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Liquid SO2
Introduction Production Compression and Condensing Partial Condensation Absorption and Acidification Sulphur Trioxide and Sulphur Product Specification Shipping and Storage Piping and Fittings Storage Tanks

Condensation Skid Introduction Liquid sulphur dioxide (SO2) is a versatile chemical with many uses, both in liquid form or as a source of gaseous SO2. Liquid SO2 is used the pulp and paper industry, mining industry, and in the food industry as a preservative. It can function as a reducing agent, an oxidizing agent, a pH controller, purifying agent, preservative, a germicide and bleaching agent. SO2 can also be used as a refrigerant, heat transfer fluid and selective solvent. Liquid SO2 can be produced from gas containing SO2 concentration in the range of 1% to 100% using different processes. Production There are several different processes for the production of liquid SO2: Compression and Condensing Partial Condensation Absorption and Acidification Sulphur Trioxide and Sulphur

Compression and Condensing >>>>> this data below for basic calculation adapated with data operational from effluent RTO At atmospheric pressure, pure SO2 will begin to condense at 10.1C (13.9F). If the gas is compressed to 388 kPa(g) (56.3 psig), SO2 will begin to condense at 32.2C (90F). This temperature is high enough

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that normal cooling water can be used to condense SO2. When the concentration of SO2 is less than 100%, the gas must be compressed to higher pressures to obtain a high enough condensing temperature to use cooling water as the condensing medium. The tail gas leaving the system may be further cooled in a refrigeration unit to achieve nearly 100% or full condensation of the SO2. Partial Condensation When the concentration of SO2 in the gas is low (typically 7-14%), it becomes impractical to attempt to fully condense all the SO2 contained in the gas. Extremely high pressures are required in order to use cooling water to condense SO2 from the gas. The alternative to full condensation is partial condensation of the SO2 is using refrigeration only. Refrigeration systems can achieve temperatures as low as 55C (-67F). Typically, only 50% of the SO2 can be condensed from the gas. The tail gas from the refrigeration process in used to pre-cool the incoming gas prior to being directed to some other process, such as a sulphuric acid plant, for further treatment. Absorption and Acidification Gas containing low concentrations of SO2 (typically 1-2% vol) is scrubbed using an ammonia solution to form ammonium bisulphite according to the following reaction: SO2(g) + NH4OH = NH4HSO3 The ammonium bisulphite solution is reacted to sulphuric acid to form ammonium sulphate, water and SO2. 2 NH4HSO3 + H2SO4 (NH4)2SO4 + 2 H2O + 2 SO2(g) The SO2 is stripped from the ammonium sulphate solution and is directed to liquid SO2 production. The gas containing essentially 100% SO2 and moisture is first dried by condensing water from the gas and then drying the gas using concentrated sulphuric acid. The dried SO2 gas is compressed and then condensed using cooling water. An absorption and acidification process has been operating at Comincos metallurgical facility since 1931. The production of liquid SO2 is unfortunately tied stoichiometrically to the production of ammonium sulphate. Sulphur Trioxide and Sulphur Pure sulphur trioxide (SO3) will react with solid sulphur to produce SO2. SO3 can be obtained by distilling oleum to drive off SO3 gas. The SO3 passes through a column packed with solid sulphur to produce SO2 out the top of the column. Product Specification A typical product specification for liquid SO2 is as follows: Purity 99.90% (min)

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Acidity Moisture Residue Sulphur 25 ppm (max) 100 ppm (max) 100 ppm (max) 5 ppm (max)

