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htm

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

Knowledge for the Technology - NOx

Sulphuric Acid July 5, 2003

Industry
Introduction Associated Links
Treatment
Sulphuric Acid on the Gas Phase Treatment NOx in Acid Regeneration Plants
Liquid Phase Treatment NOx in Sulphur Furnaces
Web
Case Study - INCO
References
Introduction
General
Equipment Suppliers
Contractor Introduction
Instrumentation
Industry News
The trend to smelting processes utilizing oxygen enrichment has resulting in more
Maintenance
Acid Traders energy efficient smelting operations, higher throughputs and smaller downstream
Organizations gas handling equipment. Higher smelter operating temperatures result from the
Fabricators smaller quantity of nitrogen present in the gas which acted as a heat sink. The
Conferences
Used Plants
higher operating temperatures result in an increase in nitrogen fixation according to
Intellectual Propoerty the following reactions:
Acid Plant Database
Market Information N2 + O2 <-> 2NO
Library

2NO + O2 <-> 2NO2

Technical Manual

Introduction Nitrogen oxides formed

General in this manner are
Definitions referred to as thermal
Instrumentation
NOx. In addition to
Plant Safety
Metallurgial Processes temperature, the
Metallurgical formation of NOx is
Sulphur Burning governed by residence
Acid Regeneration
Lead Chamber
time and oxygen
Technology concentration. High
Gas Cleaning temperatures favour the
Contact formation of nitrogen
Strong Acid
Acid Storage
monoxide (NO) but as
Loading/Unloading the gas cools, NO2 is
Transportation formed. Increasing
Sulphur Systems
residence time and
Liquid SO2
oxygen will also result in
Boiler Feed Water
Steam Systems the formation of more
Cooling Water NOx. The majority of
Effluent Treatment the nitrogen oxides
Utilities
Construction
present in the gas will be
Maintenance the result of thermal
Inspection
Analytical Procedures
NOx.
ThermalNOxFormation
Materials of Construction
Corrosion
Nitrogen oxides may
Properties also be present in the fuel that is used in the smelter to maintain operating
Vendor Data temperatures. The combustion of the fuel leads to the formation of chemical NOx.

DKL Engineering, Inc. A third source of nitrogen oxides results from the operation of the wet electrostatic
precipitators (WESP’s). Electrical arcing in the WESP’s causes the formation of
Handbook of Sulphuric Acid
nitrogen oxides.
Manufacturing
Order Form
Preface The nitrogen oxides pass from the smelter into the downstream acid plant where it
Contents ultimately contaminates the product acid. NO is insoluble in sulphuric acid so no
Feedback
NO enters the acid through the Drying Tower. Instead, NO is further oxidized by
the oxygen in the gas according to the following reaction:
Sulphuric Acid Decolourization
Order Form
Preface 2NO + O2 <-> 2NO2
Table of Contents

This reaction occurs rapidly in the catalyst beds.

Process Engineering Data
Sheets - PEDS
Order Form NO and NO2 in equal molar proportions behaves as N2O3 which is readily soluble
Table of Contents in sulphuric acid:
Introduction

Bibliography of Sulphuric Acid

NO + NO2 + 2H2SO4 <-> 2NO•HSO4 + H2O

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Technology or
Order Form
Preface
Contents N2O3 + 2H2SO4 <-> 2NO•HSO4 + H2O

Sulphuric Acid Plant Nitrosylsulphuric acid (NO•HSO4) is the dominant nitrogen-containing species that
Specifications
contaminates the acid and is commonly referred to as ‘nitrates’.

The nitrogen oxides in the gas are preferential absorbed by the submircon acid
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mist particles which have a high surface area to volume ratio. Thus, most of the
nitrates present in the acid plant are concentrated in the acid draining from the high
efficiency candle mist eliminators.

Nitrates in the acid accelerates corrosion of steel equipment and discolours the
acid reducing the quality of the acid. Some acid consumers require low or zero
nitrate levels in the acid. If nitrates are present in acid used in the sulphonation
process, a reaction will occur with the benzene ring to produce a greenish black
slurry.

If Fe+2 is present, the acid will appear pink in colour. The following reaction
occurs:

2FeSO4 + HNO3 + H2SO4 -> HNO2 + Fe2(SO4)3 + H2O

The pink colour is probably caused when N2O3 is dissolved in sulphuric acid and
NO+ is formed which reacts with Fe2+ to form a co-ordination complex. Aerating
or heating the acid will oxidize HNO2 to HNO3 which breaks the co-ordination
complex causing the pink colour to disappear. Unfortunately, the reaction is
reversible and the pink colour will return.

