Research Proposal Seminar Report

On

Process intensification of petroleum coke calcination using rotary kiln

By

M. Vinodh Kumar

Under the guidance of

Dr. R. Vinu

Dr. Arun Appadurai (External Guide)

DEPARTMENT OF CHEMICAL ENGINEERING,

INDIAN INSTITUTE OF TECHNOLOGY MADRAS

CHENNAI – 600036

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 DATA SHEET

DEPARTMENT OF CHEMICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY MADRAS

1. Name : M. Vinodh Kumar

2. Roll No. : CH17D009

3. Registered for : Ph.D.

4. Specialization : Chemical Engineering

5 Scheme : External

6. Advisor : Dr. R. Vinu

7. Date of Joining : July 2017

8. Comprehension viva-voce : 06.02.2018

9. Area of Research : Process intensification of petroleum coke using rotary

kiln

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 Details of Course Work

S.No Course No Course Title Sem/Year Credit Grade

Core Courses

Advanced Chemical Engineering

1 CH5050 July-Nov 2016 10 B
Thermodynamics

2 CA5020 Principles of Solids and Surfaces July-Nov 2017 9 B

Elective Courses

Microwave processing in Materials, Food and

1 CH6022 July-Nov 2017 9 S
Medical Sciences

2 CH5011 Colloids and Surfaces July-Nov 2017 9 B

Compulsory Courses / Optional Courses

1 ID6021 Introduction to Research July-Nov 2017 2 Pass

Signature of Research Scholar Signature of Guide: Dr. R. Vinu

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S.No. Contents P. No.

1. Introduction…………………………………………………………………. 6
2. Literature review……………………………………………………………. 8
3. Raw materials and sample preparation……………………………………... 10
4. Methods……………………………………………………………………. 12
5. Results and discussion………………………………................................... 16
6. Conclusion……………………………………………………………….…. 25
7. References………………………………………………………………….. 28

S.No. List of figures

1. Break down of aluminium smelter operational cost 8

2. Particle size distribution of three different grades. 11
3. Granular motion of the petroleum coke particles in rotary kiln 11
4. Thermogravimetric weight loss of sample 2/B
(a) @ 5oC/min. (b) @ 10oC/min (c) @ 15oC/min. (d) @ 20oC/min. 18
5. Estimation of activation energy Ea (a) by Friedman method (b) by
Kissinger-Akahira Sunose method (c) 19
6. Evolution of off gases and volatile composition (a & c - counting
counter clockwise from top left to bottom) @ < 10oC/minute (b &
d - counting clockwise from top right to bottom) @ heating rate
between 10 to 20oC/minute. 20
7. Green petroleum coke varied heating rate in a muffle furnace. 21
8. Metsim model function 22
9. Shifting a portion of tertiary air to secondary and primary air zone 24
10. Kiln rotational speed is reduced from 1.2 to 1.0 rpm 25
11. Electrically controled rotary furnace. 26
12. Electrically controled rotary furnace - Schematic. 27

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S.No. List of tables P. No.

1. Green Petroleum Coke (GPC) sample proximate analysis 12

2. Green Petroleum Coke (GPC) sample ultimate analysis 12
3. Covered crucible static furnace testing 16
4. Thermogravimetric weight loss 17
5. Specific Surface Analysis 22

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 Process intensification of petroleum coke calcination using rotary to improve
vibrated bulk density of calcined petroleum coke

Abstract

Calcined petroleum is one of the low and best commodity feedstocks for anodes used in
aluminum smelters. In the current market Calcination of petroleum coke in rotary kiln is
challenging in terms of product quality, utilities required and facing environmental norms.
Present study investigates the reduced heating rate on green coke with its effects on
calcined coke’s vibrated bulk density in a conventional static furnace. Three different
grades of green petroleum coke (GPC) is used for this study. Grades are categorized based
on their volatile matter (VM) and sulphur content. The suitable calcination temperature for
GPC was found as 1250oC. Thermogravimetric data collected for coke from ambient to
1000oC at heating rates of 5, 10, 15 & 20oC/min. Predicted activation energy (Ea) lies
between 63 to 276 kJ/mol. The Ea values indicates a multistep hydrocarbon release. This
is verified from Off-gas analysis of GPC using FTIR which shows gradual release of VM.
Heating rate ≤ 20oC/min to final calcination temperature shows increment in VBD from
0.85 to 0.877 g/cc. This is verified from specific surface area (SSA) analysis of coke at
different temperatures (0.3m2/g at 600oC; 0.7m2/g at 800oC). An industrial calcination kiln
is simulated using Metsim software version 2013.02. The exponential heating rate of coke
at tertiary air injection zone is shifted towards the discharge end of kiln where densification
begins. Additionally, reducing kiln rotational speed increases the residence time of the
material for increasing VBD. Upcoming plan for the possible ways to increase VBD are
(1) Using binders GPC fines are briquetted for calcination. Polyvinyl alcohol may be good
binder compared to conventional binders like tar-pitch. (2) Modifying the heating rate
precisely based on the major hydro carbon component’s size present in VM. Components
has to be identified by micro-pyrolysis; respective volumes shall be calculated for the
fundamental understanding using Van der waals and Mcgown volumes.