Liquid SO2 produced from sulphur burning acid plants is generally able to meet the above criteria. It will be more difficult but not impossible to meet the above requirements in a metallurgical acid plants. An efficient gas cleaning system is required to achieve the specification. Shipping and Storage Liquid SO2 can be shipped in a number of different ways. Small quantities are available in 68 kg (150 lb) cylinders similar to cylinders for welding gases. The rate of delivery will depend in the temperature of the liquid SO2 in the cylinder. In order for gas to continue to be produced some liquid SO2 must vapourize but vapourization of liquid SO2will cool the remaining liquid SO2 reducing the pressure in the cylinder. The overall rate of SO2 gas discharge will depend on the heat transfer rate from the surroundings through the walls of the cylinder. At room temperature a discharge rate of about 0.9 kg/h (2.0 lb/h) of gaseous SO2 is possible. Larger quantities of liquid SO2 are available in one tonne containers. Bulk storage of liquid SO2 can be done in large horizontal cylindrical pressure vessel specifically design for the service. These storage tanks can be designed to hold several hundred tonnes to thousands of tonnes of liquid SO2. Bulk shipments of liquid SO2 are done using either rail tank cars or tank trucks. Piping and Fittings Normally, heavy walled (i.e. schedule 80) seamless carbon steel pipe will be used to handle liquid SO2. If SO2 is produced using the refrigeration method, extremely low operating temperatures are involved. In this case the material must have adequate notch toughness to eliminate the risk of low temperature embrittlement. If the piping is installed where the ambient temperature can get very low, the requirement for adequate notch toughness is also required. Flanges should be 300 lb. ANSI rated. Screwed joints should be avoided but if it is necessary to have screwed connections, they should be back welded.

Introduction

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Liquid SO2 is generally store at ambient temperatures in carbon steel pressure vessels. Codes and Standards As a vessel containing a liquid under pressure, a liquid SO2 storage tank must be designed to the ASME Boiler and Pressure Vessel Code, Section VIII, Division 1 or equivalent. Welding procedures must be qualified in accordance to Sectin IX of the ASME Code or equivalent. The design calculations, welding procedures and qualifications must be submitted to the appropriate agency or approval and registration. Design Temperature and Pressure The design temperature must take into account the typical ambient temperatures since this affects the vapour pressure of liquid SO2. A typical maximum operating temperature is 50C. The mechanical design temperature can be conservative set at 100C. The design pressure must be set higher than the vapour pressure at the maximum operating temperature. A typical design temperature for a storage vessel is 1448 kPa(g) (210 psig). Relief valves should be set at 1379 kPa(g) (200 psig), which is 5% lower than the design pressure. Materials of Construction All materials should conform the ASME/ASTM standards. Typically, ASTM A516 Gr. 70 carbon steel will be used for all pressure containing parts. When cold product or ambient temperatures are involved, all material must be impacted tested using Charpy 'V' notch specimens at -46C (-50F). No specimen must be less than 15 ft. lbs. In addition to impact testing, all material shall be normalized. Corrosion Allowance Even though anhydrous liquid SO2 is not corrosive to carbon steel, any moisture entering the tank when in contact with liquid SO2 will be corrosive. A typical corrosion allowance will be 3 mm (1/8"). Typical Storage Tank A typical storage tank will be a horizontal cylindrical vessel. A vessel designed to hold 260 tonnes of liquid SO2 will be 12'-0" diameter by 70'-0" long.

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Gas Cleaning System - Quench Systems

Introduction Liquid System Gas Retention Time Emergency Quench Water Materials of Construction Introduction The quench tower and system serves the following functions: Adiabatic saturation of the incoming gas Partial cleaning of the gas Provide residence for the condensation of metallic vapours to facilitate their subsequent removal in downstream equipment The tower may be designed to provide a liquid reservoir for operation of the pumps and holdup of the liquid on shutdown of the system Associated Links Materials of Construction

The traditional quench tower design consisted of an open vessel in which liquid is sprayed to contact the gas. The gas typically enters the bottom of the tower through a side nozzle and flows upwards, countercurrent to liquid that has been sprayed from the top of the tower. By the time the gas has reached the top gas outlet, it has been cooled to its adiabatic saturation temperature. A variation of this design is to have the gas entering the top of the tower and contacting the liquid co-currently as it travels down through the tower. A packed tower has also be used as quench tower. The packing provides additional gas-liquid contact by the film of liquid that forms on the surface of the packing. The use of a packed tower may further enhance the removal of solids. A variation of the co-current design is to design the tower as a low pressure drop venturi. Liquid is fed into the tower above the throat of the venturi section and through sprays located below the throat. The turbulent contact between the gas and liquid in the throat quenches and cools the gas and provides some degree of cleaning, however, the design is not meant to remove the vry fine sub-micron particles. Quench towers have also been designed using the reverse jet scrubbing principle. The gas enters the top of the reverse jet scrubber barrel and flows downwards where it contacts a liquid that has been sprayed from the bottom. At some point in the barrel the momentum of the liquid is cancelled and a zone of intense mixing and turbulence is created. Highly efficient cooling and cleaning of the gas is achieved. Once the gas is cooled it proceeds into the next stages of the gas cleaning system. One of the key functions of the quench system is the cooling of the gas which allows a change in the materials of construction from bricklined carbon steel to plastics and FRP. Gas Retention Time The gas retention time must be sufficient to allow the metallic vapours to be condensed into fine particles

