SEPERATION PROCESSES FOR PETROLEUM REFINING

Basics of Separation Operations Thermodynamics: Phase Equilibrium Mass Transfer and Efficiency of Separation Operations Distillation Absorption and Stripping Liquid Liquid Extraction Crystallization Adsorption Membrane Separation

Basics of Separation Operations

Function of Separation Operation in Refining
Crude oil: complex mixture of a very large of components Given specifications petroleum products Necessary to separate out the different fractions (cuts)

I. Basics of Separation Operations

Three mains functions:
Fractionation Recycling Purification

Fractionation

Recycling

I. Basics of Separation Operations

Main separations operations:
Heterogeneous Mixtures
Decanting in an appropriate apparatus

Homogeneous Mixtures
Implementation of complex processes Series of operations designed to concentrate certain components selectivity in given fraction
Example of a homogeneous mixture of A and B Introduce new phase into the system for adding a selective external phase (Solvent, Adsorbent or Energy) Separation factor:

AB =

x A1 xB1 x A2 xB2

I. Basics of Separation Operations

Homogeneous Mixtures
Two phases thoroughly mixed in the contact stage Equilibriu m Separation factor: AB AB Theoretical stage Real stage: separation factor depending on mass transfer kinetics

I. Basics of Separation Operations

Homogeneous Mixtures
Classification according to the separating agent and the nature of the phases in contact:
Distillation Crystallization by cooling Liquid Liquid extraction Extractive distillation
(for separating components whose volatilities are close and belong to different chemical families) (Combination of the effect of a phase change by energy input with the effect of solvent addition)

Adsorption (for difficult separation operations and deep purification) Membrane separation based on kinetic selectivity, not involving a change in phase (gaseous permeation (gas), Ultra filtration,
reverse osmosis (liquid))

I. Basics of Separation Operations

Classification

I. Basics of Separation Operations

Implementation of separation processes
Thermodynamics equilibrium
Boiling, Crystallization points, Equilibrium constants

Kinetic factor
Molecular diffusion, Hydrodynamic factors Mass transfer driving force (C-C*) Mass flux through the interface
N = K(C C*)

Overall diffusion coefficients (K)

Contact between phases

I. Basics of Separation Operations

Implementation of separation processes
Contact between phases

I. Basics of Separation Operations

Implementation of separation processes
Certain examples

Gas purification operation by means of solvent

Separation by fixed-bed adsorption

I. Basics of Separation Operations

Implementation of separation processes
Membrane separation:

Still seldom used in refining Potential application: Ultra-filtration, Pervaporation and Gaseous Permeation

I. Basics of Separation Operations

I. Basics of Separation Operations

Membrane separation:

I. Basics of Separation Operations

Exercise 1: Relation between the separation operations processes in the oil refining

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
General Description:
Describing a mixture: P, T and [Zi] or P, Vap% and [Zi] or T, Vap% and [Zi] For binary and ternary mixture
Isobaric Vapor - Liquid Equilibrium Diagrams

II. Thermodynamics: Phase Equilibrium

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
Isothermal Vapor Liquid Equilibrium Diagram

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
Two phase envelope

Tc (C2H6) = 305K Ethane Benzene mixture

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
Two phase envelope
Ethane Benzene mixture

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
Azeotrope:
Ex: n-Hexane and Acetone system

A. Isothermal diagram (T = 50C)

B. Isobaric diagram (P = 1.013 bar)

II. Thermodynamics: Phase Equilibrium

Vapor-Liquid Equilibrium
Azeotrope:
Existence only in limited pressure domain (Ex: C2H6-CO2)
Exercise 2: Using the SRK model with ki,j = 0.13 for drawing up isothermal vapor-liquid equilibrium curves for the Ethane CO2 system at 263,15K.

