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Production of Carbon Black

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Ministry of Higher Education and Scientific Research

College of Chemical Engineering

Fourth stage, Project: Part 1

Production of Carbon Black

Supervisor
Suhaib S. Salih

By
Alsadeek O. Latof
Saleel N. Omar
 ABSTRACT :

Carbon Black is a fascinating material that has not only engaged the attention of those

who are concerned with the technology and applications of this material but has also

inspired a large number of fundamental investigations in scientific laboratories of

universities and research institutes around the world. Carbon black is widely used as a filler

to modify the mechanical, electrical and optical properties of the medium in which it is

dispersed. These applications play a major role in elastomers, plastics and in paints and

inks. It is, therefore, hardly surprising that the literature on carbon black and its applications

are extensive and is scattered in rubber, paint, and printing ink trade journals, in general

scientific and technical journals, and in periodicals covering such specialized subjects as

Colloid Chemistry, Rheology, Polymer Chemistry, Material Science, Carbon, etc. Since

the publication of the first edition in 1976, a huge amount of research work has been carried

out using the latest innovations such as FTIR, ESCA, inverse gas chromatography, and

STM. The examination of carbon black surfaces by these methods has led to a a better

understanding of the processing and the applications of this material as a filler. The

discovery of fullerenes has given a new twist to the mechanism of carbon black formation,

while STM has enabled scientists to have a look at carbon black structure on the atomic

scale , The literature on carbon blacks is so diverse that it appears beyond the capacity of

a single author to justify all the subjects that need to be discussed in a project on carbon

blacks.(4)

I
 CONTENTS :

Chapter 1 : Page
1.1 History of Carbon Black (1)

1.2 General Description (1)

1.3 Carbon Black Properties (3)

1.4 Application Examples of Carbon Black (6)

1.5 Manufacturing Process of Carbon Black (8)

1.5.1 Thermal Black Process (9)

1.5.2 Channel Black Process (9)

1.5.3 Lamp Black Process (11)

1.5.4 Acetylene Black Process (11)

1.5.5 Surface Oxidation / After Treatment of Carbon Black (12)

1.5.6 Furnace Black Process (12)

[Link] Production by the Furnace Black Process (13)

[Link] Description of the Process (14)

[Link] General Construction of Furnace Black Process (16)

[Link] Heat Exchanger (18)

[Link] Separation (19)

[Link] Densification and palletization (21)

II
 [Link] Storage and Packing (22)

[Link] Means of Control Downstream of the reactors (23)

[Link] After – Treatment (24)

[Link] Process Variants and Patents (24)

1.6 End – Uses for Carbon Black (24)

Table Chapter (1) :

1.1 Physical-Chemical Properties Carbon Black (3)

1.2 Kinds of Carbon Black Manufacturing Processes (9)

Figures Chapter (1) :

1.1 Illustration of the structure development of Carbon Black (5)

1.2 SEM image showing the primary particles (5)

1.3 Aggregates and agglomerates building structure (5)

1.4 3 different shades of black, depending on the surface of CB (5)

1.5 Application Example of Carbon Black (7)

1.6 Thermal Black Process (10)

1.7 Channel Black Process (10)

1.8 Lamp Black Process (11)

III
 1.9 Acetylene Black Process (11)
1.10 Surface Oxidation Process (12)
1.11 Furnace Black Process (12)
1.12 Flow diagram carbon black production (13)

1.13 Illustration of a furnace black plant (14)

1.14 Carbon black plant in Real life (15)

1.15 Heat Exchanger (19)

IV
Chapter 1 / INTRODUCTION
1.1 HISTORY OF CARBON BLACK

Carbon black was called "soot" in the west and "should" in the east. In the 1740s,
plant production started in the United States, and because of the production method
used, it was then called "lampblack." The term "carbon black" originated in the 1870s,
when products manufactured from natural gas were sold under this name. And since
then, the name prevails. Soot, which is similar to carbon black, was used for writing
letters on papyrus in ancient Egypt and on bamboo strips in ancient China.
Carbon black production became a type of cottage industry about the time when the
paper production method was established in the second century. It then became
widely used in industries after it was produced with the channel process in 1892 and

with the oil furnace method in 1947s.(5)

1.2 GENERAL DESCRIPTION

Carbon black is a generic term for an important family of products that is used
principally for the reinforcement of rubber, as a black pigment and because of its
electrically conductive properties. It is an extremely fluffy fine powder with a large
surface area and is composed essentially of elemental carbon. Carbon black is one of
the most stable chemical products. In general, it is the most widely used nanomaterial
and its aggregate dimension ranges from tens to a few hundred nanometers (nm); it
imparts special properties to composites of which it is a part. World capacity in 2005
was estimated at more than 10 million tones. Over 40 grades (listed in ASTM
International, 2005a) are used by the rubber industry alone. Many additional grades
are marketed for non-rubber applications Carbon black is a form of elemental carbon
that is manufactured by the controlled vapor-phase pyrolysis and partial combustion
of hydrocarbons. Several processes have been used to produce carbon black,
including the oil-furnace, impingement(channel), lampblack, thermal (decomposition

