EUROPEAN COMMISSION
DIRECTORATE-GENERAL JRC
JOINT RESEARCH CENTRE
Institute for Prospective Technological Studies
Sustainability in Industry, Energy and Transport
European IPPC Bureau
Integrated Pollution Prevention and Control
Information Exchanged on the
Production of Soluble Inorganic Salts of Nickel
between October 2003 and April 2005
August 2005
Edificio Expo, Inca Garcilaso s/n, E-41092 Seville – Spain
Telephone: direct line (+34-95) 4488-284, switchboard 4488-318. Fax: 4488-426.
Internet: http://eippcb.jrc.es, e-mail: JRC-IPTS-EIPPCB@ cec.eu.int
Table of contents
INTRODUCTION................................................................................................................................... III
1
GENERAL INFORMATION ........................................................................................................... 1
1.1
Uses and markets........................................................................................................................ 1
1.2
Toxicity ...................................................................................................................................... 2
1.3
Production capacity.................................................................................................................... 2
1.4
Features of the European soluble inorganic salts of nickel industry .......................................... 2
1.5
Economics and market trends .................................................................................................... 3
2
APPLIED PROCESSES AND TECHNIQUES .............................................................................. 5
2.1
Nickel sulphate........................................................................................................................... 5
2.1.1
Production from liquid nickel sulphate ............................................................................ 5
2.1.2
Production from copper refining ...................................................................................... 6
2.1.3
Production from impure nickel sulphate .......................................................................... 6
2.2
Nickel chloride ........................................................................................................................... 7
2.3
Nickel carbonates ....................................................................................................................... 7
2.3.1
Production of pure nickel carbonate................................................................................. 7
2.3.2
Production of nickel hydroxycarbonate from nickel solution .......................................... 8
2.4
Nickel dinitrate........................................................................................................................... 8
2.5
Packaging of nickel salts ............................................................................................................ 8
3
EMISSION LEVELS AND RAW MATERIALS USE................................................................... 9
3.1
Raw materials and auxiliary chemicals use.............................................................................. 10
3.2
Energy consumption................................................................................................................. 10
3.3
Water consumption .................................................................................................................. 11
3.4
Air emissions............................................................................................................................ 12
3.5
Water emissions ....................................................................................................................... 16
3.6
Wastes ...................................................................................................................................... 19
3.7
Odour and noise emissions....................................................................................................... 20
REFERENCES......................................................................................................................................... 21
GLOSSARY.............................................................................................................................................. 23
Soluble Inorganic Salts of Nickel
i
List of tables
Table 1.1: Production capacity of soluble inorganic nickel salts in Europe .................................................2
Table 1.2: Worldwide use of the most important nickel salts for the year 2003...........................................3
Table 2.1: Raw materials and processes currently used by the companies which produce nickel sulphate in
Europe ....................................................................................................................................5
Table 3.1: Global emission levels from the European production of soluble inorganic salts of nickel ........9
Table 3.2: Use of raw materials and auxiliary chemicals from the production of soluble inorganic salts of
nickel in Europe ...................................................................................................................10
Table 3.3: Use of water from the production of soluble inorganic salts of nickel in Europe......................11
Table 3.4: Emissions to air from the production of soluble inorganic salts of nickel in Europe ................12
Table 3.5: Annual air emission levels in the production of soluble inorganic salts of nickel in Europe ....13
Table 3.6: Concentration values for air emissions in the production of soluble inorganic salts of nickel in
Europe ..................................................................................................................................14
Table 3.7: Mass flow values for air emissions in the production of soluble inorganic salts of nickel in
Europe ..................................................................................................................................15
Table 3.8: Annual water emission levels in the production of soluble inorganic salts of nickel in Europe16
Table 3.9: Concentration values for water emissions in the production of soluble inorganic salts of nickel
in Europe ..............................................................................................................................17
Table 3.10: Emissions to water from the production of soluble inorganic salts of nickel in Europe..........18
Table 3.11: Wastes from the production of soluble inorganic salts of nickel in Europe ............................19
ii
Soluble Inorganic Salts of Nickel
INTRODUCTION
Within the framework of elaborating the reference document on best available techniques for
the production of Speciality Inorganic Chemicals (the SIC BREF), this document reflects the
information exchanged on the production of soluble inorganic salts of nickel between
October 2003 and April 2005.
