A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire

into Liquid Fuel and Useful Chemicals

By Ben Bahavar, Ph.D., Nerac Analyst

In many aspects, the development, refining, and commercialization of plastic-to-liquid fuel is a

classic example of the market forces being the main determining factor in adoption of a
technology that is fairly well-developed. This article provides an overview of the recent efforts to
produce a more efficient plastic/rubber-to-liquid fuel technology in order to make it a more
commercially viable venture. Patent and non-patent activity worldwide is examined, the main
drivers of technology are identified, and their unique contributions are briefly described.

The drive behind the technology

Local and municipal jurisdictions are constantly exploring ways to deal with plastic (and
rubber/tire) waste and promote reuse, recycling, and recovery of plastic waste over landfilling.
Worldwide plastic production soared from 1.5 million m.t./year in 1950 to 245 million m.t./year in
2008, a trend that is expected to continue [2013 European Commission study on the impact of
plastic waste]. Also of concern to the global community of nations is the plastic waste that is
estimated to form 80% of the enormous waste patches in the Atlantic and Pacific oceans – this
causes sea species to suffer from entanglement or ingestion of released plastic additives that can
act as endocrine disruptors.

A brief description of the technology

The production of gasoline-like fuels suitable for internal combustion engines (e.g., gasoline,
diesel) via catalyzed or non-catalyzed thermal decompositions of waste plastic has been known
for decades. The process is generally known as pyrolysis. Conventionally, pyrolysis implies a
process in which organic substances are reduced or cracked by subjecting a material to heat in
the absence of oxygen. The pyrolytic reactions are endothermic, i.e. they demand a delivery of
heat to a reactor. pyrolytic cracking is carried out in absence of oxygen in order to prevent
combustion as a potential reaction pathway.

Typically, the pyrolysis products are comprised of solids, oily liquid and vapors containing both
valuable hydrocarbon gases as well as various contaminants to be removed. In the case of tires,
the pyrolytic process reduces scrap tires into three product streams: an oily liquid, a gas, and
carbon char (PyroChar). A related decomposition process to pylolysis is gasification whereby coal
or biomass is heated under reduced oxygen levels, and the product is synthesis gas (SynGas,
consisting mainly of H2 and CO) that is utilized to produce fuels and platform chemicals via the
Fischer-Tropsch process.

High-level overview on recent patent activity

The following Table depicts 14 inventions (1981-2015, mostly since 2009) representing some of
the major improvements on the pyrolysis process to produce oil/fuel from waste plastic and scrap
tire/rubber. This is followed by a discussion that also incorporates relevant non-patent
information.

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A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire into Liquid Fuel and Useful Chemicals 2

Patent/App Year Assignee Title Technology

Number
US2015 2015 JBI Inc. System and Solid waste plastics are processed by melting
o o
001061 (Plastic2oil) process for (250-340 C), pyrolysis (340-445 C),
converting plastics vaporization, and selective condensation,
to petroleum whereby final in-spec petroleum products are
products produced (diesel, gasoline, furnace fuel,
kerosene, propane, butane, ethane or methane).
US8927797 2015 Natural Method for Waste plastic (HDPE, LDPE, PP, PS) melted in
State converting waste an aerobic atmosphere, thermally decomposing
Research plastic to lower- the plastic melt, adding cracking catalyst to the
Inc molecular weight melt, distilling at least a portion of the mixture
hydrocarbons, whereby a liquid hydrocarbon fuel/distillate is
particularly produced (gasoline & diesel, C3 to C27).
hydrocarbon fuel
materials, and the
hydrocarbon
material produced
thereby
US2014 2014 Black Bear Method for Scrap rubber, in particular tires undergo pyrolysis
o
371385 Carbon obtaining a carbon (630-670 C), the resulting char material is milled
B.V. black powder by to carbon black powder (60-98 percent carbon
pyrolyzing scrap black, less than 2.0 weight percent of volatiles,
rubber, the carbon and 0-30 weight percent of silica) - carbon black
black thus obtained powder is used as a filler or a reinforcing agent in
and the use thereof a rubber composition, an ink, a paint, a bitumen,
a thermoplastic composition or a thermoplastic
elastomer.
o
US8344195 2013 J. Process for Pyrolysis (330-400 C) of plastic waste (PE, PP,
Srinakruang producing fuel from PS), the resulting liquid is first subjected to a
(Thailand, plastic waste semi-batch catalytic cracking reaction over a
Individual material by using dolomite catalyst to obtain high quality oil for fuel
Inventor)
dolomite catalyst (mainly light and heavy naphtha).