Page | 1
of natural gas) and acetylene (decomposition) processes. Carbon blacks are
commonly referred to by the process or the source material from which they are
made, e.g., furnace black, lampblack, thermal black, acetylene black and channel black.
The different grades from the various processes have certain unique characteristics,
but it is now possible to produce reasonable approximations of most of these grades
using the oil-furnace process, by which more than 95% of the total output of carbon
black is produced (Voll & Kleinschmit, 2002; Wang et al., 2003). In contrast to carbon
black, soot is a material of varying and often unknown composition that is an
unwanted by-product of the incomplete combustion of all types of material that
contain carbon, such as waste oil, coal, paper, rubber, plastic, household waste and
also some fuel oils. Soot’s have a small surface area of available carbon due to their
large particle size and low carbon content. They typically contain large quantities of
solvent-extractable materials and their ash content can be 50% or more . Two other
commercial carbonaceous products are activated carbon (including activated
charcoal) and bone black. Activated carbon is a collective name for a group of porous
carbons, which are manufactured either by the treatment of carbon with gases or by
the carbonization of carbonaceous materials with simultaneous activation by
chemical treatment. Activated carbon possesses a porous structure, usually has small
amounts of chemically bonded oxygen and hydrogen and can contain up to 20% of
mineral matter, which usually consists of ash or residue as a result of ignition. The
nature of this mineral material depends on the raw materials used, and can consist of
silica and compounds of alkali and alkaline-earth metals, for example. X-Ray
investigations show that the carbon is mainly in the form of very small crystallites
with a graphite-like structure (Volar et al.,1986). Bone black is a pigment that is
derived as a by-product of the manufacture of bone char, which is made by
carbonizing bones and is used principally in sugar refining. Bone black is used
primarily as a colorant in artists’ paint and for tinting vinyl fabrics for upholstery and
automotive interiors. The carbon content of bone black is usually approximately 10%
(Lewis, 1988, 1993). Soot, activated carbon and bone black, as well as other forms of

carbonaceous products, are not considered in this monograph (2)

Page | 2
1.3 CARBON BLACK PROPERTIES

The complicated structure of carbon black observed under an electron microscope

shows that they have, mostly spherical particles fused together. The spherical
particles are different sizes. Particles connected as a chain are called a "structure."
Several practical assemblies such as the group of the carboxyl or hydroxyl are found
in the CB surface. The name "surface chemistry" is given for their composition or
amount. Surface chemistry particle size and structure are the simple carbon black
properties. These properties are main parameters for carbon black and have a big
effect on the properties of the particle such as dispensability and blackness when they
are mixed with inks, paints, or resins. Therefore, it can be defined the carbon black
generally as a very fine particulate aggregates of possessing of the carbon a formless
quasi-graphitic molecular structure. The greatest areas of differences between a
furnace black and thermal black are the size of the particle and the formula of the
structure. Most carbon blacks are assigned and classified a number of the grade
(4)
established on the surface area and the measurements of the structure

Table 1.1 Physical-Chemical Propertied CB

Chemical Name Carbon Black

Synonyms Acetylene Black, Channel Black,

Furnace Black, Gas Black,
Lampblack, Thermal Black

CAS Name Carbon Black

Chemical (Molecular) Formula C
Formula weight 12.011
Physical state Solid : powder or Pellet
Solubility Water : insoluble
Solvent : insoluble
Color Black

Page | 3
ELECTRON MICROSCOPE IMAGE OF CARBON BLACK

Electron microscope image of carbon black Observing carbon black particles under the
electron microscope shows that they have a complicated structure, with some spheric
particles being fused together. The size of spheric particles is called "particle size," and the
size of the particle chain is called "structure." Various functional groups such as the
hydroxyl or carboxyl group are found in the surface of carbon black, and their amount or
composition is called "surface chemistry." These three - "particle size," "structure," and
"surface chemistry" - are the basic properties of carbon black, and together are called the
three main characteristics. The three main properties have a large effect on practical
properties such as blackness and dispersibility when they are mixed with inks, paints, or

resins (4)

1) Primary particle size and distribution

The diameter of spheric particles is the fundamental property, which largely affects
blackness and dispersibility when carbon black is mixed with resins or other vehicles.
In general, the smaller the particle size, the higher the blackness of carbon black.
Dispersion however, becomes difficult due to an increase in coagulation force.

2) Structure of Carbon Black– DBP absorption

Primary particles – aggregates – agglomerates. Structure of carbon black shows the

length of the chains of agglomerates. Like particle size, the size of the structure also
affects the blackness and dispersibility of carbon black. Generally, the increase of
structure size improves dispersibility but lowers blackness. Carbon black with a
larger structure in particular shows an excellent conductive property.

3) Surface Chemistry

Various functional groups exist on carbon black’s surface. The affinity of carbon black
with inks or paint varnishes changes depending on the type and amount of the
functional groups. Carbon black, with a large amount of hydroxyl group given with
oxidation treatment, has a greatly enhanced affinity to print inks or varnishes,
showing an excellent dispersibility.

Page | 4
 Figure 1.1 Illustration of the structure development of Carbon

Below two images taken by a Scanning electron microscope (SEM) show the structure of one
Carbon Black grades in two different scales. The building of aggregates and agglomerates

become visually visible this way. (3)

Fig 1.2 SEM image showing the primary particles Fig1.3 Aggregates and agglomerates building structure

The picture below shows 3 different carbon black types with different surface areas
influencing the blackness of carbon black.

Smaller surface, bigger particles → lower tinting

Higher surface, smaller particles → higher tinting

Figure 1.4 3 different shades of black, depending on the

surface of Carbon Black.

Page | 5
1.4 APPLICATION EXAMPLES OF CARBON BLACK

Carbon black is a basic material with a long history, and it has been used as a coloring
agent since the days before Christ. Since carbon black has nano-particles with various
functions such as ultra-violet absorption and conductivity, it is still being applied to new
fields such as electronic equipment and devices. Some applications of carbon black, which

is a conventional yet new material (4)

1 ) Coloring Agent for Ink and Paints

Carbon black has higher tinting strength compared to iron black or organic pigments, and
is widely used for newspaper inks, printing inks, India inks, and paints. Carbon black is
also used as black pigment for inkjet ink or toners.