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Chemical potential and fugacity
Second principle of thermodynamics
Gibbs energy decreases to minimal: dGT,P = 0

Material balance imposing the condition: so that we can deduce: At equilibrium, the chemical potential of any component has the same value in the liquid and vapor phase

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Heterogeneous methods to calculate the K value:
Apply different models to the liquid and vapor phase

Methods using the Regular Solution model

Chao and Seader, Model 1961

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Heterogeneous methods to calculate the K value
Methods using the Concept of Local Composition
The NRTL Model (Non-Random Two Liquid)

The UNIQUAC Model (Universal Quasi Chemical)

Models Using Groups Contribution: ASOG and UNIFAC Models

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Homogeneous methods to calculate the K value
Representation of the phases at equilibrium by the same equation of state Equations of state derived from the Van der Waals theory

For a mixture:

ki,j: interaction parameter determined from experimental phase equilibrium data

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Homogeneous methods to calculate the K value

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Homogeneous methods to calculate the K value

Mean relative deviations (%) in the calculation of vapor pressures and densities by the EOS

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Relation between Homogeneous and Heterogeneous Methods Liquid Liquid Equilibrium Liquid Liquid Vapor Equilibrium

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Solid Liquid Equilibrium: Crystallization
Formulation of lube oils dewaxing Purification de paraxylene (Tf = 14C), Tf(m-xylene) = -47C

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Solid Liquid Equilibrium: Crystallization

II. Thermodynamics: Phase Equilibrium

Equilibrium conditions
Complex mixture
Small number of pseudo-component Based on TBP distillation Detailed chromatographic analysis (simulated distillation) Parameters calculated for the model used (critical coordinates) according to the data available (Tb, S) Widely used to calculate distillations Applied seldom to non-ideal due to the presence of polar components mixture or liquid liquid equilibrium

III. Mass Transfer and efficiency of separation operations

Introduction
Sizing the various pieces of equipment
Kinetics of transfer of mass Efficiency of each of the stages Height of packed column: transfer coefficient between phases in contact Membrane separation: rate of diffusion of each component

Diffusion in a homogeneous phase Mass transfer between two phases though the interface Efficiency of equipment for contact between phases COMPLEX MECHANISM NEED THE EMPIRICAL DATA

III. Mass Transfer and efficiency of separation operations Diffusion in the homogeneous phase
For binary solution
NA, NB (mol.m-2.s-1): Mass transfer to a fixed point of reference

CA, CB: molar concentration (mol.m-3), vA, vB: velocities (m.s-1) The average volume velocity v is given by the equation:

Diffusion law: Ficks law

DAB: Molecular diffusion coefficient (m2.s-1)

III. Mass Transfer and efficiency of separation operations

Diffusion in the homogeneous phase

For binary solution
Mass flow NA in relation to a fixed point of reference

By using C to stand for the total molar concentration:

Correlation designed to predict the value of a diffusion coefficient (DAB)

III. Mass Transfer and efficiency of separation operations

Diffusion in the homogeneous phase

In the gaseous phase: Chapman and Cowling (1964)

()A and ()A : diffusion volumes calculated by summing the contributing terms

III. Mass Transfer and efficiency of separation operations

Diffusion in the homogeneous phase

In the liquid phase: Wilke and Chang (1955)

D0AB: Diffusion coefficient of solute A at infinite dilution in solvent B (m2.s-1) B: Viscosity of the solvent B (mPa.s) VA: Molar volume of A at its normal boiling point (cm3.mol-1) MB: Molar mass of the solvent (g.mol-1) B: Association parameter (2.6 for water, 1.9 for methanol, 1.5 for ethanol and 1 if the solvent does not give rise to any association

Case of concentrated solution

Vignes equation (1966)

III. Mass Transfer and efficiency of separation operations

Diffusion in the solid phase:

No correlations to predict the value of the diffusion coefficient Fort dependence on the material Complexity of involved phenomena Somme typical values of diffusion coefficient
In the gaseous phase ~ 10-5 m2s-1. In the liquid phase ~ 10-9 m2s-1. In the solid phase ~ 10-16 m2s-1.

Need for used adsorbents: - In a form of porous structures - Agglomerating small sizes crystals

III. Mass Transfer and efficiency of separation operations

Transfer between phase:

Phase 1 and 2 in contact
Mass transfer takes place if they are not at thermodynamic equilibrium

Driving force of transfer: (C C*) leading the equation:

C* corresponding to equilibrium with the concentration C K [m.s-1]

III. Mass Transfer and efficiency of separation operations

Transfer between phase:

Phase 1 and 2 in contact

An individual transfer coefficient relative to phase 1

N = k(C Ci)

An individual transfer coefficient relative to phase 2

N = k(Ci C) C* = mC + q

III. Mass Transfer and efficiency of separation operations

Predicting Transfer Coefficients

Transfer coefficient depends on the diffusion coefficient Assumed that the concentration gradient limited to a very thin stagnant film in the neighborhood of the interface

