Beruflich Dokumente
Kultur Dokumente
and processes for energy: communicating current research and technological developments (A. Mndez-Vilas, Ed.)
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Automotive Industry Institute, Department of Fuels and Renewable Energy, 55 Jagiellonska Str., 03-301 Warsaw,
POLAND;
2
Institute for Ecology and Bioethics of CSWU, 1/3 Woycickiego Str. 01-938, Warsaw, POLAND.
Contact details to author: k.biernat@pimot.org.pl, phone number: 48 22 7777225
Used tires might be a rich source of valuable energy and chemical products. These products could be received in the
process of WtE and WtL by thermal decomposition of rubber in oxygen-deficient atmosphere. The gas products,
hydrocarbon oils and carbon black residue are obtained by waste tires pyrolysis. In operating systems (demonstration, pilot
installations) pyrolysis is an intermediate stage leading to the energy use of rubber raw material. Tests of using pyrolysis
oil as a feedstock to produce fuels by hydrocracking processes was carried out, however there are only experimental or
pilot installations. The recycling of tires by continuous pyrolysis process could lead to the obtaining of liquid energy
carrier (heating liquids and gases) and technical carbon black. Thermo-gravimetric study was applied for determination
basic technological parameters for producing liquid energy carriers with particular attention in determining the fractional
and structural-group composition of pyrolysis products. In this area, thermogravimetric study of thermal decomposition of
shredded car and radial tires, including analyzing the chemical composition of gaseous decomposition products and
structural composition of liquid products, was carried out. The research results and analysis showed that it is possible to
blend high-quality alternative fuels, including fuels for diesel and traction engines, with a properly compiled pyrolysis oil
distillate composition.
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Type
Process
Products
Phisical
Re-use
Barriers, covers
Retreading
New tires
Granulation
Special combustion
Pyrolysis
Pyrolysis + gasification
Gasification
Cryogenics
Thermal
Installations for the recovery or disposal of non-hazardous waste by using thermal processes have to be considered
for installations that may significantly affect the environment. Technical requirements for such a systems are also well
defined in the relevant legislation. Emission standards for co-incineration plants are related to such pollutants as:
dust
total organic carbon
hydrogen chloride
hydrogen fluoride
sulfur dioxide
nitrogen oxide and nitrogen dioxide
carbon monoxide
Measurements of these emissions should be carried out continuously. In addition, concentrations of dioxins, furans
and heavy metals listed in the Regulations should be periodically measured. Emission levels for individual substances
are shown in table 2.
Table 2. Sample emission standards for power boilers of different thermal power [2]
Name of the
substance
Total dust
Sulfur dioxide
(SO2)
Nitrogen oxides
(NO2)
Nominal thermal
power of plant
[MW]
Cp
Cw
50100
50
10
44
100300
30
10
27
>300
30
10
27
50100
850
50
730
100300
200
50
178
>300
200
50
178
50100
400
200
370
100300
200
200
200
>300
200
200
200
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decomposition are obtained generally two phases: solid and gas. Both of these phases can be subjected to further treated
in order to obtain more valuable products, such as gaseous or liquid energy carriers. Currently, in pyrolysis processes
are commonly used reactors with a capacity of 2 to 6 Mg tires/h. There are also smaller reactors with a processing
capacity of tires in a row (1...2) Mg tires/h. In certain solutions, the reactors can be heated directly or in diaphragmatic
way, and structurally are divided into vertical or horizontal, or also with a mobile or fixed bed. Some authors indicate
the possibility for pyrolysis of tires in a fluidized form. Up to now, known tire pyrolysis process involves the
introduction of tires into the reactor, through the air lock preventing access the air to the reaction chamber. The
processing time depends on the type reactor. Thus, in the turnover reactors the time is from 30 to 60 min, whereas in
