Treatment of Spent Pickling Acid

from Stainless Steel Production

A review of regeneration technologies with focus
on the neutralisation process
for implementation in Chinese industry

Lena Dahlgren

Master of Science Thesis

Stockholm 2010
 Lena Dahlgren

TREATMENT OF SPENT PICKLING ACID FROM

STAINLESS STEEL PRODUCTION
A REVIEW OF REGENERATION TECHNOLOGIES WITH FOCUS
ON THE NEUTRALISATION PROCESS
FOR IMPLEMENTATION IN CHINESE INDUSTRY

Examiner:
Per Olof Persson, Industrial Ecology

Master of Science Thesis

STOCHOLM 2010

PRESENTED AT

INDUSTRIAL ECOLOGY
ROYAL INSTITUTE OF TECHNOLOGY
www.ima.kth.se
TRITA-IM 2010:21
ISSN 1402-7615
Industrial Ecology,
Royal Institute of Technology
www.ima.kth.se
Abstract
Pickling is a unit operation within stainless steel production, which means treating the steel with
hydrofluoric acid (HF) and nitric acid (HNO3), also called mixed acid. The whole process generates
waste water streams which have to be treated before released to recipient.

The aim of this degree thesis was to make an evaluation of different possibilities for reduction of
emissions from the pickling process with China as a possible future market. The work consisted of
two different parts; the first was to describe and evaluate different treatment methods for waste
pickling acid, with emphasis on denitrification technologies. The second and main part was to make a
fundamental description of the neutralisation process and outline important parameters. The work
was performed by gathering information from literature but also from industry in both Sweden and
China. The work has been a collaboration between the Royal Institute of Technology (KTH), the
Swedish Environmental Institute (IVL) and the company Scanacon.

A review of the different acid recovery methods; ionic exchange, diffusion dialysis and extraction was
made. The study showed that ionic exchange is a robust method with relatively low cost and
therefore it has been largely implemented both in Swedish and Chinese industry. The outflow
however still requires neutralisation. Nitrate reduction can be performed as “end of pipe”, those
methods investigated in this study were; biological treatment, reverse osmosis and nanofiltration.
Meanwhile, internal solutions such as evaporation and electro-dialysis are two interesting
technologies which reduce nitrates in combination with acid recovery.

It was found that slaked lime (Ca(OH)2) is the most suitable neutralisation agent for pickling waste
and, besides the choice of chemicals, many important parameters influence the process, such as the
optimal pH, mixing and conditions during lime slaking.

Based on information from one of the visited sites in Sweden a mass balance of the neutralisation
facility was made and from that the required amount of Ca(OH)2 was calculated. The calculations
were verified by an experimental part performed by IVL, using pickling acids from the same site. The
amount of metals in the outgoing water was calculated using software “Medusa” but also by
equilibrium equations. However, the results differed somewhat; this is probably due to the fact that
Medusa takes other complexes and their interaction, besides the formed metal hydroxides, into
consideration.

Within the mining industry research has been made on different methods for neutralisation and
some have been tested in field. An example is the High Density Sludge process (HDS), were an
amount of sludge is recycled back to the neutralisation tank. It was shown that this gave improved
sludge properties and decreased lime consumption. This could perhaps also be implemented for
waste water in the stainless steel industry, and the method was also tested during the experimental
part of this project. The dry content increased after a number of cycles but further investigation is
required before any conclusion can be drawn.

iii
Sammanfattning
Betning är en enhetsprocess inom tillverkningen av rostfritt stål då godset behandlas med
fluorväte syra (HF) och salpetersyra (HNO3), också kallad blandsyra. Betningen ger upphov till vatten
strömmar som måste behandlas innan de släpps ut till recipienten.

Syftet med det här examensarbetet var att göra en utvärdering av olika tekniker för att reducera
utsläpp till vatten från betningen med Kina som potentiell framtida marknad. Arbetet bestod av två
delar; den första delen var att beskriva och utvärdera olika behandlingsmetoder av förbrukade
betbad med betoning på denitrifikationstekniker. Den andra och största delen var att göra en
grundläggande beskrivning av neutralisationsprocessen. Studien utfördes genom att inhämta
information från litteratur samt från industrin i både Sverige och Kina. Arbetet har varit ett
samarbetsprojekt mellan Kungliga Tekniska Högskolan (KTH), Svenska miljöinstitutet (IVL) och
företaget Scanacon.

Arbetet behandlar syraåtervinningsystemen; jonbytare, diffusions dialys samt extraktion. Nitrat

reduktion kan ske internt eller externt där de externa åtgärder som behandlas i denna rapport är
biologisk rening, omvänd osmos och nanofiltrering. De interna metoderna avdunstning och
elektrodialys är intressanta eftersom de återvinner syran samtidigt som de reducerar nitraterna
avsevärt. Studien visade att jonbyte, på grund av dess robusthet och relativt låga kostnad är den
mest implementerade metoden för syraåtervinning i både svensk och kinesisk industri idag.
Restprodukten från jonbytaren kräver dock fortsatt behandling, där det traditionella valet är
neutralisation.

Studien visade att släckt kalk (Ca(OH)2) är det mest passande kemikalien för neutralisation av
betsyror. Förutom kemikalieval så finns det många parametrar som påverkar effektiviteten hos
processen så som pH, omrörning och förhållanden under kalksläckningen.

Baserat på information ifrån ett av de besökta stålverken i Sverige, gjordes en massbalans över dess
neutralisationanläggning. Utifrån de flöden som denna gav kunde den teoretiska mängden kalk som
krävdes för utfällning räknas ut. Beräkningarna verifierades med en experimentell del som utfördes
av IVL på betsyror från samma verk. Resthalterna av metall i utgående vatten beräknades med
programmet ”Medusa” men också med jämviktsekvationer. Resultaten mellan de två skiljde sig,
detta beror förmodligen på att Medusa förutom hydroxidutfällning tar hänsyn till andra
utfällningskomplex och dess interaktioner.

Inom gruvvatten industrin har det forskats en del kring olika neutralisationsmetoder, en i litteraturen
föreslagen sådan är ”High Density Sludge process (HDS)”. Här återförs en del av slammet tillbaka till
neutralisationssteget, vilket visade sig ge förbättrade slamegenskaper och minskad kalkåtgång. Det
var intressant att undersöka om denna metod också gick att implementera på förbrukade betbad och
därför prövades metoden i den experimentella delen av detta projekt. Detta gav efter ett antal
återföringscykler högre torrhalt på slammet, dock krävs fortsatta undersökningar innan någon
slutsats kan dras.

iv
Preface
This thesis has been performed for the Master’s degree of Lena Dahlgren in Chemical Engineering at
the Royal Institute of Technology (KTH) in Stockholm. The work has been carried out at the Swedish
Environmental Research Institute (IVL) in Stockholm and the purpose was to collect and compile
information about different methods for treatment of pickling acid with special focus on the
neutralisation process. The work has required contacts with a number of persons in both Swedish
and Chinese industry.

I would like to give my special thanks to the people who have been involved in the process and for
making this work possible:

Uwe Fortkamp at IVL, for giving me the opportunity to perform this work at IVL and always giving me
guidance and support when I needed it!

Per Olof Persson at KTH, my supervisor and examiner for always giving me advise and encourage!

Magnus Lindberg, for introducing me to the industry, and helping me in my preparations and
arrangements for my travel to China.

Torsten Schneiker and Anders Stenqvist at Outokumpu in Avesta, for explaining the process in Avesta
and always answering my e-mails with questions and showing interest in my work.

Kåre Tjus and Mats Ek at IVL, for being responsible for the experimental part of the project and for
showing interest in my work.

Jyri Kaplin at Outokumpu in Nyby, for explaining and showing me the process in Nyby.

Mr Liu, Mr Wang, Molly and Sun at SEC office in Tianjin, for their helpfulness and great hospitality
during my stay in Tianji.

Michael Feng, Scanacon office in Shanghai, for arranging and taking time showing me around during
my stay in Shanghai.

I would also like to thank Hanna Odén, diploma worker at IVL, for all the encouraging small talks we
had during this experience!

v
vi
Table of contents
Abstract ...................................................................................................................................................iii

Sammanfattning ...................................................................................................................................... iv

Preface......................................................................................................................................................v

Table of contents .................................................................................................................................... vii

1. Introduction ..................................................................................................................................... 1

1.1 Background .................................................................................................................................... 1

1.2 Aims and Objectives ...................................................................................................................... 1

1.2.1 Objectives ............................................................................................................................... 2

1.3 Methods ........................................................................................................................................ 2

1.3.1 Limitations .................................................................................................................................. 2

2. Stainless steel production ............................................................................................................... 3

2.1 Stainless steel treatment ............................................................................................................... 3

2.1.1 Rolling ..................................................................................................................................... 3

2.1.2 Annealing ................................................................................................................................ 3

2.1.3 Pickling .................................................................................................................................... 3

Electrolytic pickling ...................................................................................................................... 3

Acid pickling ................................................................................................................................. 4

Mixed acid pickling ...................................................................................................................... 4

2.2 Waste water from the pickling process......................................................................................... 5

2.3 Environmental effects ................................................................................................................... 5

2.3.1 Chromium ............................................................................................................................... 5

2.3.2 Nickel ...................................................................................................................................... 6

2.3.3 Nitrates ................................................................................................................................... 6

2.3.4 Nitrogen oxides (NOx) ............................................................................................................. 6

2.4 Legislations .................................................................................................................................... 7

2.4.1 Sweden ................................................................................................................................... 7

vii
 2.4.2 China ....................................................................................................................................... 8

Sludge and landfills ...................................................................................................................... 9

3. Treatment methods of spent pickling acid ........................................................................................ 11

3.1 Chromium reduction ................................................................................................................... 11

3.2 Acid regeneration methods and metal treatment ...................................................................... 11

3.2.1 Ionic exchange process......................................................................................................... 11

3.2.2 Diffusion dialysis ................................................................................................................... 12

3.2.3 Extraction ............................................................................................................................. 13

3.2.4 Outokumpu process ............................................................................................................. 14

3.2.5 Nanofiltration and Crystallisation ........................................................................................ 14

3.2.6 Neutralisation ....................................................................................................................... 14

3.3 Nitrate reduction for pickling waste water ................................................................................. 14

3.3.1 Nitrate reduction methods without acid recovery .............................................................. 15

Biological treatment .................................................................................................................. 15

Reverse Osmosis and Nanofiltration ......................................................................................... 16

3.3.2 Nitrate reduction methods with acid recovery .................................................................... 16

Evaporation ............................................................................................................................... 16

Outokumpu process .............................................................................................................. 17

Electro-dialysis ........................................................................................................................... 18

4. Neutralisation theory ........................................................................................................................ 21

4.1 Theory of precipitation ................................................................................................................ 21

4.2 Parameters influencing neutralisation ........................................................................................ 22

4.2.1 The pH .................................................................................................................................. 22

4.2.2 Neutralisation chemicals ...................................................................................................... 22

Lime Slaking ............................................................................................................................... 23

Lime slurry ................................................................................................................................. 24

4.2.3 Mixing during neutralisation ................................................................................................ 24

viii
 5.3.4 Flocculation .......................................................................................................................... 25

Polymer dosage ......................................................................................................................... 26

5.4 Sludge .......................................................................................................................................... 26

5.4.1 Sludge dewatering ................................................................................................................ 28

5. 5 Chemical reactions during neutralisation................................................................................... 28

5.5.1 Calcite formation .................................................................................................................. 29

5.5.2 Oxidation of iron................................................................................................................... 30

6. Some different neutralisation technologies ...................................................................................... 31

6.1 Conventional neutralisation ........................................................................................................ 31

6.2 The High Density Sludge process (HDS)....................................................................................... 31

6.2.1 The Geco HDS Process .......................................................................................................... 32

6.2.2 Staged-Neutralisation Process ............................................................................................. 33

7. Acid treatment examples in Sweden................................................................................................. 35

7.1 Outokumpu Stainless, Avesta ...................................................................................................... 35

7.1.1 Electrolytic pickling ............................................................................................................... 35

7.1.2 Chromium reduction ............................................................................................................ 36

7.1.3 Spent pickling acid ................................................................................................................ 36

7.1.4 Neutralisation ....................................................................................................................... 37

7.1.5 Washing of gases .................................................................................................................. 38

7.2 Outokumpu Stainless Thin Strip, Nyby ........................................................................................ 38

7.2.1 Spent pickling liquid ............................................................................................................. 39

7.2.2 The rinse water ..................................................................................................................... 40

7.2.3 Flocculation and sedimentation ........................................................................................... 40

8. Acid treatment examples in China .................................................................................................... 41

8.1 Old Fonye Steel mill, Shanghai .................................................................................................... 41

8.1.1 Neutralisation ....................................................................................................................... 42

8.2 New Fonye steel mill, Shanghai ................................................................................................... 42

ix
 8.3 TPCO, Tianjin ............................................................................................................................... 44

9. Dimensioning data............................................................................................................................. 47

10. Theoretical calculations................................................................................................................... 49

10.1 Boundaries................................................................................................................................. 49

10.2 Calculations with software “Medusa” ....................................................................................... 49

10.3 Chemical properties of the nitric and hydrofluoric acid ........................................................... 50

10.4 Calculation examples ................................................................................................................. 51

10.4.1 Example 1 – Stoichiometric calculations of required Ca(OH)2 ........................................... 52

10.4.2 Example 2 – Equilibrium calculations ................................................................................. 53

Iron (Fe3+):.............................................................................................................................. 53
Nickel (Ni2+):........................................................................................................................... 54
Chromium (Cr3+): ................................................................................................................... 54
11. Experimental results ........................................................................................................................ 57

11.1 Comparison of experimental results and calculations .............................................................. 58

12. Discussion ........................................................................................................................................ 59

Acid recovery methods.......................................................................................................... 59

Neutralisation ........................................................................................................................ 60
Calculations ........................................................................................................................... 61
13. Conclusions ...................................................................................................................................... 63

14. References ....................................................................................................................................... 65

Appendix I- Calculations ........................................................................................................................ 69

Mass balance for neutralisation in Avesta .................................................................................... 69

Appendix II- Medusa figures.................................................................................................................. 73

Iron precipitation........................................................................................................................... 73

Nickel precipitation ....................................................................................................................... 73

Chromium precipitation ................................................................................................................ 74

x
1. Introduction
The following thesis has been written for the Master’s degree of Lena Dahlgren in Chemical
Engineering at the Royal Institute of Technology (KTH) in Stockholm. The degree project has been
performed at the Swedish Environmental Research Institute (IVL) in collaboration with the company
Scanacon.

1.1 Background
When stainless steel is manufactured, it goes through a unit process called pickling. The aim of this
operation is to remove oxide layers from the steel surface as well as a chromium depleted zone
underneath. The pickling solution normally consists of a mixture of nitric (NHO3) and hydrofluoric
acid (HF). During this treatment, metals such as iron, chromium, nickel and molybdenum are also
released in the bath where they form different complexes with the acids. It is beneficial both from an
economic and environmental point of view if as much of the acids as possible can be recirculated
back to the pickling bath and also, if the alloys can be recovered and reused in the steel making
process. The traditional method for treatment of spent pickling liquor before discharging to the
recipient is neutralisation where a raise in pH leads to chemical precipitation of metals as hydroxides.
The output from neutralisation is sludge with high metal content. For an optimal process
management it is important to have good measure of the acid concentrations and the amount of
added chemicals.

Since nitric acid is used, pickling gives a discharge of nitrates which are not captured in the
neutralisation process. It is difficult and expensive to reduce them and as a consequence nitrates will
follow the waste water into our natural waters where they act as excessive fertilisers.

In China, the steel industry has grown enormously over the last years; meanwhile, technology for
reduction of emissions from the pickling process is either none existing or largely inadequate for
many steel factories. Over the past years, the Swedish Environmental Research Institute (IVL) has
been involved in different industrial environmental technology projects in China, with the aim to find
suitable solutions for important emission problems. This degree thesis is a part of that work and
regards emissions from the pickling process. Scanacon is a company specialised in acid management
from the pickling process and the degree project is a collaboration between Scanacon, IVL and KTH.

1.2 Aims and Objectives

The aim of this degree thesis is to make an evaluation of different possibilities for reduction of
emissions from the pickling process with China as a future market. The work consists of two parts;
the first is to describe and evaluate different methods for waste pickling acid, where denitrification
technologies are also considered in order to reduce the amount of nitrates released in nature. The
second and main part is to make a fundamental description of the neutralisation process, for possible
implementation of neutralisation in combination with acid regeneration in Chinese industry. The
work should hopefully work as a base for designing a neutralisation facility and for proposing
improved strategies for process control. There are both economic and environmental advantages by
improved management of the process. It might lead to a reduction of the amount of chemicals
needed which will reduce the amount of waste which today is landfilled.

1
1.2.1 Objectives
The aims will be accomplished through the following objectives:

• Give a general overview of a complete pickling liquor cleaning facility by including steps such
as chromium reduction, pH-adjustment, flocculation, sedimentation, filtration, sludge
dewatering and disposal.
• In detail describe the neutralisation process; outline the necessary control principles for an
automatic and optimal dosage of chemicals. Describe the choice of chemicals with regard to
price, efficiency and management.
• Analyse the substances formed during pickling and rinsing. Calculate the expected amount of
chemicals which must be added during neutralisation. Based on this information; find the
expected reactions and calculate the amount of chemicals required for the neutralisation
process.
• Describe different technologies for reduction of nitrates and nitrate recovery options.
Compare the technologies individually based on parameters such as efficiency, investment
and maintenance costs.
• Briefly describe the legislation in Sweden and China regarding emission quantities,
environmental objectives, and threshold limit values.

1.3 Methods
The work has been performed by collecting information about the neutralisation process from
literature and also through study visits of two steel mills in Sweden; Outokumpu sites in Avesta and
Nyby. In order to get a clear picture of the Chinese situation today, a field trip to China was made,
where two steel mills in Shanghai and one in Tianjin were visited.

The chemical reactions in the neutralisation process where outlined and calculations of the amount
of chemicals necessary for precipitation was performed based on a mass balance of the
neutralisation facility in Avesta. The chemical software “Medusa” was used as a verifying tool and for
calculating the theoretical metal concentration in the outgoing water. For verification, an
experimental part of neutralisation was performed by IVL and the results are also presented in the
report.

1.3.1 Limitations
The work was limited only to pickling waste water from stainless steel. Only pickling using mixed acid
has been considered. All information, calculations and verifications as well as analyses of the
experimental part was restricted to three metals; iron (Fe2+), chromium (Cr3+) and nickel (Ni2+).

2
2. Stainless steel production
The definition of stainless steel is that it has a special alloying for resistance against corrosion.
Standard stainless steel has a minimum chromium content of 10.5 %. The chromium improves the
corrosion resistance due to the chromium oxide film which forms on the steel surface. Other alloying
metals are nickel, nitrogen and molybdenum, where nickel for instance improves the formability and
ductility of the steel [1].

