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Solvay process
The Solvay process or ammonia-soda process is the major industrial process for the production of sodium carbonate
(soda ash, Na2CO3). The ammonia-soda process was developed into its modern form by Ernest Solvay during the 1860s. The
ingredients for this are readily available and inexpensive: salt brine (from inland sources or from the sea) and limestone (from
quarries). The worldwide production of soda ash in 2005 has been estimated at 42 million metric tons,[1] which is more than
six kilograms (13 lb) per year for each person on Earth. Solvay-based chemical plants now produce roughly three-quarters of
this supply, with the remainder being mined from natural deposits. This method superseded the Leblanc process.

Contents
History
Chemistry
Byproducts and wastes
Carbon sequestration and the Solvay process
See also
References
Further reading
External links

History
The name "soda ash" is based on the principal historical method of obtaining alkali, which was by using water to extract it
from the ashes of certain plants. Wood fires yielded potash and its predominant ingredient potassium carbonate (K2CO3),
whereas the ashes from these special plants yielded "soda ash" and its predominant ingredient sodium carbonate (Na2CO3).
The word "soda" (from the Middle Latin) originally referred to certain plants that grow in salt solubles; it was discovered that
the ashes of these plants yielded the useful alkali soda ash. The cultivation of such plants reached a particularly high state of
development in the 18th century in Spain, where the plants are named barrilla; the English word is "barilla".[2][3][4] The ashes
of kelp also yield soda ash, and were the basis of an enormous 18th century industry in Scotland.[5] Alkali was also mined from
dry lakebeds in Egypt.

By the late 18th century these sources were insufficient to meet Europe's burgeoning demand for alkali for soap, textile, and
glass industries.[6] In 1791, the French physician Nicolas Leblanc developed a method to manufacture soda ash using salt,
limestone, sulfuric acid, and coal. Although the Leblanc process came to dominate alkali production in the early 19th century,
the expense of its inputs and its polluting byproducts (including hydrogen chloride gas) made it apparent that it was far from
an ideal solution.[6][7]

It has been reported that in 1811 French physicist Augustin Jean Fresnel discovered that sodium bicarbonate precipitates
when carbon dioxide is bubbled through ammonia-containing brines – which is the chemical reaction central to the Solvay
process. The discovery wasn't published. As has been noted by Desmond Reilly, "The story of the evolution of the ammonium-
soda process is an interesting example of the way in which a discovery can be made and then laid aside and not applied for a

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considerable time afterwards."[8] Serious consideration of this reaction as the basis of an industrial process dates from the
British patent issued in 1834 to H. G. Dyar and J. Hemming. There were several attempts to reduce this reaction to industrial
practice, with varying success.

In 1861, Belgian industrial chemist Ernest Solvay turned his attention to the problem; he was apparently largely unaware of
the extensive earlier work.[7] His solution, a 24 metres (79 ft) gas absorption tower in which carbon dioxide bubbled up
through a descending flow of brine. This, together with efficient recovery and recycling of the ammonia, proved effective. By
1864 Solvay and his brother Alfred had acquired financial backing and constructed a plant in Couillet, today a suburb of the
Belgian town of Charleroi. The new process proved more economical and less polluting than the Leblanc method, and its use
spread. In 1874, the Solvays expanded their facilities with a new, larger plant at Nancy, France.

In the same year, Ludwig Mond visited Solvay in Belgium and acquired rights to use the new technology. He and John
Brunner formed the firm of Brunner, Mond & Co., and built a Solvay plant at Winnington, near Northwich, Cheshire,
England. The facility began operating in 1874. Mond was instrumental in making the Solvay process a commercial success. He
made several refinements between 1873 and 1880 that removed byproducts that could slow or halt the process.

In 1884, the Solvay brothers licensed Americans William B. Cogswell and Rowland Hazard to produce soda ash in the US, and
formed a joint venture (Solvay Process Company) to build and operate a plant in Solvay, New York.

By the 1890s, Solvay-process plants produced the majority of the world's soda ash.

