HYDROGEN PEROXIDE

HANDLING &STORAGE
table of contents
1. Introduction 3
2. Physico-chemical properties 5
2.1 Physical properties
2.2 Toxicological properties
2.3 C hem ical properties
R eactions
O xidant
R eductant
Peroxy com pounds
Addition com pound
2.4 D ecom position properties
Effect of pH
Effect of light
Effect of heat
H om ogeneous decom position
H eterogeneous decom position
Effect of stabilisation
2.5 Effects of decom position
Pressure build up
H eat release and self-heating
Superheated steam
2.6 Spontaneous com bustion of organic
substances
2.7 Explosive characteristics
3. Transportation and packaging 11
R egulations
M arking and labelling
4. Storage 12
Sm all containers and IB C s
ISO tanks
B ulk storage
Site
Tank
Fittings
Piping system
Valves
Pum ps
M easuring tanks
Pretreatm ent
D ispensing from storage
5. Product handling 17
B asic rules
G eneral precautions
D ilution
Transfer into storage
6. Construction materials for storage 18
and handling
U nsuitable m aterials
Suitable m aterials
Alum inium and its alloys
Austenitic stainless steel
Plastic tanks
O ther non-m etals
Lubricants
Pum ps
Valves
G askets
7. Personnel safety instructions 22
Personnel protection
Equipm ent
First aid
8. Some common types of incidents 23
8.1 Em ergency procedures
Leaks
B ulging packages
D ecom position and self-heating
8.2 O ther aspects
C losed valves
N on-vented valves
Pum ping
Fire-fighting
D isposal
9. Further information 26
hydrogen peroxide-
h a n d l i n ga n ds t o r a g e
Introduction
A s part of S olvays declared com m itm ent to R ES P O N S IB LE C A R E

* ,
S O LVAY IN TER O X w orks ceaselessly at m inim ising the risks of its pro d u c t s
to people and the environm ent. These efforts include the provision of m any
d i ff e rent types of inform ation and advice on all aspects of operations. N um e-
rous other activities include inspections, design, analyses and trials.
O ur principle is to w ork in partnership w ith custom ers and others to achieve
our m utual objective of safe and effective peroxygen products.
This m anual presents inform ation on the safety, handling and storage of com -
m ercial solutions of hydrogen peroxide up to 70 % w /w .
O ther safety inform ation available from SO LVAY IN TER O X is listed on page 26
of this m anual.
* RESPONSIBLE CARE

is an international
initiative of the chemical industry aimed at the
continuous improvement of its performance in
the areas of health, safety and the environment.
H ydrogen peroxide has been produced by SO LVAY IN TER O X for m ore
than forty years, and during this tim e m uch experience has been
gained in the handling, storage and use of this im portant industrial
chem ical.
In the early days of its industrial production, the principal use of hydro g e n
peroxide w as as a bleaching agent, but in recent years m any other
applications have been found such as, for exam ple, in chem ical synthesis,
w ater treatm ent, soil rem ediation, environm ental applications, surface
treatm ent of m etals, electronics and disinfection.
O ne of the m ajor advantages of hydrogen peroxide over m ost other
oxidising agents used in industry is that it is non-polluting by itself since
its principal reaction by-product is w ater.
The purpose of this publication is to provide general inform ation and
advice, w hich, if follow ed, w ill help the user to handle and store concen-
trated hydrogen peroxide solutions safely and w ithout incident.
4
2.1. Physical properties
(For a m ore detailed account see SO LVAY IN TER O X D ata M anual on H ydrogen
Peroxide).
H y d rogen peroxide is a clear, colourless, liquid m iscible w ith w ater in any
proportion. Its m olecular w eight is 34.02.
H y d rogen peroxide is m arketed in the form of aqueous solutions and the follow -
ing table show s the principal characteristics of som e of these.
In addition to the D ata M anual, SO LVAY IN TER O X technical services are at the
com plete disposal of custom ers for further clarification of the physico-chem ical
data.
2.2. Toxicological properties
C oncentrations of 5 % W /W and above can cause irritation or burns, w ith the
severity increasing w ith concentration.
Splashes of dilute H
2
O
2
in the eyes cause pain. W ith solutions of 6 % W /W and
a b o v e severe and perm anent dam age m ay occur.
The ingestion of H
2
O
2
can cause burning of the m outh, throat, oesophagus
and stom ach, and internal distension from evolved oxygen. In som e instances,
ingestion of com m ercial strengths can be fatal.
5
2. Physico-chemical properties
H
2
0
2
content g/100 g 3.0 10.0 20.0 27.5 30.0 35.0 50.0 60.0 70.0
H
2
0
2
content at 20C g/100 m l 3.0 10.4 21.4 30.3 33.3 39.6 59.8 74.5 90.2
Volum e of
gaseous oxygen (litre)
given off per litre
of solution at 20C
(0C and 760 m m
H g or 101,325 kPa) I/I 10 34 71 100 110 130 197 246 298
Active oxygen
content g/kg 14.1 47.0 94.1 129.3 141.1 164.6 235.2 282.2 329.2
Freezing point C -1.6 -6.4 -14.6 -22.6 -25.7 -33.0 -52.2 -55.5 -40.3
B oiling point at
101.325 kPa
(760 m m H g at 0C ) C 100.4 101.5 103.6 105.5 106.3 107.4 113.9 119.0 125.5
D ensity at
0C kg/dm
3
1.012 1.039 1.080 1.112 1.123 1.144 1.211 1.258 1.307
25C kg/dm
3
1.007 1.032 1.069 1.098 1.108 1.128 1.191 1.236 1.284
50C kg/dm
3
0.997 1.020 1.055 1.082 1.091 1.110 1.171 1.214 1.260
% W /V
% W /W
Effect on the skin
Effect on the eyes
Effect of ingestion
Inhalation of H
2
O
2
vapours or m ists is irritating to the respiratory tract. The
occupational exposure lim it (TLV) is 1.0 ppm (1.4m g H
2
O
2
/m
3
air) for a norm al
8 hour/day and 40 hour/w eek w orking period.
