Estimation of Industrial Emissions

during Pyrolysis and Combustion of

Different Wastes Using Laboratory
Data
In our lab, we have been studying the emissions of different pollutants during pyrolysis and combustion
of wastes under different conditions for the last three decades. These studies have focused on the effect
of temperature and presence of oxygen on the production of different pollutants. Waste decomposition
has been studied in a horizontal laboratory scale reactor, but no estimate has been made of the actual
emissions in a conventional thermal decomposition system. In the present study, emissions during
these wastes’ thermal decomposition were estimated using Aspen HYSYS. In the simulation software,
the waste composition (elemental analysis) was given as an input parameter, as well as the gas flow rate
used as atmosphere during the decomposition. The emitted hydrocarbons measured in the laboratory
were equated to the emission of a single compound (propylene). The simulation permitted calculating
the percentage of oxygen in the emitted gas, and the pollutant emissions were then recalculated under
standard conditions. The emission of dioxins and furans were estimated under different conditions of
decomposition, and an adequate approximation of the waste decomposition in actual incineration
systems could be obtained.
Thermal decomposition of wastes is considered as a valid technique to recover chemicals and/or energy contained
in wastes. Uncontrolled conditions of decomposition should naturally be avoided, to ensure that the formation
of emissions is controlled and to take advantage of the process. The species emitted during uncontrolled thermal
degradation can lead to major health and environmental hazards.
The University of Alicante research group ‘Waste, Energy, Environment and Nanotechnology’ (WEEN) has
been studying the pyrolysis and combustion of different organic wastes for the past thirty years. Initial studies
were dedicated to determining the kinetics of different waste decomposition using a thermobalance. Later studies
focused on the pollutants produced under different experimental conditions, using a quartz tube reactor placed
inside a horizontal furnace. The atmospheres used in both types of studies were both nitrogen and synthetic air,
to simulate pyrolysis and combustion conditions, at temperatures between 375–1100 °C. The studied pollutants
included: carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (ClBzs),
chlorophenols (ClPhs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated
biphenyls (dl-PCBs). The wastes under study included: automotive shredder residue (ASR), solid
recovered fuel (SRF), tyres, sewage sludges, polyvinyl chloride, polychloroprene, different fractions of electric
and electronic wastes, cotton and polyester fabrics, meat and bone meals, olive oil wastes and different biomass
samples, among others.
In the present study, emissions of different wastes during thermal decomposition were simulated using Aspen
HYSYS. A carbon mass balance test was performed to calculate the oxygen percentage in the emitted gas, and the
emitted pollutants were recalculated under normal conditions (Nm3). Furthermore, we examined the evolution
of the H/C ratio under different conditions (temperature, presence of oxygen) to look for non-anticipated results.
Emissions of PCDD/Fs were also estimated under different decomposition conditions.
Previous studies on the extrapolation of laboratory emission data to industrial scale are scarce. Ficarella and
Laforgia1 pretend to optimize a hazardous waste incinerator in order to minimize the pollutant emission.

OPEN
approximation is to consider a high amount of reactions taking place in the decomposition chamber, and evaluating
the decomposition rate of dioxins in different chamber geometries. Similarly, Bensabath et al.2 estimated the
emission of polycyclic aromatic hydrocarbons (PAH) in the pyrolysis of some fuels using detailed kinetic modelling.
Black et al.3 evaluated the effect of experimental methods on the emission factors for dioxins and furans
emissions, concluding that field sampling and laboratory simulations were in good agreement, although they did
not implement mathematical simulation.
Experimental data
Over the past 30 years, numerous studies have been conducted at the University of Alicante (UA) laboratory on
the thermal decomposition of a large variety of wastes under different thermal degradation conditions. Over time,
different ovens and waste introduction systems have been used, though a general pattern, shown in Fig. 1, has
always been followed. In such systems, the waste sample is introduced at a controlled speed into an oven at a programmed
temperature. The runs’ nominal temperatures varied between 375 and 1100 °C. The evolved pollutants
were sampled in different ways. Analytical methods are detailed in the ‘Methods and materials’ section. Briefly,
the Amberlite XAD-2 resin was inserted in the exit pipe and later extracted using solvents to analyse the various
semivolatile species. Also, the gas was collected in a Tedlar bag for later analysis.
The present study comprises emission data from a total of 98 experimental runs corresponding to 20 different
types of waste. In a previous paper4 it was evaluated the reproducibility of similar runs to that presented in this
work, where it is shown that the reproducibility is quite good for all kind of compounds analysed in the emissions
from pyrolysis and combustion of polyurethane foams.
In previous studies5–17, the evolution of the different pollutants emissions’ was analysed as a function of the
experimental conditions in the decomposition zone. In addition to the temperature and residence time of the gas
in the hot zone, the presence of oxygen was controlled by using a constant air flow and by modulating the rate
of introduction of the waste inside the furnace. To quantify the excess (or deficiency) of air, an oxygen ratio was
defined as follows (modified from Fullana et al.18):
λ= =
+
+−++
ν
ν
..
·

