6 The Chlor-Alkali

Industry

6.1 Overview of the Chlor-Alkali U.S. Production of Major Products

Industry in the Caustics Chain (1997)

Chlorine (26.0 billion lbs)

Chlorine, Sodium Hydroxide, and Sodium
Sodium Carbonate (23.7 billion lbs)
Carbonate Are Primary Products of the Sodium Hydroxide (22.7 billion lbs)
Chlor-Alkali Industry
Source: CMA 1998.
The caustics chain begins with sodium chloride
(NaCl) and forms the basis for what is often
referred to as the chlor-alkali industry. Major
Most of the chlorine produced in the United
products of the chlor-alkali industry include
States (about 70 percent) is used to manufacture
chlorine , sodium hydroxide (caustic soda),
organic chemicals (e.g., vinyl chloride monomer,
soda ash (sodium carbonate), sodium
ethylene dichloride, glycerine, chlorinated
bicarbonate, potassium hydroxide, and
solvents, glycols). Nearly 40 percent is used for
potassium carbonate. Of these products,
the production of vinyl chloride, an important
chlorine, sodium hydroxide, and soda ash account
building block for poly vinyl chloride (PVC) and a
for the largest share of shipments from the chlor-
number of petrochemicals (see Figure 6-1).
alkali industry. These products are also very
Chlorine is also important to the pulp and paper
important economically, being the chemicals
industry, which consumes about 15 percent of the
produced in the eighth, ninth, and tenth largest
chlorine produced annually. Other major uses for
amounts in the United States (in 1997, their
chlorine include the manufacture of inorganic
combined production was over 72 billion pounds)
chemicals, disinfection of water, and production
(CMA 1998).
of hypochlorite (CMA 1998, Orica 1999).

175
 Ethylene dichloride/vinyl chloride
Chlorine monomer, polyurethanes, other
organic compounds, pulp and paper,
solvents, water treatment, titanium
dioxide
Salt Water

Caustic Soda Chemical manufacturing, pulp and

(Sodium paper, soaps and detergents,
Hydroxide) textiles, alumina, petroleum refining

The Caustics Chain

Salt and Glass-making, detergents and

Limestone Soda Ash soaps, neutralization, metals and
(synthetic) or (Sodium mining, sulfite paper pulping,
Trona Ore Carbonate) chemical sodium compounds,
(natural) textiles processing

Figure 6-1. Chlor-Alkali Products Chain (CMA 1998)

About 30 percent of the sodium hydroxide processing. Soda ash is also an intermediate in
produced is used by the organic chemical industry the production of sodium compounds, including
and about 20 percent is consumed by the phosphates, silicates, and sulfites.
inorganic chemical industry for neutralization and
off-gas scrubbing, and as an input into the Demand for Sodium Hydroxide and
production of various chemical products (e.g., Chlorine Is Impacted by Global
alumina, propylene oxide, polycarbonate resin, Economies
expoxies, synthetic fibers, soaps, detergents,
rayon, cellophane). Another 20 percent of The chlor-alkali industry has been growing at a
sodium hydroxide production is used by the pulp slow pace over the last 10 years and this rate is
and paper industry for pulping wood chips and for expected to continue in the early years of the
other processes. Sodium hydroxide is also used new century. Chlorine and sodium hydroxide are
to manufacture soap and cleaning products, and co-products, and the demand for one will highly
as drilling fluid for oil and gas extraction influence the demand for the other. Over the last
(CHEMX 1999, Orica 1999). several decades, market forces have switched
between chlorine and sodium hydroxide a number
Soda ash is used primarily by the glass industry of times. Chlorine demand drives the chlor-alkali
as a flux to reduce the melting point of sand. It is industry, but the demand is cyclical, with chlorine
also a raw material in the manufacture of sodium and caustic soda out of phase in the marketplace.
phosphates and sodium silicates, important When caustic soda reaches a high level of
components of domestic and industrial cleaners. demand, the direction of product flow is
Other uses are in the production of metals in dependent upon Asian and European economies
both the refining and smelting stages, in sulfite and the foreign exchange rate. Foreign
paper pulping processes, and in textiles producers may often export caustic soda to the

176
United States to keep chlorine production high, sources of trona ore . However, it is more
which impacts both markets and production in this expensive to mine soda ash than to produce 50
country (DOW 1999). percent caustic, so increased use of soda ash is
not likely to occur unless the price of caustic is
Prices for both chlorine and caustic soda are relatively high (Chenier 1992, DOW 1999).
impacted by changes in vinyl exports to Asia and Demand for sodium hydroxide may also be
weakness in the pulp and paper industry. impacted as pulp and paper mills increasingly look
Important Asian economies (e.g., Japan) will for cost-effective ways to recycle sodium
continue to drive demand for both these products hydroxide from spent pulping liquor. Currently,
and set the pace of new production facilities in however, most of these alternatives cannot
the United States. The fact that the United compete on a capital and cost basis with caustic
States remains competitive in the chlorine- soda production, and will only impact demand
caustic-vinyl cycle can be attributed to three when they become economically viable (EPA
factors: our large supplies of energy and raw 1995a, CHEMWK 1999).
materials (salt and ethylene), and our large-scale
economy. With the exception of Taiwan, world Chlorine is difficult to store and transport
scale vinyl plants are not being built in Asia economically. As a result, chlorine and caustic
(DOW 1999). soda are usually produced in close proximity to
end-users (primarily chemical manufacturers and
Other forces affecting the market for chlor- pulp and paper mills). Geographically, about 72
alkalis include environmental regulations aimed at percent of chlorine production takes place in
curtailing chlorine use. For example, restrictions chlor-alkali facilities located along the Gulf Coast;
on the production or disposal of products that other production occurs in the vicinity of pulp
require large amounts of chlorine (e.g., PVC, mills of the Southeast and Northwest.
chlorinated solvents) have had a negative impact
on the chlorine market. Several environmental 6.1.1 Manufacture of Chlorine and
groups and initiatives (e.g., International Joint Sodium Hydroxide
Commission of Great Lakes Water Quality) are
calling for a gradual phaseout or immediate ban Chlorine and Sodium Hydroxide Are Co-
on chlorine and chlorinated compounds as Products of Brine Electrolysis
industrial feedstocks, which is also impacting
commercial use of chlorine (CCC 1995, EPA Chlorine was first discovered in 1774 by the
1995a, CCC 1996, Ayres 1997). German chemist Scheele, and was identified as
an element in 1810 by an English scientist named
However, demand for PVC has been a Davy. Caustic soda, or sodium hydroxide, has
significant driver in the growth of chlorine use been an important industrial chemical since1853.
both in the United States and globally. The Until 1892 sodium hydroxide was produced by the
industrialization of Asia is expected to drive PVC reaction of slaked lime and soda ash. That year,
demand and chlorine growth well into the next the electrolysis of brine was discovered as a
century. Until a non-chlorine replacement for method of making both sodium hydroxide and
PVC is developed, demand will remain strong chlorine. Since the 1960s electrolysis has been
(DOW 1999). the predominant technique employed to
manufacture these two important chemicals
Demand for sodium hydroxide may also be (Chenier 1992, Orica 1999).
impacted by users switching to soda ash to avoid
shortages of sodium hydroxide (like the Although electrolysis of brine is the primary
worldwide shortage that occurred in the late production method, technologies for converting
1980s). Soda ash is very plentiful in the United aqueous hydrochloric acid to chlorine are also
States and is obtained almost entirely from natural used in the United States and Europe. A process