For further inform ation see the current SO LVAY IN TER O X M SD S.
First aid: (See page 22)
2.3. Chemical properties
H ydrogen peroxide reacts :
- as an oxidant
- as a reductant
- to form other inorganic and organic peroxy com pounds
- to form addition com pounds
Exam ples of such reactions are:
2.4. Decomposition properties
A further type of reaction is its decom position to w ater and oxygen represented
as:
This can occur under various conditions w hich are identified hereafter.
In alkaline solution, the rate of decom position increases rapidly as the pH is
increased.
Hydrogen peroxide and alkali must never be
inadvertently mixed.
6
Effect of inhalation
First Aid
R eactions
O xidant
R eductant
Peroxy com pounds
Addition com pound
Effect of pH
Light can cause photochem ical decom position of hydrogen peroxide. The
absorption of radiation by hydrogen peroxide solutions occurs over a w ide
continuous spectrum . H ydrogen peroxide solutions should not therefore be
exposed for long periods to light, especially direct unfiltered sunlight.
Apart from self-heating as a result of decom position, consideration m ust be
given to the effect of tem perature rises caused by outside sources of heat.
For purely physico-chem ical reasons, the rate of the decom position reaction in
solution (hom ogeneous) w ill increase 2 to 3 tim es for every 10C increase in
t e m p e r a t u re , and the rate of the surface decom position (heterogeneous) w ill
increase 1 to 2 tim es per 10C . The effect of increased contam ination from
dissolution of the surface can of course m ake the situation w orse.
Protect hydrogen peroxide from direct heat.
H ydrogen peroxide as produced by SO LVAY IN TER O X is very pure and the
decom position rate to w ater and oxygen is norm ally very low . H ow ever, if the
hydrogen peroxide becom es contam inated e.g. w ith salts of m etals such as
iron, copper, chrom ium , vanadium , tungsten, m olybdenum , silver and m etals
from the platinum group, then fast decom position to w ater and oxygen m ay
follow . This is know n as hom ogeneous decom position. The m ost active
decom position catalysts are those giving m ultivalent ions. Fast decom position
can often be caused by extrem ely low levels of contam inants, for exam ple a
few parts per m illion. This decom position is a chain reaction in w hich the m etallic
ions are successively oxidised and reduced. This explains w hy it is possible for
sm all am ounts of catalyst to cause extensive decom position of H
2
O
2
.
In addition, the effect of pH on the rate of decom position of contam inated
hydrogen peroxide is very m arked, even in acid m edium .
Fast decom position m ay also occur if the hydrogen peroxide is brought into
contact w ith insoluble solids. This is know n as heterogeneous decom position.
H ydrogen peroxide w ill decom pose to som e extent on any surface even at
am bient tem perature, although the rate varies enorm ously w ith the nature and
state of the surface. Thus, the rate of decom position on silver is 10
7
tim es faster
than that, for exam ple, on polyethylene, w hich is one of the com m on handling
m aterials. Som e of the solids w hich catalyse the decom postion of hydrogen
peroxide are the hydroxides and oxides of the heavy m etals, as w ell as t h e
noble m etals them selves. The follow ing is a list of the m ost active catalysts :
7
Effect of light
Effect of heat
H om ogeneous
decom position
H eterogeneous
decom position
R uthenium oxide R uO
4
Platinum Pt
M anganese oxides M n
2
O
3
, M nO
2
O sm ium O s
Iron oxides FeO , Fe
2
O
3
Iridium Ir
C obalt oxide C oO Palladium Pd
N ickel oxides N iO , N i
2
O
3
R hodium R h
Lead oxide and hydroxide PbO , Pb(O H )
2
Silver Ag
M ercuric oxide H gO G old Au
8
These are m ost active w hen their specific surface is large as w ith, for exam ple,
colloids and pow dered m etals. D ue to their high activity, som e of the m etals and
oxides in the above tables are used as catalysts w hen rapid decom position is
required in the use of hydrogen peroxide as a pow er source, as, for exam ple, in
rocket m otors. In addition even com patiblem aterials of construction can cause
accelerated decom position if the surface is of inadequate quality or has not
been properly prepared.
Never allow hydrogen peroxide to become contaminated.
Bring hydrogen peroxide into contact only with
SUITABLY PREPARED compatible materials.
S O LVAY IN TERO X adds stabilisers to keep decom position to a m inim um . These
are generally of tw o types, com plexing/chelating, and colloidal, w hich either
neutralise sm all am ounts of colloidal catalysts or adsorb/absorb im purities.
2.5. Effects of decomposition
Even at low dilutions, hydrogen peroxide w ill decom pose continuously into
w ater and oxygen. This rate is very low w hen hydrogen peroxide is stored in
approved m aterials and is kept free from contam inants. H ow ever, if oxygen
pressure is not relieved, then high gas pressure m ay build up.
Never store hydrogen peroxide
in hermetically sealed containers.
The decom position of hydrogen peroxide is exotherm ic and also the rate of
decom position increases w ith increasing tem perature. If the heat of decom -
position is not rem oved at the rate at w hich it is developed (by heat loss to the
surroundings or cooling), the tem perature w ill rise and the rate of decom posi-
tion w ill increase. This can result in a self-accelerating decom position w hich, in
the case of badly contam inated solutions, m ay culm inate in extrem ely rapid
decom position or boil off.
Keep the temperature of a storage tank under surveillance.
Even after the total decom position of solutions containing up to 64 % W /W
h y d ro g e n peroxide, liquid w ater is still present. B ecause of this, the final tem -
perature cannot exceed the boiling point of w ater at the pressure of the sys-
tem . B ut under adiabatic conditions the total decom position of solutions con-
taining over 64 % W /W develops sufficient heat to evaporate all the w ater to
steam and superheat it. For exam ple, if decom position is com plete, and there
a re no heat losses (i.e. adiabatic), 70 % W /W hydrogen peroxide can reach a
tem perature of 240C (513 K). O ne volum e of 70 % W /W solution, w hen
decom posed totally under adiabatic conditions and atm ospheric pressure, w ill
produce about 2,500 volum es of gas (see diagram on page 9).
