h202 handling and storage english

8/12/2019 h202 Handling and Storage English

1/26

HYDROG EN P EROXIDEHANDLING &STORAG E


2/26

table of contents

1. Introduction 3

2. Physico-chemical properties 5

2.1 P hysical properties2.2 Toxicological properties2.3 C hemical properties

R eactionsO xidantR eductantP eroxy compoundsAddition compound

2.4 Decomposition propertiesEffect of pHEffect of lightEffect of heatHomogeneous decomposition

Heterogeneous decompositionEffect of stabilisation

2.5 Effects of decompositionP ressure build upH eat release and self-heatingSuperheated steam

2.6 Spontaneous combustion of organicsubstances

2.7 Explosive characteristics

3. Transportation and packaging 11

R egulationsM arking and labelling

4. Storage 12

Sm all containers and IBC sISO tanksBulk storageSiteTankFittingsP iping systemValves

PumpsM easuring tanksP retreatmentDispensing from storage

5. Product handling 17

Basic rulesG eneral precautionsDilutionTransfer into storage

6. Construction materials for storage 18and handling

U nsuitable materialsSuitable materialsAluminium and its alloysAustenitic stainless steelP lastic tanksO ther non-metalsLubricants

PumpsValvesG askets

7. Personnel safety instructions 22

P ersonnel protectionEquipmentFirst aid

8. Some common types of incidents 23

8.1 Emergency proceduresLeaksBulging packagesD ecomposition and self-heating

8.2 O ther aspectsC losed valvesN on-vented valvesPumpingFire-fightingDisposal

9. Further information 26


3/26

hydrogen ha nd ling a nd s to ra geIntroduction

A s part of Solvays declared commitment to R ES P O N SIB LE C AR E * ,S O LVAY IN T ER O X works ceaselessly at minim ising the risks of its pro d u c t sto people and the environment. These efforts include the provision of manyd iffe rent types of information and advice on all aspects of operations. N ume-rous other activities include inspections, design, analyses and trials.

O ur principle is to work in partnership with customers and others to achieveour mutual objective of safe and effective peroxygen products.

This manual presents information on the safety, handling and storage of com-mercial solutions of hydrogen peroxide up to 70 % w/w .

O ther safety information available from SO LVAY IN TER O X is listed on page 26of this manual.

* RESPONSIBLE CARE is an international initiative of the c hemical industry aimed at the cont inuous imp rovement of its perform ance in the areas of health, safety and the environment .


4/26

H ydrogen peroxide has been produced by SO LVAY IN TER O X for morethan forty years, and during this time much experience has beengained in the handling, storage and use of this important industrialchemical.

In the early days of its industrial production, the principal use of hydro g e nperoxide was as a bleaching agent, but in recent years many otherapplications have been found such as, for example, in chemical synthesis,water treatment, soil remediation, environmental applications, surfacetreatment of metals, electronics and disinfection.

O ne of the major advantages of hydrogen peroxide over most otheroxidising agents used in industry is that it is non-polluting by itself sinceits principal reaction by-product is water.

T he purpose of this publication is to provide general information andadvice, which, if followed, will help the user to handle and store concen-trated hydrogen peroxide solutions safely and without incident.

4


5/26

2.1. Physical properties

(For a more detailed account see SO LVAY IN T ER O X D ata M anual on HydrogenP eroxide).

H y d rogen peroxide is a clear, colourless, liquid miscible with water in anyproportion. Its molecular weight is 34.02.

Hyd rogen peroxide is marketed in the form of aqueous solutions and the follow-ing table shows the principal characteristics of some of these.

In addition to the Data M anual, SO LVAY IN TER O X technical services are at thecomplete disposal of customers for further clarification of the physico-chemicaldata.

2.2. Toxicological properties

C oncentrations of 5 % W/W and above can cause irritation or burns, with theseverity increasing with concentration.

Splashes of dilute H 2 O 2 in the eyes cause pain. W ith solutions of 6 % W/W anda b ove severe and permanent damage may occur.

The ingestion of H 2 O 2 can cause burning of the mouth, throat, oesophagusand stomach, and internal distension from evolved oxygen. In some instances,ingestion of commercial strengths can be fatal.