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which will facilitate their removal in downstream equipment. The gas retention time based on the inlet gas flow is typically a minimum of 3.0 seconds. Liquid System The liquid circulating system of the quench tower consists of one or more circulating pumps, a liquid reservoir, piping system, controls and spray nozzles. Liquid is fed into the quench tower through a series of spray nozzles and/or feeder pipes. The spray nozzles are designed to provide full coverage across the quench tower cross-section and to finely atomize the liquid to provide intimate contact between the gas and liquid. The liquid fed into the tower falls to the bottom of the tower which is often used as the liquid reservoir. Alternatively, the liquid may drain from the tower into a separate pump tank. Liquid level in the reservoir is typically maintained by controlling the bleed stream from the quench system. Liquid is pumped from the reservoir by one or more operating pumps. The pumps are typically horizontal centrifugal pumps with materials of construction suitable for the liquid conditions. One or more pumps are installed a standby pumps in case one of the duty pumps should fail. The quench process results in the net evaporation of liquid into the gas. To maintain liquid in the system, liquid is added from the gas cooling system in which liquid is condensed from the gas. The acid concentration and the levels of impurities is controlled by the amount of make-up water that is added to the gas cleaning system. The more make-up water that is added, the lower the acid concentration and level of impurities in the quench system. The bleed from the quench system is usually sent to the weak acid stripper before being sent to the effluent treatment syetem. The quench system is usually operated with a weak acid concentration fo less than 10% H2SO4. In some instances, the system is operated at higher acid concentrations up to 30% H2SO4. This is done to reduce the weak acid effluent flow to the treatment system to reduce the size of the equipment. The stronger weak acid also has the potential to be treated for reuse as dilution in the acid system. Emergency Quench Water In the event of a reduction or failure of the circulating liquid flow, the gas temperature exiting the Quench Tower will rise quickly. The high temperature may result in damage to the downstream FRP ducting and equipment. When the temperature exits the Quench Tower is too high, the flow of emergency water is started. At the same time a plant shutdown is initiated. The flow of emergency water will continue until the gas exit temperature drops to a safe level. The source of emergency water must be an uninterruptable supply of water. The supply can be from a water main such as a firemain. An elevated head tank having sufficient volume for the expected duration of the high temperature can be used. The flow of emergency water is dependent on the design of the spray system for the quench tower. Emergency water may be fed into the quench tower through a set of dedicated nozzles or some of the spray nozzles may serve a dual function of emergency water and normal process spray nozzles. The flow and pressure of emergency water should be sufficient to cool the gas and the nozzles selected to provide adequate coverage across the tower. The duration that the emergency water is required to be on will depend on how long it will take to safety shutdown the plant to prevent the ingress of hot gas into the the quench tower.

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Materials of Construction The materials of construction for a quench system must be selected carefully to avoid operating and maintenance problems. The system is subject to hot gas, weak acid and regions where the conditions vary from wet to dry and hot to cold. The use of specialty alloys and brick linings are typical. Click here for more details on materials of construction. In a counter-current tower design, the area the sees the most severe conditions is the gas inlet. Here the gas is still hot but is quickly quench as it enters the tower. The design of the inlet nozzle should prevent the formation of eddies that would cause weak acid to be drawn up the gas inlet where it can attack the unprotected carbon steel ducting. When gas flow is stopped, liquid circulation over the tower usually is left on. Weak acid can migrate up the inlet gas duct and condense on the inside surface of the carbon steel duct. Weak acid is extremely corrosive to carbon steel. When the gas flow is resumed, the region is then exposed to higher temperatures which can further increase corrosion. In a co-current tower design, the gas inlet is also the most vulnerable to corrosion and attack. Spray nozzles are sometimes exposed directly to the hot gas. Materials must be selected to withstand both high temperatures and corrosion from the weak acid.

