Method of recycling of by-products for the production of soda ash and ammonium sulphate

• US 9,193,601 B2
• Filed: 09/30/2013
• Issued: 11/24/2015
• Est. Priority Date: 09/30/2013
• Status: Expired due to Fees

• Current Assignee: Council of Scientific & Industrial Research
• Original Assignee: Council of Scientific & Industrial Research
• Inventors: Ghosh, Pushpito Kumar, Somani, Rajesh Shantilal, Gandhi, Maheshkumar Ramniklal, Bajaj, Hari Chand, Chunawala, Jatin Rameshchandra, Upadhyay, Sumesh Chandra, Mody, Haresh Mahipatlal, Maiti, Pratyush
• Primary Examiner(s): SWAIN, MELISSA STALDER
• Application Number:
  US14/041,856
• Publication Number:
  US 20150093309A1
• Time in Patent Office: 785 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C01C 1/24 Sulfates of ammonium C01C1/14 takes precedence
• CPC Class Codes: C01D 7/18 Preparation by the ammonia-soda process C01D7/12 takes precedence

Abstract

A method of producing soda ash and ammonium sulphate by recycling by-products of Merseberg and Solvay processes includes treating brine with soda ash distiller waste for desulphatation of the brine to obtain gypsum, recovering pure salt from the desulphated brine and utilizing it in manufacture of soda ash in a Solvay process, washing the gypsum and reacting it with liquor ammonia and carbon dioxide to obtain CaCO₃ and ammonium sulphate, separating the CaCO₃ from the ammonium sulphate solution and recovering solid ammonium sulphate, washing the CaCO₃ followed by calcination to generate CO₂ and lime, recycling the CO₂ in the Solvay process to obtain soda ash, recycling the lime with ammonium chloride generated in the Solvay process to recover ammonia and obtain distiller waste containing CaCl₂ as a by-product, recycling the by-product distiller waste for the desulphatation of the brine, and recycling the ammonia recovered.

Claims

1. A method of recycling of by-products of Merseberg process and Solvay process in an integrated process for the production of soda ash and ammonium sulphate employing brine, ammonia and CO₂ as raw materials, the process comprising the steps of:

i. treating the brine with soda ash distiller waste for desulphatation of brine to obtain gypsum;

ii. recovering pure salt from desulphated brine and utilizing it in manufacture of soda ash in Solvay process;

iii. washing the gypsum obtained in step (i) and reacting it with liquor ammonia and carbon dioxide to obtain CaCO₃ and ammonium sulphate;

iv. separating CaCO₃ from the ammonium sulphate solution obtained in step (iii), and recovering solid ammonium sulphate from the solution;

v. washing the CaCO₃ obtained in step (iv) followed by calcination to generate CO₂ and lime;

vi. recycling the CO₂ from step (v) in the Solvay process to obtain soda ash;

vii. recycling the lime from step (v) with ammonium chloride generated in the Solvay process to recover ammonia and obtain distiller waste as a by-product;

viii. recycling the by-product distiller waste containing CaCl₂ obtained in step (vii) for the desulphatation of brine in step (i); and

ix. recycling ammonia recovered from step (vii) in step (iii).

2. The process as claimed in claim 1, wherein the brine used in step (i) is selected from the group consisting of ocean brine, sea brine, subsoil brine and lake brine comprising 1-15% (w/v) NaCl and 0.1-1.5% (w/v) sulphate.

3. The process as claimed in claim 1, wherein the CO₂ in step (iii) is obtained from flue gas emitted during said recycling process.

4. The process as claimed in claim 1, wherein 0.385 ton of CO₂ from flue gas is sequestered per ton of ammonium sulphate produced in the reaction of step (iii).

5. The process as claimed in claim 1, wherein the flue gas is used after compression or after enrichment with CO₂ and then as such or after compression.

6. The process as claimed in claim 1, wherein the yield of ammonium sulphate in step (iii) is in the range of 10-100%, more particularly in the range of 80-95% when the reaction temperature is in the range of 50-80°

C., the pressure of flue gas composition is in the range of 150-250 psig, and the reaction time is in the range of 2-4 hours.

7. The process as claimed in claim 1, wherein the gypsum produced in step (i) is sufficient to meet 15-30% of the calcium carbonate required in the form of CaO and CO₂ in steps (vi) and (vii) and thereby reducing the outsourcing of limestone in proportionate amount.

8. The process as claimed in claim 1 wherein the total requirement of limestone for the Solvay process [steps (vi) and (vii)] is met and the entire distiller waste is utilized in the desulphatation of step (i) when the brine intake for desulphatation followed by salt production matches the quantity of distiller waste generated.

9. The process as claimed in claim 1, wherein the desulphated brine of step (ii) is processed further for recovery of KCl.