production) Dual process (Na2CO3 + NH4Cl) Natural soda ash from dispersed sectors of India deposits in widely 85%

MANUFACTURE OF CAUSTIC SODA AND CHLORINE

METHODS OF PRODUCTION
CLASSIFICATION OF PROCESS
Lime soda process
Electrolytic process Mercury Electrolytic process Diaphragm Electrolyic Process Membrane Electrolytic process

LIME SODA PROCESS

Na2CO3 + Ca(OH)2

2NaOH + CaCO3

In this process sodium carbonate reacts with calcium hydroxide which in turn produces caustic soda

Electrolytic processes

Electrolysis Reactions:
Anode 2 ClCl2 (g) + 2 e-

Cathode -

Na+ + e2 Na + 2 H2O

Na 2 NaOH + H2 (g)

Side Reactions:

2 NaOH + Cl2
2 OH- + Cl2 4 OH-

NaCl + NaOCl + H2O

2 OCl- + H2 O2 (g) + 2 H2O + 4 e-

MERCURY CELL
The mercury cell has steel bottoms with rubber-coated steel sides, as well as end boxes for brine and mercury feed and exit streams with a flexible rubber or rubber-coated steel cover. Adjustable metal anodes hang from the top, and mercury (which forms the cathode of the cell) flows on the inclined bottom. The current flows from the steel bottom to the flowing mercury.
Saturated brine fed from the end box is electrolyzed at the anode to produce the chlorine gas, which flows from the top portion of the trough and then exits. The sodium ion generated reacts with the mercury to form sodium amalgam (an alloy of mercury and sodium), which flows out of the end box to a vertical cylindrical tank. About 0.25% to 0.5% sodium amalgam is produced in the cell. The sodium amalgam reacts with water in the decomposer, packed with graphite particles and produces caustic soda and hydrogen. Hydrogen, saturated with water vapor, exits from the top along with the mercury vapors. The caustic soda then flows out of the decomposer as 50% caustic. The unreacted brine flows out of the exit end box. Some cells are designed with chlorine and anolyte outlets from the end box, which are separated in the depleted brine tank. The mercury from the decomposer is pumped back to the cell.

Mercury Cathode Cell

Na+ + eNa + Hg Na (metal) Hg/Na Amalgam

Hg/Na Amalgam + H2O

Cl2

NaOH (aq) + H2 (g) + Hg (l)

Carbon Anode (+)

Brine

Hg

Hg/Na
Hg Cathode (-)

H2
Brine from wells Na2CO3

70% Caustic for purification

Steam

H2O Sludge D R Y E R

Liquid Cl2 to storage

Filter

Mercury Cell

Denuding Tower

Filter

DIAPHRAGM CELLS
The diaphragm cell is a Diaphragm cells rectangular box with metal anodes supported from the bottom with copper-base plates, which carries a positive current. The cathodes are metal screens or punch plates connected from one end to the other end of the rectangular tank. Asbestos, dispersed as a slurry in a bath, is vacuum deposited onto the cathodes, forming a diaphragm. Saturated brine enters the anode compartment and the chlorine gas liberated at the anode during electrolysis, exits from the anode compartment. It is saturated with water vapor at a partial pressure of water over the anolyte. The sodium ions are transported from the anode compartment to the cathode compartment, by the flow of the solution and by electromigration, where they combine with the hydroxyl ions generated at the cathode during the formation of the hydrogen from the water molecules. The diaphragm resists the back migration of the hydroxyl ions, which would otherwise react with the chlorine in the anode compartment. In the cathode compartment, the concentration of the sodium hydroxide is ~12%, and the salt concentration is ~14%. There is also some sodium chlorate formed in the anode compartment, dependent upon the pH of the anolyte.

Diaphragm Cell
(+) Carbon (-)

Power Supply

Carbon Cathode
H2

Anode
Cl2

NaCl (aq)

Porous Diaphragm (Teflon Mesh)

Net Flow

NaOH (aq)

Brine from wells

Na2CO3

H2
Diaphragm Cell
filter Steam
evoporators
Multiple effect

50% Caustic for purification

Sludge D R Y E R

Liquid Cl2 to storage

MEMBRANE CELL
In a membrane cell, an ion-exchange membrane separates the anode and cathode compartments. The separator is generally a bi-layer membrane made of perfluorocarboxylic and perfluorosulfonic acid-based films, sandwiched between the anode and the cathode. The saturated brine is fed to the anode compartment where chlorine is liberated at the anode, and the sodium ion migrates to the cathode compartment. Unlike in the diaphragm cells, only the sodium ions and some water migrate through the membrane. The unreacted sodium chloride and other inert ions remain in the anolyte. About 30-32% caustic soda is fed to the cathode compartment, where sodium ions react with hydroxyl ions produced during the course of the hydrogen gas evolution from the water molecules. This forms caustic, which increases the concentration of caustic solution to ~35%. The hydrogen gas, saturated with water, exits from the catholyte compartment. Only part of the caustic soda product is withdrawn from the cathode compartment. The remaining caustic is diluted to ~32% and returned to the cathode compartment.

