Information Centre Applications of the Procal 2000 analyser in Oil Refinery Processes Kittiwake Procal Ltd Page 1 of 7

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1 Kittiwake Procal Ltd Page 1 of 7 Introduction Oil refineries convert crude oil into a variety of useful products such as liquefied petroleum gases (LPG), gasoline, jet fuels, kerosene, distillate fuel oils, lubricants and bitumen. The crude oil consists of hydrocarbon molecules that are refined into useful petroleum products through chemical reactions and physical separation processes. Maintaining the efficiency of the various operating processes at the refinery is important not only for producing cost effective petroleum products but also for limiting the emissions from the refinery. The Procal 2000 analyser, which can accurately monitor up to six pollutant gases, is easily integrated into existing process control systems. The Procal 2000, like the refinery operations, operates continuously providing data that can be utilised by the process control system to optimise process control equipment, improve energy efficiency and therefore reduce emissions. Refinery emissions from crude oil heaters, boilers and incinerators Many refinery operations require process heaters and boilers to raise oil feedstock temperature to reaction and processing temperatures. The fuel burned may be refinery gas, natural gas, residual fuel oils, or combinations, depending on economics, operating conditions, and emission requirements. The Procal 2000 measures the by-products of combustion including carbon monoxide (CO), carbon dioxide (CO 2 ), sulphur dioxide (SO 2 ) and oxides of nitrogen (NO and NO 2 ). Emissions variations caused by changes in fuel type and demand can be easily accommodated by the Procal With the Procal heated probe option variations in process temperature do not present a problem as the sample probe is maintained at a constant temperature. Keeping the probe hot also ensures immediate availability when the plant is re-started after an outage. Typical measurement ranges are shown below:- SO 2 NO NO 2 0 2,000 ppm H 2 O 0 15% Refinery emissions from cracking processes Emissions arise from both thermal and catalytic cracking processes. A large range of waste gases including hydrocarbons, sulphur dioxide (SO 2 ), ammonia (NH 3 ), aldehydes, nitrogen oxides (NO and NO 2 ), cyanides, carbon monoxide (CO), and particulates are also emitted in the catalyst reforming process. The Procal P2000 is well suited to both thermal and catalytic cracking processes where the degree of particulates is high. Sintered panels on the sample probe prevent the particulates from entering the measuring chamber allowing the Procal 2000 to operate even when particulate levels are a few g/m 3. Particulate emissions are effectively controlled by cyclones and/or electrostatic precipitators. Carbon monoxide and hydrocarbon emissions are incinerated in waste heat boiler systems and the remaining flue gas is passed through a caustic scrubber to remove sulphur dioxide. The Procal 2000 can Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

2 Kittiwake Procal Ltd Page 2 of 7 be used in the catalytic reforming process to measure SO 2 scrubber efficiency together with the emission of nitrogen oxides. SO 2 (normal) SO 2 (plant upset) NO NO ppm 0 14,000 ppm ppm ppm Refinery emissions from de-sulphurisation processes Removal of sulphur from naphtha streams is important as even in extremely low concentrations sulphur can poison noble metal catalysts used in the catalytic reforming units. Hydrogen sulphide (H2S) produced by de-sulphurisation units is converted to elemental sulphur in the Claus process unit. The Procal 2000 can measure the high levels of H 2 S and SO 2 associated with this process. The Procal 2000 can be offered with special corrosionresistant materials such as Hastelloy C276 and is the only in situ IR analyser on the market that is available with optional ATEX / IEC approval for use in ZONE 1 Hazardous Areas. Procal offer a range of accessories suitable for installation in hazardous areas including steam-heated probes and bypasses that can be used to keep the sample temperature above the acid dew point. SO 2 0 2% H 2 S 0 2% Refinery emissions from power plants Procal 2000 is the ideal field-proven device to monitor emissions from refinery power plants. Emissions from burning fossil fuels include carbon monoxide, carbon dioxide and oxides of nitrogen. CO NOx NO ppm CO % Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

