Packaging HM for shipment:

Transcription

1 Packaging HM for shipment: Considerations for Selection and Filling under the HMR Dangerous Goods Instructors Symposium, 2015

2 Process flow for the HMR: Person who offers Identify Is this material hazardous for transportation? Classify Determination of Hazard Class and Packing Group Describe Determination of Basic Description Package Selection, filling and closing Communicate Marking, labeling, placarding, documentation Loading Loading, blocking and bracing

3 171.1 Applicability of Hazardous Materials Regulations (HMR) to persons and functions. (b) Pre-transportation functions... (2) Selecting a hazardous materials packaging. (3) Filling a hazardous materials packaging, including a bulk packaging. (4) Securing a closure on a filled or partially filled hazardous materials package or container or on a package or container containing a residue of a hazardous material.

4 May I use this packaging for this material?: How it looks to be done in the real world. Basic Description: UN ID#, PSN, Class, PG HMT: Column 8 and *** Package selection based on: Physical state Packing Group Density (SG) or weight

5 May I use this packaging for this material?: The path through the HMR Shipper's Responsibilities (a)(2) The person shall determine that the packaging or container is an authorized packaging, including part 173 requirements, and that it has been manufactured, assembled, and marked in accordance with: General requirements for packagings and packages. c ) Authorized packagings. (1) A packaging is authorized for a hazardous material only if (i) The packaging is prescribed or permitted for the hazardous material in a packaging section specified for that material in Column 8 of the table and conforms to applicable requirements in the special provisions of Column 7 of the table and... Basic Description of Hazardous Material Hazardous Materials Table Columns 7 + 8

6 PART 173 SHIPPERS GENERAL REQUIREMENTS FOR SHIPMENTS AND PACKAGINGS Purpose and scope. (a) This part includes: (1) Definitions of hazardous materials for transportation purposes; (2) Requirements to be observed in preparing hazardous materials for shipment by air, highway, rail, or water, or any combination thereof; and

7 Part 173: Subpart B--PREPARATION OF HAZARDOUS MATERIALS FOR TRANSPORTATION General requirements for packagings and packages a Additional general requirements for non-bulk packagings and packages b Additional general requirements for bulk packagings. [Note: Contains stacking regulations for IBC] Hazardous materials in IBCs.

8 Subpart B Preparation of Hazardous Materials for Transportation Shipper's responsibility General requirements for packagings and packages a Additional general requirements for non-bulk packagings and packages. Yes Non-bulk No IBC Yes Hazardous materials in IBCs. [Except IBC stacking b(e)] No b Additional general requirements for bulk packagings. [Except IBC stacking b(e)]

9 General requirements for packagings and packages. (a) Applicability (b) Effectiveness in transportation ( filled, its contents so limited, ) (c) Authorized (d) Meets specification requirements (e) Compatible with lading (packaging & mixed contents) (f) Closures effective (g) Venting (h) Outage and filling limits (i) Air Transportation

10 173.24a Additional general requirements for non-bulk packagings and packages. (a) Packaging design (b) Filling limits (c) Mixed contents (d) Additional outage requirement for non-bulk packages.

11 Process Questions What needs to be done? What functions are prescribed? Are we doing this? Do we have the information needed to perform the functions? Who is doing it? Are they trained in the specific function? Have we documented what we do (have done)?

12 Packaging/Material relationships Hazardous Material Basic Description Physical Characteristics of the Hazardous Material Density (Specific Gravity) Vapor Pressure Coefficient of Expansion Chemical composition Packaging Design type and performance level Physical Characteristics of the Test Material Maximum rated weight (or SG) Hydrostatic pressure rating [Also: (c)] Volumetric capacity Material(s) of construction

13 How much may I put in the package? Weight (or Specific Gravity) Vapor Pressure Outage (Ullage)

14 Filling Limits (Non-bulk): Weight/Specific Gravity a(b) Non-bulk packaging filling limits (1) A single or composite non-bulk packaging may be filled with a liquid hazardous material only when.. (2) a non-bulk packaging may not be filled with a hazardous material to a gross mass greater than the maximum gross mass marked on the packaging. (3) a single or composite non-bulk packaging which is tested and marked for liquid hazardous materials may be filled with a solid hazardous material (4) Vapor Pressure evaluation (Single packagings for liquids.)

