+

PO

A. Baria
Y. M. Gucor
G. G. Maraat
C. Torres

Production of Propylene Oxide through

the Integrated Process of Direct H2O2
Synthesis and the Catalyzed Epoxidation
of Propene

+
Propylene oxide - CH3CHCH2O

New Mexico State University (2014)

+
Total Global Propylene Oxide
Demand

3
3

+
Philippine Import of Propylene
Oxide

National Statistics Office

How is Propylene
Oxide currently
manufactured?

Chlorine
vs
Organic
Peroxide
+
Method
Chlorine Method
Description

Conversion of propylene to
chloropropanols.

Organic Peroxide
Method
Co-oxidation of Propylene
with organic chemicals in
the presence of catalyst.

Year developed

1960s

1970s

Advantage

No direct addition of oxygen

required

Uses the oxidative power

of hydroperoxides
skillfully

Disadvantages

Secondary raw materials: (For 1T

PO)
1.4T Cl2 and 1T Ca(OH)2 are
required
Byproduct: (For 1T PO)
2T of CaCl2
Extremely large waste and waste
water burden

Sumitomo Chemical Co., Ltd. (2006). Development of New Propylene Oxide Process. R&D Report, SUMITOMO KAGAKU, vol. 2006-

+ Organic Peroxide Method

Organic
Chemical
Byproduct

Disadvantage

Ethylbenzene
(For every 1T
PO) 2.5 T of
Styrene
monomer

Isobutane
(For every 1T PO)
2.1T Tert-butanol

Hydrogen
Peroxide
Water

Large supply of organic chemical required

Hydrogen Peroxide Manufacturing

Anthraquinone Process

Direct Synthesis

Description

Involves the sequential

hydrogenation and oxidation of
an alkylanthraquinone precursor

Direct reaction of
H2 + O2 H2O2

Disadvantage

Requires significant energy

input and generates waste,
which has a negative effect on
its sustainability and production
costs

H2/O2 mixtures are

explosive over a wide
range of concentrations

Advantage

Very high yield of H2O2 per cycle

Simplest method to
form hydrogen peroxide
Reduces capital
investment
and operating costs

How do we propose
to manufacture
Propylene Oxide?

+On-site H O strategy
2

Direct

10

synthesis of H2O2

Catalyzed epoxidation of alkenes

Propylene oxide production

based on the direct on-site
synthesis of hydrogen peroxide
or

HPP

Blanco-Brieva (2008). New Two-Step Process for Propene Oxide Production (HPPO) Based on the Direct Synthesis of Hydrogen Peroxide. Ind. Eng. Chem. Res. 2008,

+
The Plant

11

Blanco-Brieva (2008). New Two-Step Process for Propene Oxide Production (HPPO) Based on the Direct Synthesis of Hydrogen Peroxide. Ind. Eng. Chem. Res. 2008,

+
Reactor 1

H
2

12

+ O2 H 2O 2

Direct

Synthesis of H2O2

from H2 and O2
Trickle-bed
5%

reactor

Pd/C as catalyst

Raw Material

Price
(USD/k
g)

Consumption
Rate (kg/hr)

Source

Hydrogen (H2)

3.06

881

In situ

Air (source of O2)

632,995

Atmospheric air

http://www.ika.rwth-aachen.de/r2h/index.php/Hydrogen_Pathway:_Cost_Analysis

+
Separator 1

13

+
Reactor 2

H2O2

14

+ C3H6 CH3CHCH2O + H2O

Epoxidation

of propene

using H2O2 to yield PO

CSTR
TS-1

as catalyst

Raw Material

Price
(USD/kg
)

Consumption
Rate (kg/hr)

Source

Propene (C3H6)

1.44

18,396

Local

+
Separator 2

15

16

Plant
Capacit
y

25,390 kg/hr (195,000

MT/year)

Product
Price

1.58 USD/kg (70.3574

Php/kg)