[1, European Nickel Group, 2004, 2, European Nickel Group, 2004]
‘Soluble inorganic salts of nickel’ have been found by the SIC TWG to belong to the family of
SIC substances.
This document focuses on the following soluble inorganic salts of nickel:
•
•
•
•
nickel sulphate monohydrate and hexahydrates (NiSO4, NiSO4•H2O, NiSO4•6H2O,
NiSO4•7H2O)
nickel chlorides (NiCl2, NiCl2•6H2O)
nickel carbonates and nickel hydroxycarbonates (?NiCO3•2Ni(OH)2•zH2O)1
nickel dinitrates (Ni(NO3)2, Ni(NO3)2•6H2O).
It is important to note that, for six out of the seven companies producing these substances in
Europe, production is strongly linked to that of refined copper or nickel which is addressed in
the Reference Document on Best Available Techniques in the Non-Ferrous Metals Industries [3,
European IPPC Bureau, 2001].
The other nickel salts (e.g. nickel acetates, nickel fluorides, nickel chromates, nickel cyanides)
being of a lesser importance in Europe (production volume <1000 tonnes/year) are not
addressed in this document.
It must be stressed that this document has not been peer reviewed and information within is not
validated nor endorsed by the TWG on SIC or the European Commission.
1
"Environmental Health Criteria 108" by IPCS (International Programme on Chemical Safety), 1991, stipulates: the most common
forms range from 2NiCO3•3Ni(OH)2•zH2O to NiCO3•Ni(OH)3•zH2O.
Soluble Inorganic Salts of Nickel
iii
1 GENERAL INFORMATION
Nickel salts are generally yellow to green crystals that are usually soluble in water and
decompose when heated.
Nickel sulphates occur as yellow, green or blue crystals mainly available in anhydrous
(NiSO4), anhydrous solution, monohydrate (NiSO4•H2O), hexahydrate (NiSO4•6H2O), and
heptahydrate (NiSO4•7H2O) forms. Other forms are described in the literature but they are not
stable. The actual number of water molecules attached to solid NiSO4 in equilibrium with a
saturated NiSO4- solution depends on the temperature of the solution. Thus, in the temperature
range up to approximately 30 ºC, the heptahydrate form prevails, whereas at temperatures of
90 – 100 ºC the hexahydrate form is dominant. Nickel sulphates are readily soluble in water.
Nickel sulphate can be found in nature in the heptahydrate form in the morenosite mineral. The
predominant commercially available form is the hexahydrate, whereas for some uses, aqueous
solutions are produced.
Nickel chlorides occur as yellow (in the case of anhydrous nickel chloride – NiCl2) or green (in
the case of hexahydrate nickel chloride – NiCl2•6H2O) crystals. In saturated solutions of NiCl2,
the number of water molecules attached to the salt vary with the temperature. Nickel chlorides
are soluble in water and ethanol, and deliquescent in moist air.
Although a hydrated nickel carbonate (NiCO3•6H2O) and the anhydrous form (NiCO3) exist,
most of the commercial nickel carbonates are basic salts described more appropriately as nickel
hydroxycarbonates or basic nickel carbonates – with the general formula
xNiCO3•yNi(OH)2•zH2O. Nickel carbonates are soluble in dilute acid but insoluble in water.
The
most
important
nickel
hydroxycarbonate
commercially
available
is
NiCO3•2Ni(OH)2•4H2O.
Nickel dinitrates occur as light green crystals which easily dissolve in water, liquid ammonia,
aqueous ammonia and ethanol, and slightly in propanol. Nickel dinitrates are commercially
available in anhydrous – Ni(NO3)2 – and hydrous – Ni(NO3)2•6H2O – forms. Combustion and
explosions occur when nickel dinitrate is mixed with organic compounds.
1.1
Uses and markets
Nickel sulphate is mainly used in electroplating and electrodeless nickel plating, as a chemical
intermediate to produce other nickel compounds, in nickel flashings on steel to prepare it to be
porcelain-enamelled, and as a raw material for the production of catalysts. Nickel sulphate is
also used in the production of nickel metal and nickel hydroxycarbonate. There is a new market
for nickel sulphate, as it can be used to produce speciality chemicals for the manufacture of
nickel-based batteries. The produced nickel compounds (nickel sulphate) are mostly used in the
plating industry.
