PLANT DESIGN FOR THE PRODUCTION OF SODIUM CARBONATE

ADVISR:-DR.ING.BALAY WELDEYES
DONE BY:-MULUGETA GETENET

BACKGROUND
Soda ash is the common name for the technical

grade anhydrous sodium carbonate (Na2CO3). In the eighteenth century soda ash was produced by LeBlanc process based on roasting salt cake with carbon and limestone. The synthetic process for the manufacture of soda ash by ammonia soda process was developed by Ernest Solvay in 1861.

ANNUAL PRODUCTION OF SODIUM CARBONATE IN ETHIOPIA

Year 2003 2004 2005 2006 2007 Production 4.3769998550415 6.44399976730347 8.20699977874756 4.09999990463257 1 Unit of Measure Thousand metric tons Thousand metric tons Thousand metric tons Thousand metric tons Thousand metric tons % Change NA 47.22 % 27.36 % -50.04 % -75.61 %

Source: United States Geological Survey (USGS) Minerals Resources Program

Contd
For countries which do not posses natural resources of soda ash, the following synthetic processes are available: Solvay Process Akzo Dry Lime Process Dual Process New Ashai (NA) Process

OBJECTIVE
To produce good quality sodium carbonate by

selecting the appropriate method and reducing the exhaust carbon dioxide to the atmosphere. Evaluate different use, quality parameters and processing method of sodium carbonate Evaluate cost effectiveness of produce sodium carbonate

PROPERTIES OF SODIUM CARBONATE

Appearance White powder or granules Odor Odorless Solubility 45.5 g/100 ml water @ 100C (212F) Specific gravity 2.53 pH 11.6 Aqueous solution % Volatiles by volume @ 21oC (70F) 0 Boiling point Decomposes Melting point 851C (1564F)

USES OF SODIUM CARBONATE

For the manufacture of glass

PH regulator to maintain stable alkaline conditions

It is a common additive in municipal pools In chemistry, it is often used as an electrolyte

Used as a water softener during laundry

PRODUCTION PROCESS TYPES OF SODIUM CARBONATE

LEBLANC PROCESS

HOU'S PROCESS
SODIUM SESQUICARBONATE PROCESS Dual process

Solvay process

SOLVAY PROCESS

Contd
The Solvay process results in soda ash (predominantly sodium carbonate (Na2CO3)) from brine (as a source of sodium chloride (NaCl)) and from limestone (as a source of calcium carbonate (CaCO3)). The overall process is: 2 NaCl + CaCO3 Na2CO3 + CaCl2 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 (NaCl) and ammonia (NH3). NaCl + CO2 +NH3 + H2O NaHCO3 + NH4Cl (I)

Contd
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)

Contd
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).
2 NH4Cl+ CaO 2 NH3+ CaCl2+ H2O..................(III)

Cond
The sodium bicarbonate (NaHCO3) precipitates from reaction (I) is then converted to the final product, sodium carbonate (Na2CO3), by calcination (160 230 C), producing water and carbon dioxide as byproducts: 2 NaHCO3 Na2CO3 + H2O+ CO2.............(IV)

Cond
The carbon dioxide from step (IV) is recovered for reuse 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.

MATERIAL BALANCE
Material balance around Lime Kiln

CaCO3 CaO+CO2 80% conversion

C+O2 CO2 90% conversion Excess air is not used

Inputs: Calcium carbonate = 2,306,079.527 kg/hr Carbon = 307,477.269 kg/hr Oxygen =819,939.39 kg/hr
Out puts: Carbon di oxide = 1,014,674.99 kg/hr Calcium oxide = 1033123.628 kg/hr Carbon (unreacted) = 30747.726 kg/hr Calcium carbonate (unreacted) =461,215.80 kg/hr

Contd
Material balance around Slaker CaO + H2O Ca(OH)2 200% Excess water used Inputs: Calcium oxide = 1033123.628 kg/hr Water = 10613.2068 kg/hr (66747165.83kg/hr) Out puts: Calcium hydroxide = 1365199.08 kg/hr Water = 332,075.45 kg/hr

Contd
Material balance around ammonia absorber Assuming 99% absorption of input ammonia Meanwhile, the ammonia was regenerated from the ammonium chloride byproduct by treating it with the lime (calcium hydroxide) left over from carbon dioxide generation: Ca(OH)2 + 2 NH4Cl CaCl2 + 2 NH3 + 2 H2O

Inputs:
Calcium hydroxide = 1365199.08 kg/hr Ammonium chloride = 987002.04 kg/h Outputs: Calcium chloride = 2029349.99 kg/hr Ammonia = 313626.81 kg/hr Water = 332075.45 kg/hr

Contd
Material balance around Carbonating Tower

NaCl + NH4OH +CO2 NH4Cl + NaHCO3 Conversion 75% Inputs: Sodium chloride = 809433.924 kg/hr Carbon di oxide = 608805.00 kg/hr Ammonium hydroxide = 484276.706 kg/h
Outputs: Ammonium chloride = 987002.04 kg/hr Sodium bi carbonate = 871,698.11 kg/hr Sodium chloride (unreacted) = 202358.48 kg/hr Ammonia hydroxide (unreacted) = 121069.1763 kg/hr Carbon dioxide (unreacted) = 152201.25 kg/hr

Contd
Material balance around Ammonia distiller

NH4Cl + NaHCO3
NH4OH Inputs:

NaCl + NH4OH + CO2

NH3 + H2O

Ammonium chloride = 31544.8091 kg/hr Ammonia hydroxide = 363207.53 kg/hr Sodium bi-carbonate = 871,698.11 kg/hr
Outputs: Sodium chloride (unreacted) = 607075.443 kg/hr Ammonia = 176415.086 kg/hr Water = 141999.7521 kg/hr

