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Project Title: Processing of 550 metric tons per day of polypropylene

into Diesel by catalytic pyrolysis

Contents

Project Description ............................................................................................................................... 2


Introduction: ......................................................................................................................................... 3
Literature Review: ................................................................................................................................ 5
Reaction Mechanism: ........................................................................................................................... 7
Product characterization of thermal and catalytic cracking: ....................................................... 8
Thermal cracking: ........................................................................................................................... 8
Catalytic cracking: .......................................................................................................................... 8
Selection of Process: ............................................................................................................................ 10
Incineration: ...................................................................................................................................... 10
Gasification: ...................................................................................................................................... 10
Pyrolysis process:.............................................................................................................................. 10
Selected Process:............................................................................................................................... 10
Process description: ............................................................................................................................ 11
Pre-treatment: .................................................................................................................................... 11
Pyrolysis process:.............................................................................................................................. 11
Separation: ........................................................................................................................................ 11
Purification:....................................................................................................................................... 11
Hazards identification: ....................................................................................................................... 13
Hazards: ............................................................................................................................................ 13
Precautions: ....................................................................................................................................... 13
Scope: ................................................................................................................................................... 13
Pilot and industrial plants: ................................................................................................................. 14
Conclusion: .......................................................................................................................................... 15

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Project Description

 OBJECTIVE:
The major objective of our project is to revise and implement the Chemical
Engineering concepts by designing the process of converting waste plastic (Poly
Propylene) in to Diesel.
 PURPOSE AND NEED:
The major purpose of this project is to control the wastage of plastics and make it an
environment and eco-friendly to improve our future life. Most of the plastics used in
Pakistan are non-biodegradable therefore they are harmful for the human health and
environment. A significant quantity of waste plastics is found in our oceans due to
which life underwater is affected. Our purpose is to synthesize fuel using waste
plastics as it is a need of hour.
 Requirements:
Degradation knowledge about different types of plastics especially hydrocarbon
based, and their properties are required to decide the capacity of a reactor, type of pre-
treatment necessary for the operation, the type of catalyst to be used, the reactor
material, the condenser material, and eventually the procedure after the treatment
 Methodology:
In this project first we draw a process flow diagram of pyrolysis process, then we will
apply energy and material balance. On the basis of energy and material balance, we
will design equipment such as reactor, distillation column, cyclone, gas scrubber and
heat exchanger.
 Business Goals:
Recycling of waste plastic turns out to be economically viable as it generates fuel
resources such as diesel, gasoline, etc. which are in high demand to produce energy
and also very cheap for the further operation.
 Benefits:
A major benefit for the conversion of waste plastic into fuel is that it can be used as a
fuel in our daily life. Also, it will be a cleaner-burning fuel due to low sulfur content
present in plastics, it will be an environmental friendly to dispose of plastics.

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Introduction:
The present pace of development is unsustainable without sparing of fossil fuels like
petroleum, natural gas or coal. The use of these fuels leads to intensely elevated greenhouse
gas emissions as well as environmental damage which have huge impact on ecosystem. All
these fuels contain constituents (carbon, hydrogen and oxygen) and other materials including
metal, sulfur, and nitrogen compounds. During the combustion process, different pollutants
like ash, sulfur oxides (SO2 and SO3), nitrogen oxides (NOx = NO2 + NO), and volatile
organic compounds are emitted which produce harmful effects on environment. So, we need
to depend on the sustainable energy sources as they are environment friendly. The conversion
of waste plastic into fuel is one of the best renewable energy sources for sustainable
development.
Raw Material:
According to the static data generated by Pakistan Institute of trade and development,
Pakistan consumes around 800 tons/day of polypropylene. Latest data is available in the
following table:

2016-17 2017-18

Products Quantity (MT) Quantity (MT)

Polyethylene 476062 544641

Polypropylene 4825432 524033

Acrylonitrile butadiene styrene 23855 25796


(ABS) copolymer

PVC, EVA 65292 86839

Total 1047752 1181309

Table 1: Polymers import in Pakistan1


The increase in population, industrial growth and urbanization leads the Pakistan towards the
generation of municipal solid waste (MSW)2. It has been reported that 48 Million tons per
year of MSW by weight is generated in Pakistan. The per day generation of MSW is 131500

1
pakplas.pk all pdf PAK PLASTIC WASTE ANUUAL REORT 2018f
2
Pakistan - Waste Management | export.gov ACCESSED 2019-11-04

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tons3. 9% of the total municipal waste contains waste plastic which is 11850 tons per day of
MSW. 20% of waste plastic comprises of Polypropylene (PP) which is 2370 tons per day.
14% of polypropylene is recycle in Pakistan while rest of the amount is disposed.

