Study of Porous Carbon Materials as

Catalyst for Chemical Reactions

Undergraduate Thesis

Submitted in partial fulfillment of the requirements of

BITS F424T Thesis

By

Mahesh Bansal
ID No. 2016B2A30172P

Under the supervision of:

Dr. Bibhas Ranjan Sarkar

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI, PILANI CAMPUS

May 18, 2021
 Declaration of Authorship
I, Mahesh Bansal, declare that this Thesis titled, ‘Study of Porous Carbon Materials as Catalyst
for Chemical Reactions’ and the work presented in it are my own. I confirm that:

 This work was done completely while in candidature for the Master’s Thesis at BITS
Pilani.

 I have clearly ascribed, where ever I have consulted the work of others.

 I have acknowledged all main sources of help.

 I have ascribed all sources of simulation used for the project.

Signed:

Date:

i
 Certificate
This is to certify that the thesis entitled, “Study of Porous Carbon Materials as Catalyst for
Chemical Reactions” and submitted by Mahesh Bansal ID No. 2016B2A30172P in partial
fulfillment of the requirements of BITS F424T Thesis embodies the work done by him under my
supervision.

Supervisor
Dr. Bibhas Ranjan Sarkar
Faculty,
BITS-Pilani Pilani Campus
Date:

ii
 BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE PILANI, PILANI CAMPUS

Abstract
Master of Science (Hons.)

Study of Porous Carbon Materials as Catalyst for Chemical Reactions

by Mahesh Bansal

There has been immense developments in Porous Carbon Materials as Catalysts. These materials
have found commercial applications in many fields like drug delivery, catalysis, chromatography
etc. and hence there is continuous study going on for these reactions. In this paper we have
tried to explore the historical use of carbon in catalysis and than established the properties of
porous carbon materials which help them in catalysis. This is followed by the application of
porous carbon materials in different types of reaction highlighting mechanisms and comparison
with historical methods used etc. This is followed by the reactivation and recycling process for
these materials. The thesis is then concluded at last.
 Acknowledgements
I would like to take this opportunity to sincerely thank my Thesis adviser Prof. Bibhas Ranjan
Sarkar for his constant guidance and ever helping nature. I am grateful to him for his valuable
insights and useful discussions which have helped me resolve the questions I had. His enthusiasm
has always helped me to develop a greater interest in the subject.

I want to profoundly thank all the faculty members of BITS Pilani who have enabled me to
consolidate my knowledge in the last five years and helped me evolve as a student and also as a
human being. I also express my gratitude to my peer group from BITS Pilani for introducing me
to porous carbon materials and enriching my knowledge through constant discussions. I want to
express my gratitude for my family and friends for being a constant source of motivation and
encouragement. Their contribution to my growth is invaluable.

Finally, I would also like to thank the AUGSD Division at Birla Institute of Technology and
Science, Pilani for providing me with the opportunity of undertaking the thesis program.

iv
Contents

Declaration of Authorship i

Certificate ii

Abstract iii

Acknowledgements iv

Contents v

List of Figures vii

1 Introduction to Carbon Materials as Catalysts 1

1.1 Importance of Carbon Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Advantages of Using Carbon as a Catalyst . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Types of Carbon Material Used for Catalysis . . . . . . . . . . . . . . . . . . . . 2

2 Porous Carbon Materials 3

2.1 Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Activated Carbon- Production and Product Forms . . . . . . . . . . . . . . . . . 4
2.3 Properties of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4 Choosing the Right Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . 6
2.5 Applications of Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3 Applications of Activated Carbon as Catalyst 8

3.1 Acid Catalyzed Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2 Hydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3 Dehydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4 Electrocatalytic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.5 Methoxilation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.6 Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.7 Friedlander reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.8 Cyclohexanol Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.9 Alkylation of N-heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.10 Ring opening reaction of Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . 16

v
Contents vi

4 Reactivation and Recycling of Activated Carbon 17

4.1 Reactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.2 Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

5 Conclusion 20

Bibliography 20
List of Figures

2.1 Types of Pores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.2 Applications of Porous Carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1 naphthoquinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.2 Anthraquinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.3 Electrocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3.4 Methoxylation mechanis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3.5 Amount of oxygen on materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

3.6 Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.7 Quinoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.8 Cyclohexanol Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

3.9 Alkylation of N-heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

3.10 Ring opeining reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

vii
Chapter 1

Introduction to Carbon Materials as

Catalysts

1.1 Importance of Carbon Materials

Carbon is the fourth most common element in the solar system and the sixth most common
element in the universe and the seventeenth most common element in the Earth’s crust and also
is unique element in our world. It has been found that the abundance of carbon is between 180
and 270 parts per million. It is also the 2nd most common element in the human body after
oxygen therefore taking about 18 percent of a human’s body weight. One of the descriptions of
carbon is being of a wide range of metastable phases that can be formed at ambient conditions
and their kinetic stability. In this thesis we will discuss the various applications of porous carbon
materials in the field of catalysis.