PROCESSING OF PRODUCTS

Chlorine processing
The chlorine gas from the anode compartment contains moisture, by-product oxygen, and some back-migrated hydrogen. In addition, if the brine is alkaline, it will contain carbon dioxide and some oxygen and nitrogen from the air leakage via the process or pipelines. Chlorine is first cooled to 60oF (16oC) and passed through demisters to remove the water droplets and the particulates of salt and sodium sulfate. The cooled gas goes to sulfuric acid circulating towers, which are operated in series. Commonly, three towers are used for the removal of moisture. The dried chlorine then goes through demisters before it is compressed and liquefied at low temperatures. The non-condensed gas, called snift gas, is used for producing hypochlorite or hydrochloric acid. If there is no market for hydrochloric acid, the snift gas is neutralized with caustic soda or lime (calcium hydroxide) to form hypochlorite. The hypochlorite is either sold as bleach or decomposed to form salt and oxygen.

Hydrogen processing
The hydrogen gas from the chlor-alkali cells is normally used for the production of hydrochloric acid or used as a fuel to produce steam. Hydrogen from mercury cells is first cooled to remove the mercury, which is then returned to the cells. Occasionally, a secondary treatment is used to remove the trace levels of mercury in the hydrogen via molecular sieve columns. The hydrogen gas is then normally compressed. If a customer needs nearly pure hydrogen containing low amounts of oxygen, some plants will heat the hydrogen over a platinum catalyst (to remove the oxygen by reacting it with the hydrogen to form water), cool, and compress the diaphragm or membrane cell hydrogen, before supplying it to the customer. The heat value in the hydrogen cell gas can be recovered in a heat exchanger via heating the brine feed to the cells.

Caustic soda processing

Caustic soda is marketed as 50%, 73%, or anhydrous (dry) beads or flakes. The mercury cell can produce 50% and 73% caustic directly. The caustic from the decomposer is cooled and passed once or twice through an activated carbon filter to reduce the mercury levels in the caustic. After filtration, the mercury concentration is lowered to the parts-per-million (ppm) levels. Even these low levels of mercury may be unacceptable to some customers, who then have to switch to using membrane grade caustic soda. The mercury cell caustic soda has a few ppm salt and <5-ppm sodium chlorate. The mercury cell caustic is the highest purity caustic that can be made electrolytically if trace concentrations of mercury are tolerable in the end use of caustic. The membrane cell caustic is concentrated in a multiple effect falling film evaporator, which increases the caustic soda concentration to 50% with a high steam economy. Caustic soda from membrane cells generally has 30-ppm sodium chloride and 5-10 ppm sodium chlorate.

The catholyte from the diaphragm cells contains ~12% sodium hydroxide, ~14% sodium chloride, 0.25%-0.3% sodium sulfate, and 100-500 ppm sodium chlorate. The catholyte is evaporated in a multi-effect evaporator. Most of the salt from the catholyte will precipitate during the concentration of the caustic soda to 50% sodium hydroxide. The 50% caustic soda product will contain about 1% sodium chloride. The 50% caustic also has a high chlorate concentration (~0.1%) compared to the caustic from membrane or mercury cells (~10 ppm). The salt, separated from the caustic during evaporation, is used to re-saturate the brine fed to the cell. An additional single-effect evaporator is needed to produce 73% caustic soda. Anhydrous (dry) caustic soda is produced in a rising film evaporator, operating at 725oF (385oC) and at a few inches (one inch =2.54 cm) of water vacuum.

END USES OF CHLORINE

END USES OF CAUSTIC SODA

GALLERY OF CHLOR-ALKALI INDUSTRY

DCW Limited

Gujarat Alkalies & Chemicals

Aditya Birla Chemicals

Bihar Caustic & Chemicals

Gujarat Alkalies & Chemicals

Gujarat Alkalies & Chemicals

Grasim Industries Ltd.