3
Plastic Pollution in the World's Oceans: More than 5 Trillion Plastic Pieces Weighing over 250,000 Tons Afloat
at Sea Marcus Eriksen, Laurent C.M. Lebreton et al. PLoS ONE, 9, 12, 12 2014

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Literature Review:
 This study is based on the energy recovery and feed stock recycling, was conducted
by Merve et al.,20174 in the Selcuk University, Engineering Faculty,
Environmental Engineering Department, 42075, Konya, Turkey.
This review mainly comprises on the topic ‘A comparative study on waste plastics
pyrolysis liquid products quantity and energy recovery potential’.
In this journal, the research focus was on the selection of the type of waste plastic
such as (LDPE, PET, PP, PS). In the process, plastic was washed with caustic soda
and processed in batch pyrolysis reactor by keeping the heating rate and other
parameters constant. After the pyrolysis process, C-10 to C-40 Hydrocarbons was
obtained having different calorific values measured and compared with fossil fuels.
From the results, PET and PVC yielded lowest oil fractions, while HDPE, PP, PS,
LDPE oils had higher oil fraction.

 This research was conducted by Ramli et al., 20165 on”production of liquid fuel
from the waste plastic using pyrolysis with refinery distillation bubble cap plate
column”, in the InstitutTeknologi, SepuluhNopember, Surabaya 60111,
Indonesia.
In this process, 500g of polypropylene(pp) was processed in the fixed bed reactor
under vacuum condition (-3mm H2O). Vacuum was created to minimize the presence
of oxygen in the reactor to avoid combustion.
After the pyrolysis, the 4-tray bubble cap plate column was operated by utilizing the
heat from the reactor. The distillation column was operated at the temperature ranging
500-650oC. The results of the process are given below:

Fuels Temperatures Fractions (wt.%)

88 wt.%
Tray I Kerosene/Diesel 600-650oC

Tray II Gasoline/Kerosene 580oC 63 – 84 wt.%

Tray III Gasoline 500oC 67 wt.%

Tray IV Charcoal

Table 2

4
A Comparative Study on Waste Plastics Pyrolysis Liquid Products Quantity and Energy Recovery Potential
Merve Sogancioglu, Gulnare Ahmetli et al..Energy Procedia, 118, 2017
5
Production of liquid fuel from plastic waste using integrated pyrolysis method with refinery distillation bubble
cap plate column Ramli Thahir, Ali Altway et al.Energy Reports, 5, 11 2019

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 This review was conducted by Mochamad et al.,6 2014 on “fuel oil production from
municipal plastic wastes in sequential pyrolysis and catalytic reforming reactors”,
Department of Mechanical Engineering, Janabadra University, Jalan TR
Mataram 57, Yogyakarta 55231, Indonesia.
They collected 3 types of the municipal waste plastic which were comprised on the
polyethylene PE (bag2), PE (bag1) and HDPE (high density polyethylene) processed
with and without washing and crushing. To conduct the process successfully, two
stage reactor using batch system was used. First one was the pyrolysis reactor and the
latter one was catalytic reforming reactor.
In the experiment, 1.6-2.6 kg of feedstock was fed to the pyrolysis reactor. The
pyrolizer and reformer was then heated up to the certain temperature. The catalyst
100gm was then fed to the catalytic reactor.7 The hydrocarbon gases and liquid fuel
produced at different temperature ranges from 500oC to 650oC, and different fractions
of liquid fuel was obtained. It could be gasoline, diesel or kerosene depending upon
their carbon content and operating temperature. The calorific value of these fuels was
almost same as fossil fuels.

6
Fuel oil production from municipal plastic wastes in sequential pyrolysis and catalytic reforming reactors
Mochamad Syamsiro, Harwin Saptoadi et al.
Energy Procedia, 47, 2014
7
Catalytic pyrolysis of municipal plastic waste to fuel with nickel-loaded silica-alumina catalysts
Ji Lin Wang, L. L. Wang
Energy Sources, Part A: Recovery, Utilization and Environmental Effects, 33, 21, 2011

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Reaction Mechanism:8
The degradation of polymer is also known as depolymerization. In depolymerization or cracking,
higher hydrocarbon polymers are break down into the low molecular weight hydrocarbons by the
application of heat. The general mechanism of thermal cracking is described as followed:

 Initiation occur at random or end-chain position.


