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Prop
ylene
Oxid
eSt
orag
e & H
andli
ng G
uideli
nes
This manual is provided by The Dow Chemical Company. It is based upon a previous industry publication by the American Chemistry Council (ACC) in support of the North American propylene oxide industry and was developed through the combined efforts of the following companies:
i
Table ofContents
Contact Information & Legal Notice EmergencyContactInformation . . . . . . . . . . . . . . . . . . . . . . 1 LegalNotice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
General Information ProductIdentification . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 InstabilityandReactivityHazards . . . . . . . . . . . . . . . . . . . . . 3 PhysicalProperties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 AcronymsandAbbreviations . . . . . . . . . . . . . . . . . . . . . . . 9
First Aid EyeExposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 SkinExposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Inhalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 Ingestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Hazard Assessment AcuteEffectsofOverexposure . . . . . . . . . . . . . . . . . . . . . . 13 RepeatedExposures . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 ChronicEffectsofOverexposure . . . . . . . . . . . . . . . . . . . . 14 Carcinogenicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 ReproductiveandDevelopmentalToxicity . . . . . . . . . . . . . . 14 GeneticToxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 ExposureLimits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Personal Protective EquipmentEyeProtection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
RespiratoryProtection . . . . . . . . . . . . . . . . . . . . . . . . . . 17 GeneralProtectiveClothing . . . . . . . . . . . . . . . . . . . . . . . 17 ImperviousGlovesandClothing . . . . . . . . . . . . . . . . . . . . . 18 ProtectiveEquipmentTraining . . . . . . . . . . . . . . . . . . . . . . 19
Sampling EquipmentOn-streamMethods . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
ManualMethods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Safety-CoatedGlassBottleMethod . . . . . . . . . . . . . . . . . . 20 StainlessSteelCylinderMethod . . . . . . . . . . . . . . . . . . . . 20 OtherSafetyConsiderations . . . . . . . . . . . . . . . . . . . . . . . 20
ii
Emergency Planning PlanDevelopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 FireHazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 FirePreventionandProtection . . . . . . . . . . . . . . . . . . . . . . 23 StaticElectricity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 FireandExplosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 FireFighting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 FireSuppression . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Environmental SpillsandLeaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 WasteDisposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 Absorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Bulk Handling GeneralDesignConsiderations . . . . . . . . . . . . . . . . . . . . . 30 Vessels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Piping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Valves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Tank Cleaning & Equipment Repair WorkPreparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 ControlofHazardousEnergy . . . . . . . . . . . . . . . . . . . . . . 36 ConfinedSpaceEntry . . . . . . . . . . . . . . . . . . . . . . . . . . 36 EquipmentCleanoutandRecommissioningVessels . . . . . . . . . . . 36 MaintenanceandInspection . . . . . . . . . . . . . . . . . . . . . . . 37
Delivery & Transfer ConsiderationsforDelivery . . . . . . . . . . . . . . . . . . . . . . . 38 RailCars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 ConsiderationsforUnloadingRailCars . . . . . . . . . . . . . . . . 46 GeneralGuidelinesforUnloadingRailCars . . . . . . . . . . . . . . 47 TankTrucks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 ConsiderationforUnloadingTankTrucks . . . . . . . . . . . . . . 48 GeneralProceduresforUnloadingTankTrucks . . . . . . . . . . . 50 ISOContainers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 ISOTankShipmentsandUnloadingGuidelines . . . . . . . . . . . 51 Materialand/orContainerReturnGuidelines . . . . . . . . . . . . . 51
Table ofContents
iii
Security . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Tables Table 1 PropyleneOxidePhysicalProperties . . . . . . . . . . . . . . 4 Table 2 PropyleneOxideDensityasaFunctionofTemperature . . . . 5 Table 3 PropyleneOxideVaporPressureasaFunctionofTemperature . 6
Figures Figure1 FlammabilityDiagramforPropyleneOxide . . . . . . . . . . 7 Figure2 FlammabilityTriangleforPropyleneOxide . . . . . . . . . . 8 Figure3 TypicalPressureStorageTankConfiguration . . . . . . . . 31 Figure4 TypicalTankCarDomeConfiguration . . . . . . . . . . . 42 Figure 5 TypicalTankCarConfiguration . . . . . . . . . . . . . . . 44 Figure6 TypicalTankCarUnloadingSystemConfiguration . . . . . 45 Figure7 TypicalIMOTankConfiguration . . . . . . . . . . . . . . 52
Table ofContents
�
Contact Information & Legal Notice
Contact Information & Legal Notice
Emergency Contact Information
24 hour Emergency HotlinesIN CASE OF TRANSPORTATION
EMERGENCY CALL:
CHEMTREC 1-800-424-9300
International (call collect) 703-527-3887
Company Contact Information:The Dow Chemical Company (Local) 989-636-4400(Toll-free) �-800-258-2436 www.dow.com
Huntsman LLC(Local) 7�3-727-083� (Toll-free) �-800-328-850� www.huntsman.com
Lyondell Chemical Company (Toll-free) �-800-245-4532 www.lyondell.com
Legal NoticeThismanualisprovidedthroughthecombinedeffortsofTheDowChemicalCompany,Huntsman,andLyondell .ThePropylene Oxide Storage & Handling Guidelines Manualisintendedtoprovidegeneralinformationtopersonswhomanu-facture,use,orhandlepropyleneoxide .TheManualisnotintendedtobea“how-to”manual,norisitaprescriptiveguide .
IndividualcompaniesmayneedtovaryapproachestoparticularpracticesdescribedintheManualbasedonspecificfactualcircumstances,thepracticalityandeffec-tivenessofparticularactions,oreconomicandtechnologicalfeasibility .
TheManualisnotintendedtobeasubstituteforin-depthtrainingorspecificrequirements,norisitintendedtodefineorcreatelegalrightsorotherobligations .Allpersonsinvolvedinmanufacturing,using,orhandlingpropyleneoxidehaveanindependentobliga-tiontoascertainthattheiractionsareincompliancewithcurrentfederal,state,andlocallawsandregulationsandshouldconsultlegalcounselconcerningsuchmatters .
Neitherthecontributingcompanies,noranyoftheiremployees,subcontractors,consultants,orotherassigns,makesanywarrantyorrepresentation,eitherexpressedorimplied,withrespecttotheaccuracyorcompletenessoftheinformationcontainedintheManual .Thecontributingcompaniesassumenoliabilityorresponsibilityforanyuse,ortheresultsofsuchuse,ofanyinformation,procedure,conclusion,opinion,product,orprocessdisclosedinthisManual .
PropyleneoxideusersareencouragedtoconsultDow’scurrentMaterialSafetyDataSheet(MSDS)forspecificguidanceandupdatesonsafehandlinganduse .ShouldyouhavespecificquestionsaboutinformationcontainedintheManual,youmaycontacttheidentifiedmembercompaniesforfurtherinformation .
2 General Information
Product Information
Formula C3H6OCAS Number 75–56–9EINECS Number 200-879-2IUPAC Name 2–Methyl OxiraneChemical Family Alkylene Oxides Common Names Propylene oxide �, 2–Propyleneoxide Alkyl Epoxide �, 2–Epoxypropane Propene epoxide Propene oxide
Methyl Ethylene Oxide
ApplicationsPropyleneoxideisaversatilechemicalintermediateusedinawiderangeofindus-trialandcommercialproductsandisamongthetop50chemicals,byvolume,producedintheworld .Propyleneoxideisamemberofagroupofcompoundsknownasalkyleneoxides .Alkyleneoxidesreactreadilywithcompoundscontaininganactivehydrogenatom,suchasalcohols,amines,andacids .Thesereactionsaregenerallyknownasalkoxylationsandarechemicalroutestomanyimportantproducts,suchasspecialtysurfactants,solvents,foodadditives,andoilfieldchemicals .
Thepolyurethaneindustryisthelargestconsumerofpropyleneoxide .Itusespoly-etherpolyolsmadebyreactingpropyleneoxidealoneorincombinationwithotheralkyleneoxides .Themostcommoninitiators
arepolyolsorpolyaminessuchasglycerin,glycols,pentaerythritol,ethylenediamine,toluenediamine,sucrose,sorbitol,trialkanolamines,andtrimethylolpropane .Polyetherpolyolsarereactedwithvariousdiisocyanatestoformpolyurethanefoamsandresins .
Thesecondlargestuseofpropyleneoxideistheproductionofpropyleneglycolandlesseramountsofco-produceddipropyleneglycolandhigherpropyleneglycols .Propyleneglycolisoneofthemostwidelyusedsyntheticchemicals,findingitswayintosuchdiverseapplicationsasthemanufactureofthermosetpolyestersforbuildingboats,homeconstruc-tioncomponents,additivesforhumanandanimalfoods,andpharmaceuticalexcipients .Itisalsoaprimaryingredientincosmeticsandlaundrydetergents .
Propyleneoxideisalsousedtomanufacturefunctionalfluidsbyreactionofpropyleneoxideormixturesofpropyleneoxideandethyleneoxidewithglycols,glycerin,alco-hols,andphenols .Thetypesoffunctionalfluidsproducedincludeheattransferfluids,hydraulicfluids,andlubricants .
Otherpropyleneoxidederivativesincludeblockcopolymersofpropyleneoxideandethyleneoxide,whichhavebeenfoundtobeefficientandversatilesurfactants .Propyleneoxide-basedsurfactantscanalsobeproducedbythepropoxylationofvariousalcohols .Thewatersolubilityofpropyleneglycolswithmolecularweightlessthan800makespropyleneoxideespeciallyusefulintheseapplications .
General Information
3
Propyleneoxideisalsousedtopropoxylateormodifycarbohydrates(starches) .Propoxy-latedcarbohydrates,orstarches,areusedinavarietyofapplicationsintheconstruction,paint,food,andpharmaceuticalindustries .
Propyleneoxideisalsousedasareactanttoproducealkanolaminesfromammoniaoraminesandasanintermediateintheproduc-tionofallylalcohol .
Instability and Reactivity HazardsPropyleneoxideisastablematerialthatwillnotdecomposeundernormalconditionsoftemperatureandpressure .
Propyleneoxidemayreactvigorouslywithoxidizingmaterials,anhydrousmetalhalides,acids,bases,clay-basedadsorbentmaterials,andperoxides .Propyleneoxidemixedwithammoniumhydroxide,chlorosulfonicacid,hydrochloricacid,hydrofluoricacid,nitricacid,oleum(fumingsulfuricacid),orsulfuricacidcausesviolentreactions .Propyleneoxidereactsslowlyinneutralwater .However,thepresenceofacidsorbasesinwaterwillcatalyzethehydrolysisofpropyleneoxide,andahighlyexothermicreactionmayoccur .
General Information
General Information
4
PROPERTY VALUE
Physical State Liquid
Color Colorless
Molecular Weight 58.08 g/mol
Boiling Point, �0�.3 kPa 34.5˚C (94.�˚F)
Freezing Point -���.93˚C (-�69.47˚F)
Density 25˚C (77˚F) 0.823 g/cm3 (6.87 lb/gal)
Density of Saturated Liquid See Table 2
Vapor Density (Air=�.0) 2.0
Vapor Pressure See Table 3
Index of Refraction
@ 25˚C (77˚F)
@ 20˚C (68˚F)
�.3632
�.3670
Coefficient of Cubical Expansion @ 20˚C (68˚F) 0.00�5�/˚C (0.00084/˚F)
Critical Temperature 209.�˚C (408.4˚F)
Critical Pressure 4.92 MPa
Critical Volume 3.2025 cm3/g (0.5�3 ft3/lb)
Critical Compression 0.228
Acentric Factor 0.2683
Heat of Combustion, Liquid @ 25˚C (77˚F) -426.745 kcal/mol
Heat of Formation, Vapor @ 25˚C (77˚F) -22.395 kcal/mol
Heat of Formation, Liquid @ 25˚C (77˚F) -29.302 kcal/mol
Heat of Fusion @ -��2˚C (-�70˚F) �560.9 cal/mol (2809.6 BTU/lbmol)
Flash Point, TAG-Closed Cup -37.2˚C (-35˚F)
Autoignition Temperature 449˚C (840˚F)
Upper Explosion Limit 42 vol%
Lower Explosion Limit �.6 vol%
Solubility @ 20˚C (68˚F) 39.5% PO in Water, �2.5% Water in PO
Alcohol: ∞ Ether: ∞
Saturation Concentration in Air @ 25˚C (77˚F) 82.6 wt% (70.32 mol%)
Dipole Moment 6.70 x �0-30 C∙m
Electrical Conductivity 2.4 x �0-8 mhos/cm
Specific Heat, 0˚C (32˚F) 2.0 J/(g∙˚C) (0.48 BTU/lb/˚F)
Viscosity, 25˚C (77˚F) 0.29 centipoise (mPa∙s)
Specific Gravity See Table 2
Physical PropertiesTable � Propylene Oxide Physical Properties
General Information
General Information
(Rowley et al.,2004)
5
°C °F °C °F4.4 40 0.8488 7.083 �.0�64 2�.7 7� 0.8275 6.905 0.9908
5.0 4� 0.848� 7.077 �.0�56 22.2 72 0.8268 6.899 0.9900
5.6 42 0.8475 7.072 �.0�48 22.8 73 0.826� 6.893 0.989�
6.� 43 0.8468 7.066 �.0�40 23.3 74 0.8254 6.887 0.9883
6.7 44 0.846� 7.060 �.0�3� 23.9 75 0.8247 6.88� 0.9875
7.2 45 0.8454 7.055 �.0�23 24.4 76 0.8239 6.875 0.9866
7.8 46 0.8448 7.049 �.0��5 25.0 77 0.8233 6.870 0.9858
8.3 47 0.844� 7.043 �.0�07 25.6 78 0.8226 6.864 0.9849
8.9 48 0.8434 7.038 �.0099 26.� 79 0.82�9 6.858 0.984�
9.4 49 0.8427 7.032 �.009� 26.7 80 0.82�� 6.852 0.9832
�0.0 50 0.8420 7.026 �.0082 27.2 8� 0.8204 6.846 0.9824
�0.6 5� 0.84�4 7.02� �.0074 27.8 82 0.8�97 6.840 0.98�5
��.� 52 0.8407 7.0�5 �.0066 28.3 83 0.8�90 6.834 0.9807
��.7 53 0.8400 7.009 �.0058 28.9 84 0.8�83 6.828 0.9798
�2.2 54 0.8393 7.003 �.0050 29.4 85 0.8�76 6.822 0.9790
�2.8 55 0.8386 6.998 �.004� 30.0 86 0.8�68 6.8�6 0.978�
�3.3 56 0.8379 6.992 �.0033 30.6 87 0.8�6� 6.8�0 0.9772
�3.9 57 0.8372 6.986 �.0025 3�.� 88 0.8�54 6.804 0.9764
�4.4 58 0.8365 6.980 �.00�7 3�.7 89 0.8�47 6.798 0.9755
�5.0 59 0.8359 6.975 �.0008 32.2 90 0.8�40 6.792 0.9747
�5.6 60 0.8352 6.969 �.0000 32.8 9� 0.8�33 6.786 0.9738
�6.� 6� 0.8345 6.963 0.9992 33.3 92 0.8�25 6.780 0.9729
�6.7 62 0.8337 6.957 0.9983 33.9 93 0.8��8 6.774 0.972�
�7.2 63 0.8330 6.95� 0.9975 34.4 94 0.8��� 6.768 0.97�2
�7.8 64 0.8324 6.946 0.9967 35.0 95 0.8�04 6.762 0.9703
�8.3 65 0.83�7 6.940 0.9958 35.5 96 0.8097 6.756 0.9695
�8.9 66 0.83�0 6.934 0.9950 36.� 97 0.8089 6.750 0.9686
�9.4 67 0.8303 6.928 0.9942 36.7 98 0.8082 6.744 0.9677
20.0 68 0.8295 6.922 0.9933 37.2 99 0.8075 6.738 0.9669
20.6 69 0.8289 6.9�7 0.9925 37.8 �00 0.8068 6.732 0.9660
2�.� 70 0.8282 6.9�� 0.99�7
General Information
General Information
(Rowleyet al.,2004)
Temperature Grams per
Cubic cm
Lb. perU.S.
