Personal Protective Equipment (PPE) Hydrogen Fluoride Hydrofluoric Acid Solutions

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Personal Protective Equipment (PPE) Hydrogen Fluoride Hydrofluoric Acid Solutions Eurofluor (European Technical Committee for Fluorine) www.eurofluor.org Version: 06.04.2016

CONTENT PPE INTRODUCTION CLASSIFICATION OF HF REGULATIONS LEVELS OF PROTECTION α Level β Level γ Level δ Level TRAINING CHOICE OF SUITABLE PPE HOW TO USE PPE MORE INFORMATION

INTRODUCTION This Recommendation is based on the various measures taken by member companies of Eurofluor. It in no way is intended as a substitute for the various national or international regulations, which should be respected in an integral manner. It results from the understanding and many years experience of the AHF/HF producers in their respective countries at the date of issue of this particular document. Established in good faith, this recommendation should not be used as a standard or a comprehensive specification, but rather as a guide which should, in each particular case, be adapted and utilised in consultation with an AHF/HF manufacturer, supplier or user, or other experts in the field.

INTRODUCTION It has been assumed in the preparation of this publication that the user will ensure that the contents are relevant to the application selected and are correctly applied by appropriately qualified and experienced people for whose guidance it has been prepared. Eurofluor does not, and indeed cannot, make any representation or give any warranty of guarantee in connection with material published in Eurofluor publications and expressly disclaims any legal liability or responsibility for damage or loss resulting from the use, or misuse, of information contained in this document.

GENERAL INFORMATION ABOUT ANHYDROUS HF Concentration % CLP CLASSIFICATION CLP Classification, Labelling and Packaging ADR / RID CLASSIFICATION ADR - European Agreement on International Carriage of Dangerous Goods RID Regulations Concerning the International Carriage of Dangerous Goods ACUTE TOXICITY (oral, dermal and inhalation) Cat. 1 and 2 SKIN CORROSION Cat 1A HYDROGEN FLUORIDE, ANHYDROUS CLASS 8 PG I CT1 : CORROSIVE SUBSTANCE, TOXIC, LIQUID AHF HF > 85% 886 1052 Hazard statements (H Statement) H300: Fatal if swallowed H310: Fatal in contact with skin H330: Fatal if inhaled H314: Causes severe skin burns and eye damage HYDROFLUORIC ACID with more than 85% of hydrogen fluoride CLASS 8 PG I CT1 : CORROSIVE SUBSTANCE, TOXIC, LIQUID 886 1790

GENERAL INFORMATION ON AQUEOUS HYDROFLUORIC ACID (HF) Concentration % HF > 60% HF < 85% CLP CLASSIFICATION CLP Classification, Labelling and Packaging ACUTE TOXICITY (oral, dermal and inhalation) Cat 1 and 2 SKIN CORROSION Cat 1A ADR / RID CLASSIFICATION ADR - European Agreement on International Carriage of Dangerous Goods RID Regulations Concerning the International Carriage of Dangerous Goods HYDROFLUORIC ACID with more than 60% but not more than 85%hydrogen fluoride CLASS 8 PG I CT1 : CORROSIVE SUBSTANCE, TOXIC, LIQUID 886 1790 HF 60% Hazard statements (H Statement) H300: Fatal if swallowed H310: Fatal in contact with skin H330: Fatal if inhaled H314: Causes severe skin burns and eye damage HYDROFLUORIC ACID with not more than 60% of hydrogen fluoride CLASS 8 PG II CT1 : CORROSIVE SUBSTANCE, TOXIC, LIQUID 86 1790

REGULATIONS Directive 89/686/EEC on personal protective equipment HOW TO MANUFACTURE AND COMERCIALIZE PPE It lays down the conditions governing its placing on the market and free movement within the Community and the basic safety requirements which PPE must satisfy in order to ensure the health protection and safety of users. ALL personal protective equipment is required to carry the 'CE' marking as a sign that the product complies with the essential requirements of directive 89/686/EEC. Personal protective equipment must be tested using the standard test protocol against the relevant hazard(s) and manufactured under an approved Quality Assurance system (e.g. ISO 9002).

REGULATIONS Directive 89/686/EEC on personal protective equipment HOW TO MANUFACTURE AND COMERCIALIZE PPE An EC-type examination certificate is then issued by the notified body certifying that the personal protective equipment satisfies the relevant provisions of the Personal Protective Equipment Directive. The manufacturer then issues an EC Declaration of Conformity for the personal protective equipment and affixes a CE mark.

