6 DELIVERY OF HYDROCHLORIC ACID .................................................................................7 DRIVERS INSTRUCTIONS FOR DISCHARGE.............................................................................. 7 OVERFLOW FROM BULK TANK .................................................................................................... 8 DISCHARGE OF HYDROCHLORIC ACID ..............................................................................9 DISCHARGE DANGERS.................................................................................................................... 9 LEAKS & SPRAYS.............................................................................................................................. 9 ACCESS FOR TANKERS ................................................................................................................... 9 HAZARDOUS CHEMICAL LABELLING................................................................................10 Hazardous Substances Act .................................................................................................................. 10 Safety Wall Charts .............................................................................................................................. 10 STORAGE INSTALLATIONS ................................................................................................11 MATERIALS OF CONSTRUCTION................................................................................................ 11 HANDLING PRECAUTIONS ........................................................................................................... 11 SITING................................................................................................................................................ 11 FUME ABSORPTION ....................................................................................................................... 11 REQUIREMENTS OF BULK INSTALLATIONS ........................................................................... 12 Bulk Tank Requirements .................................................................................................................... 12 Spillage Area....................................................................................................................................... 12 Bund Arrangement.............................................................................................................................. 13 SIZING OF TANKS ........................................................................................................................... 13 Stock Tank Capacity ........................................................................................................................... 13 Foundations......................................................................................................................................... 13 SAFETY EQUIPMENT ..................................................................................................................... 13 VENT AND OVERFLOW ARRANGEMENT ................................................................................. 14 GASKETS........................................................................................................................................... 14 LEVEL INDICATION ....................................................................................................................... 14 PROCESS PIPEWORK...................................................................................................................... 15 PUMPS................................................................................................................................................ 15 VALVES............................................................................................................................................. 16 CLEANING OF BULK TANKS........................................................................................................ 16 HYDROCHLORID ACID FLANGE .........................................................................................17
ACCIDENTAL RELEASE MEASURES .................................................................................17 ACCIDENTAL RELEASE MEASURES .................................................................................18 CLEAN-UP METHODS..................................................................................................................... 18 NEUTRALISATION TABLE ...................................................................................................20 SAFE HANDLING OF HYDROCHLORIC ACID ....................................................................22 PERSONAL PROTECTION .............................................................................................................. 22 Resistance of Protective Clothing ....................................................................................................... 23 FIRST AID MEASURES .........................................................................................................24 First Aid Comment: ............................................................................................................................ 24 Product in Eye..................................................................................................................................... 24 Product on Skin................................................................................................................................... 24 Product Ingested.................................................................................................................................. 24 Product Inhaled ................................................................................................................................... 24 Traumatic Shock ................................................................................................................................. 24 Signs of Shock .................................................................................................................................... 24 THE BOILING POINT OF HYDROCHLORIC ACID AT 101,3 kPa .........................................25 THE FREEZING POINT OF HYDROCHLORIC ACID ............................................................26 THE VISCOSITY OF HYDROCHLORIC ACID .......................................................................27 SUMMARY .............................................................................................................................28
INTRODUCTION
Hydrochloric acid is a colourless to slightly yellow solution of hydrogen chloride gas (30% m/m) in water and is one of the most widely used chemicals throughout industry. It is used for the manufacture of other chemicals and pharmaceuticals, refining and processing of sugars, synthetic rubber production, leather processing, pickling of metals, scale removing, metallurgical extraction processing and regeneration of cation resins. Hydrochloric acid can be handled, transported and stored without creating an undue threat to man and the environment, provided that suitable systems are implemented and the necessary precautions taken. This publication offers advice on systems, equipment and safety procedures to enable hydrochloric acid to be handled safely and with confidence. Storage installations should be designed to suit individual requirements. Guidance is given on the most important items, but NCP Chlorchem welcomes the opportunity to discuss a customers needs in detail at an early stage. In accordance with the policy of NCP Chlorchem, all bulk storage installations must be inspected prior to the first delivery. The inspection is to ensure that essential requirements are present, and should not be interpreted as an approval of the installation by NCP Chlorchem. The suitability and safety of the installation is primarily the responsibility of the customer in terms of South African law. Should you be contemplating modifying a system, or installation a new one, NCP Chlorchem will be happy to provide advice and assistance.
