DEPARTMENT OF MINING

ENGINEERING

INSTITUTE OF TECHNOLOGY, 2005

BANARAS HINDU UNIVERSITY,
VARANASI.
BHU MINERS
• Nelanuthula Srikanth
• Nikhil Ninad Sirdesai

MENTORED BY:
Dr. Aarif Jamal
Reader, Institute of Technology
Banaras Hindu University,
Varanasi
CARBON DIOXIDE SEQUESTRATION
BY ROCKS AND MINERALS
 INDEX:
• INTRODUCTION
CO2 Emission, Consequences,
Strategies for Control, Global Scenario

• MINERAL CO2 SEQUESTRATION

Chemistry, Selection Of Minerals,
Thermodynamics, Kinetics , Mechanism,
Optimisation

• PROPOSED TECHNIQUE
Construction and Working

• CONCLUSION
INTRODUCTION:
• We have reached the pinnacle of
industrial and technological development,
on the expense of CO2 concentration in
the atmosphere.
• The level of CO2 in the atmosphere has increased by 36.07% i.e.
280-381ppm since the industrial revolution which has led to:
 The Greenhouse Effect.

 Acidification of the surface of the ocean.

 Fertilization of Eco-system

YEAR 1990 2000 2007 2025

CO2 (MMT) 21563 23899 27715 37124
EMISSION
 INTRODUCTION:

• Consequences of excess CO2 emission:

• Global surface temperature increased by
0.74 ± 0.18ºC (1.33 ± 0.32ºF) during the
last 100 years.
• Surveys indicate that the surface temperature
will rise a further by 1.1 to 6.4ºC ( 2 to 11.5ºF).
• Other effects include: Ozone Layer Depletion,
Melting of Ice Caps and Glaciers leading to increase in sea-level.
• Main Strategies use for reducing the level of CO2 in atmosphere:
• Improvement of energy efficiency
• Use of renewable energy
• Carbon Dioxide Sequestration
 INTRODUCTION:
INTRODUCTION
CARBON SEQUESTRATION:
It refers to the capture and the storage of CO2 in repositories in such a way that
it remains stored and will not release into the atmosphere. All CO2 sequestration
technologies consist of two steps. First, the carbon dioxide is captured and
separated from the flue gas or the air. Second, the CO2 is stored.

OPTION Estimated Global

Capacity (GtC)
Mineral Very large
Sequestration
Sea-Bottom 1000
Geological 345
Repositories
Biological 50-100
Sequestration
 MINERAL CO2 SEQUESTRATION

• Mineral CO2 sequestration refers to a technology whereby carbon

dioxide is reacted with metal (Ca-Mg) cations to form solid
carbonate minerals.
• In nature such a reaction is called silicate weathering and takes
place on a geological time scale.
• Metal cations are mainly obtained
from silicates of Ca-Mg bearing
rocks such as:
 Olivine (MgSiO4)
 Serpentine ((Mg,Fe)3 Si2O5 )
 Wollastonite (CaSiO3 )
 Others
CHEMISTRY OF MINERAL CO2 SEQUESTRATION.
GENERAL EQUATION:
MO + CO2 MCO3 + heat
 OLIVINE:
Mg2SiO4 + 2CO2 2MgCO3 + SiO2 + 89 kJmol-1CO2

 SERPENTINE:
Mg3Si2O5(OH)4 + 3CO2 3MgCO3 + 2SiO2+ 2H2O +
64 kJmol-1CO2

 WOLLASTONITE:
CaSiO3 + CO2 CaCO3 + SiO2 + 90 kJmol-1CO2
MINERAL CO2 SEQUESTRATION
Mineral Carbon Dioxide Sequestration technique can
be discussed under the following four heads:
1. SELECTION OF MINERALS :
• Alkaline Earth Metal Oxides are considered over alkali
metal oxides as alkali metal carbonates are very soluble in water.
• As oxides are more reactive, silicates from Mafic and Ultramafic
rocks are preferred.
• Alkaline solid waste materials ( pulverized fuel ash, bottom ash, fly
ash, de-inking ash) from industries are also used.