Nickel chloride is used in electroplating, as a raw material for the production of catalysts and in
the production of chemicals containing nickel. It is estimated that, at present, 72 % of the
European production of nickel chloride is used for the production of catalysts, 26 % in
electroplating, and 2 % for other uses.
Nickel hydroxycarbonate is used to prepare nickel monoxide, nickel powder, nickel catalysts,
coloured glass, and certain nickel pigments. It is also used in electroplating and as a catalyst to
remove organic contaminants from water. Approximately 70 % of the European production of
nickel hydroxycarbonate is used for plating, 20 % for the production of catalysts, 5 % for the
production of pigments, and 5 % for other uses.
Soluble Inorganic Salts of Nickel
1
The main use of nickel dinitrate is in the production of catalysts, especially sulphur sensitive
catalysts, and as an intermediate in the production of nickel-cadmium batteries. Nickel dinitrate
is also used to make products used in the pretreatment of metals prior to painting and prior to
cold-forming processes.
1.2
Toxicity
Soluble inorganic nickel salts are classified as toxic via inhalation, and environmentally
hazardous under Council Directive 67/548/EEC on classification, packaging and labelling of
dangerous substances. Nickel nitrate also has oxidising properties. The carcinogenic assessment
of soluble inorganic nickel salts has been somewhat controversial, with no consensus in the
scientific community regarding the hazard classification of them.
1.3
Production capacity
The production capacity of soluble inorganic nickel salts in Europe is given in Table 1.1.
Product(s)
Nickel sulphate monohydrate
- from copper refining
Nickel sulphate hexahydrate
- from nickel production
Nickel sulphate (crude)
Nickel dichloride
- liquid
- solid
Nickel (di)nitrate
Nickel hydroxycarbonate
Nickel carbonate
Production capacity
in 2004
(tonnes/year)
Production capacity
in 2004
(tonnes Ni/year)
14000
~3100
22000
7500
~4600
4350
8700
7000
6500
0
~1000
~2000
~1400
~3300
0
Table 1.1: Production capacity of soluble inorganic nickel salts in Europe
A little over one third of the nickel sulphate produced in the EU-15 is exported, predominantly
to the Far East.
1.4
Features of the European soluble inorganic salts of
nickel industry
In Europe, large enterprises (over 250 employees) and medium sized enterprises (between 50
and 249 employees) manufacture nickel salts. The workforce employed within these companies
to run an installation producing nickel salts is between 10 and 400. Production is carried out in
medium sized facilities using a continuous or a batch mode of operation. Production is generally
carried out in installations that are part of a larger metallurgical complex generally either
dedicated to the production of refined copper or nickel, or to the recovery of metals from scraps
or recycled materials (e.g. spent catalysts, electronic and metal scraps, slags).
2
Soluble Inorganic Salts of Nickel
1.5
Economics and market trends
Table 1.2 shows the worldwide use of the most important nickel salts for the year 2003.
Nickel salt
Chemical formula
Nickel sulphate
Nickel chloride
Nickel
hydroxycarbonate
NiSO4•(6)H2O
NiCl2•6H2O
Use
(tonnes)
60000
7000
NiCO3•2Ni(OH)2•zH2O
5750
Ni(NO3)2•6H2O
Not
available
Nickel dinitrate
Table 1.2: Worldwide use of the most important nickel salts for the year 2003
Future trends in nickel sulphate production are difficult to predict. According to information
from the nickel sulphate producers, some companies are planning to increase production. The
producers also foresee growth in the different uses of nickel sulphate (i.e. plating, catalysts and
nickel-based batteries) so that, in general, an increasing need is predicted. A large amount of
nickel is found in recovered recycling materials, so that with increasing quantities of materials
being recycled, the amount of nickel recovered also automatically increases. The analysis of
trends for the use of metallic nickel supports this assessment of growth in the use of nickel for
batteries, but suggests that there is little growth expected in total nickel use in plating. The low
growth in use seen for plating uses reflects, in part, a trend for plated products to be imported
into Europe from countries with lower production cost (especially Asia), rather than to be
manufactured in Europe.