The interface renewal model: limited contact time, transfer in a transient state:

ONLY IN THE STAGNANT MEDIUM OR BOUDARY LAYER EQUATION IN THE CASE OF A LAMINAR SYSTEM

III. Mass Transfer and efficiency of separation operations

Predicting Transfer Coefficients

In practice: Complexity of hydrodynamic conditions Impossible to determine the coefficient of transfer of mass Using the dimensionless numbers

Sherwoods number: Reynoldss : Schmidts number:

III. Mass Transfer and efficiency of separation operations

Predicting Transfer Coefficients

Calculate of Sho(Re,Sc) inside a spherical particle
(Diffusion only) For a short contact time (Dt/d2 < 0,035): For fairly large contact time:

Calculate of Sho(Re,Sc) outside a spherical particle

(Diffusion and convection)

III. Mass Transfer and efficiency of separation operations

Predicting Transfer Coefficients

Calculate of Sho(Re,Sc) outside a spherical particle
(Diffusion and convection)

By Hughmark (1967)

III. Mass Transfer and efficiency of separation operations

Efficiency and Transfer Coefficients

Tray efficiency

(viscosity in cP or mPa.s)

III. Mass Transfer and efficiency of separation operations

Efficiency and Transfer Coefficients

HETP for packed column

IV. Distillation, Absorption and Stripping

IV. Distillation, Absorption and Stripping

IV. Distillation, Absorption and Stripping

Realized in the tray column or packing column Comparison the factors in favor of Tray and Packing
Tray Column Packed Column Easier to clean, draining, washing, inspection Lower pressure drop (manholes) Complex column (feed injection product draw off) Large diameter column Overly high/low liquid flow rate - flexibility of tray design (perforation, use cap, valve) Star-up and shut-down: attenuated mechanical phenomena Minimize the column weight Low liquid retention Operation when residence time minimized Small diameter column: Easier install of contact equipment Minimize the tendency to foam

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil, including the important desalting operation Vacuum distillation of the atmospheric residue Gasoline distillation and gas fractionation

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping) Producing the cuts:
Gasoline cut: feed for the gasoline and gas fractionation Naphtha cut for the petrochemical industry Kerosene cut for use in producing aviation fuel One or two gas oil cuts used to make FOD and DO Atmospheric residue as feed to the vacuum distillation unit

Eventually:
Distillate cut drawn off between HGO and the flash zone for use as a fluxing agent for FO Possible to draw off a light gasoline cut in the distillation unit at the top and heavy naphtha laterally via stripper (corrosion problem at the top)

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Designed to allow crudes of different characteristics
A base crude, representative of the refinerys average oil supply A lighter crude, which sizes the top of the scheme and furnace zones A heavier crude, which sets the dimensions of the bottom of the column and the exchanger train Allowing the variation in the cut points amounting to about twenty degree Celsius on TBP Unit able to operate properly at approximately 60% of its normal capacity

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Description of the process
- Pressure: 1 3 barg. - Products drawn off as side streams by means of strippers - Generally steam stripped or reboiled - Behaving like reflux absorber, equipped one to three pumparounds - Overflash Internal reflux of the first tray above the feed sent back to the bottom of tower - Overhead condensation total or partial: residual gas taken up by compressor and sent to gas plant - Main column (~50m high): 30 50 conventional trays - Side stripper: 4 10 trays - Crude preheated in an exchanger train by recovering heat to 120 160C and desalted

- Desalting takes place at high pressure (~10 bars) - Heated in a second exchanger train and furnace to 330 390C - Into the main column in a partially vaporized state

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Fractionation quality: GAP or OVELAP

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Fractionation quality: GAP or OVELAP

- Other internal specifications - Flash point of kerosene and gas oils - End boiling point ASTM D86 of heavy naphtha (generally < 185C) - Cloud point of heavy gas oil - Flash point of atmospheric residue

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Computerized calculation
Choose the thermodynamic model

- Deviations between two extreme models - Amount of vapor generated in the flash zone: 5% - So, thermal load of overhead condenser: 5% - Off take temperature: 3 5C - Overflash: 20%

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Computerized calculation
Entering Data and Analyzing Results
TBP or ASTM D86 of the crude Hypothetical component or pseudo-component Density, Boiling point temperature, molar mass

