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Refinery processes

Refinery
Refinery is the processing of one complex mixture of hydrocarbons into a number of other complex mixture of hydrocarbons. A crude or semi-finished substance (such as metal, oil, or sugar) is converted (refined) into a finished or higher grade product, usually through distillation or electrolysis. Refinery begins with the distillation by boiling crude into separate fractions or cuts. As all crudes undergo separation process through distillation, so it is common to express the capacity of refinery in terms of its distillation capacity Two measures are generally used: BPSD : Barrels per stream day BPCD : Barrels per calendar day

Properties of Crude oil:


Crude oil / Petroleum is a complex mixture of many HC compounds occur in the earth in liquid, gaseous and solid forms. Crude oil has several chemical composition . Crude oil range in consistency from water to tar like solids and in color from clear to black. An avg crude oil has C: 84%, H: 14%, S-1-3%,N,O, metals and salts <1% Crude oil is classified as Paraffinic, naphthenic, aromatic and mixed. Crude oil has 3 imp properties: Gravity, Sulfur content and Total Acid Number. Crude oil defined in terms of API.(American petroleum gravity).Higher the API gravity , lighter the crude. TAN is a measure of potential corrosivity. No. of mgs of KOH needed to neutralize 1 g of crude oil.

Crude oil is a mixture of HC and properties of HC depends upon the number and arrangement of carbon and hydrogen atoms in the molecule. C and H atoms may include 1-60 C atoms. From 1-4 C atoms : Usually gases 4-20 C atoms: Liquid 20 onwards: solids

Principal groups of HCs


Paraffin's: General Formula: CnH2n+2 Aromatics ::Unsaturated ring compounds having general Formulae: CnH2n. All aromatics compound have atleast one benzene ring. Naphthenes: Saturated HC grouping having general formulae CnH2n arranged in the from of closed rings.Ex. cyclohexane Alkenes: These are monoolefins with formula CnH2n and contain only one carbon- carbon double bond like ethylene: C2H4 Dienes: These are the diloefins having two C-C double bonds. Alkynes :Unsaturated HC having a C-C triple bond and having the formula CnH2n-2 like acetylene: C2H2

Major Refinery Products


Gasoline Kerosene-middle distillate petroleum product like jet and turbine fuels LPG Distillate fuels includes diesel fuels , heating oils Residual fuels Coke and Asphalt Solvents like benzene , toluene, xylene Petrochemicals like Ethylene, propylene etc Lubricants

Processes
There are five basic steps under which the whole refinery processes can be defined: 1. Fractionation 2. Conversion processes Decomposition (Dividing)-Thermal and catalytic cracking Unification ( Combining)- Alkylation, Polymerization Alteration ( Rearranging)-Isomerization, Catalytic reforming 3. Treatment processes- Desalting, Hydrodesulphurization, solvent extraction, dew axing, sweetening processes 4. Blending Process of mixing and combining HC fractions, additives and other components to produce finished product with sp. Properties. 5. Other refinery operations

Processes description
Process Name ADU VDU Action Separation Separation Method Thermal Thermal Purpose Sep fractions Sep w/o cracking Feedstock(s) Desalted crude ADU residual Product(s) Gas, Gasoil, Distillate Gasoil, lube stock,residual

Conversion Processes- Decomposition processes


Cat Cracking Coking Alteration Polymerize Catalytic Thermal Upgrade Gas Convert vacuum residuals Convert to lighter HC Reduce viscosity Gas oil, coke, distillate Gas oil, coke distillate Gasoline, PCFS Gasoline, PCFS

Hydro cracking Visbreaking

Hydrogenate Decompose

Catalytic Thermal

Gas oil, cracked Lighter, high oil qlty pdct ADU residual Distillate, Tar

Conversion-Unification Alkylation Combining Catalytic Unite olefins & Isoparaffins Tower isobutane Isooctane

Polymerizing

Polymerize

Catalytic

Unite olefins

Cracked olefin

High octane

Process description continued..


Conversion-Arrangement processes Catalytic Reforming Dehydration Catalytic Cat Upgrade low Coker/HC octane napth naphtha Convert st .to Butane, branch pentane Treatment processes Desalting Dehydration Absorption Remove salts Crude oil Desalted CO High octane reformate Isobutane/pe ntane Isomerization Rearrange

Sweetining

Treatment

Catalytic
Catalytic

Remove H2S
Remove H2S Remove impurities Remove wax

Gasoline
High S residual Residuals, cracked HC Vacuum tower Gasoil, reformate

High gasoline
Desulfurized olefin Cracker feed Dewaxed lube oil High octane galoine

Hydrodesulfu Treatment rization Hydro treating Solvent dewaxing Solvent extraction

Hydregenatio Catalytic n Treatment Cool/filter

First Process: Fractionation


Fractionation can also be named as distillation. It involves the separation of crude oil on the basis of boiling point ranges and molecular size of the hydrocarbons. There are two processes under the distillation: 1. Atmospheric Distillation 2. Vacuum Distillation The feed stock for the ADU is crude oil and the feed stock for the VDU is residue of the ADU. Vacuum Distillation is used for the heavier portion of the crude oil into fractions, because the high temp required to vaporize the topped crude at atmospheric pr cause thermal cracking to occur with the resulting loss of dry gas, discoloration of product and equipment fouling due to coke formation.

