Crude Oil & Petroleum Products

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CRUDE OIL AND PETROLEUM PRODUCTS

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What is the crude oil, how is classified and which are the main products and fractions (cuts) used in the refining industry How t o infer main characteristic of crude oils based upon simple properties such as API density, sulphur and K factor What is a crude oil assay and which properties can be extracted from it. What are the main factor for selecting a crude oil What are the main qualities of the petroleum cuts and compare them to final products specification To learn : OBJECTIVES

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CONTENT CRUDE OIL Composition Crude cuts and petroleum products Laboratory test associated to crude and petroleum products characterization and properties Classification Assay and properties Selection and Trading PETROLEUM PRODUCTS Refining Introduction Quality and Specifications

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CRUDE OIL

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It is a complex mixture of hydrocarbons of different size, molecular weight and physical state, which are not easily separable from the chemical point of view. “Crude Oil” means all kinds of hydrocarbons in liquid form in their natural state or obtained by Natural Gas by condensation or extraction. It is formed by bacterial transformation of Organic matter (carbohydrates/proteins/from plant & animal origin) by decay in presence and/or absence of air into HC rich sediments by undergoing biological/physical and chemical alterations Its components are obtained in groups of boiling ranges by distillation. These groups are called fractions, cuts or petroleum products WHAT IS CRUDE OIL?

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CRUDE OIL COMPOSITION C H 83-87 % 10-14 % HYDROCARBONS . Water (0,1-0,8%vol) . Inorganic Salts (CaCl2; MgCl2, NaCl ) . Sediments . Sulfur compounds (0,05-6%) . Oxigen compounds (0,1-1,5%) . Nitrogen compounds (0,1-2%) . Organic - metallic cmpounds (0 - 14%) Oleophobic IMPURITIES Oleofilics

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The majority of crude oil is alkanes, cycloalkanes ( naphthenes ), aromatics, polycyclic aromatics (resins and asphalthenes , S-containing compounds, etc . CRUDE OIL COMPOSITION PARAFFINS N-PARAFFINS C C C C ISO-PARAFFINS C C C C C C NAPHTHENES CYCLE-PARAFFINS C C C C C C C C AROMÁTIC C C C C C C C C POLYAROMATIC

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Sulphur Compounds CRUDE OIL COMPOSITION Hydrogen Sulfide (H2S) Mercaptans (R-SH ) Thiophenes Sulfides (R-S-R) and Disulfides (R-S-S-R) Benzothiophene s Effect of sulphur compounds    Great environmental concern, contribute to particulate matter, emission of obnoxious odoured sulphur oxide gases Receding sulphur level in all petroleum products   Refining & Technology Focus shifted to sulphur removal from hydrocarbons

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  Alcohols/Ether/Cyclic ether/furan Carboxylic acids Naphthenic acids American crude oils : 0.006 to 0.35% wt Russian crudes oils : 0.2 to 1.05 % wt North Gujarat crude oil : 0.2%wt Increasingly High TAN Crude is being processed Oxygen compounds Nitrogen Compounds Pyrrole Pyridine Indole Quinoline Carbozole Indoline Benzocarbozole Benzoquinoline   Effect: Catalysts poison & Nitrogen oxide emission CRUDE OIL COMPOSITION Naphtenic rings Acid Fucntion Naphthenic acids Phenol Product of thermal cracking Corrosive at high temperatures (>250 ºC ) Indoles Pyridines Pyrroles

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  Ni & Va metals are contained in very big molecules (organometallic compounds) called asphaltenes Also Mg, Na and Ca presented as inorganic salts Salts mostly removed in desalting operation Ni & Va porphyrins are catalyst poisons Metals Inorganic and organometallic compounds CRUDE OIL COMPOSITION CH 3 CH 3 CH 3 CH 3 CH 3 CH 2 CH 3 CH 3 CH 3 CH 2 S H C C S C C C C C C C C CH 2 C H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2 C H 2 C H 3 C H 3 C 2 H 3 CRUDE OIL B CH 3 CH 3 CH 3 O S N CH 3 S CH 3 CH 3 CH 2 (C 74 H 87 NS 2 O) 4 S S S S S Insoluble in n- heptane (standard method ) and soluble in hot toluene CRUDE OIL A Molecular structure of asphaltenes