177
to convert anhydrous hydrochloric acid to caustic soda solution, which requires several
chlorine, developed jointly by Dupont and concentrative operations to achieve the purity
Kvarner Chemetics, was also recently unveiled. needed for industrial use. The caustic contains 2
Similar technology is also being marketed in to 3 percent NaCl, requiring further purification
Europe by DeNora, an Italian firm. for some industrial uses. The diaphragm cell is
also known to be a source of pollution from
Chlorine and sodium hydroxide are co-products asbestos fibers, the primary material of the
that are produced in roughly equivalent amounts diaphragm.
through electrolysis of common salt in a brine
solution (about 1.1 tons of sodium hydroxide for Because of these disadvantages, mercury
every ton of chlorine produced). Hydrogen is cathode cells began to compete with diaphragm
also produced in equal molar amounts with cells early in the twentieth century. Mercury
chlorine and caustic. Chemical demand for cells produce a much purer and extremely
hydrogen on the Gulf Coast is significant, and it is concentrated caustic product that can be used
often transported by pipeline long distances to without further treatment in most cases.
meet the needs of oil refineries. There is also an However, mercury has extremely serious
opportunity to use fuel cell technology to closely ecological impacts and when dispersed from
couple the hydrogen produced with electrical chemical process effluents, can enter the food
power units that can feed DC power to chlorine chain and lead to mercury poisoning in humans.
cells. Some demonstration units using this
technology are in operation outside the United Membrane cells are the most environmentally
States (DOW 1999). benign of all the cell technologies, and have
electricity requirements similar to those of
During electrolysis, two electrodes are immersed diaphragm cells. The caustic solution produced is
in a brine solution. When a source of direct also essentially salt-free and more concentrated
current is attached to the electrodes, sodium ions than that produced from diaphragm cells.
begin to move toward the negative electrode Chemical companies have been slow to adopt
(cathode) and chlorine ions toward the positive membrane technology because of operational
electrode (anode) (Sittig 1977, IND CHEM 1990, problems encountered in early installations, and
EPA 1995a, Orica 1999). because existing facilities are fully depreciated
but still functional (IND CHEM 1990, Ayres
If the primary products from salt electrolysis 1997).
remain in contact after formation, they can react
with each other to form oxygenated compounds Diaphragm and mercury cells include an anode
of chlorine. Three electrolytic processes are and cathode in contact with a brine solution. The
available and use different methods to keep the membrane cell cathode is only in contact with 20
chlorine produced at the anode separated from to 32 percent NaOH, with very low chloride
the caustic soda and hydrogen produced at the content. Features that distinguish the cells from
cathode. In historical order, these cells include each other include the method used to keep the
diaphragm cells, mercury cathode or "amalgam" three major products separated and unable to mix
cells, and membrane cells. Table 6-1 provides a (chlorine gas, sodium hydroxide, and hydrogen),
comparison of the various aspects of the three and the resulting product concentration (see
electrolysis cells, including electrical energy Figure 6-2). Hydrogen must be separated from
consumption. the chlorine gas as mixtures of these two gases
can be explosive.
Diaphragm cells use a simple and economical
brine system and require less electrical energy
than mercury cells. A primary disadvantage of
the diaphragm cell is the low concentration of the

178
Diaphragm cells account for 71 percent of domestic
production, mercury cells for 12 percent, and
membrane cells for 16 percent, with other methods
producing about 1 percent (CI 1999). Total
production costs for using cells are a function of raw Chemical Reaction in Salt Electrolysis
materials, energy, operating costs, and capital
depreciation. Today, membrane cell technology is 2NaCl + 2 H2O 62NaOH + Cl2 + H2
only a small factor in new capacity. Membrane cell Salt Water Sodium Chlorine Hydrogen
technology requires a secondary brine treatment, Hydroxide
disposal or recycling of spent anolyte, and has
relatively high capital costs. Most diaphragm cell
producers continue to rebuild their existing diaphragm
cells, rather than convert to membranes.

Table 6-1. Characteristics of Various Chlorine/Sodium Hydroxide Electrolysis Cells

Component Diaphragm Cell Mercury Cell Membrane Cell

Cathode Steel/steel coating with Mercury flowing over steel Steel or nickel with a
nickel nickel-based coating

Anode Titanium with ruthenium Titanium with ruthenium Titanium with ruthenium
and titanium oxide and titanium oxide and titanium oxide
coatings; iridium oxide coatings; iridium oxide coatings; iridium oxide
added to improve added to improve added to improve
performance and extend performance and extend performance and extend
life life life

Diaphragm/ Asbestos and fibrous None Ion-exchange membrane

Membrane Material polytetrafluoroethylene (fluorinated polymers)

Cathode Product 10 to15% sodium Sodium amalgam (sent for 30-33% sodium
hydroxide solution, further processing through hydroxide solution (sent
containing 15 to17% salt a decomposer cell) to evaporator for further
(NaCl) (sent to evaporator processing); hydrogen
for further processing); gas
hydrogen gas

Anode Product Chlorine gas containing Chlorine gas containing Chlorine gas containing
some oxygen, salt, water some oxygen, salt, and some oxygen, salt, and
vapor, and sodium water vapor water vapor
hydroxide

Evaporator/Decom- 50% sodium hydroxide 50% sodium hydroxide 50% sodium hydroxide
position Product solution containing 1% solution; hydrogen gas solution with very little
salt; solid salt from salt
evaporator

Electricity 2,550 to 2,900 kWh/ton 3,250 to 3,450 kWh/ton 2,530 to 2,600 kWh/ton
Consumption chlorine gas chlorine gas chlorine gas

Sources: Sittig 1977, EPA 1990, EPA 1992b, EPA 1995b, DOW 1999.

