Production of Hydrogen

Peroxide by Autoxidation
of Anthraquinone
(Reidl-Pfleiderer Process)
 Project Advisers
Prof. Dr. Shaukat Rasool
Muhammad Nazim

Group Members
Hafiz Ihsan Ullah Khan 2005-CHEM-02
Muhammad Waqas Manzoor 2005-CHEM-14
Haji Ghulam Qutab 2005-CHEM-30
Zaeem Bin Baber Hashmi 2005-CHEM-48
3
 Synopsis
• Hydrogen Peroxide basic facts
• Available Manufacturing Procedures
• Process Selection
• Capacity Selection
• Process Description
• Material and Energy Balance

4
 Introduction
Chemical Name: Hydrogen Peroxide
Different Trade Names: Hybrite® 32.5%
Oxypure® 35%
Chlorate Grade, 20%
Molecular Formula: H2O2
Molecular Weight: 34.08 kg/kgmole
Appearance: Colorless odourless Liquid
Boiling Point: 150°C

5
6
 Available Technologies
1. The barium peroxide process
2. Electrolytic Method
3. Direct combination of hydrogen and oxygen
4. Autoxidation processes
a. Nitrogen compounds autoxidation
b. Hydrocarbon hydro peroxides indirect
autoxidation
c. Ethyl-Anthraquinone autoxidation

7
 Why we selected Anthraquinone
Autoxidation
• Well standardized process
• Better catalyst activity
• High Selectivity
• High yield
• High rates of reaction
• Regeneration of working solution
• Toxic gases are not produced

8
 Capacity Selection
In order to select capacity of our plant for
producing Hydrogen Peroxide we consider the
following factors:
• Its consumption in different sectors of
Pakistan
• Its annual import from different countries
• Its current production rate in Pakistan.

9
 Consumption
Cosmetic
Industry Military
2% Uses
8%
Chemicals Textile
Synthesis
Industry
17%
45%
Paper and
Pulp Industry
28%

Ref: IGI Research

10
 Total Annual Import

11
Ref: “Imports by Commodities and Countries” report by Lahore Chamber of Commerce
 Production

Only two production plants in Pakistan

1. SITARA Peroxide

2. OXYCHEM Descon
Capacity of both plants is 30000 metric tons per year
• While the annual demand for the year 2009 is
90000 tons.
• So, we selected the capacity of our plant to be
30000 tons/year.
12
Process Description

13
 Block Diagram
Ethyl Anthraquinone

Hydrogen Hydrogenerator Regenerator

Solvent
N2 and O2

Oxidizer Separator Extractor Water

Distillation 95 % water
Column
Air

95 % pure Hydrogen Peroxide

14
 Equipment Coding

C = Column
E = Heat Exchanger
S = Separator
P = Pump
B = Compressor
T = Storage Tank

15
 Process Flow Diagram

Recovery
Section
Purification
Section
Production
Section

Feed
Section

16
 Chemical Reactions
Reactions in the Hydrogenator

C2H5 C2H5
Pd

ΔH°r= -1541.6Kcal/gmole

Reaction Temperature = 50°C

Reaction Pressure = 4 atm

17
 Chemical Reactions
Side Reaction in the Hydrogenator
C2H5 C2H5
Pd
3

ΔH°r = -862.5 Kcal/gmole

Reaction Temperature = 50°C
Reaction Pressure = 4 atm
18
 Chemical Reactions
Reaction in the Oxidizer
C2H5
C2H5

ΔH°r = -341.6 Kcal/gmole

Reaction Temperature = 60°C
Reaction Pressure = 3 atm
19
 Chemical Reactions
Reactions in the Regenerator
Reaction # 1:

C2H5 C2H5
Al2O3
3 ΔH°r = 862.5 Kcal/gmole

Reaction # 2:

C2H5 C2H5
Al2O3
ΔH°r = 1541 Kcal/gmole

20
21
 Basis
• 3424 kg/hr of 95 % pure Hydrogen Peroxide
• Hydrogenation yield is 80 % based on Ethyl
anthraquinone feed
• Oxidation yield is 90 % based on Ethyl Hydro
Anthraquinone

22
 Overall Material Balance
8 Nitrogen and unreacted Oxygen

5% Hydrogen Peroxide
Hydrogen 1 15
Air 5 16 95 % Hydrogen Peroxide

17 Water
Total mass going in = Total mass going out
Stream 1 + Stream 5 + Stream 17 = Stream 8 + Stream 15 + Stream 16
2.91 x 104 kg/hr = 2.91 x 104 kg/hr

