Pyrolysis Project
Pyrolysis Project
Pyrolysis Project
1.1 INTRODUCTION
It was in the 1950s that plastics began to come into wide use, yet within
few years, production has risen at an unparalleled rate. Plastic products have
become an indispensable part of our daily lives as many objects of daily use are
made from some kind of plastic. Plastic has many advantages over other materials
as it costs less, resists corrosion and is highly flexible and strong. While all these
properties make it the ideal material for making many substances. Because of the
advantages that plastic products offer, its use has increased plastic waste. Plastic
consumption has increased much more than the world average due to rapid
urbanization and economic development. Due to the increase in generation, waste
plastics are becoming a major stream in solid waste.
Plastic products cannot be decomposable, it cannot be biodegradable.
Plastic can be produced once, it stay on earth forever. The manufacturing of
plastic also consumes water and releases greenhouse gases in the atmosphere
contributing to global warming. Plastic being light weight can be transported to
long distance easily by water or air. It is also responsible for the deaths of many
animals, fishes and birds.
On the other hand, another biggest problem is that we are facing increasing
prices of petroleum. Our India is one of the biggest consumers of fuel like petrol,
diesel and kerosene. India imported about 2/3rd of its petroleum requirements last
year which involved a cost of approximately Rs.80, 000 crores in foreign
exchange. Even 5% replacement of petroleum fuel by plastic fuel can help India,
to save Rs. 4000 crores per year. It is important that the option for substitution of
petroleum fuels be explored to control this rapidly growing import bill.
Todays age is generally known as plastic age. Our future is depended on
this plastic. Though it is too useful, improper management of this plastic waste is
subject of concern. There isnt any process for disposing the plastic waste. Hence,
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it is the needed that plastic products must be recycled and must not end in
landfills. Plastic recycling offers a viable solution to these problems.
Over the years, different waste management, treatment and disposal
methods have been adopted apart from the traditional options of landfill and
incineration. Emphasis is now shifting to technologies that will be acceptable to
the end users. One of such technologies is pyrolysis. Pyrolytic technology among
other methods is a way of harnessing the energy in these wastes, providing a good
method of disposing the wastes without affecting the ecological system. On the
other hand, it can provide an opportunity to collect and dispose of plastic waste in
the most environmental friendly way and it can be converted into a resource.
In its simplest form, this involves heating and decomposing mixed plastics
in the absence of oxygen. Unlike mechanical recycling techniques, in which the
long polymeric chains of the plastic are preserved intact, pyrolysis produces lower
molecular weight fragments. By adjusting operating conditions, the rate and
extent of decomposition can be controlled. In this way, it is possible to obtain a
predominantly liquid hydrocarbon product with potential for use as a fuel or a
refinery feedstock.
This approach can be applied to 80% of commodity plastics, so mixed
plastic wastes can usually be handled without the need for segregation by polymer
type. In most of the situations, plastic waste recycling could also be economically
viable, as it generates resources, which are in high demand. Plastic waste
recycling also has a great potential for resource conservation. If pyrolysis is
studied economical and efficiency point of view it is much better technique of
recycling mixed plastic waste.
OBJECTIVE
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Since the global energy crises of the 1970s, there has been a trend towards use of
alternative energy sources to replace fossil fuel worldwide. In this project we
trying to minimized the plastic waste by recycling. We get energy recovery from
it. Product obtained during this project may replace or use as alternative to any of
petroleum product. We compare the characteristics of the product with other
petroleum product. The results are shown in chapter 3.
2. Literature Review
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2.1
WHAT IS WASTE?
Waste is generally termed as a material which is unwanted or unusable.
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This data is regarding to the Municipals Solid waste. The below data shows
the waste of plastic material before recycling. The pie chart of total MSW
generation exhibited 12.0% of plastic waste & it shows also other materials
wastes.
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2.2
according to their origins; these groups have different qualities and properties and
are subjected to different management strategies. Plastic wastes represent a
considerable part of municipal wastes; furthermore huge amounts of plastic waste
arise as a by-product or faulty product in industry and agriculture.
Of the total plastic waste, over 78 wt% of this total corresponds to
thermoplastics and the remaining to thermosets. Thermoplastics are composed of
polyolefins such as polyethylene, polypropylene, polystyrene and polyvinyl
chloride and can be recycled. On the other hand thermosets mainly include epoxy
resins and polyurethanes and cannot be recycled.
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greater than water such as polystyrene and polyvinyl chloride, and those with a
density lower than that of water such as polyethylene, polypropylene, and
expanded polystyrene. The latter group is much larger than the first group.
Consequently, recycling of municipal plastic wastes should deal with
plastic mixtures of polyethylene, polypropylene and polystyrene, provided that the
above separation procedures are practiced. Although MSW separation
technologies have been studied extensively, it is still not possible to classify MSW
mechanically and obtain marketable fractions. So waste separation at the
household would be a better option with where household wastes are separately
disposed into three parts:
(i) combustibles such as paper, kitchen waste, textiles, and wood,
(ii) incombustibles such as metals, glass, ceramics, and
(iii) plastics
Municipal plastic wastes
Hospital
Textile
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kitchen
Other
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E-waste
Scrap
Complex scrap
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2.3
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clogging of drains
2.4
5-R
Concept
for
Integrated
Plastic
waste
management
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Reduce.
Reuse.
Recycle.
Recover.
Regulated disposal.
3 RECYCLING
Recycling is the process of turning used products into raw materials that
can be used to make new products. Its purpose is to conserve natural resources
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contamination
techniques
done
by
various
type
of granulators,
cryogenic
grinding,
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ways
-
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Chemical Recycling
The chemical recycling is the recovery of different chemicals from plastic
waste. There is a solution possible to recuperate the chemical components of
plastics waste, but it is delicate to handle and the economics of the system are not
so evident.
The solution consists in considering the plastic portion of waste as crude oil,
heating it to high temperature in a vacuum for example and recuperating the
products of decomposition. These products are hydrocarbons which are partially
usable in the chemical industry and partly hydrocarbons with no chemical value,
but which can be used to provide combustion for pyrolysis kiln.
Two methods are used:
-
pyrolysis and
Pyrolysis
It is the physical and chemical decomposition of organic materials caused
by heating in an oxygen free or oxygen deficient atmosphere. This process,
sometimes called destructive distillation, drives off volatile components and
leaves a char consisting of carbon and quite often fairly large ash content. By
varying temperature and pressure, it is felt that it is possible to vary the properties
of liquid or gaseous products. Plastics are considered as asset in pyrolysis.
Quaternary recycling
Thermal recycling/Incineration:
Incineration represents a treatment option for the destruction, safe
transformation or reduction of waste. Incineration itself is a generalized term
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which covers a wide range of combustion techniques from open pits through
furnaces to sophisticated high temperature detected, or merchant incineration
facilities.
Plastic alone or mixed with other waste, may be burn for disposal, with or
without heat recovery. They may be included with other wastes for the production
of waste derived fuel. The first large scale MSW incinerator was built in England
in 1870, similar plants, some with heat recovery, were operating in other
European countries and United States before the end of 19 th centuries.
In modern incineration plants combustion, air and water emissions are
controlled. Incineration is controlled by metering the waste to the combustion
chamber and by controlling the volume of air over and under the burning bed by
means of grate. As the waste descends, the grate, the usual the slightly inclined of
turn moving back and forth, pass through three zones: drying, combustion, burn
out, followed by ash removal. An alternative method uses less than the
stoichometric amount of air during combustion. The gases product passes to the
second chamber where they are burn in an excess of air. Particulate and gases
emission are controlled. This design is typical of small units.
In any incinerator, the temperature must be controlled to prevent failure of
materials of construction. This may be achieved by controlling the amount of air
added which may be in 80% 100% excess over stoichometric requirements,
cooling the gases or a walls by water pipes (and generating steam), and
monitoring the input waste. Typically, the temperature must be above 750 oc to
ensure adequate combustion and below 1000oc to prevent ash from melting and
clogging the grate or shortening the life of the refractory materials of construction.
