Safety Advice For Storage And Handling Of Anhydrous Titanium Tetrachloride

Published by the TiCl4 Subcommittee of TDMA  
Ninth Edition  
May 2017

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Chemistry making a world of difference

European Chemical Industry Council
Avenue E. van Nieuwenhuyse 4
B - 1160 Brussels
Belgium
Tel: +32 2 676 72 33
nde@efic.be
www.cefic.org

Titanium Dioxide Manufacturers Association
TDMA
TiCl4

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"This document is intended for information only and sets out advice for the safe storage and handling of anhydrous titanium tetrachloride. The information contained in these guidelines is provided in good faith and, while it is accurate as far as the authors are aware, no representations or warranties are made with regards to its completeness. For guidance on individual circumstances specific advice should be sought and in all cases the applica- ble national, European and international regulations should always be complied with. No responsibility will be assumed by Cefic or TDMA in relation to the information contained in these guidelines."

Table of Contents

1. INTRODUCTION
2. SECTION 1 - STORAGE INSTALLATIONS
   • 1.1. General Layout and Siting
   • 1.2. Equipment
     • 1.2.1. Vessel Design
     • 1.2.2. Pipework
     • 1.2.3. Valves
     • 1.2.4. Instruments
     • 1.2.5. Pumps and Pumping Systems
     • 1.2.6. Safety/Security Equipment
     • 1.2.7. Vent Disposal Systems
   • 1.3. Operation
     • 1.3.1. Operator Selection
     • 1.3.2. Operator Training
     • 1.3.3. Operating Instructions
     • 1.3.4. Loading Operations
     • 1.3.5. Unloading Operations
   • 1.4. Maintenance
     • 1.4.1. Scheduled Maintenance
     • 1.4.2. Inspection Procedures
     • 1.4.3. Maintenance Preparation Procedures
     • 1.4.4. Post Maintenance Procedures
     • 1.4.5. Maintenance Procedures
     • 1.4.6. Permit to Work System
     • 1.4.7. Training
     • 1.4.8. Selection of Maintenance Personnel
     • 1.4.9. Control of Modifications and Changes
     • 1.4.10. Protective Devices
3. SECTION 2 - LOADING AND UNLOADING OF TRANSPORT CONTAINERS
   • 2.1. Equipment
     • 2.1.1. The Filling Tank
     • 2.1.2. The Transport Container
     • 2.2. Loading of Transport Containers
     • 2.3. Unloading from Transport Containers to Storage Installations
4. SECTION 3 - TRANSPORT CONTAINERS
   • 3.1. Engineering Procedure
     • 3.1.1. Scope
     • 3.1.2. Definitions
     • 3.1.3. Principles
     • 3.1.4. Responsibilities
   • 3.2. Engineering Guide
     • 3.2.1. Scope
     • 3.2.2. Definitions Additional to those in the Procedure
     • 3.2.3. Application of Principles
     • 3.2.4. Auditing
5. SECTION 4 - BASIC HEALTH HAZARDS AND SAFETY MEASURES
   • 4.1. Exposure of TiCl4 Fume
   • 4.2. Contact with Liquid TiCl4
     • 4.2.1. Skin Contact
     • 4.2.2. Eyes
     • 4.2.3. Ingestion
   • 4.3. Personal Protective Equipment
     • 4.3.1. Respiratory Equipment
     • 4.3.2. Protective Clothing
6. SECTION 5 - EMERGENCY PROCEDURES
   • 5.1. General points when Handling Spillages within a Factory
     • 5.1.1. Environmental Effects
     • 5.1.2. Informing Neighbours
     • 5.1.3. Upwind Approach
     • 5.1.4. Isolate Source of Leak
     • 5.1.5. Minor Spillages
     • 5.1.6. Containment
     • 5.1.7. Quenching Using Fire Hoses
     • 5.1.8. Use of Solid Alkali Compounds
     • 5.1.9. Drains and Gulleys
   • 5.2. Major Incidents
     • 5.2.1. Major Spillage
     • 5.2.2. Spillage Transfer
     • 5.2.3. Emergency Service
     • 5.2.4. Fire Brigade
     • 5.2.5. TiCl4 'Pools'
     • 5.2.6. Effects on Visibility
     • 5.2.7. Escalation of an Incident
     • 5.2.8. Evacuation
   • 5.3. Transport Emergencies
     • 5.3.1. General Points
     • 5.3.2. Instructions in Writing - Hazardous Chemical Information
     • 5.3.3. Control at the Scene of an Incident
7. SECTION 6 - CHEMICAL AND PHYSICAL PROPERTIES OF TiCl4
   • 6.1. General Information
   • 6.2. Typical Impurities
   • 6.3. Labelling and Classification
   • 6.4. Labelling as in regulation EC n° 1272/2008
   • 6.5. Occupational Exposure Limit Values
   • 6.6. Source of Exposure
   • 6.7. Physico-Chemical Data
     • 6.7.1. Melting Point
     • 6.7.2. Boiling Point
     • 6.7.3. Density
     • 6.7.4. Vapour Pressure
   • 6.8. Water Solubility
   • 6.9. Environmental Fate and Pathways
     • 6.9.1. Stability in Water
   • 6.10. Toxicity
     • 6.10.1. Acute Oral Toxicity
     • 6.10.2. Acute Inhalation Toxicity
     • 6.10.3. Acute Dermal Toxicity
     • 6.10.4. Reference
8. APPENDICES
   • APPENDIX 1 - TYPICAL SPECIFICATIONS
   • APPENDIX 2 - INSPECTION GUIDELINES
   • APPENDIX 3 - PACKAGING PURCHASING SPECIFICATION
   • APPENDIX 4 - CLEANING PROCEDURES
   • APPENDIX 5 - DESIGN SPECIFICATIONS PORTABLE TANKERS
   • APPENDIX 6 - DESIGN CODE REQUIREMENTS TO ADR.