In 1938 large deposits of the mineral trona were discovered near the Green River
in Wyoming from which sodium carbonate can be extracted more cheaply than
produced by the process. With the closing of the original Solvay, New York plant in
1986, there have been no Solvay-based plants operating in North America.
Throughout the rest of the world the Solvay process remains the major source of
soda ash.
Solvay Process Plant in Solvay,
New York; the Erie Canal passed
Chemistry through this plant until about 1917.
From the Solvay Process collection
The Solvay process results in soda ash (predominantly sodium carbonate of the Solvay, New York, Public
(Na2CO3)) from brine (as a source of sodium chloride (NaCl)) and from limestone Library.
(as a source of calcium carbonate (CaCO3)).[7] The overall process is:

2 NaCl + CaCO3 → Na2CO3 + CaCl2

The actual implementation of this global, overall reaction is intricate.[9][10][11] A

simplified description can be given using the four different, interacting chemical
reactions illustrated in the figure. In the first step in the process, carbon dioxide
(CO2) passes through a concentrated aqueous solution of sodium chloride (table
salt, NaCl) and ammonia (NH3).

NaCl + CO2 + NH3 + H2O → NaHCO3 + NH4Cl (I)

In industrial practice, the reaction is carried out by passing concentrated brine Chemistry of the Solvay Process.
(salt water) through two towers. In the first, ammonia bubbles up through the Each circle represents a reaction.
brine and is absorbed by it. In the second, carbon dioxide bubbles up through the
ammoniated brine, and sodium bicarbonate (baking soda) precipitates out of the
solution. Note that, in a basic solution, NaHCO3 is less water-soluble than sodium chloride. The ammonia (NH3) buffers the
solution at a basic (high) pH; without the ammonia, a hydrochloric acid byproduct would render the solution acidic, and
arrest the precipitation. Here, NH4 acts as a "mother liquor".
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The necessary ammonia "catalyst" for reaction (I) is reclaimed in a later step, and
relatively little ammonia is consumed. The carbon dioxide required for reaction (I)
is produced by heating ("calcination") of the limestone at 950–1100 °C. The
calcium carbonate (CaCO3) in the limestone is partially converted to quicklime
(calcium oxide (CaO)) and carbon dioxide:

CaCO3 → CO2 + CaO (II)

The sodium bicarbonate (NaHCO3) that precipitates out in reaction (I) is filtered
out from the hot ammonium chloride (NH4Cl) solution, and the solution is then
reacted with the quicklime (calcium oxide (CaO)) left over from heating the
limestone in step (II).

The Solvay Process as an example

2 NH4Cl + CaO → 2 NH3 + CaCl2 + H2O (III)
of a cyclic process in chemical
industry (green = reactants, black =
CaO makes a strong basic solution. The ammonia from reaction (III) is recycled
intermediates, red = products)
back to the initial brine solution of reaction (I).

The sodium bicarbonate (NaHCO3) precipitate from reaction (I) is then converted
to the final product, sodium carbonate (washing soda: Na2CO3), by calcination (160–230 °C), producing water and carbon
dioxide as byproducts:

2 NaHCO3 → Na2CO3 + H2O + CO2 (IV)

The carbon dioxide from step (IV) is recovered for re-use in step (I). When properly designed and operated, a Solvay plant can
reclaim almost all its ammonia, and consumes only small amounts of additional ammonia to make up for losses. The only
major inputs to the Solvay process are salt, limestone and thermal energy, and its only major byproduct is calcium chloride,
which is sold as road salt.

In the modified Solvay process developed by Chinese chemist Hou Debang in 1930s, the first few steps are the same as the
Solvay process. However, the CaCl2 is supplanted by ammonium chloride (NH4Cl). Instead of treating the remaining solution
with lime, carbon dioxide and ammonia are pumped into the solution, then sodium chloride is added until the solution
saturates at 40 °C. Next, the solution is cooled to 10 °C. Ammonium chloride precipitates and is removed by filtration, and the
solution is recycled to produce more sodium carbonate. Hou's process eliminates the production of calcium chloride. The
byproduct ammonium chloride can be refined, used as a fertilizer and may have greater commercial value than CaCl2, thus
reducing the extent of waste beds.

Additional details of the industrial implementation of this process are available in the report prepared for the European Soda
Ash Producer's Association.[10]

Byproducts and wastes

The principal byproduct of the Solvay process is calcium chloride (CaCl2) in aqueous solution. The process has other waste
and byproducts as well.[10] Not all of the limestone that is calcined is converted to quicklime and carbon dioxide (in reaction
II); the residual calcium carbonate and other components of the limestone become wastes. In addition, the salt brine used by
the process is usually purified to remove magnesium and calcium ions, typically to form carbonates; otherwise, these
impurities would lead to scale in the various reaction vessels and towers. These carbonates are additional waste products.