179
 Figure 6-2. Comparison of Chlorine/Sodium Hydroxide
Electrolysis Cells (IND CHEM 1990, EPA 1995a)

Chlorine

Saturated Anode (+)

brine
Mercury
Ions (Na +) Cell
Depleted Cathode (-)
brine Na-Hg amalgam

Amalgam
Mercury in to decomposer

Chlorine Hydrogen

Saturated
Sodium
brine ions (Na +)

Chloride Hydroxy Diaphragm

ions (Cl -) ions (OH -)
Cell

Anode Brine Cathode

(+) (-)

Dilute caustic soda

Diaphragm and sodium chloride

Chlorine Hydrogen
Saturated Water
Sodium
ions (Na +)
brine

Chloride
ions (Cl -) Membrane
OH - Cell
Depleted
Anode Cathode
brine (+) (-)

Concentrated
Ion-exchange caustic soda
membrane

180
In a diaphragm cell, multiple cells containing an The overall process flow is shown in Figure 6-4.
anode and cathode pair are mounted vertically Brine flows continuously into the anode chamber
and parallel to each other (see Figure 6-3). and then through the diaphragm to the cathode.
Cathodes are usually a flat hollow steel mesh or Chlorine gas is formed at the anodes, and
perforated steel sheet covered with asbestos sodium hydroxide solution and hydrogen gas are
fibers and fibrous polytetrafluoro-ethylene formed directly at the cathode. By allowing
(PFTE), and function as the diaphragm. The liquid to pass through to the cathode, but not the
mix of fibers is typically about 75 percent fine chlorine gas bubbles, the diaphragm
asbestos and 25 percent PFTE. The anode is prevents the mixing of hydrogen and chlorine.
usually constructed of titanium plates covered The diaphragm also limits the back-diffusion of
with layers of Group VIII oxides with metal hydroxide ions formed at the cathode. The
conductivity (ruthenium oxide, titanium oxide). back-migration of hydrogen

Figure 6-3. Typical Diaphragm Cell (Chenier 1992)

181
 Figure 6-4. Diaphragm Cell Process (IND CHEM 1990, EPA 1992b, EPA 1995a)

Key Energy and Environmental Facts - Diaphragm Cell Process

Energy Emissions Effluents Wastes/Byproducts

Net Electricity use: Largest source - fugitive Largest source - wash water Scrapped diaphragms (lead,
and point source from chlorine processing asbestos) and cell parts
4,649 Btu/lb chlorine emissions (chlorine (spent sulfuric acid, which is
2,725 kWhr/ton chlorine gas, carbon dioxide, reclaimed and reused)
carbon monoxide,
hydrogen, and Freon)

ions across the diaphragm represents the most cells will have dissolved air and carbon dioxide that
inefficient aspect of the cell. The hydrogen gas and enter with the brine, and leave the process via
chlorine gas are drawn off separately from the top chlorine purification.
of the cell, and the residual brine containing 10 to 15
percent sodium hydroxide is taken from the bottom Demand for purified chlorine is high, and
of the cell. After being de-humidified and cooled, represents the largest share of chlorine produced.
the hydrogen is sent to storage. For a less pure Purified chlorine is produced by compressing and
product, the chlorine is first cooled (using a Freon cooling the gas to a liquid state. The liquid chlorine
or similar refrigerant), then washed with sulfuric is fractionally distilled to remove chlorinated tars
acid in a packed column to dry it. The spent called “taffy” in the heavy fraction. The light
sulfuric acid is recovered and reused. Diaphragm fraction contains inerts such as air, carbon dioxide,

182
and impurities such as bromine and iodine. into the cell cover and suspended horizontally in
Gaseous chlorine is transferred for use by pipeline the brine solutions. The height of the anodes in the
or liquid chlorine is transported by rail car to offsite brine is adjusted to obtain an optimum distance
customers (DOW 1999). Rail cars and barges are from the mercury cathode.
generally purged with nitrogen to remove the
chlorine and the chlorine is scrubbed in a tower In the electrolyzer, chlorine evolves from the
with caustic. The resulting hypochlorite is treated electrolytic decomposition of NaCl and moves
with bisulfite and the effluent is treated for disposal. upward through gas extraction slits in the cell
cover. The chlorine gas is removed, purified, and
The dilute sodium hydroxide solution contains sent to storage. Sodium ions are absorbed in the
residual salt and must undergo an evaporative mercury layer, and the resulting sodium and
process to produce a product at a usable mercury mixture (amalgam) is sent on to the
concentration. The greatest disadvantage to decomposer cell.
diaphragm cells is the large amount of salt that must
be removed at this stage. The need for salt The decomposer is essentially a short-circuited
columns, centrifuges, cyclones, clarifiers, and filters galvanic cell and consists of a small cylindrical
increases the complexity, capital cost, and energy steel tower divided into two parts. The amalgam
use in a diaphragm-based caustic plant (DOW is semi-decomposed in the upper section, and the
1999). decomposition is then completed in the lower part.
Graphite serves as the anode and amalgam serves
Figure 6-5 shows the general arrangement for the as the cathode. The amalgam and water flowing
concentration and production of the final sodium through the cell come into direct contact with the
hydroxide product. This process concentrates the graphite. In both parts of the tower the amalgam
cell liquor from the diaphragm cell by evaporating is decomposed by water with the formation of
water from the dilute caustic and separating the sodium hydroxide, the reformation of mercury, and
residual salt. The end result is a 50 percent sodium the production of hydrogen gas.
hydroxide solution with 1 percent residual sodium
chloride. The mercury generated can be reused in the
primary electrolytic cell. A relatively highly
The advantage of diaphragm cells is that they concentrated (50 percent) solution of sodium
operate at a lower voltage than mercury cells and hydroxide is formed and can be used as it is or
use less electricity. The brine feedstock can also after it is further concentrated. The hydrogen gas
be less pure than that required by mercury or is purified and used elsewhere in the plant.
membrane cells.
The depleted brine leaving the cell contains a high
The mercury cell process (see Figure 6-6) uses concentration of NaCl (21 to 22 percent by
two cells: an electrolyzer cell and a decomposer weight). Dissolved chlorine is removed from this
cell. The electrolyzer is essentially an electrolysis solution, and it is resaturated with NaCl and
cell consisting of a large steel container shaped like purified for re-use. The high concentration of
a rectangular parallelogram with lined walls under a sodium hydroxide solution produced and the
covering of flexible and anti-explosive rubber. A absence of residual salt are the major advantages
thin layer of mercury of about 3 millimeters in depth of the mercury cell. No further evaporation or salt
flows over the bottom of the steel container, serving separation is needed to produce the finished
as the cathode for the process. A saturated brine product. However, mercury cells require higher
solution of about 25 percent NaCl by weight flows voltage than both diaphragm and membrane
through the container above the mercury.

The anode, consisting of titanium sheet coated with

ruthenium oxide and titanium oxide, is incorporated

183
 Electrolysis Cell
Liquor (10-15%
Sodium Hydroxide

Water
Vapor
Steam
Sodium Hydroxide Emissions
(Caustic)
Evaporation

Condensate to Boiler

Salt Removal System Primary Product 50% Sodium

(salt columns,
centrifuges, cyclones, Hydroxide
clarifiers, filters) (1% Nacl)
Caustic
Concentration 70-74%
Sodium
Recovered Hydroxide
Salt (NaCl) Caustic Fusion and
Flaking Anhydrous
Sodium
Hydroxide

Figure 6-5. Sodium Hydroxide (Caustic) Evaporation Process

(Sittig 1977, IND CHEM 1990, Chenier 1992, EPA 1992b, Orica 1999)

cells, and use more energy. The process also from these plants. However, precautions are
requires as input a very pure brine solution taken to prevent releases of mercury to the
without metal contaminants. environment. Liquid effluents from the mercury
process are treated with sodium sulfide to
There are also environmental consequences to remove mercury before any discharge. The
the use of mercury. Through contaminated mercury compounds are combined with brine
effluents it can enter the food chain via plankton treatment sludges for further treatment and
and accumulate in the adipose tissue of fish. Fish disposal. Traces of mercury occur in caustic
products can then act as a vehicle in conveying soda and hydrogen generated from the mercury
mercury compounds with neurotoxic properties cell process. These are removed from caustic
(e.g., mercury poisoning). Tremendous soda by filtration. With hydrogen, they are
improvements in the cell technology have removed by cooling followed by absorption with
significantly reduced emissions activated carbon (Orica 1999, DOW 1999).