Treatment

The nitrate problem in an acid plant can be treated either in the gas phase or the
liquid phase. The quantity of nitrogen oxides formed in the smelter can be
minimized by ensuring the process operates steadily and minimizing local hot spots
in the furnace, however, the formation of NOx cannot be totally eliminated.

Gas Phase Treatment

Treating the NOx as far upstream in the process is the most desirable
route for any contaminate. Treatment of NOx in the gas phase
involves reducing the nitrogen oxides to nitrogen gas. In other
industries, NOx is treated in the gas phase by Selective Catalytic
Reduction (SCR), Selective Non-Catalytic Reduction (SNCR) and
various scrubber technologies.

The SCR process involves the reaction of NO and NO2 with ammonia
or urea in the presence of a catalyst to form nitrogen and water.

4NO + 4NH3 + O2 -> 4 N2 + 6H2O

6NO2 + 8NH3 -> N2 + 12H2O

Excess ammonia will react with oxygen to ultimately form nitrogen

and water.

4NH3 + 5O2 -> 4NO + 6H2O

4NH3 + 3O2 -> 2N2 + 6H2O

The reaction occurs in the presence of the catalyst at a temperature

between 300°C and 425°C. The ideal location for the treatment of
NOx by SCR is immediately prior to the first catalyst pass which is
well upstream of the point where NOx will enter the acid system. The
operating temperature at this location falls into the operating range of
the SCR catalyst so no additional heat or cooling of the process gas
is required. As well, no SO3 is present which would react with
ammonia to produce ammonia sulphate.

In addition to nitrogen, the other product from the SCR reactions is

water. The presence of water in the process gas has always been a
concern otherwise there wouldn’t be a drying tower designed to dry
the gas coming from the gas cleaning system. The water formed in
the reaction will react with the SO3 formed to produce sulphuric acid
and remain as a gas through most of the plant except where the gas
is cooled close to its dewpoint prior to entering the absorber towers.
Increased corrosion of the heat exchangers may occur if
condensation of acid is not monitored.

The technology has been successfully implemented at a zinc smelter

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operated by Budel Zink in The Netherlands. With inlet NOx

concentration in the range of 150-200 ppm, outlet concentrations of 4
to 6 ppm have been achieved. Stack emission are typically 6 ppm
and product acid nitrate levels meet the quality specification of less
than 9 mg/L. To date, no feedback is available on the affect the
moisture in the gas has on the corrosion of the equipment.

Liquid Phase Treatment

Treating nitrates in the acid begins by segregating the acid draining

from the high efficiency candle mist eliminators to avoid
contaminating the main acid stream. This accounts for
approximately 50% of the NOx entering the acid plant. The
remaining NOx will be absorbed into the acid or exit in the plant
stack.

The method used to segregate the candle drainings will depend on

whether or not the candles are the standing or the hanging type. For
standing candles, the majority of the acid will collect on the candle
tubesheet and is easily pipe outside of the tower. For hanging
candles, each candle is equipped with a drain which must be piped
individually to header inside the tower and then taken outside the
tower.

The acid from the candles can be disposed of or treated to try and
recover the acid values. Disposal will involve the neutralization of the
acid but this creates a hazard to personnel because NO and NO2 will
be liberated when the acid is diluted. This fact forms the basis for a
system to remove NOx and recover the acid.

When acid containing nitrosylsulphuric acid is diluted to about 70%

H2SO4 and the temperature of the acid is maintained above 50°C, the
following reaction takes place liberating NO and NO2 as a gas.

2NO•HSO4 + H2O -> NO + NO2 + 2H2SO4

The removal of nitrosylsulphuric acid can be enhance by using air or

steam to strip the acid to produce an acid stream than can be
blended back into the main acid stream.

The NO and NO2 gas stripped from the acid can be sent up the stack
but this results in a brown plume which may not be desirable. An
alternative to this method of disposal is to absorb the NO and NO2 in
water to form a weak nitric acid solution. The weak nitric acid
solution can then be neutralized without the formation of NO or NO2.

The equipment required to treat the acid in this manner consists of

small diameter packed columns. The flow of acid draining from the
candles is not always constant so a surge tank is recommended to
collect the candle drainings in order to smooth out the flow to the
stripping column. Controls are required to regulate the flow of acid
and dilution water. Operating temperatures in the column should also
be monitored.

