SUMMER TRAINING REPORT IOCL PANIPAT

ETHANOL DOPING
(Marketing Complex)

Kamal Aggarwal B.Tech, Chemical Engineering, Dr. B R Ambedkar National Institute of Technology, Jalandhar

ACKNOWLEDGEMENT
I have completed my 8 weeks of Industrial Training at IOCL Panipat successfully in Effluent Treatment Plant (Marketing Division). It was a great learning experience for me and I tried to cover all the aspects of refining within my limitations. At the outset, I would like to thank Mr. Ravi Sharma (Chief Terminal Manager Marketing Terminal, IOCL Panipat) for providing me the opportunity to do a project at Indian Oil Corporation limited. I would also like to thank Mr. Vinod Sharma (Sr. Manager) and to all concerned for their support in making my training successful. I wish to express my gratitude to my supervisors, Mr. Prakrin Kumar, Mr. Abhishek Gupta, Mr. jaipal singh who was abundantly helpful and offered invaluable assistance, support and guidance. I would also like to thank Mrs. Aditi Sharma for her concerned support.

Indian Oil Corporation Ltd. - A Brief Overview

Indian Oil Corporation Limited, or Indian Oil, is an Indian stateowned oil and gas company headquartered at Mumbai, India. It is Indias largest commercial enterprise, ranking 125th on the Fortune Global 500 list in 2010. Indian Oil and its subsidiaries account for a 47% share in the petroleum products market, 34.8% share in refining capacity and 67% downstream sector pipelines capacity in India. The Indian Oil Group of Companies owns and operates 10 of India's 19 refineries with a combined refining capacity of 65.7 million metric tons per year.

Major Divisions:
It comprises of three major divisions viz. Refinery, Pipeline and Marketing.

REFINERY:
At present, Indian Oil controls 10 of Indias 20 refineries. The strength of Indian Oil springs from its experience of operating the largest number of refineries in India and adapting to a variety of refining processes along the way. Indian Oil in an excellent position to offer O&M services for latest technologies such as distillate FCCUs, Resid FCCUs, hydrocrackers, reformers (both semiregenerative and continuous catalytic regeneration types), lube processing units, catalytic de-waxing units, cokers, coke calciners, visbreakers, merox, hydrotreaters for kero and gasoil streams, etc. Indian Oil refineries also have units for producing specialty products such as bitumen, LPG, MTBE, Butene-1, Propylene, Xylenes, Di-Methyl Terephthalate (DMT), polyester staple fibre (PSF) and other petrochemicals like Linear Alkyl Benzene, Paraxylene (PX), Purified Terepthalic Acid (PTA), etc. Indian Oils Refineries team have a deep understanding of the complexities of all the process units of modern refineries and can offer comprehensive services of a highly professional nature on different facets. With strategies and plans for several value-added projects in place, IndianOil refineries will continue to play a leading role in the downstream hydrocarbon sector for meeting the rising energy needs of our country.

PIPELINE
IndianOil, the pioneer in cross-country petroleum product pipeline in the Indian sub-continent constructed and commissioned its first petroleum product pipeline, Guwahati-Siliguri Pipeline in the year 1964. Since then IndianOil has mastered the art and technology of pipeline engineering. Over the last four decades the pipeline network of IndianOil has grown to 10,899 km IndianOils sustained pursuit and implementation of proven safety and environmental management systems have brought rich results. All operating pipeline units have been accredited with ISO 9000 and ISO 14001 certificates. The pipelines transport petroleum products from refineries to demand areas and crude oil from import terminals as well as domestic sources to the inland refineries.

MARKETING
Indian Oil provides a wide range of marketing services and consultancy in fuel handling, distribution, storage and fuel/lube technical services. With a formidable bank of technical and engineering talent, Indian Oil is fully equipped to handle small to large-scale infrastructural projects in the petroleum downstream sector anywhere in the country. IOCL project teams have independently or jointly as a consortium, have set up depots, terminals, pipelines, aviation fuel stations, filling plants, LPG bottling plants, amongst others.

IOCL PANIPAT-INTRODUCTION
Panipat Refinery, the 7th Refinery of Indian Oil, a Global Fortune 500 company having vision to become a major, diversified, transnational, integrated energy company, with national leadership and a strong environment conscience, playing national role in oil security & public distribution. Panipat Refinery is referred to as the countrys technically advanced refinery. 6 MMTPA refinery was built and commissioned in 1998 at a cost of Rs. 3868 Crore (includes Marketing Complex & Pipelines installation). Refinery capacity has been further augumented to 12 MMTPA in June 2006 at a cost of Rs. 4165 crore and Rs. 850 crores are further invested in its expansion from 12 MMTPA to 15 MMTPA in 2009.It receives crude oil from Vadinar and Mundra Ports in Gujarat coast. The refinery is designed for processing both indigenous & imported crude oil. The refinery has processed about 30 types of imported crude oil from countries like Saudi Arabia, Iran, Iraq, Dubai, Kuwait, Malaysia, Nigeria and other African countries since commissioning. Panipat marketing Complex envisages the product marketing facilities for handling the products produced at the 15.0 MMTPA Panipat Refinery, Panipat, Haryana. The terminal incudes storage tanks for the products such as naphtha, Motor Spirit, Aviation turbine Fuel, High Speed diesel, Light diesel oil, Superior kerosene oil, etc. with associated facilities including road and rail, tank wagon loading, drainage facilities, road and rail network, pumping etc.

Indian Oils marketing operations network of storage, distribution and supply hubs is backed by efficient sourcing, on-time logistics, custom-designed deliveries and round-the-clock after sales service and consultancy.

IndianOil's supply and distribution network is strategically located across the country linked through a customized supply chain system backed by front offices located in conceivably every single town of consequence. PMC's fuel management system to bulk customers offer customized solutions that deliver least cost supplies keeping in mind usage patterns and inventory levels and to adopt safe and environmental friendly practices. It has its own lubricant and fuel testing laboratory for quality check and better fuel handling services.

Gasoline
Gasoline or petrol , is a toxic translucent, yellow-tinted liquid mixture, derived from petroleum, which is primarily used as a fuel in internal combustion engines. It is also used as a solvent, mainly known for its ability to dilute paints. It consists mostly of aliphatic hydrocarbons obtained by the fractional distillation of petroleum, enhanced with isooctane or the aromatic hydrocarbons like toluene and benzene to increase its octane rating. Automotive gasoline and gasoline-oxygenate blends are used in internal combustion spark-ignition engines. These spark ignition engine fuels are primarily used for passenger cars. They are also used in off-highway utility vans, farm machinery and in other spark ignition engines employed in a variety of service applications. Gasoline is a complex mixture of relatively volatile hydrocarbons that vary widely in chemical & physical properties and are derived from fractional distillation of crude petroleum with a further treatment mainly in terms of improvement of its octane rating. The hundreds of individual hydrocarbons in gasoline range from c4 to c11.Small quantities of various additives are common, for the purposes of tuning engine performance or reducing harmful exhaust emissions. In view of the auto fuel policy issued by Govt of India, more & more stringent specifications oxygenates are being added to the gasoline. Oxygenate is an oxygen-containing, ash less organic compound which can be used as a fuel or fuel supplement. This has led to reduction of environmentally polluting factors in gasolines.The most common oxygenate used for blending with petrol is ethanol. Brazil and Sweden are the largest producers of vehicles that run on ethanol-gasoline blended fuel. Brazil is the largest producer of ethanol and therefore switched over to ethanol-blended fuel to reduce oil imports. 40% of the Brazil cars are fueled with pure ethanol and the remaining 60% cars with blended ethanol. With the growing awareness of ethanol-gasoline blends, India has also initiated the use of ethanol as an automotive fuel. In india 5%ethanol & 95% gasoline mixture is used. Indian automobile engines can work with 8% ethanol blend without any changes.

ETHANOL
Ethanol is an agricultural based product, mainly a by-product of sugar industries, available in sugar belt areas. Doping of ethanol in gasoline is a well established worldwide practice and is mainly used in countries like Brazil, Mexico, USA, etc. One of the main motivations for use of ethanol in MS is to improve air quality by reducing pollution. It is primarily used in MS to meet minimum oxygenate air requirements making fuel more eco-friendly.

TERMINOLOGY 1. Ethanol: Ethanol is the pure chemical, otherwise known as hydroxyethane, corresponding to the constitution CH3 CH2OH and molecular formula C2H5OH.

2. Ethyl Alcohol (Absolute Alcohol): Ethyl alcohol (absolute alcohol) is a clear, colorless and homogenous liquid, consisting essentially of ethanol admixed with not more than 0.5% by vol. of water.

3. Anhydrous Ethanol: Anhydrous ethanol is essentially ethyl alcohol, which is denatured and is meant for use as fuel in automobile engines. The IS 15464: 2004 prescribes requirements, methods of sampling and test for anhydrous ethanol, which is used either s such or more usually in admixture with petrol and diesel as a fuel for automobile engines.

4. Denaturant: Denaturant is a substance completely miscible in ethyl alcohol and of such character that while its addition makes the material or any aqueous dilution of it unpleasant and unwholesome for potable purposes, its presence does not render anhydrous ethanol, either as such or doped with petrol or diesel, unsuitable for use in automobile engines. The denaturant to be admixed with ethyl alcohol and the proportion in which it is to be used shall be as prescribed by law from time to time.