15 Filling Limits (IBC): Weight/Specific Gravity (l) Hazardous Materials in IBC (1) an IBC may not be filled with a hazardous material in excess of the maximum gross mass marked on that container.. (3) An IBC which is tested and marked for liquid hazardous materials may be filled with a solid hazardous material to a gross mass not exceeding the maximum gross mass marked on that container

16 Vapor Pressure/Outage: Why? Temperature Increase = Product expansion + Increased Vapor Pressure = Increase in Internal Pressure!!!

17 Volume Differential /Temperature Change

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22 Outage (Ullage) (h), a(d), (d)

23 Outage: Non-bulk (h) When filling packagings and receptacles for liquids, sufficient ullage (outage) must be left to ensure that neither leakage nor permanent distortion of the packaging or receptacle will occur as a result of an expansion of the liquid caused by temperatures likely to be encountered during transportation. Requirements for outage and filling limits for non-bulk and bulk packagings are specified in a(d) and b(a), respectively. Additionally: a (d) Liquids must not completely fill a receptacle at a temperature of 55 C (131 F) or less.

24 Outage: IBC (h) No leakage or permanent deformation Additionally: (d) Notwithstanding requirements in b of this subpart, when filling an IBC with liquids, sufficient ullage must be left to ensure that, at the mean bulk temperature of 50 C (122 F), the IBC is not filled to more than 98 percent of its water capacity.

25 Definition: COEFFICIENT OF EXPANSION the ratio of the increase of length, area, or volume of a body per degree rise in temperature to its length, area, or volume, respectively, at some specified temperature, commonly 0 C, the pressure being kept constant called also expansivity. For our purposes, temperature range (usually) = Filling temp 15 C (59 F) 55 C (131 F) [or: 50 C (122 F)]

26 Examples: Coefficient of Expansion Liquid Volumetric Coefficient of Expansion (1/K, 1/ o C) (1/ o F) Acetic acid Acetone Alcohol, ethyl (ethanol) Alcohol, methyl (methanol,wood alcohol, wood naphtha, wood spirits, CH 3 OH) Ammonia Chloroform Water

27 Methanol Expansion (Simplified version): 15 C-55 C 208 liters x (ΔT: 40) x (CoE:.00149) = 12.4 liters 208 liters (@15 C) liters = C

28 Volume Differential /Temperature Change

29 Vapor Pressure Evaluation a(b)(4); (h)(1)

30 Definition: Vapor Pressure The vapor pressure of a liquid is the equilibrium pressure of a vapor above its liquid (or solid); that is, the pressure of the vapor resulting from evaporation of a liquid (or solid) above a sample of the liquid (or solid) in a closed container.

31 173.24a(b) (4) Packagings tested as prescribed in of this subchapter and marked with the hydrostatic test pressure as prescribed in (a)(5) of this subchapter may be used for liquids only when the vapor pressure of the liquid conforms to one of the following: (i) The vapor pressure must be such that the total pressure in the packaging (i.e., the vapor pressure of the liquid plus the partial pressure of air or other inert gases, less 100 kpa (15 psia)) at 55 C (131 F), determined on the basis of a maximum degree of filling in accordance with paragraph (d) of this section and a filling temperature of 15 C (59 F)), will not exceed two-thirds of the marked test pressure; (ii) The vapor pressure at 50 C (122 F) must be less than four-sevenths of the sum of the marked test pressure plus 100 kpa (15 psia); or (iii) The vapor pressure at 55 C (131 F) must be less than two-thirds of the sum of the marked test pressure plus 100 kpa (15 psia).