Desalting
If the salt content is greater than 10 lb/1000bbl, then the crude requires the desalting to minimize fouling and corrosion. The salt is present in the form of dissolved or suspended salt crystals in water emulsified with crude oil. Two processes are used for desalting: Chemical separation Electrostatic separation

Atmospheric distillation
After the desalting process, crude oil pass on to the distillation column. The temp of the distillation column is between 343 399 deg c. The various major products are: Lubricating oil Heating oil Kerosene Gasoline The naphtha obtained from ADU sent to reformer to improve the gasoline quality The gas oil to Catalytic Cracking Residual to Visbreaker

Vacuum distillation unit


The residue of ADU is sent to the VDU. The furnace outlet temp. required for atm pr distillation of the heavier fractions of crude oil are so high that thermal cracking would occur with resultant loss of product and equipment fouling. So these products are distilled under vacuum, as the boiling temp decrease with a lowering of the pressure In ADU, the distillation is carried out at pr of 25-40 mm hg but in VDU, the pressure is being lowered to 10 mm hg or less, by the addition of steam to the furnace inlet and at the bottom of the vacuum tower. The main products are gas oils, lubricate oil, heavy residual oils. Gas oil is being further processed in cat cracker, lubricants to hydrotreater or solvent and residual to visbreaker or coker.

Cracking
Process that cracks the heavier, higher boiling point petroleum fractions into more valuable products such as gasoline, fuel oil and gas oils. As the simple distillation processes does not meat all the basic requirements so this cracking process is being required. Two cracking processes: Thermal Cracking Catalytic Cracking Thermal cracking is being done by the heat and pressure and there is no requirement of catalyst. The examples of thermal cracking are Visbreaking unit, Delayed coker unit In catalytic cracking, the cracking takes place in the presence of some catalyst. The catalytic cracking includes the Fluid catalytic cracking(FCC), Thermo for catalytic cracking.

Catalytic Hydro treating


Process is required to remove about 90% of contaminants such as N,S,O and metals from liquid petroleum fractions. This process is in use before the catalytic reforming process as well catalytic cracking process. Catalytic hydro treating involves: Catalytic Hydro desulfurization Solvent extraction, Dew axing, Sweetening processes

Catalytic Reformer
It is an process to improve the low octane naphtha to high octane gasoline blending components called reformates. Numerous reactions like Cracking, polymerization, dehydrogenation and isomerization are taking place depending upon the properties of naphtha feed stock. Hydrogen is a significant byproduct . Major processes are Plat forming, Power forming, ultraforming and thermofor catalytic reforming. Mainly platinum is used as a catalyst.

Isomerization
This process involves the rearrangement of HCs . It converts n-butane, n-pentane into their respective isoparaffins with high octane number. It is similar to catalytic reformer, but unlike catalytic reformer, Isomerization just converts normal paraffins to Isoparaffins as the Isoparaffins products have high octane number as compare to the normal paraffins. Catalyst : Aluminum chloride catalyst plus Hydrogen chloride for low temp processes Platinum and other metal catalyst

Polymerization
Process to convert the light olefin gases including ethylene, propylene and butylenes into HC of higher mol wt. and higher octane no and which can be further used as gasoline blending stocks. It combines two or more identical olefin molecule to form a single molecule. It can be accomplishes either thermally or in the presence of catalyst.

Hydro cracking
It is a two stage process combining: Catalytic Cracking and Hydrogenation Heavier feed stock is cracked in the presence of hydrogen . Process employs high pr, high temp, a catalyst and hydrogen. It is required for feed stock which is difficult to process either through Cracking or through reforming. Imp role of hydrogen is to reduce tar formation and prevent build up of coke on the catalyst. Hydrogenation converts the S and N to Hydrogen sulphides and Ammonia

TARGET SPECIFICATIONS FOR MS & HSD MS SPEC


SPECIFICATION TOTAL SULPHUR, WT% RON, Min. MON, Min. OLEFINS, VOL% (Max) AROMATICS, VOL% (Max) BENZENE, VOL% (Max) VAPOR PRESSURE, Kpa DENSITY @ 15C (Max) HSD SPEC SPECIFICATION TOTAL SULPHUR, WT% CETANE NUMBER, Min. DISTILLATION 85%V REC. AT 0C MAX 95%V REC. AT 0C MAX BIS-2000 0.1 87 No Spec No Spec No Spec 5 (3 FOR METROS) 35-60 700-750 EURO-II 0.05 95 85 5 35-100 725-780 EURO-III 0.015 95 85 18 42 1 35-100 725-780 EURO-IV 0.005 95 85 7 35 1 -