Gallon
Specific Gravity to
60°C (140°F)
Temperature Grams per
Cubic cm
Lb. perU.S.
Gallon
Physical PropertiesTable 2 Propylene Oxide Density as a Function of Temperature
Specific Gravity to
60°C (140°F)
6
Keypsia: pounds per square inch absolutepsig: pounds per square inch gauge
General Information
General Information
°C °F mm Hg psia
-28.00 -�8.40 40.20 0.78
-26.00 -�4.80 45.43 0.88
-24.00 -��.20 5�.2� 0.99
-22.00 -7.60 57.60 �.��
-20.00 -4.00 64.65 �.25
-�8.00 -0.40 72.39 �.40
-�6.00 3.20 80.89 �.56
-�4.00 6.80 90.20 �.74
-�2.00 �0.40 �00.38 �.94
-�0.00 �4.00 ���.50 2.�6
-8.00 �7.60 �23.60 2.39
-6.00 2�.20 �36.76 2.64
-4.00 24.80 �5�.06 2.92
-2.00 28.40 �66.55 3.22
0.00 32.00 �83.3� 3.54
2.00 35.60 20�.42 3.89
4.00 39.20 220.97 4.27
6.00 42.80 242.02 4.68
8.00 46.40 264.66 5.�2
�0.00 50.00 288.99 5.59
�2.00 53.60 3�5.08 6.09
�4.00 57.20 343.04 6.63
�6.00 60.80 372.96 7.2�
�8.00 64.40 404.93 7.83
20.00 68.00 439.05 8.49
22.00 7�.60 475.42 9.�9
24.00 75.20 5�4.�6 9.94
26.00 78.80 555.35 �0.74
28.00 82.40 599.�3 ��.59
30.00 86.00 645.59 �2.48
32.00 89.60 694.85 �3.44
34.00 93.20 747.02 �4.45
Temperature Vapor Pressure
°C °F mm Hg psia psig
34.48 94.06 760.00 �4.70 0.00
35.00 95.00 774.24 �4.97 0.28
40.00 �04.00 922.24 �7.83 3.�4
45.00 ��3.00 �09�.5� 2�.�� 6.4�
50.00 �22.00 �284.06 24.83 �0.�3
55.00 �3�.00 �502.00 29.04 �4.35
60.00 �40.00 �747.5� 33.79 �9.�0
65.00 �49.00 2022.85 39.�2 24.42
70.00 �58.00 2330.38 45.06 30.37
75.00 �67.00 2672.54 5�.68 36.98
Temperature Vapor Pressure
(Rowleyet al.,2004)
Physical PropertiesTable 3 Propylene Oxide Vapor Pressure as a Function of Temperature
7
0 5 10 15 20 250
10
20
30
40
50
LFL (Lower Flammability Limit) LOC (Lower Oygen Content) UFL (Upper Flammability Limit)
AIR LINE=20.95 mol %
Oxygen
Oxygen (mol %)
Prop
ylene
Oxid
e (m
ol %
)
Flammable Region
Lower Flammability Limit = 1.56%
Lower Oygen Content = 6.9%
Upper Flammability Limit = 41.6%(Air)
General Information
Test MethodsASTM E 2079 Limiting Oxygen (Oxidant) Concentration in Gases and VaporsASTM E 68� Concentration Limits of Flammability of Chemicals (Vapors and Gases)
Test Conditions5-liter stainless sphere�00°C (2�2°F) at � atmosphere
Figure � Flammability Diagram for Propylene Oxide
Larry Britton, Neolytica, February 2005All values are in percent mole.
General Information
8
Oxygen100%
100%0%
0%
0%100%
Lower Flammability Limit = 1.56%
Lower Oygen Content = 6.9%
NitrogenAIR LINE
Propy
lene O
xide
Flammable Region
Upper FlammabilityLimit = 86.5% Oxygen
LFL (Lower Flammability Limit) LOC (Lower Oygen Content) UFL (Upper Flammability Limit)
General Information
Figure 2 Flammability Triangle for Propylene Oxide
Larry Britton, Neolytica, February 2005All values are in percent mole.
General Information
9
Acronyms and AbbreviationsACGIH American Conference of Governmental Industrial Hygienists
ANSI American National Standards Institute
API American Petroleum Institute
ASME American Society of Mechanical Engineers
ASTM American Society for Testing Materials
CAER Community Awareness and Emergency Response
CAS Chemical Abstracts Service
CEFIC Conseil Européen des Federations de l’Industrie Chimique (European Chemical Industry Association)
CERCLA Comprehensive Environmental Response, Compensation and Liability Act (U.S.)
CFR Code of Federal Regulations (U.S.)
DIPPR Design Institute for Physical Property Data
DOT Department of Transportation (U.S.)
EINECS European Inventory of Existing Commercial Chemical Substances
EPA Environmental Protection Agency (U.S.)
EU European Union
HAZWOPER Hazardous Waste Operations and Emergency Response
IARC International Agency for Research on Cancer (United Nations World Health Organization)
ID Inside diameter
IMO International Maritime Organization
ISO International Standards Organization
LFL Lower Flammability Limit
LOC Lower Oxygen Content
mg/m3 milligram per cubic meter
MSDS Material Safety Data Sheet
MSHA Mine Safety and Health Administration (U.S.)
NEC National Electrical Code (U.S.)
NFPA National Fire Protection Association
NIOSH National Institute for Occupational Safety and Health (U.S.)
NTP National Toxicology Program (U.S.)
OSHA Occupational Safety and Health Administration (U.S.)
PEL Permissible Exposure Limit
POTW Publicly Owned Treatment Works
General Information
General Information
�0
PPE Personal Protective Equipment
ppm parts per million
psi pounds per square inch
psia pounds per square inch absolute
psig pounds per square inch gauge
PSV Pressure Safety Valves
PTFE Polytetrafluoroethylene
RCRA Resource Conservation and Recovery Act (U.S.)
RMP Risk Management Plan
RoC Report on Carcinogens (U.S.)
RQ Reportable Quantity
SARA Superfund Amendments and Reauthorization Act (U.S.)
SCBA Self-contained breathing apparatus
STEL Short Term Exposure Limit
TLV Threshold Limit Value
TSCA Toxic Substances Control Act (U.S.)
TWA Time-weighted average
UFL Upper Flammability Limit
Acronyms and Abbreviations (con’t)
General Information
General Information
��
TheinformationinthissectionisgeneralinnatureandshouldbeusedinconjunctionwithDow’scurrentpropyleneoxideMaterialSafetyDataSheet(MSDS) .TheMSDSshouldbereviewedpriortoworkingwithpropyleneoxide .
Personnelinvolvedinhandlingpropyleneoxideshouldbetrainedaboutthespecifichazardsofthischemicalandaboutdecon-taminationproceduresintheeventofoverexposure .
Respondersprovidingassistancetoanoverexposedpersonshouldbecautiousnottocontaminatethemselvesbytouchingtheperson’sclothingunlesswearingappropriateprotectiveapparel .Thevictim’sclothingshouldberemovedtominimizecontinuedskincontact,andtopreventcontinuedoff-gassingofpropyleneoxideduringtransporttoanemergencycarefacility .Emergencytransportservicesshouldbeequippedtoprovidecontinualflushingoftheskinandeyeswithwater,especiallywhenthevictimiscomplainingofburningorirritation .
Eye ExposurePropyleneoxidemaycausesevereeyeirritationandpossiblycornealburns .Highlevelsofpropyleneoxidevaporsmayalsoirritatetheeyes .Ifpropyleneoxidegetsintotheeyes,immediatelywashthemwithcleanwaterforatleast30minuteswhileperiodi-callyliftingtheloweranduppereyelidstoenhanceflushing .Removecontactlensesafterthefirst5minutesandcontinuewashing .Continuewashingandhavethe
exposedpersonattendedtobyaphysicianimmediately .Vehiclesusedtotransporttheexposedpersonmustbeequippedwithfacilitiestocontinuewashingduringtransport .
Skin ExposurePropyleneoxidegenerallydoesnotcauseadverseeffectstotheskinifitcanfreelyevaporate .Confinedcontactorcontactwithpropyleneoxideinaqueoussolutionscancausedamagerangingfromirritationtosevereburns .Ifskinisexposed,allclothingcoveringtheaffectedareashouldberemovedandtheareawashedwithflowingwaterorashowerforatleast15minutes .Removewatches,rings,oranythingelsethatcouldholdpropyleneoxideincontactwiththeskin .Putonacompletechangeofclothing .Donotwearcontaminatedclothinguntilithasbeenproperlycleaned .Removeanddiscardcontaminateditemssuchasleatherbelts,wallets,andshoes .Leathercannotbeadequatelydecontaminatedandcanincreaselocalizedburnpotentialbyholdingthepropyleneoxideagainsttheskin .Also,discardrubberfootwearifpropyleneoxidewasinsidetheshoeorboot .Discardedclothing,accessories,and/orfootwearshouldbeproperlycontainedanddiscarded .
Itisnotadvisabletoenteranareawithapropyleneoxideleakbecauseoftheextremeflammabilityhazard .Whenentryintoanareaisnecessarytocontainorcontrolalife-threateningspill,afullrubberslickersuitshouldbewornwithpantsoutsiderubber
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boots .Chemicalgogglesandproperrespira-toryprotectionshouldalsobeworn .Ifafirehazardexists,asuitableflashsuitandhoodshouldbesubstitutedfortherubberslickersuit .
Inhalation Propyleneoxidemaybeirritatingtothemembranesoftherespiratorytractandtotheeyes .Highconcentrationsmaycauseseriousadverseeffects,evendeath .Inareaswithpoorventilation,leaksorspillsmayresultinaccumulationofacutelytoxicandpotentiallylethalconcentrations .Signsandsymptomsofexcessiveexposuremayincludeeyeandrespiratorytractirritation,cyanosis,andpossiblyanesthesiaandnarcosis .
Ifovercomefrominhalationofpropyleneoxide,avictimshouldbemovedfromthecontaminatedatmosphereintofreshairatoncebypersonsproperlyequippedwithappropriatepersonalprotectiveequipment(PPE) .Treatforshockifnecessary .Ifthevictimhasstoppedbreathing,giveartificialrespiration .Cautionshouldbeusedtopreventresponderexposuretopropyleneoxidefromthevictim .Ifbreathingisdif-ficult,oxygenshouldbeadministeredbyqualifiedpersonnel .Oncerevived,keepthevictimwarmandcalm .Seekpromptmedicalattention .
Ingestion Exposurethroughingestionofpropyleneoxideisunlikely .Ifpropyleneoxideshouldbeingested,givethepatient,ifconscious,lukewarmwater .Do not induce vomiting.
Becauserapidabsorptionmayoccurthroughthelungsifaspiratedandcauseasystemiceffect,thedecisiontoinducevomitingornotshouldbemadeonlybyaphysician .Whenstabilizedsufficientlyasdeterminedbymedicalauthorities,thepatientshouldbetransportedtoamedicalfacilityforcontinuedtreatment .
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Theprimaryrouteofexposuretopropyleneoxideisthroughinhalationoffugitiveemissionsintheworkplace .Propyleneoxideislikelytobereadilyabsorbedthroughtherespiratorytractandrapidlymetabolizedbyconjugationwithglutathione,orhydrolyzedto1,2–propanediol(propyleneglycol) .Acutely,propyleneoxideisasevereskin,eye,andrespiratoryirritant .
Long-termstudiesinanimalshaveclearlyshownthatchronicexposuretohighlevelsofpropyleneoxidecaninducesite-of-contactmalignanttumorsandthatpropyleneoxideshouldbeconsideredapossiblehumancarcinogen(seepage14,“Carcinogenicity”) .
Consistentwithgoodindustrialhygienepractice,exposuresshouldbecarefullycontrolledtopreventadversehealtheffects;theACGIHTLV(8-hrTWA)is2ppm .FormoredetailedtoxicityinformationandthemostrecentMaterialSafetyDataSheet(MSDS),contactDow .
Acute Effects of OverexposureSingleexposurestoliquidpropyleneoxidecancausesevereskinandeyeirritation,whichmayleadtoseveretissueinjuryifnottreatedpromptly .Therearereportsintheliteraturethatindicatethatexcessiveexposuretoliquidpropyleneoxidemayinduceallergicskinreactionsinworkers;ACGIHnotespropyleneoxideasaskincontactsensitizer .Exposuretohighvaporconcentrationscancauseirritationoftheeyesandrespiratorytract,cyanosis,and
possiblycentralnervoussystemeffectssuchascoordinationproblemsandgeneraldepression .
Propyleneoxidegenerallydoesnotcauseadverseeffectstotheskinifitcanfreelyevaporate .However,confinementunderclothingorinshoesorjewelrypreventsevaporationresultinginirritation,blistering,andpossibleburns .Contactwithevendilutesolutionsofpropyleneoxide(10%)cancauseirritation,blistering,andburnswithasingleshort-termexposure .
Datafromanimalstudiesindicatesthatsingleexposuretopropyleneoxidebying-estionorbyinhalationismoderatelytoxic .
Repeated ExposuresRepeatedexposuretoexcessivelevelsofpropyleneoxidevaporsmaycauseeyeandrespiratoryirritation,andlungandnasaltissueinjury .Effectstothenervesoftheextremities(peripheralneuropathy)havebeennotedfollowingextremelyhigh(>1000ppm),repeatedexposuresinlaboratoryanimals .
Inshort-term,repeatedanimalexposurestudies,concentrationsofpropyleneoxideabove1000mg/m3(420ppm)wereirri-tatingtotheeyesandrespiratorytract,causinglungedema(fluidinthelungs)andcentralnervoussystemdepression .Repeatedhighoraldosesofpropyleneoxideresultedindamagetothestomachliningandaslightdepressionofbodyweight .
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Chronic Effects of OverexposureCarcinogenicityLong-termstudiesonratsandmicehaveshownthatpropyleneoxideinducestumorsatthefirstsiteoftissuecontact .Tumorswereproducedthroughvariousroutesofexposure,includinginhalation,whichismostrelevanttoindustrialapplications .
