2016-09-29

1

CBE4016 CBE4016

1

2

3

CBE4016

1. Introduction

l Refining Industry (, Chapter 2)

l Petrochemical Industry (, Chapter 3)

(Petroleum Industry)

CBE4016

1. Introductionl Refining Industry (, ):

v Refinery products : gasoline, , , , grease, asphalt, , , ,

v Process (straight-run distillation) (conversion): cracking, reforming and others (purification) (formulation) others: alkylation, dehydration, isomerization,

polymerization, hydrotreating, coking, etc.

2016-09-29

2

CBE4016

1. Introductionl Petrochemical industry

,

v , , () , , , , , ,

() , , ()

v Process Manufacture of base chemicals by naphtha cracking Conversion into main product groups Processing of finished products

CBE4016

CBE4016

5

1 2 3 4 5

2011

2012

2013

M$

CBE4016

2016-09-29

3

CBE4016

CBE4016

1. Introduction

1)

: hydrocarbon (H: 10~14%, C:79~88%)*

Oxygen compounds (0~3%):

in naphthenic acid, alkyl acid, phenolic acidNitrogen (0.1~0.7%): found in naphthenic acid,

in the form of basic compounds (alkyl quinoline)Sulfur (0.1~5%): present in crude oil or produced during refining; free S, H-S-H, organic compounds

foul smell, , , Trace amount (ppm) of metal-organic compounds

1.

CBE4016

Organosulfur Compounds

CBE4016

1. Introduction

2)

) Hydrocarbon (HC) series:

CnH2n+2, CnH2n, CnH2n-2, CnH2n-4, CnH2n-6, CnH2n-8, CnH2n-10, CnH2n-14, CnH2n-20, etc.

2016-09-29

4

CBE4016

Structural Formulae of HC Series (C6)

H C C

H

H

H

H

C C

H

H

C C

H

H

H

H

H

H

H

H C C

H

H

H

H

C C

H

H

C C

H

H

H

H

H

H

H HH

H

H

H

H H

H

H

H

H

H

H

H

H

H

H

C C

H

H

H

C C

H

H

C C

H

H

H H

H

H C C

H

H

H

H

C C

H

H

C

H

H

H

H

CH

H

HH C

H

H

C C

H

H

C

H

H

H

CH

H

H

CH H

H

(a) Normal Hexane, C6H14 (b) Normal Hexene, C6H12

(c) Cyclohexane, C6H14 (d) Benzene, C6H6

(e) Hexadiene-1, 5, C6H10

(d) 2 Methylpenthane, C6H14 (f) 2-2 Dimethylbutane, C6H14

Isomeric IsoparaffinCompounds

CBE4016

1. Introduction) Hydrocarbon (HC) series:

Paraffin series (CnH2n+2) physical state b.p: normal > iso- > neo-

Olefin series (CnH2n) direct reaction with Cl, Br, HCl, H2SO4 recovered by H2SO4 (dissolution) low bp olefin: not present in crude oil by thermal

cracking

Naphthenic series (CnH2n) ring or cyclic compounds aromatic olefin

CBE4016

1. Introduction Aromatic series (CnH2n-6) or benzene series (Bz)

: susceptible to oxidation organic acid (high b.p) ENPLA

Diolefin series (CnH2n-2) : extremely active polymerize, combine with unsaturated compounds

higher MW

Cyclic series (CnH2n-2, (CnH2n-4 ) Not well known

CBE4016

1. Introduction) Sulfur compounds - Structural formulae

H S HH S R

H S CH3H S C6H5

R S RH3C S CH3C4H9 S C4H9

S S RRS S CH3H3C

S

CH2

CH2 n

R O

S

OR O

O

R

S

OH O

O

R S R

O

R S

O

O

R

C

S

C

C C

HH

H H

Hydrogen sulfideMercaptans:

Methyl

Benzyl

Sulfides:Methyl

n-Butyl

Cyclic sulfide:

Alkyl sulfide

Sulfonic acid

Sulfoxides

Sulfones

Thiophene

Disulfides:Methyl

2016-09-29

5

CBE4016

1. Introductionv Problems:

Corrosion of metals by H-S-H, free S, some of lowest bp sulfides, disulfides, mercaptans

Pollution: rxn with O2 SO2 acid rain

Obnoxious odor: with low b.p or gaseous sulfur compounds such as H-S-H, SO2 in flue gas, mercaptanup to 6 carbon atoms, sulfides up to 8 carbon atoms, methyl disulfides

Poor explosion characteristics of gasoline fuel

removed by sweetening treatment or alkalies

CBE4016

1. Introduction

1) /: (~ ) (low bp sat. HC, aromatics) (N-, S-compounds, HC)

(vs. high bp HC)

2) : 0.65 ~ 0.95 (refers to 60 oF = 15 oC)aromatics > naphthene > paraffinl specific gravity ()

l API gravity ()

l characterization factor

2.