Land filling (disposal)
Highest portion of the solid waste including plastics have been subjected to
landfill. However, disposing of the waste to landfill is becoming undesirable due
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to legislative pressures (where waste to landfill must be reduced by 35% over the
period from 1995 to 2020), rising costs, the generation of explosive greenhouse
gases (such as methane) and the poor biodegradability of commonly used
packaging polymers. In light of these hazards, the EPA has improved federal
regulations for land filling by normalizing the use of liners in the landfill bed,
ground water testing for waste leaks, and post landfill closure care; however, since
waste plastics have a high volume to weight ratio, appropriate landfill space is
becoming both scare and expensive. So, the other methods outlined in scheme 1
should be preferred as an alternative waste management procedure to replace land
filling.
FIG3. Flow chart for Different routes for plastic waste management
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Descriptions
Examples
Polymers consisting of
Polyethylene, polypropylene,
polystyrene.
wastes
and
fuel.
PET,
oxygen
above plastics
polyvinyl
Polymers containing
polyoxymethylene
Nitrogen:
polyamide,
nitrogen or sulfur
plastic is a source of
polyurethane
hazardous components
such as NOx or Sox in
phenolic
resin,
alcohol,
flue gas.
Flue gas cleaning is
required to avoid emission
of hazardous components
Polymers containing
in exhaust gas.
Source of hazardous and
Polyvinyl
chloride,
halogens of chlorine,
Polyvinylidene
chloride,
bromine-containing
combustion.
flame
polymers.
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Chapter3
3.1 PYROLYSIS
Various methodologies have been tried and tested to process waste plastics
for many years, with recycling becoming the most common method reflecting
todays environmental requirements. Plastics that cannot be processed are handled
by waste management companies by normal land filling or incineration.
In recent years, the building or expanding of gasifiers (most notably the
levels of emissions) has become difficult due to opposition from governments and
community groups with environmental concerns. Liquefaction of plastic is a
superior method of reusing this resource. The distillate product is an excellent fuel
and makes pyrolysis one of the best, economically feasible and environmentally
sensitive recycling systems in the world today.
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DEFINITIONS OF PYROLYSIS
Pyrolysis is the chemical decomposition of organic substances by heating
in absence of oxygen.
The word is coined from the Greek-derived elements pyro "fire" and lysys
"decomposition".
It is the physical and chemical decomposition of organic materials caused
by heating in an oxygen free or oxygen deficient atmosphere.
The pyrolysis of plastics produces a liquid product, pyrolysis oil or oil that
can be readily stored and transported. Pyrolysis oil can be used directly as fuel or
further refined into diesel or jet fuel.
As feedstock recycling and pyrolysis is not incineration there are no toxic
or environ- mentally harmful emissions. Pyrolysis recycling of mixed plastics thus
has great potential for heterogenous plastic waste that cannot be economically
separated.Pyrolysis is one of the best methods for preserving valuable petroleum
resources in addition to protecting the environment by decreasing the volume of
non-degradable waste.
In its simplest denition pyrolysis is the degradation of polymers at high
temperatures under nonoxidative conditions to yield valuable products (e.g. fuels
and oils). Pyrolysis is also referred to as polymer cracking and its main
advantages are that it can deal with plastic waste which is otherwise difficult to
recycle and it creates reusable products with unlimited market acceptance.
Pyrolysis typically occurs under pressure and at operating temperatures
above 430 C (800 F). In practice, it is not possible to achieve a completely
oxygen-free atmosphere. Because some oxygen is present in any pyrolysis system,
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3.1TYPES OF PYROLYSIS
Pyrolysis can be categorized in many types on the basis of reaction speed,
parameters of process, etc. following are the types of pyrolysis.
1. Again pyrolysis is classified on two major classes on the basis of catalyst
useda. Catalytic pyrolysis
b. Non-catalytic pyrolysis
Catalytic Pyrolysis:Pyrolysis oil consists of a complex mixture of aliphatic and aromatic
oxygenates and particulates. It is very viscous, acidic and unstable liquid with
relatively low-energy density compared to conventional fossil oil. Such poor
quality of the oil requires costly post treatment and makes complete process
economically less attractive. Presence of proper catalysts during the Pyrolysis
process can affect the network of reactions and upgrade the oil. Providing good
contact between the catalyst and solid waste is essential to improve the efficiency
of Pyrolysis process. Lower Pyrolysis temperature is crucial maximizing oil yield
and quality.
Catalytic pyrolysis makes whole process very efficient only drawback
associated with system is high cost. Example of catalyst used are zeolite, ZSM-5,
silica-alumina, SAHA/ZSM-5, MCM-41/ZSM-5, FCC.
Non-catalytic pyrolysis
This pyrolysis process is carried out in absence of catalyst. It requires more
temperature conditions. Its main advantage is good efficiency of process with low
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cost. The only thing about this process is we cannot target specific product.
Thermal pyrolysis is type of non-catalytic pyrolysis.
2. On the basis of speed (residence time of waste) of pyrolysis. It is classified
into main two groupsa. Fast Pyrolysis, and
b. Slow Pyrolysis.
Fast Pyrolysis:Flash Pyrolysis is characterized by moderate temperatures between 400600oC and rapid heating rates >2oC/s. Vapor residence times are usually less than
two seconds.
Due to the short vapor residence time, products are high quality,
ethylenerich gases that could subsequently be used to produce alcohols or
gasoline. The production of char and tar is considerable less during this process.
Fast Pyrolysis can be further categorized into the following:
Ablative Fast Pyrolysis - pressure is applied to biomass to increase speed of
decomposition through use of centrifugal or mechanical force. Larger particles
of biomass can be used in this process.
Cyclonic Fast Pyrolysis - also called vortex fast pyrolysis, separates the solids
from the non-condensible gases and returns them to the mixer.
Rotating Cone Fast Pyrolysis - uses a compact high intensity reactor in
which biomass of ambient temperature is mixed with hot sand. Upon mixing
with the hot sand, the biomass decomposes into 70% condensible gases with
15% non-condensible gases and 15% char.
Slow Pyrolysis:Slow Pyrolysis is characterized by slow heating rates, low temperatures
and lengthy gas and solids residence times. Depending on the system, heating
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rates are about 0.1 to 2 oC/s and prevailing temperatures are around 500 oC. Gas
residence time may be greater than five seconds. During conventional Pyrolysis,
the waste is slowly devolatillized; hence tar and char are the main products.
Vacuum pyrolysis
3. On the basis of temperature used pyrolysis again can be classified into two
classesa. High temperature pyrolysis
b. Low temperature pyrolysis
High temperature
High temperature pyrolysis takes place at 500 0C - 10000C. It takes less
residence time and gives more gaseous product.
Low temperature
Low temperature pyrolysis takes place below 5000C temperature. It takes
more residence time and gives more liquid product.
4. Again there are two major classes of pyrolysis on the basis of type of gas used
for purginga. Oxidative pyrolysis
b. Non-oxidative pyrolysis
Oxidative pyrolysis
Oxidative pyrolysis is the process of pyrolysis which allow measured
amount of oxygen in system. In this process co2 is used as purging gas. It
requ1ires less temperature than that of non-oxidative pyrolysis.
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Non-oxidative
Non-oxidative pyrolysis is the process of pyrolysis which does not allow
oxygen in the system. In this type of pyrolysis nitrogen is used as purging gas.
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Liquid hydrocarbons
Liquid hydrocarbons
Type of plastics
Polyethylene (PE)
Allowed.
Polypropylene (PP)
Allowed.
Polystyrene (PS)
Allowed.
Polymethylmetacrylate
Allowed.