Intwoseparateinhalationstudiesinrats,lifetimeexposuretohighlevelsofpropyleneoxide-inducedadenomasinthenasalpassages(atexposures≥700mg/m3or300ppm) .Inathirdinhalationstudy,hyperplasia(anincreaseinthenumberofcells)inthetargettissueofthenasalepitheliumoftheratswasreported,althoughnonasaltumorswereidentified;inaddition,anincreaseinthetotalnumberoftumorsinthetumor-bearinganimalswasreported .
Onthebasisofthedatafromthesestudiesandothers,propyleneoxideisconsideredcarcinogenictoexperimentalanimalsandhasbeenclassifiedasapossiblehumancarcinogen(group2B)bytheInternationalAgencyforResearchonCancer(IARC) .ConsistentwiththeIARCclassification,intheU .S .,propyleneoxideislistedasReasonably Anticipated to be a Human CarcinogenintheNationalToxicologyProgram’sReport on Carcinogens .IntheEU,propyleneoxideisclassifiedasaCategory2carcinogen,whichindicatesthatpropyleneoxidemaycausecancer .
Reproductive and Developmental ToxicityPropyleneoxidehasbeenreportedtohaveonlyminimalreproductiveeffectsinmaleandfemaleratsathighexposurelevels(upto300ppm),withnosignificantvariationsfromcontrolanimalsinanyofthereproduc-tiveindicesmeasured .Highexposurelevelsofpropyleneoxide(500ppm)inducedonlyminimalbodyweightchangesinpregnantratsandaslightskeletalvariationintheoffspring .TheEU’sClassificationandLabelingauthoritydoesnotconsiderpropyleneoxidetobeareproductivehazardinanimals .
Genetic ToxicologyPropyleneoxideisadirectalkylatingagentandcaninteractwithtissuemacromoleculesandproduceadducts .ThepresenceoftissueDNAadductsisevidenceofexposuretopropyleneoxide .Inin vitromicrobialandmammaliancellstestsystems,propyleneoxideisdemonstratedtobeadirectactinggenotoxicant,producingmutationsandchromosomeaberrations .Theevidencefollowingin vivoexposure,however,isnotconclusive .Allofthein vivocytogeneticandmutagenicdatawasnegativewiththeexceptionofwhenpropyleneoxidewasadministeredbyinjectionintotheabdominalcavityathighdoses .InEurope,propyleneoxideislistedasaCategory2mutagen .
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Takentogether,theavailableinformationindicatesthatpropyleneoxideisabletoreactwithgeneticmaterialformingadductsand,undercertainextremeconditions,producedamageasevidencebymutationsandchromosomeaberrations .However,currentlyithasnotbeenestablishedthatthesefindingsarelinkedtoanysignificantadverseresponsesinhumansunderusualconditionsofexposure .
Exposure LimitsThecompaniesstronglyrecommendthatuserscomplywiththeACGIHTLVguidelineof2ppm(establishedin2002) .UsersshouldremainawareoflocalTWA,STEL,PEL,orotheroccupationalexposurelevelrequirements .PropyleneoxideuserscanfindcurrentinformationaboutACGIHevaluationsofpropyleneoxideontheorganization’swebsite(www .acgih .org) .CurrentinformationcanalsobefoundontheMaterialSafetyDataSheet(MSDS)providedbyDowwithshipmentsofpro-pyleneoxide .
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Systemdesignsshouldfocusoneliminatingtheneedforpersonalprotectiveequipment .However,personalprotectiveequipmentmayberequiredincertainoperations,orinlocationswhereexposuretovapororliquidispossible,suchasintheeventofasystemfailure .Identificationofuserequirementsandselectionofpersonalprotectiveequipmentdemandcarefulmanagementconsideration .
Anoverallappraisalshouldbemadeofplantoperations,exposurepotentials,expectedexposureduration,thespecificactivitiesbeingperformed,andthetrainingonpersonalprotectiveequipmenttobeprovidedtoworkers .Thisappraisalshouldbeperformedbyaqualifiedindustrialhygienistinconjunctionwithengineering,maintenance,supervisory,andmanagementstaff .Awrittenexposurecontrolplanshouldbedeveloped .Theplanshouldidentify:
•typesofapprovedequipment(includingmanufacturer,make,andmodel);
•typesofprotectiveequipmenttouseforspecificsituations;
•proceduresformaintenance,cleaning,andstorageoftheprotectiveequipment;
•trainingrequiredinproperuseoftheprotectiveequipment;and
•otherissuesrelevanttospecificoperations .
Whenselectingpersonalprotectiveequip-mentandmanagingequipmentprograms,theoverallassessmentofpotentialexposuresshouldbeconsidered .Issuestobeaddressedincludethefollowing:
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•Aretherewaystoreduceexpectedexposuresbyinstitutingchangesineitherequipmentuseorprocedures?
•Istheexposurelikelytobeatlevelsabovetheoccupationalexposureguidelines?
•Istheexposurelikelytobeofveryshortduration,afterwhichdecontaminationcanbeimmediatelyaccomplished,orisalengthyexposurelikely?
•Istheexposurelikelytooccuronlyonceortwicepermonthasmightoccurinsomeunloadingoperations?
•Issingle-useequipmentdesirable?
NOTE: The Material Safety Data Sheet (MSDS) for propylene oxide suggests that air purifying respirators, supplied air, or self-contained breathing apparatus be used depending on conditions and when respira-tory protection is required.
Eye ProtectionPropyleneoxidemaycausesevereeyeirritationandpossiblycornealburns .Highlevelsofpropyleneoxidevaporsmayalsoirritatetheeyes .Cup-typeplasticchemicalsafetygoggles—ofgas-tightdesignandequippedwithimpact-resistantlenses—shouldbewornwheneverthereispotentialforexposuretovapororliquid .Afaceshield(8-inchminimum)maybeworntoprovideaddedsplashprotection .Or,ifvaporscauseeyediscomfort,afull-facerespiratorshouldbeworn .EyeprotectivemeasuresshouldmeetANSIZ87 .1specifications .
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Individualswearingcontactlenseswhileworkingwithoraroundpropyleneoxideshouldwearchemicalsafetygogglesatalltimes .Thepotentialforanincreaseineyeinjuryofcontactlenswearersexposedtochemicalshasnotbeendetermined .Aconservativeapproachintheselectionofpersonalprotectiveequipmentiswarranted .
Respiratory ProtectionPropyleneoxidehasasweet,penetratingodorthatdoesnotprovideadequatewarningtopreventoverexposure .Theodorthresholdforpropyleneoxideformostpeopleisbetween10-200ppm .However,theeight-hourTLV(thresholdlimitvalue)recommendedbytheACGIHis2ppmandtheOSHAPEL(permissibleexposurelimit)is100ppm .Anactivepropyleneoxidetestingandmonitoringprogramisrecommended .
Atmosphericlevelsshouldbemaintainedbelowtheappropriateexposureguidelineforpropyleneoxide .Whenrespiratoryprotectionisrequired,useanapprovedair-purifyingorpositive-pressuresupplied-airrespirator,dependingonpotentialairborneconcentrations .Forshort-termorlimitedsingle-usesituations,anapprovedair-purifyingrespiratorwithacartridgefororganicvaporsisrecommended .However,thelimitationsandbenefitsofusingair-purifyingrespiratorsshouldbeclearlyunderstood .
Foremergenciesandotherconditionswhentheexposureguidelinemaybeexceeded(forexample,inconfinedspacesorpoorly
ventilatedareas),useanapprovedpositive-pressureself-containedbreathingapparatusorpositive-pressureairlinewithanauxiliaryself-containedairsupply .
General Protective ClothingEvenwell-engineeredsystemswillrequiretheuseofpersonalprotectiveclothingintheeventofspillsorotherpotentialexposuresituations .
NOTE: Personnel should be required to wear “work” clothes, stored separately from their “street” clothes. This allows the industrial laundry to handle and wash work clothes that could be chemically contaminated.
Inalloperationsinvolvingpropyleneoxide,andwhereemployeeexposureispossible,workersshouldwearchemicalworkers’goggles,safetyhats,imperviousboots,gloves,andprotectiveouterclothing .
Trousersshouldbewornoutsidethebootsandsleevesshouldbetapedtogloves(withtaperedsleeveinsertsbetweensleeveandglove)topreventcontactofpropyleneoxidewiththeskin .
Clothingtype,make,andmaterialsofconstructionshouldbecarefullyevaluatedusingan“exposurecontrolmanagement”approachthatevaluateseachpotentialexposuresituation .Forexample,protectiveclothingforsplashprotection(whichisdisposedoforimmediatelycleanedafterexposure)maynotneedtobeasdurableasprotectiveclothingforcontinuousexposuresituations .Thoroughlyevaluatethedatasuppliedbyyourclothingmanufacturer,
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payingparticularattentiontotheexpectedclothingperformanceintheeventofexpo-suretopropyleneoxide .
Itisimportanttorecognizethehazardsassociatedwiththechoiceofclothingmaterials .Forexample,leatherisahazardwhencontaminatedwithpropyleneoxideandshouldnotbespecifiedforuse .Leathercanabsorbpropyleneoxideandmaintainalowexposureleveloveraprolongedperiodoftime,causingasevereburnbeforedis-comfortregisters .
Itisalsonecessarytosetguidelinesfordecontaminatinganddestroyingprotectiveclothing .Leatherarticlesshouldbedestroyed topreventaccidentalreuse .
Impervious Gloves and ClothingThefollowinginformationisprovidedwiththecautionthatitshouldbeunderstoodthatglovesandclothingareusedasameansofpreventing incidentalcontactonly .
Whenchoosingimperviousprotectiveclothing,thereareseveralfactorstoconsiderinadditiontotheintrinsicbarrierproperties .Performancefactorstoconsiderinclude:
•Thicknessofclothingmaterial .
•Permeationresistancetopropyleneoxideandotherchemicalswithwhichtheclothingmaycomeincontact .
•Fabricationtechnique(particularlyhowseamsaresealedand/orconstructed) .
•Laminateconstruction,ifapplicable .
•Physicalrequirementsoftheclothingthatmayberequireddependingonspecificconditionsofuse,suchasstrength,dexterity,abrasionandtearresistance,orthermalprotection .
•Durationofpotentialexposure .
•Otherfactorsspecifictoyourapplicationoruse .
Customersarestronglyadvisedtoobtaininformationfromclothingandsafetyequip-mentsuppliersaboutproductperformanceingivensituationsandthebarrierpropertiesoftheprotectiveequipmenttopropyleneoxide .Selectionofspecificitemssuchasfaceshields,gloves,boots,apron,orfullbodysuitwilldependonthespecificoperationaswellascharacteristicsoftheitemsthemselves .
Examplesofglovebarriermaterialsthathavebeenfoundtobeprotectiveinpropyleneoxideexposuresinclude:
•butylrubber,
•chlorinatedpolyethylene,
•polyethylene,
•ethylvinylalcohol(EVOH)laminate,
•polyvinylalcohol(“PVA”),and
•styrene/butadienerubber .
Inspecificsituations,anddependingonsupplierinformation,naturalrubber(“latex”),Neoprene®,nitrile/butadienerubber(“nitrile”or“NBR”),polyvinylchloride(“PVC”or“vinyl”),orViton®maybeacceptable .
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Protective Equipment TrainingThekeytoasuccessfulprogramistrainingpersonnelintheuseofprotectiveequipment .Withoutagoodunderstandingofthewaystheprotectiveequipmentworksanditslimit-ations,aswellasofcorrectmaintenanceprocedures,theexpectedprotectionfactorsareunlikelytobeachieved .Specificpropertiesofpropyleneoxide,suchastoxicityofpropyleneoxidevaporsthroughskinexposure,andtheprotectionrequiredtomitigatetheeffectshouldbepartofthetrainingprogram .Awell-designedtrainingprogramalsoincludesinstructionintheproperwaytowear,use,clean,andmain-taineachpieceofequipment .
Respiratoruserequiresmedicalapprovalforeachindividualuserandapersonalfit-testtoensureeffectiveprotection .Detailsregardingrespiratorusecanbefoundin29CFR§1910 .134 .
Trainingshouldbedocumentedandreviewedwitheachemployeeonaregularbasiswithretrainingscheduledonaspecifiedandregularbasis .
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Threedifferentmethodsarerecommendedforsamplingpropyleneoxide—on-streamanalyticalequipment,safety-coatedglassbottles,orstainlesssteelcylinders .Whichevermethodisused,proceduresandequipmentshouldbecarefullydesignedtominimizepersonnelexposureorventingtotheatmosphere .
On-stream MethodsOn-streamsamplingequipmenthastwoadvantagesinpropyleneoxideoperations .First,personalexposurelevelsarekepttoaminimum .Second,samplecollectiondoesnotexposesamplestotheair .Isolatingsamplesfromtheatmosphereisimportantforpropyleneoxide,which,becauseofitshygroscopicnature,willpickupwaterfromtheairifanopensamplingsystemisused,resultinginanartificiallyhighapparentwatercontent .
Manual MethodsSafety-Coated Glass Bottle MethodConsiderminimizingthedead-volumeandallowthesampletobecollectedwithverylittlepurging .
Bottlecapsshouldhaveapolyethylenesealtopreventcontaminationfromagluedorpaperseal .
•Tominimizepersonnelexposure,useeitherclosed-loopsamplingorsurroundthesamplepointwithaboxconnectedtoavacuumsource .Theairflowvolumemustbegreatenoughtocreatethesamevelocityacrosstheopendoorfaceasisrequiredinalaboratoryhood .
•Becauseofthehygroscopicnatureofpropyleneoxide,samplesmayindicateanartificiallyhighwatercontentwhenthismethodisused .
•Materialsshouldbebelowabout32°C(90°F)whencollectingsamplesinbottlestopreventover-pressuring .
Stainless Steel Cylinder Method•Forpropyleneoxidesamples,aDOT3E
cylinderwithaservicepressureof1800psigshouldbeused .Thespecificationforthiscylinderisoutlinedin49CFR§178 .42 .
•Screwedconnectionsmustbesealed .Apolytetrafluoroethylene(PTFE)tapewithappropriatechemicalpropertiesmaybeused .
•Areliefvalveshouldbeprovidedonthecylinderassembly .
•Thecylindershouldcontainadiptubetopreventitfromfillinghydraulically .
•Thecontentsandsamplingdateshouldbeclearlymarkedonthecylinder .
•Thecylindermaybeevacuated,con-nectedtoalowdeadvolumesampleconnection,filled,andthendisconnected;orconnectedtoaconstantrecycleflow-throughsystem,flushed,filled,andthendisconnected .
Other Safety Considerations•Asafetyshowerwitheyewashcapability
shouldbelocatednearthesamplingpoint .
•Theareaaroundthesamplelocationshouldbefreeofignitionsourcesandotherhazards .
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•Samplingcontainersshouldbeclearlylabeledanddedicatedtopropyleneoxideservicetominimizethechanceofcon-taminationorpossibleviolentreactions .
•Onlytheamountofsampleneededforanalysisshouldbecollected,andanyresiduemustbedisposedofaccordingtoallapplicablerulesandregulations .
•Avoidsmokingareas,controlrooms,andareaswhere“hotwork”isinprogresswhentransportingsamplestothelaboratory .
•Alllaboratoryequipmentusedinanalyzingpropyleneoxidesamples(suchastheventilationhoodandrefrigerator)shouldconformtoelectricalstandardsequivalenttoClass1,Division1,GroupB*oftheNFPA70,NationalElectricalCode .