CBE4016

1. Introduction3) ()

- its resistance to internal flow or indication of oilness in the lubrication / :

l relative viscosity (): numerically equal to viscosity in cp

l kinematic viscosity, l fluidity: reciprocal of viscosity

l viscosity index (VI): Pennsylvania crude oil (H): VI = 100 Gulf coast crude oil (L): VI = 0

the higher, the better 100VI --

=HLUL

CBE4016

1. Introduction

4) (specific heat, cal/g oC): 0.3 ~ 0.5 @ 25 oC (0.3 ~ 0.5) H

5) (heat of vaporization/mole- or g-basis) 70 ~90 cal/g (less than H2O, alcohol) HC () g

u , Q (calorific value): 9,500~12,000 kcal/kg (> coal)( g )

v TOE: ton of oil equivalent, 1 107kcal

2016-09-29

6

CBE4016

1

2

3

CBE4016

kcal MJ

kg 10,750 45.0 1.075 8,000 33.5 0.800

8,800 36.8 0.880B-C 9,900 41.4 0.990 kg 12,050 50.4 1.205 kg 11.850 49.6 1.185

(LNG) kg 13,000 54.5 1.300(LNG) Nm3 10,550 44.2 1.055(LPG) Nm3 15,000 62.8 1.500

kg 4,650 19.5 0.456 kg 6,550 27.4 0.655

() kg 6,200 26.0 0.620

kWh 2,150 9.0 0.215 kg 4,500 18.8 0.450

CBE4016

One pound of hydrogen holds 52,000 Btu, three times the energy of a pound of gasoline

CBE4016

Transition to Hydrogen Economy

2016-09-29

7

CBE4016

1. Introduction

6) Cloud point & Pour point- useful in estimation of relative amount of wax cloud point (): solid point: 5

(heat to 115 oF and then cooled to 90 oF, DT = 5 oF) pour point (): cold filter plugging point:

v flow improver: poly(isobutene), poly(methacrylic ester), poly(alkyl styrene)

CBE4016

1. Introduction7)

8) Smoke point: (in mm)

9) (distillate) eg. 10%

95% boiling point (LPG)

* (distillate, cut, fraction)

CBE4016

1. Introduction

1) l 1870. () Ohio Standard Oil

(10 )l 1882. :

Standard Petroleum Trust ( )l 1885. Benz: /Ford:

l 1890. : Royal Dutch Petroleum ()l 1898. Diesel engine l 1907. Shell Royal Dutch Shell l 1903. Wright: Application of gasoline engine to air plane

*

3.

CBE4016

1. Introduction

l 1908. DArcy (): Anglo Persian Petroleum ( ) British Petroleum (BP)

l 1909. Standard Oil: * l 1911. Anti-Trust law ( ):

Standard Petroleum Trust 34 NJ Standard Exxon Indiana Mobil Ohio Sohio Atlantic, Continental, etc.

l 1913. / l 1914~1918. 1

2016-09-29

8

CBE4016

1. Introduction

l 1920. San Remo ( ) (Turkey )

l 1928. (Anglo Persian, Royal Dutch Shell, NJ Standard) Major

Major: (50s ~ 1973)(, , , )

7 Sisters: Exxon, Mobil, Texaco, GulfChevron, Shell, BP

8 Sisters: + CFP Independent /OPEC

(1960 )

CBE4016

1. Introduction

l 1960. 9 OPEC (S.A, Kuwait, Iran, Iraq, Venezuela) 11 (97)

l 1973. 1st oil shock ( 4 ), OPEC (, , ) Major ( )

(2.5 11.25 $/9)l 1979. 2nd oil shock ( ) (12.95 32 $/10)l 1980 - l 1990. Gulf war (17 41 $/3)l 1992. 17 $/bbl

CBE4016

1. Introduction

l 2004. l 2005. 3rd oil shock ? (28 32 >60 $)

OPEC (, 8/30: 80 $ ?)

l 2008. 3 ~ 100 $ (WTI) : Another Oil Shock ?l 2008. 10 ~ 70 $l 2009. 9 ~ 70 $/bbll 2001. 9. 11 100$ l 2012. 9 ~ 91 (WTI) ~ 108 (Brent) $/bbl

CBE4016

2016-09-29

9

CBE4016

3.0

,

(: 110$ (7) 85$ (14) 76$ ??)