2.1 Stainless steel treatment

Production of stainless steel is a complicated process where the steel goes through a number of unit
operations. Once the steel is cast, it has to be treated further in order to gain improved material
properties and surface qualities. Examples of such operations are rolling, annealing and pickling.

2.1.1 Rolling
After casting, the steel is subjected to deformation between two rotating cylinders, also called
rolling. The thickness of the steel will thereby decrease and the inner structure of the steel will
change. The steel is often both hot and cold rolled. Hot rolling is performed at high temperatures,
around 600 – 700 °C and cold rolling at room temperature [2].

2.1.2 Annealing
During annealing, the steel is heated and kept at a specific temperature, after which it is cooled
under control. Annealing allows the steel to gain desirable and specific material properties [3].

2.1.3 Pickling
The very high temperatures during hot rolling and annealing will lead to diffusion of alloying metals
from the steel matrix to the surface where they will react with oxygen in the air resulting in the
formation of oxide layers. These layers can be subdivided into an outer layer consisting of simpler
oxides and underneath a layer of more complex oxides. The total oxide layer can be up to 50 μm
thick. Beneath the oxides, a zone which has been depleted of chromium has formed, since these
atoms have diffused to the steel surface due to the high temperature [4]. The chromium depleted
zone gives the steel deficient strength properties and lower resistance towards corrosion. To avoid
that the oxide layers and the chromium depleted zone is worked into the material matrix during
further processing of the steel, it is essential to remove them, this is accomplished through a process
called pickling. Pickling can be performed in many steps. The most common pickling methods are
electrolytic and acid pickling [5].

Electrolytic pickling
Usually, after annealing the steel is subjected to mechanical descaling followed by electrolytic
pickling, where the steel is submerged in an electrolyte and a current is applied. Both of these are
performed to facilitate the final chemical pickling. Electrolytic pickling is therefore performed as a
pre-step to the acid pickling. The aim of electrolytic pickling is to alter the oxide layer
electrochemically in order to increase their solubility in the pickling solution. Electrolytic pickling is
performed in a slight acidic electrolyte of sodium sulfate (Na2SO4) [6].

During exposure of the electrolyte, the metals in the oxides are oxidized to metallic ions which are
dissolved in the electrolyte; the oxide layer is hence undercut and removed. Also during the
treatment, trivalent chromium (Cr3+) is oxidized to hexavalent chromium (Cr6+) [6]. Before treatment
3
of the waste water from the electrolytic pickling, it is important to reduce the highly toxic Cr6+ to the
less toxic Cr3+, this is done in a chromium reduction system, see chapter 3.1 for description.

Acid pickling
Acid pickling is the final pickling step. Here the steel is submerged in acid and the oxide layers are
thereby removed. The two most common used acids are sulphuric acid (H2SO4) or mixed acid which is
a mixture of nitric acid (HNO3) and fluoric acid (HF), also called mixed acid pickling. For stainless steel
production, mixed acid is used exclusively [4].

Mixed acid pickling

During mixed acid pickling, a mixture of nitric acid (HNO3) and fluoric acid (HF) are used. The oxides
are depleted from the steel surface and will form a sludge in the bath. Also, metals such as Fe, Cr and
Ni are dissolved from the steel into the pickling bath. A typical composition of some substances in a
pickling liquor can be seen in table 1.

Table 1. Composition of some

components in a pickling liquor [7].

Component Composition (g/l)

Free HNO3 100-130
Total NO3- 120-160
Free HF 20-40
-
Total F 60-80
Fe(III) 35-45
Cr(III) 5-10
Ni(II) 3-6

The HNO3 and HF acids have different tasks. The HNO3 main task is to remove the oxides and the
chromium depleted layer. It is also a very strong oxidant which results in the formation of Fe3+, Cr3+
and Ni2+ ions. The nitric acid will therefore be consumed as the metal concentration increases in the
bath. The HF prevents new oxide layers from forming and the fluorides will form complexes with the
Fe3+, Cr3+ and Ni2+ ions which will precipitate as sludge. HF also contributes to the formation of new
HNO3 by providing hydrogen ions (H+). The composition of the bath will thereby change during
pickling [5].

The metals reduce nitrates, resulting in the formation of NOx gases. These gases have an impact on
the oxide removal; by blasting them. The HF concentration is decreased due to formation of metal
complexes which are precipitated when the metal concentration becomes high enough. Therefore,
an increased metal concentration will lead to a decreased pickling activity and a reduction of the
pickling bath’s lifetime. The activity can be increased by addition of fresh acid or a raise in
temperature. As long as the metal content is kept below 40-50 g/l, free fluoride ion concentration
can be maintained at a constant level by addition of fresh acid. If the iron concentration increases
further, the addition of new acid becomes uneconomical. The temperature has to be kept below
60°C; otherwise the stainless layer is also attacked by the acids and evaporation of acid to air
increases [4]. By adding fresh acid in combination with regeneration of the bath in order to decrease

4
the metal concentration, the lifetime of the bath can be prolonged. It is essential to continuously
separate the metals from the bath as well as having good control over the acid concentrations [8].

2.2 Waste water from the pickling process

The pickling process as well as any possible acid recycling system varies of course between different
production sites but in general there are three different waste water streams which can be identified
for any site [9]:
• Water used for achieving the right acid concentrations of the pickling bath; waste water will
be generated during regeneration or dumping of the pickling baths. This stream is usually
called waste acid or pickling waste. The flow of the stream will be relatively small but
contain a high metal and acid concentration.
• Water used for rinsing of the steel surface after pickling in order to remove acid residues
and particles. This flow will be larger but with a smaller acid and metal concentration than
above.
• Water used for scrubbing of gases. During pickling, gases containing NOX and F- are
generated; generally these are led to an exhaust gas cleaning system where a scrubber
washes out the fluorides.
If the steel mill has electrolytic pickling, a fourth stream is obtained;

• Rinse water from the electrolytic pickling containing Cr6+, which has to be reduced to Cr3+
before any further treatment.
The pickling waste stream and rinse water contain high amounts of metals and all the above streams
are very acidic; therefore none of them can be discharged directly to the environment [9].

2.3 Environmental effects

The most severe environmental and health problems associated with waste water from the steel
industry originate from high levels of metals such as chromium and nickel. Iron exists naturally in the
water and has low toxicity. Nitrates have over the last decades gained more attention since it causes
indirect effects of the environment.

2.3.1 Chromium
Chromium is widely used within different production processes. Around 107 ton chromium is utilized
per year. Out of this, 60-70 % is used for alloys such as in stainless steel and 15 % for chemical
industrial process such as pigments and in leather tanning. Due to the extensive utilisation of
chromium, it has become a pollutant of air, soil and water [10].
Chromium can exist in many oxidation forms, although, the most stable and therefore most common
forms are the trivalent (Cr3+) and hexavalent (Cr6+) states, although, they exhibit quite different
chemical properties. The Cr6+ is the most toxic one and together with oxygen it forms compounds
such as chromate (CrO42-) and dichromate (Cr2O72-). These are the most mobile, toxic and water
soluble Cr6+-compounds. Chromate is easily transported across biological membranes in plants and
animals and once the compound has enter the cell, Cr6+ is reduced to the more stable Cr3+ form. The
Cr3+ state is on the other hand insoluble and thus immobile and in the form of oxides and hydroxides,
Cr3+ exists mainly bound to organic matter in soil and aquatic environment [10].

5
The Cr6+ compounds have shown to induce tumours in animal experiments. Cr6+ is more toxic than
Cr3+ since Cr6+ easily enters the cells by the sulphate anion transport system. Exposure to high levels
of chromium has been shown to have toxic and carcinogenic effects [11].

2.3.2 Nickel
Nickel (Ni) can be found in oxidation states from Ni-1 to Ni+4; the most common form is the Ni+2 state.
Nickel compound are used in industry such as electroplating, nickel-cadmium batteries production
and stainless steel production. Nickel as contaminants in the environment originates from nickel
production, recycling of nickel containing products and waste disposal. Nickel can be found in soil in
both soluble and insoluble form. Nickel emitted from anthropogenic sources is mainly in the form of
soluble compounds, oxides and sulphides and to a lesser extent in metallic form. In aquatic sources,
divalent nickel (Ni2+) is the dominating form of nickel present. The existence of other nickel
compounds depends on the pH and possible other binding-partners [12].

Human and animal exposure of high nickel dosages and in a certain form is toxic. Humans are mainly
exposed to nickel trough inhalation and ingestion. Vegetables such as cocoa, spinach and nuts have
shown to contain high amount of nickel. The metabolism of nickel in the human body has not been
totally understood, but the impact on human health is obvious with nickel allergy as a well known
reaction. Nickel has also been shown to have carcinogenic effects during long-term exposure, but it
might also lead to lung fibrosis and kidney diseases [12].

2.3.3 Nitrates
Excessive amount of plant nutrients in waters leads to eutrophication which causes enhanced
vegetation growth and disturbance of the natural balance of organisms. Nutrient loading of nitrogen
leads to overgrowth of algae and plankton; as a consequence the sunlight will be obstructed for
deeper living plants and algae. These will instead submerge to the seafloor where they are
decomposed by organisms. The decomposition process consumes dissolved oxygen in the water. As a
consequence, there will be a shortage of oxygen on the seafloors. This will in turn lead to death of
the seafloor life. Today, eutrophication of lakes and seas has become an extensive problem all over
the world [13].

2.3.4 Nitrogen oxides (NOx)

During all sorts of combustion where oxygen is involved, nitrogen oxides (nitrogen monoxide (NO)
and nitrogen dioxide (NO2)) are formed. These two compounds form a pair and through fast reaction
in the atmosphere, one is formed out of the other. Therefore they go under the common name
of NOx-gases. In the atmosphere NO is oxidised by air, ozone and radicals and NO2 is dissociated by
the sunlight back to NO. This is illustrated in the following reactions [13]:

NO + O2 → NO2 + O • (1)

NO + O3 → NO2 + O2 (2)

NO + RO • 2 → NO2 + RO • (3)

NO2 + sunlight → NO + O • (4)

6
Higher in the atmosphere the NOx-gases are transformed to nitric acid (HNO3), which will acidify the
rainfall and the nitrate ions will deposit with the rain on ground and vegetation. The acidic rain is
damaging to the plant life since it corrodes the outer protection layer of needles and leaves, which
increases the risk of nutrition lost and dehydration [13].

Reaction (4) above can also take place close to the ground. The free oxygen atoms formed can then
react with oxygen in the air forming tropospheric ozone according to the following reaction [13]:

O • + O2 → O3 (5)

Tropospheric ozone is damaging to humans and plants. It is irritating for human lungs and it disturbs
the photosynthesis [13].

2.4 Legislations
Discharge and emission standards in waste water are regulated by the authorities. Due to historical
and political reasons the legislations differ between different countries in the world. A brief
description of the legislations in both Sweden and China are presented in the following chapters.

2.4.1 Sweden
When the European Union (EU) was formed, it was decided to have common guidelines and
environmental goals for all countries in the EU. These are summarized in the BAT-document
(Best Available Technology). The BAT-document is set as a European standard and should be
implemented as a minimum demand from the local authorities regarding emissions [14]. According
to the BAT-document, standards regarding waste water from the steel industry are summarised in
table 2.

Table 2. Standards according to the BAT-document [14]

Susp. solids Oil Fe Crtot Ni Zn

[mg/l] < 20 <5 < 10 < 0.5 < 0.5 <2

In Sweden it is mainly the PARCOM-recommendations (Paris commission 1992) which have affected
the development of regulations. The PARCOM-recommendations are seen in table 3. These
standards have been set as guideline values and are stricter than the BAT standards for some
substances.

Table 3. Standards according to the PARACOM-recommendations [15]

Susp. solids Crtot Cr6+ Ni

[mg/l] 10 0.5 0.1 0.5

In Sweden it is expected that any facility should be able to keep below these values, but they are
allowed to be temporary exceeded. These should not be confused with the limit values, which are
never allowed to be exceeded, if so, it might lead to prosecution [15]. The limit values are defined for
each facility through a permit. Each steel mill applies for a permit from the relevant authority, which
makes a decision. Since the permit is set for each steel mill individually; the permit differs from mill

7
to mill. A number of factors are taken into account, for instance, the permit differs if the steel
production is based on scrap or ore. The standard can also be set in various units for different mills,
such as mg/l or ton/year [16].

It should be noted that no recommended guideline value is given for iron in table 3, this is due to its
low toxicity [15].

2.4.2 China
In China, the Environmental Protection Bureau (EPB) sets the standards of emissions to air and water.
The EPB is subdivided according to figure 1. The National EPB is the highest and under them there is
provins, municipal, city and district EPB. All laws are set by the national level, but in some areas the
laws are set on the local level, (city level for instance). Sometimes the local laws apply instead of the
national laws. It is very difficult to tell when and why the local or national law applies. Also, one can
not tell which laws are more stringent, the national or the local [17].

National EPB

Provins EPB Municipal EPB

City EPB District EPB

Figure 1. The structure of the Chinese Environmental Protection Bureau (EPB)

The environmental protection bureau controls so that the standards are followed. If the emissions
are too high they get a warning and if they do not decrease their emissions, the factory is forced to
pay a high fee to the government [17]. In figure 2, the division of the different standards is shown.

Environmental
standard system

National Local

Environmental Emission
quality standard standard

Water environment Air quality Sound environment Waste water Air emissions Solid waste Noise

Figure 2. Division of different standards in China

8
In China there are 3 different levels for emissions standards regarding waste water [18]:

• Level 1: Applies if the water goes directly to the sea or lake where the sea life is used as food
for humans.

• Level 2: Applies if the water is directed to an area which is a cultural scenery such a as in a
park for instance. The sea life from such an area is not used for human food.

• Level 3: Applies if the water is directly directed to the municipal waste water treatment plant
for further treatment.

Regardless of which level applies, the mills usually have some sort of waste water treatment facility
and the emissions are measured in the water going out from this treatment [17].

In table 4, the standards for the 3 different levels for emissions in waste water from the steel
industry are shown [19]. In China, there are no standards or regulations regarding emissions of iron
(Fe3+/Fe2+) or nitrates (NO3-) in waste water.

Table 4. National standards for waste water emissions from the steel industry in China [19]

Level pH Susp. CODCr Oil Crtot Cr6+ Zn Ni Cu

solids
[mg/l] [mg/l] [mg/l] [mg/l] [mg/l] [mg/l] [mg/l]
[mg/l]
1 6-9 70 100 8 1.5 0.5 2 1 0.5

2 6-9 150 150 10 1.5 0.5 4 1 1

3 6-9 400 500 30 1.5 1 5 1 2

Sludge and landfills

The sludge generated from industry in China is usually landfilled or used as raw material for
construction materials. The industrial company have to pay a fee for putting their generated waste
on landfill. There are national standards if the sludge can be landfilled as normal waste, hazardous
waste or not landfilled at all. Table 5 shows the standards for some metals in the sludge. If the
content in the sludge is equal or beneath these standards, the sludge can be landfilled in a normal
landfill. If any substance exceeds these values the sludge has to be handled as hazardous waste.

Table 5. Standards for waste which can be

landfilled in a normal landfill [20]

Crtot [mg/l] Cr6+ [mg/l] Ni [mg/l]

4.5 1.5 0.5

9
Table 6 shows standards for some metals in sludge. If the content in the sludge is equal or beneath
these standards, the sludge can be landfilled as hazardous waste. If any of the substances exceeds
these values, the sludge is not allowed to be landfilled but instead has to be treated in some other
way [20].

Table 6. Standards for waste which can be

landfilled as hazardous waste [20]

Crtot [mg/l] Cr6+ [mg/l] Ni [mg/l]

12 2.5 15

Regarding landfills of hazardous waste there are three different arrangement of the landfill,
depending on the toxicity of the waste, see figure 3. For instance, if the sludge is considered very
dangerous, arrangement A has to be applied. The different layers are natural material, polymer layer
and pipes for the leachate. Each layer should be about 2.4-4 m and the total landfill should not
exceed 9 m [20].

Sludge A B C
Pipes (for main
leach water)

Polymer
Layers with
natural
materials

Figure 3. The different arrangements of landfills for hazardous waste

10
3. Treatment methods of spent pickling acid
The traditional treatment method for pickling waste is neutralisation where by increasing the pH, the
metals are precipitated as metal hydroxide forming a sludge which can be disposed. A deeper
investigation of the neutralisation process is given in chapter 4. Due to the growing environmental
problems, which have lead to tougher legislations, treatment of waste water generated from pickling
has become an area of development. Different technologies, where a part of the acid is recycled back
to the pickling bath have been proposed. The most common ones are presented in chapter 3.2.
However, none of them are able to reduce the amount of nitrates in the water, this have lead to
further development of treatment methods for nitrate reduction, the most common ones are
presented in chapter 3.3.

3.1 Chromium reduction

During electrolytic pickling, Cr6+ is generated. To enable precipitation of chromium hydroxide in the
neutralisation facility, it is necessary to reduce Cr6+ to Cr3+. This step is called chromium reduction.
Usually sodium sulphate (Na2SO4) is used as reducing agent. Some facilities use iron (Fe2+) or sulfur
dioxide (SO2) but this is less common. The reaction rate for chromium reduction is highest in an acidic
environment; therefore the pH is set to around 2.5. The reaction is controlled and operated by
redox-electrodes. The retention time is usually around 15 min. In an acid solution the following
redox-reactions takes place [6]:

2− 2−
3SO3 → 3SO4 + 6e − (7)

2Cr 6+ + 6e − → 2Cr 3+ (8)

3.2 Acid regeneration methods and metal treatment

Acid regeneration is when consumed acid from the pickling is recycled back to the process. Some
existing technologies for regeneration of pickling acid without nitrate reduction are presented below.

3.2.1 Ionic exchange process

In the ionic exchange process, spent pickling acids are separated from the metals and recirculated
back to the pickling bath by an ionic exchange technology. Here the metals are retained in an anionic
bed and are therefore separated from the acid which can be recirculated back to the pickling bath.
Regeneration is made with water thereby releasing the metals from the bed. It is essential to first
have a pre-treatment in order to separate particles from the mixture. The commonly way is
sedimentation followed by a micro-filtration stage for removal of suspended material [21].

A variant is to retain the free acid instead of the metals. Regeneration then releases the acid from
the bed which is recirculated back to the pickling bath [4]. The principle of ionic exchange is given in
figure 4.

11
 Me2+ An- Me2+

Low conc. High conc.

Ionic exchange R-H+ R-Me+ Regeneration

H+ An- H+

2 R − H + Me 2+ → R2 − Me + 2 H + R2 − Me + 2 H + → 2 R − H + Me 2+

Figure 4. Principle of ionic exchange and regeneration.

Acid recovery only allows recycling of free acid; meaning fluorides and nitrates bound in complexes
are not absorbed by the bed, therefore, an additional step is required and the most common method
is neutralisation [21].

