Presentation On
CRUDE OIL CHARACTERISTIC CHARACTERISTICS S AND REFINERY PRODUCTS By
U.Venkata Ramana, DGM (Technical) Refinery HQ, IOCL, New Delhi
Industry –Academia Workshop On “Refining & Petrochemicals” 25th–28 AUG 2010
P et etrroleum oleum/C /Crrude oil • It is Nat Natu ure’ e’s s gift gift to man man-kin -kind d. • “Crude Oil” means all kinds kinds of hydr hydrocarbon ocarbons s in liquid liquid form in their natural state or obtained by Natural Gas by condensation or extraction. It is a hydrocarbon
mixture having simple to most complex structures such as resins, asphaltenes etc.
• Cru rud de oil is for form med by bact bacter erial ial tran trans sfor form mat ation ion 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
Chemical Composition • Carbon • Hydrogen • Sulphur • Nitrogen • Oxygen • Metals
83.0 to 87.0% 10.0 to 14.0 % 0.05 to 6.0 % 0.1 to 2.0 % 0.05 to 1.5 % 0.00 to 0.14 %
The majority of crude oil is alkanes, alkanes, cycloalkanes cycloalkanes (naphthenes), (naphthenes), aromatics, polycyclic aromatics, S-containing compounds, etc. Gasoline: branched alkanes Diesel: linear alkanes
Sulphur Compounds Thiols Sulphides Cyclic sulphides Disulphides Thiophenes Benzothiophenes Dibenzothiophenes Naphthobenzothiophenes
Effect of sulphur compounds • Great environmental concern, contribute to
particulate matter, emission of obnoxious odoured sulphur oxide gases
• Receding
products
sulphur level in all petroleum
• Refining & Technology Focus shifted to
sulphur removal from hydrocarbons
Oxygen compounds • 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
Nitrogen Compounds Non-basic Pyrrole Indole Carbozole Benzocarbozole
Basic Pyridine Quinoline Indoline Benzoquinoline
Effect: Catalysts poison & Nitrogen oxide emission
Metals • Present as inorganic salts & organic
porphy porp hyri rins ns ( Ni, Ni, V, V, Mg et etc. c.)) in in ppm ppm • Salts mostly removed in desalting operation • Ni & V porphyrins are catalyst poisons
Crude Oil Characterization • TRA RAD DING : Density, API Gravity • TRA RAN NSP SPO ORT RTA ATION: RVP VP,, Po P our P oint, KV, KV, Wax content • CON CONTA TAM MINATI TIO ON : Salt content, BS&W • P RO ROCESSA CESSAB BILITY : Sulfur, Nitrogen, TAN, Asphaltene, MCR • CRA CRACK CKIING P OINT : ASTM Distillation • LPG PO P OTEN ENT TIAL : Light hydrocarbons (GC) • CL CLA ASSI SSIFI FICA CAT TION : Characterization factor
Classification of Crude Oil API Gravity AP I =(14 (141.5/s 1.5/sp.grav p.gravit ity y))-13 131.5 1.5 • Light Cr Cru ude Oil >31 • Mixed Based 22-31 • Heavy crude <22 API is a major factor for Crude pricing
API & Sulphur 50 40
Light Petroelum
I P 30 A . g e 20 D
Heavy oils and residua
10 0 0
1
2
3
4
5.0
API & Nitrogen 50 40
Light Petroelum
I P 30 A . g e 20 D
Heavy oils and residua
10 0 0.0
0.2
0.4
0.6
Wt. % Nitrogen
0.8
1.0
API & Asphaltene 50 40
Light Petroelum
I P 30 A . g e 20 D
Heavy oils and residua
10 0 0
1
2
3
Wt. % Asphaltene
4
5.0
Typ Ty pes of Crudes BITUMINOUS
NON-BITUMINOUS
Lube bearing Basrah Light Arab mix
High sulphur Arab medium Kuwait
Non-lube bearing
Low sulphur
Suez Mix Dubai
Qua I boe Miri light
Hydrocarb ocarbon on Clas Class sif ificat ication ion • P ARAFF RAFFIINIC BAS E WAX AXY Y , LE LES S S ASP ASPH HALTI ALTIC, C, LOW S ULP ULPH HUR, HIGH HI GH P OUR
• NAP HTH THEN ENIIC BA BAS E NAP HTH NAP THE E NI NIC C BAS BAS E STOCKS S TOCKS,, LE LES S S WAX, WAX, LESS LES S ASP ASPH HAL ALTIC, TIC, LOW P OU OUR R
• ASP SPH HALTIC BA BASE HIGH SULPH HIGH SULP HUR, NITROGE NITROGEN, N, S UITA UITABLE BLE F OR BAS BA S E OILS
Hydrocarbon Classification UOP Characterization factor K UOP UOP : Cube root of average boiling point(R) divided by specific gravity • P araffinic : >12.1 • Mixed based : 12.1 - 11.5 • Naphthenic :<11.5
Typ Ty pes of Crudes-Imported • Low S ulphur Crudes • Hig High h su sulf lfu ur Crudes – Lube & Bit itu umen prod odu ucin cing g • S ui uittab able le for Lub ube e prod producin ucing g refin refineri eries. es.
