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Revisiting The Merseburg Process Economic Opportunity and Enviro

This document summarizes a presentation given at the Beneficiation of Phosphates VIII conference about revisiting the Merseburg process for producing ammonium sulfate from gypsum. The Merseburg process involves reacting ammonium carbonate with gypsum to produce ammonium sulfate and calcium carbonate. While used historically, obstacles to the process include the need for carbon dioxide and ammonia supplies. Producing calcium carbonate as a byproduct could help mitigate ocean acidification by adding it to oceans, providing an environmental benefit. Further analysis is needed considering regional market factors.

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Shruti indurkar
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200 views28 pages

Revisiting The Merseburg Process Economic Opportunity and Enviro

This document summarizes a presentation given at the Beneficiation of Phosphates VIII conference about revisiting the Merseburg process for producing ammonium sulfate from gypsum. The Merseburg process involves reacting ammonium carbonate with gypsum to produce ammonium sulfate and calcium carbonate. While used historically, obstacles to the process include the need for carbon dioxide and ammonia supplies. Producing calcium carbonate as a byproduct could help mitigate ocean acidification by adding it to oceans, providing an environmental benefit. Further analysis is needed considering regional market factors.

Uploaded by

Shruti indurkar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Engineering Conferences International

ECI Digital Archives


Beneficiation of Phosphates VIII Proceedings

5-3-2018

Revisiting the Merseburg Process: Economic


Opportunity and Environmental Benefit?
Gary Albarelli
Florida Industrial and Phosphate Research Institute, USA, [email protected]

Follow this and additional works at: http://dc.engconfintl.org/phosphates_viii


Part of the Engineering Commons

Recommended Citation
Gary Albarelli, "Revisiting the Merseburg Process: Economic Opportunity and Environmental Benefit?" in "Beneficiation of
Phosphates VIII", Dr. Patrick Zhang, Florida Industrial and Phosphate Research Institute, USA Professor Jan Miller, University of
Utah, USA Professor Laurindo Leal Filho, Vale Institute of Technology (ITV), Brazil Marius Porteus, Foskor-Mining Division, South
Africa Professor Neil Snyders, Stellenbosch University, South Africa Mr. Ewan Wingate, WorleyParsons Services Pty Ltd., Australia
Prof. Guven Akdogan, Stellenbosch University, South Africa Eds, ECI Symposium Series, (2018). http://dc.engconfintl.org/
phosphates_viii/14

This Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion
in Beneficiation of Phosphates VIII by an authorized administrator of ECI Digital Archives. For more information, please contact [email protected].
Revisiting the Merseberg Process:
Economic Opportunity and Environmental Benefit?

Gary Albarelli
Florida Industrial & Phosphate Research Institute

Beneficiation of Phosphates VIII


April 29 – May 4, 2018
Cape Town, South Africa

Florida Industrial and Phosphate Research Institute


Merseberg Reaction Sequence

1. NH3 + H2O → NH4OH


2. 2NH4OH + CO2 → (NH4)2CO3 + H2O
3. CaSO4 ∙ 2H2O + (NH4)2CO3 →
CaCO3 + (NH4)2SO4 + 2H2O

Florida Industrial and Phosphate Research Institute


History of the Merseberg Process

• Developed in Merseberg, Germany – 1913


• Two plants in Germany in operation – pre WWII
• Plants in UK and France built – 1923
• First plant utilizing phosphogypsum – France 1942
• 1950s – 1960s: Plants utilizing natural gypsum built
in India, Pakistan, Austria, Italy, Turkey
• 1950s – 1960s: Plants utilizing phosphogypsum
built in India, Japan

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate History as a Fertiliser

• Oldest manufactured N fertiliser


• Lower analysis: 21% N, 24% S
• Replaced by higher analysis fertilisers
• Now less than 5% of N market
• But regionally significant
• Ex: Brazil 20%

Florida Industrial and Phosphate Research Institute


Routes to Ammonium Sulphate Production

• Synthetic: Direct reaction of ammonia and


sulphuric acid
• Scrubbing coke-oven gas with sulphuric acid
• Recovery from industrial byproduct liquors
• Most common is from waste streams of caprolactam
production
• Merseberg Process
• Ammonium carbonate – gypsum reaction

Florida Industrial and Phosphate Research Institute


Routes to Ammonium Sulphate Production

Source: Integer

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Market

• Global market expected to reach $7 billion by 2025

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Market

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Market

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Market
• Production: dramatic move to China

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Market
• Example: Canada – Nutrien Redwater
• Green Markets, March 2, 2018

• Cites expanding AS market in western Canada


• Higher margins

Florida Industrial and Phosphate Research Institute


Merseberg Process Economics
• To produce one short ton ammonium sulphate (FIPR 2006)
Raw material and utilities requirements
Ammonia 0.3 ton
Gypsum 1.6 ton
Carbon dioxide 0.4 ton
Sulphuric acid 0.005 ton
Cooling water (make-up) 1700 gal
Power 75 kW-hr
Coal 0.17 ton
Process water 770 gal
Steam 1.25 ton
• Total cost: < $100/ton including raw materials, operating
and plant capital.

