“Treatment option for safe disposal and recovery of by-product from

residue from spray drying of concentrated waste streams”

A Dissertation submitted to
The Maharaja Sayajirao University of Baroda
in the partial fulfilment for the award of the degree of

MASTER OF ENGINEERING
(CIVIL)
IN
ENVIRONMENTAL ENGINEERING

SUBMITTED BY
BHAVESH H TILOKANI

GUIDE
Dr. UPENDRA D PATEL

Professor

Department of Civil Engineering

Faculty of Technology & Engineering
The M.S. University of Baroda

CIVIL ENGINEERING DEPARTMENT FACULTY OF TECHNOLOGY

THE MAHARAJA SAYAJIRAO UNIVERSITY OF BARODA

VADODARA
JULY 2018
 THE MAHARAJA SAYAJIRAO UNIVERSITY OF BARODA

CERTIFICATE

This is to certify that the dissertation entitled, “Treatment option for safe disposal and recovery
of by-product from residue from spray drying of concentrated waste streams”, which is being
submitted by Bhavesh H Tilokani in partial fulfillment of the requirements for the award of the
degree of Master of Engineering (Civil) in Environmental Engineering is the record of the
work that has been carried out by him under my supervision and guidance. The matter complied
in this dissertation has not been submitted earlier for the award of any other degree or
fellowship.

GUIDE EXTERNAL EXAMINER

Dr. Upendra D Patel
Professor
Department of Civil Engineering
Faculty of Technology & Engineering
The M. S. University of Baroda

HEAD DEAN
Dr. (Prof.) H. M. Patel Dr. (Prof.) Arun Pratap
Department of Civil Engineering Faculty of Technology & Engineering
Faculty of Technology & Engineering The M. S. University of Baroda
The M. S. University of Baroda
 Acknowledgement

I am proud to be a part of the institute, The Maharaja Sayajirao University of Baroda,

Vadodara that has given me an opportunity to place a feather in my hat. I would like to express
my sincere gratitude to my guide Dr. U. D. Patel for his patience, motivation, guidance,
cooperation, constant encouragement, support, helpful comments, insightful suggestions and
recommendations which were very useful in completion of my thesis during the course of the
project. I truly appreciate his esteemed guidance and encouragement from beginning to the end
of the thesis, his knowledge and company at the time of crisis would be remembered lifelong.

I am thankful to all the professors of the department Dr. A. R. Makwana, Mrs. A. D. Galgale,
Dr. N. G. Shah, and Dr. K. A. Shah for their valuable teaching, help and encouragement during
my course of study. I would like to thank Dr. H. M. Patel, Head of Civil Engineering
Department for providing all the facilities available at his command. I would also like to thanks
to Ms. Sangeeta Patel, Mr. Jignesh Sagar, Rameshbhai and Dineshbhai for their support
and kindness during my laboratory work and without their help my work would have not
achieved this feat.

Finally, I wish to thank my friends especially Ruchita Goyani, Ayushi Sharma, Dhruti
Mistry, Vyoma Jani, Poonam Katara, Katha Hirpara, Vishva Odedra, Govind Tiwari,
Sanket Boghara, Jalpit Marden, Shashi Patel, Atri Dave and Divyesh Ratanpara who have
always supported, helped and encouraged me at every moment during my research work. The
time spent with them is unforgettable. They are the main inspiration and source of energy for
me.

Special thanks go to my Family for providing me with unfailing support and continuous
encouragement throughout my year of study. This accomplishment would not have been
possible without them.

I do believe in the blessing of GOD, as a result I see the grace of GOD for my successful
completion of my study. The faith in GOD always kept me inspired, healthy and energetic during
my research work.

BHAVESH H TILOKANI
CONTENTS
1. INTRODUCTION .............................................................................................................. 2

1.1 General: ........................................................................................................................ 2

1.2 Spray Dryer: ................................................................................................................. 5

1.2.1 Advantages of spray dryer: ................................................................................... 6

1.3 Spray dryer in waste water:.......................................................................................... 6

1.4 Spray dried residue and its environmental significance: ............................................. 6

1.5 Treatment options for hazardous waste: ...................................................................... 7

1.6 Need of the study: ........................................................................................................ 9

1.7 Goal of the study: ........................................................................................................... 9

1.8 Objectives of the study: .................................................................................................... 9

2. LITERATURE REVIEW: ................................................................................................ 10

2.1 Studies related to treatment of hazardous waste by pyrolysis method: .......................... 10

3. MATERIALS AND METHODS: .................................................................................... 17

3.1 Materials: ................................................................................................................... 17

3.1.1 Reactor: ............................................................................................................... 17

3.1.2 Gas supply: ......................................................................................................... 18

3.1.3 Air supply: .......................................................................................................... 18

3.1.4 Water jacket: ...................................................................................................... 18

3.1.5 Spray dried residue (sample collection): ............................................................ 18

3.1.6 Dyes: ........................................................................................................................ 19

3.1.7 Rotary shaker: .......................................................................................................... 19

3.1.8 Instruments: ............................................................................................................. 19

3.2 Methodology: ............................................................................................................. 21

3.2.1 Characterization of raw spray dried residue: ...................................................... 21

3.2.2 Calculation for requirement of gas for heating: ................................................. 21

3.2.3 Batch studies for pyrolysis: ................................................................................ 22

3.2.4 Characterization of treated spray dried residue: ................................................. 23

3.2.5 Determination of Methylene number of carbon: ................................................ 23

 3.2.6 Determination of adsorption isotherm (Langmuir and Freundlich): .................. 24

4. RESULT AND DISCUSSION: ........................................................................................ 26

4.1 Characterization of raw spray dried residue: .................................................................. 26

4.2 Results of pyrolysis batch studies: ................................................................................. 27

4.2.1 Result of 1 and 1.5 hour run for SDR 1 sample: ..................................................... 27

4.2.2 Result of 1 and 1.5 hour run for SDR 2 sample: ..................................................... 28

4.2.3 Result of 1 and 1.5 hour for SDR 3 sample: ............................................................ 29

4.3 Mass balances for spray dried residue: ........................................................................... 31

4.4 Methylene blue number for the carbon obtained after treatment: .................................. 33

4.5 Isotherm model for Methylene blue dye: ....................................................................... 35

4.5.1 Langmuir model for Methylene blue dye: ............................................................... 35

4.5.2 Freundlich model for Methylene blue dye: ............................................................. 37

5. CONCLUSION: ............................................................................................................... 39

6. REFRENCES: .................................................................................................................. 40
LIST OF FIGURES

Figure 1 Process of spray drying ................................................................................................ 5

