Sunday 22 October 2017

What is Boudouard Reaction

The Boudouard reaction is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide and graphite or its reverse.

2CO --------> 2CO + C



Coal
While formation enthalpy of CO2 is higher than that of CO, the formation entropy is much lower. Consequently, according to the Ellingham diagram, the overall free energy change of formation of CO2 by oxidation of carbon is almost constant and indifferent of the temperature, while the free energy change of formation of CO is a decreasing line. These two lines meet at 700℃, so the Boudouard reaction implies that on lower temperatures the equilibrium is on the exothermic carbon dioxide side and on higher temperatures the endothermic formation of carbon monoxide is the dominant reaction.
For instance, in the high temperature reducing environment of a smokestack, carbon monoxide is the stable product. When the carbon monoxide reaches the top of the smokestack, and the cooler air, the Boudouard Reaction takes place; the carbon monoxide is oxidized into carbon dioxide, and the graphite precipitates (reduces) as soot. The Ellingham diagram is a plot of the Gibbs free energy change for a reaction (ΔG), versus temperature.

In industrial catalysis, this is not just an eyesore; the coking can cause irreversible damage to catalysts and catalyst beds. This reaction also takes place in blast furnaces where carbon monoxide is used as the reductive agent on purifying metallic iron from its oxides in ore.

The reaction is named after the French chemist, Octave Leopold Boudouard (1872—1923) who investigated this equilibrium in 1905. 

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Saturday 21 October 2017

What is Boudouard reaction

The Boudouard reaction is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide and graphite or its reverse.
 
2CO \rightleftharpoons  CO2 + C
 
Coal
While formation enthalpy of CO2 is higher than that of CO, the formation entropy is much lower. Consequently, according to the Ellingham diagram, the overall free energy change of formation of CO2 by oxidation of carbon is almost constant and indifferent of the temperature, while the free energy change of formation of CO is a decreasing line. These two lines meet at 700℃, so the Boudouard reaction implies that on lower temperatures the equilibrium is on the exothermic carbon dioxide side and on higher temperatures the endothermic formation of carbon monoxide is the dominant reaction.
For instance, in the high temperature reducing environment of a smokestack, carbon monoxide is the stable product. When the carbon monoxide reaches the top of the smokestack, and the cooler air, the Boudouard Reaction takes place; the carbon monoxide is oxidized into carbon dioxide, and the graphite precipitates (reduces) as soot. The Ellingham diagram is a plot of the Gibbs free energy change for a reaction (ΔG), versus temperature.

In industrial catalysis, this is not just an eyesore; the coking can cause irreversible damage to catalysts and catalyst beds. This reaction also takes place in blast furnaces where carbon monoxide is used as the reductive agent on purifying metallic iron from its oxides in ore.
 
The reaction is named after the French chemist, Octave Leopold Boudouard (1872—1923) who investigated this equilibrium in 1905. 
 
Read more....
 
 
 

Thursday 12 October 2017

COMBUSTION OF COAL (SOLID FUEL)

The combustion of solid fuel has the following stages
  1. Preheating and drying of fuel.
  2. pyrogenous decomposition of fuel with evolution of volatiles and formation of Coke Residue (carbon).
Evolution of volatile on being heated to 200 degree centigrade or more solid fuels liberated gaseous components are H2, CO, CO2, CH4 etc.

With combustion of coal dust the main mass of volatiles has no time to evolve before ignition of dust particles i.e.  volatiles burn essentially at the same time with the carbon

  • Reaction of burning of carbon
                C + O2 = CO2                          +399253.5 KJ/K mole    (exo)
                2C + O2 = 2CO                        +246623.4 KJ/K mole
  • Decomposition of carbon dioxide and water vapour by carbon
                C + CO2 = 2CO                        - 162530.1 KJ/K mole    (endo)
                C + 2H2O = CO2 + 2H2           -65294.2  KJ/K mole    (endo)
  • Oxidation of carbon monoxide by oxygen
                2CO + O2 = 2CO2                    +571683.6  KJ/K mole    (exo)
                
It is not definitely established yet weather CO or CO2 is formed first step. There are some reasons to support that CO and CO2 are formed simultaneously by the reaction  4C +3O2 = 2CO2 + 2CO

 Before carbon burning oxygen penetrates deep into the crystal lattice of fuel. The rate of combustion of solid depends on rate of chemical reaction and the rate of oxygen diffusion.