Design of tanks should allow for adequate venting
capacity to permit gases and vapours to escape
in case of serious decomposition.
H eat release
and self-heating
Superheated steam
Effect of stabilisation
Pressure build up
9
Volume Expansion Ratio on Total Adiabatic
Decomposition of Liquid at Constant Pressure
and Initial Temperature of 20C (293.15 K)
Calculated using data from Gigure, Morisette, Olmos & Knop, Can. J . Chem., 1955, 33,804-820; National
Bureau of Standards, Circular 500; and ideal enthalpy data from National Bureau of Standards, Circular 564.
H
2
O
2
concentration, % W /W
760 m m H g (0.101325 x 10
6
Pa)
15200 m m H g (2.0265 x 10
6
Pa)
25840 m m H g (3.44505 x 10
6
Pa)
2584m m H g (0.344505 x 10
6
Pa)
10
2 . 6 . Spontaneous combustion of organic substances
H ydrogen peroxide can cause spontaneous com bustion of m any organic
m aterials, such as cloth, paper, w ood, etc. Even dilute com m ercial solutions
can concentrate by evaporation and spontaneous com bustion m ay occur after
a delay period. This effect is com m on in hot clim ates.
Spilt hydrogen peroxide must never be allowed to
evaporate but must be diluted with water immediately.
2.7. Explosive characteristics
C o m m e rcial hydrogen peroxide solutions up to 70 % W /W are not in them selves
explosive.
H o w e v e r, explosions m ay occur under certain conditions w hen aqueous hydro g e n
peroxide of m ore than 44 % W /W is m ixed w ith organic com pounds to form a
single phase, em ulsion or suspension. The m ost im portant factors w hich
govern w hether or not an explosion occurs are:
a ) the concentration of hydrogen peroxide, w ater and organic m aterial pre s e n t ,
b) the nature of the organic m aterial,
c) the presence of an initiation source,
d) the tem perature of the m ixture.
This hazard can occur w hen using H
2
O
2
even at less than 44 % initial concen-
tration, if there is a potential for the concentration to subsequently increase,
e.g. by w ater evaporation.
In addition, hydrogen peroxide reacts w ith certain organic com pounds to form
organic peroxides w hich m ay them selves have explosive properties. Explosions
m ay also occur if hydrogen peroxide is brought into contact w ith certain incom -
patible inorganic m aterials such as pow erful reducing or oxidising agents.
D ecom position of hydrogen peroxide can lead to oxygen enrichm ent of the
a t m o s p h e re above it. U nder certain conditions, e.g. in the presence of flam m able
liquids or flam m able gases, this can lead to a high risk of fires or vapour phase
explosions.
Investigation of new applications involving hydrogen
peroxide and other chemicals should be carried out on a
small scale, with adequate precautions taken for dealing
with uncontrolled and potentially explosive reactions.
If you are in doubt about the safety of your hydrogen
peroxide application, then consult SOLVAY INTEROX.
11
R egulations place various constraints on the w ay in w hich hydrogen peroxide
solutions can be packed, transported and handled.
It is essential that every person responsible for the transport and handling of
these solutions should ensure com pliance w ith the relevant regulations. For
instance, under no circum stances should hydrogen peroxide be sent via m ail
or courier services.
Transport regulations are prim arily concerned w ith the nature and m arking of
containers, loading m ethods, vehicle equipm ent, transport docum ents, etc.
M any countries have signed international agreem ents concerning the various
m eans of transportation and these agreem ents apply if transportation takes
place over the territory of at least tw o of the contracting countries.
These agreem ents include
R ID - International regulations concerning the carriage of dangerous goods
by rail; form ing Annex 1 of the International C onvention concerning the
carriage of goods by rail (C .I.M .).
AD R - European agreem ent concerning the carriage of dangerous goods by
road, draw n up by the U N Econom ic C om m ission for Europe.
IM O - I n t e rnational M aritim e D angerous G oods code, draw n up by the
IN TER N ATIO N AL M AR ITIM E O R G AN ISATIO N .
IC AO -Technical Instructions for the Safe Transport of D angerous G oods draw n
up by the IN TER N ATIO N AL C IVIL AVIATIO N O R G AN ISATIO N .
N ational regulations m ay differ from one country to another, and are being re v i s e d
continuously. C ustom ers w ho w ish to transport
hydrogen peroxide w ithin particular national
boundaries should refer to the national regula-
tions w hich are applicable.
M any countries have draw n up regulations on
m arking, labelling and packaging of dangerous
substances w ithin the fram ew ork of safety at
w ork regulations. R eference should be m ade to
national provisions on this subject.
The European U nion m em ber states have adop-
ted directive 67/548/EEC , brought up to date
regularly, w hich defines the form and nature of
m arkings relating to the product, the m anufactu-
rer, the risks of the product and advice on pre-
cautions to be taken.
3. Transportation and packaging
R egulations
R ail transport
R oad transport
Sea transport
Air transport
M arking and labelling
12
4. Storage
Sm all containers
and IB C s
H y d rogen peroxide can be delivered in sm all packs, in interm ediate bulk c o n t a i n-
ers (IBC s) or in bulk quantities by rail, road tankers, or in ISO tank containers.
Sm all containers and IB C s should be stored unopened, in an upright position
and taking account of good w arehousing practice w ith respect to stacking
height. The breather vents m ust not be blocked. Storage should be such that
faulty containers can be easily detected and rem oved. They m ust never be ro l l e d
or laid on their side. They m ay be stored in a building w ith a concrete floor
slightly inclined tow ards drainage and designed in the form of a shallow sum p
about 10 cm deep and w ith a sm all drive-on ram p to the threshold. The storage
area should norm ally be unheated and adequate ventilation ensured. Although
heat sources are to be avoided, in certain circum stances such as extrem e
clim atic conditions, heating m ay be required, but H
2
O
2
containers m ust not be
placed unduly close to sources of heat. C ontainers m ay be stored outside,
preferably protected from direct sunlight. A canopy m ay be required in hot,
sunny clim ates. The storage area m ust be kept clean and free from com bustible
m aterials and other incom patible chem icals. A w ater hose should be available
for flushing aw ay spillages and leaks to a safe place. A safety show er and an
eye bath should be provided for treatm ent of personnel w ho com e into bodily
contact w ith hydrogen peroxide. Pipelines, especially those carrying chem icals,
m ust not pass through the storage area.
