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Sulphuric Acid on the WebTM Technical Manual DKL Engineering, Inc.

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Metallugical Processes
 May 25, 2013

Introduction
SO3 Formation		 Associated Links

Copper
Lead
Zinc

Introduction

There are a variety of metallurgical process generating off-gases containing a variety of SO2 concentrations and impurities.  Each process is unique which dictates that the gas be treated in different ways in order to remove impurities and treat the SO2 in the gas.  The following table list the type of metallurgical operation and the type of hot gas cleaning employed prior to sending the gas to a sulphuric acid plant or in some cases an alternate treament method.

Operation Metal Gas Source Hot Gas Cleaning System SO2 Fixation
Ashio Smelter
Furukawa Co. Ltd.
Japan		 Copper Flash Furnace Waste Heat Boiler Cyclones Hot ESP's Acid Plant
Utah Copper Division
Kennecott Minerals Co.
Utah, USA		 Copper Noranda Reactors  Waste Heat Boiler Cyclone Hot ESP's Hot Gas Fan Acid Plant
PS Converters  Gravity Settling Chamber Heat Exchanger Hot Gas Fan
Philippine Associated Smelting & Refining Corp. Copper Flash Smelting  Waste Heat Boiler Cyclone Hot ESP Acid Plant
Converters  Waste Heat Boiler ESP
Tamano Smelter
HIBI Kyodo Smelting Co. Ltd.
Japan		 Copper Flash Smelting Waste Heat Boiler Acid Plant
Saganoseki
Nippon mining Co. Ltd.
Japan		 Copper Flash Smelting Waste Heat Boiler Hot ESP's Acid Plant
Converter Waste Heat Boiler Hot ESP's
Horne Smelter
Xstrata Copper
Canada		 Copper Noranda Reactor Spray Chamber Hot Gas Fan Acid Plant
Hudson Bay Mining and Smelting
Flin Flon, Manitoba
Canada		 Copper Roasters Hot ESP None
Reverb Hot ESP Bag House
Fuming Furnace Bag House
Cananea Smelter
Compania minera de Cananea S.A.		 Copper Reverb Spray Chamber
Converters Gravity Settling Chamber
BCL Nickel Smelter
Bamangwato Concessions Limited		 Nickel Flash Smelting Waste Heat Boiler Hot ESP Hot Gas Fan Stack
Kalgoorlie Nickel Smelter
BHP Billiton		 Nickel Flash Smelting Waste Heat Boiler Hot ESP Acid Plant
P.T. Inco
Indonesia		 Nickel PS Converters Gravity Settling Chamber Spray Chamber Hot ESP Hot Gas Fan Stack
Thompson Smelter
INCO
Canada		 Nickel Roasters Cyclone Hot ESP None
Hidalgo Smelter
Phelps Dodge Corporation		 Copper Flash Smelting Wste Heat Boiler Hot ESP Hot Gas Fan Acid Plant
Converters Waste Heat Boiler Gravity Settling Chamber Hot ESP Hot Gas Fan
Brunswick Mining and Smelting Corporation Limited Lead Sinter Hot ESP Acid Plant
Boliden Odda Zinc Zinc Fluid Bed Roaster Waste Heat Boiler Acid Plant
Mikkaichi Smelter
Nikko Zinc Co. Ltd.		 Zinc/Lead Sinter Hot ESP Spray Chamber Wet ESP Stack
Hachinohe Smelting Company Ltd. Zinc Sinter Hot Gas Fan Hot ESP Acid Plant
Amax Zinc Company
Illinois, USA		 Zinc Roasters Waste Heat Boiler Cyclone Hot ESP Acid Plant
Harjavalta Copper Smelter Copper Flash Smelting Waste Heat Boiler Hot ESP Hot Gas Fan Acid Plant
Converters Waste Heat Boiler
Copper Cliff Smelter
Vale		 Copper Flash Smelting Spray Chamber Heat Exchanger
Xstrata Nickel
Sudbury, Canada		 Copper/Nickel Roaster Primary Cyclones Secondary Cyclones Heat Exchanger Hot ESP Hot Gas Fan Acid Plant

SO3 Formation

Smelting of sulphide ores results in large amounts of SO2 being produced.  Modern smelting processes use oxygen enrichment to generate off-gases containing from 15% to 80% SO2.  Unfortunately, the increase in SO2 concentration results in higher SO3 concentrations in the flue gases.

Higher SO3 concentrations leads to the formation of sulphate and sulphuric acid in the downstream gas handling systems causing corrosion of the equipment.  As well, larger amounts of SO3 reporting to the wet gas cleaning system resulting in higher treatment costs for the effluent treatment system and larger wet electrostatic precipitators for the final removal of SO3 prior to the contact section of the sulphuric acid plant.

The oxidation of SO2 to SO3 can occur by one of two process:

The formation of SO3 by homogeneous reaction occurs primarily at temperatures above 1200°C (2192°F) which are only present in the flame.  The process is dependent on the flame temperature and amount of excess oxygen.  The use of tonnage oxygen increases oxygen concentrations and flame temperatures leading to an increase in SO3 content.  

Catalytic oxidation of SO2 to SO3 take place at temperatures below 700°C (1292°F) in the presence of a catalyst.  It is known that vanadium pentoxide (V2O5) and iron oxide (Fe2O3) acts as catalyst for the reaction.   These materials can be found in the ash, dust and deposits found throughout the hot off-gas handling system.  Fortunately, the reaction rates are slow and the SO3 concentrations obtained are nowhere near the equilibrium values possible. 

One source states that 1 to 3% of the SO2 in the gas is converted to SO3.   Formation of SO3 appear to be maximized at temperatures between 570 to 640°C (1060-1185°F).  The equilibrium conversion of SO2 to SO3 is small at high temperatures but the equilibrium SO3 increases rapidly as the gas is diluted and cooled.  The actual SO3 formed is determined by the rate of reaction and the time available for the reaction to take place.  At lower temperatures thermodynamics favour the formation of more SO3 but the reaction rates are slow.  Therefore, SO3 formation can be minimized by rapid cooling of the gas.

The following general observations have been made about the formation of SO3:

When SO3 and H2O are present in the gas they react together quickly to form gaseous sulphuric acid (H2SO4).  The equilibrium conversion of this reaction is a function of temperature as illustrated in the following chart.  The data is for a water partial pressure of 0.034 atm and where H2O is present in large excess compared to SO3.

so3equil.JPG (23231 bytes)

The formation of H2SO4 is a problem in the flue gas system when it condenses onto the surface of equipment where the temperature is below the dewpoint of the gas.  The dewpoint depends on the partial pressure of gaseous H2O and H2SO4.