3 Kittiwake Procal Ltd Page 3 of 7 Emissions from other processes Methane (CH 4 ) emissions from asphalt blowing, delayed coking units, and blow down systems can also be measured by the Procal Refineries have been shown to be a major source of volatile organic compounds (VOCs) and specific VOCs can be measured by the Procal 2000 in venting and evaporation applications. Emission regulations for refineries NESHAP the National Standards for Hazardous Air Pollutants (NESHAP) requires petroleum refineries in the USA to use maximum achievable control technology (MACT) to meet emission standards. The aim of the MACT standard is to control and limit emissions by testing, continuous monitoring, adopting accurate reporting and record keeping procedures and through control equipment. Procal s Continuous Emission Monitoring Systems (CEMs) are compliant with US EPA 40 CFR Part 60 and Part 75 measurement and reporting standards. Oil refineries are categorised as a major source of Hazardous Air Pollutants (HAPs) and therefore have to implement controls on all process units and emissions points that meet the criteria for control under the MACT standard. Emission points covered by the MACT standard include process vents, storage vessel loading, wastewater collection and treatment systems, gasoline loading racks, marine tank vessel loading, and equipment leaks. Alternatively, refineries can comply with the MACT standard by using a method of emissions averaging. This allows certain emission points to be selected and over controlled while other emission points are under controlled with the result of a net reduction in the overall level of emissions. The Crude Oil Feedstock The quality of crude oil is defined by the density of the oil and by the sulphur content. Oil feedstock is referred to as light, medium or heavy and is described as either sweet (<0.5% sulphur) or sour (>0.5% sulphur). Light and sweet crude oils are more expensive as greater yields of higher value refined petroleum products can be produced, such as gasoline, diesel and aviation fuels. Heavier and sour crude oils are less expensive as higher quantities of lower value petroleum products can be produced, such as fuel oils. Types of Refinery The arrangement of the refinery operations and processes depends on the composition of the crude oil feedstock and the desired petroleum products. The Topping refinery is the simplest in which a distillation tower is used to produce naphtha and other intermediate products, but not gasoline, from the crude oil. Distillation products such as Butane, Propane and aviation fuel require no further processing. However, the majority of petroleum products, including gasoline, are blends that contain a combination of other oil products and additives. To produce the different blends subsequent refining processes are required. oline is produced by Hydro-skimming refineries that are equipped with additional conversion processes such as reforming and treating units. To upgrade heavier components of the crude oil more complex refineries are required. Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

4 Kittiwake Procal Ltd Page 4 of 7 Refinery Figure 1 shows the oil refinery atmospheric and vacuum distillation processes. Before processing can start contaminants such as inorganic salts, grit and water are removed to prevent problems downstream such as build-up of deposits, fouling of heat exchangers and poisoning of catalysts. The de-salting process is achieved using either chemical or electrostatic cleaning. In chemical de-salting heated water and chemical surfactants are added to the crude oil causing salts and other impurities to dissolve in the water which is then separated from the oil. In electrical desalting high voltage electrostatic charges are applied to concentrate suspended water globules at the bottom of a settling tank. Cleaned oil is pre-heated to C ( F) before entering the atmospheric distillation tower. The distillation tower contains a number of perforated trays which divide the tower into a series of chambers. es boil off from the oil as it is heated and rise upwards through the chambers. The gases condense into liquids inside the chambers and are run off into collection tanks. The distillation tower separates the components of the oil into mixtures or fractions which are characterised by the boiling point range (see Table 1). The lightest and most volatile hydrocarbons form at the top of the tower and intermediate and heavier fractions condense in the middle of the tower. The heaviest fractions, known as topped crude, are left at the bottom of the tower. The separated fractions are further processed using chemical, catalytic and thermal processes to increase the products value. The heavy bottom fractions are often cracked into lighter, more useful products. Table 1 Common Fractions and their boiling point range Group Butane, Propane and LPG Naphtha oline Kerosene (Aviation Fuel) Diesel Fuels & Heating Oils Lubricating Oils Heavy or Fuel oil Vacuum gas oil (VGO) Vacuum residua (Bitumen) Boiling Point Range <32 C (<90 F) C ( F) C ( F) C ( F) C ( F) C ( F) C ( F) F 525 C (977 F) Vacuum Distillation To recover more distillate product from the Topped crude requires a separate vacuum distillation process that is operated at a reduced pressure and higher temperature. Vacuum distillation products include lube distillates, vacuum oil, asphalt stocks, and residual oils. Steam ejectors or vacuum pumps that are used to maintain the vacuum also withdraw hydrocarbon vapours from the distillation process. The majority of the vapours can be recovered in condensers but the remainder (the non condensable vapours) can be released to the atmosphere unless emissions control technology methods are employed. The efficiency of emission control techniques such as venting into blow down systems or incineration of flue gases in incinerators can be monitored by the Procal 2000 as shown in Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

5 Kittiwake Procal Ltd Page 5 of 7 figure 1. Hydrocarbon emissions from leaking seals and fittings are also associated with the vacuum distillation unit, but these are minimized by the low operating pressures and low vapour pressures in the unit. Figure 1: Oil refinery atmospheric and vacuum distillation processes. Naphta & Light Hydrocarbons (gas) Heated Crude Oil Refinery Desalter Furnace Atmospheric Distillation Tower Separator Diesel Kerosene Light Oil Heavy Oil Vacuum Pump oline or Naphta es Emissions Control P2000 Water Sludge Water Furnace Vacuum Distillation Tower Light Vacuum Oil Heavy Vacuum & Lube Oils Residuum Cracking Thermal Catalytic Cracking Secondary stage refining processes such as thermal cracking include visbreaking and coking. In these processes heavy oil molecules are broken down by exposing them to high temperatures ( C) and pressures ranging from atmospheric to 70 Bar. The visbreaking process reduces the normally high viscosity of residual fuels making them easier to blend with high value distillate in the production of heavy fuel oil. The visbreaking process reduces the quantity of high value distillate allowing more of the high value distillate to be used in other processes. Coking is another thermal cracking process used to convert low value residual fuel oil to higher value gas oil and petroleum coke. Thermal cracking emissions include coke dust from decoking operations, combustion gases from the visbreaking and coking process heaters, and fugitive emissions. Particulate emissions from delayed coking operations are potentially very significant. These emissions Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

