Commission of the European Communities

environment and quality of life

TECHNICAL NOTE
ON BEST AVAILABLE TECHNOLOGIES
NOT ENTAILING EXCESSIVE COST
FOR SULPHURIC ACID PRODUCTION

Report
EUR 13006 EN
Blow-up from microfiche original

Commission of the European Communities

environment and quality of life

TECHNICAL NOTE
ON BEST AVAILABLE TECHNOLOGIES
NOT ENTAILING EXCESSIVE COST
FOR SULPHURIC ACID PRODUCTION

CITEPA
3, rue H. Heine
F-75016 Paris

Contract No. B.6611-555-88

Directorate-General Environment, Nuclear Safety and Civil Protection

1990

EUR 13006 EN

Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General
Telecommunications, Information Industries and Innovation
L-2920 LUXEMBOURG

LEGAL NOTICE
Neither the Commission of the European Communities nor any person acting on behalf
of the Commission is responsible for the use which might be made of the following
information

Catalogue number: CD-NA-13006-EN-C

ECSC EEC EAEC, Brussels - Luxembourg, 1990

III

TECHNICAL NOTE
ON BEST AVAILABLE TECHNOLOGIES
FOR SULPHURIC ACID PRODUCTION
PREFACE
The Council of the European Communities adopted a Directive (1) on 28 June, 1984
aimed at the provision of measures and procedures to prevent or reduce air pollution
from stationary sources (i.e. industrial process or utility plant). The basis of the
Directive is the requirement that a wide range of industrial processes shall be subject
to prior authorisation by competent authorities in each Member State. A key element
of the Directive is the concept of the Best Available Technology "that does not entail
excessive costs" (BAT) to prevent or reduce air pollution, that must be incorporated
into a plant prior to the issue of an authorisation to operate. The provisions of the
Directive apply to both new plant and existing plant undergoing major modification.
Member States were required to bring into force the relevant administrative
infrastructure and national legislation necessary for full compliance with the
provisions of the Directive by not later than 30 June 1987.
An important provision of the Directive (Article 7) requires Member States to
exchange (amongst themselves and the Commission), information concerning (amongst
others) measures for the prevention and reduction of air pollution as well as technical
processes and equipment (including BAT). The principal aim of Article 7 is to ensure
that the necessary background information is made available (via information
exchange) so as to ensure a harmonious implementation of the Directive in all Member
States.
In this regard, BAT is to be interpreted as that technology (or set of technologies)
which operating experience has adequately demonstrated to be the best technology
commercially available as regards the minimisation of emissions to atmosphere,
providing it has been proven to be economically viable when applied to the industrial
sector concerned. Applications for authorisation will be deemed to meet BAT criterion
if the performance of the proposed plant, in terms of emissions to atmosphere, is
guaranteed to be equivalent or better than that of the designated BAT. It is the
Commission's intention, via the information exchange framework, to identify both
BAT and the emission values associated with this designated BAT. These emission
values will then become the principal criteria by which future applications for
authorisation will be judged by the Authorisation Authorities in Member States. This
will give industry the flexibility to incorporate any reasonable measures provided the
proposed plant meet the emission values and conform to broad principles of acceptable
design practise. As new processes, equipment or techniques are developed, are proven
to be economically viable and to consistently better the emission values associated with
a designated BAT, so the new innovation will become the designated BAT and the
emission values associated with this new technology would become the emission values
by which future applications for authorisation are measured. This is consistent with
the evolutionary nature inherent in the BAT concept.
The Commission have taken the initiative in this regard by establishing a Working
Group of experts to designate BAT pertaining to the manufacture of sulphuric acid.
This technical note summarises the Working Group's deliberations and it is intended
that it will be used as a set of guidelines by both industry and authorisation
authorities alike in the intended and consistent implementation of Directive
84/360/EEC throughout the Community.

IV

The aim of this technical note is to Identify both Best Available

Technologies not entailing excessive costs (BAT) and the emission values
associated with the designated BAT. These emission values will then become
the principal criterium by which future applications for authorization will
be Judged by the competent authorities in Member States.
The technical note, which Is prepared by the Commission In collaboration
with experts from the
Industry and from national
administrations,
designates BAT pertaining to the production of sulphuric acid.
The technical note ensures the intended and consistent
directive 84/360/EEC throughout the Community.

implementation of

As new procedures, equipment or techniques are developed and proven to be

economically viable, they will become the designated BAT and the relevant
technical note will be updated.

C O N T E N T S

Page
Preface

III

Summary

IV

PART A : GENERAL ASPECTS

AI

Introduction
AI.l.
AI.2.

All

AHI

Conversion of SO
Absorption of SO

into SO

1
. 2

Installation for which authorisation is required

in Member States

Installations covered by technical note

AIII.l.

Sources of SO

AHI.2.

Sulphuric acid production

AIV

Pollutants emitted to the atmosphere

18

AV

Emission limits applied in Member States

19

PART : BEST AVAILABLE TECHNOLOGIES NOT ENTAILING EXCESSIVE

COSTS (BAT) FOR THE PRODUCTION OF SULPHURIC ACID

20

BI

Introduction

20

BII

Best available technology for new plants

BII.l.
Sulphuric burning
BII.2.
Metal sulphide roasting
BII.3.
Sulphuric acid regeneration
BII.4.
Metal sulphate roasting
BII.5.
Incineration of H S and other S-containing
gases
BII.6.
General considerations
Bii.7.
Synthesis of the proposals
BAT for storage, handling and shipping of sulphuric

20
20
20
22
23

Bill

23
23
23

acid

25

BIV

Monitoring of pollution

25

BV

Operational controls

26

VI
BVI

Stack height

27

BVII

Cross-media impact

27

Bibliography

28

PART C : ANNEXES
Cl

Presentation of a panel of sulphuric acid plants

29

C2

Procedure for manual analysis of S0 3 emissions

34

C3

Plant authorisation procedures in EC Member States

35

List of Members of BAT Working Group

41

PART A: GENERAL ASPECTS

AI

Introduction

Many processes of sulphuric acid production have been developed according to the
large number of sources of raw materials (SO,) and their specific characteristics. The
present document deals neither with the production of S 0 3 (Sulphur trioxide) nor the
production of oleum; nevertheless the problem of storage, handling and shipping of
oleum is outlined in Bill.
It is possible to draw a general diagram of sulphuric acid production distinguishing
the two fundamental steps of the process (sec figure A 1(a)):
(a)
(b)

conversion of S 0 2 into S 0 3
absorption of SO,

AI.l

Conversion of S 0 2 into S 0 3
The design and operation of sulphuric acid plant are focused on the
following gas phase chemical reaction with a catalyst:
S 0 2 + 1/2 0 2 ** S 0 3 + Heat
This reaction is characterised by the conversion rate which is defined as
follows:
conversion rate - P_2 ,

- SQ 2

. 100 (%)

Both thermodynamic and stoichiometric considerations are taken into

account in maximising the formation of S0 3 . In deciding how to optimise
the equilibrium, usually the Lechatclier-Braun Principle, which states that
when an equilibration system is subjected to stress, the system will tend
to adjust itself in such a way as to partly relieve the stress, is taken into
account. The stresses arc, for instance, a variation of temperature, of
pressure, or of concentration of a reactant.
For S 0 2 / S O , systems, the following methods are available to maximise the
formation of S0 3 :
heat removal, a decrease in temperature will favour the formation
of S 0 3 since this is an exothermic process
increase oxygen concentration
remove S 0 3 (as in the case of the double absorption process)
raise system pressure
select a catalyst, in order to reduce the working temperature
(equilibrium)
longer reaction time.
Optimum overall system behaviour requires a balance between reaction
velocity and equilibrium.
However, this optimum depends also on the S 0 2 concentration in the raw
gas and on its variability in time.
Consequently, each process is more or less specific for a particular S 0 2
source.

.2

Absorption of S 0 3
Sulphuric acid is obtained from the absorption of S 0 3 into H2S0 4 (with
a concentration of at least 98%).
The efficiency of the absorption step is related to:
the H 2 S 0 4 concentration of the absorbing liquid (98.5 - 99.5%)
the range of temperature of the liquid (normally 70 ' C - 120 C)
the technique of the distribution of acid
the raw gas humidity (mist passes the absorption equipment)
the mist filter
the temperature of incoming gas
the co-current or counter-current character of the gas stream in the
absorbing liquid.
S 0 3 emissions depend on:
the temperature of gas leaving absorption
the construction and operation of the final absorber
the device for separating H 2 S0 4 aerosols
the acid mist formed upstream of the absorber through the presence
of water vapour.