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1. Introduction

The increasing consumption of carbon anodes in aluminum smelters led the industry to
reconsider the choice of using good quality of calcined petroleum coke (CPC) for
producing anodes. Coke quality is measured in terms various terminologies viz., (1) Real
Density (RD) / True Density (TD), (2) Vibrated Bulk Density (VBD), (3) Apparent Density
(AD), (4) Tapped Bulk Density (TBD), (5) Crystallite lattice length (Lc), (6) Coke
Resistivity, (7) Coke air/CO2 reactivity etc., Each measurement has a specific application.
Real density indicates the measure of coke conductivity in the smelter and it accounts for
surface porosity. Vibrated bulk density decides the binder requirement and the carbon
consumption in the smelter. lower VBD indicates higher binder requirement and increased
carbon consumption in smelter. VBD accounts for both open and closed porosity.
Crystallite lattice differentiate the usage of coke based on its lattice constant. Lc below 20
Å is categorized as fuel grade coke. Lc between 20 to 40 Å belongs to anode grade coke.
Lc greater than 40 Å is a graphitic coke. Around 15-20% of aluminium electrolysis
operational cost is taken by anode consumption [1]. Historical average carbon consumption
cost increased from 8 – 10% to 18%. CPC cost – $ 270 to 290/ ton of CPC (₹18900 to
20300/ton of CPC). Increase in Vibrated bulk density of 0.01 g/cm3 reduces carbon
consumption by 0.45% (i.e.,1.8 kg C/ton of Al to 2.02 kg C/ton of Al = $ 0.54 to 0.58/ton
of CPC [21]. Break down of the smelter operational cost is shown in figure 1. Calcined
petroleum coke is the major part of baked anodes. Extensive studies made years ago and
proved that calcined petroleum coke has low impurity levels, readily available and low-
cost material in the market for making anodes [2]. However, the quality of petroleum coke
produced after calcination depends on various factors. The prime factors include starting
from raw green petroleum coke composition (volatile matter (VM), moisture, sulphur
content etc.,), particle size, hardness, calcining conditions (temperature, residence time and
heating rate) and the type of technology chosen for calcination (Rotary Kiln, Vertical Shaft
Kiln and Rotary hearth furnace). Vibrated bulk density (VBD) is the indicator of calcined
petroleum coke porosity and its packing ability which depends on inter and intra particle
porosity, particle size distribution, shape of the particle. Bulk density (BD) is the indirect

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 measurement of the calcined petroleum coke porosity; inter particle friction and its packing
ability [3].

Figure 1. Break down of aluminium smelter operational cost [1]

2. Literature review

P.J. Rhedey [4] reported the physical structure of the coke increases significantly above the
heating rate of 50oC/minute. The rate of heating does not affect the degree of calcination.
Calcined coke porosity is not increased due to partial oxidation of coke in kiln. Effect of
different heating rates at three kiln zones is not well documented. M. P. Whittaker et. al [5]
articulated the maximum rate of coke contraction, apparent density increase, crystallite
growth, porosity increases between 700 to 800oC. However, specific coke heating rate of
30oC/minute alone would be difficult to draw an inference. Author used isotropic (15 to 21
wt.% VM) and anisotropic coke (5 to 6 wt.% VM) for the studies. Based on the VM content
alone one cannot conclude whether the coke is isotropic or anisotropic. Though there was
significant difference in coke porosity, the real density of two cokes used were very close.
P.J. Rhedy [6] described the porosity of calcined petroleum coke is influenced by coke
nature from delayed coking. Delayed coker feed shall be classified as isotropic, mosaic and
sponge based on refinery residue asphaltic, intermediate and paraffinic respectively. All
these has VM content between 12 to 14 wt.%. Isotropic coke with VM of 12.4 wt.% yielded
95.2 g/100 cc vibrated bulk density. This was not in agreement with previous work. M.
Long et. al [7] emphasized with increasing temperature, coefficient of heat conductivity
and specific heat capacity of coke increases with decreasing variation rate. It indicates at
increasing temperature micro porosity increases, but these phenomena are not related to
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variation of vibrated bulk density. D. Kocaefe et. al [8] discussed properties of coke
(density, porosity and crystallite size) are affected by the factors such as heating rate,
temperature and holding time. The work targeted with the following heating rates
47oC/minute, 92.6oC/minute and 147oC/minute but the calcination temperature limited to
1200oC. E.E. Hardin et. al [9, 10] reported the VBD of coke reaches the maximum of 84.7
to 92.2 g/100cc at calcination temperature of 1300oC, the same degrades beyond this
temperature due to thermal desulfurization effect. The work established to discuss the VBD
changes between the temperature 1200 to 1500oC only. L. Edwards [11] compared the
thermal desulphurization of coke in rotary and shaft kiln. Shaft kiln found to be slight
beneficial which produces a VBD of 88 g/100cc against 86 g/100cc in rotary kiln. To know
the devolatilization behavior of petroleum coke for its combustion characteristics K.S
Milenkovaa et.al, related the reactivity with its morphology. However it was found
different due to heterogenous nature of coke. The differences are not related to their bulk
chemical analysis alone [12]. V. Buzunov et. al [13] claims that the VBD of calcined coke
in kiln is higher for lower volatiles present in coke before calcination. The author also states
larger pore formation is not due to volatile content but due to rate of volatile release. The
comparison made between laboratory (10oC/minute) and industrial kiln calcination are
unrealistic as the coke heating rate at kiln is greater than 50oC/minute. The VBD of the
calcined coke depends on the Hard groove index (HGI) of the green coke. Higher the HGI
lower will be the VBD and vice versa. M.J. Dion et.al [14] predicted the calcined VBD
with green coke HGI. The work depicted the dependence on HGI, but the trial was
conducted at a coke heating rate of 50oC/minute. Therefore, its effect below the mentioned
heating rate is not documented. J.H. Zou et.al [15] investigated petroleum coke gasification
under CO2 atmosphere at constant temperature. The gasification rate follows the normal
distribution function that accounts for the structural transformation. As the coke begins to
graphitize at a temperature greater than 800oC. The more the graphitization lesser will be
gasification. The gasification increases to peak and falls rapidly because of aforesaid
process. The model has a closer fit the reaction rates are different for different temperature.
Moreover, the work limited to the temperature of 1050oC only. J. Perron et. al [16] suggests
in his mathematical modelling, quality of petroleum coke shall be improved by reducing
kiln temperature gradient, axial velocity or modifying coke maximum temperature profile