5

2. Physico-chemical properties

H2 0 2 content g/100 g 3.0 10.0 20.0 27.5 30.0 35.0 50.0 60.0 70.0

H20 2 content at 20C g/100 ml 3.0 10.4 21.4 30.3 33.3 39.6 59.8 74.5 90.2

Volume of gaseous oxygen (litre)given off per litreof solution at 20C(0C and 760 mmHg or 101,325 kP a) I/I 10 34 71 100 110 130 197 246 298

Active oxygencontent 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

Boiling point at101.325 kPa(760 mm Hg at 0C ) C 100.4 101.5 103.6 105.5 106.3 107.4 113.9 119.0 125.5

Density at0C kg/dm 3 1.012 1.039 1.080 1.112 1.123 1.144 1.211 1.258 1.30725C kg/dm 3 1.007 1.032 1.069 1.098 1.108 1.128 1.191 1.236 1.28450C 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


6/26

Inhalation of H 2 O2 vapours or mists is irritating to the respiratory tract. T heoccupational exposure limit (TLV ) is 1.0 ppm (1.4mg H 2 O2 /m 3 air) for a normal8 hour/day and 40 hour/week working period.

For further information 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 compounds- to form addition compounds

Examples of such reactions are:

2.4. Decomposition properties

A further type of reaction is its decomposition to water and oxygen representedas:

This can occur under various conditions which are identified hereafter.

In alkaline solution, the rate of decomposition increases rapidly as the pH isincreased.

Hydrogen peroxide and alkali must never beinadvertently mixed.

6

Effect of inhalation

First Aid

R eactions

O xidant

R eductant

P eroxy compounds

Addition compound

Effect of pH


7/26

Light can cause photochemical decomposition of hydrogen peroxide. Theabsorption of radiation by hydrogen peroxide solutions occurs over a widecontinuous spectrum. H ydrogen peroxide solutions should not therefore beexposed for long periods to light, especially direct unfiltered sunlight.

Apart from self-heating as a result of decomposition, consideration must begiven to the effect of temperature rises caused by outside sources of heat.For purely physico-chemical reasons, the rate of the decomposition reaction insolution (homogeneous) will increase 2 to 3 times for every 10C increase inte m p e ra ture , and the rate of the surface decomposition (heterogeneous) willincrease 1 to 2 times per 10C . The effect of increased contamination fromdissolution of the surface can of course make the situation worse.

Protect hydrogen peroxide from direct heat.

H ydrogen peroxide as produced by SO LVAY IN TER O X is very pure and thedecomposition rate to water and oxygen is normally very low. H owever, if thehydrogen peroxide becomes contaminated e.g. with salts of metals such asiron, copper, chromium, vanadium, tungsten, molybdenum, silver and metalsfrom the platinum group, then fast decomposition to water and oxygen mayfollow. T his is known as homogeneous decomposition. T he most activedecomposition catalysts are those giving multivalent ions. Fast decompositioncan often be caused by extremely low levels of contaminants, for example afew parts per million. T his decomposition is a chain reaction in which the metallicions are successively oxidised and reduced. This explains why it is possible forsmall amounts of catalyst to cause extensive decomposition of H

2O

2.

In addition, the effect of pH on the rate of decomposition of contaminatedhydrogen peroxide is very marked, even in acid medium.

Fast decomposition may also occur if the hydrogen peroxide is brought intocontact with insoluble solids. This is known as heterogeneous decomposition.H ydrogen peroxide will decompose to some extent on any surface even atambient temperature, although the rate varies enormously with the nature andstate of the surface. Thus, the rate of decomposition on silver is 10 7 times fasterthan that, for example, on polyethylene, which is one of the common handlingmaterials. Some of the solids which catalyse the decompostion of hydrogenperoxide are the hydroxides and oxides of the heavy metals, as well as t henoble metals themselves. T he following is a list of the most active catalysts :

7

Effect of light

Effect of heat

Homogeneousdecomposition

H eterogeneousdecomposition

R uthenium oxide R uO 4 P latinum P t

M anganese oxides M n 2 O 3 , M nO2 O smium O s

Iron oxides FeO , Fe 2O 3 Iridium Ir

C obalt oxide C oO P alladium P d

N ickel oxides N iO , N i 2 O3 R hodium R h

Lead oxide and hydroxide PbO, P b(O H) 2 Silver AgM ercuric oxide H gO G old Au


8/26

8

These are most active when their specific surface is large as with, for example,colloids and powdered metals. D ue to their high activity, some of the metals andoxides in the above tables are used as catalysts when rapid decomposition isrequired in the use of hydrogen peroxide as a power source, as, for example, inrocket motors. In addition even compatible materials of construction can causeaccelerated decomposition if the surface is of inadequate quality or has notbeen properly prepared.