Figure 2 Process diagram of the fixed bed reactor ................................................................... 15
Figure 3 Setup for activation scheme ....................................................................................... 16
Figure 4 Downward gasifier reactor ......................................................................................... 16
Figure 5 Design of the reactor .................................................................................................. 17
Figure 6 Rotary shaker for methylene blue .............................................................................. 19
Figure 7 Experimental setup for pyrolysis ............................................................................... 23
Figure 8 Figure of raw sample of spray dried residue .............................................................. 26
Figure 9 Mass vs % COD reduction for1and 1.5 hour run for SDR 1 sample ......................... 27
Figure 10 Mass vs % COD reduction for 1 and 1.5 hour for SDR 2 sample ........................... 28
Figure 11 Mass vs % COD reduction for 1 and 1.5 hour of SDR 3 sample ............................. 30
Figure 12 Untreated and treated sample comparison .............................................................. 32
Figure 13 Langmuir model for MBN for SDR 1 sample carbon.............................................. 35
Figure 14 Langmuir model for MBN of SDR 2 carbon sample ............................................... 35
Figure 15 Langmuir model for MBN for SDR 3 carbon sample ............................................. 36
Figure 16 Freundlich model for MBN for SDR 1 carbon sample ............................................ 37
Figure 17 Freundlich model for MBN for SDR 2 carbon sample ............................................ 38
Figure 18 Freundlich model for MBN for SDR 3 carbon sample ............................................ 38
LIST OF TABLES
Table 1 Common spray dryer facilities in Gujarat ..................................................................... 4
Table 2 Physico chemical properties of spray dried residue .................................................... 26
Table 3 Reduction in COD for 1 hour in SDR 1 sample .......................................................... 27
Table 4 Reduction in COD for 1.5 hour in SDR 1 sample ....................................................... 27
Table 5 Reduction in COD for 1 hour in SDR 2 sample .......................................................... 28
Table 6 Reduction in COD for 1.5 hour in SDR 2 sample ....................................................... 28
Table 7 Reduction in COD for 1 hour in SDR 3 sample .......................................................... 29
Table 8 Reduction in COD for 1.5 hour in SDR 3 sample ....................................................... 29
Table 9 Mass balance for treated samples ................................................................................ 31
Table 10 Methylene blue number for carbon from SDR 1 sample .......................................... 33
Table 11 Methylene blue number for carbon from SDR 2 sample .......................................... 33
Table 12 Methylene blue number for carbon from SDR 3 sample .......................................... 34
Table 13 Nature of adsorption process (M. Arulkumar et al. 2011) ........................................ 36
Table 14 Comparision of Isotherm constant ............................................................................ 38
Abstract
Conventionally, concentrated wastewater streams generated from Dye and Dye
intermediate, Pesticide, Pharmaceuticals industries, have been subjected to multiple effect
evaporation (MEE) followed by thermal incineration. Due to several problems and high
cost of operation of MEE and thermal incineration, industries have recently resorted to
spray drying of concentrated wastewaters. However, disposal of spray dryer residue (SDR)
in a landfill site poses great environmental risk as the organic pollutants in original
wastewater remains intact in SDR. Such residue easily gets dissolved in water and emerges
as concentrated leachate. It may completely ruin groundwater also if it percolates through
damaged protective layers of landfill. Thus, pretreatment of spray dryer residue before its
disposal in landfill is of extreme importance.

Different masses of SDR samples (5-25 g) were treated for different time durations (1 and
1.5h) in the pyrolysis reactor in batch mode. For all the SDR samples, COD reduction
obtained at 1 h reaction time was lesser than that obtained at 1.5 h reaction time for all the
initial masses of samples. Except for SDR 3 (Vatva sample) where %VSS in raw sample
was the highest (0.081 g/g), COD reduction of 88 and 78% were obtained for 15 g initial
masses of SDR 1 and SDR 2, respectively. Methylene Blue (MB) values of carbon samples
recovered after pyrolysis ranged from 230 to 241 mg/g which shows high adsorptive
capacity. Overall, it was found that SDR obtained from spray drying of concentrated
wastewaters can be subjected to pyrolysis to obtain a valuable by-product (powdered
activated carbon) and significant COD reduction. The residue after pyrolysis and following
recovery of carbon can be disposed off in landfill with environmental impact much smaller
than the raw SDR disposal.

1
1. INTRODUCTION
1.1 General:
In our day to day life we use water for many purposes, it can be used for direct and indirect
purposes. Direct purposes include bathing, drinking and cooking while indirect purposes
include use in industries for manufacturing goods and final products. The bulk of water the
world’s water use is for agriculture, industry and electricity. This water is not consumed whole
in the above applications but part of it is converted into waste water. The main problem to
mankind is that how to treat the waste water and how to deal with the quantum of sludge
generated after treatment.

Sludge handling and disposing is also a great concern for environment engineers because this
sludge can be hazardous to ecology and humans. The hazardous waste means any waste which
by reason of characteristics such as physical, chemical, biological, reactive, toxic, flammable,
explosive or corrosive, causes danger or likely to cause danger to health or environment,
whether alone or likely in contact with other substances.(Hazardous and Other Wastes
(Management and Transboundary Movement) Rules, 2016)

The rapid industrialization in Asia during the last few decades has resulted in the uphill task of
finding means to manage the wastes generated. Some of these wastes are extremely hazardous
which, if not properly managed, can create serious environmental damage. The mercury
poisoning at Minamata bay, Japan and the Love canal incident in the US, are two examples of
the havoc caused by improperly disposed hazardous wastes. A number of incidents of ground
water contamination, surface water contamination, air pollution, fires, explosion and poisoning
due to hazardous wastes have been reported from many parts of the world. (Chongrak
polprasert, L.R.J Liyanage, 1996)

Hazardous wastes are classified on the basis of their biological, chemical, and physical
properties. These properties generate materials that are either toxic, reactive, ignitable,
corrosive, infectious, or radioactive.

The main sources of hazardous waste include industries, petroleum refineries, transportation,
coke-ovens, blast furnaces sludge and biological waste generating laboratories, waste water
spray drying facilities, thermal and nuclear power plants and nuclear reactors etc.

Gujarat has 7,751 hazardous waste generating units contributing to 28.76 percent of the total
hazardous waste generation of India, which is the highest in the country. The state has been
2
generating major quantities of waste which is land disposable hazardous waste. The land
disposable hazardous waste generation in the state accounts for 61.75 percent, while incinerable
and recyclable waste together accounts for 38.25 percent. The contributions of various states
with respect to the country’s total land disposable hazardous waste generation amounts to 40.58
percent while 36.75 percent comprises incinerable and remaining recyclable waste.

The major hotspots of waste generation may be found in the Bharuch and Ahmadabad districts.
They account for 46 percent of the total amount of industrial hazardous waste generated in
Gujarat. An inventory prepared by the Central Pollution Control Board (CPCB) reveals that the
total land disposable hazardous waste generation in the state stands at 11,07,128 tonnes per
annum (TPA) while the total treatment stabilisation disposal facilities (TSDF) capacity is at
4,47,401 TPA. It shows that TSDF capacity has a deficit of 6,59,727 TPA. Immediate attention
is called for to lower this gap to reduce environmental and land degradation.

The huge amount of hazardous waste generated by industries would require land for its disposal
through scientific channels. Industrial hazardous waste contains certain heavy metals as well
asphyto-toxic organic compounds among other substances. When discharged on land, even at
relatively low levels can affect the soil health, soil quality, and productivity of land. Industries
also generate non-hazardous (high volume-low hazard) wastes that are mostly discarded over
open, low lying land. This can degrade both land quality and the aesthetic value of the place.
The size of land required to dispose the waste in an engineered landfill, assuming the average
density of waste to be around 1.2 tonnes/m3 and the depth of the landfill 4 meter, would be
around 108 ha every year. This can be applied to future waste projections to arrive at future
land requirements for the disposal of hazardous waste. A state like Gujarat which generates the
largest share of hazardous waste in the country, would require more land for waste disposal in
order to prevent high rate of land degradation. (www.counterview.org, 2014)

Apart from the solid waste hazardous waste also include high concentrated liquid streams
having very high chemical oxygen demand ranging from 60,000 to 2,00,000 milligram / litre
and very low biodegradability for high toxicity. Disposal of such streams by conventional
methods such as physico-chemical and biological process is not possible.

This highly concentrated streams which are generated from the waste waters of pesticides, dyes
intermediates, pharmaceuticals and fertilizers have very high concentration of inorganic solids
which can be treated with multi effect evaporator, incinerator or spray dryer.

However, operation and maintenance of multi effect evaporator and incinerators becomes
extremely difficult when processing such streams.

3
Recently spray drying of such concentrated streams has been increasingly employed by
chemical industries to get rid of problems associated with multi effect evaporators and
incinerators. In spray drying the concentrated streams are converted to atomized sludge known
as spray dried residue.

The quantum of such concentrated streams in common spray dryer facilities and spray dried
residue generation are shown below in the table:

Table 1 Common spray dryer facilities in Gujarat

Spray dryer facility Location Capacity ( kilolitre/ Spray dried residue

day) generation (ton/
day)
Society For Clean Vatva (Ahmedabad) 240 40
Earth
The Green Enviro Vatva (Ahmedabad) 240 40
Society Co- 384 64
Operative Ltd.
Ankleshwar Cleaner Ankleshwar 250 x 4 167
Process Technology (Bharuch)
Center Ltd.
Chhatral Chhatral 500 82
Environment (Gandhinagar)
Management System

The above data just states the facilities with common spray dryer apart from this, there are large
number of industries in Gujarat having captive spray dryer for converting the concentrated
streams into residues which are disposed of in their nearest landfill sites whose data is not
available.

