Petroleum industry in India

Exploration-O.N.G.C,O.I.L,Cairn,Reliance,Essar RefiningI.O.C(Digboi,Guwahati,Haldia,Baruni,Mathura,Pan ipat,Koyali,CPCL,BRPL) BPCL-Mumbai,KRL,NRL HPCL-Mumbai,Vizag, MRPL RELIANCE Essar oil

Refineries under construction1.BPCL Bina refinery-M.P 2.IOC Paradeep-Orissa 3.HPCL Bhatinda-Punjab 4.Expansion of Reliance,Essar Marketing1.IOC,2.BPCl,3.HPCL,4.IBP,5.Reliance,6.Essar 7.GAIL(Natural gas)

Petrochemical1.Reliance 2.GAIL 3.FACT-PD 4.GSFC 15 th largest consumer in world 22 nd rank in production Crude oil reserve is 0.59% Crude Production-33mmta Crude consumption-130 mmta Refining capacity-175mmta

India had only 15 days of crude stock First oil well in India-1866 at Nahorpung(Assam) 1890 at Digboi First refinery -1893 (Assam oil company) Japan & U.S have 6 months stock 1barrel-42 us gallon -35 imperial gallon OPEC-Organization for Petroleum exporting countries(producers) IEA-International energy agency(consumers)

 First oil well in the world-1855(Pennsylvania) First oil refinery in world-1859 Only major refinery till 1954 in India is Assam Oil company - 1955 with help of Russia,They conducted survey,BH,Ankleshwar oil fields are developed - ONGC set up in 1956 - OIL-1958 - IOC-1964

1947-Production-0.25mmta Refining-0.5mmta Consumption-2.6mmta Major Oil fields1.BH(south,North,Heera,Gandhar,Neelam) 2.KG basin 3.Ankleshwar in Gujarat 4.Upper assam(OIL) 5.Mangala oil field-Cairn energy 6.Nagapatnam 7.Rauva oil field

NELP-New exploration licensing policy APM-Administrative pricing mechanism MDPM-Market determined pricing mechanism Total 742 refinery in the world Exxon mobil is the largest refiner Shell is the second U.S is the largest consumer Saudi is the largest producer

Major products
Light distillate-LPG,Gasoline,Naphtha Middle distillate-Kerosene,ATF,HSD Heavy distillate-Furnace oil,LSHS,HSHS,Lube oil,Bitumen,Pet coke,Paraffin wax Petrochemical-Aromatics,PXylene,PTA,Ethylene,Propylene etc. Solvents Sulphur

Euro specification of Gasoline

Euro 1 Colour Density Lead(gm/lit) Sulphur % Benzene Vol% Aromatics Vol% Olefin RON MON Oxygen wt% 95 85 2.5 95 85 2.5 orange 710-771 0.013 0.05 5 Euro2 orange 710-772 0.013 0.025 5 Euro3 orange 710-773 0.005 0.015 1 42 18 95 85 2.7 euro4 orange 710-774 0.005 0.005 1 35 10 95 85 2.9

Euro specification of diesel

Euro1 Sulphur % 95% Recovery Temp Poly cyclic aromatics Density 0.2 370 No spec 820-860 Euro2 0.05 49 370 No spec 820-860 Euro3 0.035 51 360 11 845 Euro4 0.005 53 340 11 840 Cetane number 49

History and development of Refining

The invention of Kerosene lamp in 1854 Henry Ford invented automobile Gasoline production increased tremendously after the development of cracking process Steam- Naphtha reforming Maximize Propylene production Naphtha converted into gasoline

Refining Technology
A.D.U-L.P.G,Naphtha,Kerosene,Diesel,R.C V.D.U-L.V.G.O,H.V.G.O,V.R Visbreaking unit Bitumen unit FCCU/Hydrocracking/Coking(Secondary) Reformer/CCR LEFPU Purification-Merox,Hydro desulphurisation Sulphur Recovery

Origin and formation of Petroleum

Petoleum means rock oil is a complex mixture of hydrocarbons which occurs in gaseous or liquid state in geological traps Origin of Petroleum 1. Inorganic theory Berthelots view Mendeleeffs view The above two theories failed to explain optical activity and occurrence of oil in Sedimentary rock

 Organic theory Englers theory- 1.Marine animal/vegitable matter decomposed by bacteria form bituminous residue 2.Cracking- give liquid product rich in olefin called Protopetroleum 3.Polymerisation,Polyolefin so formed undergo changes to become Naphthenic and Paraffinic hydrocarbon