5. Prohibited Denaturants: Specific mention must be made of some materials that have extremely adverse effects on fuel stability, automotive engines and fuel systems. These materials shall not be used as denaturants, for anhydrous ethanol for use in automobile fuels, under any circumstances. They are as follows: Methanol Pyrroles, Turpentine, Ketones and Tars (high molecular weight pyrolysis products of fossil and non-fossil vegetable matter). Unless a denaturant, such as a higher aliphatic alcohol or ether, is known to have no adverse effect on gasoline-ethanol mixture or on automotive engines or fuel systems, it shall not be used.

Motor gasoline A volatile mixture of liquid hydrocarbons, generally containing a small amount of additives, suitable for use as a fuel in spark ignition and internal combustion engines conforming current BIS specification IS: 2796 and or as per the requirement of the Gazette notification issued by Govt. of India from time to time and or guideline issued by MOP & NG regulatory authorities from time to time.

Ethanol doped motor gasoline A fuel consisting primarily of motor gasoline doped with 5%vol./vol. of denatured anhydrous ethanol for fuel conforming to motor gasoline specification.

Oxygenate Oxygen containing ash less, organic compound such as an alcohol or ether which may be used as a fuel or fuel supplement.

Denatured anhydrous ethanol for fuel Denatured anhydrous ethanol for fuel is made unfit for use as beverage by addition of denaturants as per IS 15464 for Anhydrous ethanol for use in Automotive Fuel Specification. In the following sections wherever the term ethanol is used it refers to denatured anhydrous ethanol for fuel.

SALIENT FEATURES OF ETHANOL: 1. Ethanol is completely soluble in water, which presents potential problems for storage and handling. However, Ethanol will not be significantly degraded by small amount of clean water, though water addition dilutes its values as a fuel. 2. A higher conductivity suggests that ethanol will dissipate static charges that build up when pumping fuel transfers faster than motor gasoline, as static electrical charges generated will be dissipated more quickly. 3. Viscosity of Ethanol is higher than that of motor gasoline. However, it does not pose any problem in handling in cold weather. 4. The auto-ignition temperature of Ethanol is significantly higher thn that of motor gasoline. This makes Ethanol less susceptible to ignition when spilled on hot surfaces such as Engine Exhaust Manifolds. 5. The lower flammable limit of Ethanol is higher than Motor Gasoline. This is another advantage over Motor Gasoline. 6. Pure Ethanol burns with a flame that is not clearly visible in bright sunlight. However, Ethanol doped Motor Gasoline flame is visible.

Quality control
Quality control is a process by which entities review the quality of all factors involved in production. Quality control emphasizes testing of products to uncover defects, and reporting to management who make the decision to allow or deny the release, whereas quality assurance attempts to improve and stabilize production, and associated processes, to avoid, or at least minimize, issues that led to the defects in the first place. It implies a complete overview and reevaluation of the specification of a product, rather than just considering a more limited set of changeable features within an existing product. Quality protects the image of the organisation and control helps to meet prescribed specifications. Quality checks are carried out at various stages of stock handling 1. 2. 3. 4. During receipt of stock. During storage of stock. Monthly tests. During dispatch.

SAMPLING
It is the process of securing representative quantities from a part or from the whole of a quantity of material for various tests. Sampling of petroleum products is covered by 1. ASTM, D-270 2. IP-2546 3. IS:1447,1966

Types of samples 1.
ALL LEVEL SAMPLE CLOSED SAMPLER TO BE SUBMERGED AND OPENED NEAR DRAW OFF LEVEL AND RAISED AT A UNIFORM RATE SUCH THAT IT IS NEARLY FULL WHEN IT COMES OUT.

2.

TOP SAMPLE

DRAWN BELOW 15 CMS. FROM TOP SURFACE OF PRODUCT. 1/6TH OF THE DEPTH OF PRODUCT BELOW TOP SURFACE IN A TANK. OF THE DEPTH OF PRODUCT BELOW TOP SURFACE IN A TANK. 5/6TH OF THE DEPTH OF PRODUCT BELOW TOP SURFACE IN A TANK. A. MIXTURE OF EQUAL QUANTITY OF UPPER MIDDLE LOWER SAMPLES. (>12) B. UPPER & LOWER SAMPLES (6 12). C. MIDDLE SAMPLE (<6). SAMPLE TAKEN FROM LOWEST PART OF THE TANK.

3. 4. 5. 6.

UPPER SAMPLE MIDDLE SAMPLE LOWER SAMPLE COMPOSITE SAMPLE

7.

BOTTOM SAMPLE

GENERAL PRECAUTIONS FOR SAMPLING 1. SAMPLES SHALL NOT INCLUDE MATERIAL OTHER THAN THAT TO BE SAMPLED. 2. SAMPLE DURING COOLEST PART OF THE DAY PREVENT EVAPORATION LOSS. 3. SAMPLE HIGHLY VOLATILE PRODUCTS WITH JUDGEMENT, SKILL & EXPERIENCE. 4. SAMPLES SHALL BE DRAWN THROUGH GAUGE HATCHES OR SAMPLING HATCHES GIVING DIRECT AND UNCONFINED ACCESS TO THE BULK OF THE PRODUCT. 5. SAMPLES SHALL BE DRAWN BY APPROPRIATE METHOD IN APPROVED CONTAINERS. 6. . STRAINERS AND FILTERS SHALL NOT BE USED IN PREPARATION OF SAMPLES. 7. 8. 9. USE CLEAN AND DRY CONTAINER AND EQUIPMENT, CONTAINER SHOULD NOT BE LEAKY. USE SEPARATE SAMPLING EQUIPMENT FOR EACH PRODUCT. RINSE EQUIPMENT AND CONTAINER PRIOR TO FILLING.

10. LEAVE EXPANSION SPACE.

Quality control measures for ethanol

Receipt of ethanol 1. Receipt of Ethanol: 1. Ethanol shall be received at depots in dedicated tank trucks. All care shall be taken to prevent ingress of water into the compartments during transportation. 2. The fittings in tank trucks used for transportation of ethanol to receiving locations shall be the same as used for storage and handling of class A petroleum products. 3. The consignment of Ethanol must carry quality certificate as per IS 15464 specification covering the specification as per table no. 1 with foot note under section 4. this quality certificate should also contain the batch number and the name of the denaturant used along with its dosage. 2. On arrival, one litre top and bottom sample from each compartment of the tank truck shall be drawn after the line content is drained off.

3. These samples should be tested for visual appearance and specific gravity (SG) at 15.6 C / 15.6 C. for conversion of SG from ambient temperature to 15.6 C / 15.6 C, separate charts as per IS 2302 Table 1 & Table 2 as well as IS 321 Appendix B are to be used. The SG should be within +_0.0005 of the dispatch Specific gravity. A composite sample should be made from these samples for future tests. (Relative Density at 15.6 C / 15.6 C of IS 15464 as mentioned in table 1 of section 4 is same as specific gravity in air 15.6 C / 15.6 C of IS 321, table 1. Alternative to the above ASTM D4052 method for density and relative density of liquids by digital density meter may be used for measurement of specific gravity, however, the method under IS 15464:2004 will be the referee method. 4. The above composite sample should be tested for the following characteristics: 1. Appearance 2. Colour (Visual) 3. Ethanol Content % Vol. IS 2302

4. Hydrocarbon contamination checks (Refer Clause 5.7) Specific gravity at 15.6 C / 15.6 C for computing quantity can be calculated from the percentage of Ethanol content using the table 1 & 2 of IS 2302 and table 1, in appendix B of IS 321. 5. For determining Ethanol content IS 2302 tables for alcoholometry by hydrometer method should be used. 6. Specific gravity can be derived by using the Ethanol content and the Appendix B of IS 321. The specification, however, includes option to determine specific gravity by the method given in IS 321. 7. To ensure that there is no contamination of hydrocarbon with Ethanol, take 50ml of water in 100ml clean graduated stoppered glass cylinder (A class), put 50ml of Ethanol at the top of it. Stopper the cylinder and shake thoroughly for 15 sec. Set aside the cylinder. Observe that water is fully soluble with Ethanol and no layer is formed. This ensures no contamination of hydrocarbons with Ethanol. 8. One litre composite sample of Ethanol from the tank truck should be drawn, sealed, labelled and jointly signed by the driver/authorized representative of the transporter and the receiving officer of the oil company. These samples shall be retained for a period of 30 days. Only glass or stainless steel sample containers should be used. Aluminium containers should not be used for storing Ethanol samples. 9. Product can be decanted into tank, after ensuring that it conforms to the requirements of the characteristics as mentioned in table no. 1 of section 4 as well as physical verification carried out as per clause 5.3 and 5.4. 10. The unloading operations shall be carried out through special Nitrile rubber or any other compatible hoses. Ethanol being hygroscopic in nature, utmost precaution needs to be taken to ensure that there is no ingress of water or humidity. Both the ends of the hoses after use shall be capped. 80 mesh strainers (material as specified in section: 6) shall be provided before the pump / tank inlet as the case may be. All safety precautions shall be taken as that for class A product.

