HYDROTHERMAL LIQUEFACTION OF SCRAP TIRES FOR LIQUID FUEL

PRODUCTION
CHAPTER 2: REVIEW OF RELATED LITERATURE
2.1 RELATED LITERATURE
2.1-1 RUBBER TIRES CHEMICAL COMPOSITION
The composition of tires is 85% carbon, 10-15% fabric materials and 0.9-1.25 % sulfur,
with elemental analysis of 85.4% carbon, 7.7% hydrogen, 0.5% nitrogen, and 2.7% sulfur. Tires
are composite of synthetic rubber (polystyrene and polybutadiene) natural rubber (polyisoprene),
antioxidants, plasticizers, antizonants, and additives such as carbon black and fabric, and n-
alkanes, n-alkanoic acids, methyl n-alkanoates, phenolic antioxidants, resin acids, hopane
biomarkers (fossil fuel tracers), and an unresolved complex mixture (UCM) of branched and
cyclic compounds. Having this composition of large carbon content, scrap tires is a very potent
source of oil through conversion technologies.
2.1-2 WASTE TIRE PRODUCTION
Various studies quantify the global waste tire problem at between 1 billion and 1.8 billion
used tires disposed of worldwide each year. This represents approximately 2-3% of all waste
material collected. The estimated data showed that globally in each year, approximately 1000
million tires are not suitable for further use or retreading. European Tyre and Rubber
Manufacturers’ Association (ETRMA) estimated that around 65% of the general rubber goods
production is dedicated for automotive sector (e.g. tires, wiper blades, seals, hoses
seatbelts, gaskets, insulators, etc.) [4]. Gerrard and Kandlikar performed comprehensive analysis
of materials used in a passenger vehicles and showed that tires are 3.5 %wt., while the other
rubber goods are 1.6 %wt. This indicates that the mainstream of waste rubbers are end-of-life
tires. The estimated data showed that globally in each year, approximately 1000 million tires are
not suitable for further use or retreading. According to predictions, up to 2030 the number of
waste tires generated to the environment will increase to 1200 million tires/per year. Assuming
that the predicted data are correct and development of rubber recycling will held the current
relatively low level, this means increase by 20% within next 10 years.
In the Philippines as of 2012, a data from Department of Transportation and
Communication recorded a total of 11,857,064 registered vehicles from which 2,684,760 or 22%
of this vehicles are from NCR. From this data, it was estimated that Philippines produces 4
million waste tire per year and and 0.88 million of this scrap tires is produced in NCR.
2.1-3 DANGERS OF INCREASED NUMBERS OF UNRECYCLED SCRAP TIRES
Scrap tires are inherently non-biodegradable, resistant to photochemical decomposition,
abrasion, and corrosion (Chen et al., 2019a; Chen et al., 2019b; Okoye et al., 2021). They were
generally landfilled or directly burned. Landfill may generate leachate, which can destroy the
soil and breed bacteria. During combustion, the high concentrations of N, S, halogen elements,
and heavy metals in tires will be released into the atmosphere with high-temperature flue gas,
causing serious air pollution (Peng, 2017; Bockstal et al., 2019).Increasing number of waste tires
are serious threat to the natural environment and human health. Illegally dumped or stockpiled
waste tires are potential risk of uncontrolled combustion. Fire of waste tire rubber resulted in
emissions of sulfur oxides, polycyclic aromatic hydrocarbons, fine particulates and other
hazardous compounds. As a consequence, risk of cancer is higher for population living near to
illegal waste tire dumps and also selected recycling rubber plants, especially those based on
prototype lines without strong basics in studies conducted at laboratory scale. Moreover, illegal
disposal of waste tires can collect stagnant rain water pools in their curvy shapes. These
conditions enhance the leaching of toxic compounds (e.g. heavy metals) from waste rubber,
which pollutes groundwater and have negative impact on aquatic organisms. High humidity
inside disposed tires also creates ideal conditions for breeding grounds for rodents and
mosquitoes, which can carry various diseases.
2.1-4 WASTE TIRE MANAGEMENT
Dynamic development of the automotive industry and the growing number of various
vehicles generate demand for the global production of tires. Simultaneously, high performance of
tires cause serious problems with further management and recycling of end-of-life tires.
Therefore, searching for novel, environmentally-friendly and cost-effective rubber recycling
methods is currently one of the biggest environmental challenges in the 21st century.
Nowadays, common method for waste tires management is energy recovery, where
whole or scrap tires are used as alternative fuel in cement kilns, paper mills, or power plants. The
newest statistical report on the management of end-of-life tires published by ETRMA showed
that in 2018 around 91% of waste tires in the European Union countries, as well as Norway,
Serbia, Switzerland and Turkey were collected and properly managed through material recycling
(56.4%) and energy recovery (34.9%).
It is worth to mention that in the statistical data presented by ETRMA, material recycling is
mainly grinding/shredding of waste tires, which in 2018 was the most popular solution among
various recycling methods of end-of-life tires. The shredding process includes the production of
the so-called “chips” commonly used as alternative fuel (energy recovery). Other disturbing data
presented by ETRMA, points increase the level of unknown utilization of waste tires in 2018
(318 800 t) by 12% comparing to value from 2017.
Above mentioned data confirm that waste tires management is a global environmental
problem and a huge challenge for scientists and industry representatives. Therefore research
works focused on material recycling technologies for waste tires are fully justified.

