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CHEMISTRY AND TECHNOLOGY OF

PETROLEUM

By Dr. Dang Saebea

REFINING CHEMISTRY

INTRODUCTION
Petroleum refining plays an important role in our lives.  Most transportation vehicles are powered by refined products such as gasoline, diesel, aviation turbine kerosene (ATK) and fuel oil.

THE REFINING INDUSTRY IN THREE WAYS

An increased search for fuel products from non-fossil sources such as biodiesel and alcohols from vegetable sources. The development of better methods to process tar sand, coal gasification and synthesis of fuels by new technology. The initiation of long-term plans to look for renewable energy sources.

. To improve product . . To a pure state. to remove impurities 2. 1.REFINING MEANS.

REFINING IS CARRIED OUT IN THREE MAIN STEPS Step 1 – Separation Step 2 – Conversion Step3 .Purification .

Separation  The oil is separated into its constituents by distillation. .REFINING IS CARRIED OUT Step 1 . and some of these components (such as the refinery gas) are further separated with chemical reactions and by using solvents.

o For example.REFINING IS CARRIED OUT Step 2 . . naphthas are "reformed" from paraffins and naphthenes into aromatics.Conversion o The various hydrocarbons produced are then chemically altered to make them more suitable for their intended purpose.

.REFINING IS CARRIED OUT Step3 .Purification o The hydrogen sulfide gas which was extracted from the refinery gas in Step 1 is converted to sulfur. which is solid in liquid form to fertiliser manufacturers.

Physical Separation Processes .REFINERY-PETROCHEMICAL INTEGRATION 1.

R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION .2.

Thermal Chemical Conversion Processes .3.

R Physical Separation Processes EFINERY -PETROCHEMICAL INTEGRATION Crude Distillation .1.

Crude Distillation  Crude oils are first desalted and then introduced with steam to an atmospheric distillation column.  The atmospheric residue is then introduced to a vacuum distillation tower operating at about 50 mmHg. Atmospheric distillation Vacuum distillation . where heavier products are obtained.

R Physical Separation Processes EFINERY -PETROCHEMICAL INTEGRATION .1.

This oil is also called ‘‘Bright Stock’’ and is used as feedstock for lube oil plant. leaving asphaltene to precipitate.Solvent Deasphalting  This is the only physical process where carbon is rejected from heavy petroleum fraction such as vacuum residue.  Propane in liquid form (at moderate pressure) is usually to dissolve the whole oil.  The DAO can also be sent to cracking units to increase light oil production. Solvent deasphalting process .  The deasphalted oil (DAO) has low sulphur and metal contents since these are removed with asphaltene.

R Physical Separation Processes EFINERY -PETROCHEMICAL INTEGRATION .1.

Solvent Extraction . which can dissolve the aromatic components in one phase (extract) and the rest of the oil in another phase (raffinate).  The solvent is removed from both phases and the raffinate is dewaxed. lube oil stock is treated by a solvent. such as phenol and furfural.Solvent Extraction  In this process.

R Physical Separation Processes EFINERY -PETROCHEMICAL INTEGRATION .1.

during which high molecular weight paraffin (wax) is crystallized. MEK) and the solution is gradually chilled.Solvent Dewaxing  The raffinate is dissolved in a solvent (methyl ethyl ketone. In some modern refineries removal of aromatics and waxes is carried out by catalytic processes in all ‘‘ hydrogenation process”  .  The extracted and dewaxed resulting oil is called ‘‘lube oil’’. and the remaining solution is filtered.

R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION .2.

This reformate is used in gasoline formulation and as a feedstock for aromatic production (benzene–toluene–xylene.  The produced naphtha reformate has a much higher octane number than the feed. .Catalytic Reforming  In this process a special catalyst (platinum metal supported on silica or silica base alumina) is used to restructure naphtha fraction (C6–C10) into aromatics and isoparaffins. BTX).

R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION .2.

are commonly used.  The catalyst is selected to suit the degree of hydrotreating and type of impurity. oxy-compounds. waxes and metals using hydrogen.Hydrotreating  This is one of the major processes for the cleaning of petroleum fractions from impurities such as sulphur. aromatics. Catalysts. . chloro-compounds. such as cobalt and molybdenum oxides on alumina matrix. nitrogen.

R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION .2.

It is composed of a zeolite catalyst for the cracking function and rare earth metals supported on alumina for the hydrogenation function.  In this case a dual function catalyst is used.  . The main products are kerosene. diesel and fuel oil.Catalytic Hydrocracking  For higher molecular weight fractions such as atmospheric residues (AR) and vacuum gas oils (VGOs). cracking in the presence of hydrogen is required to get light products. jet fuel.