Segregating and treating the acid draining from the candles will
prevent the majority of the nitrogen oxides from entering the product
acid stream. To further reduce and eliminate the nitrates in the acid
the addition of a strong reducing agent is required. The most
common reducing agent used is hydrazine (H2N4), hydrazine hydrate
or hydrazine sulphate. Other reducing agents are urea and
hydroxylamine. The reaction between hydrazine hydrate and
nitrosylsulphuric acid is as follows:

3N2H4•H2O + 4HNOSO4 -> 2SO4 + 5N2 + 5H2O

The elimination of NOx using hydrazine is affected by several

factors:

Acid Strength – reaction rate is higher in 93% H2SO4 than

98% H2SO4

Acid Temperature – reaction rate increases with increasing

temperature

Excess Hydrazine – the reaction rate is roughly proportional to

% excess hydrazine

Sulphur Dioxide – the presence of SO2 reduces the reaction

rate

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Other chemical reducing agents can be used but none are as

effective as the hydrazine compounds. The addition of any treatment
chemical to the product acid should be done carefully to avoid excess
unreacted chemical which may in itself be a contaminant. As well,
chemicals such as hydrazine are toxic and possible carcinogenics.

Hydrazine is added to the mist eliminator drainings to destroy the

NOx and then return the treated acid to the drying acid system. The
nitrosylsulphuric acid is collected in a holding tank and is them fed to
a NOx reaction column at a constant rate. Water is added to dilute
the acid to 93% H2SO4 and hydrazine is added. Dilution of the acid
to 93% H2SO4 and the subsequent increase in temperature both
contribute to an increase in the rate of reaction.

The treated acid is returned to the drying acid in system and gas from
the NOx reactor column are vented up the stack. Excess hydrazine
is added to the treated acid where it will react with the NOx in the
drying acid circulating system to produce an overall product acid
within specification. Hydrogen peroxide is added to the product acid
stream to eliminate any excess hydrazine.

Lurgi have develop a NOx removal process based on the lead

chamber process. The reactions involved are:

2HNOSO4 + 2H2O <-> 2H2SO4 + 2HNO2

3SO2 + 2H2O <-> 3H2SO3

2HNO2 + 3H2SO3 <-> 3H2SO4 + N2 + H2O

The process is characterized by its simplicity, low capital and

operating cost. No expensive chemical reagents are required and
there are no effluents.

The process is being used at the Lurgi designed and built

metallurgical sulphuric acid plant operated by Western Mining
Fertilizer at Mount Isa, Australia.

Case Study - INCO

In October 1991, the new acid plant at INCO Copper Cliff, Ontario, Canada began
operation. The acid quality produced from the plant generally met specification,
however, the presence of NOx was of concern.

In 1992, a program was initiated to identify the source, concentrations and

distribution of NOx within the acid plant. The operation of the furnaces with
oxy-natural gas burners produced a gas containing typically 20 ppm NOx . With
increased throughput and the use of coke instead of natural, NOx levels were
reduced to the 0 to 10 ppm range. The NOx levels would spike to approximately
400 ppm whenever combustion gases were vented to the acid plant but they were
for short durations and somewhat controllable.

In August 1992, the drains from the candle mist eliminators were piped together
and directed outside of the tower for disposal, to ensure product acid specification
could be met with respect to NOx.

In May 1993, the copper reactor was started resulting in NOx levels in the off-gas of
300 to 400 ppm. Operating the conventional oxy-fuel burners at 50 to 70%
stoichiometry was able to reduce NOx levels to approximately 100 ppm. This
resulted in high NOx levels in the product acid despite the fact that the candle
drainings were being collected and separated from the circulating acid.

It was hypothesized that some of the mist collected by the candles was draining to
the outside of the candle instead of the inside where it is collected. To test this
theory, a collecting bath was installed on one candle in order to collect any mist
draining to the outside of the candle. The results of the testwork showed that a
significant portion of mist was draining to the outside of the candle rather than the
inside and this occurred most often when the plant was operating at less than
design flows.

The solution was to equip the bottom of each candle with a collecting bath. The
bath was deep enough to allow acid to accumulate to a sufficient depth that the
acid would begin to drain through the candle to the inside where it would be
collected through the drain system. The modifications to the candles proved to be
effective in preventing mist from draining back into the circulating acid and
contaminating the product acid. The interpass system collects about 40 kg/h of 4
to 6% NO3 and the final system about 30 kg/h of 2% NO3.

References

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NOx http://www.sulphuric-acid.com/techmanual/Technology/nox.htm

Humphris, M.J., Liu, J., Javor, F., Gas Cleaning and Acid Plant Operations at the
INCO Copper Cliff Smelter, Nickel-Colbalt '97.

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