Number of tray

Thermal exchange zone: 2 4 real trays Pressure drop between the top and flash zones: 0,4 0,6 bar

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Computerized calculation Estimating the Overhead pressure Amounts of stripping steams
Kerosene and gas oils: 15 to 30 kg of steam/m3 of product Residue: 20 to 30 kg of steam/m3 of residue

Regulating the overflash

3 to 5% of the feed

Analyzing the results

TBP and ASTM product curves Product specifications (gap or overlap) Flow rate of withdrawn products Amount of heat extracted by various pumparounds

Convergence Difficulties

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Technology Conventional technology
Ordinary carbon steel except for hot zones steel alloys Usually clad with 12% weight chromium steel Zone exposed to cold corrosion (top of the tower, reflux drum): Monel (Ni Cu ( Fe) alloys) or special coatings Conventional valve trays of steel alloy 12%Cr Tray efficiency diminishes from the top to the feed inlet Wash zones structured packing Draw off tray - feed the side strippers and the pumparound: total draw off type (chimney tray) Main column feed inlet of the tangential type Furnace of cabin or cylindrical type Heat exchangers of TEMA type the nominal working pressure does not exceed of 30 bars Diameter 9m for a tower processing 1000 t.h-1 of crude

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Process variation
Double condensation at the top of the column Other flow diagrams

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting: Essential operation in the refinery
Fouling of exchanger and the furnace Corrosion of overhead equipment Atmospheric residue with high sodium content: fouling rate of the vacuum distillation furnace; shorter cycle length for visbreakers, Catalyst poisoning in catalytic cracking, Fouling and corrosion of boiler superheaters Severe environment problems

Sources of the salt in the crude (10 80 mg.l-1)

Inevitable Delibarable contamination (5 to 50 mg.l-1) Accidental contamination

Concentration in chlorides of overhead water in the tower should not exceed 10 ppm

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting:

Salt content of a number of crude oils (before and after transportation)

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting and topping

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting: Mechanism Diffusion of the crudes salts in water (by washing)
The mixture of water and crude through a mixing valve placed at the desalter inlet - P = 0,5 (viscous) 1,5 bar(light cude) Sufficiently fine water-crude emulsion from 1 to 10m

Coalescence of water droplets (by electrocoalescence)

Asphaltenes and FeS adsorbed on the water-oil interface stabilizing emulsion agents

Settling (by gravity Stokes law)

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting: Industrial Implementation
E1 = 200 Volt.cm-1 E2 = 1000 Volt.cm-1

Electrostatic desalter with one stage

Electrostatic desalter with two stages

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Crude Oil Desalting: Industrial Implementation

Desalters performances
Desalting efficiency of 85 95% Water content in the desalted crude: mower than 0,2% V (0,4 0,5% for heavy crudes) Hydrocarbon concentration in the water coming out not exceed 200ppm

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Corrosion and Erosion
Corrosive agents: Chlorides, organic acids, non-organic salts, sulfur compound Corrosion by salts
Injection of caustic Metals or metal alloys uses: Ti, Monel, Hastelloy

High Temperature sulfur corrosion

T: 300 420C for ordinary carbon steel 5%Cr-5%Mo steel or 12% - 18%Cr steel

Naphthenic Acid corrosion

T: 220C 240C Severe corrosion above 350C (furnace 18/10/3 steel alloy) Erosion Transfer line, overhead line: high velocity and mitered elbow used

IV. Distillation in the Petroleum Industry

Atmospheric distillation of crude oil (Topping)
Precaution to guard against corrosion risks in topping unit

IV. Distillation in the Petroleum Industry

Vacuum distillation of the Atmospheric residue
Purposes:
Extraction of the distillate cuts to feed conversion unit Feed for bitumen manufacture Base stocks for lube oil manufacture

Technologies:
Dry vacuum distillation without injection of steam very low pressure (10 15 mmHg at the top) Wet vacuum distillation with injection of steam in the furnace feed and stripping steam in the bottom of tower (40 60 mmHg at the top) Semi-wet vacuum distillation with injection only at the bottom of the column Use of un ejector (called booster ejector)

Fractionation:
Typical cut points for a 350C TBP atmospheric residue: VGO 350 390C (T90 or T95 ASTM D86 360C), Vacuum Distillate: 390 550C (C, Me) Reduce heavy oil production: to prolong distillates (exceed 585C TBP)