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AccordingtotheOccupationalSafetyandHealthAdministration(OSHA),thechem-icalindustryintheU .S .hasoneofthebestsafetyrecordsofanyindustrialsector .Tomaintain—andevenimprove—thissuperiorsafetyrecord,itisveryimportantthatchemicalmanufacturersandprocessorsestablishaneffective,well-developedplantoensurequickandeffectiveresponsetoemergencies .
Emergencyplanningshouldconsiderallaspectsofemergencysituations,includingnotonlythosethatmayoccuron-site,butalsoincidentsthatmayoccurenroutetothesite,inthesurroundingcommunity,orinthecommunityatlarge .
Thissectiondescribesaprocessforemergencyplanningandprovidesspecificinformationaboutspills,fire-fighting,andassociatedwastedisposal .Plansshouldbedevelopedwiththeassistanceoflocalfirefightersandotheremergencyresponsepersonnel .
Plan Development Manyorganizationshavepublishedcomprehensiveguidanceondevelopingcrisismanagementplans .Forexample,OSHAhasdevelopedabookletcalledHow to Plan for Workplace Emergencies and Evacuations (http://www .osha .gov/Publications/osha3088 .html) .Thediscussionpresentedhereisnotall-encompassing;rather,generalprin-ciplesimportantforpropyleneoxideuserstoconsiderarediscussed .
Oneofthefirststepsindevelopingacrisismanagementplanistodefinevariouspotentialcrisisscenariosastheyarerelatedtoplanning,preparation,mobilization,response,recovery,andpost-incidentfollow-up .Theprocessshouldbecomprehensiveandconsiderallaspectsofpotentialemergencies,includingwarningalarms,evacuationassemblyareasandescaperoutes,personnelaccountability,communicationvehicles,chainofcommand,notificationofauthorities,dealingwiththemedia,andotherimportantconcerns .Ifyourplantdoesnothaveacrisismanagementplan,itisrecommendedthatonebedeveloped .
Assumingthatageneralplanexistsforyourfacility,thetaskofpreparingforanewinstal-lationstartswithproperdesign .Engineersshoulddesignthebulkstorageandhandlingsystemtominimizehazardousconditionsandtoallowquickresponseifemergenciesoccur .Forexample,theuseofnitrogenpaddingisrecommendedonpropyleneoxidestoragevesselstoeliminateoxygenfromthevesselandtherebyreducetheriskoffire .Anexcel-lentwaytotestanewdesignistoperformaprocesshazardanalysis .Aspartofthehazardidentificationandmanagementprocess,itisalsoimportanttodevelopsafeoperatingprocedures .
Aftercompletingbothanoverallcrisismanagementplanandaprocesshazardanalysis,thenextlogicalstepistodevelopwrittenproceduresforrespondingtopos-sibleemergenciesassociatedwiththenewinstallation .Theseplansshouldbecarefully
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tiedintotheemergencyplanandcoveralloftheaspectsrequiredintheoverallplan .Theproceduresshouldalsoincludeaspecificplanforcontrollingtheemergency .Proceduresshouldcoverallparameters,includingfireextinguishersandotherfixedfireprotectionequipment,emergencyblockvalves,spillcontainment,personalprotectiveequipmentandclothing,andsoon .Allpost-emergencyprocedures,suchaswastecleanup,wastedisposalandequipmentchecks,andproperreportingshouldalsobeconsidered .Theplanshouldbetestedinasimulatedsituationtoensureitseffectivenessinarealemergency .
Anotherimportantstepindevelopinganemergencyplaninvolvescommunityinterac-tion .Theplanshouldbeintegratedintothecommunity-wideemergencyresponseplan .
Fire Hazards TheOccupationalSafetyandHealthAdministrationclassifiespropyleneoxide1asaClass1Aflammableliquid .TheNationalFireProtectionAssociation(NFPA)Code30definespropyleneoxideasaClass1Aflammableliquid .ForapplicationoftheNationalElectricalCode2,propyleneoxideisaClass1,GroupB*flammableliquid .
Vaporsofpropyleneoxideatconcentrationsbetween1 .6%and42%inaircanexplodeifanignitionsourceispresent3 .Propyleneoxidevaporsareheavierthanairandmaytravelaconsiderabledistancetowardasourceofignitionandflashback .Allprecautionsnecessaryforthesafehandlingandstorageofavolatileflammableliquidorvaporshouldbestrictlyobservedfor
propyleneoxide .Aqueousmixturesaslowas0 .75%propyleneoxidemaybeflammable .
Storageareasshouldbedesignedtopreventexposureofpropyleneoxidecontainerstohazardsfrompotentialfires(seepage30,“BulkHandling”) .Page38,“Delivery&Transfer,”includesrecommendationsforthesafeunloadingandtransferofpropyleneoxide,whicharenecessarytominimizethefireandexplosionhazardwhileperformingtheseoperations .
Ifpropyleneoxideisinvolvedinafire,preventunauthorizedindividualsfromenteringthearea,andevacuatetheareadownwindfromthefire .Firesshouldbefoughtfromasafedistanceupwind .Thermaldecompositionproducts,suchascarbondioxide,carbonmonoxide,andperhapsothertoxicgasesandvapors,maybegenerated .Propyleneoxide,wheninvolvedinafire,burnsrapidlywithtremendousheat .Table1(page4)andFigure1(page7)providepropyleneoxideflammabilitylimits .
Fire Prevention and ProtectionPropyleneoxide,whenignited,burnsrapidlywithhighheat .Becauseofthehighvaporpressureofpropyleneoxide,itiscapableofreadilyformingexplosivemixtures .Sourcesofignition,includingheat,sparks,flames,andstaticelectricity,mustbeavoided .Compliancewiththisbasicrulerequirescontinualoversightandmanagementthatshouldtypicallyincludethefollowingcombinationofworkpracticesandmechanicalcontrols:
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1 29CFR§1910 .106
2 NEC-NFPA70
3 SeeFigure1onpage7 .
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•Defining“nosmoking”and“hotwork”policiesinareaswherepropyleneoxideisused;
•Usingnon-sparkingtoolsifworkinginanareawherepropyleneoxidevaporscouldbepresent;
•Groundingmetalliccontainers/vesselsinwhichpropyleneoxideisstored;
•Bondingandgroundingmetallicreceivingcontainers;
•Enforcingstringentwelding,cutting,andburningpermitsystems;and
•Implementinginsideandoutsidestoragemethodsthatcomplywithlegalrequirementsandgoodindustrypractice .
Tanksandequipmentcontainingliquidpropyleneoxideshouldbeprotectedwithautomaticdelugeorsprinklersystemsincludingcoverageofpumpsandshaftsealareas(perNFPAdesigncriteria) .Amanuallyactivated,remotelylocatedswitchshouldalsobeprovided .
Theuseofinstalledflammable(combustible)gasdetectorsinat-riskareas—suchasthosearoundpropyleneoxidepumpsorloadingandunloadingoperations—isrecommended .
Heatmaycreateabuild-upofpressureandcauseclosedcontainerstorupture .Awaterfogmaybeusedtocoolthecontainers .Watermaybeineffectiveasanextinguishingagent .Preventliquidfromenteringexternalwatersourcesandsewersbybuildingdikesasnecessarytocontainflow .
PertheNFPA,theelectricalclassificationforwell-designedandmaintainedpropyleneoxidehandlingareasisClass1,Division2,GroupB* .Areaswherethepresenceofpropyleneoxidevaporsisprobable,suchasimmediatelyabovetanksorvessels,nearvents,orwithinbuildingsorretainingwallsshouldbeclassifiedasClass1,Division1,GroupB* .
Static ElectricityThetransferofpropyleneoxidecancreatestaticelectricitycharges,whichcanactasanignitionsourceforflammablevapors .Thechargecandevelopevenwhentheliquidflowsorispouredthroughair .Tominimizetheriskofignition,bondingandgroundingofequipmentisrequiredbyfederalregula-tion(29CFR§1910 .107),buildingandfirecodes,andindustrypractice(NFPA70,NFPA77,NFPA30) .Bondingprovidesalow-resistancepathtocurrentflowbetweentwosurfacesthatarephysicallyseparatedorbecomeseparated .PerNFPA77,amaximumof1megaohmisacceptable,thoughlowervaluesreducerisk .
Groundingconnectsthecontainmentvessels,pipes,etc .,toagroundingelectrode(ground)intheearthbymeansofconductorsweldedorattachedtoboththeequipmentandtheground .
Fillingvesselsandcontainersthroughadiptubeorthroughabottomnozzletominimizethestaticcreatedbyfree-fallingliquidisrecommended .
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Fire and ExplosionPropyleneoxidefirescanbedifficulttoextinguishbecauseofthematerial’slowflashpointandhighvaporpressure .Considertheuseofwaterfog,drychemical,alcoholfoam,orcarbondioxidewhenfightingfires .WatermaybeusedtocoolpropyleneoxidecontainersexposedtoafiretoreducethepotentialforaBLEVE(BoilingLiquidExpandingVaporExplosion) .Ifaleakorspillhasnotignited,waterfogmaybeusedtodispersethevaporsandtoprovideprotec-tionforworkersattemptingtostopaleak .Waterfogmayalsobeusedtoflushspillsawayfrompotentialignitionsources,bearinginmindthatanaqueoussolutionaslowas0 .75%propyleneoxidemaystillbeflammable .
Thosewhomaycomeintocontactwiththevaporsshouldwearappropriatesafetyequipment,suchasapositive-pressure,self-containedbreathingapparatus .Ifcontactwithvaporsispossible,wearfullprotectiveclothing .
Formoreinformation,reviewtheFlammableandCombustibleLiquidsCode(NFPANo .30),NationalElectricalCode(NFPANo .70),LightningProtectionCode(NFPANo .78),andFire-HazardPropertiesofFlammableLiquids,GasesandVolatileSolids(NFPANo .325M) .
Fire FightingIfyourfacilityreliesoncommunityfirecompaniesforfireresponse,informationregardingpropyleneoxideoperationsandstorageshouldbeprovidedtothe
responders .Informationshouldincludefacilitylayoutsindicatingthestoragelocationsandquantitiesofpropyleneoxide .Drillsshouldbeconductedperiodicallywiththefirecompany,andfacilityinformationshouldbeupdatedonaregularbasis .
Ifyourfacilityhaschosentheoptionofaninternalfirebrigadeforstructuralfirefighting,compliancewiththeOSHAFireBrigadeStandardisrequired .Theserequire-ments,asdefinedin29CFR§1910 .156,includetheorganizationofafirebrigade,personalfirefightingequipment,andtrainingrequirements .
Firefightersshouldusefullprotectiveclothingandequipment,includingNationalInstituteforOccupationalSafetyandHealth/MineSafetyandHealthAdministration(NIOSH/MSHA)-approvedself-containedbreathingapparatuswithfullfacemaskoperatedinthepressuredemandmode(seepage12,“Inhalation”and“Ingestion”) .Waterspraycanbeusedtodispersevaporstoprotectthefirefightersthatmaybeattemptingtostopaleak .
Ifafireiscontrollableorpropyleneoxidecontainersarenotexposedtodirectflame,anevacuationzonewithaminimumradiusof1,500feetmaybeneeded .Ifthefirebecomesuncontrollableorpropyleneoxidecontainersareexposedtodirectflame,anevacuationzonewithaminimumradiusof5,000feetmayberequired .Insomeinstances,dependingonspecificfacilityhazards,itmaybeprudenttoallowapropyleneoxidefiretoburnitselfout .Aqualifiedfirefightingexpertshouldmakethisdecision .
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Afterafirehasbeenextinguished,residualpropyleneoxidecontaminationmayoccur .Residualcontaminationmayrequireacleanupoftheliquid .Individualswhoengageinsuchacleanupshouldbethor-oughlytrainedinpropertechniquesandhavereceivedtraininginaccordancewiththeOSHAHazardousWasteOperationsandEmergencyResponse(HAZWOPER)standard,29CFR§1910 .120 .
Fire SuppressionSomefoamsystemsmaybeusedtoextinguishfires,buttheeffectivenessofthefoamsmustbereviewedwiththefoammanufacturer .Theintensityofapropyleneoxidefiremaysignificantlydiminishtheeffectivenessofcertainfoams .Foamapplieddirectlytoopensurfacefireswillrequireahigherconcentration,ahigherapplicationrate,and/orrepeatedapplications .Becauseofpropyleneoxide’slowflashpointandhighvaporpressure,propyleneoxidemayreignitefromhotsurfaces .
Theemergencyresponseplan(seepage22,“PlanDevelopment”)shouldincludetheamountandlocationsofextinguishingequipmentnecessarytoextinguishapropyleneoxidefireandanevaluationofaworst-casefirescenarioisprudent .
Propyleneoxideissolubleinwaterandtheresultingsolutionrequiressubstantialdilutiontocontrolthevaporabovethemixture .Inconfinedspacessuchassumpsorsewers,adilutionfactorgreaterthan150to1,orlessthan0 .75%propyleneoxide,maybenecessarytopreventvaporconcentrationsabovethe20%lowerexposurelimit(LEL) .
Portablefireextinguishersshouldbeplacedinthevicinitywherepropyleneoxideishandledorstoredandinlocationswherethepotentialforspillsorleaksexists .ClassBdrychemicalorfoamextinguishersshouldbeusedwhenfightingsmallpropyleneoxidefires .NFPA10containsguidelinesforthecorrectselection,use,distribution,inspection,maintenance,andrechargingofportablefireextinguishersandshouldbereferredtowhendesigningaworkarea .
Emergency Planning
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Aqueoussolutionsofpropyleneoxidedegradeintheenvironmentandarehydro-lyzedtopropyleneglycolwithanaveragehalf-lifeof13days .Thelengthoftimeforpropyleneoxidedegradationvariesdependingonconditionsoftheaquaticmedium .Aquaticorganismscanmetabolizepropyleneglycol .Propyleneglycolisclassifiedasreadilybiodegradable .
C3H6O + H2O C3H8O2
Propylene + Water Propylene Oxide Glycol
Propyleneoxidemaycontaminatesoilifaccidentallyspilledandspreadbyrainorgroundwater .Degradationinwetsoiloccursthroughhydrolysistopropyleneglycol .Indrysoil,propyleneoxideevaporatesintotheair .
Studiesindicatethatpropyleneoxide,becauseofitswatersolubilityandconversiontopropyleneglycol,doesnotaccumulateinaquaticorterrestriallifeforms .
Spills and LeaksFacilitiesinwhichpropyleneoxidewillbestoredand/orhandledshouldbedesignedtocontainand/orcontrolspillsinprocessareasaswellasinloading/unloadingoperations .Soilandgroundwatercontaminationthatmayresultfromanaccidentalspillofpropyleneoxidecanbeminimizedbyinstallationofcurbs,sumps,andimperviouscontain-mentareas .
Concretecurbsorearthendikesshouldbeslopedfromthepointofthepotentialspilltoacollectionbasinorsumpandshouldbe
usedtoretainpropyleneoxidewithinthecontainmentarea,thusminimizingworkerexposureandoverallenvironmentalimpact .Thetotalvolumeofthecontainmentareashouldbeadequatetohandleaworst-casereleaseofpropyleneoxide .Forstoragetanks,thecapacityofthecontainmentareais,ataminimum,generallythevolumeofthelargeststoragetankinthedikearea .Dikeorcurbdesignshouldprovideanallowanceforaccumulatedrainfall .