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 towards the kiln discharge. Coke heating rate is related to devolatilization, coke
temperature and volatiles combustion. Though there was an argument to adjust the third
air flow, the work had a gap to discuss its controllability. The present study illustrates the
optimization of petroleum coke heating rate during calcination in a rotary kiln. The work
investigates from raw material characterization, identifying the suitable grade,
establishment of optimal calcination temperature, estimation of activation energies under
devolatilization, verification of volatile composition by FTIR analysis, establishing the
minimal coke heating rate. The work emphasizes coke heating rate below 20oC/minute to
target for improving VBD of calcined coke. Using the results from laboratory calcination
results, critical parameters like tertiary air flow and kiln rotational speed is adjusted. Part
of tertiary air quantity is routed towards the kiln discharge end. METSIM version 2013.02
software used to simulate the results under as is kiln operating and improved condition
with increased vibrated bulk density

3. Raw materials and sample preparation

Three different grades of petroleum coke 5 kg each procured from Rain Carbon India
Private Limited. Initial sample categorization is based coke source of origin.
a. Grade 1/A – Saudi
b. Grade 2/B – Kuwait
c. Grade 3/C – Indonesia
Particle size distribution of the as received sample is shown in figure 2. The major portion
of the particle size is + 4.75 mm. In reality there is no fine fraction restriction in feed for
rotary kiln compared to feed for vertical shaft kiln (< 1 mm below 30 wt.%). More fines in
the rotary kiln feed will result in more carbon loss which will affect the plant yield. Particle
size shall be categorized in three fractions in petroleum coke plants. + 4.75 mm – Coarser
(promotes tumbling and mixing of the bed and exposed to higher radiant heat– results in
uniform calcination of the particles and can lead to thermal de sulfurization) 1.75 to 4.75
mm – medium size fractions. Less than 1.75 mm – fines fractions (expected to present at
the core of the bed and it is less exposed to radiant heat). For the static furnace testing
particles are crushed < 6.4 mm and for other material characterizations material is crushed
to finer fractions.

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 Figure 2. Particle size distribution of three different grades.

Figure 3. Granular motion of the petroleum coke particles in rotary kiln [20]
Green petroleum coke (GPC) is also categorized based on hard groove index (HGI) to
volatile matter (VM) composition. If the (HGI/VM) is 12 then, it is an anisotropic coke
(material property changes in all three directions when stress is applied). If the ratio is 8
[22] then it is anode grade coke, if it is 4 then it is a isotropic coke (material property will
remain same in all direction irrespective of the stress applied). HGI below 100 is a soft
coke which produces good quality CPC whereas HGI above 100 is a hard coke which
produces lower VBD CPC.

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4. Methods
i. Petroleum coke characterization
Proximate analysis of petroleum coke was carried out as per ASTM-E1131-08 (2014)
procedure in a thermogravimetric analyzer (TGA, SDT Q600, T.A. Instruments). The
three grades of sample results are tabulated in table 1. Samples are then categorized
based on the VM and sulphur content present as Lower VM & higher sulphur content,
Moderate VM & sulphur content and Higher VM & lower sulphur content. Among the
three grades, moderate sulfur (3.19%) and VM (12.04%) Grade 2/B is identified to
respond for various thermal heating conditions. However, VBD is tested for all three
grades to find the good shift in the values and confirm which grade suits for further
investigation. Ultimate analysis (table 2.) of GPC was carried out as per ASTM D353
procedure in CHNS analyzer (Leco instruments). Mineral matter analysis done as per
ASTM D5600. Petroleum coke is ashed at 700oC. The ash is fused with lithium borate.
The melt is dissolved in a dilute hydrochloric acid and the resultant solution is analyzed
using inductively coupled plasma atomic emission spectroscopy (ICPAES) using
aqueous calibration standards.
Table 1: Green Petroleum Coke (GPC) sample proximate analysis
Sample Grade 1/A Grade 2/B Grade 3/C
Temperature (o C) 950 950 950
VM (Weight %) 9.37 12.04 16.26
Ash (Weight %) 0.21 0.41 0.36
Moisture (Weight %) 4.80 4.81 5.91
Fixed Carbon (Weight %) 85.61 82.74 77.47
Sulfur (Weight %) 8.76 3.19 0.67

Table 2: Green Petroleum Coke (GPC) sample ultimate analysis

Sample Grade 1/A Grade 2/B Grade 3/C
Carbon (Weight %) 85.6 90.5 91.8
Hydrogen (Weight %) 3.13 3.67 4.06
Sulphur (Weight %) 8.20 3.52 0.98

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 Sample Grade 1/A Grade 2/B Grade 3/C
Nitrogen (Weight %) 0.92 0.98 1.33
Oxygen (Weight %) 1.15 0.43 0.63
Mineral matter (Weight %) 4.60 1.90 0.80
Gross calorific value (kJ/kg) 34215 35805 36441
Net calorific value (kJ/kg) 33527 35003 35554

ii. Thermogravimetric Analysis (TGA) of petroleum coke:

TGA is performed in all the three samples to know about the rate of moisture, VM
release rate. Procedure is carried out in a thermogravimetric analyzer (TGA, SDT
Q600, T.A. Instruments). < 5 mg of sample is used for each trial at a Nitrogen flow of
100 ml/min. Data collected for four ramping programs say 5, 10, 15 and 20oC/minute
to the target temperature (1000oC). After the target temperature each ramping program
had a holding time variation say 15, 30 and 45 minutes. Table 2 summarizes the
operating condition of sample that is programmed in the nitrogen atmosphere. The
weight loss from the three grades are closely matching (volatile matter + moisture) as
per proximate analysis. Some weight losses show greater value this may be due to
instrumental error which is acceptable. The weight loss of sample 2/B falls between the
sample 1/A & 3/C. Sample 2/B shows the closer mass loss, no matter whatever be the
change in heating rate. Weight loss increases with temperature with decreasing weight
loss variation rate. This is distinguished in the figure 3. This is in relation with change
of heat conductivity and specific heat capacity variation reported by M. Long et. al.
Similarly weight loss variation curves for other grades as well. Region I steep weight
loss indicates the release of moisture. Region II steep slope may indicate VM release.
Region III with reduced weight loss indicates the exhaust of volatiles present.
Friedman, Kissinger–Akahira–Sunose and Ozawa–Flynn–Wall iso-conversional
methods are used to estimate the activation energy of the coke. The increase and
decrease of activation energy between 63 to 276 kJ/mol for sample 2/B indicates
moisture and volatile release (combined loss/conversion of ≈ 17%), a multistep process.
R.J. Tyler [19] reported the activation energy ranges of petroleum coke under CO2
atmosphere between 203 – 237 kJ/mol for 21 to 44.7 % conversion.

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iii. FTIR Analysis:
Sample grade 2/B heated in a nitrogen atmosphere with two heating time (60 and 120
minutes). 3 gm of Sample placed in a tube furnace with the back-ground gas of 30%
CO2, 5%O2 and 65% N2 furnace for Jum Analyzer and 100% N2 for FTIR analysis.
One branch of off-gas line is fitted with Jum Analyzer for Total Hydrocarbon (THC)
and methane analysis. Another branch is connected to FTIR Multigas 2030 to analyze
the hydrocarbon composition followed by ultramat23 for the analyzing CO, CO2, NO2
SO2, O2. Slower heating rate shown in figure 5 & 6 shows more hydrocarbon species
in the off gas compared to the higher heating rate shown in figure 7 & 8. It indicates
the slower heating shall tend to open the pores gradually by the release of higher
molecular weight hydrocarbon which results in higher VBD of coke after calcination.

iv. Muffle furnace test using the crucible and plate:

Sample calcination testing is carried out in the muffle furnace. Approximately 200 g of
samples used for each trial. To damp the effects of thermal gradient in the samples
while heating they are divided into four equal parts and placed in four same
dimensional size crucibles/plates. Two method of calcination test executed viz. placing
the sample in a plate and in covered crucible. Two final temperatures are targeted viz.
1250 and 1400oC to identify the suitable calcination temperature. (1) Covered crucible
method: Samples are crushed to <6.4mm and charged the large crucible up to a height
of 75mm. Followed by covering and injecting a small quantity of N2 (0.25 lpm).
Crucible with material is placed in the furnace and heated to a final temperature as
mentioned above. Heating carried over a period of 1 & 3 hours to final temperature as
fast and slow heating rate respectively. Once the furnace reaches the target temperature,
power turned off to let the sample cool. Followed by measuring real density (RD –
ASTM D2638 measured using Quanta chrome Pycnometer) and vibrated bulk density
(VBD – ASTM D4292). (2) Plate method: Second series of furnace burns carried out
as per the following procedure. Crushed petroleum coke sample placed on a ceramic
plate up to a thickness of 13mm. N2 is injected into the furnace to make the furnace
chamber inert. Furnace ramping rate is repeated as depicted in table 4 with the same

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 calcination temperature. The results shown in table 4 and 5 respectively. To see the
impact of VBD & RD and under what condition the VBD will be improved, baseline
line condition is simulated by ramping furnace from ambient to 600°C at 14°C/min.
Then ramped up to 1250°C at the maximum rate the furnace can support
(20°C/min). Followed by cooling and the measuring RD & VBD. Similarly, the
improved heating profile using sample in plate is also simulated. Sample heated from
ambient to 800°C at 9°C/min and then ramped up to 1250°C at the maximum rate the
furnace can support (20°C/min). Followed by cooling and the measuring RD & VBD.

v. Real Density measurement:

Sample is dried and ground to pass a 75 μm screen. The mass of the volume is
determined directly, and the volume derived by the volume of helium displaced when
the sample is introduced into a helium pycnometer. The ratio of the mass of the sample
to the volume is reported as the real density

vi. Vibrated Bulk Density measurement:

100 g of the coke fraction (-30/+50 US mesh) is poured into a graduated cylinder. The
transfer time is between 70 to 100 s at a rate of 10 to 14 g/10s. It is achieved using
vibratory feeder. Cylinder with material is closed tightly with rubber cork and then it
is placed over the vibrator for vibrating it for 5 min at an amplitude of 0.2 to 0.22 mm
(60 Hz). VBD is calculated by the following formula,
VBD (g/cc) = Weight in grams/volume in milliliters

vii. Specific surface area analysis:

Specific surface area of the samples measured using Quanta Chrome Monosorb – BET
instrument (ASTM D5604-96). BET test measurement of the calcined petroleum coke
shows that the higher VBD obtained sample (Grade 2/B – calcination by crucible
method) has the highest specific surface area 0.6 m2/g against lower VBD obtained
sample (Grade 2/B – calcination by plate method) with specific surface area of 0.1
m2/g. Samples with richer pores will have higher specific surface area according to J.H.
Zou et. al [12]. The results are shown in table 7.