11. Appropriate recommended dosage of metal deactivator and Corrosion inhibiter shall be added during the decantation of Ethanol from tank truck into the storage tank, so as to ensure homogeneity of additives with Ethanol in the storage tank. A separate operations and inventory logbook shall be maintained for the additive. 12. The location shall maintain a Batch-Control Logbook tank-wise for receipt of Ethanol in the storage tank as per the following format

STORAGE AND HANDLING OF ETHANOL:

1. Material recommendations: The compatibility of Ethanol/Ethanol Doped motor gasoline with material coming in contact while handling means not only that equipment made from material will not deteriorate but also that the quality of Ethanol as well as Ethanol Doped motor gasoline in contact with the material will not degrade. The supplier/contractor will ensure in this regard. It is recommended that integrity of all materials coming in to contact with the fuel will be verified with Soak testing as per standard engineering practice. 2. Nozzles, fittings, connectors, piping, pump and impellers may be of best suitable material compatible with Ethanol as recommended for the storage tanks. 3. Zinc, brass, lead, copper and Aluminium are some of the sensitive materials known to be degraded while contact with Ethanol. Lead based solders are also incompatible with Ethanol. Avoid using them. 4. Un-plated steel, Stainless steel, black iron and Bronze have shown acceptable resistance to corrosion by Ethanol. 5. Non-metallic materials that degrade when in contact with Ethanol include natural Rubber, Polyurethane, Cork gasket material, leather, polyester bounded Fiberglas laminate, Polyvinyl Chlorides, Polyamides and Methyl and Methacrylate Plastics. 6. Non-metallic materials that have been successfully used with fuel Ethanol include Buna-N, Neoprene rubber, Polyethylene, Nylon, Polypropylene, Nitrile, Glass, Viton and Teflon. 7. Ethanol can be stored in a above ground or underground tank(S). Factors like the size of the tank, the space available, requirements for stationary evaporative emissions and safety aspects will determine which type of tank is best for use. 8. Epicoating is not recommended for the tanks proposed for storage of Ethanol. 9. Epicoating recommended in storage tank for general hydrocarbons may not be compatible for system handling Ethanol/Ethanol Doped motor gasoline and it may be ensured before any application or use.

10. Ethanol falls under the same handling and storage requirements as motor gasoline within the provision of applicable norms.

11. Tank should be constructed of low carbon, cold finished steel and buttwelded. Do not use any plated material tank. 12. The storage tanks and allied facilities for Ethanol shall be positively segregated. The existing Class A product storage tank fitted with Pressure Vacuum Valve (PV valve) can be used for storing Ethanol after thorough cleaning. The tank shall be absolutely free from water at all times. 13. Ethanol storage tanks shall be cleaned once in two years or more frequently depending on the need. Tank cleaning certificate shall be maintained as per Appendix A of IQCM. Date of tank cleaning and due date of next tank cleaning shall be painted on the manhole cover. For underground tanks, the details of tank cleaning shall be displayed on a suitable display card. 14. All level samples after receipt of first parcel in a newly commissioned tank / after tank cleaning shall be sent to laboratory for Batch Formation Test (Clause No. 9.2.2). The product from the tank shall be released only if the laboratory confirms that the product meets specifications requirement in respect of the tests carried out. 15. As Ethanol is hygroscopic and will absorb moisture from the air, Silica Gel trap must be provided in the vent pipe of the tank to prevent ingress of moisture into the tank. Regular check on the colour of silica gel shall be maintained (Blue Colour) and shall need immediate replacement on showing signs of saturation by way of change of colour. Say, Silica get turns from blue to pink after it absorbs moisture. 16. The silica gel can also be reactivated on heating in an air oven for about one hour at 110 C, till it again turns blue. Then it will become ready for re-use. 17. Other storage tank openings / pipeline fittings shall be airtight and the threaded connections if any shall be tightened with the help of Teflon paste or Teflon tapes. Bolted connections shall have gaskets of Teflon.

Colour Coding for Ethanol: The colour band for Ethanol on the pipeline shall be purple (ISC No. 796). The procedure for colour coding shall be in accordance with Clause 4.3.3 of industry quality control manual for non aviation products (IQCM)

Quality Monitoring for Ethanol: One litre composite sample of Ethanol from the storage tanks shall be collected in stainless steel or glass container for monitoring tests and sent to the nearest lab once in a month.

Doping of Ethanol in motor Gasoline and quality control checks:

At Depot / installation / Terminal: It is necessary that adequate care be taken to ensure the correct dosage in online doping of Ethanol with in motor gasoline. Ethanol is to be doped in motor gasoline with the concentration of 5% v/v. Manufacturing specification of motor gasoline to be kept at refinery end such that the end product from marketing after doping 5% v/v Ethanol into motor gasoline remains within specification IS 2796.

Procedure for doping anhydrous Ethanol in motor gasoline: To ensure uniform doping of Ethanol with motor gasoline, online doping of Ethanol shall be carried out through a closed system, with proper interlocks, while maintaining efficacy of mixing Ethanol in the right proportion of 5% v/v as per specification. The quantity of Ethanol to be doped into the motor gasoline is worked out for each compartment of the tank truck on the basis of 5% vol. of Ethanol in motor gasoline. Doping shall be carried out by synchronizing with the total delivery of desired 5% vol. of Ethanol with motor gasoline in that compartment. This can be verified by test method given in appendix-1 An 80-mesh filter shall be provided on the delivery side of Ethanol storage tank i.e. between pump and TLF Gantry point.

The following QC checks are recommended for the doping: All samples shall be drawn, tested and retained as per the procedure laid down in IQCM. A sample of Ethanol Doped Motor Gasoline shall be drawn in each shift and whenever there is a switch over of motor gasoline / Ethanol tank on an hourly basis. The sample should be tested for appearance, density at 15 C and alcohol content. In case ethanol content of motor gasoline exceeds / less than the permissible level of 5%, corrective steps are to be taken immediately. Retention of ethanol doped motor gasoline sample from TLF shall be followed as per IQCM requirements (before commencements of loading in each shift and whenever there is a switchover of motor gasoline / ethanol tank). In addition, one litre sample of ethanol from the storage tank should also be retained for 15 days along with TLF sample(s).

Lab facilities required for testing:

At depot / installation: Facilities required for the field test of Anhydrous Ethanol content: Hydrometers / Alcoholometers (IS:3608 part 2 : 1987), Thermometers, Glass cylinders, 150ml graduated glass cylinder (A class) with stopper. Specific gravity at 15.6 C/15.6 C for computing quantity can be calculated from the percentage of ethanol content using the table 1 and 2 of IS 2302: 1989 and table 1 of IS 321: 1964.

At QC labs: As per full specification test of Ethanol other than copper content and methyl alcohol content (Batch formation test) However, colour of Ethanol may be slightly vary due to addition of special additive like, Metal deactivator and corrosion inhibitors..

Tank Trucks for Transportation of Ethanol doped Motor Gasoline: The tank trucks can be upgraded for the purposes as specified in IQCM for handling non-aviation products and inspect from inside for cleanliness and dry out any accumulated water or product before loading Ethanol doped motor Gasoline. The tank truck fit for transportation of motor gasoline shall be used for ethanol doped motor gasoline. Adequate care shall be taken to ensure that the tank truck fittings are absolutely airtight and no ingress of water or air is allowed. The Epicoating applied in tank trucks for transportation of petroleum products may not be compatible with ethanol doped motor gasoline. The compatibility needs to be ensured before use of such tank trucks.

Handling of Ethanol doped motor gasoline at retail outlets:

Underground tanks, dispensers and fittings Storage tank shall be suitable for class A product and openings/ pipeline fittings shall be airtight and the threaded connections if any shall be tightened with the help of Teflon tapes. Bolted connections shall be provided with proper gaskets. Storage tanks shall be thoroughly cleaned; ensuring absence of any trace of water before commissioning on Ethanol doped motor gasoline. Fill cap and dip cap fittings shall be watertight and have suitable gaskets / packing to prevent entry of moisture. The fill/dip caps shall be raised sufficiently high above the ground level. In case these are situated in chambers, the chambers shall be constructed in a manner so as to avoid entry of water into the tank and the caps positioned sufficiently above the bottom of the chamber. The presence of any water in the underground tank shall be checked by using water-finding paste every day. During the rainy season the water shall be promptly removed from the tank. Ethanol being hygroscopic in nature, utmost precautions needs to be taken to ensure that there is no ingress of water or moisture in the storage tanks. Suitable silica gel trap shall be fitted in the vent of the tank storing Ethanol Doped motor Gasoline at Retail Outlet to prevent ingress of moisture. Regular check on the colour of silica gel shall be maintained and it should be immediately replaced on its change. The colour of silica gel turns from blue to pink after absorbing moisture.

Sampling procedures at the retail outlets would be the same as mentioned in the industry marketing discipline guidelines. Dispensing units are typically manufactured with steel, cast iron, aluminium , brass, bronze and sometimes stainless steel components. Ethanol doped motor gasoline should not pose problem with any of these metals. Normal dispensing hoses can be used for Ethanol doped Motor Gasoline.

Receipt of Ethanol Doped Motor Gasoline:

1 The procedure will remain same as is being followed for un-doped Motor Gasoline. 2 During rainy seasons, wherever the canopy is available, the tank lorry shall be checked under the canopy, to avoid ingress of water. Tarpaulin cover shall be used during tank lorry discharge. The dip cap of underground tanks shall be kept closed during tank lorry unloading operation.

3 Colour coding for dispensing pumps for Ethanol Doped motor Gasoline: The colour coding for the dispensing pumps used for ethanol doped motor gasoline remains same as that of un-doped Motor Gasoline.

4 Fire fighting system: The most accepted system is dry chemical powder (DCP), which works as effectively on Ethanol fire as being used for motor gasoline fire. The personnel should be informed about the properties of ethanol doped MS and safe practices for operating, fuelling etc.