Pumps,piping,andequipmentdesignedtooperatewithinpotentialspillareasshouldbecompatiblewithpropyleneoxideandfreeofpotentialignitionsources .
Ifpossible,allpumpsandancillaryequip-mentshouldbelocatedoutsidetheprimarycontainmentareaandshouldbeprovidedwithcurbingtocollectdrips,leaks,andminorspills .Drainvalvesmaybeinstalledatthelowpointofthecontainmentareaorsump .Duringnormaloperations,alldrainvalvesshouldbeinaclosedposition .
Thereportablequantity(RQ)forpropyleneoxidespillsintheU .S .is100pounds .Intheeventofapropyleneoxidereleasetotheenvironmentequaltoorgreaterthan100pounds,theNationalResponseCentermustbenotified .ThetelephonenumberoftheNationalResponseCenteris(800)424-8802 .ThisreportingrequirementisaprovisionofSections103(a)and(b)oftheComprehensiveEmergencyResponse,CompensationandLiabilityActof1980(CERCLA),asamended .Reportablequantitiesarelistedin40CFR§302 .4,Table302 .4 .
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Environmental Protection Agency National Response Center
IN CASE OF PROPYLENE OXIDE RELEASE OF �00 OR MORE POUNDS
NOTIFY 1-800-424-8802
Inadditiontotheabovereportingrequire-ment,Section304oftheSuperfundAmendmentsandReauthorizationActof1986(SARA)requiresthatareleasetotheenvironmentofhazardoussubstancesinquantitiesequaltoorgreaterthantheappli-cableRQbereportedtostateandlocalauthorities .Theseagenciesarelocationspecificandshouldbeincludedinthefacility’semergencyresponseplan .
Anyaccidentaldischargeofpropyleneoxideorwastecontainingpropyleneoxideintothemunicipalsewersystemshouldbereportedimmediatelytolocalauthorities .Thedis-chargeshouldbedilutedwithcopiousquantitiesofwatertoreducethefireandexplosionhazard .NationalPretreatmentStandards,40CFR§403 .5,prohibitthedischargeofpollutantsthatmaycreateafireorexplosionhazardinthesewersystemorpubliclyownedtreatmentworks .
Intheeventofaspillofpropyleneoxide,allnon-essentialpersonnelshouldbeevacuated .Allignitionsourcesmustbeextinguishedimmediately .Afterdonningtheappropriatepersonalprotectiveequipment(seepage16,“PersonalProtectiveEquipment”),thespillshouldbecoveredwithwatersprayorfoamtominimizepotentialfirehazardfromvaporizationofthepropyleneoxide .
Dependingonthevolumeandlocationofthespill,recoverybyavacuumtruckmaybesuitable .Residualpropyleneoxideinthecontainmentareashouldbeflushedwithwaterintoasumporcollectionareaforsubsequenttreatmentordisposal .
Waste DisposalPropyleneoxideisaflammableliquidandishazardouswhendischargedtotheenviron-ment .Inareaswherepropyleneoxidemaybereleasedorhandled,accessshouldbelimitedtorequiredpersonnelonly .
OccupationalSafetyandHealthAdministrationregulation29CFR§1910 .120appliestothehandlingofspillsofpropyleneoxidewaste .Thisregulationappliestopersonnelengagedinthefollowingactivities:hazardouswasteresponseunderCERCLA,cleanupoperationsundertheResourceConservationandRecoveryAct(RCRA),operationsinvolvinghazardouswastestorage,hazardouswastesites,andemergencyresponse .
Aqueoussolutionscontaininglowconcen-trationsofpropyleneoxidecanbetreatedbiologicallyinawastetreatmentplant .Biologicaltreatmentcanalsobeconsideredfordisposalofminorspillsprovidedthatthesystemisacclimatedtopropyleneoxideandpropyleneglycol,andthetreatmentsystemhasanyrequiredpermitapprovals .
Incinerationofcontaminatedsoilandliquidpropyleneoxideisalsoanacceptabledisposalalternative .
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Ifpropyleneoxideprocesswasteistreatedbiologicallyatapubliclyownedtreatmentworksfacility,thelocalauthorityshouldbeconsultedtodetermineappropriaterequirements .Ifpropyleneoxideisbiologi-callytreatedon-siteandthendischargedtosurfacewaters,thetreatmentplanteffluentshouldcomplywithapplicablefederal,state,andlocaldischargepermitprovisions .
Allwastedisposalofpropyleneoxideshouldcomplywithallapplicablelawsandregulations .
AbsorbentsClay-basedabsorbentsshouldnotbeusedbecausetheycanreactwithpropyleneoxideresultingintheevolutionofheat(seepage3,“InstabilityandReactivityHazards”) .Heatfromthisreactioncanresultinspontaneouscombustionasauto-ignitiontemperaturescanbereached .
Ingeneral,highsurfaceareaabsorbentsmayresultingenerationofflammablevapors .Therefore,theuseofwater,ratherthanabsorbents,isthepreferredmethodofcleaningupapropyleneoxidespill .
Environmental
Environmental
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Someimportantconsiderationsinthedesignandconstructionofpropyleneoxidestorageandhandlingfacilitiesareflammability,environmentalcontamination,volume,andworkerexposure .Specificdesignrequirementsforpropyleneoxidereceivingandstoragefacilitiesandforhandlingpropyleneoxidedependonseveralfactors,includingvolumesstoredorhandled,containertype,modeoftransportation,processesusedatthefacility,proximitytootherhazardousmaterials,andtheapplicablelawsandregulationsregardingthestorageanduseofpropyleneoxide .
General Design ConsiderationsSystemsforunloading,handling,andstoringpropyleneoxiderequirethesameanalysisanddesignexpertiseassystemsforotherhazardouschemicalproducts .Thefollowinginformationlistsgeneralconsiderationsimportantindesigningsuchsystems .
Fragiledevicessuchasglassorplasticsightandgaugeglasses,bull’s-eyeflowindicators,andothersuchdevicesaresubjecttofailurefromshockandthusshouldnotbeusedinpipingsystems,vessels,orequipmentinpropyleneoxideservice .
Expansionbellowsorflexibleconnectionsshouldnotbeusedinfixedorpermanentpropyleneoxidepipinginstallations .
Gasketsofspiral-woundstainlesssteelwithflexiblegraphiteorPTFEfillerandcircumferentialinternalandexternalmetalretainingringsarepreferredforpipeandvesselflanges .Metal-reinforcedflatflexiblegraphitegasketsarealsoacceptableinclass150and300service .Valvebonnetgasketsandpumpbodygasketsmustbeofspiral-woundstainlesssteelwithflexiblegraphiteorPTFEfiller,ormetal-reinforcedflatflexiblegraphitegasket .
Fewelastomersaresuitableforliquidpropyleneoxideservice .ElastomerssuchasChemraz505®andKalrez2035®areacceptable .
Generally,insulationisnotneededonpropyleneoxidetransferpipingandequipment .Ifrequired,selectaninsulationmaterialthatisneitherreactivewith,norsolublein,propyleneoxide .Knownacceptablematerialsincludeglassfoam,expandedperlite,andcertainpolyurethane-typeinsulatingmaterials .Otherinsulationmaterialsshouldbetestedpriortouse .
Bulk Handling
Bulk Handling
3�
Bulk Handling
Bulk Handling
M
LT
LT LI
PC
TI
1. PRESSURE SAFETY VALVE2. TANK SUPPORT3. TANK DRAIN4. SAFETY RAILING5. MANWAY6. LEVEL TRANSMITTER W/OUTPUT GAUGE
TO PROCESS
TO CONTAINMENT DEVICE TO CONTAINMENT DEVICE
RECY
CLE
DIP
TUBE
PROPYLENE OXIDE
NITROGEN SUPPLY
FROM TANK CAR OR TRUCK
REFRIGERATIONSYSTEM
MAXIMUM FLOW CAPACITY OF PRESSURE CONTROL VALVE (13) SHALL NOT EXCEED RELIEF CAPACITY OF PRESSURE SAFETY VALVE (1)
TO SHUTDOWNINTERLOCKSAND ALARMS
7. OUTLET LINE8. APPROVED GROUND9. FILTER
10. PUMP11. PRESSURE GAUGE W/DIAPHRAGM SEAL12. PRESSURE CONTROLLER (SPLIT RANGE)
13. PRESSURE CONTROL VALVE14. N.F.P.A INDENTIFICATION CODE15. BLOCK VALVE16. CHECK VALVE17. CONTAINMENT DIKE18. TEMPERATURE INDICATION19. LEVEL TRANSMITTER
6
32 2
1
4
5
13 13
14
15 15 15 15
15 15 15
15
15161717
18
19
7
1011
9
12
8 88
Figure 3 Typical Pressure Storage Tank ConfigurationThisfigureillustratesatypicalconfiguration,andisnotintendedtobeusedasadesignspecification .Qualifiedprofessionalsmustexerciseengineeringjudgmenttoestablishsitespecificationsthatmeetapplicablerequirements .
�. Pressure Safety Valve 2. Tank Support 3. Tank Drain 4. Safety Railing 5. Manway 6. Level Transmitter with Output Gauge 7. Outlet Line 8. Approved Ground 9. Filter �0. Pump
��. Pressure Gauge with Diaphragm Seal �2. Pressure Controller (Split Range) �3. Pressure Control Valve �4. NFPA Identification Code �5. Block Valve �6. Check Valve �7. Containment Dike �8. Temperature Indication �9. Level Transmitter
32
Vessels Storagevessels,pressurevessels,andequip-mentthatwillcontainpropyleneoxideatoperatingpressuresabove15psig(1 .02bar)shouldbedesignedinaccordancewiththeASME(AmericanSocietyofMechanicalEngineers)BoilerandPressureCodeorequivalentstandards .
Storageandprocesstanksdesignedtocontainpropyleneoxidewithoperatingpressureslessthan15psigshouldbedesignedinaccordancewithAPI(AmericanPetroleumInstitute)standard620orequivalentstandards .ThedesignpressureofAPI620tanksshouldbeashighaspractical,atleast5psigfortankslargerthan50feetindiam-eterandaminimumof10psigforsmallertanks .Requirementsforvesselstorage,includingsecondarycontainment,arepresentedinNFPA30 .Considerationsinsiteselectionandtankspacingincludeproximitytootherflammablematerialstoragefacili-ties,nearbysourcesofignition,accessibilityforfirefightingequipment,andimpactofavaporcloudexplosiononnearbyareas .InstallationsshouldcomplywithNFPA30andNFPA70regardingtheseissues .Thesestandardsareintendedtoensurethattankspossesssufficientstructuralstrengthandpressurereliefsystemstopreventcata-strophiclossofcontentsineithernormalserviceorunderfireconditions .
Storagetanksshouldbesituatedwithincontainmentsystemsthatareequippedtoprovidedetectionandcontrolofanaccidentalreleaseofpropyleneoxide .
Storagetanksandfacilitiesforloadingandunloadingpropyleneoxidefromtankcarsortrucksshouldhavespillretentionwalls,dikes,orcurbstodirectspillsintocontain-mentareas,whicharesufficientlyremotetoaccommodatesaferecoveryordisposal .Iftanksaregrouped,thepondshouldhold110%ofthelargesttank’scapacity,orbelargeenoughtoaccommodateavolumeofdelugewaterthatallowsadequatetimetodetectandrectifyasignificantleakorspill .Theroutingofpropyleneoxidetotheimpoundingareashouldavoidpossibleignitionsources,andshouldnotexposeotherstorageorprocesssystemstodamageintheeventthatthespillageisignited .Routingthroughundergroundlineswithfiresealsispreferred .ContainmentsystemdesignandoperationshouldconformtoNFPA30 .
Instrumentationattheunloadingstationshouldwarntheoperatorofthepotentialforoverfillingandactivateatotallyindependentflowshut-offdevicewheneveroverfillisimminent .Thedeviceshouldnotbeusedasaregularoperatingtoolfordeterminingtanklevel .Bulkstoragetanksshouldbeventedtoacontainmentdevice,whicheliminatesdischargesofpropyleneoxidevaporstotheatmosphere .Thecontainmentdeviceshouldbedesignedtopreventthepassageofaflamefromonecontainertoanother .
Alltanksandvesselsshouldbeprotectedfromover-pressure .Pressurereliefsystemsshouldemploydualinstallation,three-way
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33
pressurereliefvalves,soonevalveisinserviceatalltimes .Dischargefrompressurereliefvalvesshouldnotbemanifoldedandshouldbedirectedawayfromequipment,piping,andpersonnel .Designofsafetyvalvesshouldconsiderthepossibilityoffiredamagetothevesselbeingprotected .Rupturediscs,usedinconjunctionwithpressurereliefvalves,shouldbeprovidedwithableed-typeopeningbetweenthediscandvalve,andtheconnectionshouldbepipedintothereliefvalvedischargepipingthrougharestrictingorifice .Acombustiblegasdetectorthatactivatesanalarmshouldbeplaceddownstreamfromthebleedreturnandreliefvalves .
Designallvesselssothatpropyleneoxidecannotfree-fallthroughthevaporspaceofthevessel .Onedesignthathasbeenfoundeffectiveistoinstalldiplegswithsiphonbreakersinvesselswhereentryisthroughtheupperportionofthevessel .Designalltanksandequipmenttoeliminatestagnantareaswherelittleornofluidturnoveroccursineitherthevapororliquid .Flat-bottomedpressurestoragetanksshouldbedesignedwithfoundationsthatwillwithstandthecompressionloadofthetankfullofwater,andshouldbereinforcedwithaheadstiff-eningringandanchoredaroundthebottom .
Thenumberofvesselnozzlesshouldbeheldtoaminimum .Specialattentionshouldbegiventoallnormallyactivenozzlesintheliquidzone,astheseshouldbefittedwithmotor-operatedemergencyblockvalves .
Bothlocalandremoteoperationofthevalvesshouldbeprovided .Thevalvesshouldfailclosedintheeventofinstrumentairorelectricalfailure .Theclosurerateoftheemergencyblockvalvesshouldbeadjustedsoastopreventhydraulicshockuponclosure .
Emissionsresultingfromloadingandunloadingoperationsshouldbecontrolledusingcontainedsystems;vaporbalancingandproductrecoveryarethepreferredmethods .Ventsmaybedirectedtoflaresorincinerators,providedtheyareremotelylocatedandaredesignedwithflamearrestorsandassociatedinstrumentationtopreventflashback .
Refrigerationandinsulationofstoragetanksarenecessaryonlywhendictatedbytheuser’sprocess .Forrefrigeratedstorageofpropyleneoxide,coolingbyplatecoilsattachedtothetankexteriorisrecommendedtopreventpossiblecontaminationbythecoolant .Whenagreaterdegreeofcoolingisrequired,anexternalheatexchangerwithpropyleneoxidecirculationisrecommendedoveraninternalcoil .