184
 Figure 6-6. Mercury Cell Process
(IND CHEM 1990, EPA 1992b, EPA 1995a, Orica 1999)

Key Energy and Environmental Facts - Mercury Cell Process

Energy Emissions Effluents Wastes/Byproducts

Net Electricity use: Largest source - Largest source - wastewater from Spent graphite from
fugitive and point brine pumps, cell wash water, decomposer cells, spent
Gross: 5,715 Btu/lb chlorine source emissions sumps (small amounts of caustic filtration cartridges from
3,350 kWhr/ton chlorine (chlorine, Freon, and mercury); chlorine processing the filtration of caustic soda
mercury) wastewater (sulfuric acid) solution, spilled mercury from
sumps, and mercury cell
“butters”

185
In a membrane cell the anode and cathode are Disadvantages of the membrane cell include the
separated by a water-impermeable, ion-conducting need for processing of the chlorine gas to remove
membrane (see Figure 6-7). In this process the oxygen and water vapor, and for moderate
brine solution flows through the anode evaporation to increase the concentration of the
compartment and chlorine gas is generated at the caustic solution. Another disadvantage is that the
anode. Sodium ions migrate through the brine entering a membrane cell must be of very
membrane to the cathode compartment, where high purity to prevent contamination of the
sodium hydroxide solution is flowing. Water membrane, which requires costly purification of
hydrolizes at the cathode and releases hydrogen the brine prior to electrolysis. The membrane
gas and hydroxide ions. separator in these cells is expensive and easily
damaged, and has a shorter lifetime than
The combination of sodium and hydroxide ions diaphragm and mercury separators.
produces sodium hydroxide which reaches a
concentration of about 30 to33 percent before 6.1.2 Brine Production
leaving the cell. The membrane preferentially
passes positive sodium ions from the anode Brine Production and Purification Are
chamber to the cathode chamber. Negatively Required for All Cells
charged chloride and hydroxide ions are primarily
rejected by the membrane. As a result, the Regardless of the type of cell employed, a
sodium hydroxide solution typically contains less suitable brine must be prepared prior to entering
than 100 ppm NaCl. The depleted brine leaves the cell. Different levels of purification are
the anode compartment and is resaturated with required for the various cells, and some require
salt for reuse in the membrane cell. removal of metals or other impurities.

Stainless steel or nickel is typically used as a Salt is obtained from the mining of natural
cathode in the membrane cell. The cathodes are deposits or from seawater (via solar evaporation),
also often coated with a catalyst (nickel-sulfur, and contains impurities that must be removed
nickel-aluminum, nickel-nickel oxide, platinum before it can be used in the electrolytic cell.
group metals) to increase surface area and reduce Impurities include primarily calcium, magnesium,
the hydrogen evolution potential. Anodes are barium, iron, aluminum, sulfates, and trace
similar to those used in both diaphragm and metals. Impurities can negatively affect the
mercury cells (ruthenium and titanium oxide on electrolytic cell by precipitating out and blocking
titanium). or damaging membrane or diaphragm materials.
Impurities can also poison the catalytic coating on
The membrane’s material and design are critical to the anode and cathode. In the case of the
cell operation. Membranes must maintain stability mercury cell, some trace metals (e.g., vanadium)
after exposure to both chlorine and strong caustic can reduce efficiency and cause the production
solution. They require low electrical resistance of potentially dangerous amounts of hydrogen
and must allow the transport of sodium ions but not gas. Impurities can also lead to the production of
chloride ions. Membrane materials currently in chlorinated compounds, a situation that can
use are fluorinated polymers with pendant negatively impact cell performance (EPA 1995a).
functional groups that make them ion-selective.
The first phase of brine preparation includes the
The advantage of membrane cells is the relatively dissolution of sea salt and rock salt in a water and
pure sodium hydroxide solution produced and the dilute brine mix (see Figure 6-8). The amount of
lower electricity requirements than either material dissolved is a function of brine
diaphragm or mercury cells. In addition, concentration, residence time, and temperature.
membrane cells do not require the use of toxic In all cases the brine-solid salt mixture is allowed
materials (e.g., asbestos, mercury). to reach equilibrium so that a saturated solution of

186
approximately 25 weight percent is produced. Sulfate levels in the brine can be controlled by
Purification is accomplished through two steps: adding calcium chloride to a side stream to
precipitate the sulfate as calcium sulfate. The
C The addition of Na2 CO3 (soda ash) and NaOH sludge containing this compound can then be
(caustic soda) to precipitate Ca2+ , Mg2+ , Fe3+ , removed and disposed of in a landfill. In some
and Al3+ ions cases the brine is evaporated to a solid salt to
C The addition of NaOCl if there is any ammonia remove sulfates (DOW 1999, Orica 1999).
present, and CaCl2 to eliminate (SO 2-)4 ions

High Purity Brine Brine Resaturation

Water

Hydrogen Gas (H2) Recovered

Chlorine Gas (Cl2), Membrane
Electricity Salt (NaCl)
Oxygen, Water Vapor Cell

Cell Liquor (32-35%

Sodium Hydroxide) Liquor Recirculation 50% Sodium
Liquor Evaporation
Condensate Hydroxide
Steam/Fuel (1% Nacl)
Salt
Sulfuric Slurry
Acid
Solution Liquor Separation
Brine Recycle

Chlorine Processing
Purified
Chlorine
Hydrogen Processing Purified
Activated Hydrogen
Carbon

Figure 6-7. Membrane Cell Process

(IND CHEM 1990, EPA 1992b, EPA 1995a, Orica 1999)

Key Energy and Environmental Facts - Membrane Cell Process

Energy Emissions Effluents Wastes/Byproducts

Net Electricity use: Largest sources - fugitive and Largest source - chlorine Scrapped cell parts
point source emissions processing wastewater (used membranes,
4,375 Btu/lb chlorine (chlorine and Freon) (sulfuric acid); ion- anodes, cathodes)
2,565 kWhr/ton chlorine exchange wash water.