CBE4016

3.0

(IEA: - 22%)

-

(: 9240 bpd; 20 bpd )

- , /

- 70 (IEA)

, -

- , , , ()

- OPEC

CBE4016

3rd

4th

CBE4016

2015

40$

2015 8 16

49$

08-14

42.5$

2016-09-29

10

CBE4016

(500 bbl/d to 850 bbl/d: 70% )

OPEC

()

CBE4016

41.87$ (817) 6 ( 2009.03) " 30 : 15 ,

CBE4016

,

: - 90% , ()

- :

( 10% 0.02%P)

- ( 20%) : - - () :

CBE4016

I

2016-09-29

11

CBE4016

II

,

CBE4016

,

,

10 ~ 20$ ??

CBE4016

3. :

CBE4016

2016-09-29

12

CBE4016

70()

80()

80 ~90

()

90

( )

00 ~()

()

()

()

M&A

Capa()

155/(1)

505/(2)

4,330/(8)

5,700/(7)

8,500/(15)/(6)

GDP()

2.9(28.0%)

1.4(12.0%)

1.3(10.0%)

1.0(3.0%)

IT,BT,NT

/('86)

( )

) -

( )

()

*Restructuring, M&A*/

Mega competition

*/ * *

CBE4016

07/13

B/D

CBE4016

2013

CBE4016

2016-09-29

13

CBE4016

(103 bbl)

(103 bbl)

1986 219,667 209,729 17,477 575 4.3 790 72.7

1990 308,368 307,281 25,607 842 3.6 840 100.2

1994 573,714 560,866 46,739 1,537 3.1 1,700 90.4

1995 624,945 631,078 52,590 1,729 12.5 1,818 95.1

1996 721,927 720,846 60,071 1,970 13.9 2,438 80.8

1997 873,415 871,974 72,665 2,389 21.3 2,438 98.0

2000 893,943 890,304 74,192 2,433 1.7 2,438 99.8

2001 859,367 860,115 71,676 2,356 -3.1 2,438 96.7

2002 790,992 786,805 65,567 2,156 -8.5 2,438 88.4

2003 804,809 782,951 65,246 2,145 -0.5 2,438 88.0

2004 825,790 826,551 68,879 2,258 5.3 2,438 92.6

2005 843,203 852,439 71,037 2,335 3.4 2,735 85.4

2006 888,794 878,395 73,200 2,407 3.0 2,808 85.7

2008 864,872 865,663 72,139 2,365 -2.1 2,875 82.3

2010 872,415 872,247 72,687 2,390 4.0 2,935 81.4

2011 927,044 924,441 77,037 2,533 6.0 3,039 83.3

2012 947,292 945,162 78,764 2,582 2.0 2,949 87.6

2013 915,075 906,674 75,556 2,484 -3.8 2,949 84.2

CBE4016

2(2008 1~12)

2008 370 $

CBE4016 CBE4016

2016-09-29

14

CBE4016

2015

(7 ~ 9 : 75$ )

1$

(9 : 7,279$)

CBE4016

CBE4016

(Jan. 2015)

CBE4016

2016-09-29

15

CBE4016

GDP

2.22%

1.59%

1.46%

1.31%

0.66%

?

CBE4016

1. Introduction

2) l 1960s (3)

/ ( ) (Major )

1962. (, ) + Gulf ( ) 35,000 bpd (1964) 810,000 bpd (2003, SK)

1965. () + Shell 50,000 bpd () (, 92) (93) 310,000 bpd (02)

1966. (, ) + Caltex LG 60,000 bpd (1969) 600,000 bpd (GS-Caltex)

1967. (1966)

CBE4016

1. Introduction

2) ()l 1970s (3~4 )

Major ( ) /

1972. (, ) + Indep. Union Oil 50,000 bpd

Oil bank (99) (275,000 bpd)

1972.10 1973. 1979.02

CBE4016

1. Introduction

2) ()l 1980s *

, (83~86) 1980. () + NIOC:

60,000 bbl 443,000 bbl (S-Oil)

l 1981.9 (1990s)l 1980s 3

/* (, )

l 1989 () 60,000 bpd

2016-09-29

16

CBE4016

1. Introduction

*

* : / /

CBE4016

1. Introduction

2) ()l 1990s , 1990~91. (90.08)

- NCC, PE/PP 1992~93.

- downsizing, reengineering 1992. () 60,000 bbl

- hydrocracking (7 $) 1993. : 1993.12 (3.14 *) 1994~95 : 1994. : Oil Bank (02)

(310,000 bbl)

CBE4016

1. Introduction

2) () 1990s . ,

:

,

CBE4016

1. Introduction

l2000s 100$ 2001 (9.11), 2002 (: 31.5 35)

: - > 60%,- ,

: - / ,

, () &

2009 ~70$ 2010 BP: Gulf oil spill (~ 80$)

2016-09-29

17

CBE4016

SK()

LG-Caltex( Group)

( Group)

S-Oil()

Oil Bank()

1962.10 1967.05 1968.09 1976.01 1965

1964.04 1969.06 1971.06 1980.05 1965.03

() (1989)

(BPDS)