2 ) Resin and Film Coloring Agents

Carbon black has high tinting strength and is thermally stable, and therefore it is suitable
for coloring resins and films that are heat-formed. Carbon black is also excellent for
absorbing ultraviolet light, providing both a superb resistance against ultraviolet rays and
a coloring effect when just a small amount is mixed with resins. Carbon black is widely
used for general coloring for resins and films. Resins with carbon black are used in
automobile bumpers, wire coverings and steel pipe linings which require weather
resistance in particular.3

3 ) Electric Conductive Agent

Carbon black particles have the graphite-type crystalline structure, providing an excellent
electric conductivity. Therefore, carbon black is widely used as conductive filler, being
mixed in plastics, elastomer, paints, adhesives, films, and pastes. Fuel caps and fuel-
introducing pipes of automobiles, for example, are required of electric conductivity for
preventing static. Therefore, carbon black is used as an excellent antistatic agent

Page | 6
4 ) Electronic Equipment Related Material

Carbon black also provides stable resistance, and therefore is used as electronic equipment
related material in various display components, magnetic recording materials, and Orals.
Furthermore, Mitsubishi Chemical has been developing carbon black with various
combined functions for special applications

Figure 1.5 Application Example of Carbon Black

Page | 7
1.5 MANUFACTURING PROCESS OF CARBON BLACK

CB is produced by combusting oil or gas with a great deal of oxygen inside large furnaces.
The furnace walls lined with bricks become very hot because the oxygen and oil combust.
By varying the amount of oil and air, the internal temperature of the furnace can be altered,
which permits manipulation of the particle size and particle connections of the carbon black
being produced. The time required to produce CB from oil is so short that it cannot be
observed by the human eye. The large industrial scale, in general for carbon blacks
manufacturing consists of the following sections: storage facilities for feedstocks, carbon
black production units, equipment for the separation of CB from the process off. gas (tail
gas), final processing of the carbon black, and finally storage facilities for the end product,
utilization of waste gases. The individual sections are interconnected by transport and
conveying facilities which are completely closed systems in modern carbon black plants
avoiding the release of carbon black dust into the surroundings. Industrial carbon blacks
constitute no health hazard. However, because of its considerable coloring strength the
product is regarded as a nuisance dust. Therefore, emission controls are an important aspect

of carbon black production (2)

1.5 CLASSIFICATION OF CARBON BLACK MANUFACTURING PROCESSES

It is crucial, from the chemical perspective, to classify CB production processes into two
main groups of incomplete combustion and thermal decomposition of hydrocarbons,
depending upon the absence or occurrence of oxygen. The process of incomplete
combustion, termed thermal-oxidative decomposition, is by far the most important. In
terms of quantity, the second process i.e., the thermal decomposition of hydrocarbons in
the absence of oxygen, plays only a very limited role. In practice, the methods used to

produce CB can be classified according to the criteria shown in Table 1.2 (3)

Page | 8
 Table 1.2 Kinds of Carbon Black Manufacturing Processes

Manufacturing Manufacturing
Raw Material Explanation
Process Method

This is currently the

Natural Gas or Oil Furnace Black most
common method

Oldest industrial
Mineral / Vegetable Oils Lamp Black
method

Incomplete Flames contact the

Combustion lower
Natural Gas Channel
surface of a channel (an
H-shaped steel beam)

Gas Furnace Useful for fine-particle

Acetylene
carbon black

As this is a heat
Acetylene generation
Decomposition reaction,
Thermal continuous production
Decomposition is
possible
Combustion and
Natural Gas Thermal thermal
decomposition is
repeated in cycles

Table 1.2 shows the steps of CB manufacture as an individual process. The heart of the
process is the CB production unit (Reactor or Apparatus) which, depending on the process,
may consist of reactor(s) or apparatus. The initial product of the unit is a mixture of process
gas and CB suspended in the form of an aerosol. This aerosol is cooled and directed into
collecting systems (Filter), where the solids are separated from the process gas. The CB
thus obtained has a fluffy appearance, hence the designation “fluffy black". Due to its low

bulk density and its tendency to dust, the black cannot be handled in this form (4)

Page | 9
1.5.1 THERMAL BLACK PROCESS
Discontinuous or cyclic process, with natural gas methane as the most commonly used
feedstock, although higher grade hydrocarbon oils are also used as feedstock material. The
natural gas is injected into the inert atmosphere of the furnace where it decomposes into
carbon black and hydrogen. It has the largest particle size and is among the lowest degrees
of particle aggregation or structure. Since it is made from natural gas, it is also one of the
purest forms of carbon available on an industrial scale.

Fig 1.6 Thermal Black Process

1.5.2 CHANNEL BLACK PROCESS

The crude oil is vaporized in the channel black process and is fed to the burners together
with the carrier gasses. A specific influence on the structure of the carbon blacks
produced in this way is not possible. Nowadays the channel black process is primarily used
to manufacture carbon black pigments with very fine particles, which are primarily

distinguished by their high content of oxygenic surface groups. (3)

Fig 1.7 Channel Black Process

Page | 10
1.5.3 LAMP BLACK PROCESS
This method obtains carbon black by collecting soot from fumes generated by burning oils
or pine wood. This method has been used since the days before Christ and is not suitable
for mass production. However, it is used as raw material for ink sticks as it provides carbon
black with a specific color.