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Wednesday 11 October 2017

CONCEPTION OF SPONGE IRON

Iron Ore

The iron ore when is converted to sponge iron the appearance of iron is completely changed with more or less its coposition. Therefore it is important to know the conception of sponge iron before going details to the production.

Sponge Iron
The hematite iron ore whose chemical formula Fe2O3 is most suitable raw material for DRI/Sponge Iron. the oxide ore Fe2O3 during reduction reaction is converted to metallic Fe which is termed in solid state as SPONGE IRON.

The Oxygen concentration in Hematite iron ore is as Follows

Fe2O3 ----> 2 X Fe + 3O2 ---> 2 X 55.85 + 3 X 16

In the hematite ore 111.70 parts of iron combine with 48 part of oxygen.
when Hematite iron ore is of 65% Fe oxygen will be calculated as follows.

111.70     Parts of Fe contains      48 Parts of    O2
    1          Parts of Fe contains      48/111.70 Parts of    O2
   65         Parts of Fe contains      (48*65)/111.70 = 27.93 Parts of    O2

The Coposition of heatite iron ore is as follows.

  • Fe 
  • O2, SiO2, Al2O3, CaO, MgO, Pb, Cu, Zn, V, S, P = Gangue
  • LOI
During Reduction reaction Only O2 and LOI are reoved and all other elements remains intact.
So after reduction reaction the hematite ore is called DRI/Sponge iron and the weght of the product becomes lighter due to removal of O2 and LOI.
the Chemical composition of 65% hematite iron ore is supposed to be as follows.

Fe                                =                  65%
O2                                =                  27.93%
SiO2+Al2O3                =                   4.52%
CaO & MgO etc         =                  1.00%
LOI                             =                   1.55%

Total                           =                   100.00%

After 100% reduction of oxygen the sponge iron contains


Fe                                =                  65%
O2                                =                                                                 27.93%
SiO2+Al2O3                 =                  4.52%
CaO & MgO etc         =                  1.00%
LOI                             =                                                                  1.55%

Total                          =                   70.52%                                   29.48        = 100%

So like scrape the Fe(Iron) contains in sponge iron goes high depending on Fe% in Ore.


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Sunday 4 September 2016

Theories of Re-Oxidation of DRI

Re-Oxidation of DRI is related to the theory of corrosion caused by atmospheric oxidation in presence of oxidizing gas and moisture. The reasons for the high tendency of DRI to oxidize in the presence of air, and atmospheric moisture, rain are as follows..

HIGH POROSITY
Due to reduction of iron oxide of the Iron ore in the solid state, the porosity of the mass increases 50-70%. Thus, the surface to volume ratio of the iron ore becomes very high, as a result of which re-oxidation of DRI takes place at a faster rate.

ROUGH SURFACE
The ruptured surface of the DRI permits dust to accumulate and become solidly lodged. This cause rapid condensation of moisture, and thus accelerates corrosion

POOR THERMAL CONDUCTIVITY 
Sponge iron produced either by coal or gas based route posses poor thermal conductivity as a result, heat generated by exothermic re-oxidation reaction within the pile cannot be dissipated away and lead to temperature build-up in DRI, and thus, leads to accelerates the corrosion.

RE-OXIDATION REACTION

In Presence of Air
Hot sponge iron will react with oxygen present in air to form ferric oxide (Fe2O3) and Ferrosoferric Oxide (Fe3O4).
4Fe + 3O2 = 2Fe2O3                                   -1760 kcal/kg Fe
The reaction is quite sluggish in dry air, at ambient temperature.
3Fe + 2OFe3O4                                                 -1590 kcal/kg Fe

In presence of Moisture
The reaction continues as long as sponge iron remains hot and sufficient oxygen is available. Moisture pressure enhance the reaction rate.

2Fe + 3H2O = Fe2O3  + 3H2

This is a corrosion reaction.

In the presence of dissolved oxygen 
This reaction is accelerated by dissolved oxygen, which depolarized the cathodic area and produces ferrous hydroxide.

 2Fe + 3H2O + O= 2Fe(OH)

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