stationary reactors the time may be extended up to 8 h. The effect of deep tires pyrolysis are: charred residue containing
small quantity of volatile matter, and (3...5)% of sulfur and about 15% ash and a mixture of hydrocarbon gases. The
quantity of ash may be greater in the case of pyrolysis of tires containing silica. Pyrolysis residue containing mainly
carbon has a calorific value of about 28 MJ/kg and after magnetic separation of metal weave elements is used as a solid
alternative fuel. The gas phase is condensed partly to give a fraction type "pyrolytic oil" with a calorific value of about
40 MJ/kg. Uncondensed hydrocarbon gases having a calorific value of 35 MJ/ kg are generally used with pyrolytic oil
as an energy source for the reactor. There were conducted attempts to use of pyrolytic oil as a raw material for the fuel
production by hydrocracking processes, but so far, there are basically only experimental or pilot installations. Processes
of tire pyrolysis conversion in experimental or pilot scale were carried out using a reactor heated in diaphragmatic way
or in rotating reactors by companies: THIDE-PKA, Svedala, Karbon Produkt International and RAT; in the reactors,
type string feeder moving bed by companies: Traidec, Pyrocycling and Alcyon (Multipurpose blade); the rotary reactor,
heated directly by the company Basse Sambre-ERI in fixed-bed reactors by Nexus (fed batch) and company Terra
(vertical reactor) and multideck reactors, moving bed reactors by NESSA.
In the field of the above processes, are ongoing research related to tire pyrolysis process with simultaneous attempts
of total use of pyrolytic products. New developed technologies are covered by many patents. All of these technologies
are based on direct pyrolysis reactors or with pre-heating, have heat exchangers and scrubbers and also magnetic metal
separators, allow the steam activation of residues and pyrolytic oil filtration and possible purification of the residue to
the form of semi-active carbon black. Process emissivity is about 2 kg/h SOx, 2 kg/h NOx, i 1 kg/h PM.
Tire pyrolysis processes are shown in Figures 1 and 2.
Most processes performing thermal treatment process of waste tires are carried out in a cyclic manner, which may
cause less favorable value of EIOER ratio ("Energy Invested on Energy Returned"). According to the literature data it
can be concluded that technology enables the processing of used tires that are environmentally troublesome waste, is
not currently implemented on the industrial scale process, continuously. Tire recycling technology in a continuous
recycling process, in the pyrolysis process, can lead to the preparation of liquid fuels (gas and heating liquids) and
carbon black.
Most of technologies were described in patents, mainly American ones, i.a.: U.S Patents No: 4,084,521; 4,235,676;
5,389,691; 5,720,232, 6,736,940 and: 3,787,292; 4,261,795, 4,347,119; 4,501,644; 5,198,018, 5,411,714; 5,523,060,
5,589,599, 6,226,889; 6,398,825; 6,758,150. In both groups of patents that concern the same process and apparatus are
disclosed no material handling methods and disposal of pyrolitic products with a flexible screw conveyor, independent
from the axis of the reactor and the stirrers in the outlet channel, allowing discharge of gas and condensate recovery.
One of the pyrolytic decomposition products, which after suitable processing can be used as the liquid energy carrier,
is an pyrolytic oil. Table 3 shows the comparison of the basic properties of diesel fuel with properties of crude oil,
pyrolytic oil and distilled oil.
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Table 3. Comparison of diesel oil properties with pyrolytic oil from pyrolysis of tires (TPO) and distilled TPO [3]
Properties
Diesel oil
TPO crude
TPO distilled
Density in 150C [kg/m3]
890
935
871
Kinematic viscosity in 4000C [mm2/s]
2
3,2
1,7
Calorific value [MJ/kg]
46,5
42,83
45,78
Ignition temperature [0C]
50
43
36
Self-ignition temperature [0C]
56
50
48
Sulfur content [%]
0,045
0,95
0,26
Ash content [%]
0,01
0,31
Residual carbon [%]
0,35
2,14
0,02
As can be seen from the data presented in Table 3, the properties of the distilled pyrolytic oil are as similar to those
of diesel fuel, which may indicate the rationality of the tires pyrolysis process, including the processing of the liquid and
gaseous energy carriers.
