SODA ASH

(SODIUM CARBONATE)

Na2co3

Chemical formula: Na2CO3 O || Structural formula: Na -- O -- C -- O NA Common names: Sodium carbonate, calcined soda, disodium carbonate

TYPES OF PROCESS FOR MANUFACTURE OF SODA ASH

SOLVAY PROCESS DUAL PROCESS

EXTRACTION FROM NATURAL DEPOSITS

 Trona: Sodium Sesquicarbonate

Naturally occurring chemical: Na2CO3,NaHCO3,2H20
Green River Formation in southwest Wyoming = largest bedded trona resource

Trona currently mined for soda ash (Na2CO3) production

Na2CO3-NaHCO3 Solutions & CO2

Equilibrium established between CO2 in air and Na2CO3-NaHCO3 liquid

Na2CO3 + CO2 + H20 = 2NaHCO3

Want less than equilibrium value of NaHCO3 in solution

Two phase system with three components: Gibbs Rule

[Na+]; Temperature

Solvay process or Ammonia-soda process

The discovery of the chemistry of the ammonia-soda process can be traced back to the early 1800s. A few British and French plants operated in 1840-1860, but without success.

The ammonia-soda process is usually called the Solvay process because in 1865 Ernest Solvay started the first really successful plant at couillet in Belgium. In 1874, the first successful ammonia-soda plant was erected in England.
The ammonia-soda process isthe dominant technology used throughout the world, hence this process is selected forproduction of soda ash.

* SALT
* COAL
* LIME STONE * WATER * AMMONIA

1) MOLECULAR WEIGHT

106

2) MELTING POINT

851 C

3) BOILING POINT

DECOMPOSES

4) SOLUBLE IN WATER

Chemical reactions
Overall reaction
(a) CaCO3 + 2NaCl Na2CO3 + CaCl2

This reaction takes place in a number of steps

(b) CaCO3 CaO + CO2 (c) C + O2 CO2 (d) CaO + H2O Ca(OH)2 (e) NH3 + H2O NH4OH (f) NaCl + NH4OH NH4Cl + NaHCO3 (g) 2NaHCO3 Na2CO3 + CO2 + H2O (h) 2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2O

1) AMMONIATION 2) CARBONATION

3) FILTERATION
4) CALCINATION 5) AMMONIA RECOVERY

APPLIED PROCESS AND TECHNIQUES PROCESS

The SOLVAY process relative to the production of soda ash could be summarized by the theoretical global equation involving the two main components: sodium chloride and calcium carbonate. 2 NaCl + CaCO3 Na2CO3 + CaCl2

 In practice this direct way is not possible and it needs the participation of other substances and many different process steps to get the final product: soda ash. First reactions occur in salt solution (brine). First of all, ammonia is absorbed and then, the ammoniated brine is reacted with carbon dioxide to form successive intermediate compounds: ammonium carbonate , then ammonium bicarbonate . Chemical reactions are as follows..

NaCl + H2O + NH3 NaCl + NH4OH (1) 2 NH4OH + CO2 (NH4)2 CO3 + H2O (2) (NH4)2CO3 + CO2 + H2O 2 NH4HCO3 (3) 2 NH4HCO3 + 2 NaCl 2 NaHCO3 + 2 NH4Cl (4) Sodium bicarbonate crystals are separated from the mother liquor by filtration, then sodium bicarbonate is decomposed thermally into sodium carbonate, water and carbon dioxide . 2 NaHCO3 Na2CO3 + H2O + CO2 (5) CO2 is recovered in the carbonation step (see equations 2 and 3 above).