187
 Water
Salt Mining By
Solution Electricity

Water Salt Dissolving/

Make- Up Brine Sodium
Carbonate/
Calcium
Brine Purification Chloride
Caustic
and Filtration
Soda/Soda Sludge/
Recycle Ash
Salt
Brine Mud

Steam/Fuel
Brine Heating

Purified Brine to
Electrolysis Cells

Figure 6-8. Brine Purification (Sittig 1977, EPA 1995a)

Key Energy and Environmental Facts - Brine Purification

Energy Emissions Effluents Wastes/Byproducts

Net Energy use: Largest sources - heater Recycle brine/brine Brine mud (magnesium hydroxide,
stack gas (CO, SOx, NOx, purge calcium carbonate, and barium
1,424 Btu/lb chlorine hydrocarbons, and sulfate; mercury in elemental form
particulates) or as mercuric chloride; calcium
sulfate; mercury sulfide)

Purification creates a precipitation sludge (brine feed the cells. Sand filters are commonly used
mud) that is washed to recover entrained sodium for clarification and filtration.
chloride and then disposed of in a landfill. If the
mercury process is used, brine purification sludges Brine for mercury and diaphragm processes
will contain trace levels of mercury. In this case contains less than 4 parts per million (ppm)of
the sludge is treated with sodium sulfide to bind the calcium and 0.5 ppm of magnesium. Membrane
mercury as mercury sulfide (an insoluble cell processes require a more purified brine (less
compound) and the sludge may be further bound by than 20 parts per billion of magnesium and
casting the sludge into concrete blocks. These calcium combined), which is usually passed
blocks are tested for leachability and then disposed through ion exchange columns to remove
of into a controlled landfill. impurities to the needed level.

The second step in brine preparation includes After purification the purified brine is heated to
clarification, filtration, the addition of recycled brine, bring it up to the correct process temperature for
adjustment of pH value, and collection into tanks to each cell (Sittig 1977, EPA 1995a).

188
 Table 6.2 Average Operating Conditions for Cells
Brine Limits on Impurities
Concen-
Cell Type tration (g//l) CaO MgO SO2 Temperature pH
o
F

Diaphragm 315-330 5 ppm 0.8 ppm 0-0.3 g/l 194-221 10.5 - 11

Mercury 300-320 < 5 ppm < 3 ppm < 2g/l 165 -185 3-5

Membrane ~ 445 nila nila nil 165 - 195 7

a
less than 20 parts per billion of calcium and magnesium combined.

Sources: IND CHEM 1990, Ayres 1997.

6.1.3 Manufacture of Soda Ash solution is then treated with carbon dioxide to
precipitate out sodium carbonate. The crystals are
Trona Ore Is the Feedstock for U.S. Soda then dissolved again in water, precipitated with
Ash Production carbon dioxide, and filtered. Calcining is then
employed to produce a dense soda ash.
In 1864, a Belgium chemist named Ernest
Solvay invented the ammonia-soda or Solvay All other methods of trona ore mining require
process for manufacture of sodium carbonate blasting. A combination of prilled ammonium
(soda ash). While this process is still popular nitrate and fuel oil is the most commonly used
world-wide, in the United States all soda ash is blasting agent. In this process the trona ore is
produced from natural trona ore. In the 1940s, crushed, dissolved in water, filtered to remove
large deposits of this ore were found in insoluble impurities, subjected to vacuum
Wyoming, which ultimately led to the closing of crystallization to precipitate sesquicarbonate, then
the last Solvay process plant in 1986. calcined to produce sodium carbonate.
Conversion from the synthetic Solvay process to
natural soda ash has been touted as one of the Alternatively, a monohydrate process is employed.
most successful transformations of the chemical In this process crushed trona ore is calcined in a
industry during the 1970s and 1980s (Chenier rotary kiln, yielding dense soda ash and carbon
1992). dioxide as byproducts. The calcined material is
combined withwater to settle out impurities, and is
Trona ore, also called sesquicarbonate, is a then concentrated using triple effect evaporators
complex of sodium, carbon, hydrogen, and or mechanical vapor recompression. For every
oxygen (2NA2 CO3 •NAHCO3 •2H 2 0). Upon pound of soda ash created in this process, 0.42
heating it produces soda ash and carbon dioxide pounds of carbon dioxide are also produced and
(see Figure 6-8). Approximately 1.8 tons of vented to the atmosphere (Brown 1996, EPA
trona ore are required to produce one ton of 1997g, EIA 1998).
soda ash.

There are four methods currently used to mine

Wyoming trona ore: 1) solution mining, 2) room-
and-pillar, 3) longwall, and 4) shortwall. In
solution mining, dilute sodium hydroxide is
injected into the trona ore to dissolve it. The

189
 Water
Electricity

Trona Ore Dissolving/

Crusher Clarification Thickener Filter Sludge
Unit

Electricity
Waste
Water
Cooling
Electricity Waste Water Vacuum
Sludge Condensed
Crystallizer
Vapors
Electricity/SteamAir
Cooling/
Calciner Dewatering
Cooling
Water Soda Ash
(30% Solids)
Solid Soda C O2
Waste
Electricity
Water
Ash

Figure 6-8. Manufacture of Soda Ash (Brown 1996)

Key Energy and Environmental Facts - Soda Ash Manufacture

Energy Emissions Effluents Wastes/Byproducts

Net Energy use: Largest sources - carbon Waste water Clarification sludge,
dioxide, boiler emissions, condensed vapors
3,393 Btu/lb particulates (soda ash)

6.2 Summary of Inputs and Chlorine/Sodium Hydroxide

Outputs
Inputs: Outputs:
The following is a summary of inputs and
Purified Brine Chlorine
outputs for important chemicals of the chlor-
Sulfuric Acid Sodium Hydroxide
alkali industry.
Hydrochloric Acid Hydrogen
Water Recycle Brine
Electricity Water Vapor
Steam Sludge
Cooling Water Process Water
Anode/Cathode Salt
Materials

190
Soda Ash For every category, energy use for process heat is
distributed according to the various fuel types used
throughout the industry. Fuel distribution for 1997
Inputs: Outputs:
was as follows: fuel oil and LPG - 3 percent;
Trona Ore Soda Ash natural gas - 77 percent; coal and coke - 10
Cooling Water Carbon Dioxide percent; other - 10 percent (CMA 1998). The
Steam/Fuel Condensed Vapors “other” category includes any other fuel source
Electricity Waste Sludge (e.g., byproduct fuel gases).
Air Waste Water
Among the three types of chlorine cells, the
Brine Purification mercury cell is the most energy-intensive, with
electricity requirements of nearly 3600 kWhr per
metric ton of chlorine. The membrane cell is the
Inputs: Outputs: least energy-intensive in terms of both steam and
electricity requirements. Steam requirements are
Salt Purified Brine less than half those of the diaphragm or mercury
Water Brine Mud/Sludge cell. Electricity requirements for the membrane
Make-up Brine cell are in the range of 2800 kWhr per metric ton
Sodium Carbonate of chlorine. The diaphragm cell is intermediate
Caustic Soda/ between these energy consumption ranges.
Soda Ash
Steam/Fuel
Overall, the electrical energy requirements for
Electricity
chlorine electrolysis cells are high, accounting for
nearly 130 trillion Btu annually. When losses due
to transmission and generation of electricity are
6.3 Energy Requirements considered, they reach nearly 400 trillion Btu
annually. Thus, efficient operation of the cell is
critical to optimized energy use and cost-effective
Electricity Is the Largest Energy Source
production. Sources of energy losses in chlorine
Used for Production of Chlorine and
cells include anode or cathode overvoltage, too
Sodium Hydroxide
large a drop across the diaphragm, oxygen
Data on the process energy used for the co- evolution on the anode, and failure to recover heat
and energy from hydrogen, chlorine, and cell liquor
production of chlorine and sodium hydroxide
streams.
is shown in Table 6-3. Electricity fuels the
electrolysis process and represents the primary
A key consideration in membrane processes is the
energy source. The amount of electricity
purity of the brine. Using very pure brine at an
required depends on the design of the cell, the
optimum flow rate minimizes blockage through the
design operating current, concentration of
membrane and allows sodium to penetrate freely.
electrolytes, temperature, and pressure. The
Brine purity is also important in mercury cells.
values shown in Table 6-3 represent an average
Impurities tend to increase hydrogen by-product
of energy consumption for the various cell types.
and reduce the current efficiency.
Energy in the form of fuels or steam is used
primarily for evaporation of the sodium
Another issue is brine flowrate. Flowrates that
hydroxide solution to a useable state. Some
are too high increase cell temperature and
fuels are also consumed in the production and
electrical conductivity of the medium. Brine rates
purification of brine feedstock before it is sent to
that are too low create temperatures and high cell
the electrolysis cell.
voltages that are higher than the most efficient
voltage (3.1 to 3.7 volts) (Sittig 1977, Orica 1999).

