Accepted Manuscript

Title: Study of co-pyrolysis of olive kernel with waste biomass

using TGA/DTG/MS

Authors: S. Sfakiotakis, D. Vamvuka

PII: S0040-6031(18)30233-8
DOI: https://doi.org/10.1016/j.tca.2018.10.006
Reference: TCA 78112

To appear in: Thermochimica Acta

Received date: 17-5-2018

Revised date: 8-10-2018
Accepted date: 10-10-2018

Please cite this article as: Sfakiotakis S, Vamvuka D, Study of co-pyrolysis of

olive kernel with waste biomass using TGA/DTG/MS, Thermochimica Acta (2018),
https://doi.org/10.1016/j.tca.2018.10.006

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 Study of co-pyrolysis of olive kernel with waste biomass using

TGA/DTG/MS

S. Sfakiotakis* and D. Vamvuka

Department of Mineral Resources Engineering, Technical University of Crete,

University Campus, Hania 73100, Greece

*

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Corresponding author, e-mail: ssfakiot@mred.tuc.gr

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Highlights

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 TG/DTG/MS analysis of pyrolysis of three waste biomass materials and their
mixtures

 U
Satisfactory calorific value of light gases from pyrolysis, low water content
Strong synergy effects of co-pyrolysis on CO and H2 production
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 More or less additive behavior for CO2, hydrocarbons, NH3, HCN, HCl
production
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 No significant effect of co-pyrolysis on char, tar yield and heating value of gases
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.
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ABSTRACT
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The evolution of the pyrolysis products of olive kernel, a municipal solid waste fraction
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and a sewage sludge was analyzed qualitatively and quantitatively, using a properly
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developed and calibrated system of coupled thermogravimetry-mass spectrometry

(TG/MS). The TG/MS profiles of the volatile products were also related to the pyrolysis
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thermograms, after their deconvolution which was performed using an independent

parallel reaction kinetic model. The results from the co-pyrolysis of two mixtures of

olive kernel with the municipal waste fraction and with sewage sludge at 7:3 mixing

ratio revealed strong synergy effects on the production of CO up to 600oC and the
production of H2 at elevated temperatures. Other compounds were found to present

slight synergistic (hydrocarbons up to C3, HCl, HCN) or additive behavior (CO2, H2O,

NH3). No significant effect of co-pyrolysis on the anticipated quantities of char, tar and

on the heating value of the pyrolysis gases of the mixtures was observed.

Keywords: TG/MS, olive kernel, municipal solid waste, sewage sludge, co-pyrolysis,

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synergy

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1. Introduction

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Sustainable biomass utilization in the heat and power sector is anticipated to rise in the

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2020-30 decade (COM(2014) 15 final) and plays a decisive role for the achievement of
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2020 EU targets for renewables share increase in gross final energy consumption and
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GHG emission reductions, according to Directives 2009/28/EC and 2009/29/EC.
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Residual forms of biomass, such as the agro-industrial byproducts of olive are produced

in large quantities in the EU and especially in the Mediterranean region, but still remain
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largely unexploited [1,2]. Furthermore, other types of waste biomass such as municipal

solid wastes and sewage sludge are increasing in volume and have become a matter of
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public concern in terms of their potential environmental and health problems and their
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proper management, including efficient energy utilization. In this context, Proposal

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COM(2015) 595 final of EU emphasizes the need for gradual reduction of municipal

wastes landfilling to 10% by 2030. Furthermore, according to Directive 2008/98/EC,

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energy exploitation precedes the alternative of final deposition in landfills in the

hierarchy pyramid of sustainable management of municipal wastes, even if the last is

carried out in modern landfills and accompanied by biogas production.

Pyrolysis is an attractive thermal treatment method that can be used to reduce the

volume of biomass wastes, destroying their pathogen’s content and convert them to

useful energy and added-value products [3,4]. Bio-oil and gas from biomass pyrolysis

can be used as a substitute of fossil energy for providing heat and electricity and as a

source of chemicals [5]. The solid pyrolysis product, namely biochar, is receiving

special attention due to its potential to improve some of the physicochemical and

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biological properties of soils [6]. The yield, the composition and the properties of all

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pyrolysis products greatly depend on the type of raw biomass material used and the

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experimental conditions of the process [7,8]. Thermogravimetric analysis, when

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especially coupled with mass spectrometry (TGA/DTG/MS), is a simple, rapid and

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powerful tool for the comprehensive study of thermal decomposition events and the
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analysis of the products [9]. In combination with accurate kinetic models for the
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deconvolution of the thermal degradation curves, this thermal analysis method can be
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very useful for the design of the pyrolysis process [10].

Despite greater immaturity of technology implementation, pyrolysis presents some

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advantages comparing to other thermal methods such as incineration, as it is carried out

at lower temperatures and in the absence of air, leading to lower pollutants and heavy
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metals emissions and absence of dioxin and furan production [11,12].

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Taking into account the high contents of moisture, ash, nitrogen and possibly sulfur of
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waste biomass materials, such as municipal solid waste and sewage sludge, co-

pyrolysis with other forms of biomass can be an effective way of improving the quality
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of the pyrolysis products and the energy utilization [13]. In this context, synergy effects

during the co-pyrolysis of different materials is an important issue and experimental

results have been found to be sometimes controversial, depending on the experimental

conditions (heating rate, temperature), the type of materials and their ratio in the
mixture, as well as the experimental setup, e.g. fixed bed, thermogravimeters, etc. [14].