MINERAL STORAGE CAPACITY

Serpentine (50% MgO) 0.507 kg/kg of rock
Olivine (50% MgO) 0.398 kg/kg of rock
Wollastonite (10% Cao) 0.080 kg/kg of rock
 2. THERMODYNAMICS

• The Carbon Dioxide Sequestration reactions are exothermic in

nature. Formation of carbonates is favored at low temperature and
low partial pressure.
• Whereas at high temperature (above 900ºC for calcium carbonate
and above 300ºC for magnesium carbonate, at CO2 partial pressure
of 1bar) the reverse reaction, i.e. calcinations is favoured.
• Even at low partial pressure of atmospheric CO2 and at ambient
temperature carbonation of minerals occur spontaneously.
• In aqueous systems temperature is typically kept below 200ºC,
since high temperature favours gaseous CO2 over precipitated
carbonates.
3. KINETICS:
• Simplest approach to mineral carbonation is the reaction of gaseous CO2 and
particulate metal oxide bearing material at suitable temperature and pressure.
• As the above mentioned process is slow, the alternative requires the
extraction of metal from the solid. This is done by suspending the solids
material in an aqueous solution. The metal oxide dissolution is the rate-limiting
step.
• Ways to speed up the extraction of the metal include:
Activation:
 Heat treatment at 650 ºC for serpentine.
 Ultrafine (attrition) grinding for olivine and wollastonite.
Additives And Catalysts:
 Catalysts eliminates of interference between
metal oxide dissolution and carbonate precipitation.
 Important catalyst include: Carbonic acid(H2CO3),
Hydrochloric acid (HCl), Ammonium Chloride(NH4Cl),
EDTA, Sodium Bicarbonate (NaHCO3).
4. MECHANISM :
• Process routes comprises of the following methods:
• Mineral pre-treatment:
Mineral pre-treatment, excluding the chemical processing steps,
involves crushing, grinding and milling, as well as some mechanical
separation, for example magnetic extraction of magnetite (Fe3O4).
• CO2 pre-processing:
Carbon dioxide should be used at a pressure similar to pipeline
pressure, requiring minimal or no compression.
Purity demands in carbonation are minimal as acidic components of the
flue gas are neutralized by the base and disposed.
Most carbonation processes would preheat CO2 ,100-150ºC for aqueous
processes whereas in gas-solid reactions it is 300-500ºC.
• Sequestration Routes:
The pre-treatment is followed by sequestration routes. Two main types of
routes can be distinguished.
1. Direct Routes (One Step)
2. Indirect Routes (More than one step)
• Direct Route:
Direct route of a mineral can be conducted in two ways:
Direct Gas-Solid Carbonation with CO2 : Its direct gas-solid carbonation. As
an example, the direct gas-solid reaction of olivine is given:
Mg2SiO4(s)+ 2CO2 (g) 2MgCO3 (s)+ SiO2(s)
High CO2 pressures obtain reasonable reaction rates. The rates can be
enhances by the use of supercritical CO2 which dissolves the produced water.
The reaction can be expressed as:
Mg3Si2O5(OH)4 (s)+ 3CO2(sc) 3MgCO3(s) + 2SiO2(s)+ 2H2O(l/g)
Aqueous Scheme:
In this method CO2 reacts at high pressure in aqueous suspension of serpentine.
Carbonic acid is used in this method.
Aqueous Scheme:
CO2 , NaHCO3 dissolves in water to form H+ and HCO3- ion which consequently react
with silicate mineral forming respective carbonate
• Mg2SiO4 (s) + 4NaHCO3 (aq) 2MgCO3 (s) + 2Na2CO3 (aq) + SiO2 (s) +
2H2O (l)
• 2Na2CO3 (aq) + 2H2CO3 (aq) 4NaHCO3 (aq)
NaHCO3 is regenerated in this process and NaCl acts as catalyst to increase Mg 2+ ions.
• Indirect Route:
In this method reactive components are first extracted from the mineral matrix and then
carbonated in a separate step. It includes :
HCl extraction route:
This process is used for serpentine. To extract Mg from the mineral matrix HCl is used.
HCl is recovered by heating solution from 100 to 250ºC. MgCl(OH) is formed as
intermediate which converts to Mg(OH)2 which on carbonation gives MgCO3. Changing
the extraction medium can lower energy consumption, so molten salt MgCl 2 3.5 H2O is
used as medium.
Method via Calcium Hydroxide from Calcium-rich silicate rock
This method is HCl extraction route used with CaSiO3 .
CaSiO3 + 2HCl CaCl2 (aq) + SiO2 (s) + H2O (l)
CaCl2 obtained is converted and precipitated as Ca(OH)2 for easy separation of
HCl, which inturn gets converted to carbonate.
Wollastonite Carbonation using carbonic acid:
It uses acetic acid and wollastonite as reactants. First step consists of
wollastonite reaction with acetic acid.
CaSiO3 + 2CH3COOH Ca2+ (aq) + 2CH3COO- (aq) + H2O+ SiO2
Next step includes carbonation of calcium and recovery of acetic acid.
Ca2+ (aq) + 2CH3COO- (aq) + CO2 + H2O CaCO3 ↓+ 2CH3COOH (l)
OPTIMISATIONS:
Surface Area
Sulphuric acid ( 1.5M,51ºC ) can be used
for increase of surface area of serpentine.
There was change of surface area from
8m2/g to 172m2/g in the first 3 hours ,
further no notable change is observed.