23
 Material Balance around Hydrogenator
13
1 4
2
3
Stream 1 2 3 4 13
Temperature (°C) 50 50 50 50 50
Pressure (atm) 4 4 4 3.8 4
Ethyl Anthraquinone (Kg/hr) - 387 - 4952 3.71x 104
Ethyl Hydroanthraquinone (Kg/hr) - - - 3.00 x 104 -
Tetra form of EHA (Kg/hr) - - - 2518 -
Hydrogen (Kg/hr) 227 - - - 88
Benzene (Kg/hr) - - 456 1.67x 105 1.67x 105
Butanol (Kg/hr) - - 456 1.67x 105 1.67x 105
Nitrogen (Kg/hr) - - - - -
O2 (Kg/hr) - - - - -
Water (Kg/hr) - - - - -
H2O2 (Kg/hr) - - - - -
Total Mass Flowrate (Kg/hr) 227 387 912 3.72x 104 3.72x 104
24
 Material Balance around Hydrogenator

13
1 4
2
3

Hydrogenator Mass Balance

Total Mass Going into Hydrogenator = Total Mass going out of Hydrogenator
Stream 1 + Stream 2 + Stream 3 + Stream 13 = Stream 4
3.72 x 105 kg/hr = 3.72 x 105 kg/hr

25
 Material Balance around Oxidizer
R-101

22
6
5

Stream 22 5 6
Temperature (°C) 60 60 60
Pressure (atm) 3 3 2.8
Ethyl Anthraquinone (Kg/hr) 4952 - 3.17 x 105
Ethyl Hydroanthraquinone (Kg/hr) 3.0x 104 - 2997
Tetra form of EHA (Kg/hr) 2518 - 2518
Hydrogen (Kg/hr) - - -
Benzene (Kg/hr) 1.67x 105 - 1.67x 105
Butanol (Kg/hr) 1.67x 105 - 1.67x 105
Nitrogen (kg/hr) - 1.33x 104 1.33x 104
O2 (kg/hr) - 4029 403
Water (kg/hr) - - -
H2O2 (kg/hr) - - 3853
Total Mass Flowrate (kg/hr) 3.72 x 105 1.73 x 104 3.89x 105
26
 Material Balance around Oxidizer
R-101

22
6
5

Oxidizer Mass Balance:

Total Mass Going into oxidizer = Total Mass going out of Oxidizer

Stream 22 + Stream 5 = Stream 6

3.89 x 105 kg/hr = 3.89 x 105 kg/hr

27
 Material Balance around Separator
S-100

8
6
7
Steam 6 7 8
Temperature (°C) 60 60 60
Pressure (atm) 2.8 2.5 2.5
Ethyl Anthraquinone (Kg/hr) 3.17 x 104 3.17 x 104 -
Ethyl Hydroanthraquinone (Kg/hr) 3.00x 103 3.00x 103 -
Tetra form of EHA (Kg/hr) 2.52x 103 2.52x 103 -
Hydrogen (Kg/hr) - - -
Benzene (Kg/hr) 1.67x 105 1.67x 10 5 -
Butanol (Kg/hr) 1.67x 105 1.67x 10 5 -
Nitrogen (kg/hr) 1.33x 104 - 1.33x 104
O2 (kg/hr) 4.03x 102 - 4.03x 102
Water (kg/hr) - - -
H2O2 (kg/hr) 3.85x 103 3.85x 10 3 -
Total Mass Flowrate (kg/hr) 3.89x 105 3.75x 105 1.37x 104

28
 Material Balance around Separator

S-100

8
6
7

Separator Mass Balance:

Total Mass Going into separator = Total Mass going out of separator

Stream 6 = Stream 7 + Stream 8

3.89 x 105 kg/hr = 3.89 x 105 kg/hr

29
 Material Balance around Extractor
C-100

7 10

17 9
Stream 7 17 9 10
Temperature (°C) 60 30 60 60
Pressure (atm) 2.5 2.5 2 2
Ethyl Anthraquinone (Kg/hr) 3.17x 104 - - 3.17x 10 4
Ethyl Hydroanthraquinone (Kg/hr) 2997 - - 2997
Tetra form of EHA (Kg/hr) 2518 - - 2518
Hydrogen (Kg/hr) 0 - - -
Benzene (Kg/hr) 1.67x 10 5 - - 1.67x 10 5
Butanol (Kg/hr) 1.67x 10 5 - - 1.67x 10 5
Nitrogen (kg/hr) - - - -
O2 (kg/hr) - - - -
Water (kg/hr) - 1.16x 10 4 1.16x 10 4 -
H2O2 (kg/hr) 3853 - 3853 -
Total Mass Flowrate (kg/hr) 3.75x 10 5 1.16x 10 4 1.54x 10 4 3.71x 10 5