The recycling rate of free nitric acid is about 85-90 % and for free hydrofluoric acid about 80 %. The
need for fresh acid during pickling is therefore decreased to 45-50 % for nitric acid and 30 % for
hydrofluoric acid. The investment cost for an ion exchange facility is approximately 1.5 million SEK.
The energy consumption is about 10 kWh and 1 m3 water is required per m3 treated acid [4].

Due to its small space, low cost, simplicity and reliability, the ion exchange method is the most widely
used process for purification of mixed acid pickling liquor [22]. The company Scanacon has developed
an acid retardation system called SAR (Scanacon Acid Retardation System) which is commercially
used in Swedish and international industry today.

3.2.2 Diffusion dialysis

During diffusion dialysis two liquid streams meet each other, one is consumed acid and the other is
clean water. The streams are separated by an anion selective membrane (positively charged) and the
concentration gradient between the liquid streams is the driving force for the process. The feature of
the membrane allows transportation of free acid to the water through the membrane, figure 5. The
process requires a pre-treatment step; otherwise the channels distributing the liquid flow over the
membrane surface can become clogged [4].

Some drawbacks with this process are that only free acid can be recycled and therefore the method
requires an additional step, such as neutralisation/precipitation. Also, the process is not entirely
selective, therefore about 5 % of the metal salts will be found in the recovered acid [4].

The recycling rate of free acid is about 80-85 %. The facilities are simple and requires little
supervision. The investment cost for diffusion dialysis with the capacity of 1 m3/h mixed acid is about
1.5 million SEK [4].

12
 Metals and bound Water
acid, to neutralisation

H+
X- H+

----- Membrane MeX

X-
MeX Salt
X-
H+X- Acid H+
H+

MeX X-

Waste acid Recycled acid

Figure 5. Principle of diffusion dialysis

3.2.3 Extraction
In Japan, a method for extraction of mixed acid has been developed. Here different complexes of
fluoric acid (HF) are removed in different extraction steps, described schematically in figure 6. In the
first extraction step, di-2-ethylhexyl phosphoric acid and n-paraffin are added (solvent 1, figure 6).
Then the extract is mixed with NH4HF2, which precipitates iron-ammonium-fluoride complexes. These
are then roasted and iron oxide is formed. In the second extraction step, hydrochloric acid is added,
which turns metal nitrates into metal chloride after which nitrate and fluoride ions are then
extracted with tributyl phosphate and n-paraffin (solvent 2, figure 6). The acid ions are then dissolved
from the extraction fluid with water and recirculated to the pickling bath. The method is actually
much more complicated than what it seems to be. Steps such as filtration, drying and scrubbing are
necessary between the different extraction steps. This method only recycles the free acid and the
recycling rate is 95 % for HNO3 and 70 % for HF [4].

Solvent 1 HCl Solvent 2

NO3- and F-
Mixed
acids Extraction 1 Extraction 2 Extraction 3

Extract Metal chloride NO3- and F- and

extraction fluid
NH4HF2
Water
Iron-ammonium-fluoride
precipitation complexes
NO3- and F-
recirculated to the
pickling
Roasting Iron oxide

Figure 6. Simplified scheme of the extraction of mixed acids

13
3.2.4 Outokumpu process
Outokumpu site in Tornio have developed a process where the pickling liquor is mixed with sulphuric
acid and then evaporated. By crystallisation of the remaining slurry, different metal sulphates are
precipitated. The process allows precipitation of nickel hydroxide, for possible nickel recycling. The
method has a very high recycling rate of the free acid and therefore reduces the amount of nitrates
considerably [4]. The process is described in more detail in chapter 3.3.2

3.2.5 Nanofiltration and Crystallisation

Crystallisation has shown to be a possible method for separation of metals from the acid, see
figure 7. It is important to concentrate the metal fluorides before crystallisation; this can be achieved
by nanofiltration. The crystallisation takes place in a separate tank and the crystals are separated
from using a filter press. The free acid is recycled to the pickling tank. This method reduces the
amount of nitrates very efficiently since it recycles the bound acid; therefore, nanofiltration in
combination with crystallisation is a possible method for pickling acid recycling [23].

Pickling tank

HF, HNO3
HF, HNO3

Crystallisation
Nano-filtration MeF
+ filter press

Concentrated MeF
+ HF and HNO3
Figure 7. A suggestion implementation of nanofiltration in combination with crystallisation

3.2.6 Neutralisation
The probably most conventional and utilised method is neutralisation. By increasing the pH of the
waste water, through addition of a chemical, the metals will precipitate as metal hydroxides, forming
a sludge. Today, neutralisation is usually the final treatment step of waste water form the pickling
process, before it is released to the recipient.

3.3 Nitrate reduction for pickling waste water

None of the previously mentioned processes are able to reduce the nitrate level in the water to an
amount which meets the European waste water regulations. Even if the water is after-treated with
neutralisation, where calcium nitrate Ca(NO3)2 has the ability to form, the nitrates remains
unaffected due to the high solubility of Ca(NO3)2 in water and the nitrates are released to natural
waters where they act as excessive fertilisers. The problem of nitrates is one of the important
environmental issues the steel industry is encountered with today and there are many research
projects going on in Europe to solve this problem. There are four main approaches for reduction of
nitrates from the pickling process [9]:

14
Nitric free pickling: The water as well as the NOx problem is solved by simply pickle without HNO3,
although, it has been shown that this is not appropriate for continuous pickling lines within
Outokumpu. It is however utilised in batch pickling where for example H2SO4 and HF is used.

Three acid pickling: By substituting parts of the nitric acid with sulphuric acid, the consumption of
nitric acid and therefore the discharge of nitrates are reduced.

Waste water treatment: The problem could be solved by the “end of the pipe” method, meaning at
the discharge point instead of at the source. Examples of such methods are biological denitrification
and membrane filtration. These methods are described in chapter 3.3.1.

Recycling of nitric acid: Internal recycling of acid instead of discharge has today become the main
focus for future development projects. The most interesting possibility would be to create a closed
loop pickling system where both the nitric and hydrofluoric acids are recycled. One of the
Outokumpu sites, in Tornio Finland, uses this method. They have an acid recycling system which is
based on metal sulphate crystallisation. The system in Tornio recycles both nitric and hydrofluoric
acids up to 98 % which reduces the waste acid stream to about zero, see chapter 3.3.2 for further
description. Also, a recycling system based on electro-dialysis like the one used in Outokumpu Nyby
can be used for acid recycling for reduction of nitrates, see also chapter 3.3.2.

3.3.1 Nitrate reduction methods without acid recovery

The two most common “end of pipe” methods for nitrate reduction are described in the following
chapters.

Biological treatment
Denitrification differs from the other nitrate removal processes because it does not concentrate the
nitrate but instead converts nitrate to free nitrogen gas (N2). Even though this is generally used for
municipal waste waters, where microorganisms convert NO3- to N2 in an anoxic environment, the
treatment is actually applied in some stainless steel manufacturers in Japan today [24].

Denitrification requires anoxic conditions and organic carbon compounds for reducing nitrate to
nitrite and finally to nitrogen gas (N2) which is released to the atmosphere. The total reduction is
shown is reaction 6 [25]:

− −
NO3 → NO2 → NO ( g ) → N 2 O( g ) → N 2 ( g ) (6)

When the waste water does not contain any carbon source, it has to be added, methanol is the most
commonly used. Waste water from stainless steel production contain high levels of nitrate
(600-1000 mg/l) and calcium (up to 1000 mg/l) due to neutralisation with lime as a pre-treatment
[25]. The high concentration of calcium ions in the outgoing water might have an impact on a
possible subsequent system for treatment of nitrate [24].

Fernandez-Nava et al [25] investigated the removal of nitrate from stainless steel rinse water after
pre-treatment with lime by denitrification in a batch reactor using methanol as carbon source. The
results showed that the presence of calcium ions had a negative effect where the denitrification rate
decreased for high calcium concentrations. This shows that it is important to have strict calcium
dosage in the neutralisation pre-treatment step [25].
15
Outokumpu have investigated this method in their sites in both Tornio and Långshyttan. The process
did actually work but it was decided not to continue with this option due to drawbacks such as not
being able to reuse the nitrates, as they are converted to nitrogen gas, and the need of a carbon
source which led to high costs [9].

Reverse Osmosis and Nanofiltration

The biological denitrification process requires a constant supply of a carbon source. Also, the removal
rate is much affected by the chemistry in the water and the treatment becomes less efficient for low
nitrate levels. Membrane separation could be used as an alternative to the biological treatment for
waste water from stainless steel production due to its low organic content and suspended solids.
Traditional reverse osmosis (RO) membranes have high operating and maintenance costs since they
require high pressure and extensive pre-treatment. A new generation of ultra-low-pressure
membranes have been developed, which can be applied for low molecule compounds such as
nitrates [24].

During nanofiltration of pickling acid, the metal fluorides are separated from the free acid. The metal
fluorides are simply retained by the membrane while the acids are allowed to pass. The life time of
the membranes and the flow capacity is the most challenging questions for this kind of method [23].

Kim et al. [24] investigated the feasibility of commercially available nanomembranes (NF) and reverse
osmosis (RO) for treatment of stainless steel wastewater containing high nitrate concentrations and
calcium as co-existing ion. The nitrate concentration was increased from 20 to 1000 mg/l in the feed
water and the rejection rate was measured in the variation of pH (5-10) and calcium and nitrate
concentration. The results showed that the rejection rate (correlated to the effectiveness) was higher
for the RO membranes than for the NF. The rejection rate for RO was not highly affected by
variations in pH or by having Ca2+ as co-existing ion. The rejection rate of NF decreased as pH
decreased and Ca2+ concentration increased. It also decreased as nitrate concentration increased.
The results implicate that RO could perhaps be used as an alternative for nitrates removal from
waste water from stainless steel production [24]. A drawback with membrane processes are their
sensitivity towards filter clogging, the membrane therefore requires cleaning on a regular basis. In
some applications, this is not sufficient during long-time usage, and therefore the membrane also has
to be replaced regularly. In other applications the membranes can have a longer life time [21].

3.3.2 Nitrate reduction methods with acid recovery

It is of great interest to find systems which increases the recycling rate of bound acid, therefore
decreasing the amount of nitrates released to environment. Systems which theoretically can do this
are very expensive and complicated in relation to the costs for preparing a new pickling bath;
therefore they are not often put into practise [4]. Although, for some mills, they have been
implemented because strict legislations due to environmental problems. A presentation of some
theoretical and existing technologies is presented below.

Evaporation
The principal of evaporation is to utilize the fact that different liquids have different boiling points in
order to separate them. During heating of a liquid mixture the most volatile substance will
evaporate. The vapour is led to a condenser where it by cooling will condense back to liquid. A good
separation is obtained if the boiling points of the substances which are to be separated largely differ
16
from each other. One advantage with this method is that the heat of evaporation can be exploited
for heating the liquid mixture in question, therefore decreasing the energy consumption
substantially [4].

The process becomes somewhat more complicated for azeotropes. The feature of an azeotrope is
that evaporation takes place until the composition of the vapour equals that of the liquid, then no
further enrichment can occur. Such substances can not at all or only partly be separated using
evaporation. A water-nitric acid mixture is a typical azeotropic mixture [26].

Due to the azeotropic characteristics of mixed acid, a number of methods for evaporation of used
pickling acid have been developed. One way is to first mix it with sulphuric acid (H2SO4). The high
boiling point of H2SO4 allows HNO3 and HF to evaporate which leaves a slurry of H2SO4 and different
metal salts. It is important that the evaporation takes place during vacuum; otherwise HNO3 might
decompose to nitric gases [4].

Another way is to let the evaporation take place in two steps. In the first step the mixed acid is
evaporated to 50 % and only a small amount of acid (0.03 % HF and 0.1 % HNO3) will be found in the
condensate which is led to the waste water facility. In the second step, sulphuric acid is added to the
concentrate and HF and HNO3 are evaporated. The remaining slurry consisting of H2SO4 and metal
salts is treated gravimetrically, for example centrifugation, in order to separate the sulphuric acid
which is recirculated back to the evaporator. This process is a bit more complicated but gives a larger
recycling rate than the other methods. Also, nickel will be in the form of nickel hydroxide which
facilitates possible nickel recycling [4].

Outokumpu process
An example of an authentic evaporation facility is the system used by Outokumpu in Tornio, see
figure 8. Here, the pickling liquor is first mixed with sulphuric acid before it enters the evaporator.
The evaporation takes place under vacuum at 80°C and at a pressure of 5 kPa which vaporizes HF and
HNO3. These are then condensed and recirculated back to the pickling bath. The slurry is led to a
crystallisation tank for precipitation of different metal sulphates. After thickening, the metal sulphate
slurry can be separated from the excess sulphuric acid, which is recirculated to the evaporator [4].

17
 HF (l), HNO3 (l)

HF (g), HNO3 (g)

Condensor

H2SO4
HF, HNO3
Evaporator
Pickling tank

Metal sulphate slurry

Thickening 1
Crystallisation
H2SO4

HF (l), HNO3 (l)

Scrubber Incineration

Metal sulphate slurry

Limestone
Ni(OH)2 Leaching

Figure 8. A schematic picture of the process used by Outokumpu in Tornio

In order to increase the precipitation of metal sulphate a part of the slurry after thickening, is taken
for an extra thickening step, in which the slurry is incinerated, thereby vaporizing the water. The
combustion gases are washed in a ventury scrubber with condensor. This way, the remaining HF and
HNO3 can be recycled. The metal sulphate slurry is leached using sodium sulphate leading to
precipitation of sodium jarosite (sodium iron sulphate hydroxide). In order to increase crystallisation
of iron and chromium, the pH is raised to 3.5 using limestone. Precipitation of nickel hydroxide then
takes place at alkaline pH. This process has shown a reduction of NO3- emissions by two thirds. The
recycling rate for HNO3 is 98 % and 99 % for HF [4].

Another method has been developed in Austria. The facility has a capacity of 100 l/h mixed acid and
450 kWh energy is needed per treated m3 acid. Here the evaporation takes place without addition of
sulphuric acid and the concentrate is then led to a separate tank for crystallisation. It is very
important that the crystallisation does not start in the evaporator but by utilizing the time delay
between oversaturation and crystallisation, this can be avoided. The solution is then filtrated and the
filtrate is mixed with the condensate which is upgraded and recirculated back to the pickling bath.
The condensate has an amount of 1 % HNO3 and HF each. This method gives a recycling rate of over
90 % for nitrates. In this process 4 kg of fluoride crystals are formed per kg dissolved iron during
pickling. These crystals are treated with neutralisation. The costs as well as the sludge volumes
during neutralisation can be decreased by granulation of the crystals. This is done by mixing the
crystals with an excess of calcium hydroxide in a reactor. The granules which are formed can be
reused in the steel making process [4].

Electro-dialysis
Electrochemical processes utilize the difference in chemical potential between anode and cathode, at
the anode an oxidation takes place and at the cathode a reduction. The fluid subjected to the
electrolyse acts as electrolyte through which the current flows. It is therefore important that the fluid
has good conductivity [4].
18
Electro-dialysis (ED) is a membrane filtration method where spent pickling acid is divided into acid
and base, the principle is seen in figure 9. A stream with waste acid and metals enters the ED where
anion and cation selective membranes are used to separate the different types of ions. At the anode
and cathode, hydrogen and hydroxyl ions are generated respectively. From the waste acid stream,
nitric acid is recycled and concentrated to the degree that it can be reused in the pickling process.
The different liquid flows are separated by using ion selective membranes and an electric field. The
cation selective membranes have a negative charge and will therefore repel anions and vice-versa for
anion selective membranes. When a current is applied, the negatively charged ions are transported
to the anode and the positively ions are transported to the cathode. The outflow from ED will be a
stream with diluted acid and high metal concentration and a concentrate of acids which is recycled to
the pickling process [4].

HF, HNO3, Me
HF, HNO3, Me

- + - + -
H+
F- H+
NO3-
H2 Me2+ O2
Cathode
- F- + Anode
OH- NO3- H +
H+ Me2+

Electrode rinse Electrode rinse

- + - + -
Diluted acid with metal ions Concentrate: HNO3, HF

Figure 9. The principle of electro-dialysis (ED)

One implementation of ED is to first neutralise the pickling liquor with potassium hydroxide (KOH)
resulting in a salt solution of KNO3 and KF besides the acid solution. This is beneficial since the
nitrates and fluorides are retained in solution, which is not the case when neutralising with
limestone. Formed metal hydroxides are separated using a filter press. The salt solution is taken to
an electro-dialysis cell where it is divided into acid and base and the depleted salt solution is taken to
an electro-dialysis cell with only monopolar membranes which leads to a more concentrated
solution. The concentrate is recycled to the first electro-dialysis cell and the depleted part as well as
the potassium hydroxide is led back to the neutralisation. Recycled acid is lead back to the pickling
bath. The energy consumption is calculated to 2000 kWh per tonne recycled HF/HNO3. Pilot tests
have reached a recycling rate of 93 % F, 99 % NO3 and 96 % K [4].

There are some problems encountered for electro-dialysis. The effect of the electrodes can quickly
decrease since the electrolyte fluid around the electrode becomes depleted of metal ions. This will
result in a decrease of the velocity at which metal ions in the bulk are transported to the electrode
surface, reducing the rate of the entire electrolysis. Also, since a large amount of nitrate ions exists in
the mixed acid, these will be reduced to gaseous nitrogen oxides (NOx) [4].

19
20
4. Neutralisation theory
The oldest and most utilised method for waste water treatment from the pickling process today is
neutralisation. Even though many steel mills uses the ionic exchange process, the outflow will still be
acidic water with high metal concentration, water too toxic to be released directly to recipient,
therefore neutralisation is used as an after-treatment. This will give a reduction in metal
concentration and rise in pH.

Neutralisation is simply increasing the pH, which will lead to precipitation of metal hydroxides due to
their low solubility in water. The metal hydroxides solubility is strongly pH dependent. An optimal
precipitation of a specific metal is received in a very narrow pH-interval and this interval is different
for various metals. The pH is usually increased using either slaked lime (Ca(OH)2) or sodium hydroxide
(NaOH) [21].

Spent pickling liquor is usually neutralised with slaked lime (Ca(OH)2) [4]. The dissolved metals form
hydroxides. The final product will be a sludge with high metal concentration. The fluoride ions in the
water will form calcium fluoride (CaF2) which also precipitates [27].

4.1 Theory of precipitation

A solution in thermodynamic equilibrium with a solid phase at a given temperature is said to be
saturated. If the solution contains more dissolved solute than given by the equilibrium saturation,
the solution is supersaturated. Precipitation will not occur spontaneously when the saturation limit is
reached since the smallest particles will dissolve immediately as they are formed. A degree of
supersaturation is essential for precipitation to take place, when this is reached, precipitation will
occur immediately [23].