Fig 1.8 Lamp Black Process

1.5.4 ACETYLENE BLACK PROCESS

Acetylene Black is a high purity carbon black produced in closed reactors obtained from
the thermal decomposition of acetylene. Due to the production process, acetylene blacks
differ from other carbon black grades. Acetylene blacks are available in powder form, as
they are characterized by a high structure, which makes it difficult to densify and
impossible to pelletize them. Due to a very high thermal as well as electrical conductivity,
acetylene blacks are primarily used as conductive blacks in electric cells, antistatic rubber

and plastic applications, and cable manufacturing. (3)

Fig 1.9 Acetylene Black Process

Page | 11
1.5.5 SURFACE OXIDATION / AFTER TREATMENT OF CARBON BLACK
After treatment of Carbon Black – so-called surface oxidation – is not a classical
production process. The surface of the Carbon Blacks produced in the furnace- thermal-,
gas- and lamp black process can be modified by the use of oxidative agents, which will

influence the tinting, coloristic, PH, and wetting of the Carbon Black(3)

Fig 1.10 Surface Oxidation Process

1.5.6 FURNACE BLACK PROCESS

The worldwide most common production process uses a closed reactor to atomize heavy
aromatic oils under pressure and temperature-controlled conditions. This feedstock is
inducted into a hot gas stream and a preheated air stream where it vaporizes and then
pyrolyzes in the vapor phase to form microscopic carbon particles. In most furnace
reactors, the reaction rate is controlled by steam or water sprays. The carbon black
produced is conveyed through the reactor, cooled and collected in bag filters in a
continuous process, and we will explain in detail later

Fig 1.11 Furnace Black Process

Page | 12
 Figure 1.12 flow diagram carbon black production.

[Link] Production By the Furnace Black Process

The furnace black process is the most modern process for the manufacture of carbon black
and is particularly flexible and economical. By the criteria described above, this process
uses the principle of oxidative decomposition. The process is continuous and is operated
in closed reactors where highly turbulent flows prevail due to high flow velocities. Because
of its importance for large-scale industrial carbon black production, this process will be
described in detail. Except for the actual carbon black production unit, i.e., the furnace
black reactor, other plant sections such as the Conveying, filtering, and pelletizing
installations, are very similar to those used in other carbon black manufacturing processes.
These will, therefore, be discussed in detail only in the section dealing with the furnace
black process. Specific differences regarding other processes will be pointed out in the

appropriate sections (2)

Page | 13
[Link] Description of the Process

The carbon black feedstock is pumped from the storage tank to the reactor via an oil
preheater. Gas and preheated process air are also fed into the reactor. At a certain distance
from the feedstock injection, the thermal-oxidative reaction is arrested by the injection of
water, whereby the carbon black formed and the reactor off-gas are cooled. After further
cooling in heat exchangers

Figure 1.13 Illustration of a furnace black plant.

the mixture of carbon black and off-gas is directed into filters where the carbon black is
separated from the tail gas. The filtered carbon black is then conveyed pneumatically to the
pelletizing section. Grit that may be present in the form of coarse particles is usually
reduced to an acceptable size by the use of a hammer mill .After separation and prior to the
pelletizing unit, the carbon black enters a surge bin or agitator tank which acts as a material
buffer for the pelletizing unit and where some initial densification of the black takes place.
Controlled amounts of black are then fed from the surge bin into a pelletizer or pin mixer
and mixed with approximately the same amount of water. The wet pellets formed are
subsequently dried in a rotary kiln dryer which is heated by hot gases preferably from the
combustion of tail gas. Carbon black dust carried off by the dryer exhaust gases is collected
in a filter and recycled into the process. After leaving the dryer and before entering the
storage silo, the carbon black pellets pass through screens which act as classifiers for the
pellet sizes, and through powerful magnetic separators to remove any ferrous metal and

Page | 14
rust contamination. The carbon black is conveyed to the storage silos by means of bucket
elevators conveyor belts, and/or screw conveyors. From there it is discharged into the
packaging units or directly to the bulk loading station. A separate storage facility serves as
an off-spec silo and receives carbon black which does not meet the specifications. This
may occur upon starting a production line or upon switching to a different grade.
Depending on the type and extent of the deviation, carefully controlled quantities of the
off-spec black may be blended with material from subsequent production or eventually be
used for applications not critical with respect to the quality deviation. As previously
mentioned, the tail gas is burned, and the generated heat is utilized in the dryers. Any excess
gas can also be employed for the generation of steam. (Fig1.14) depicts a plant for the
production of furnace blacks. This general survey of the manufacturing process is now

followed by a description of the individual process steps (2)

Figure 1.14 Carbon black plant in Real life

Page | 15
[Link] General Construction of Furnace Black Reactors

A feature common to all furnace black reactors is that they are enclosed in a gas-tight steel
jacket. This is a major prerequisite permitting flows of all material to be closely controlled.
This steel jacket is usually refractory-lined with highly heat-resistant material consisting
of several layers of different types of ceramics. For the innermost layer, gas-tight material
possessing the greatest heat resistance is used. It usually consists of alumina with very
small amounts of silica, in order to improve the resistance against changes in temperature.
Towards the outside is several layers having increasing silica contents and increasing
porosity. This provides a gradually increasing insulating effect and a decreasing heat
resistance. Instead of alumina/silica, chrome/aluminum oxides may also be used. Both
materials provide refractory linings which allow reaction temperatures of up to, and
sometimes above, 1900°C. When zirconia is used, the temperatures may even exceed
2000°C, but the use of this material is limited to oxidizing atmospheres found in the
combustion chamber. The refractory lining may be constructed of bricks or from material
that is cast and compacted. The use of bricks ensures the longest service life but is the most
time-consuming and expensive method of producing shaped refractory sections. A
relatively fast and easy way of preparing refractory linings, especially for intricately shaped
reactors, is the use of material that is cast and compacted in situ. However, since the
compaction is less than that of bricks and since it can only be sintered inside the reactor,
cast refractories are less resistant to wear and have a shorter life cycle. Depending on the
use of the reactor, the material employed and its location within the reactor, the life span
of the refractory lining may be anything between a few months and several years. The
individual ceramic layers are chosen in such a way as to ensure that each layer offers the
maximum insulating effect and the required heat resistance at the moment when the
adjoining inner the layer is at its maximum temperature. It is usually not possible to insulate
the steel jacket, since a certain flow of heat is necessary to maintain the required
temperature profile within the refractory lining. To avoid condensation, the outer steel
jacket temperature should be approx. 130 to 150°C. If the lining is designed correctly, the
heat loss from the reactor shell is in the order of 1 to 2% of the energy input. In special
cases, when extremely high energy densities and temperatures are to be generated,