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As it seen in Figure 3, the process of thermal decomposition, associated with loss of sample mass starts from the
temperature 367.9 C., wherein the heavy weight changes of the sample are presented in the two compartments
identifiable, that is weight reduction of 27.56% in the temperature range (367.9 ... 425.1) C and at 34.13% in the
temperature range (425.1 ... 486.0) C. At the same time the process takes the form of an endothermic decomposition,
just as it shown in Figure 4.
Fig. 4 Enthalpy changes of thermal decomposition of the sample from used car tire
As is apparent from the curve, the thermal decomposition process carried out in a non-oxidizing atmosphere has an
endothermic nature, from the temperature at 367.9 C. Heat value is cumulatively 159 J/g and is necessary to generate
process, wherein in the temperature of 486.0 C, the process continues at the expense of the enthalpy values. This
means that the optimum values of temperature, which allows to operate the process with a gradual recovery of the
fraction of gas and liquid is temperature of about 400 C. Due to, specified in research, energy needs (159 J/g)
necessary to maintain the process, the process of feeding the raw material should be done on a continuous basis, which
is designed to reduce the energy demand.
3.2. Building the model reactor.
Pyrolysis experiment was carried out under nitrogen atmosphere in a tubular reactor made of stainless steel. This reactor
was constructed for research purposes, as a reactor model. The tubular reactor (40 1.1 cm) was used for pyrolysis of
shredded, used tires and was externally heated by electric furnace ( 31 9.5 cm) with adjustable temperature with a
thermo steam inside the bed. A line connecting the outlet with the reactor and cold trap was heated with heating tapes to
300 C to avoid the condensation of the bio oil vapors. Experiments were carried out in a tubular reactor in order to
define the influence of pyrolysis temperature and intensity of natural gas on the performance of pyrolysis products.
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Experiments have been conducted using the 7 K/min-1 temperature increasing to a final temperature in the range
(400...700) C under a nitrogen atmosphere. The gas flow was adjusted in the range (50...400) cm3 /min-1. Liquid
products were collected in a trap at the temperature of 0 C. They consisted of the oil phase, which was isolated and
weighed. Eventual increases of carbon deposit can be determined by weight from gain of weight reactor. The gaseous
products can be analyzed on-line on GC with TCD/FID detectors with a 1ml loop attached to the "Valco" type valve,
controlled automatically. In an ongoing study, pyrolysis gases were directed through shut-off valve to the
chromatography bottle, and then transferred to a GC chromatographic analysis. Liquid products were submitted for
further analysis.
3.3. Analysis of gaseous products of thermal decomposition of the tire material.
Gaseous products of pyrolysis of used car tire samples were sent directly from the model reactor for GC chromatograph
with TCD/FID detectors. As a result of analysis, it was obtained the basic composition of pyrolytic gas, divided on
identified as to type and content (% v/v) hydrocarbons, which composition is given in Table 4.
Table 4. Composition of gas products of used tires pyrolysis
No.
1
2
3
4
5
6
7
8
a)
b)
c)
d)
e)
f)
g)
h)
i)
j)
k)
l)
Chemical composition
Nitrogen
Oxygen
Carbon dioxide
Carbon oxide
Hydrogen
Argon
Steam
Hydrocarbons:
methane
ethen (ethylene)
ethan
propene (propylene)
propane
isobutane
n-butane
butene
isopentane
n-pentane
pentene
hexane
Test result
% v/v
0,71
below threshold
19,6
2,29
10,1
below threshold
22,5
7,73
6,02
5,98
3,63
7,23
1,64
0,55
1,74
5,19
1,22
1,77
From the data in Table 4, results a preferred pyrolytic gas composition, because of the possibility of its energy use.