IV. Distillation in the Petroleum Industry

Vacuum distillation of the Atmospheric residue
Definition of terms specific to vacuum distillation: LVGO MVGO HVGO Cracked hydrocarbons Non condensable
Air entering through leaks Non condensable dissolved in the feed Light hydrocarbon produced by cracking in the furnace

Slop cut and overflash (3 5% of the feed): internal reflux

IV. Distillation in the Petroleum Industry

Flow diagram of a dry vacuum distillation unit

IV. Distillation in the Petroleum Industry

Flow diagram of a wet vacuum distillation unit

IV. Distillation in the Petroleum Industry

Wet vacuum distillation unit operating parameter

Conversion scheme: tree side cuts

Lube oil production scheme

IV. Distillation in the Petroleum Industry

Crude oil vacuum distillation Configuration of fractionation
Heat Exchange zones:
Random packing of metal ring and grates (grids)

Fractionation zones:
Structured packing: more effective and expensive

Wash zone
Less sophisticated grates (grids)

Distributors
Sprays or Gravity

IV. Distillation in the Petroleum Industry

Comparison of two columns

IV. Distillation in the Petroleum Industry

Vacuum distillation Vacuum pumps and Ejector Condenser
To create the vacuum
Ejector (venturi effect)-low pressure steam about of 6 bar Combination ejector and liquid ring pump similar to eccentric rotor gas compressors with a seal provided By a ring of cooled water moving around in a closed circuit with compression ratio of about 10 (eq. to 2 or 3 ejectors)

IV. Distillation in the Petroleum Industry

Gasoline Distillation and Gas Fractionation
Conventional Flow Scheme
Series of column working at different pressure chosen so that the condensation can be done by air-cooler exchanger or cooling water First column: stabilization column or debutanizer After the amine washing, the overhead cut is sent to deethanizer Stabilized gasoline is usually fractionated into 2 cuts gasoline splitter LPG are fractionated in a depropanizer

IV. Distillation in the Petroleum Industry

Gasoline Distillation and Gas Fractionation

IV. Distillation in the Petroleum Industry

Gasoline Distillation and Gas Fractionation with absorber and stripper

IV. Distillation in the Petroleum Industry

Gasoline Distillation and Gas Fractionation
Main Operating Conditions

Common Specification
Debutanizer C5 content in butane: 0,5% mass or 1% volume maximum 1% volume maximum C4 in light gasoline Depropanizer or Deethanizer Commercial specifications for the products Propane in Butane: vapor pressure not exceeded 6 bar rel. at 50C Ethane content in propane: vapor pressure not exceeded 14 bar rel at 38,8C

Splitter
GAP 20C

IV. Distillation in the Petroleum Industry

Gasoline Distillation and Gas Fractionation
Other configurations
Cryogenic scheme in some applications to recover olefins contained in gas coming from conversion unit Set up with a deisobutanizer to recover isobutane for the alkylation unit, deisopentanizer, de isohexanizer, Columns for extracting aromatic compound Gas treatment unit with the diethanolamine (DEA) washing, LPG sweetening, sulfur trap and drier type in order to meet commercial specification

IV. Distillation in the Petroleum Industry

FCC Primary Fractionation
Similar to a crude topping unit but has two major differences
Totally vaporized and superheated feed (480 540C) Large proportion of the gases

Feed always contains traces of catalyst Problem of pressure drop to the limits of capacity of compressor and the activity of the FCC unit (blower, pressure in the reactor) A convention configuration includes:
HCO LCO Heavy naphtha Overhead vapors: C2-, C3, C4, light gasoline Eventually an added draw-off of intermediate gasoline

IV. Distillation in the Petroleum Industry

Treatment of FCC gas
Including the following sequence:
Compressor Deethanizer, primary absorber/stripper Debutanizer C3/C4 separation

Some characteristics
Working at a relatively high pressure (10 20 bars) High specific liquid load in comparison to vapor loads High vapor gravity low liquid gravity Favorable for tray Sour water stripping Remove H2S and NH3 contained in the water condensed at the top of atmospheric fractionation column before the biological treatment Stripping column supplied with the live steam at the bottom Equipped with random or structured packing