30
 Material Balance around Extractor
C-100

7 10

17 9

Extractor Mass Balance

Total Mass Going in to extrator = Total Mass going out of extractor

Stream 7 + Stream 17 = Stream 9 + Stream 10

3.87 x 105 kg/hr = 3.87 x 105 kg/hr

31
 Material Balance around Regenerator

11 12

Stream 11 12
Temperature (°C) 600 600
Pressure (atm) 4.2 4
Ethyl Anthraquinone (Kg/hr) 3.17x 104 3.71x 104
Ethyl Hydroanthraquinone (Kg/hr) 2997 -
Tetra form of EHA (Kg/hr) 2518 -
Hydrogen (Kg/hr) - 88
Benzene (Kg/hr) 1.67x 105 1.67x 105
Butanol (Kg/hr) 1.67x 105 1.67x 105
Nitrogen (kg/hr) - -
O2 (kg/hr) - -
Water (kg/hr) - -
H2O2 (kg/hr) - -
Total Mass Flowrate (kg/hr) 3.7x 105 3.7x 105
32
 Material Balance around Regenerator

11 12

Regenerator Mass Balance

Total Mass Going in to Regenerator = Total Mass going out of Regenerator

Mass in Stream 11 = Mass in Stream 12

3.7 x 105 kg/hr = 3.7 x 105 kg/hr

33
 Material Balance around Distillation Column

15
14
16
Stream 14 15 16
Temperature (°C) 124 105 188
Pressure (atm) 2 1 3
Ethyl Anthraquinone (Kg/hr) - - -
Ethyl Hydroanthraquinone (Kg/hr) - - -
Tetra form of EHA (Kg/hr) - - -
Hydrogen (Kg/hr) - - -
Benzene (Kg/hr) - - -
Butanol (Kg/hr) - - -
Nitrogen (kg/hr) - - -
O2 (kg/hr) - - -
Water (kg/hr) 1.16x 104 1.14x 104 1.71x 102
H2O2 (kg/hr) 3.85x 103 5.99x 102 3.25x 103
Total Mass Flowrate (kg/hr) 1.54x 104 1.20x 104 3.42x 103
34
 Material Balance around Distillation Column

15
14

16

Distillation Column Mass Balance

Total Mass Entering Distllation Column = Total Mass leaving Distillation Column

Mass in Stream 14 = Stream 15 + Stream 16

1.54 x 104 kg/hr = 1.54 x 104 kg/hr

35
Energy Balance

36
 Basis
• Time = 1 hr
• Reference Temperature = 25°C
• Maximum Pressure = 4 atm

37
 Energy Balance across Hydrogenator
13
1 4
Reference Temperature = 25°C
2
3
Stream 1 2 3 13 4
Temperature (°C) 50 50 50 50 50
Pressure (atm) 4 4 4 4 3.8
Enthalpy of Ethyl Anthraquinone (Kcal/hr) - 9.23x 103 - 7.87x 105 1.05 x 105
Enthalpy of EHA (Kcal/hr) - - - - 2.70 x 109
Enthalpy of Tetra form of EHA (Kcal/hr) - - - - 6.85 x 107
Enthalpy of Hydrogen (Kcal/hr) 6.20x 101 - - 2.41x 101 -
Enthalpy of Benzene (Kcal/hr) - - 2.3x104 6.86x 103 6.86 x 103
Enthalpy of Butanol (Kcal/hr) - - 9.98x104 9.92x 103 9.92 x 103
Enthalpy of Nitrogen (Kcal/hr) - - - - -
Enthalpy of O2 (Kcal/hr) - - - - -
Enthalpy of Water (Kcal/hr) - - - - -
Enthalpy of H2O2 (Kcal/hr) - - - - -
Total Enthalpy (Kcal/hr) 6.20x 101 9.23x 103 1.23x105 8.04x 105 2.77 x 109

38
 Energy Balance across Hydrogenator
13
1 4
2
3

Energy Balance across Hydrogenator (R-100):

Heat of Main Reaction = -4.66 x 106 Kcal/hr

Heat of Side Reaction = -2.17 x 105 Kcal/hr

Heat Supplied (Qp) = 2.76x 109 Kcal/hr
Total Enthalpy of the streams entering = Total Enthalpy of the leaving streams

