1) Distillation 2) Conversion (전환 전화

1 2.. Chapter 2. Petroleum Refining 1) Distillation 2) Conversion ( , ). 3) Purification CBE4016. 2.. Chapter 2. Petroleum Refining 1) Distillation ( ).. (straight run process). (straight-run . ) (desalting). , emulsion . ( ) . ( ) - .. ( ) blocking CBE4016. 2.. Chapter 2. Petroleum Refining micelle: aggregation of surfactant (5~6 nm). CMC: micelle . <CMC >. Surface tension Conductivity C C. CMC C. Concentration i C CMC Concentration C. - : (alcohol, (alcohol ) emulsion . - : emulsion . - : 50 ~ 95%, > 15 g/1000 lit CBE4016. 2.. Chapter 2. Petroleum Refining ) (atmospheric P Distillation or topping). CBE4016. 2.. Chapter 2. Petroleum Refining pipe still: pipe.

2 Fractionator: (bubble tower, ). flash zone: . tray zone: 45 ~ 90cm trays ( / ). reflux: fl , . stripper: , . CBE4016. 2.. Chapter 2. Petroleum Refining ( ) . gases -161 ~ 1~4 LPG, refining fuel naphtha (cracking). 30 ~ 130 5~8. (light distillate) blending for gasoline (low ON). naphtha 80 ~ 170 7 ~ 12 catalytic reforming (ON 95). (light distillate). domestic fuel ( ). 150 ~ 280 9 ~ 19. (kerosine) , jet fuel, tractor fuel diesel fuel 230 ~ 350 14 ~ 23. (diesel or gas oil) central heating fuel fuel for power station, ship, large > 350 > 17. (residue) heating installation CBE4016. 2.. Chapter 2. Petroleum Refining (heavyy or fuel oil, heavyy distillate). asphalt.

3 : Bunker A / . Bunker B . Bunker C . B/C . ( boiler ). CBE4016. 2.. Chapter 2. Petroleum Refining ) (vacuum Distillation unit). - . - / . - : 30. 30~80. 80 mmHg - . vac. gas oil (VGO) LBO . vac. vac residue (VR) .. CBE4016. 2.. Chapter 2. Petroleum Refining . CBE4016. 2.. Chapter 2. Petroleum Refining ) Steam Distillation - .. - . - . - . ) Azeotropic Distillation ) E. Extractive t ti Distillation di till ti CBE4016. 2.. Chapter 2. Petroleum Refining 2) Conversion ( , ).. cracking . - gasoline (Standard Oil, 1912). - cracked gasoline, unsaturated HC . Reforming . R f i - high ON gasoline , aromatics .. Others - isomerization, coking, (de)alkylayion,(de)hydrogenation, hydrotreating.

4 CBE4016. 2.. Chapter 2. Petroleum Refining . Cracking - C5~C12 (gasoline range) . - Saturated HC unsaturated HC (recently). - branched chain and aromatics (high ON). CBE4016. 2.. Chapter 2. Petroleum Refining . Cracking ( ). - . cracking of paraffin paraffin + olefin R-CH. R CH2-CH. CH2-CH. CH2-R . R R. R-CH=CH. CH CH2 + CH3-R . R. (olefin) (paraffin). dehydrogenation y g of p paraffin R-CH2-CH2-R R-CH=CH-R + H2. isomerization of paraffin R-CH2-CH2-CH3 R-CH-CH3. |. CH3. CBE4016. 2.. Chapter 2. Petroleum Refining dealkylation of cycloparaffin (i the (in th case off naphthenic hth i HC). + CH2=CH-CH. =CH CH3. CH2-CH. CH2-CH. CH3. CBE4016. 2.. Chapter 2. Petroleum Refining - process thermal cracking ( ).)

5 Cracking under high P and T. high HC cracked gasolin (gas oil, oil residue). resid e) (lo ). (low b p). low ON, , . visbreaking gpprocess ((viscosityy breaking). g).. ( , P = 12 ~ 25 kg/cm2, T ~ 500 oC). AR, VR . ( ). CBE4016. 2.. Chapter 2. Petroleum Refining delayed coking process , , .. catalytic y cracking g ( >35% crude oil)). largest volume catalytic process high ON gasoline (gasoline ). Catalysts - 1936 ~ World War II: Houdry clay catalyst - 1950s ~ '60s: 60s: synthetic silica silica-alumina alumina (FB). - since then: riser catalytic unit (zeolite). high T & shorter contact time CBE4016. 2.. Chapter 2. Petroleum Refining Fluidized Catalytic Cracking Process H2 C4.