A.II

Installations for which Authorisation is Required in Member States

Each Member State has authorisation procedures of its own covering
installations where sulphuric acid is manufactured or where sulphuric acid
is packaged and/or loaded in bulk. A brief summary of the relevant
national provisions is given in Annex C3.

AHI

Installations Covered bv Technical Note

Since the technique of conversion of SO, to S 0 3 and of absorption of S 0 3 depends on

the concentration of S 0 2 in the feed gas entering the installation and on the
variability of S 0 2 concentration, the general presentation of the technique of
production of sulphuric acid is divided into two parts:
o

Sources of SO,
o
o
o
o
o
o
o

Sulphur burning
Pyrite roasting
Metal sulphide roasting
Sulphuric acid regeneration
Metal sulphate roasting
Incineration of H2S or other Sulphur containing gases
Other processes

Sulphuric acid production

o
o
o
o
o
o
o

Single contact process

Double contact process
Wet Contact Process (WCP)
Modified Lead Chamber Process (MLCP)
^2^2 P r o c e s s
Unsteady state process
Other processes

Figure Al(a)
General diagram of H^S0 4 Production

Possible dilution with air

Conversion of S 0 2

Source of S 0 2

SO-

SO,
V.

S 0 2 formation

H2SO4 mist
SO,

SO,

so 2

"sT"

Absorption of S 0 3

SO

~v~
Sulphuric acid production

{y HjSO
^J

This technical note does not deal in detail with the storage and handling of sulphur
containing materials, but care must be taken to avoid fires which can result in sulphur
dioxide emissions. The measures to be taken in the handling of sulphuric acid, oleum
and sulphur trioxide are outlined in section Bill of this Technical Note.
All!.I

Sources of S 0 2
The principal sources of S 0 2 are:
o

Combustion of Sulphur: Combustion of sulphur, which is obtained

either from natural deposits or from desulphurisation of natural gas
or crude oil, is carried out in one-stage or two-stage sulphur
combustion units at between 900C and 1800C. The combustion
unit consists of a combustion chamber followed by a process gas
cooler. The S 0 2 content of the combustion gases is generally up to
18% by volume and the 0 2 content is low (but higher than 3%).
The gases are generally diluted to 10-11% before entering the
conversion process. The S 0 2 content in the gases is very stable over
time.

Pyrite roasting: For pyrite (iron sulphide) roasting, many kinds of

furnace are used: multiple-hearth furnaces, rotary kiln, fluid bed
roasters, etc.
The S 0 2 content of gases is generally about 15% and the 0 2 content
is zero.
The gases are always treated in a dust collector (often an electric
dust collector) with a high efficiency and diluted to 8-10% before
entering the conversion process (very often double absorption).
Due to the heterogeneous character of the raw material (pyrite), the
S 0 2 content in the gases is very variable over time.

Metal sulphide roasting: Many metal sulphides (other than pyrite),

when roasted during metallurgical processes, produce gases
containing S0 2 . It is necessary to distinguish the main ores as
indicated in Table A.III.1(a).

Table Alll.l(a)

Principal Metal Sulphides Producing S0 2

Metal Sulphide

Raw Gases

Process
Gases

Variability
in time

so 2 %

o,%

so 2 %

Zn S containing ores

6 - 10

6 - 11

6 - 10

Relatively
low

Cu S containing ores

1 -20

8 - 15

1 - 13

Can be very
high

Pb S containing ores
sintering
other lead
smelters

2-6

-v/15

2 -6

Relatively high

7-20

->/15

7 - 13

Low to very
high (Batch
process)

Mo S containing ores

0,5 - 1,5

0,5 - 1,5

Relatively low

Other ores

variable

variable

variable

15
variable

Regeneration of sulphuric acid: Decomposition of spent sulphuric

acid to sulphur dioxide by injection into a hot gas stream or into a
moving bed of hot solids such as coke, sand or ore is carried out at
800" C to 1300"C. Depending on the type of fuel used, these
processes produce decomposition gases with an S0 2 content of 2 to
10%.
The variability in time of the S0 2 content depends on the "quality"
of the spent acid. These processes sometimes have a liquid sulphur
burner fitted to supplement the S0 2 feed and to compensate for the
variability of the waste acid strength.
Gas phase thermolysis of sulphuric acid is represented by the overall
equation:
H2S04 - S0 2 + H 2 0 + 0.5 0 2

H - +202 kJ/mol

To ensure not only that the acid will be completely decomposed but
also that organic impurities will be completely burnt, in practice the
decomposition is carried out under oxidising conditions at about
1000'C.
The energy requirement for acid decomposition depends mainly on
the composition of the spent acid. It rises steeply with decreasing
H2SO4 concentrations in proportion to the amount of water to be
evaporated and it is diminished by the heating value of the organic
impurities. In the case of dilute spent acids, it is always
energetically more favourable to preconcentrate to about 60-75%

H 2 S 0 4 so as to separate the bulk of the water before decomposition

rather than to decompose the dilute acid directly. This acid
preconcentration is by evaporation, usually under a vacuum.
The sulphur dioxide-containing gases produced in the decomposition
of sulphuric acid arc heavily diluted by the combustion gases
introduced for direct heating. However, the amount of flue gas can
be substantially reduced by preheating the combustion air. To
obtain gases from decomposition with a high enough sulphur dioxide
content for processing in a double-contact sulphuric acid plant when
using fuel oil, the spent acid must contain at least 60% H2SO^ even
when the combustion air is being preheated to 450 ' C .
The figure A.III. 1(a) shows a possible scheme
regeneration plant.

for

an

acid

In this particular decomposition technique, spent acid is fed to the

top of a vertical, brick-lined furnace and is finely distributed by
means of a rotary atomiser.
Other decomposing systems are available.
Metal sulphate roasting: Decomposition of sulphates, particularly
iron sulphate, is carried out in multiple-hearth furnaces, rotary kiln
or fluid bed furnaces at over 700 C with addition of elemental
sulphur, pyrite, coke, tar, lignite, hard coal or oil as fuel and
reductant. The S 0 2 content of the gases obtained is dependent on
the type of fuel; after cleaning and drying, the S 0 2 content is about
6%. The variability in time of the S0 2 content is nigh.
Ferrous sulphate is obtained in large quantities as its heptahydrate
during the regeneration of pickling liquors or as a side product in
the T i 0 2 process via the sulphate route.
During the first step, the heptahydrate is dehydrated at 130-200C
by flue gases in spray driers or fluid-bed driers to a monohydrate
or mixed hydrate. In a second step, the material is decomposed at
about 900'C.
The gases thus obtained contain about 7% by volume of sulphur
dioxide. Today it is common practice for ferrous sulphate to be
decomposed in a fluid-bed pyrite roasting furnace at 850 "C or more.
Elemental sulphur, coal or fuel oil may be used as supplementary
fuels. The sulphur dioxide containing gas leaving the furnace is
cooled in a waste heat boiler to about 350-400 " C a n d i s subsequently
passed to the gas cleaning system. The cleaned gases are fed to the
sulphuric acid plant.
A mixture of metal sulphates and eventually sulphuric acid
(resulting from the concentration of acid wastes of titanium dioxide
production) can similarly be processed in a fluid-bed reactor. In
individual cases, ferrous sulphate is also decomposed in multiplehearth furnaces with flue gases from fuel oil or natural gas
combustion.
Combustion of sulphur containing gases: Combustion of hydrogen
sulphide (HjS), carbon di-sulphide (CSj) and carbon sulfoxide (COS)
is carried out in a muffle furnace at 0 0 O C to 1200C, producing
combustion gases with an S 0 2 content of 0,5 to 12%.

Figure AHI.1(a)

Sulphuric Acid Rgnration Plant

waste j e !
fuel uil

steam
superheater

fuel

iWcompoi'i'O'i
furnace

vfniu"
scrubber

ekcwoM.'i.
precettato'i
m i c i medidle ite.rt
ec't<*nge<s

The variability over time of the S0 2 content is variable and mainly

depends on the raw material and the process used.
Other processes: Many other processes produce gases containing S0 2 ,
such as iron sinter plant, the Wellman-Lord process, etc. The S0 2
content varies from 0,1 to 20% and the variability over time is
changeable. Table A.m. 1(b) summarises the characteristics of the
principal sources of S0 2 .

