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Chemicals Based on
Propylene
CH 2 = 14 CHCH 3 + O 2 CH 2 = 14 CHCHO + H 2 O
14 hv
CH 2 = CHCHO CH 2 = 14 CH 2 + CO
Dr. Bassam El Ali_CHEM 453 8
OXIDATION OF PROPYLENE
ACROLEIN (CH2=CHCHO)
MECHANISM OF PROPENE OXIDATION
O C H 2C H = C H 2
O O=M OH
O=M O O
O
O2
OH
M + C H 2= C H C H O
H 2O + O =M O
O OH
H2
CH 2 =CH-CHO + H 2 O HO-CH 2 -CH 2 -CHO HO-CH 2 CH 2 CH 2 -OH
O O
CH2=CHCH + 1/2O2 CH2=CHCOH
Dr. Bassam El Ali_CHEM 453 14
OXIDATION OF PROPYLENE O
ACRYLIC ACID (CH2=CHCOH)
O
Dr. Bassam El Ali_CHEM 453 C H 2= C H COR + H 2 O15
AMMOXIDATION OF PROPYLENE
Acrylonitrile [CH2=CHCN]
cation-exchange
- m em brane + 2H + + 2e -
H 2O - 2 e 2 C H 2 =C H C N
1/2O 2 + 2H + N C (C H 2 ) 4 C N
A nolite C atholite
Dr. Bassam El Ali_CHEM 453 21
OXIDATION OF PROPYLENE O
C H 3C H = C H 2 + H O C l C H 3C H C H 2C l
OH
P r o p y le n e
c h lo r o h y d r in
The next step is the dehydrochlorination of the
chlorohydrin with a 5% Ca(OH)2 solution.
O
2CH 3CHOHCH 2Cl + Ca(OH)2 2CH 3CH CH 2 + CaCl2 + 2H 2O
CH 3 O OH
C 6 H 5 COOH + CH 3 CH=CH 2 CH 3 CH CH 2 + C 6 H 5 CHCH 3
H
Dr. Bassam El Ali_CHEM 453 25
OXIDATION OF PROPYLENE O
C6H5CH2CH3 + O2 C6H5CHCH3
OOH
Epoxidation with hydrogen peroxide is catalyzed with
compounds of As, Mo, and B, which are claimed to
produce propylene oxide in high yield.
O
CH 3CH=CH 2 + H 2O 2 CH 3CH CH 2 + H 2O
C H 3C H C H 2 + H 2O C H 3C H O H C H 2O H
P r o p y le n e g ly c o l
O
O
CH 3CH CH 2 + CO 2 O
Dr. Bassam El Ali_CHEM 453 CH 3 O 30
Derivatives and Uses of Propylene Oxide
Allyl Alcohol (CH2=CHCH2OH)
Glycerol via Allyl Alcohol
Glycerol (1,2,3-propanetriol) is a trihydric alcohol of
great utility due to the presence of three hydroxyl
groups.
It is a colorless, somewhat viscous liquid with a sweet
odor.
Glycerin is the name usually used by pharmacists for
glycerol.
There are different routes for obtaining glycerol.
C H 2 = C H C H 2 C l + C l2 + H 2 O C lC H 2 C H O H C H 2 C l + H C l
2 C lC H 2 C H O H C H 2 C l + C a ( O H ) 2 2 CH2 C H C H 2 C l + C a C l2 + 2 H 2 O
O
E p ic h lo r o h y d r in
CH2 C H C H 2C l + 2 H 2O H O C H 2C H O H C H 2O H + H C l
O G ly c e r o l
Dr. Bassam El Ali_CHEM 453 35
HYDRATION OF PROPYLENE
Isopropanol [CH3CHOHCH3]
Isopropanol (2-propanol) is an important alcohol of
great synthetic utility.
It is the second-largest volume alcohol after methanol.
The production of isopropanol from propylene occurs by
either a direct hydration reaction (the newer method) or
by the older sulfation reaction followed by hydrolysis.
In the direct hydration method, the reaction could be
effected either in a liquid or in a vapor-phase process.
The slightly exothermic reaction evolves 51.5 KJ/mol.
CH3CH=CH2 + H2O Æ CH3CHOHCH3
Dr. Bassam El Ali_CHEM 453 36
HYDRATION OF PROPYLENE
Isopropanol [CH3CHOHCH3]
In the liquid-phase process, high pressures in the range
of 80-100 atmospheres are used.
A sulfonated polystyrene cation exchange resin is the
catalyst commonly used at about 150°C.
An isopropanol yield of 93.5% can be realized at 75%
propylene conversion. The only important byproduct is
diisopropyl ether (about 5%).
Gas phase hydration, on the other hand, is carried out
at temperatures above 200°C and approximately 25
atmospheres.
The ICI process employs WO3 on a silica carrier as
catalyst.
Dr. Bassam El Ali_CHEM 453 37
HYDRATION OF PROPYLENE
Properties and uses of Isopropanol
O
CH 3 CHOHCH 3 CH 3 CCH 3 + H 2
CH3 CH3 O
+ -
CH3C CN + H2SO4 CH2 = C C NH3HSO4
OH
CH3 O CH3
+ -
CH2=C C NH3HSO4 + CH3OH CH2=C COOCH3 + NH4HSO4
Dr. Bassam El Ali_CHEM 453 45
Uses of Acetone CH3
Methyl Methacrylate (CH2=C-COOCH3).
O
CH 3 CH=CH 2 + CH 3 COOH CH 3 COCH(CH 3 ) 2
n -B u ty ra ld eh y d e Iso b u ty ra ld eh y d e
O OH H
2 C H 3C H 2C H 2C H C H 3 (C H 2 ) 2 C H -C H C H O
C 2H 5
OH H C 2H 5
C H 3 (C H 2 ) 2 C H -C H C H O C H 3 (C H 2 ) 2 C H = C C H O + H 2O
C 2H 5
C 2H 5 C 2H 5
C H 3 (C H 2 ) 2 C H = C C H O + 2 H 2 C H 3 (C H 2 ) 3 C H C H 2 O H
M (C O ) 6 A l2O 3
M oO 3 A l2O 3
C oO .M oO 3 A l2O 3
R e2O 7 A l2O 3
W O3 S iO 2
W C l 6 (E tO H ) E tA LC l 2
M X 2 (N ) 2 L 2 * R 3 A l2 C l3
R 4 N [M (C O ) 5 X ]* R A lX 2
R eC l 5 /O 2 R alC l 2
_____________________________________________________________________
*M = M o or W ; X = halengen (C l, B r, l); L = Lew is base (e.g. triphenyl-phosphine, pyridine, etc.);
R = A llyl groups (butyl)
Dr. Bassam El Ali_CHEM 453 54