(PMMA)
Acrylonitrile-Butadiene-
Allowed.
Styrene
copolymer (ABS)
Nitrogen-containing fuel is
obtained. Special attention
Polyurethane (PUR)
Not suitable.
Not allowed.
Polyvinylidene chloride
Not allowed.
Polyethyleneterephthalate
(PET)
Carbonous products
Hydrogen chloride and
carbonous products
(PVDC)
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elements such as carbon and hydrogen, they increase the density of the plastic also
material having heteroatom such as polyvinylchloride (chlorine is heteroatom),
polysulfide (sulfur is heteratom) may cause corrosion of reactor and emission of
hazardous gases.
Polyolefins give the best yield of distillate due to their straight-chain
hydrocarbon structure. Polystyrene is beneficial in the mix since it contributes
aromatic character to the distillate and improves the pour point properties (i.e. the
low-temperature viscosity properties).
Material having low decomposition temperature are suitable for
pyrolysis.if we consider polycarbonate,polyethylene terepthalate are not suitable
for process of pyrolysis.because they require more temperature for degradation
and there pyrolysis will not be economical nor feasible.
So while selecting material for pyrolysis care must be taken that it should
have low decomposition temperature and must not contain heteroatom.following
table shows the material and its suitability for pyrolysis.
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OPERATION OF PYROLYSIS
The pyrolysis system consists of the prime chamber, which performs the
essential functions of homogenisation, controlled decomposition and outgassing
in a single process. The process requires minimal maintenance apart from carbon
residue removal, and produces consistent quality distillate from mixed and lowgrade plastic waste.
The key to an efficient pyrolysis process is to ensure the plastic is heated
uniformly and rapidly. If temperature gradients develop in the molten plastic mass
then different degrees of cracking will occur and products with a wide distribution
of chain lengths will be formed.
Another important aspect of pyrolysis is to use a negative pressure (or a
partial vacuum) environment. This ensures that oxidation reactions are minimized
and that gaseous pyrolysis vapours are quickly removed from the process chamber
thereby reducing the incidence of secondary reactions and the formation of
undesirable by-products.
The polymer is gently 'cracked' at relatively low temperatures to give
predominantly straight chain aliphatic hydrocarbons with little formation of byproducts. These hydrocarbons are then selectively condensed and cleaved further
catalytically to produce the average carbon chain length required for distillate
fuel.
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CRACKING
Cracking process break down polymer chains into useful lower molecular
weight compounds. The products of plastic pyrolysis process could be utilized as
fuels or chemicals. Three different cracking processes such as hydrocracking,
thermal cracking and catalytic cracking are reported.
Hydrocracking
Hydrocracking of polymer waste typically involves reaction with hydrogen
over a catalyst in a stirred batch autoclave at moderate temperatures and pressures
(typically 423 673 K and 310 MPa hydrogen). The work reported, mainly
focuses on obtaining a high quality gasoline starting from a wide range of feeds.
Typical feeds include polyethylene, polyethylene terephthalate, polystyrene,
polyvinyl chloride and mixed polymers, polymer waste from municipal solid
waste and other sources, co-mixing of polymers with coal, co-mixing of polymers
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processed with coal. To aid mixing and reaction, solvents such as 1-methyl
naphthalene, tetralin and decalin have been used with some success. Several
catalysts, classically used in refinery hydrocracking reactions, have been
evaluated and include transition metals (e.g., Pt, Ni, Mo, Fe) supported on acid
solids (such as alumina, amorphous silicaalumina, zeolites and sulphated
zirconia).These catalysts incorporate both cracking and hydrogenation activities
and although gasoline product range streams have been obtained.
Thermal cracking
Thermal cracking, or Pyrolysis, involves the degradation of the polymeric
materials by heating in the absence of oxygen. The process is usually conducted at
temperatures between 3500c and 9000C and results in the formation of a
carbonized char (solid residues) and a volatile fraction that may be separated into
condensable hydrocarbon oil consisting of paraffins, isoparaffins, olefins,
naphthenes and aromatics, and a noncondensable high calorific value gas. The
proportion of each fraction and their precise composition depends primarily on the
nature of the plastic waste but also on process conditions. The extent and the
nature of these reactions depend both on the reaction temperature and also on the
residence of the products in the reaction zone, an aspect that is primarily affected
by the reactor design. However, the thermal degradation of polymers to low
molecular weight materials requires high temperatures and has a major drawback
in that a very broad product range is obtained. Catalytic pyrolysis provides a
means to address these problems.
Catalytic cracking
In this method a suitable catalyst is used to carry out the cracking reaction.
The presence of catalyst lowers the reaction temperature and time. In addition,
catalytic degradation yields a much narrower product distribution of carbon atom
number with a peak at lighter hydrocarbons and occurs at considerably lower
temperatures. From an economic perspective, reducing the cost even further will
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make this process an even more attractive option. This option can be optimized by
reuse of catalysts and the use of effective catalysts in lesser quantities. This
method seem to be the most promising to be developed into a cost-effective
commercial polymer recycling process to solve the acute environmental problem
of plastic waste disposal.
Thermal cracking involves following reactionsInitiation reactions, where a single molecule breaks apart into two free radicals.
Only a small fraction of the feed molecules actually undergo initiation, but these
reactions are necessary to produce the free radicals that drive the rest of the
reactions. In steam cracking, initiation usually involves breaking a chemical bond
between two carbon atoms, rather than the bond between a carbon and a hydrogen
atom.
CH3CH3 2 CH3
Hydrogen abstraction, where a free radical removes a hydrogen atom from
another molecule, turning the second molecule into a free radical.
CH3 + CH3CH3 CH4 + CH3CH2
Radical decomposition, where a free radical breaks apart into two molecules, one
an alkene, the other a free radical. This is the process that results in the alkene
products of steam cracking.
CH3CH2 CH2=CH2 + H
Radical addition, the reverse of radical decomposition, in which a radical reacts
with an alkene to form a single, larger free radical. These processes are involved
in forming the aromatic products that result when heavier feedstocks are used.
CH3CH2 + CH2=CH2 CH3CH2CH2CH2
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Termination reactions, which happen when two free radicals react with each other
to produce products that are not free radicals. Two common forms of termination
are recombination, where the two radicals combine to form one larger molecule,
and disproportionation, where one radical transfers a hydrogen atom to the other,
giving an alkene and an alkane.
CH3 + CH3CH2 CH3CH2CH3
CH3CH2 + CH3CH2 CH2=CH2 + CH3CH3
Here is an example of cracking with butane CH3-CH2-CH2-CH3
1st possibility (48%): breaking is done on the CH3-CH2 bond.
CH3* / *CH2-CH2-CH3
after a certain number of steps, we will obtain an alkane and an alkene:
CH4 + CH2=CH-CH3
2nd possibility (38%): breaking is done on the CH2-CH2 bond.
CH3-CH2* / *CH2-CH3
after a certain number of steps, we will obtain an alkane and an alkene from
different types: CH3-CH3 + CH2=CH2
3rd possibility (14%): breaking of a C-H bond
After a certain number of steps, we will obtain an alkene and hydrogen gas:
CH2=CH-CH2-CH3 + H2
this is very useful since the catalyst can be recycled.
Another mechanism of HC cracking is as follow
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Similarly Peterson et. al. observed that in the thermal pyrolysis of PP, the
main products were pentane, 2-methyl-1-pentene and 2,4 dimethyl1-heptene.
During degradation, methyl, primary and secondary alkyl radicals are formed, and
by hydrogen abstractions and recombination of radical units, methane, olefins and
monomers are produced.
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3.4THERMODYNAMICS OF PYROLYSIS
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G=H-TS
Although the bond dissociation energy D for a carbon-carbon single bond
is relatively high (about 375 kJ/mol) and cracking is highly endothermic, the large
positive entropy change resulting from the fragmentation of one large molecule
into several smaller pieces, together with the extremely high temperature, makes
TS term larger than the H term, thereby favoring the cracking reaction.