BIS-2000 0.25 / 0.05 48

EURO-II 0.05 49

EURO-III 0.035 51

EURO-IV 0.005 -

350 370

370

360

340

CRUDE & VACUUM DISTILLATION UNIT


FUEL GAS LPG (H2S = 250 ~ 2000 PPMW)

ATU ATU CAS WASH ISOM


(BENZENE < 0.1 wt%) (H2S = NIL) (RON = 70~80)

FG HEADER H2S<100ppm

LPG POOL
H2S = NIL

ATM.
CRUDE FEED

NAPHTHA (RON = 70-80)

NSU

MS POOL
RON = 87 ~ 91

BENSAT DISTILLATION UNIT


KERO MEROX S=0.015~0.3%wt GAS OIL (S=0.15~1.5%wt) (RON = 98~102)

CRU ALKYLATI ON

S = 0.1 % WT

(RON = 94)

SK POOL
(S < 50 PPMW)
S = 0.25 % WT S.P = 18 MM

DHDS HSD POOL


S=0.25~0.05% CN = 48

VACUUM RCO DISTILLATION UNIT

VGO

FCC HCU

VR

VBU DCU BBU FO POOL

FLUID CATALYTIC CRACKING UNIT


S T A C K (H2S = 50~100 ppmw) FG HEADER H2S<100ppm (SOX=2.5kg/t, SPM < 50)

FLUE GASES (SOX=3000~4000ppm, SPM = 250~450 mg/Nm3

FGD

FUEL GAS (H2S = 1~1.3 % WT)

ATU
(H2S = NIL)

LPG (S = 1.2% WT)

FLUID CATALYTIC
VGO FEED

ATU MEROX

LPG POOL
H2S = NIL

MS POOL
RON = 87 ~ 91

CRACKING UNIT

Cr. NAPHTHA (RON = 89~93, S=0.1~.3%wt)

SELECTIVE DESULPHURIS.

(RON=87~91) (S < 50 ppmw)

S = 0.1 % WT

CYCLE OIL

DHDS

(S < 50 ppmw, CN =27~30)

HSD POOL
S=0.25~0.05% CN = 48

(S=1.8~2.1% WT, CN =25~28)

CLARIFIED OIL (S=5~11% wt)

FO POOL
CAT= 0.2 WT%

HYDROCRACKER UNIT
FUEL GAS (H2S =1.8~12% WT

ATU

(H2S = 50~100 ppmw)

FG HEADER H2S<100ppm

LPG (H2S =150~1000ppmw)

ATU CAUSTIC WASH

LPG POOL
H2S = NIL

HC NAPHTHA ( S< 5ppmw, RON =77)

HYDRO
HC KERO / ATF (S.P = 25~27mm, S < 5ppmw) VGO FEED

NAPHTHA POOL SK / ATF POOL

CRACKING UNIT
HC DIESEL (S < 5 ppmw, CN =58~65)

HSD POOL
S=0.25~0.05% CN = 48

UNCONVERTED OIL (S < 10 ppmw)

FO POOL / FCC

DELAYED COKER UNIT

FUEL GAS (H2S =1.5% WT

ATU

(H2S = 50~100 ppmw)

FG HEADER H2S<100ppm

LPG (H2S = 0.6 ~ 2 % WT)

ATU MEROX CAUSTIC WASH

LPG POOL
H2S = NIL

COKER NAPHTHA (S= 1.5~2.5%WT)

DELAYED
COKER DIESEL (S = 2~3%WT, CN = 43) RCO / VR FEED

NAPHTHA POOL HSD POOL


S=0.25~0.05w% CN = 48

COKER UNIT
Hv COKER GO (S=3.5~5%WT)

HCU DHDS

HCU FO POOL

COKE (S =5~7% WT)

ANODE / FUEL GRADE

TYPICAL PROCESSING SCHEME FOR MS UPGRADATION

HDS / ISOMERISATION
SR NAPHTHA

SPLITTER BENZENE SATURATION SPLITTER

COKER / VB NAPHTHA

HDS CCR REFORMER EXTR. MEROX

GASOLINE

FC GASOLINE

SPLITTER

SELECTIVE HDS

TYPICAL PROCESSING SCHEME FOR HSD UPGRADATION

SRGO CDU VDU VGO

DHDS

HCU

DIESEL

FCC VBGO VBU

TCO

DHDT

DCU

CGO

SDU

DAO

RDS

RFCC