We know that both inorganic and organic carbons play a key role in catalysis. Organic molecules
form the backbone of a huge discipline of organic chemistry and they are the most of the
times both the substrates and the products of the process under consideration in catalytic
applications. In homogeneous catalysis carbon is often the major constituent of the organic
ligands surrounding the metallic center. In enzymatic catalysis carbon is the backbone of the
active species. In heterogeneous catalysis carbon materials act as unique catalyst supports which
allows the anchoring of the active phase as well as also act as catalysts or catalyst poisons by
themselves.

1
Chapter 1. Introduction 2

1.2 Advantages of Using Carbon as a Catalyst

• Carbon materials are generally hydrophobic and they generally show a low affinity towards
polar solvents such as water and a high affinity towards solvents such as acetone. Even
though the hydrophobic nature of carbon materials may affect the dispersion of the active
phase over the carbon support the surface chemistry of carbon materials can easily be
changed by using different processes for example by oxidation to favor ionic exchange and
increase their hydrophilicity.[2]

• Porous structure and surface chemistry which is easily tailorable.

• Metals on the support can be easily reduced.

• The carbon structure is resistant to bases and acids

• The structure is stable at high temperatures ,i.e, even above 1023 K under inert atmosphere.

• Porous carbon catalysts can be prepared in different physical forms, such as cloth, fibers,
granules, pellets, etc.

• The active phase can be easily recovered.

• The cost of conventional carbon supports is generally lower than that of conventional
supports such as alumina and silica.

1.3 Types of Carbon Material Used for Catalysis

Many carbon materials have been studied but activated carbon (AC) and carbon black
(CB) are the most commonly used carbon supports. Surface area and porosity of activated
carbon are very large and this favors the dispersion of the active phase over the support and
also increase its resistance to sintering at high metal loadings. The pore size can be adjusted to
suit the requirements of multiple reactions. The surface chemistry of carbon catalysts influences
both their performance as catalysts and catalyst supports. In this discussion we will mainly
focus on activated carbon and its various applications in catalysis.
Chapter 2

Porous Carbon Materials

2.1 Activated Carbon

Activated carbon which is also known as activated charcoal are a group of materials with huge
internal surface area and porosity and hence have a large capacity for adsorbing chemicals from
gases and liquids. The adsorption on the surface is mainly because of Van der Waals/London
dispersion forces. This force is very strong over short distances and is equal between all carbon
atoms and does not depend on external parameters such as pressure or temperature and therefore
the adsorbed molecules are held most strongly where they are surrounded by the most carbon
atoms. The area which presents high density of graphitic basal structural units favors a high
adsorption. High temperature treatment, i.e., ¿1500 K of an activated carbon can favor the
adsorption sites by increasing the density of “-sites” which are present on partly graphitized
structure. Almost all precursors which contain a high fixed carbon content can potentially be
activated. The most commonly used raw materials for activated carbon include coconut shells,
coal, wood, peat and petroleum based residues or agricultural residues.

Activated Carbon has highly developed porosity and, consequently a high surface area, which
can reach more than 2000 m2/g. The determination of the pore size is very important to define
the application of an activated carbon. According to the IUPAC pores are classified based on
the average pore size: micropores which have a dimension ¡ 2 nm, mesopores(2 nm ¡ dimension ¡
50 nm) and macropores with a dimension ¿ 50 nm. Each group of pores has a specific function,
the macropores are used as transport pores, the mesopores are used as transitional pores both
in the adsorption of larger molecules and in the transport of smaller molecules, and micropores
are the pores where adsorption occurs.

3
Chapter 2. Porous Carbon Materials 4

Figure 2.1: Types of Pores

2.2 Activated Carbon- Production and Product Forms

Activated carbon is made from carbonaceous raw materials such as peat, lignite, charcoal,
bituminous coal, fruit stones, coconut shell, etc and these materials are activated using one of
two distinct methods.

