SHITAL JAGTAP

SACHIN HADAVALE

MAYUR ZUNJARRAO

GUIDE:- PROF. A K BANDSODE

INTRODUCTIONHydrogen peroxide (H2O2) is the simplest peroxide

Hydrogen peroxide is a clear liquid, slightly more viscous than water.

HISTORY Hydrogen peroxide was first manufactured in 1818 by Louis Jacques Thenard

by reacting barium peroxide with nitric acid. An improved version of this process used hydrochloric acid, followed by sulfuric acid to precipitate the barium sulfate byproduct. Thenard's process was used from the end of the 19th century until the middle of the 20th century.

LITERATURE SURVEYNo Process Date Auther

1 Direct production of hydrogen peroxide from oxygen and

hydrogen applying membrane-permeation mechanism

1 Jan 2010 Tomoya Inoue, Yusuke Tanaka,

Koichi Sato

2 Anthraquinone process for the production of hydrogen

peroxide

May 2008 Qunlai Chen

3 Hydrogen Peroxide production by water electrolysis

13 October 2004

Yuji Ando, Tadayoshi Tanaka

4 Hydrogen Peroxide production by oxidation of cyanide

15 October 2007

Susana Silva Martínez

5 Hydrogen peroxide formation by direct combination of H2 and O2 in a

micro reactor

16 January 2010

Yury Voloshin, Adeniyi Lawal

6 Hydrogen peroxide synthesis by direct photo reduction of 2-

ethylanthraquinone

1 January 2011 Mao Mao,

Xue-You Duan,

7 Catalytic synthesis of hydrogen peroxide in micro reactors

4 April 2008 K. Kusakabe,

Maehara

8 Photochemical production of hydrogen peroxide in Antarctic

Waters

6 June 2000 David J. Kieber

9 Direct synthesis of hydrogen peroxide from hydrogen and oxygen

over palladium catalyst

25 July 2009 Ji Chul Jung,

Sunyoung Park,

10 Direct synthesis of hydrogen peroxide from H2 and O2 using zeolite supported Au catalysts

30 May 2006 Albert F. Carley,

Jennifer Edwards

PHYSICAL PROPERTIESMolecular formula H2O2

Molar mass 34.0147 g/mol

Appearance light blue to colourless

Density 1.450 g/cm3 (20 °C)

Melting point -0.43 °C, 273 K, 31 °F

Boiling point 150 °C, 423 K, 302 °F

Solubility Soluble in ether

Refractive index 1.34

Viscosity 1.245 cP (20 °C )

Specific heat capacity 2.619 J/g K (liquid)

pH 6.2

Std enthalpy offormation ΔHf 298 k

-4.007 kJ/g

USES Pulp and paper Mining Textile bleaching Controlling fungus on fish and eggs Waste water treatment Healing wounds Explosive

MARKET SURVEY

0

20000

40000

60000

80000

100000

120000

140000

160000

2005-06 2006-07 2007-08 2008-09 2009-10 2010-11

DEMAND

SUPPLY

IMPORT AND EXPORTIMPORT EXPORT

COUNTRY QUANTITY (Kg)

COUNTRY QUANTITY (Kg)

China 5155989 Untd. Arab Emts.

1167115

Indonesia 2268897 Bangladesh 1156390

Rep. Of Korea

1121118 Maldives 400000

Turkey 887374 Sri Lanka 259830

Taiwan 600277 Kenya 105000

MANUFACTURING PROCESSES Wet Chemical Process Electrochemical Process Autoxidation Process

The Wet Chemical Process Disadvantages

High capital costLow hydrogen peroxide contentUnsatisfactory stability

Electrochemical processAdvantages

More conc. H2o2

High purity H2o2

DisadvantagesHigh capital investmentHigh electricity consumption

AUTOXIDATION PROCESS Hydrogen peroxide is manufactured almost

exclusively by the autoxidation (AO) process. The process is based on a reduction of anthraquinone, followed by oxidation resulting in the formation of H2O2.

Hydrogen peroxide is separated from water with extraction and is concentrated to produce grades at standard commercial strengths of 35 - 65%.

Reactions Of Autoxidation Process

Hydrogenation

Oxidation

Process Selection

Higher industrial applicabilityGreater purity of H2O2

Ease of operationEasy availability of raw materialLesser cost of raw materialRecycle of raw materialLesser power requirement

THERMODYNAMIC FEASIBILITY

Components Heat Of Formation(KJ/mol)

Heat Capacity(KJ/ Kmol °C)

2-Ethyl Anthraquinone

C16H12O2

-111.021 453.4

2-Ethyl Hydroquinone

C16H14O2

-132.46 489.4

Hydrogen Peroxide

H2O2

-45.16 70.79

HydrogenH2

0 28.65

OxygenO2

0 26.1

For Hydrogenation Reaction that is

C16H12O2 + H2 →C16H14O2

Heat of Formation of above reaction at 298 K is

ΔHf 298K = ΣΔHf Products - ΣΔHf Reactant

= - 132.46 - ( - 111.021)

= - 21.439 KJ/molThe specific heat is givaen as follows

ΔCP = ΣΔCP Products - ΣΔCP Reactant

= 489.4 - (453.4 + 28.65)

=7.35 KJ/ Kmol °C

The heat of reaction at working temp.

ΔHR 313 K = ΔHf 298K

= -21439 + (7.35) (40 - 25)

= -21328 KJ/KmolThe entropy of Hydrogenation Reaction

ΔSR 313 K = ΔSR° +

At const temp ΔSR°= 0

ΔSR 313 K = 7.35 ln (40/25)

= 3.454 KJ/Kmol °C

40

25

PdtC

dtT/C40

25

P

The Gibbs free energy

Δ G 313 k = ΔHR 313 K - T ΔSR 313 K

= -21328.75 - 40 X 3.54

=- 21446.93 KJ/Kmol (Less than zero)

Consider second reaction taking place in oxidizer

C16H14O2 + O2 →C16H12O2 + H2O2

ΔHf 298K = ΣΔHf Products - ΣΔHf Reactant

= ( - 111.021 - 45.16) - ( - 132.46 )

= -23.721 KJ/mol

ΔCP = ΣΔCP Products - ΣΔCP Reactant

= 453.4 + 70.79 - 489.4 - 26.1

= 8.69 KJ/ Kmol °C

ΔHR 323 K = ΔHf 298K

= -23721 + 8.69 ( 50 - 25 )

=-23503.75 KJ/Kmol

ΔSR 323 K = ΔSR° +

= 0 + 8.69 ln ( 50/25 )

= 6.023 KJ/ Kmol °C

50

25

PdtC

dtT/C50

25

P

The Gibbs free energy

Δ G 323 k = ΔHR 323 K - T ΔSR 323 K

= - 23503.75 - 50 X 6.023

= -23804.922 KJ/Kmol (Less than zero)

From the above values it can be seen that the values of Gibbs Free energy at respective working temp. is less than zero, which is the ideal case scenario. Thus both the reactions are feasible and thereby the selected process is also feasible.

BibliographyPerry's handbook of chemical engineering 8th

editionUllmans Encyclopedia WikipediaSciencedirect.comwww.cheresources.com

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