 Second step is de-propagation in which olefinic monomers are released from primary
radical.
 The next step is hydrogen chain transfer reaction. It may be inter-molecule or intra-
molecule hydrogen transfer. In the result, olefinic species and polymeric fragments
are formed along with secondary radical which are formed by inter-molecule
hydrogen transfer reaction between primary radical and polymeric fragment.
 After hydrogen transfer, - cleavage or scission reaction in which -cleavage of
secondary radical leads to the formation of olefinic end chain and primary radical.
 The last step of the mechanism is termination. In this step bimolecular mode
termination either by coupling two primary radical or by disproportion of primary
macromolecule occurs
The general mechanism is followed:
1) Initiation step:
Random scission

End-chain scission

2) De-propagation:

3) Hydrogen chain transfer:


Inter-molecule

8
Feedstock Recycling and Pyrolysis of Waste plastics: Converting Waste Plastics into Diesel and Other Fuels
Edited by J. Scheirs and W. Kaminsky 2006 John Wiley & Sons, Ltd ISBN: 0-470-02152-7

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Intra-molecule

4) -cleavage:

5) Formation of branches:

6) Termination:
Bi-molecular coupling:

Disproportionation:

Product characterization of thermal and catalytic cracking:


The characteristics of product by thermal and catalytic cracking of heavy hydrocarbons are
followed:
Thermal cracking:
 High production of C1 and C2’s fraction in gas
 Less branched olefin production
 Due to high temperature some diolefins produce
 Gasoline selectivity is poor
 The oil product distribution is in wide range
 Production of Coke and gas is high
 Reaction is too slow compared with catalytic reaction

Catalytic cracking:
 High fraction of C3 and C4 in gas product
 The primary product is olefins and more branched by isomerization
 Gasoline selectivity is high
 Short distribution of oil products

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 By naphthene dehydrogenation and olefin cyclization aromatics are produced
 Larger molecules are more reactive
 Pure aromatics are not reactive
 By hydrogen transfer, paraffins are produced
 Some isomerization occurs

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Selection of Process:
In the modern development, different techniques of processing of waste plastic into energy
has been introduced. Some of them, are economical, environmentally friendly and feasible in
managing the waste plastic.
Following are some modern methods and techniques which are being utilized in world for the
processing of waste plastic:
Incineration:
Incineration is a process, in which direct burning and combustion of waste plastic is being
taken place for the recovery of energy and some useful hydrocarbon gases along with the flue
gases. The decomposition reaction takes place in fluidized bed reactor at high temperature.
Hydrocarbon gases are separated from flue gases and condensed which can be used as fuel.
Gasification:
It is a process, in which waste plastics is converted into syn gas, char and some water by the
heating of waste plastic at high temperature range 750◦C to 1000◦C with the application of
steam or air. Products of gasification process are mainly syn gas which is used as gaseous
fuel.
Pyrolysis process:
The process in which waste plastic is being converted mainly into liquid oil with lower
fraction of gases and char. The process is takes place in the absence of oxygen with the
temperature range 450◦C to 800◦C. At this temperature range thermal cracking of waste
plastic is takes place. Gas produced in the process is condensed into liquid oil. There are two
main types of pyrolysis process which are catalytic pyrolysis and thermal pyrolysis. In
catalytic pyrolysis temperature is reduced which gives narrow range of liquid oil distribution
in comparison to the thermal pyrolysis.
Products Thermal pyrolysis Catalytical pyrolysis

Oil ~76.7% ~81.4%


Gas ~7.3% ~9.6%
Char and CaO ~16% ~9%

Table 3: comparison between catalytic and thermal pyrolysis

Selected Process:
On the bases of above discussion, the process selected for FYDP is catalytic pyrolysis to
produce 550 metric tonne per day fuel oil as main product from waste plastic.