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5. Results and discussion
Identification of GPC composition and Calcination temperature
At final target temperature 1400oC, Sample 1/A gives RD of 1.94 g/cc which is below the
minimum requirement for the aluminium smelter operation. The reduction is due to the
presence of high sulfur and its thermal desulfurization beyond 1300oC. Sample 2/B gives
no significant difference in RD and VBD values at slow and fast heating rate
(Ttarget1400oC). However, at Ttarget1250oC the significant difference observed in RD and
VBD values at both heating rates. Here the slow heating rate fetches higher RD and VBD
which is due to the gradual pore opening during VM release. Similarly, for sample 3/C the
same has been observed (Ttarget1250oC), but the VBD values are less compared to sample
2/B. This is due to higher VM content compared to sample 2/B. From this it is concluded
that the calcination temperature for the better product quality is 1250oC. The better choice
of GPC composition shall be VM (11 to 13 wt%), Sulfur (3 to 5 wt.%). From this study
grade 2/B is chosen for further investigation. In practice either similar composition of the
grade or various grades of GPC shall be blended to arrive closer to this specification for a
suitable kiln feed. The above results are summarized in table 3 & 1.

Table 3: Covered crucible static furnace testing

Calcination Fast Heating
Slow Heating (g/cc)
Sample Temperature (g/cc)
oC RD VBD RD VBD
Grade 1/A 1400 1.94 N/A N/A N/A
Grade 2/B 1400 2.11 0.893 2.14 0.892
Grade 2/B 1250 2.07 0.925 2.06 0.813
Grade 3/C 1400 2.11 0.877 2.10 0.819
Grade 3/C 1250 2.05 0.909 2.03 0.802

Estimation of activation energy for combined release of VM and moisture

The collected data from TGA trials are used in differential and integral iso-conversional
methods such as Friedman, Kissinger–Akahira–Sunose and Ozawa–Flynn–Wall

16
respectively to estimate the activation energy Ea. Combined release of moisture and
volatiles represented in the form of weight loss between 16.47 to 21.25 %. This closely
matches as per the proximate analysis. Figure 4 a to d represents the weight loss curve for
different ramping rate say 5, 10, 15 and 20oC/minute from ambient to final temperature of
1000oC. This study focusses only on the energy required to liberate moisture and volatiles
in close intervals of ramping rate. In all of the four thermal program the operating
temperature of rotary kiln is arrived. At about a temperature range of 650 to 800oC major
volatile loss occurs. Therefore all the devolatilization process in the kiln should be operated
before 800oC with slow heating rate < 20oC/minute. This was not documented in any of
the literature. The activation energy varies between 63 to 276 kJ/mole. The increase and
decrease of activation energy, from beginning of the conversion say 5% to 100%
conversion end (exhaust of combined moisture and VM loss) shows, the process is
multistep. Plots (figure 5 a to c) of these conversion for three iso-conversional methods
shows activation energy varies in broader range. It indicates GPC volatiles is heterogenous
in nature. But the variation rate of the slope is decreasing towards the conversion end.
Apparently there is a three region of volatile evolution rate. The first region signifies the
evaporation loss (region I) which is accompanied by the lower activation energy < 100
kJ/mole, followed by the steepest (region II) and decreasing variation curve (region III).
This is due to the release and cracking of higher chain hydrocarbons. Among the four-
ramping rate, the program at 15oC/minute gives the closer shift of weight loss when the
holding time is varied say 15, 30 and 45 minutes to the final temperature. This indicates
the ramping rate ≤ 20oC/minute implies the mass release (VM + moisture) is appropriate
for the list of hydrocarbons that is getting cracked gradually from longer chain to least
possible hydrocarbons.

Table 4: Thermogravimetric weight loss

Ramping rate 5 oC /minute (weight loss %)
Hold time (min) 0 15 30 45
Grade 1/A 13.88 14.84 19.71 17.72
Grade 2/B 16.47 18.18 21.25 20.63
Grade 3/C 25.42 27.86 24.09 25.17

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 Ramping rate 10 oC /minute (weight loss %)
Grade 1/A 16.50 15.77 17.67 17.36
Grade 2/B 17.99 19.26 20.21 20.01
Grade 3/C 22.99 23.07 25.37 28.18
Ramping rate 15 oC /minute (weight loss %)
Grade 1/A 13.40 14.77 17.02 15.20
Grade 2/B 16.16 16.94 18.74 19.76
Grade 3/C 26.07 26.20 27.18 21.19
Ramping rate 20 oC /minute (weight loss %)
Grade 1/A 13.17 16.58 16.85 15.25
Grade 2/B 18.32 15.82 19.18 20.14
Grade 3/C 23.58 25.24 21.37 23.93

Figure 4. Thermogravimetric weight loss of sample 2/B (a) @ 5oC/min. (b) @ 10oC/min.

Figure 4. Thermogravimetric weight loss of sample 2/B (c) @ 15oC/min. (d) @ 20oC/min.