In inland plants, such as that in Solvay, New York, the byproducts have been deposited in "waste beds"; the weight of material
deposited in these waste beds exceeded that of the soda ash produced by about 50%. These waste beds have led to water
pollution, principally by calcium and chloride. The waste beds in Solvay, New York substantially increased the salinity in

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nearby Onondaga Lake, which used to be among the most polluted lakes in the U.S.[12] and is a superfund pollution site.[13] As
such waste beds age, they do begin to support plant communities which have been the subject of several scientific
studies.[14][15]

At seaside locations, such as those at Saurashtra, Gujarat, India,[16] the CaCl2 solution may be discharged directly into the sea,
apparently without substantial environmental harm, the major concern is discharge location falls within the Marine National
Park of Gulf of Kutch which serves as habitat for coral reefs, seagrass and seaweed community. At Osborne, South
Australia,[17] a settling pond is now used to remove 99% of the CaCl2 as the former discharge was silting up the shipping
channel. At Rosignano Solvay in Tuscany, Italy the limestone waste produced by the Solvay factory has changed the
landscape, producing the "White Sands" beaches that are a fine sight for tourists, but cannot be used for bathing, due to the
concentration of toxic chemicals, especially mercury, in the water. According to a report published in 1999 by the United
Nations Environment Programme, the Spiagge Bianche has been among the 15 most polluted coastal sites on the
Mediterranean Sea.

Carbon sequestration and the Solvay process

Variations in the Solvay process have been proposed for carbon sequestration. One idea is to react carbon dioxide, produced
perhaps by the combustion of coal, to form solid carbonates (such as sodium bicarbonate) that could be permanently stored,
thus avoiding carbon dioxide emission into the atmosphere.[18][19] Variations in the Solvay process have been proposed to
convert carbon dioxide emissions into sodium carbonates, but carbon sequestration by calcium or magnesium carbonates
appears more promising. However, the amount of carbon dioxide exhausted by mankind as compared to the amount which
can be used for carbon sequestration with calcium or magnesium is very low. Moreover, variation on the Solvay process will
most probably add an additional energy step, which will increase carbon dioxide emissions.

See also
Chloralkali process

References
1. Kostick, Dennis (2006). "Soda Ash" (http://minerals.usgs. 4. Grieve, M. (1931). A Modern Herbal, ISBN 0-486-22798-
gov/minerals/pubs/commodity/soda_ash/soda_myb05.pd 7 & 0486227995. See section on glasswort (http://www.b
f), chapter in 2005 Minerals Yearbook, United States otanical.com/botanical/mgmh/g/glassw18.html).
Geological Survey. See Table I. Retrieved October 21, 2005.
2. The barilla used for soda ash production refers to any of 5. Hothersall, Susan (2012). "The Scottish kelp industry
several bushy plants that are well adapted to grow in salt and its archaeology" (http://www.lahsoc.org.uk/journals/j
marshes, and that are common in Spain and Italy. The ournal_2012/6%20Kelp%20industry.pdf) (PDF). Historic
ashes of these plants can contain as much as 30% Argyll: 32–36.
sodium carbonate. The principal species for soda ash 6. Kiefer, David M. "It was all about alkali" (https://web.archi
production were the "saltworts" Salsola soda or Salsola ve.org/web/20021107104036/http://pubs.acs.org/subscri
kali, but several other species could also be used. be/journals/tcaw/11/i01/html/01chemchron.html). Today's
3. Pérez, Joaquín Fernández (1998). "From the barrilla to Chemist at Work. 11 (1): 45–6. Archived from the original
the Solvay factory in Torrelavega: The Manufacture of on November 7, 2002. Online version archived at
Saltwort in Spain," (https://www.webcitation.org/5W0IroD WebCite from this original URL (http://pubs.acs.org/subs
9s) Antilia: The Spanish Journal of History of Natural cribe/journals/tcaw/11/i01/html/01chemchron.html) on
Sciences and Technology, Vol. IV, Art. 1. ISSN 1136- 2008-03-12.
2049. Archived by WebCite from this original URL (http://
www.ucm.es/info/antilia/revista/vol4-en/ant4-1-en.htm)
on 2008-03-01.