 Mother liquor is treated to recover ammonia. The ammonium chloride filtrate (4) is reacted with alkali, generally milk of lime (6), followed by steam stripping to recover free gaseous ammonia: 2 NH4Cl + Ca(OH)2 CaCl2 + 2 NH3 + 2 H2O (6) NH3 is recycled to the absorption step (see equation 1 above). Ammonia recovery cycle is shown in Figure 2. Carbon dioxide and calcium hydroxide originate from limestone calcination (7) followed by calcium oxide hydration (8). CaCO3 CaO + CO2 (7) CaO + H2O Ca(OH)2 (8)

 Brine (NaCl) has to be treated before the input in the process to remove impurities : calcium and magnesium. If not removed they would react with alkali and carbon dioxide to produce insoluble salts contributing to scale formation inside equipment. Brine purification reactions are described in the following equations: Ca2 + (CO3)2- CaCO3 (9) Mg2 + 2 OH- Mg(OH)2 (10)

 Sodium carbonate formed (equation 5) is called "light soda ash" because its bulk density is approximately 0.5 t/m3. A subsequent operation called densification enables this value to be doubled by crystallisation into sodium monohydrate, by adding water (equation 11) then followed by drying (equation 12). Final product is "dense soda". Na2CO3 + H2O -------- > Na2CO3.H2O (11) Na2CO3.H2O --------- > Na2CO3 + H2O (12)

Brine Preparation
Sodium chloride solutions are occasionally available naturally but are more often obtained by solution mining of salt deposits to give raw, near saturated brine containing low concentrations of impurities such as magnesium and calcium salts. Some brines contain significant quantities of sulfates. Brine purification is required to prevent scaling of processing equipment and contamination of the product. Brine is usually purified by a lime soda treatment where the magnesium is precipitated with Ca(OH)2 (milk of lime) and the calcium is precipitated with soda ash. The brine, separated from precipitated impurities, is sent to the ammonia absorbers.

Ammonia Absorption
The strong brine is saturated with ammonia gas in the absorption tower. The ammonia, recycled from various process steps, contains water vapour and carbon dioxide. Small amounts of ammonia are added to make up for losses. During ammoniation, the brine requires cooling (approx 1650 MJ/t or 394 kcal/kg of product soda ash). The absorption operation is generally carried out at atmospheric pressure. The brine descends through the main part of the absorber counter current to the Rising ammoniacal gases. The temperature of inlet brine is about 300C and that of exit is about 360 to 420C.

Precipitation of Bicarbonate
The ammoniated brine from the absorber coolers is pumped to the top of one column in a block of columns used to precipitate bicarbonate. This column which has been fouled or partially plugged with sodium bicarbonate after several days of crystallization is referred to as a cleaning column. Lime kiln gas, compressed to about 414 kPa (60psi), enters the bottom of the cleaning column and bubbles up through the solution to absorb most of the carbon dioxide. The concentration of carbon dioxide in the liquor is kept below the precipitation concentration. Relatively little cooling is required. The scale is dissolved off the cooling surfaces of the cleaning column by the fresh ammoniated brine, assisted by gas agitation.

Filtration of Bicarbonate
The slurry, collected from the crystallizing towers, is fed to continuous vacuum filters or centrifuges which separate the crystals from the filter liquor. The filter cake is carefully washed with fresh water to control the residual chloride to meet customer specifications. The dewatering characteristics of the bicarbonate crystals are very dependent on operating conditions in the crystallizing columns. Air drawn through the vacuum filter (or the vent gas from the centrifuge operation) is returned to the absorption section. The filter cake, often called crude bicarbonate or ammonia soda, liquor and is made up of sodium bicarbonate and small amounts (5 mol% on a dry basis) of ammonia primarily in the form of ammonium bicarbonate. The cake is then conveyed to the calcining operation.

Recovery of Ammonia
The filter liquor contains unreacted sodium chloride and substantially all the ammonia with which the brine was originally saturated, present as fixed and free ammonia. The fixed ammonia or ammonium chloride corresponds stoichiometrically to the sodium bicarbonate that had been precipitated. Free ammonia includes ammonium hydroxide, bicarbonate, carbamate, and the several possible carbon compounds of ammonia that decompose at moderate temperatures. Before preheating, sulfide solution may be added for corrosion protection. The sulfide is distilled for eventual absorption by the brine in the absorber. The filter liquor is preheated by indirect contact with the gases leaving the distiller.