In the gas activation process, carbonized material is oxidized using the stream of gas, such
as steam, carbon dioxide, air or a mixture of these. Activation temperatures typically lie in the
range from 700 to 1100° C. In the resulting water-gas reaction the carbon is partially gasified
and a porous and highly activated carbon skeleton is formed.

In the chemical activation process, nonincinerated carbonaceous material is initially mixed

with dehydrating or oxidizing chemicals and heated to between 400 and 800° C. The activation
agent – zinc chloride, phosphoric acid, sulphuric acid, etc. which may be used – is leached out
and recovered.

The activation process itself is generally carried out in rotary kilns, multiplehearth, shaft
or fluidized bed furnaces or in fluid bed reactors.

The most common product forms of activated carbon are:

• extruded (genreally in the form ofcylindrical pellets)

• broken (granular or broken activated carbon)

• powder, in specified particle sizes

Specially manufactured types include:

Chapter 2. Porous Carbon Materials 5

• spherical activated carbon pellets

• activated carbon fibres and fibre mats and

• honeycombs

The determining factor for the adsorptive capacity of activated carbon products in use are
manufacturing and activation processes and the basic raw material used. The size of the inner
surface area and the pore structure are primarily dependent on the activation process used.

2.3 Properties of Activated Carbon

Activated Carbon is an extremely environmentally-friendly carbon porous material and it has

an ever increasing number of applications in different domains. These materials have enormous
desirable characteristics such as tunable porosity, light weight, electrical conductivity, chemical
and physical stability and a possibility to present different morphologies.

Carbon Materials have found application in multiple areas such as drug delivery, catalysis,
chromatography systems, energy storage , water treatment, air and gas purification.

In most pf these applications, controlled porosity and tunable surface chemistry are deter-
minant for activated carbon performance and carbon materials technology have presented
extraordinary developments in recent years.

Figure 2.2: Applications of Porous Carbons

Chapter 2. Porous Carbon Materials 6

2.4 Choosing the Right Activated Carbon

Due to high performance requirements in complex technical processes, activated carbon of highest
quality is selected[10]

Powdered Activated Carbon Performance Requirements

Kinetics and filterability : This is done by controlling particle size distribution. A wider particle
size distribution gives better kinetics between reactants and the actual catalyst. Although narrow
particle size will give fast filtration but also sacrifice suspension characteristics.

Optimal catalyst activities : Larger mesoporosity has benefits in terms of available surface area
for catalyst dispersion, faster transport of reactants in and out the pores, and adsorption of
unwanted byproducts.

Optimal catalyst activities : Activated carbon with high purity is required to prevent side reac-
tion or poisoning of the catalyst.

Extruded Activated Carbon Performance Requirements

Minimizing metal loss : To prevent collapse of the carbon bed, a high crushing strength is
required . High hardness gives in a low abrasion to avoid catalyst into fines so that it minimizes
the loss of our precious metals.

Longer life and higher yield : If we effectively overcome the poisoning of the actual catalyst, it
will extend the catalyst’s life span.

Higher activity : It is achieved by the larger surface area of carbons with higher mesoporosity.
In this situation the “egg shell” metal catalyst is mainly dispersed on the outside of the carbon
particle.

2.5 Applications of Activated Carbon

Commercially available carbon-supported materials[9] are well known as heterogeneous catalysts

and are used for a variety of reactions such as :

• hydrogenation

• dehydrogenation
Chapter 2. Porous Carbon Materials 7

• oxidation

• hydrodesulfurization

• hydrodenitrogenation

• hydrodeoxygenation

• electrocatalytic reactions

• NO reduction

This is primarily because of desirable properties such as chemical inertness, stability in the
absence of molecular oxygen at high or low pH values, mechanical resistance and high surface
area. Pore size distribution and surface areas are the most important factors in catalytic re-
actions involving large molecules, where accessible mesopores are preferred over micropores.
Impregnation, Ion exchange,colloid dispersion, vapor-deposition methods and electroless plating
are the typical preparation methods for metal loaded functionalized carbon. The control of the
carbon surface chemistry which include surface oxygen and other heteroatoms, amphoteric charac-
ter and hydrophobicity, are very important for control over the pore structure of carbon supports.

In the next chapter we will discuss in detail the various types of reactions in which carbon is
used as a catalyst.
Chapter 3

Applications of Activated Carbon as

Catalyst

Multiple types of reactions have been studied with various forms of activated carbon and the
results have been published. Some of those are listed in this chapter.