REGULATIONS Directive 89/686/EEC on personal protective equipment PPE is divided into one of three categories: Simple Design This equipment is designed for minimal risks only and where the effects of any hazard are of minimal risk and the consequences of any exposure are reversible. Intermediate Design Personal protective equipment which has been tested against at least one hazard and is approved by a notified body.

REGULATIONS Directive 89/686/EEC on personal protective equipment PPE is divided into one of three categories : Complex Design This equipment is designed for hazards which cause irreversible effects or mortal danger. For use in tasks where contact with HF may occur only Complex Design personal protective equipment is acceptable. Where personal protective equipment does not display the relevant CE mark it cannot be employed at a European facility handling HF. Relevant test protocol and standards are referred to where possible.

REGULATIONS Directive 89/656/EEC use of personal protective equipment HOW TO USE THE PPE S BY WORKERS Lays down minimum requirements for personal protective equipment used by workers at work.

LEVELS OF PROTECTION There are four levels of protection: α Level (emergency response) β Level (operational equipment for increased risks)

LEVELS OF PROTECTION There are four levels of protection: γ Level (routine operational equipment) δ Level (standard on plant equipment)

LEVELS OF PROTECTION α Level (emergency response) is used for emergency response or where the risk assessment has identified a high degree of probability that the task could result in a significant exposure and when an air line is not a practical option, for example, the air line will not give sufficient mobility. α Level should use equipment designed to prevent ingress of HF and should give full protection from potential HF exposures. The health impact of using this level of personal protective equipment should not be under-estimated. The wearing of fully encapsulated suits and breathing apparatus (BA) whilst working, particularly in hot climates, can lead to additional health risks for the employees involved. The additional risks associated should be identified and assessed in the risk assessment. α Level personal protective equipment is used for emergency response and is designed to be gas tight and to provide full protection against the ingress of HF. Specific training is required to ensure correct fitting and safe undressing.

LEVELS OF PROTECTION α Level (emergency response) Fully encompassing HF resistant suit (EN 943-2) Suitable gloves either built in or completely sealed at the wrists (EN 488) BA (Breathing Aparatus) Set (EN 132 : 1990 Annex A) or, if practicable, air line providing suitable supply of breathing air (EN 132 : 1990 Annex A; EN 270 : 1994; EN 137) Standard hard hat or bump cap worn inside the suit (EN 397) HF resistant Wellington-type boot with steel toe and shank worn inside outer leg seal (EN 943-2: 1995)

LEVELS OF PROTECTION β Level (Operational Equipment for Increased Risks) β Level personal protective equipment is used for routine operational tasks involving invasive interactions with process equipment or for non-routine interactions which have been identified as requiring a higher level of protection. β Level equipment is designed to prevent the ingress of HF and should give full protection from potential HF exposures. β Level personal protective equipment is to be used for operations where the risk of contact with process fluid may be reasonably significant.

LEVELS OF PROTECTION β Level (operational equipment for increased risks) AirfedHF resistant jacket with high waistedtrousers (EN 467 : 1995) sealed at Wellington-type boots and gloves with integral, air fed hood (Visor to EN 146; air fed hood to EN 270) or fully encompassing HF resistant one piece suit (Visor to EN 146; pren 943-2) Standard hard hat or bump cap worn inside the jacket (EN 397) HF resistant gloves (EN 374-3) Air line (resistant to HF attack) providing suitable supply of breathing air (EN 132 : 1990 Annex A; EN 270 : 1994; EN 137) HF resistant Wellington-type boots or overboots with steel toe and shank (EN 345 with additional testing to EN 369 [specifically for HF]) Boots permanently attached to a one-piece, gas tight suit may also be worn (EN 943)

LEVELS OF PROTECTION γ Level (routine operational equipment) γ Level personal protective equipment is used for routine operational tasks involving non-invasive interactions with process equipment. It is designed to give a greater degree of protection against incidental contact with process fluids for individuals working in the HF handling area. γ Level personal protective equipment should be used for operations which involve interaction with the process but which are not expected to cause a release of process fluids.

