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 . 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).

2 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 .. : 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.

3 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 . 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).

4 + CH2=CH-CH. =CH CH3. CH2-CH. CH2-CH. CH3. CBE4016. 2.. Chapter 2. Petroleum Refining - process thermal cracking ( ). 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. gas oil CBE4016. 2.. Chapter 2. Petroleum Refining 510 oC.

5 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*. 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).

6 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. 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.

7 ( 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 - , , . - 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%).

8 (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. 2. Petroleum Refining ON of HC. HC: ON . (1 pentene t 91;. 91 1 hexene h 76). HC: aromatics > naphthene > olefin > paraffin paraffin: ON . olefin: 2 ON . iso iso-paraffin paraffin > olefin > n n-paraffin paraffin naphthene and aromatics: ON.)

9 CBE4016. 2.. Chapter 2. 2. Petroleum Refining Process thermal reforming olefin . HC . olefin . catalytic reforming (1950 UOP). most widely used refinery reaction (1/4 of crude oil in USA). CBE4016. 2.. Chapter 2. 2. Petroleum Refining Reactions isomerization of paraffin to branched chain molecules (iso paraffin). CH 3. n-C 7 H 16 H 3 CCH 2CH 2 CCH 3. CH 3. dehydrocyclization of paraffin to cycloparaffin CH3 CH3. -3H2. n-C7H16 + H2. CH2CH3. n-C7H16 + H2. CBE4016. 2.. Chapter 2. 2. Petroleum Refining hydrocracking of paraffin to paraffin n-C9H20 + H2 n-C5H12 + n-C4H10. hydroisomerization of olefin to iso-paraffin CH3. Heptene-1 + H2 H3 CCH2CH2CH2 CHCH3. dehydrogenation of naphthenes to aromatics CH 3 CH 3. + 3H 2 (very rapid). CH3. + 3H2 (rapid). CBE4016. 2.. Chapter 2. 2. Petroleum Refining hydrodealkylation of cyclic hydrocarbons CH3 CH3. C2H5.

10 + H2 + C2H6. CH3 CH3. + 2. CH3. hydrodesulfurization of S-compounds + 4H2 C5H12 + H2S. S CH3. hydrodenitrogenation of N-compounds + 3H2 + H2 + H2. C5H11NH2 C5H12 + NH3. N N. H. CBE4016. 2.. Chapter 2. 2. Petroleum Refining Name Formula Structure Representative Heterocyclic Nitrogen Compounds P. Pyrrole l C4H5N N. H. Indole C8H7N. N. H. Carbazole C12H9N. N. H. Pyridine C5H5N. N. Quinoline C9H7N. N. Isoquinoline C9H7N N. Acridine C13H9N. N CBE4016. 2.. Chapter 2. 2. Petroleum Refining Variation of Sulfur Content of Kuwait Crude Oil Sulfur content, Fraction: boiling point range, ( ). wt%. Naphtha: C4-150 (300) Kerosene: 150. 150-230. 230 (300. (300-450). 450) 0 175. Furnace oil: 230-345 (450-650) Heavy furnace oil: 345-370 (650-700) Heavy gas oil: 350-550 (660-1020) Residue: >370 (700) Residue: >550 (1020) 5 12. CBE4016. 2.. Chapter 2. 2. Petroleum Refining Summaryy of Catalytic y Reforming g Dehydrocyclization Alkylcyclopentanes Isoparaffins Hydrogenolysis Isomerization (.)