The precipitated substance can either have an amorphous or crystalline structure. Factors which
favour production of crystalline compounds are high temperature and low supersaturation. Many
precipitants formed are amorphous due to either low temperature or lack of supersaturation control
or both. Upon ageing the amorphous structure are sometimes converted into crystalline
compounds [28].

The solubility of a substance is affected by pH and temperature. The solubility often increases with
increased temperature; therefore, cooling the solution can lead to earlier crystallisation due to
supersaturation. If the solubility is not decreased by lowering the temperature, the appropriate
degree of supersaturation can be achieved by concentrating the solution, which can be done by
evaporating some of the fluid [23].

During neutralisation, the metals in the water precipitate as hydroxides within a special pH interval.
Commonly, the precipitants have an amorphous structure; this is usually the case when fast
precipitation occurs. The crystalline structure can form over a longer time. It is therefore common
that some of the amorphous components in the sludge are converted into a crystalline structure
during landfill. Crystalline structures have smaller volume than amorphous structures, because in a
crystalline structure the atoms are more arranged and can therefore be more closely packed [29].

A phenomena which can occur during metal precipitation, is that as soon as iron hydroxide starts to
precipitate, this will enhance further precipitation. The mechanism is not fully understood, but it

21
seems as if further precipitation takes place onto the already existing iron hydroxides which gives a
more efficient precipitation, the phenomena is called co-precipitation [29].

4.2 Parameters influencing neutralisation

The neutralisation process is influenced by a number of parameters, such as the choice of chemicals
and their dosage, the pH and the mixing rate. For an efficient process it is important to find the
optimum alternative of the different parameters with economic factors in mind.

4.2.1 The pH
When the neutralisation chemical is added, the acid water will be neutralised, and as the pH rises,
the metals will precipitate as hydroxides. Chromium hydroxide is least soluble at pH between 8 and 9
and nickel hydroxide between 10 and 11 [30]. Since different metals have diverse pH-optimum, it is
difficult for water containing various metals, to find one optimal pH where precipitation of all the
metals is most favourable. Therefore, a compromise has to be made. The optimal pH usually lies
between 8.5 and 10 but the exact pH should be decided upon experiments [15].

Some problems with a pH controlled process are that when working close to the equivalence point,
due to the buffering properties, the pH varies with time, is non-linear and sensitive to small
disturbances. It is therefore important to have a good pH control system. The control system must be
able to regulate the transitions between different regimes. The reliability of existing control systems
have been a topic over the recent years [31].

4.2.2 Neutralisation chemicals

The choice of chemicals for neutralisation is a question of weighing costs and efficiency against each
other. The most common and least expensive chemicals used for neutralisation is lime. Usually in the
form of limestone (CaCO3), quick lime (CaO) or slaked lime (Ca(OH)2) [32]. Sodium hydroxide (NaOH)
or potassium hydroxide (KOH) are more expensive chemicals but they provide a faster and more
efficient neutralisation resulting in a smaller amount required than as in the case for lime or
limestone [33]. Usually, sulphuric acid (H2SO4) is used for lowering the pH [15].

Sodium hydroxide is 100 times more soluble than lime in water and therefore the precipitation
reaction is completed in 5-10 minutes. Lime requires 20-30 minutes of retention time to react when
properly mixed. Although, NaOH is more expensive than lime, switching to NaOH instead of lime can
sometimes be is an alternative for process improvements such as for faster reaction time. This might
be a more cost efficient alternative instead of replacing tanks or changing the mixers
for instance [30].

There are some advantages with lime over sodium hydroxide; lime gives better sedimentation and
dewatering properties of the formed metal hydroxide. Also, the risk of re-dissolution of the
hydroxides at higher pH becomes lower, as in the case of chromium [15]. An important factor for
neutralisation of mixed acid is that the fluorides have to be reduced. This problem is solved when
neutralising with lime, since the fluorides bind to the calcium and form calcium fluoride (CaF2) which
have low solubility in water (0.016 g/l) and will therefore precipitate as sludge. Sodium fluoride (NaF)
will form when neutralising with NaOH [34], but the solubility in water (41.3 g/l) is higher then for
CaF2, which makes the fluoride reduction more efficient when using lime.

22
Lime Slaking
Slaking is the process when quicklime (CaO) and water are mixed in different proportions so that a
hydrated or slaked lime slurry (Ca(OH)2) is received according to the following reaction [35]:

CaO + H 2 O → Ca (OH )2 + heat (9)

Lime slaking is an exothermic process resulting in a temperature raise in the reactor, therefore, water
is added for dilution which results in a lime slurry, usually around 10-20 %. The slaking can be
preformed batch wise or continuously. Batch wise lime slaking usually takes about 45 minutes for
complete reaction and for continuously slaking 1 m3/h [34].

The neutralisation efficiency of the lime slurry is of course affected by the gradation of quicklime but
also by factors such as; reactivity, particle size, slacking temperature and the quantity of water used
for slacking. If an excessive amount of water is added; the surface of the CaO particle will quickly
hydrate and this mass will obstruct the diffusion of water into the centre of the particle which results
in incomplete hydration and formation of coarser instead of finer particles. If on the other hand
insufficient water is added, a large number of particles become non-hydrated. Both of these cases
decrease the lime efficiency [32].

Smaller particles (<20 µm) are formed at higher slacking temperatures. If larger particles appear, they
become unavailable during neutralisation since they might not dissolve entirely or become coated
with metal hydroxides during neutralisation, making them inaccessible for reaction. Either way the
large particles will settle with the sludge which results in an increased sludge volume and increased
lime consumption. Slacking at higher temperatures therefore results in an increase in lime efficiency
and a decrease in sludge volume due to the appearance of smaller particles. Some tests have shown
that less water addition and high temperature (just below the boiling point of water) during slacking
is favourable [32].

The surface area of the lime particle is an important factor which affects hydration. Smaller particles
results in a higher surface area and are therefore more reactive. Also, the form and porosity of the
particles plays a part. Therefore, two lime particles with the same surface area can differ in
efficiency. It has been shown that a particle which is very porous and has a plate-like form will be
more reactive due to the greater surface area. [32].

The quality of the quick lime (CaO) used for neutralisation is of course an important parameter. If the
quick lime is more reactive, the slaked lime (Ca(OH)2) will have better qualities and therefore the
neutralisation reaction will proceed faster. The reactivity of the quick lime can be evaluated by
studying the slaking-curve. Since lime slaking is an exothermic reaction, (see reaction 9) a slaking
curve can be drawn by a simple experiment; a sample of about 100 g CaO is placed in a thermo-
bottle and 500 ml of water, which has a temperature of 20 °C, is added. The raise in temperature is
then measured during a period of 10 minutes. The faster and higher the temperature is reached
indicates a more reactive quick lime [36]. Figure 10 is an example of how two different types of
slaking curves can look; the thicker curve indicates a more reactive quick lime.

23
 Figure 10. Example of slaking curves of two different quick lime,
the thicker curves indicates a more reactive quick lime

In Sweden today there are a number of different quick lime suppliers and they differ in their
manufacturing method. Outokumpu in Avesta and Degerfors uses two different suppliers for quick
lime in their neutralisation processes. By studying the slaking curve of these limes it was clearly seen
that the lime used in Avesta had the best reactivity. This quick lime was manufactured in a double
shaft kiln and the one used in Degerfors was manufactured in a rotary kiln [36].

Lime slurry
After slacking, the lime slurry is usually diluted and stored in a vessel before it is fed to control the
pH. This dilution will cool the hydrated particles and therefore prevent re-crystallization. Experience
has shown that lime slurries which have a lower solid content often have problems with plugging in
the lime distribution system due to settled grits which have slipped through the grit removal system.
An explanation of this is that higher density lime slurries (more solids) will have a higher viscosity and
can therefore easier retain grits in suspension. In literature, a lime slurry density of 20 % to 25 % is
therefore recommended [32].

4.2.3 Mixing during neutralisation

It is important to have good mixing for optimal sludge production. Higher agitation rate will result in
better dispersion of the lime and also larger particles will remain in suspension, although, mixing will
results in an increased energy consumption. If the mixing rate becomes too high it might lead to
particle abrasion [32].

In many cases, when the performance in a waste water treatment plant is poor, it is easy to blame it
on inadequate mixing. As a consequence, installations such as larger reaction tanks with higher
retention time, more powerful mixers or new motors to the existing mixer shaft are made. Such
installations can become expensive and unnecessary when one instead can simply evaluate the
existing technology. For example, if the impellers are inadequate, then by simply installing a larger
motor on an existing mixer shaft will not always give better mixing, instead perhaps the impeller
should be replaced. For general mixing if proper shaft length and impeller are used, a rule of thumb is
one horsepower per 7500 gallons of waste water (about 0.027 kW/m3 waste water). More mixing
energy may be required if vigorous mixing is necessary to complete a chemical reaction, up to
1/2 horsepower per 1000 gallons of wastewater (about 0.1 kW/m3 waste water) [30].
24
Baffling is also an important factor, mixing will suffer if the tanks are not properly baffled. Without
baffles, it may appear visually as if mixing occurs due to swirling, when in fact very little mixing takes
place. The tank can simply be upgraded by installing baffles to the wall of the tank; this is also less
expensive and can provide much better mixing then for instance changing the tank to a larger one, or
installing larger mixers [30].

Rapid mixing level out local regions of high supersaturation and improves lime dissolution. In
conventional treatment systems with no mechanical mixing, lime dissolution is poor and as metal
precipitate, a gelatinous fine-grained sludge with poor solid/liquid separation tendency is produced.
This is explained by the high condition of supersaturation in the reactor, which results in particle
nucleation rather than particle growth [32].

In conventional reactor systems with mixing, increased agitation tends to increase sludge density and
settling rate. This is simply because the diffusion of metal ions to the hydroxide surface is enhanced
and therefore particle growth is accelerated. Also, increased mixing speed tends to reduce voids
making porous fragile flocks to become dense and compact aggregations, which settle
more quickly [32].

5.3.4 Flocculation
The purpose of flocculation is to aggregate finer colloid particles and enhance settling, resulting in a
clear effluent. By adding a flocculation agent, flocks will form and settle more rapidly. The type of
flocculant and concentration has a large impact on the properties of the final sludge. Often some sort
of polymer is used as flocculation agent. Polymers are high to very high molecular weight molecules.
The dosage of the polymer will besides the settling rate also affect the sludge viscosity, effluent
quality and the final density of the sludge [32].

Polymers can be charged, called polyelectrolytes, they are thereby able to neutralise the charge of
the colloid particles, therefore allowing them to come in contact and agglomerate. Polymers with
positively charged groups are called cationic polymers, and with negatively charged groups, anionic.
Polymers without charge are called non-ionic [37]. The most common used polymers are
polyelectrolytes based on polyacrylamide (PAM). The polymers have groups which will help forming
bridges (crosslinking) between the colloid particles which thereby forms larger flocks [21].

Polyacrylamide is made from the monomer acrylamide CH 2 = CH − CONH 2 . The monomer can
either be polymerised with itself or with a different polymer. The repeating unit of a non-ionic
polyacrylamide is shown in figure 11A. By polymerising acrylamide with sodium acrylate, a negatively
charged polyacrylamide is gained, see figure 11B. The negatively polyacrylamide is the most
commonly used flocculation agent for metal precipitation [37].

The efficiency of the flocculent can be measured by turbidity, suspended solid content or
concentration of metal integrated in the suspended solids [32].

25
 CH2 CH CH2 CH2
C O COO- Na+
A NH2 B

Figure 11. Repeating unit of A) Non-ionic polyacrylamide

B) Negatively charged polyacrylamide

Polymer dosage
In mining industry, there are two definitions of polymer dosage. The first is defined in ppm or mg of
dry polymer added per litre of treated effluent. The second definition relates the mass of polymer
used to settle a specific mass of sludge, in other words; g of polymer per tonne of sludge. When
performing pilot tests and scientific studies the latter definition is much better to use for comparison
of different processes, although, it requires that the solid content of the final slurry is known [32].

It is beneficial to have a minimum dosage of polymer. If the dosage becomes too high, the settling
rate may increase until shear on the particles becomes too large, therefore causing particle break-up
which result in an increase in turbidity. When a very high molecular weight polymer is used, particle
break-up is higher. If the polymer dosage passes a certain threshold value, the chains begin to
entangle and they become difficult to pull apart which will lead to an increase in the sludge viscosity.
Usually the threshold value lies in the range for acceptable effluent quality [32].

The optimal dosage usually lies between 2-200 g polymer per tonne of dry material flocculated. The
relationship between the solid content of the slurry and the optimal polymer dosage has been
calculated as a mass ratio (mg/g) and it was found that for a low solid content, a large excess of
polymer was needed to entangle the particles [32].

According to experience, at low dosages of polymer, flocculation increase density of the settled
sludge but as the dosage increases, the density decrease. This of course depends on which polymer is
used. Polymers with higher charges repel each other more which will decrease the sludge density
more extensively as the dosage is increased [32].

The most common mistake made by operators when it comes to flocculation is over-dosing the
polymer so that effluent targets are met and an acceptable sludge density is gained, but instead
leading to a very high sludge viscosity and also a raise in the polymer costs. A suggested way to
determine the optimum polymer dosage is to decrease the polymer feed until the quality effluent is
affected and then raise it 5 % to 10 % [32].

5.4 Sludge
Disposal of the sludge constitutes a great part of the total treatment costs. The larger the volume of
the sludge, the higher the costs for disposal, therefore, a higher sludge density lead to a considerable
reduction in disposal costs [32].

The sludge may continue to densify after emplacement. This is due to freeze-thaw (expansion of
water as it freezes) and long-term settling. The final content of solids in the sludge depends on the
initial solid content of the sludge and disposal method. For some sites an increase of 1.5 to 3 times
the initial solid content has been reported. Sludge density should be maximized in order to decrease
the long term disposal costs; this can be done by sludge dewatering [32].
26
For acid mine drainage, different methods have been developed, such as the High Density Sludge
(HDS), where a part of the sludge is recycled back to the neutralisation stage, and the step-wise
neutralisation (also called supersaturation-controlled or staged-neutralisation process), where the pH
is controlled in many steps. These technologies are further described in chapter 6.

Demopoulos [28] investigated and compared three different neutralisation paths of acid mine
drainage; conventional, HDS process and step-wise neutralisation. In order to examine the effect of
the supersaturation-controlled treatment, tests were carried out to neutralise a synthetic
H2SO42-/Fe2(SO4)3 (1000mg/l Fe3+) solution with initial pH 2.5, using caustic soda (NaOH). First, the
solution was neutralised in a conventional manner by increasing the pH in one step. This produced a
completely amorphous sludge with low solid content (< 5%) and the settling rate
was quite poor (<2 m/h) [28].

Secondly, the solution was neutralised using the High Density Sludge process (HDS) meaning some
sludge was recycled. This was performed in a number of cycles and in each test 90 % of the
precipitates where recycled to be used as seeds in the next test. It was found that the sludge quality
improved and after 15 recycles, the solid content of the sludge was 25-30 %. The settling rate was
also improved and varied between 2-4 m/h [28].

In the final experiment, neutralisation was performed in a step-wise way and sludge was recycled
here as well, so called controlled supersaturation process. In the step-wise neutralisation an acid
solution with metal concentration C0 and pH0 was neutralised to pH1. The pH was kept constant
through addition of base, seeds was added for initiating precipitation. When the pH became stable it
indicated that precipitation was complete and more base was added for a raise to pH2, the procedure
is then repeated. In an industrial scale the different pH steps is performed in different tanks [28].

The step-wise neutralisation was the significantly best method of the three. The sludge had 55 %
solid content after only 8 cycles. The particles were coarse and the size distribution was more
uniform. The sludge settling rate was much faster (12 m/h). The experiments proved that step-wise
neutralisation produces a much denser sludge. The step-wise experiment was then repeated using
slaked lime (Ca(OH)2) instead of NaOH. In these tests the solid content was 67 % after only 10
recycles. No unreacted lime was found in the sludge which proves the high efficiency
of this method [28].

It is beneficial to have a low CaO as well as a low Ca(OH)2 content in the sludge. In a report from
Outokumpu [36] some simple improvements are suggested for receiving a better quality of the
sludge:

• Introduce “on-line process control” by using pH-electrodes which are self-cleaning.

• Do not overdose the lime milk.
• Do not exceed pH 10.
• Control water leakage from broken filter so that the water is not running to the sludge
container.
• For economical reasons, make sure that the water content of the sludge does not exceed
45-50 %

27
5.4.1 Sludge dewatering
The sludge from the sedimentation will have a dry content of about 1-2 %, the rest is water. The cost
for transportation of such sludge is very expensive meanwhile it can easily contaminate the ground
water, therefore, the sludge must be dewatered to at least 30 % dry content. At this concentration,
the sludge is more manageable. Dewatered is performed by a filter press, during which the water
passes through the filter meanwhile the sludge is retained. At the end of the press cycle, the whole
area between the filter plates are filled with sludge. The press is stopped and the sludge cakes are
removed. The reject water is circulated back to the neutralisation step. The filter press is operated
batch wise. Today it is the dominating process for dewatering of metal hydroxide sludge. The dry
content of such sludge is usually more than 30 %. The sludge cakes are placed in an open container,
which allows the sludge to dry of even further through evaporation. After six months a dry content of
about 50 % can be gained [15].

The sludge which contains metals are today stored on special landfills which are controlled and
approved by the government. It would be interesting if one could exploit the metal in the sludge, but
today this is not economically advantageous. Sludge which only contains one sort of metal is called
monosludge. This type of sludge can normally be upgraded at a lower cost than sludge with mixed
metals. In many countries, the cost for landfilling monosludge is much less than mixed sludge. For a
future possible recycling of sludge, the cleaning facility should be designed so that a mono sludge is
received. In USA today metals from both mono and mixed sludge metal hydroxide sludge are often
recycled. The reason for this is that the cost for landfilling the metal hydroxide sludge is 5-10 times
more expensive than in Sweden [15].

5. 5 Chemical reactions during neutralisation

The feature of an acid is that when it is dissolved in water, it dissociates, giving a free hydrogen (H+)
ion which will bound to a water molecule. This is illustrated in reaction (10) where the acid is HA.
Different acids have different ionisation capacity; a strong acid is easily dissociated then a weak acid.

HA + H 2 O ↔ A − + H 3O + (10)

Upon neutralisation, hydroxide ions (OH-) are added which have the ability to bind the free hydrogen
ions, therefore, forming water. This is illustrated in reaction (11).

H 3O + + OH − ↔ 2 H 2 O (11)

Weak acids have a buffering property, meaning the ability to resist a change in pH on addition of
hydroxide ions.