All staff in the retail Outlets must be trained in handling any emergencies.

Safety:
Ethanol comes under class A and hence all safety precautions need to be taken as required for class A product. Ethanol is a flammable liquid with a flash point of 13 C. it requires fire-fighting facilities like, alcohol type concentrate foam (ATC) or CO2/Dry Chemical powder (DCP) extinguishers.

Ethanol material safety data sheet

Chemical formula : Mol. Wt. : Appearance and odour : RON/MON : Octane no. : Reid vapour pressure : Ignition point A) Fuel in air % : B) Temperature : Specific gravity : Boiling point Solubility in water@210C Flame visibility : Flash point :

C2H5OH 46.07 clear,colourless with an ethereal odour 108.6/89.7 98-100 2.3 psi 3-19 4550C 0.7936 : 780C : 100% poor 13.00C

Extinguishing media: Carbon-di-oxide, dry chemical Powder & water for small fires and Polar Solvent Foam for large fires.

Specific fire fighting procedures: Use necessary protective equipment & breathing apparatus as would normally be used when fighting fires where there may be danger of breathing hazardous products of combustion.

Unusual fire and explosion hazards: Flammable liquid

Stability: Stable

Conditions to avoid in normal use (incompatibility, material to avoid): May react vigorously with oxidizing material

Hazardous decomposition or by-products: Combustion may produce Cox, NOx and reactive hydrocarbons. Hazardous polymerization will not occur.

Health hazards: Roots of entry inhalation / skin / ingestion

Acute and chronic health hazards: May cause mucus membrane irritation, unconsciousness, respiratory failures and death.

Toxicity: Moderate

Signs and symptoms of exposures: May cause dizziness, loss of balance and co-ordination

Emergency and safety procedures: If swallowed, induce vomiting. If inhaled, remove person to fresh air. Give artificial respiration if breathing has stopped and call a physician. If splashed in eyes or on skin, flush immediately with copious amounts of water.

Precautions for safe handling and use: In case spilled, released out then eliminate all sources of ignition. Small spills should be flushed with large quantities of water. Large spills should be collected for waste disposal.

Waste disposal methods: Do not allow entering sewers where vapours may become ignited. Incinerate under the law. Explore for resale to supplier.

Precautions to be taken in handling and storage: Keep away from heat, sparks and open flames; Keep containers closed; Use with adequate ventilation; Use explosion proof electrical equipment and Non-sparking tools.

Protective Controlled measures: Air supplied mask to be used for a high concentration as a respiratory precaution. Use protective rubber gloves and goggles for eyes. Eye bath and safety shower is recommended as outer protective equipment.

Salient features: Carcinogenic compounds are not present in pure Ethanol.

Test Method for Determination of Ethanol Content

A. In Ethanol (received by T/L): For determining the percentage of Ethanol content table 1 and table 2 of IS 2302: 1989 should be used.

B. In Ethanol doped motor Gasoline: Method for determination of Ethanol content in 5% ethanol doped motor Gasoline by using water A Field Test

1. Scope: This method covers the determination of ethanol content in ethanol doped motor gasoline as field test at supply point. Retail outlet etc. by using water. This method provides a test of on line ethanol doped gasoline for ethanol content by % by vol. The method can suitably be used for quality monitoring of ethanol doped gasoline for ethanol content in downstream. In case of dispute the sample may be subjected to a method ASTMD 4815 as referred in BIS IS 2796 Amendment 3, for Motor Gasoline.

2. Apparatus: a. 150ml glass stopper cylinder with 0.5ml graduation. b. 10ml and 5ml glass pipette. c. Water

3. Definitions: a. Ethanol / Denatured Ethanol: Ethanol is the pure chemical, otherwise known as hydroxyl ethane, corresponding to the constitution CH3CH2OH and molecular formula: C2H5OH. Nominally anhydrous ethanol made unfit for beverage use by the addition of noxious of toxic materials (denaturants) and same is used as ethanol for the purpose of this test method.

b. Motor Gasoline: A volatile mixture of liquid hydrocarbon, generally containing a small amount of additives, suitable for use as a fuel in spark ignition and internal combustion engines conforming to IS: 2796.

c. Ethanol Doped Motor Gasoline: A fuel consisting primarily of motor Gasoline doped with 5% vol./vol. of denatured anhydrous Ethanol for fuel conforming to IS:2796.

d. Water: Water is preferred for extraction procedure, but potable water may be used.

4. procedure
1) Take 100 ml sample of ethanol blended gasoline under test in 150 ml graduated stoppered glass cylinder. 2) Add precisely 30ml water to the sample taken in a glass cylinder. 3) Shake the stopper cylinder vigorously for at least 30 seconds. 4) Loosen the stopper of glass cylinder to release the vapour pressure in the cylinder but do not remove the stopper. 5) Tighten the stopper of glass and allow the stopper cylinder to sit undisturbed at ambient temperature upright on the leveled surface for a period of at least five minutes to allow the water-ethanol mixture to settle to the bottom. 6) If separation of two layers is not complete lightly tap the cylinder to encourage the complete separation. 7) Record the level of aqueous layer in glass cylinder by reading the measurement at the lowest part of the meniscus. 8) Presence of ethanol % in ethanol doped gasoline= (volume of aqueous layer in graduated cylinder) 30ml.

5. Calibration on known ethanol content in EDP and its extraction

1) Prepare twelve number of synthetic EDP with the concentration pf 1-12ml ethanol in 100 ml EDP. 2) Take 100ml sample in 150ml graduated stoppered glass cylinder. 3) Shake the stopper cylinder to vigorously for at least for 30 seconds. 4) Loosen the stopper of glass cylinder to release the vapour pressure in the cylinder but do not remove the stopper. 5) Tighten the stopper and allow the stopper cylinder to sit undisturbed at ambient temperature upright on the leveled surface for a period of at least five minutes to allow the water-ethanol mixture to settle to the bottom.

6) If separation of two layers is not complete lightly tap the cylinder to encourage the complete separation. 7) Record the level of aqueous layer in glass cylinder by reading the measurement at the lowest part of the meniscus. 8) Presence of ethanol % in ethanol doped gasoline= (volume of aqueous layer in graduated cylinder) 30ml. 9) Plot a graph on various values obtained for ethanol volume extracted with water to the ethanol doped in petrol.

6. Calculation: a. Observation made is to put on the graph and find corresponding concentration of ethanol doped in petrol. b. Whenever there is change in source of petrol, it is recommended to re-plot the graph. 7. Report: Report the fully corrected results to the nearest 0.5ml as the ethanol water mixture and report after deducting 30ml.

8. Significance
The test method is employed to check the percentage of ethanol

in ethanol doped petrol, as ethanol is having more affinity for mixing with water. The addition of water in ethanol doped petrol extracts the present in the ethanol doped petrol in to aqueous phase. The increase in the water level indicates the quantity of ethanol in ethanol doped petrol.

Quality Tests for ethanol at PMC Lab.

1. For ethanol content and density.
An alcoholometer is a device that measures the concentration of ethanol in a water-ethanol mixture. The depth to which an alcoholometer sinks in a waterethanol mixture is related to the mass density of the mixture, but the device is calibrated to indicate the concentration of ethanol at some fixed temperature. The density of a water-ethanol mixture varies with the temperature as well as the concentration of ethanol; therefore, a correction table is required if one wants to measure the concentration of ethanol at a temperature other than the one at which the alcoholometer was calibrated. Procedure 1. Pour your sample into a smooth, clear cylinder or jar that is dry or well rinsed with a portion of the sample. 2. Make sure your sample is thoroughly mixed before testing. 3. Immerse the alcoholometer in the liquid to a point slightly below the place where it naturally floats. Make sure the alcoholometer and liquid are at rest and free of air bubbles. 4. Measure the temperature of the sample. Ideally, the sample temperature should be equal to the temperature standard of the alcoholometer, generally 60F. 5. If temperature differences are unavoidable, correction tables can help to adjust readings. 6. Take your reading at the point where the surface of the liquid crosses the alcoholometer.

Alcoholometer TEST FOR MISCIBILITY WITH WATER

PROCEDURE: Mix 10ml of the material with 190ml of water in a suitable glass vine and allow to stand at ambient temperature for minimum 10 min. Compare the clarity of the mixture with that of an equal volume of water. The material shall be taken to comply with the specified requirement, if there is no noticeable difference in clarity between the mixture and water.

TEST FOR ALKALINITY AND DETERMINATION OF ACIDITY

REAGENTS: 1. Standard Sodium Hydroxide Solution- 0.1N. 2. Phenolphthalein Indicator- Dissolve 0.5g of phenolphthalein in 100ml of rectified spirit and carefully add standard sodium hydroxide solution till the colour is rendered faintly pink.

PROCEDURE: 1. Place 100ml of water and a few pieces of clean porous pot in a 500ml conical flask of resistance glass, and boil gently for 5 min to eliminate carbon dioxide. Cool slightly and add 100ml of the material. Boil gently for a further period of 5 min. At the end of this period, close the neck of the flask with a stopper carrying a soda-lime guard tube, and allow to cool. When cool, examine for alkalinity; if not alkaline, titrate with standard sodium hydroxide solution using a micro-burette. 2. Determine the specific gravity of the material at room temperature using a specific gravity bottle or a pyknometer or a suitable hydrometer. CALCULATION AND REPORT: 1. Report whether the material is alkaline or acidic 2. Calculate the acidity, if any, in terms of acetic acid and express as percentage by weight of the material taken for the test: Acidity (as CH3COOH), mg/l = 600 VN Where V= volume, in ml, of standard sodium hydroxide solution required for the titration; and N= normality of standard sodium hydroxide solution.