4
1.2 Spray Dryer:
By definition, “Spray drying is the transformation of feed from a fluid into a dried particulate
form by spraying the feed into a hot drying medium.” (Masters, 1991) A spray dryer operates
on convection mode. The principle of working is moisture removal by application of heat to the
feed product and controlling the humidity of the drying medium. Here, the uniqueness is that
the evaporation of moisture is promoted by spraying the feed into a heated atmosphere, resulting
in improved drying rate.

A liquid feed entering the spray dryer undergoes a series of transformations before it becomes
powder. The changes are due to the influence of each of the four stages involved in spray drying,
namely:

1. Atomization of the feed solution.

2. Contact of spray with the hot gas.

3. Evaporation of moisture.

4. Particle separation.

Figure 1 Process of spray drying

5
 1.2.1 Advantages of spray dryer:
1) Ceramic industries e.g. aluminium oxide, carbides, iron oxides, kaoline etc.
2) Chemical industries e.g. phenol-formaldehyde resin, catalysts, PVC emulsion type,
amino acids etc.
3) Dye stuffs and pigments e.g. chrome yellow, food colour, titanium dioxide, paint
pigments etc.
4) Fertilizer production e.g. nitrates, ammonium salts, phosphates etc.
5) Detergent and surface active agent’s e.g. detergent enzymes, bleach powders,
emulsifying agents etc.
6) Food industries e.g. milk, whey, egg, soya protein etc.
7) Fruits and vegetables e.g. banana, tomatoes, coconut milk etc.
8) Beverage e.g. coffee, tea etc.
9) Biochemical industries e.g. algae, fodder antibiotics, yeast extracts, enzymes etc.
(www.pharma approach.com)

1.3 Spray dryer in waste water:

Spray dryer has not only applications in the above stated fields but also in the field of
environment pollution. Recent trends to cope up with the standards and in the race of getting
the certificates of zero liquid discharge, firms are diverging to use this. In the conventional
effluent treatment plants there was a huge problem of dealing with the concentrated streams of
different salts, for such spray dryer became a blessing because in waste water treatment it
converts the concentrated streams of effluents into an atomized sludge which could be handled
easily and transported and no larger spaces are required for water treatment. It removes all
moisture from the waste water and the product is powdered dry sludge of very fine particle size.

1.4 Spray dried residue and its environmental significance:

Spray dried residue is the outcome of spray drier in a form of atomized sludge. It is mostly
inorganic salts remained after spray drying. However mainly concentrated liquid streams
contain significantly high organic compounds which also comes in this residues. The spray
dried residue has chlorides and sulphates in majority which are hygroscopic in nature so proper
care is taken for the storage that it should not come in contact with moisture or water. This
waste comes under the category of hazardous waste so a check has to made that it doesn’t harm
the ecology and human beings.

At present this residue is disposed in the landfill sites, no other treatment is given to the residue
before dumping it. As it is water soluble, when in contact with moisture it can generate
concentrated liquid streams in landfill sites and contaminate environment.
6
It is advocated that residue obtained from spray drying are mostly inorganic in nature and thus
damage to the environment in case of leachates may not be adverse to environment. Thus an
alternative for dispose of spray dryer residue from concentrated waste need to develop.

1.5 Treatment options for hazardous waste:

The treatment technologies have been categorized as physical, chemical, biological, thermal, or
stabilization/fixation.

Physical treatment processes include gravity separation, phase change systems, such as air and
steam stripping of volatiles from liquid wastes, and various filtering operations, including
carbon adsorption.

Chemical treatment transforms waste into less hazardous substances using such techniques as
pH neutralisation, oxidation or reduction, and precipitation. Biological treatment uses
microorganisms to degrade organic compounds in the waste stream.

Thermal destruction processes include incineration, which is increasingly becoming a preferred

option for the treatment of hazardous wastes, and pyrolysis, which is the chemical
decomposition of waste, is brought about by heating the material in the absence of oxygen.

Pyrolysis:

Pyrolysis, the chemical decomposition of organic (carbon-based) materials through the

application of heat. Pyrolysis, which is also the first step in gasification and combustion, occurs
in the absence or near absence of oxygen, and it is thus distinct from combustion (burning),
which can take place only if sufficient oxygen is present. The rate of pyrolysis increases with
temperature. In industrial applications the temperatures used are often 430 °C (about 800 °F) or
higher, whereas in smaller-scale operations the temperature may be much lower. Two well-
known products created by pyrolysis are a form of charcoal called biochar, created by heating
wood, and coke (which is used as an industrial fuel and a heat shield), create by heating coal.
Pyrolysis also produces condensable liquids (or tar) and noncondensable gases.

Pyrolysis transforms organic materials into their gaseous components, a solid residue of carbon
and ash, and a liquid called pyrolytic oil (or bio-oil). Pyrolysis has two primary methods for
removing contaminants from a substance: destruction and removal. In destruction, the organic
contaminants are broken down into compounds with lower molecular weight, whereas in the
removal process, they are not destroyed but are separated from the contaminated material.
Pyrolysis is a useful process for treating organic materials that “crack” or decompose under the
presence of heat; examples include polychlorinated biphenyls (PCBs), dioxins, and polycyclic

7
aromatic hydrocarbons (PAHs). Although pyrolysis is not useful for removing or destroying
inorganic materials such as metals, it can be used in techniques that render those materials inert.

Pyrolysis has numerous applications of interest to green technology. It is useful in extracting

materials from goods such as vehicle tires, removing organic contaminants from soils and oily
sludges, and creating biofuel from crops and waste products. Pyrolysis can help break down
vehicle tires into useful components, thus reducing the environmental burden of discarding the
tires. Tires are a significant landfill component in many areas, and they release PAHs and heavy
metals into the air when they are burned. However, when tires are pyrolyzed, they break down
into gas and oil (usable for fuel) and carbon black (usable as filler in rubber products, including
new tires, and as activated charcoal in filters and fuel cells). In addition, pyrolysis can remove
organic contaminants, such as synthetic hormones, from sewage sludge (semisolid materials
that remain after wastewater is treated and the water content reduced) and make heavy metals
remaining in the sludge inert, which allows the sludge to be used safely as fertilizer.

Furthermore, pyrolyzing biomass (biological materials such as wood and sugarcane) holds great
promise for producing energy sources that could supplement or replace petroleum-based
energy. Pyrolysis causes the cellulose, hemicellulose, and part of the lignin in the biomass to
disintegrate to smaller molecules in gaseous form. When cooled, those gases condense to
the liquid state and become bio-oil, while the remainder of the original mass (mainly the
remaining lignin) is left as solid biochar and noncondensable gases. (www.britanica.com)

Carbonization:

Carbonization (or carbonisation) is the conversion of an organic substance into carbon or a

carbon-containing residue through pyrolysis or destructive distillation. It is often used in
organic chemistry with reference to the generation of coal gas and coal tar from raw coal. Fossil
fuels generally are the products of the carbonization of vegetable matter. The term carbonization
is also applied to the pyrolysis of coal to produce coke. Carbonization is also a stage in the
charcoal making process, and is considered the most important step of all since it has such
power to influence the whole process from the growing tree to the final distribution of charcoal
to various sources.

The carbonization of wood in an industrial setting usually requires a temperature above 280°C,
which liberates energy and hence this reaction is said to be exothermic. This carbonization,
which can also be seen as a spontaneous breakdown of the wood, continues until only the
carbonised residue called charcoal remains. Unless further external heat is provided, the process
stops and the temperature reaches a maximum of about 400°C. (en.wikipedia.org)

8
1.6 Need of the study:
 Present disposal of this residue include landfill deposition.