Table A.III.1(b) Summary of the Principal Sources of SO

Process

Ra w Gas

Inlet
conversion
S 0 2 content0 2 content S 0 2 content
(%)
(%)
(%)

Variability
in time

S-burning

18

10-11 (8-13)

Very low

Pyrite roasting

15

8 - 10

High

6 - 11

6 - 10
1 - 13

Relatively low
Can be very

Roasting processes
"ZnS"
6 - 10
"CuS"
1 -20
"PbS"
sintering
2-6
other lead
smelters
7-20
"MoS"

0,5 - 1,5

H2SO4
regeneration

2 - 10

Metal sulphate
roasting

high
' V 15

2-6

Relatively high

/ 15

7 - 13

Low to very
high (Batch pr.)

0,5 - 1,5

Relatively low

2-8

Depends on the
"quality" of
spent acid

/15

High

Incineration of
H2S or other
S-gases

0 , 5 - 12

Other (Ag)

0,1 - 20

0,5 - 10

Variable
Variable

A.III.2

Sulphuric Acid Production

Six process routes are discussed in this section of the Note.
represent the principal process routes which are available.
o

These

Single contact process (single absorption): The only contact process

without intermediate absorption is nowadays only used in new plants
to process S 0 2 gases with low and widely varying S 0 2 contents.
The S0 2 -containing gases, which have been carefully cleaned and
dried, are oxidised to sulphur trioxidc in the presence of catalysts
containing alkali and vanadium oxides. The sulphur trioxide is
absorbed by concentrated sulphuric acid in absorbers, where
necessary preceded by oleum absorbers. In the absorbers, the sulphur
trioxidc is converted to sulphuric acid by the existing water in the
absorber acid. The absorber acid is kept at the desired concentration
of approximately 99% by wt. by adding water or dilute sulphuric
acid as shown in Figure A.III.2(a).
The single contact process is generally used with S 0 2 content inlet
gases of 6 to 10%; in new plants, the conversion efficiency is about
98,5% as a daily average; in existing plants, it is difficult to obtain
better than 98,0% conversion, however, in some existing plants, a
conversion efficiency of 98,5% can be achieved. In case of gases
with 3 to 6% S0 2 , th conversion rate is 97,5 to 98,5%.

Double contact process (double absorption): In the double contact

process, a primary conversion efficiency of 80% to 93%, depending
on the arrangement of the contact beds and of contact time, is
obtained in the primary contact stage of a convenor preceding the
intermediate absorber. After cooling the gases to approx. 190 "C in
a heat exchanger, the sulphur trioxide already formed is absorbed
in the intermediate absorber by means of sulphuric acid with a
concentration of 98,5 to 99,5% by weight. The intermediate absorber
is preceded by an oleum absorber if required. The absorption of the
sulphur trioxide brings about a considerable shift in the reaction
equilibrium towards the formation of S0 3 , resulting in considerably
higher overall conversion efficiencies when the residual gas is passed
through one or two secondary contact beds. The sulphur trioxide
formed in the secondary stage is absorbed in the final absorber.
In general, S 0 2 feed gases containing 10 to 11% S 0 2 are used for this
process.
Figure A.111.2(b) below shows the layout of a sulphuric acid plant
(double catalysis) based on sulphur combustion.
The conversion efficiency is about 99,6% as a daily average in the
case of sulphur burning.
As the oxidation of S 0 2 is favourised by pressure, Pressure Contact
Processes have been developed in which the sulphur combustion,
sulphur dioxide conversion and sulphur trioxide absorption stages
are effected at elevated pressure. The idea of conducting a contact
process under pressure is not new. So far it has only been embodied
in one industrial double-absorption plant with a capacity of 550575 tonnes per day of H,SO, which is being operated in France. The
maximum pressure in this plant is 5 bar. It first came into operation
in 1972.

10

Figure AIII.2(a)
Sulphuric acid plant (single catalysis) based on roasting

-c=>
Sutph.dic oret

feed nler

Steam

-SSHJ

Wine hen
boil*'

Cyclont

-c=0>
Cooler

Venturi
Hoi
icrubbet
electro
italic
precipiutor

foat t er product
Wet
precip-

<=>
Watte $*t to Hack
/ Fnef/ absorber

Sulphuric

Dryer

ejcid

11

Figure AIII.2(b)
Sulphuric acid plant (double catalysis) based on sulphur combustion

fflXXXX
Wttfr

XXKgfrg

Weste teet

feed

-<Sh
Steam

superheater

< sssss - ^ J

Combustion lufnece
Sulphur

Steam

<&1
Waste gas to stack

baile:

czC>

Converter

water

<=>Ed

SI

=5
Dryer

Intermediate

adsorber

-cO
JLL_
r**/*/ absorber

Sulphuric acid
Weste gas filter

12

Compared with the conventional double-absorption process, two

especial advantages have been claimed for the pressure contact
process:
i)

The position of the chemical equilibrium in the sulphur

dioxide oxidation reaction is more favourable, allowing a
higher conversion efficiency to be attained with a reduced
amount of catalyst. The plant is reported to have achieved
99.80-98.85% conversion. The tail gas sulphur dioxide content
is reported to be reduced to about 200-250 ppm v. However, the
high temperatures in the sulphur furnace increase the rate of
formation of nitrogen oxide.

ii)

On account of the lower operating volumes of the converter

gases, smaller equipment can be used. This reduces materials
and site area requirements, and it raises the capacity limit of
shop-fabricated equipment. The resulting capital cost savings
are said to be abut 10-17% in comparison with current doubleabsorption plants. It should be mentioned, however, that in
some countries these savings would be nullified by the cost of
conforming with the requirements for extra wall thickness and
higher-grade materials of construction laid down in the safety
regulations relating to pressure vessels.

The principal disadvantages of the pressure contact process in

comparison with the conventional double-absorption process is that
it consumes more power and produces less steam.
Wet Contact Process (WCP): This process is not sensitive to the
water balance and has been used to treat of f-gas from a molybdenum
smelter as well as being installed in two desulphurisation plants (one
in a Flue Gas Desulphurisation system, the other on an industrial
boiler) currently under construction. An earlier version of the WCP
technology was used to treat lean hydrogen sulphide gases. For all
gas feeds, sulphurous components in the gas are converted to
sulphuric acid without the need to dry the gas first.
When treating roaster off-gas, the off-gas is cleaned in a standard
purification system and then fed through a blower, which provides
the pressure necessary to overcome the pressure drop across the
system. The gas is preheated initially in the tower and, secondly, in
a heat exchanger. It is next fed to a converter, where sulphur
dioxide is oxidised over a catalyst to sulphur trioxide. Depending
on the conditions, a cooled reactor or an adiabatic reactor is used.
Sulphur trioxide-containing gas is then cooled in a gas-gas heat
exchanger. Consequently, part of the sulphur trioxide reacts with
the water vapour in the gas to form sulphuric acid vapour. Finally,
the sulphuric acid vapour is condensed and concentrated, without
acid mist formation, in a multi-tube falling film condenser. Cooling
is provided by the cold feed gas supplied to the shell side.
The only utilities required are cooling water for the acid coolers,
electricity for the blower and fuel to enable autothermal operation
if the feed gas contains below about 1.5-2.0% S0 2 .
Figure AIII.2(c) shows one typical plant layout using the Wet Contact
Process for producing 96% sulphuric acid from the combustion of
H2S gases.

13

Figure AIII.2(c)
Sulphuric acid plant (wet contact) for production of 96% by wt. sulphuric acid

IV.lie pj, io sleet.

HjS caset

C C mb ut t

furnace

s \

Cet cooler

feed molet

Weite heet
bo.ler

I
Oryer

Converter

Condensation tower

Fig. 5. Sulphunc seid plant (wet contact) (or production of 96% by wt. sulphuric acid

Weste ces filier

14

0,05 to 7%. The conversion efficiency is about 98% as daily average.

o

Proces based on NO^ The Modified Lead Chamber Process is able

to treat gases with low S02-content (as low as 0,05%) up to 8%. The
process is also able to treat gases containing a mixing of S0 2 and
NO r
From the chemical point of view, the process is a development of
lead chamber sulphuric acid technology, in which nitrogen oxides
are used to promote sulphuric acid production directly from sulphur
dioxide through the formation of an intermediate, nitrosyl sulphuric
acid. Widely used in the early 1900s, this technology has been
largely superseded by the contact process.
At the end of the 1970s though, it was modified and is now under
discussion as a method for cleaning off-gases from power plants or
from ore-roasting.
After dust removal and purification, the sulphur dioxide-containing
gas is fed through a denitrification system, where final traces of
nitrogen oxides remaining in the sulphuric acid are removed, and
then through the Glover tower, where the bulk of the nitrogen oxides
are removed from sulphuric acid. Sulphur dioxide is absorbed from
the gas stream next in sulphuric acid (59 to 66%) in a packed tower.
In both the Glover and absorption towers, the gas flow is counter
current to the liquid flow (see figure AIII.2(d)).
The final step of the process is removal of nitrogen oxides from the
gas stream by absorption in sulphuric acid (74%), so forming nitrosyl
sulphuric acid. Absorption is achieved in three stages in a specially
designed packed vessel through which the gas flows horizontally.
This vessel allows multiple absorption without dead space between
stages. (This design is also employed for final removal of nitrogen
oxides from sulphuric acid). The absorber has dividing walls that
are permeable to the gas between each stage. A packing is placed
between the dividing walls.
Regulation of the NO/N0 2 ratio, which is important for the
absorption of nitrogen oxides, is achieved by adjusting the amount
of nitrosyl sulphuric acid fed to the Glover tower. If necessary the
nitrogen oxide's balance is maintained by adding nitric acid to the
Glover tower.
For S0 2 content of 0,5 to 8%, the conversion efficiency is about 100%
but emissions of NOx occur (up to 1 g/m'N of NO + NO2). Since
1974, Ciba-Geigy has been developing such a process specifically
designed for processing gases with about 0.5-3% volume S0 2 .