TRADITIONAL APPLICATIONS
Regeneration of cation exchange resins pH adjustment Chemical raw material Etching of mild steel Neutralising agent in chemical processes Descaling agent for boilers and activated carbon Extractant for mineralogical process
PRODUCT IDENTIFICATION
Technical Name and Description Trade Name Chemicals Family Chemical Name Synonyms
: : : : :
Hydrochloric Acid Solution Hydrochloric Acid Inorganic Acid Hydrochloric Acid Aqueous Hydrogen Chloride Hydrogen Chloride Muriatic Acid Spirits of Salt
Hazard Classification Group II Hazardous Substance Act No. 15 of 1973. Class 8 Corrosives: SABS 0228 1990 The identification and classification of dangerous substances and goods. Danger: Group II. Labelling requirements: Corrosive. Chemical Abstracts No.: 7647-01-0. Miosh No.: MW 402500. Hazchem Code: 2R UN No.: 1789 Flash point: Not applicable. USA TLV (TWA): 7mg/m3
PRODUCT SPECIFICATION
Description Density Hydrochloric Acid (HC) Iron (Fe) Clear, very pale yellow solution of hydrogen chloride gas in water, which fumes in air. g/cm3 at 20C 1,14 Min. % m/m Mg/ 30 15 Min. Max.
PRODUCT PACKAGING
1. BULK ROAD TANKERS: Minimum quantity per delivery 10 ton. Maximum quantity per delivery 30 ton.
UNLOADING EQUIPMENT 1) 2) 3) All road tankers are fitted with transfer pumps. The maximum head is 10 m. Heights greater than 10 m: the customer must provide a discharge pump. The rubber discharge hose is
Each tanker has two discharge outlets, i.e. one on either side. interchangeable.
Each vehicle is equipped with 5 m of 50 cm bore flexible hose with a standard flange.
DRIVERS INSTRUCTIONS FOR DISCHARGE A typical set of instructions to the Tanker Services driver for discharge by transfer pump is indicated below. In the interest of safety it is strongly advised that customers ensure that the responsible person follow these recommendations. 1. On arrival the driver will report to the customers responsible person. 2. The customers responsible person will indicate the filling point at which the discharge is required. 3. The driver will position his vehicle safely and apply the hand brake. If the vehicle is on a slope, chocks must be used. 4. The driver will connect the flexible hose to the filling point. connections, all eight bolts and rubber gasket most be used. These are flange-to-flange
5. The customers responsible person will sign the delivery note in the space provided to confirm that: a) b) c) d) The receiving installation is in order and can take the quantity to be delivered. The tanker is connected to the correct inlet valve. The receiving inlet valve is open and the consignment may now be discharged. There are no inflammable vapours within the discharge area.
The customers responsible person must be available continuously during the discharge. We would recommend that the customers responsible person wear full protective clothing, but that as a minimum requirement the responsible person concerned must wear goggles and rubber gloves during the discharge and subsequent operations. The driver will wear full protective
clothing with which he is provided (full face protection, rubber gloves, jacket, trousers and rubber boots). As a safety precaution it is advisable that at all times during off-loading, water is running from a water hose adjacent to the unloading point. 6. The driver will open both outlet valve and the non-return valve on the tanker and start the pump. If the hydrochloric acid does not discharge the pump must be shut-off and the outlet valves closed before taking action. 7. At the end of the discharge the transfer pump must be switched off. 8. The driver will close the tankers outlet and non-return valve and the drain valve on the unloading point and the customer's responsible person will close the inlet valve. 9. The driver will place a suitable container provided by the customer beneath the drain valve on the unloading point, and by opening this valve and raising the flexible hose, drain any hydrochloric acid remaining into the container. The customers responsible person will then dispose of the drainings in a responsible manner. 10. The driver will close the tankers outlet and non-return valve and the drain valve on the unloading point and the customers representative will close the inlet valve. 11. The driver will then disconnect the flexible hose, replace the stoppers in the hose and returning it to its housing on the tanker and securing it. The drains should then be flushed clear with water. 12. The driver will request a further signature from the customers responsible person, on the two delivery notes to certify that the load has been received in a satisfactory condition. The driver will then give one copy of the delivery note to the customers responsible person for retention.
OVERFLOW FROM BULK TANK If during discharge, the stock tank being filled should overflow, the driver is responsible for the immediate closing of the tanker outlet valve, and will then stop the transfer pump as soon as possible.
LEAKS & SPRAYS A leak caused by flange failure is the more common type of leak. Because the product is normally under pressure it sprays in all directions and is capable of covering a large area. Many injuries result from operators having to move into the danger area to switch off the controls. It is therefore important that all equipment be easily accessible and clear of potential leaks/sprays.