IV. Distillation in the Petroleum Industry

Treatment of FCC gas

IV. Distillation in the Petroleum Industry

Treatment of FCC gas
The primary absorber:
To absorb most of LPG contained in the gas coming from HP seperator drum with FCC gasoline Equipped with some thirty tray made of 410S One or two pumparounds to evacuate the heat of absorption Reflux with a draw-off sump to collect the water or supplying the top of the column with the debutanized subcooled FCC gasoline

Stripper
Remove th lightest fraction (C1, C2, H2S ) from wild gasoline Equipped with some thirty tray made of 410S Reboiled with LCO coming from primary fractionation

Secondary absorber
Gas from the top of the absorber washed with lean oil LCO (T < 40C)

Debutanizer
Adjust the FCC gasoline vapor pressure some forty trays of 410S Reboiled with HCO coming from primary column

IV. Distillation in the Petroleum Industry

Coker primary fractionation Visbreaker primary fractionation Fractionation of HF Alkylation Effluents Treatment of Reforming Effluents

V. Liquid Liquid Extraction in the Petroleum Industry

Separation technique based on the differences in solubility between the components of a homogeneous liquid feed in a appropriate solvent Employed when distillation alone can not provide an economically satisfactory solution (azeotropy, too small relative volatility) Good for separating components by chemical family In oil and gas industry: dearomatizing gas oil, deasphalting heavy cut and extracting BTX aromatics Compose of two main complementary steps:
Extraction implemented in different ways: One-stage, Crosscurrent, single countercurrent, Countercurrent with reflux, Dual solvent Solvent regeneration generally by distillation

V. Liquid Liquid Extraction in the Petroleum Industry

Solvent characteristics
Solvent properties related to the thermodynamics of L L equilibrium Capacity or Solvent power
Selectivity

Physical properties
Viscosity: pumping, dispersion energy, mass and heat transfer, settling velocities Density: density of the extracted phase, difference between the densities of extract and raffinate for operating the extractor Surface tension: low surface tension promotes the dispersion of one phase in the other, large interfacial surface area favorable to mass transfer, stable emulsion Boiling point: differences in volatility great enough to avoid azeotropic phenomena, minimize equipment size and energy consumption

Other properties
Thermal stability Chemical inertia Low toxicity, Biodegradable and high flash point

VI. Solvent Extraction in the Petroleum Industry

Extraction of aromatic compound from lube oil stocks in order to produce lubricants Deasphalting of distillation residues to produce both DAO and Asphats Extraction of Aromatic compound from lighter stocks: gasolines or kerosenes in order to comply with present and future regulation

VI. Solvent Extraction in the Petroleum Industry

Extraction of aromatic compound from lube oil stocks in order to produce lubricants

VI. Solvent Extraction in the Petroleum Industry

Choice of solvent
Solvent power (Solvent capacity) High selectivity for aromatics molecules Other points enter into consideration in the choice of a solvent

VI. Solvent Extraction in the Petroleum Industry

Extraction of aromatic compound Furfural Extraction
Extraction solvents are numerous, among which furfural meet the target criteria adequately Examined different variables: External variables: Solvent, Extractor, feed composition, extraction efficiency Internal variables : Solvent ratio, Extraction temperature, Temperature gradient, extractor feed flow rate, Solvent purity

Furfural

Phenol N-methyl-2pyrrolidone (NMP)

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction - Comparison

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction Points to consider for understanding
Water and furfural form a heteroazetrope The mutual solubility of water and furfural are not negligible The solvent power of furfural increases when the temperature increases and degreases with the molecular mass The selectivity of furfural toward aromatics degreases when the temperature increases Furfural is chemical compound that is sensitive to oxidation, acids and temperature.
Inhibitors such as amines protect furfural during the storage against the action of oxidizing agents but they are difficult to use in a unit in operation Metal such as copper accelerate the oxidation process that form acids, they in turn make furfural break down into resins Rate of degradation is proportional to the concentration in H+, so water can also affect furfural Furfural has tendency to break down with temperature (at 230C, 5% is degraded in 80h) with the formation of resin insoluble in aromatics Furfural is not inert toward some components of feeds so giving rise to complex polymers

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction Choice of extractor

Present-day trend is to use the high efficiency RDC (Rotating Disc Contactor) -High number of theoretical stages (up to 10 compared with 5-7 conventional columns) -Very clear-cut raffinate/Extract interface - Raffinate yield 3 to 5% higher -Possibility of optimizing extraction quality depending on the type and flow rate of feed by using rotating disc

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction - Flow Scheme
Feed deaeration
DAO, thermal exchange with the extract to 100C, 50mmHg, eliminate the moisture and air, furfural sensible to oxidation and to presence of water

Extraction
Extractor working under pressure (6 bar at the top) Introduction of feed at the bottom of the extraction zone, solvent at the top of column Adjusting the feed temperature by an exchanger Mixed extract side stream drawn off under the feed inlet, cooled in exchanger and sent back to the tower Regulated Top/feed/bottom temperature gradient with the set point of the temperature of the top Equipped exchanger and furnace to heat the raffinate to 200C for vaporizing the furfural in flash drum and recovering the solvent trace in the steam stripping zone.