After lime slaking, the slurry is added and dissolves in the acid liquid, which results in an increase of
pH. The free hydroxide ions (OH-) ions react with the acids and the metal ions to form metal
hydroxides which precipitate at a certain alkaline pH, illustrated in the following reactions [9]:

28
Waste acids:

2 HF + Ca (OH )2 ↔ CaF2 ( s ) + 2 H 2 O (12)

2 HNO3 + Ca (OH )2 ↔ Ca ( NO3 )2 + 2 H 2 O (13)

Metal hydroxide precipitation:

2 Fe 3+ + 3Ca (OH )2 ↔ 2 Fe(OH )3 ( s ) + 3Ca 2+ (14)

2Cr 3+ + 3Ca (OH )2 ↔ 2Cr (OH )3 ( s ) + 3Ca 2+ (15)

Ni 2+ + Ca (OH )2 ↔ Ni (OH )2 ( s ) + Ca 2+ (16)

From the metal hydroxide reactions it is seen that 1.5 mole Ca2+ will be formed for each mole metal
hydroxide formed. As seen above, calcium nitrate Ca(NO3) is formed, but the solubility of this
component in water is high (1290 g/l) and Ca(NO3)2 will therefore exist in ionic form as Ca2+ and NO3-.
Due to this the nitrates will flow through the neutralisation system, unaffected and at the end be
released to the recipient [9].

The discharge of metals is related to the efficiency of the neutralisation process. Although, the
efficiency is not only related to the chemical neutralisation reactions but is also depending on specific
parameters on the plant such as hydraulic load (m3/h through the plant). Therefore, the discharge
values vary to some extent between different production sites [9].

5.5.1 Calcite formation

During neutralisation carbon dioxide (CO2) in air might dissolve in the water and react with the lime.
Carbon dioxide can also already exist in the liquor itself. During its reaction with the slaked lime
bicarbonate and a fraction carbonate forms. The carbonate will react with calcium and form calcite
(CaCO3) which precipitates [35]. This reaction will consume two hydroxyl groups which are meant for
the formation of metal hydroxides and is explained by the following reactions [32]:

CO2 ( g ) + H 2O ↔ HCO3 + H +
−
(17)

− 2−
HCO3 ↔ CO3 + H + (18)

Ca (OH )2 + CO3 + 2 H + ↔ CaCO3 + 2 H 2O

2−
(19)

Total reaction: Ca (OH )2 + CO2 ↔ CaCO3 + H 2 O (20)

The reactions show that each mole of calcite formed consumes one mole of lime intended for the
neutralisation [32].

Calcite is an indicator of the lime efficiency; a more efficient process will produce less amount of
calcite. One can measure the amount of calcite in the sludge, and this calcite might have been
formed either during neutralisation seen in the above equations or origin from unreacted lime in the
29
sludge which over time have reacted with carbon dioxide in the air. If a lot of calcite is found in the
sludge it might therefore indicate poor utilisation of lime during neutralisation [32]. Although, calcite
is important for the stability of the final sludge since it provides neutralising potential to the sludge
during storage. A high neutralisation potential is an indicator of either the existence of unreacted
lime or that there is excess calcium carbonate in the system [35].

5.5.2 Oxidation of iron

Iron exists either as ferric (Fe3+) or ferrous (Fe2+). In the pH range of 4-12 the solubility of ferric
hydroxide Fe(OH)3 is less then 0.1 mg /l. For ferrous iron Fe(OH)2 the pH has to be raised above 9 for
precipitation and to receive a concentration less than 2 mg/l left in solution. Ferric iron is more
chemically stable than precipitations of ferrous iron which will oxidize over time to ferric iron. For
these reasons, for an optimum precipitation and removal of iron, it is essential to oxidize ferrous iron
to ferric; for water with a high amount of Fe2+, this is commonly achieved by aeration [38]. When
ferrous iron (Fe3+) is exposed to oxygen the oxidation rate to ferric iron (Fe2+) is determined by; the
concentration of ferrous iron, dissolved oxygen and pH of the solution. At pH values greater than 6
the reaction rate is described by equation 1 [32]:

[
− d Fe 2+ ] [ ] [
= k Fe 2+ [O2 ] OH − ]2
(1)
dt

The equation shows that the oxidation rate decreases as the concentration of either Fe2+ or O2
decreases and the rate increases 100 times for one unit rise in pH (for pH above 6) [32].

At alkaline pH the iron oxidation reaction is [32]:

1 1
Fe(OH )2 + H 2 O + O2 → Fe(OH )3 (21)
2 4

In the acidic water from the pickling process, the main part of iron already exists as ferric iron and
therefore no aeration is necessary.

30
6. Some different neutralisation technologies
In literature, three general processes for neutralisation can be found; basic, conventional and High
Density Sludge process (HDS), these are described below.

6.1 Conventional neutralisation

In basic neutralisation, lime is added directly to the effluent stream and separation of solid/liquid
occurs in a sludge settling stage. In the conventional process, the addition of lime is controlled by the
pH and the process takes place in a reactor with agitators. The discharge from the reactor is led to
either a clarifier or a sludge settling pond for solid/liquid separation, figure 12.

Ca(OH)2
Flocculant

Effluent
Reactor
Clarifier

Sludge to
Waste water
landfill

Figure 12. Conventional neutralisation

This is different from the High Density Sludge (HDS) process which takes place in one or many
reactors, a clarifier then separates the treated effluent from the sludge, and a portion of the sludge is
recycled back to the neutralisation process. This is beneficial since the sludge recycling increases the
sludge density and therefore decreases sludge volume. Also, recycled sludge facilitates further
precipitation [32]. The HDS process and some alternatives of it are presented in the following
chapters.

6.2 The High Density Sludge process (HDS)

In the High Density Sludge process (HDS), a part of the sludge is recycled from the clarifier back to the
neutralisation stage for sludge density increase [32]. The HDS process is usually quite advanced and a
facility can consist of a number of reactors, clarifiers and sludge dewatering systems. Sludge density
can vary from 1 % to 30 % solids depending on the treatment process and metal concentration in the
water [38].
Ca(OH)2 Waste water Flocculant

Effluent
Mixing
Rapid mix Lime Flocculation Clarifier
tank tank reactor tank

Sludge to
landfill
Recycled Sludge

Figure 13. The HDS process

31
An example of a HDS process is given in figure 13. Here, the recycled sludge is first mixed with lime to
the desired pH in a mixing tank. The different solids come in contact with each other and lime
particles are coagulated on the recycled precipitates. The stream then overflows to a rapid mix tank,
where the waste water is added. Precipitation can either occur here or in a lime reactor where the
precipitation takes place (shown as the dotted reactor in figure 13). Since the lime was mixed with
recycled sludge, the precipitation is forced to take place on the surfaces of these already existing
particles which will therefore increase their size and density. The slurry then overflows to a
flocculation tank where the flocculant is added for agglomeration and the final step is the clarifier.
The flocculation tank can be removed and instead the flocculant can be added directly in the conduit
leading from the lime reactor to the clarifier, although, good turbulence in the conduit is essential for
proper flocculant contact. The flocculant may also be added in the clarifier feed well [35].

The HDS method has many advantages such as reduction in lime consumption and co-precipitation of
metal ions which removes metals more efficiently. The HDS process minimizes sludge volumes and
gives a denser sludge. The sludge particles become more granular and hydrophobic and therefore
they repel water and attract heavy metals. The sludge settles more rapidly and drains faster which
leads to a sludge with high solid content. Due to the reduction in sludge volume, the size of the
clarifier and costs of sludge pumping is reduced as well as treatment per volume of treated water.
Also, the sludge is both chemically and physically more stable than the sludge from conventional
neutralisation processes. The HDS process has become standard for acid mine drainage today [38].

6.2.1 The Geco HDS Process

The Geco HDS process is similar to the HDS process, but it does not have a mixing tank for the lime
and the recycled sludge. The sludge is instead recycled from the clarifier to a tank where it is mixed
with the waste water directly. The sludge is partially dissolved and metals are precipitated. Lime is
then added for pH control in the subsequent step which is the rapid mix tank see figure 14. If the
water contains ferrous iron, aeration takes place in reactor 2, leading to oxidation and precipitation
of ferrous to ferric iron. The flocculant is added in a separate step and the solution is then led to a
clarifier.

Aubé and Zinck [35] compared sludges from the Geco and the HDS process. They showed that the
sludge from a Geco plant was the only sludge to have a crystalline component; all other sludge was
entirely amorphous. Geco sludge also had the lowest neutralising potential, which means that the
process is more lime efficient. A high neutralisation potential is an indicator of either the existence of
unreacted lime or that there is excess calcium carbonate in the system. This is avoided when allowing
direct contact of the lime to the waste water, unreacted lime is then consumed and the carbonates
are dissolved. On the other hand, a low neutralisation potential is disadvantageous for the long-term
stability of the sludge [35]. It is difficult to conclude why such is the case [29].

32
 Waste water Ca(OH)2 Air Flocculant

Effluent
Floc tank
Reactor Rapid Reactor
Clarifier
1 2
mix tank

Sludge
to
Recycled sludge landfill

Figure 14. The Geco HDS process

6.2.2 Staged-Neutralisation Process

In the Staged-Neutralisation process, (also called supersaturation controlled recycling), neutralisation
takes place in a series of steps, figure 15. This leads to better control of the level of supersaturation
during metal precipitation. It is utilised in order to increase the sludge crystallinity and therefore
obtain a reduction of sludge volume. Recycled sludge is added in the first, or the two first reactors,
and the waste water is hence partially neutralised. In the third and fourth reactor, lime is added to
reach the desired pH. The desired pH is target in each reactor and the number of reactors required is
decided on the concentration and metal type in the water as well as the desired sludge density [35].

Ca(OH)2 Ca(OH)2 Ca(OH)2 Ca(OH)2

Flocculant

Floc
pH=pH1 pH=pH2 pH=pH3 pH=pH4 tank Effluent

Clarifier

Recycled sludge Sludge to

landfill

Figure 15. The Staged-Neutralisation process

Laboratory tests showed an increase in densification from 25 % to 50 % solids for this process. The
sludge consisted of a crystalline iron precipitate rather than only amorphous compounds. For this
process to work in full scale, 4 reactors are needed which will lead to higher capital costs than for
other processes, but better sludge properties and decreased lime consumption are expected. Both
the Geco HDS and the Staged-Neutralisation process are more lime efficient then
conventional HDS [35].

33
34
7. Acid treatment examples in Sweden
In order to get a clear picture of the situation and manage of pickling acids in Swedish industry today,
two cases has been studied; Outokumpu Stainless sites in Nyby and Avesta.

Outokumpu is one of the world leaders in stainless steel production with plants in Finland, Sweden,
UK and USA. Their products include both hot and cold rolled material in a variety of dimensions and
surface finishes. Their products have different applications ranging from cutlery to chemical
processing plants. Outokumpu employs 7600 people in over 30 countries. The head office is located
in Espoo in Finland. Two of the Outokumpu group production facilities are the scrap based steel mill
in Avesta and the cold rolling mill in Nyby [39].

7.1 Outokumpu Stainless, Avesta

In Avesta, stainless steel is manufactured from scrap. After casting and hot rolling the steel is send to
the annealing and pickling line (AP-line) in the form of coils. The AP-line in Avesta is a combi-line,
meaning it can process both hot and cold rolled material. After the first run in the AP-line some of
the coils are cold rolled to receive desired surface qualities. Before the material enters the AP-line,
many coils are welded together to one long strip. The AP-line can handle strip widths of up to 2 m.
There are only three mills in the world which has that capacity.

During the annealing treatment, the steel becomes somewhat crooked, which requires treatment in
a stretch leveller for evening out the steel. Before entering the pickling, the steel is treated in a shot
blaster. This is a mechanical treatment for oxide depletion where the steel is blasted with small
shots. Both the stretch leveller and the shot blaster works as a pre-treatment for the pickling by
making the formed oxide layers more sensitive [40].

Cold rolled material is instead pickled electrolytically. Here, direct current is applied in an electrolyte
consisting of sodium sulphate (Na2SO4). The material is then rinsed with water. The final step for both
hot and cold rolled material is the mixed acid pickling [40].

7.1.1 Electrolytic pickling

As can be seen in figure 16, which is a flow chart of the electrolytic pickling, the electrolyte is
recirculated between the pickling bath and a circulation tank. Sodium sulphite is recirculated and a
partial flow is continuously taken from the circulation tank to lamellar separator for desludging. The
sludge from the separator is lead to the mixing tank where it is merged with rinse water [40].

35
 Strip to acid pickling Strip
Rinsing Electrolytic pickling

NaHSO3 Sludge and

NaHSO3

Leach water
from landfill

Sludge Circulation tank

To neutralisation Cr-reduction Mixing tank

Sludge

H 2SO 4 NaHSO 3

Figure 16. The electrolytic pickling of Outokumpu in Avesta

7.1.2 Chromium reduction

The plant was built in 1992 and works continuously. During the electrolytic pickling Cr6+ is formed,
therefore, both the rinse and waste water from this step is led to the chromium reduction facility,
situated close to the neutralisation tanks. All fluids containing Cr6+ is taken here, meaning both sludge
and rinse water from the electrolytic pickling as well as leachate from the sludge landfill. The total
flow to the Cr-reduction is 2 m3/h. The chromium reduction takes place in two tanks, for better
retention time, each with a volume of 2.7 m3. For an efficient reduction the pH is lowered from
about 7 to around 2.5. This is done by adding sulphuric acid (H2SO4) towards the set pH. Sodium
sulphate (NaHSO3) is then added for chromium reduction [40].

In the first tank the pH is set to 2.5 and the redox potential to 350 mV. In the second tank the pH is
only maintained at 2.5 and the redox potential is set to 310 mV. There is a pH electrode in each tank
for control of the dosage of sulphuric acid. Similarly, two redox-electrodes control the dosage of
sodium sulphate. In the outflow, the Cr6+ content is not allowed to exceed 0.1 mg/l. A redox
electrode is placed at the discharge to ensure that the reaction is complete. Both the formed sludge
and the chromium-reduced fluid is led to receiving tank for neutralisation [40].

7.1.3 Spent pickling acid

The mixed acid pickling line consists of 3 tanks. The mixed acid has a composition of 15 vol% HNO3
and 5 vol% HF. Next to the pickling line, 3 circulation tanks are situated, each one has a volume of
20 m3 and each one is connected to one of the pickling tank, area A in figure 17. The purpose of the
circulation tanks is to pump a mixture of fresh and recycled acid from the acid regeneration unit
(SAR) to the pickling bath. The SAR is a strongly basic anionic exchanger where the free nitrate and
fluoride ions are retarded. Metal ions, fluorides, and nitrate which are bound as complexes flows
trough the bed and are treated separately at the neutralisation facility. The purposes of the
circulation tanks are also to store the pickling acid during production stops [40].

A continuous stream of 4 m3/h, is taken from the pickling tank, it is filtrated from particles and led to
the SAR facility which consists of 8 modules. From the SAR the concentrated stream of acid is
pumped to the circulation tanks where the temperature is controlled and fresh acid is added for acid
36
concentration adjustment. The acid is then pumped back to the pickling bath. The circulation tanks
are cleaned once a week since sludge settles in the tanks, this sludge is led to the receiving tank for
pickling sludge in the neutralisation facility from where it is neutralised separately. The waste stream
from the SAR has an average metal content of 20 g/l and is led to the receiving tank, which is working
as a buffer tank, in the neutralisation facility. This stream is 1/5 of the total flows going into the
receiving tank [40].

Sometimes the acid volume might become too high in the pickling and circulation tanks, therefore it
is necessary to pump this excess acid to a separate storage tank (75 m3), area B in figure 17. A stream
is lead by gravity from the production line to a pump pit, from where it is pumped to the pickling acid
storage tank, both situated close to the neutralisation facility. Since the acid concentration of this
stream is much higher then the other streams, neutralisation takes place in a separate tank. A small
stream is also led directly to the receiving tank. This addition of acid leads to the formation of more
sludge during neutralisation which will improve the conditions for flocculation. The pH during
flocculation is constant at about 10 [40].

Circulation tanks
Diluted A
stream
SAR 1 2 3 Gases from the Scrubber
pickling line (mixed
To the acid section)
receiving
Strip
tank Rinsing Mixed acid pickling Rinsing Electrolytic pickling
B
Water
Pickling acid
storage tank
Leach
water from
landfill
From SAR Cr-reduction
Pump pit
Ca(OH)2
Neutralisation
of mixed acid
Receiving H2SO4 NaHSO3
tank CaO
Clean silo
Clean Sedimentation
water
water
Polymer
Filter press Lime slaking

Flocculation Neutralisation Neutralisation Water

tank 2 tank 1
Sludge pH = 10 pH = 4
to landfill
Ca(OH)2

Figure 17. Flowchart of the process in Avesta

7.1.4 Neutralisation
Five streams are merged in the receiving tank; water from the chromium reduction, rinse water from
the mixed acid pickling, waste water from SAR, water from the neutralisation of pickling acid (only
sometimes) and water from the filter press. The outlet from the receiving tank is one stream led to
neutralisation. Quick lime (CaO) is taken from a silo and slaked by addition of water giving a 20 %
37
slurry, which is added automatically towards the set pH. First, a rough neutralisation is performed in
tank 1, (25 m3) to pH 4, and then the pH is adjusted to 10 in tank 2, (see figure 17) [40].

The flocculation is performed in a separate tank (30 m3) and then lead to lamella settling stage for
sedimentation. The flocculation is performed with Magnafloc 10 (an anionic polyacrylamide). The
polymer is delivered to the plant in powder form which is mixed to a slurry. The addition of flocculant
is performed manually by visually observing the flocks [40].

Nitrate and metal concentrations are measured on the clean water before it is released to recipient,
the river Dalälven. The sludge from the sedimentation has the possibility to be pumped to a
thickener before the filter press, although, the thickener is mostly not utilised. Instead the sludge is
pumped directly to a filter press where it will receive a dry content of 50 %. The filter cake is
transported by truck to a landfill, situated within the industrial area. The water gained from the filter
press is so clean that is can be released to recipient but as a safety measure, in case a filter in the
press would break, the water is recirculated back to the receiving tank from where it goes through
the neutralisation process again [40].

In Avesta, there is a problem with high amounts of nitrates in the outgoing water; therefore
investments have been made in a new treatment facility which is under construction today. The idea
is to recirculate spent acid meanwhile reducing the nitrates by utilising nanofiltration in combination
with crystallisation (see chapter 3.2.5). For reduction of the liquid volume, it is first evaporated.
When this facility is put into operation (in about one year), the acid retardation unit (SAR) will be
used only as a backup. There has been up for discussions if recirculation of sludge from
sedimentation to the flocculation, then could be an alternative for receiving the right properties
during flocculation [40].