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Figure 5. Estimation of activation energy Ea (a) by Friedman method (b) by
Kissinger-Akahira-Sunose method (c)

Confirmation of VM composition by FTIR Analysis

Composition of Volatiles present in GPC is found to contain qualitatively m-Xylene,
Ethane, Propane, Butane, Ethylene, Acetylene, Ammonia. The total hydrocarbon is found
to evolve between 450 to 850oC whereas, m-Xylene starts to get crack beyond 250oC. From
the off-gas test, it is clearly seen the least molecular weight hydrocarbon that is formed as
a cracked product is methane. The fast heating rate indicates the maximum gradual release
of hydrocarbon whereas the slow heating rate indicates fast and reduced release rate of
hydrocarbons present in GPC. From this it confirmed that the release of volatiles and
moisture from VM is a multistep process. Therefore, this heterogenous nature of GPC’s
VM requires a slower heating rate to yield a better quality in calcination process. The
summary of these analysis is graphically represented in figures from 6 a to d. The heating
rate between 10 to 20oC/minute indicates the volatile release is rate and the extent of
volatile release time is longer duration compared to the heating rate below 10oC/minute.
The below figure shows the evolved off gases and the volatile composition of the sample
2/B.

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Figure 6. Evolution of off gases and volatile composition (a & c - counting counter
clockwise from top left to bottom) @ < 10oC/minute (b & d - counting clockwise from
top right to bottom) @ heating rate between 10 to 20oC/minute.

Impact of heating rate and static furnace testing method that affects the calcined coke
quality
Starting with (1) Plate type method, samples heated at a uniform ramping rate (7oC/minute)
to calcination temperature gives a no change in VBD from the conventional average
heating rate of 20oC/minute. Spliting heating rate to two steps viz., 9oC/minute to 800oC
and from there to 1250oC at 20oC/min. This gives a marginal improvement from 0.847 to
0.849 g/cc. Similarly, 14oC/minute from ambient to 600oC and from there to 1250oC at
20oC/minute gives a VBD increase from 0.849 to 0.852 g/cc. Response on two step heating
rates is fair compared to single step heating rate. It indicates the combination of volatile
release at slower heating rate (gradual pore opening) and coke densification (no formation
of pore opening may be pores may coalesce or shrink) at higher heating rate will give an
improvement in VBD. Moreover, as per the FTIR analysis most of the volatiles released
between 450 to 850oC, this is also a reason to have a lower heating rate in this range. (2)

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Under crucible method the two step heating rates are favourable with lower heating rate at
the devolatilization phase and higher heating rate at densification phase. But the
improvement in VBD is higher (0.847 to 0.877 g/cc) compared to plate method. First
significant inference that crucible method gives better VBD is due to large thermal gradient
maintained when samples are heated. The results are shown in figure 7. Second inference
is may be due to lean thickness of the coke bed compared to the bed thickness in the
crucible method. It indicates that the larger L/D ratio of Kiln should not run with lower
kiln filling, which will result in reduced yield and product quality. The optimum kiln L/D
ratio with the optimum filling rate should be chosen to achieve operational stability.

Figure 7. Green petroleum coke varied heating rate in a muffle furnace.

Impact of heating rate on specific surface analysis

Specific surface area (SSA) analysis of calcined coke at different ramping in reaching the
calcination temperature links the connect between volatile diffusion from the core coke
matrix to its surface. As the instrument (Quantachrome Monosorb) used measures the
quantity of a gas adsorbed on a solid surface by sensing the change in thermal conductivity
of flowing mixture of an adsorbate and the inert carrier gas (Nitrogen). This happens when
the volatile releases by diffusion i.e., layers of pores formed will lead a concentration
difference from the matrix with volatile and the one where volatile released. By this way
pores are get connected to form a network for the remaining volatiles to release. At the

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onset of devolatilization (450 to 850oC) SSA (0.3m2/g at 600oC) is less whereas it increases
with temperature (800oC) SSA (0.7m2/g) which is due to gradual pore opening. The same
is decreased to 0.6 m2/g at 1250oC due to the shrink of some of the pore networks that are
connected during devolatilization. Other possible reasoning is also well explained in the
below table 5.
Table 5. Specific Surface Analysis

Metsim (version 2013.02) simulation in optimizing kiln operation using furnace burn
results

Figure 8. Metsim model function

Metsim is a commercially available metallurgical simulation software. Empty boxes in

Figure 8 indicates a unit operation/process. This solves mass, energy, momentum transport
equation for the phases involved (two phase in this case – gas & solid) by establishing

22
equilibrium states for each phases formed from the reactants. Such a process of forming
equilibrium states reduces its available free energy. There it is called as a Free Energy
Minimizer (FEM). By this was the heat and mass balance are solved for the specific
equipment. k1 and k2 are specific transfer coefficients (mass/heat/momentum).

An industrial scale rotary kiln of L/D ratio 18 (78 m length and a dimeter of 3.9 m) is
simulated to run the GPC calcination using Metsim (version 2013.02) software.