R eturnable em pty containers should be kept closed and clean and returned to
the storage area as soon as possible. They should not be w ashed out except
w ith non-contam inated w ater.
Hydrogen peroxide containers must never be used
for the storage of other materials.
13
ISO tanks
B ulk storage
In addition to local regulations for storage on site, S O LVAY IN TERO X re c o m m e n d s
a contained concrete area w ith drain. The storage area, preferably outdoors,
m ust generally conform to agreed standards of accessibility and cleanliness.
Particular care should be taken to ensure that the ISO tank cannot be dam aged
by passing vehicles.
C are m ust also be taken to ensure that the m anhole is kept closed, to avoid
sources of contam ination. The breather vent m ust not be blocked or obstruc-
ted, otherw ise overpressurisation can occur.
ISO tanks m ust never be w ashed out or used for the storage of other m aterials
or for any other purpose.
If there are any doubts about procedures
with ISO tanks,
SOLVAY INTEROX should be consulted.
W ith an annual usage re q u i rem ent of, say, 50 tonnes or m ore of hydrogen pero x i-
d e solution, it m ay becom e econom ical to construct a bulk storage unit.
H
2
O
2
storage tanks com prise num erous specific design features and fittings.
Sim ilarly, associated pipew ork, pum ps, ancilliary equipm ent and instrum ents
are highly specific to H
2
O
2
.
O ther im portant considerations are the layout and installation, w hich require
expert advice. Factors such as statutory requirem ents, tank location, correct
m aterials of construction, and preconditioning of equipm ent to receive hydro g e n
peroxide are also im portant.
We strongly recommend that customers planning
a storage unit consult SOLVAY INTEROX.
14
An engineering code of practice and designs for standard tanks of various
sizes have been developed by SO LVAY IN TER O X.
The site should be chosen so as to avoid contam ination and contact w ith
incom patible chem icals, and yet be convenient to the areas of usage. It is
preferable, in the interest of safety, that the storage vessel be outdoors. An
adequate w ater supply m ust be available for eye baths, safety show ers and
norm al w ashing dow n, and w here appropriate this should be frost protected.
For em ergency flooding non-contam inated w ater should be used. W here there
is a risk of public access, security fencing and clear m arking are required.
The size and m aterial of the tank should be discussed w ith SO LVAY IN TER O X.
Features for horizontal and vertical m etal storage tanks are show n on these
tw o pages.
It is essential that the tanks be built only by firm s w hich are able to m eet the
highly specific requirem ents for producing com patible high integrity tanks and
fittings.
The m inim um equipm ent for a hydrogen peroxide storage tank includes a com -
bined m anhole and em ergency vent, a breather vent w ith filter, an overflow p i p e
w ith dow ncom er, a level indicator, a filling connection, a hydrogen peroxide outlet,
a tem perature indicator, drain valve and a bund.
Site
Tank
Fittings
Typical features for a hydrogen peroxide tank
(basic equipment)
1. Manhole and emergency vent
2. Overflow pipe with downcomer
3. Level indicator (with alarm)
4. Filling connection
5. Hydrogen peroxide outlet
6. Bund
7. Vent with filter
8. Temperature indicator
9. Drain valve
10. Watersupply for
shower, eyewash
or spillage dilution
15
Additional features include level indicator and tem perature indicator alarm s.
These are recom m ended for safety reasons. Som e tanks are also fitted w ith a
dilution connection and a m ixing device. Alarm sw itches and therm om eters m u s t
not be of the m ercury type, and no oil should be used in the therm ocouple w ell.
The manhole cover assembly should be adequate
to provide relief in case of decomposition
(recommended minimum surface area is 200cm
2
per tonne of 100 % hydrogen peroxide).
It is desirable that m anholes be fitted w ith a loose alum inium or stainless steel
w ire m esh cover to prevent large objects such as inspection torches, safety
helm ets, tools and spectacles falling into the tank.
If tanks are fitted w ith an em ergency flooding connection, care m ust be taken
to ensure that it cannot provide a source of contam ination. The point of
connection to the em ergency w ater supply should be located to allow w ater
introduction during a decom position w ithout risk to personnel.
Tanks should be surrounded by a retaining w all or bund w hich is capable of
containing at least the w hole content of the tank in case of rupture, and in any
case com ply w ith local regulations.
C atw alks and rails are not show n, but should be included w here necessary.
The tank should be labelled as required (e.g. w arning signs, product nam e and
concentration) and the tanker coupling should also be clearly m arked, to
prevent delivery of a different substance w hich could be extrem ely dangerous.
Typical features for a hydrogen peroxide tank
(fully equipped)
1. Manhole and emergency vent
2. Overflow pipe with downcomer
3. Level indicator (with alarm)
4. Filling connection
5. Hydrogen peroxide outlet
6. Bund
7. Vent with filter
8. Temperature indicator (with alarm)
9. Spare branch
10. Sparge (optional)
11. Drain valve
12. Water connection
16
Piping system
Valves
Pum ps
M easuring
Pretreatm ent
D ispensing from storage
All transfer lines should be self-draining. Preferably the lines should not pass
over w ooden floors or other com bustible areas. Particular care should be taken
to prevent the liquid in the receiving vessel being returned into the upstream
pipew ork and storage tank by siphoning or any other m eans. A siphon breaker
m ust be fitted if such an event is considered to be a possibility. Flange bolts
and gaskets should not be greased.
M inim ize the num ber of valves although m ore than one valve is usually neces-
sary on the outlet system s of static storage tanks, and arrangem ents to pre v e n t
pressure build up betw een valves m ust be m ade. O nly valves that are capable
of venting gas should be used (see page 20). Valves located in the bund
should be installed so that they can be reached from outside the bund.