Plant Location
Brgy. Lamao,
Limay, Bataan,
Central Luzon

17

+
The Process

18

Reactor
Unit
1

Direct
Synthesis
of
+
Hydrogen Peroxide in a TBR

Separation
Unit
1

Flash
Drum
+

Reactor Unit 2 Epoxidation of Propylene

+
Using Hydrogen Peroxide in a CSTR

Separation
Unit
2

Distillation
+
Columns

Reactor
Unit
1

Direct
Synthesis
of
+
Hydrogen Peroxide in a TBR

Main Reaction:

Reactor
Unit
1

Direct
Synthesis
of
+
Hydrogen Peroxide in a TBR

74.22% N2
21.16% O2
0.01% H2
1.53% Methanol
1.14% Water
1.95% H2O2

66%
Methanol
34% Water

Separation
Unit
1

Flash
Drum
+
0.01% H2
21.82% O2
76.54% N2
1.54% Methanol
0.09% Water
0.01% H2O2

1.17% Methanol
34.66% Water
64.17% H2O2

Reactor Unit 2 Epoxidation of Propylene

+
Using Hydrogen Peroxide in a CSTR

Main Reaction:

Reactor Unit 2 Epoxidation of Propylene

+
Using Hydrogen Peroxide in a CSTR
1.17%
Methanol
34.66% Water
64.17% H2O2

100%
C3 H 6

100%
C3 H 6

47.01% Propylene
Oxide
0.75% Methanol
37.26% H2O
13.87% H2O2
1.10% By-products

Separation
Unit
2

Distillation
+
Columns
47.01% Propylene
Oxide
0.75% Methanol
37.26% H2O
13.87% H2O2
1.10% By-products

100%
C3H6
Water
Methanol
Hydrogen Peroxide

66% Methanol
34% Water

Ethylene Glycol
Water
Methanol
Hydrogen Peroxide

Ethylene Glycol
Water
Hydrogen Peroxide

+
Cost Estimation

31

+
Equipment Cost

Reactor Unit 1

Separation Unit 1

Reactor Unit 2

Separation Unit 2

+
Equipment Cost

Reactor Unit 1

Separation Unit 1

Reactor Unit 2

Separation Unit 2

+
Reactor Unit 1
Equipment Description

Cost ($)

Air purification unit (including

installation cost)*

500,000.00

R-100

Trickle bed reactor

55,432.70

P-100

Pump in Cooling System

6,374.53

PM-100

Pump Motor in Cooling System

12,845.38

V-100

Vessel in Cooling System

15,838.32

E-101

Heat Exchanger in Cooling System

62,698.87

Total

*Sir Tonys estimate

653,189.81

+
Equipment Cost

Reactor Unit 1

Separation Unit 1

Reactor Unit 2

Separation Unit 2

+
Separation Unit 1
Equipment Description

Cost ($)

T-100

Flash Vessel

1,089,388.90

Heat Exchanger for Flash Vessel

20,336.20

E-202

Heat Exchanger

14,331.18

P-100A/B

Pump

5,643.75

PM-100A/B

Pump Motor

1,656.16

Total

1,131,356.20

+
Equipment Cost

Reactor Unit 1

Separation Unit 1

Reactor Unit 2

Separation Unit 2

+
Reactor Unit 2
Equipment Description

Cost ($)

P-200A/B

Pump

7,719.92

PM-200A/B

Pump Motor

3,311.23

E-200

Heat Exchanger

18,445.49

P-201A/B

Pump in Cooling system

1,325,139.27

PM-201A/B

Pump Motor in Cooling System

52,007.04

E-201

Heat Exchanger on Cooling System

89,159.28

R-200

CSTR

12,565.20

V-200

Vessel in Cooling System

1,455,938.67

Total

2,964,286.09

+
Equipment Cost

Reactor Unit 1

Separation Unit 1

Reactor Unit 2

Separation Unit 2

+
Separation Unit 2
Equipmen
t

Description

Cost ($)

E-204

Heat Exchanger

20,870.00

E-206

Heat Exchanger

197,386.00

E-209

Heat Exchanger

12,284,798.00

E-203

Condenser

30,488.49

E-205

Condenser

323,148.94

E-208

Condenser

20,000,000

P-202A/B

Pump

899,150.69

P-202A/B

Pump Motor

41,238.69

T-200

Distillation Column

46,673.00

T-201

Distillation Column

30,042.00

T-202

Distillation Column

466,824.00

Total

32,250,102.30

+
Summary of Equipment Cost
Unit

Cost ($)