DETERMINATION OF RESIDUE ON EVAPORATION

PROCEDURE: Evaporate, on a water bath, 100ml or more of the material to dryness in a weighed, clean, dry platinum, silica or resistance glass dish. Dry the residue for 30 min in an oven at a temperature of 100 +- 2 C. Cool in a desiccator and weigh.

CALCULATION: Residue on evaporation, Percent by mass = [(B-A)*100] / VS

Where B = weight, in g, of dish after evaporation, drying and cooling; A = weight, in g, of empty dish; V = volume, in ml, of the material taken for the test; and S = specific gravity of the material determined at room temperature.

DETERMINATION OF ALDEHYDE CONTENT

METHODS: a. For low aldehyde content: A suitable colour reaction is available when the aldehyde content (as CH3CHO) is expected not to exceed 60 mg/I of the material. This is based on the resinification that takes place and the yellow colour that results on treatment of acetaldehyde with sodium hydroxide. The procedure described under F-4.1 provides as satisfactory qualitative limit test, but in case of dispute, the quantitative procedure described under F-4.2 shall be adopted in the qualitative procedure, acetals are also included as aldehydes. b. For Higher Aldehyde Content For materials containing 0.05 to 0.5 percent of aldehydes, only the quantitative procedure described under F-4.2 shall be adopted. APPARATUS: Stoppered Flasks- Two each of 250 ml capacity and identical in shape, size and colour.

REAGENTS: Sodium Hydroxide Solution- dissolve 20 g of sodium hydroxide in water and dilute to 100 ml with water. Stock Solution of Hydroxylamine Hydrochloride- Dissolve 20 g of hydroxylamine hydrochloride in 100 ml of water. Metaphenylenediamine Hydrochloride Aldehyde Free Alcohol- Re-distill rectified spirit over solid caustic soda or caustic potash, add 2 to 3 g of metaphenylenediamine hydrochloride per litre of rectified spirit, digest at ordinary temperature for several days or under a reflux condenser on a stream bath for several hours and distil slowly, rejecting the first 100 ml and the last 200 ml of the distillate. Standard Sodium Hydroxide Solution- 0.1 N. Bromophenol Blue Solution- Dissolve 0.1 g of bromophenol blue in 1.5 ml of standard sodium hydroxide solution of hydroxylamine hydrochloride with 100

ml of aldehyde-free alcohol, add 2 ml of bromophenol blue solution and then add standard sodium hydroxide solution till the characteristic dichlroic yellowish green colour is obtained.

PROCEDURE: Qualitative Test: Mix 10 ml of the material with 5 ml of sodium hydroxide solution and set aside for 5 min. The limits prescribed for aldehyde content (0.006g/100ml) shall be taken as not have exceeded, if no yellowish colour is produced in 5 min. Quantitative Test: Take 50 ml of the material in a flask; add 25 ml of hydroxylamine reagent and 25 ml of distilled water. Allow to stand for 15 min. Meanwhile prepare a blank in a similar flask by using 25 ml of hydroxylamine reagent and 75 ml of distilled water. Titrate this solution with standard sodium hydroxide solution until the characteristic dischlroic yellowish green colour appears. Titrate the sample solution with standard sodium hydroxide solution until the colour matches with that of the blank solution.

Calculation
Aldehyde content (as CH3CHO), mg/l= 880 (V-v) N Where V= volume, in ml, of standard sodium hydroxide solution required for the titration; v= volume, in ml, of standard sodium hydroxide solution required, if any, in the blank; and N= normality of standard sodium hydroxide solution.

SPECIFICATIONS OF PETROL

SR. NO. 1

PROPERTY
Appearance

2 3 4 5

5 6 7 8

colour Density Copper strip corrosion DISTILLATION RECOVERY AT 0 o 70 C 0 o 100 C 0 o 150 C 0 o 180 C FBP RESIDUE % EXTENT GUM Lead content Benzene content Sulphur content

SPECIFICATION Free from undisolved water and visible impurities. Orange/ red 710-770 Not more than no. 1

10-40% 40-70% >75% >90% >215 <2% Max 40gm/m3 Max .005 % Max 3.0% Max .05%

Quality tests for petrol at PMC lab.

1. Colour
Determination of the colour of petroleum products is used mainly for manufacturing control purposes and is an important quality characteristic since colour is readily observed by the user of the product. In some cases the colour may serve as an indication of the degree of refinement of the material. When the colour range of a particular product is known, a variation outside the established range may indicate possible contamination with another product. However, colour is not always a reliable guide to product quality and should not be used indiscriminately in product specifications. Simply note down the colour by visual appearance.

2. EXISTENT GUM IN FUELS

High gum can cause induction-system deposits and sticking of intake valves, and in most instances it can be assumed that low gum will ensure absence of induction system difficulties. However, the test by itself is not correlative to induction system deposits. The test is applied to motor gasolines to measure the oxidation products formed in the sample prior to or during the comparatively mild conditions of the test procedure. Since many motor gasolines are purposely blended with non-volatile oils or additives, the heptane extraction step is necessary to remove these from the evaporation residue so that the deleterious material, gum, may be determined. With respect to aviation turbine fuels, large quantities of gum are indicative of contamination of fuel by higher boiling oils or particulate matter and generally reflect poor handling practices in distribution downstream of the refinery.

Test Procedure A known amount of the sample i.e. 50 ml in a standard beaker is evaporated at 1500 C by passing heated air for 30 minutes. The beaker is taken out, cool and weigh. Again give n-heptane washing to the beaker, dry it & weigh. This weight gives the indicative of Gummy material where as before washing if the quantity is more, it shows that it is contaminated/ adulterated with kerosene or other high boiling liquid.

3. DENSITY
Accurate determination of the gravity of petroleum and its products is necessary for the conversion of measured volumes to volumes at the standard temperature. Gravity is a factor governing the quality of crude oils. However, the gravity of a petroleum product is an uncertain indication of its quality. Correlated with other properties, gravity can be used to give approximate hydrocarbon composition and heat of combustion. This test method covers the determination by means of a glass hydrometer of the API gravity of crude petroleum and petroleum products normally handled as liquids and having a Reid vapour pressure of 26 psi (180 kPa) or less. Gravities are determined at 600F or converted to values at 600F by means of standard tables. These tables are not applicable to non-hydrocarbons or essentially pure hydrocarbons such as the aromatics.

Hydrometer

TEST SUMMARY This test method is based on the principle that the gravity of a liquid varies directly with the depth of immersion of a body floating in it. The floating body, which is graduated by API gravity units in this method, is called an API hydrometer. The API gravity is read by observing the freely floating API hydrometer and noting the graduation nearest to the apparent intersection of the horizontal plane surface of the liquid with the vertical scale of the hydrometer, after temperature equilibrium has been reached. The temperature of the sample is read from a separate accurate ASTM thermometer in the sample or from the thermometer which is an integral part of the hydrometer. Significance: Aromatics have the highest density. Paraffins have the lowest density. Cycloparaffins and Olefins have the intermediate density.

Increase in density (above 770 Kg/M3) indicates the presence of possible adulterants like Kerosene, Diesel, High Aromatic Naphtha (HAN) and narrow cut aromatics like Benzene, Toluene, etc., Decrease in density (below 710 Kg/M3) indicates the presence of possible adulterants like SBP solvents, narrow cut solvents mainly aliphatics. Intermediate density (between 750 770 Kg/M3) indicates the presence of possible adulterants like HAN, BTX (C6, C7 & C9 aromatics), etc.,

Copper corrosion test

This international method specifies a method for the determination of the corrosiveness to copper of liquid petroleum products. Volatile products having a maximum vapour pressure of 124kpa at 37.8 0C are included. PRINCIPLE A polished copper strip is immersed in a specified volume of sample and heated under conditions of temperature and time that are specific to the class of material being tested. Aviation fuels and natural gasoline are tested in a pressure vessel and other products are tested under atmospheric pressure. At the end of the heating period, the strip is removed, washed, and the colour assessed against corrosion standards. REAGENTS AND MATERIALS WASH SOLVENTS Isooctane of minimum 99.7% purity is the referee solvent.

POLISHING MATERIAL Silicon carbide powders of 150 mesh size. Adsorbent cotton of pharmaceutical grade.

APPARATUS Copper strips, cut from smooth- surfaced, hard temper, cold-finished electrolytic type copper of more than 99.9% purity. The strips shall be 75mm (+/-) 2mm in length, and 1.5mm to 3.0mm in thickness. Strips must be free from pitting or deep scratches that cannot be removed by the specified polishing procedures.

Pressure vessels constructed of stainless steel. The vessel should be capable of withstanding a test pressure of 700kPa gauge. Test tubes, of borosilicate glass. The internal dimensions shall be checked with a metal strip copper inserted in test tube. When 30 ml of liquid is added, a minimum of 5mm shall be above the top surface of the strip.

Test baths Test bath should be capable of maintaining the product at the specified test temperature within a range of 10C.