 Modern theory-Plant/animal-fatty acidKerogen(aliphatic material)-Oil/gas in sedimentary rock Occurrence of Petroleum- in pockets of porous rock such as sand stone surrounded by non porous rock.Gas,oil,water have seeped into such pocket and been trapped Three types of traps 1.Anticline-arch or bulge Fault-earth movement cause crack and shift Stratigraphic-barrier to fluid flow

Exploration
1.Identify the potential area 2.Drilling 3.Recovery of oil and gas from the well Identify the potential area 1.Geophysical method A.Gravimetric method B.Electrical conductivity method C.Magnetic method D.Seismic survey

2.Geochemical method A.Gas survey B.Bacterial method C.Gass logging-gamma ray logging,Neutron logging Drilling Mud fluid circulating system Coring

Types of drilling 1.Percussion drilling 2.Rotary drilling 3.Vibratory drilling 4.Augar drilling 5.Turbo drilling

Recovery of oil 1.Primary oil recovery(Natural method) Dissolved gas drive Gas cap drive Water drive Gravity drive Secondary recovery-Producing more oil by introducing more energy into a reservoir Water flooding Gas flooding

 Enhanced oil recovery-ultimate oil can be economically recovered from a petroleum reservoir Thermal methods -Steam injection -Steam flooding -In situ combustion .Miscible/Immiscible displacement process -CO2 injection -L.P.G injection -Inert gas injection

 Chemical flooding process Surfactant/Polymer injection Alkaline flooding

Transportation of crude
Crude oil contain a mixture of light and heavy hydrocarbon.Stabilized oil may cotain paraffinic,naphthenic,and aromatic components.In addition asphaltenes and resins may also present. Pipe line Marine carriers 1.ULCC-350TMT VLCC-250,SUEZ MAX-135,LR1-85,LR11-65,MR-40 Tank trucks by road

Transportation of Waxy crude

Presence of wax crystal changes the flow behaviour from Newtonian to non newtonian Low sulphur Good distillate and product yeild Low viscous flow at fair temp Middle east crude-Pour point below 0 and wax content below 7% BH-30-12.5%

Methods of pipeline transportation

Select pumps to allow a parallel/series arrangement Separate low flow,high head pumps for restarting Reverse pumping Hydrocarbon diluent less waxy crude or light distillate Use pour point depressants/flow improvers Mixing water with crude to form an emulsion Conditioning the crude to change the structure of wax crystal

Pour point depressants

Alkyl acrylate polymers and copolymer Olefin alkyl maleate copolymer Vinyl ester Alkylated polystyrene Developed by RRL SWAT-104,SWAT-106

Composition of crude oil

Hydrocarbon along with sulphur,N2,O2,and some metals Elemental composition C-84-87%,H2-11-14%,S-0.06-8%,N2-0.021.7%,O2-0.68-1.82%,Metals-0-.14% -Hydrocarbons 1.Parffins,2.Naphthenes,3.Aromatics -Non hydrocarbons 1.Sulphur compounds(0.05 to 8%)

Free elemental Sulphur Hydrogen sulphide Thiols(R-SH) Sulphides(RSR) Disulphides(RSSR) 2.Nitrogen compounds(0.2%) Basic-Pyrrole,Indole,Carbazole Non basic-Pyridine,Quinoline

 3.Oxygen compounds(2%) Phenol,Cyclohexanone,Benzaldehyde, 4.Resins and Asphaltenes-half of the total combined N2, O2,and S present in the crude oil in the form of resins and asphaltenes 5.Metallic constituents Nickel and Vanadium are the most abundant trace metal found in crude oil Fe,Cu,Al,Ba,Bo,Ca,Co,

Natural gas
Methane together with small amounts of heavier hydrocarbon and some non hydrocarbon gases like N2,Co2,H2,H2S,He 1.Non associated gas 2.Associated gas 3.Dissolved gas-dry or lean gas,wet gas,Sour gas,Sweet gas,residue gas,casing head gas 4.Natural gas liquid(LNG)

Characterization of crude oil

Crude oils differ from each other based on their place of origin,hydrocarbon content. Paraffin base-paraffin wax,lubricating oil,high grade kerosene(More than 5% paraffin in residue) Naphthenic/Asphaltic base-Non hydrocarbons relatively high,high quality gasoline,M/C lubricating oil and asphalt(less than 2% paraffin) Mixed base-both wax and asphalt,lower yeild(25% paraffin)

Methods for determination of base of crude

1.Correlation index-U.S .Bureau of mines CI=473.7d-456.8+(48.64/K) K=average B.P 0 to 15=paraffinic,15 to 50 =naphthenic,above 50 aromatic 2. Characterization factor,K uop 10.5 to 12.5-paraffinic,12.5 to 13 naphthenic 3.Watson factor Kw