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INTRODUCTION

The Guiding Principles of the Responsible Care Programme are central to the European Chemical Industry Council (CEFIC) policy. Members have signed a commitment to these principles which ensure that they:

• operate to the best practices of the industry
• reflect the commitment of continued improvement in their health, safety and environmental policies
• make available to employees, customers and the public, all relevant information about activities that affect health, safety and the environment.

This Safety Advice for the Storage and Handling of Anhydrous Titanium Tetrachloride was developed by the TDMA (Titanium Dioxide Manufacturers Association) in support of the Responsible Care initiative.

The advice was prepared by a working party under the auspices of CEFIC comprising representatives of the titanium tetrachloride sub-group of the TDMA, currently involving the following companies:

• Chemours
• Venator
• Kronos International Inc.
• Cristal
• Tronox Pigments b.v., (Holland)

Since first publication of this document, SCM Chemicals and Thann & Mulhouse have become part of Millennium Inorganic Chemicals which became a part of Lyondell, which transferred to Cristal in 2007. Kerr-McGee Pigments was re-named to Tronox Pigments. Tioxide Europe was re-named to Huntsman Tioxide, then Huntsman Pigments, then Huntsman Pigments and Additives after the acquisition of the Rockwood Business, then Venator. Chemours used to be part of DuPont.

The document should be considered as providing advice only and not as a detailed design code.

Existing installations may not meet all the recommendations and, in some cases, not all the recommendations may be appropriate, as these may be over-ruled by local legislation, or by experience. It is the responsibility of the titanium tetrachloride user, in consultation with the manufacturer (if this is not the user), to assess the needs in any particular case. The final responsibility rests with the operator of the plant to operate safely.

The advice covers four main areas:

• Storage installations
• Loading and unloading transport containers
• Transport containers
• Basic health and safety measures, emergency procedures and chemical and physical properties.

The document gives examples of storage, loading and unloading installations. Arrangement of plant other than those shown may be equally suitable. Users are recommended to consult with suppliers regarding alternative arrangements and particular aspects of detailed design.

