HOMEPAPER PART-1 SUBMISSION

TOPIC: Manufacturing process of Hydrogen Peroxide

SUBMITTED BY: Shubham Ashokrao Shinde

Final year Bachelor of chemical engineering

ROLL NO.: 16CHE165

KVM
Contents
1. Introduction .............................................................................................................................................................. 3
1.1 Physical Properties: ........................................................................................................................................... 3
1.2 Chemical Properties: ......................................................................................................................................... 3
1.3 Applications of Hydrogen Peroxide: ................................................................................................................. 4
1.4 Current market of Hydrogen peroxide: ............................................................................................................. 4
1.5 History of Synthesis of Hydrogen Peroxide: .................................................................................................... 4
2. Process Selection: ..................................................................................................................................................... 6
3. Manufacturing Process: ............................................................................................................................................ 6
4. Kinetics of the Reaction: ........................................................................................................................................... 9
5. Utilities Required: ..................................................................................................................................................... 9
6. Site Selection:.......................................................................................................................................................... 10
6.1 Profitability Factors: ............................................................................................................................................. 10
6.2 Productivity Factors: ............................................................................................................................................. 11
7. References .............................................................................................................................................................. 13
 1. Introduction
Hydrogen peroxide is an inorganic, weak acid. It is a powerful oxidizing agent. It is also a good reducing agent
against more powerful oxidizing agents. On reaction, it releases oxygen and water. Thus, it is non-polluting
in nature, unlike many other oxidizing agents. It is unstable and slowly decomposes in the presence of light.
Because of its instability, hydrogen peroxide is typically stored with a stabilizer in a weakly acidic solution.

1.1 Physical Properties:

Hydrogen peroxide [CAS = 7722-84-1] is a clear, colourless liquid which is miscible with water in all
proportions. Its highly concentrated aqueous solutions (>65 wt%) are soluble in a variety of organic solvents
such as carboxylic esters. H2O2 and water does not form an azeotropic mixture.

Table 1: Physical properties of hydrogen peroxide

1.2 Chemical Properties:

Dissociation constant of hydrogen peroxide at 20˚C is 1.78 × 10-12 (pK 11.75) indicating weak acidic nature
in aqueous solution. It can behave both as oxidizing and a reducing agent.

 Decomposition: 2H2O2 → 2H2O + O2

 Molecular addition: H2O2 + Y → Y.H2O2

 Substitution: H2O2 + RX → ROOH + HX

 H2O2 + 2RX → ROOR + 2HX

 Oxidation: H2O2 + W → WO + H2O

 Reduction: H2O2 + Z → ZH2 + O2

Where R, W, X, Y, Z represent various functional groups or molecules.

1.3 Applications of Hydrogen Peroxide:

1.4 Current market of Hydrogen peroxide:

The global market for hydrogen peroxide is projected to reach 6.0 million metric tons by 2024. As per the
market in India is observed; Currently a huge quantity of product is being imported from countries like
Thailand, Bangladesh and Pakistan. However, domestic manufacturers have started ramping up their
capacities to meet the growing demand for their product. As per market reports, the domestic demand for the
product is expected to grow at 5 to 7 percent per annum.

1.5 History of Synthesis of Hydrogen Peroxide:

1) Wet Chemical Process:
In 1818, L.J. Thenard obtained hydrogen peroxide by treating barium peroxide [CAS = 1302-29-6]
with nitric acid. This process is then improved by using Hydrochloric acid. The reactions are as follows
BaO2 + 2HCl → BaCl2 + H2O2
BaCl2 + H2SO4 → BaSO4 + 2HCl

BaO2 + H2SO4 → BaSO4 + H2O2

The 3% aqueous hydrogen peroxide solutions manufactured by this process had only a limited market because
of their high production cost, low hydrogen peroxide content, and unsatisfactory stability due to impurities.