2.R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION .

Catalytic Cracking  Fluid catalytic cracking (FCC) is the main player for the production of gasoline. The catalyst in this case is a zeolite base for the cracking function.

The main feed to FCC is VGO and the product is gasoline, but some gas oil and refinery gases are also produced.

2.R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION

Alkylation  Alkylation is the process in which isobutane reacts with olefins such as butylene (C4 ) to produce a gasoline range alkylate.

The catalyst in this case is either sulphuric acid or hydrofluoric acid. The hydrocarbons and acid react in liquid phase. Isobutane and olefins are collected mainly from FCC and delayed coker

2.R Chemical Conversion Processes EFINERY-Catalytic PETROCHEMICAL INTEGRATION

C6) are transformed to a branched product with the same carbon number.  One main advantage of this process is to separate hexane (C6) before it enters the reformer.Isomerization  Isomerization of light naphtha is the process in which low octane number hydrocarbons (C4. This process produces high octane number products. The main catalyst in this case is a Pt-zeolite base. thus preventing the formation of benzene which produces carcinogenic products on combustion with gasoline.  . C5.

3. Thermal Chemical Conversion Processes .

 The vacuum residue is heated in a furnace and flashed into large drums where coke is deposited on the walls of these drums. and the rest of the products are separated by distillation. .Delayed Coking  This process is based on the thermal cracking of vacuum residue by carbon rejection forming coke and lighter products such as gases. gasoline and gas oils.

most of the coke is gasified into fuel gas using steam and air. gasoline and gas oils with very little coke.  The burning of coke by air will provide the heat required for thermal cracking.Flexicoking  In this thermal process. The products are gases.  .

Thermal Chemical Conversion Processes .3.

Visbreaking  This is a mild thermal cracking process used to break the high viscosity and pour points of vacuum residue to the level which can be used in further downstream processes.  In this case. gas oil and the unconverted residue. gasoline.  . The products are gases. the residue is either broken in the furnace coil (coil visbreaking) or soaked in a reactor for a few minutes (soaker visbreaker).

The End .

CRUDE DISTILLATION .

and limiting the aromatic contents. or atmospheric distillation unit.  . also known as topping unit.  It receives high flow rates hence its size and operating cost are the largest in the refinery.  This involves the removal of undesirable components like sulphur. nitrogen and metal compounds.CRUDE DISTILLATION Crude distillation unit (CDU) is at the front-end of the refinery.

TYPICAL PRODUCTS FROM THE UNIT ARE: .

. This water cannot be separated by gravity or through mechanical means.CRUDE OIL DESALTING o o o The crude oil contains salt in the form of dissolved salt in the tiny droplet of water which forms a water-in oil emulsion. This process is called desalting. It is separated through electrostatic water separation.

CRUDE OIL DESALTING In the electrostatic desalter. It involves mixing the crude with dilution water (5–6 vol%) through a mixing valve. . the salty water droplets are caused to coalesce and migrate to the aqueous phase by gravity.

Corrosion of overhead equipment. The salts carried with the products act as catalyst poisons in catalytic cracking units.POOR DESALTING HAS THE FOLLOWING EFFECTS: 1. . thus reducing the heat transfer efficiency. Salts deposit inside the tubes of furnaces and on the tube bundles of heat exchangers creating fouling. 3. 2.

The salts can also be present in the form of salts crystals suspended in the crude oil.  .  These are mostly magnesium.TYPES OF SALTS IN CRUDE OIL Salts in the crude oil are mostly in the form of dissolved salts in fine water droplets emulsified in the crude oil. calcium and sodium chlorides with sodium chloride being the abundant type.

except for NaCl.TYPES OF SALTS IN CRUDE OIL  These chlorides. hydrolyze at high temperatures to hydrogen chloride: CaCl2  2 H 2O  Ca(OH )2  2 HCl MgCl2  2 H 2O  Mg (OH )2  2 HCl  Hydrogen chloride dissolves in the overhead system water. an extremely corrosive acid . producing hydrochloric acid.

.DESALTING PROCESS The process is accomplished through the following steps: 1. uniformly producing very tiny droplets.Water is mixed with the incoming crude oil through a mixing valve.Demulsifying agents are added at this stage to aide in breaking the emulsion by removing the asphaltenes from the surface of the droplets. .The water dissolves salt crystals and the mixing distributes the salts into the water. . Water washing: .

The crude oil temperature should be in the range of 49-54 ˚C (120–130 F) since the water–oil separation is affected by the viscosity and density of the oil. . Heating: .DESALTING PROCESS 2.