– Non Lu Lube Pr P rod odu ucin cing g & Bit Bitu umen P rod odu ucin cing g • S uit uitable able dur during ing Non Monsoon Monsoon period periods s when when Bitum Bitumen en demand takes place
– Non Lube / Non Bit Bitu umin inou ous s • S uit uitable able during during Mo Monso nsoon on period period when when Bit itum umen en produ product ction ion is not required.
• Crude oils oils for Blen lend din ing g at Mun Mund dra-H a-Heav eavy y, High acidic etc (LS or HS)
World Crude Oil Quality Properties of Crude Oil
19 85
1990
19 95
2001 2 010 (Proj)
‘S ’ in cr cru ude 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
19.4
19.8
20.2
21.3
3.26
3.61
3.91
4.0
Residue in crude (vol%) 19 ‘S ’ in cr cru ude oil residu esidue e (wt%)
3.07
Crude Oil Assay ¾ 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 resid
¾ Typically,
the data contained in a crude assay includes yields generated from the physical distillation & Distillate/resid properties
Crude Oil Evaluation Scheme TBP Distillation
Naphtha C5-140C
Kero 140-240C
Gas oil 240-370C
Atm.Resid 370C+
Vac Gas Oi Oil 370-540/600C
SR 540-600C+
ALL TESTS ARE CONDUCTED AS PER STANDARD TEST METHODS : ASTM/IP/IS
Combined TBP curves of Basrah Light Crude oil 100.0 90.0 80.0 70.0
d l 60.0 e i Y 50.0 % 40.0
vol% wt%
30.0 20.0 10.0 0.0 0
100
200
300
400 o
Temperature, C
500
600
Properties of Crude oil Characteristics
Basrah Light
Bombay High
Arab mix
Kuwait
North Gujarat
Density, gm/ml API gravity o Pour point, C Kinematic Viscosity o @40 C o @50 C Water content, %wt Salt content, ptb Sulphur, %wt TAN, mgKOH/gm CCR, %wt Wax, %wt Asphaltene, Asph altene, %wt ASTMDistillation cracking o point, C Metal content, ppm Nickel/vanadium
0.8745 30.3 -30
0.8200 41.0 21
0.8664 31.6 -24
0.8741 30.3 -27
0.8932 26.8 27
nil 10 3.1 5.9 1.2 2.6
3.4 nil 0.09 0.1 1.1 12.7 0.25
10.0 8.9 nil L20 2.7 0.14 6.4 2.5 2.3
11.1 8.5 nil 2.0 2.8 0.14 5.4 6.0 2.5
65.6 31.4 4.1 200 0.08 1.93 2.5 5.9 0.05
339
372
322
335
367
-
-
4/23
4/33
61/L10
Laboratory Distillation • ASTM D86 • ASTM D1160 • TBP Distillation – ASTM D2892 • High vacuum Distillation, ASTM D5236 • Simulated Distillations based on gas
chromatography principle
Tes Te st methods- Density • Density Density is de defin fined ed as the the mas mass s pe perr uni unitt volu olum me of a substan ance. ce. (Units (Units:g :g/m /mL L or g/cm3 or kg/m3). Density is temperature-dependent. • Den Densit sity y is measu measurred usin ing g an Ant Anton on P ar arrr DMA 48/Kyoto digital density meter, and following ASTM met ethod hod D 5002 5002 - Densit Density y and R elat elativ ive e Dens Densit ity y of Crude Oils by Digital Density Analyzer (ASTM, 1996a). • Densit Density y of cru crude de oils : 0.83 0.83 to 0.90 0.90 g/ g/m ml. Densities Densities can be measured to 0.0001 g/ml with a repeatability of "0.0005 g/ml.