LEVELS OF PROTECTION γ Level (routine operational equipment) Standard hard hat (EN 397) with HF resistant nape (EN 467 : 1995) and face visor (Visor MUST be in the down position when in the HF handling area) (EN 166-B) Chemical goggles (Goggles MUST be worn under visor when within the plant boundaries) (EN 166-345-B) HF resistant gloves (EN 374-3) HF resistant jacket with sleeves sealed at gloves (EN 467 : 1995) HF resistant high waistedtrousers sealed at Wellington-type boots (EN 467 : 1995) HF resistant Wellington-type boots or overbootswith steel toe and shank (EN 345 with additional testing to EN 369 [specifically for HF])

LEVELS OF PROTECTION δ Level (standard on-plant equipment) δ Level personal protective equipment is the minimum level of personal protective equipment required to enter an HF handling facility and is not designed for use when there is a risk of potential exposure to HF. δ Level personal protective equipment is specified when the risk assessment has indicated that no physical contact with acid containing equipment is likely and, therefore, only minimal protection is needed. Acid resistant clothes Type 6 It is intended to give protection against potentially small, unforeseen exposures e.g. drips, surface

LEVELS OF PROTECTION δ Level (standard on-plant equipment) Acid resistant clothes Type 6 Standard hard hat (EN 397) Safety spectacles with side shields or chemical goggles (EN 166-345-B) HF resistant boots, overboots or safety shoes with steel toe (EN 345) HF resistant gloves (may also be required) (EN 374-3) Acid resistant jacket and trousers (EN 340 pren13034 (type 6)) Escape air packs or suitable filtration systems should also be readily available to enable an escape in the unlikely event of a leak.

COMPARISON ACTION Eurofluor / CTEF CIA UK HFIPI USA API OSHA / EPA EMERGENCY RESPONSE α Emergency Response A D A SIGNIFICANT EXPOSURE IS EXPECTED (E.G. SMALL LEAKAGES) β High Risk B C B MAINTENANCE AFTER GROSS HF REMOVAL β - γ High Risk B C B ROUTINE OPERATIONAL WORK IN ACID HANDLING AREAS (E.G. LOADING / UNLOADING STATION) β - γ Medium Risk C B C HF (> 40%) SAMPLING γ High Risk C B C STANDARD ON-PLANT EQUIPMENT (OPERATIONS) δ Low Risk D A D CIA UK HFIPI API OSHA EPA Chemical Industry Association United Kingdom North American Hydrogen Fluoride Industry Practices Institute American Petroleum Institute Safe Operation of Hydrofluoric Acid Alkylation Units US Occupational Safety and Health Administration US Environmental Protection Agency

TRAINING In all cases personal protective equipment should only be worn by those trained in its use, application and decontamination. Training must include to dress and undress with the specific PPE. The training requirements for operators, maintenance, contractors, management and visitors should be clearly identified and must be strictly followed. Periodic re-training should also be provided. In all cases training and re-training should be recorded and these records maintained for a suitable period.

CHOICE OF PPE FOR WORKING WITH AHF/HF It should be noted that all materials have some permeability to HF, particularly liquid HF, and direct contact should be avoided. Procedures should therefore ensure that, where contact with liquid HF may have taken place, the wearer should endeavour to decontaminate and inspect the equipment at the earliest possible opportunity. Also, once HF has penetrated the outer protective layer, it cannot be removed by the decontamination process, therefore a suitable operational lifespan should be determined.

CHOICE OF PPE FOR WORKING WITH AHF/HF

CHOICE OF PPE FOR WORKING WITH AHF/HF Protection against permeation Protection index Breakthrough time 1 >10 minutes 2 >30 minutes 3 > 60 minutes 4 >120 minutes 5 >240 minutes 6 > 480 minutes

CHOICE OF PPE FOR WORKING WITH AHF/HF In order to select the most appropriate material the user should contact the various companies supplying personal protective equipment and should request the up to date data on breakthrough times for the various products, the test procedure followed and the recommended maximum working time. Alternatively, contact your supplier of HF and request information on suitable personal protective equipment. It is recommended to check the fabric in the facilities to verify if the material is suitable for AHF and diluted HF.

HOW TO USE PPE STORAGE VERIFICATION (make sure the PPE is safe) VERIFICATION (make sure the PPE is safe) WASH DISINFECTION DRYING USE DECONTA- MINATION

MORE INFORMATION PPE For more information, please download: STS Group 7: Recommendation on safety management for handling of Anhydrous Hydrogen Fluoride and Hydrofluoric Acid solutions www.eurofluor.org If you need any other information do not hesitate to contact to info@eurofluor.org