 Having very high solubility in water it can affect the quality of underground water.

 Its complex reactions with other hazardous waste are unknown.

 It also constitute of smaller fraction of organic contaminants which can severely damage
the environment.

1.7 Goal of the study:

So the purpose of the study is to stabilize the residue into simpler forms by reducing the
chemical oxygen demand by pyrolysis and to recover carbon, so that if it is disposed off in
landfill possess no threat to environment and its resources.

1.8 Objectives of the study:

The objectives of the study are as follows:

 Physico-chemical characterization of the spray dried residue samples from 3 different

sources.
 Design and fabrication of the pyrolysis reactor.
 To investigate the effect of mass of sample and run time for the reduction in chemical
oxygen demand for stoichiometric air fuel supply on spray dried residue samples.
 To extract carbon from the treated waste.
 To investigate the adsorption potential and Methylene blue number for the carbon
extracted from the treated samples.
 To describe the adsorption isotherms by using Langmuir and Freundlich models.

9
2. LITERATURE REVIEW:
2.1 Studies related to treatment of hazardous waste by pyrolysis method:
Application of pyrolysis to recycling organics from waste tantalum capacitors (Bo Niu,
Zhenyang Chen, Zhenming Xu, 2017)

This study proposed an argon (Ar) pyrolysis process to recycle the organics from WTCs. The
organic decomposition kinetic was first analyzed by thermogravimetry. The results showed that
the organics were decomposed in two major steps and the average activation energy was
calculated to 234 KJ/mol. Then, the suitable pyrolysis parameters were determined as 550
degree C, 30 min and 100 ml/min. The organics were effectively decomposed and converted to
oils (mainly contained phenol homologs and benzene homologs) and gases (some
hydrocarbon). These pyrolysis products could be reutilized as energy sources.

The pyrolysis products consisted of 3.13 wt% oil, 3.26 wt% gas and 93.61 wt% residue. The
gas was mainly hydrocarbon (such as ethylene, propene and ethane), so the gaseous product
could be directly incinerated or recycled as gas fuel. The pyrolysis oil mainly contained phenol
homologs and benzene homologs. Under high temperature combustion conditions, these
organic matters will release energy and ultimately transform into CO2 and H2O. For the
pyrolysis residue, since the package (SiO2 and carbon residue) still covered the other materials,
mechanical separation methods can be applied.

Moreover, based on the products and bond energy theory, the pyrolysis mechanisms of the
organics were also discussed. This study contributes to the efficient recycling the organics
before valuable material recovery from WTCs.

Microwave-assisted pyrolysis of textile dyeing sludge, and migration and distribution of

heavy metals (Hedong Zhang, Zuopeng Gao, Yang Liu, Chunmei Ran, Xiao Mao, Qinhao
Kang, Wenya Ao, Jie Fu, Jing Li, Guangqing Liu, Jianjun Dai, 2018)

The pyrolysis characteristic of textile dyeing sludge (DS) using an auger pyrolyser under
microwave irradiation at different pyrolysis temperature was studied. The migration and
distribution characteristic of heavy metals and their potential ecological risks were investigated
using ICP-MS techniques.

Temperature and additives (e.g. Ca-bentonite, kaolin and CaO) significantly affected product
distribution and yields. Heavy metals showed different enrichment characteristics during
pyrolysis and a great percentage of the heavy metals was retained in the sludge char, depending
on different temperatures and additives. CaO had a strong ability for retention of S, Pb and Ni.

10
Ca-bentonite, kaolin and CaO had considerable ability to retain Cr at 650℃. Cabentonite and
CaO had positive effects on Ni retention at 450oC and 650oC. As was enriched at 450oC with
addition of Ca-bentonite. Cu and Zn were enriched at 450oC and 850oC without additives and
the corresponding residue ratios (RRs) were 88.68- 100%, which indicated good stability of
these heavy metals during microwave pyrolysis of DS. The heavy metal contents in SC were
lower than those in the national standards (CJ/T 362-2011, China) and these heavy metals
showed slight potential ecological risk to the environment.

En masse pyrolysis of flexible printed circuit board wastes quantitatively yielding

environmental resources (Jang Won Kim, Albert S. Lee, Seunggun Yu, Jeong Whan Han,
2017)

Paper reports the recycling of flexible printed circuit board (FPCB) waste through
carbonization of polyimide by dual pyrolysis processes. The organic matter was recovered as
pyrolyzed oil at low temperatures, while valuable metals and polyimide-derived carbon were
effectively recovered through secondary high temperature pyrolysis.

The major component of organics extracted from FPCB waste comprised of epoxy resins were
identified as pyrolysis oils containing bisphenol-A. The valuable metals (Cu, Ni, Ag, Sn, Au,
Pd) in waste FPCB were recovered as granular shape and quantitatively analyzed via ICP-OES.
In attempt to produce carbonaceous material with increased degree of graphitization at low heat-
treatment conditions, the catalytic effect of transition metals within FPCB waste was
investigated for the efficient carbonization of polyimide films.

The morphology of the carbon powder was observed by scanning electron microscopy and
graphitic carbonization was investigated with X-ray analysis. The protocols outlined in this
study may allow for propitious opportunities to salvage both organic and inorganic materials
from FPCB waste products for a sustainable future.

Pyrolysis characteristics and pyrolysis products separation for recycling organic

materials from waste liquid crystal display panels (Ruixue Wang Zhenming Xu, 2016)

In the present study, pyrolysis process is used to remove the organic materials and recycle
acetic as well as and triphenyl phosphate (TPP) from waste LCD panels in an environmental
friendly way. Several highlights of this study are summarized as follows:

(i) Pyrolysis characteristics and pyrolysis kinetics analysis are conducted which is significant
to get a better understanding of the pyrolysis process.

11
(ii) Optimum design is developed by applying Box-Behnken Design (BBD) under response
surface methodology (RSM) for engineering application which is significant to guide the further
industrial recycling process. The oil yield could reach 70.53 wt % and the residue rate could
reach 14.05 wt% when the pyrolysis temperature is 570 °C, nitrogen flow rate is 6 L·min-1 and
the particle size is 0.5 mm.

(iii) Furthermore, acetic acid and TPP are recycled, and then separated by rotary evaporation,
which could reduce the consumption of fossil energy for producing acetic acid, and be reused
in electronics manufacturing industry.

Pyrolysis of Wastewater Biosolids Significantly Reduces Estrogenicity (T.C. Hoffman

D.H. Zitomer P.J. McNamara, 2016)

Most wastewater treatment processes are not specifically designed to remove micropollutants.
Many micropollutants are hydrophobic so they remain in the biosolids and are discharged to
the environment through land-application of biosolids. Micropollutants encompass a broad
range of organic chemicals, including estrogenic compounds (natural and synthetic) that reside
in the environment, a.k.a. environmental estrogens. Public concern over land application of
biosolids stemming from the occurrence of micropollutants hampers the value of biosolids
which are important to wastewater treatment plants as a valuable by-product.

This research evaluated pyrolysis, the partial decomposition of organic material in an oxygen-
deprived system under high temperatures, as a biosolids treatment process that could remove
estrogenic compounds from solids while producing a less hormonally active biochar for soil
amendment. The estrogenicity, measured in estradiol equivalents (EEQ) by the yeast estrogen
screen (YES) assay, of pyrolyzed biosolids was compared to primary and anaerobically digested
biosolids. The estrogenic responses from primary solids and anaerobically digested solids were
not statistically significantly different, but pyrolysis anaerobically digested solids resulted in a
significant reduction in EEQ; increasing pyrolysis temperature from 100°C to 500°C increased
the removal of EEQ with greater than 95% removal occurring at or above 400 °C.

Research demonstrates that biosolids treatment with pyrolysis would substantially decrease
(removal > 95%) the estrogens associated with this biosolids product. Thus, pyrolysis of
biosolids can be used to produce a valuable soil amendment product, biochar, minimizes
discharge of estrogens to the environment.

