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This document summarizes a study characterizing the physicochemical properties and applications of naphtha produced at an Oil and Natural Gas Corporation plant in Uran, India. Key findings include:
1) The naphtha has high paraffin content, low aromatic content, no olefins, and very low metallic contaminant levels. It has a low sulfur content of 22 ppm.
2) Distillation characteristics classify the naphtha as group 1. Analysis found it to have good hydrogen content, making it suitable for hydrogen-dependent processes.
3) Comprehensive testing of samples from storage tanks found the naphtha to have properties like low residue, bright color, and low vapor pressure
Deskripsi Asli:
Quality of naphtha which is a raw material for ammonia.
This document summarizes a study characterizing the physicochemical properties and applications of naphtha produced at an Oil and Natural Gas Corporation plant in Uran, India. Key findings include:
1) The naphtha has high paraffin content, low aromatic content, no olefins, and very low metallic contaminant levels. It has a low sulfur content of 22 ppm.
2) Distillation characteristics classify the naphtha as group 1. Analysis found it to have good hydrogen content, making it suitable for hydrogen-dependent processes.
3) Comprehensive testing of samples from storage tanks found the naphtha to have properties like low residue, bright color, and low vapor pressure
This document summarizes a study characterizing the physicochemical properties and applications of naphtha produced at an Oil and Natural Gas Corporation plant in Uran, India. Key findings include:
1) The naphtha has high paraffin content, low aromatic content, no olefins, and very low metallic contaminant levels. It has a low sulfur content of 22 ppm.
2) Distillation characteristics classify the naphtha as group 1. Analysis found it to have good hydrogen content, making it suitable for hydrogen-dependent processes.
3) Comprehensive testing of samples from storage tanks found the naphtha to have properties like low residue, bright color, and low vapor pressure
Physicochemical characterization and applications of naphtha S C Pandey, D K Ralli, A K Saxena and W K Alamkhan Process & Products Control Laboratory, Uran Plant, Oil and Natural Gas Corporation, Uran 400 702, District Raigad Received: 28 July 2003; accepted: 27 November 2003 The present work aims at comprehensive evaluation of naphtha quality at physicochemical levels along with its applications. The study monitors the changes in the quality parameters by drawing samples from the storage tanks at Uran plant as well as at Indian Oil Tanking Limited (IOTL) terminal. Group characteristic assigns this LAN group1 category. It is observed that this LAN possesses high paraffin, low aromatic content, no olefins, and metallic constituents in a fraction of a ppm. The presence of metals in minute concentrations may not cause significant corrosion problems, catalytic poisoning, ash formation and any adverse impact on the quality of the product. Sulphur content is as low as 22ppm. Very small quantity of residue left on evaporation (4.18 mg/100mL) indicates lesser coke forming and carbon depositing propensity. Preponderance of paraffins renders faint odor to the product. Water whiteness of naphtha results owing to low concentration of aromatics. Saybolt colour indices towards the brightest end of the scale (+28 to +30) show high degree of freedom from contamination and cleanness of the product. High heating value, and C/H ratio indicate its hydrogen richness hence, it becomes suitable for many hydrogen dependent processes. Average value of Reid Vapor Pressure (at 37.8 o C) at the level of 10.2 psia makes it safer for handling, storage and processing. Keywords: Physicochemical characterization, Characterization, Naphtha, Hydrogen dependent processes IPC: Int Cl. 7 : C 10 G 45/08
