soluble inorganic salts of nickel - the european ippc...

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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

http://eippcb.jrc.es/

http://eippcb.jrc.es/

Soluble Inorganic Salts of Nickel i

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

ii Soluble Inorganic Salts of Nickel

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

Soluble Inorganic Salts of Nickel iii

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 1

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.

2 Soluble Inorganic Salts of Nickel

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) Production capacity

in 2004 (tonnes/year)

Production capacity in 2004

(tonnes Ni/year) Nickel sulphate monohydrate - from copper refining Nickel sulphate hexahydrate - from nickel production

14000

22000

~3100

~4600 Nickel sulphate (crude) 7500 Nickel dichloride - liquid - solid

4350 8700

~1000 ~2000

Nickel (di)nitrate 7000 ~1400 Nickel hydroxycarbonate Nickel carbonate

6500 0

~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).


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 Use (tonnes)

Nickel sulphate NiSO4•(6)H2O 60000 Nickel chloride NiCl2•6H2O 7000 Nickel hydroxycarbonate NiCO3•2Ni(OH)2•zH2O 5750

Nickel dinitrate Ni(NO3)2•6H2ONot

available

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.


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 Raw materials Process Nickel sulphate monohydrate

- from copper refining

Nickel sulphate hexahydrate - from copper refining

- from nickel production

Copper tankhouse liquor

Crude nickel sulphate Ni/Co secondary raw materials

Liquid nickel sulphate

Section 2.1.2

Section 2.1.3 Section 2.1.2

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.


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.


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 Nickel carbonates 2.3.1 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.


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.


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

Emission levels (kg Ni/year)

Air Water Waste

13.5

<20

0.2

1850

0

Iron cake

Nickel sulphate monohydrate:- from copper refining

Nickel sulphate hexahydrate:- from copper refining



Crude nickel sulphate Ni secondary raw materials


Nickel chloride (liquid) Nickel matte Nickel chloride (solid) Nickel chloride (liquid)

<60 0 0

Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3

0.0001 7 25

Nickel dinitrate Nickel metal, nitric acid 0.01 348 1523

Table 3.1: Global emission levels from the European production of soluble inorganic salts of nickel


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 Remarks

Nickel sulphate monohydrate: - from copper refining

Nickel sulphate hexahydrate: - from copper refining



Crude nickel sulphate Ni secondary raw materials


Nickel chloride (liquid) Nickel matte Raw material: Nickel chloride solution (Ni >180 g/l) coming from the nickel metal refining process.

Nickel chloride (solid) Nickel chloride (liquid) Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3

Nickel dinitrate Nickel metal, nitric acid

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.


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) Raw materials usedWater

consumption(m3/t of product)

Remarks

Nickel sulphatemonohydrate


Nickel sulphate hexahydrate- from copper refining


Copper tankhouseliquor, CaOH, SO2,H2S, HF

Crude nickel sulphate

Nickel secondary rawmaterials

Liquid nickel sulpahte

The use of cooling water, which mainly arises from the precipitation of thevapour during evaporation of the decopperised electrolyte, amounts toabout 1800000 m³/yr.The cooling water consumption amounts to 750 m³/t

No information is available on the use or on the recycling ratio for water

Nickel chloride (liquid) Nickel matte

Nickel chloride (solid) Nickel chloride (liquid)

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 ofthe cooling circuit)

Nickel sulphate, NaOH,Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH,Na2CO3

≈ 80

Nickel dinitrate Nickel metal, nitric acid ≈ 0.5

Table 3.3: Use of water from the production of soluble inorganic salts of nickel in Europe


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) Raw materials used Emissions to air RemarksNickel sulphatemonohydrate






Nickel secondary raw materials


Ni: 13.5 kg/yrAs: 9 kg/yrPb: 9 kg/yrTotal dust: <5 mg/Nm3

Flowrate: <10000 m3/hNi concentration: belowdetection limitNi: <20 kg/yr

The wet washing column of the nickel plantemits 9 kg/yr each of Ni, As and Pb. Theemissions of NiSO4 from the packaging step is4.5 kg/yr (output from the bag filter). Others,particularly off-gases containing SO2, aretransferred to the acid plants [4, EuropeanIPPC Bureau, 2004] and converted intosulphuric acid with a conversion rateof >99.7 %. Off-gases bearing dust are cleanedin a filter bag so that the discharged off-gascontains <5 mg/Nm³ of total dust.

The maximum value observed in 2003was 1.1 mg Ni/Nm3.All the off-gases are scrubbed with water. Theefficiency of the scrubber is not measured asno inlet concentration measurements are taken.