191
 Table 6-3. Estimated Energy Use in Manufacture of
Chlorine/Sodium Hydroxide (Caustic Soda) Co-Products - 1997
Specific Energyd Average Specificd Total Industry Use e
Energy (Btu/lb of Cl 2) Energy (1012 Btu)
(Btu/lb of Cl 2)

Electricitya 4,353 - 5,561 4,957 128.8

Fuel Oil and LPGb 62 - 112 87 2.3

Natural Gas 1,601 - 2,880 2,240 58.3

Coal and Coke 208 - 374 291 7.6

Otherc 208 - 374 291 7.6

NET PROCESS ENERGY 6,432 - 9,301 7,867 204.5

Electricity Losses 9,039 - 11,547 10,293 267.6

Energy Export 0 0 0.0

TOTAL PROCESS 15,471 - 20,848 18,160 472.2

ENERGY

a Does not Include losses incurred during the generation and transmission of electricity. Conversion factor: 3412
Btu/kWh. Based on range of cell currents for diaphragm, mercury, and membrane cells. Includes electricity for brine
purification.
b Includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed (e.g., renewables).
d Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for diaphragm, mercury, and membrane cell technologies . Includes
steam for brine purification and caustic evaporation (Sources: IND CHEM 1990, Brown 1996, Orica 1999, Ayres
1999).
e Calculated by multiplying average energy use (Btu/lb) by1997 production values for chlorine (26 billion lbs) (CMA
1998). Note that 1.12 to1.43 lbs of sodium hydroxide are produced for every lb of chlorine.

At present, U.S. chlorine production is vacuum crystallization of the trona solution to

dominated by the diaphragm cell, and the use of produce an initial 30 percent solids solution of
the more energy-intensive mercury cell sodium carbonate, and for calcining. Electricity
continues to decline. In Europe, however, is used for dissolution, clarifying, thickening,
production is still dominated by use of the precipitation, dewatering, and calcining. Overall
mercury cell, although European manufacturers electricity use for this process is very low, about
have committed to build no new mercury cells in 127 Btu per pound of solid product. Annual
the future (Ayres 1997). energy use for producing sodium carbonate,
however, is considerable–over 80 trillion
Energy requirements for the manufacture of Btus–due to the large production value of nearly
sodium carbonate from trona ore are shown 24 billion pounds annually.
in Table 6-4. A large share of the energy
consumed is in the form of steam used for

192
 Table 6-4. Estimated Energy Use in Manufacture of
Sodium Carbonate (Soda Ash) From Trona Ore - 1997
Average Specificd Energy Total Industry Use e
Energy (Btu/lb) (1012 Btu)

Electricitya 127 3.0

Fuel Oil and LPGb 98 2.3
Natural Gas 2,515 59.6
Coal and Coke 327 7.7
Otherc 327 7.7
NET PROCESS ENERGY 3,393 80.4
Electricity Losses 264 6.3
Energy Export 0 0.0
TOTAL PROCESS ENERGY 3,657 86.7

a Does not Include losses incurred during the generation and transmission of electricity.
b Includes ethane, ethylene, propane, propylene, normal butane, butylenes, and mixtures of these gases.
c Includes net purchased steam, and any other energy source not listed (e.g., renewables).
d Steam/fuel use estimated based on current distribution of fuels in chemical plants (CMA 1998). Values are based on
published fuel use and electricity requirements for process based on trona ore (Brown 1996).
e Calculated by multiplying average energy use (Btu/lb) by1997 production values for sodium carbonate (23.7 billion lbs)
(CMA 1998).

6.4 Air Emissions factors for mercury emissions from chlor-alkali

production (EPA 1992b).
Chlorine Gas and Freon Are Primary Air
Emissions from Brine Electrolysis Diaphragm cells and membrane cells release
chlorine as fugitive emissions from the cell itself
Air emissions from brine electrolysis include and in process tail gases, which are wet-scrubbed
chlorine gas and freon emissions (both fugitive with soda ash or caustic soda to remove chlorine.
and point source) and other vapors. Fugitive The spent caustic solution from this wash is
emissions arise from cells, scrubbers, and vents neutralized and then discharged to water
throughout the system. While individual leaks treatment facilities (EPA 1992b, EPA 1995a).
may be minor, the combination of fugitive
emissions from various sources can be Mercury cells release small amounts of
substantial. In 1995, nearly 3 million pounds of mercury vapor and chlorine gas from the cell
chlorine fugitive and point source emissions were itself. Process tail gases from chlorine
reportedly released by the inorganic chemical processing, caustic soda processing, and
industry (EPA 1997c). These emissions are hydrogen processing also release small amounts.
controlled through leak-resistant equipment Mercury is removed from the hydrogen gas
modifications, source reduction, and programs to stream by cooling followed by absorption with
monitor such leaks. Table 6-5 lists emission activated carbon. (EPA 1992b, Orica 1999).

193
Before the hazards of mercury emissions were
fully recognized, actual emissions from mercury Production of sodium carbonate from trona ore
cells were as high as 3 kg per metric ton. also creates emissions of carbon dioxide, a
Mercury emissions from chlorine production have suspected greenhouse gas. Emission factors for
dramatically declined in response to tighter carbon dioxide emitted from this process are
regulations, better housekeeping, and technology given in Table 6-6. Additional carbon dioxide
improvements. However, there are considerable may be emitted as sodium carbonate is processed
variations in the estimated mercury emissions in other manufacturing processes (glass-making,
from chlorine manufacture (Ayres 1997). water treatment, flue gas desulfurization, soap
and detergent production, pulp and paper
making). Data is listed on releases of carbon
dioxide from these processes.
Varying Estimates of Mercury Emissions per
Ton of Chlorine Manufactured
According to a recent study (EIA 1998),
0.6 gram/metric ton (EPA 1992b) approximately 113 metric tons of carbon are
0.47 gram/metric ton (Habersatter 1991) released for every 1000 metric tons of soda ash
2.47 gram/metric ton (Manzone 1993) consumed in glass manufacturing or flue gas
2.50 gram/metric ton (Euro Chlor 1995)
3.00 gram/metric ton (SRI 1989) desulfurization. The same source indicates about
97 million metric tons of carbon released for
every 1000 tons of trona ore produced annually
for sodium carbonate production.