The number of nickel chloride production sites in Europe has fallen significantly in the past
two decades. In 1988, there were 11 companies producing nickel chloride in Europe, but
currently there is only one. At the present time, the trend of nickel chloride production shows a
slow increase. No major changes are expected in the short-term, either in the number of
producers or in the use of the substance. It is possible that some new applications for nickel
chloride will appear in the electronics industry. However, the quantities that could potentially be
used in these new applications would be small compared to other uses of nickel chloride.
No information indicating any significant trend in nickel hydroxycarbonate production was
found.
Nickel dinitrate is usually used as an intermediate in the production of batteries and catalysts. It
can also be used to produce nickel hydroxycarbonate.
Soluble Inorganic Salts of Nickel
3
2 APPLIED PROCESSES AND TECHNIQUES
As the production of nickel salts is strongly related to the production of refined nickel or copper,
it is recommended that the reader refers to the Reference Document on Best Available
Techniques in the Non-Ferrous Metals Industries [3, European IPPC Bureau, 2001] for a better
understanding of the terms used in this section.
2.1
Nickel sulphate
There are different ways of producing nickel sulphate depending on the raw materials used
(e.g. nickel pellets, nickel/cobalt matte, mixed copper/nickel/cobalt secondary raw materials,
crude nickel sulphate, copper tankhouse liquor).
At present, nickel sulphate is produced in the following ways in Europe:
•
•
•
•
Production from liquid nickel sulphate (Section 2.1.1)
production from other leaching processes (Section 2.1.2)
production from copper refining (Section 2.1.2)
production from impure nickel sulphate (Section 2.1.3).
Nickel sulphate typically contains impurities of cobalt, iron, copper, lead, zinc, cadmium and
arsenic. The purity of nickel sulphate depends on the raw materials used and on the efficiency of
purification.
Table 2.1 indicates the raw materials and processes currently used to produce nickel sulphate in
Europe.
Products
Nickel sulphate monohydrate
- from copper refining
Nickel sulphate hexahydrate
- from copper refining
- from nickel production
Raw materials
Process
Copper tankhouse liquor
Section 2.1.2
Crude nickel sulphate
Ni/Co secondary raw materials
Section 2.1.3
Section 2.1.2
Liquid nickel sulphate
Section 2.1.1
Table 2.1: Raw materials and processes currently used by the companies which produce nickel
sulphate in Europe
2.1.1
Production from liquid nickel sulphate
Liquid nickel sulphate is produced by leaching nickel matte, which is a product of the smelting
process and other raw materials containing nickel, as crude nickel sulphates. Nickel matte
contains nickel, copper, iron, sulphur, cobalt and precious metals.
The raw nickel sulphate solution is refined using solvent extraction. This purified nickel
sulphate solution is the raw material for nickel sulphate production.
The nickel sulphate solution is crystallised in a continuously working vacuum crystalliser. The
crystals are separated from the mother liquor by a centrifuge, dried and finally packed. The final
product is the high purity nickel sulphate hexahydrate.
Soluble Inorganic Salts of Nickel
5
The leaching residue is copper sulphide containing some nickel (3 – 6 %) and precious metals.
This residue is smelted together with copper concentrates. Nickel is recovered in copper anodes,
which are refined in the electrolysis of copper.
All process steps are carried out in closed systems.
2.1.2
Production from copper refining
Copper production is based on a multistage smelting process followed by electrolytic refining.
The raw materials used may be primary copper ores containing sometimes also nickel or
secondary materials containing both copper and nickel.
Among the secondary materials recycled copper nickel alloys and drosses play an important
role.
During the smelting operations that are carried out to produce copper anodes, nickel remains in
the metal phase. The products of copper smelting are copper anodes containing about 99 %
copper. Copper is refined by electrolysis (transferred from anodes to cathodes) in the tankhouse
containing a 20 % sulphuric acid solution (electrolyte). The used sulphuric acid concentrations
are about 150 – 250 g/l H2SO4. Copper anodes are refined to copper cathodes
containing 99.99 % copper. During this process, the nickel contained in the anodes is dissolved
in the electrolyte.
To keep the nickel content in the tankhouse liquor at a constant level, part of the tankhouse
liquor has to be withdrawn and treated in a special purification unit. In the purification unit,
copper is removed from the liquor usually by reduction via electrolysis. After the copper has
been removed, crude nickel sulphate is produced by evaporation/crystallisation. Alternatively,
copper sulphate can be produced by evaporation/crystallisation processes before the electrolysis
step.