ACCESS FOR TANKERS Vehicles are approximately: 15 m in length 3,3 m in height 2,25 m in width 1) Access for vehicles of this size should be kept clear at all times. 2) Adequate room to manoeuvre the tanker must be available. 3) An overhead clearance height of 4,5m is required.
Safety Wall Charts These are available from NCP Chlorchem and must be prominently displayed at all points where acid is used or handled.
STORAGE INSTALLATIONS
MATERIALS OF CONSTRUCTION 1) Suitable Materials Rubber-lined steel, fibre reinforced plastic (FRP), rigid PVC reinforced FRP, RFP lined steel, HDPE/LLDPE rotary moulded are the most commonly used corrosion-resistant materials of construction. Rubber, glass, plastic and ceramic are also resistant to corrosion. (Suitable metals such as Hastelloy B may be used, but are not usually financial viable). Polymer tanks are especially recommended for customers with a low off-take. 2) Unsuitable Materials Very corrosive to metals (which will liberate highly flammable hydrogen or explosive mixtures of hydrogen and air).
HANDLING PRECAUTIONS Prevent release of vapour or mist into the workplace air. Always ensure adequate ventilation in handling areas. When diluting or preparing solutions, slowly add acid to water to avoid boiling or splattering. Use the smallest possible amounts in designated areas with adequate ventilation. Have emergency equipment (for fires, spills, leaks, etc.) readily available. Label containers. Keep containers closed.
SITING 1. Fumes are emitted from HC bulk storage tanks during storage and during off-loading. 2. Fumes escaping during the offloading procedure are more serious. 3. Bulk storage tanks should be located in an isolated area away from buildings. FUME ABSORPTION Concentrated hydrochloric acid gives off fumes, which may result in an unacceptable environmental problem, particularly in humid weather conditions. Consideration should be given, therefore, to the installation of a fume scrubber in the stock tank vent system. There are a number of proprietary fume scrubbers available on the market, which uses water as the scrubbing fluid. It is important that the specific purpose and required duty of the scrubber are discussed in detail with the scrubber supplier. If a fume scrubber is installed in the vent system, the scrubber should be designed so that a backpressure is not imposed on the stock tank. For efficient operation, an adequate water supply to the scrubber must be available and this should be protected against freezing in winter.
Storage installation should be designed to suit individual requirements. Hydrochloric acid should be handled as a toxic and corrosive product. Note: Any storage site requires the following parts to successfully handle and store hydrochloric acid safely and deal with any hazards, which may arise. 1) 2) 3) 4) 5) 6) 7) 8) Easy Access. Bulk Tanks (clearly identified). Spillage area. Bund. Shower and eye wash/bath First aid equipment. Water hose. Respirators.
Bulk Tank Requirements Minimum requirements: 1) 2) 3) 4) 5) 6) 7) Discharge Line. Process Pipe work. Level indicator. Vent. Overflow. Drain outlets. Tank manhole.
Spillage Area Hydrochloric acid is extremely corrosive to concrete and tar. Concrete surfaces should be protected with an epoxy or similar surface coating. Storage vessels should be erected inside a bund, which forms part of a spillage area. Note: A bund is not a spillage area. Leaks, spills or sprays during off-loading must be contained. Product must not be allowed to spill into the drainage network.
Bund Arrangement Whenever possible, stock tanks should be located inside a bund wall. The bund should be capable to containing 110% of the capacity of the largest tank within the bund. Chemicals that react together should not be stored within the same bund, e.g. sodium hypochlorite and hydrochloric acid. The base of the bund should be concrete and sloped to one end where a sump should be located to collect rainwater, or in the event of a bulk tank overflow, the chemical. Some means should be provided for emptying the sump, i.e. small hand pump or a pipeline sealed into the bund with a valve on the outside.
SIZING OF TANKS Stock Tank Capacity 1) 2) The storage capacity of the bulk tank should be one weeks usage plus one normal delivery. A minimum capacity of approximately 20 tons is recommended.
Foundations 1) 2) 3) 4) Plastic tanks bedded on sand or seated on timber planks. Steel or timber Steel tanks to be elevated on frame or structures to allow inspection. 3 Coats of Dulux Epoxy tar will protect steelwork.
SAFETY EQUIPMENT All bulk tank installations should be equipped with the following: 1) 2) 3) 4) 5) 6) Safety showers. Hose pipes. Eye baths or bubble fountains. Respirators. Safety wall charts. First aid equipment plus instructions.
b) c)
Personnel must be trained to operate the safety equipment. Safety equipment must be visible from all points.