Brine preparation and caustic evaporation In 1997, reported annual emissions of carbon
processes release emissions through the dioxide from manufacture of sodium carbonate
combustion of fuels in process heaters and in were 1.08 million metric tons; emissions from use
boilers that produce process steam. When of sodium carbonate were 0.86 million metric
operating in an optimum condition and burning tons (EIA 1998). More than 88 percent of
cleaner fuels (e.g., natural gas, refinery gas), emissions from the use of sodium carbonate were
these heating units create relatively low emissions associated with flue gas desulfurization.
of SO x , NOx , CO, particulates, and volatile
hydrocarbon emissions. A table of emission Controlled and uncontrolled emissions of filterable
factors for combustion of fossil fuels in fired and total particulate matter from sodium
heaters and boilers is provided in Chapter 7, carbonate production processes are shown in
Supporting Processes. Table 6-7. Emissions of particulates from
calciners and dryers are most often controlled by
During the production of sodium carbonate, venturi scrubbers, electrostatic precipitators, or
particulate emissions are created from ore cyclones. The high moisture content of exiting
calciners, soda ash coolers and dryers, ore gases makes it difficult to use baghouse-type
crushing, screening and transporting, and product filters. Control of particulates from ore and
handling and shipping. Combustion products product handling systems, however, is often
(SO x , NOx , CO, particulates, and volatile accomplished by baghouse filters or venturi
hydrocarbons) are also emitted from direct-fired scrubbers. These are essential to the cost-
process heating units (ore calcining kilns, soda effectiveness of the process as they permit
ash dryers). Little data is available on capture and recovery of valuable product.
combustion products from these units, although
emissions from similar equipment are categorized
by the U.S. Environmental Protection Agency for
the mineral industries, in AP 42 Chapter 11,
Mineral Products Industry.

194
 Table 6-5 Mercury Emissions from Chlorine/Caustic Soda Manufacture
Mercury Gas Mercury Gas
(lb/ton of chlorine (grams/metric ton of
Source produced) chlorine produced)

Uncontrolled Hydrogen vent 0.0033 0.17

Controlled Hydrogen vents 0.0012 0.6

End Box 0.010 5.0

Source : EPA 1992b.

Table 6-6. Uncontrolled Emission Factors for Carbon Dioxide

from Sodium Carbonate Production
lb CO2/ton of
Process sodium carbonate

Trona ore process: rotary ore calciner 310

Trona ore process: fluid bed calciner 180

Rotary soda ash dryers 130

Source: EPA 1997g.

Table 6-7 Particulate Emission Factors for Sodium Carbonate Manufacture

Controlled Emissions Uncontrolled
(lb/ton of sodium carbonate) Emissions (lb/ton of
Source sodium carbonate)
Filterable Total

Ore mining 0.0033 no data 3.3

Ore crushing and screening 0.0021 0.0035 3.5

Ore transfer 0.0002 0.0002 0.2

Trona ore process: rotary calciner 0.72 0.73 72

Trona ore process: fluid bed calciner 0.043 no data 4.3

Rotary soda ash dryers 0.50 0.52 50

Fluid bed soda ash dryers/coolers 0.030 0.39 3.0

Soda ash screening 0.019 0.026 19

Soda ash storage/loading/unloading 0.0041 0.0051 5.2

Source: EPA 1997g.

195
6.5 Effluents Wastewater streams are generated from
mercury cells during the chlorine drying process,
Wastewater Is Treated To Remove brine purge, and from other sources. Mercury is
Chlorine and Acids Prior to Discharge present in the brine purge and other sources
(floor sumps, cell wash water) in small amounts.
Wastewater from diaphragm and membrane This mercury is generally present in
cells originates from caustic evaporation, chlorine concentrations ranging from 0 to 20 parts per
drying, washing of the ion-exchange resin, and million, and is precipitated out using sodium
from purification of salt recovered from hydrosulfide to form mercuric sulfide. The
evaporators. mercuric sulfide is removed through filtration
before the water is discharged (EPA 1995a,
Caustic evaporation, where the sodium Orica 1999).
hydroxide solution is concentrated to a 50 or 70
percent solution, evaporates about 5 tons of water Sodium carbonate manufacture creates
per ton of 50 percent caustic soda produced. The significant volumes of wastewater that must be
water vapor from the evaporators is condensed, treated prior to discharge or recycling to the
and in the case of the diaphragm process, will process. These may contain both mineral (e.g.,
contain about 15 percent caustic soda solution and shale) and salt impurities (EPA 1997g).
a relatively high salt content of 15 to 17 percent. Limitations for toxic or hazardous compounds
If sodium sulfate is not removed during the brine contained in these wastewaters are given by the
purification process, salt recovered from U.S. Environmental Protection Agency in 40
evaporators may be recrystallized to avoid buildup CFR, Chapter 1, Part 415, which was originally
of sulfate in the brine. If the salt is recrystallized, promulgated in 1974 and has been revised several
the wastewater may contain sodium sulfates. times since then. The chemicals in the chlor-
alkali industry and sodium carbonate are covered
Wastewater from membrane processes contains under Subparts F and O. Specific limitations for
caustic soda solution, but is virtually free of salt or restricted compounds and total suspended solids
sodium sulfates. Wastewater from caustic soda (TSS) are shown in Tables 6-8 through 6-10.
processing is usually neutralized with hydrochloric “BPT Standards” refers to the use of the best
acid, then lagooned and discharged to and or to practicable control technology currently available.
receiving ponds. “BAT” refers to the best available technology
economically achievable. “NSPS” refers to new
During chlorine gas processing, water vapor is source performance standards that apply to new
removed by scrubbing with concentrated sulfuric process water impoundment or treatment
acid. Between 6 kilograms and 35 kilograms of 79 facilities.
percent sulfuric acid wastewater is generated per
1000 kilograms of chlorine produced (EPA 1995a). Table 6-10 provides BPT limitations only for the
Most of this wastewater is shipped off-site for production of sodium chloride (the primary
processing into concentrated sulfuric acid or for input to chlor-alkali manufacture) by solution
use in other processes. The remainder is used for brine-mining. In this process water is pumped
pH control or discharged to water treatment into a salt deposit and a saturated salt solution is
facilities for disposal (EPA 1995a). removed that is about one-third salt. Provisions
are that no process wastewater pollutant may be
Ion-exchange wash water from membrane cell returned to navigable waters. The exception is
processes usually contains dilute hydrochloric acid unused bitterns (saturated brine solution
with small amounts of dissolved calcium, remaining after precipitation of sodium chloride),
magnesium, and aluminum chloride. This which may be returned to the body of water from
wastewater is usually treated along with other which the process brine solution was originally
acidic wastewaters by neutralization. withdrawn.