6 Gas oil CBE4016. 2.. Chapter 2. Petroleum Refining 510 oC. Riser Catalytic Cracking Unit 650 ~ 710 oC. CBE4016. 2.. Chapter 2. Petroleum Refining hydrocracking ( ). catalytic cracking + hydrogenation purpose: - hydrogenate y g coke p precursor on the catalyst y to minimize coke formation and long life of cat. - convert objectionable S-, N-, O- compounds to volatile H2S, NH3. and H2O. CBE4016. 2.. Chapter 2. Petroleum Refining process - 1930'. 1930's: (Germany (G / England). E l d). (P > 20 MPa uneconomic). - 1959: Standard Oil of California, dual function catalyst (versatility of process). - modern process: to process high g content of polycyclic y y aromatic compounds*.

7 For high ON gasoline (T = 200 ~ 400 oC, PH2 = 1 ~ 10 MPa). - vac. gas oil, deasphalted vac. residue, - heavy gas oil from coking, catalytic cycle oil CBE4016. 2.. Chapter 2. Petroleum Refining mechanism thermal cracking (free radical scission). C:C C + C . C:H C + H . - olefin ( ethylene). y . - diolefin . - gas (C1, C2) , . - : paraffin/olefin > naphthene > aromatics CBE4016. 2.. Chapter 2. Petroleum Refining ex)) thermal cracking g of n-decane ((C10). CBE4016. 2.. Chapter 2. Petroleum Refining catalytic cracking (ionic fission). C:C C+ + C:- C:H C+ + H:- - , . - C3 ~ C6 branched (iso-) paraffin - diolefin di l fi . - : olefin > paraffin ~ naphthene > aromatics CBE4016.

8 2.. Chapter 2. Petroleum Refining ex) catalytic cracking of n-decane (C10). stable CBE4016. 2.. Chapter 2. Petroleum Refining ex) isomerization by catalytic cracking 1) n-butane CBE4016. 2.. Chapter 2. Petroleum Refining 2) n-butylene in the presence of H+. CBE4016. 2.. Chapter 2. Petroleum Refining . Thermal Cracking Catalytic Cracking ethylene propylene Gas (C1, C2 ) (C4 paraffin, olefin). more p paraffin Main more olefin than olefin product than paraffin . ( C3 ~ C6).. / . Diolefin . CBE4016. 2.. Chapter 2. Petroleum Refining visbreaking process (viscosity breaking). - . ( , P = 12 ~ 25 kgf/cm2, T ~ 500 oC). - AR, VR . ( ). delayed coking process.

9 - cokes . - . CBE4016. (2009). Chapter 2. Petroleum Refining SK LG-Caltex S-Oil Oil Bank ( ) ( Group) ( Group) ( ) ( ). 1965.. (1989).. ( BPSD). 35 60 50 60 50. 2000 810 600 275 443 310.. GULF Caltex Union Oil ARAMCO Shell ( ) 1980 - 1983 1977. CBE4016. 2.. Chapter 2. Petroleum Refining CBE4016. 2.. Chapter 2. 2. Petroleum Refining . Reforming g gasoline range molecules are reconstructed or reformed without change g in their C numbers to improve p fuel q quality y (high ON ). principal source of aromatic chemicals (BTX). by dehydrogenation of both straight chain and cyclic aliphatics feed stock: a large quantity of straight chain paraffin (15 75% , ON < 50%).

10 (15~75%. and a small amount of branched chain paraffin, naphthene, olefin, and aromatics CBE4016. 2.. Chapter 2. 2. Petroleum Refining Octane Numbers (ON) of Pure Hydrocarbons Paraffins : n-Butane 113. n-Pentane 62. n-Hexane 19. n-Heptane 0. n-Octane 19. 2-Methylhexane 41. 2,2-Dimethylpentane 89. 2 2 3-Trimethylbutane 2,2,3 Trimethylbutane 113. Naphthenes (cycloparaffins) : Methylcyclopentane 107. 1,1-Dimethylcyclopentane 96. Cyclohexane 97. Methylcyclohexane 104. Ethylcyclohexane 43. Aromatics : Benzene 99. Toluene 124. 1,3-Dimethylbenzene 145. Isopropylbenzene 132. 1,3,5-Trimethylbenzene 171. Iso-octane (2,2,4-trimethyl pentane) 100 CBE4016. 2.. Chapter 2.)