Materials of Construction - Quench Towers

Introduction Tower Shell Lining Rubber Acid Brick Carbon Brick Spray Nozzles and Feed Pipes PTFE Silicon Iron Metals Introduction Tower Shell The tower shell is generally carbon steel which has been lined with a corrosion resistant lining. Once the gas has been quenched and cooled, the materials of construction can be changed to a plastic material or FRP. Lining The lining will be dependent in the gas and circulating liquid composition as well as the temperature of the gas. Associated Links Gas Cleaning System - Quench Systems

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Rubber Linning A rubber lining is used to prevent the weak acid from attacking the carbon steel shell . The type of rubber used will vary from application to application. Natural and chlorobutyl rubber are two types of rubber that have been specified for the service. The selection of the type of rubber will depend on the availability, cost, installation requirements, etc. If the ambient temperature of the site is low, chlorobutyl rubber should be specified due to its better low temperature flexibility over natural rubber. The minimum thickness of rubber is generally 5 mm. The maximum operating temperature is 60C (140F). Brick thicknesses should be specified to achieve this temperature at the rubber lining Acid Brick At least one layer of acid resistant brick is required to protect the rubber lining from the high gas temperatures especially in the region of the gas inlet. Multiple layers of brick are preferred as this provides an added degree of safety if a flaw or crack should develop in the outer layer. Each additional layer of brick is laid so as to stagger the joints. This eliminates any direct paths to the rubber lining should a crack develop in the mortar. The mortar used to lay the acid brick should be a furan mortar. The mortar is applied with a trowel to the sides of the brick before laying it in the course. Either a red shale or fireclay brick is suitable for the service. If there is no requirement for an outer layer of carbon brick, a fireclay brick is recommended due to its greater resistance to thermal shock. If a layer of carbon brick will be laid on top of the acid brick, the less expansive red shale brick can be used. Carbon Brick Carbon brick is required when there are fluorides present in the gas and circulating liquid. Fluorides will attack the silica in the acid brick resulting in failure of the acid brick lining. A single layer of carbon brick laid on top of the layer(s) of acid brick will prevent fluoride attack. A thin layer of carbon filled furan mortar (3 mm) is trowelled on top of the acid brick prior to laying the carbon brick. The mortar use to lay carbon brick should be furan mortar. As with the acid brick, the carbon brick is laid by applying mortar to the sides of the brick before laying it in the course. Carbon can be oxidized if the brick is exposed for prolonged periods to the hot gas with no liquid flowing over the brick surface. Risk of oxidization occurs when the gas temperature exceeds 350C . The design of the tower should ensure that the carbon brick is not exposed to the hot gas without liquid flowing on the brick surface. Specification: Low-Ash Chemical Carbon Brick

Spray Nozzles and Feed Pipes Many materials have been specified for quench tower service. The selection of a suitable material will be dependent on the gas and liquid compositions, gas and liquid temperature, mechanical strength,

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resistance to abrasion and wear, etc. PTFE PTFE has excellent resistance to chemical attack and is suitable for all gas and liquid compositions. However, PTFE lacks mechanical strength at high temperatures. PTFE nozzles are best suited for counter-current tower designs where they are not exposed to hot gases. Silicon Iron Silicon iron is resistant to most gas and liquid compositions that are found in typical quench tower applications. The material has excellent resistance to abrasion and wear due to solids in the circulating liquid. However, silicon iron is brittle and can break easily if there is excessive mechanical forces exerted on the nozzle or feed pipe Metals There are some metals that maybe suitable for spray nozzles and feed pipes depending on the gas and liquid compositions. Hastelloy C-276, G, X, alloy 20, stainless steel maybe specified for the service. Careful study of the suitability of the metal must be done before specifying it.