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CRUDE CUTS AND PETROLEUM PRODUCTS

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CRUDE CUTS Fuel Gas Propane Butane Light N aphtha Heavy Naphtha Kerosene Light Gasoil Heavy Gasoil Light vacuum Gasoil Heavy vacuum Gasoil Vacuum Residue 0°C 80 -90°C 185°C 220-240°C 360-380°C 550-600°C NAPHTHA ATMOSPHERIC DISTILLATES VACUUM DISTILLATES LPG ATMOSPHERIC RESIDUE Due its complexity of the crude, its components are not easily separable, so they are obtained in groups of boiling ranges by distillation called fractions, cuts or petroleum products

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LGN -200 -100 0 +100 +200 +300 +400 +500 +600 C 1 C 2 C 3 C 4 C 5 C 6 C 7 C 8 C 11 C 14 C 20 C 25 C 35 C 55 L.P.G BUTANE PROPANE AUTOMOTIVE GASOLINE GAS + LPG GASOLINES INTERMEDIATE PRODUCTS HEAVY PRODUCTS PETROCHEMICAL NAPHTHAS DIESEL HOME HEATING FUEL JET A1 LUBRICANTS BASES HEAVY FUEL OIL ASPHALT °C PETROLEUM PRODUCTS

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LABORATORY TESTS ASSOCIATED TO CRUDE AND PETROLEUM PRODUCTS CHARACTERIZATION AND PROPERTIES

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ASTM distillation and TBP (actual boiling temperature) are laboratory tests used to define the volatility of petroleum fractions and complex mixtures of hydrocarbons Both are batch distillations (BATCH) which differ mainly from the degree of fractionation obtained during separation The ASTM distillation is simpler, economical, requires less sample and the execution time is 10 times lower than the TBP TESTS RELATED TO THE VOLATILITY OF PETROLEUM PRODUCTS ASTM and TBP Distillation Fractionation quality

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DISTILLATI O N TBP, 15/5 (ASTM D-2892) TBP = True Boiling Point Only reference for crude oil fractionation Allows to define the yields and quality of the distillates = price value of a crude. Column of 15 theoretical steps (packed) and a reflux ratio of 5: 1 Temperature of the condenser cooling medium is -20 ° C When the bottom temperature reaches 310 ° C, the test is run at vacuum pressures to avoid cracking of the bottom product Pressure can be set between 100 mmHg - 2 mmHg TESTS RELATED TO THE VOLATILITY OF PETROLEUM PRODUCTS

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DISTILLATION ASTM D-86 Apply to naphtha and atmospheric distilllates Used to determine to control product quality There is no reflux or internal in the column DISTILLATION ASTM D-1160 Apply to heavy fractions (> 340°C < 580°C ) that can decompose if distilled at atmospheric pressure. Operating pressure interval: 1 mmHg to 50 mmHg There is no reflux or internal in the column TESTS RELATED TO THE VOLATILITY OF PETROLEUM PRODUCTS

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  Density is defined as the mass per unit volume of a substance. ( u nits:g /mL or g/cm3 or kg/m3). Density is temperature-dependent. Density is measured using an Anton Parr DMA 48/Kyoto digital density meter, and following ASTM method D 5002 - Density and Relative Density of Crude Oils by Digital Density Analyzer (ASTM,1996a). Density of crude oils : 0.83 to 0.90 g/ml. Densities can be measured to 0.0001 g/ml with a repeatability of 0.0005 g/ml. TESTS RELATED TO STORAGE AND FLOWING OF PETROLEUM PRODUCTS DENSITY (ASTM D5002; 1966a) API GRAVITY (ASTM D 1298 ) Specific Gravity (sp.gr) is defined as the ratio between the density of crude at 60 ° F and that of water at the same temperature Specific gravity The °API are a specific gravity conversion to better define the density scale of crude oil and products . The °API is defined by following correlation Hydrometer