The total content of methane and hydrogen is 33.6% v/v, which indicates a very high calorific value of the gas. High
calorific value will be characterized a mixture of ethane, propane and butane, with total content reaches 18.52% v/v.
Pyrolytic gas does not contain water vapor, but contains a certain amount, prone to polymerization, of unsaturated
hydrocarbon gas in the amount of 15.48% v/v, and a small amount of pentane vapor (small hexane vapor concentrations
haven't adverse effects). Hence, this gas should be directly used as energy source for the pyrolysis reactor. You can also
consider the evolution of the synthesis gas components for further processing into hydrocarbons - components of
alternative fuels.
3.4 Research on the properties of pyrolytic liquid oil and distillate.
Resulting pyrolytic oil in a model reactor and separated distillate was analyzed to assess basic normative properties,
together with normal distillation. As a result of these analyzes, carried out in accordance with the applicable standards
for test methods, it was specified, for both oil and distillate, the basic characteristics that determine the suitability of this
oil (distillate) as an alternative fuel. Analysis results for liquid oil pyrolytic are shown in Table 5. Table 6 shows the
course of the distillation carried out pyrolytic oil, and in Table 7 - the results of the analysis performed for the distillate,
respectively, separated from the pyrolytic oil.
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No.
Properties
Test method
Test result
1
Density in temperature 15oC, kg/m3
PN-EN ISO 12185:2002 (A)
907,3
2
Calorific value, MJ/kg
PN-C-04062:1986 (A)
40,92
3
Kinematic viscosity at 40oC, mm2/s
PN-EN ISO 3104:2004 (A)
2,56
4
Sulphur content, % (m/m)
PN-EN ISO 20846:2006
0,58
1)
5
Ignition emperature in closed cup, oC
PN-EN ISO 2719:2007 (A)
6
Ash residue, % (m/m)
PN-EN ISO 6245:2008 (A)
0,010
A methods accredited by the PCA (AB098)
1)
determination cannot be done, because at the lowest point at 25 oC, product is lighting up on the first
inclination filament
Table 6. Course of the distillation, carried out at a pressure of 760 mm Hg (normal), for pyrolytic oil
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
% v/v distil
Start of distillation
5
10
20
30
40
50
60
70
80
90
End of distillation
Distilled
On the basis of the normal course of the distillation process, from the liquid pyrolytic oil was isolated light distillate
in boiling temperatures range from the start of distillation to 60% (v/v) distillation temperature, and this fraction were
analyzed in accordance with the requirements for liquid fuels. Results of the analysis are shown in Table 7.
Table 7. Basic propertied of light distillate of pyrolytic oil
No.
1
2
3
4
5
6
7
Properties
Density in temperature 15oC, kg/m3
Calorific value, MJ/kg
Ignition emperature in closed cup, oC
Ash residue, % (m/m)
Sulphur content, % (m/m)
Kinematic viscosity at 40oC, mm2/s
IR spectrum
Test method
PN-EN ISO 12185:2002 (A)
PN-C-04062:1986 (A)
PN-EN ISO 2719:2007 (A)
PN-EN ISO 6245:2008 (A)
PN-EN ISO 20846:2006
PN-EN ISO 3104:2004 (A)
MB-MPS 020:2002 (A)
Test result
779,8
40,92
1)
0,001
0,98
2)
Fig.5
As it can be seen from the presented results, the light fraction may be a component of alternative fuels for diesel
engine, but because of too bad, for these engines, rheological properties and ignition temperature, it cannot enforce a
compliant fuel for those engines. Hence the conclusion is that the need to determine the self-ignition temperature of the
fractions that can be distillated from the liquid pyrolytic oil, to develop a formulation of the appropriate composition of
distillate with proper cetane number or at least a ignitability pointer of those compositions.