API Gravity API Gravity AP I =(14 (141.5/s 1.5/sp.grav p.gravit ity y))-13 131.5 1.5 • Light Cr Cru ude Oil >31 • Mixed Based 22-31 • Heavy crude <22
API is a major factor for Crude pricing
BS&W • Base sed sedim imen entts an and d Water Water det eter erm min ined ed by Kar arll Fischer F ischer titration using a Met Rohm 701 KF Automatic Titrator (ASTM D 4377) or by Distillation method, ASTM D4006 • Oils wit ith h sign ignificant ificant wat ater er cont content ents s, (>5%), do not represent the properties of the "dry" oil. • F or 0.1% .1%v vol chan chang ge, th the cost im imp plicat lication ion F or 10 MMT purchase purchase at ~$60 $60/barrel /barrel US$420/MT x (0.1/100)x10 MMT ~US$4.20 million
F lash P oint The ere ¾ Th
are se sev veral ASTM methods for me measu surring fl flash points. The minimum flash point that can be determined by met ethod hod D93/I D93/IP P 34 is 10oC. Method D 56 is intended for liquids with a viscosity less than 9.5 cSt at 25oC. The The flash points and fire points of lubricating oils can be determ det ermined ined by by AS TM met ethod hod D 92/IP 92/IP 36
¾
Many fresh crude oils have flash points below 10oC and/or viscosities above 9.5 cSt at 25oC
P our P oint ¾
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.
¾
ASTM metho ASTM method d D 97 97 - Sta Standa ndard rd Tes Testt Metho Method d for for Pour Point of Petroleum Oils (ASTM, 1996a) for pour point determinations.
¾
Heavy & waxy oil transportation is a challenge
Viscosity The ere ¾ Th
are se sev veral ASTM Sta Standard Methods fo for measu surring the viscosity of oils. Of these, only methods D 445 Standard Test Method for Kinematic Viscosity of Tra Tr ansp spa arent and Op Opa aque Li Liq quids (the Ca Callculation of Dynam Dy namic ic Vis Viscos cosit ity y) and and D 4486 4486 - S tand andard ard Test Met Method hod for Kinematic Viscosity of Volatile and Reactive Liquids, will yield absolute viscosity measurements (ASTM, 1996a). ¾ Both of these methods 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 (viscosity independent of the rate of shear).
Flow curve of waxy crude at different temperatures 300
60 D eg C 40 D eg C
50 Deg C 35 Deg C
45 Deg C
250 ) a P ( s s e r t S r a e h S
200
150
100
50
0 0
100
200
300 -1
Shear R ate ate (s )
400
500
Factors Effecting the Selection of Crude oil Choice of crude oil for a refinery depends on:
P rodu roduct ct mix mix P rodu roduct ct qu quality ality Refinery configuration P roduct treat treatm ment facilit facilities ies R efi efine nery ry de des sign spe pecc- Met Metallu allurg rgy y, de des salt alter er etc etc Environment stipulation for pollution control P ipelin ipeline e design design for for inland refin refineries eries
•P roper crud crude e selec selecttion is neces necess sary for opt optim imis isat ation ion of refinery margin.