3.1 Acid Catalyzed Reactions

We know that many fine chemical synthesis reactions are catalyzed by acids. Historically such
reactions are performed in the presence of strong inorganic acids and in a homogeneous phase.
Acids like nitric acid,sulfuric acid or hydrochloric acid have many disadvantages for the process,
although they have fast kinetics and high conversions, they often present low selectivity. They
are also corrosive and aggressive compounds and are very demanding on the equipment, and have
a post reaction treatment that can be complicated, tedious and can be potentially very harmful
for the environment. Activated carbon is a most friendly, and economic alternative among the
many heterogeneous catalysts that have been developed and employed as acid catalyst in fine
chemical synthesis.[5]

3.2 Hydrogenation Reactions

Hydrogenation reactions were conducted over activated carbon where Naphthalene, benzene,
phenanthrene, anthracene, 2,3-naphthacene were used as substrates at 300 °C to examine the
relationship between their molecular structures and reactivities. The results show that the
activated carbon catalyzed the hydrogenation of the PAs selectively and that the reactivities of
the these substrates(arenes) toward hydrogenation were dependent on the hydrogen-accepting

8
Chapter 3. Applications 9

abilities of the substrates and on the adsorption strengths of the substrates on the catalyst
surface.[7]

The reactivities of these aromatic compounds toward hydrogenation are known to be dom-
inated by their hydrogen-accepting abilities, which can be evaluated by the superdelocalizability
Sr; i.e., an atom in an aromatic ring with a larger Sr value accepts a H atom more readily. The
order found for the materials used was benzene (0.833 in any position) , naphthalene (0.994 in
the 1-position) ¡ phenanthrene (0.998 in the 9-position) , anthracene(1.314 in the 9-position)
, 2,3-naphthacene(1.505 in the 5-position). A similar pattern was found in the hydrogenation
using activated carbon also.

3.3 Dehydrogenation Reactions

In a study done it was found that the activated carbonmolecular oxygen system promotes the
conversion of hydroquinones to naphthoquinones, benzoquinones, and anthraquinones, which are
often found in pharmaceuticals and natural products. In particular, the one-pot synthesis of
naphthoquinones and anthraquinones involving a DielsAlder reaction is a useful protocol for this
purpose.[4]

A one-pot synthesis of naphthoquinones via a dehydrogenation, DielsAlder reaction, and dehy-

drogenation sequence was carried out.
Chapter 3. Applications 10

Figure 3.1: One-Pot Synthetic Strategy for Naphthoquinone

During the investigation of the synthesis of naphthoqui- nones, it was found that when excess
amount of 1,3- dienes were used, anthraquinone derivatives were obtained including two times of
DielsAlder reaction. After optimization, the conditions for one-pot synthesis of anthraquinones
in excellent yield were established.

Figure 3.2: One-Pot Synthesis of Anthraquinones from Hydroquinones

Chapter 3. Applications 11

3.4 Electrocatalytic Reactions

An emerging cost-effective strategy is conversion of bio-wastes to useful doped carbon materials

for various energy applications. In this study activated carbon electrocatalyst which is derived
from chicken feather rachis (RCF) which is a poultry industry bio-waste was explored for oxygen
reduction reaction (ORR) catalysis. The rachis is the central stem from which the fibrous ramus
is completely removed and it is more crystalline compared to feather ramus. Using the chemical
activation coupled pyrolysis, Nitrogen doped activated carbon (CNAx) electrocatalyst was
prepared. The chemical activators used include phosphoric acid (H3PO4 ) , potassium hydroxide
(KOH) and zinc chloride (ZnCl2 ) followed by pyrolysis at 500, 700 and 900 C. Electrochemical
performance was evaluated using cyclic voltammetry (CV) and linear sweep voltammetry (LSV).
It was found that KOH activated electrocatalyst exhibits remarkable improvement in surface area
favouring improved onset potential (0.02 V vs Ag/AgCl). This increase in activity is attributed
to increase in number of well-exposed ORR active sites on activation.[8]

Figure 3.3: Electrocatalysis

3.5 Methoxilation

The presence of functional groups on the surface of the material are particularly relevant for
these specific catalytic reactions. The application of these materials as acid catalyst is deter-
mined by nature, type and concentration of such groups as some of them may act as active sites.[6]
Chapter 3. Applications 12

The type and concentration of Oxygen functional groups on AC can be modified by oxida-
tive agents which can either be in gas-phase or in solution, and through thermal treatments
which is being tuned by careful selection of the preparation conditions. It has been established
that it is possible to have several oxygenated groups at same time in different amounts at the
surface of an activated carbon : carboxylic acids, carbonyl, quinone, ether, phenol, lactone.