Page | 16
particularly with oxygen enrichment, parts of the reactor may be provided with water
cooling, sometimes without the refractory lining or with only a thin layer of refractory
material. Reactor geometries differ not only between the manufacturers but are also
dependent on the product range and the available fuels and feedstocks. In general, two main
types of reactors are used to produce rubber-grade blacks. The reactors referred to as hard
black or tread black reactors are used for the production of fine-particle carbon blacks of
the ASTM 100, 200, and 300 series while those commonly referred to as soft black or
carcass black reactors manufacture the coarser carbon blacks of the 500, 600, and 700
series. Carbon blacks having fine primary particles are obtained at higher reaction
temperatures than the blacks with coarser particles. Hence the reaction is faster and the
reactors are therefore designed for higher reaction velocities and shorter residence times.
For the production of coarser carbon blacks, the reaction takes place at comparatively low
temperatures. and longer residence times are required, which can be accomplished in large

volume reactors. The functions of the individual elements of a furnace black reactor (2)

Energy is generated in the combustion chamber by reacting an oxidizing agent, usually,

air, sometimes enriched with oxygen, with the gaseous or liquid fuel. It is particularly
important that air and fuel is mixed thoroughly since the degree of combustion and the
volume of the combustion chamber is determined mainly by the mixing time. A complete
conversion of the fuel into carbon dioxide and water in the combustion zone is required for
optimum utilization of the energy input. High conversion rates are obtained through
premixing of the fuel and process air, for instance by injecting the fuel transversely to the
airstream at high pressure. By suitable choice of the size and number of gas nozzles,
optimum premixing of the process air with the fuel is achieved at the location, where the
gas is injected. Shear forces are utilized to achieve further mixing. They are generated by
either injecting the gas transversely to the flow of air or by changing the cross-section of
the combustion chamber using chokes, venturis, restrictors, or baffles. High flow velocities
lead to increased turbulence and improve the combustion of the fuel. In some types of
combustion chambers, the turbulence is further increased by creating a vortex in the flow,
but care has to be exercised as this may cause a considerable backflow. All elements
comprising the combustion chamber have to be carefully matched to obtain stable flames

Page | 17
at the highest possible reaction rates. Modern combustion chambers allow energy densities
of up to 100 MJ/m3 to be achieved. The process air is preheated by the waste heat generated
by the process. Air temperatures of up to approximately 800°C are quite common.
Compared to the stoichiometric air requirement of the fuel, the process air is usually in
excess. This excess is necessary to limit the combustion temperature since the conventional
refractory-lined combustion chambers are only able to withstand temperatures of up to
1900°C. In addition, the excess of air promotes the complete conversion of the fuel,
especially at very high temperatures where the products carbon dioxide and water begin to
undergo dissociation reactions. The reaction in the combustion chamber is determined by
the mass flows of process air and fuel, as well as by the process air temperature and the
composition of the fuel. These are important parameters since they determine the
temperature, amount, and composition of the gas leaving the combustion chamber. The
fuel to- air ratio is a key component in percent, defines the fraction of the total oxygen
content of the process air consumed and is best characterized by the air consumption factor.

[Link] Heat Exchanger

The reactor connects directly to a heat exchanger in which the reactor off-gas containing
the carbon black is cooled and the process air is preheated. It is usually constructed as a
tubular heat exchanger through which the process air passes in counterflow to the reactor
off-gas. The reactor off-gas with the carbon black passes through a bundle of tubes which,
depending on the size of the installation, may consist of between 50 and 200 tubes with
diameters of 50 to 100 mm. The flow velocities are sufficiently high to prevent the carbon
black from being deposited on the heat exchanger walls. In addition, special cleaning
systems are employed to remove such deposits and to prevent plugging. {With reactor off-
gas temperature between 700 and 1000°C at the inlet of the heat exchanger, and 400 to
600°C at the outlet, process air temperatures range between 400 and 800°C, with the most
common air temperature lying between 600 and 750°C} Higher preheat temperatures are
possible, but they would require the heat exchanger to be constructed from specialized and
usually very expensive materials. In terms of energy, it would seem appropriate to always
achieve the highest possible air, preheat temperature. However, this is not always possible
due to the temperature limitations of the combustion chamber, the possibility of fowling in

Page | 18
the heat exchanger, and restrictions with respect to carbon black properties. The mixture
of carbon black and reactor off-gas leaving the heat exchanger at a temperature of at least
400°C has to be further cooled to 260-280°C before it may enter the carbon black
separation units. This may be achieved by a second heat exchanger in the form of an air or
feedstock preheater, a waste heat boiler, or simply by the injection of water. With the
second heat exchanger, also of a tubular type, air may be preheated for use in other
processes. The steam obtained from a waste heat boiler may be utilized to preheat the
feedstock or for other heating purposes. If the installation has an integrated oil preheater,

additional cooling by injection of water is necessary (2)