Refinery Constraints • Ref efin iner ery y Con Conffig igu urat atio ion n • Ref efin iner ery y met etallu allurrgy • Catalyst • Do Dow wn-s n-sttream treat reatm ment facil facilit ities ies • P ip ipeli elin ne design design con cons strain aintts
Opportunity • Hi Hig gh S crude oil • Hig High h Aci cid d cr cru ude oil oils s • Beat the mark market et by pr proper oper selec electtion of crude • Overcom ercome e refiner refinery y de des sign cons consttrain raintts to widen crude basket • Crude Blen Blendin ing g F ac acil ilit ity y
MAJ OR THRUST THRUST BY BY OIL REF RE F INE RY 1 Optim timis ise e crude mix 2 Wi Wid dening cr cru ude bask ske et 3 Ocea ean n freig eigh ht red edu uction 4 De Dem murrag age e con ontr trol ol 5 In Inv ven entor tory y con ontr trol ol 6 Oc Oce ean Los oss s reduction 7 Reduce F&L
: Hig High h or Low sulf lfu ur : Incr cre ease sed d No. of of cr cru udes : Hig High her Car arg go siz ize e : Minim inimis ise e tan tanker ker waiting : Min pos oss sible inven entor tory y : P rop ope er con onttrols : P roper design,operation
Gross product Worth of crude Oil API S, wt%
Price, /MT
32.4
32.6
32.7
0.079
0.081
0.13
Yield, wt fraction
GPW GP W
Miri
Widuri
Cabinda
Miri
Widuri
Cabinda
LP G
220
0.9%
0.1%
1.5%
2.0
0.2
3.3
Naphtha
289
6.4%
1.5%
5.0%
18.5
4.3
14.5
MS
298
8.0%
1.6%
5.4%
23.8
4.8
16.1
Kero
290
21.5%
7.7%
13.0%
62.4
22.3
37.7
Gasoil
264
42.5%
51.2%
45.0%
112.2
135.2
118.8
F uel oil
166
12.7%
29.9%
22.1%
21.1
49.6
36.7
8.0%
8.0%
8.0%
100.0%
100.0%
100.0%
239.95
216.46
227.03
BPT
7.28
7.28
7.28
GPW, $/bbl
32.96
29.73
31.19
Freight
1.2
0.75
1
Crude Price (Calc for Netback-Zero)
31.8
29.0
30.2
Landed Price, $/bbl
30.51
Gross Margin,$/bbl
2.45
F uel & Loss
Total
E LE LEM ME NTS OF IMP IMP ORTE ORTED D CRUD UDE E COST COS CO ST ELEM EL EMENT ENT
%
1 FOB
90%
2 OCEA N FREI GHT
3.9%
3 DA UGHTER V ESSEL FREI GHT
0.8%
4 INSURANCE
0.05%
5 OCEA N L OSS
0.2%
6 PORT CHA RGES
0.08%
7 CUSTOM DUTY
5.0%
8 DEMURRA GE
0.002%
9 ENTRY TA X
0.09%
TOTA TO TAL L
100.0%
Gross product Worth of crude Oil API S, wt%
Price, /MT
32.4
32.6
32.7
0.079
0.081
0.13
Yield, wt fraction
GPW GP W
Miri
Widuri
Cabinda
Miri
Widuri
Cabinda
LP G
220
0.9%
0.1%
1.5%
2.0
0.2
3.3
Naphtha
289
6.4%
1.5%
5.0%
18.5
4.3
14.5
MS
298
8.0%
1.6%
5.4%
23.8
4.8
16.1
Kero
290
21.5%
7.7%
13.0%
62.4
22.3
37.7
Gasoil
264
42.5%
51.2%
45.0%
112.2
135.2
118.8
F uel oil
166
12.7%
29.9%
22.1%
21.1
49.6
36.7
8.0%
8.0%
8.0%
100.0%
100.0%
100.0%
239.95
216.46
227.03
BPT
7.28
7.28
7.28
GPW, $/bbl
32.96
29.73
31.19
Freight
1.2
0.75
1
Crude Price (Calc for Netback-Zero)
31.8
29.0
30.2
Landed Price, $/bbl
30.51
Gross Margin,$/bbl
2.45
F uel & Loss
Total