32 Non-bulk: Vapor Pressure Material/Test Pressure Packaging a(b)(4) (ii) The vapor pressure at 50 C (122 F) must be less than four-sevenths of the sum of the marked test pressure plus 100 kpa (15 psia); or VP 50C (kpa).571 [P marked (kpa) + 100] (d)(5) The hydraulic pressure (gauge) applied, taken at the top of the receptacle, and determined by any one of the following methods must be: (2) Not less than 1.75 times the vapor pressure at 50 C (122 F) of the material to be transported minus 100 kpa (15 psi), but with a minimum test pressure of 100 kpa (15 psig); or P marked (kpa) 1.75 VP 50C (kpa) - 100

33 Non-bulk: Vapor Pressure Material/Test Pressure Packaging a(b)(4) (iii) The vapor pressure at 55 C (131 F) must be less than two-thirds of the sum of the marked test pressure plus 100 kpa (15 psia). VP 55C (kpa).666 [P marked (kpa) + 100] (d).The hydraulic pressure (gauge) applied, taken at the top of the receptacle, and determined by any one of the following methods must be:. (3) Not less than 1.5 times the vapor pressure at 55 C (131 F) of the material to be transported minus 100 kpa (15 psi), but with a minimum test pressure of 100 kpa (15 psig). P marked (kpa) 1.5 VP 55C (kpa) 100

34 IBC: Vapor Pressure Material/Test Pressure Packaging (h)(1) (iii) The absolute pressure (vapor pressure of the hazardous material plus atmospheric pressure) in the IBC at 55 C (131 F). This absolute pressure must not exceed two-thirds of the sum of the marked test pressure and 100 kpa (14.5 psia) (d)(5) (i) The pressure determined by any one of the following methods:... (C) If absolute pressure (vapor pressure of the hazardous material plus atmospheric pressure) is used, 1.75 multiplied by the vapor pressure of the hazardous material at 50 C (122 F) minus 100 kpa (14.5 psi). If this method is chosen, the hydrostatic test pressure applied must be at least 100 kpa gauge pressure (14.5 psig); or

35 Vapor Pressure: Chloroform P kpa = P mm Hg x mm Hg x.134 = 102 approx. 60 C P in mm Hg T in C

36 173.24a(b)(4) Chloroform (iii) VP 55C (kpa).666 [P marked (kpa) + 100] P marked (kpa) 1.5 VP 55C (kpa) 100 P marked (kpa) (kPa) 100 P marked (kpa) 53 kpa (minimum 100 kpa)

37 UN No IMDG Examples of required marked test pressures for packagings, including IBCs, calculated as in Name Tetrahydrofuran n-decane Dichloromethane Diethyl ether Class Packing group II III III I Vp55 (kpa) Vp55 x 1.5 (kpa) (Vp55 x 1.5) minus 100 (kpa) Required minimum test pressure (gauge) under (kpa) Minimum test pressure (gauge) to be marked on the packaging (kpa) Note 1: For pure liquids the vapour pressure at 55 C (Vp55) can often be obtained from scientific tables. Note 2: The table refers to the use of only, which means that the marked test pressure shall exceed 1.5 times the vapour pressure at 55 C less 100 kpa. When, for example, the test pressure for n-decane is determined according to , the minimum marked test pressure may be lower.

38 Vapor Pressure Analysis: non-bulk Vapor Pressure Qualification You may use a(b)(4)(ii) or (iii) Yes Single or composite packaging marked at 100 kpa or higher? No You must use a(b)(4)(i) and perform required analysis. Package may be used if properly filled (outage). Yes Is the VP of the material below the required threshold of the rating on the packaging No Find packaging with higher VP rating; or use method in a(b)(4)(i) Select Package based on result of analysis

39 Initial VP screen for a(b)(4) If: Marked test pressure of all packagings is greater than or equal to 100 kpa And: Highest vapor pressure component of your compound is less than or equal to: VP50: 50 C or VP55: C Then: Material meets VP requirements of a(b)(4)(ii) or (iii) as applicable

40 Compatibility (e)

41 Packaging Materials Glass-For packaging purposes considered a barrier material with few exceptions. Metal-Barrier material for most common permeants, but has many compatibility issues. Plastic-Not considered a barrier material. Some plastics have barrier capabilities to some permeants.