2000 35 60 50 60 50

2003 810 600 275 443 310

2008 1.115 770 275 580 390

()

GULF

1980

Caltex

-

Union Oil

1983

ARAMCO

Shell

1977

39.1 28.7 10.4 12.5 5.8

CBE4016

SK()

LG-Caltex( Group)

( Group)

S-Oil()

Oil Bank()

1962.10 1967.05 1968.09 1976.01 1965

1964.04 1969.06 1971.06 1980.05 1965.03

() (1989)

(BPDS)

2000 35 60 50 60 50

2003 810 600 275 443 310

2008 1.115 770 0 580 390

()

GULF

1980

Caltex

-

Union Oil

1983

ARAMCO

Shell

1977

39.1 27.0 0 20.3 13.7

CBE4016

SK LG-Caltex S-Oil

1969 115 60 0 5 0 1801970 115 100 0 5 0 2201971 115 100 50 5 0 2701972 175 160 60 5 0 4001974 215 160 60 5 0 4401977 215 160 60 5 0 4401978 280 230 60 10 0 5801979 280 230 60 10 0 5801980 280 230 60 10 60 6401981 280 380 60 10 60 7901988 280 380 60 10 60 7901989 280 380 60 60 60 8401990 280 380 60 60 60 8401991 375 380 60 60 160 1,0351992 585 380 275 110 325 1,6751993 585 380 275 110 325 1,6751994 610 380 275 110 325 1,7001995 610 380 275 110 443 1,8181996 810 600 275 310 443 2,4381997 810 600 275 310 443 2,4381998 810 600 275 310 443 2,4381999 810 600 275 310 443 2,4382000 810 600 275 310 443 2,4382003 810 600 275 310 443 2,4382004 840 650 275 390 580 2,7352005 840 650 275 390 580 2,7352006 840 687 275 390 580 2,7722007 840 727 275 390 580 2,8122008 1,115 770 0 390 580 2,855

( : BPSD)

CBE4016

4

2016-09-29

18

CBE4016

1. Introduction

1) + (< 50 years) (uncertainty): / (volatility)

4.

CBE4016

CBE4016

: 1.2 bbl CBE4016

OPEC (2014)

2,634

~ 3,300

tb/d = 103 b/d

2016-09-29

19

CBE4016

non-OPEC liquids supply

CBE4016

Medium-term liquids supply outlook

MB/D

CBE4016

World Oil Demand and Supply

91.6

MB/D

CBE4016

Crude Oil Prices

2016-09-29

20

CBE4016

CBE4016

2015.08.14

: 49: 49 WTI: 42.5

CBE4016

World supply of primary energy

CBE4016

World supply of primary energy by fuel type

2016-09-29

21

CBE4016

Technically recoverable shale gas

CBE4016

1 MTOE

CBE4016

CBE4016

2) Major (~1973)

l ///

OPEC (1973 ~ 1980)l l Independent l OPEC l 1, 2 oil shock ,

OPEC: Organization of Petroleum Exporting Countries60.09 SA, , , , : UAE, , , , ,

(11, 96.6 )( 12, 14 )

2016-09-29

22

CBE4016

(spot market) l l l 1980

(Non-OPEC OPEC )

Paper : 1990 l 90.8 ( ) 41$/bbl l l (future), (forward) option l

CBE4016

()

Trader

Major term

Spot term

Spot

CBE4016

(spot market): ~ 40%l ( )

l 2 OPEC (, , )

l OPEC

l *

l (Physical Market):

CBE4016

(term-contract market)l l ,

l, , l :

2016-09-29

23

CBE4016

: , , ,

:

(, , , , , )

( )

CBE4016

WTI spot 50 5

Brent spot 40 10

(Oman+Dubai)/2

Arabian Light

l WTI: API 39.6, 0.24(% weight); light sweet crude, 70 bpd

l Brent: API 38.3, 0.37(% weight); light sour crude, 75 bpd

l Dubai: API 31.0, 2.04(% weight); 20 bpd

CBE4016

* Paper : (hedging/speculation )

(future market)l l / l (NYMEX, IPE, SIMEX)

XG.Oheating oil

gasoline

CBE4016

(forward market)

l l

l / l l :

2016-09-29

24

CBE4016

Option l () l (, holder), (, writer)l (premium)l l call or put option

CBE4016

:

l

l l

:l , , l

: WTI, Brent, Dubai

CBE4016

CBE4016

1. Introduction

1)

l C LPG, LNG, l

, (NON-OPEC: / )

2) l l l

4.

2016-09-29

25

CBE4016

1. Introduction

1) + paper market (30~40%) , spot (30~40%)

2) / () or NG gashol Fuel cell, solar cell green energy

3) // : = 75 : 25 ()

5.

CBE4016

4) () 1970 4 20 Africa, ,

CBE4016