InstrumentationsituatedonorinpropyleneoxidetanksandvesselsshouldmeetelectricalclassificationNFPA30guidelines[Class1,GroupB*] .Instrumentationshouldbedesignedsothatpropyleneoxidewillnotmakecontactwithenergizedelectricalconnectionsandwillnotenterairsupplylinesbecauseofaruptureddiaphragmorotherfailure .
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Theminimumrecommendedinstrumentationforpropyleneoxidevesselsis:
•Temperature,levels,andpressuresindicationgauges(recordinginstrumentsarepreferred) .
•Audio-visualalarmsforhightemperature,highandlowpressure,andhigh-fill-levellimits .
•Asecondhigh-fill-leveldevicesettoactuateanalarmatahigherlevelthanthefirstandtoautomaticallyclosethemotor-operatedblockvalveinthefillline .
•Anautomaticpadanddepadsystemusingnitrogenasthepadgasonallstoragevessels .Devicestopreventbackflowshouldbeinstalledinthenitrogensupplylineaswellastheprocesslines .Ahigh-puritynitrogensupplyshouldbeusedandmustnotcontainammoniaoramines .
Flammable(combustible)gasdetectorsshouldbeuniformlydispersedaroundequipmentcontainingpropyleneoxide .Thedispersionpatternshouldensurecoverageregardlessofwinddirection .Locatingdetectorsatlowpointsneardrainagestructuresandoutletsinprocessandstorageareasisalsoadvisable .
PipingThepipingsystemshouldcomplywiththelatesteditionofAmericanSocietyofMechanicalEngineers/AmericanNationalStandardsInstitute(AMSE/ANSI)B31 .3 .
Thefollowingkeypointsshouldbeconsideredinanypropyleneoxidepipinginstallation:
Pipingshouldbeweldedandflanged .Minimizepotentialleakpointsbyminimizingthenumberofvalves,flanges,couplings,etc .Useofthreadedconnectionsisnotadvisable .Integrallyreinforcedfittingsorreinforcingpadsshouldbeusedforbranchconnections1-1/2inchesandunderinsize .Allpipenipplesusedforinstrumentationandtestconnectionsshouldbeofminimumschedule80thickness .
Steamtracingshouldnotbeinstalledonpropyleneoxidepiping .Pipingsystemsshouldnotbemanifoldedtogetherwithsystemscontainingotherproducts .Thedesignofpipingsystemsshouldpreventbackflowofprocessmaterialsintostoragefacilities,andshouldallowforpressurereliefduetoliquidexpansionintheentiresystem,aswellassectionsthatcanbeisolatedusingvalves .Allinactiveterminalconnectionsinoxidepipingshouldbepluggedorblinded .Nogalvanizedpipingshouldbeusedinpropyleneoxideservice .
Linesthatareburiedshouldbeofweldedconstruction .Flangeconnectionsshouldnotbeused,exceptinvalveboxeswithaccessforservice .Cathodicprotectionshouldbeprovidedforburiedlines .
ValvesValvesshouldmeetfire-testeddesignrequirementstoAPI607 .Ballvalvesshouldhaveself-relievingseats,duetopotentialthermalexpansionfromtrappedliquids .
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PumpsCentrifugalpumpswithbodiesandwettedpartsconstructedofcaststeelorstainlesssteelarerecommended .Doublemechanicalsealswithbufferfluid(suchaspropyleneglycol),ordouble-drygassealsandmoni-toringinstrumentsarerecommended .Thesealsshouldbefittedwithcarbonstationaryelementsandtungstenrotatingelements .Theresilientorcompressiblecomponentsofthesealassemblyshouldbeofethyl-propylrubberorfluoroelastomer(forexample,Chemraz505®andKalrez2035®areacceptableforpropyleneoxideservice) .Pumpswithdouble-drygassealsshouldhaveprovisionsmadeforventingthepumpbeforestarting .
Pumpsshouldbeinstalledwithindikeorcurbedareas,withthedikeorcurbslopedtodirectanyleaksorspillstoasecondarycontainmentarea .Preferably,pumpsshouldnotbelocatedinthesameprimarycontain-mentareawithstoragetanks .
Seal-lesspumps,suchasmagneticdrivepumps,arealsoacceptableforuseinpro-pyleneoxideservice .Careshouldbetakentoensurethatthepumpsarenotrundrytopreventdamagetothepump .
Pumpsusedtounloadpropyleneoxideshouldbesizedaccordingly,consideringtheexcessflowcheckvalvesthatareinstalledontherailcarsandtrucks .Interlockinggroundingdeviceswithalarmsshouldbeusedwiththetransfersystemtoprovideanautomaticshutdownifthegroundingislost .Aninterlockshouldalsobeusedtopreventover-flowingthestoragetank .
Allpumpsshouldbeprotectedagainstabnormaltemperaturerisebyahigh-temperaturealarmandshutdown .ThesensingelementshouldbeofaClass1,GroupB*electricalclassificationandpreferablyshouldbelocatedinthepumpbody .Locatingthedeviceimmediatelyadjacenttothedischargepipingbeforethefirstblockvalvemaybeasuitablealternative .
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Work PreparationAppropriateproceduresfortankcleaningandequipmentrepairarenecessarytopreventexposuretohazardouschemicals .Preparationshouldincludeacleardefinitionofthetaskstobeperformed,anidentifica-tionofhazardousmaterials,andrelatedhazardousconditions .Ahazardousworkpermitsystemshouldbeusedtoidentifythejob-relatedhazardsandplanforthesafecompletionofthiswork .Employeeprotectionshouldincludetheuseofengineeringcontrols(seepage30,“BulkHandling”)andtheselectionofpersonalprotectiveequipment(seepage16,“PersonalProtectiveEquipment”and29CFR§1910 .133–136) .
Emptytanksandequipmentthatcontainedpropyleneoxidevapororliquidshouldbeclearedofresidualmaterialbeforecleaningand/orrepair .Liquidsshouldberemovedfromalowpointofthevessel .Residualliquidandvaporshouldbeflushedwithwateroranothersuitablematerial,andvaporshouldbepurgedwithnitrogen(see“ConfinedSpaceEntry,”following) .Flushandsweepmaterialsshouldbedisposedofproperlytopreventreleasetotheenvironment(seepage27,“Environmental,”andpage30,“BulkHandling”) .
Onlyproperlytrainedworkersshouldbeinvolvedinthecleaningandrepairoftanksandequipmentthathavepreviouslyheldpropyleneoxide(seepage16,“PersonalProtectiveEquipment”andHAZWOPER29CFR§1910 .120) .
Eyewashandsafetyshowersshouldbelocatedneartheworkoperation .Appropriatefireextinguishingequipmentshouldbepresent(seepage22,“EmergencyPlanning,”and29CFR§1910 .38) .
Control of Hazardous EnergyAfacilitymusthaveproceduresforcontrol-linghazardousenergysourcesthatcomplywiththerequirementsof29CFR§1910 .147 .Theproceduresprotectworkersinareaswherepropyleneoxidevesselsorequipmentarecleaned,maintained,orentered .Afterthesystemispurged,ensurethatallpoten-tialsourcesofpropyleneoxideorhazardousenergyarephysicallytaggedand/orlockedout,andaffectedpersonsnotified .
Confined Space EntryTheOccupationalSafetyandHealthAdministrationestablishesrequirementsforentryintoconfinedspaces(29CFR§1910 .146) .Precautionsshouldbetakentopreventasphyxiationfromanyinertgasflushoperation,suchasnitrogenpurging .
Appropriaterespiratoryprotectionforpropyleneoxidevaporexposures(seepage17,“RespiratoryProtection”and29CFR§1910 .134)mayalsoberequired .
Equipment Cleanout and Recommissioning VesselsIfanewtankistobeputintoservice,itiscriticalthatitbecleanofallrust,dirt,grease,andwater .Soapordetergentsandwatershouldbeusedtoremovegreaseand
Tank Cleaning & Equipment Repair
Tank Cleaning & Equipment Repair
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oils .ThecleanedsurfaceshouldberinsedwithwateruntilaneutralpHisobtained .Nosolventscontainingorganicorinorganicchloridesshouldbeused .
Ironoxideisacatalystforpropyleneoxidepolymerization .Toeliminatelooserust(ironoxide)andscalefrominsideatank,ahigh-pressurefreshwaterblastiseffective .Acidicorbasiccleaningorpicklingsystemsshouldbeavoidedbecausetheirresiduescancausevigorousreactionswithpropyleneoxide .Afterthisstep,thetankwallsshouldbedriedandthebottomcleanedofallsolidsandwater .Thetankshouldthenbepurgedwithnitrogengastobelow2%concentra-tionofresidualoxygen .
Maintenance and InspectionPreventivemaintenanceandinspectionofcontainers,hoses,pumps,fittings,fireprotectionequipment,andrefrigerationunitsusedforpropyleneoxideshouldbeconducted .Anadequatesupplyofsparepartsforrefrigerationunitsshouldbemaintained .Overpressureandoverfilldetectorsandflammable(combustible)gasdetectorsshouldbemaintainedandcalibratedregularly .
Theinspectionprogramshouldalsoincludeappropriatelyscheduledinspectionofequip-mentstorageareasandventilationsystems .
Preventivemaintenanceschedulesshouldbedevelopedforcriticalequipmentsuchastankinstrumentation,firefightingequipment,combustiblegasdetectors,pumps,safetyreliefvalves,gaskets,andemissioncontrolequipment .
Tank Cleaning & Equipment Repair
Tank Cleaning & Equipment Repair
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Priortodelivery,customersshouldbepreparedtosafelyreceive,off-load,andstorepropyleneoxide .Topromotesafetyandsecurity(seepage53,“Security”),Dowwillmakedeliveriesonlytositeswithwhichitisfamiliarorhasotherwisebeenassuredthatthepersonnelarecapableofsafelyhandlingpropyleneoxide .Ingeneral,thisnormallymeansthatthesitewillbevisitedandreviewedbyarepresentativefromDowpriortotheitsfirstdelivery .
Itisimportanttocarefullyinstructallpersonnelinvolvedinplantdesignandthehandlingofpropyleneoxideontheproper-tiesofthismaterial .Becausethedegreeofhazardvariesfromoneoperationtoanother,individualsituationsshouldbecarefullyevaluatedtodetermineallappropriatesafetymeasures .
Avarietyofvessels—includingrailtankcarsandtanktrucks—areusedtotransportpropyleneoxide .Allappropriatenationalandinternationalregulationsmustbemet .
Forregulatoryrequirementsconcerningunloadingandstorageofhazardouschemicals,Title49oftheCodeofFederalRegulations,theUnitedStatesDepartmentofTransportation(DOT),shouldbecon-sulted .Becausegovernmentalrequirementsmaydifferbetweenlocal,state,federal,orothersovereignauthorities,afullreviewofallapplicablelawsandregulationsshouldbecompletedbeforedesigningandinstallingastorageandunloadingfacility .
Considerations for DeliveryThefollowingaresomeconsiderationsdesignedtohelpprepareforaninitialbulkdeliverytoanewfacility .Forspecificinfor-mationabouthardware,youmaywanttocontactDow .
•HasDowvisitedyourfacilityandreviewedyourbulkpropyleneoxidehandlingandstoragefacility?
NOTE: Dow may decline to deliver to a facility until an on-site review is conducted to verify that the facility meets Dow’s minimum standards.
•Isitnecessary,orpreferable,forDowtoattendthefirstdelivery?
•Wastheoff-loadingpipingandvalvesystempressure-testedtoensurethatitisleak-free?Ifwaterwasusedforthepressuretest,howwasthesystemdried?
NOTE: Any water in the system can create quality and safety problems.
•Wastheoff-loadingpumptestedwithliquidafterinstallation?
•Isawrittenoff-loadingprocedureavailabletoemployees?
•Wastheprocedurereviewedbytheoff-loadingoperator?Willtheoperatoruseitasachecklistforoff-loading?
•Howwillthevehiclebemanagedforspillcontainment?
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NOTE: It is recommended that the spill-containment volume is large enough to hold the entire contents of the vehicle scheduled for off-loading.
•Aretherevalvepositionchangesrequiredtosecurethecontainmentsystem?Ifso,aretheydescribedintheoff-loadingprocedure?
•Arespotting,choking,andbrakesecure-mentrequirementsclearlyidentified?
NOTE: For trucks, the driver should have clear instructions to surrender the keys and leave the truck cab.
•Istheappropriatepersonalprotectiveequipmentavailabletotheoperatorbeforeoff-loading?Istheequipmentspecifiedinaprocedure?
•Arethesafetyshowerandeyewashstationsimmediatelyaccessibleintheoff-loadingarea?
•Arethesafetyshowersandeyewashstationstestedbeforeanyconnectionsaremadetothevehicle?
•Istheoff-loadingareacordonedofforbarricadedtokeepunauthorizedper-sonnelandvehiclesout?
•Howwillthevehicle’selectricalgroundbeverified?
•Hastheoff-loadingoperatorreceivedtrainingonthehazardsoftheproductandreviewedcurrentMaterialSafetyDataSheets(MSDS)?
•Willacheckbemadeofthevehicle’snumber,seals,andproductidentificationtag(ontheoff-loadingline)toverifytheproductagainstboththeinvoiceandCertificateofAnalysis?
NOTE: Product stencils and accompa-nying documents on rail cars also should be checked.
•Willasamplebedrawnandanalyzedpriortooff-loading?
NOTE: If so, what precautions will be taken to avoid personnel exposure?
•Arealllinesandvesselsproperlylabeledandidentified?
•Ifconnectionshavetobemadeonthetopofthetransportvehicle,isprotectionagainstfallsadequate?
•Wastheoxygenlevelinthestoragetankcheckedandverifiedtobebelow2%?
•Areallterminallinesplugged(blinded)topreventspillsfromanaccidentalvalveopening(e .g .,samplingandblow-downlines)?
•Arefireextinguishersandadelugeorwatermonitor(cannon)availableintheimmediatearea?
•Isthereacommunicationlinktothecontrolroom?Howwillitbemaintainedduringoff-loading?
•Havecalculationsbeenmadeandcon-firmedtoensurethattheloadwillfitintotheavailabletankspace?
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40
•Howwillthetransferoftheloadintothetankbemonitoredtoverifymove-mentofproductwhenthepumpisstartedandtoensurethattheproductisgoingtothecorrectlocations?Howwillthemovementofvaporsthroughthevaporreturnlinetothevehiclebeestablishedandverified?
NOTE: At any sign of safety relief valve activation, the transfer should be stopped.
•Istheoff-loadingprocedureclearaboutthelocationandsizeoftheliquidandvaporlines?
•Ifdrydisconnectsareused,aretheylockedinplacebysecuringthearmsinaclosedposition?
•Whenopeningthevalvesonboththeventandliquidsides,willacarefulcheckforleaksbemade?
•Areflammable(combustible)gasdetectorsinstalledatstrategicpointstosoundanalarmifaleakoccurs?
•Whatisthepressureinsidethestoragetank?
NOTE: If it is at a pressure that exceeds the vehicle safety system, the pressure relief valve will open and a vapor cloud will be released. Relief pressure can vary, depending on the type of vessel used by the supplier.
•Afterthetransferisinitiated,istheoperatorrequiredtostaywithinacertaindistanceoftheconnectionsuntiltheloadiscompletelytransferred?