Reactor Unit 1

653,189.81

Separation Unit 1

1,131,356.20

Reactor Unit 2

2,964,286.09

Separation Unit 2

32,250,102.30

Total

36,998,934.39

+
Fixed Capital Investment: Direct
Cost
Percent
of
delivere
d
equipme
Minimu Maximu nt for
m
m
processi
Range Range ng plant

Cost

Final
Normali
ze

Direct Cost
Purchased equipment cost
Purchased equipment
installation
Instrumentation and
Control (installed)
Piping (installed)
Electrical systems
(installed)
Building (including services)
Yard improvements
Service facilities (installed)

15

40

40%

14

14%

36,998,934.3
9
12,949,627.0
4

2
3

8
20

8%
9%

7,399,786.88
8,324,760.24

5.26
5.92

10

10%

6.58

3
2
8

18
5
20

15%
2%
10%

9,249,733.60
13,874,600.4
0
1,849,946.72
9,249,733.60

26.32
9.21

9.87
1.32
6.58

+
Fixed Capital Investment: Indirect
Cost
Percent
of
delivere
d
equipme
Minimu Maximu nt for
m
m
processi
Range Range ng plant
Indirect cost
Engineering and
supervision
Construction expenses

21

13%

16

9%

Legal expenses

1%

Contractor's fee

4%

Contingency

15

15%

Cost

Final
Normalize

12,024,653.6 8.5526315
8
79
5.9210526
8,324,760.24
32
0.6578947
924,973.36
37
2.6315789
3,699,893.44
47
13,874,600.4 9.8684210
0
53
38,848,881

+
Total Fixed Capital Investment
Fixed Capital
Investment
Cost of H2 plant*

$ 140,595,950.69

Total Fixed
Capital
Investment

$
156,921,278.
78

$ 16,325,328.09

*Source: Mr. Koos Overwater of Technip Stone & Webster Process Technology

+
Working Capital
Annual
consumption
(kg/yr)
141550387.20
74464281.60
410.28
7140.91

Price
Material
(USD/kg)
Propylene
1.44
Methanol
0.49
TS-1 Catalyst
5600
5% Pd/C catalyst
666.4
41.9/1000
LP Steam Cost
kg
116501486.60
Cooling water 0.05/1000
cost
kg
31828325972.48
Demineralized 1.30/1000
water
kg
41891742.74
130/1000
Electricity
kWh

Total

Cost per year

203,832,557.57
36,487,497.98
2,297,555.11
4,758,702.42
4,881,412.29
1,591,416.30
54,459.27
792,028.51

254,695,629.
45

+
Annual Sales
Price
Annual
(USD/k production Revenue per
Material
g)
(kg/yr)
year ($)
1.58
167,991,715.7
Propylene
106,323,871
4
Oxide

+
Annual Sales
Price
Annual
(USD/k production Revenue per
Material
g)
(kg/yr)
year ($)
Propylene 1.58 106,323,871 167,991,715.74
Oxide
308,092,41
194,995,200

6.00

+
Cash Flow
200,000,000.00

$ 124,852,180.91

100,000,000.00

0.00
0

-100,000,000.00

-200,000,000.00

-300,000,000.00

-400,000,000.00

-500,000,000.00

$ -411,636,908.23

10

+
Profitability Analysis

49

+
IRR and NPV

IRR
NPV

26.73%
$ 394,566,100.49

+
Payback
500,000,000.00
400,000,000.00
300,000,000.00
200,000,000.00
100,000,000.00

Cumulative Discount Cash flow ($/ yr)

0.00
0 5 10 15
-100,000,000.00
-200,000,000.00
-300,000,000.00
-400,000,000.00
-500,000,000.00

Investment Year

+
Conclusions and
Recommendations

Propylene Oxide has an increasing demand

Direct synthesis of H2 is more environment-friendly

Building an HPPO plant is profitable if the designed

plant capacity is reached

52

53

Thank you PO.