The design should avoid any possibility of pum ping against a dead end (see
pages 20 and 25).
Trapping of hydrogen peroxide between valves
and in pumps must be avoided.
The flow of hydrogen peroxide from large storage vessels m ay be m easured in
a num ber of w ays, for exam ple, via a dynam ic flow m eter or m easuring tanks.
These arrangem ents should be discussed w ith SO LVAY IN TER O X w hen the
installation is designed.
The cleaning and passivation of m etallic tanks and all other com ponents of these
installations is a specialist operation and should be discussed w ith SO LVAY
IN TER O X.
Sm all containers m ust not be em ptied by pressurising them . They m ay be
em ptied by pouring, siphoning or pum ping out.
ISO tank containers are usually equipped w ith a top discharge. They can be
em ptied by a pum p or by pressurising the container in accordance w ith the
suppliers instructions. The gas (either com pressed air or nitrogen) m ust be
clean and free from oil.
17
B asic rules
Transfer into storage
D ilution
G eneral precautions
5. Product handling
H ydrogen Peroxide should only be handled by trained personnel w ho are w ell
aw are of its hazards and the necessary safety precautions.
H ydrogen peroxide should be handled w ith care so that no product is spilled
during unloading or transfer. If spillage does occur, it m ust be diluted w ith w ater
and cleaned up thoroughly, ensuring that all cleaning equipm ent is thoroughly
rinsed after use.
H ydrogen peroxide should be kept in its original container. H andling and trans-
ferring m ust be done only w ith approved dedicated equipm ent m ade of com -
patible m aterial (see section 6). O nce hydrogen peroxide has been draw n from
a storage container, it m ust not be returned since it m ay have becom e conta-
m inated.
H ydrogen peroxide m ust be kept aw ay from heat sources. H ydrogen peroxide
should not be contam inated during storage and handling, and contact w ith
incom patible surfaces m ust be avoided. Scrupulous cleanliness is required
w hen handling solutions of hydrogen peroxide.
Apart from dilute products sold generally in sm all packs, com m ercial solutions
of hydrogen peroxide present little or no risk of freezing in tem perate clim ates
and thus no special protection against frost needs to be taken, except in extre m e
clim ates (See page 5, section 2.1., for freezing points).
D ilution w ater (even som e tapw aters) m ay destabilise H
2
O
2
.
S O LVAY INTEROX should be consulted when hydro g e n
p e roxide is to be store dat a low concentration
after dilution by the user.
All tanks and sm all packages should be m aintained in an upright position
during the transfer operation and should not be jolted violently. N eglect of these
sim ple rules can lead to spillages, w hich m ay subsequently give rise to hazard-
ous situations.
18
U nsuitable m aterials
Suitable m aterials
Austenitic stainless steel
Alum inium and its alloys
6. Construction materials for storage and
handling of hydrogen peroxide
The selection of m aterials of construction for equipm ent to be used in service w ith
hydrogen peroxide m ust be undertaken w ith care, otherw ise decom position
problem s w ill be encountered.
In cases of doubt, assume incompatibility.
The inform ation given below m ay not apply to special grades of hydrogen
peroxide; for these SO LVAY IN TER O X should be consulted.
M any com m on m aterials of construction such as iron, steel, copper, brass, nickel
and chrom ium are not suitable for handling solutions of hydrogen peroxide,
and recom m ended m aterials m ust be used.
Suitable grades of m etals for service w ith hydrogen peroxide are indicated below .
Alum inium of 99.5 % m inim um purity and certain Al-M g alloys can be used for
long duration storage of concentrated hydrogen peroxide, but they are expensive
and difficult to fabricate. SO LVAY IN TER O X hydrogen peroxide, as delivered,
w ill not significantly corrode alum inium over long periods, and the corrosion
products do not seriously affect the stability of the chem ical. H ow ever, in the
presence of chloride ions, serious pitting can occur, so contam ination w ith
chlorides from , for exam ple, dilution w ater m ust be avoided.
For fabrication w ork, argon shielded arc w elding m ethods are used w ith rods of
parent m etal, w ith care taken to avoid im pressing im purities into the soft m etal.
It is essential to use only approved fabricating com panies.
Fully austenitic stainless steels m ay be used in service w ith hydrogen peroxide,
including storage. H ow ever, it m ust be em phasised that special care is needed
w ith finishing and treatm ent of surfaces, w elding, and stabilisation system s
because, if corrosion should occur, the corrosion pro d u c t s w ould be pow erful
catalysts for hydrogen peroxide decom position. The pre f e r re d grade of stainless
steel for storage and transport vessels is 304 L, 316 L. Equivalents w hich
conform to the alloy com position are also acceptable.
W elding quality and surface finishing are very im portant, and pre-polished plate
is preferred. The w elding should be by inert gas shielded processes. M etal inert
gas (M .I.G .) is preferred. If other processes are to be used, consult SO LVAY
IN TER O X first. All w elds and w eld splashes should be ground and polished to
m atch the surface finish of the plate.
19
SO LVAY IN TER O X have developed detailed engineering codes and specifica-
tions covering the fabrication of hydrogen peroxide storage equipm ent. Advice
and assistance are available on request.
M etallic m aterials have contam inants loosely adhering or som etim es em bedded
in the surface, and before being used in service w ith hydrogen peroxide they
m ust be subjected to som e, if not all, of the follow ing processes: cleaning and
degreasing w ith detergent, pickling to rem ove m etal and im purities, passivating
and conditioning.
C ustom ers should consult SO LVAY IN TER O X concerning the precise details of
these treatm ents.
Plastic tanks are suitable for up to 50 % W /W hydrogen peroxide provided they
are m ade of correct polym eric m aterial.
They are subject to em brittlem ent, environm ental stress cracking and ageing.
They are m ore susceptible to physical dam age than alum inium or stainless steel
tanks. Their physical properties can be seriously affected by extrem es of am bient
t e m p e r a t u re, and it is difficult to obtain satisfactory quality control during fabrication.
C ustom ers should consult SO LVAY IN TER O X concerning the design character-
istics of plastic storage tanks and the type of plastic used.