Several treatments are performed to obtain an oxidised carbon surface which include treatment
in liquid phase with acids,typically HNO3, H2SO4 or a mixture of both; treatment with hydrogen
peroxide H2O2, or treatment with gases, such as N2 doped with O2 or air, or even N2O and
ammonia (NH3), where also other heteroatoms may be introduced.

Figure 3.4: Mechanism of methoxylation of -pinene

Chapter 3. Applications 13

Methoxilation of -pinene was studied by using three HNO3 oxidised carbon materials: a meso-
microporous activated carbon prepared from olive stones (CBN), a xerogel carbon (CMN) and a
commercial microporous carbon (NoritN), as acid catalysts in yielding -terpinyl methyl ether as
main product of the reaction. Although some effect of the textural properties could be observed,
the results indicated that the most important feature of these catalysts was the surface chemistry
(Fig. 3.5). The olive stone based carbon was obtained by chemical activation with phosphoric
acid and resulted in a biomass catalyst with better characteristics for the reaction studied, due
to the introduction of phosphate groups during its synthesis. The order for catalytic activity
increased as NoritN ¡ CMN ¡ CBN, showing that the textural properties also have some influence
and all catalysts showed good selectivity towards the -terpinyl methyl ether.

Figure 3.5: Comparative amount of oxygen containing surface groups determined by TPD for
CBN, CMN and Norit N.

3.6 Esterification

Palm kernel shell was used as raw material to prepare biomass based carbon, a low value
residue of the palm oil industry. The solid acid catalyst was subjected to treatment with
concentrated sulfuric acids after carbonization. The obtained solid acid proven to be highly
active for cellobiose hydrolysis reactions. The results were studied and they evidenced a relation
between the amount of sulfonic groups on the surface and the catalytic activity. A mecha-
nism for the reaction which had preferred sulfonation position at the surface was proposed
and confirmed by quantitative XPS where lower amounts of sulfonic groups are located at
positions with better access to reactants thus resulting in higher turnover numbers. The re-
sults that were obtained with the carbons were better than the ones obtained with synthetic
resins presenting higher sulphur content. Therefore after seeing the result the importance of
Chapter 3. Applications 14

other functional groups present in the surface of the carbon in a synergetic action was inferred.[3]

Figure 3.6: Biomass based activated carbon for esterification

3.7 Friedlander reaction

In the Friedlander reaction, the carbon materials which were most acidic and microporous and
having sulfonic groups in the surface proved to be efficient catalysts and a cheap alternative for
the synthesis of quinolines with high conversions and moderate selectivity. The importance of
the functional acidic group was also suggested by theoretical calculations. It was observed that
the computed results show a lower flexibility for the intermediate formed after binding to the
surface. Prosity and specific surface area of the carbon materials also play an important role in
these results, probably contributing to the selectivity.

Figure 3.7: 2-aminobenzaldehyde with ketones to form quinoline derivative

Chapter 3. Applications 15

3.8 Cyclohexanol Conversion

Cyclohexene, cyclohexanone, phenol and benzene are the possible products in the gas phase
reaction of cyclohexanol and the surface functional groups play an important role for both
conversion and selectivity. In this study different catalysts were prepared by varying the oxidation
treatment applied to the same parent carbon and the resulting materials were characterized
in order to determine the amount and nature of the surface groups as a consequence of the
different oxidative procedures. It was concluded that cyclohexanol dehydration occurs mainly
in the carboxylic acid groups, resulting from the HNO3 treatment. The carbons which were
obtained with peroxide or oxygen presented high content in phenolic groups and offered best
selectivities to cyclohexanone. The carbon which was obtained with N2O treatment resulted in
high selectivity to phenol but in this case, it should be considered the participation of the nitro
groups in the reaction mechanism.

Figure 3.8: Conversion of Cyclohexanol over the carbon catalysts

Chapter 3. Applications 16

3.9 Alkylation of N-heterocycles

Commercial activated carbons prepared with HNO3 and H2SO4 were found to be very efficient
and selective catalysts for alkylation of N-heterocycles. This reaction may be used in the synthesis
of imidazolium ionic liquid, a high value product in increasing demand. The acidity of the carbon
obtained was the main feature and the results were enhanced when the reaction was carried
out in the absence of solvent which also reinforced the environmental benign nature of these
catalysts.

