HYDRATION OF PROPYLENE

(Isopropanol [CH3CHOHCH3])

• production of isopropanol from propylene occurs by either a direct hydration reaction (the
newer method) or by the older sulfation reaction followed by hydrolysis

• 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.

• 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%).

• Figure 8-4 is a flow diagram of the propylene hydration process

• Gas phase hydration, on the other hand, is carried out at temperatures above 200°C an
approximately 25 atmospheres.

• The ICI process employs WO3 on a silica carrier as catalyst.

PROPERTIES AND USES OF ISOPROPANOL

• About 50% of isopropanol use is to produce acetone.

• Other important synthetic uses are :

– to produce esters of many acids, such as acetic (isopropyl acetate, solvent for
cellulose nitrate),

– myristic, and oleic acids (used in lipsticks and lubricants).

– Isopropylpalmitate is used as an emulsifier for cosmetic materials.

– Isopropyl alcohol is a solvent for alkaloids, essential oils, and cellulose derivatives

Isopropanol (2-propanol) is an important alcohol of great synthetic utility. It is the second-

largest volume alcohol after methanol (1998 U.S. production was approximately 1.5 billion
pounds) and it was the 49th ranked chemical. Isopropanol under the name “isopropyl alcohol”
was the first industrial chemical synthesized from a petroleum-derived olefin (1920). 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 r 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%). Figure 8-4 is a flow diagram of
the propylene hydration process. 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.

The first commercial production of (IPA, or 2-propanol) by the addition of water to

propene was done in 1930 by Standard Oil of New Jersey (USA). This was also the first
example of the manufacture of a petrochemical from a refinery product.
In the classical process, propene hydration with H2SO4 took place in the liquid phase.
Along with this process, which is till operated today, other processes bascd on propene
have also been established involving, however, a single-stage catalytic hydration in the
gas, trickle, or liquid phase. Depending on the mode of operation, various acidic catalysts
can be employed, such as:
1. supported heteropoly acids or mineral acids in the gas phase,
2. acidic ion-exchangers in the trickle phase,
3. water-soluble heteropoly acids containing tungsten.
The older, two-step sulfuric acid process is still operated by BP and Shell. A Deutsche
Texaco nlant used this technoloey until 1986, when it was convertcd to direct hydration
over an acidic ion exchanger. The H2O addition to propene in the H2SO4 process takes
place indirectly via the sulfuric acid monoester. In the second step, the acid content is
lowered to less than 40% by dilution with steam or water, and the ester is hydrolyzed:

The resulting dilute H2SO4 is then concentrated. At the same time, the higher boiling
organic byproducts are burned, usually with the addition of small amounts of HNO3. In
commercial implementation, two modifications are common. The strong acid process,
which is two-step, has separate reactors for absorption and hydrolysis. The absorption is
done with 94% H2SO4 at 10- 12 bar and 20°C. The weak acid process is single stage, and
is carried out in a bubble reactor with only 70% H2SO4; the pressure and temperature must
be increased to 25 bar and 60-65 °C. The isopropanol selectivity reaches more than 90%
and the byproducts are and acetone.
The catalytic gas-phase hydration of propene takes place in a manner similar to ethanol
manufacture from ethylene:

In contrast to ethylene, the protonization of propene occurs much more readily during the
first stage of the reaction as the resulting secondary propyl carbenium ion is more stable
than the primary ethyl carbenium ion. Therefore, higher conversions are attainable with
propene than with ethylene.
In this exothermic reaction, the equilibrium is displaced towards the desired product by
high pressure and low temperatures. However, the catalyst requires a certain minimum
temperature to be effective, so it is not possible to benefit fully from the thermodynamic
advantages of low temperature.
Suitable catalysts include WO3/SiO2 combinations (heteropoly acids), which have been
used by IG Farben. Isopropanol was manufactured from 1951 until the end of the 1970s
by ICI in a unit with a capacity of 48000 tomes per year, using WO3/SiO2with ZnO as
promoter. In Germany, Hüls (formerly Veba) uses H3PO4 on a SiO2 support in a 110000
tonne-per-year (1993) plant. Typical operating conditions are 270°C and 250 bar for the
ICI process, and 170-190°C and 25-45 bar in the Hüls process.
In the gas-phase process, isopropanol selectivity is 97% and therefore higher than in the
H2SO4 liquid-phase process. The workup of the aqueous solutions is conducted in a
manner similar to that described below. The disadvantages of both gasphase processes are
low propene conversion (5-6%) and high plant costs due to pressurized operation and gas
recycles.
Selectivity to isopropanol is 92- 94%, with 2-4% diisopropyl ether as well as alcohols of
the C3H6 oligomers formed as byproducts. The catalyst life is at least 8 months, and is
essentially determined by the hydrolytic degradation of the SO3H groups of the ion-
exchanger. After removal of the low boiling substances, an isopropanol/ H2O azeotrope is
distilled from the aqueous reaction product which originally contained 12- 15%
isopropanol. is added to the distillate, and further distillation gives anhydrous alcohol.