Piping from plastic tanks m ay be in alum inium or stainless steel.
Som e fluorinated plastics and rubbers can be used in service w ith hydrogen
peroxide, for exam ple, polytetrafluoroethylene, polyvinylidene fluoride such as
Solvay SO LEF

, and a co-polym er of vinylidene fluoride and hexafluoro p ro p y l e n e

*
Plastic com patibility can be grade dependent betw een suppliers, and the nature
of fillers, pigm ents and other additives is im portant.
W hite chem ical porcelain and borosilicate glass are both com patible w ith hydro-
gen peroxide and are w idely used for sm all scale laboratory apparatus. D ue to
the risk of breakage, these m aterials are not generally recom m ended for large
scale apparatus or plants.
M ost com m on lubricants are incom patible w ith hydrogen peroxide because
they can form hazardous peroxide/organic m ixtures. This problem m ay be
overcom e, for exam ple, by using fluorinated oils, but then these oils tend to be
poor lubricants.
* Reg. US trademark, E.I. du Pont de Nemours
Plastic tanks
O ther non-m etals
Lubricants
C om patible m aterials of construction m ust be used for all contact surfaces and
all non-contact surfaces w here exposure is both foreseable and dangerous.
SO LVAY IN TER O X does not recom m end the use of pum ps w ith packed glands
but instead advises the use of pum ps w ith m echanical seals. The use of seal
faces of ceram ic on the one side and glass or ceram ic filled PTFE on the other
is advised.
The recom m ended m aterial of construction for pum ps is austenitic stainless steel
(304L or 316L), although PTFE pum ps are acceptable. In diaphragm pum ps, a
pressure burst m ay occur if the diaphragm fails. O n such pum ps, provision
should be m ade for pressure relief on the non-peroxide side of the diaphragm .
For high strength hydrogen peroxide, i.e. above 50 % W /W , the use of double
diaphragm s w ith com patible buffer fluid and leak detection is advised.
SO LVAY IN TER O X recom m ends ball-valves w ith suitable venting arrangem ents
for releasing potential pressure build-up from the decom position of hydrogen
peroxide trapped in the valve. D iaphragm valves can be dangerous if hydrogen
peroxide gets into the bonnet, and hence the valve bonnets m ust be drilled.
Plug-type valves need a lubricant, and therefore SO LVAY IN TER O X does not
advise the use of this type of valve.
Acceptable valves have a seat, usually polytetrafluorethylene, and a sm all hole
drilled in the ball so that in the off position the channel through the ball is in
com m unication w ith the shut-off higher pressure side.
G askets m ay be m ade from polyethylene or polytetrafluoroethylene (PTFE).
C o m p ressed asbestos fibre (C AF) gaskets m ay only be used in a PTFE envelope.
Pum ps
G askets
Valves
D iaphragm valve w ith sm all hole drilled in the bonnet.
Valve w ith sm all hole drilled in ball.
20
hydrogen peroxide
solution containing up to 70% wt/wt hydrogen pero x i d e
warning
Strong oxidant.
Can cause eye damage and skin burns.
Reacts with many substances generating heat with fire risk.
Can decompose generating gas with risk of bursting.
Always have an adequate supply of water readily available.
recommended practice
Wear safety goggles and gloves. If there is a
splashing risk w ear face shield, plastic apron and
boots.
Have eye bath available and safety showers
if possible. Ensure there is adequate ventilation
w here peroxide vapours m ay occur.
Have water hoses available for fire fighting.
W ash spilled peroxide aw ay from handling and
storage areas w ith plenty of w ater.
Store in original container in a cool place.
Keep containers upright.Ensure vents rem ain
effective.
Keep storage area free of combustible
materials. U se it for peroxide storage only.
Use clean vessels and equipment
constructed from compatible materials.
Em pty all utensils and drain equipm ent after use.
W ash out w ith w ater.
Ensure that peroxide does not become
contaminated. D o not return unused product to
original container. D ilute it w ith plenty of w ater and
flush to drain.
Wash contaminated materials at once.
O n no account allow them to dry out before
rinsing (e.g. clothing).
Use only vessels or containers fitted with a
safety vent in operable condition. D o not confine
peroxide in any enclosed spaces (e.g. betw een
closed valves).
emergencies
contact with skin
W ash affected skin w ith plenty of water.
R em ove contam inated clothing im m ediately.
In case of burns or shock, seek m edicalattention.
contact with eyes
W ash out im m ediately w ith plenty of water.
C ontinue w ashing for at least 15 m inutes.
Seek m edicalattention.
leak or spill
D rench withwater. W ash the liquid off allcontam inated
surfaces w ith plenty of w ater.
D o not absorb in saw dust or other com bustible m aterials.
D o not attem pt to recover spilled liquid.
fire
D rench with wateronly. D o not use foam or dry chem ical
e x t in g u is h e r s .
Keep adjacent containers coolby spraying w ith w ater.
W ear a fire-suit equipped w ith independent bre a t h in g
apparatus before entering the contam inated zone.
ingestion
Drink plenty of water.
Seek m edical attention.
inhalation
Move the victimout into the fresh air - w ear an
independent breathing apparatus.
In case of suffocation, seek m edicalattention.
Allinform ation in this docum entis given
in good faith and from bestknow ledge available.
N ationalorlocalregulations m ustalw ays be applied.
E m e rgency telephone No:
00/44/1925/31 200
For detailed inform ation please apply to:
S OLVAY INTEROXLIMITED
B a ronetWorks - Baronet Road
GB - Warrington (Cheshire)WA4 6HB
Tel : 44 /1925 /651 277
Fax : 44 /1925 /655 856
Telex : 0151 /627 834 SOLIXG
WAT E R
7. Personnel safety instructions
See the SO LVAY IN TER O X-H ydrogen Peroxide Safety D ata Sheet (M SD S) for
further inform ation.
The m ost im portant safety points m entioned in this section have been sum -
m arised on the SO LVAY IN TER O X H ydrogen Peroxide Safety Poster w hich is
available on request.