6 Kittiwake Procal Ltd Page 6 of 7 are associated with removing the coke from the coke drum and subsequent handling and storage operations. Hydrocarbon emissions are also associated with cooling and venting the coke drum before coke removal. Particulate emission control is accomplished in the decoking operation by wetting down the coke. Hydrocarbon emissions can be collected from the coke drum and combusted in a refinery flare. Catalytic Cracking Process In this important process heavy hydrocarbon fractions are catalytically cracked into gasoline, home heating oil and diesel fuel. Catalytic cracking uses heat, pressure, and catalysts to break long chain hydrocarbons (with a boiling point range C (650 to 1000 F) into smaller molecules in the naphtha and distillate boiling point range. Catalytic cracking processes take the form of either a fluidized-bed or moving-bed. The fluidised-bed process uses a catalyst in the form of very fine particles that act as a fluid when aerated with vapour. When the hot fluid catalyst is introduced into a vertical, oil carrying, transfer line the oil is vaporised allowing cracking reactions, which are temperature dependant, to take place as the oil and catalyst mixture flows upward into a reactor. In the reactor hydrocarbon vapours are separated from the catalyst particles by cyclones and the oil products are passed to a fractionator for separation. In the moving bed process catalysts in the form of small beads (0.5cm in diameter) flow downwards into a reactor and come into contact with a mixed phase oil feed causing cracking reactions to take place. The catalyst is separated from the vapours at the bottom of the reactor and the gaseous reaction products flow out of the reactor to the fractionator. Hydrogen, which is released during the catalytic reactions, can be used later in hydro-treatment processes. The used catalysts can be reformed and recycled. Absorbed hydrocarbons are removed from the catalyst by a steam stripping process. The catalyst is then regenerated in a controlled combustion process which burns off coke deposited on the catalyst as a result of the cracking reactions. The catalyst is separated from the flue gases before being re-used. Emissions from catalytic cracking processes arise from process heater combustion products and flue gas from the catalyst regeneration. Other Refinery Alkylation Process In the alkylation process small molecules are combined into larger molecules. For example, iso-butane is reacted with either isobutylene or propylene to form complex paraffin isomers. The reactions take place in the presence of hydrofluoric or sulphuric acid catalysts. By combing these molecules the octane level of the paraffin isomer or alkylate is increased to around octane. This process is used to improve the octane level of the gasoline pool. Isomerization Process In the isomerisation process the structure of the petroleum molecules can be re-arranged to produce high value molecules. For example, the octane number of light naphtha can be improved by the use of an isomerization process using a platinum catalyst where the pentane paraffin (62 octane) is converted to an isomer iso-pentane (92 octane). Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

7 Kittiwake Procal Ltd Page 7 of 7 Hydrotreating Process This process removes impurities such as sulphur by reacting a petroleum fraction with hydrogen produced in the catalytic cracking process or generated from the hydrogen plant at the refinery. Product Blending Process Different petroleum fractions are combined together to make the final product in a blending process. Fractions are mixed to produce products that meet a required specification based on a specific recipe of petroleum fractions. oline is a mixture of naphtha, reformate, catalytic gasoline, alkylate and butane. Using the correct blend a gasoline with a specific octane number, vapour pressure, sulphur level and aromatic content can be produced. Treating Asphalt blowing is a treating process used to improve the weathering characteristics of asphalt. Heated air is used to oxidise asphaltic residual oils increasing their melting temperature and hardness. The emissions from asphalt blowing, which are primarily hydrocarbon vapours vented with the blowing air, are controlled by vapour scrubbing and incineration. Sulphur Recovery Plant Sulphur recovery plants are used in petroleum refineries to convert the hydrogen sulphide (H 2 S) separated from refinery gas streams into the more disposable byproduct, elemental sulphur. The Procal 2000 can be used to monitor SO 2 gases associated with this process. Blowdown System A blowdown system provides for the safe disposal of hydrocarbons (vapour and liquid) when discharged from pressure relief devices. By connecting the release points to a manifold the hydrocarbons can be collected. The blowdown system consists of a series of flash drums and condensers, arranged in decreasing pressure, which allows vapour and liquid cuts to be separated. The separated liquid is recycled back into the refinery and the gaseous cuts can either be flared or recycled. To obtain complete combustion steam is injected into the combustion zone of the flare to provide turbulence and air. Steam injection also reduces emissions of nitrogen oxides by lowering the flame temperature. Procal 2000 analyser in Oil Refinery Change Note: Date: 19/03/12

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