Never allow hydrogen peroxide to become contaminated.Bring hydrogen peroxide into contact only with

SUITABLY PREPARED compatible materials.

S O LVAY IN TER O X adds stabilisers to keep decomposition to a minimum. Theseare generally of two types, complexing/chelating, and colloidal, which eitherneutralise small amounts of colloidal catalysts or adsorb/absorb impurities.

2.5. Effects of decomposition

Even at low dilutions, hydrogen peroxide will decompose continuously intowater and oxygen. T his rate is very low when hydrogen peroxide is stored inapproved materials and is kept free from contaminants. H owever, if oxygenpressure is not relieved, then high gas pressure may build up.

Never store hydrogen peroxidein hermetically sealed containers.

The decomposition of hydrogen peroxide is exothermic and also the rate of decomposition increases with increasing temperature. If the heat of decom-position is not removed at the rate at which it is developed (by heat loss to thesurroundings or cooling), the temperature will rise and the rate of decomposi-tion will increase. This can result in a self-accelerating decomposition which, inthe case of badly contaminated solutions, may culminate in extremely rapiddecomposition or boil off.

Keep the temperature of a storage tank under surveillance.

Even after the total decomposition of solutions containing up to 64 % W/Whyd ro ge n peroxide, liquid water is still present. Because of this, the final tem-perature cannot exceed the boiling point of water at the pressure of the sys-tem. But under adiabatic conditions the total decomposition of solutions con-taining over 64 % W/W develops sufficient heat to evaporate all the water tosteam and superheat it. For example, if decomposition is complete, and therea re no heat losses (i.e. adiabatic), 70 % W/W hydrogen peroxide can reach atemperature of 240C (513 K). O ne volume of 70 % W/W solution, whendecomposed totally under adiabatic conditions and atmospheric pressure, willproduce about 2,500 volumes of gas (see diagram on page 9).

Design of tanks should allow for adequate ventingcapacity to permit gases and vapours to escape

in case of serious decomposition.

H eat releaseand self-heating

Superheated steam

Effect of stabilisation

P ressure build up


9/26

9

Volume Expansion Ratio on Total AdiabaticDecomposition of Liquid at Constant Pressure

and Initial Temperature of 20C (293.15 K)Calculated using data from Gigure, Morisette, Olmos & Knop , Can. J. Chem., 195 5, 33,804 -820; National Bureau of Standards, Circular 500; and ideal enthalpy data from National Bureau of Standards, Circular 564.

H2O2 concentration, % W/W

760 mm Hg (0.101325 x 10 6 P a)

15200 mm Hg (2.0265 x 10 6 P a)

25840 mm Hg (3.44505 x 10 6 P a)

2584mm Hg (0.344505 x 10 6 P a)


10/26


11/26


12/26

12

4. Storage

Small containersand IBC s

Hyd rogen peroxide can be delivered in small packs, in intermediate bulk c onta in-ers (IBC s) or in bulk quantities by rail, road tankers, or in ISO tank containers.

Small containers and IB C s should be stored unopened, in an upright positionand taking account of good warehousing practice with respect to stackingheight. T he breather vents must not be blocked. Storage should be such thatfaulty containers can be easily detected and removed. They must never be ro lle dor laid on their side. They may be stored in a building with a concrete floorslightly inclined towards drainage and designed in the form of a shallow sumpabout 10 cm deep and with a small drive-on ramp to the threshold. T he storagearea should normally be unheated and adequate ventilation ensured. Althoughheat sources are to be avoided, in certain circumstances such as extremeclimatic conditions, heating may be required, but H 2 O 2 containers must not beplaced unduly close to sources of heat. C ontainers may be stored outside,preferably protected from direct sunlight. A canopy may be required in hot,sunny climates. T he storage area must be kept clean and free from combustiblematerials and other incompatible chemicals. A water hose should be availablefor flushing away spillages and leaks to a safe place. A safety shower and aneye bath should be provided for treatment of personnel who come into bodilycontact with hydrogen peroxide. P ipelines, especially those carrying chemicals,must not pass through the storage area.