7.1.5 Washing of gases

All gases which are formed in the different pickling processes are collected and led by an exhaust
system to a gas Selective Catalytic Reduction facility (SCR), situated next to the line. Here, the gases
first pass through a scrubber where the HF is washed with water; this water is led to the receiving
tank. About 95 % of the acid is washed out from the gas which then passes trough a heat exchanger,
for energy recovery, where the ingoing gas meets the outgoing gas and the ingoing gas is thereby
heated to a certain degree, for energy savings. The gas then passes through a calcium bed, where
lime stones reduce the fluorides. The gas is then heated by an oil heater to about 300 °C. Ammonia is
added and then it passes a catalyst which converts NOX to nitrogen gas (N2). The final stage is the
heat exchanger, before it is released to air. The outgoing gas has a NOX content of
about 100-150 ppm [40].

7.2 Outokumpu Stainless Thin Strip, Nyby

Nyby is located outside Eskilstuna in Sweden and here Outokumpu have a cold rolling mill which
specialises in thin gauge material and special grades. Steel which have been casted and hot rolled is
transported to Nyby by train. The thin strip has two annealing lines with separate pickling on both.
Line60 is a preparatory annealing line with one pickling tank and Line55 which is a finish annealing
line has two pickling tanks. On Line55, an acid retardation system (SAR) has been installed. This helps
to maintain a stable concentration of metals in the pickling bath. As in Avesta, the steel is also pickled
electrolytic [41].
38
After pickling there will be two separate streams of water which has to be cleaned before it is
released to recipient. The first stream originates from the pickling bath and the second one is formed
during rinsing of the steel. The first stream is continuously taped off from the pickling tank and will
therefore have a high metal and acid concentration but a low flow (around 1.6-2 m3/24 hours). The
rinse water on the other hand will have a larger flow (around 40-50 m3/h) but a much lower
concentration of metals and acids. Due to the different characteristics of the two streams, they have
to be treated separately. Figure 18 is a flowchart of the process in Nyby [41].

Scrubber Gases from the

pickling line

Strip
Electrolytic Rinsing Mixed acid pickling Rinsing
pickling

Concentrated
H2SO4 acids
Cr-reduction SAR
NaHSO3

Oil separation Water ED Storage tank

Oil to Water
destruction Polymer Filter press

Clean Small Small Sludge/ Large

Water neutralisation, neutralisation, buffer neutralisation
Flocculation
tank 2 tank 1 tank tank

Water from filter press Ca(OH)2

NaOH
CaO
Water to tank 1 silo
CaO Lime slaking

Sludge pool Filter press Sludge to landfill

Water

Figure 18. Flowchart of the process in Nyby

7.2.1 Spent pickling liquid

Water from the pickling tank on Line55 first passes a number of filters for separation of particles and
then the stream is led to the SAR, where about 90 % of the free acid is recycled back to the pickling
bath. The diluted stream out from the SAR is lead to an electro-dialyse facility (ED), which is a
membrane filtration where spent pickling acid is divided into acid and base by applying a current, see
chapter 3.3.2 for a complete description of electro-dialysis. From the ED, a concentrated stream of
acid will be recycled back to the pickling bath. This will also reduce the amount of nitrates released to
nature. Totally 90 % of the acid is recycled. The diluted stream from the ED contains metal ions and
will flow to a special tank for subsequent neutralisation. Additional acid is added to the pickling tank
in order to maintain the necessary acid concentration. Figure 19 is a flowchart over this operation,
using arbitrary values [41].

39
 Frech acid 120 g/l

Mixed acid pickling

Concentrated stream
90 g/l 100 g/l

Diluted stream to
neutralisation 10 g/l
ED SAR

Figure 19. Flowchart of the acid recycling system in Nyby

Quick lime (CaO) is delivered from the supplier Nordkalk and the first step is lime slaking. This is
performed in a separate tank by addition of water resulting in a 20 % lime slurry. The slacking
reaction is exothermic and the temperature will rise to about 100 °C. The slacked lime is then led to a
storage tank from where it is added to the waste water towards a set pH. The neutralisation of
pickling acid takes place outdoors and the whole process including pH control is automatic [41].

7.2.2 The rinse water

After the electrolytic pickling the steel is rinsed, this rinse water will contain Cr6+ and the water is
therefore led to a chromium reduction stage. Here, Cr6+ is reduced to Cr3+ by the addition of (H2SO4)
and sodium bisulphate (NaHSO3). The Cr-reduced water then flows to a tank for oil removal; here it is
mixed with rinse water from the mixed acid pickling. The oil is separated by simple pumping. The oil
reduced water then flows to a neutralisation tank placed indoors. Since the flow of rinse water is
large, rapid mixing of the lime into the water is required. This is done by adding CaO directly to the
water i.e. without slacking. The CaO becomes hydrated during the neutralisation which also raises
the temperature of the water. Addition of CaO is called pre-neutralisation (small neutralisation,
tank 1 in figure 18) and the pH is raised to about 7.5. The rinse water and the water from the mixed
acid pickling tank are then merged and a final adjustment (small neutralisation, tank 2 in figure 18) is
performed with CaO. Sometimes the ingoing water has a very low pH, then, neutralisation with
sodium hydroxide (NaOH) is also performed (in tank 2). The final pH is adjusted to about 9.5 [41].

7.2.3 Flocculation and sedimentation

After the final neutralisation, a polymer (Magnafloc 10) is added for flocculation. In Nyby, 2-3
different polymers are tested every year. So far Magnafloc 10 has shown to be the best choice. The
water is then led to a lamella settling stage, and as the sludge settles it is pumped to a sludge pool
and then to a filter press. The water from the filter press is led back to the pre-neutralisation tank for
a second treatment. The sludge is transported to a stock before disposal on landfill [41].

All dosage of the chemicals is adjusted automatically and little maintenance is required. The pH-
meters are calibrated once a month. The pH and turbidity is measured on the outgoing water stream.
Neutralisation with NaOH is more efficient but leads to a higher effluent turbidity. Perhaps choosing
another polymer for flocculation when neutralising with NaOH, might solve this
problem [41].

40
8. Acid treatment examples in China
As part of this degree project, a field trip to China was made, where 3 mills where visited; 2 mills of
Fonye steel outside Shanghai, one old and one newer, and TPCO mill in Tianjin.

8.1 Old Fonye Steel mill, Shanghai

Fonye steel is a large private owned stainless pipe producer. The Old Fonye steel mill is located in
Wenzhou, an hour flight outside Shanghai. The plant produces 210 ton product per month. The mill is
situated in an industrial park meaning in an area where many small pipe producers are located.

None of the companies situated in the industrial park have their own waste water treatment, instead
the water from the different mills is lead to a neutralisation plant, located in the park. This plant is
owned and run by the government. The different mills have to pay a fee for this, which includes
management of both emissions to air and water. According to the plant manager the fee for
emissions is paid to the government 11 out of 12 months each year. This is due to the spring festival
one month per year, where they are free of charge. The fee is based on the amount released. The old
Fonye steel mill pays around 14 000 Yuen/month.

The authority which states the regulations for Fonye mill is the Chinese Environmental Protection
Bureau (EPB) in Beijing. The EPB makes regular inspections and if the emission standards are
exceeded, the plant receives a warning. If this warning is not obeyed, the plant is forced to stop their
production. The old Fonye mill has been stopped two times due to too high metal concentration in
the water.

The pickling is performed in mixed acid and the composition in the pickling bath is 20 vol% HNO3,
5 vol% HF and 75 vol% water. The costs and usage of fresh acid is shown in table 7. The water
consumption also shown is for the entire pipe production. The whole plant uses about
150 000 kWh/month and the cost for this is about 90 000-100 000 Yuen/ month.

Table 7. Total water consumption and usage and cost

of fresh acid for old Fonye steel mill

Used amount Costs

[ton/month] [Yuen/ton]
Fresh HF (35%) 7 3400
Fresh HNO3 (98%) 15 2850
Total water consumption 500 3.75

Today, there is no acid recovery system at the mill. According to the plant manager, the cost for
installing one would be too large in comparison with how they treat today.

When the acid concentration in the pickling tank becomes too low, they lead the water to the
industrial park, and add fresh acid. The addition of fresh acid is based on personal experience. After
pickling, the steel is rinsed and degreased in different steps, by simply placing the pipes in different
rinsing tanks containing water. The water in each tank will therefore have different acid and metal
concentrations. When these concentrations become high, the water is led to the neutralisation

41
facility. The steel manager think that the pickling line is easy to manage but today, it is not running
optimal from an environmental point of view.

8.1.1 Neutralisation
All waste water including rinse water and spent pickling acid from all mills in the industrial park is
lead to the neutralisation facility where it is collected in a large pool. Lime slurry in the form of
Ca(OH)2 is added towards a set pH of 10.5. A polymer polyacrylamide (PAM) is then added for
flocculation, followed by lamellar sedimentation. The pH of the water is then decreased to about 8
by adding H2SO4. This is so that the pH standard set by the government is followed. More polymer is
then added and a second lamellar sedimentation takes place. The water is then micro filtrated in
a 6 m depth pool. The water outflow goes to the municipal sewage plant where household waste
water is being treated. This plant is located close to the area. From the municipal sewage plant a part
of the water is taken recycled to the steel production process.

In the neutralisation plant, all chemicals are added automatically by pumping. The plant use 3 ton
lime/day (Ca(OH)2) and the plant runs 24 hour per day. The costs for lime is 20 000-30 000
Yuen/month.

The sludge from the process is passed in a filter press which is operated manually and the final water
content in the sludge is 35 %. The sludge is transported and used by a company for building material,
such as concrete and bricks. Before the economical crisis, the sludge was sold but now the treatment
plant has to pay the company for removal of sludge. The sludge from the pickling line is also used for
building material.

Table 8 shows values for nickel and fluoride of the in- and outgoing water to the neutralisation
facility, the water flow is 500 ton/day.

Table 8. Nickel and fluoride content of the

in- and outgoing water from the neutralisation facility

Substance In [mg/l] Out [mg/l]

Nickel 1000 0.15
-
F 1200 6.7

8.2 New Fonye steel mill, Shanghai

The new Fonye steel mill is a small stainless pipe producer located outside Shanghai. The plant
produce 100 ton product per month.

The pipes are pickled in mixed acid and the acid concentration in the pickling bath is 15 vol% HNO3
and 10 vol% HF. Table 9 shows the costs and usage of fresh acid at the mill. When the acid
concentration in the pickling becomes too low, fresh acid is added. There are five different tanks for
rinsing and degreasing. Today, there is no acid recovery system or gas cleaning system for the
pickling line [42].

42
 Table 9. Usage and cost for fresh acid at the old Fonye steel mill

Used amount Costs

[kg/day] [Yuen/day]
Fresh HF (35%) 150 360
Fresh HNO3 (98%) 25 690

The plant has their own neutralisation located on site where they treat the rinse water from the
pickling. The neutralisation facility has a design capacity of 40 ton/day, but the actual amount treated
is 30 ton/day and it works 8-10 h/day. The pH of ingoing water is 3-4 and the pH of outgoing water is
6-8. The oil content of the rinsing water is 20-30 mg/l and the COD is 300 mg/l. Both lime and lye are
used and polyacrylamide (PAM) is added for flocculation, followed by lamellar sedimentation. All
chemicals are added automatically, but the pH is measured manually.

The sludge is dewatered in a filter press and then collected in bags which are then taken care of by
the EPB. The cost for this is 1000 Yuen/ton and the amount sludge produced is 0.3 ton/day. The dry
content of the sludge is about 30 %. The water cost is 4.4 Yuen/ton and table 10 shows the daily
usage and costs for chemicals and water at the neutralisation facility. Table 11 shows the usage and
costs of electricity for the neutralisation [42].

Table 10. Daily usage and costs for chemicals and water for neutralisation

Used amount [kg/day] Costs [Yuen/day]

Lime [Ca(OH)2] 84 30
Lye [NaOH (13 %)] 1500 -
Polymer 1.1 50
Water 40 000 176

Table 11. Daily usage and cost of electricity for the neutralisation

Used amount [kWh/day] Costs [Yuen/day]

Electricity used for neutralisation 60 50

Table 12 shows the produced amount of sludge and the costs for disposal. According to the plant
manager the neutralisation could be more modern with an automatic management system [42].

Table 12. Amount of sludge produced and costs for disposal

Produced amount Costs for sludge disposal by EPB

[ton/day] [Yuen/ton]
Sludge 0.3 1000

43
8.3 TPCO, Tianjin
TPCO steel mill is a located outside Tianjin and is a government owned large producer of stainless
steel band. The production works 24 h per day [43].

The plant has both electrolytic and mixed acid pickling. An acid retardation facility (SAR) is operating
at the acid pickling line. Therefore, three different types of streams are lead to the neutralisation
plant; rinse water which contains oil, water with Cr6+ and acid water without Cr6+ originating from the
SAR. The neutralisation plant is located on site and it is not managed by the TPCO itself, but by a
private company. The facility was designed by the German company UVK. Table 13 shows the flow of
the different streams entering the facility [43].

Table 13. Flows of the different water streams entering the neutralisation facility

Type of water Flow to the neutralisation facility

Waste water containing oil 13 m3/day

Waste water with Cr6+ 10 m3/h
Acid water from acid retardation 40 m3/h

The water containing Cr6+ is led to a chromium reduction stage, which consists of 2 tanks. There
NaHSO3 is added for reduction to Cr3+, and H2SO4 is added for pH adjustment to pH 2.5. The water is
then led to a conventional sedimentation tank for sludge removal and finally to a collection tank
where it is mixed with the other water streams before entering the neutralisation tank [43].

The stream from the SAR is led to two pools, which works semi-batch wise; from there it is led to a
collection tank. Water which contains oil is led to a separate tank where H2SO4 and HCl are added for
oil destruction. It is then merged in the collection tank with water from the SAR and water from the
chromium reduction [43].

The neutralisation is performed with slaked lime (Ca(OH)2) and works continuously in two tanks for a
rough and fine pH adjustment to pH 9. The water is then led to a reaction tank where no chemicals
are added, the purpose is only for completing the reaction. Flocculation and conventional
sedimentation takes place in a separate tank by addition of polyacrylamide (PAM). The whole
process is operated automatically, including addition of chemicals [43].

The clean water after sedimentation is passed trough a sand filter for polishing and then it is led back
to the production process. Although, the water is so clean that it could be released directly to
recipient [43].

There are three filter presses in the plant. Two for sludge from the neutralisation and one for sludge
from the chromium reduction. The water from the filter press is recirculated back to the
neutralisation. The sludge from the neutralisation and chromium reduction are transported by a
professional treatment company who treats the sludge and manufactures bricks for building
material. TPCO pays 180 0000 Yuen/year to the company for waste water treatment and sludge
disposal [43].

44
Table 14 shows the monthly lime consumption and costs. In table 15, the produced amount of sludge
and costs for disposal for the different sludge types can be seen. Figure 20 shows some typical in-
and outgoing values to the neutralisation [43].

Table 14.Cost and consumption of lime

Used amount [ton/month] Costs [Yuen/ton]

Lime [Ca(OH)2] 300 600

Table 15. Amount of sludge produced and costs for disposal

Produced amount [ton/month] Costs for disposal [Yuen/ton]

Common sludge 1000 240
Sludge from Cr6+ reduction 20-30 1000

Ca(OH)2

Ingoing water (acid water, water from oil reduction

and water from Cr-reduction): Outgoing water:

pH = 1-3 pH = 6-9

Ni = 20-25 mg/l Ni = 0.2 mg/l

F = 600-700 mg/l F = 6 mg/l

Neutralisation
Cr6+
= 20-25 mg/l Cr6+ = 0.1 mg/l

Crtot = 150-225 mg/l Crtot = 0.5 mg/l

Flow = 31 m3/h Flow = 31 m3/h

Figure 20. In- and outgoing values, flow and pH for the neutralisation at TPCO

45
46
9. Dimensioning data
The Swedish EPA gives advises on how a neutralisation facility should be designed. If the waste water
has large variation in flow and pH, the neutralisation should be performed in two steps, one rough
and one fine adjustment. For facilities working continuously, the retention time should be at least 10
min but not more than 30 min, due to the risk of destroying the formed hydroxides. The optimal pH
should be decided based on experiments for each specific facility [15].

During flocculation, the polymer type and dosage should be set based on practical experiments. If
only one flocculation step is used, the polymer should be added before the flocculation tank, and the
time for flocculation should be 10-20 minutes. The polymer should be mixed rapidly with
the water [15].

It is optimal if the water flows from the flocculation step to the sedimentation step with an even flow
as possible, preferably by free fall, since this reduces the risk of destroying the formed flocks.
Lamellar sedimentation is the best choice for waste water within the steel industry. This should be
dimensioned with a load per surface area (which is the relation between flow and surface of the
sedimentation pool and gives a measure of the particle sedimentation velocity at a certain flow) of
less then 0.4 m3/m2×h and a retention time of at least 4 h [15].

Due to the low toxicity of iron, and wide pH range for precipitation, a neutralisation facility for metal
hydroxides should never be optimised after iron. During precipitation of the other metals, iron will
automatically precipitate to sufficiently low concentrations [15].

The retention time (t) and flow (ν ) decides the tank volume according to equation 2.

V
t= (2)
ν

V = volume [m 3 ]

ν = flow [ m 3 / h]

47
48
10. Theoretical calculations
For designing a neutralisation facility, one must have an estimation of the amount of neutralisation
agent which must be added for complete reaction; therefore theoretical calculations on the amount
of neutralisation agent required was made in this project. Calculations of metal concentration in the
out-going water for a specific pH, where also performed, both with equilibrium calculations and
software “Medusa”.

10.1 Boundaries
The calculations where based on a water-acid (HF and HNO3) system containing metals. For
simplification the metals in the system where limited to only Fe3+, Ni2+ and Cr3+. In reality, the system
contains a number of different metals, as well as different metal complexes which is formed during
pickling.

Slaked lime (Ca(OH)2) has shown to be the most suitable and commonly used chemical for
neutralisation of spent pickling acid. Therefore, the calculations were made on the amount Ca(OH)2
required for neutralisation and metal precipitation.

It should be mentioned that the calculations in this report only gives a rough estimation of the
amount of chemical which must be added. This is because in reality a wide range of complex
substances will form in the water which might have a buffering effect (some examples can be seen in
the figures and table 18 in appendix II). These substances concentrations and therefore also the
buffering effect will differ widely with from site to site. Due to their complexity and diversity, it is
very difficult to take these substances into consideration when performing theoretical calculations.
As a consequence, one can not based on only theoretical calculations find the exact amount of slaked
lime needed for precipitation without a large factor of uncertainty. However, if those substances are
disregarded, one can calculate the theoretical stoichiometric amount of Ca(OH)2, given the ingoing
metal and acid concentrations, see example 1 in chapter 10.4.1.

To find the optimal pH, when designing a neutralisation facility one must do a so called jar test based
on the water which is to be treated. In such test, a number of samples are taken and the optimal pH
which gives the best precipitation is found by allowing precipitation at different pH. The reason is, as
mentioned earlier, due to the different circumstances which will vary from case to case [29].