Q= m cp t
Where,
difference
Q = 0.1*2200*428
Hence,
Q=94160 J
The value of the rate of heat flow is positive that is there is no loss of
heat occur, so we can say that the process is feasible.
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Polymer
Melting
Density
point,
Temp
Max.rate of
Apparent
range (C)
decomp at
(C)
reaction
(C)
order, n
HDPE
134
0.954
340500
475
0.83
PP
163
0.91
340460
425
0.3
PS
110
1.05
320415
355
1.04
PET
260
1.41
360410
400
1.20
Material
Trade
Repeating
name/Manufact
unit
urer
Polyethylene (PE)
LDPE
C2H4
Polypropylene (PP)
Polysciences Inc.
C3H6
hc
hc/
(k (kJ/g)
J/
g)
(kJ/g
44.60
13.01
42.66
12.44
41.96
13.64
23.22
13.93
Qc
47.74
45.80
0.48
Polystyrene (PS)
Polysciences Inc.
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C8H8
C10H8O
43.65
424.13
0.39
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very short life span. To form article from mixed plastic waste it is needed that that
waste must be of good quality and should not be degraded or dirty.
Another way of recycling of waste is Incineration which is purely used for
reduction of volume of waste. It includes burning of plastic waste in presence of
oxygen. It emits hazardous gases and unable to give amount of energy plastic
could generate.
Another way of dealing with plastic waste is Land Filling. Land filling not
only responsible for loss in potential of plastic waste and loss in resources but also
for land pollution. It just helps to minimize volume of plastic waste.
Pyrolysis is highly efficient technique of recycling. If 20000 kg of plastic
waste under go for pyrolysis 19000 liter of liquid is come as yield. It means
process is highly efficient. Again special feature of pyrolysis is that, mixed plastic
waste, unsorted, unclean can be processed through this technique. Third most
important feature is that it is environmentally attractive process. Neither has it
evolved any harmful gases nor any solid waste to cause any pollution.
So it is environmentally friendly technique to process plastic waste. Liquid
fuel produced in this technique can be used as automotive fuel after blending with
Diesel. Gases produced in pyrolysis can be used for pyrolysis unit itself (to
generate temperature required for system). It means pyrolysis is self dependent
process for its energy source. It is economical process because it gives more
amount of energy as output than it utilizes. Pyrolysis utilizes total efficiency of
plastic waste to come in use. We believe this much reasons are sufficient for
question why to go for pyrolysis.
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Chapter4
4.1 DESCRIPTION OF PYROLYSIS SET UP
1. FURNACE
Description of furnace
The essential condition to carry process of pyrolysis in laboratory is to
obtain and maintain temperature requirement for the process of pyrolysis.
Minimum temperature requirement for process of pyrolysis is 450 oc and the
maximum can reach up to 650oc. temperature need for our project was limited for
the range of 430oc to 600oc. To achieve this much temperature at constant rate
laboratory furnace is needed furnace available to us was muffle furnace. Detail
related to muffle furnace is given bellowName Muffle Furnace
Specifications:
Voltage 250 volts
Load 10 amps.
Temp. Range 0 1200oc
Dimensions:
Space available 150*150*300 mm2 cross section.
Insulation used - glass wool, asbestos sheets.
Modification in furnace
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Page 48
2. REACTOR
Description of reactor
It is feed containing vessel made up of stainless steel. Reactor consists of
three opening on its top for different purposes as shown in below pictures.
Modification in reactor
The previous reactor present was leaked from opening present at top due to
improper matching of condenser and reactor so modify the reactor by welding the
tapper section to the outlet for attaching the condenser system properly in order to
minimizes the leakages as shown in picture. We also attached the sensor from one
of the opening present to the reactor which shows inside temperature of reactor. It
is really difficult to attach the sensor to the reactor for this we sealed a hole of
reactor and kept a small opening through which we can insert the cable of the
sensor inside the reactor so that we minimizes leakages.
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7a.Front view
C.O.E.T.A/Chemical/2012
Temperature sensor
3. DOOR OF FURNACE
Door is opening provided for insertion of reactor into the furnace
Description of DOOR
Material mild steel (ms)
Dimensions:
Surface area- 260*260 mm2
Height 50 mm
Reactor opening diameter - 78 mm
Insulating material used - glass wool (250 gm),Plaster of Paris (100 gm),
Asbestos sheets (3sheets)(150*150 mm2).
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10.Picture of door
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2. Condensation system
Condensation system is used to receive vapours formed due to process of
pyrolysis. It consists of one reflux condenser. Inlet of condenser is attached to
opening of rector provided for condensation system using bent. Product vessel is
attached to the outlet of condenser by bent. It is attached in inclined shape so that
liquid travels easily to collection system. Inlet is provided from bottom of the
condenser & outlet is provided from top condenser, care should be taken that
whole condenser should be filled by cooling water.
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3. Cooling system
Cooling system is to provide cool water continuously for condensation of
vapours formed as product of pyrolysis.
Cooling system consist of one bucket to which one outlet system is drilled
at bottom tap is fixed to drilled portion of bucket. Care is taken while fixing tap
because small leakage may cause huge water loss. Pipe is extended from top of
bucket to bottom inlet of condenser inlet of condenser. From top of condenser
opening pipe is extended to bucket for use of water. Bucket is placed at the height
of 3 ft. from height of condenser so that water should flow without use of any
force. We used chilled water as cooling media.
4. Collection system
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Chapter5
5.1PROCESS DESCRIPTION
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Followings are the steps which takes place during the run of the set up.
1. Cleaning of reactor
2. Material preparation
3. Filling of reactor
4. Insertion of reactor into the furnace
5. Purging
6. Switch on the furnace
7. Condensation and product collection
It is necessary to clean the reactor and other accessories such as condenser
product vessel etc. before the start of process because unclean reactor may cause
physical changes i.e. contamination of final product or may cause problem in
material balance. We used detergent and scrubber to wash the reactor using
moderate temperature water. The condenser is clean by using hot water so that the
dust or trapped product of earlier batch can remove easily. After cleaning
equipments are kept for drying. Sometime manual drying may require.
Secondly is raw material preparation which includes cutting of raw
materials, washing and drying, for uniform temperature distribution through the
raw material it is cut into pieces having similar or nearly similar surface area.
After cutting raw material in pieces next step is washing or cleaning of raw
material by water. After washing water is removed and material is kept for drying
or preheating in furnace. Preheating removes water and other volatiles impurities.
In next step, dried or preheated material is then filled into the reactor.
Bolts attached to flanges are screwed tightly to avoid leakage problem. At this this
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step we inserted sensor into the reactor from one of the opening present at top of
reactor which measures and shows temperature in the reactor. The reactor is then
placed in to the furnace.
Condenser assembly is attached to the reactor as shown in the fig. cooling
system consist of one bucket having one opening for outlet water two pipes to two
openings of condenser is provided. First flow rate and flow temperature of inlet
water is measured, and then it is attached to condenser. As the water comes out of
condenser its outlet flow rate & out let temperature is measured. Here we are
using inclined product condenser. As the product vapours starts coming out they
are condensed by cooling water & condensed product dripped inside the
collection vessels.
Care must be taken to make whole system leak proof. Leak may cause
entry of oxygen inside reactor or loss of product through leaks. To make system
leak proof silica gel, white cement and plaster of paries are used.
As the process starts purging is done initially for 5 to 7 minutes. Every
process condition such as flow rates, various temperatures, resident time, and
purging pressure is noted. To make system oxygen free purging is done after every
15 minutes.
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5.2
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There are several simple tests that can be used to distinguish between the
common types of polymers so that they may be separated for processing.