R eturnable empty containers should be kept closed and clean and returned tothe storage area as soon as possible. They should not be washed out exceptwith non-contaminated water.

Hydrogen peroxide containers must never be usedfor the storage of other materials.


13/26

13

ISO tanks

Bulk storage

In addition to local regulations for storage on site, S OLVAY INTERO X rec om m e nd sa contained concrete area with drain. T he storage area, preferably outdoors,must generally conform to agreed standards of accessibility and cleanliness.P articular care should be taken to ensure that the IS O tank cannot be damagedby passing vehicles.

C are must also be tak en to ensure that the manhole is kept closed, to avoidsources of contamination. T he breather vent must not be blocked or obstruc-ted, otherwise overpressurisation can occur.

IS O tanks must never be washed out or used for the storage of other materialsor for any other purpose.

If there are any doubts about procedureswith ISO tanks,

SOLVAY INTEROX should be consulted.

With an annual usage re q uirement of, say, 50 tonnes or more of hydrogen pero xi-d e solution, it may become economical to construct a bulk storage unit.

H2 O2 storage tanks comprise numerous specific design features and fittings.Similarly, associated pipework, pumps, ancilliary equipment and instrumentsare highly specific to H 2 O 2 .

O ther important considerations are the layout and installation, which requireexpert advice. Factors such as statutory requirements, tank location, correctmaterials of construction, and preconditioning of equipment to receive hydro ge nperoxide are also important.

We strongly recommend that customers planninga storage unit consult SOLVAY INTEROX.


14/26

14

An engineering code of practice and designs for standard tanks of varioussizes have been developed by SO LVAY IN TER O X.

The site should be chosen so as to avoid contamination and contact withincompatible chemicals, and yet be convenient to the areas of usage. It ispreferable, in the interest of safety, that the storage vessel be outdoors. Anadequate water supply must be available for eye baths, safety showers andnormal washing down, and where appropriate this should be frost protected.For emergency flooding non-contaminated water should be used. Where thereis a risk of public access, security fencing and clear marking are required.

The size and material of the tank should be discussed with SO LVAY IN TER O X.Features for horizontal and vertical metal storage tanks are shown on thesetwo pages.

It is essential that the tanks be built only by firms which are able to meet thehighly specific requirements for producing compatible high integrity tanks andfittings.

The minimum equipment for a hydrogen peroxide storage tank includes a com-bined manhole and emergency vent, a breather vent with filter, an overflow p ip ewith downcomer, a level indicator, a filling connection, a hydrogen peroxide outlet,a temperature indicator, drain valve and a bund.

Site

Tank

Fittings

Typical features for a hydrogen peroxide tank(basic equipment)

1. Manhole and emergency vent2. Overflow pipe with downcomer3. Level indicator (with alarm)4. Filling connection5. Hydrogen peroxide outlet6. Bund7. Vent with filter8. Temperature indicator9. Drain valve

10. Watersupply forshower, eyewashor spillage dilution


15/26

15

Additional features include level indicator and temperature indicator alarms.These are recommended for safety reasons. S ome tanks are also fitted with adilution connection and a mixing device. A larm switches and thermometers m us tnot be of the mercury type, and no oil should be used in the thermocouple well.

The manhole cover assembly should be adequateto provide relief in case of decomposition

(recommended minimum surface area is 200 cm 2per tonne of 100 % hydrogen peroxide).

It is desirable that manholes be fitted with a loose aluminium or stainless steelwire mesh cover to prevent large objects such as inspection torches, safetyhelmets, tools and spectacles falling into the tank.

If tanks are fitted with an emergency flooding connection, care must be takento ensure that it cannot provide a source of contamination. The point ofconnection to the emergency water supply should be located to allow waterintroduction during a decomposition without risk to personnel.

Tanks should be surrounded by a retaining wall or bund which is capable of containing at least the whole content of the tank in case of rupture, and in anycase comply with local regulations.

C atwalks and rails are not shown, but should be included where necessary.The tank should be labelled as required (e.g. warning signs, product name andconcentration) and the tanker coupling should also be clearly marked, toprevent delivery of a different substance which could be extremely dangerous.