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Process Flow Diagram:9
Pre- Treatment

Waste plastic conveyor


washer Fuel gas

Gas Holder
Gasoline + Gasoline + Naptha
Cooled water condensor Naptha +
crusher Kerosine

Kerosine
Liquid Oil
Distillation Distillation Column 3
dryer Column 1
Gas Scrubber Diesel

Pump

Melter reactor Fuel oil +


Diesel

Feed tank Fuel Oil


Fluidized bed Reactor cyclone
(350 – 450 oC)
Charcoal
Distillation Column 2
N2 tank compressor

Process description:
Pre-treatment:
Waste plastic is required to be pre-treated. For this, waste plastic is washed to remove
contamination and impurities. The second stage of pre-treatment is to reduce the size of
plastic up to the 6-60 mm, on the wet bases. After washing, the reduce sized plastic is dried
to remove moisture content. The final step of pre-treatment is to melt the dried plastic at the
temperature ranging between 150◦C to 180◦C.
Pyrolysis process:
The melted feed is fed into the fluidized bed reactor in the absence of oxygen at the
temperature range of 350◦C to 450◦C with Silica Alumina containing Zeolite as catalyst. The
thermal and catalytic cracking takes places simultaneously to break down the waste plastic
melted material into vapors, liquid and solid(char).
Separation:
In the reactor, three types of products are produced. The gas produced goes to the scrubber,
where solid particles are separated from gas and collected in charcoal storage. The scrubbed
gas is condensed into liquid oil in water-cooled condenser. The un-condensable gas is stored
in gas holder. On the other hand, solid particles are separated from liquid oil, produced in
reactor by cyclone. On the principle of centrifuge, liquid oil and charcoal is separated in
cyclone.
Purification:
Purification of liquid oil is done in a series of distillation column. The crude liquid oil is
separated into two fractions, the top product contains Gasoline, naphtha, kerosene and gas, is
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Conversion technology: A complement to plastic recycling, Schematic courtesy of Cynar Plc, 2011

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separated and gas is collected in gas holder while the bottom product contains fuel oil and
Diesel. The bottom product undergoes second distillation process. The top product of second
distillation column is Diesel and bottom product is Fuel oil. The top product of first
distillation column processed in third distillation column. In the third distillation process
stage, top product contains Gasoline and naphtha. The bottom product is kerosene.

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Hazards identification:
Hazards:

 In pyrolysis plant, safety became a major issue to secure life and environment.
Because numerous peoples faced serious injuries even death due to explosion in plant
during pyrolysis process. In most cases, the hazards associated with pyrolysis plant
caused by toxic or explosive gas emission, because hydrocarbons produced by
pyrolysis are highly explosive if they come in contact with oxygen. Explosions can be
caused leakage of combustible gases from waste treatment chambers. All pyrolysis
materials vary in the comparative toxicity of their thermal degradation products,
depending upon the conditions of degradation and human exposure.
 In 2012, a Russian pyrolysis plant faced an explosion due to pyrolysis gas leakage and
carbon monoxide poisoning which results in eight deaths and eight people poisoned
due to carbon monoxide gas.
 In 1998, failure in plant occurs in Germany pyrolysis plant. The pyrolysis gas was
released into air, which brought some surrounding communities in difficult condition.
 And in the beginning of this year, an explosion occurs in Finland, because the process
gas emission led to an explosion. The gas emission occurs due to nitrogen route
blockage and opening of hatch due to fluctuation of liquid levels.
Due to this leakage explosion occurs and the toxic gases covered the whole area.
 Another explosion occurs in Panchkula (India) in 2011. It was due to high pressure in
the reactor and causes serious injuries to plant operator and other workers.10
 In 2014, pyrolysis plant of Indian manufacturing company was exploded because the
boiler was flung up to 30 meters.
 In 2014, a pyrolysis plant of a Russian company in budennovsk was exploded because
the aluminum heat exchanger was depressurized, and fire accrued in gas separation
unit.

Precautions:

 The issue of gas emission can be resolved by multistage gas purification system,
where the gas is scrubbed of acid components.
 The issue of controlling pressure and temperature can be resolved by monitoring all
process parameters by automatically controlled system control system is used to
control process parameters in pyrolysis plant. In addition, the nitrogen ramp is
designed for emergency shutdown and too controls the pressure vacuum conditions, if
oxygen leak into reactor... The pressure in the chamber is also controlled by
temperature rise rate which should be 2-3°C.