According to that we choose PS and HDPE for our process. For that purpose we
choose college articles and milk pouches, which have to pass from few tests listed
below:Table:6
Test
Water
Material
Stationary
Burning
Sinks
articles
Prediction
characteristics
Drips.
PS
flame
(glassy pens,
scales , set
squares, etc)
Milk pouches
Floats
Blue flame
Like candle
with yellow
wax.
tip,
LDPE and PP waste. We used packaging bags such as for food and vegetables as a
polyolefinic waste. The process is done two times for each plastic waste.
We changes temperature during both batches and study changes in product
yield with respect to temperature. The temperature at which product yield or
liquid dripping is more is selected as optimum temperature. Another factor
consider while choosing optimum temperatures product composition & sealing
condition of reactor.
At first we set temperature at 600 oc on controller, as we do not know the
exact temperature at which the fumes will observe, in this case we seen that less
temperature is reach to the reactor due to the time lack. But we also observe that
when the temperature is in between 150 oc -300 oc of the reactor the fumes are
seen. Hence for second batch we set temperature on 450 oc on controller and
observed the results.
Following graphs and tables shows results of two batches for three
different materials.
We observe that, if temperature increased more than 570 oc silica grease
used for sealing collapse and leakages increases. So we keep our temperature
requirement below 550oc.
Temperature of cooling water is also have marked effect on product. More
freeze water may cause freezing of vapours in condenser only for this we keep
temperature of cooling water in the range of 19oc 20oc. About flow rate, initially
flow rate of cooling water is kept low as residence time increases flow rate is
increase by little fraction. Before the batch raw material is prepared (cutting,
washing, drying) and weighed properly. As the batch starts flow rate and
temperature of inlet, outlet cooling water is measured.
17.DIFFERENT TYPES OF WASTE
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PS WASTE
HDPE WASTE
POLYOLEFINIC WASTE
Second Batch
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Material
PS
PS
Amount
100gm
250gm
Temp. set on
600 oc
450 oc
15 oc
18 oc
17 oc
19.5 oc
0.0142lit/sec
0.0142lit/sec
0.0142lit/sec
0.0142lit/sec
40min
50min
controller
Inlet water
temp.
Outlet water
temp.
Inlet water flow
rate
Outlet water
flow rate
Residence time
600
Furnace
500
Reacto
r
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400
Material PS
Fumes at temp
Furnace temp:370C
Reactor Temp:224C
300
200
100
0
10
20
30
40
50
Above graph shows the temperature of reactor and furnace at which fumes are observe
for first batch of PS waste. When fumes are seen during the process the temperature of
furnace is 370 oc and rector temperature is 224 oc and time is 17min from start of the
process.
MATERIAL BALANCE
Batch no.
Material
Liquid obt.
Liquid obt.
Residue
Losses
amount
(gm)
(ml)
First
100gm
67.54gm
71.09ml
16.37gm
16.09gm
Second
250gm
182.25gm
191.84ml
61.46gm
6.29gm
Material
First batch
Second batch
HDPE
HDPE
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Amount
100gm
250gm
Temp. set on
600C
450C
15C
16C
18C
19C
0.0133lit/sec
0.0133lit/sec
0.0133lit/sec
0.0133lit/sec
30min
45min
controller
Inlet water
temp.
Outlet water
temp.
Inlet water flow
rate
Outlet water
flow rate
Residence time
600
Furnace
500
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React
or
Material HDPE
Fumes at temp
Furnace temp:350C
Reactor Temp:195C
400
Temp
300
200
100
0
10
20
30
40
50 time
Above graph shows the temperature of reactor and furnace at which fumes are
observe for first batch of HDPE waste. When fumes are seen during the process
the temperature of furnace is 350 oc and rector temperature is 195 oc, at the time
25min from start of process.
MATERIAL BALANCE
Batch no.
Material
Liquid obt.
Liquid
Residue
Losses
amount
(gm)
obt. (ml)
First
100gm
61.32gm
64.54ml
20.47gm
18.21gm
Second
250gm
189.51gm
199.48ml
54.75gm
5.74gm
Material
First batch
Second batch
polyolefin
Polyolefin
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Amount
100gm
200gm
Temp. set
600C
450C
15C
17C
Outlet water
16C
18C
0.0125lit/sec
0.0125lit/sec
0.0125lit/sec
0.0125lit/sec
30min
40min
temp.
Inlet water flow
rate
Outlet water flow
rate
Residence time
600
Furnace
500
400
Temp
React
or
Material :Polyolefins
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300
Fumes at temp
Furnace temp:370C
Reactor Temp:210C
200
100
0
10
20
30
40
50 time
Above graph shows the temperature of reactor and furnace at which fumes are
observe for first batch of POLYOLIFINIC waste. When fumes are seen during the
process the temperature of furnace is 370 oc and rector temperature is 210oc, and
the time is 14min from start of process.
MATERIAL BALANCE
Batch no.
Material
Liquid obt.
Liquid
amount
(gm)
obt.
Residue
Losses
(ml)
First
100gm
66.22gm
69.70ml
23.57gm
10.21gm
Second
200gm
166.10gm
174.84ml
25.23gm
8.67gm
Chapter6
6.1TESTING OF PRODUCT AND COMPARATIVE STUDY
Product yield from pyrolysis is necessary to pass through various tests to compare
the results with other fuel. Following are the few testing, there results and
comparative study of results with diesel is given bellow.
The product obtained in pyrolysis process is overhead and bottom product. The
overhead obtained is in crude form and bottom product obtained is residue.
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Product of pyrolysis
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Flash point
Ethanol (70%)
16.6 C (61.88 F)
Gasoline (petrol)
-43 C (-45 F)
Diesel
>62 C (143 F)
Jet fuel
>60 C (140 F)
>3872 C (100162 F)
327 C (620 F)
Biodiesel
>130 C (266 F)
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69
81
55
60
Olefinic waste
40
56
72
84
53
62
Olefinic waste
42
58
By observing above results and comparing it from reference table of flash point.
We may say we are approaching nearest values of diesel.
DENSITY(gm/cc)
Olefinic
0.4711
HDPE
0.6713
PS
0.8794
Diesel
0.843
From above table the density of polystyrene and HDPE shows near range to the
density of diesel.
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C.O.E.T.A/Chemical/2012
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This test of our product is carried out at UDCT Jalgoan, results of FT-IR
technique for different product (for crude and residue) is given below.
FT-IR technique is giving brief knowledge about type of linkages and brief
idea about compound which is present in liquid. Still we cant predict whether it is
belongs to fuel group or just a fuel. Result test, fire point test, density test,
calorific value test will help us to know our product in more detail manner.
Infrared spectroscopy exploits the fact that molecules absorb specific
frequencies that are characteristic of their structure. These absorptions are
resonant frequencies, i.e. the frequency of the absorbed radiation matches the
frequency of the bond or group that vibrates. The energies are determined by the
shape of the molecular potential energy surfaces, the masses of the atoms, and the
associated vibronic coupling.
Practical IR spectroscopy
The infrared spectrum of a sample is recorded by passing a beam of
infrared light through the sample. Examination of the transmitted light reveals
how much energy was absorbed at each wavelength. This can be done with a
monochromatic beam, which changes in wavelength over time, or by using a
Fourier transform instrument to measure all wavelengths at once. From this, a
transmittance or absorbance spectrum can be produced, showing at which IR
wavelengths the sample absorbs. Analysis of these absorption characteristics
reveals details about the molecular structure of the sample. When the frequency of
the IR is the same as the vibrational frequency of a bond, absorption occurs.
This technique works almost exclusively on samples with covalent bonds.
Simple spectra are obtained from samples with few IR active bonds and high
levels of purity. More complex molecular structures lead to more absorption bands
and more complex spectra. The technique has been used for the characterization
of very complex mixtures.