2) Electrochemical Process:
Introduction of this process eliminated the disadvantages of the Wet Chemical process. In 1853,
Meidinger discovered the formation of hydrogen peroxide during electrolysis of aqueous sulfuric acid.
 2H2SO4 → H2S2O8 + H2
H2S2O8 + H2O → H2SO5 + H2SO4
H2SO5 + H2O → H2SO4 + H2O2
2H2O → H2O2 + H2

In 1950, the production of hydrogen peroxide using this process reached up-to approximately 30 kt/a.

3) Organic Autooxidation process:

The discovery of this process was the major breakthrough in industrial production of hydrogen
peroxide, which enabled the construction of modern large-scale plants. In 1901, Manchot discovered
that hydroquinone reacts quantitatively with oxygen to form quinone and hydrogen peroxide.
However, this process had two major drawbacks: hydrogenation of azobenzene (quinone) was
performed with sodium amalgam, and oxidation of hydrazo-benzene proceeded satisfactorily only in
alkaline solution. These two problems were overcome by using alkylated anthraquinones instead of
azobenzene between 1935 and 1945.

4) Production from Hydrogen and Oxygen:

Hydrogen peroxide can be formed by direct reaction of oxygen and hydrogen. The direct synthesis by
heterogeneous catalysis is emerging as a relevant alternative to the anthraquinone autooxidation (AO)
process. One of the main issues with this process is the catalyst: it promotes both hydrogen peroxide
formation and the unwanted side reaction (Scheme 1).

Scheme 1: Reactions involved in the direct synthesis of H2O2.

 2. Process Selection:
Comparison between Direct process and Indirect auto-oxidation process is shown below

Above comparison shows that there is an issue of selectivity of catalyst in direct synthesis process, while
production from anthraquinone is well known and well-developed process which is being used commercially.

3. Manufacturing Process:
The manufacturing process involves the catalysis of the reaction of H2 (obtained from processing Maui Gas)
with atmospheric O2 to give H2O2. Anthraquinone (Q) is used as a
H2 carrier.
Step1 - Hydrogenation
Palladium catalyzes the reaction between H2 and anthraquinone to create anthrahydroquinone (H2Q):

Q + H2 → H2Q

Step 2 - Filtration
The palladium catalyst is filtered out of the solution.
Step 3 - Oxidation
The solution is oxidised by blowing air through the solution, forming the H2O2:

H2Q + O2 → Q + H2O2

Step 4 - H2O2 Extraction

The hydrogen peroxide is removed in a liquid-liquid extraction column and concentrated by vacuum
distillation.
 Flow diagram 1: The Anthraquinone Process for H2O2
Manufacture

Hydrogen peroxide is manufactured using the anthraquinone process. This process is a cyclic operation
where the alkyl anthraquinone is reused. The Synthesis Loop consists of sequential hydrogenation, filtration,
oxidation and extraction stages (Figure 1). A number of ancillaries processes are also involved.