Introduction Naphtha is a generic term applied to refined, partly refined or unrefined petroleum products and liquid products of natural gas which distill below 240 o C; the volatile fraction of the petroleum, which is used as a solvent or as a precursor to gasoline. In fact, not less than 10 per cent of material should distil below 75 o C; not less than 95 per cent of the material should distil below 240 o C under standard distillation conditions 1 .Naphtha contains varying amounts of its constituents viz., paraffins, naphthenes, aromatics and olefins in different proportions in addition to potential isomers of paraffin that exist in naphtha boiling range. Naphtha resembles gasoline in terms of boiling range and carbon number, being a precursor to gasoline. Naphtha is used as automotive fuel, engine fuel, and jet-B (naphtha type). Broadly, naphtha is classified as Light Naphtha and Heavy Naphtha. Light naphtha is used as rubber solvent, lacquer diluent, while heavy naphtha finds its application as varnish solvent, dyer , s naphtha, and cleaner , s naphtha. Volatility, solvent properties (dissolving power), purity and odor determine the suitability of naphtha for a particular use. The use of naphtha as an incendiary device in warfare, and as an illuminant dates back to 1200 AD. Naphtha is characterized as lean (high paraffin content) or rich (low paraffin content). The rich naphtha with higher proportion of naphthene content is easier to process in the platforming unit. A rich naphthene charge produces greater volumetric yield of reformate than does a lean charge The wide range of naphtha available from ordinary paraffinic straight run to highly aromatic type and the varying degree of volatility offer products suitable for many uses. Naphtha solvents may belong to categories such as, special boiling spirits having distillation range 30-165 o C, white spirit (mineral spirit) boiling within 150-210 o C, and high boiling petroleum fractions(160-325 o C).In aromatic complexes, naphtha is converted into basic petrochemical intermediates: Benzene, toluene and xylene (BTX). Petroleum naphtha is by far most popular feedstock for aromatics production. __________ * Author for correspondence PANDEY et al.: APPLICATIONS OF NAPHTHA
277 The Uran Plant Mumbai region of Oil and Natural Gas Corporation is a prolific producer of hydrocarbons in the country. Uran processing facilities were established in 1981 along the eastern shore of Bombay Harbor. This plant receives oil, gas, and condensate from western offshore. The plant possesses in-built capacity to handle 16 MMSCMD of Gas, 20 MMT/y of crude oil and 1500 MT/d of condensate. The extraction of natural gas liquid from natural gas is achieved as a result of fractionation of natural gas into hydrocarbon constituents. Gas condensates contain relatively high amount of high molecular weight liquid hydrocarbons. Uran plant processes natural gas by using cryogenic technology to produce liquefied petroleum gas, natural gasoline liquid, low aromatic naphtha, propane, and ethane- propane mixture. Typical composition of feed gas and condensate is presented in Table 1. This plant is also engaged in stabilization of crude oil prior to its dispatch to refineries. Uran plant has ISO 9001:2000, ISO 14001:1996 certification and achieved level-7 of international safety rating system (ISRS). Characterization Parameters An accurate description of naphtha quality requires its characterization at physical and chemical levels. Prescribed sampling protocols form the basis of sound analytical analysis. Preliminary and comprehensive assays are combined together to evaluate the quality of low aromatic naphtha (LAN) employing the latest international standards. Analytical Methods and Practices Sampling Protocol The correct sampling protocol is extremely crucial for any product destined for analytical evaluation as accuracy and precision of any analytical technique hinges on representative sample. Because of high standards set for naphtha, it is essential to employ correct sampling technique. Samples are required to be drawn in containers that are scrupulously clean, and free from odor while ensuring minimal disturbance to avoid loss of volatile components. Samples are drawn in accordance with upper third, middle third and lower third from the bigger tanks at the premises of Indian Oil Tanking Limited (IOTL), and tap sampling procedure is followed for drawing samples from smaller tanks at Uran plant as per method ASTM D-4057.