Influence of pyrolysis temperature on properties and environmental safety of heavy

metals in biochars derived from municipal sewage sludge (Junwei Jina, Yanan Li a,

12
Jianyun Zhanga, Shengchun Wua, Yucheng Caoa, Peng Lianga, Jin Zhanga,b, Ming
Hung Wong b, Minyan Wangc, Shengdao Shand, Peter Christie, 2016 )

Dried raw sludge was pyrolyzed at temperatures ranging from 400 to 600 ◦C at the increase of
50 ◦C intervals to investigate the influence of pyrolysis temperature on properties and
environmental safety of heavy metals in biochar derived from municipal sewage sludge.

The sludge biochar yield decreased significantly with increasing pyrolysis temperature but the
pH, ash content and specific surface area increased. Conversion of sludge to biochar markedly
decreased the H/C and N/C ratios. FT-IR analysis confirmed a dramatic depletion of H and N
and a higher degree of aromatic condensation in process of biochar formation at higher
temperatures. The total concentrations of Cu, Zn, Pb, Cr, Mn, and Ni increased with conversion
of sludge to biochar and increasing pyrolysis temperature. However, using BCR sequential
extraction and analysis, it was found that most of the heavy metals existed in the oxizable and
residual forms after pyrolysis, especially at 600 ◦C, resulting in a significant reduction in their
bioavailability, leading to a very low environmental risk of the biochar.

The present study indicates pyrolysis is a promising sludge treatment method for heavy metals
immobilization in biochar, and highlights the potential to minimize the harmful effects of
biochar by controlling pyrolysis temperature.

Pyrolysis of a waste from the grinding of scrap tyres (A.M. Fernández, C. Barriocanal ,
R. Alvarez, 2012)

In this paper beneficiation through pyrolysis is studied since the fibres are made up of polymers
with a small amount of rubber because the latter is difficult to separate. The raw materials used
for the pyrolysis experiments were the tyre crumbs (TC3) and the fluff/fibres obtained as a
waste during grinding and shredding of scrap tyres (F3) obtained from the processing of car and
truck tyres.

The experiments were performed at three temperatures (400, 550 and 900 ◦C) in a horizontal
oven. The three products – gas, oil and char – obtained from the pyrolysis were investigated.
The composition of the gas was analyzed by means of gas chromatography. The oil was studied
by gas chromatography and infrared spectroscopy. The char porous structure was determined
by N2 adsorption. In addition, the topography of the chars was studied by means of scanning
electron microscopy (SEM). The products resulting from the pyrolysis of the fibres were
compared with those obtained from scrap rubber.

In summary, the characteristics of the products derived from the pyrolysis of F3 are of a similar
quality to that of TC3, although an increase in the pyrolysis temperature has a greater influence
13
on the products of F3 pyrolysis than on those of TC3. Consequently, a higher pyrolysis
temperature is needed to ensure the complete decomposition of the constituents of F3.

Physico-chemical properties of chars obtained in the co-pyrolysis of waste mixtures (M.

Bernardoa, N. Lapaa, M. Gonc¸ alves a, B. Mendes a, F. Pinto b, I. Fonsecac, H. Lopes,
2012)

The present work aims to perform a multistep upgrading of chars obtained in the co-pyrolysis
of PE, PP and PS plastic wastes, pine biomass and used tires. The quality of the upgraded chars
was evaluated by measuring some of their physico-chemical properties in order to assess their
valorisation as adsorbents’ precursors. The crude chars were submitted to a sequential solvent
extraction with organic solvents of increasing polarity (hexane, mixture 1:1 v/v hexane : acetone
and acetone) followed by an acidic demineralization procedure with 1 M HCl solution.

The results obtained showed that the upgrading treatment allow the recovery of 63–81% of the
pyrolysis oils trapped in the crude chars and a reduction in the char’s ash content in the range
of 64–86%. The textural and adsorption properties of the upgraded chars were evaluated and
the results indicate that the chars are mainly mesoporous and macroporous materials, with
adsorption capacities in the range of 3.59–22.2 mg/g for the methylene blue dye.

The chars were submitted to sequential organic solvent extractions with high yields of
removal/recovery of the pyrolysis liquid-phase products. In order to decrease the ash content of
the chars, a demineralization procedure was successfully applied and high efficiency removals
of the major metallic elements were achieved. Heteroatoms such as oxygen, sulphur and
nitrogen are present in the upgraded chars, which can be indicative of the presence of polar
functional groups on chars’ surface. The upgrading treatment allowed to obtain carbonaceous
materials with quality to be reused as adsorbents or as precursors for activated carbon.

Synthesis of carbon nanotubes and porous carbons from printed circuit board waste
pyrolysis oil (Cui Quan, Aimin Li ∗, Ningbo Gao, 2010)

. The PCB waste was first pyrolyzed in a laboratory scale fixed bed reactor at 600 ◦C to prepare
pyrolysis oil. The analysis of pyrolysis oil by gas chromatography–mass spectroscopy indicated
that it contained a very high proportion of phenol and phenol derivatives. It was then
polymerized in formaldehyde solution to synthesize pyrolysis oil-based resin which was used
as a precursor to prepare carbon nanotubes (CNTs) and porous carbons. Scanning electron
microscopy and transmission microscopy investigation showed that the resulting CNTs had
hollow cores with outer diameter of ∼338 nm and wall thickness of ∼86 nm and most of them
were filled with metal nanoparticles or nanorods. X-ray diffraction reveals that CNTs have an

14
amorphous structure. Nitrogen adsorption isotherm analysis indicated the prepared porous
carbons had a Brunauer–Emmett–Teller surface area of 1214 m2/g.

(1) Electric furnace, (2) reactor tube, (3) PID controller, (4) thermocouple, (5) water condenser,
(6) liquid collector and (7) glass wool filter.

Figure 2 Process diagram of the fixed bed reactor

It is unambiguously demonstrated that PCB waste pyrolysis oil may be a good precursor for
making ACMs, which develops a new route for the application of the PCB waste pyrolysis oil.
Analyses of molecular compositions of the PCB waste pyrolysis oil reveal that it contained high
concentrations of phenol-group species. The components may be polymerized with
formaldehyde into pyrolysis oil-based resin, and then CNTs and porous carbons were
successfully developed from the pyrolysis oil-based resin.

Synthesis and characterization of activated carbon from sawdust of Algarroba wood. 1.

Physical activation and pyrolysis (Juan Matos, Carol Nahas, Laura Rojas, Maibelín
Rosales, 2011)

Synthesis of activated carbon (AC) from sawdust of Algarroba wood was performed as a
function of the temperature under CO2 and N2 flow. Characterization was performed by
adsorption–desorption N2 isotherms, FTIR, XPS and SEM. Functional acid or basic groups
were detected on the surface of AC. For both studied atmospheres, the maximum value of
surface area was obtained at 800 ◦C. A monotonic correlation between temperature and mean
pore diameter was detected being the higher the activation temperature the lower the mean pore
width of AC. Ultramicroporous AC with pore diameters of 6.7A˚ and 5.3A˚ were obtained at
900 ◦C under CO2 and N2 flow, respectively. It can be concluded that pore diameter and the
functionalization of the AC surface can be controlled easily controlling the temperature of

15
activation, independently of the gas atmosphere. The present results suggest that waste biomass
is a potential source for the synthesis of carbon materials with potential novel applications.

Figure 3 Setup for activation scheme

Experimental studies on producer gas generation from wood waste in a downdraft

biomass gasifier. (Pratik N Sheth, B. V. Babu, 2009)

Figure 4 Downward gasifier reactor

16
3. MATERIALS AND METHODS:
3.1 Materials:
3.1.1 Reactor:
 The reactor was made from stainless steel grade 304 having nominal thickness of 2 mm.
 The dimension and design of the reactor are shown in the line diagram below:

Figure 5 Design of the reactor

 Four nozzles of size 10 mm were provided at the side portion of cylindrical part of the
reactor for air supply and gas on each side respectively.
17
 The top portion of the reactor had a T-section made up of half inch stainless steel pipe
out of which a valve was fixed for the control of the exhaust gases.
 Steel balls of size 3mm size were used to check the dropping of residue in the reactor
and for proper transfer of heat.
 Internal cone of steel having 26mm diameter at bottom and top diameter 36mm and
length 170mm was used for transferring the air from combustion zone to T-section of
the reactor.
 The bottom part and top part of the reactor were fixed with six numbers of stainless steel
bolt having diameter 10mm and was provided with a flange type coupling and between
the connection rubber insulators was used to make the reactor air tight.