The crude nickel sulphate produced is a monohydrate which contains impurities of other metal
sulphates and sulphuric acid, as well as water. The nickel content is 20 – 30 %. Dissolution and
recrystallisation result in the formation of nickel sulphate hexahydrate. Additional purification
steps are needed in order to prepare a product of sufficient purity for use in plating and other
applications.
The tankhouse liquor can also be withdrawn from the process and used to dissolve other
unrefined by-products containing copper, arsenic and nickel. After the removal of copper, the
impure nickel sulphate is produced by crystallisation. The obtained nickel sulphate crystals are
separated by centrifugation, and then redissolved and sent to the production line for further
purification.
2.1.3
Production from impure nickel sulphate
The nickel sulphate from copper refining is a crude product. As the crude nickel sulphate is too
impure for usual applications, further purification is needed. This is either carried out directly
on-site or off-site by other nickel sulphate producing companies.
6
Soluble Inorganic Salts of Nickel
2.2
Nickel chloride
There is only one plant producing nickel chloride crystals in Europe. The raw material used in
this production is crude nickel chloride solution.
The following production steps are carried out for the production of nickel chloride crystals (the
nickel chloride solution is directly obtained from the nickel refinery process without any
particular additional treatment):
•
•
•
•
•
evaporation: the nickel chloride solution is first concentrated by evaporating excess water
using steam as the heating agent
precipitation: the nickel chloride crystals are precipitated by cooling the solution in several
steps
solid-liquid separation: the slurry flows through solid-liquid separation equipment in order
to separate the solid phase (crystals) from the nickel depleted liquid phase (mother liquor).
The mother liquor is recycled back into the nickel refinery process
drying: the moist nickel chloride crystals are dried in a steam heated dryer in order to
obtain the required commercial product
weighing and packaging: the nickel chloride crystals are then weighed, packaged and
palletised.
No waste water is generated in the production of nickel chloride.
Nickel chloride typically contains impurities of cobalt, iron, copper, lead, and zinc. The purity
of nickel chloride depends on the raw materials used and on the efficiency of purification.
2.3
2.3.1
Nickel carbonates
Production of pure nickel carbonate
Large scale production of pure nickel carbonate (NiCO3•xH2O) is not viable. Small amounts of
this substance are used in the electronic industry where very high purities are required.
Pure nickel carbonates are reported to be products of aqueous nickel salts and alkali metal
hydrogen carbonate, i.e. sodium bicarbonate at low temperatures (<50 ºC) and at a low pH (<5)
levels.
The production of anhydrous nickel carbonate requires very special conditions (McMullen et
al., 1966). Nickel carbonate can also be prepared by oxidation of nickel powder on ammonia
and dioxide. Boiling away the ammonia causes precipitation of pure nickel carbonate
(Antonsen, 1996).
Nickel carbonate is not known to be produced in Europe.
Soluble Inorganic Salts of Nickel
7
2.3.2
Production of nickel hydroxycarbonate from nickel solution
The following production steps are carried out for the production of nickel hydroxycarbonate:
•
•
•
•
precipitation: a solution containing nickel (usually a nickel sulphate solution; but also a
nickel dinitrate or chloride solution) is brought to a reactor containing a hot sodium
hydroxide solution. Nickel hydroxycarbonate precipitates under high temperatures (>50 ºC)
and pH (>6) by the addition of a solution of sodium carbonate (Na2CO3) or some other
alkali metal
filtration: the precipitate is separated from the mother liquor and washed on a filter. The
filtrate is sent to a waste water treatment plant (WWTP). The filtration can be carried out on
suction press or band filters
drying: the moist nickel hydroxycarbonate crystals can be dried, e.g. in a spray dryer
packaging: finally, the nickel hydroxycarbonate crystals are packaged to be sent to
customers.
2.4
Nickel dinitrate
There are about ten producers of nickel dinitrate in Europe. They partly produce nickel dinitrate
as an intermediate in their production of catalysts; they partly sell it to other companies.
Nickel dinitrate is obtained by the leaching of nickel metal (e.g. broken cathodes, briquettes,
nickel sheets) in nitric acid. The reaction is carried out in closed stainless steel or glass reactors.