Pressure
Raising the partial pressure of CO 2,increases
the extent of reaction in one hour due to

increased activity of CO2 .It also completes

the reaction due to volume change desiring

products of reaction
Temperature
The rate of reaction increased until particular
temperature and then decreased as CO2
Solubility decreases. The temperature is
185ºC for olivine and 155ºC for pre-treated
serpentine
PROPOSED TECHNIQUE
• Thermal Power Plants (coal based) are one of the leading CO2 emitters of
the world, considering this fact we proposed a design which could
sequestrate CO2 and store it for future needs
• On the basis of the literature discusses above, it is suggested that Ca-Mg
silicate rich minerals may be used as liner in duct ,which is to be fitted on
chimneys of coal based Thermal Power Plants or any plants using coal as
fuel
• The proposed design is given below in steps:

Hot Flue Gases Serpentine/Olivine Duct

Cooled Flue Gas Ca-Mg carbonates CO 2 get adsorbed

Water Methanol (CH 3OH)

 Outlet

Acids and Methanol are

collected

Proposed
Design
Water Chamber Concrete

Coolant

Pre-treated Serpentine / Brick wall

Olivine Layering
Air Filter
Inlet for Flue Gases
Heat Regulator
CONCLUSION:
• The sources of Carbon dioxide emission are mostly non-point and aerial in
nature. The CO2 absorbing properties of the above mentioned minerals can
be used to design the roofs of houses in such a way that they absorb
maximum amount of CO2 as possible.
• Mineral carbon sequestration has advantages such as formation of
thermodynamically stable solid carbonates which can be permanently
stored, large sequestration capacity due to large volumes of suitable
feedstock deposits of Ca-Mg bearing rocks worldwide. Finally the
carbonation reactions are exothermic and occur spontaneous in nature
• It may be concluded from the above survey that minerals are most suitable,
logical and play an active role in sequestration of CO2 on a large scale
among the available Carbon Sequestration techniques.
• The experimental setup at laboratories stage will further conform the
application of technique for CO2 sequestration.
And Please make an attempt
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