Temperature sensor, For indicating the test temperature for liquid baths, a total immersion liquid in glass thermometer is suitable, with graduation of 10C or less. It shall be submerged in the liquid such that not more than 25mm of the thread extends above the liquid surface.

Corrosion standards For the evaluation of the tarnish at the end of the test.

Corrosion standards by ASTM

Preparation of test strips

Surface preparation Remove all surfaces blemishes from all six sides of the copper strip with silicon carbide paper or cloth for such degrees of fineness as are needed to achieve the desired results efficiently. Immerse the copper strip in wash solvent. Withdraw immediately for final polishing, or store for future use. Rub the strip against the filter paper with a rotary motion. Protecting the strip to contact with the fingers with an ash less filter paper.

Final polishing Remove a strip from the wash solvent. Holding it in fingers protected by ash less filter paper, polish the first with the silicon carbide powder and absorbent cotton moistened with a drop of wash solvent. Wipe vigorously with fresh pads of cotton pads and subsequently handle only with forceps. Do not touch the strip with the fingers. Clamp in the strips and polish the main surfaces with silicon carbide powder on adsorbent cotton. After polishing immerse it in prepared sample.

Procedure Place a 30ml test portion completely clear and free from any suspected or entrained water in a chemically clean, dry test tube. Slide the copper strip into the test portion in the test tube. Stopper with a vented cork, and place the test tube in the test bath maintained the test temperature range of 10C. At the end of the specified test period, remove the test tube. If during this process the level of liquid decreases discard and start with the fresh solvent.

Strip examination Empty the contents of the test tube into a suitably sized beaker, such as a 150ml tall form, letting the copper strip slide in gently so as to avoid breaking the beaker. Immediately withdraw the strip with the forceps and immerse it in wash solvent. Withdraw the strip at once, dry with filter paper and inspect for evidence of tarnishing corrosion by comparison with the corrosion standards. Hold both the test strip and the standard strip in such a manner that light reflected from them at an angle of approximately 450 will be observed.

Distillation
This method of test covers the distillation of motor gasoline. Distillation characteristics of petroleum products are indicative of performance in their intended applications. Petroleum product specifications generally include distillation limits to ensure products of suitable volatility performance. It gives an idea of volatility characteristics of the fuel. It can be determined by Non-fractionating type ASTM Manual Non-fractionating type ASTM Automatic TERMINOLOGY Initial boiling point The thermometer reading which is observed at the instant that the first drop of condensate falls from the lower end of the condenser tube.

End point or final boiling point The maximum thermometer reading obtained during the test. This usually occurs after the evaporation of all liquid from the bottom of the flask.

Dry point The thermometer reading observed at the instant the last drop of the liquid evaporates from the lowest point in the flask.

Decomposition point The thermometer reading which coincides with the first indication of thermal decomposition of the liquid in the flask.

Percent recovered The volume in ml of condensate observed in the receiving graduate, in connection with a simultaneous thermometer reading.

Percent recovery The maximum percent recovered at final boiling point.

Percent total recovery The combined percent recovery and residue in the flask.

Percent loss it is the percent of material lost during the distillation. It is equal to ( 100percent total recovery).

Percent residue It is the volume of the material left no evaporated in the flask.

Percent evaporated The sum of the percent recovered in graduate and the percent loss.

APPARATUS: 1. Distillation flask Distillation flasks of heat resistant glass and capacity 150ml.

2. Condenser and cooling bath The condenser shall be made of seamless brass tubing, the capacity of the cooling bath shall be not less than 5.55 litres of cooling media. Its main pupose is to cool the vapours coming from the flask. Any cooling media may be used like brine, crushed ice, cooling water etc. For distillation of petrol. Temperature of cooling bath is kept at 4oC.

3. Heat source a. Gas burner Gas burner should be so constructed that sufficient heat from the available gas can be obtained to distil the product at the specified rate. A sensitive regulating valve and gas pressure governor to give complete control of heating may be provided. b. Electric heater Electric heater may be used instead of a gas burner, provided it is capable of bringing over the first drop from a cold start within the time specified and of continuing the distillation at the specified rate. Heater units of low heat retention, adjustable from 0-1000 W, have been found satisfactory. 4. Flask support The top of the electric heater shall consist of a ceramic heat resistant flask support board with a centre hole. Provision shall be made for moving the heater unit, with its top in order to place the distillation flask so that direct heat shall be applied to the flask only through the opening in the flask support board. 5. Graduated cylinder A 100 ml graduated cylinder with 1 ml subdivisions shall be provided. Construction details and tolerances given in figure.

6. Thermometers For partly or fully automatic apparatus and procedure, an alternative means of measuring or recording temperature may also be used provided this gives the same reading under distillation test conditions and has a precision not less than that of the prescribed thermometer.

SAMPLE a. in case of any product having a Reid vapour pressure of 655 mbar or higher, cool the sample bottle to a temperature in the range of

13-180C. Collect the sample in the previously cooled bottle, preferably by immersing the bottle in the liquid, where possible, and discarding the first sample. Where immersion is not possible, the sample shall be drawn off into the previously cooled bottle in such a manner that agitation is kept at a minimum. Close the bottle immediately with a tight-fitting stopper, and place it in an ice bath or refrigerator capable of maintaining the sample at a temperature not to exceed 150C. b. Samples of materials that visibly contain water are not suitable for testing. If the sample is not dry, and the initial boiling point is below 660C, shake the sample with anhydrous sodium sulphate or other suitable drying agent and separate it from the drying agent by decanting. Preparation of apparatus a. Fill the condenser box to cover the condenser tube with any nonflammable coolant which is suitable for the temperature required bt table 1, such as chopped ice, water, brine or ethylene glycol solution. If chopped ice is used add sufficient water to cover the tube. If necessary make any suitable provision such as stirring or air blowing, so as to maintain the required condenser bath temperature throughout the test. b. Remove any residual liquid in the condenser tube by swabbing with a piece of soft, lint-free cloth attached to a cord or copper wire. c. Measure 100 ml of the sample in the graduated cylinder and transfer it as completely as practicable to the distillation flask, taking care that none of the liquid flows into the vapour tube. d. Fit the thermometer provided with a snug-fitting, well-rolled cork, tightly into the neck of the flask so that the bulb is centred in the neck and the lower end of the capillary is level with the highest point on the bottom of the inner wall of the vapour tube. e. Place the flask containing the charge in its support; and by means of a cork through which the vapour tube has been passed, make a tight connection with the condenser tube. Adjust the flask so that it is in a vertical position, and so that the vapour tube extends into the condenser tube for a distance of 25-50mm.

f. Place the graduate that was used to measure the charge, without drying, into its bath under the lower end of the condenser tube so that the end of the condenser tube is centred in the graduate flask and extends therein for a distance of at least 25mm, but not below the 100ml mark. Cover the graduate and extends closely with a piece blotting paper. Maintain the level of the bath around the graduate flask so that it is at least as high as the the 100ml mark. g. Note the record and prevailing barometric pressure, and proceed at once with the distillation.

AUTOMATIC DISTILLATION MACHINE

PROCEDURE a. Apply heat to the distillation flask and contents. The heating at this stage shall be so regulated that the time interval between the first application of heat and the initial boiling point does not exceed the prescribed limit. b. Immediately after observing the initial boiling point, move the graduate so that the tip of the condenser touches its inner wall. Continue to regulate the heating so that the rate of condensation into the graduate shall be uniform. c. In the interval between the initial boiling point and the end distillation, observe and record whatever data are necessary for the calculation and reporting of the results of the test. These observed data may include thermometer reading at prescribed percentage recovered, or percentage recovered at prescribed thermometer readings, or both. Record all volumes in the graduate to the nearest 0.5ml and all thermometer readings to the nearest 0.50C. also record the final boiling point and also the percentage recovered at final boiling point. d. When the residual liquid in the flask is approximately 5ml, make a final adjustment of the heat so that time taken to final boiling point must not exceed the prescribed time. e. Observe and record the end point or dry point, and discontinue the heating. At the end point, observe if all the liquid has evaporated from the bottom of the flask. f. While the condenser tube continues to drain into the graduate, observe the volume of condensate at 2 minutes interval until two successive reading agree. Measure this volume to the nearest 0.5ml, as percent recovery. g. If the decomposition point is observed, discontinue the heating. Deduct the percentage recovery from 100, report this difference as percent residue and loss. h. After the flask has cooled, pour its contents into the condensate in the graduate and allow it to drain until no increase in the volume of liquid is observed. Record this volume as percent total recovery. CALCULATIONS

a. Make a table for temperature indicated by thermometer at prescribed percentage recovered and plot a graph between the percentage recovery and temperature indicated. The distillation criteria of standard Petrol will be Temp oC IBP 70oC 100oC 1800C FBP Residue % by volume Distillate% by volume to report 10- 45 40 - 70 90 (minimum) 215 2 (maximum)

SIGNIFICANCE 1. Distillation characteristics of petroleum products are indicative of performance in their intended applications. Petroleum product specifications generally include distillation limits to ensure products of suitable volatility performance. 2. The empirical results obtained by use of this distillation method have been found to correlate with automotive equipment performance of petroleum products relative to volatility. 3. Depending upon the nature of adulterant the IBP and FBP will vary. 4. Depending upon the nature of adulterant the E70, E100 and E180 will vary. 5. Residue percent by volume depends upon the volatility of the solvent. High boiling compound normally leaves more residue than low boiling compound (eg: Kerosene, Diesel and High Aromatics) 6. Constant boiling temperature shows the possible presence of adulterants like narrow cut solvents (aliphatic, aromatic or cyclic) like Benzene, Hexane, etc., Hexane (64C -- 70C) Benzene (80C -- 82C)

