PROCEDURE

Direct catalytic hydration of propylene

Hydration of propylene via sulfation hydration

3.1 Hydration of Propylene via Sulfation and Hydrolysis

3.1.1. Reference Flow sheet : Figure

3.1.2. Chemical reactions

(a) Sulfation

CH3CH=CH2 + H2SO4 (CH3)2CH(OSO3H)

propene Isopropyl acid Sulphate

(b) Hydrolysis CH3

CH3CH CH3 + H2O O + H2SO4

H O SO3 CH3

(c) Ether formation – side reaction

CH3CH O (CH3)2CH

S OH + H2O O + H2SO4

CH3CH O (CH3)2CH

Diisopropyl sulphate Diisopropyl ether

3.1.3 Quantitative Requirements

(a) Basis : 1 ton of isopropanol ( 88% wt. purity ,95% yield )

Propylene

Sulphuric acid (75%)

Sodium Hydroxide

By – Products : Isopropyl ether (optional), poymers

(b) Plant capacities: 50-200 tons per day

3.1.4. Process description mixed with other C2-C3 hydrocarbons, is absorbed in 70-75%

H2SO4 in a packed or sieve tray absorption tower or in a species of agitated reactors

Operating at 20-30 atms. The strongly exothermic sulfation reaction is kept at 20-30 C

By refrigerated brine circulation. The solution is hydrolysed in a steam stripper which

removes organic phase

Propylene

as vapour. The weak acid bottoms are sent to H2SO4 concen-

tration plant after nuetralisation in a caustic solution. The product vapour is fractionally

condensed, with non-condensible olefins fraction returned to the sulfation step.

The crude isopropanol is distilled to remove the more volatile isopropyl ether.

A portion of the reflux is shunted to a decanter where the ether- rich top layer is pumped

Back to the sulfation step or dried for product sales. The water alcohol bottom layer is ret-

urned to the reflux column feed.

Ether column bottoms are pumped to the isopropanol column where an 87% IPA azeotrope
can is taken off the top. This can be sold as product or sent to a ternary azeotropic distillation colu-
mn where isopropyl ether removes the water as overhead and the bottom are 99% absolute isopro-
panol.

3.1.5. Major engineering problems

(a) Sulfation reactions

Ehtylene in feed gas are not adsorbed at low temperature andacid concentration used.
This eliminates prior fractionation requirements of light ends. The absorption of propylene depends
on keeping the H2SO4 contact between 70-80%. If C4 or higher olefins are presents, these will show
up in the bottoms from the isopropanol column as they are more readily absorbed and come
through the system.

(b) Direct hydration reaction

A great deal of research went into direct hydration of propylene as it was not as easy as
commercial process developed for ethanol. The process conditions of higher temperature, acid
catalysis and vapour phase can cause much polymerisation of propylene. The ICI now operates a
catalytic process where propylene and water are preheated and passesd over catalyst pellets
(tungsten oxide with zinc and other metal oxide promoters) at 250-300 C and at 250 atms. Both
liquid and vapour phases are presents, thus creating an unusual reactor design problem.

Economics

Isopropyl production is closely related the acetone demands. One phenol process gives acetone as a
co-product. The synthetic glycerine process outlined in chapter IIIA uses isopropanol as a starting
raw material and producses acetone as co-product. The wacker process for producing acetone
directly from propylene will undoubtedly have an impact on isopropyl alcohol markets.

Required Chemical Are:

Propylene Intermediates:

Sulphuric acid Diisopropyl ether

Caustic solution Isopropyl acid sulphate

Water Disiopropyl sulphate

Some Basic Properties of Chemical Involving in Reaction:

Chemicals M.W. M.P. B.P. Latent Specific Density Flash

(gm/mole) (0C) (0C) Heat of Heat (kg/m3) Point
Vap(j/kg) (J/kg (0c)
0
C)
Propylene 42.08 -185.2 -47 342 15.56 613 -108
@ 700C
H2SO4 98.08 10 337 1.34 1840 40
J/g k
NAOH 40 318 1388 59.66 2130
Diisopropyl 102.18 -60 68.5 725 -28
Ether
H2O 18 0 100 2257 4200 1000 0
Isopropyl 140.15
acid - - - - - -
Sulphate
Diisopropyl 182.23 -19 94/7mm 1100
sulphate hg - - -
Isopropanol 60.1 -88.5 82.5 4000 165 786 399

M.S.D.S. FOR ISOPROPANOL PLANT

1) Flash Point : 11.6670C-12.780C

2) Product is flammable, so avoid skin contacts, eye contanct, keep away from source of ignition.

Donot breath gas/vapours. Wear sufficient clothing.

3) Routes of entry- It can be absorbed through the skin,dermal contact, inhalation, eye contanct.

4) Toxicity to animals : Mouse – 3600 mm/kg

Rabbit- 12800mm/kg

5) Ecotoxicity : Ecotoxicity in water 100000/l exposed for 96 hr

6) Toxic effect on human : continuous contanct with isopropyl alcohol can cause skin irritation,
breathing problem, sometimes affect the CNS which may leadasto headache, dizziness,drowsiness,
liver, respiratory problems.