Design Exercise Report 1

Group 10
Production of Isopropyl Alcohol (2-Propanol)
Process Routes:

Process: Indirect Hydration ( Weak Acid Process)

Temperature (℃) 75-85
Pressure (MPa) 0.59-1.0MPa
Feedstock 1. Propene-containing feed gas (propene content≤60%)
2. Sulphuric acid(ca. 60%)
3. Water
4. Zeolites beta catalyst
Selectivity ( wt%) >90
Reaction First Step: A mixture of mono- and diisopropyl sulfate esters is formed
from reaction of propene with sulfuric acid. The reaction is exothermic,
yielding about 50kJ/mol.

3C𝐻3 𝐶𝐻=𝐶𝐻2 + 2𝐻2 𝑆𝑂4 → (C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2

←

Second Step: The sulfate esters are then hydrolyzed to product 2-

propanol
𝐻2 𝑜
(C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2 → 3(C𝐻3 )2 𝐶𝐻𝑂𝐻 + 2𝐻2 𝑆𝑂4

Byproduct A major byproduct is diisopropyl ether, which is formed from reaction of

the sulfate esters with product 2-propanol.

(C𝐻3 )2 𝐶𝐻𝑂𝐻
(C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2 → 2[(C𝐻3 )2 𝐶𝐻]2 𝑂 +
2𝐻2 𝑆𝑂4

Advantage 1. Ability to use low-purity propene feed

2. gives a reasonable conversion and efficiency

Disadvantage 1. The process suffers from high corrosion rates and disposal problems
with water, acid, caustic and off-gas wastes
2. high energy costs,
-The hydrolysis step yields a dilute aqueous
sulfuric acid solution, which is regenerated by submerged combustion.
-The high temperatures involved in this process result in high energy
costs as well as corrosive damage.
3. pollution problems.
-During the regeneration of the sulfuric acid, large amounts of
so2 are given off. This compound is an environmental nuisance from the
standpoint of air pollution.
-Also, large amounts of waste water are generated which must be
treated before disposal. These factors add to the capital and operating
costs.
Process: Indirect Hydration (Strong Acid Process)
Temperature (℃) 20-30
Pressure (MPa) 1.0-1.2MPa
Feedstock 0.8t propene, 0.35t 𝐻2 𝑆𝑂4, 3.5t steam, and zeolites beta catalyst
are required for production 1t of 2-propanol
Selectivity ( wt%) >90
Reaction First Step: A mixture of mono- and diisopropyl sulfate esters is formed
from reaction of propene with sulfuric acid. The reaction is exothermic,
yielding about 50kJ/mol.

3C𝐻3 𝐶𝐻=𝐶𝐻2 + 2𝐻2 𝑆𝑂4 → (C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2

←

Second Step: The sulfate esters are then hydrolyzed to product 2-

propanol
𝐻2 𝑜
(C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2 → 3(C𝐻3 )2 𝐶𝐻𝑂𝐻 + 2𝐻2 𝑆𝑂4

Byproduct A major byproduct is diisopropyl ether, which is formed from reaction of

the sulfate esters with product 2-propanol.

(C𝐻3 )2 𝐶𝐻𝑂𝐻
(C𝐻3 )2 𝐶𝐻𝑂𝑆𝑂3 𝐻 + [(C𝐻3 )2 𝐶𝐻𝑂]2 𝑆𝑂2 → 2[(C𝐻3 )2 𝐶𝐻]2 𝑂 +
2𝐻2 𝑆𝑂4

Advantage 1. Low temperature required compared to the weak acid process

2. can use a dilute refinery stream

Disadvantage 1. waste-disposal problems.

2. high energy costs,
-The hydrolysis step yields a dilute aqueous
sulfuric acid solution, which is regenerated by submerged combustion.
-The high temperatures involved in this process result in high energy
costs as well as corrosive damage.
3. pollution problems.
-During the regeneration of the sulfuric acid, large amounts of
so2 are given off. This compound is an environmental nuisance from the
standpoint of air pollution.
-Also, large amounts of waste water are generated which must be
treated before disposal. These factors add to the capital and operating
costs.
Process: Direct Hydration (Low temperature Process)
Temperature (℃) 130-160
Pressure (MPa) 8.0-10.0MPa
Feedstock 1. about 92% of propene gas
2. liquid water
3. a sulfonated polystyrene ion-exchange resin catalyst
Selectivity ( wt%) About 75
Reaction Propylene and liquid water are heated and the liquid-vapour mixture
under pressure passes into a trickle flow reactor containing
sulphonated polystyrene cation ion exchange resins.

𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
C𝐻3 𝐶𝐻=𝐶𝐻2 + 𝐻2 𝑂 ⇔ (C𝐻3 )2 𝐶𝐻𝑂𝐻 ∆𝐻 = −50𝑘𝐽/𝑚𝑜𝑙

The IPA is obtained from the aqueous solution by distillation.

Byproduct About 5% diisopropyl ether and about 1.5% oxygenates (alcohols) of

propene oligomers (hexenes) are formed as byproducts

Advantage 1. Low temperature required

2. Reduces by-products
3. Less degradation
4. Less corrosive
5. Lower commercial and capital cost

Disadvantage 1. Require high-pressure equipment

2. could suffer from problems of short catalyst life
3. requires a pure propylene feed
Process: Direct Hydration (High temperature Process)
Temperature (℃) 230-270
Pressure (MPa) 20-30MPa
Feedstock 1. about 92% of propene gas
2. liquid water (molar ratio of 2.5water: 1 propene)
3. reduce tungsten oxide catalyst
Selectivity ( wt%) 98-99
Reaction Propylene and liquid water are heated and the liquid-vapour mixture
under pressure passes into a trickle flow reactor containing reduce
tungsten oxide catalyst.

𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
C𝐻3 𝐶𝐻=𝐶𝐻2 + 𝐻2 𝑂 ⇔ (C𝐻3 )2 𝐶𝐻𝑂𝐻 ∆𝐻 = −50𝑘𝐽/𝑚𝑜𝑙

The IPA is obtained from the aqueous solution by distillation.

Byproduct About 5% diisopropyl ether and about 1.5% oxygenates (alcohols) of

propene oligomers (hexenes) are formed as byproducts

Advantage 1. High propene conversions of 60-70% per pass

2. high propanol selectivity
3. Catalyst has higher catalyst activity
4. Reduces by-products
5. Less degradation
6. Less corrosive
7. Lower commercial and capital cost

Disadvantage 1. Require high-pressure equipment

2. the catalyst must be durable(stable in the presence of water)
3. requires a pure propylene feed
4. high operating pressure
Process: Direct Hydration (Vapor phase)
Temperature (℃) 180-260
Pressure (MPa) 1.0-6.5MPa-to maintain reactants in gaseous state
Feedstock 1. propene gas(>99%)
2. steam
3. mineral acid such as phosphoric acid on silica
Selectivity ( wt%) 10
Reaction Propylene and liquid water are heated and the reaction are carried
out in the gas phase over a phosphoric acid-based fixed bed catalyst.

𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
C𝐻3 𝐶𝐻=𝐶𝐻2 + 𝐻2 𝑂 ⇔ (C𝐻3 )2 𝐶𝐻𝑂𝐻 ∆𝐻 = −50𝑘𝐽/𝑚𝑜𝑙

The IPA is obtained from the aqueous solution by distillation.

Byproduct About 5% diisopropyl ether and about 1.5% oxygenates (alcohols) of

propene oligomers (hexenes) are formed as byproducts

Advantage 1. low operating pressure

2. phosphoric acid catalyst more commercial
3. Reduces by-products
4. Less degradation
5. Less corrosive
6. Lower commercial and capital cost

Disadvantage 1. Require high propene recycle (less than 10% conversion per pass)
2. High utility cost
3. requires a pure propylene feed
Process: Hydrogenation of Acetone
Temperature (℃) 120
Pressure (MPa) 196kPa
Feedstock 1. acetone
2. Raney-nickel catalyst or copper oxide-chromium oxide

Selectivity ( wt%) 99.9% (Raney-nickel catalyst), 98%( copper oxide-chromium

oxide)
Reaction
𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
C𝐻3 𝐶𝑂C𝐻3 + 𝐻2 ⇔ (C𝐻3 )2 𝐶𝐻𝑂𝐻

Byproduct Methyl isobutyl ketone, 4-methyl-2-penthanol, hexylene glycol.

A small amount of heavy ends by-product containing mostly butanol
and methyl isobutyl carbinol (MIBC) is also produced in the unit.