Determination of sulfur content

1. Scope This International Standard specifies an energy dispersive x-ray fluorescence (EDXRF) test method by the determination of the sulfur content of motor gasoline, including those containing up to 2.7% (m/m) oxygen, and of diesel fuels, including those containing up to 5%(v/v)fatty acid and methyl ester (FAME, having sulfur content in the range 30 mg/kg to 500 mg/kg. Other products may be analyzed and other sulfur, contents may be determined according to the test method; however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this International Standard. For reasons of spectral overlap, this International Standard is not applicable to leaded motor gasoline lead-replacement gasoline containing 8 mg/kg potassium to 20 mg/kg potassium, or to products and feed stocks containing lead, silicon, phosphorous, calcium, potassium or halides at concentrations greater than one-tenth of the concentration of sulfur measured. NOTE- For purposes of this International Standard, the terms %(m/m) and %(v/v) are used to represent the mass fraction and the volume fraction of a material respectively. 2. Principle The test portion, in a cup fitted with an X-ray transparent window, is placed in a beam of exiting radiation from an X-ray tube. The intensity of the sulfur K characteristic X-radiation is measured, and the number of accumulated counts is compared with the curve constructed from sulfur standards covering the range of sulfur contents under examination. NOTE the exiting radiation may be either direct, or indirect via a secondary target.

3. Reagents and materials 3.1Diluent oil a. The reference diluents oil is white oil (light paraffin oil) of high purity, with sulfur content of 1 mg/kg maximum. However, if only one type of matrix is to be analysed (e.g. motor gasolines), the accuracy of results may be improved by using matrix-matched diluents. These should match approximately the aromatic and oxygen content of the material to be analysed, and should consist of high purity components of less than 1mg/kg sulfur content. NOTE Suitable components for the matched matrix diluent include heptanes,2,2,4-trimethylpentane, toluene, xylenes, ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl (ETBE), tertiary amyl methyl ether (TAME) and fatty acid methyl ester (FAME). b. For analysis of diesel fuels containing FAME at contents greater than 5%(v/v), a matched matrix diluent oil of the white FAME shall be used. 3.2 Sulfur compounds General Sulfur compounds of known sulfur content shall be used for the preparation of primary standards. The compounds given in 4.2.2 to 4.2.5 are suitable, and their nominal sulfur contents are given. Where the purity of these compounds is less than 99% (m/m), either the concentrations and nature of all impurities are to be known or certified reference materials shall be used. Dibenothipphene (DB), with nominal sulfur content of 17,399 % (m/m). Dibutylsulfide (DBS), with nominal sulfur content of 21,915 % (m/m) Thionaphthene (Benzothiophene) (TNA), with nominal sulfur content of 23,890 % (m/m) Dibutylsulfide (DBDS), with nominal sulfur content of 35,950 % (m/m)

Reference materials Certified reference materials (CRMs) from accredited suppliers, containing a range of sulfur concentration, are suitable alternative to the compounds listed in 4.2 for use as calibration standards.

3.4 Quality control samples Stable samples representative of the materials being analyzed, that have sulfur content that is known by this test method over a substantial period of time, or supplied commercially with value. Ensure before use that that material is within its shelf life.

4. Apparatus 4.1 Energy-dispersive X-ray fluorescence analyzer a. Energy-dispersive X-ray fluorescence analyzer, having facilities for measuring and subtracting the background to give net sulfur intensities. The instruments shall be capable of measuring the content of sulfur at 50 mg/kg with an error due to counting statistics of 3 % relative standard deviation (RSD) maximum. b. Source of X-ray excitation, with significant flux at X-ray energies above 2.5 keV c. Removable sample cup, providing a sample depth of at least 5 mm, and equipped with replaceable X-ray transparent film. NOTE the transparent film is normally of polyester or polycarbonate with a thickness between 2 m and 6 m. Polyester film is the preferred choice as samples of every high aromatic content can dissolve or enhancement effects would be cancelled out when samples and standards are analyzed using the dame material. It is important that standards and blanks are measured using the same batch of film to avoid bias. d. X-ray detector, with high sensitivity, and resolution not exceeding 800 eV at 2.3 keV

e. Means of discriminating between sulfur K characteristic X-ray and other X-ray of higher energy (e.g. filters) f. Signal conditioning and data handling electronics, including the functions of pulse counting and a minimum of two energy regions (to correct for background X-ray). When matrix of samples and standards is not used, the instrument shall also be able to measure an energy region corresponding to scattered radiation, and to use this measurement to compensate for matrix effects. The latter measurement can also be used as the second energy region specified above and used to calculate the background. NOTE Differences in carbon/hydrogen ratios, or oxygen contents, between samples and standards can cause matrix effects which may lead to bias in the analytical result. 4.2 Analytical balance, single-pan or double-pan, capable of weighing to the nearest 0.1 mg. 4.3 Mixer, magnetic stirrer with PTFE-coated stirring rods. 4.4 Flasks, of 100 ml capacity, narrow-necked, conical, and made of borosilicate glass.

5 Sampling and sample handling 5.1 Unless otherwise specified, samples shall be taken by the procedures described in ISO 3170 or ISO 3171. 5.2 Store samples which contain light fractions (e.g. motor gasoline and naphtha) in refrigerator. 5.3 Mix samples by gently shaking by hand prior to the removal of the test portion. 5.4 Allow test portions to attain ambient temperature prior to analysis.

6 Apparatus preparation 6.1 Analyser a. Set up the analyzer (5.1) in accordance with the manufacturers instructions. Whenever possible, the instrument shall be continuously switched on to maintain optimum stability. b. Purge the optical system with helium (99 % purity) following the manufacturers guidelines of minimum flush to ensure stability of measurements.

6.2 Sample cups It is recommended that disposable sample cups be used. If disposable cups are not used, thoroughly cleaned the sample cups with an appropriate solvent and dry before use. Do not re-use disposable cups. Use the same batch of window material for each run of verification and sampling analysis. Keep handling of window material to the absolute minimum. Differences in window material thickness between batches, or the presence of even partial finger marks, are sufficient to affect results.

7. Calibration 7.1 General Use either certified reference materials (4.3) or primary standards prepared from sulfur compounds (4.2) dissolved in diluents oil (4.1) as a basis for the preparation of two primary calibration standards. 7.2 Preparation of primary standards a. Prepare two primary standards with sulfur contents of approximately 5,000 mg/kg and 1,000 mg/kg. b. Weigh, to the nearest 0.1 mg, the appropriate quantity of diluents oil (4.1), into a flask (5.4) and add the appropriate quantity of the selected sulfur compound (4.2) or certified reference material (4.3), weighed to the nearest 0.1 mg. Mix the contents of the flask thoroughly at room temperature using the mixer (5.3). Table 1 Composition of primary standards based on nominal sulfur

contents Approximate content mg/kg 1,000 5,000 sulfur White oil G 50.0 50.0 DBT (4.2.2) G 0.29 1.48 DBS (4.2.3) g 0.23 1.17 TNA (4.2.4) g 0.21 1.07

c. Calculate the sulfur content, net of that included in diluents oil, wS, in milligrams per kilogram to three decimal places in each case, from the amounts of diluents oil and sulfur compound used as follows. wS = 10,000 where, mS is the mass of sulfur compound expressed in grams (g). wSc is the sulfur content of the compound, expressed in percent mass % (m/m). mW is the mass of white oil, expressed in grams (g). d. Store primary standards in tightly closed glass containers in a dark cool place, preferably in a refrigerator. Before use, example for any phase separation or discoloration, shake vigorously, and allow to stand to allow removal of air bubbles. Discard any standard that shows sediment phase or discoloration. 7.3 Calibration standards a. Prepare calibration standards from the primary standards (8.2) in the selected diluents oil, and calculate the exact sulfur content of the calibration standard using the equation given in 8.2.3. Prepare calibration standard of nominal sulfur content of 700 mg/kg and 300 mg/kg from the 5,000 mg/kg primary standard, and calibration standard of nominal sulfur content of 500mg/kg and 100 mg/kg from the 1,000 mg/kg primary standard. Use the reference diluent oil as the blank or zero point and the 1,000 mg/kg primary standard as the top point of the calibration.