Typical features for a hydrogen peroxide tank(fully equipped)

1. Manhole and emergency vent2. Overflow pipe with downcomer3. Level indicator (with alarm)4. Filling connection5. Hydrogen peroxide outlet6. Bund7. Vent with filter8. Temperature indicator (with alarm)9. Spare branch

10. Sparge (optional)11. Drain valve12. Water connection


16/26


17/26

17

Basic rules

Transfer into storage

Dilution

G eneral precautions

5. Product handling

H ydrogen P eroxide should only be handled by trained personnel who are wellaware of its hazards and the necessary safety precautions.

H ydrogen peroxide should be handled with care so that no product is spilledduring unloading or transfer. If spillage does occur, it must be diluted with waterand cleaned up thoroughly, ensuring that all cleaning equipment is thoroughlyrinsed after use.

H ydrogen peroxide should be k ept in its original container. H andling and trans-ferring must be done only with approved dedicated equipment made of com-patible material (see section 6). O nce hydrogen peroxide has been drawn froma storage container, it must not be returned since it may have become conta-minated.

H ydrogen peroxide must be k ept away from heat sources. H ydrogen peroxideshould not be contaminated during storage and handling, and contact withincompatible surfaces must be avoided. Scrupulous cleanliness is requiredwhen handling solutions of hydrogen peroxide.

Apart from dilute products sold generally in small packs, commercial solutionsof hydrogen peroxide present little or no risk of freezing in temperate climatesand thus no special protection against frost needs to be taken, except in extre m eclimates (See page 5, section 2.1., for freezing points).

D ilution water (even some tapwaters) may destabilise H 2 O 2 .

SOLVAY INTEROX should be consulted when hydro g e npe roxide is to be store d at a low concentration

after dilution by the user.

All tanks and small packages should be maintained in an upright positionduring the transfer operation and should not be jolted violently. N eglect of thesesimple rules can lead to spillages, which may subsequently give rise to hazard-ous situations.


18/26

18

U nsuitable materials

Suitable materials

Austenitic stainless steel

Aluminium and its alloys

6. Construction materials for storage andhandling of hydrogen peroxide

The selection of materials of construction for equipment to be used in service withhydrogen peroxide must be undertaken with care, otherwise decompositionproblems will be encountered.

In cases of doubt, assume incompatibility.

The information given below may not apply to special grades of hydrogenperoxide; for these SO LVAY IN TER O X should be consulted.

M any common materials of construction such as iron, steel, copper, brass, nickeland chromium are not suitable for handling solutions of hydrogen peroxide,and recommended materials must be used.

Suitable grades of metals for service with hydrogen peroxide are indicated below.

Aluminium of 99.5 % minimum purity and certain Al-M g alloys can be used forlong duration storage of concentrated hydrogen peroxide, but they are expensiveand difficult to fabricate. S O LVAY IN TER O X hydrogen peroxide, as delivered,will not significantly corrode aluminium over long periods, and the corrosionproducts do not seriously affect the stability of the chemical. H owever, in thepresence of chloride ions, serious pitting can occur, so contamination withchlorides from, for example, dilution water must be avoided.

For fabrication work, argon shielded arc welding methods are used with rods of parent metal, with care taken to avoid impressing impurities into the soft metal.It is essential to use only approved fabricating companies.

Fully austenitic stainless steels may be used in service with hydrogen peroxide,including storage. H owever, it must be emphasised that special care is neededwith finishing and treatment of surfaces, welding, and stabilisation systemsbecause, if corrosion should occur, the corrosion pro d uc ts would be powerfulcatalysts for hydrogen peroxide decomposition. T he pre fe rre d grade of stainlesssteel for storage and transport vessels is 304 L, 316 L. Equivalents whichconform to the alloy composition are also acceptable.

Welding quality and surface finishing are very important, and pre-polished plateis preferred. T he welding should be by inert gas shielded processes. M etal inertgas (M .I.G .) is preferred. If other processes are to be used, consult SO LVAYIN T ER O X first. A ll welds and weld splashes should be ground and polished tomatch the surface finish of the plate.


19/26

19

SO LVAY IN TER O X have developed detailed engineering codes and specifica-tions covering the fabrication of hydrogen peroxide storage equipment. Adviceand assistance are available on request.

M etallic materials have contaminants loosely adhering or sometimes embeddedin the surface, and before being used in service with hydrogen peroxide theymust be subjected to some, if not all, of the following processes: cleaning anddegreasing with detergent, pickling to remove metal and impurities, passivatingand conditioning.

C ustomers should consult S O LVAY IN TER O X concerning the precise details of these treatments.