Figure 1.15 Heat Exchanger

[Link] Separation

The carbon black is separated from the tail gas by means of bag filters. Two different filter
systems are in use, repress bag filters and pulse-jet filters. In repress-type filters, the
deposited carbon black is removed from the filter bags in sequence by depressurization
with filtered tail gas. Typical filter loads are in the range of 0.2-0.4 m3m-2min-1. In pulse-
jet filters, pulses of pressurized air or steam are applied to clean the filters bags. The
advantage of pulse-jet filters is the higher specific load of the filter surfaces so that
compared to the repress type, these filters may be built smaller for the same filter capacity.
A disadvantage is the greater mechanical strain on the filter bags. If air is used as a cleaning

Page | 19
medium, the amount of air has to be limited so as to prevent the formation of flammable
mixtures with the combustible tail gas. In all types of carbon black filters, the carbon black
is discharged from the filter bags into the filter cone or hopper, from which it is conveyed
by means of a screw conveyor and rotary star valves. In the past, carbon black was
separated from the tail gas by means of cyclones. Today, cyclones are only used
infrequently as pre-separators or as agglomeration cyclones where a large part of the carbon
black is first separated and then taken up again by the tail gas. The purpose of this technique
is to achieve a limited agglomeration of the carbon black and thus facilitate the ensuing
separation in the filters. The filter inlet temperatures are in the range of 260 to 280°C, these
comparatively high inlet temperatures being necessary to prevent condensation. Since the
tail gas contains approximately 3040% water, the dew point lies at least in the range of
7080°C. The actual dew point may be much higher, depending on the sulfur content of the
tail gases. In addition, the temperature of the walls of the filter housing may be far lower
than that of the gas in the filter due to the excellent insulating capacity of the carbon black
which becomes deposited on the filter walls. The filter bags are usually made of special
surface-treated glass fiber cloth. The service life of these filters may be up to two years
depending on operating conditions and the sulfur content of the feedstock. The residual
carbon black content of the purified tail gas varies slightly according to the carbon black
grade. Values of 10 to 20 mg/m3 can be achieved. Due to the presence of combustible
substances such as hydrogen, carbon monoxide, and some low molecular weight
hydrocarbons, the filtered tail gas in most cases is utilized to generate heat for drying of
the carbon black (Densification and Palletization) and for the generation of steam. Some
of the steam is consumed internally, but the largest part can be sold or used to generate
electricity. A modern carbon black plant is capable of generating approximately three times
the amount of electricity it consumes; the excess usually being sold to the local distribution

network (2)

Page | 20
[Link] Densification and Palletization

The fluffy black separated from the pneumatic system still contains considerable amounts
of air or gas and has a very low bulk density. Therefore, it has to be further densified before
it can be used commercially. The extent and the means of densification depend on the
intended use of carbon black. Initial densification is achieved in the loose black surge bin,
where the black is stirred slowly. The loose black surge bin is, therefore, also termed an
agitator tank. It not only ensures the initial densification of the black but also acts as a
buffer. Sensors allow their product level to be monitored and kept at a constant level so as
to maintain a certain flow of carbon black through the screw conveyors or rotary star valves
into subsequent densification processes. The most controlled form of densification of the
powder black is vacuum densification. It is achieved by passing the carbon black over
porous rollers, the insides of which are under vacuum. The effect can be enhanced by gently
pressing the carbon black against the vacuum roller by means of a second roller. This form
of densification is adopted mainly for pigment blacks which are used in the powder form
and must be very easy to disperse. It is self-evident that such blacks require special care
during packaging, storage, and transport to avoid any further densification.

Higher densification : of the carbon black is achieved by palletization. It is the

preferred method if the application system and mixing equipment of the customer develop
high shear forces for a more intensive dispersion of the black into the active media. With
few exceptions, rubber-grade blacks are always pelletized, since only in this form can they
be handled and incorporated into the various polymers using standard industrial equipment.
Other advantages of pelletized blacks are smaller transport volumes, more favorable free-
flow properties, and reduced dusting. Because of their different characteristics, it is
necessary to differentiate between the two pelletizing methods commonly used, namely
wet palletization and dry palletization. The process of dry palletization makes use of the
fact that densified carbon black particles can be formed into small round pellets in a rotating
drum (dry mill). This process is continuous but limited in its application. The higher the

carbon black structure, the more difficult is to dry palletization. (2)

Page | 21
[Link] Storage and Packaging

Powder Black : The densified fluffy black is collected in a silo from which it is
transported to turbo or screw packing machines that are automated and make use of
appropriate robotics to eliminate the former manual operations. The level of the
product in the silo is kept low to prevent additional uncontrolled densification. Most
carbon blacks are packed in multilayered paper sacks, but polyethylene bags are also
used for products that are sensitive to moisture. The bags are stacked on pallets and
shipped as such. In the case of powdered blacks, the pallets may not be stacked.

Pelletized Black : From the pelletizing section, the pelletized black is transported
by bucket elevators, conveyor belts, and screw conveyors to single-or multiple-
compartment storage silos with capacities between 100 and 1000 t. The pelletized
black is stored in these silos from where it is discharged directly into road or rail
tankers, intermediate bulk containers, or into automatic packaging lines.