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Sample preparation
Liquid samples can be sandwiched between two plates of a salt (commonly
sodium chloride, or common salt, although a number of other salts such as
potassium bromide or calcium fluoride are also used).[1] The plates are transparent
to the infrared light and do not introduce any lines onto the spectra.
Solid samples can be prepared in a variety of ways. One common method is
to crush the sample with an oily mulling agent (usually Nujol) in a marble or
agate mortar, with a pestle. A thin film of the mull is smeared onto salt plates and
measured. The second method is to grind a quantity of the sample with a specially
purified salt (usually potassium bromide) finely (to remove scattering effects from
large crystals). This powder mixture is then pressed in a mechanical press to form
a translucent pellet through which the beam of the spectrometer can pass. [1] A third
technique is the "cast film" technique, which is used mainly for polymeric
materials. The sample is first dissolved in a suitable, non hygroscopic solvent. A
drop of this solution is deposited on surface of KBr or NaCl cell. The solution is
then evaporated to dryness and the film formed on the cell is analysed directly.
Care is important to ensure that the film is not too thick otherwise light cannot
pass through. This technique is suitable for qualitative analysis. The final method
is to use microtomy to cut a thin (20100 m) film from a solid sample. This is
one of the most important ways of analysing failed plastic products for example
because the integrity of the solid is preserved.
In photoacoustic spectroscopy the need for sample treatment is minimal.
The sample, liquid or solid, is placed into the sample cup which is inserted into
the photoacoustic cell which is then sealed for the measurement. The sample may
be one solid piece, powder or basically in any form for the measurement. In
example a piece of rock can be inserted into the sample cup and the spectrum
measured from it.
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C.O.E.T.A/Chemical/2012
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Graph4:FTIR
the
interferometer.
The
signal
directly
recorded,
called
an
"interferogram", represents light output as a function of mirror position. A dataprocessing technique called Fourier transform turns this raw data into the desired
result (the sample's spectrum): Light output as a function of infrared wavelength
(or equivalently, wavenumber). As described above, the sample's spectrum is
always compared to a reference.
There is an alternate method for taking spectra (the "dispersive" or
"scanning monochromator" method), where one wavelength at a time passes
through the sample. The dispersive method is more common in UV-Vis
spectroscopy, but is less practical in the infrared than the FTIR method. One
reason that FTIR is favored is called "Fellgett's advantage" or the "multiplex
advantage": The information at all frequencies is collected simultaneously,
improving both speed and signal-to-noise ratio. Another is called "Jacquinot's
C.O.E.T.A/Chemical/2012
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40
540.09
476.43
758.05
702.11
904.64
1074.39
1020.38
1263.42
1492.95
1448.59
1612.54
1807.36
1734.06
1952.03
1878.73
2233.64
2858.60
50
2928.04
60
3068.85
3028.34
70
3385.18
80
3688.02
90
2320.44
110
%T
100
30
20
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Liquid
1/cm
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Peak Value
476.43
2
3
4
5
6
7
8
540.09
702.11
758.05
904.64
1020.38
1074.39
1263.42
Type Of Bond
Iodoalkanes
C-H
Aromatices
Aromatices
C-H
C-O
C-O
C-O
Types Of Compound
Any
Alkynes
Monosubstituted Benzene
Metasubstituted Benzene
Alkene
Alcohols, ethers
Alcohols, ethers
Alcohols,ethers carboxylic, acids
C-N
C-N
C=C
C=O
& esters
Amines
Amines
Aromatic
Aldehydes, Ketonecarboxylic
1807.36
Phenyl Ring
1878.73
Substitution
Phenyl Ring
Any
1952.03
Substitution
Cis-
16
17
18
19
2233.64
2320.44
2858.6
2928.04
RCH=CHR
CC
CC
C-H
Carboxylic
Alkynes
Alkynes
Alkane
Any
20
21
3028.34
3068.85
acid
C-H
Aromatic
Alkene
Any
22
23
3385.18
3688.02
Ring
C-H
O-H
Alkynes
H-Bonded Alcohol& Phenol
9
10
11
12
13
14
15
1448.59
1492.95
1612.54
1734.06
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40
30
1950.10
1878.73
1809.29
1737.92
543.94
484.15
827.49
426.28
1371.43
1263.42
1082.10
1022.31
902.72
754.19
700.18
20
2326.23
2235.57
80
%T
70
1608.69
1595.18
1498.74
1448.59
50
3068.85
3026.41
2928.04
2858.60
60
3688.02
3545.28
3421.83
10
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Liquid
1/cm
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Sr. No.
1
2
3
4
5
6
Peak Value
426.28
484.15
543.94
700.18
754.19
827.49
Type Of Bond
Iodoalkanes
Iodoalkanes
C-H
Aromatices
Aromatices
C-H
7
8
9
902.72
1022.31
1082.1
C-H
C-H
C-O
10
1263.42
C-O
11
12
13
14
15
16
17
1371.43
1448.59
1498.74
1595.18
1608.69
1737.92
1809.29
18
1878.73
19
20
21
22
23
24
25
26
27
28
1950.1
2235.57
23226.23
2858.6
2928.04
3026.41
3069.85
3421.83
3545.28
3688.02
CH3
C-H
C=C
C=C
C=C
C=O
Carboxylic acid &
derivatives
Carboxylic acid &
derivatives
C-H
C-N
CC
C-H
C-H
=C-H & =CH2
=C-H & =CH2
N-H
O-H
N-H
Types Of Compound
Any
Any
Alkynes
Monosubstituted Benzene
Metasubstituted Benzene
Phenyl Ring Substitution Bands
Alkenes
Alkenes
Alcohols, ether, carboxylic acids
& esters
Alcohols, ether, carboxylic acids
& esters
Isopropyl. t-butyl
Alkane
Aromatic ring
Aromatic ring
Alkene
Aldehydes
Acyl halides
Acyl halides
Phenyl Ring Substitution Bands
Nitriles
Alkynes
Alkane
Alkane
Alkene
Alkene
Amine
Alcohol& Phenol
Amide
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538.16
472.58
416.64
698.25
862.21
804.34
1604.83
2359.02
1730.21
1504.53
1454.38
1406.15
1095.60
75
1020.38
82.5
1261.49
90
2960.83
3689.95
3618.58
97.5
3410.26
112.5
%T
105
1950.10
67.5
60
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Solid
1/cm
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Peak Value
Type Of Bond
Types Of Compound
416.64
Iodoalkanes
Monosubstituted
472.58
Iodoalkanes
Metasubstituted
538.16
Phenyl Ring
Any
698.25
Phenyl Ring
Any
804.34
C-H
Phenyl Ring
862.21
C-H
Phenyl Ring
1020.38
C-N
Amines
1095.16
C-N
Amines
1261.49
C-O
Alcohols, ethers
10
1406.15
C-N
Amines
11
1454.38
C=C
Aromatic ring
12
1504.53
C=C
Aromatic ring
13
2604.83
C=C
Alkenes
14
1730.21
C=O
Aldehydes, Ketone
,carboxylic acids & esters
15
1950.1
CisRCH=CHR
C=C Asymmetric
compound
16
2359.02
C=N
Nitrile
17
2960.83
Alkyl
Methyl
18
3410.26
N-H
Amines
19
3618.58
O-H
20
3689.95
O-H
10
543.94
804.34
2920.32
2856.67
20
1454.38
30
738.76
711.76
40
1084.03
1006.88
985.66
902.72
1265.35
1367.58
50
3068.85
60
1732.13
2675.36
70
1643.41
2330.09
90
%T
80
1942.38
0
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Liquid
1/cm
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Sr. No.