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TESTS RELATED TO STORAGE AND FLOWING OF PETROLEUM PRODUCTS POUR POINT (ASTM D-97) KINEMATIC VISCOSITY (ASTM D 445)    The pour point of an oil is the lowest temperature at which the oil will just flow, under standard test conditions. The pour point of the oils is therefore an indication, and not an exact measure, of the temperature at which flow ceases.Heavy & waxy oil transportation is a challenge ASTM D 445 – is used for Viscosity of Transparent and Opaque Liquids. The method make use of glass capillary kinematic viscometers and will produce absolute measurements in units of centistokes ( cSt ) only for oils that exhibit Newtonian flow behavior

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TESTS RELATED TO STORAGE AND QUALITY OF PETROLEUM PRODUCTS BASE SEDIMENTS AND WATER BSW (ASTM D-97) FLASH POINT (ASTM D 56) Water and sediment content Iin crude oils ASTM D-96 and ASTM D 1796 They are measured by centrifugation in the presence of toluene Base sediments and Water of othe petroleum products can be determined by Karl Fischer titration using a Met Rohm 701 KF Automatic Titrator (ASTM D 4377) or by Distillation method, ASTM D4006   Oils with significant water contents, (>5%), do not represent the properties of the "dry" oil.   For 0.1%vol change, the cost implication For 10 MMT purchase at ~$60/barrel US$420/MT x (0.1/100)x10 MMT ~US$4.20 million The flash point is the lowest temperature to which a petroleum product must be raised and at which the application of an ignition source (flame) causes the vapor above the sample to ignite under specified test conditions There are safety regulations regarding the storage of crude oil and petroleum products according to the flash point (storage temperature must be 15 ° F lower than the flash point)

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CRUDE OIL CLASSIFICATION

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Naftenic for general purposes Paraffinic and or naftenic for general purposes Paraffinic for general purposes or production of paraffinic lubricants 32 - 43 o API 23 - 31 o API 10 - 22 o API Light Medium Heavy Extra heavy Natural Condensate > 43 o API < 10 o API Mixture of light hydrocarbons that can evaporate at atmospheric pressure Naftenic for general purposes o r naftenic lubricants CRUDE OIL CLASSIFICATION BY ITS DENSITY API is a major factor for Crude pricing

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Sweetening of petroleum product means the removal of A . Sulphur & its compounds B . Water C . Organic impurities D . wax SULPHUR CONTENT   CLASSIFICATION Below than 0.5% S Sweet 0.5 – 1.5 %S Medium Higher than 1.5 %S Sour CRUDE OIL CLASSIFICATION BY ITS SULPHUR CONTENT API & Sulphur

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API & Nitrogen API & Asphaltene CRUDE OIL CLASSIFICATION. ASPHALTENE & NITROGEN

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It is based on the Characterization Factor K of UOP. The Characterization Factor is calculated from the following formula: : where: T B: Mean average boiling temperature of the crude, MEANBP (R °) Sp.gr = Specific gravity 60/60 CRUDE OIL CLASSIFICATION BY TYPE OF HYDROCARBONS TYPE OF CRUDE K (UOP) Paraffinic > 11,5 Naphtenic 10,5 - 11,5 Aromatic < 10,5

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TYPES OF CRUDE HYDROCARBON CLASSIFICATION   BITUMINOUS NON-BITUMINOUS   Lube bearing High sulphur Basrah Light Arab medium Arab mix Kuwait   Non-lube bearing l ow sulphur   Suez Mix Qua I boe Dubai Miri light   PARAFFINIC BASE   WAXY, LESS ASPHALTIC, LOW SULPHUR, HIGH POUR NAPHTHENIC BASE   NAPHTHENIC BASE STOCKS, LESS WAX, LESS ASPHALTIC, LOW POUR   ASPHALTIC BASE   HIGH SULPHUR, NITROGEN, SUITABLE FOR BASE OILS CRUDE OIL CLASSIFICATION BY TYPE OF HYDROCARBONS

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   Low Sulphur Crudes   High sulfphur Crudes   Lube & Bitumen producing   Suitable for Lube producing refineries.   Non Lube Producing & Bitumen Producing   Suitable during Non Monsoon periods when Bitumen demand takes place   Non Lube / Non Bituminous   Suitable during Monsoon period when Bitumen production is not required.   Crude oils for Blending -Heavy, High acidic etc (LS or HS) TYPES OF CRUDES