Lime Preparation
The most suitable limestone, hard and strong with low concentrations of impurities, is graded to reasonably uniform coarse size. Although other fuels may be used, the limestone is usually mixed with about 7% metallurgical grade coke or anthracite and then burned in vertical shaft kilns. Air is admitted continuously into the bottom of the kiln an gas is sucked off the top. The fuel burns in a zone a little below the middle of the kiln, and the stone burns to lime. Carbon dioxide is generated by decomposition of limestone and combustion of carbon in the fuel. The kiln gases are diluted with nitrogen from the air used to burn the fuel and usually stone dust, ash particles, and gaseous impurities. The gas is partially cooled in the kiln by the upper layers of stone, and further cooled and cleaned before entering the compressors feeding the carbonating columns.

Calcining the Bicarbonate to Soda Ash

To prevent dilution of the decomposition gases, the crude filtered bicarbonate is continuously calcined by indirect heating. Various techniques are used to heat the material in which is recycled after compression to enrich the makeup kiln-gas feed to the carbonation operation. The hot soda ash discharged from the calciner is cooled, screened, and packaged or shipped in bulk. This product, called light ash because of its low bulk density, is converted to dense ash

By-Products
Calcium Chloride

Relatively few synthetic soda ash plants recover calcium chloride, and most of those that do utilize only a small part of the total amount available in the distiller waste. To produce calcium chloride, the distiller waste liquor is settled and then evaporated in multiple effect evaporators. During concentration most of the sodium chloride separates. The remaining solution is further concentrated to the equivalent of CaCl2.2H2O. this solution is cooled, forming flakes which are dried in a rotary dryer,giving a product sold as 77-80% calcium chloride. A small amount is processed to the anhydrous state.

Ammonium Chloride
Ammonium chloride is the principal salt present in the mother liquor from the crude sodium bicarbonate filtration in the ammonia soda process. Small amounts have been produced in soda ash plants by carbonation of the filter liquor, concentration, and crystallization of the ammonium chloride. Most of the demands in the United States are low tonnage. The end uses are primarily in dry cells and fluxing agents. However, ammonium chloride is also a good fertilizer for important crops in rainy climates, particularly for rice.

Carbonate-bicarbonate Ratio

Must have less than Equilibrium value of HCO3- to absorb CO2

http://www.cas.astate.edu/geochemistry/geochemistry/downloads/alk1.doc

XRD GROUP LIMITED

INDUSTRY IN PALANUR

EVAPORATOR

WORLD
CONSUMPTION OF

SODIUM CARBONATE

FLOW SHEET
REPRESENTATION

Co2,n2 to brine purifier

A M M O N T O W E R C A R T O W E R

co2

H2O
calciner

co2

B O N A T I N G

Purified brine solution

I A T

I
O N

water cooler

H2O
COKE LIMESTONE

S O D A A S h F
S

H2O
air

LIME
KILN

C O M N T B H I I

R E E N H 3

S
T I L L

MAKE UP NH3

H2O
SLAKER

MILK OF LIME

3 L
l

N E

WASTE CACL2 IMPURITY

 APPLICATIONS
water treatment; as an additive in food and drinks eg baking powder; for blowing foams such as expanded polystyrene; in pharmaceutical products as an antacid; in personal care products such as toothpaste.

Advantages of Solvay process

Can use low-grade brine Less electric power Less corrosion problems No co-products to dispose of Does not require ammonia plant investment

Disadvantages of Solvay process

Higher salt consumption Higher investment in ammonia recovery unit verses crystallization units for ammonium chloride Waste disposal of calcium chloride brine stream More steam consumption Higher capacity plant for economic break-even operation

With current fertilizer shortage, all of the ammonium chloride will be used as a mixed chemical fertilizer ingredient, so coproduct disposal no problem

PROJECT
DONE BY

FIRST BATCH

STUDENTS