Advantage 1. low operating pressure

2. high conversion of the acetone(94-99.9%)
3. Use of inexpensive acetone feedstock rather than propylene
4. Stable catalyst with long continuous run length, environmentally
friendly catalyst; easy catalyst handling and spent catalyst disposal
5. High IPA product purity

Disadvantage 1. Required high operating temperature

2. Isolation of isopropyl alcohol after catalytic hydrogenation of
acetone-containing liquid phase is costly
3. High cost in preparation of catalyst
Comparison of the process

Hydrogenation of Direct hydration of Indirect hydration of

acetone propylene propylene
Establishment Does not commercially First commercial First commercial
work in practice process was introduced production done in
in 1951 1930 by Standard Oil of
New Jersey (USA)
First direct hydration
process developed by
the Shell Development
Company in 1947

30,000 metric
tons/year of IPA in
operation since June
1972 at Tokuyama Soda
Co Ltd
Features of High reaction rate & High activity & Requires quality of
process provide large amount of selectivity to hydrate propylene gas (45wt%)
product propylene to IPA
2 steps reaction –
High cost in preparation Long life span of Reaction of propylene
of catalyst catalyst gas with sulphuric acid
& reaction of water to
Requires high pressure Requires high quality of hydrolyses
in the operation propylene (~99wt%) intermediate product

Small amount of Hydrolysis step takes

byproducts place at reasonable
rate and in good yield
Unit operation Simple reactor High energy usage to High capital cost to
structure operate complex treat waste water &
distillation columns to maintain the process at
recover IPA from high temperature
product stream &
maintain process at Large amount of waste
high pressure water to be treated

Difficult and expensive

to separate IPA from
azeotropic mixture

Easy operation &

maintenance of
equipments
Safety & Acetone is extremely Propylene is flammable Units of plant expose to
Environmental flammable gas highly corrosive of
Impact sulphuric acid

Regeneration of
sulphuric acid produce
sulphuric dioxide that
causes environmental
effect

Propylene is flammable
gas
Production 100 000 metric tons of 30 000 metric tons of 2.8 million pounds of
IPA/year IPA/year IPA/year

Purity of IPA ~99% Purity of IPA ~99.8wt%

Indirect Hydration Costing

Raw Materials Price

Propylene 815.0 (EUR/tonne) = 1002.96 USD/tonne
Purity : 99.5%min
Location : Beijing, China (Mainland)
Water RM0.99 /m3 (Malaysia)
Estimed 30000 m3/operation
1 Operation = 7595.6 USD
Sulphuric Acid 100.0 (USD/tonne)
Purity : 98%
Location : Hubei, China (Mainland)
Zeolites 1083.0 (USD/tonne)
(catalyst) Location : Shandong, China (Mainland)

Total operation 1002.96 USD + 7595.6 USD + 100.0 USD + 1083.0 USD =
( 1 tonne /raw materials ) 9781.56 USD
Direct Hydration Costing

Raw Materials Price

Propylene 815.0 (EUR/tonne) = 1002.96 USD/tonne
Purity : 99.5%min
Location : Beijing, China (Mainland)
Water RM0.99 /m3 (Malaysia)
Estimated 30000 m3/operation
1 Operation = 7595.6 USD
Phosphoric Acid 600 USD/tonne
Purity : 87%
Location : Shanghai, China
Heteropolyacids on Silica 1.99 USD/ Kilogram
BET Surface Area : 90 𝒎𝟐 /g
SP : 1990 USD/tonne
Location : Liaoning, China.
Sulphuric Acid 100.0 (USD/tonne)
Purity : 98%
Location : Hubei, China (Mainland)
Zeolites 1083.0 (USD/tonne)
Location : Shandong, China(Mainland)
Amberlyst-15 25.0 USD/Kilogram
(For Organic Synthesis) Purity : 99%
Assume 10 kg : 250 USD
Location : Shandong, China
Hydrochloric Acid 120 USD/tonne
Purity : 33%
Location : Liaoning, China
 Total operation
( 1 tonne / raw materials )
Hydrogenation of Acetone
Raw Materials
Acetone
Water
Nickel
Titanium Dioxide
Aluminium Oxide
Zirconium Dioxide
Total operation
( 1 tonne / raw materials )
1002.96 + 7595.6 + 600 + 1990 + 100 + 1083.0 +
250 + 120 = 12371.56USD
Price
4250 USD / tonne
Purity : 99.0%
Location : Shandong, China
RM0.99 /m3 (Malaysia)
Estimed 30000 m3/operation
1 Operation = 7595.6 USD
3000 USD / tonne
Purity : 99.8%
Location : Hunan, China
1350 USD / tonne
Purity : 93.0%
Location : Shanghai, China
1200 USD / tonne
Purity : 97.4%
Location : Hunan, China
3500 USD / tonne
Purity : 99.5%
Location : Hunan, China
4250 +7595.6 +3000 +1350 +1200+3500 = 20,895.60 USD
Comparison of Direct and Indirect Hydration (1 tonne/raw materials)