VENT AND OVERFLOW ARRANGEMENT Bulk storage tanks should be adequately vented. The design of the vent/overflow arrangement will depend upon the material of construction of the tank and the design of the tank. General recommendations are: a) Vertical rubber-lined carbon steel tanks, plus all types of plastic tanks, should have separate vent and overflow lines. A lowest point discharge line is recommended for complete drainage. The overflow lines should be at least 100 mm diameter, and should be located on the side of the tank away from the inlet line. The overflow line should be extended down inside the bund and arranged to cause the minimum amount of splashing. The overflow line should be luted if a vent scrubber is fitted to the tank. The vent line must be at least 150 mm diameter, and located on the top of the tank away from the inlet line. As a minimum requirement, the vent line should point vertically upwards and be fitted with a weather cowl, or be turned through 180. There must be adequate disengagement space of at least 350 mm between the level of the overflow line and the level of the vent. b) Horizontal lined carbon steel tanks, designed to withstand a pressure of 2.1 bar gauge (30 psig) in accordance with BS.5500: 1985, should have as a minimum requirement an 80 mm diameter combined vent/overflow line. The line should be taken off vertically from the top of the tank and then turned through 180 and extended down inside the bund in order to confine any spray, which may ensure from it at the end of the discharge. A small anti-vacuum hole (6mm diameter) should be drilled in the vent line, facing the tank and just above bund wall level, to prevent the tank being put under vacuum conditions should the end of the vent line become sealed (i.e. excessive level of rain water in the bund could possible cover the end of the vent line).
GASKETS Gaskets should comprise chemically resistant natural rubber or PTFE. Polypropylene valves should be regarded as the first choice or Saunders valves with appropriate diaphragms. Rubber or glass-lined valves are also suitable.
LEVEL INDICATION
ALL STOCK TANKS SHOULD BE FITTED WITH A LEVEL INDICATOR. Polymer tanks can be fitted with a suitable sight panel, which is well protected. Other suitable level indication equipment:
1. 2. 3. 4.
Sight glass. Dip tube pneumercator (FRP or Polypropylene). D.P. cell. Hydrostatic gauge.
PROCESS PIPEWORK 1. 2. 3. 4. 5. Unplasticised PVC. PVC reinforced with fibreglass. Rubber-lined mild steel. Polyethylene. Polypropylene can be used satisfactorily for pipe work conveying hydrochloric acid. Nonmetallic pipes have the advantage of not requiring painting, but may be more costly to support. Natural rubber gaskets are recommenced for flanged joints. The use of other materials that may be considered suitable should be discussed with the bulk tank supplier before use. For small installations, piping manufactured from polymer materials have the advantage of: 1. 2. 3. Low cost. Simplicity of fitting. Readily available.
Rubber lined steel while satisfactory has the following disadvantages: 1. 2. 3. 4. Expensive to repair. Subject to external corrosion. Difficult to detect failure of linings. High costs.
Caution:
PUMPS 1. 2. Centrifugal pumps of rubber lined cast iron or suitable plastic construction are recommended. Braided PTFE should be used for packed glands.
3. 4.
Mechanical seals of corrosion resistant material may be used. Magnetically driven pumps suitable for all plastic construction are also recommended.
VALVES 1. Plastic valves. 2. Saunders Ebonite Line Q diaphragm. 3. Rubber or glass lined valves.
CLEANING OF BULK TANKS It is unlikely that hydrochloric acid tanks will require cleaning. However for maintenance purposes: 1. Empty the tank to process or alternative storage. 2. Add one of the Alkali agents detailed in table 2 until the remaining liquid is alkaline. Caution: During neutralisation a vigorous reaction will occur which will result in the CO2 fumes being released.
1. 2. 3. 4.
Agitate the solution for several hours. Empty the vessel to effluent. Hose down all surfaces, with large amounts of water. Run to effluent.
CLEAN-UP METHODS
Small spills 1. 2. 3. 4. 5. 6. Contact fire and emergency services and supplier for additional advice. NCP Chlorchem emergency number is (011) 976-2115. Contain and soak up spill with absorbent material, which does not react with spilled chemical. (Earth, sand or absorbent material). Put material in suitable, covered, labelled containers. Neutralise spill area with lime or soda ash and flush area with water. Do not get water inside containers. Contaminated absorbent material may pose the same hazards as the spilled product.