In the Philippines, the Philippine Rubber Industries Association’s (PRIA) objectives does
not include scrap tires management. There is no particular association or agency in the country
that handles and manages scrap tires and in recycling these wastes. This a very alarming situation
which implies that recycling means and technologies to convert scrap tires to useful products is
crucial in the country.

2.1-5 HYDROTHERMAL LIQUEFACTION (HTL)

Hydrothermal liquefaction which also known as hydrous pyrolysis is a thermal
depolymerization technique that reduces complex organic materials into light crude oil. It is a
process in which the macromolecules making up the biomass are hydrolyzed or degraded by
means of water at average temperatures and high pressures. This process is usually carried out in
temperature ranges between 280°C and 370°C and pressures that are in the range from 10 to 25
MPa .Hydrothermal liquefaction (HTL) converts biomass into liquid fuels in the presence of
water or water-containing solvent/cosolvent and a catalyst. It differs from ordinary pyrolysis in a
way that it uses water as the key element in the process. It also operates at lower temperatures
and efficient. It consist of two thermal treatments; the first one being the hydrothermal treatment
which “cook” the feedstock and the second being the thermal cracking. In between the
treatments is the flash evaporation to separate the water from the organic soup. Energy released
from the flashing water is used to heat the first treatment. The gases produced in the second
treatment is burned to heat the second reactor. By this way, energy is conserved and the process
is efficient.
HTL technologies are focused on increasing the yields of biocrude production by the reduction
of processing time as well as on the minimization of cost for the development of an environment-
sustainable process. Earlier research on biomass HTL has been reported in both the batch and
continuous modes for the processing of different types of biomass feedstocks. However, for an
efficient and larger scale, a continuous HTL process design is required that is far better than
batch systems for large-scale commercial production. 
HTL, also known as hydrous pyrolysis, is a very flexible technology as far as various types of
feedstocks are concerned. HTL converts a wide variety of biobased and waste feedstocks such as
woody biomass, industrial wastes, food wastes, swine manure, algae, arborous crops, various
wastes from the forest industry, and so on. During the HTL process, biomass is directly
converted to biocrude in the presence of a solvent and in some cases catalysts at temperatures
lower than 400°C. Earlier studies in the past have been carried out in small-scale batch type-
reactors with slow heating rates and long residence times. In this context, in order to become
more efficient, feasible, and chemically controllable research in continuous system reactors is
required. Pedersen et al. reported that a continuous flow reactor yields a significant amount of
heating values. Elliot et al. also stressed the potential of introducing continuous flow reactors
rather than the conventional batch process for higher scale processing of various waste
biomasses and higher yields of HTL products.  The wet manure and sewage sludge feedstocks
have not been processed in continuous systems, although results from batch systems are
promising for their application in continuous systems.
2.1-6 ADVANTAGES OF HYDROTHERMAL LIQUEFACTION
This process has an advantage over the rest of depolymerisation techniques since it uses water
that is found in abundance, low cost, and eco-friendly. Furthermore, the separation of product
liquid oil from water is easy and inexpensive. This conversion process has been employed on
industrial scale to convert the agricultural organic waste into valued products like fuels,
fertilizers, and other chemicals. However, the yield of liquid oil achieved is high as compared to
other by-products. Furthermore, the oil produced by hydrous pyrolysis shows similar
characteristic as naturally occurring crude oil. In addition, one of the most essential advantages
of HTL for sludges and manures is the effect of sterilizing bioactive contaminants. There are also
a number of advantages of continuous HTL such as cost and waste reduction, safety, and
chemical and the process operability, etc. Continuous HTL has great potential for large-scale
commercial conversion of various wet biomasses to energy-rich fuels and valuable chemicals.
During continuous HTL biomass is subjected to hydrothermal states and water molecules
degrade the larger molecules in biomass into smaller fragments. Furthermore, HTL produces
lesser harmful chemicals, unlike ordinary pyrolyctic processes. Liquid fuel produced separates
from the water physically without need for drying.