3.1.2 Gas supply:

 Liquefied petroleum gas was used for the reactor as gas supply source.
 For the control of gas, rotameter of range 0-2 litre per minute (Flowtech) was provided
and T brass was used for a two supply to the reactor.

3.1.3 Air supply:

 Bosch air blower 800 E professional with six speed was used for the air supply during
the run of the reactor.
 For the control of the air flow, rotameter of range 0-25 litre per minute (Flowtech) was
provided and T brass was used for two way supply to the reactor.
 Valve was also provided for the control of air as a secondary measure before the
rotameter to reduce the air pressure.

3.1.4 Water jacket:

 A transparent acrylic tray of 200mm * 200mm * 50mm for providing support and was
used as a water jacket to make the combustion zone under stoichiometric air fuel ratio.
 Mirror of dimension 80mm * 60mm was provide to check the flame in the reactor during
the run.

3.1.5 Spray dried residue (sample collection):

 Total 3 samples were collected from different facilities in a dry powdered form from
 Nandesari, Vadodara - SDR 1(Chemical intermediates origin)
 Padra, Vadodara - SDR 2 (Dyes and dyes intermediates)
 Vatva, Ahmedabad – SDR 3 (Dyes and dyes intermediates)

18
3.1.6 Dyes:
 Methylene blue dye available in laboratory was used for determining Methylene blue
number.

3.1.7 Rotary shaker:

 Rotary shaker was made with the wheel of the bicycle, fan, stand and rope for power
transmission.
 The shaker was made in such a way that it completes 30 rotations in one minute.
 Special arrangement was done to hold the vials during the rotations.

Figure 6 Rotary shaker for methylene blue

3.1.8 Instruments:
a) pH meter: pH of the solution was monitored by pH meter (Global pH 500). Instrument
was calibrated by freshly prepared buffer solution (pH 3 to 11) time to time throughout
the study.
b) Spectrophotometer: UV- Spectrophotometer (Shimadzu UV-1800), Quartz Cell (1 cm
path length).
c) Centrifuge: Centrifuge (REMI RM-12 C) was used to separate the particles from the
solution mixture after experiments and the supernatant was used for chemical oxygen
demand analysis.
d) Hot air oven: Hot air oven (Janki Impex Pvt Ltd.) was used for the digestion of the vials
for the chemical oxygen demand and for drying of samples.

19
e) Muffle furnace: Muffle furnace (Janki Impex Pvt Ltd.) was used to get the percent of
volatile solids in the sample.
f) Weighing machine: To weigh the chemicals, dye, sample, crucibles in the range of
0.0001 to 120 gram (Afcoset).
g) Magnetic stirrer: Magnetic stirrer (Janki Pvt. Ltd.) was used to provide mixing the
experimental solution or mixture.
h) Infrared thermometer: Temperature of the outer part of the reactor was measured with
the thermometer (MTC infrared thermometer -50 degree to 550 degree Celsius operating
range).

20
3.2 Methodology:
3.2.1 Characterization of raw spray dried residue:
The moisture content of the sample was determined by keeping the weighted sample in hot air
oven for 2 hours at 105 degree Celsius and the change in the weight was observed. The percent
volatile solids was determined by the muffle furnace by keeping the sample at 550 degree
Celsius for 1 hour and the remaining fraction would determine the inorganic salts in the sample.

3.2.2 Calculation for requirement of gas for heating:

For calculation of gas stoichiometric ratio is taken into account, air supply has to provide for
only gas, no air should take part in the reaction zone of the reactor if additional air is supplied
it will oxidise the carbonaceous material and may form dioxins which is to be prohibited.

The gas supplied to the reactor is liquefied petroleum gas which is in the proportion of 40 %
propane and 60 % butane. As the supply of the gas to the reactor is fixed, the stoichiometric air
fuel ratio should be maintained throughout the run and is calculated as follows:

The chemical formula for butane is C4H10, to calculate the stoichiometric air required the
equation used is:

C4H10 + x (O2 + 3.76N2) yCO2 + zH2O + kN2

Here y =4, z = 5, x = 6.5, k =12.2 by balancing the equation

Therefore air to fuel air is: 892.32/58 = 15.38 gram/gram

Now the specific gravity for butane is 2, so butane air fuel ratio in volume by 60 % is

= 15.38 x 2 x .60

= 18.55 ml of air /ml of butane

In the same way for propane chemical formula is C3H8, air required is:

C3H8 + x (O2 + 3.76N2) yCO2 + zH2O + kN2

Here y =3, z =4, x =5, k =24.44 by balancing the equation

Air to fuel ratio is: 686.4/44 = 15.6 gram/gram

The specific gravity of propane is 1.5, so propane air fuel ratio in volume by 40 %is

= 15.6 x 1.5 x .40

= 9.36 ml of air/ ml of propane

For stoichiometric combustion for 1 ml liquefied petroleum gas

21
 = 18.55 + 9.36

= 27.91 ml of air

3.2.3 Batch studies for pyrolysis:

Batch pyrolysis experiments were conducted for the treatment of 3 samples of spray dried
residue as a function of:

 Reaction time,
 Mass of sample

This was done by opening the lower part of the reactor and putting the cone in the inverted
position and filling it with the metal balls so the sample do not fall down and to make a seal that
air cannot enter the pyrolysis zone.

When the material was filled the upper part of the reactor was fastened with the six numbers of
bolts provided a packing between them. The top of the reactor for the removal of exhaust gas
and steam was provided with a valve opening having a pipe which would drop into water to
catch the carbon or any other exhaust dust.

The air supply was given from the top two nozzles at a rate of 25 litre per minute by a two way
supply and the air was supplied by a blower. The gas was supplied from the bottom two nozzles
at a rate of one litre per minute. The reactor was covered with glass wool during the run for
insulation purpose.

The reactor was supported on a water jacket filled with distilled water to collect the ash or
carbon if falls, mirror was kept below the tray to check whether flame is lighted during the run
in the reactor or not.

The gas was lighted by a gas lighter from the bottom cylindrical part of the reactor by lifting in
the hand.

The spray dried residue was filled around the inverted cone on the base on the mass, as 30, 25,
20, 15 grams for 1 hour and 1.5 hours respectively.

The temperature during the run was noted on the outer part of the reaction zone by putting a
black coloured layer and was measured by infrared thermometer.

The temperature was noted at the start of the run, the initial temperature was 190 degree Celsius
for first five minutes and its increases to around 250 degree Celsius in just half an hour and
there by remains constant for 1 and 1.5 hour run.

22
The actual temperature in the reactor would be more than measured temperature because the
emissivity of the insulating black material was 0.9, so surface temperature of the reactor would
be actual 275 degree Celsius and the material thickness of the outer reactor was 2 mm and the
inner inverted cone was 1 mm so there is loss in conduction and taking this into account the
reactor core temperature will be slightly higher than the outer.

After the run the treated spray dried residue was withdrawn from the bottom after unlocking the
bolts and removing the inverted cone then sample was analysed for chemical oxygen demand,
for chemical oxygen demand the solution of 0.1 gram was dissolved in 100 millilitre water and
was centrifuged for the settling and the supernatant was used.

Treated sample in a solution form was then filtered through a filter paper and carbon was
separated.

Figure 7 Experimental setup for pyrolysis

3.2.4 Characterization of treated spray dried residue:

The treated sample weighing 1 gram in solution form is filtered for separating the carbon and
the remaining sample was dried for 24 hours in hot air oven and weighed. After that it was kept
in muffle furnace to calculate the remaining volatile solids and inorganic salts.