Figure 3.9: Scheme of reaction synthesis of N,N-di-n-butyl-imidazolium bromide.

3.10 Ring opening reaction of Epoxides

In the ring opening reaction of epoxides by alcohols, mesoporous activated carbons proved to be
effective catalysts presenting high conversion and selectivity, being possible to regenerate the
catalyst and restore its original activity.

Figure 3.10: Reaction of epoxides with alcohols.

Chapter 4

Reactivation and Recycling of

Activated Carbon

4.1 Reactivation

Exhausted granular activated carbon can often be reactivated using a thermal process that is
very similar to the original activation process and the activated carbon can then be reused. Thus
reactivation is an economical and environmentally sound alternative to disposal.

A number of different technical systems can be used in the reactivation of activated carbon,
including:

• rotary kilns

• multiple-hearth furnaces

• fluidized bed furnaces

The recycling process comprises two main processes: 1) The reactivation process. 2) Off gas
treatment and energy recovery process.[1]

The reactivation process itself can be subdivided in four steps:

• Drying of the used carbon : In this step the used carbon is fed into the furnace and heated
up from ambient to 105 – 110°C and then water and some low boiling compounds are
evapourated and released into the furnace atmosphere as a result of which the temperature
of the carbon remains between 105 and 110°C as long as there is still water in the pores.

17
Chapter 4. Reactivation and Recycling 18

• Desorption of the organics with a low boiling point : We increase the temperature further
to approximately 450°C when the carbon is dry and hence various organic compounds will
desorb from the carbon and escape into the furnace atmosphere during this temperature
increase.

• Pyrolysis of the strongly adsorbed organics with high boiling point/molecular weight : We
further heat the carbon in this step to about 600°C as a result of which the remaining
organics will decompose into smaller molecules that are released in the furnace atmosphere
and form a char residue in the pore structure of the activated carbon.

• Gasification of the char residue : In this step we increase the temprature to 850°C and
also inject steam as a result of which the pore structure in the carbon is reformed. We
observe that steam at temperatures above 600°C will oxidise the carbon in an endothermic
way, the so-called steam carbon gasification reaction. The zone of the furnace will have
following reactions:

Solid-gas reactions

Gas-gas reactions

Some observation that were made were : the solid gas reaction (1) is three times faster the
solid-gas reaction (2) and for this reason, steam is injected in the furnace. The pore structure
will be recovered to optimum activation levels necessary for the application in which the product
is used by controlling the operating conditions of the furnace.
The resulting gases leaving the furnaces are fed through an afterburner and an off-gas treatment
system to allow emission to atmosphere in accordance with the most stringent local environmental
regulations. Recycling by thermal reactivation is an environmentally responsible disposal method
that helps to reduce CO emissions over the activated carbon and contributes to a sustainable
use of the world’s resources.
Other regeneration techniques:

• TSA (thermal swing adsorption)

Chapter 4. Reactivation and Recycling 19

• MWR (microwave regeneration)

• Chemical and solvent regeneration

• Microbial regeneration

• Electrochemical regeneration

• Ultrasonic regeneration

• Wet air oxidation

4.2 Recycling

We know it is not always possible to regenerate or reactivate used activated carbon. Some
companies through intensive development efforts have created an environmentally safe method
for recycling such activated carbon using a carbide process.
In one of these process, the used, exhausted activated carbon is introduced through hollow
electrodes directly into the molten carbide, where all of the pollutants attached to the activated
carbon are thermally decomposed at a temperature of roughly 2000° C. In this process, the
activated carbon is converted along with the burnt lime into carbide.
Chapter 5

Conclusion

The application of carbon materials as catalyst and the properties which help them were
established and further extending the discussion the properties of porous carbon materials
which include tunable prorosity, electrical conductivity, chemical and physical stability etc. were
established. There are multiple types of activated carbon and the choosing the right one is
important and hence the parameters to do that were established. Several applications of porous
carbon materials in catalysis which include acid catalyzed reactions,hydrogenation reactions,
dehydrogenation reactions, electrocatalytic reactions etc. were discussed. Finally we know that
the process to develop activated carbon are costly and hence it should be reactivated and reused
as much as possible and the methods for same have been discussed.
In all this discussion we can clearly see the potential that porous carbon materials have for
applications in various fields and especially catalysis. New materials are being established daily
and their applications are being studied widely which clearly indicates that these have immense
potential for the future.

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