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A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire into Liquid Fuel and Useful Chemicals 3

Patent/App Year Assignee Title Technology

Number
US8425731 2013 Advanced Pyrolysis process Shredded tires are fed constantly into the
Pyrotech for decomposing pyrolysis vessel while the by-products of the
SDN BHD rubber products pyrolysis are continually discharged – the waste
tire particles fed into carbonizing reactor are
conveyed through the reactor by a continuously
rotating drag chain conveyor that travels bi-
directionally in a continuously loop in transfer
cylinders that operate in a partial vacuum
(oxygen is below its stoichiometric level to
prevent combustion). As the waste tire
chemically decomposes through a pyrolysis
process inside the reactor, oil vapor, referred as
second by-product, and a synthesis gas
(SynGas) are recovered from the waste tire
particles while the waste tire is conveyed through
the first transfer cylinder leaving small a quantity
of partially decomposed waste tire, carbon black,
referred as fifth by-product and the remaining
steel wire to be transferred through the second
transfer cylinder.
US2012261 2012 Cynar Conversion of pyrolysis in an oxygen-free atmosphere (240-280
o
247 Plastics waste plastics C) to provide pyrolysis gases followed by
Recycling material to fuel conversion to diesel and kerosene
Ltd.
o
US7959890 2011 RIPP Method of Tires are shredded and pyrolyzed (450-550 C)
Resource reclaiming under an anaerobic environment to produce a
Recovery carbonaceous char, volatile organics and the char are removed
Corp. materials from from the reaction chamber, the char is cooled in
scrap tires and a second anaerobic environment, metal and
products derived textile components (steel & fiber cords) are
therefrom removed to obtain pyrolytic carbon black which is
milled into particles of 325 mesh size or smaller,
and utilized in a polymerization process that
produces recycled rubber.
US7758729 2010 Agilyx System for The plastic material is placed in a treatment
o
Corp. and recycling plastics chamber and heated to 270-375 C that results in
Plas2Fuel pyrolytic cracking in absence of oxygen so as to
Corp. prevent combustion as a potential reaction
pathway from occurring. A vacuum removes
vapor (pyrolyzed inorganic species and gaseous
organic species) from the chamber – the
chamber is heated in incremental steps – the
vapor from pyrolytic cracking is contacted with a
pH buffered aqueous media resulting in
condensation of gaseous organic species
contained within the vapor. Chlorine and bromine
are separated from the oil end-product.

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A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire into Liquid Fuel and Useful Chemicals 4

Patent/App Year Assignee Title Technology

Number
US7626061 2009 MPCP Method and Waste polymeric material (scrap tires, rubber,
GmbH apparatus for polyurethane) are turned into valuable liquid
continuous chemicals and/or liquid fuels. Decomposition
decomposing process is carried out under moderate
o
waste polymeric temperatures (less than 850 C) and atmospheric
materials pressure in the presence of air and a feed of
liquids containing oxygen. This continuous
process is characterized by the low residence
time (3-25 minutes). The liquid containing
oxygen is acetone, methanol, ethanol, water or
mixtures thereof. At least one of hydrogen,
carbon monoxide, a gaseous hydrocarbon and
carbon is also recovered in this process. Liquid
oil and solid, oil free carbon is also recovered.
US5811606 1998 Plastic Process and Waste plastics (PE, PP and PS) and a catalyst
Advanced equipment for are mixed into a reactor for catalytic cracking
o
Recycling treatment of waste reaction (280-480 C) removing the solid
Corp. plastics impurities in the generated vapor, condensing
the vapor in condenser, and returning the non-
condensable gas to be burnt in the heating
furnace, distilling and separating the condensate
to obtain gasoline and diesel oil which will be
stabilized to get high quality gasoline and diesel
oil.
US5821396 1998 Fabspec, Batch process for A pyrolysis batch process is described for
Inc. recycling recycling scrap tires and plastics (ABS,
hydrocarbon polystyrene and other non-chlorinated
containing used thermoplastics) so as to obtain useful light oil and
materials fuel gases. Used tire cuttings are loaded into a
rotatable reactor which is closed, evacuated,
rotated and heated until exothermic reaction is
initiated.
US5414169 1995 Mazda Method of obtaining Thermal cracking of waste plastic/rubber
Motor hydrocarbon oil followed by acid catalysis
Corp. from waste plastic
material or waste
rubber material and
apparatus for
carrying out the
method
o
US4515659 1985 Ford Motor Pyrolytic Pyrolysis under nitrogen at 400-700 C and in the
Co. conversion of presence of one percent basic salt catalyst
plastic and rubber
waste to
hydrocarbons with
basic salt catalysts
o
US4251500 1981 Bridge- Process for Hydrocracking (350-500 C) under a hydrogen
stone Tire hydrocracking a partial pressure of 100-300 atm. Waste rubber
waste rubber such as used tires, used conveyor belts, used
hoses etc.

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A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire into Liquid Fuel and Useful Chemicals 5

What is the patent activity telling us about the challenges and the opportunities?