During the reaction, nitrogen monoxide and nitrogen dioxide (NOx) are formed. The off-gas is
treated by washing with water through columns or by a catalytic system. In the first case, the
gas is transformed into nitric acid, which is recycled back into the process. The product obtained
is nickel dinitrate in water solution. Solid nickel dinitrate can be produced by concentrating this
solution. Other nickel salts (i.e. nickel hydroxycarbonate, phosphate and acetate) can be
produced using the nickel dinitrate water solution as the raw material.
Water is needed for cleaning out equipment. The waste water generated by the cleaning
operations is treated in the site’s waste water treatment plant.
Other production methods exist but they are not published.
2.5
Packaging of nickel salts
Nickel salts are packed into woven-polypropylene bags lined with high strength, moisture-proof
polyethylene. It can be delivered by cardboard boxes, by pallet boxes or by pallets covered by
plastic wrap. Liquid nickel chloride is sold in bulk and delivered to customers by road tankers
with approximately 17 m3 capacity.
8
Soluble Inorganic Salts of Nickel
3 EMISSION LEVELS AND RAW MATERIALS USE
Table 3.1 presents the global nickel emission levels from the European production of soluble
inorganic salts of nickel.
Product(s)
Raw materials and
auxiliary chemicals used
Air
Nickel sulphate
monohydrate:
- from copper refining
Nickel sulphate
hexahydrate:
- from copper refining
Copper tankhouse liquor
13.5
0.2
0
Crude nickel sulphate
Ni secondary raw materials
<20
1850
Iron cake
<60
0
0
0.0001
7
25
0.01
348
1523
- from nickel production
Liquid nickel sulphate
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH,
Na2CO3
Nickel dinitrate, NaOH,
Na2CO3
Nickel metal, nitric acid
Nickel hydroxycarbonate
Nickel dinitrate
Emission levels
(kg Ni/year)
Water
Waste
Table 3.1: Global emission levels from the European production of soluble inorganic salts of nickel
Soluble Inorganic Salts of Nickel
9
3.1
Raw materials and auxiliary chemicals use
The use of raw materials and auxiliary chemicals from the production of soluble inorganic salts
of nickel in Europe is presented in Table 3.2.
Product(s)
Raw materials and auxiliary
chemicals used
Nickel sulphate
monohydrate:
- from copper refining
Copper tankhouse liquor
Nickel sulphate
hexahydrate:
- from copper refining
Crude nickel sulphate
Remarks
Ni secondary raw materials
- from nickel production
Liquid nickel sulphate
Nickel chloride (liquid)
Nickel matte
Nickel chloride (solid)
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
Nickel hydroxycarbonate
Nickel dinitrate
Raw material: Nickel chloride
solution (Ni >180 g/l) coming from
the nickel metal refining process.
Table 3.2: Use of raw materials and auxiliary chemicals from the production of soluble inorganic
salts of nickel in Europe
3.2
Energy consumption
The consumption of electricity and steam for the sole production of nickel salts is not
monitored. Data on energy consumption are available for the whole production at the site
including production of non-ferrous metals.
10
Soluble Inorganic Salts of Nickel
3.3
Water consumption
The use of fresh water from the production of soluble inorganic salts of nickel in Europe is presented in Table 3.3.
Product(s)
Nickel sulphate
monohydrate
- from copper refining
Nickel sulphate hexahydrate
- from copper refining
Raw materials used
Water
consumption
(m3/t of product)
Copper tankhouse
liquor, CaOH, SO2,
H2S, HF
Remarks
The use of cooling water, which mainly arises from the precipitation of the
vapour during evaporation of the decopperised electrolyte, amounts to
about 1800000 m³/yr.The cooling water consumption amounts to 750 m³/t
Crude nickel sulphate
No information is available on the use or on the recycling ratio for water
Nickel secondary raw
materials
- from nickel production
Nickel chloride (liquid)
Liquid nickel sulpahte
Nickel matte
Nickel chloride (solid)
Nickel chloride (liquid)
Nickel hydroxycarbonate
Nickel dinitrate
Nickel sulphate, NaOH,
Na2CO3
Nickel dinitrate, NaOH,
Na2CO3
Nickel metal, nitric acid
Water use is limited to the off-gas treatment equipment (approx. 1 m3/h)
and to the cooling water (to compensate the evaporation and the bleed of
the cooling circuit)
O 80
O 0.5
Table 3.3: Use of water from the production of soluble inorganic salts of nickel in Europe
Soluble Inorganic Salts of Nickel
11
3.4
Air emissions
The air emissions from the production of soluble inorganic salts of nickel in Europe are presented in Table 3.4, Table 3.5, Table 3.6 and Table 3.7.