DISADVANTAGES OF MERCURY CELL PROCESS

INTRODUCTION
Mercury has been used in chlorine and caustic soda production for more than one hundred years. Technology that eliminates the need to use mercury in chlor-alkali production has been readily available for just as long. Yet, in the United States, five chlor-alkali plants have still not committed to stop using the outdated mercury-cell technology to produce their products. In 2005, these five plants reported emissions of more than 4,400 pounds of mercury into the air.1 On average, these plants release more than four times the average amount of mercury released from a typical power plant; earning them the title The Filthy Five (See Figure 1). Unlike coal-fired power plants in which mercury emissions can only be reduced, technology can completely eliminate mercury pollution from chlor-alkali production. Thus, the release of tons of mercury to the environment reported by these companies, not to mention the many more tons lost by mercury cell chlorine plants, is entirely unnecessary. Mercury is a dangerous neurotoxin that can accumulate in fish when released to the environment. According to the Madison Declaration on Mercury Pollution, a consensus of over 1,100 scientists released in March 2007, about two-thirds of the mercury in the environment is attributable to human activities, such as chlor-alkali production.2

Most human exposure to mercury is dietary, resulting from consumption of fish or seafood.3 Once mercury builds up in the body, it can cause a variety of health problems that can be both subtle such as numbness in fingers4 and quite serious such as an increased risk of heart disease.5

The greatest concern about mercury surrounds its effects on the early development of the fetus and on later childhood development. Methylmercury can travel across the placenta from the mother to the fetus, meaning exposure to the dangerous poison often begins in the womb during a babys most vulnerable developmental period. Not only does it take lower levels to harm a developing fetus than it would an adult, but mercury levels are also magnified in the womb.6 Mercury can irreversibly impair childrens brain functions as they grow.7 Infants and children exposed to high doses of mercury may have problems with attention span, language, visual-spatial skills, memory and coordination. Very high levels of exposure in children can lead to brain damage, speech problems, seizures, blindness and mental retardation.8

This analysis has identified 115 plants that already have switched or are in the process of switching to technology that neither uses nor releases mercury (See Table 3). It then goes on to focus on the five remaining mercury-cell chlor-alkali plants in the United States that have not committed to stop using mercury, and tallies the benefits against the cost of switching to membrane-cell technology.

An Environmental Protection Agency (EPA) scientist has estimated that one in six women has enough mercury in her blood to pose neurological risks to her developing baby.9 This means that hundreds of thousands of newborns each year in the United States may be exposed to enough mercury to hinder nervous system development.While there are a variety of industrial sources of mercury, all of which need to be reduced, this report focuses on the problem of mercury releases from chlorine, or chloralkali,production.

PLANTS THAT HAVE CONVERTED ILLUSTRATE BENEFITS OF CONVERSION

History of Mercury-Free Chlorine Production
Mercury-free technology has been readily available and installed around the world for decades. Many plants were constructed using either diaphragm or membrane-cell technology. However, many others were built to use mercury. Of those, more than one-hundred mercury-cell chlor-alkali plants already have switched or plan to switch to mercury-free technology. This analysis has identified 115 such facilities, making it the most comprehensive compilation of this information to date. However, some plants undoubtedly have been converted that were not identified in this analysis. Although chlorine plants stop using mercury for a variety of reasons, including government-initiated bans on mercury-cell plants and environmental concerns, the economics of conversion are more attractive to the managers of facilities that consider them than one might think. While the up-front costs associated with installing mercury-free technology may appear to be high, there are many variables that balance out the cost of an upgrade, such as an increase in energy efficiency and the opportunity to increase capacity due to the shift.

Membrane-cell technology is the newest mercury-free technology, despite having been in use for over thirty years. It is now considered the best available technology for chlorine production, and currently most chlorine plants choose this technology when converting. Shifting to membrane-cell technology typically saves plants between 25 percent and 37 percent of their prior energy costs (Table 1). This is significant since electricity is a large portion, sometimes nearly half, of a chlorine facilitys operating budget. In fact, individual mercury-cell chlor-alkali plants can consume as much electricity as small cities.

Another benefit of mercury-free membrane cells is their ability to produce as much chlorine as a mercury cell in a smaller space. Most plants that have converted or are in the process of doing so have taken advantage of this fact by increasing their chlor-alkali capacity by 20 to 30 percent during their conversion, although others have increased chlorine capacity by up to 80 percent (Table 2). The corresponding increase in capacity obviously leads to an increase in sales potential. By increasing enrgy efficiency and increasing capacity, some plants have been able to pay off their conversion investments in fewer than five years.

Besides these direct benefits, conversion also brings indirect benefits to public and environmental health. For example, increasing energy efficiency reduces the plants demand for fossil fuels and cuts down on its per unit generation of carbon dioxide, a greenhouse gas. Assuming no change in fuel type, a 25 percent decrease in fuel use results in a 25 percent decrease in greenhouse gas emissions. Minimizing mercury releases to the environment is another obvious benefit, although it is difficult to measure in dollars.

The world map (Figure 3A-3D) shows the global distribution of chlorine facilities that have converted.

THE END