The majority of rubber-grade blacks in Europe is shipped by road and through some
rail tankers with a capacity of about 20 and 45 tons, respectively. In the U.S.A., rail
tankers are preferred. Some carbon black is also packed and shipped in big bags of
500 or 1000 kg capacities. Smaller sacks containing 1530 kg are packaged by

automated high-speed packaging lines and stacked on pallets ready for shipment. (2)

Page | 22
[Link] Means of Control Downstream of the Reactor

Densification: As described above, freshly produced carbon black is densified after

separation in the process filters either by stirring the fluffy black in the surge bin or
by means of vacuum rollers. The bulk weight of the fresh carbon black, which may be
1060 g/l depending on its structure, can thus be raised to 100300 g/l. This
densification is necessary to improve the handling properties. However, the
treatment has to be careful and reproducible since excessive densification has
adverse effects on dispersibility, and the best method for powder blacks as final

product is, therefore, vacuum densification. (2)

Dry palletization: is usually performed on pigment blacks which are required to be

largely non-dusting. With regard to dispersibility, the dry-pelletized blacks’ range
between powder black and the wet-pelletized products. The resulting bulk densities
lie between 300 and 500 g/l, depending on the structure of the carbon black. A dry-
pelletized carbon black is characterized by particularly small pellets and usually
contains a relatively high proportion of micro-pellets which are less than 0.1 mm in
diameter. The influence of process parameters on pellet size and pellet size
distribution is comparatively small. Not all carbon black grades lend themselves to
dry palletization. Low-structure carbon blacks are particularly suited for dry
palletization. Large-particle high structure blacks, however, are problematic. Pellet
hardness can be increased by increasing the residence time in the drum, e.g., by
increased bed depth in the pelletizing drum or by recycling of pelletized material into
the drum. However, since the pellet hardness is still low; attrition of the pellets may
occur in certain conveying systems. Dry-pelletized blacks are nevertheless preferred

in certain applications which require ease of dispersion. (2)

Page | 23
[Link] After - Treatment

After-treatment of carbon blacks constitutes a drastic intervention in the chemical

and physical properties of the carbon black surface and Control of the Carbon Black
Process, Quality Assurance, Safety Consumer requirements regarding carbon black
quality are very stringent since deviations affect the end product performance. The
process requires exact and reproducible operating conditions, not only to produce
the multitude of carbon black grades required but also to maintain the individual
properties at a constant level. Carbon black manufacturers, therefore, implemented
sophisticated quality assurance systems which enable them to meet and guarantee

the parameters laid down in the specifications. (2)

[Link] Process Variants and Patents

Since the furnace black process replaced most of the other manufacturing processes
during the 1950s and 1960s, the majority of patents and publications refer to this
process. They mostly describe designs or procedures related to the reactor, since this
is what determines the most important carbon black properties. This short survey of
the technology of different manufacturers will therefore be limited to reactors and

their operation (2)

1.6 End-Uses for Carbon Black

The particle size, structure, and surface area of carbon black play a significant role in
the material properties of rubber, plastics, inks, paint, coatings, cosmetics, fibers,
paper, energy, foundry, metallurgic, friction, and refractory products. The total
market for carbon black was probably around 13 million metric tons in 2016. For this
reason, carbon black is made in various grades to meet the varying material needs

and specifications of manufacturers. (3)

Page | 24
Chapter 2 / MATRAIL BALANCE

Page | 25
2.1 Material balance on Reactor :
Basis = 1 hour
Working day = 310 day
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
Production rate of carbon black = 50,000
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 1000 𝑘𝑘𝑘𝑘 1 𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 1 𝑑𝑑𝑑𝑑𝑑𝑑 𝑘𝑘𝑘𝑘
Production = 50,000 ∗ ∗ ∗ 6720.4
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 1 𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 310 𝑑𝑑𝑑𝑑𝑑𝑑 24 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 ℎ𝑜𝑜𝑜𝑜𝑜𝑜
𝑊𝑊𝑊𝑊 𝑘𝑘𝑘𝑘 1 𝑘𝑘𝑘𝑘 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾
[Link] = → Production = 6720.4 ∗ 559.52
𝑀𝑀.𝑤𝑤𝑤𝑤 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 12.001 ℎ𝑜𝑜𝑜𝑜𝑜𝑜

CH4 → C + 2H2 ……………………………. Reaction (1)

CH4 + 2O2 → 2H2O + CO2 ..……………… Reaction (2)
2H2 + O2 → 2H2O ………………………. Reaction (3)

By Stichometry :

Conversion of CH4 into C is 45% (1)

559.52 1
So, mole of CH4 in feed gas = ∗ ∗ = 1243.37𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘
0.45 1
No. of Mole CH4 converted to CB is = 559.52 kmole

Reaction (1)
No. of Mole of H2
𝐶𝐶ℎ4 𝐻𝐻2
1 2 X = 1119.04 kmole
559.52 𝑋𝑋

Page | 26
Reaction (2)
No. of Mole of CH4 burning in Second reaction
1243.37 - 559.52 = 683.85 Kmole
No. of Mole O2 required
𝑂𝑂2 𝐶𝐶ℎ4
2 1 X = 1367.7 Kmole
𝑋𝑋 683.85
No. of Mole CO2 Produced
𝐶𝐶𝐶𝐶2 𝐶𝐶ℎ4
1 1 X = 683.85 Kmole
𝑋𝑋 683.85
No. of mole H2O Produced
𝐻𝐻2𝑜𝑜 𝐶𝐶ℎ4
𝑋𝑋 683.85 X = 1367.7 Kmole
2 1

Reaction (3)
No. of Mole O2 required
𝑂𝑂2 𝐻𝐻2
𝑋𝑋 1119.04 X = 559.52 Kmole
1 2
No. of mole H2O Produced
𝐻𝐻2𝑜𝑜 𝐻𝐻2
2 2 X = 1119.04 Kmole
𝑋𝑋 1119.04
Total O2 required for all reactions
= 1377.7 + 559.54 = 1927.22 Kmole

Page | 27
 With an excess O2 = 50 % (1)
No. of Mole of O2 excess = 0.5 * 1927.22 = 963.61 kmole
Total Mole of O2 for inter reactor furnace
1927.22 + 963.61 = 2890.83 Kmole
No. of mole N2 inter the reactor furnace
𝑂𝑂2 𝑁𝑁2
21 79 X = 10875.02 Kmole
2890.83 𝑋𝑋