Group Characteristics
The selection of distillation characteristic at atmospheric pressure has an important bearing on safety and performance of fuels (ASTM D86, IP123, ISO: 3405). The boiling range provides information on composition and behavior during storage and use. On the basis of group characteristics LAN produced at Uran plant falls under group1 category (Table 2). The conditions required for sampling, preparation of apparatus, and conditions to be maintained during test procedure for group1 naphtha are shown in Table 3. Table 1 Typical composition of feed gas and condensate Feed gas Condensate Component Feed gas1 Feed gas2 Component N-paraffins Iso-paraffins Naphthenes Aromatics mol per cent (Volume per cent) C1 83.67 83.63 C1 C2 8.18 8.14 C2 0.12 C3 5.09 5.15 C3 2.10 IC4 0.97 0.98 C4 7.12 2.59 NC4 1.19 1.15 C5 11.91 8.38 2.41 IC5 0.24 0.23 C6 8.70 9.61 11.68 7.65 NC5 0.21 0.22 C7 3.71 2.47 9.72 3.99 C6+ 0.10 0.11 C8 1.34 0.71 2.84 1.94 N2 0.35 0.39 C9 0.07
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278 Physicochemical Characteristics Density Density is an important parameter as it is the main basis of sale transactions. Usually a hydrometer (ASTM D1298; IP-160) or more modern digital densitometer (ASTM D-4052 or D-5002) is used for determination of density. However, ASTM D1298 is the most commonly used method. Composition Adsorption chromatography ASTM D1319: IP156 gives first level of composition information as group-totals in terms of volume per cent of saturates, olefins, and aromatics in materials that boil below 315 o C. Naphtha composition, however, is monitored mainly by gas chromatography. Although most of the methods have been developed for gasoline, yet the applicability of these methods for naphtha is sound. A detailed analysis of petroleum naphtha can be carried out by capillary gas chromatography (ASTM D5134). A flame ionization detector detects the eluted components. Residue on Evaporation The carbon residue is a property that can be related with several other properties of petroleum. It presents an indication of volatility and coke forming propensity. Petroleum products are mixture of many compounds that differ widely in their physical and chemical properties. Some of them may be vaporized in the absence of air at atmospheric pressure without leaving any appreciable residue: other non-volatile compounds leave carbonaceous residue when destructively distilled. Methods ASTM D189, IP13 and ASTM D524, IP14 are used to determine carbon residue in relatively non-volatile portions of petroleum and petroleum products. Another common method to determine carbon residue, and to assess the propensity to form deposits is ASTM D1353. Carbon depositing characteristics of fuels are used in certain types of oil burning equipments and internal combustion engine. Odor and Colour Naphtha is required to have a low level of odor to meet the specifications for use. In general the paraffinic hydrocarbons possess the mildest odor, and the aromatics the strongest. The odor level is related to chemical character and volatility of constituents. Naphtha containing higher aromatic fractions may be pale yellow. Usually, naphtha is colourless (water white). Method ASTM D156, IP17 provides a rapid method of checking the degree of freedom of Table 2 Group characteristics of naphtha Sample characteristic Group 0 Group 1 Group2 Group3 Group 4 Distillate type Natural gasoline Vapour pressure at 37.8 o C (psi) 9.5 <9.5 <9.5 <9.5 Distillation IBP o C EP o C
250
250 100 >250 >100 >250 Table 3 Group 1 naphtha sampling, apparatus, and test procedure conditions Description Condition Description Condition Temperature of sample bottle, o C <10 Bath temperature, o C 0 -1 Temperature of stored sample, o C <10 Temperature of bath around receiving cylinder, o C 13 - 18 Flask, mL 125 Thermometer 7C(7F) Time from first application of heat to IBP, min 5 - 10 Flask temp. at start of test, o C 13 18 Time from IBP to 5 per cent recovered, s 60 100 Rate of condensation from 5 per cent recovered to 5mL in flask, mL/min 4 5 Receiving cylinder and 100 ml charge, o C 13 18 Time recorded from 5 mL residue to end point, min 5max
PANDEY et al.: APPLICATIONS OF NAPHTHA