P lastic tanks are suitable for up to 50 % W/W hydrogen peroxide provided theyare made of correct polymeric material.

They are subject to embrittlement, environmental stress cracking and ageing.They are more susceptible to physical damage than aluminium or stainless steeltanks. T heir physical properties can be seriously affected by extremes of ambientte m p e ra ture, and it is difficult to obtain satisfactory quality control during fabrication.

C ustomers should consult SO LVAY IN TER O X concerning the design character-istics of plastic storage tanks and the type of plastic used.

P iping from plastic tanks may be in aluminium or stainless steel.

Some fluorinated plastics and rubbers can be used in service with hydrogen

peroxide, for example, polytetrafluoroethylene, polyvinylidene fluoride such asSolvay SO LEF , and a co-polymer of vinylidene fluoride and hexafluoro p ro p yle nesuch as VIT O N *

P lastic compatibility can be grade dependent between suppliers, and the natureof fillers, pigments and other additives is important.

White chemical porcelain and borosilicate glass are both compatible with hydro-gen peroxide and are widely used for small scale laboratory apparatus. D ue tothe risk of breakage, these materials are not generally recommended for largescale apparatus or plants.

M ost common lubricants are incompatible with hydrogen peroxide becausethey can form hazardous peroxide/organic mixtures. This problem may beovercome, for example, by using fluorinated oils, but then these oils tend to bepoor lubricants.

* Reg. US trademark, E.I. du Pont de Nem ours

P lastic tanks

O ther non-metals

Lubricants


20/26

C ompatible materials of construction must be used for all contact surfaces andall non-contact surfaces where exposure is both foreseable and dangerous.

SO LVAY IN TER O X does not recommend the use of pumps with packed glandsbut instead advises the use of pumps with mechanical seals. T he use of sealfaces of ceramic on the one side and glass or ceramic filled PTFE on the otheris advised.

The recommended material of construction for pumps is austenitic stainless steel(304L or 316L), although P TFE pumps are acceptable. In diaphragm pumps, apressure burst may occur if the diaphragm fails. O n such pumps, provisionshould be made 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 doublediaphragms with compatible buffer fluid and leak detection is advised.

SO LVAY IN TER O X recommends ball-valves with suitable venting arrangementsfor releasing potential pressure build-up from the decomposition of hydrogenperoxide trapped in the valve. D iaphragm valves can be dangerous if hydrogenperoxide gets into the bonnet, and hence the valve bonnets must be drilled.P lug-type valves need a lubricant, and therefore SO LVAY IN T ER O X does notadvise the use of this type of valve.

Acceptable valves have a seat, usually polytetrafluorethylene, and a small holedrilled in the ball so that in the off position the channel through the ball is incommunication with the shut-off higher pressure side.

G askets may be made from polyethylene or polytetrafluoroethylene (P TFE).C om p ressed asbestos fibre (C AF) gaskets may only be used in a P TFE envelope.

Pumps

G askets

Valves

Diaphragm valve with small hole drilled in the bonnet.

Valve with small hole drilled in ball.20


21/26

hydrogen peroxidesolution containing up to 70% wt/wt hydrogen pero x i d e

warning St rong oxidant . Can ca use eye damage and skin burns.

Reac ts with many substa nces g enerating heat with fire risk. Ca n decompo se 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 wear face shield, plastic apron andboots.

Have eye bath available and safety showersif possible. Ensure there is adequate ventilationwhere peroxide vapours may occur.

Have water hoses available for fire fighting.Wash spilled peroxide away from handling andstorage areas with plenty of water.

Store in original container in a cool place.K eep containers upright. Ensure vents remaineffective.

Keep storage area free of combustiblematerials. Use it for peroxide storage only.

Use clean vessels and equipmentconstructed from compatible materials.Empty all utensils and drain equipment after use.Wash out wi th water.

Ensure that peroxide does not becomecontaminated. Do not return unused product tooriginal container. D ilute it with plenty of water andflush to drain.

Wash contaminated materials at once.

O n no account allow them to dry out beforerinsing (e.g. clothing).

Use only vessels or containers fitted with asafety vent in operable condition. Do not confineperoxide in any enclosed spaces (e.g. betweenclosed valves).

emergenciescontact with skin

Wash affected sk in with plenty of water. R emove contaminated clothing immedia tely. In case of burns or shock, seek m edical attention.

contact with eyes

Wash out immediately with plenty of water. C ontinue washing for at least 15 minutes. Seek medical attention.

leak or spill

D rench with water. Wash the liquid off all contaminatedsurfaces with plenty of water.