Large spills 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. Contact fire and emergency services and supplier for additional advice. NCP Chlorchem emergency number is (011) 976-2115. Avoid contact with spilled material. Keep upwind and out of low areas. Avoid inhaling vapour. Prevent material entering sewers, waterways or confined spaces. Stop or reduce leak if it can be done without risk. Recover spilled HC if feasible. Contain spill with earth, sand, or absorbent material, which does not react with spilled material. Collect material in suitable, covered, labelled containers. Dispose of contaminated product and materials used in cleaning in a manner approved for this chemical. After removal, neutralise spill area with lime or soda ash and flush spill area with water to an approved sewer. Water fog or spray may be necessary to know down vapours. When neutralizing large spills personal protection i.e. acid proof suits must be worn.
14. 15.
Breathing apparatus sets may also be required depending on the density of the fumes emitted. Notify Government Occupational Health & Safety and Environmental Authorities.
NEUTRALISATION TABLE
Quantities of Various Alkalies Required to Neutralize 455 litres of Hydrochloric Acid Hydrochloric (Muriatic) Acid Acid Concentration Mass % HC 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1 2 USE 1.000 USE 1.000 USE 1.000 USE 1.000 USE 1.0015 USE 1.0015 USE 1.0015 USE 1.0015 USE 1.0015 1.0032 1.0082 Specific Gravity Solution Actual Kg of Acid per 455 litres 0,377 0,753 1,130 1,508 1,886 2,259 2,637 3,015 3,389 3,767 7,574 0,290 0,576 0,869 1,161 1,436 1,737 2,030 2,318 2,606 2,898 5,823 0,383 0,765 1,134 1,535 1,899 2,300 2,669 3,069 3,434 3,834 7,704 Neutralizing Chemicals CaO Quicklime kgs Ca(OH)2 Lime kg Na2CO3 Anhydrous Soda Ash kg 0,572 1,143 1,715 2,286 2,858 3,429 4,000 4,572 5,144 5,715 11,070 50% NaOH Liquid Caustic Soda kg 0,826 1,652 2,475 3,303 4,131 4,959 5,787 6,606 7,434 8,262 16,632 NaOH Bead/Flake Caustic Soda kg 0,413 0,826 1,238 1,652 2,066 2,480 2,894 3,303 3,717 4,131 8,316
3 4 5 6 10 20 25 30 35
PERSONAL PROTECTION Respiratory Because of the pungent odour of the Hydrochloric acid fumes it is highly unlikely that they will go unnoticed. According to the concentration of the vapour or fumes the following symptoms will be apparent: 3 ppm: Irritation of eyes, nose and throat can be severe. 5 ppm: Nausea. UP TO 50 ppm: SAR; or SCBA; or chemical cartridge respirator with cartridge(s) to protect against hydrogen chloride. UP TO 100 ppm: SAR operated in a continuous flow mode; or full face piece SCBA; or full face piece SAR; or gas mask with canister to protect against hydrogen chloride; or full face piece chemical cartridge respirator with cartridge(s) to protect against hydrogen chloride; or powered air-purifying respirator with cartridge(s) to protect against hydrogen chloride. Abbreviations: SAR = supplied-air respirator. SCBA = self-contained breathing apparatus.
Hand Neoprene, Viton or butyl rubber gloves. Eye Gas-tight chemical safety goggles. A face shield may also be necessary.
Skin Impervious gloves, coveralls, boots, and/or other resistant protective clothing to prevent all possible skin contact. Neoprene, Viton and butyl rubber are suitable materials for protective clothing. An impervious acid-resistant full-body encapsulating suit and respiratory protection may be required in some operations. Have a safety shower/eye-wash fountain readily available in the immediate work area. Resistance of Protective Clothing Resistance EXCELLENT GOOD Protective Clothing Neoprene, nitrile blended polyvinyl chloride (PVC). Chlorinated polyethylene, viton coated neoprene, natural rubber, nitrile, Viten Saranex, butyl coated neoprene, chlorobutyl, polycarbonate, neoprene blended PVC, styrene-butadiene rubber (SBR). PVC, polyurethane, neoprene blended SBR, SBR coated neoprene.
FAIR/POOR
SUMMARY
PRODUCT:
Hydrochloric Acid
FACTORY:
Chloorkop
VEHICLE:
Various
LOAD:
DISCHARGE FLANGE:
O.D.:
150 mm
P.C.D.:
115 mm
HOLES