H 2 0 2 Process: The conversion of S0 2 to S0 3 can be achieved by the

use of H 2 0 2 . Conversion efficiency is higher than 99% but the cost
of H 2 0 2 makes this an expensive process for sulphuric acid
production. However, since the process leaves no waste, it is very
useful for tail gas scrubbing where especially difficult local
conditions cannot tolerate the emission even from an installation
as efficient as the best contact plant. It is reported that such units
have been installed in Germany by Degussa and Sud-Chemie. The
H 2 0 2 is used either directly or is produced by electrolysing H 2 S0 4
to peroxydisulphuric acid in the "Peracidox" process.

15

Figure AIILl(d)
The Modified lead Chamber Process

. *?W*7Y/3> VfS

IJ

<: oco/M

<
AbSOkPlION

PHuOuClL-J
uuClLJ

c4"

(tOtMSO,/
H2S04
-fVr-Vf K O N C .
NO - t f i V

(MO)H0/

NO

-Her

tefy

NO
ABSORPTION

SO 2

THAL
*%VCCSOAI>

H2S0 4
KONZ.

NOx

OESORPTION

KON2.

H >0 *
ABSORPTION

'; <" o

*
so2-r??<?ccA<//vi

so,

TfZrf<ZS

NO

- /=
/ Vol.',.
> U,8 Vol.-*; /v-r 11NO3-Produktion.

NO oesoRPTiONs

O^CWTEATT

16

Unsteady state oxidation process: One of the most recent

developments in sulphuric acid technology, and perhaps one of the
most radical, has taken place in the USSR. Rather than use a
multiple-bed converter, a process using a single-bed converter, in
which the gas flow is periodically reversed, has been developed and
used in several plants. The unsteady-state method of oxidising
sulphur dioxide is said to enable gases with low and variable sulphur
dioxide concentrations to be processed, and to exclude the need for
much of the expensive heat exchange equipment.
Too little reliable information is available from USSR and it is not
possible, at present, to present relevant process and operation
characteristics.

The following data on production processes have been presented in detail

in the previous paragraphs and are summarised here in Table A.III.2(a)
using an O2/SO2 ratio of about 1 + 0,2 (possibly 0,8 to 3).

17

Table A.III.2(a) Sulphuric Acid Production Processes for New Plants

NEW PLANTS

S0 2 content
in feed gas
(% vol)

Conversion rate State of the art

daily average
emission for new
(%)
plants
S0 3 [2]

Single contact

6 - 10
3- 6

98,5% [4]
97,5 to 98,5

0,4 kg/t [5]

Double contact

8-11

99,6% [1]

0,15kg/t[5]

Wet contact
process

0,05 - 7

98,0%

< 10 ppmv SO3

Process based
on NO x

0,05 - 8

nearly 100% [3]

No data

H 2 0 2 process

> 99,0%

Very low

Unsteady state
conversion
process

No data

No data

[1]
[2]
[3]
[4]
[5]

when sulphur burning

SO3 + H2SO4 expressed as S0 3
possible emissions of NO,
for existing plants the conversion rate is 98%
per ton of acid produced

18

.IV

Pollutants Emitted to the Atmosphere

The main pol l utants emitted are:

o

S0 2 resulting from the uncompl ete character of the reaction of oxidation

S0 3 resul ting from the uncompl ete absorption of S0 3

o
o

l
vsicu es of H^O^ resul ting from absorption
H 2 S0 4 vapour from scrubbing.

According to the source of SO, and the process of H2S04 production, many other
pollutants can be (or coul d be) emitted as traces, such as (NO + N0 2 ) in al l
processes but mainl y in the process based on .
NO and N0 2 in the Modified Lead Chamber Process
Heavy metal s (for exampl e, Mercury) when certain ores are treated.

19

A.V

Emission Limits Applied in Member States for Sulphuric Acid Plants

Table A.V(a) presents the emission limits applied in EC Member States.

Table A.V(a)

Emission Limits for Sulphuric Acid Plants in EC Member States

COUNTRY

S02

S03

NOx

Belgium

(5)

(5)

(5)

Denmark

5 kg/t H2S0 4

(1)

Germany

97,5 to 99,6
conversion rate

(4)

Greece

0,5 kg S03/t H2S0 4 (1)

(5)

^OtoOmg/n^N

500mg
NO^m^N

(4)

10 kg/t H2S0 4

0,8 kg SOj/t H2S0 4

{ 5 600 mg/n^N (2)

{615 mg/n^N

(2)

(6)

{ 4 275 mg/nv^N (1)

{ 500 mg/nr'N

(1)

(6)

Contact process

8 550 m g / m ^ (2)
^ e S O m g / n ^ N (1)
1 425 mg/nv'N (3)

500 mg/m^N
pOOing/ar^N
{ISOmg/nrfa

(2)
(1)
(3)

France

6 kg SOi/t H2S0 4 (7)

0,5 kg SO^t H2S0 4 (7)

NO, process
Spain

(5)
3 0 0 0mg
NOj/nr^N (2)
1000mg
N02/m 3 N (1)
(5)
(5)

Ireland

(5)

(5)

(5)

Italy

(5)

(5)

(5)

Luxembourg

(5)

(5)

(5)

The Netherlands

(5)

(5)

(5)

Portugal

(5)

(5)

(5)

United
Kingdom

(1)
(2)
(3)
(4)
(5)
(6)
(7)

Sulphur emitted to
air as S0 2 +S0 3 shall
not exceed o,5% of
sulphur burnt

No substantial visible
emission

(5)

New plants
Existing plants
Plants built after 1980
Depending on S 0 2 content in raw gas and its variability
No limitation
H2S0 4 mist
These figures are not official or national emission limits; they are used as
guide values by licensing authorities during registration procedures.

20

PART
BEST AVAILABLE TECHN OLOGIES
NOT ENTAILING EXCESSIVE COSTS (BAT)
FOR THE PRODUCTION OF SULPHURIC ACID
BI

Introduction

The present technical note does not deal in detail with the storage and handling of
raw materials (sulphur, pyrites, ore, spent acid, sulphates, etc.) used to produce S0 2 .
Part A has presented the different sources of S0 2 , the techniques of conversion of S0 2
to SO3 best adapted to each kind of source. These techniques of conversion have their
own typical conversion rate and consequently their S0 2 emission concentration
expressed in mg S0 2 /m 3 N .
The process conditions and the S0 2 concentration in the gas entering the converter
determine the conversion efficiencies which directly influences the S0 2 emission
concentration (see figure B.I(a)).
The SO3 and H 4 content in the tail gases depends on the raw material and process.
The content of gaseous SO3 and H SO,, mist of tail gases is essentially a function of
the temperature and concentration of the irrigation acid in the final absorber.
The following BAT's are presented for new plants due to the fact that it is generally
not possible to change the source of S0 2 or to change or modify the conversion process.
For existing plants, only tail gas scrubbing can be generally considered as a BAT
taking into account that addition of a tail gas scrubbing to a double absorption is
considered as entailing excessive costs (see Annex 2) and could be justified only for
severe local considerations.
BII

Best Available Technology for N ew Plants

BII 1

Sulphur Burning
Due to the high concentration of S0 2 and stability over time, the BAT
proposed is without doubt the double contact process. A conversion
efficiency of 99,6% (daily average except startup and shutdown
conditions) could be achieved.