Do not absorb in sawdust or other combustible materials. Do not attempt to recover spilled liquid.

fire

D rench with water only. Do not use foam or drychemicale xting uis he rs .

Keep adjacent containers cool byspraying with water. Wear a fire-suit equipped with independent bre a th ing

apparatus before entering the contaminated zone.

ingestion

Drink plenty of water. Seek medical attention.

inhalation

Move the victim out into the fresh air - wear anindependent breathing app aratus.

In case of suffocation, seek m edical attention.

Allinformationinthisdocument isgivenin good faithand from best knowledge available.Nationalor localregulationsmust alwaysbe applied.

Em ergency telephone No:00/44/1925 /31 200

For detailed information please applyto:

SOLVAY INTEROX LIMITEDBaronetWorks - BaronetRoad

GB - Warrington (Cheshire)WA4 6HBTel : 44/1925 /651277

Fax: 44 /1925/655 856Telex: 0151/627834 SOLIXG

WATER


22/26

7. Personnel safety instructions

See the SO LVAY IN TER O X-Hydrogen Peroxide Safety D ata Sheet (M SD S) forfurther information.

The most important safety points mentioned in this section have been sum-marised on the SO LVAY IN TER O X H ydrogen Peroxide Safety P oster which isavailable on request.

As a minimum, personnel handling hydrogen peroxide must wear long-wristedplastic gloves and suitable eye protection. P VC aprons are also recommended.

If there is any risk of splashing, then a protective face mask, full body protec-tion, and suitable boots made of polyvinylchloride or rubber must be worn.

P ipetting of commercial solutions should be done mechanically and not bymouth.

Eye wash bottles and showers must be available in sufficient number in thestorage and working areas.

The effect of hydrogen peroxide solutions on skin and mucous membranesdepends on the concentration, but increases also as a function o f the timeof contact. Hence, the first immediate action in the event of any skin contactwith hydrogen peroxide is repeated rinsing of the affected area with cleanwater.

In case of splashes in the eye, the opened affected eye must be rinsedwith clean water, initially with an eye wash bottle. Rinsing must be doneimmediately and continuously for at least 15 minutes after which medicaladvice should be obtained.

Any clothing which has been in contact with hydrogen peroxide must beimmediately drenched with water. When large areas of clot hing have beenwetted with hydrogen peroxide, it is recommended that the clothing be

removed under a running shower and then rinsed thoroughly. Never lethydrogen peroxide-contaminated clothing dry without washing since theremay be a risk of spontaneous ignition at a later time. Spillage onto or insideshoes is especially dangerous.

In cases of accidental ingestion, it is recommended that copiousamounts of water be drunk, and that vomiting NOT be induced. Medicaladvice must be sought.

Fresh air is the best answer to respiratory irritation caused by hydrogenp e roxide. An unconsc ious person should be brought int o the open.Re s c u e r s should wear suitable air-masks if necessary. Medical advicemust then be sought.

P ersonnel protection

First aid

Equipment

22


23/26


24/26

24

Decompositionand self-heating

If a plastic container appears to be bulging then this is an indication of highinternal gas pressure. This may occur after very long storage with a blocked orfaulty vent. Alternatively, it may be the result of excessively high decompositiontaking place. In such an event the container will at first start to bulge and mayeventually rupture. A situation such as this must, therefore, be treated withextreme caution.The container should not be approached except by competent personnel whoare wearing full protective clothing.

The ultimate risk is a violent bursting of the container and widespreadejection of liquid. The first step is to assess the situation from a safe loca-tion. Any of the following indications should be considered as a sign ofdanger, in which case nobod y should approach the package.- noise e.g. gas escaping;- visible signs of advanced decomposition e.g. steam, liquid escape from

vent;- severe distension of the package;- increasing extent of distension.

In the absence of any of the above indications then a trained, fully pro tec tedperson may approach and carefully remove the cap (which may in itselfresult in an emission of liquid). If any of the danger signs develop, thecontainer must be abandoned. If there are signs, but the situationremains unchanged for a period of 1 day, then the pack should be sprayedwith water, before removing the cap as above. If there are any signs ofdecomposition (e.g. bubbling, warm to the touch), after removing the cap,then the contents should be diluted to drain with copious quantities ofwater.