42 THE FRONT IN OUR WAR AGAINST ENTROPY Schematic diagram of permeation parameters through a package wall. Same general process for scalping or permeation. From: Plastics Packaging; Selke, Cutler, Hernandez; Hanser

43 Container Fights Forces of Equilibration: Container always loses, only question when?

44 General requirements for packagings and packages (e) Compatibility. (1) Even though certain packagings are specified in this part, it is, nevertheless, the responsibility of the person offering a hazardous material for transportation to ensure that such packagings are compatible with their lading. This particularly applies to corrosivity, permeability, softening, premature aging and embrittlement. (2) Packaging materials and contents must be such that there will be no significant chemical or galvanic reaction between the materials and contents of the package. (3) Plastic packagings and receptacles. (i) Plastic used in packagings and receptacles must be of a type compatible with the lading and may not be permeable to an extent that a hazardous condition is likely to occur during transportation, handling or refilling.

45 (ii) Each plastic packaging or receptacle which is used for liquid hazardous materials must be capable of withstanding without failure the procedure specified in appendix B of this part ( Procedure for Testing Chemical Compatibility and Rate of Permeation in Plastic Packagings and Receptacles ). The procedure specified in appendix B of this part must be performed on each plastic packaging or receptacle used for Packing Group I materials. PG I liquid in plastic receptacle Yes Appendix B Test on Receptacle No Meet maximum permeation rates listed in (ii)(a)-(c) Documentation??? See IATA:

46 Appendix B 7. Each of the following constitute test failure: a. Visible evidence of permanent deformation due to vapor pressure build-up or collapse of walls, deterioration, swelling, crazing, cracking, excessive corrosion, oxidization, embrittlement, leakage, rupture or other defects likely to cause premature failure or a hazardous condition.

47 Think they ll notice?

48 Closures are part of the package. Closure, gasket and liner materials are susceptible to chemical attack and the same types of diffusion effects as container walls. Compatibility determination should include intended closures.

49 This is an exception that may prove useful.

50 Possible compatibility clue? PSN UN ID # PG Label Codes Special provisions ( ) Class/ Division Exceptions Packaging (173.***) (2) (3) (4) (5) (6) (7) (8A) (8B) (8C) Methanol 3 UN1230 II 3, 6.1 IB2, T7, TP Non Bulk Bulk Diallyether 3 UN2360 II 3,6.1 Hydrogen peroxide, aqueous solutions with not less than 20 percent but not more than 40 percent hydrogen peroxide (stabilized as necessary) IB2, N12, T7, TP1, TP UN2014 II 5.1, 8 A2, A3, A6, B53, IB2, IP5, T7, TP2, TP6, TP24, TP None Ammonia solutions, relative density between and at 15 degrees C in water, with more than 10 percent but not more than 35 percent ammonia 8 UN2672 III 8 336, IB3, IP8, T7, TP

51 Chloroform: Stability and Reactivity Incompatibility with various substances: Reactive with metals, alkalis. Corrosivity: Non-corrosive in presence of glass. Special Remarks on Reactivity: Light Sensitive. Incompatible with triisopropyl phosphine, acetone, disilane, fluorine, strong bases and reactive metals (aluminum, magnesium in powdered form), light. Special Remarks on Corrosivity: It will attack some forms of plastics, rubber, and coatings.

52 Additional compatibility considerations: (4) Mixed contents. Hazardous materials may not be packed or mixed together in the same outer packaging with other hazardous or nonhazardous materials if such materials are capable of reacting dangerously with each other and causing (i) Combustion or dangerous evolution of heat; (ii) Evolution of flammable, poisonous, or asphyxiant gases; or (iii) Formation of unstable or corrosive materials. (5) Packagings used for solids, which may become liquid at temperatures likely to be encountered during transportation, must be capable of containing the hazardous material in the liquid state.

53 Questions? Thank You, Lonnie Jaycox