BII.2

Metal Sulphide Roasting

0

Pyrite Roasting: Although the stability over time is considered as

low, it is generally admitted that the BAT could be the double
contact process with a conversion efficiency of about 99,5 to 99,6%
depending on the quality of the ore (daily average excluding start
up and shutdown conditions).

Zinc ores: As the range of S02content after possible dilution is

about 6 to 13% and the variability over time is low, the double
contact process can be used as a BAT with a conversion efficiency
of about 99,6% (daily average except startup and shutdown
conditions) when using gases with S0 2 content >8%; with gases with
lower S 0 2 content the conversion rate is 99%.

21

Figure Bl(a)
Emission of S 0 2 *\s a function of the S02 concentration at the converter inlet and the
S02 conrersion rate.

-5000
mg/m3

1000
o
o
c
)
o
c
o
o
c
o

100

50
99.9

99,8 99.7 99.5

99

98

97 % 94

SO2 conversion rate

l ' I '

0.7

'

I I

3 4

I I 1I I 1 _ i

20

40

Specific S02 emission rate kg S02 per t /V^SO^

22

Copper ores: When the S 0 2 content in gases is high (6 to 13% after

possible dilution) and the variability over time is low, the double
contact process can be considered as BAT with a conversion
efficiency of about 99,6% (daily average except start-up and shutdown conditions).
When the SO, content in gases is low (1 to 6%) and the variability
over time is nigh, the single contact process can be considered as
BAT with a conversion efficiency of about 98,5% (daily average
except start-up and shut-down conditions). When the S 0 2 content is
5 to 9% and the variability over time is high, a conversion rate of
99,0 to 99,5% can be achieved by using the double contact process.
When one plant experiences the full range of variability, the
efficiency will vary between 98 and 99,5%. Similar circumstances
will permit an achievable S 0 2 level, in terms of convenor
throughput based on 100% H 2 S0 4 acid, of between 0,3 up to 0,6 kg/t
due to fluctuating absorption conditions.

Lead ores: In the case of sintering lead orcs,the variability is

relatively high and S 0 2 content can be very low, the single contact
process but also the wet process and the process based on NO x can
be considered as BAT with a conversion efficiency of about 98,5, 98
and 100% respectively. In other cases (lead smelters), the S 0 2 can be
much higher and less variable over time. In this case the double
contact process can be considered as a BAT with a conversion
efficiency of about 99,5% (daily average except start-up and shutdown conditions).

Molybdenum ores: Some roasting plants of molybdenum sulphide

ores arc rather small in size and the production of sulphuric acid is
not considered as being of interest. That is the reason why, for small
plants, alkaline tail gas scrubbing is considered as a BAT with an
efficiency of reduction of the emissions of 50 to 75% or better.
Molybdenum ore roasting plants without sulphuric acid production
are outside the remit of this note.
Roasting plants can be associated with a sulphuric acid plant of
reasonable size; the Wet Process or the Process based on NO can be
used as a BAT with a conversion efficiency of about 98 and nearly
100% respectively (daily average except start-up and shut-down
conditions).
It has not been possible to arrive at precise limits for the size of the
plant when choosing for one BAT or another; costs and conversion
rates have to be taken into account. The Technical Note on BAT on
Heavy Metals covers this point and it is recommended that this
document should be consulted on this issue.

BII.3

Sulphuric Acid Regeneration

Every technique can be considered as a BAT and the choice of techniques
depends on the S 0 2 content in the feed gases.
The conversion rates can be:
about 99% if S 0 2 content > 8%
98 to 99% if SO, content = 5 to 8%
about 98% if S 0 2 content < 5%

23

BII.4

Metal Sulphate Roasting

The conclusions are exactly the same as those for sulphuric acid
regeneration (see BII.3).

BII.5

Incineration of H and Other S-Containing Gases

The conclusions are the same as those for sulphuric acid regeneration (see
B.II.3).

BII.6

General Considerations
For the time being, the H 2 0 2 process, the Unsteady State Process and the
Pressure Contact Process cannot be considered as BAT due to the lack of
relevant information.
If, for local considerations, and if the contact process and absorption in
use result in a too high emission of SO v additional tail gas scrubbing is
required in order to reduce the emissions, it is likely that, for new plants,
the solution of single absorption + scrubbing should be preferred to the
solution of using double absorption. Double absorption + scrubbing may
be adopted in very particular high air pollution level zones, but is not
considered as a BAT in the definition of this present Technical Note.
When scrubbing is used, the problem of wastes has to be taken into account
and the possibility of producing fertilisers or other marketable products
has to be considered.

BII.7

Synthesis of the Proposals

Table BII.7(a) presents a synthesis of the results of the discussions.

Table B0.7(a) Summary of Proposed BAT tbr Sulphuric Acid Production

Double
Contact

S-burning

99.6%

Pyrite roasting

99.6%

Single
Contact

Wet
Contact

Process
based on
NO,

H202
process

Unsteady
state
process (*)

Tail Gas
scrubbing

C)

ting process
ZnS

99.6%

CuS

High SO,
99.6%
stable

LowS0 2
983%
variable

PbS

993%

practicable

tv

Mo S

practicable

practicable

practicable

practicable

H 2 S0 4 regeneration
Metal Sulphate roasting
H 2 S incineration

All kinds of techniques are practicable; conversion rate

Other processes

No possibility to reasonably propose BAT

C)

Not considered as BAT

small size plant

99% if S 0 2 content > 8%
98 to 99% if S 0 2 content 5-8%
98% if S 0 2 content < 5%

25

BUI

BAT for Storme, Handling and Shipping of Sulphuric Acid

Due to very low vapour pressure of H2S04 in normal temperature conditions, there is
no air pollution problem connected with the storage, handling and shipping of
sulphuric acid.
The handling of pure S0 3 and oleum requires safety procedures and managements in
order to avoid atmospheric pollution in the case of accidental release.
With regard to the ancillary operations referred above, important considerations are
as follows:
The receipt, handling and storage of powdered raw materials should be
carried out so as to minimise the emission of dust. Liquid and gaseous
feeds should be carefully contained to prevent the emission of odorous
fumes or gases. Precautions must be taken against fire. This applies
especially to the handling of elemental sulphur which can be ignited even
by the friction of a conveyor belt.
Oleum and S0 3 storage and handling operations which are often linked
with H2S04 production should be installed with means of controlling fume
emissions. Venting should be directed towards acid tanks or scrubbing
systems. Installations should be built by following the best engineering
practice. The emissions can condense and solidify in cool areas so this
must be very carefully guarded against to prevent over-pressurisation of
storage tanks.
BIV

Monitoring of Pollution

Two approaches are used to monitor emissions:

monitoring the process: temperature of contact layers, S02content entering
the contact and behind the intermediate absorption
monitoring of the emissions.
o

Monitoring of S 0 2 emissions: Continuous emission monitoring

equipment for S0 2 is available and suitable for sulphuric acid plants
and should be installed on all new plants. Dual range instruments
are available so that the much higher S0 2 emission concentration
during start-up can be monitored as well as the relatively low
concentration in the emission during steady operation. Emission
monitors should be capable of recording the data for future
reference. Emission monitor records should be retained and the
competent authorities should consider the appropriate statistical
analysis or reporting which is required.
Provision should be made for zero and calibration checks of emission
monitors, and for alternative testing in the event of breakdown or
suspected malfunctioning of the monitoring equipment. The regular
observation of monitors by plant operators for detecting
abnormalities in the process operation is as important an aspect of
monitoring as is the compliance function, and should be encouraged
by the competent authorities.

26

monitoring of mist emissions in the stack: There is at present no

known equipment available for carrying out reliable continuous
monitoring of sulphur trioxide. However, when such an instrument
is available, it should be fitted, together with a recorder.
Meanwhile, sulphur trioxide and acid mist can be measured by
manual sampling and chemical analysis. The combined SO, and acid
mist is easily measured by sampling a known gas volume through a
small amount of filter medium and titrating against a standard
alkali solution. Alternatively, the method described in VDI 2463
Part 7 (sopropanol method) can be used (see Annex 2 of this Note).

Sampling points for the above measurements should be provided. They must be easily
accessible and kept in good condition so that they can be used at very short notice.
Sealable openings 20 to 50mm diameter are generally considered as suitable, provided
that a sampling probe can be inserted into the exhaust gas stream, except in cases
when standardised methods require use of larger openings.