1
Peak Value
543.94
Type Of Bond
Phenol Ring
Types Of Compound
Any
711.76
Substitution
Aromatices
Monosubstituted
738.76
Aromatices
Benzene
Monosubstituted
804.34
Aromatices
Benzene
Metasubstituted
902.72
Vinyl
Benzene
Monosubstituted
985.66
Vinyl
Alkene
Monosubstituted
7
8
9
1006.88
1084.03
1265.35
C-N
C-N
C-O CH3
Alkene
Amines
Amines
Alcohols,
carboxylic
10
11
12
13
1367.58
1454.38
1643.41
1732.13
CH3
C-H
C=C
C=O
ether,
acids
&
esters
Isopropyl. t-butyl
Alkane
Alkene
Aldehydes,
Ketonecarboxylic
14
1942.38
Cis-
15
16
17
18
19
2330.09
2675.36
2856.67
2920.32
3068.85
RCH=CHR
O-H
O-H
C-H
C-H
C-H
compound
carboxylic acids
carboxylic acids
Alkane
Alkane
Alkene
C.O.E.T.A/Chemical/2012
Page 95
536.23
472.58
424.35
723.33
2922.25
2850.88
30
20
802.41
1462.09
40
1091.75
1028.09
50
1261.49
1371.43
1710.92
2343.59
2663.78
60
3375.54
70
3691.88
3616.65
90
%T
80
2021.47
10
0
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Solid
1/cm
C.O.E.T.A/Chemical/2012
Page 96
Sr. No.
Peak Value
Type Of Bond
Types Of Compound
424.35
Iodoalkanes
Any
472.58
Iodoalkanes
Any
536.23
C-H
Alkynes
723.33
Aromatic
Monosubstituted
Benzene
802.41
Phenyl Ring
Metasubstituted
Benzene
1028.09
C-N
Amines
1091.75
C-N
Amines
1261.49
C-O
Alcohols, ethers
1371.43
CH3
Isopropyl. t-butyl
10
1462.09
C-N
Amines
11
1710.92
C=O
Aldehydes,
Ketone
2021.47
-N=C=O,-
Isocyanates,diimides
N=C=N-,C=C
& ketones
=O
13
2343.59
C=N
Nitrile
14
2663.78
C=O,C-H
Aldehydes, Ketone
15
2850.88
C=O
carboxylic acids
16
2922.35
C=O
carboxylic acids
17
3375.54
N-H
Amines
18
3616.65
O-H
Monomeric Alcohols
& phenols
19
3691.88
O-H
H -bonded Alcohols
& phenols
C.O.E.T.A/Chemical/2012
Page 98
542.02
468.72
719.47
896.93
802.41
2922.25
2852.81
10
1458.23
20
1095.60
1022.31
30
1261.49
1375.29
40
3072.71
50
1701.27
1645.33
2727.44
60
3695.73
3618.58
80
%T
70
2366.74
0
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Viscous
1/cm
C.O.E.T.A/Chemical/2012
Page 99
Peak Value
468.72
542.02
719.47
802.41
896.93
1022.31
1095.6
1261.49
Type Of Bond
Iodoalkanes
C-H
Aromatic
Phenol Ring
C-H
C-N
C-N
C-O
9
10
11
12
1375.29
1458.23
1645.33
1701.27
13
14
15
2366.74
2727.44
2852.81
C=N
C-H
carboxylic, acids &
Derivatives
Nitrile
Aldehydes & Ketone
Any
2922.25
Derivatives
carboxylic, acids &
Any
17
18
3072.71
3618.58
Derivatives
Aromatic Ring
O-H
Any
Monomeric Alcohols &
19
3695.73
16
CH3
C-N
N-H
C=O
Types Of Compound
Any
Alkynes
Monosubstituted Benzene
Metasubstituted Benzene
Phenyl Ring
Amines
Amines
Alcohols, ethers carboxylic,
O-H
phenols
H -bonded Alcohols &
phenols
C.O.E.T.A/Chemical/2012
Page 101
543.94
719.47
804.34
896.93
1097.53
2920.32
2856.67
20
1456.30
30
1008.80
1271.13
1703.20
40
3070.78
50
1645.33
2729.37
2673.43
1604.83
60
1373.36
70
3691.88
3624.37
%T
462.93
2322.37
2185.42
80
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Liquid
1/cm
C.O.E.T.A/Chemical/2012
Page 102
Peak Value
462.93
543.94
719.47
804.34
896.93
1008.8
Type Of Bond
Iodoalkanes
C-H
Aromatices
C-H
C-H
C-O
Types Of Compound
Any
Alkynes
Any
Phenyl Ring Substitution
Phenyl Ring Substitution
Alcohols, ethers carboxylic,
1097.53
C-O
1271.13
C-O
9
10
11
12
13
1373.36
1456.3
1604.83
1645.33
1703.2
CH3
C-N
C=C
C=C
C=O
14
2185.42
-N=C=O,
Derivatives
Isocyanates,diimides &
-N=C=N,
ketones
15
16
17
18
2322.37
2673.43
2729.37
2856.67
C=C=O
C=N
C=O
C-H
Carboxylic
Nitrile
Aldehydes & Ketone
Aldehydes & Ketone
Any
19
2920.32
acid
Carboxylic
Any
20
3070.78
acid
Aromatic Ring
Any
21
3634.37
O-H
22
3691.88
O-H
phenols
H-Bonded Alcohol& Phenol
C.O.E.T.A/Chemical/2012
Page 104
20
530.44
470.65
719.47
875.71
804.34
1097.53
2920.32
2850.88
30
1371.43
1599.04
40
1460.16
1261.49
50
1024.24
1795.79
3695.73
3618.58
60
2515.26
80
%T
70
2359.02
10
0
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Solid
1/cm
C.O.E.T.A/Chemical/2012
Page 105
Sr. No.
Peak Value
Type Of Bond
Types Of Compound
470.65
Iodoalkanes
Metasubstituted
530.44
Phenol Ring
Any
719.47
Aromatic
Monosubstituted
Benzene
804.34
Phenyl Ring
Metasubstituted Benzene
875.71
C-H
Phenyl Ring
1024.24
C-N
Amines
1097.53
C-N
Amines
1261.49
C-O
Alcohols,
ethers
1371.43
CH3
Isopropyl. t-butyl
10
1460.16
C-N
Amines
11
1599.04
C-H
Aromatic bonding
12
1795.79
C=O
carboxylic, acids
13
2359.02
C=N
Nitrile
14
2515.26
C=O
Saturated ketone
15
2850.88
C=O
16
2920.32
C=O
17
3618.58
O-H
18
3695.73
O-H
The residue obtained at 6000c is in coal form so we cannot do the FT-IR test of
residues of all three wastes obtained at 6000c.
Fig7:CALORIMETER
Fuels
1.Commercial fuels
Coal
Hard coal
Lignite beown coal
2.Petroleum products
Diesel
Gasoline/naptha
Kerosene
Jet fuel
Fuel oil
Natural gas
3.Biomass
Agricultural residues
Paddy straw
Rice husk
Mango leaves
Groundnut
Sugarcane
Wheaat straw
Cotton stalks
Maize stalks
Maize cobs
Bajra stalks
Gram straw
Masoor straw
Moong straw
Values(Kcal/gm)
5000
2310
6900
10800
10500
10300
10400
9600
8000 - 9480
3000
3040
3390
4200
3800
3800
4700
3500
3850
3950
3810
3980
4.Forestry residues
Wood wastes
Bark
2500 - 3850
2500 - 2850
5.Animal wastes
Cowdung
Cowdung cake
3290
3140
Table 34: Results for calorific value of product obtained at 450 0c.
C.O.E.T.A/Chemical/2012
Page 109
Sr. No.
Name of Product
(crude form)
Calorific Value
(Kcal/gm)
Polystyrene
16473.9
Polyolefines
17682.8
19377.2
From above tables we compare the different calorific values of standard fuel
product with our product. So we can say that our product values come near to
the petroleum product i.e. diesel.