3.2.5 Determination of Methylene number of carbon:

The methylene blue number is defined as the maximum amount of dye adsorbed on 1 gram of
adsorbent (qe). In this assay, 10 milligram of activated carbon are placed in contact with 10
millilitre of a methylene blue solution at different concentrations (10, 25, 50, 100, 250, 500

23
milligram/litre) for 6 hours at approximately 22 degree Celsius in an air conditioned room. The
remaining concentration of methylene blue is analysed using a UV-VIS spectrophotometer at
645 nm.

The amount of methylene adsorbed from each solution is calculated by the following equation:

qe = [(Co- Ce) V/M]

Where,

Co is the concentration of the methylene blue solution at starting time (t = 0) in milligram/litre,

Ce is the concentration of methylene blue solution at equilibrium time in milligram/litre,

V is the volume of solution treated in litre,

M is the mass of the adsorbent in gram

3.2.6 Determination of adsorption isotherm (Langmuir and Freundlich):

The sorption isotherms of dye onto the sorbents were evaluated by plotting the equilibrium
sorption data using the Langmuir and freundlich models (Langmuir, 1916; Freundlich, 1906).
The assumptions of the Langmuir model are that sorption of sorbate occurs in monolayer on a
homogeneous sorbent surface, and sorbate species do not interact with each other.

However, the Freundlich isotherm model work based on the assumption that the sorption of
sorbate occurs in multilayer on heterogeneous sorbent surfaces since the active sites of
sorbent have heterogeneous surface energy. In this study, physically the Langmuir model
represent that sorption of monolayer dye take place on the homogeneous surface of sorbents
and dye species do not interact with each other during the sorption process. On the other hand,
the Freundlich, model expresses that multilayer dye sorption occurs on heterogeneous
surfaces of sorbents.

The Langmuir and Freundlich models are expressed linearly in equations below, respectively.

= + ………………… (a)

Equation 11 yields equation 12 as follows:

24
 = . + …………… (b)

Where C0 is the initial concentration of dye in the solution in mg/L, Ce is the equilibrium
concentration of Ni in mg/L, V is the volume of the solution in L, and m is the dry mass of
sorbent in gram.

= K .C ⁄
……………………(c)

Equation (a) yields equation (b) as follows:

= Log ( ) + log (K )…… (d)

Where Ce is the equilibrium concentration of dye in mg/L, qe is the equilibrium sorption

capacity of sorbent in (mg/g), qm is the maximum sorbet amount of dye per mass of sorbent for
complete monolayer coverage (mg/g), KL is the Langmuir equilibrium sorption constant related
to the affinity of sorption (L/mg), KF is the Freundlich coefficient related to the sorption
capacity [(mg/g)(L/mg) ⁄
],and 1⁄ is the sorption intensity evaluate the Langmuir isotherm,
the values 1⁄ were plotted against 1⁄ .

25
4. RESULT AND DISCUSSION:
4.1 Characterization of raw spray dried residue:
The physico-chemical characteristics of residue are shown in the table:

Table 2 Physico chemical properties of spray dried residue

Properties SDR 1 SDR 2 SDR 3

Moisture (%) 2 0 0
Volatile solids (%) 20 15 30
Inorganic solids (%) 80 85 70
Chemical oxygen 0.29 0.14 0.25
demand (gram/gram
of sample)
Colour Soil brown Greyish brown Brownish yellow

Figure 8 Figure of raw sample of spray dried residue

26
4.2 Results of pyrolysis batch studies:
4.2.1 Result of 1 and 1.5 hour run for SDR 1 sample:
Table 3 Reduction in COD for 1 hour in SDR 1 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

15 290 171.1 41
20 290 160 44.8
25 290 162.4 44
30 290 152 48.6

Table 4 Reduction in COD for 1.5 hour in SDR 1 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

15 290 36 88
20 290 90 69.1
25 290 143 50.7
30 290 155 46.6

1 and 1.5 hour comparison

100

80
% COD Reduction

60

40

20

0
0 5 10 15 20 25 30 35
Mass in gram

1 hour 1.5 hour

Figure 9 Mass vs % COD reduction for1and 1.5 hour run for SDR 1 sample

 COD reduction is minimum for 30 gram sample which is 41 % and maximum for 15
gram sample is 48.6 % for 1 hour run and reduction is minimum for 30 gram sample
which is 46.6 % and maximum for 15 gram sample which is 88 % for 1.5 hour run.
 This is notable that maximum efficiency is achieved at 15 gram for both 1 and 1.5 hour
run.
27
  Higher efficiency at 15 gram sample is due to fact that proper conduction of heating is
achieved throughout the sample.
 At higher masses the sample remained unburnt in the upper zone due to less space of
the optimum reaction zone.

4.2.2 Result of 1 and 1.5 hour run for SDR 2 sample:

Table 5 Reduction in COD for 1 hour in SDR 2 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

15 0.15 0.06 61.1
20 0.15 0.08 46.6
25 0.15 0.081 46
30 0.15 0.078 47.6

Table 6 Reduction in COD for 1.5 hour in SDR 2 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

15 0.15 0.033 77.7
20 0.15 0.055 60.22
25 0.15 0.06 56.44
30 0.15 0.065 55.4

1 and 1.5 hour comparison

90
80
70
% COD reduction

60
50
40
30
20
10
0
0 5 10 15 20 25 30 35
Mass in gram

1 hour 1.5 hour

Figure 10 Mass vs % COD reduction for 1 and 1.5 hour for SDR 2 sample

 Here it is also the same results, COD reduction is minimum for 25 gram sample which
is 46 % and maximum for 15 gram sample is 61.1 % for 1 hour run and reduction is

28
 minimum for 30 gram sample which is 55.4 % and maximum for 15 gram sample which
is 77.7 % for 1.5 hour run.
 Maximum efficiency for both run of 1 and 1.5 hour is at 15 gram mass.
 The sample remained unburnt in the top portion of the larger masses because more space
was acquired for sample so complete heating was not achieved.

4.2.3 Result of 1 and 1.5 hour for SDR 3 sample:

 The sample collected from SDR 3 was very fluffy in nature so it was accommodated in
the reaction zone of the reactor at masses larger than 20 gram, so for this sample the
mass range is choose as 5-20 gram.

Table 7 Reduction in COD for 1 hour in SDR 3 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

5 0.25 0.085 64.93
10 0.25 0.147 39.8
15 0.25 0.169 34
20 0.25 0.183 24.8

Table 8 Reduction in COD for 1.5 hour in SDR 3 sample

Mass in gram Initial COD (mg/g) Final COD (mg/g) % Reduction

5 0.25 0.051 77.88
10 0.25 0.142 40.2
15 0.25 0.16 35.4
20 0.25 0.151 32.66

29
 1 and 1.5 hour comparison
90
80
70

% COD reduction
60
50
40
30
20
10
0
0 5 10 15 20 25
Mass in gram

1.5 hour 1 hour

Figure 11 Mass vs % COD reduction for 1 and 1.5 hour of SDR 3 sample

 In this sample the minimum reduction is achieved at 20 gram which is 24.8 % and
maximum is achieved at 5 gram which is 64.93 % for 1 hour and minimum reduction is
at 20 gram which is 32.66 % and maximum is at 5 gram which is 77.88 % for 1.5 hour
run.
 The lower is the sample quantity the higher is the reduction is achieved for the sample
because of proper heating is achieved.
 The reason for lower reduction at higher masses is same as more space is required and
the upper portion of sample remained unburnt after the run.

30
4.3 Mass balances for spray dried residue:
All the treated samples were in the dry powdered form only.

The mass balances for the 3 samples of spray dried residue were done on 1 gram on each treated
samples.

The mass balances were conducted on the highest percentage of COD removal.