BV

Operational Controls

Operational controls should include means for:

Warning of absorber acid feed failure by possibly using a flow meter;
Warning of absorber acid feed over-temperature and controls of
temperature along the conversion tower;
Indication of sulphur feed rate and air flow rate;
Detection of acid leaks in acid coolers (pH-meter) and controlling level of
acid reservoir;
Acid-concentration > 98,5%;
Emergency plant trips;
pH-control on cooling water systems.
To aid start-up the following will be necessary:
Efficient catalyst preheating facilities, vented to the chimney. At least,
two catalyst stages must be above "strike" temperature before sulphur
dioxide is admitted to the contact;
Optimisation of absorber acid strength and temperature before sulphur
is admitted to the burner;
Use of additional controls to ensure that sulphur cannot enter the system
during shut-down;
Before a long shut-down period the catalyst bed should be efficiently
purged;
Good practices should be observed as set out in the Recommended
Guidelines for plant start-up (National Sulphuric Acid Association, 1982).

27

BVi

stack Height

The height of the exhaust stack conditions the maximum S0 2 /S0 3 concentration value
in the ambient air surrounding a sulphuric acid plant. It is also well known that this
concentration is widely fluctuating in space and in time due to the thermoaerodynamic conditions of the low level atmosphere (0 to 500m), these conditions can
vary due to the following factors:
vertical temperature and humidity structure
wind speed and direction
turbulence of the atmosphere
sunshine intensity
etc.
Proposals of stack heights could consequently have a questionable character.
For the time being, every Member State has its own method for estimating the height
of stacks. In the future, it is foreseen that a specific Technical Note on this topic will
be published by the Commission.

B.VII

Cross Media Impact on Other Environmental Media

The production of sulphuric acid has a very low cross-media impact.

During storage and handling of sulphuric acid, leaks may have an impact on the soil
or on waters. Precautions have to be taken in order to reduce the possibility and the
gravity of these leaks.
Tail gas scrubbing produces sulphites and sulphates which possibly entail problems of
reasonable disposal of wastes.

28
BIBLIOGRAPHY
(1)

Emissionsminderung Schwefelsureanlagen. VDI 2298

(September 1984)

(2)

Sulphuric acid (class II) works - Sulphuric acid manufacture - Note on Best
Practicable Means. BPM 17 (1985)

(3)

Recommended guidelines for the starting-up of sulphuric acid

manufacturing plants - National Sulphuric Acid Association Ltd (1982)

(4)

Sulphur, Sulphur Dioxide and Sulphuric Acid.

U.H.F. Sander, H. Fischer, U. Rother, R. Kola
B.S.C. Ltd and Verlag Chemie International Inc. (1982)

29
ANNEX Cl

A survey of the main characteristics of sulphuric acid production units has been
carried out in the EC Member States.
These tables of data are not exhaustive: the data has been chosen by experts of the
Working Group according to various criteria, such as:
new or old plants
high performance
typical process
etc.
The data are presented in order of capacity of production.

capecity
<t HjS0 4 100X / day)

125

280

300

300

350

360

350

SO,

thermal
decomposition
of spent acid

combustion
of elemental
sulphur

M2S
combustion

H2S
combustion

combustion
of pyrite

Pb-Cu smelter

combustion of
elemental sulphur

single contact

double contact

single contact

single contact

single contact

new contact
single absorption

double contact

22

50

50

57

32

96

96

99.1

99.6

ource

proces* m e d

ges volime ( I O V N / M

conversion rece (X)

98.2

99.5

mission standard
SOj
so 3
NOx

NO

the proportion
0.35 kg
of S emitted
SO2/tH2S04
shall not exceed
0.7X of that burnt

emission
S0 2 (kg/h)
SOj U g / h )
NOx

70
0.4

additional emission

NO

No

tail gas
scrubbing with
NH3 for ammonium
sulphate
production

batch

conti nous

technology abatement

emission monitoring
S0 2
so 3
NOx
cost of emission monitoring
investment
operation

0.35 kg
S02/tH2SO4

10 kg
S02/tH2S04
0.8 kg
S03/tH2S04

the proportion of S
emitted shell not
exceed 0.5X of that
burnt

18
0.12

96.9

tail gas
scrubbing with
NH3 for armonium
sulphate
production

No

No

conti nous

c ont1 nous

conti nous

26
H with abatement

26
H with abatement

26
<1

No

50,000 Ofls/year
40,000 Dfts/year

cost of absorption process

investment
operation
age(year)

16

O.'

capacity
(t HjSOj 100X / day)

400

490

500

525

550

550

SOj - source

combustion of
elemental sulphur

thermal
decomposition of
spent acid

combustion of
elemental sulphur

combustion of
sulphates & pyrite

combustion of
elemental sulphur

combustion of
elemental sulphur

process used

single contact

double contact

single contact

double contact

double contact

single contact

70

65

58

50

70

>99

98.2

99.5

99.7

98

99.0 to 99.5X
depending on S0 2
content
120 mg/m3N
500 mg/m3N

99.6X

0.5 kg SO2/tH2S04

60 mg/m3N
500 mg/m3N

0.2 kg S03/tH2S04

gas volume (10 3 m 3 N/h)

emission standard
SOj

10 kg S02/tN2S04

14.6

SO3
NOx

0.8 kg S03/tH2S04

3.0
3.0 dust

emission
S0 2 (kg/h)
SOj (kg/h)
NOx
additional emission

3.5
0.16

119
8

0.2
1.25

75
4 - 7
<500 mg/m3N

40
2.S
<500 mg/m3N

tail gos scrubbing

with NH3

NO

tail gas scrubbing

with N H 3 '

No

No

tail gat scrubbing

with NH3 for armoni un
sulphate production

conti nous

continous

continous

continous

cont i nous

conti nout

technology abetement
emission monitoring
SOj
SO3
NOx
cost of emission monitoring
Investment
operation

50,000 Of Is/year
40,000 Dfls/year

cost of absorption process

Investment
operation
age (year)

12
3 with scrubbing

23
13 with abatement

capacity
(t NjS0 4 100X / day)

650

700

700

720

725

770

combustion of
elemental sulphur

combustion of
elemental sulphur

combustion of
elemental sulphur
and pyrite

combustion of
sulphates & pyrite

combustion of
elemental sulphur

roasting of Zn
ores

process used

double contact

double contact

double contact

double contact

double contact

contact double
ebsorptlon

gas votum* (10 3 m 3 N/h)

50

60

60

80.5

conversion rat* (X)

99.6

99.5 - 99.7

99.6

99.6

99.5

the proportion of S
emitted hell not
exceed O.SX of thet
burnt

conversion rete

10 kg S02/tH2S04

>99.2X

0.8 kg S03/tH2S04

the proportion of S
emitted shall not
exceed 0.5X of that
burnt

the proportion of S
emitted shall not
exceed 0.5X of that
burnt

3.5
0.45

<20
not detectable

50
<1

emission standard
SO,
SOj
NOX

emission
SOj (kg/h)
S0 3 (kg/h)
NOx

45
<1

additional emission

No

NO

No

No

NO

No

conti nous

cont i nous

conti nous

continous

continous

continous
off-line alarm

No data

2.0 H BEF (1988)

0.3 H K F (1988)

technology abatement
emission monitoring
SO,

so 3

NOx
cost of emission monitoring
Investment
operation
investment
operation
age (year)

21

15

16

16

ro

capacity
(t HjSO., 100X / day)

800

800-900

900

980

1000

H00

S0 2 source

combustion of
elemental sulphur

combustion of
elemental sulphur

roasting of
sulphidic ores

combustion of
elemental sulphur

roast ing of ZnS

concentrate

raw pyrite
roasting

double contact

single contact

double contact

double contact

double contact

doubt* contact

110

100

87

108

140

98.2

99.5

99.6

99.7

99.5 / 99.6

440
25

99

144
5

process used
ges volume (10 3 m 3 N/h)
conversion rate (X)
emission standard
SO,
S0 3
NOx
emission
SOj (kg/h)
S0 3 (kg/h)
NOx

10 kg S02/tH2S04
0.8 kg S03/tH2S04

3
0.1

additional emission

120 mg/m3
380
25

80
8
5

130
5

85

NO

No

NO

No

NO

contI nous

conn nous

cont f nous

contInou*
manual

continous

25,000 Dfls/yeer
20,000 Dfls/year

47,500 Ofls
50,000 Ofls

Co

technology abatement
emission monitoring
SO,
S0 3
NOx
cost of emission monitoring
investment
operation

conti nous

25,000 DfIs/year
20,000 Ofls/year

average
on 4 years

cost of absorption process

investment
operation

age (year)

150,000 Ofls 1989

high efficiency
catalyst
"2!