Stream 1 + Stream 2 + Stream 3 + Stream 13 + Qp = Stream 4

2.7x 109 Kcal/hr = 2.7 x 109 Kcal/hr

39
 Energy Balance across Oxidizer
R-101

5
22 6
Reference Temperature = 25°C
Stream 22 5 6
Temperature (°C) 60 60 60
Pressure (atm) 3 3 2.8
Enthalpy of Ethyl Anthraquinone (Kcal/hr) 1.47 x 105 - 1.47 x 10 5
Enthalpy of Ethyl Hydroanthraquinone(Kcal/hr) 3.78 x 109 - 3.78 x108
Enthalpy of Tetra form of EHA (Kcal/hr) 9.58 x 107 - 9.58 x 107
Enthalpy of Hydrogen (Kcal/hr) - - -
Enthalpy of Benzene (Kcal/hr) 9.60 x 103 - 7.49x105
Enthalpy of Butanol (Kcal/hr) 1.39 x 104 - 8.89 x 105
Enthalpy of Nitrogen (Kcal/hr) - 1.66xx 10 7 1.16 x 108
Enthalpy of O2 (Kcal/hr) - 4.63x 10 6 3.24 x 106
Enthalpy of Water (Kcal/hr) - - -
Enthalpy of H2O2 (Kcal/hr) - - 7.54 x101
Total Enthalpy (Kcal/hr) 3.88 x 109 2.12x 10 7 5.95 x 108

40
 Energy Balance across Oxidizer

R-101

5
6
22

Energy Balance Across Oxidizer (R-102):

Heat of Reaction = -4.46 x 107 Kcal/hr

Heat Removed (Qp) = 3.28 x 109 kcal/hr

Total Enthalpy of the streams entering = Total Enthalpy of the streams coming out

Stream 22 + Stream 5 = Stream 6 + Qp

3.9 x 109 kcal/hr = 3.9x 109 kcal/hr

41
 Energy Balance across Regenerator

11 12
Reference Temperature = 25°C
Stream 11 12
Temperature (°C) 600 600
Pressure (atm) 4.2 4
Enthalpy of Ethyl Anthraquinone (Kcal/hr) 2.41x 106 1.81x 107
Enthalpy of Ethyl Hydroanthraquinone (Kcal/hr) 6.21x 109 -
Enthalpy of Tetra form of EHA (Kcal/hr) 1.57x 109 -
Enthalpy of Hydrogen (Kcal/hr) - 5.55x 102
Enthalpy of Benzene (Kcal/hr) 1.58x 105 1.58x 105
Enthalpy of Butanol (Kcal/hr) 2.28x 105 2.28x 105
Enthalpy of Nitrogen (Kcal/hr) - -
Enthalpy of O2 (Kcal/hr) - -
Enthalpy of Water (Kcal/hr) - -
Enthalpy of H2O2 (Kcal/hr) - -
Total Enthalpy (Kcal/hr) 7.79x 109 1.85x 107

42
 Energy Balance across Regenerator

11 12

Energy Balance Across Regenerator (R-103):

Heat of Reaction # 1 = 2.09 x 107 kcal/hr

Heat of Reaction # 2 = 2.24 x 107 kcal/hr

Heat Removed (Qp) = 7.77 x 109 kcal/hr

Total Energy of the streams entering = Total Energy of the streams coming out

Total Enthalpy of Stream 11 = Stream 12 + Qp

7.79 x 109 kcal/hr = 7.79 x 109 kcal/hr

43
 Energy Balance across Distillation Column

15
14
16
Reference Temperature = 25°C

Stream Enthalpy (Kcal/hr)

Feed 6.13x 104

Top Product 5.82x 104

Bottom Product 1.53x 103

Condenser (Duty) -1.59x 107

Reboiler (Duty) 2.94x 107

44
 Energy Balance across Heat Exchangers
Reference Temperature = 25°C

Total Enthalpy of Total Enthalpy of

Heat Entering Leaving Streams Heat Duty
Exchangers Streams(Kcal/hr) (kcal/hr) (Kcal/hr)

E-100 3.30 x 103 6.20 x 101 -3.25 x 103

E-101 1.64x 1010 2.12x 107 -1.64x 1010

E-102 1.59x 1010 2.12x 107 -1.59x 1010

E-103 4.76x 108 7.79x 109 7.31x 109

E-104 1.85x 107 8.04x 105 -1.77x 107

E-105 3.15x 103 6.13x 104 5.81x 104

45
 YET TO PERFORM
• Heat integration of the process
• Heat Exchanger Network (HEN) design for
the process
• Equipment Design
• Mechanical design
• Process Equipment cost estimation
• Process Economic cost evaluation
• Process control
• HAZOP study
46