Recovery of solvent in the raffinate Recovery of solvent in the extract

Complex circuit to reduce the energy consumption involved in vaporizing furfural Made up of four consecutive vaporization stages and ends with steam stripping

Water removal and azeotropic distillation section Drainage system and Inert Gas system

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction
10-15% Furfural

20% Furfural recovery

60% Furfural recovery 10% Furfural recovery

90-85% Furfural

VI. Solvent Extraction in the Petroleum Industry

Furfural Extraction
Azeotrope: 35% Furfural 65% H2O

VI. Solvent Extraction in the Petroleum Industry

N-methyl-2-pyrrolidone (NMP) Extraction
In comparison with furfural, it has the following advantages Better stability Better oxidation resistance Less carryover in the raffinate and the extract Higher solvent power toward aromatics Lower process temperature Less toxicity The following drawbacks Lower specific gravity Less selectivity Higher boiling point

VI. Solvent Extraction in the Petroleum Industry

N-methyl-2-pyrrolidone (NMP) Extraction

VI. Solvent Extraction in the Petroleum Industry

N-methyl-2-pyrrolidone (NMP) Extraction Dehydration section

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Purpose of process
Oily fractions
Production of bright stock and waxes Preparation of FCC feed with or without an intermediate hydrorefining step Feed specs for FCC unit: 2000ppm Maxi. Basic nitrogen, 2% Maxi. Conradson carbon content 20ppm mass Maxi. metal Preparation of hydrocracking feeds to increase the production of high quality middle distillates

Asphaltic fractions
Production of road quality Use as components in industrial fuel oil or solid fuels Feed for conversion unit as visbreakers, oxyvapogasifiers and cokers

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Incorporation of deasphalting process in the lube oil stock production process

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Incorporation of deasphalting process es an extra conversion unit

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Products and properties

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Solvent characteristics and operating conditions

VI. Solvent Extraction in the Petroleum Industry

Deasphalting Solvent characteristics and operating conditions

VII. Crystallization in Oil Industry

Solvent Dewaxing
Most common Oil/Wax separation based on crystallization with a solvent Ideal solvent: Dissolve the Oil and Precipitate all the Wax
Solubility and selectivity: good solubility for the oil and good crystallization selectivity for the wax Low boiling point Low heat of vaporization Low congeal point: remain liquid at filtration temperature No toxicity or corrosivity Low price and wide availability

In the industry using the mixture of Methyl Ethyl Ketone (MKE) and Toluene (80%) or Methylisobutylketone

VII. Crystallization in Oil Industry

Solvent Dewaxing
Physical properties of MEK and Toluene

VII. Crystallization in Oil Industry

Dewaxing Process Using an MEK-Toluene Mixture as solvent
Crystallization in presence of solvent Filtration Separation between the solvent and the oil or the wax by distillation

VII. Crystallization in Oil Industry

Dewaxing Process Using an MEK-Toluene Mixture as solvent
Products - Dewaxed oil and -Wax with oil content of 10 20% (slack wax or petrolatum wax) -Deoiling (wax with very low oil content and foots oil)

VII. Crystallization in Oil Industry

Dewaxing Process Using an MEK-Toluene Mixture as solvent
(Without in line deoiling)

VII. Crystallization in Oil Industry

Dewaxing Process Using an MEK-Toluene Mixture as solvent
Four main section: - Crystallization section to cool the raffinate and solvent, thereby crystallizing the waxes - Filtration section to separate the dexaed oil from the wax cake -- Distillation section with two operation for dewaxing unit without in line deoiling and three with in line deoiling to separate the solvent from de dewaxed oil, the wax and the foots oil - Solvent system recovering the solvent exiting the distillation operation and redistrubuting it in the form of dilution