NOTE: This is required by DOT for trucks. If a rail car is involved, how will it be monitored?
•Howwilltheoperatorknowwhenthevehicleisemptysothatthepumpcanbeshutdownafteritlosessuctionpressure?
•Iftheliquidlinewillbeblownclearpriortodisconnection,howwillthenitrogenberegulatedtonotexceedthepressureatwhichthevehicle’ssafetysystembeginstorelieve?Whatstepswillbefollowedifablow-downisperformed?
NOTE: Hoses should not be left hydraulically full.
•Whatprocedurewillbeusedtoensureallliquidandvaporreturnlinesonthecarandpipingsystemarecorrectlyblownclear,depressurized,andblockedtosecurethesystemandthedeliveryvehicle?
•Whendisconnectingthefitting,doestheprocedurerequiretheuseofappropriateprotectivegear?
•Howwillthehosesbesecuredtokeepthemcleanandcontamination-freeforthenextload?
•Howwilltheoperatorensurethatthefallrestraint,chocks,groundstrap,andbarricadesareremoved(andthattheplacardsarereversedandderailandwarningsignsareremovedbeforereleasingarailcar)?
•Railcarsandsomeintermodalcontainershavetopdischargelines;establishingpumpsuctionrequiresspecificoperating
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4�
procedures .Theproceduresmusteitherutilizethepressureinthecaruponarrivalorprovidethepressuretopushtheproductoutofthecartofloodthepumpsuction .Howwillthisbemanaged?
•Isthereverificationofre-sealing?
•Whatmechanismisinplacethatallowstheoperatortofactoranylearningexperiencesintothenextoff-loadingexperiencetocontinuouslyimproveperformance?
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Delivery & Transfer
42 Delivery & Transfer
Delivery & Transfer
NITROGEN
NITROGEN
LIQUID
LIQUID
LIQUID LIQUID
LIQUID
LIQUID
1. STRAIGHT BALL VALVE2. GAUGING DEVICE3. SAFETY VAVLE 225#4. EDUCATION PIPE5. SUPPORT6. THERMOWELL7. SAMPLE LINE
4
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7
1 1
1
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5
5
13
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B
A ACC
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CC
SECTION “C-C”MANWAY BONNET
SIDE COVER(ACCESS TO VALVES)
SECTION “B-B”SECTION “A-A”
NITROGEN OR VAPORBALANCE LINE
Figure 4 Typical Tank Car Dome ConfigurationThisfigureillustratesatypicalconfiguration,andisnotintendedtobeusedasadesignspecification .Qualifiedprofessionalsmustexerciseengineeringjudgmenttoestablishsitespecificationsthatmeetapplicablerequirements .
�. Straight Ball Valve 2. Gauging Device 3. Safety Valve 225# 4. Eduction Pipe 5. Support 6. Thermowell 7. Sample Line
43
Rail CarsPropyleneoxideistypicallyshippedinDOT105J300railcars,whichareratedfor300psig .Theyareconstructedofweldedcarbonsteel,insulatedwithfourinchesoffiber-glass,andcoveredbya1/8-inchsteeljacket .Thejacketheadsoneachheadare1/2-inchthickforprotectionintheeventofatrans-portationemergency .
Theonlypipingattachmentstothecarsaremadethrougha20-inchmanwaynozzleontopofthecenterofthecar .Externalpipingandvalvesareprotectedbyametalhousingwithacoverthatissecuredwithalockingpin .Sketchesofthelayoutoftheseattach-mentsareshowninFigures4and5 .Liquidisremovedthrougha2-inchvalveconnectedtodippipesterminatingnearoronthebottomofthecarinashallowsumpthatcontainsabout10gallonsofliquid .Theheadspaceventisthrougha2-inchvalvewithpipingthatterminatesjustbelowthemanwayflange .Bothliquidandvaporlinesareequippedwithexcessflowcheckvalvesthatrestrictflowtoabout125gpm,butwillnotfunctiontoprotectagainstslowleaksinplantpiping .
NOTE: While unloading, if flow shuts off after having started, the excess flow valve may be checking. When this occurs, shut off flow and restart slowly, transferring at a slightly lower flow than previously used.
Thereisalsoamagneticfloatgaugingdevicethatmeasurestheliquidlevelfortheupperhalfofthecaronly .Aworkingplatformsurroundsthedomeandisabout12feet6inchesfromtheground .Considerusingadditionalfallprotectiondevices .Carsarecommonlyequippedwithapressurereliefsafetyvalvethatcanbesetaslowas75psig .
CAUTION: Do not exceed 60 psig on the tank car, as this may cause premature relieving of the pressure relief safety valve.
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44 Delivery & Transfer
Delivery & Transfer
Figure 5 Typical Tank Car ConfigurationThisfigureillustratesatypicalconfiguration,andisnotintendedtobeusedasadesignspecification .Qualifiedprofessionalsmustexerciseengineeringjudgmenttoestablishsitespecificationsthatmeetapplicablerequirements .
1. VAPOR VALVE2. MANWAY (see figure 9-3)3. LIQUID VALVE4. PLACARD (Figure 11-2 & 11-3) (ALL 4 SIDES)5 WHEEL CLOCKS6. APPROVED GROUND CLAMP7. FILTER8. PRESSURE CONTROL VALVE
CHEMTREC (800) 424-9300
PROPYLENE OXIDE
NITROGEN SUPPLY
TO STORAGE
FROM SHUTDOWNINTERLOCKS
ATMOSPHERE
DOT 105J
9. PRESSURE SAFETY VALVE (N2)10. CHECK VALVE11. BLOCK VALVE12. FLEX. HOSE ASSEMBLY W/2” NPT CONN.13. DRY DISCONNECT & FLEX. HOSE ASSEMBLY W/2” NPT CONNECTIONS14. NITROGEN HIGH POINT PURGE W/BLOCK VALVE15. PUMP 16. PRESSURE GAUGE W/DIAPHRAGM SEAL
17. APPROVED GROUND18. CHEMTREC EMERGENCY NUMBER 800/424-930019. HANDRAIL20. HAND BRAKE WHEEL21. DERAILER22. PRESSURE GAUGE 23. DOT CLASSIFICATION NO.
19 19
1 3
2021
23
15
16M
7
18
12 13
6
14
5 5
1111
11
22
11 11 11 1110
10 8
9
1717
4
4
4
2
�. Vapor Valve 2. Manway 3. Liquid Valve 4. Placard (All 4 Sides) 5. Wheel Chocks 6. Approved Ground Clamp 7. Filter 8. Pressure Control Valve 9. Pressure Safety Valve (N2) �0. Check Valve ��. Block Valve �2. Flexible Hose Assembly with 2” NPT Connections
�3. Dry Disconnect & Flexible Hose Assembly with 2” NPT Connections �4. Nitrogen High-Point Purge with Block Valve �5. Pump �6. Pressure Gauge with Diaphragm Seal �7. Approved Ground �8. CHEMTREC Emergency Number (800) 424-9300 �9. Handrail 20. Hand Brake Wheel 2�. Derailer 22. Pressure Gauge 23. DOT Classification No.
45
Delivery & Transfer
Delivery & Transfer
5
5
6 6
NITROGEN
TANKCAR
10
11 11 11 15
13
6
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8
9
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�. Excess Flow Check Valves 2. Pressure Relief Valve 3. Tank Car Sample Valve 4. Magnetic Level Gauge 5. Rigid Pipe with Swing Joints 6. Pressure Gauge
7. Sample Points 8. Double Seal Leak Detector 9. Centrifugal Pump �0. Emergency Block Valve ��. Ground Wires �2. Indicating Ground Detector
�3. High-Temperature Shutdown �4. Sprinkler System �5. Combustible Gas Detector Alarm �6. Below-Grade Grounding System �7. Grounding Clamp
Figure 6 Typical Tank Car Unloading System ConfigurationThisfigureillustratesatypicalconfiguration,andisnotintendedtobeusedasadesignspecification .Qualifiedprofessionalsmustexerciseengineeringjudgmenttoestablishsitespecificationsthatmeetapplicablerequirements .
46
Considerations for Unloading Rail CarsFigure6showsatypicalunloadingset-upforpropyleneoxide .
•Thesiteshouldbesafelyremotefromtraffic,generalactivity,andignitionsources .
•Thesurfaceshouldbeslopedtoprovidedrainageintoacontainmentareaforspillcontrol .
•Therailcarshouldbeconnectedtoacommonearthground .Interlockinggroundingdevicesandalarmsshouldbeusedwiththetransfersystemtoprovideautomaticshutdownifthegroundislost .
•Allfixedcomponentsoftheunloadingsystemmustbelocatedoutsideanareathatcomplieswiththeappropriatecodesandstandardstoprovideadequatephysicalclearance .
•Allelectricalequipment,includingphones,radios,andintercomsystemsintheunloadingarea,shouldcomplywiththeappropriatecodesandstandards .
•Theunloadingfacilityandthedomeareaoftherailcarshouldhavesomeformoffireprotectiondevice,suchasanautomaticsprinklersystem .Itisrecommendedthatflammable(combus-tible)gasdetectorsarestrategicallyplacedinthegeneralarea .Dry-powderfireextinguishersshouldbepresentandafirewatermonitorshouldbelocatedwithin40feetofthecardome .
•Counter-balancedsteelpipeandswingjointsfortankcarliquidandvent
connectionsarepreferred .Dedicatedflexiblestainlesssteelhosesarealsoacceptable .Ifflexiblehosesareused,astorageareaforthehosesshouldbeprovidedthatwillprotectthemfromdamageandcontamination .Adocumentedhosetestingprogramisrecommended,astheyareprobablythemostvulnerablepartoftheunloadingsystem .Allhosesshouldbepressuretestedpriortoeachuse .Emergencyblockvalvesintheliquidandvaporpipingshouldbecapableofactivationfromboththeelevatedplatformandgroundlevel .Ifapumpisused,provideastopswitchattheremotelocation .
•Eyewashandsafetyshowerstationsshouldbelocatedonboththegroundandplatformlevel .Providepersonalprotectiveequipmentandhaveappro-priatetoolsstorednearby .
•Alltransferlinesshouldbeproperlyidentified,sothatproperalignmentcanbemade .
•Topreventrollingduringunloadingoperations,thecar’shandbrakemustbesetandthewheelsmustbechocked .
•Toprotectacarfromothertrafficontherailsduringunloading,aderaildeviceshouldbepositionedonthetrack50feetfromtheendofthecarbeingprotected .
•PerDOTregulations,awarningsign(bluebackgroundwithwhiteletters)mustbeattachedtotherailaboutfourfeetbeyondthederaildevice .Ifunloadingatnight,abluelanternistobehungonthewarningsign .Ifthetrackisactive
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47
frombothdirections,aderaildevice,sign,andlanternshouldbeplacedateachendofthetankcar .
•Allregulations,includingDOTatten-dancerequirements,mustbefollowed .Foradditionalsafety,apersonshouldbestationedcloseenoughtomaintainvisualcontactwiththecarduringtheunloadingoperation .
•Unloadinghosesandarmsshouldbedisconnectedwhenthereisnooneinattendanceorwhentransferisstopped .
Tamperevidentsealsareappliedtoallshipmentsofpropyleneoxide .ShippersareencouragedtoapplytamperevidentsealsonresiduerailcarsreturningtoDow .
General Guidelines for Unloading Rail Cars 1 . Confirmthattherailcarcontains
propyleneoxide,i .e .,performapositiveIDcheckorcheckshippingdocumenta-tionsuchasthecarnumber,theDOTplacards,thecarlabel,andothershippingdocumentation .
2 . PerDOTregulations,placeabluecautionsign(orlantern)onthetrack .Putabluelanternontheflagifthejobisbeingdoneatnight .Putthederaildeviceinthederailingposition .Chockthewheels .Setthehandbrake .Activatethebarricadesystemandoperationallights .
3 . Attachthelowergroundcabletothecarriagesupportandconfirmthatthegroundinterlockisactive .Extendandsecuretheloadingracktothetopofthecar .Openthedomecoverandattachtheuppergroundingcabletothedome .
4 . Checkthatthebulktagcorrectlyidenti-fiesthecontentsaspropyleneoxide .Samplingthecarcanconfirmproductidentityanddetermineifthematerialissuitableforunloading(seepage20,“SamplingEquipment”) .
5 . Ensurethatappropriatemeasuresaretakentopreventstoragetankoverflow .
6 . Connecttheliquidandventlinestothecar .Openthebleedvalvesatthetankcarend .Purgeairfromtheunloadingandventlineswithnitrogenandpressurethelines(maximum60psig) .Pressuretestthelinesadequately,i .e .,foraboutoneminute .Ifthepressuredoesnothold,searchforleakswithsoapsudsorotherleak-detectingfluids,andcorrectleaks .
7 . Openthevaporvalveonthetankcaranddeterminethecarpressure,whichmayrangefrom10-40psig .Confirmthattheliquidandvaporvalvesatthestoragetankareopen .Equalizethepressureonthetwotanksbyopeningthefinalvaporblockvalveattherailcarrack .
8 . Opentheliquidlineontherailcar,attherack,andatthepump .Starttheunloadingpump .Checkthepumpforleaksandproperoperation .Tankcarsmaybeoff-loadedusingnitrogenpres-sureof40-50psiginlieuofpumping .
CAUTION: Do not exceed 60 psig in the tank car, as this may cause premature relieving of the pressure relief safety valve.
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48
9 . Assoonasthecarisempty,stoptheunloadingpump .Avoidallowingthepumptorundrytopreventdamagetothemechanicalseal .
10 .Cleartheliquidunloadinglineintothecarbypurgingwithnitrogen .Closetheliquidvalveonthecarandemptytheliquidlinefromthecarintothestoragetankbycontinuingtopurgewithnitrogen .Closetherackliquidvalves,thepumpvalves,andtheliquidinletvalveintothetank .Closethevaporlineintothetank .Adjustthenitrogenpres-sureinthecartothe10-15psigrangeandclosethevaporvalveonthecarandrack .Bleeddownanddisconnecttheloadinglines .Capthemandsecurethemtotheloadingramp .Replacetheplugsintherailcarvalves .Securethemagneticgauge .Removetheuppergroundcablefromthedome,closethedomecover,andboltitdown .Retracttheloadingramp .Removethelowergroundcablesfromthecarriagesupport .Removetheblueflag,bluelights,andderails .Removethewheelchocksonthecar .Leavethebrakeengagedfortherailroadcrewtorelease .Deactivatethebarri-cadesystem .
Tamperevidentsealsareappliedtoallshipmentsofpropyleneoxide .ShippersareencouragedtoapplytamperevidentsealsonresiduerailcarsreturningtoDow .
Tank TrucksAcceptabletanktruckstotransportpropyleneoxidearedefinedin49CFR§173 .243 .
DifferenttypesofdedicatedtrailersareusedbysupplierstotransportpropyleneoxideinNorthAmerica .TypicallyDOT412orMC331-typetrailersareused .Safetyvalvepressuresettingsofcommonlyusedpro-pyleneoxidetanktruckscanvaryfrom25-260psig,dependingonthespecificationsusedtodesignandmanufacturethevessel .ContactDowforspecificdetails .