Step 1 - Hydrogenation
An alkyl anthraquinone is dissolved in two solvents, one nonpolar and the other polar. Collectively the
anthraquinone and solvents are called the working solution. This working solution is recycled.
The working solution containing the dissolved anthraquinone is hydrogenated using hydrogen gas in
a slurry-type hydrogenator using alumina loaded with a small amount of palladium catalyst. Temperature is
controlled to around 45oC and the reactor is agitated to ensure good mixing of catalyst with working solution
and hydrogen. During hydrogenation the alkylanthraquinone is converted to both the alkylanthrahydroquinone
and the tetrahydroalkyl-anthrahydroquinone, although production of the tetra-form of the quinone is preferred
because it can be more easily hydrogenated.
Step 2 - Filtration
The working solution that now contains hydrogenated anthraquinone is then filtered to remove any trace levels
of catalyst. If the catalyst is not removed then it will decompose the hydrogen peroxide in later stages, reducing
yields and causing potential hazards.
Step 3 - Oxidation
The working solution is oxidised by blowing air through it. The tetrahydroalkyl-anthrahydroquinone is
oxidised, forming hydrogen peroxide in an organic phase. No catalyst is used and hence this step is often
referred to as auto-oxidation.
Step 4 - H2O2 Extraction
Since the hydrogen peroxide is present in an organic phase and the product is required in aqueous
phase, demineralized water is added to the top of a 35-metre-high liquid-liquid extraction column. The water
flows down the column over perforated trays while the working solution is pumped up the column. The
extractor design and operation ensure a maximum contact of water with the working solution.
The water reaches the bottom of the extractor and contains 25-35% w/w crude hydrogen peroxide, whilst the
working solution that leaves the top of the extractor is free of hydrogen peroxide and is pumped back to the
hydrogenator. This working solution now contains the original alkylanthraquinone and tetrahydro-
alkylanthraquinone.
The crude hydrogen peroxide is subsequently purified and vacuum distilled to concentrations of up to 70%
w/w. This concentrated product is stabilised against unwanted decomposition by adding proprietary stabilisers
and then pumped to product storage tanks for final testing.

4. Kinetics of the Reaction:

Kinetics and thermodynamic parameters for the oxidation of 2-Ethyltetrahydroanthraquinone is as follows:
 Order of reaction: First Order
 Henry const: H20˚C = 112,100 atm cm3/mol
o H50˚C = 109,000 atm cm3/mol
 Mass transfer coefficient: kL(20˚C) = 5.5 × 10-3 cm/s
o kL(50˚C) = 6.6 × 10-3 cm/s
 Kinetic Constant kc = 3830 ± 300 cm3/(mol.s)
 Temperature requirement: 50˚C

5. Utilities Required:
1) Hydrogen Plant

This plant processes natural gas through a steam reforming stage and subsequent high temperature shift
catalytic stage to produce high purity hydrogen gas. The gas is finally purified in a pressure swing absorber
before being used by the hydrogenator. Details of this process can be found in the manufacture of methanol.

2) Demineralised Water

High purity water is used to feed the extractor, concentrator as well as the package boiler. Conventional
degassing followed by cation and anion exchange beds is used to purify town water for use in the peroxide
process.

3) Package Boiler

A small boiler generates steam for use in concentrating crude peroxide from 25-35% to 35-70%
 4) Waste Gas System

The oxidiser can produce an exit gas containing trace levels of solvents. The solvent entrained gas is fed to a
bed of activated carbon where the solvents are absorbed onto the carbon. The activated carbon is purged with
nitrogen gas and the solvent is stripped off and recovered for reuse in the synthesis loop.

5) Calciner Systems

A calciner is used to regenerate spent catalyst on a periodic basis. The catalyst is removed from the
regenerators, washed and then roasted to remove any other organics that might be present. These organics, if
not removed, will block the catalytic sites on the catalyst and lower its activity.

6. Site Selection:
Plant location plays critical role in the economic viability of the process. Hence it is desirable to select a plant
place with safer working condition, cheap and skilled labor, availability of raw material and probable effect
of waste generated. The choice of location of a chemical plant depends upon number of factors and their
effects on personnel on the plants. It is a crucial parameter, which can affect the profitability of the project
and the scope for future expansion. These two aspects depend on various parameters:

6.1 Profitability Factors:

1. Raw Material

For this plant raw materials are:

 Hydrogen supply
 Alkyl anthraquinone
 Palladium catalyst

Supplier of Hydrogen gas:

1) Maharashtra Gas Company, Turbhe MIDC, Navi Mumbai

2) Southern gas limited, Margao, Goa
3) Praxair India, Andheri East, Mumbai
4) Navyug Industries, Ankleshwar, Gujarat

Suppliers of Alkyl anthraquinone are

1) Anjani Dyes & Intermediates Private Limited Navrangpura, Ahmedabad

2) EMCO dyestuffs PVT. LTD. Borivali (East), Mumbai
3) Akar Dyes and Chemicals, Mumbai
 4) Prolife Industries Ltd, Ankleshwar, Gujarat