Contd
Material balance around calciner 2NaHCO3 Na2CO3 + CO2 + H2O

Complete decomposition Inputs: Sodium bi carbonate = 871,698.11 kg/hr Outputs: Sodium carbonate = 550,000 kg/hr Carbon di oxide = 114,150.938 kg/hr Water = 46,698.11 kg/hr

ENERGY BALANCE
Energy balance around the Lime kiln

CaCO3
C+O2

CaO+CO2
CO2

H25= 43.4 Kcal/mole

H25= -96.4 Kcal/mole

For all calculation the initial temperature for calculation is taken as 30 C. (303K) Temperature of reaction is 11000 C Inputs: Temperature of input reactants = 300 C Therefore heat of reactants =0 Heat of reaction at 11000C(H1100) = -3.8*1009 calories Outputs: Output temperature of products = T Kelvin Heat output = (mcpt)Cao + (mcpt)Co2 + (mcpt)C(unreated)+(mcpt)CaCO3(unreacted)+(mcpt)N2 = (4798.5T 1.347*1011/T2 + 15.58*1006)(T-303) From heat balance we get: 3.8*109 = (4798.5T 1.347*1011/T2 + 15.58*1006)(T-303) T= 520 K

Contd
Energy balance around Slaker

CaO + H2O Ca(OH)2 H25= -15.6 Kcal/mole Temperature of Reaction = 1000C Inputs: Temperature of input water stream = 300C Temperature of input calcium oxide stream = 2470C Heat input by reactants = 0.775*1009 calories Heat of reaction (H100) = -4.824*1009 calories Out puts: Temperature of output stream = T Kelvin Heat output = (mcpt)Ca(OH)2+ (mcpt)H2O = (10.698*1006 + 3862.02T 0.1054T2)(T-303) From heat balance we get: 4.824*1006 = (10.698*1006 + 3862.02T 0.1054T2)(T-303) therefore T= 720 K

Cond
Energy balance around ammonia absorption tower

Inputs: Temperature of input brine = 300C Temperature of input gases = 600C Heat input = (mcpt)gases = (1666.9*7440*30) = 0.372*1009 outputs: Temperature of output liquid stream = 400C Temperature of output gas stream = 300C heat output = (mcpt)NaCl+(mcpt)NH3+(mcpt)H2O = (786.16*12200+1070.18*8671.9+6523.87*18026)(40-30) = 1.363*1009 calories From heat balance 0.372*1009 = 1.363*1009 + heat removed Heat removed = 0.99*1009 calories Water required for cooling the tower = 0.99*1009/(1000*(45-30)) = 66000 kg/hr

Contd
Energy balance around carbonating tower NaCl + NH4OH +CO2 NH4Cl + NaHCO3 Reaction temperature = 600C Temperature of reactants = 300C Heat input =0 Heat of reaction (H60) = -5.8229*109 calorie Heat output = 25.29*106 From heat balance we get: 5.8229*109 =- 25.29*106 + heat removed Heat removed = 5.848*109 Cooling water required = 5.848*109/(1000*(45-25)) = 292400 kg/hr

Cond
Heat balance around ammonia distiller 2NH4Cl + Ca (OH)2 NH4OH 2NH3 + CaCl2 + 2H2O NH3 + H2O

Reaction temperature = 750C Inputs: Heat input =(mcpt)Ca(OH)2 + (mcpt)H2O +(mcpt)NH4Cl+(mcpt)Nacl(unreacted)+(mcpt)NH4OH

=(294.8113*22489.6+122736.3866*4180+589.6226*22936+196.5408*12337.2+480.56*11.560)(25) = 0.5411*1009 calories Heat of reaction (H75)= 4.506*1009 calories Outputs: Temperature of output stream = 600C Heat output = (mcpt)NH3 + (mcpt)H2O +(mcpt)CaCl2+(mcpt)Nacl(unreacted) = 0.2824*1009+1.78*1010+0.1608*1009 +2.413*1006 = 1.824*1010 From heat balance 0.5411*1009- 4.506*1009 + 2.25*1009 = 1.824*1010 + heat removed Heat removed = 0.2951*1009 calories

Contd
Heat balance around calciner

2NaHCO3

Na2CO3 + CO2 + H2O

Reaction temperature =200oC Inputs: Reactant temperature=300C Heat input=0 Heat of reaction = 2.02*1010 calories Outputs: Output stream temperature= 1800C Heat output=(mcpt)Na2CO3 + (mcpt)H2O +(mcpt)CO2 = 294.811*28900*150+294.812*8311.8*150+294.8113*10610.4*150 = 2.114*1009 calories From heat balance -2.02*1010 + heat supplied = 2.114*1009 heat supplied = 2.23*1010 calories

COST ESTIMATION
SUMMARY OF COST ESTIMATION Fixed Capital Cost (FCI) = Rs. 5.33108 Direct cost = Rs. 4.41108 Total capital investment = Rs. 6.8213108 GROSS EARNINGS/INCOME
Net profit = (1.401108) (0.63108) = Rs. 0.771108

RATE OF RETURN Rate of Return = 11.3%

CONCLUSION
Based on the result the following conclusions are important: The amount of carbon dioxide from the process is very large amount so it is important to reuse again or it needs to treat before to remove to the atmosphere. The analysis on financial feasibility of the proposed enterprise revealed that based on the assumptions made, the enterprise is profitable. The enterprise is projected to have a healthy cash flow and is viable over long term. The positive financial feasibility is, however, dependent on stable inflation and macro economic conditions.

THANK YOU!