.Agitation is also produced and aides in coalescence.The electric field ionizes the water droplets and orients them so that they are attracted to each other. .The water droplets are so fine in diameter in the range of 1– 10 mm that they do not settle by gravity.DESALTING PROCESS 3. . Coalescence: . Coalescence produces larger drops that can be settled by gravity. .This is accomplished through an electrostatic electric field between two electrodes.

. Settling: According to Stock’s law the settling rate of the water droplets after coalescence is given by k( H 2O  Oil )d 2 Settling rate = oil where is the density  is the viscosity.DESALTING PROCESS 4. d is the droplet diameter k is a constant.

DESCRIPTION OF DESALTER Two electrodes Simplified flow diagram of an electrostatic desalter .

Simplified flow diagram of an electrostatic desalter .DESCRIPTION OF DESALTER A primary field of about 600 V/cm This field helps the water droplets settle faster.

DESCRIPTION OF DESALTER A secondary field of about 1000 V/cm The ionization of the water droplets and coalescence takes place here Simplified flow diagram of an electrostatic desalter .

The desalter of this design achieves 90% salt removal. -The crude unit can be operated with a one stage desalter while the other is cleaned. .TWO-STAGE DESALTING . -A second stage is also essential since desalter maintenance requires a lengthy amount of time to remove the dirt and sediment which settle at the bottom. However 99% salt removal is possible with two-stage desalters.

the following variables are controlled:  Desalting temperature: The settling rate depends on the density and viscosity of the crude T density & viscosity settling rate Desalting temperature can vary between 50 and 150 ˚C Washing water ratio: Adding water to the crude oil helps in salt removal.DESALTER OPERATING VARIABLES For an efficient desalter operation. Wash water rate Coalescence rate .

Raising the water level reduces the settling time for the water droplets in the crude oil -However.DESALTER OPERATING VARIABLES Water level: . if the water level gets too high and reaches the lower electrode. . . it shorts out the desalter.it is always better to keep the level constant for stable operation.

.DESALTER OPERATING VARIABLES Washing water injection point: -Usually the washing water is injected at the mixing valve. if it is feared that salt deposition may occur in the preheat exchangers.However. . part or all of the washing water is injected right after the crude feed pump.

It should be free from hydrogen sulphide and ammonia so as to not create more corrosion problems.DESALTER OPERATING VARIABLES Type of washing water: -Process water in addition of fresh water is used for desalting.It should be slightly acidic with a pH in the range of 6. . . The water should be relatively soft in order to prevent scaling.

ATMOSPHERIC DISTILLATION 330 ˚C Process flow diagram of an atmospheric distillation unit .

COMPONENT OF ATMOSPHERIC DISTILLATION Rectifying section Flash zone Stripping section .

liquid portion of feed go down to bottom of tower .Description OF ATMOSPHERIC DISTILLATION The vapor from pipestill furnace discharge as a foaming stream into distillation tower. The partially vaporized crude is transferred to the flash zone. The vapour goes up the tower to be fractionated into gas oil that is called the overhead product .

The bottom product from the tower enters the rebolier where part is vaporized by heat from steam coil. . The hot vapor is directed back to the bottom of the tower and the nonvolatile leaves the rebolier and passes through a heat exchanger.Description OF STRIPPING SECTION  Steam reboilers may take the form of a steam coil in the bottom of the tower or a separate vessel. where its heat is transferred to the feed to the tower.

Description OF STRIPPING SECTION  Steam is also injected into the column -To strip the atmospheric residue of any light hydrocarbon. This has the effect of lowering the boiling point of the hydrocarbons and causing more hydrocarbons to boil and go up the column to be eventually condensed and withdrawn as side streams. . .To lower the partial pressure of the hydrocarbon vapours in the flash zone.

.Description OF RECTIFYING SECTION As the hot vapours from the flash zone rise through the trays up the column. they are contacted by the colder reflux down the column. In the overhead condenser.  Reflux is provided by several pumparound streams along the column. the vapours are condensed and part of the light naphtha is returned to the column as reflux.

The addition to the heat removal from the condenser. The thermal efficiency of the column is improved and the required furnace duty is reduced.  .IMPROVEMENT OF DISTILLATION EFFICIENCY WITH PUMPAROUND  Vapours Cold liquid condenses Reflux To compensate for the withdrawal of products from the column.

Description OF RECTIFYING SECTION Liquid collects on each tray to a depth. As the liquid spills over the weir into a channel. . and the depth controlled by a dam or weir. which carries the liquid to the tray below.