Propyleneoxidetrailersarecommonlyequippedwithamechanicaloutagegauge,adialthermometer,andapressuregauge .Allliquidandventconnectionsaretypicallylocatedattheback,behindtherearwheels,andaretypicallyequippedwith2-inchdrydisconnectfittings .
Tanktrucksaresometimesequippedwithexcessflowvalvesontheliquidline .Quick-actinglever-cablesystemsforremoteshut-offmaybeaccessiblefromdifferentlocationsonthetrailers .Therearealsoterminalvalvesandquick-connecttypeplugsontheliquidandvaporconnections .Ableedvalveforblow-downisconnectedtoateebetweentheinsidevalveandtheterminalblockvalve .
Trailersmaynotbeloadedcompletelyfullbecausetheymustcomplywithmaximumloadrestrictionsdeterminedbystateandfederalregulations .Priortoloading,thetrailerispurgedwithnitrogen .Afterloading,aresidualnitrogenblanketintherangeof25-30psigwillbeleftonthetrailer .
Considerations for Unloading Tank Trucks•Thesiteshouldbesafelyremotefrom
traffic,generalactivity,andignitionsources .
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49
•Considertheuseofroadbarricadesandwarninglightstorestricttrafficorotheroperationsfromtheunloadingarea .
•Thesurfaceshouldbeslopedtoprovidedrainageintoacontainmentareaforspillcontrol .
•Thetanktruckshouldbeproperlyelectricallygrounded .Interlockinggroundingdevicesandalarmsshouldbeusedwiththetransfersystemtoprovideautomaticshutdownifthegroundislost .
•Allelectricalequipment,includingphones,radios,andintercomsystemsintheunloadingarea,shouldcomplywiththeappropriatecodes .
•Theunloadingfacilityandtherearareaofthetruckshouldhavesomeformoffireprotectiondevices,suchasanautomaticsprinklersystem .Itisrecommendedthatcombustiblegasdetectorsarestrategicallyplacedinthegeneralarea .Dry-powderfireextinguishersshouldbepresentandafirewatermonitorshouldbelocatedwithin40feetofthetrailer .
•Truckunloadingcanbedonebyeitherpumpingorapplyingnitrogenpressuretothetruck .Theadvantagesanddisad-vantagesofeachmethodoftransferringproductshouldbereviewedtomakecertainallsafetyandenvironmentalquestionsareanswered .
NOTE: To minimize personnel exposure to propylene oxide, Dow encourages customers to use a dedicated hose
permanently attached to the pumping system. For this reason, Dow does not supply hoses or truck pumps.
•Steelpipeandswingjointsfortruckliquidandventconnectionsarepre-ferred .Dedicatedflexiblestainlesssteelhosesarealsoacceptable .Ifflexiblehosesareused,astorageareaforthehosesshouldbeprovidedthatwillprotectthemfromdamageandcon-tamination .Adocumentedhosetestingprogramisrecommended,astheyareprobablythemostvulnerablepartoftheunloadingsystem .Allhosesshouldbepressuretestedpriortoeachuse .Emergencyblockvalvesintheliquidandvaporpipingshouldbecapableofactivationfromboththeelevatedplatformandgroundlevel .
•Eyewashandsafetyshowerstationsshouldbelocatedonboththegroundandplatformlevels .Providepersonalprotectiveequipmentandhaveappro-priatetoolsstorednearby .
•Alltransferlinesshouldbeproperlyidentified,sothatproperalignmentcanbemade .
•Allregulations,includingDOTatten-dancerequirements,mustbefollowed .Anattendantmustbestationedcloseenoughtomaintainvisualcontactwiththetruckduringtheunloadingoperation .
•Unloadinghosesandarmsshouldbedisconnectedwhenthereisnooneinattendanceorwhentransferisstopped .
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General Procedures for Unloading Tank Trucks 1 . Makesuretheunitisspottedcorrectly
andthatitswheelsarechocked,itsbrakesareset,andtheroadbarricadesareup .Turnontheflashinglightsorothervisualwarningsystemsattheroadentrance .
2 . Placeaplacardonthewindshieldorsteeringwheelofthetrucktowarnagainstmovingthevehicle,orremovethekeysandplaceinasecurearea .Directthedrivertowaitinadesignatedarea .Thedrivershouldnotremaininthecab .
3 . Attachthelowergroundcabletothecarriagesupportandconfirmthatgroundinterlockisactive .
4 . Confirmthattherailcarcontainspropyleneoxide,i .e .,checkthecarnumber,theDOTplacards,thecarlabel,andshippingdocumentation .Samplingthecarcanconfirmproductidentityanddetermineifthematerialissuitableforunloading(seepage20,“SamplingEquipment”) .
5 . Ensurethatappropriatemeasuresaretakentopreventstoragetankoverflow .
6 . Connecttheunloadinglinetothetruckliquidline .
7 . Connectthevent-back(vapor)linetothetruck .
8 . Purgetheunloadingandvent-backlineswithnitrogenandpressureupto60psigtoconductapressurecheck .Isolatetheunloadinglineswithappropriateblock
valvesandobservethepressureforaboutoneminute .Ifthepressuredoesnothold,searchforleakswithsoapsudsoranequivalentleakdetectingliquidandmakenecessaryrepairs .
CAUTION: Some trailers are designed for lower pressures.
9 . Confirmthattheventandliquidinletvalvesatthestoragetankareopen .Slowlyequalizethepressureonthetruckandthevaporlinetothetruck .
10 .Openthevalvesintheliquidlineonthetanktruck,attheemergencyblockvalveatthepumpsuction,anddischarge .Checkforleaksandproperoperation .
11 .Ifpressuringoffthepropyleneoxidewithnitrogen,makecertainthatthenitrogenisdryandcontainslessthan2%oxygen .Thenopenthetankventlinetoanappropriatescrubberandpressurethetruckwithnitrogen .Opentheliquidlinetobeginthetransfer .
CAUTION: Low-pressure trucks may not be suitable for pressure off-loading. Provide provisions to ensure that the tank truck is protected against vacuum to prevent collapsing the cargo tank during the unloading operation.
12 .Assoonasthetrailerisempty,stoptheunloadingpump .Avoidallowingthepumptorundrytopreventdamagetothemechanicalseal .
13 .Cleartheliquidunloadinglineintothetruckbypurgingwithnitrogen .Closetheliquidvalveonthetruckandemptytheliquidlinefromthetruckintothe
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5�
storagetankbycontinuingtopurgewithnitrogen .Closethepumpvalves,theemergencyblockvalves,andtheliquidinletvalveintothetank .Closethevaporlineintothetank .Adjustthenitrogenpressureinthecartothe10-15psigrangeandclosethevaporvalveonthetankandattheloadrack .Bleeddownanddisconnecttheloadinglines .Capandsecurethehoses .Placecapsontruckpiping .Hosesneedtobestoredinase-curelocation .Removetheuppergroundcables .CheckthetrailerDOTplacardstoseethattheyareproperlyaffixedandingoodcondition .Removethewheelchocks,takedownthebarricade,turnoffthevisualwarningsystem,andreleasethetrucktothedriver .
ISO ContainersAcceptableportablecontainersusedtotransportpropyleneoxidearedefinedin49CFR§173 .243 .
Propyleneoxideisshippedinothertypesofcontainers,suchasIM101andIM105portabletanks,whichcontainapproxi-mately4,000-6,000gallonsofproduct,shippedunderanitrogenblanketofbetween15-30psig .Unloadingvalvesaretypicallylocatedattherearofthetank(seeFigure7) .
ISO Tank Shipments and Unloading GuidelinesTheISOtankshipmentsandunloadingproceduresaresimilartothetanktruckprocedureslocatedonpage48,“TankTrucks .”
Material and/or Container Return GuidelinesAlwayscontactDowifthereisreasontosuspecttheproducthasbeentamperedwithordamagedwhileenroutetoyourfacility .
For safety and security reasons, DO NOT RETURN THE PRODUCT WITHOUT PRIOR CONSULTATION WITH AND APPROVAL from Dow.
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52 Delivery & Transfer
Delivery & Transfer
1. TANK FRAME2. TANK SHELL IN STAINLESS STEEL WITH INSULATION AND ALUMINUM CLADDING PROTECTION3. MALE BOTTOM DISCHARGE4. DATA PLATE LADDER5. LADDER6. WALKWAY7. STEAM HEATING(NOT USED FOR P.O. SERVICE)8. THERMOMETER
9. SAFETY RELIEF VALVES (2) W/TANK10. MANHOLE11. NITROGEN INLET12. PROVISION FOR FILLING/DRAIN SYSTEM13. BALL VALVE14. FLEX HOSE ASSEMBLY15. BLOCK VALVE16. CHECK VALVE17. PRESSURE RELIEF VALVE18. PRESSURE CONTROL VALVE19. FILTER
20. PUMP21. PRESSURE GAUGE W/DIAPHRAGM SEAL22. GROUND WIRE23. FLEXIBLE HOSE ASSEMBLY24. DOT CLASSIFICATION NUMBER25. PRESSURE GAUGE26. DOT PLACARD (ALL FOUR SIDES)27. CHEMTREC EMERGENCY800/424-930028. CARRIER’S NAMECONTAINER OWNER/LESSOR’S NAMECERTIFICATION DECALS
FROM SHUTDOWN INTERLOCKS
PROPYLENE OXIDE
CHEMTREC (800) 424-9300
IM-101
TO STORAGE
ATMOSPHERE
NITROGEN SUPPLYOR VAPOR BALANCE LINE
1124
910 12
1
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(2)
3
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M
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�. Tank Frame 2. Tank Shell In Stainless Steel with Insulation and Aluminum Cladding Protection 3. Male Bottom Discharge 4. Data Plate 5. Ladder 6. Walkway 7. Steam Heating (Not Used for P.O. Service) 8. Thermometer 9. Safety Relief Valves (2) with Tank �0. Manhole ��. Nitrogen Inlet �2. Provision For Filling/Drain System �3. Ball Valve �4. Flexible Hose Assembly
�5. Block Valve �6. Check Valve �7. Pressure Relief Valve �8. Pressure Control Valve �9. Filter 20. Pump 2�. Pressure Gauge with Diaphragm Seal 22. Ground Wire 23. Flexible Hose Assembly 24. DOT Classification Number 25. Pressure Gauge 26. DOT Placard (All 4 Sides) 27. CHEMTREC Emergency Number (800) 424-9300 28. Carrier’s Name Container Owner/Lessor’s Name Certification Decals
Figure 7 Typical IMO Tank ConfigurationThisfigureillustratesatypicalconfiguration,andisnotintendedtobeusedasadesignspecification .Qualifiedprofessionalsmustexerciseengineeringjudgmenttoestablishsitespecificationsthatmeetapplicablerequirements .
53
Employeesmustbesensitivetotheirworkenvironmentandabletorecognizenormalandsuspiciousactivities,unusualbehaviors,aswellasanycontainerabnormality .Employeesmustalsobeabletoimplementanactionplanornotificationsequence .Possiblethreatsmayincludefraudulentorintentionallyfalsestatementstoinitiateashipmentofpropyleneoxide .Possiblethreatstothecontainerintransportationorstorage/tankcarmustalsobetakenintoaccount .Aplanisimportanttopreventunauthorizedaccesstopropyleneoxidecontainersateverypointinthesupplychainandtoensurecarefulmonitoringofthemovementandreportingofoverdueorout-of-routeshipmentstosupervisors,shippingcompanies,andappropriatelawenforcementagencies .
Additionally,usingcablesealstosecuretheloadingorunloadingfittingsduringtransitisstronglyrecommended .Personnelrespon-sibleforloading,transporting,andunloadingpropyleneoxideshouldbetrainedtorecognizeandreporttamperingwiththecontainers,whensealsaremissing,orwhensealshaveadifferentnumberthanindicatedontheloadingdocuments .
Theelementsoftheplanshould,therefore,address:
•Ensuringfulfillmentonlyoflegitimateorders
•Accesstostorageareas
•Sealingcontainersandrecognitionofcompromisedseals
Security
Security
54
Thefollowingregulatoryinformationconcerningpropyleneoxideisnotnecessarilyacompletelistofallapplicablelawsandregulations,butisintendedforconsiderationonly(notaslegaladvice)andisbelievedtobecurrentonthedatethismanualwaspublished .Itisyourresponsibilitytoinvesti-gateandcomplywiththeregulationsinyourlocality,state,province,and/orcountry .Consultregulationsperiodicallyforotherapplicableregulations,changes,andupdates .
National Fire Protection Association (NFPA) HazardRatings:health3,flammability4,reactivity/instability2 .
Section 8(a) Toxic Substances Control Act (TSCA)Reportingrequirementsestablishedforpersonswhomanufacture,import,orprocess .
Section 3�� Clean Water ActSpillageinnavigablewatersisregulatedbytheproceduresestablishedbythisprovision .
Section ��� Clean Air ActPropyleneoxideisidentifiedasapotentialhumanhealthhazardforwhichspecificcontroltechnologiesareprescribed .
Section ��2 Clean Air ActPropyleneoxideisidentifiedasaHazardousAirPollutant .
Comprehensive Environmental Response, Compensation and Liability Act of �980 (CERCLA)Apropyleneoxidereleaseequaltoorexceedingthereportablequantity(RQ)prescribedmustbereportedimmediately(RQinpounds=100) .
Section 302 Superfund Amendments and Reauthorization Act (SARA)EmergencyplanningandnotificationrequirementsareapplicableifmorethantheThresholdPlanningQuantity(TPQ)ofanyextremelyhazardoussubstanceispresentinafacility .TheTPQisestablishedat10,000pounds .
Section 3�� and 3�2 Superfund Amend-ments and Reauthorization Act (SARA)The“HazardCategories”establishedforCommunityRight-to-Knowreportingrequirementsare:immediatehealthhazard,delayedhealthhazard,firehazard,reactiveandsuddenreleaseofpressure .
Section 3�3 Emergency Planning and Community Right-to-Know Acts of �986Annualreportingofreleasestotheenvironmentrequired .
American Conference of Governmental Industrial Hygienists (ACGIH)AThresholdLimitValue-TimeWeightedAverage(TLV-TWA)of2ppmhasbeenadoptedforpropyleneoxide .
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National Toxicology Program (NTP)PropyleneoxideislistedinNTP’sReportofCarcinogens .
International Agency for Research on Cancer (IARC)IARCevaluatedpropyleneoxideandcon-cludedthatthereissufficientevidenceofcarcinogenicityinexperimentalanimalstolistasananimalcarcinogen,category2B(possiblehumancarcinogen) .
Department of Transportation (DOT)TheDOTHazardousMaterialTableidenti-fiespropyleneoxideasaflammableliquidandhazardoussubstance .
Proper Shipping Name: Propylene Oxide
UN Number: 1280
North American Emergency Response Guidebook: 127P
Regulations
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R .L .Rowley,W .V .Wilding,J .L .Oscarson,Y .Yang,N .A .Zundel,T .E .Daubert,R .P .Danner,DIPPR® DataCompilation of Pure Chemicals Properties,DesignInstituteforPhysicalProperties,AIChE,NewYork,NY(2004) .
References
References
For current contact information for propylene oxide. The Americas (except Brazil and Mexico)
�-800-447-4369 �-989-832-�542
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Published January 2007 ®™Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Form No: ��7-0�736-0�07 CRCG