Refining
39
Yield Structure of Various Crudes
40
TYPICAL REFINERY CONFIGURATION (MATHURA REFINERY) FUEL GAS SRU ARU SR LPG MEROX
CRUDE
SULPHUR
LPG PROPYLENE
PRU
STABILISER
NSU
C CCRU
D U
NAPTHA CAUSTIC WASH
GASOLINE MEROX
NAPTHA
MS
GCU
DHDT SK/ ATF MEROX
O H C U
ATF SK
HSD FCCU
VDU
LPG MEROX
VBU
LDO VBN MEROX
FO
BBU
BITUMEN RFO
Oil Products & Cut Points
42
Products • • • • • • • • • •
LP G Naphtha P etrol (BSBS-III/ I/BSI BSIII II)) Kerosene ATF Diesel (BS(BS-II II//BSBS-II III) I) LOBS Bitumen RP C Wax
•Fuel Oi Oill (H (Hiigh S, Lo L ow S) •Fuel Oi Oill (H (Hiigh or lo low V iscosity) •L SH SHS S •HPS
•Petrochemical feed stock •L A BF BFS S •HPL Naphth tha a
•Petrochemicals •pX, PTA •L AB etc
Yiield P attern of Crude Oi Y Oills Yield, Yie ld, %wt LPG LPG Naphtha Kerosene Gas oil VGO VG O Short resid
Basrah Basra h Light 1.0 12.0 15.0 20.0 36.0 16.0
Bombay Arab mix Kuw Kuwait ait North Jodhpur High Gujarat crude 1.0 1.0 2.0 1.0 21.0 12.0 15.0 5.0 1.0 20.0 16.0 18.0 10.0 13.0 27.0 20.0 17.0 21.0 24.0 27.0 29.0 25.0 33.0 21.0 4.0 22.0 23.0 30.0 41.0
P roper opertties of Nap Naph htha Characteristics
Basrah Bombay Light High
Density, gm/ml Sulphur, ppm RSH, ppm Octane number Aromatics, %wt
0.6912 175 33 9.5
0.7378 L0.01 nil 68.1 25.8
Arab mix
Kuwait
North Gujarat
MS Spec
0.6493 0.6958 0.06 L0.02 117 4.8 53.9 47.4 4.3
0.7407 L0.01 1 56.8 -
0.005 95 35
Gasoline Specification Euro I Euro II Euro I II Euro IV RON
95
95
95
95
Sulphur, Wt%
0.05
0.05
0.015
0.005
Benzene %wt
5
5
1
1
A romatics %wt
-
-
42
35
Olefins,Wt%
-
-
18
-
Properties of Kero / ATF Characteristics Basrah Of SK/ATF from Lt.. Lt the Crude:
MH
Arab mix
Density, gm/ml
0.783
0.7918
0.7902 0.787 0.7975
-
S moke, mm
29
21
27
27
28
18
S ulphur, %wt
0.18
0.02
1.3
0.16
0.13
RS H, ppm
30
nil
8.8
12.9
1
<30
H2S , ppm
nil
nil
nil
3.9
nil
nil
Freezing, C
<-60
-54
-59
-53
-47
-47
Aromatics, %wt
18.1
27.7
20.6
20
9.2
20
o
KE C
NG
ATF Spec
Properties of Gas oil Characteristics
Basrah Mumbai Light High
Arab mix
Density, gm/ml
0.8549
0.852 0.85 0.847
-6/18
o
KE C NG
P our point point,, C
-15
6
-18
-6
S ulphur, %wt
2.05
0.13
1.7
1.51 0.05
0.005
Cetane No.
48.8
59.5
54.9
56.8 60.6
53
Distillation , T95, C
-
3
Diesel Spec
340
Diesel Specification Euro I
Euro I I
Euro I I I
EuroI V
Cetane Number
49
49
51
53
Sulphur,Wt%
0.2
0.05
0.035
0.005
370
370
360
340
o
Dis Di stillation T-95, C
LOBS AP I cl cla ass ssiification CLAS S
COMP OS ITION
SULPHUR % WT.
VISCOSITY INDEX
Group-I
<90% Saturates
>0.03
95-120
Group-I I
>90% Saturates
<0.03
95-120
Group-I I I
>90% Saturates
<0.03
>120
Group-I V
Poly alp lph ha ole lefin fin
Group-V
Others
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