3.5 The study of the structural composition of the liquid phase of pyrolytic oil distillate
The structural composition of the determined distillate was examined by removing the IR spectrum of the liquid phase
of distilled pyrolytic oil. The progress of spectra is shown in Figure 5. The IR spectrum analysis shows the nature
determination of the bonds, and thus also allowances to specify the mutual participation in the distillation of certain
compounds as bonds. From the course of the spectral lines is resulting that in the wave number range (3100... 3050) cm-1
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are observed both aliphatic and aromatic compounds with bonds of C=C type, wherein the concentration of these
compounds is relatively small. In the range of 2980 cm-1 to 2850 cm-1 are observed C-H bonds, characteristic for
alkanes in the CH3 and CH2 groups, and tertiary carbons. Carbonyl bonds C=O, typical for aldehydes, esters and
ketones (oxygen derivatives) of low concentration are observed in the range of about 1700cm-1.
There was also a small concentration of C=C bonds, characteristic for alkenes in the wave number 1630 cm-1 and
arenas (wave number 1600 cm-1). The presence of ester bonds and optionally also carbonyl bonds were found at a wave
number 1400 cm-1. Small concentration of aromatic rings was observed in the wave number approximately 850 cm-1,
while the presence of the alkanes with chains above C4 in the area of 720 cm-1. In summary, it should be noted that the
use of the composition of the pyrolytic oil distillate, resulting in specific process conditions, there are no
contraindications for the use of these components as a high-grade fuel components for diesel engines in stationary
operating conditions, and even under traction conditions.
Conclusions
The analysis of the process of thermal decomposition (light pyrolysis) of used tires, run on a model conditions,
supported by the results of research on process kinetics and analysis of decomposition products allows for the following
conclusions relevant to the technology of the process, namely:
1. Due to the kinetics of the process and the possibility to obtain a positive energy balance, taking into account
the results of derivatographic research, it advantages to operate the process continuously.
2. It is necessary to perform calculations of the reactor efficiency with, respect to the speed of substrate feed
process.
3. An important part of the process should be design of separator, which accepts and adequately disperses
material. It should be a separator that can equalize the pressure and prevents air from entering into the reactor.
4. Technological system should have a cooling system in the form of closed circuit of coolant (water), as it results
from the process carried out in a model reactor.
5. It is necessary to specify time of stay of the material in the reactor. It should contain in the range of (30...45)
min.
6. For proper use of products of pyrolytic decomposition, taking into account the possibility of use gas fraction as
the process energy carrier, it would be beneficial to determine the possibility of further use of excess amounts
of process pyrolytic gas.
7. It is possible to compose high-value alternative fuels, including diesel engines, traction engines, from the
properly compiled pyrolytic oil distillates. This will require an additional study, taking into account the
requirements of these engines in the field of rheology, lubricity properties, and in the field of properties of the
ignition delay period.
References
[1] Heermann C. i in.: "Pyrolysis & Gasification of Waste. A Worldwide Technology and Business Review", Juniper Consultancy
Services Ltd, 2001;
[2] T. Pajk Wybrane aspekty wspspalania odpadw w instalacjach przemysowych, VI Midzynarodowe Forum Gospodarki
Odpadami (Some aspects of co-incineration in industrial plants, VI International Forum on Waste Management) Pozna, MayJune 2005, pages.341-352;
[3] J.Jesila, G.Nagarajan, S.Murugan Distilled Tyre Pyrolisis Oil as an Alternative Fuel for CI Engine
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[4] Technology Evaluation and Economic Analysis of Waste Tire Pyrolysis, Gasification, and Liquefaction, California
Environmental Protection Agency, March 2006;
[5] C. Roy, H. Darmstadt, B. Benallal, A. Chaala, A.E. Schwardtfeger Vacuum pyrolysis of used tires
[6] Yang Yongrong, Chen Jizhong , Zhao Guibin Technical Advance On The Pyrolysis of Used Tires in China (Symposium
China Japan International Academic Symposium Environmental Problem in Chinese Iron-Steelmaking Industries and
Effective Technology Transfer);
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