279 contamination. Saybolt colour of a clear petroleum liquid is measured on a scale of 16 (darkest) to +30 (lightest).The sample is viewed through a length of column. Visually it is matched with one of the appropriate glass standards. Volatility/Distribution of Boiling Range Volatility or distribution of boiling range has been an important aspect of product specification in petroleum industry. It is a primary characteristic, and is indicative of tendency of liquid fuel to vaporize, and the ease with which material can be refined. This characteristic has an important bearing on the safety and the performance, especially in the case of fuels and solvents. Volatility is an important property for coating applications. It is critically important for automotive fuels, and gasoline affecting start/ warming up, and tendency to form vapor lock at high temperatures, and high altitudes or both. The distillation data consisting of initial temperature, final temperature along with sufficient temperature and volume observations can provide useful information on volatility. Reid Vapor Pressure Vapor pressure is an important physical property of volatile liquids, having critical implications on safety of operations of equipment and handling. Reid vapor pressure (RVP) is an indirect measure of evaporation rate of such liquids. It is also used in regulations relating to emission and air quality control. RVP of petroleum and petroleum products is determined by using method ASTM D323, IP69, ISO 3007. Procedure A of this method is applicable for petroleum products having RVP below 180Kpa (26psi). Sulphur Content Impurities, other than hydrocarbons, are of concern in petroleum industry. Quality of many petroleum products is related to the amount of sulphur. For example, many catalytic processes are sensitive to sulphur contaminant. Sulphur compounds contribute to corrosion of refinery equipment and poisoning of catalyst, cause corrosiveness in refined products, and they contribute to environmental pollution as a result of combustion of such fuel products. Sulphur is present in petroleum as sulphides, thiophenes, benzothiophenes, and dibenzothiophenes. A series of methods are utilized to determine trace concentration of sulphur. Method ASTM D4294, IP336, ISO 4785 utilizes energy dispersive x-ray fluorescence spectrometry for determination of sulphur in naphtha as well as in other fuels. Metallic Constituents Petroleum contains metallic constituents but they may also get incorporated during recovery, transportation, and storage. Range of principal trace elements found in petroleum is mentioned in Table 4. Even trace of these metals can be deleterious in refinery as they can cause corrosion, catalytic poisoning, and affect the quality of refined product. Nickel and vanadium along with iron and sodium (from brines) are the major metallic constituents. The presence of even small amounts of iron, copper, nickel and vanadium in the charging stocks for catalytic cracking affect the activity of the catalyst and result in increased gas and coke formation and reduced yield of gasoline. In oil-fired gas turbines the presence of metallic constituents, particularly V may lead to ash deposits on the turbine rotors, thus reducing clearances and disturbing their balance. The ash resulting from combustion of fuels containing sodium and specially V reacts with refractory furnace linings to lower their fusions and so cause their deterioration. Metals can be determined by A A Spectrophotometry (ASTM D-5863, IP285, IP288, IP465), wavelength dispersive X-ray fluorescence spectrometry and inductively coupled plasma emission spectrometry (ASTM D5185). Table 4 Principal trace elements in petroleum (ppm) (Source: Applied energy technology series by Mushrush and Speight) Elements Cu Ca Mg Ba Sr Zn Hg Ce B Al Range 0.2-12.0 1.0-2.5 1.0-2.5 0.001-0.10 0.001-0.10 0.5-1.0 0.03-0.10 0.001-0.6 0.001-0.10 0.5-1.0 Elements Ga Ti Zr Si Sn Pb V Fe Co Ni Range 0.001-0.10 0.001-0.40 0.001-0.40 0.10-5.0 0.10-0.30 0.001-0.2 5.0-1500 0.04-120 0.001-12.0 3.0-120