Product(s)
Nickel sulphate
monohydrate
- from copper refining
Raw materials used
Emissions to air
Copper tankhouse liquor
Ni: 13.5 kg/yr
As: 9 kg/yr
Pb: 9 kg/yr
Total dust: <5 mg/Nm3
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
Flowrate: <10000 m3/h
Ni concentration: below
detection limit
Ni: <20 kg/yr
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Liquid nickel sulphate
Nickel matte
Nickel hydroxycarbonate
Nickel dinitrate
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
The wet washing column of the nickel plant
emits 9 kg/yr each of Ni, As and Pb. The
emissions of NiSO4 from the packaging step is
4.5 kg/yr (output from the bag filter). Others,
particularly off-gases containing SO2, are
transferred to the acid plants [4, European
IPPC Bureau, 2004] and converted into
sulphuric acid with a conversion rate
of >99.7 %. Off-gases bearing dust are cleaned
in a filter bag so that the discharged off-gas
contains <5 mg/Nm³ of total dust.
The maximum value observed in 2003
was 1.1 mg Ni/Nm3.
All the off-gases are scrubbed with water. The
efficiency of the scrubber is not measured as
no inlet concentration measurements are taken.
Ni emission: 0 kg/yr
3
Nickel chloride (solid)
Remarks
Flowrate: 7800 Nm /h
Ni: <1 mg/Nm3
Ni: <60 kg/yr
No emissions to air
Waste gases from the process and air streams
from the production buildings are treated in a
wet washing column. The efficiency of the
abatement equipment is >99.9 %
Ni: 0.0014 g/h
Ni: 0.0014 g/h
Table 3.4: Emissions to air from the production of soluble inorganic salts of nickel in Europe
12
Soluble Inorganic Salts of Nickel
Product(s)
Raw materials
Nickel sulphate
monohydrate
- from copper refining
Copper tankhouse liquor
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
As
Cu
Dust
NOx
Ni
Pb
kg/t of end product
Sb
Remarks
0.0015
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH,
Na2CO3
Nickel dinitrate, NaOH,
Na2CO3
Nickel metal, nitric acid
0
0.007
-
5
-
-
5
-
Table 3.5: Annual air emission levels in the production of soluble inorganic salts of nickel in Europe
Soluble Inorganic Salts of Nickel
13
Product(s)
Raw materials
As
Cu
Dust
NOx
Ni
mg/Nm3
Pb
Sb
Remarks
Nickel sulphate
monohydrate
- from copper refining
Copper tankhouse liquor
Total: <5
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
Below
detection
limits.
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
0
1
0.00009
0.00009
853
853
0.0008
0.0008
Table 3.6: Concentration values for air emissions in the production of soluble inorganic salts of nickel in Europe
14
Soluble Inorganic Salts of Nickel
Product(s)
Raw materials
As
Cu
Dust
NOx
Ni
Pb
Sb
Remarks
g/h
Nickel sulphate
monohydrate
- from copper refining
Copper tankhouse liquor
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
2
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
0.0002
0.0002
1570
1570
0.0014
0.0014
Table 3.7: Mass flow values for air emissions in the production of soluble inorganic salts of nickel in Europe
Soluble Inorganic Salts of Nickel
15
3.5
Water emissions
Product(s)
Raw materials
As
Cu
Ni
Pb
Sb
Zn
kg/t of end product
Nickel sulphate monohydrate
- from copper refining
Copper tankhouse liquor
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
Nickel secondary raw
materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Volume of
waste water
treated
Production
m3/yr
t of end
product/yr
0.142
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH,
Na2CO3
Nickel dinitrate, NaOH,
Na2CO3
Nickel metal, nitric acid
Remarks
13000
0
0
5000
500000
Table 3.8: Annual water emission levels in the production of soluble inorganic salts of nickel in Europe
16
Soluble Inorganic Salts of Nickel
Product(s)
Raw materials
As
Cu
Ni
Pb
Sb
Zn
mg/l
Nickel sulphate
monohydrate
- from copper refining
Copper tankhouse liquor
Nickel sulphate
hexahydrate
- from copper refining
Crude nickel sulphate
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH,
Na2CO3
Nickel dinitrate, NaOH,
Na2CO3
Nickel metal, nitric acid
Volume of waste
water treated
m3/h
Remarks
1
0
0
1.8
7
0.5
6
1.8
7
0.5
6
Table 3.9: Concentration values for water emissions in the production of soluble inorganic salts of nickel in Europe
Soluble Inorganic Salts of Nickel
17
The water emissions from the production of soluble inorganic salts of nickel in Europe are presented in Table 3.10.