2.1-7 LIMITATIONS OF HYDROTHERMAL LIQUEFACTION

Although hydrous pyrolysis is a very convenient technology to recycle scrap tires for energy
conversion of this waste material, it also has its own setbacks. This process breaks long
molecular chains into shorter ones, so small molecules such as carbon dioxide or methane cannot
be converted to oil through this type of pyrolysis. Although it creates less harmful chemical than
ordinary pyrolysis, it still produces small amounts of toxic fumes (including volatile organic
compounds such as benzene, metals such as lead, polycyclic aromatic hydrocarbons such as
benzo(a)yrene, and synthetic rubber components such as butadiene and styrene). Additionally,
the chlorine content in tires leads to the creations of dioxins and furans (which are extremely
toxic chemicals).
2.1-8 PRODUCT YIELD
Products formed through hydrous pyrolysis includes fixed carbon solids which can be used as a
filter or fertilizer. It is also a good fuel source with a heating value of approximately 27.9 MJ/kg
(12 000 Btu/lb). Fuel gases which is a mixture of CO2, CO, H2O and light hydrocarbons with a
heating value of 13.3 and 25.5 MJ per cubic meter (350 and 750 Btu per cubic feet) which can be
utilized for gas turbines. HTL also produces gasoline split which is comparable to gasoline but
has shorter chains and narrower chains range resulting to lower combustion pollutants emission.
It also yields sulfur in form of hydrogen sulfide in the fuel gas which can be removed by an
alkaline scrubbing of the fuel gas. A 100 lbs of scrap rubber tires that undergoes hydrous
pyrolysis yields 44 lbs of oil, 10 lbs, of gas, 42 lbs of carbon and 4 pounds of water.
2.2 RELATED STUDIES

2.3 THEORETICAL AND CONCEPTUAL FRAMEWORK

 RECYCLING
THERMOCHEMICAL
SCRAP TIRE (ENERGY CONVERSION
CONVERSION)

HEXANE ACETONE HYDROUS

EXTRACTION EXTRACTION PYROLYSIS (HTL)

LIQUID FUEL
OIL
DISTILLATION (LIGHT OIL & HEAVY
OIL)

REFERENCES:
https://www.sciencedirect.com/topics/engineering/hydrothermal-liquefaction
https://www.sciencedirect.com/science/article/pii/S254250482100035X
https://www.azocleantech.com/article.aspx?ArticleID=1227
https://www.frontiersin.org/articles/10.3389/fenrg.2022.841752/full
https://www.researchgate.net/publication/
322735596_Liquefaction_of_natural_rubber_to_liquid_fuels_via_hydrous_pyrolysis
https://www.researchgate.net/publication/
283236560_Hydrothermal_conversion_of_scrap_tire_to_liquid_fuel
https://www.sciencedirect.com/topics/engineering/hydrous-pyrolysis
CHAPTER 3
This chapter discusses the methods in hydrothermal liquefaction of scrap tires to produce
liquid fuel as desired product.
3.1 MATERIALS
In the production of liquid fuel, scrap car tires was used as raw materials for thermal
cracking. The feedstocks was purchased from Ilawod 3 Junkshop in Segovia St. Bagumbayan,
Daraga, Albay. The car tires was already cleaned when it was purchased.
3.2 MATERIAL PREPARATION
Materials is grated or broken down to pieces (about 2-5 cm2 [3-4]), and then macerated
by two-stage preheating, which is powered by the heat released by the flash evaporation process
after the first reactor. In TDP, there is no need to dry the product because water is an important
component of the process. Figure 6 shows the consistency and appearance of the macerated
product.

3.3 EXPERIMENTAL PROCEDURE

1. Hydrothermal Treatment (1st stage reactor). Materials are super-hydrated or “cooked”

to prepare them for thermal cracking. Here, the pre-heated feed is sent to the first reactor.
The reactor is heavily insulated, and wrapped with electric heating (dimension is a
function of the capacity of the plant; in this paper, the capacity is 300 tons/day) .
Operating temperatures is 200-250oC (about 500oF) and pressures of about >30 atm
(some sources 600 lbf) for most organic material—which are not at all extreme or energy
intensive. Cooking time is short, usually about 15 minutes. Product is usually called an
“organic soup.”
2. Dehydration by depressurization (Flash Evaporation). To separate most of free water,
the slurry or settled product is sent to a flash evaporator, where pressure is suddenly
reduced. Water is flashed to atmospheric pressure. The energy released by the process is
used to heat the pre-treatment process and the hydrothermal treatment. By employing this
stage, the 1st stage reactor is said to have an efficiency of about 85%. Figure 7 shows the
schematic diagram of Steps (1) to (4), which also indicates how the energy is recycled.
3. Centrifugation/Settling. The organic soup from the first reactor is sent to a centrifuge or
settling tower to separate the organic part from water. Other sources indicated that the
slurry (i.e., the organic soup) is dropped automatically to the next process. This stage is
employed depending on the type of feedstock. Figure 8 shows the products after settling
without flash evaporation; bottoms contains the mineral, oil on top and water in the
middle
4. Thermal cracking (2nd stage thermal treatment). The concentrated organic soup is sent
to the second stage thermal treatment or thermal cracking to break down large organic
polymers to shorter carbon compounds (usually C15 to C20). Operating temperature is
 about 500oC. Process is isothermal and is similar to delayed coking, with rapid heat
transfer to oil. Decarboxylation and deamination are the main reactions in this stage. The
fuel gas produced here is combusted to heat the 2nd stage.
5. Fractional distillation. The cracked liquid is fed to a series of distillation columns to
separate its components. The top of the final distillation column contains the fuel gas, the
middle contains the oil, while the bottoms contains the powdered carbon.