D ecomposition and subsequent self-heating in tank s can occur if the tank con-tents become contaminated with a decomposition catalyst. Such catalystsmay be introduced in a number of ways, for example:

a) Tools or equipment accidentally dropped into the tank.b) Airborne contaminants entering the tank, e.g. via an open manhole.c) Process liquors possibly flowing back into the tank.d) Contaminated hydrogen peroxide being returned to the tank.e) Incompatible fittings.f) Contamination via poor quality dilution water or mixing air.

T he first indications of decomposition are that the temperature of the tank con-tents will start to rise above ambient. D ecomposition is normally slow in theearly stages and can possibly be controlled by cooling the outside of the tank.After a certain stage when the temperature of the tank contents is rising fast,decomposition can be very rapid and is likely to result in gas evolution, foamingand spraying of hot liquid over a wide area. If the venting facility is not ade-quate this may lead to pressure build up and even tank rupture.

Bulging packages


25/26

25

Under no circumstances should the tank be approached if gassing or jetting isoccurring, or if there are any other indications of advanced decomposition, e.g.noise or high temperature.

Ho we ve r, the activation (from a safe location) of a safety system such as dousingor dumping may be carried out. S O LVAY IN TER O X will help to define suchsafety systems.N o attempt should be made to transfer or use decomposing product. It mustbe diluted and disposed of safely. The tank must not be used for hydrogenperoxide again until the cause of the decomposition has been established andthe tank subsequently cleaned and repassivated, if necessary.

Customers should consult SOLVAY INTEROXif poor stability is suspected.

8.2. Other aspects

H ydrogen peroxide solutions, if confined between closed valves, can lead to apressure burst even when uncontaminated. The problem can be overcome bya number of methods:- vents,- pressure relief valves,- elimination of valves where possible, and locking open certain valves during

normal running, where appropriate.

Vents and pressure relief valves must be in suitable materials and directed to asafe place.

Even non-contaminated hydrogen peroxide solutions, in ball valves or dia-phragm valves, may lead to pressure bursts if the ball or the bonnet are notvented (see section 6).

If hydrogen peroxide is pumped against a dead end (e.g. closed valve) the heatgenerated can lead to rapid decomposition with gas evolution, and a pressureburst can subsequently follow. Steps must 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 combustible materials should befought with water.

In most countries there will be statutory regulations governing the disposal of hydrogen peroxide. Solutions containing less than 0.1 % W/W can normally beflushed down drains. H owever, in certain cases it may need to be more diluted.

C losed valves

N on-vented valves

Pumping

Disposal

Fire-fighting


26/26

1998, Solvay S.A.

Responsible editor: Solvay S.A.Photog raphy:Y. Glavie /Milo /ARGO /Y. FonckCon cept a nd cre ation: ARGO N.V., Be lgiumPrinted in Belgium

" All information in this document is de emed to be a ccurate b y Solva y at the time of going into pre s s . It is given in goodfa ith. All regulations, a t the na tional or loca l level, re garding s afety a nd hea lth in the wo rk place a nd environmental pro-tection are always to be applied but Solvay disclaims liability for any failure in this document to comply with the above.Freedom of use under existing patents or other intellectual property rights must be duly considered before use."

For further information or d etailed technical docum entation, p lease contac t your loc al SOLVAY INTEROX office. (See the comp lete list of addresses on the op posite page).

9. Further information

1. SO LVAY IN TER O X - Hydrogen P eroxide M aterialSafety D ata Sheet (M SD S).

2. Wall P oster.

3. Safety Video: Working with H 2O 2 The SO LVAY INT ER O X G uide to Safety.

4. D esign M anual for H 2O 2 bulk storage and handling.

5. A summary of H 2 O 2 hazards: J. M ackenzie.

6. C onsiderations for the safe design of processes using H 2O 2 and organics.P lant O perations Progress, July 1991.

7 . Fire and explosion hazards associated with the storage and handling of H 2 O2 .R . M errifield, H SE Technology D ivision, S IR N 19.

8. SO LVAY IN TER O X - H ydrogen peroxide data manual.

9. SO LVAY IN T ER O X - The safe use of hydrogen peroxide in liquid effluenttreatment.

h202 handling and storage english

Documents