A review of the full-text for the above patents point to some of the major drawbacks or challenges
encountered in commercial-scale processes: A) chlorine/halogen removal when halogen-
containing polymeric materials (e.g., PVC, PTFE) are among the plastic wastes, B) heat gradients
due to poor heat conductivity of plastics, resulting in char accumulation at heat transfer surfaces,
and C) economics, varying from high catalyst costs/consumption to high energy consumption.
The object of the various inventions is to remedy one or more of these drawbacks.

Another challenge identified as an impetus for the above inventions is the need for the continuous
operation as opposed to the batch mode so as to enhance the economic viability of the
conversion process. It should be noted that the continuous operation mode for scrap tires is much
more complicated than the continuous processing of other polymeric wastes because of a
significant content of carbon (and steel) that cannot be completely converted into gaseous or
liquid products and, therefore, should be permanently removed out of a decomposition reactor.

The current reality and opportunities

As indicated at the outset of this article, the well-established pyrolysis process is further improved
and is being improved, but the market adoption has been elusive. As indicated in one of the
above inventions, some early commercial installations in Europe were short-lived for economic
reasons, but commercial installations continue in Japan, and other countries. It is interesting to
note that the three earlier patents (1981-1995) in the above Table are assigned to Bridgestone
Tire, Ford Motor Company, and Mazda Motor Corporation. However, these patents do not seem
to have been commercialized in any significant manner.

Even more revealing about the lack of commercial viability of this technology is the
announcement in 1994 by BP Chemicals that it had put together a consortium of European
petrochemical companies to help develop its polymer cracking technology [Miller, 1994, “Industry
Invests in Reusing Plastics”]. Petrofina, DSM, Elf-Atochem, and Enichem were said to have
participated in a pilot-plant at BP’s Grangemouth site in Scotland. Despite the very promising
results from this pilot plant with a capacity of 50 kg/hr plastics waste, and despite a slated 2001
expansion to a demonstration plant by the consortium with a capacity of 25,000 m.t./year (a $30-
40 million investment), we could not find any evidence of continuation of this high-profile effort.

Not all the news on commercialization of this technology is gloom! Indeed, two of the patent
assignees in the above Table have been running commercial operations over the past few years:
Plastic2Oil (Buffalo, NY – a 2015 patent assigned to JBI Inc.), and Cynar (Ireland – a 2012 patent
assigned to Cynar Plastics Recycling Ltd.). There are also established pyrolysis operations in
Asia. For instance, a joint venture between a Malaysian company and a South Korean company
is said to be in operations since 2008 with a capacity of 120 m.t./year. This commercial plant was
designed for scrap tire being broken down into carbon black (30%), recovered oil (50%), and non-
condensable flammable gas and steel wires (10% each).

The only constant in this technology space is the variability of market forces. For instance, the
tipping fee for tires (the cost to the transporter for tipping his truck’s contents at a disposal site)
can range from $10/ton to $110/ton depending on the jurisdiction – the tipping fee at a Nevada
landfill was at some point so low that the State had no tire processing or recycling/diversion
industry. In recent years, the uncertainty in permitting the plants to burn tires (tire-derived-fuel,
TDF) as well as lack of experience with TDF, has retarded the U.S. implementation of TDF. For
instance, a TDF utility plant in Sterling, Connecticut had to shut down in 2013 after 22 years in
operation because the State modified its regulations on the definition of renewable energy. Thus,
various factors can make the price and supply of scrap tire to be quite volatile, and this further
clouds the prospect of long term planning for adoption of pyrolysis technology.

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A Patent Review on Pyrolysis of Waste Plastic and Scrap Tire into Liquid Fuel and Useful Chemicals 6

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About the Analyst

Ben Bahavar, Ph.D.

Ben Bahavar, Ph.D., is an experimentalist researcher with multidisciplinary training and 17 years
of experience in applied chemistry, semiconductor materials, and chemical engineering. His
analyses help companies assess new applications of products and processes, seek solutions to
technical problems, and perform feasibility studies. Before joining Nerac, Dr. Bahavar was a
research engineer at University of Toronto and Clarkson University, where he earned his doctoral
degree in chemical engineering. While at Clarkson, he introduced an innovative method of
producing silicon carbide thin films with enhanced purity and without sacrificing growth rate. At
University of Toronto, in a collaborative research project with Environment Canada, he developed
an innovative application of atomic force microscopy (AFM) for surface and sub-surface analysis
of atmospherically derived organic films on impervious surfaces. He also has industry experience
as applications consultant and project manager at WS-Technologies and Yekan Design &
Engineering.

Credentials

 Ph.D., Chemical Engineering, Clarkson University

 M.S., Chemical Engineering, University of Maine
 B.S., Chemistry, SUNY at Stony Brook

About Nerac
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food and nutraceuticals, medical device, engineering, energy and advanced materials.

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