Properties - Sulphur Dioxide

Introduction Physical Properties Vapour Pressure

Introduction Sulphur dioxide is a clear, colourless gas or liquid. At standard temperature and pressure, it is colourless gas with a sharp pungent odour. Sulphur dioxide gas is twice the density of air. At atmospheric pressure, and at -10C (14F), it condenses to form a liquid almost 1 times the density of water. As the temperature of liquid sulphur dioxide rises, its vapour pressure increases. Liquid sulphur dioxide is not flammable and not explosive but it is intensely irritating to the eyes and respiratory tract. Dry sulphur dioxide is relatively benign to most common metals. However, when even a small amount of moisture is present, sulphur dioxide will react with the moisture to fomr sulphurous acid which will corrode most common metals. Physical Properties Colour Odour Colourless as a gas or liquid Intense, pungent, irritating

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Flammability Not flammable, not explosive in either the gaseous or liquid state SO2 64.063 -10.1C (14F) @ 101.3 kPa, 1.0 atmosphere -75.5C (-103.9F) @ 101.3 kPa, 1.0 atmosphere

Molecular Formula Molecular Weight Boiling Point Freezing Point Specific Gravity Gas Critical Temperature Critical Pressure Critical Volume

2.2636 @0C, 1 atm

157.5C (315.5F) 7883 kPa (1143.3 psia) 122 cm/mol Liquid Properties

Specific Gravity Dielectric Constant Thermal Conductivity Flammability

1.437 @ 0C (32F) / Water @ 4C (39.2F) 16.5 @ -10.1C (14F) 0.0005715 cal/s cm C Not Flammable

Vapour Pressure deg C -40 -28.9 -17.8 -12.2 deg F -40 -20 0 10 kPa 21.5 40.5 70.7 91.7 psia 3.1 5.9 10.3 13.3

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-6.7 -1.1 4.4 10 15.6 21.1 26.7 32.2 37.8 43.3 48.9 54.4 60.0

20 30 40 50 60 70 80 90 100 110 120 130 140

116.5 146.9 183.4 226.8 277.9 338.5 408.9 489.5 579.8 683.3 801.9 936.3 1087.3

16.9 21.3 26.6 32.9 40.3 49.1 59.3 71.0 84.1 99.1 116.3 135.8 157.7

The following Antoine equation adequate correlates the above vapour pressure data. log10 P = 7.32776 1022.80 / (240 + T) where T Temperature (C) P vapour pressure (mm Hg)

Liquid SO2 - Storage Tanks

Introduction Codes and Standards Design Temperature and Pressure Materials of Construction Corrosion Allowance Typical Storage Tank

Properties of Liquid SO2

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Introduction Liquid SO2 is generally store at ambient temperatures in carbon steel pressure vessels. Codes and Standards As a vessel containing a liquid under pressure, a liquid SO2 storage tank must be designed to the ASME Boiler and Pressure Vessel Code, Section VIII, Division 1 or equivalent. Welding procedures must be qualified in accordance to Sectin IX of the ASME Code or equivalent. The design calculations, welding procedures and qualifications must be submitted to the appropriate agency or approval and registration. Design Temperature and Pressure The design temperature must take into account the typical ambient temperatures since this affects the vapour pressure of liquid SO2. A typical maximum operating temperature is 50C. The mechanical design temperature can be conservative set at 100C. The design pressure must be set higher than the vapour pressure at the maximum operating temperature. A typical design temperature for a storage vessel is 1448 kPa(g) (210 psig). Relief valves should be set at 1379 kPa(g) (200 psig), which is 5% lower than the design pressure. Materials of Construction All materials should conform the ASME/ASTM standards. Typically, ASTM A516 Gr. 70 carbon steel will be used for all pressure containing parts. When cold product or ambient temperatures are involved, all material must be impacted tested using Charpy 'V' notch specimens at -46C (-50F). No specimen must be less than 15 ft. lbs. In addition to impact testing, all material shall be normalized. Corrosion Allowance Even though anhydrous liquid SO2 is not corrosive to carbon steel, any moisture entering the tank when in contact with liquid SO2 will be corrosive. A typical corrosion allowance will be 3 mm (1/8"). Typical Storage Tank A typical storage tank will be a horizontal cylindrical vessel. A vessel designed to hold 260 tonnes of liquid SO2 will be 12'-0" diameter by 70'-0" long.

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Phase diagram SO2,