250,000 Ofls 1988

high efficiency
catalyst

1 M Ofils 1986
high ef f iciency
catalyst

80 M Lire- (1984;

conversion of single
to double contact
38500 l i r e (1984)

34

ANNEX C2

PROCEDURE FOR MANUAL ANALYSIS OF SOj EMISSIONS

In the VDI 2463, part 7, (Isopropanol method), it is essential to test the isopropanol
used for the absorption of sulphur trioxide for freedom from peroxide, as the presence
of peroxide in the isopropanol, which is often observed, leads to elevated values for
sulphur trioxide.
The test may be conducted as follows:
10ml of the alcohol to be tested is mixed by shaking with 10ml fresh potassium iodide
solution (10% in water). After approximately 1 minute, absorption at 352 nm is
measured with a spectrophotometer.
If the absorption exceeds 0.1 (referred to a depth of 1 cm), the isopropanol should be
rejected. As a reference solution for this test, a blank sample should be made up with
water in place of isopropanol.
Similar VDI methods are available for the spot sampling of S0 2 . Alternatively the
collection of a known gas volume, shaking with neutralised excess hydrogen peroxide
solution to absorb and oxidise the S0 2 . and titration against a standard alkali solution
is easily carried out. However, this measures the total acidity of the exhaust gases, not
only S0 2 , and is the basis for the UK standard.

35

ANNEX CHI
INSTALLATIONS FOR WHICH AUTHORISATION IS REQUIRED
IN MEMBER STATES
Legal Pror.giQB of Member States Relevant to Plant Authorisation
According to Article 16 of Directive 84/360/EEC, Member States shall
bring into force the laws, regulations and administrative provisions
necessary to comply with its provisions not later than 30 June 1987. At
that date, only Greece failed to communicate its internal regulatary
measures to the Commission, so that nothing can be said about the actual
legal situation that this country. With regard to the other countries, the
situation is as follows:
o

In Belgium, the Directive is implemented by the following laws and

orders:
reglementering op als gevaarlijk, ongezond of hinderlijk
ingedeelde inrichtingen, zijnde, titel I van het Algemeen
Reglement van de Arbeidsbescherming, R.B. 11.2.1946
wet van 28.12.1964 op de bestrijding van de
luchtverontreiniging, B.S. 14.1.1965
KB 13.12.1966 betreffende de voorwaarden en modaliteiten
voor de erkenning van de laboratoria en instellingen die belast
zijn met de monsternemingen, ontledingen, proeven, en
onderzoekingen in het kader van de bestrijding van de
luchtvervuiling
KB 26.7.1971 tot oprichting van zones voor speciale
bescherming tegen luchtvervuiling
KB 8.8.1975 ter voorkoming van luchtvervuiling door S0 2 en
stof, afkomstieg van industrile verbrandingsinstallaties
KB 25.9.1978 tot regelementering van het gebruik der
benamingen enkenmerken van zware minerale olien, bestemd
om als brandstof to worden gebruikt.
It should be mentioned that the three administratively independent
regions of Belgium have the possibility to impose particular
requirements for the establishment and operation of a plant.

Denmark is of the opinion that the Directive is in accordance with

the Danish Environmental Protection law. The following legislation
is of relevance:
Lovbekendtgrelse no. 68 af 24. januar 1989 om
miljbeskyttelse.
Miljministeriets bekendtgrelse nr. 783 af 21. november 1986
om godkendelse af srligt forurenende virksomheder m.v.
Vcjledniing fra Miljstyrelsen nr. 7, 1974: Begrnsning af
luftforurening fra virksomheder.

The Federal Republic of Germany is of the opinion that its

comprehensive air pollution control legislation covers all
requirements of the Directive. In particular the following laws,
orders and regulations are of relevance:
Gesetz zum Schutz vor schdlichen Umwelteinwirkungen
durch Luftverunreinigungen, Gerusche, Erschtterungen und
hnlichen Vorgngen (Bundes-Immissionsschutzgesetz -

36

BImSch) vom 15. Mrz 1974 (BGBl. I S. 721, 1193), zuletzt

gendert durch Art. 5 der Dritten ZustndigkeitsanpassungsVerordnumg vom 26. November 1986 (BgBI. I S. 2089)
Vierte Verordnung zur Durchfuhrung des BundesImmissionsschutzgesetz (Verordnung ber genehmnigungsbedrftige Anlagen - 4. BImSchV) (BGBl. I S. 1586), f zuletzt
gendert durch Verordnung zur Neufassung der Ersten und
Vierten Verordnung zur Durchfhrung des BundesImmissionsschutzgesetzes vom 15. Juli 1988 (BGBL. I S. 1059)
Neunte Verordnung zur Durchfhrung des BundesImmissionsschutzgesetzes (Grundstze des Genehmigungsverfahresn - 9. ;BImSchV) vom 18. Februar 1977 (BgBI. I S.
274), gendert durch Verordnung vom 27. Juni 1980 (BGBL.
I S. 277)
Erste Allgemeine Verwaltungsvorschrift zum BundesImmissionsschetzgesetz (Technische Anleitung zur Reinhaltung
der Luft - TA Luft) vom 27. Februar 1986 (GMB1. S. 95, 202)
France has implemented the Directive by:
Nomenclature des installations classes pour la Protection dc
l'Environment: Loi 76-663 du 19/8/1976, dcret du 21/9/1977
Dcret 85-582 du 7/6/1985 sur taxe parafiscale sur les rejets
de S0 2
Etude d'impact
Etude des dangers
Arrt prfectoral
Ireland has implemented the Directive by its:
Air Pollution Act of 1987
Licensing of Industrial Plant Regulations of 1988
In Italy, the government considers the following laws and orders as
satisfying the implementation of the Directive:
Leggen. 615 del 13.7.1966
D.P.R. n. 322 del 15.4.1971
D.P.CMn. 30 del 28.3.1983
D.M. n. 105 del 10.3.1987
D.P.R. no. 203 del 24.5.1988
Luxembourg has informed the Commission that all requirements of
the Directive are covered by:
Loi du 16 avril 1979 relative aux tablissements dangereux,
insalubres et incommodes
Rglement grand-ducal du 23 dcembre 1987 relatif aux
installations de combustion alimentes du combustible liquide
ou gaseux
Rglement ministriel du 22 juillet 1987 portant publication
de la Directive 84/360.

37

The Netherlands regard the provisions of the Directive as being

implemented by:
Besluit van 6 september 1972 tot uitveoring van de artikelen
21, eerste en derde lid, 24, eerste en derde lid, 32, 33, tweede
lid, 34, derde lid, 40, eerste lid, en 73, eerste lid, van de Wet
inzake de luchtverontreiniging
(stb. 1970,
580)
(Vergunningenbesluit inrichtingen luchtverontreiniging)
Hinderwet (29-8-1985, Stb. 494)
Wet inzake de luchtverontreiniging (12-12-1985, Stb. 655;
entered into force 1-2-1986)
hinderbesluit (statutory instrument, 12-1-1984, Stb. 7)
Inrichtingenbcsluit ex. art. 19 Wet Luvo, 28-12-1984, Stb. 709,
25-8-1978, Stb. 444, statutory instrument)
Vergunningenbesluit luchtverontreiniging
(statutory
instrument, 23-4-1980, Stb. 407)
Wet algemene bepalingen Milieuhygiene, 23-4-1986, Stb. 211
In Portugal the following legislation
implementation of the Directive:

is

relevant

for

the

Decree-Law No 46 923 of 28 March 1966

Decree-Law No 46 924 of 28 March 1966
Decree-Law No 255/80 of 30 July 1980
Administrative Order No 110/85 of 20 november 1985
Law No 1947 of 12 February 1937
Decree No 29 034 of 1 October 1948
Regulation No 446.76 of 5 June 1976 on the licensing of
electricity generating plants
Spain has laid down the following relevant legislation:
Decree 2414/61,30 November 1961. Rules and Regulations for
Annoying, Insalubrious, Noxious and dangerous Industries
Law No. 38/72; 22 December 1972. Protection of the
Atmospheric Environment
Decree No. 795/1972; 20 March 1972. Development of article
11 of Law No. 38/72.
Decree No. 833.1975; 6 February 1975. Development of Law
38/72
Order, 18 October 1976. Prevention and Correction of
Atmospheric Pollution from industrial activities. Procedure
and regulations for the authorisation of new plants and
vigilance of actual and new plants. Sampling methods.
Calculation methods for stack height. Requirements for cooperating laboratories.
Legislative Royal Decree, No. 1302/86, 28 June 1986.
Environment and EEC. Evaluation of Environmental Impact.
Based on the 85/377/EEC Directive. (BOE No. 155, 30 June
1986)
Royal Decree No 717/1987, 27 May 1987
Royal Decree No 833/1988, 20 July 1988
Royal Decree, No 1131/1988, 30 September 1988. Rules and
regulations for the implementation of the Legislative Royal
Decree No 1302/1986. (BOE No. 239, 5 October 1988)