(())·
m
m
m
H
()
()
23
% 32 (1)
C
O actual
O stoichometric
air
Om
L
m
L
C Cl S Cu
(% )
%
12
1
4
%
35 5
%
32
%
63 5
sample
sample
2
2
where:
%O, %H, %S, %C, % Cl, %Cu = weight percentage of oxygen, hydrogen, sulphur, carbon, chlorine and cupper
in the waste sample; mair = air flow rate (kg/s); msample = weight of the waste (kg); L = length of the tube occupied
by the residue (m); ν = linear velocity of introduction of the sample in the furnace (m/s).
Using this definition, a λC value below one implies combustion under sub-stoichiometric conditions, while λC
values above one represent excess air. In pyrolytic conditions, the λC value can be different from zero if the sample
waste contains oxygen. In this case, a limited amount of oxygen can be a source of production of oxygenated
compounds, particularly PCDD/Fs and related compounds19,20.
Simulation runs and discussion
We calculated the different compound emissions on a weight/weight basis for each run in such a way that emitted
hydrocarbons (and PAHs in some cases) were analysed and referred to the input weight of waste (emitted compound
mass/waste mass in the run).
Calculation of the average H/C emission ratio and representativeness of the propylene. To
determine a representative compound of total hydrocarbon emissions, the average H/C ratio was calculated for
each run, based on the following relationship:
Average H C
HC
/
(/)
(2)
i
all analysed HCs mg of compound i
g of waste i
i
all analysed HCs mg of compound i
g of waste
According to this equation, the average H/C ratio underwent a drop between 0,80 and 3,90 in all the runs considered,
as will be shown later. A single compound representing output hydrocarbon emissions was propylene, as
its H/C ratio was 2 and the formation of this compound was very common in most of the runs.
Figure 1. Schematic diagram of the batch laboratory scale tubular reactor used in the different studies on the
decomposition of wastes.
Scientific Reports | (2020) 10:6750 | https://doi.org/10.1038/s41598-020-63807-w 3
www.nature.com/scientificreports/ www.nature.com/scientificreports
Run simulations in HYSYS and calculation of the gas emission composition. The experimental
runs were simulated using Aspen HYSYS V10 setting a Fluid Package based on the Peng-Robinson Equation of
State. To simulate each experiment performed in the laboratory furnace, one current per element was added, representing
the different elements composing the waste (C, H, O, N, S, Cl and moisture); later, another current with
air at 1 atm was added (Fig. 2). In each run, the λC value was known based on laboratory data, together with the
waste input velocity and air flowrate. The simulated currents entered a conversion reactor (set at each run’s combustion
temperature) where the reaction operates on a stoichiometric basis and will run until either the limiting
reagent is exhausted, or the specified conversion has been achieved. In this conversion reactor, the reactions that
took place were the formation of HCl from the corresponding halogen and hydrogen, the formation of H2O with
the rest of the hydrogen present, the formation of SO2 from sulphur, the oxidation of copper when present in the
residue, and the formation of CO and CO2. Note that mass balances are solved and forced to fulfil the analytical
results, and the conditions of P, V and T are calculated following the Peng Robinson equation of state, being all
calculations integrated in the HYSYS tool. The mass balance is fitted to the experimental data manually, so that to
the gas stream the consumed O2 is eliminated and the generated CO2, CO and COT are added.
The production of the different hydrocarbons was also modelled using only one compound: propylene; it
enabled obtaining an adequate approximation of the average composition of the hydrocarbons produced, as mentioned
before. During the modelling, we assessed the conversion of the different reactions to match the final
production of the known species with that obtained experimentally.
The reactor’s bottom stream contains all the solid products that can be produced, such as Sulphur or Carbon
excess that does not react during pyrolysis or combustions with a low O2 ratio. The model includes a component
splitter, coming after the reactor, that eliminates water vapour without producing any changes to other properties.
The final current is then cooled at 25 °C (normal conditions). The oxygen’s molar fraction is then obtained, and
the normalised flowrate can be calculated based on this last current, by using the following relationship 21:
Normalized gas flowrate Nm
h
Output gas flowrate Nm
h Oin the output gas
21 11
21 % (3)
33
In the previous equation, the oxygen percentage under normal conditions was established at 11%. Following
this procedure, the different simulation runs performed in the laboratory allowed calculating the emissions on a
normalised standard basis and then estimating the emissions of industrial-scale equipment.
Using this model, it is possible to estimate the total gas flow rate produced as well as its oxygen content. As an
example, Table 1 shows the calculations conducted during the decomposition modelling of automotive shredder
residue (ASR) waste. Following this procedure, it is possible to calculate the normalised flow rate (25 °C, 1 atm,
11% O2) and then to estimate the corresponding emissions based on industrial equipment.
The operation is as follows:
PCDD Fsemission pgI TEQ
Nm
PCDD Fs emission factor pgI TEQ
g
Sample flowrate
g
h
Normalized gas flowrate Nm
h
//
(4)
sample
sample
3
31
The key point in this calculation is to check whether the legal limit (0,1 ng ITEQ/Nm 3 of the EU21 and the
0,5 ng TEQ/Nm3 of the Chinese emissions standards22) is exceeded or not.
Comparison of different waste emissions. evolution of H/C ratio vs. temperature and oxygen
ratio. The different wastes’ decomposition produced a variety of compounds that depended on each run’s particular
conditions, specifically on oxygen excess and temperature. An average H/C ratio could be calculated for