As a m inim um , personnel handling hydrogen peroxide m ust w ear long-w risted
plastic gloves and suitable eye protection. PVC aprons are also recom m ended.
If there is any risk of splashing, then a protective face m ask, full body protec-
tion, and suitable boots m ade of polyvinylchloride or rubber m ust be w orn.
Pipetting of com m ercial solutions should be done m echanically and not by
m outh.
Eye w ash bottles and show ers m ust be available in sufficient num ber in the
storage and w orking areas.
T h e e ffe c t o f h yd ro g e n p e ro x id e so lu tio n s o n ski n a n d m u c o u s m e m b ra n e s
d e p e n d s o n th e c o n c e n tra tio n , b u t i n c re a se s a lso a s a fu n c tio n o f th e tim e
o f c o n ta c t. H e n c e , th e first im m e d ia te ac tio n in th e e ve n t o f an y skin c o n ta c t
with h yd ro g e n p e ro x id e is re p e a te d rin sin g o f th e a ffe c te d a re a with c le a n
wa te r.
I n c a se o f sp la sh e s in th e e ye , th e o p e n e d a ffe c te d e ye m u st b e rin se d
with c le a n wa te r, in itia lly with a n e ye wa sh b o ttle . R in sin g m u st b e d o n e
im m e d ia te ly a n d c o n tin u o u sly fo r a t le a st 1 5 m in u te s a fte r wh ic h m e d ic a l
a d vic e sh o u ld b e o b ta in e d .
A n y c lo th in g wh ic h h a s b e e n in c o n ta c t with h yd ro g e n p e ro x id e m u st b e
im m e d ia te ly d re n c h e d with wa te r. Wh e n la rg e a re a s o f c lo th in g h a ve b e e n
we tte d with h yd ro g e n p e ro x id e , it is re c o m m e n d e d th a t th e c lo th in g b e
re m o ve d u n d e r a ru n n in g sh o we r a n d th e n rin se d th o ro u g h ly. N e ve r le t
h y d ro g e n p e ro xi d e -c o n ta m in a te d c lo th in g d ry with o u t wa sh in g s in c e th e re
m a y b e a risk o f sp o n ta n e o u s ig n itio n a t a la te r tim e . S p illa g e o n to o r in sid e
sh o e s is e sp e c ia lly d a n g e ro u s.
I n c a se s o f a c c id e n ta l in g e stio n , it is re c o m m e n d e d th a t c o p io u s
a m o u n ts o f wa te r b e d ru n k , a n d th a t vo m itin g N O T b e in d u c e d . M e d ic a l
a d vic e m u st b e so u g h t.
F re sh a ir is th e b e st a n swe r to re sp ira to ry irrita tio n c a u se d b y h yd ro g e n
p e ro x i d e . A n u n c o n sc io u s p e rso n s h o u ld b e b ro u g h t in to th e o p e n .
R e s c u e r s sh o u ld we a r su ita b le a ir-m a sk s if n e c e ssa ry. M e d ic a l a d vic e
m u st th e n b e so u g h t.
Personnel protection
First aid
Equipm ent
22
23
8. Some common types of incidents
If the precautions outlined in the previous sections are follow ed, then incidents
or accidents w ith hydrogen peroxide are unlikely to occur. H ow ever, it m ay be
helpful to the user to know w hat types of incident m ay arise and how best to
deal w ith them . The single m ost im portant requirem ent is to have preplanned
em ergency procedures. SO LVAY IN TER O X can help in defining these.
Personnel called upon to deal with incidents must wear
suitable protective equipment.
8.1. Emergency procedures
Sm all containers used by SO LVAY IN TER O X are usually of polyethylene and of
a capacity of 25-60 litres. A container m ay leak because it has been subjected
to unduly high m echanical stress such as, for exam ple, by being stacked w ith
too heavy a top loading, or being subjected to a severe m echanical blow from
a crane or fork-lift truck. Alternatively the container m ay have been punctured
by a nail or a sharp protrusion.
The container m ay also leak because it has been tipped over so that the bre a t h e r
vent is covered by liquid. In this position liquid w ill escape through the vent if
there is any slight rise in pressure in the container.
As soon as a leak is discovered it must be
dealt with promptly.
If the container is sim ply leaking through its vent as a result of having been tipped
on its side, then the only action re q u i red w ill be to re s t o re it to a vertical position
and to w ash the outside of the container and the surrounding area w ith
copious quantities of w ater.
If the container is obviously dam aged, the contents should be diluted w ith large
quantities of w ater and run to a safe draining location for disposal.
W hilst leaks in pipeline flanges and in ancillary equipm ent, such as pum ps, m ay
occur from tim e to tim e, leaks in the w all of static storage tanks are exceedingly
rare.
If the leak is large and serious, and cannot be safey stopped by isolating valves,
then copious am ounts of w ater should be directed into the affected area.
C are should be taken to introduce a m inim um of contam ination during repairs.
It is essential that the re p a i red section be properly cleaned and passivated before
being put back into service.
Sm all container leaks
Storage tanks leaks
24
D ecom position
and self-heating
If a plastic container appears to be bulging then this is an indication of high
internal gas pressure. This m ay occur after very long storage w ith a blocked or
faulty vent. Alternatively, it m ay be the result of excessively high decom position
taking place. In such an event the container w ill at first start to bulge and m ay
eventually rupture. A situation such as this m ust, therefore, be treated w ith
extrem e caution.
The container should not be approached except by com petent personnel w ho
are w earing full protective clothing.
T h e u ltim a te risk is a vio le n t b u rstin g o f th e c o n ta in e r a n d wid e sp re a d
e je c tio n o f liq u id . T h e first ste p is to a sse ss th e situ a tio n fro m a sa fe lo c a -
tio n . A n y o f th e fo llo win g in d ic a tio n s sh o u ld b e c o n sid e re d a s a sig n o f
d a n g e r, in wh ic h c a se n o b o d y sh o u ld a p p ro a c h th e p a c k a g e .