IMPORTANT OF STRIPPING AND RECTIFYING SECTION  Stripping section The more volatile component are stripped the descending liquid from  Rectifying section The concentration of the less volatile component in the vapor is reduced .

Straight-Run Naphtha and Gases 125 ˚C 160 ˚C 250 ˚C Crude Oil 300 ˚C  Heavy Naphtha Kerosene Gas Oil The Temperature of tray is progressively cooler from bottom to top Residuum .

.THE EFFICIENT OPERATION OF THE DISTILLATION Tower requires the rising vapors to mix with liquid on each tray. The cap forces the vapor to go below the surface of the liquid and to bubble up through it. This is usually achieved by installing a bubble caps.

 .  Formation of coke would result in plugging the tubes in the furnace and the piping from the furnace to the distillation column as well as in the column itself. The constraint imposed by limiting the column inlet crude oil to a temperature of less than 350 °C yields a residual oil from the bottom of the atmospheric distillation column.LIMITING TEMPERATURE OF ATMOSPHERERIC DISTILLATION  It is important not to subject the crude oil to temperatures above 350 °C because the high molecular weight components in the crude oil will undergo thermal cracking and form petroleum coke .

Vacuum distillation is the reduced temperature requirement at lower pressures. Vacuum distillation increases the relative volatility of the key components. the distillation must be performed at absolute pressures as low as 10 to 50 mmHg so as to limit the operating temperature to less than 350°C.VACUUM DISTILLATION  To further distill the residual oil from the atmospheric distillation column.   .

 Reduction of product degradation or polymer formation because of reduced mean residence time especially in columns using packing rather than trays.  .  Reduction of capital cost because of reduced the height and diameter.Vacuum distillation can improve a separation by: Prevention of product degradation or polymer formation because of reduced pressure leading to lower tower bottoms temperatures.

FRACTIONS OBTAINED BY VACUUM DISTILLATION Gas Oil used as catalytic cracking stock or. after suitable treatment. light lubricating oil Atmospheric Residuum Vacuum Distillation Light Medium Heavy Lube oil Residuum. Nonvolatile used directly as asphalt or converted to asphalt .

OPERATION OF CRUDE DISTILLATION UNITS The factors affect the design and operation of the unit are explored 1. Lighter product: kerosene end boiling point Heavier product: LGO initial boiling point In the ideal case there would be no overlap . Fractionation The degree of fractionation in a crude unit is determined by the gap or overlap between two adjacent side stream products. Example: The gap or overlap in the boiling point range between kerosene and LGO.

. Since determining the initial and end point on the laboratory test is not always possible or accurate. and since ASTM distillation does not give perfect fractionation. The fractionation gap is defined as the difference between the ASTM 5% boiling point of the heavier product and the 95% point of the lighter product. if we compare the ASTM distillation boiling points.However.

a gap indicating good fractionation some of the light product is still in the heavier product .

  . Overflash  The partially vaporized crude is transferred to the flash zone. The overflash improve fractionation on the trays above the flash zone. The furnace outlet temperature should be enough to vaporize all products withdrawn above the flash zone plus about 3–5 vol% of the bottom product.2. thereby improving the quality of the HGO and reducing the overlap with the bottom products below the flash zone. This overflash has the function of providing liquid wash to the vapours going up the column from the flash zone.

 Pflash zone > PTop tray > Preflux drum .4–0.34 bar gauge (3–5 psig).2–0.34–0.  The top tray pressure is 0. Column Pressure The pressure inside the CDU column is controlled by the back pressure of the overhead reflux drum at about 0.  The flash zone pressure is usually 0.54 bar (5–8 psi) higher than the top tray.7 bar gauge (6–10 psig) higher than the reflux drum.3.

Overhead Temperature The overhead temperature must be controlled to be 14–17 ˚C higher than the dew point temperature for the water at the column overhead pressure so that no liquid water is condensed in the column. .4. This is to prevent corrosion due to the hydrogen chloride dissolved in liquid water (hydrochloric acid).

7 psia (2.5 mol% water at a pressure of 34. .36 bars).EXAMPLE If the overhead stream contains 8. calculate the overhead temperature for safe operation.

Solution: The saturation temperature of water at the partial pressure of water in the overhead vapour.7 psia (2.2 bars From the steam tables: Saturated steam temperature at 0.5 mol% water at a pressure of 34. calculate the overhead temperature for safe operation.085 x 2.36 =0.36 bars).2 bars = 61 ˚C Safe overhead operating temperature = 61+17 ˚C .EXAMPLE If the overhead stream contains 8. Water partial pressure = 0.

The End .