10.2 Calculations with software “Medusa”

Medusa is a software which uses equilibrium data for calculating different parameters. In Medusa
one defines a system by choosing the ingoing substances and their respective concentrations, from
this, different graphs are drawn. Medusa illustrates the ideal cases.

Figure 21 is a graph made in Medusa on the current system, where the solubility of the different
metals is shown as a function pH. The concentrations of the components are based on a mass
balance using data from the neutralisation facility of Outokumpu in Avesta (see appendix I for mass
balance calculations), although, the graph will have the same appearance for any concentrations.

Figure 21 should be interpreted as follows; precipitation of iron occurs directly as the pH start to rise,
giving Fe(OH)3, this is seen as a decrease of the solubility of Fe3+. The total metal precipitation is
enhanced by the ferric hydroxides, so called co-precipitation. One can see that nickel is the most
49
critical component, requiring the highest pH for precipitation. Due to this, a pH around 8-10.5 is
suggested for an optimal precipitation, also supported by literature [15]. The figure also clearly
shows that no precipitation of nitrates will occur for the system.

[Ni2+ ] TOT = 4.80 mM Log {Ca(OH) 2 (c)} = 0.00

[Cr 3+ ] TOT = 12.20 mM [HF] TOT = 100.00 mM
[Fe 3+ ] TOT = 47.00 mM [NO3 − ] TOT = 165.00 mM
Ca(OH) 2 (c)
0 NO3−
Fe 3+ HF
Cr 3+
Ni2+

-5
Log Solubl.

-10

-15
0 2 4 6 8 10 12 14
pH
Figure 21. The logarithm of the solubility for the components
in the system have been plotted as a function of pH

The logarithm of the solubility can be read of directly from figure 21 (y-axis), from which the rest
metal concentrations are obtained. This gives the following concentrations:

Fe 3+ = 10 −12 mg / l

Ni 2+ = 5 × 10 −9 mg / l

Cr 3+ = 4 × 10 −9 mg / l

10.3 Chemical properties of the nitric and hydrofluoric acid

Nitric acid (HNO3) is a very strong acid and will therefore be completely dissociated in water.
Hydrofluoric acid (HF) on the other hand is a relatively weak acid and therefore doesn’t start to ionize
until the pH has risen to about 2. The feature of both acids is illustrated in figure 22 and 23 where the
fraction of the different states is plotted as a function of the pH.

50
 [NO3−] TOT = 50.00 mM
NO3−
1.0

0.8

0.6
Fraction

0.4

0.2

0.0
2 4 6 8 10 12
pH

Figure 22. Displaying that nitric acid will be

completely dissociated in the system

[F− ] TOT = 50.00 mM

F−
1.0

HF
0.8

0.6
Fraction

0.4

0.2 H2F2

HF 2 −
0.0
2 4 6 8 10 12
pH

Figure 23. Displaying that the hydroflouric acid

will be undissociated for low pH

10.4 Calculation examples

In example 1 below, the amount of Ca(OH)2 required for metal precipitation is calculated. The
procedure is to find the amount of hydroxide ions (OH-) required for acid neutralisation and for the
formation of the different metal hydroxides. In example 1, the metal and acid concentrations are
based on a mass balance from the neutralisation facility of Outokumpu in Avesta,
see appendix I for the total mass balance calculations.

51
10.4.1 Example 1 – Stoichiometric calculations of required Ca(OH)2
The ingoing concentrations from the mass balance are:
Fe3+: 0.047 M
Cr3+: 0.0122 M
Ni2+: 0.0048 M
HNO3: 0.165 M
HF: 0.111 M

The oxidation state of the metals influences the necessary amount of OH-. By multiplying the metal
concentration with respective oxidation state, the molar amount OH- required for each metal is
found:

For Fe3+: 0.047 × 3 = 0.141 M

For Cr3+: 0.0122 × 3 = 0.0366 M

For Ni2+: 0.0048 × 2 = 0.0096 M

Both HF and HNO3 are monoprotic acids, meaning one mole of acid will give one mole of H+ which
will require one mole of OH- for neutralisation. The amount of OH- required for the acids therefore
equals the acid concentration:

For HNO3: 0.165 M

For HF: 0.111 M

Summarising all of the above gives that a total concentration of [OH-] = 0.4632 M is required. Since
each mole slaked lime has two hydroxides this gives:

0.4632 / 2 = 0.2316 mol/l Ca(OH)2

From this, the amount of Ca(OH)2 in g/l can be calculated:

M Ca (OH ) 2 = 74 g/mol

 74 × 0.2316 = 17.138 g/l

Hence, the stoichiometric amount Ca(OH)2 that should be added if the above metal and acid
concentrations apply (based on the mass balance) is 17 g/l.

If the flow of the waste water is known, (here, from mass balance 24 200 l/h), the required amount
of Ca(OH)2 per hour can be found:

l g
24200 × 17.138
 h l = 414.8 kg Ca (OH )
2
g h
1000
kg

52
Based on information of the yearly amount CaO bought in to the neutralisation plant in Avesta, this
gave an average amount of 313 kg/h Ca(OH)2 used for the process [40]. Compared to the calculations
which gave an amount of 415 kg/h, one can assume the calculations made in this report are well
corresponding to the reality. An assumption of the difference is due to the large uncertainty factor
that not all streams in the mass balance are known (see appendix I) and that the flows and
concentrations fluctuates on a daily basis.

One can not with adequate accuracy calculate the exact pH which will be received for a certain
amount of Ca(OH)2 added, due to complexity of the system, the pH must simply be measured.

Based on above calculations an excel file was made, where the input data is the ingoing metal and
acid concentrations and flow, thereby the required amount of slaked lime can be obtained for
different concentrations.

10.4.2 Example 2 – Equilibrium calculations

Based on equilibrium equations, the metal concentrations of the outgoing water can be calculated if
the pH is known.

The following correlations apply:

pH = -log[H+]  [H+] = 10-pH (3)

pOH = -log[OH-]  [OH-] = 10-pOH (4)

pH + pOH = 14 (5)

Assuming pH = 9 gives pOH = 5, from which the OH- concentration can be calculated
 [OH-] = 10-5
This concentration is then used for the following equilibration equation:

Iron (Fe3+):
Total precipitation reaction: 2 Fe 3+ + 3Ca (OH )2 ↔ 2 Fe(OH )3 + 3Ca 2+ (14)

The equilibrium constant K, is found for the following reaction:

Fe(OH )3 ( s ) ↔ Fe 3+ (aq) + 3OH − (aq ) (22)

K = 10 −37.4 [7]

For reaction (22) the following relationship applies (equation 3):

[ ][
 K = Fe 3+ OH − ]
3
= 10 −37.4 (3)

Hence, from (3) the rest concentration of iron in the outgoing water can be calculated:

10 −37 , 4
 [Fe ] =
3+ K
= = 4 × 10 −23 M
[OH ] (10 )
− 3 −5 3

53
M Fe = 55.8 g / mol

[ ]
 Fe 3+ = 55.8
g
mol
× 4 × 10 −23
mol
l
× 1000 = 2.2 × 10 −18 mg / l

The concentrations of the other metals are calculated in the similar way:

Nickel (Ni2+):
Total precipitation reaction: Ni 2+ + Ca (OH )2 ↔ Ni (OH )2 + Ca 2+

The equilibrium constant K, is found for the following reaction:

Ni(OH )2 ( s ) ↔ Ni 2+ (aq ) + 2OH − (aq)

K = 10 −17.2 [44]

[
 K = Ni 2+ OH − ][ ] 2
= 10 −17.2

[ ]
 Ni 2+ = 3.7 × 10 −3 mg / l

Chromium (Cr3+):
Total precipitation reaction: 2Cr 3+ + 3Ca (OH )2 ↔ 2Cr (OH )3 + 3Ca 2+

The equilibrium constant K, is found for the following reaction:

Cr (OH )3 ( s) ↔ Cr 3+ (aq) + 3OH − (aq )

K = 10 −30 [44]

[
 K = Cr 3+ OH − ][ ]
3
= 10 −30

[ ]
 Cr 3+ = 5.2 × 10 −11 mg / l

Table 16 summarises the metal concentrations in the outgoing water based on the above
calculations and the values received from figure 21. It is clearly a difference between the two. This is
probably because the equilibrium calculations only consider the precipitation reaction for hydroxides
and for each metal separately, regarding no interactions between the metals. Meanwhile, Medusa
takes into account that other complexes besides hydroxides will form, and their interactions. This will
affect the system and probably reflects somewhat more the real case.

54
 Table 16. Comparison of the rest concentrations of metals,
between calculated and Medusa values.

From
Calculated
Medusa
[mg/l]
[mg/l]

Fe3+ 2.2 × 10 −18 10 −12

Ni2+ 3.7 ×10 −3 5 × 10 −9

Cr3+ 5.2 ×10 −11 4 ×10 −9

However, the calculations but also the figures from Medusa can not represent the reality. Medusa
shows the ideal case and therefore the metal concentrations in the outgoing water will in reality be
higher then according to table 16.

55
56
11. Experimental results
An experimental part was made by IVL with pickling acids supplied by Outokumpu site in Avesta. The
samples were taken after the acid retardation (SAR) and had a concentration of 0.37 M HNO3 and
0.5 M HF, the metal concentration was 6.3 g/l. The purpose was to identify three different
parameters:

• the optimal pH (precipitation at pH 9.2 and 10.3 were tested)

• the amount of polymer (13.3 g and 39.9 g were tested (0.1 g solution))

• recirculation of sludge (HDS method)

The purpose was also to see which effect these parameters had on the metal removal.

Slaked lime as a slurry was added during mixing, and when the pH was stable the polymer was
added. The sample was then mixed rapidly for 1 minute and then slowly for 10 minutes.
Sedimentation was then allowed during 1 hour. The pH had a tendency to decrease during
sedimentation; the new pH was therefore also noted. The required amount of slaked lime and its dry
content was measured for each sample. The metal content after neutralisation was measured and
calculated as gram per liter of the original solution.
The experiment is presented in table 17, which shows the pH before and after sedimentation, the
amount of polymer required, the rest metal concentration and the amount of slaked lime required to
reach the corresponding pH.
Sludge recycling was performed in experiment 5-12 and 16-18, where 90 % of the metal hydroxide
sludge was recirculated to the next batch. The results from the sludge recycling showed no indication
of improving the neutralisation process such as decreased lime consumption. Therefore,
complementary tests where performed where the sludge was recycled in many cycles, this gave a
denser sludge and the dry content increased form 12 % to 21 % after 9 cycles. This also lowered the
lime consumption by 3-5 %. However, optimisation of this process is required and therefore no
conclusion can be drawn at this stage.
The average amount of required Ca(OH)2 was 54.8 g/l (excluding the tests with sludge recycling).
The results also showed that a pH of 9.0 is optimal for chromium precipitation and the rest
concentrations of nickel is not significantly affected by having a pH around 9-10.5. The results also
showed that an increase in polymer gave an increase in outgoing metal concentrations. For
information about the entire experiment see reference [45].

57
 Table 17. The results from the experiments [45]

Polymer pH pH
Fe Fe Cr Ni Ca(OH)2
solution* Recirculation before after
Test mg/l* mg/l** mg/l mg/l consumption
(g) sed. 1h
(g/l)
sed.

1 13,3 0 9,2 8,9 1,86 3,43 1,08 1,64 53.3

2 13,3 0 10,3 10,0 0,40 0,79 0,24 0,14 56.3

3 39,9 0 9,2 8,9 0,04 0,07 0,05 0,48 53.3

4 39,9 0 10,3 10,2 1,83 1,69 0,52 0,33 56.5

(5) 13,3 1 9,2 7,8 52.8

(6) 13,3 1 10,3 8,2 54.0

(7) 39,9 1 9,2 8,2 51.3

(8) 39,9 1 10,4 8,6 54.3

9 13,3 2 9,0 9,1 30,57 61.0

10 13,3 2 10,3 9,3 5,51 58.5

11 39,9 2 9,2 9,0 0,55 56.3

12 39,9 2 10,6 10,5 0,82 62.0

(13) 26,6 0 9,7 8,9 0,23 0,19 0,07 0,29 x

(14) 26,6 0 9,8 9,7 2,32 2,09 0,72 0,56 x

(15) 26,6 0 9,8 9,7 3,25 2,96 0,80 0,52 x

16 26,6 1 9,9 9,1 6,89 60.3

17 26,6 1 9,8 9,3 4,85 59.5

18 26,6 1 9,7 9,7 5,70 64.5

* 0,1 wt% Magnafloc 351

** Analysis using Dr Lange method
*** ICP analysis performed by ALS Scandinavia

11.1 Comparison of experimental results and calculations

By inserting the same ingoing acid and metal concentrations as the ones measured in the experiment
in the excel file, a theoretical amount of 44.5 g/l Ca(OH)2 was obtained. The experimental part gave
an average amount of 54.8 g/l. Hence, there is a difference of about 10 g/l between the theoretical
and experimental values.

The rest concentration of metals gave in theory much lower values than the experimental part. This
is again probably due to the complexity of the real case, such as interactions of other compounds
than the metal hydroxides which are not considered in the calculations.

58
12. Discussion
Acid recovery methods
Of the acid recovery methods mentioned in this report (ion exchange, diffusion dialysis and
extraction) one can see that all of them only allow recycling of the free acid. The outflow from ion
exchange and diffusion dialysis will be acid water with high metal concentration which requires an
additional treatment step. Ion exchange and diffusion dialysis have about equal investment costs and
recycling rate. The extraction method has the highest acid recycling rate but this process is on the
other hand more complicated which will lead to higher capital costs. This is probably why it is not
implemented extensively today. None of the methods are alone able to reduce nitrates enough so
that it becomes environmentally acceptable.

Sweden seems to have somewhat more stringent laws for waste water then China. For instance lacks
China regulations for nitrates. If no standard is set for this it will become an enormous problem for
Chinese environment. Since regulations of nitrates are none existing in China today, a steel mill in
China will almost certainly not be interested of investing in a method which reduces the amount of
nitrates in the water, but instead in a method which only recovers the acid, thereby giving economic
advantages due to the decrease in acid consumption. Due to the more stringent regulations in
Sweden regarding nitrates, the mills in Sweden which were visited during this thesis work have been
forced to invest in more advance technology as an additional step.

The methods which recover acid as well as reduces nitrates mentioned in this report, can either be
“end of pipe” or internal solutions. Reverse osmosis (RO) rather than nano-filtration (NF) could
perhaps be a possible method as an “end of pipe” after the neutralisation stage for nitrates removal.
Of the two, RO is best suited since the rejection rate, which is correlated to the effectiveness, was
not affected by pH or by having Ca2+ as co-existing ion, which will be the case if slaked lime is used
(Ca(OH)2). The rejection rate was however affected with the NF method. However, membrane
processes are till quite expensive methods, have low flow capacity and since the membrane has to be
replaced regularly due to clogging, reduces the flux. These are all important factors which need to be
considered. Biological treatment requires a carbon source; meanwhile the nitrates aren’t recycled,
but instead converted into nitrogen gas. This method is perhaps not suited since it should be more
beneficial from an economic point of view, if the nitric acid could instead be recycled.

Most optimal are of course internal solutions, such as evaporation and electro-dialysis. Some
drawbacks with evaporation are that it consumes an extra acid (sulfuric acid). It has high investment
and operation costs. On the other hand, the acid recycling rate is very high, it gives no dust emission
and almost zero nitrates in the waste water. Electro-dialysis reduces nitrates and has a relatively high
recycling rate for the acids therefore, it also decreases the amount of chemicals used for
neutralisation. ED has a relatively high investment cost and does not recover HF to a large extent.

A drawback when implementing ionic exchange with neutralisation is that the separated metals
aren’t recycled. This is definitely an area for future research. In China there is a nickel shortage and
therefore the cost of nickel is very high. During the China visit, there was an interest in technologies
of recycling nickel from the sludge. Therefore, one can speculate; if a possible future regulation of
nitrate emissions in China will come, the most interesting method for Chinese steel industry would
59
perhaps be the evaporation method, since it has high acid recycling rate, reduces nitrates and gives
nickel in the form of nickel hydroxide which facilitates possible nickel recycling.

Neutralisation
The most implemented and traditionally used method for metal removal is neutralisation. Many steel
mills all over the world have such facility as a final waste water treatment step. This is because it is
robust, easy to manage and gives adequate results to a relatively low cost.

Some advantages of neutralisation:

• Simple technique and equipment

• Easily applied at small scale plants

Some disadvantages of neutralisation are:

• No recovery of acid

• Expensive sludge disposal

• High nitrogen content in water after treatment

Due to the above features, neutralisation could be an alternative for small scale steel mills which
have to meet legislation standards at a low cost. It is however not alone adequate in the long run
from an environmental point of view.

Although, due to its long tradition it seems as little have been done for optimisation of the process
for the stainless steel sector. Meanwhile, research has been made on different methods for
neutralisation within the mining industry. Methods such as the High Density Sludge (HDS) process
and alternatives of it are the result of this research. Some of these methods have also been put into
practise at different mining sites. It is clearly shown that the HDS process have many advantages over
conventional neutralisation, such as more efficient removal of metals due to co-precipitation which
leads to reduction in lime consumption. Since the sludge settles more rapidly and drains faster, the
process will produce a denser sludge, therefore minimizing sludge volumes. This can lead to reduced
costs for sludge handling. Also, the sludge becomes both chemically and physically more stable than
sludge from conventional neutralisation processes, which is positive for the long-term stability upon
landfilling.

There are some variations of HDS process, such as the Geco-HDS and staged-neutralisation process.
Research has shown that when comparing them, the Geco-HDS and the staged-neutralisation
process both gave a crystalline component in the sludge, giving a further reduction in sludge volume.
Both the Geco-HDS process and the staged-neutralisation process are more lime efficient then
conventional HDS process. All of the three methods (HDS, Geco-HDS and staged neutralisation) will
require additional reactors; this will lead to higher capital costs then for conventional neutralisation.
Also, since a pumping system for recycling the sludge is required, costs will increase further. This will
perhaps be outweighed by the reduction in costs for chemicals. A cost analysis has to be made for
each site before any conclusion can be drawn regarding the economic advantages of any of the three
methods.
60
It is interesting to investigate if the HDS method could be implemented for neutralisation of waste
water from the stainless steel sector for improved precipitation. As a consequence, improved sludge
properties and less chemical usage will have positive outcome both from an environmental and
economic point of view.

The choice of chemicals is of major importance for the neutralisation process. For waste water from
the stainless steel industry, slaked lime is perhaps the best choice, since it provides good efficiency at
a low cost and gives better sedimentation and dewatering properties of the formed metal hydroxides
compared to for instance sodium hydroxide (NaOH). Another advantage by using slaked lime, is that
the fluorides are reduced efficiently by the formation of calcium fluoride (CaF2) which precipitates in
the sludge. Also, slaked lime has been used extensively in industry and is therefore well-tried to meet
the environmental standards.

