1 CHM 585 / 490 Chapter 4

2 Benzene / Toluene / Xylene Terephthalic Acid Cumene Phenol / Acetone / Bisphenol A

3 BTX Benzene / Toluene / Xylene Predominantly ( about 90%) from oil From reformate gasoline and pyrolysis gasoline BTX Content –Reformate: 3/13/18 –Pyrolysis gasoline: 40/20/5

4 Reformate Gasoline Distillation of crude oil gives low octane fractions which must be “reformed” before using as gasoline. The fractions are mainly branched and unbranched alkanes and cycloalkanes Reforming involves heating at 500ºC with acidic isomerization catalysts (e.g. Al 2 O 3. SiO 2 ) and Pt followed by distillation

5 Pyrolysis gasoline From the cracking of naptha for the production of ethylene, propylene, and other olefins.

6 Isolation of Aromatics from Reformate and Pyrolysis Gas Problems with fractional distillation –Cyclohexane, n-heptane, and other alkanes form azeotropes with benzene and toluene –Minor difference between boiling points of the C8 components. e.g.: Ethylbenzene ºC p-xylene ºC m-xylene ºC o-xylene ºC Separation requires special processes

7 Separation Techniques Azeotropic distillation Extractive distillation Liquid-liquid extraction Crystallization Adsorption Let’s review azeotropes before continuing

8 Fractional Distillation Begin at a1 and heat to T 2. –a 2 is the liquid composition. –a 2 ’ is the vapor composition. –Vapor is richer in A than the liquid. Cool the vapor until condenses at T 3. –a 3 is the liquid composition. –a 3 ’ is the vapor composition. –Vapor is even richer in A Repeat until pure A is obtained.

9 Fractionating Column and Efficiency The number of theoretical plates is the number of effective vaporization and condensation steps required to achieve a condensation of given composition from a given distillate.

10 Azeotropes In some real systems, the temperature / composition curve is far from ideal. A maximum or minimum in the curve is possible; this is an azeotrope. At the azeotrope, the liquid and vapor have the same composition

11 High boiling azeotrope Low boiling azeotrope Makes physical separation of the two components impossible.

12 Distillation of Ethanol Azeotrope is around 95 % ethanol..

13 Impossible to distill ethanol to greater than 95%.

14 Azeotropic Distillation to Isolate Aromatics Best when high aromatic content The addition of strongly polar agents (amines, alcohols, ketones, water) facilitates the removal of alkanes and cycloalkanes as lower boiling azeotropes For example, add acetone to remove nonaromatics from the benzene fraction and then extract the acetone from the benzene with water.

15 Extractive Distillation An additive is used to increase the differences in boiling points For example, add NMP (N-methylpyrrolidone) This increases the boiling point of the aromatics by “complexation” of the  electrons in the aromatic ring with the NMP and therefore facilitates separation

16 Liquid-liquid extraction Same principle as the separatory funnel, but continuous. Based upon countercurrent flow. The mixture is added to the middle of a column. The extraction liquid is added to the top. The non aromatics leave the column at the top and the aromatics with solvent exits from the lower part of the column Most extraction processes provide a mixing zone followed by a settling zone.

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18 Crystallization Mainly to separate xylene isomers p –xylene can be separated from a mixture by cooling to -20 ºC to -75ºC. Melting point p-xylene+13.3 o-xylene-25.2 m-xylene-47.9 ethylbenzene-95.0

19 Adsorption Depends upon selective adsorption on a column, followed by desorption Molecular sieves = zeolites = alumino- silicates having different pore size UOP process involves selective adsorption of p-xylene ( from a C8 stream) followed by desorption

20 p-Xylene 7 billion pounds BP-Amoco the biggest with 4.6 billion pounds of U.S. capacity Virtually all goes to production of terephthalic acid and dimethyl terephthalate

21 Air oxidation. Common catalysts are: CoBr 2, MoBr 2 or HBr

22 By esterification with methanol.

23 TA & DMT Dupont Cape Fear plant makes terephthalic acid ( sold to Alpek, a Mexican petrochemicals group) Kosa ( Wilmington plant) makes terephthalic acid and dimethyl terephthalate Kosa makes about 1.5 billion pounds per year of dimethylterephthalate – largest in North America

24 Cumene 8 billion pounds used in U.S. Essentially all used for phenol production

25 Cumene Capacity (million pounds) 8.7 Billion total Chevron Port Arthur, Tex. 1,000 Citgo Petroleum, Corpus Christi, Tex. 1,100 Coastal Eagle Point, Westville, N.J. 140 Georgia Gulf, Pasadena, Tex. 1,500 JLM Chemicals, Blue Island, Ill. 145 Koch Petroleum, Corpus Christi, Tex. 1,500 Marathon Ashland, Catlettsburg, Ky. 800 Shell Chemical, Deer Park, Tex. 1,100 Sun, Philadelphia, Pa. 1,200

26 Phenol from Cumene

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28 Sunoco Phenol Plant Haverhill, Ohio

29 Kellogg Phenol Plants

30 Phenol Uses 41 %: Bisphenol-A 28 % phenolic resins 13 % caprolactam

31 Major Phenol Producers Sun, Shell, Dow, GE, and Georgia Gulf are major producers GE plant at 700 million pounds JLM has a 95 million pound plant in Illinois (same JLM that operates shipping in Wilmington) Current demand about 5 billion pounds 0.62 pounds acetone per pound phenol

32 Bisphenol-A Cumene gives 1 mole of phenol per mole of acetone BPA uses 2 moles of phenol per mole of acetone Typically, phenol is in demand and acetone is a glut on the market

33 On to bigger things!