38

The United Kingdom considers the provisions of the Directive as

implemented by the following legislative measures:
Acts
Alkali etc. Works Regulation Act 1906 as it applies to Great
Britain (this is further amended by the Health and Safety
(Emissions into the Atmosphere) Regulations 1983)
Alkali etc. Works Regulation Act 1906 (as it applies to
Northern Ireland)
Health and Safety at Work etc. Act 1974
Regulations and Orders
The Alkali etc. Works Regulation Order (Scotland) 1933
The Alkali etc. Works (Registration) Order 1957
The Alkali etc. Works (Registration) Order (Northern Ireland)
1981
The Health and Safety (Emissions into the Atmosphere)
Regulations 1983
The Alkali etc. Works Order (Northern Ireland 1987)
The Control of Industrial Air Pollution (Registration of Work)
Regulations 1989
The Health and Safety (Emissions into the
Atmosphere)(Amendment) Regulations 1989

Further proposals are under consideration as parts of a major updating of

the air pollution legislation of the United Kingdom.
CHI.2

Installations for which Authorisation is Required in Member States

All countries but Greece claim that their national legislation covers all
aspects of the Directive. In more detail, some countries have laid down
in their legislation a detailed list of installations which have to undergo
a licensing procedure prior to operation.
In Belgium, a "List and Classification of Dangerous, Dirty and Noxious
Industries" (tablissements classs) is given in the General Regulation for
the Protection of Labour, Chapter II, Title I (Arrte du Regent du
11.2.1946). All installations mentioned there must be subject to an
authorisation procedure prior to construction, conversion, relocation and,
consequently, operation. According to the danger emanating from these
installations, they are divided into three categories:
1.

source of major hazard, approval at provincial level

2.

less important, small installations, approval at local government level

3.

notifiable installations which by virtue of their inferior importance

do not require any formal approval

39

Sulphuric acid installations covered by this Technical Note are part of

category 1.
In Denmark, the "Miljministeriets bekendtgrelse nr. 783 af 21. november
1986" lists a number of activities and processes requiring authorisation
prior to operation.
In the Federal Republic of Germany, the Fourth Order implementing the
Federal Immission Control Law (Order of Installations Subject to
Licensing) contains a list of installations which have to go through a
licensing procedure. The order distinguishes between installations which
have to undergo the full licensing procedure according to Article 10 of
the Federal Immission Control Law and installations which have to
undergo the simplified procedure laid down in Article 19 of the Federal
Immission Control Law.
In France, the act of 19.7.1976 lists some 400 headings of "classified
installations", divided into two main categories: the largest installations
are subjected to authorisations and have to meet certain requirements
governed by prefectoral decrees; notification by the owner or operator of
installations suffices for the other ones. For sulphuric acid production,
the headings arc: no. 29 - 30 - 31 - 31 bis.
In Ireland, in accordance with 1988 regulations made under the Air
Pollution Act, 1987, all new industrial plant must be licensed from 1.2.1989
by the local authority. Article 6 (1) of the act defines the term "Industrial
plant" as follows:
"Industrial Plant" in this Act means any plant, equipment, appliance,
apparatus, machinery, works, building or other structure or any land or
any part of any land which is used in the course of trade, business or
industry for the purposes of, or incidental to, any industrial process
specified in the Third Schedule.
The Third Schedule mentioned in this Article is to a large extent identical
with the Annex I of Directive 84/360/EEC.
In Ireland, there is no sulphuric acid production.
In Italy, trade and industrial processes which cause air pollution are
classified into two groups, the first group relates to industrial installations
which must be established far away from residential areas; all units need
authorisation. The second relates to trade activities.
In Luxembourg, Annex I of Directive 84/360/EEC has been introduced
literally into national law (Rglement ministriel du 22.8.1987). However,
more important for the practice of licensing is the list of classified
installations attached to the law of 16.4.1979, relating to dangerous, dirty
or noxious installations. The establishments arc divided into three classes.
The existence, operation, transfer, extension or conversion of
establishments in classes 1 and 2 is subject to authorisation; class 3
establishments are subject to a written declaration to the Inspection of
Works and Mines.

40

In the Netherlands, the Air Pollution Act requires that no establishment

belonging to a list of about 400 industrial installations may be set up or
operated without a permit to be issued by the provincial authorities.
In Spain, the Decree 833/988 dated July 20 lists some 700 industrial
installations which may produce noxious and dangerous wastes and
therefore are subject to authorisation. Table 6 of the Decree lists the
installations and activities relevant for this Technical Note.
In the United Kingdom, the authorisation policy is implemented by two
different approval
procedures. Plants subject to the national air pollution
inspectorates1 are required to have a certificate of registration issued by
the responsible inspectorate. Local authorities must be notified of
proposals to install furnaces not subject to the approval of the
inspectorates. The inspectorates are responsible for some sixty processes,
known as "alkali works" and "scheduled processes", which are listed in the
relevant legislation.
In Portugal, sulphuric acid manufacture is considered as a first class
installation, which means that the permit will be granted only after an
approval of the project and the permit can include the necessary
conditions for the prevention of air pollution. During the life of the
installation it is submitted to periodic inspections and the initial
conditions can, if necessary, be changed. The whole process involves the
Ministry of Industry, Environment and Health.
In Greece all manufacturing and production units require a permit to
operate and produce - this is in accordance with Law No 3214 of 1955 in
Conditions regarding the setting up of industries (Official Journal
108A/1955 and Law No 207 of 1967 the construction and use of factories
(workshops),storage facilities etc (Offical Journal 216A/1967).

In England and Wales, the control authority is "Her Majesty's Inspectorate

of Pollution", in Scotland "Her Majesty's Industrial Pollution Inspectorate",
in Northern Ireland the "Alkali and Radiochemical Inspectorate".

41
Liat of Mambars of BAT Working Group on

Sulphuric Acid Production

Technical coordination of the Working Group

Mr R. Bouscaren
CITEPA
rue Henri Heine
F-75016 Paris

Belgium

Denmark

Ir. Leo Steenhoudt

c/o Metallurgie HobokenOverpelt NV
Adolph Grelnerstraat 14
B-2710 Hoboken

Mr Oluf Nielsen
Superfos Fertilizers
Kongensgade 107
DK-7000 Fredericia

France
Mr G. Desrumaux
Rhone-Poulene Chimie
Qual Paul Doumer 25
F-92408 Courbevole Cedex

Mrs V. Fert
Ministore de l'Environnement
14 Bd. du Gnral Ledere
F-92524 Neul My-sur-Selne

Germany
Dr K. Braendle
BAYER AG Leverkusen
Bayer A6
D-5090 Leverkusen-Bayerwerk

Mr . Felter
Bude I co bv
P.O. Box 2001
0-6020 AA Bude I

Greece

Italy

Dr N. Con i ordos
Industries Chimiques du Nord
de la Grce SA
BP 10183
GR-54110 Thassaloniki

Mr Mario Vichi
Nuova Solmine SpA
Stabilimento di Scarlino
Casei la Postale 110
I-58022 Fol Ionica (Gr)

The Netherlands
Mr W.J. Koken
DSM Chemical Products
P.O. Box 27
Koestraat 1
NL-6167 MB Geleen

Mr M. Koopman
Ministerie van VROM
Postbus 450
NL-2260 MB Le Idschendam

WD Dr H. Poh le
Umweltbundesamt
Blsmarckplatz 1
D-1000 Beri in 33

42

Portugal
Ms. Clara M. Lopes
Dlreccao-Geral da
Qualidade do Ambiente
Rua do Sculo 51-3
P-1200 Lisboa

Ms. Gabr i e I a Nunes

Direco Geral da Industria
Av. Conselheiro Fernando
de Sousa, 11
-1092 Lisboa

Sain
Mr Jos M. Poncet
Astur lana de Zinc SA
Apartado 178
E-33400 Aviles (Asturla)

Un ted Kingdom
Dr J. Lane
HMIP
Sovereign House
40 SI Iver St
UK-Sheffleld S1 2ES

Dr J.P. Shields
Hayes Chemical Distribution Ltd.
Sandbach
UK-Cheshire CW11 9PZ