Vous êtes sur la page 1sur 5

Issued on behalf of the Group Technical Director

This bulletin is published for general information and is not intended as professional advice. As every
situation depends on its own peculiar facts and circumstances, specialist advice should be obtained
where required.
ATD, VOHE Tel: +27 11 638 3045
Administrative Contact: 5
th
Floor, 45 Main Street Fax: +27 11 638 2610
Marshalltown, Johannesburg e-mail: jguthrie@anglo.co.za

1
Safety, Health & Environment Bulletin


May 2002 S111/2002


XANTHATE REAGENT:
CONTROL OF RISKS ASSOCIATED WITH STORAGE AND USE


1 Introduction
Large quantities of various xanthate compounds are widely used in the Anglo American Plc
Operations as collectors in sulphide flotation. Incidences have been recorded involving
accidents associated with xanthate, notably an incident during August 2000 involving an
explosion at Amandelbult, but also in various literature.
The purpose of this bulletin is to highlight the risks associated with the use and storage of
xanthate and to reiterate methods for the control of these risks.
This bulletin is based on a detailed report on the subject prepared by the Anglo Technical
Division (Reference 1). (AAC_SHEG_000111)

2 Physical and Chemical Characteristics of Xanthate
Xanthates are delivered to operations as solids (pellets or powder) in drums or bulk bags,
or in liquid form by bulk road tankers, depending the transport distances and the make-up
facilities on-site.
Solid xanthates are hygroscopic and may decompose in the presence of water to form
carbon disulphide, hydrogen sulphide, alcohols and hydroxides. These pose a risk to health
and of explosions and fire.
Liquid xanthates are considered to offer advantages of reduced fire risk, reduced operator
exposure and of consistent concentration delivered by suppliers. An excess of alcohol
(ethanol, iso-butanol, iso-propanol amyl, etc.) and hydroxide are added in order to stabilize
the xanthate.
Occupational risk exposure scenarios are similar for both solid and liquid xanthates.
However, risk exposures tend to be greater during the storage and mixing stages for solid
xanthates.
Liquid xanthates are in themselves safe to handle, but have a limited shelf life and must be
consumed within a prescribed period (10 to 20 days).







Issued on behalf of the Group Technical Director
This bulletin is published for general information and is not intended as professional advice. As every
situation depends on its own peculiar facts and circumstances, specialist advice should be obtained
where required.
ATD, VOHE Tel: +27 11 638 3045
Administrative Contact: 5
th
Floor, 45 Main Street Fax: +27 11 638 2610
Marshalltown, Johannesburg e-mail: jguthrie@anglo.co.za

2

3 Risks Associated With Xanthates
Xanthates decompose on aging to form a number of byproducts, depending on the pH,
temperature, etc. Fire and explosion risks associated with xanthate are, therefore, a
function of the breakdown of the product or un-reacted raw materials remaining in the
product.
Apart from the corrosive nature of sodium hydroxide and its effect on the skin the main
hazards are from carbon di-sulphide (CS
2
) and from the alcohol.
Carbon Di-sulphide
CS
2
is both a reagent in the manufacture, as well as a decomposition product of xanthates.
It has an extremely low flash point (-27
o
C) and will start to burn with a spark or even a hot
surface in the presence of oxygen. CS
2
is relatively insoluble in water and heavier than
water and, therefore, it will collect in a layer under water. Spills or CS
2
fires in containment
areas, e.g. bunded areas, are therefore easier to manage by the use of water. In other
areas the use of water to extinguish CS
2
fires may lead to spreading of the fire along the
water run-off routes.
CS
2
can be problematic with solid xanthates and storage, particularly if the packaging
becomes damaged. A number of xanthate (CS
2
) fires have been recorded in this regard.
Alcohols
Alcohols are both reagents used in the manufacture, as well as decomposition products of
xanthates. The specific alcohol depends on the xanthate species. The alcohols in question
range from ethyl to amyl alcohol. They have low flash points (about 20
o
C to 50
o
C) and they
burn easily. They also have low vapour pressures and will form explosive mixtures with air
in confined spaces (e.g. the vapour space above the xanthate solution in enclosed tanks).
The ignition of these vapours has also been recorded in the past.
Xanthate Manufacturing
Xanthates are reasonably stable when pure. The production of pure xanthates requires
pure raw materials and then the reaction must also be driven to completion. This requires
sophisticated process design and control of the manufacturing process which, in turn,
influence the price and metallurgical efficiency of the product. Problems in the handling and
use of xanthate have arisen when:
Impure raw materials were used and side reactions occur which do not produce
Xanthate, but other unstable compounds.
The reaction between raw materials (CS
2
, sodium hydroxide and the alcohol) is not
driven to completion and significant amounts of the un-reacted materials are left in the
product. Intermediate, unstable thio compounds are also created and may be left in the
product.
The product degrades into CS
2
and alcohol, either after manufacture in the solid form or
after dissolution before use.
Packaging, transport or storage results in contact of the product with air.