Process Indirect Hydration direct Hydration Hydrogenation Acetone

No. Raw Material 4 8 6
Price 9781.56 USD = 12371.56USD = 20,895.60 USD
RM38329.04 RM48477.96 = RM81,701.80

Cost of direct Hydration and Hydrogenation of Acetone is 26.5% and 113% higher than
indirect Hydration respectively

Comparing three process routes for the production of isopropyl alcohol by the establishment,
feature of process, unit operation, safety and environmental impact and the production, it is
shown that the direct hydration of propylene has the promising potential for an economically
practical route to isopropyl alcohol. Furthermore, direct hydration of propylene is widely used in
industries and is a more establish way to obtain isopropyl alcohol compared to hydrogenation of
acetone and indirect hydration of propylene. These three processes require catalyst in the
reaction, but preparing catalyst for hydrogenation of acetone is more expensive compared to
direct and indirect hydration of propylene. In term of life span of catalyst, direct hydration of
propylene is better. In term of environmental impact, indirect hydration uses sulphuric acid as
the catalyst which may cause harm to the environment thus this process is not chosen as it is not
environmental friendly and require a lot of cost to treat waste product. Besides, hydrogenation
of acetone is not chosen as the acetone is highly flammable which may give out explosion if not
handle carefully. Last but not least, when the cost of three processes are compared, it can be see
that direct hydration is cheaper than hydrogenation of acetone and is slightly higher than indirect
hydration. Thus, based on technical feasibility study, economic feasibility study as well as safety
issue, direct hydration of propylene is chosen.
Among the three processes of direct hydration of propylene, high temperature process is
favorable. This is because it has the highest selectivity and conversion per pass when compared
to low temperature and vapor phase process.
Direct hydration of Propylene (High Temperature) developed by Tokuyama Soda

 The process that had been developed by Tokuyama Soda at the end of 1972
 First commercial plant which having a capacity of 30 000 metric tons of isopropyl alcohol
were produced.
Technical Feasibility study:

Criteria Elaboration
Raw Material 1. Propylene gas (about 95%)
2. Catalyst: Tungsten oxide in liquid phase
- Highly active and remarkably selective for the
specific process
- Very stable (resistant to hydrolysis)
- Spend longer in continuous operation
- Able to give high per pass conversions of the
propylene
Unit Operation 1. Reactor ( Reaction in Liquid Phase)
- Temperature: 240 ℃ - 270℃
- Pressure: 150atm – 250atm
2. Heat Exchanger
3. Gas Separator
- To separate & recycle unconverted propylene
dissolve in solution
4. Azeotropic Column
- To separate azeotropic mixture of isopropyl alcohol
and water by separating agents
- Catalyst solution joins with water and then recycle
- Minimum boiling point of azeotrope mixture is
81℃
5. Rectifying Column
- Remove light impurities from IPA solution
6. Distillation Column (2 or 3 column)
- Benzene(separating agent) is added for further
purification
Quality of Product 1. Purity: 99.99%
2. Conversion of propylene per pass: 60% - 70%
3. Selectivity of IPA over converted propylene: 98% - 99%
By-product 1. Di-isopropyl ether
2. N-propanol
3. Propylene oligomers

***Spent gas from reactor and by-products from purification section are completely utilized as
fuel in heating system
Advantages
1. The catalyst able to maintain high activity and excellent selectivity for the process
2. Catalyst highly stable and the life time is very long
3. High conversion rate of propylene
4. Does not require high concentration of propylene
5. Small amount of by-products released (because in aqueous solution which give high
selectivity)
6. High grade of IPA easily to obtain at purification system
7. Heat loss incidental to evaporation & condensation of water can be avoid since the reaction
in liquid phase
8. Easy operation & maintenance of equipment (no corrosion)
9. Process is simple and the free from waste substance. (reduce cost in treated operation)