Following table show the mass balance of 3 samples:

Table 9 Mass balance for treated samples

Treated samples
Sample Volatile solids (g/g) Inorganic solids Carbon (g/g)
(g/g)
SDR 1 0.027 0.797 0.176
SDR 2 0.012 0.852 0.136
SDR 3 0.081 0.698 0.221
Raw samples

Sample Volatile solids (g/g) Inorganic solids (g/g)

SDR 1 0.20 0.80

SDR 2 0.15 0.85

SDR 3 0.30 0.70

 The initial volatile solids for SDR 1 sample was 0.2g/g which reduces to 0.027 g/g which
means that 86.5 % of volatiles were converted to rich source of carbon and resulting
carbon content becomes 0.176 g/g.
 For SDR 2 sample the initial volatile solids were 0.15 g/g which reduces to 0.012 g/g
with a reduction of 92 %, this states that 92% of solids were converted to 0.136 gram of
carbon.
 The initial volatile solids for SDR 3 sample was 0.30 g/g which reduces to 0.081 g/g
gives 73 %, this states that 73 % of volatile solids get converted to 0.221 gram of carbon.
 Out of the three samples the maximum conversion of volatile solids to carbon is for
SDR 2 sample being 0.136 g/g of sample which is 92 % of volatile solids.

31
Figure 12 Untreated and treated sample comparison

32
4.4 Methylene blue number for the carbon obtained after treatment:
The methylene blue test was conducted on the carbon obtained after filtering the maximum
COD removal samples.

The test was conducted in a laboratory having room temperature 22 degree Celsius same
throughout the process. Different concentrations of Methylene blue dye solutions were filled in
vials of volume 10 millilitre and 10 milligram of carbon was added for testing and was rotated
at 35 rpm for 6 hours, after that absorption was detected using spectrophotometer at 645 nm
and % removal for dye and Methylene blue number was calculated. The following table shows
the % removal of dye, dye adsorbed on the carbon and respective Methylene blue numbers for
the 3 samples.

Table 10 Methylene blue number for carbon from SDR 1 sample

Concentration of % Removal of dye Ce (dye remained in Qe (dye adsorbed on

dye (mg/l) the solution, mg/l) carbon, mg/g)
10 94.13 0.587 9.413
25 97.70 0.575 24.425
50 96.63 1.685 48.315
100 98.24 1.760 98.240
250 91.87 20.235 229.675
500 14.27 428.850 71.150

The Methylene blue number for this sample is 229.675 which is close to 230 mg/g and it is
selected as 230mg/g.

Table 11 Methylene blue number for carbon from SDR 2 sample

Concentration of % Removal of dye Ce (dye remained in Qe (dye adsorbed on

dye (mg/l) the solution, mg/l) carbon, mg/g)
10 85.64 1.436 8.564
25 90.93 2.2675 22.732
50 86.71 6.645 43.355
100 98.53 1.470 98.530
250 71.36 71.600 178.400
500 47.12 264.200 235.600

33
So Methylene blue number is 235.6 mg/g which is approximately counts to 236 mg/g.

Table 12 Methylene blue number for carbon from SDR 3 sample

Concentration of % Removal of dye Ce (dye remained in Qe (dye adsorbed on

dye (mg/l) the solution, mg/l) carbon, mg/g)
10 86 1.40 8.60
25 91.55 2.12 22.88
50 88.05 5.98 44.02
100 98.59 1.41 98.59
250 90.39 4.03 225.97
500 48.21 259.22 240.78

The Methylene blue number for this sample is 240.78 which is close to 241 mg/g and it is
selected as 241 mg/g.

34
4.5 Isotherm model for Methylene blue dye:
4.5.1 Langmuir model for Methylene blue dye:
Langmuir theory is based on the assumptions of homogeneous distribution of finite sites over
the surface of adsorbent and a monolayer adsorption (Istretie et al.2015)

Langmuir model
25

20

15 y = 230.49x - 5.4865
R² = 0.6273

10
Ce/Qe

0
0 0.02 0.04 0.06 0.08 0.1
-5
Ce

Figure 13 Langmuir model for MBN for SDR 1 sample carbon

Langmuir model
200
180 y = 557.64x - 51.339
160 R² = 0.9131
140
120
100
Ce/Qe

80
60
40
20
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Ce

Figure 14 Langmuir model for MBN of SDR 2 carbon sample

35
 Langmuir model
7

5 y = 20.661x + 2.0388
R² = 0.357
4
Ce/Qe
3

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
Ce

Figure 15 Langmuir model for MBN for SDR 3 carbon sample

For Langmuir isotherm, the nature of adsorption process can be expressed by using
dimensionless equilibrium parameter (RL).

=( )
……………… (e)

Where,

C0 = Initial Concentration of Dyes (mg/L),

b = Langmuir constant (L/mg) and

RL = dimensionless equilibrium parameter

Table 13 Nature of adsorption process (M. Arulkumar et al. 2011)

Value of RL Nature of isotherm

RL > 1 Unfavourable
RL = 1 Linear
0 < RL < 1 Favourable
RL = 0 Irreversible

As per experiments, RL values are found in the range of 0 < RL <1.So the nature of adsorption
for all 3 samples are favorable.

36
4.5.2 Freundlich model for Methylene blue dye:
The Freundlich isotherm is an empirical equation employed to describe heterogeneous systems. It
can be expressed as:

= K .C ⁄
………… (f)

= Log ( ) + log (K ) ………… (g)

Where;
Ce = concentration of dye in aqueous phase at equilibrium (mg /L),
qe = adsorbent phase concentration after equilibrium (mg/g),
Kf = adsorption capacity (mg/g),
n = adsorption intensity i.e., affinity of the adsorbate for adsorbent.

Freundlich model
3

2.5 y = 0.5968x + 1.6269

R² = 0.8752
2

1.5
log Qe

0.5

0
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4
log Ce

Figure 16 Freundlich model for MBN for SDR 1 carbon sample

37
 Freundlich model
3

2.5

1.5 y = 0.5102x + 1.2086

log Qe R² = 0.9779
1

0.5

0
0 0.5 1 1.5 2 2.5 3
log Ce

Figure 17 Freundlich model for MBN for SDR 2 carbon sample

Freundlich model
3
2.5 y = 0.5655x + 1.0603
R² = 0.9241
2
1.5
log Qe

1
0.5
0
0 0.5 1 1.5 2 2.5
log Ce

Figure 18 Freundlich model for MBN for SDR 3 carbon sample

Table 14 Comparision of Isotherm constant

Model Langmuir Freundlich

Parameters Q b(L/mg) RL R2 N Kf(L/g) R2
(mg/g)
SDR 1 24.4 0.04 0.50 0.6273 1.675 42.55 0.857
SDR 2 256.4 0.038 0.62 0.913 1.953 16.16 0.977
SDR 3 238.1 0.06 0.64 0.357 1.768 11.70 0.9241

38
 5. CONCLUSION:
Pyrolysis was effectively used to treat the spray dried residue to reduce the strength of the waste.

 Optimum results for the batch studies were obtained at 1.5 hour and 15 gram for SDR 1
and SDR 2 samples which was about 88 % and 77.7 % chemical oxygen demand
reduction from the initial. Highest reduction for SDR 3 sample was obtained at 1.5 hour
and 5 gram and was about 77.8 %. With such a reduction, this residues are less liable
threat to the environment than the raw samples.
 Volatile solids converted to carbon from all the three residues which in process reduces
the strength of waste and material recovery is obtained. The conversion % of volatile
solids to carbon ranges from 75 % to 90 %.
 The conversion of volatile solids to carbon achieved at very low temperature (280-330
degree Celsius) than actual pyrolysis temperature range (300 -800 degree Celsius) large
amount of energy can be conserved and high temperature pyrolysis would fuse the other
inorganics which would be unwanted for landfill deposition.
 The Methylene Blue number for the carbon are found to be 230, 236 and 241 for SDR
1, SDR 2 and SDR 3 samples respectively which shows high adsorptive capacity and
can be used for various purposes.
 For the adsorption the best fitted isotherm is Freundlich for the obtained data for all the
samples this shows that adsorption is multi-layered.

39
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