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  TRADING : Density, API Gravity TRANSPORTATION :RVP , Pour Point, KV, Wax content CONTAMINATION : Salt content, BS&W PROCESSABILITY : Sulfur, Nitrogen, TAN, Asphaltene , MCR CRACKING POINT : ASTM Distillation LPG POTENTIAL : Light hydrocarbons (GC) CLASSIFICATION : Characterization factor CRUDE OIL CHARACTERIZATION

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WORLD CRUDE OIL QUALITY Properties   of Crude Oil 1985 1990 1995 2001 2010 ‘S’ i n crude Oil ( wt %) 1.14 1.12 1.31 1.41 1.51 API Gravity of Crude oil 32.7 32.6 32.4 32.2 31.8 Metal in crude oil Residue (ppm wt ) 275 286 297 309 320 Residue in crude ( vol %) 19 19.4 19.8 20.2 21.3 ‘S’ i n crude oil Residue ( wt %) 3.07 3.26 3.61 3.91 4.0

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CRUDE OIL ASSAYS AND PROPERTIES

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Crude assay is a detailed report which describes the properties of the whole crude, as well as the major fractions into which a crude is distilled at the refinery - gasoline, naphtha, kerosene, jet fuel, middle distillates, gas oils and residue. CRUDE OIL ASSAY

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CRUDE ASSAYS Combined TBP curves of Basrah Light Crude oil

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PROPERTIES OF CRUDE OIL

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FLOW CURVE OF WAXY CRUDE AT DIFFERENT TEMPERATURES

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CRUDE OIL TRADING AND SELECTION

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  Choice of crude oil for a refinery depends on: Product mix Product quality Refinery configuration Product treatment facilities Refinery design spec- Metallurgy, desalter…etc. Environment stipulation for pollution control Pipeline design for inland refineries Proper crude selection is necessary for optimization of refinery margin. FACTORS EFFECTING THE SELECTION OF CRUDE OIL

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  Refinery Configuration   Refinery metallurgy   Catalyst   Down-stream treatment facilities   Pipeline design constraints REFINERY CONSTRAINTS

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    High S crude oil High Acid crude oils Beat the market by proper selection of crude Overcome refinery design constraints to widen crude basket Crude Blending Facility OPPORTUNITY

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MAJOR THRUST BY OIL REFINERY 1 Optimize cr ud e m i x H i g h o r Lo w s u l f ur 2 W i den i n g c r ud e ba sk et In c r ea s e d N o . o f cr udes 3 O c ea n f r e i gh t r edu c t i on H i ghe r C a r g o s i z e 4 D e m u rr ag e c o n t r o l Minimize t a n k e r w a i t i n g 5 I n v en t o r y c o n t r o l M i n po s s i b l e i n v e n t o r y 6 O c e a n Lo s s r edu c t i o n P r ope r c o n t r o l s 7 R edu ce F & L P r ope r de s i gn ope r a t i o n

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GROSS PRODUCT WORTH OF CRUDE OIL

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ELEMENTS OF IMPORTED CRUDE COST

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PETROLEUM PRODUCTS Refining Introduction

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REFINING OVERVIEW

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YIELD STRUCTURE OF VARIOS CRUDES

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TYPICAL REFINERY CONFIGURATION

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PETROLEUM PRODUCTS Quality and Specfications

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PRODUCTS & CUT POINTS

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LPG Naphtha Petrol (BS-II/BSIII) Kerosene ATF Diesel (BS-II/BS-III) LOBS Bitumen RPC Wax Fuel Oil (High S, Low S) Fuel Oil (High or low Viscosity) LSHS HPS Petrochemical feed stock LABFS HPL Naphtha Petrochemicals pX, PTA LAB etc PRODUCTS

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YIELD PATTERN OF CRUDE OILS

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PROPERTIES OF NAPHTHA

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GASOLINE SPECIFICATION

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PROPERTIES OF KERO / ATF

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PROPERTIES OF GAS OIL

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DIESEL SPECIFICATION

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LOBS API CLASSIFICATION

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