Following are the parameters considered for the simulation,

Feed – 55209 dry kg/h; Product – 43343 kg/h; Feed moisture – 10 wt.%

C – 84.9 wt.%; H2 – 2.1 wt.%; CH4 – 9.9 wt.%; S – 3.0 wt.%; SiO2 – 0.1 wt.%

Primary, Secondary air – 21205 kg/h; Tertiary air – 91488 kg/h; Fuel (Natural gas) – 1243
kg/h Reactions considered:

1. Burner – 2 + 3 → 2 + 4  , 2 +  → 2

2. Kiln –   →  
2 + 3 → 2 + 4 
2 +  → 2 ,  +  → 
 +  →  ,  +   →  + 
The average heating rate of the pet coke along the length of the kiln is ≤20oC/minute. The
initial increase of heating rate at the feed end is may be due to release of moisture (phase
change from water to water vapor). The heating rate rises exponentially between 22nd
meter (distance from the discharge end) to 40th meter (towards the feed end). The decrease
in heating rate after 27th meter (from feed end towards discharge end) may be the generated
heat (from exothermic reaction) utilized for coke densification. The discharge end material
and gas temperature are 1350 to 1500oC is due to the presence of flame from the burner
front. The heating rate increases after it descend due to presence of burner flame. The major
weight loss from the feed to discharge occurs at the maximum heating rate point. Most of
the volatiles undergo maximum combustion in this zone. This leads to the increase gas and
material temperature. The zero-oxygen concentration is maintained throughout except the
tertiary air injection location. The below profile shown in figure 9 coincides with the work
of Zang et.al [17]. Current study focuses the additional modeling of the rotary kiln system

23
starting with the baseline model previously generated. Main objective is to reduce the rate
of material heating. The improved profile has the material temperature 800oC below which
all the volatiles are removed. The first step involved shifting a portion of the tertiary air to
secondary air. This shifted the rapid heating zone in the TA injection area. The next step
included reducing the kiln rotational speed from 1.2 rpm to 1.0 rpm to maximize solids
loading and residence time. The impacts to temperature profiles and heating rates can be
seen in the figures (9 & 10) below with relativeness to the baseline conditions. The average
heating rate is reduced to 18oC/minute from 39oC/minute and the peak heating rate is
reduced 72 from 80oC/minute.

1. Case 1: Shifting portion of secondary air to tertiary air

Tertiary air fan – 55000 kg/h
Primary + Secondary air – 57000 kg/h
2. Case 2: Shifting portion of secondary air to tertiary air and reducing kiln speed
Tertiary air fan – 53000 kg/h
Primary + Secondary air – 58000 kg/h

Figure 9 – Shifting a portion of tertiary air to secondary and primary air zone

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 Tests performed using covered “crucible” method in furnace, yielded the following VBD
between 0.862 g/cc- 0.877 g/cc shall be achieved by optimizing the above two cases. These
ensures the potential increase in VBD due to shift of heating rate towards the discharged
end and increasing the residence time.

Figure 10 – Kiln rotational speed is reduced from 1.2 to 1.0 rpm

6. Conclusion
Estimated activation energy of the grade 2/B increase from 63 to 276 kJ/mol indicates the
volatile and moisture release is a multistep process. To substantiate this FTIR analysis
indicates the gradual release of hydracarbon requires slow heating rate. Direct reduction of
petroleum coke profile heating rate alone gives a less significant improvements in the
increase of calcined petroleum coke VBD. It also requires shifting part of tertiary air
towards the kiln discharge end (primary and secondary air) and by increasing the residence
of the material in kiln. However further investigation on the pore development along the
heating rate of coke will give a significant information to aid the reactor design and kiln
operating condition. Salient featurs of the conclusion is as follows,

25

Static furnace test gives a better VBD at heating rate < 20oC/minute with the residence time
≈ 110 minutes

BET results reveals lower heating rate until VM vanishes yields better VBD

Estimated activation energy - 100 to 280 kJ/mol indicates multistep process

Evolution of off gas –10 < HR < 20oC/minute volatile release in definite regime (400 to
800oC)

Using experimental data in the simulator - Shifting the exponential heating rate at tertiary
air towards the kiln discharge end and reducing to some extent with increased residence
time .

Static furnace test has to be validated in the below shown pilot kiln

Figure 11. Electrically controled rotary furnace.

Specifications: Tube speed – 0.1 to 1.5 rpm (variable speed), Slope – 0 to 5% (adjustable),
Length – 3.2 m , Diameter – 0.16m, Zone 1 (from feed end) – ambient to 900oC Zone 2 –
ambient to 1000oC, Zone 3 – ambient to 1300oC. Tube MOC – Inconel 55, Screw feeder –
SS MOC, speed variable from 0 to 18 rpm. ID fan speed is variable.

26
` Figure 12. Electrically controled rotary furnace - Schematic.