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280 Thermal Property (Heating Value) Calorific value or heat of combustion is a direct measure of fuel energy content and is determined as per method ASTM D-240, IP12. In the case of non- availability of experimental determination, it can be estimated satisfactorily, using ASTM D-6446. An alternative criterion of energy content is the aniline gravity product (AGP), which is related to calorific value (ASTM D1405, IP193). In another method (ASTM D3338 or IS 1448) the heat of combustion is calculated from the fuel density, the 10 per cent, 50 per cent and 90 per cent distillation temperature and the aromatic content. However the method ASTM D240 is preferred. Product Specifications Specifications of LAN and test methods followed at Uran plant are mentioned in Table 5. Results and Discussion Natural gasoline liquids produced from two LPG plants and condensate fractionation unit are blended to obtain final product Low aromatic naphtha. Quality parameters are evaluated at in-process stage as well as prior to dispatch. Batch samples of naphtha were drawn from tanks at Uran Plant and IOTL as per procedure laid down in method ASTM D4057. Naphtha from Uran plant is assigned Group-1 category on the basis of Group characteristics and all experimental conditions are set for this particular group.Density of LAN has been monitored at plant level as well as for tanks at IOTL (sold parcels) to observe the general trend of density variation. It varies between 0.6749-0.6838 g/mL, and 0.6785 - 0.6822 g/mL for plant tanks and IOTL tanks, respectively. Density profile vis--vis FBP is presented in Figure 1. Specification of the product permits variation limit between 0.67-0.69 g/mL. Compositional Information in the Form of Group Type Totals have been deduced by chromatographic method. The results indicate the paraffinic nature (>77 per cent v/v) with low aromatic content ( 7.3 per cent v/v). Concentration of naphthenes ranges between 14.29 - 15.55 per cent vol (Table 6). This naphtha may be characterized as lean. Average values of paraffins, isoparaffins, naphthenes, and aromatics are reflective of types by carbon number (Table 7). Dominance of paraffins in the chemical composition renders LAN very mild odor. Very small amount of carbon residue as low as 0.8 mg/100mL to a max of 7.60 mg/100mL against prescribed limit of 50 mg/100mL left after evaporation shows high volatility, little coke forming propensity, and carbon depositing characteristics. Owing to low aromatic and high paraffinic content the colour of naphtha is similar to water. Saybolt colour index of samples of plant tanks (average +27) and of IOTL tanks (average +29) shows fairly high degree of freedom from contaminants and fares well against the stipulated limit (+25 min). Volatility is assessed on the basis of distillation data. Average IBP, and temperatures ( o C) Table 5 Test methods and specifications of low aromatic naphtha Characteristic Test method Specification Paraffins ASTM D5134 75 per cent by vol. (Min) Aromatics ASTM D5134 10 per cent by vol (Max) Olefins ASTM D5134 1 per cent by vol (Max) Naphthenes ASTM D5134 Balance Lead ASTM D5185 250 ppb (Max) Sulphur ASTM D4294 250 ppm (Max) RVP at 37.8 o C ASTM D 323 12 psi (Max) Color saybolt ASTM D156 +25 (Min) Residue on Evaporation ASTM D 1353 50 mg/100ml (Max) Density at 15 0c ASTM D1298 Min 0.67-0.69 g/mL Max IBP ASTM D 86 35 o C (Min.) FBP ASTM D 86 150 o C (Max) Calorific value IS 1448 P:7 As observed C:H ratio ASTM D 3343 As observed Iso : N-paraffin ratio Calculated As observed
Figure 1 FBP vs density profilofLAN PANDEY et al.: APPLICATIONS OF NAPHTHA
281 corresponding to 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95 per cent, respectively, whereas recovery and FBP are 37, 43, 45, 47, 50, 52, 56, 61, 68, 78, 92, 111 and 134, respectively. Distillation curve is presented in Figure 2. Reid vapor pressure at 37.8 o C varies from 10.2 - 11 psi and from 10.0 - 10.5 psi for the plant storage, and IOTL tanks respectively. This meets well the prescribed specification limits of 12 psi. Naphtha produced at Uran Plant contains sulphur 20-100 ppm only (below 45 ppm in most of the cases). Hence, it is quite safe to use this LAN as fuel without any hazardous effects. Mercury, arsenic, lead, sodium, potassium, vanadium, zinc, nickel, and calcium were monitored for four months for assessing the level of these metals in the LAN (Table 8). Out of these, mercury and arsenic are <0.1 ppb, sodium 0.12 ppm, potassium 0.02 ppm, zinc 0.06 ppm, nickel 0.006 ppm, calcium 0.25 ppm, and vanadium with nil values. Lead was observed in the range of 16-100 ppb. Hence, metallic constituents are present at a level