C.O.E.T.A/Chemical/2012
Page 110
Special Grade
6
Grade -A
6
Grade B
12
Table35:Pour point
2. Smoke Point
Smoke Point is the maximum flame height in millimeters to which a diesel
will burn without smoking in a standard apparatus.
Test
Smoke point
Superior Grade
20
Inferior Grade
12
Table36:Smoke point
3. Aniline Point
It is defined as the temperature at which a liquid just becomes
completely miscible with an equal volume of aniline. Aniline is a organic
compound. The molecular formula is (C6H5N2).Aniline point of diesel is 600c.
Cetane Number
C.O.E.T.A/Chemical/2012
Page 111
Chapter7
C.O.E.T.A/Chemical/2012
Page 112
Cost Estimation
The primary intention to demonstrate is that waste plastics has great potentials for
resource such as fuel production. Such kind of project will first focus on technical,
environmental and social viability with its financial returns as the least priority.
From below table the operating costs involves feedstock cost, electricity cost, fixed
cost (auxiliary equipments).Feedstock is the waste plastic and which has a variable
cost and is very cheap among all other. Fixed cost involves the cost of reactor, muffle
furnace, cooling system and condensing system which is a one time investment cost.
The output will depend totally on the input. And in this case the input is waste plastic
which is available at 9-10 rupees per kg. And from 1 kg of waste plastic we can obtain
approximately 900ml of liquid fuel considering negligible losses. So considering the
addition of all other financial aspects we can approximately say that plastic fuel will
be around 25-30 rupees per liter. And the fuel available in market is 50 rupees per liter.
From this comparison it is observed that financially pyrolysis of waste plastic is cost
effective. Which will not only minimize the plastic waste problem but will also help to
save our depriving natural resources of petroleum.Table37:
Sr.No Particulars
1
Fixed cost(setup)
2
Operating
3
4
Cost(electricity)
Feedstock(Waste Plastic)
Coolant(ice)
Total
Quantity
1
3unit
Amount(Rs)
One time investment(45-50000)
15/-
1kg
0.5kg
6/4/25/-
Chapter 8
Result and Discussion
C.O.E.T.A/Chemical/2012
Page 113
Temperature
(oc)
Polystyrene waste
250
220
Olefinic waste
240
C.O.E.T.A/Chemical/2012
Page 114
Sr.No
Material
Tests
PS
HDPE
POLY
OLEFINES
Diesel
Flash point
55
69
40
>62
Fire point
60
81
56
>81
Density
(g/cm3)
0.8894
0.6251
0.4701
0.823
FTIR
Aromatic
compounds,
alkane,
unhydride,
ketone, esters,
aldehyde, amide
75%
saturated
hydrocarbons
(primarily
paraffins
including n, iso,
and
cycloparaffins),
and 25% aromatic
hydrocarbons
(including
naphthalenes and
alkylbenzenes)
Alkenes,
aromatic
ring,
nitriles,
alcohole,et
her,Metasu
bstituted
Benzene
-----
C.O.E.T.A/Chemical/2012
Page 115
Sr.No
Material
Tests
PS
HDPE
Flash point
53
Fire point
Density
(g/cm3)
FTIR
Diesel
72
POLY
OLEFINE
S
42
62
84
58
>81
0.8794
0.6713
0.4711
0.843
Monosubst
ituted
Benzene,
Alkynes,
Phenyl
Ring
Substitutio
n Bands,
Aromatic
ring,
Alcohols,
ether,
carboxylic
acids
&
esters
Monosubstit
uted
Benzene,
Alcohols,
ether,
carboxylic
acids
&
esters,
Alkane,
Aldehydes,
Ketonecarbo
xylic acids &
esters
Alcohols,
ethers
carboxylic,
acids & esters,
carboxylic,
acids
&
Derivatives,
Nitrile
75% saturated
hydrocarbons
(primarily
paraffins
including n, iso,
and
cycloparaffins),
and
25%
aromatic
hydrocarbons
(including
naphthalenes
and
alkylbenzenes)
19377.2
17682.8
10800
>61
in the residence time the liquid quantity obtained also increases.From both the studies
that is studies at two different temperature it is observed that the optimum temperature
required for the pyrolysis of polystyrene is 250C.
In case of olefins pyrolysis favors mostly the formation of paraffins.It is also seen
thar conversion increases with temperature resulting in decrease of aliphatic
content.And also the conversion increases with the increase in residence time.In
general the decomposition of polyolefin mixtures occurs roghly in the same range as
their virgin counterparts240C.However waste polyolefins may degrade at slightly
lower temperatures and achieve higher conversion rates.
In case of HDPE waste pyrolysisat 450C monosubstitued benzene,monosubstituted
alkenes,amines and carboxylic acid are found more with oter compounds while at
600C amines.monomeric alcohols,hydrogen bonded alcohols and ester groups are
found more with other compound.The optimum temperature at which the pyrolysis of
waste HDPE should be carried out is observed to be220C.
And after comparing the results of all the wastes with the standard table, properties or
results obtained from pyrolysis of HDPE waste are more likely matches with
properties of diesel.
By comparative study at two different temperature we can say that at 450C we get
higher volatile product and at 600C we get lower volatile product. By comparative
study of results of flash point, fire point, density, FT-IR and calorific value we are
concluding that this process yielding fuel near to diesel or just belonging to diesel
group.
THERMAL PYROLYSIS is most suitable technique to process plastic
waste.
ADVANTAGES OF PYROLYSIS
C.O.E.T.A/Chemical/2012
Page 117
9. Conclusion
C.O.E.T.A/Chemical/2012
Page 118
C.O.E.T.A/Chemical/2012
Page 119
REFERENCES
Books:
1. Mark, Bikales, Birger and Menges, Encyclopedia of polymesr science and
Engineering, volume 8, second edition, John Wiley and Sons publication, pg.no. 3999 & volume 7, second edition,p.g.no.156.
2. Dr. R. Chandra, Mr. A. Adab , Rubber & Plastic Waste CBS Publishers &
Distributors, Chapter 2&3, Page No.52-78.
3. J. A.Brydson, Plastic Material , second edition ,butter worth group, chapter 11, page
no.247 to 273.
4. B. K. Rao,A Textbook of Petrochemical Technology, first edition,page no 135-149
5. Project report on pyrolysis guided by Prof.N.R.Bhalerao, batch 2009-2010.
PAPERS:
1. Turning mixed plastic wastes into a useable liquid fuel S.L. Low, M.A. Connor and
G.H. Covey Department of Chemical Engineering University of Melbourne
Melbourne, Victoria 3010 Australia.
2. Converting Waste Plastics into a Resource Compendium of Technologies Compiled
by United Nations Environmental Programme Division of Technology, Industry and
Economics International Environmental Technology Centre Osaka/Shiga, Japan.
3. Thermolysis of waste plastics to liquid fuel A suitable method for plastic waste
management and production of value added productsA world prospective Achyut
K. Panda a,b,*, R.K. Singh a,1, D.K. Mishra b,2 a Department of Chemical
Engineering, National Institute of Technology, Rourkela, Orissa, India b Jagannath
Institute for Technology and Management, Parlakhemundi, 67 Suryanagar,
Bhubaneswar 751003, Orissa, India.
4. EnvoSmart Technologies overview waste plastic to diesel fuel
innovative environment technology.
C.O.E.T.A/Chemical/2012
Page 120
Laboratory
Liquid
C.O.E.T.A/Chemical/2012
Page 121
WEBSITES:
1.
2.
3.
4.
5.
6.
7.
8.
9.
www.envis.com
www.ekosvest.com
www.enviroliteracy.com
www.thermo.com
www.motherearthnews.com
www.biodiesel.org
www.greenstudentu.com/encyclopedia/recycling/plastic.
www.hubbertpeak.com/Hubbert/1956/1956.pdf.
www.wcaslab.com/tech/tbftir.htm.
C.O.E.T.A/Chemical/2012
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