Product(s)
Nickel sulphate monohydrate
- from copper refining
Raw materials
Emissions to water
Copper tankhouse liquor
Ni emission: 0.2 kg/yr
As emission: 3.5 kg/yr
Pb emission: 13.2 kg/yr
Zn emission: 9.4 kg/yr
Cu emission: 0.6 kg/yr
In 2002, 1705000 m³ of cooling water were
discharged to the river. The effluent was
loaded with metals in quantities shown in
the column to the left, which is considered
a typical load.
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
Ni concentration: <1 mg/l
Ni emission: 1850 kg/yr
The waste water containing nickel are
neutralised with soda in the production
facility. The residue obtained is recovered
while the filtrates are sent to the plant
sewerage system. The overall waste water
streams from all the different activities are
then collected in one of the two WWTP and
after pH control and decantation of solids,
sent to the surface waters.
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
Ni emission: 0 kg/yr
Remarks
There is no outlet of industrial waste water
from the production process.
7 kg/yr
348 kg/yr
Table 3.10: Emissions to water from the production of soluble inorganic salts of nickel in Europe
18
Soluble Inorganic Salts of Nickel
3.6
Wastes
The wastes from the production of soluble inorganic salts of nickel in Europe are presented in Table 3.11.
Product(s)
Nickel sulphate monohydrate
- from copper refining
Raw materials
Copper tankhouse liquor
Nickel sulphate hexahydrate
- from copper refining
Crude nickel sulphate
Nickel secondary raw materials
- from nickel production
Nickel chloride (liquid)
Nickel chloride (solid)
Nickel hydroxycarbonate
Nickel dinitrate
Wastes
0
No waste for disposal
1000000 kg in 2003
In 2003, about 1000 tonnes of wet residues
(iron cake) were sent for disposal at the
company’s own disposal site (NiSO4
production was about 7000 tonnes)
Liquid nickel sulphate
Nickel matte
Nickel chloride (liquid)
Nickel sulphate, NaOH, Na2CO3
Nickel dinitrate, NaOH, Na2CO3
Nickel metal, nitric acid
Remarks
0 kg/yr
The wastes generated are limited to some
polluted packaging (when problems occur
during the filling of polyethylene bags)
25 kg/yr
1523 kg/yr
Mud from the waste water treatment plant
Table 3.11: Wastes from the production of soluble inorganic salts of nickel in Europe
Soluble Inorganic Salts of Nickel
19
3.7
Odour and noise emissions
Odour is not an issue at installations producing inorganic salts of nickel. Noise (generated by the
use of mechanical equipment) is an issue only for plant personnel that have to use ear-plugs
when working in the production areas. Technical measures such as encapsulation of process
equipment are used where necessary.
20
Soluble Inorganic Salts of Nickel
References
REFERENCES
1
European Nickel Group (2004). "Speciality Inorganic Chemicals BREF Note - Soluble
Inorganic Salts of Nickel - General Information - Final Draft - Rev 2 - March 2004".
2
European Nickel Group (2004). "SIC BREF NOTES - INORGANIC SOLUBLE
NICKEL SALTS - DATA FROM THE PRODUCERS".
3
European IPPC Bureau (2001). "Reference Document on Best Available Techniques in
the Non Ferrous Metals Industries".
4
European IPPC Bureau (2004). "Draft Reference Document on Best Available
Techniques for the Production of Large Volume Inorganic Chemicals (Ammonia, Acids
and Fertilisers)".
Soluble Inorganic Salts of Nickel
21
Glossary
GLOSSARY
BAT
BREF
IPPC
SIC
TWG
best available techniques
BAT reference document
integrated pollution prevention and control
speciality inorganic chemicals
technical working group
Soluble Inorganic Salts of Nickel
23