Although great care has been taken in the compilation and preparation of the advice to ensure accuracy, CEFIC or the TDMA cannot in any circumstances accept responsibility for errors, omissions or advice given in this publication.

It is the responsibility of the manufacturer/user to determine the applicability of National Regulations or local planning requirements which may apply to the design, operation and maintenance of the plant. In Europe, particular attention should be paid to the requirements of the Seveso II Directive and the incoming Seveso III Directive.

Only containers complying with the procedure and guidelines described in Section 3 shall be used to distribute TiCl4.

It is the policy to update information periodically, therefore you are advised to check that this document is the latest issue.

Individual sections as shown in the table of contents can be obtained from the European Chemical Industry Council.

It cannot be over-emphasised that the most significant hazardous property of TiCl4 is its violent reaction with water, where hydrolysis takes place to produce hydrochloric acid mist, and finely divided particles of titanium dioxide and oxychloride which create a dense white, highly visible cloud.

This reaction also takes place with moisture in the atmosphere. It is therefore vital to take all necessary precautions to prevent loss of containment of TiCl4. This is particularly important during maintenance activities where joints on pipes or equipment have to be broken.

All such activities should be pre-planned, with risk assessments carried out, and executed by trained personnel wearing appropriate PPE as detailed in Section 4.

SECTION 1 - STORAGE INSTALLATIONS

1.1 General Layout and Siting

1.1.1 Where possible, the installation should be located away from production areas preferably in the open air, but a compromise must be reached here, as pipework between the storage installation and processing plant should be kept to a minimum.

1.1.2 The location of new installations within a site should take into account possible damage caused by failures of neighbouring equipment on the site. The location should be positioned at sufficient distance from the boundary so as not to be subject to damage from off-site incidents e.g. accidents on public roads, etc.

1.1.3 Layout for the area should be planned to provide all facilities necessary for good housekeeping. Ample storage space is required for maintenance and safety equipment which must be readily accessible in the event of an emergency.

1.1.4 TiCl4 storage tanks should be positioned above ground level on plinths which allow adequate access to the external surface. This is to permit regular inspection of the vessel and its protective coating. Installation in deep pits is not recommended because it increases the difficulties of treatment and disposal of TiCl4 emissions and of access for maintenance and repairs.

1.1.5 Storage tanks for the export or receipt of TiCl4 should be installed in a bund which is impervious to liquid TiCl4 and of a suitable capacity to contain spillage. The design of the foundation and bund walls must take into account the density of the liquid. The bund should have a sloping floor and gullies leading to a collection area. If there are sub-divisions to give separate bunds under each tank in a group, each section should have a sloping floor leading to a collection area which may serve more than one tank. The collection area, which may be a sump, should not be connected to drain. Valves or other entries into the bund wall should be avoided or sealed effectively.

1.1.6 Accumulation of rain water in bunds must be minimised. One way of achieving this is by roofing over the storage area. Other means include regular inspection by plant operators and removal of water over the bund wall, which must be manually controlled by the operator to prevent unintentional pumping of any spilled product.

1.1.7 In considering the capacity and the number of individual storage tanks in a storage facility, the following points should be taken into account:

1.1.7.1 The minimum size of a tank should be adequate to accommodate the maximum foreseen unit of delivery.

1.1.7.2 If continuity of supply is essential, at least two tanks will be required to allow time for necessary inspections and to facilitate maintenance. This also provides greater flexibility of operation. Design and operation should also make provision to be able to transfer the contents of a tank in an emergency to other tanks.

1.1.7.3 Increasing the number of storage tanks leads to an increase in the ancillary plant and equipment with a corresponding increase in complexity of operation. The number of storage tanks should be kept to the minimum.

1.1.8 The distance between storage tanks should be adequate to provide good access and egress to the tanks under all circumstances, including those in which bulky protective equipment, such as self-contained breathing apparatus, needs to be used.

1.1.9 All vessels, valves and pipework in the installation should be readily identifiable, e.g. by labelling and/or colour coding.