Many different factors given in this report have been shown to influence the neutralisation process,
such as the quality of quicklime (CaO), which might be correlated to the manufacturing method, and
also the temperature and hydration of CaO during slaking.

For an efficient process some small improvements of neutralisation is suggested:

• For optimal dosage, make sure that the pH probes are located in an optimum location, as
well as the feed of chemicals. It is also important that the pH meters are calibrated and
cleaned regularly; otherwise the reliability of the pH measure can become questionable,
leading to chemical over dosage.

• Introduction of HDS and/or iron co-precipitation have been shown in literature to enhance
the performance of the system, although, further investigation and experiments are
required.

• Try a different flocculation agent if another neutralisation agent such as NaOH is used.

Calculations
There is a large uncertainty factor for the mass balance in this report, since the values given can
fluctuate up to 50 % on a daily basis. The largest sources of errors from the mass balance are:

• Fluctuations in flows

• Fluctuations in metal and acid concentrations

• The fact that the metal and acid concentrations of the stream from the chromium reduction
are unknown

The errors in the mass balance will of course influence the further calculations for the required
amount of Ca(OH)2 and was perhaps the reason for receiving a higher amount of Ca(OH)2 than what
was actually required at Avesta. It is more likely that the theoretical calculations should give a lower
amount than in reality. This was the outcome when using the same input concentrations as the ones
measured in the experimental part, which gave a theoretical amount of 44.5 g/l Ca(OH)2, when the
experiments showed an average of 54.8 g/l, therefore the calculations are assumed to be well
corresponding with reality.
61
The optimal pH interval can be found theoretically in literature but the best method is to establish
the optimal pH from experiments, this is also supported by literature [15, 34].

62
13. Conclusions
For precipitation of waste water form the steel industry, the most significant parameters for
neutralisation found from this study are presented below:

• The pH should lie in the interval of 8-10.5 but the optimal pH should be decided upon
experiments.

• The optimal pH interval according to experiments in this project was 9-10.5. This gave the
lowest nickel and chromium content.

• Slacked lime Ca(OH)2 requires 20-30 minutes retention time for complete reaction.

• Sodium hydroxide (NaOH) requires 5-10 retention time for complete reaction.

• The time for flocculation should be 10-20 minutes.

• The volume of the tank is based on the flow and retention time according to

V
t=
ν

V = volume [m 3 ]

ν = flow [ m 3 / h]

• The best suited chemical for neutralisation is slaked lime, Ca(OH)2, due to its relatively
efficiency at a low price. Neutralisation with slaked lime gives the following reactions:

2 Fe 3+ + 3Ca(OH )2 ↔ 2 Fe(OH )3 + 3Ca 2+

Ni 2+ + Ca(OH )2 ↔ Ni (OH )2 + Ca 2+

2Cr 3+ + 3Ca(OH )2 ↔ 2Cr (OH )3 + 3Ca 2+

2 HF + Ca(OH )2 ↔ CaF2 + 2 H 2O

2 HNO3 + Ca(OH )2 ↔ Ca( NO3 )2 + 2 H 2O

• Due to variations in the quick lime (CaO) quality by different suppliers, the most efficient CaO
can be found through a slaking-curve experiment.

• Do not add an excessive amount of water and keep just below the boiling point of water
during lime slacking for optimal qualities of the slaked lime.

• Batch wise lime slaking usually takes about 45 minutes for complete reaction. For
continuously slaking it is 1 m3/h.
63
• The most commonly used polymer for flocculation is polyacrylamid (Magnafloc 10)

• Usually, the optimal polymer dosage lies between 2 to 200 g of polymer per tonne of dry
material flocculated.

• A suggested way to determine the optimum polymer dosage is to decrease the polymer feed
until the quality effluent is affected and then raise it 5 % to 10 %.

• The experimental results, where pickling acid from the SAR was neutralised, an average
amount of 54.8 g/l Ca(OH)2 required (excluding sludge recycling test).

• The theoretical calculations based on the same values as the experimental part, gave 44.5 g/l
Ca(OH)2 required. This shows that the theoretical calculations are quite accurate.

• Sludge recycling has shown to improve the neutralisation process in literature and the
experiments made in this report gave an increase in the sludge dry content; however, no
conclusion can be drawn on sludge recycling for pickling acids at this stage and further
investigation is required.

64
14. References
[1] Outokumpu 2010. About stainless steel [Online]
Availible at: http://www.outokumpu.com/Pages/AreaPage____39753.aspx
[Accessed 7 May 2010]

[2] Nationalencyklopedin 2010. Varmbearbetning [Online] Available at:

http://www.ne.se/varmbearbetning [Accessed 4 May 2010]

[3] Nationalencyklopedin 2010. Glödgning [Online]

Available at: http://www.ne.se/glödgning
[Accessed 4 May 2010]

[4] Ekengren, Ö., Tolft, J., IVL; Rapport B1153: Rengereringsmetoder vid blandsyrabetning (För
dåvarande Avesta-Sheffield), Stockholm 1994

[5] Lagerberg, S., β Consulting; Rapport: Påverkan av olika faktorer på bethastigheten i vitbad,
(Delprojekt av sluten betbadshantering inkl. metallåtervinning), Sandviken 2001

[6] Li, L.F., Caenen, P., Jiang, M.F., 2008. Electrolytic pickling of the oxide layer on hot-rolled 304
stainless steel in sodium sulphate. Corrosion Science, 50, pp. 2824-2830

[7] Gálvez, J.L., Dufour, J., Negro, C., López-Mateos., F., 2006. Fluoride Speciation in Stainless Steel
Pickling Liquor. ISIJ International 46, No. 2, pp. 281-286

[8] Fortkamp, U., Tjus, K., Jansson, Å., IVL; Rapport B1519: Factors influencing crystallisation from
mixed acid pickling baths for stainless steel, Stockholm 2003

[9] Schneiker, T., Outokumpu; Report: Discharge to water, Avesta

[10] Cervantes, C., Campos-Garcia, J., Devars, S., Gutierrez-Corona, F., Loza-Tavera, H., Torres-
Guzman, J.C., Moreno-Sanchez, R., 2001. Interactions of chromium with microorganisms and plants.
FEMS Microbiology Reviews, 25, pp. 335-347

[11] Sugiyama, M., 1992. Role of physiological antioxidants in chromium(VI)-induced cellular injury.
Free Radical Biology and Medicine, 12, pp. 397-407

[12] Denkhaus, E., Salnikow, K., 2002. Nickel essentiality, toxicity, and carcinogenicity. Critical
Reviews in Oncology/Hematology, 42, pp. 35-56

[13] Brandt, N., Gröndahl, F., Kompendium i miljöskydd del 4: Miljöeffekter, 4.e upplagan, Industriell
Ekologi KTH, Stockholm 2005

[14] Integrated Pollution Prevention and Control (IPPC)

Reference Document on Best Available Techniques in the Ferrous Metals Processing Industry
December 2001 [Online] Available at: ftp://ftp.jrc.es/pub/eippcb/doc/fmp_bref_1201.pdf
[Accessed 11 May 2010]

[15] Oorganisk ytbehandling, Allmäna råd 97:5 [Online] Available at:

http://www.swedishepa.se/Documents/allmrad/ar_97_5.pdf [Accessed 21 May 2010]
65
[16] Telephone contact: Jard Gidlund, Naturvårdsverket, handläggare inom järn- och stålindustri på
enheten för miljöfarlig verksamhet. Tel: 08-6981601

[17] Interview with Sun Jinxiang on the Sino-Swedish Environmental Technology Development Center
(SEC) in Tianjin

[18] Chinese legislation: GB 3838-2002 translated by Sun Jinxiang, SEC in Tianjin

[19] Chinese legislation: GB 13456-1992 translated by Sun Jinxiang on SEC in Tianjin

[20] GB 18598-2001: Standards for pollution control on the security landfill site for hazardous waste,
by EPB translated by Sun Jinxiang on SEC in Tianjin

[21] Persson, P.O. (red), Kompendium i miljöskydd del 2: Miljöskyddsteknik - Strategier och teknik för
ett hållbart miljöskydd, 7.e upplagan, Industriell Ekologi KTH, Stockholm 2005

[22] Agrawal, A., Sahu, K.K., 2009. An overview of the recovery of acid from spent acidic solutions
from steel and electroplating industries. Journal of Hazardous Materials, 171, pp. 61-75

[23] Fortkamp, U., Filipsson, S., Tjus, K., Bjurhem, J-E., Ekengren, Ö., IVL; Rapport B1441: Avskiljning
av metallflourider vid blandsyrabetning - ökad förståelse av kemiska processer och framtagande av
separationsmetoder, Stockholm 2002

[24] Kim, Y.H., Hwang, E.D., Shin, W.S., Choi, J.H., Ha, T.W., Choi, S.J., 2007. Treatments of stainless
steel wastewater containing a high concentration of nitrate using reverse osmosis and
nanomembranes. Desalination, 202, pp. 286-292

[25] Fernandez-Nava, Y., Maranon, E., Soons, J., Castrillon, L., 2008. Denitrification of wastewater
containing high nitrate and calcium concentrations. Bioresource Technology, 99, pp. 7976-7981

[26] Richardson, J.F. & Harker, J.H. with Backhurst, J.R., 2002. Coulsons & Richardson’s Chemical
Engineering. 5th ed. Vol 2. Elsevier Ltd. ISBN: 978-0-7506-4445-7

[27] Kreppler Recovery of nitric and hydrofluoric acids from pickling solutions for stainless steel
Ruthner Ind AG, Vienna

[28] Demopoulos, G.P., 2009. Aqueous precipitation and crystallization for the production of particle
solids with desired properties. Hydrometallurgy, 96, pp. 199-214

[29] Discussion with Professor Olle Wahlberg, at the institution of inorganic chemistry KTH,
Stockholm

[30] Woodrow, T. W., 2001. Practical solutions for optimizing Steel Mill Wastewater Treatment
Plants, AISE Steel Technology [Online]
Available at: http://www.hatchmott.com/documents/adobe/Woodrow%20Article.pdf
[Accessed 14 May 2010]

[31] Fuente, M.J., Robles, C., Casado, S., Tadeo, F., 2006. Fuzzy control of a neutralization process.
Engineering Applications of Artificial Intelligence, 19, pp. 905-914

66
[32] Aubé, B.C., Zinck, J.M., 2008. Optimization of lime treatment processes.
Mineral Processing 93, pp. 98-105

[33] Nemerow, N.L., Dasgupta, A., Industrial and Hazardous Waste Treatment, 2nd edition, Van
Nostrand Reinhold 1991, ISBN: 0-442-31934-7

[34] Telephone contact: Eero Kohlemainen, Ecorec

[35] Aubé, B., Zinck, J., 2003. Lime Treatment of Acid Mine Drainage in Canada. Brazil-Canada
Seminar on Mine Rehabilitation, Florianopolis, Brazil

[36] Lunner, S.E.; Outokumpu; Report: Framtida förbättringar i neutralisationsverken,

Avesta, 2006-05-31

[37] Lindquist, A., (red), Konsten att rena vatten, Kemira Kemwater 2003, ISBN: 91-631-4353-4

[38] Kuyucak, N., Lindvall, M., Sundqvist, T., Sturk, H., Implementation of a high density sludge ”HDS”
treatment process at the Kristineberg mine site.

[39] Outokumpu 2010. Outokumpu [Online]

Available at: http://www.outokumpu.com/Pages/AreaPage____39748.aspx
[Accessed 20 April 2010]

[40] Field trip to Outokumpu in Avesta, interview with Anders Stenqvist and Thorsten Schneiker

[41] Field trip to Outokumpu in Nyby, interview with Juyri Kapplin

[42] Interview with Li Song Liang, plant manager of Fonye steel mill, Shanghai, China.

[43] Interview with Mr Lui, at TPCO plant, Tianjin

[44] Jämviktskonstanttabell 2007, Avdelningen för oorganisk kemi, Kungliga Tekniska Högskolan,
Stockholm

[45] Tjus, K., Fortkamp, U., IVL; Rapport U2813: Screening test med fällning av metaller ur förbrukad
betsyra efter syraretardation, (för Scanacon), Stockholm 2010

67
68
Appendix I- Calculations
Mass balance for neutralisation in Avesta
Pickling
•HNO3 = 2 g/l
acid tank
Rinsing •HF = 0,2 g/l From SAR
and •Metal conc. = 0,1 g/l
Scrubber
•Flow = 8 m3/h 3 •Acid conc. = 0.5 M
(30 g/l HNO3 10g/l
HF)
2 •Metal conc. = 20 g/l
Neutralisation •Flow = 4 m3/h
of mixed acid 4

1
Filter press
Water from filter press Receiving tank
Cr-reduction
•HNO3 = 10 g/l 5
•HF = 0 g/l
•Metal conc. = 0 g/l
•Acid conc. = 0
•Flow = 8 m3/h
•Acid conc. = ?
Sedimentation •Metal conc. = ?
•Metal conc. = ?
•Flow = 4 m3/h
•Flow = ?
Neutralisation tank 1

Acids

Stream 1 (filter press)

Flow = 8m 3 / h = 8000l / h
HNO3 = 10 g / l = 10 × 8000 = 80000 g / h
HF = 0 g / l

Stream 2 (rinse water and water from scrubber):

Flow = 8m 3 / h = 8000l / h
HNO3 = 2 g / l = 2 × 8000 = 16000 g / h
HF = 0.2 g / l = 0.2 × 8000 = 1600 g / h

Stream 3 (SAR):

Flow = 4m 3 / h = 4000l / h
HNO3 = 30 g / l = 30 × 4000 = 120000 g / h
HF = 10 g / l = 10 × 4000 = 120000 g / h
69
Stream 4 (pickling acid tank):

Flow = 0.2m 3 / h = 200m 3 / h

HNO3 = 180 g / l = 180 × 200 = 36000 g / h
HF = 60 g / l = 60 × 200 = 12000 g / h

Stream 5 (chromium reduction):

Flow = 4m 3 / h = 4000l / h
HNO3 = 0 g / l
HF = 0 g / l

The acids are added respectively for all streams and total mole acid entering is calculated:

HNO3total = 16000 + 120000 + 36000 + 80000 = 252000 g / h

252000
M HNO3 = 63 g / mol  = 4000mol / h
63

HFtotal = 1600 + 40000 + 12000 = 53600 g / h

53600
M HF = 20 g / mol  = 2680mol / h
20

Mass balance for the flow into the neutralisation:

Total flow = 8 + 8 + 4 + 0.2 + 4 = 24.2m 3 / h = 24200l / h

Acid concentrations into neutralisation:

mol
4000
HNO3 = h = 0.165mol / l
l
24200
h

mol
2680
HNO3 = h = 0.111mol / l
l
24200
h

Metals:

Assuming the water contains the following metal concentration:

Fe3+ 74 %
Cr3+ 18 %
Ni2+ 8 %

70
Calculations are only made on stream 2, 3 and 4 since they are the only ones containing metals:

Fe 3+ :
0.74 × (0.1× 8000 + 20 × 4000 + 25 × 200) = 63492 g / h
M Fe = 55.8 g / mol
 63492 
Total =   / 24200 = 0.047 mol / l
 55.8 

Cr 3+ :
0.18 × (0.1× 8000 + 20 × 4000 + 25 × 200) = 15444 g / h
M Cr = 52 g / mol
 15444 
Total =   / 24200 = 0.0122mol / l
 52 

Ni 2+ :
0.08 × (0.1× 8000 + 20 × 4000 + 25 × 200) = 6864 g / h
M Ni = 58.7 g / mol
 6864 
Total =   / 24200 = 0.0048mol / l
 58.7 

Now the amount of OH- needed for neutralisation of acids and metal precipitation can be calculated.
Depending on the oxidation state of the metals, they will require different many OH-:

For Fe3+: 0.047 × 3 = 0.141 M

For Cr3+: 0.0122 × 3 = 0.0366 M

For Ni2+: 0.0048 × 2 = 0.0096 M

For HNO3: 0.165 M

For HF: 0.111 M

Summarising all of the above gives [OH-] = 0.4632 M is required. Since each mole slaked lime has two
hydroxides this gives

0.4632 / 2 = 0.2316mol Ca(OH)2

71
M Ca ( OH ) 2 = 74 g / mol
 74 × 0.2316 = 17.138 g / l
l g
24200 × 17.138
 h l = 414.8 kg Ca (OH )
2
g h
1000
kg

The stoichiometric amount Ca(OH)2 that should be added if the above concentrations apply is 17 g/l.

72
Appendix II- Medusa figures

Iron precipitation

[Fe 3+ ] TOT = 800.00 mM

H+
Fe 3+ OH−
0 Fe2O3(cr)

FeOH2+
Fe2(OH) 24+

-5 Fe(OH) 2+
Fe 3(OH) 4 5+
Log Conc.

Fe(OH) 4 −

-10

Fe(OH) 3

-15
0 5 10
pH

Nickel precipitation

[Ni2+ ] TOT = 80.00 mM

0
H+ Ni(OH) 2(c)
Ni2+
OH−
-2
Log Conc.

-4
NiOH+

-6 Ni2OH3+
Ni(OH) 3 −

-8

2 4 6 8 10 12
pH

73
Chromium precipitation

[Cr 3+] TOT = 200.00 mM

0 Cr 3+
H+ Cr 3 (OH) 4 5+ Cr 2O3(cr)
CrOH2+
OH−
-2 Cr 2(OH) 24+
Log Conc.

-4

Cr(OH) 2 +

-6
Cr(OH) 4 −

-8 Cr(OH) 3

2 4 6 8 10 12
pH

Table 18. Equilibrium reactions and species [7]

Equilibrium Reaction Species

Pattern
− −
Acid-Base HF ↔ H + + F − HNO3 , HF , H + , F − HF2 , NO3 , OH −
−
HNO3 ↔ H + + NO3
3− n + −
Fe(III) Fe 3+ + nF − ↔ FeFn Fe 3+ , FeF 2+ , FeF2 , FeF3 , FeF4 ,
complexes − 2+ 2− 3−
Fe 3+ + NO3 ↔ FeNO3 FeF5 , FeF6 , Fe
3m−n
mFe 3+ + nOH − ↔ FeOH n

Cr 3+ , CrF 3+ , CrF2 , CrF3 , Cr (OH ) ,

3− n + 2+
Cr(III) Cr 3+ + nF − ↔ CrF3
complexes
Cr (OH )2 , CrO2 , CrO3
3m−n + − 3−
mCr 3+ + nOH − ↔ CrOH n
Ni 2+ , NiF + , Ni (OH ) , Ni (OH )2 , NiO2 H −
+
Ni(II) Ni 2+ + F − ↔ NiF +
complexes 2− n
Ni 2+ + nOH − ↔ NiOH n

74
TRITA-IM 2010:21
ISSN 1402-7615

Industrial Ecology,
Royal Institute of Technology
www.ima.kth.se