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7. Kiefer, David M. (February 2002). "Soda Ash, Solvay 14. Cohn, E.V.J.; Rostanski, A.; Tokarska-Guzik, B.;
Style" (https://web.archive.org/web/20030120041011/htt Trueman, I.C.; Wozniak, G. (2001). "The flora and
p://pubs.acs.org/subscribe/journals/tcaw/11/i02/html/02c vegetation of an old Solvay process tip in Jaworzno
hemchron.html). Today's Chemist at Work. 11 (2): 87–88, (Upper Silesia, Poland)". Acta Soc. Bot. Pol. 70 (1): 47–
90. Archived from the original on January 20, 2003. 60. doi:10.5586/asbp.2001.008 (https://doi.org/10.5586%
Online version archived at WebCite from this original 2Fasbp.2001.008).
URL (http://pubs.acs.org/subscribe/journals/tcaw/11/i02/h 15. Michalenko, Edward M. (1991). "Pedogenesis and
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8. Reilly, Desmond (December 1951). "Salts, Acids & soils originating from chlor-alkali wastes," doctoral
Alkalis in the 19th Century. A Comparison between dissertation, State University of New York College of
Advances in France, England & Germany". Isis. 42 (4): Environmental Science and Forestry.
287–296. doi:10.1086/349348 (https://doi.org/10.1086%2 16. "Technology in the Indian Soda Ash Industry" (https://ww
F349348). JSTOR 226807 (https://www.jstor.org/stable/2 w.webcitation.org/5W0KjAKfk), Technology Status
26807). PMID 14888349 (https://www.ncbi.nlm.nih.gov/p Report #148 (October, 1995), Department of Scientific
ubmed/14888349). and Industrial Research (http://dsir.nic.in), Ministry of
9. Speight, James (2001). Chemical Process and Design Science & Technology, India. Archived by WebCite from
Handbook. McGraw Hill. doi:10.1036/0071374337 (http this original URL (http://dsir.nic.in/reports/techreps/tsr14
s://doi.org/10.1036%2F0071374337). ISBN 978-0-07- 8.pdf) on 2008-03-01.
137433-0. 17. Penrice Soda Holdings Limited (https://archive.today/201
10. "Process Best Practices Reference Document (BREF) 20910072845/http://www.penrice.com.au/company.htm).
for Soda Ash," (https://www.webcitation.org/5W0IxdohY) Retrieved 2006-10-14.
report produced by the European Soda Ash Producer's 18. Huijgen, W.J.J. and Comans, R.N.J. (February, 2003).
Association (http://www.cefic.be/templates/shwAssocDet "Carbon dioxide sequestration by mineral carbonation:
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Archived at WebCite from this original URL (http://www.c 2003/c03016.pdf) Report ECN C-03-016, Energy
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REF3.pdf) on 2008-03-01. n/). Retrieved 2006-10-14.
11. Moore, John T. Edd (2005). Chemistry Made Simple. 19. Lackner, Klaus S. (2002). "Carbonate Chemistry for
Broadway Books. p. 190. ISBN 978-0-7679-1702-5. Sequestering Fossil Carbon". Annual Review of Energy
12. Onondaga Lake Partnership (http://www.onlakepartners. and the Environment. 27 (1): 193–232.
org/p12036.html). Retrieved 2006-10-14. doi:10.1146/annurev.energy.27.122001.083433 (https://d
13. U.S. Environmental Protection Agency, superfund ID oi.org/10.1146%2Fannurev.energy.27.122001.083433).
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Further reading
Moffat, Wicky; Walmsley, M. R. W. (2006). "Understanding Lime Calcination Kinetics for Energy Cost Reduction" (http://w
ww.tappsa.co.za/archive2/Journal_papers/Understanding_lime_calcination/understanding_lime_calcination.html).
Technical Association of the Pulp and Paper Industry of South Africa. The minimum energy required to calcine limestone
is about 3.16 gigajoules (3.00 MMBtu) per tonne.

External links
European Soda Ash Producer's Association (ESAPA) (http://www.cefic.be/Templates/shwAssocDetails.asp?NID=473&HI
D=27&ID=60)
Timeline of US plant at Solvay, New York (http://www.onondaganation.org/land-rights/the-offenders/honeywell-onondaga-l
ake-a-timeline/)
Salt and the Chemical Revolution (http://www.saltassociation.co.uk/education/salt-history/salt-the-chemical-revolution/)
Process flow diagram of Solvay process (http://www.inclusive-science-engineering.com/sodium-carbonate-manufacturing
-synthetic-processes-chlor-alkali-industry/production-of-soda-ash-by-solvay-process/)

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