- n o ise e . g . g a s e sc a p in g ;
- visib le sig n s o f a d va n c e d d e c o m p o sitio n e . g . ste a m , liq u id e sc a p e fro m
ve n t;
- se ve re d iste n sio n o f th e p a c k a g e ;
- in c re a sin g e x te n t o f d iste n sio n .
In th e a b se n c e o f a n y o f th e a b o ve in d ic a tio n s th e n a tra in e d , fu lly p ro t e c t e d
p e rso n m a y a p p ro a c h a n d c a re fu lly re m o ve th e c a p wh ic h m a y in itse lf
re su lt in a n e m issio n o f liq u id ) . I f a n y o f th e d a n g e r sig n s d e ve lo p , th e
c o n ta in e r m u st b e a b a n d o n e d . I f th e re a re sig n s, b u t th e situ a tio n
re m a in s u n c h a n g e d fo r a p e rio d o f 1 d a y, th e n th e p a c k sh o u ld b e sp ra y e d
with wa te r, b e fo re re m o vin g th e c a p a s a b o ve . I f th e re a re a n y si g n s o f
d e c o m p o si tio n e . g . b u b b lin g , wa rm to th e to u c h ) , a fte r re m o vin g th e c a p ,
th e n th e c o n te n ts sh o u ld b e d ilu te d to d ra in with c o p io u s q u a n titie s o f
wa te r.
D ecom position and subsequent self-heating in tanks can occur if the tank con-
tents becom e contam inated w ith a decom position catalyst. Such catalysts
m ay be introduced in a num ber of w ays, for exam ple:
a ) To o ls o r e q u ip m e n t a c c id e n ta lly d ro p p e d in to th e ta n k .
b ) A irb o rn e c o n ta m in a n ts e n te rin g th e ta n k , e . g . via a n o p e n m a n h o le .
c ) P ro c e ss liq u o rs p o ssib ly flo win g b a c k in to th e ta n k .
d ) C o n ta m in a te d h yd ro g e n p e ro x id e b e in g re tu rn e d to th e ta n k .
e ) I n c o m p a tib le fittin g s.
f) C o n ta m in a tio n via p o o r q u a lity d ilu tio n wa te r o r m ix in g a ir.
The first indications of decom position are that the tem perature of the tank con-
tents w ill start to rise above am bient. D ecom position is norm ally slow in the
early stages and can possibly be controlled by cooling the outside of the tank.
After a certain stage w hen the tem perature of the tank contents is rising fast,
decom position can be very rapid and is likely to result in gas evolution, foam ing
and spraying of hot liquid over a w ide area. If the venting facility is not ade-
quate this m ay lead to pressure build up and even tank rupture.
B ulging packages
25
U nder no circum stances should the tank be approached if gassing or jetting is
occurring, or if there are any other indications of advanced decom position, e.g.
noise or high tem perature.
H o w e v e r, the activation (from a safe location) of a safety system such as dousing
or dum ping m ay be carried out. SO LVAY IN TER O X w ill help to define such
safety system s.
N o attem pt should be m ade to transfer or use decom posing product. It m ust
be diluted and disposed of safely. The tank m ust not be used for hydrogen
peroxide again until the cause of the decom position has been established and
the tank subsequently cleaned and repassivated, if necessary.
Customers should consult SOLVAY INTEROX
if poor stability is suspected.
8.2. Other aspects
H ydrogen peroxide solutions, if confined betw een closed valves, can lead to a
pressure burst even w hen uncontam inated. The problem can be overcom e by
a num ber of m ethods:
- vents,
- pressure relief valves,
- elim ination of valves w here possible, and locking open certain valves during
norm al running, w here appropriate.
Vents and pressure relief valves m ust be in suitable m aterials and directed to a
safe place.
Even non-contam inated hydrogen peroxide solutions, in ball valves or dia-
phragm valves, m ay lead to pressure bursts if the ball or the bonnet are not
vented (see section 6).
If hydrogen peroxide is pum ped against a dead end (e.g. closed valve) the heat
generated can lead to rapid decom position w ith gas evolution, and a pressure
burst can subsequently follow . Steps m ust be taken during the design (e.g. no-
flow trip, kickback line or pressure relief) to avoid this happening.
Fires caused by hydrogen peroxide and com bustible m aterials should be
fought w ith w ater.
In m ost countries there w ill be statutory regulations governing the disposal of
hydrogen peroxide. Solutions containing less than 0.1 % W /W can norm ally be
flushed dow n drains. H ow ever, in certain cases it m ay need to be m ore diluted.
C losed valves
N on-vented valves
Pum ping
D isposal
Fire-fighting
1998, Solvay S.A.
Responsible editor: Solvay S.A.
Photography: Y. Glavie /Milo /ARGO /Y. Fonck
Concept and creation: ARGO N.V., Belgium
Printed in Belgium
"All information in this document is deemed to be accurate by Solvay at the time of going into pre s s . It is given in good
f a i t h . All regulations, at the national or local level, re g a rding safety and health in the work place and environmental pro-
tection are always to be applied but Solvay disclaims liability for any failure in this document to comply with the above.
F reedom of use under existing patents or other intellectual property rights must be duly considered before use."
For further information or detailed
technical documentation, please
contact your local SOLVAY INTEROX
office. (See the complete list of
addresses on the opposite page).
9. Further information
26
1.SO LVAY IN TER O X - H ydrogen Peroxide M aterialSafety D ata Sheet (M SD S).
2.W all Poster.
3.Safety Video: W orking w ith H
2
O
2
The SO LVAY IN TER O X G uide to Safety.
4.D esign M anual for H
2
O
2
bulk storage and handling.
5.A sum m ary of H
2
O
2
hazards: J. M ackenzie.
6. C onsiderations for the safe design of processes using H
2
O
2
and organics.
Plant O perations Progress, July 1991.
7 .F i re and explosion hazards associated w ith the storage and handling of H
2
O
2
.
R . M errifield, H SE Technology D ivision, SIR N 19.
8.SO LVAY IN TER O X - H ydrogen peroxide data m anual.
9.SO LVAY IN TER O X - The safe use of hydrogen peroxide in liquid effluent
treatm ent.