Suppliers of Palladium Catalyst:

1) Evan Chem Pvt Ltd., Vile Parle, Mumbai

2) Sud-Chemie India Pvt Ltd, Vadodara, Gujarat
3) Johnson Matthey Chemicals IPL, Kanpur, Uttar Pradesh

2. Land

Cost of land should be as low as possible. Keeping in mind the size and the capacity of the plant, the cost of
land required is not going to play an important role in the actual selection of the site.

3. Product Market

Hydrogen peroxide product market is described as follows.

Paper bleaching and pulp industry 41%
Chemical Synthesis 43%
Textile 8%
Environmental 4%
Other uses 4%
Most of the paper industries and chemical industries are in Maharashtra, Andhra Pradesh and Gujarat. Hence,
while selection a particular site we must consider its proximity from these sites.
4. Environmental aspects:

Present states of environment, proximity to archaeological/historical area, density of population is some

factors that come under environmental issues.

5. Tax rates

Tax rates should be as low as possible.

6. Support from state government

This factor is also very important especially in a country like India where the administrative delays in

approvals and licensing can transform a plausible fortune-making project to a hapless one.

6.2 Productivity Factors:

1. Energy consideration
Continuous supply of power and fuel is critical parameter in running plant continuously. To enhance
productivity continuous supply of energy is essential.
 2. Labour
Hostile labour can affect continuous profile of the plant. Hence to maintain the productivity labour factors
should be considered.

3. Storage
Timely delivery of raw materials should be ensured to minimize inventory.

4. Transportation and Airport

The final product hydrogen peroxide has a good market potential in India as well as abroad. So, proximity to
a port is essential.

5. Rivers
Water is the basic utility required in each and every chemical industry. Hence, supply of water must be
continuous.

6. Soil survey
This includes the type of soil, its bearing capacity, and identification of seismic zones and the height of water
table.

7. Infrastructure
The site should be accessible by road, rail and air. Not much amount can be afforded for building infrastructure
in this project. Existence of a good infrastructure is important.

8. Roads
For better transportation, proper network of roads must be present.

9. Residential facility

The cost of land should be as low as possible, so that we can have a housing facility.

As Gujarat state has major manufacturers and suppliers of the raw materials required for the process. Land,
market for the product and Tax benefits are available along with cheap labors and proper infrastructure.
Ankleshwar is a major industrial zone in Gujarat hence Considering all the factors, the plant location
should be in Ankleshwar, Gujarat.
7. References

1) Ullmann’s 6th edition, Vol. 17, hydrogen peroxide, Page number: 253 - 268
2) https://www.strategyr.com/MarketResearch/market-report-infographic-hydrogen-peroxide-forecasts-
global-industry-analysts-inc.asp
3) https://www.maharashtradirectory.com/product/anthraquinones.html
4) Article on ‘The Manufacture of Hydrogen Peroxide’ written by Terry Deed (Du Pont Peroxide Ltd.)
with editing by Heather Wansbrough.
5) Hydrogen Peroxide Direct Synthesis: Enhancement of Selectivity and Production with non-
Conventional Methods Pierdomenico Biasia, Juan Garcia Sernab, Tapio O. Salmia, Jyri-Pekka
Mikkola, CET chemical engineering transactions, Vol. 32, 2013.
6) E. Santacesaria, r. Ferro, S. Ricci, S. Carra, Ind. Eng. Chem. Res. 1987,26, 155-159 Kinetic Aspects
in the Oxidation of Hydrogenated 2-Ethyltetrahydroanthraquinone.
7) P. Oinas, G. Wild, N. Midoux, H. Haario, Chem. Eng. Proc 1995,34(6), 503-516, Identification of
mass transfer parameters in case of simultaneous gas absorption and chemical reaction.