of fraction of a ppm, which indicates that any deleterious effect in terms of corrosion, catalytic poisoning, ash residue or any adverse effect on the product quality due to the presence of metallic constituents is insignificant in this naphtha. Table 6 Assessment of LAN quality (Source: IOTL terminal) Characteristic Unit Min. Max. Average Paraffins Per cent v/v 77.61 79.12 78.21 Aromatics Per cent v/v 6.59 7.30 6.83 Naphthenes Per cent v/v 14.29 15.55 15.00 Lead Ppb 16.00 110.00 66.27 Sulphur Ppm 22.00 100.00 51.18 RVP at 37.8 0c Psi 10.00 10.50 10.18 Color Saybolt Saybolt unit 28 30 29 ROE* mg/100mL 0.80 7.60 4.18 Density at 15 0c g/mL 0.6785 0.6817 0.6802 IBP o C 37.00 42.00 39.18 FBP o C 129.00 137.00 132.64 Calorific value K cal/ Kg 11420 11430 11423 *ROE stands for residue on evaporation Table 7 Types by carbon number Average volume per cent Carbon no. Aromatics Isoparaffins Naphthenes Normal paraffins 4 - - - 0.39 5 - 23.01 0.84 25.69 6 4.46 12.15 7.94 8.64 7 1.88 3.18 5.39 2.58 8 0.44 1.05 1.00 0.66 9 - 0.31 0.23 0.16 Total 6.78 39.70 15.40 38.12
Figure 2 Distillation curve of LAN Table 8 Monitoring of LAN quality at Uran plant during December 2002-March 2003 Source Unit Min Max Average Mercury ppb <0.1 <0.1 <0.1 Arsenic ppb <0.1 <0.1 <0.1 Sodium ppm 0.11 0.12 0.12 Potassium ppm 0.01 0.02 0.02 Vanadium ppm nil nil nil Zinc ppm 0.054 0.096 0.067 Nickel ppm 0.005 0.007 0.006 Calcium ppm 0.24 0.27 0.25 Gross calorific value k cal/Kg 11420 11450 11436 Net calorific value K cal/Kg 10610 10635 10624 C/H Ratio 5.28 5.35 5.32
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282 Calculated value of gross calorific value ranges from 11420-11450 kcal/kg, while the net calorific value varies from 10610 kcal/kg -10635 kcal/kg for LAN samples drawn from tanks at Uran. For sold parcels ex-IOTL the gross calorific value ranges between 11420 - 11430 kcal/kg. Carbon-Hydrogen ratio of LAN lies between 5.28:1 and 5.35:1. Because of this characteristic, naphtha may be used as a feedstock for many hydrogen dependent processes like hydro-cracking, sulphur removal, nitrogen removal and olefins removal. The demand for hydrogen is increasing over last several decades, which is utilized for conversion of petroleum to match changes in product slate. Conclusions Studies conducted on samples from plant storage tanks and IOTL tanks corroborate each other. Enormous database provides finer compositional details of the product and it may serve as a good pool of information for buyers in national and international markets. LAN produced at Uran plant is low boiling light naphtha beonging to group-I category on the basis of distillation characteristics. Predominance of paraffins makes it lean naphtha, hence it has a good market potential. All the quality parameters, as demanded by market forces, fall well within required limits. In addition to monitoring quality parameters, metallic constituents, heating values and C/H ratio have been evaluated on a continual basis. It is observed that it contains low level of metallic constituents, high calorific value and C/H ratio, and sulphur content as low as 22 ppm. Hydrogen richness of this LAN may render it suitable as feedstock for hydrogen dependent processes. Minute level of carbon residue shows lesser coke forming and carbon depositing propensity. Colour indices towards brightest side of scale are indicative of freedom from contaminants. Low RVP makes it safe for storage, handling, and processing. Acknowledgements The authors are grateful to Shri M L Panwar, Group General Manager-Head Uran Plant and Shri K Raman, Dy General Manager-Operations Manager for permission and guidance to carry out the study. Our thanks are also due to Shri R Kher, Chief Engineer (P) for his valuable suggestions. Bibliography 1 Handbook of petroleum product analysis, by James G Speight (John Wiley & Sons Inc, New Jersey, USA) 2002. 2 Petroleum refining processes, by James G Speight and Baki Ozum (Marcel Dekker Inc, New York, USA) 2002 3 Modern petroleum technology, edited by Alan G Lucas (The Institute of Petroleum) 2001 4 The Institute of Petroleum Standard Methods, 2003 and Annual book of ASTM Standards, 2000 5 Ralli D K, Pandey S C, Saxena A K and Alamkhan W K, Impact of quality management system on product quality at ONGC, Uran, J Sci Ind Res, 62 (2003) 1001-7.