Nickel chloride (liquid) Nickel matte Ni emission: 0 kg/yr No emissions to air

Nickel chloride (solid) Nickel chloride (liquid)Flowrate: 7800 Nm3/hNi: <1 mg/Nm3

Ni: <60 kg/yr

Waste gases from the process and air streamsfrom the production buildings are treated in awet washing column. The efficiency of theabatement equipment is >99.9 %

Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3 Ni: 0.0014 g/hNickel dinitrate Nickel metal, nitric acid Ni: 0.0014 g/h

Table 3.4: Emissions to air from the production of soluble inorganic salts of nickel in Europe


Product(s) Raw materials As Cu Dust NOx Ni Pb Sb Remarkskg/t of end product









0.0015

Nickel chloride (liquid) Nickel matte 0Nickel chloride (solid) Nickel chloride (liquid) 0.007


- 5 -

Nickel dinitrate Nickel metal, nitric acid - 5 -

Table 3.5: Annual air emission levels in the production of soluble inorganic salts of nickel in Europe


Product(s) Raw materials As Cu Dust NOx Ni Pb Sb Remarksmg/Nm3









Total: <5

Belowdetectionlimits.

Nickel chloride (liquid) Nickel matte 0Nickel chloride (solid) Nickel chloride (liquid) 1

Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonateNickel dinitrate, NaOH, Na2CO3 0.00009 853 0.0008

Nickel dinitrate Nickel metal, nitric acid 0.00009 853 0.0008

Table 3.6: Concentration values for air emissions in the production of soluble inorganic salts of nickel in Europe


Product(s) Raw materials As Cu Dust NOx Ni Pb Sb Remarksg/h









2

Nickel chloride (liquid) Nickel matteNickel chloride (solid) Nickel chloride (liquid)

Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3 0.0002 1570 0.0014Nickel dinitrate Nickel metal, nitric acid 0.0002 1570 0.0014

Table 3.7: Mass flow values for air emissions in the production of soluble inorganic salts of nickel in Europe


3.5 Water emissions

Product(s) Raw materials As Cu Ni Pb Sb ZnVolume of

waste watertreated

Production Remarks

kg/t of end product m3/yr t of endproduct/yr

Nickel sulphate monohydrate- from copper refining





Nickel secondary rawmaterials


0.142 13000


Nickel hydroxycarbonate Nickel sulphate, NaOH,Na2CO3

Nickel dinitrate, NaOH,Na2CO3

5000

Nickel dinitrate Nickel metal, nitric acid 500000

Table 3.8: Annual water emission levels in the production of soluble inorganic salts of nickel in Europe


Product(s) Raw materials As Cu Ni Pb Sb Zn Volume of wastewater treated Remarks

mg/l m3/hNickel sulphatemonohydrate


Nickel sulphatehexahydrate







1



1.8 7 0.5 6

Nickel dinitrate Nickel metal, nitric acid 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


The water emissions from the production of soluble inorganic salts of nickel in Europe are presented in Table 3.10.

Product(s) Raw materials Emissions to water RemarksNickel sulphate monohydrate








Ni emission: 0.2 kg/yrAs emission: 3.5 kg/yrPb emission: 13.2 kg/yrZn emission: 9.4 kg/yrCu emission: 0.6 kg/yr

Ni concentration: <1 mg/lNi emission: 1850 kg/yr

In 2002, 1705000 m³ of cooling water weredischarged to the river. The effluent wasloaded with metals in quantities shown inthe column to the left, which is considereda typical load.

The waste water containing nickel areneutralised with soda in the productionfacility. The residue obtained is recoveredwhile the filtrates are sent to the plantsewerage system. The overall waste waterstreams from all the different activities arethen collected in one of the two WWTP andafter pH control and decantation of solids,sent to the surface waters.

Nickel chloride (liquid) Nickel matteNickel chloride (solid) Nickel chloride (liquid) Ni emission: 0 kg/yr There is no outlet of industrial waste water

from the production process.Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3 7 kg/yr

Nickel dinitrate Nickel metal, nitric acid 348 kg/yr

Table 3.10: Emissions to water from the production of soluble inorganic salts of nickel in Europe


3.6 Wastes

The wastes from the production of soluble inorganic salts of nickel in Europe are presented in Table 3.11.

Product(s) Raw materials Wastes RemarksNickel sulphate monohydrate








0

1000000 kg in 2003

No waste for disposal

In 2003, about 1000 tonnes of wet residues(iron cake) were sent for disposal at thecompany’s own disposal site (NiSO4production was about 7000 tonnes)

Nickel chloride (liquid) Nickel matte

Nickel chloride (solid) Nickel chloride (liquid) 0 kg/yrThe wastes generated are limited to somepolluted packaging (when problems occurduring the filling of polyethylene bags)

Nickel sulphate, NaOH, Na2CO3Nickel hydroxycarbonate Nickel dinitrate, NaOH, Na2CO3 25 kg/yrNickel dinitrate Nickel metal, nitric acid 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


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.

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)".

Glossary


GLOSSARY BAT best available techniques BREF BAT reference document IPPC integrated pollution prevention and control SIC speciality inorganic chemicals TWG technical working group

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