Air

Natural C
Reactor Furnace
Gas Tail Gas

Over all Material Balance :

Input = Output
F+A=P

Stream F ( Input ) = ( Natural Gas ) 100% CH4

Total Mole of CH4 → 1243.37 + 683.84 = 1927.22 Kmole

Stream A ( Input ) = Air

Total Mole of Air ( O2 + N2 ) → 10875+2890.83 =1376.56 Kmole

Page | 28
Stream P ( Output ) = ( C ) + ( H2o + Co2 + N2 +O2 + H2 )
Total Mole of H2O → 1119.04 + 1367.7 = 2586.74 Kmole
Total Mole of Co2 → 683.84 Kmole
Total Mole of C → 559.52 Kmole
Total Mole of O2 → 963.61 Kmole
Total Mole of N2 → 10875 Kmole
Total Mole of O2 → 963.61 Kmole

Checking → Input = Output

Stream ( Input ) F + A = 15869.07 Kmole

Stream ( Output ) P = 15668.72 Kmole

Comp Stream F Stream A Stream P

C ------- ------- 559.52
H2O ------- ------- 2586.74
Co2 ------- ------- 683.84
N2 ------- 2890.83 10875
O2 ------- 10875 963.61
H2 ------- ------- Consume
Ch4 1972.22 ------- -------
Total 1972.22 13765.9 15668.72

Page | 29
 2.2 Material balance on Filter Cascade 1 :

P Filter Cascade (1) C

Filter Cascade (1) They are bags to filter Carbon Black gas and water vapor from
the tail gas , which contains unwanted substance ( Co2 + O2 + H2o + N2 ) and
stream T will be out from the plant .

Over all Material Balance :

Input = Output
Stream T
P=T+C Comp [Link] Percent
H2O 1293.37 9%
Co2 683.85 5%
Stream P N2 10875 79%
Comp [Link] Percent O2 963.61 7%
C 559.52 4% Total 13815.83 100%
H2O 2586.74 17%
Co2 683.85 4%
N2 10875 69% Stream C
O2 963.61 6% Comp [Link] Percent
Total 15668.7 100% C 559.52 30%
H2O 1293.37 70%
Total 1852.89 100%

Streams Input ( kmole ) Output ( kmole )

P 15668.7 -------
T ------ 13815.83
C ------ 1852.89
Total 15668.7 15668.7

Page | 30
 2.3 Material balance on Filter Cascade 2 :

C Filter Cascade (2) F

Filter Cascade (2) filtered the Carbon Black vapor from the powder when it came
from the pulverizer, only a physical change

Over all Material Balance :

Input = Output
P=F

Stream P Stream F
Comp [Link] Percent Comp [Link] Percent
C Smoke 559.52 30% C Powder 559.52 30%
H2O 1293.37 70% H2O 1293.37 70%
Total 1852.89 100% Total 1852.89 100%

Streams Input ( kmole ) Output ( kmole )

P 1852.89 -------
F ------ 1852.89
Total 1852.89 1852.89

Page | 31
 2.4 Material balance on Granulator :

F Granulator G

Granulator equipment for granulating carbon black powder into small pellets by
removing water from it

Over all Material Balance :

Input = Output
F=G

Stream F
Stream G
Comp [Link] Percent
Comp [Link] Percent
C Powder 559.52 30%
C Pellets 1852.89 100%
H2O 1293.37 70%
Total 1852.89 100%
Total 1852.89 100%

Streams Input ( kmole ) Output ( kmole )

F 1852.89 -------
G ------ 1852.89
Total 1852.89 1852.89

Page | 32
 2.5 Material balance on Dryer :

G Dryer D

Drying Carbon Black granules with hot air and get rid of the amount of
water in the granules

Over all Material Balance :

Input = Output
G=D

Stream G Stream D
Comp [Link] Percent Comp [Link] Percent
C Wet 1550.89 84% C Dry 1800.89 97%
Hot Air 302 16% H2o 51.89 3%
Total 1852.89 100% Total 1852.78 100%

Streams Input ( kmole ) Output ( kmole )

F 1852.89 -------
D ------ 1852.89
Total 1852.89 1852.78

Page | 33
 2.6 Material balance on Classifiers :

D Classifiers C

Equipment that separates the unwanted product from the desired

carbon black

Over all Material Balance :

Input = Output
D=C

Stream C
Stream D Comp [Link] Percent
Comp [Link] Percent CB 1760.25 95%
C Dry 1852.89 100% Ash 92.6446 5%
Total 1852.89 100% Total 1852.89 100%

Streams Input ( kmole ) Output ( kmole )

D 1852.89 -------
C ------ 1852.89
Total 1852.89 1852.78

Page | 34
 REFERNCEE :
1) Kirk-Othmer Encyclopedia of Chemical Technology.

2) Jean-Baptiste Donnet, Roop Chand Bansal, Meng-Jiao Wang -

Carbon black science and technology-Dekker (1993)

3) Carbon Black Wiki [Link]

4) Carbon Black Production / By SHADHA KHALID JEBUR

5) What is the Carbon Black ? / Orion Carbons Engrained

6) Anonymous. 2011. “Insights on Carbon Black Fundamentals.

“ModernDispersions,Incorporated(MDI).[Link]

[Link]/CARBON_20BLACK_20F

[Link]. ASTM. 1990. Annual Book of ASTM

Standards ASTM D1298 - 85.

7) ASTM International. 2012. D6556 ASTM International

Standard Test Method for Carbon Black — Total and External

Surface Area by Nitrogen. [Link]

org/sites/default/files/ASTM D6556-10 N2 BET for Carbon

Black .[Link].

Page | 35

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