4.Viscosity gravity index VGC=10G-1.072 log(V-38)/10-log(V-38) V=viscosity at 37.8C G=gravity at 15.6C Lower the index number more paraffinic is crude 5.A.S.T.M distillation 6.T.B.P distillation 7.E.F.V

Different types of B.P

1.volume average B.P 2.Weight average B.P 3.Molal average B.P 4.Mean average B.P 5.Cubic average B.P

Evaluation of crude oil

1.Colour-green,dark brown,black, C/H2 ratio 6 to 8 2.Specific gravity Light crude-less than 0.825 Medium crude-less than 0.875 Heavy crude-less than 1.0 Extra heavy crude-more than 1.0

3.Crude oil Pour point Pumpability of crude varies from -60 to 30c 4.Crude oil viscosity Pressure drop in pipelines.Viscosity of paraffinic crude increase rapidly with decrease in temp 5. V.P and Flash point of crude oil Assess the amount of light hydrocarbon present in it and assess the amount of light hydrocarbon that may be lost during filling and draining

6.Sulphur content of Crude oil(0.05 to 5%) More than 6 ppm H2S Sour crude Less than 6ppm H2S-Sweet crude 7.Nitrogen content of Crude oil On heating they decompose to give organic bases or Ammonia,which reduce the acidity of refining catalysts and initiate gum formation 8.Bottom sediments

 9.Salt content of crude oil Scale formation,H.E fouling,begin to hydrolyse at 120C releasing HCl gas 10.Crude oil Acid number Presence of Carboxylic acid Form emulsion with caustic solution Corrosive at high temp Attack ordinary carbon steel

Benchmark crude
North sea brent crude(Europe) West texas intermediate crude(U.S) Dubai crude (India) Desirable crude oil properties API gravity-30-40 Pour point <18C N2<1400ppm Acid number <0.5 mg of KOH/gm of crude Sulphur <0.3 wt%

Thermal properties of Petroleum fraction

1.Flash point- is the lowest temp at which application of test flame causes the vapour above the oil give momentary flash 2.Fire point- is the lowest temp at which application of test flame causes the vopour above the oil to ignite and continues to burn for 5 sec. Flash point and fire point can be taken as indirect measure of volatility of the product. Method of storage, transportation, safety

 3.Cloud point- is the temp at which a cloud or haze of wax crystal appears at the bottom of the test jar when the oil is cooled under prescribed conditions. Cloud point give rough idea of the temp above which the oil can be safely handled without any fear of congealing or filter clogging. 4.Pour point-is the lowest temp expressed in multiples of 3C at which oil is observed to flow when cooled and examined under prescribed conditions.

 Indicate pump ability of crude Waxy nature of the oils 5.Freezing point-is the temp at which crystals of hydrocarbons formed on cooling disappear when temp of fuel is allowed to rise Jet fuel test is very important. 6.Viscosity Dynamic viscosity-is the ratio of applied shear stress to rate of shear and thus a measure of the resistance of a fluid flow

 Kinematic viscosity-is defined as the measure of the resistance to gravity flow of fluid. The time of flow of a fixed volume of fluid is directly proportional to its Kinematic viscosity. Viscosity is an important characteristics of a fuel it is used for pump design, flow through pipe line, orifice, atomization of fuel Redwood ,Say bolt universal,Engler viscometer

 7.Viscosity index-is the most widely used way of characterizing the effect change of temp on the viscosity of any oil. An oil with min change in viscosity with temp has a high VI,oil whose viscosity changes rapidly with change in temp has a low VI VI=(L-U/L-H)x100 U-K.V at 40C of the oil whose VI is to be calculated L- K.V at 40C of the oil of 0 VI H- K.V at 40C of the oil of100 VI

T.B.P Apparatus

T.B.P Distillation
T.B.P apparatus Distillation flask with heating system Distillation column and reflux divider Condenser head with coolant supply Fraction collector and liquid cooler for removal of product Vacuum producing equipment

Sequence-1, Debutanisation Sequence-2,Distillation at atm pressure Sequence-3,Distillation at 100mm Hg Sequence-4,Distillation at 2mm Hg Observation which are to be recorded 1.Time in hours and minute 2.Volume in ml 3.Vapour temp 4.Temp of boiling liquid 5.Pressure and pressure drop in column

 Report-Different cut obtained are collected,their initial and final distillation temp are recorded along with their volume/weight and specific gravities.Temp v/s cumulative volume%. A.S.T.M distillation It is non fractionating distillation system,distinguishing itself as a differential distillation carried out with std A.S.T.M flask

Distillation flask with heating arrangement Condenser Receiver Vacuum equipment Equilibrium flash vaporisation-conduct flash distillation T.B.P slope A.S.T.M gap T.B.P overlap