Scope:
The scope is to minimize the use of fossil fuels which are harmful for the environment by
using synthetic fuel as substitute, and utilization of waste plastic into useful energy source.
Main outcome is to produce less toxic fuel which gives no sulfur content and minimum
Nox’s and Ox’s, and a fuel which is economically stable beneficial for the environment.

10
adminwppnet. (2017, January 20). Automatic PLC Control System of Waste Tyre Pyrolysis Oil Plant.
Retrieved October 29, 2019, from Waste Plastic/Tyre Recycling Pyrolysis Plant For Sale website:
https://wastepyrolysisplant.net/automatic-plc-control-system-waste-tyre-pyrolysis-oil-plant.html.

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Pilot and industrial plants:
Some feasible processes are reviewed as follows:11
1) Hamburg University, Ebenhausen Germany:
A pyrolysis plant was built at Edenhausen with the capacity of 5000 tonnes per year.
The polyolefins contain PE/PP were pyrolyzed in to fuel of composition typically
51% (m/m) gas, 42% (m/m) liquids and balanced solid. Under present conditions,
profit and economic viability was not satisfactory at the small-scale production
.
2) BASF, Ludwigshafen:
BASF, Ludwigshafen is a world’s largest Chemical Complex located in Germany.
The BASF feedstock recycling process was designed in 1994 in Ludwigshafen of
capacity of 15000 tonne/yr. the feedstock was mixed packaging plastic which was
available in the capacity of 750,000 tonne/yr. the pilot plant then erected a full-scale
industrial plant of production capacity 300,000 ton/yr.
In this plant, waste PVC is converted in to petrochemical products in three stages.
In the first stage, feedstock is pretreated at 300˚C, HCL gas is evolved which is
absorbed in water washer. The pre-treated feedstock is fed to the second stage in
which liquification and cracking of PVC plastic occur at 400˚C in Tubular cracker
reactor. The cracked feedstock is went to the third stage of process which is a
separating stage. At this stage, naphtha, aromatic fractions and high boiling oils are
separated. About 20-30% of gases and 60-70% of oils are produced which is
subsequently separate in Distillation Column
The products produced in this industry are;
 HCL gas which is processed in to the hydrochloric acid
 Naphtha which is to be converted in to monomers
 Various monomers to produce virgin polymers
 Process residue containing 5% minerals and metals
 High boiling oil

3) BP, Grangemouth, Scotland:


In early 1990s, BP Chemicals Scotland first tested a technology for plastic recycling
using Fluidized bed reactor for mixed waste packaging. This pilot scale plant was
erected to a joined project (POLSCO)of BP Chemicals, VALPAK and Shanks &
McEwan in 1998. The project capacity was 25,000 tonne/yr. as a remedy to the
expected UK shortage in recycling capability.
In the process pre-treated feedstock (size reduction and removal of non-plastic) is fed
to the Fluidized bed Reactor, operating at 500˚C temperature in the absence of air.
By thermal cracking of PVC, HCl gas is produced which leads to the production of
HCl acid production. So, the HCl hot gas produced is neutralized by contacting with
lime which results CaCl2 which is then landfilled. The light hydrocarbon pyrolysis gas
is then compressed, cooled and is used as fuel gas for reactor. Through this, plant can
run self-sufficient heating mode. The products of this process are heavy fraction of

11
A. Tukker (TNO-STB), Ing H. de Groot (TNO Industrial Research), Ir.L. Simons(TNO-STB), Ir. S. Wiegersma (TNO
Industrial Research), Chemical Recycling ofPlastics Waste (PVC and Other Resins), TNO-Report STB-99-55 Final,
1999, EuropeanCommission, DG III

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hydrocarbons, becomes wax at 60˚C. The heavy and light fraction is produced 85%
by weight in the product. The gas produced have fraction of ethylene, propylene and
only 15% methane. The solid is separated as a waste product.

Conclusion:
It is concluded that pyrolysis is the most efficient process rather than other thermal methods
for the conversion of waste plastic into fuel it is confirmed through literature review which
includes different methods and catalytic pyrolysis is the most promising. However, the
product quality can be achieved by adjusting operating conditions. Main benefit of catalytic
pyrolysis it provides low operating conditions and high yield of liquid fuel with less emission
of Nox’s and Sox’s. Since every country is affected by plastic waste and is available in
millions of tons, by this process waste can be utilized in an effective way.

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