196
 Table 6-8. Effluent Pretreatment Standards: Mercury Cells
BPT Standards: BAT Standards: NSPS Standards:
Average of Daily Average of Daily Average of Daily
Values for 30 Values for 30 Values for 30
Effluent Consecutive Days Consecutive Days Consecutive Days
(lb/1000 lb product) (lb/1000 lb product) (lb/1000 lb product)

TSS 0.32 -- 0.32

Mercury 0.00014 0.00010 0.00010

Total Residual Chlorine -- 0.0019 0.0019

pH 6-9 6-9 6-9

Source: 40 CFR Chapter 1, Part 415, Inorganic Chemicals Manufacturing Point Source Category, Subpart F.

Table 6-9. Effluent Pretreatment Standards: Diaphragm Cells

BAT Standards: NSPS Standards:
BPT Standards: Average Average of Daily Average of Daily
of Daily Values for 30 Values for 30 Values for 30
Effluent Consecutive Days Consecutive Days Consecutive Days
(lb/1000 lb product) (lb/1000 lb product) (lb/1000 lb product)

TSS 0.51 -- 0.51

Copper 0.0070 0.0049 0.0019

Lead 0.010 0.0024 0.0019

Nickel 0.0056 0.0037 --

Total Residual -- 0.0079 0.0079

Chlorine

pH 6-9 6-9 6-9

Source: 40 CFR Chapter 1, Part 415, Inorganic Chemicals Manufacturing Point Source Category, Subpart F.

Table 6-10. Effluent Pretreatment Standards:

Production of Sodium Chloride by Solution Brine-Mining
BAT Standards: Average of Daily Values
Effluent for 30 Consecutive Days
(lb/1000 lb product)

TSS 0.17

pH 6-9
Source: 40 CFR Chapter 1, Part 415, Inorganic Chemicals Manufacturing Point Source Category, Subpart P.

197
6.6 Hazardous Wastes and formed when an excess of barium is used
during purification). Mercury is recovered
Byproducts from these wastes where possible, and the
remainder is disposed of in secure landfills to
Brine Mud Constitutes the Largest Solid
Waste Stream from Chlor-Alkali prevent migration of mercury, which can
Production cause significant damage to the environment.

Brine purification results in brine mud, one of Mercury cell brine muds may also contain
the largest waste streams from the chlor-alkali mercury in elemental form or as mercuric
industry. About 30 kilograms of brine mud are chloride. These muds are considered
generated for every 1000 kilograms of chlorine hazardous and must be disposed of in a
produced, but this varies with the purity of the RCRA Subtitle C landfill after treatment with
salt used to produce the brine. Pre-purified sodium sulfide, which creates an insoluble
salts, for example, will generate only about 0.7 to sulfide compound (EPA 1995a). Other brine
6.0 kilograms per 1000 kilograms of chlorine muds are segregated and stored in lagoons,
produced. The brine mud contains a variety of which are periodically dredged or drained and
compounds, typically magnesium hydroxide and covered over. The dredgings are usually
calcium carbonate formed during the addition of landfilled off-site.
compounds to purify the brine. The sludge or
brine mud containing these impurities must be The processing of hydrogen gas from
disposed of in a landfill (EPA 1995a, Orica mercury cells also creates hazardous waste.
1999). If a mercury process is being used, the In this process, small amounts of mercury
brine mud may contain trace levels of mercury. present in the hydrogen gas are extracted by
In this case, the sludge is treated with sodium cooling the gas. A large part of the
sulfide to create mercury sulfide, an insoluble condensed mercury is removed in this fashion
compound. The sludge is further treated by and returned to the electrolytic cell. Some
casting it into concrete blocks, which are treated facilities use activated carbon treatment to
for leachability and sent to a controlled landfill. further purify the hydrogen of mercury, and
the spent carbon is shipped off-site for
Both diaphragm and membrane cell disposal as a hazardous waste.
processes generate solid wastes from scrapping
of cell parts (cell covers, piping, used The effluents and solid wastes and hazardous
diaphragms, used membranes, cathodes, and wastes from chlor-alkali production are
anodes). Discarded cell parts are landfilled on- summarized in Table 6-11. Specific wastes
site or shipped off-site for disposal. Used from chlor-alkali manufacture that are listed
cathodes and anodes are shipped off-site to a by the EPA as hazardous as shown in Table
third party recovery facility. Depending on the 6-12. Most of the hazardous wastes are
cell technology, the cathodes may be refurbished generated from the mercury cell process.
and reused, particularly those made of nickel.
The anodes for diaphragm cells are refurbished The dissolving and clarification steps in
and rec-coated with RuO 2 /TiO2 and returned to sodium carbonate production create a
service. waste sludge containing non-hazardous
impurities, such as salts and minerals. This
Solid wastes from mercury cells include spent sludge is disposed of in landfills.
graphite from decomposer cells, spent caustic
filtration cartridges from the filtration of caustic
soda solution, spilled mercury from sumps, and
mercury cell “butters.” (The latter are semi-solid
amalgams of mercury with barium or iron,

198
 Table 6-11. Summary of Effluents and Solid and Hazardous Waste Streams
from Chlorine/Sodium Hydroxide Production
Diaphragm/ Chlorine/
Source Membrane Mercury Cells Caustic Hydrogen Brine
Cells Evaporation Processing Purification

Wastewater Ion-exchange Brine pumps, 5 tons 79% sulfuric

wash water, cell wash water/ton acid solution (6
cell wash water, sumps 50% caustic to 35 kg/1000 kg
water, brine (small amounts soda solution chlorine)
purge of mercury)

Solid Scrapped cell Spent caustic Brine mud

Wastes parts (cell filtration (0.7 to 30
covers, piping, cartridges from kg/1000 kg
used the filtration of chlorine)
diaphragms, caustic soda
used solution, spent
membranes, graphite from
cathodes, and decomposer
anodes) cells

Hazardous Chlorinated Spilled mercury Spent activated Brine mud

Wastes hydrocarbon from sumps, carbon containing
waste from the and mercury mercury
purification step cell “butters”; (K071)
of the dia- wastewater
phragm cell treatment
process (K073) sludge (K106)

Source: EPA 1995a.

Table 6-12. Hazardous Wastes from Chlor-Alkali Manufacture

Waste Hazardous Constituents
Classification Description

K071 Brine purification muds from the mercury cell Mercury

process in chlorine production, where
separately pre-purified brine is not used

K073 Chlorinated hydrocarbon waste from the Chloroform, carbon tetrachloride,

purification step of the diaphragm cell process hexachloroethane, trichloroethane,
tetrachloroethylene,
dichloroethylene, 1,1,2,2-
tetrachloroethane

K106 Wastewater treatment sludge from the mercury Mercury

cell process in chlorine production

Source: BNA 1995.

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