27
7. References

[1] Jin Xiaoa, Fachuang Lia, Qifan Zhonga, Jindi Huanga, Bingjie Wanga, Yanbing Zhanga,
"Effect of high-temperature pyrolysis on the structure and properties of coal and petroleum
coke", J. of Anal. and Appl. Pyrolysis 117 (2016) 64–71
[2] Les Edwards, Rain CII Carbon, Covington, "The History and Future Challenges of Calcined
Petroleum Coke Production and Use in Aluminum Smelting", JOM, 67, 2 (2015) 308-321.
[3] Kamran Azari, Wilinthon Bogoya-Forero, Carl Duchesne, Jayson Tessier, "Measurement of
Vibrated Bulk Density of Coke Particle Blends Using Image Texture Analysis", The Minerals,
Metals & Materials Society, 69, 9 (2017) 1613–1623
[4] P. J. Rhedey, “Structural Changes in petroleum coke during calcination”, Transactions of the
Metellurgical Society of AIME, 239 (1967) 1084 – 91
[5] Mack P. Whittaker, Fred C. Miller, and Harlan C. Fritz, “Structural changes accompanying
coke calcination”, Indian Engineering Chemical Product. Research and Development, 9, 2
(1970) 187-190,
[6] P. J. Rhedey, “Anode filler Coke Porosity Studies”, Light Metals, (1988) 114 -118.
[7] Mujun Long, Junhao Sheng, Tao Liu, Dengfu Chen, Yi Yang, Shikai Gong, Chunmei Chen,
“Thermo-Physical Properties of Petroleum Coke during Calcining Graphitization Process”,
The Minerals, Metals & Materials Society, (2015) 193-199.
[8] D. Kocaefe, A. Charette and L. Castonguay, “Green coke pyrolysis: investigation of
simultaneous changes in gas and solid phases”, Fuel, 74, 6 (1995) 791-799.
[9] E. E. Hardin C. L. Beilharz, L. L. Melvin, "A Comprehensive Review of the Effect of Coke
Structure and Properties When Calcined at Various Temperatures – Part I ", Light Metals,
(1993) 501-508.
[10] E. E. Hardin C. L. Beilharz, L. L. Melvin, "A Comprehensive Review of the Effect of Coke
Structure and Properties When Calcined at Various Temperatures – Part II", Light Metals,
(1994) 73-83.
[11] Les Edwards, “Thermal Desulfurization of Petroleum Coke for Anode Use”, Travaux 46,
Proceedings of 35th International ICSOBA Conference, Hamburg, Germany, (2017) 625-633.
[12] K.S. Milenkovaa, A.G. Borregoa, D. Alvareza, J. Xibertab, R. Mene´ndez, “Devolatilisation
behaviour of petroleum coke under pulverized fuel combustion conditions”, Fuel 82 (2003)
1883–1891.
28
[13] Victor Buzunov, Victor Mann, Sergey Khramenko, and John Johnson, “Influence of
Calcination Temperature and Sulfur Level on Coke Properties”, The Minerals, Metals &
Materials Society, (2017) 1150 – 1156.
[14] Marie-Josée Dion , Hans Darmstadt , Nigel Backhouse, Mike Canada, and Frank Cannova,
“Prediction of Calcined Coke Bulk Density, Light Metals, (2011) 931 – 936.
[15] Jian Hui Zou, Zhi Jie Zhou, Fu Chen Wang ∗, Wei Zhang, Zheng Hua Dai, Hai Feng Liu, Zun
Hong Yu, “Modeling reaction kinetics of petroleum coke gasification with CO2”, Chem.
Engg. and Proc. 46 (2007) 630–636.
[16] J. Perron, L. Castonguay, R.T. Bui and T.H. Nguyen. “Optimization of Coke Calcining Kiln
operation using mathematical modelling”, Light Metals, (1990) 559 – 563.
[17] Z. Zhang et. al., “Simulation of combustion and thermal-flow inside a petroleum coke rotary
calcining kiln - Part II: analysis of effects of tertiary airflow and rotation” J. Therm. Sci. Eng.
Appl. 2, (2010) 1-7.
[18] Sandesh Y. Sawant, K. Munusamy , Rajesh S. Somani , Mathew John b, Bharat L. Newalkar,
Hari C. Bajaj, “Precursor suitability and pilot scale production of super activated carbon for
greenhouse gas adsorption and fuel gas storage”, Chem. Engg. Journal 315, (2017) 415–425.
[19] Ralph J. Tyler and Ian W. Smith, “Reactivity of petroleum coke to carbon dioxide between
1030 and 1180 K”, Fuel Vol 54, (1975) 99-103
[20] L. P. Lossius et.al., “ Coke and anode desulfurization studies”,The Minerals, Metals &
Materials Society) (2008) 881-886
[21] P. Rhedey, "A review of factors affecting carbon anode consumption in the electrolytic
production of aluminum", A.Tomsett and J.Johnson (Eds), Essential readings in light metals,
TMS (2016)
[22] M. Meier, R.Perruchoud, “Coke: From crude oil to prebaded anodes”, Report by R&D Carbon
(2018).
[23] Y.H. Zhao et.al, J.Org.Chem., 68 (2003) 7368-7373
[24] Patented 2018 by G. Banerjee et.al ESSAR Steels confidential.

Visible output:

1. Paper populated - Vinodh Kumar M, Michael E. Prokesch, R.Vinu “Impact of heating

rates on the vibrated bulk density of calcined petroleum coke”

29
Conference Presentations:

1. Poster presented at Pyroasia2019 1st international Symposium - Vinodh Kumar M,

Michael E. Prokesch, R. Vinu, Shankarabalan G “Impact of heating rates on the vibrated
bulk density of calcined petroleum coke” Awarded best poster presentation during the
symposium on 12-13th December 2019

Onging and Future Works:

A. Fundamental understanding of vapor composition and its relationship with VBD is planned
to explore [23].

 = ∑     − 5.92%& − 14.7)* − 3.8),* ;

%& = % − 1 + )* + ),*

- .  / = 0     − 1% − 126.56

Where, VvdW – Van der waals volume (Å3/molecule) using bondi radii, Mcgowan volume
calculated using pauling’s radii NB – No. of bonds, RA – No. of Aromatic ring, RNA –
No. of Non–Aromatic ring, N – Total No. of atoms

B. GPC fines briquetted using binders for calcination Cokes fines in the kiln feed shall be
briquetted using binders.

 Coal tar pitch, Bentonite clay, Polyvinyl alcohol are suitable binders.

Based on pollution hazards (Chrysene, Benzo(a)-pyrene etc.,) coal tar pitch is not
suitable.

 Bentonite requires high temperature of order 1200-1300°C for strong briquette

 PVA becomes infusible material at high temperature to protect coke from instantaneous
heating [24].

30