Issued on behalf of the Group Technical Director
This bulletin is published for general information and is not intended as professional advice. As every
situation depends on its own peculiar facts and circumstances, specialist advice should be obtained
where required.
ATD, VOHE Tel: +27 11 638 3045
Administrative Contact: 5
th
Floor, 45 Main Street Fax: +27 11 638 2610
Marshalltown, Johannesburg e-mail: jguthrie@anglo.co.za

3

4 Control of Xanthate Risks
On the basis of the risks highlighted above a number of control measures are
recommended by suppliers and end users for the safe handling of both solid and liquid
xanthates (see reference report for further detail).
Isolation
The separation of people from the hazards of xanthate is achieved by locating xanthate off-
loading, storage and mixing in a separately demarcated area/s of the plant. The
classification of these areas must include standards pertaining to the selection of
instrumentation and electrical equipment for use in hazardous locations (corrosion and
fire/explosion risk).
Design and Engineering Controls
The objective of engineering controls is to minimise the hazards that arise during the
design, construction and operation of facilities. Engineering controls that are generally
implemented for xanthate storage and mixing facilities would include:
A comprehensive specification of the requirements for potentially flammable/explosive
areas such as solid xanthate storage areas and bulk liquid storages.
Comprehensive HAZOP during the design phase to unsure that necessary hazard
assessments are made during the early stages of design. The participation of experts in
the field and suppliers is necessary in these exercises.
Local mechanical forced ventilation systems to ensure that potential
flammable/explosive vapours are removed from the tanks and vented to atmosphere as
per the recommendations of the Material Safety Data Sheet.
Carbon steel is suitable for the fabrication of mixing and storage tanks.
Removal of all potential sources of ignition by appropriate selection of e.g. agitators,
mechanical seals and appropriately rated electrical equipment and instrumentation,
including static electricity.
Comprehensive specification of mechanical, electrical and instrumentation equipment
for use in these areas.
Good ventilation of areas where solid xanthates are stored and mixed.
Bunding of the area to contain spillage.
Tanks to be kept cool to reduce the decomposition rate of xanthate and to limit the
alcohol vapour concentration. The temperature should preferably be below the flash
point of the alcohol used (note iso-butanol in SIBX has a flash point of 28
o
C) and
above 5
o
C where xanthate will crystallise.
Storage and mixing tanks to be designed with conically shaped bottoms that slope
towards the transfer pump suction to facilitate removal of carbon di-sulphide and
sludges that may accumulate at the bottom.
Use of two storage tanks in the case of liquid xanthate deliveries for offloading into one
and drawing from the other. In this way either tank could be emptied and drained of
unwanted build up from time to time.




Issued on behalf of the Group Technical Director
This bulletin is published for general information and is not intended as professional advice. As every
situation depends on its own peculiar facts and circumstances, specialist advice should be obtained
where required.
ATD, VOHE Tel: +27 11 638 3045
Administrative Contact: 5
th
Floor, 45 Main Street Fax: +27 11 638 2610
Marshalltown, Johannesburg e-mail: jguthrie@anglo.co.za

4

Additional engineering controls in place at some Anglo sites include:
Deluge spray systems on storage and mixing tanks
Foam drop systems in the bunded areas.

Safe Work Practices
Safe work practices pertaining to offloading, storage and mixing of xanthate would include:
Restricted access to the area.
Storage of solid xanthates in cool dry places.
Prohibition of all ignition sources e.g. no smoking, no naked flames, etc.
Prompt cleaning of spills and maintenance of good house keeping standards.
Regular drainage and cleaning of tanks (note the requirements for working in confined
spaces and associated risk).
Regular checks on the condition of equipment and maintenance of equipment and
components that may cause a source of ignition or spillage. Maintenance in particular is
considered to be a higher risk and requires special attention.
Avoid dust generation during solid xanthate make-up.
Personnel must be trained and periodically retrained in the hazards associated with
xanthate and the required control procedures implemented.
In the event of an incident /explosion ensure that the area is made safe prior to
investigation. This should include the isolation of potential sources of ignition such as
the agitator.

Disposal
The requirements for the disposal of xanthate (solid or liquid) or degraded products,
spillage, etc. will vary depending on the circumstances. All disposals require special
consideration and reference must be made to the suppliers Material Safety Data Sheet.

Personal Protection
Appropriate personal protection is to be worn when working with xanthates. This equipment
would include respiratory protection, gloves, Safety glasses/goggles and safety shoes rated
to withstand the chemicals involved.
Reference must be made to the manufactures Material Safety Data Sheet for the
specification of emergency treatment and first aid requirements. The facilities generally
specified for chemical installations in this regard should be adequate in most instances.

Reference
The Process, Health, Safety and Engineering Issues Related to the Storage and Use of
Xanthates, I.D Ralston, ATD Report No. PRE-2002-003, May 2002 (available through the
administrative contact below).


5

Disclaimer

As contributors of this information, Anglo American plc or any of its Group
companies or their servants, agents or contractors, (generally referred to as the
Company), are not responsible for any actions (or lack thereof) taken as a result of
the information contained herein and the Company cannot be held liable for any
damages resulting from reliance on or use of this information. Without limiting the
above, as contributors, the Company shall have no responsibility for any act or
omission of any other contributor.

It is recorded that this material is presented for information purposes only, in the
interests of sharing good practice. Whilst the information may be regarded as
indicative of good practice, and effort has been made to ensure that it is accurate,
no representation or warranty, express or implied, is made as to the accuracy,
currency or completeness thereof. It is provided solely on the basis that users will
be responsible for making their own assessments of the information. Users are
accordingly advised to obtain independent advice before acting on the information
contained herein, and to take specific advice from a qualified professional when
dealing with specific situations.

The Company will accordingly not accept any liability for any loss or damage of any
kind whatsoever (including consequential loss), suffered by any person acting in
reliance upon the information, howsoever such loss or damage may have been
caused or sustained. The Company expressly disclaims liability for any such loss or
damage. By accessing the information presented on the terms and conditions
indicated, the user hereby indemnifies and holds the Company harmless against all
such loss or damage.