Calibration standards of certified sulfur content in a specified diluents oil (e.g. diesel), are suitable for analysis of known similar materials. Where concentrations of less than 100 mg/kg are to be measured, additional standards of sulfur content 25 mg/kg and 50 mg/kg should be included in the calibration. 7.4 Calibration procedure a. When carrying out measurements at low contents ( < 100 mg/kg). b. Carry out the calibration procedure in accordance with the manufacturers instructions both the sulfur K line and background intensity are measured and to calculate net intensities for the sulfur line. If required for matrix corrections, the scattered radiation (e.g. from an X-ray tube line) shall also be measured. c. Prepare the sample cup by covering the base of the cup with film, and fill to a minimum depth of 50 % of the cup capacity. If closed cells are used, provide a vent hole in the top to prevent bowing of the film during analysis of volatile samples. Ensure that there are no air bubbles between the window and the liquid, and that there are no wrinkles in the film or sagging of the window. NOTE Scatter from the sample cell and the sample may vary with depth, and thus matrix corrections may be affected if the depth is not relatively consistent. d. obtain three reading on each calibration standard and run in random order, taking a freash sample aliquot and cell for each reading. Set the counting times for the sulfur K peak, and the background measurement (and the scattered radiation if used) to be long enough to obtain an overall precision estimate of better than 3% relative standard deviation (RSD) at 50mg/kg sulfur content [i.e. at 50 mg/kg sulfur content, results should be within 3 mg/kg sulfur (95 % confidence)]. Measure the diluents oil as a blank. NOTE The objective at low sulfur levels is to obtain adequate counts to satisfy the above requirements, with the reproducibility of measurement improved in relation to the number of counts collected. At very low sulfur levels, thus counting time is related to instrument count rate and the background count rate (estimated from a sample with less than 1 mg/kg

sulfur). Where the manufacturers data sheet does not recommend specific counting times, the user should refer to the instrument, manufacturer for the correct equation to estimate the required counting time for each sulfur level. e. Construct a calibration curve from the calibration standards. Check the curve at a minimum of three points with certified reference materials or laboratory secondary working standards of appropriate sulfur content and diluents type, with sulfur values either assigned from determinations on another instrument or directly traceable to a primary standard. Result from this check shall be within the control limits allowed for each standard. If the result fall outside these limits (after repeat tests), repeat the primary calibration procedure. Control limits are established from the laboratory statistical control charts, but initial values should be set before experience is established. Limits of the repeatability of this method, or 0.7 times the reproducibility, are reasonable starting points. f. From the primary calibration graph, assign set-up standards and use them for frequent restandardization of the graph in order to compensate for changes in instrument stability and sensitivity. Check the graph regularly against calibration standards. Whenever tests on the calibration standards show sulfur content results which differ from their assigned valued by more than the repeatability precision limits of the test method, standardize (prepare fresh set-up standards) or recalibrate the analyser. If the instrument does not meet the minimum precision requirements or the setup standards do not give acceptable results even after repeated recalibration, consul1t the instrument manufacturer. Provided the quality control check remains within limits, recalibration is not required. If it is outside the limits, follow the calibration given in 8.4.4. NOTE 1 Set-up standards may be calibration standards. But are more commonly secondary standards such as oils or the manufacturers supplied setting-up samples (SUS). NOTE 2 Instrument drift may be influenced by temperature. NOTE 3 The typical frequency of primary calibration checks is daily, or each time the instrument is used if less frequently.

8 Procedure 8.1 when carrying out measurements at low sulfur contents (< 100 mg/kg), follow the guidelines given in Annex B. 8.2 Prepare and fill the samples cup with portion as described in 8.4.3, taking the same precautions as for test portion capacity, venting and film continuity. 8.3 Take measurements for the sulfur K line and background (and scatter peak if used) using the same counting time as used for calibration. Repeat the measurement using a fresh test portion in a new cell, and calculate the mea net count. 8.4 After every five to ten unknown sample analyses, analyse an appropriate quality control sample. Each day analyse a blank sample. If the values of these quality control samples or the blank fall outside the control limits, recalibrate the instruments.

9 Calculation Read the content of sulfur in the sample from the calibration curve, using the mean count for each test portion, or by direct reading from those analyzers which have computing facilities. 10 Expression of results Report the sulfur content to the nearest 1 mg/kg. 11 Test report The test report shall contain at least the following information: a) b) c) d) A reference to this International Standards, The type and complete identification of the procedure tested; The result of the test Any deviation, by agreement or otherwise, from the procedure specified; e) The date of the test.

BENEFITS of Ethanol doped Gasoline

1. Ethanol is a renewable fuel. Renewable fuels are fuels that we can make again and again without depleting valuable resources in the earth. Extracting crude oil from the ground depletes resources from the earths crust. The crops we use for ethanol, on the other hand, can be grown, harvested, and grown again every year. This means that we can make ethanol this year, next year, and the year after that by growing corn or other crops. By using renewable fuels, we can preserve the resources that are remaining in the earth - but still get the fuel our economy needs. 2. Ethanol reduces pollution and greenhouse gas emissions. Ethanol contains a higher percentage of oxygen than traditional petroleum-based gasoline. Because of it, Ethanol burns more completely than petroleumbased gasoline, and does not contribute to global warming like burning petroleum-based fuels does. In fact, using ethanol as a motor fuel reduces greenhouse gas emissions by as much as 46%. Using just 10% ethanol in your gas tank reduces greenhouse gas emissions by up to 19%. 3. Ethanol does not pollute ground water. Because of ethanols chemical structure, ethanol phase separates when it comes into contact with water. This makes it very safe for the environment because ethanol is biodegradable. It also means that ethanol will not pollute ground water like many other potential fuel sources could. 4. Ethanol Is Cheaper To Make Than Gasoline. Ethanol costs about 75 per gallon to make. Gasoline cost about $1.60 per gallon to refine. It only costs about $30 to convert a car to be a flex fuel vehicle, but doing it can save hundreds of gallons of fuel per year. 5. Ethanol Is Easy To Switch To. Ethanol can use todays vehicles, todays fuel distribution infrastructure, and allows us to leverage todays technologies in order to use these renewable resources. We can blend ethanol with traditional gasoline in grades from E10 to E85. Even hybrid vehicles can run off of ethanol.

6. Ethanol supports local farmers. Ethanol is produced in local markets from available renewable resources, such as corn and sugar cane. When

you purchase ethanol, your money stays nearby, going to local farmers that produced the crops used and the refineries that produced the fuel. But when you buy gasoline, some of each dollar boosts oil companies record profits - and the rest goes overseas. 7. Ethanol reduces our dependence on foreign oil. About 45% of all of American oil consumption is used as gasoline fuel for consumer vehicles. By using ethanol as a substitute and/or additive to petroleum-based gasoline, ethanol helps to reduce regional dependence on imported oil and petroleum products. We import millions of barrels of oil and millions of gallons of refined gasoline every day. By switching to ethanol and ethanol blends, we can continue to grow our economy while reducing our addiction to foreign oil. 8. Ethanol can be made from nearly anything. Though ethanol was first made decades ago, the technologies used in todays ethanol industry are still in their infancy. Most of todays ethanol production is made from corn and sugar. The technology for using waste products, such as unusable portions of crops, to produce cellulosic ethanol is on the horizon - and it will completely revolutionize the way we fuel our cars.

Demerits of ethanol blended gasoline

1. Ethanol can absorb water and may cause serious problems in some engines. 2. Production of ethanol requires significant energy and large

amounts of land. 3. Fuels with more than 10% ethanol are not compatible with non E85-ready fuel system components and may cause corrosion of ferrous components. 4. Can negatively affect electric fuel pumps by increasing internal wear and undesirable spark generation. 5. Is not compatible with capacitance fuel level gauging indicators and may cause erroneous fuel quantity indications in vehicles that employ that system. 6. Decreases fuel-economy by 15-30%.

PROJECT OBJECTIVES
To suggest an effective mechanism for dosing of ethanol in petrol Proper accounting of doped ethanol in petrol.

Existing mechanism of ethanol doping at panipat marketing complex:

At panipat marketing complex petrol and ethanol are filled in truck tanks separately. Corrosion inhibitor mixed ethanol comes from four underground storage tanks to the TLF gantry in bay no. 2, 5 and 6. And petrol comes from the storage tanks to bay no. 1, 2, 3, 4, 5 and 6. First air is removed from the petrol with the help of a deareator at every bay. Here at IOCL Panipat marketing complex ethanol is doped in two ways: 1. Truck tank is first filled with ethanol from any of bay no. 2, 4 or 5. Operator set the value of ethanol in meter according to the 5% of the MS to be filled. The line is lowered in the opening of the truck tank and then operator presses the start button to initialize ethanol loading. After filling ethanol in every container it goes to the bay no. 1, 2, 3, 4, 5 or 6. For the filling of petrol in bay no. 2, 4 and 5, petrol comes from the same line from which ethanol comes.

2. In second case first petrol is filled from any of the bay no. 1, 2, 3, 4, 5 or 6. It is done as same way as done for ethanol. Operator sets the amount of petrol to be filled in the meter and after filling petrol, it comes to bay no. 2, 4 or 5 for ethanol filling.

After filling of ethanol and petrol in truck tank, a dip is immersed in each container to measure the quantity of MS filled in it. Among two ways of doping of ethanol in petrol described above the latter way of doping is more effective. Because ethanol is denser than petrol so it settles down and petrol will float on ethanol. If we first fill ethanol in truck tank and then petrol, it will keep on floating on the surface of the ethanol and proper mixing of ethanol and petrol will not be possible.

But if we first fill petrol and then we fill ethanol, latter will tend to move downward towards the bottom of the truck container and petrol will tend to move upward towards the surface. So that will provide adequate time for the mixing of ethanol and petrol. So by this method proper mixing of ethanol and petrol can be achieved.

SUGGESTIONS
Online doping of ethanol and petrol For effective mixing of ethanol online doping of ethanol in petrol must be used. In this type of doping ethanol and petrol comes from their respective storage tanks, lines coming from both the storage tanks joins at some point and ethanol and petrol are mixed in the line itself. Now this mixture is filled in tank trucks. This will provide sufficient time for the mixing. Flow rates must be controlled to dose accurate 5% ethanol in petrol.

Providing baffles at the end of the fill pipes so that the mixture of ethanol and petrol enters in the tank with turbulent flow which enhances the mixing of ethanol and petrol.