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Price History

• Southeast US ($/ton)

Florida Industrial and Phosphate Research Institute


Ammonium Sulphate Price History

Florida Industrial and Phosphate Research Institute


Main obstacles

• Regional variations in production cost vs price


• CO2 supply
• Depends on power source for plant
• If coal burned, CO2 requirement is met
• If other sources of power used, (e.g. sulphuric
acid co-generation) to consume all gypsum:
• Ammonia would need to be produced on-site
• For this would need natural gas supply

Florida Industrial and Phosphate Research Institute


Possible Environmental Benefit

• Ammonia production
• Ammonia
- Haber-Bosch Process
- N2 + 3H2 → 2NH3

• Hydrogen
- Steam reforming from natural gas
- CH4 + H2O → CO + 3H2
- CO + H2O → CO2 + H2

• Ammonia production accounts for 1% of global greenhouse gas


emissions
• Consuming a portion by Merseberg would be great benefit

Florida Industrial and Phosphate Research Institute


Main obstacles

• If no coal or natural gas supply


• It would be difficult to make this scheme workable
• Case example:
• OCP Morocco:
• 24 MMTpy phosphate rock processed
• 38 MMTpy phosphogypsum produced
• CO2 produced at dryers and reactors would only provide
enough CO2 to consume 4 MMTpy gypsum

Florida Industrial and Phosphate Research Institute


Review of Merseberg

• CaSO4 + (NH4)2CO3  (NH4)2SO4 + CaCO3

Florida Industrial and Phosphate Research Institute


What to do with the calcium carbonate?

• Calcium carbonate can be used in cement


production
• But requires calcining to clinker
• Requires power and emits CO2
• Defeats purpose
• Most radionuclides and metals report to CaCO3
• Higher concentration than gypsum
• Building materials may not practical

Florida Industrial and Phosphate Research Institute


What to do with the calcium carbonate?

• Calcium carbonate does not stack well


• So must be contained in landfill
• Occupying valuable land
• There is another alternative

Florida Industrial and Phosphate Research Institute


Ocean acidification

• The other carbon dioxide problem


• Approx one quarter of the CO2 emitted into
atmosphere is absorbed by the world’s oceans
• pH has decreased from 8.2 to 8.1 since industrial
revolution (30% rise in acidity)
• Projected to drop another .3 - .4 units if CO2
levels reach 800 ppm
• Threatens many marine organisms

Florida Industrial and Phosphate Research Institute


Ocean acidification

Source: NOAA

Florida Industrial and Phosphate Research Institute


Ocean acidification

• 2008 paper: Harvey, “Mitigating Ocean


Acidification,” Jrnl of Geophys Rsch
• Concludes process can be reversed by addition of
calcium carbonate to oceans in large amounts
• Reverses process:
• CaCO3  Ca2+ + CO32-

Florida Industrial and Phosphate Research Institute


Another solution with environmental benefit?

• Calcium carbonate disposal in ocean


• Possible only where phosphoric acid plants
located in close proximity to oceans
• There are many such plants

Florida Industrial and Phosphate Research Institute


GSFC Paradeep
Baroda Paradip BCIC
Chittagong
EID Oswal
Rashtriya Parry Paradip
Trombay Ennore Coromandel
Visakhapatnam
OCP FACT
Greenstar
Jorf Lasfar Cochin
Tuticorin
OCP
Safi

Grupo Fertinal ICS PHILPHOS


Lázaro Cárdenas Darou Khoudoss Isabel

PT Petrochimika
Gresik PT Petro Jordan Abadi
Vale (Mosaic) Gresik Gresik
Cubatão

Vale (Mosaic) Foskor


Piaçaguera Richards Bay
Source: Vecteezy.com

Florida Industrial and Phosphate Research Institute


Factors to consider

• Regional demand for ammonium sulphate


• Regional cost to produce vs price
• Infrastructure cost to pump offshore
• Regional availability of raw materials
• Ocean currents for dispersal

Florida Industrial and Phosphate Research Institute

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