1.1.10 In the case of installations which are not subject to regular frequent visits by operating personnel, the layout should be such that the storage area is either directly visible from a control room, or is kept under surveillance by the use of TV monitors or other appropriate equipment.

1.1.11 Taking into account the strong hydrolysis reaction of the product, in such case a spillage dependant on the site / plant location could have a large impact on the local neighbourhood. In such instances a confinement of the storage installations, transportation vessel discharging station and the user workshop (processing operation) may be envisaged in order to reduce/mitigate any potential impact on the neighbourhood of the site/plant. Obviously such lay-out requires also the installation of an adequate emergency gas scrubbing system.

1.2 Equipment

1.2.1 Vessel Design

1.2.1.1 Storage tanks for TiCl4 should be designed to an appropriate national or international standard, for example BS5500, ASME Section VIII Div. 1 or equivalent. The minimum standard of design should be that which compares with ADR (European Agreement Concerning the International Carriage of Dangerous Goods by Road).

New vessels should be designed and manufactured to BS5500 category 1 or equivalent standards. The user should retain copies of all documents and drawings relevant to design and manufacture.

1.2.1.2 The corrosion allowance for storage vessels should be, at a minimum, 2 mm.

1.2.1.3 The vessel supports should be designed in accordance with the design code to permit thermal expansion and contraction over the design temperature range. Thermal expansion needs to be considered in cases where load cells are used for determining the tank contents.

1.2.1.4 Manhole access should be provided on the top of the vessel. The opening for man entry should preferably be 900 mm and should not normally be less than 600 mm.

1.2.1.5 The dimensions of nozzles should be limited to the minimum required, particularly for the liquid lines. All nozzles should preferably be mounted on a manhole cover to aid replacement / renewal.

1.2.1.6 Connections to the storage tank are:

• Liquid TiCl4 inlet
• Liquid TiCl4 outlet
• Venting and padding lines (see also 1.2.7).
• High level interconnection between tanks
• Connections for instrumentation

1.2.1.7 The number of connections should be kept to a minimum to reduce the potential sources of leakage.

1.2.1.8 The arrangements of valves and pipework should be made as simple as possible to minimise errors in operation. Valves should be fitted directly to nozzles so that pipework can be isolated from the vessel.

1.2.1.9 For guidance on bolted joints, refer to “Guidelines for the management of the integrity of bolted joints for pressurised systems” Published by The Energy Institute (EI), in association with UK Oil and Gas (formerly UKOOA) and ASME PCC-1 “Guidelines for Pressure Boundary Bolted Joints”

1.2.1.10 Gaskets
Asbestos regulations prohibit the use of compressed asbestos fiber (CAF), which has been the universally accepted jointing material up to the year 2000. Present alternative gaskets are based on PTFE bound fiber sheet material such as Novatec Premium and Klingersil C4400. For specific information please seek advice from the TiCl4 supplier.

1.2.2 Pipework

1.2.2.1 Permanent pipework at the loading/unloading station consists of the following lines: a) pipework for TiCl4 transfer, articulated arms with swivelled joints on installations with high output, and/or flexible hoses; b) pipework for off-gas venting, connected to bulk carrier with flexible hoses; c) pipework for services dry nitrogen, dry air.

1.2.2.2 Lines should be colour-coded and labelled according to national and/or site standards.

1.2.2.3 Routing of pipelines for TiCl4 should normally be above ground and should be such as to maximise protection from mechanical damage. Pipework should be designed, fabricated and tested in accordance with a recognised code. Where practicable, the nominal bore of pipe work should preferably be not less than 50 mm, this is to reduce possibility of choking due to oxychloride deposits present on contact with atmospheric conditions and eliminate any high velocity flows which will result in internal pipework erosion.

It is recommended that pipework is constructed minimising horizontal flanged sections and with sufficient slope in order to facilitate self-drainage in the event of shut-down or maintenance – recommended minimum pipework slope 1 in 100.

1.2.2.4 All