Co-pyrolysis of coal with biomass has been extensively studied [15-23], while several

research efforts have been also focused on co-pyrolysis of biomass with plastics [24].

However, a systematic research of co-pyrolysis of various kinds of biomass mixtures is

at an early stage, limited mainly to the last three years [25,26]. Furthermore, to the best

of authors’ knowledge, there is no relevant information regarding co-pyrolysis of the

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agricultural by-product olive kernel and waste biomass materials such as municipal

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solid waste and sewage sludge.

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Based on the above, the objective of this work was firstly to investigate the thermal

behavior of olive kernel, a municipal solid waste fraction and a sewage sludge during

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pyrolysis and analyze qualitatively and quantitatively the evolution of the products and
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the calorific value of the gas. The investigation was carried out using a coupled
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thermogravimetry-mass spectrometry (TG/MS) setup, properly calibrated and a
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pyrolysis kinetic model for the deconvolution of the differential thermogravimetry

curves to the pseudo-components that constitute each sample. At a second stage,

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possible synergy effects on the results from co-pyrolysis of olive kernel with municipal

solid waste and olive kernel with sewage sludge at a specified ratio 7:3 were thoroughly
PT

studied, with special attention for the light gas evolved at a continuous online mode,
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including pollutants such as NH3, HCN, HCl. Finally, the effect of co-pyrolysis on
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calorific value of gas, as well as on other quantitative results, such as tar and char yield,

were also examined.

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2. Materials and Methods

2.1 Raw materials, preparation and characterization

The raw materials of this study were olive kernel (OK) provided by a local olive oil

industry, undigested sewage sludge (SS) produced in the wastewater treatment plant of

Chania in Crete and municipal solid waste (MSW) from a solid waste management

company of Chania. The SS sample comes from the wastewater treatment plant of

Chania as a mixture from the primary and secondary stages and after the processes of

thickening and dewatering that take place in this unit. Τhe MSW sample was free of

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glasses, plastic and metals that had been removed for recycling purposes by shredding,

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sieving, magnetic separation and hand sorting in the industry and secondly in the

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laboratory for any residuals. MSW average composition after removal of glasses,

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plastic and metals was organic materials (49%), paper (31%), leather and woody waste

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materials (12%), as well as inerts and other materials (8%). OK and SS samples were
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collected on a daily basis during one month period, while MSW was collected during
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one year. As agglomerative hierarchical clustering revealed, MSW monthly fractions
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of a year could be classified to two major groups, June to October group and November

to May group, in terms of similarity in C, H, N and ash composition [27]. The examined
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fraction finally chosen was the group of June to October months as it had greater

calorific value and lower ash content.

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Representative fractions of all the examined samples of this study were taken after air
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drying, milling and riffling and they were sieved to a particle size of less than 200μm.
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Furthermore, mixtures of OK with SS and OK with MSW samples of < 200μm particle

size were prepared at a blend mass ratio of 70/30 respectively. OK, SS and MSW
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samples were characterized in terms of proximate analysis according to the EN14774,

EN15148, EN14775 standards, ultimate analysis according to EN15104, EN15289

standards and calorific value following EN14918 standard.

2.2 Thermogravimetric (TGA/DTG) and TGA/MS analysis

Thermogravimetric experiments were carried out in a Perkin Elmer thermogravimeter

with microbalance maximum sensitivity of 5μg, balance accuracy better than 0.2% of

total weight and temperature measurement precision of 2oC. The thermogravimeter was

firstly calibrated in terms of furnace and sample temperature, as well as of weight

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measurements at the experimental conditions (including heating rate variation). All

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pyrolysis tests were carried out under argon atmosphere and for a series of five linear

heating rate thermal programs, i.e. 5, 10, 20, 30, 40oC/min. The sample mass was kept

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below 7 mg (or less for higher heating rates), while the particle size was below 200 μm

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in order to assure that the experiments would be carried out in the kinetic regime,

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eliminating heat and mass transfer effects on the results [28,29].
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Thermogravimetric-mass spectrometric (TG/MS) analysis was also carried out in order
A
to analyze qualitatively and quantitatively the evolved volatiles during pyrolysis of the
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examined samples. The TG-MS system comprised of the Perkin Elmer

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thermogravimeter and a Balzers QME 200 quadrupole mass spectrometer. A fused

silicon capillary line was used as the pressure reducing system and for the transfer of
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the evolved volatiles of pyrolysis to the MS. The capillary was continuously heated to

200oC in order to prevent the condensation of the gaseous products in it, while the
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whole TG/MS system was air-tightly sealed by using special fittings for all connections.
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The purge gas used was Argon and the sampling probe was properly adjusted to

eliminate the influence of the TGA furnace temperature increase. The criteria for
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accurate MS response to the evolved gases were checked to be met, comparing DTG

and MS signal profile characteristics in calcium oxalate monohydrate TG/MS

experiments, at the temperature range of 40-850oC. In a series of the aforementioned

experiments with different mass samples of calcium oxalate monohydrate, flow

stability and linearity of the capillary response were also confirmed at an anticipated,

during the pyrolysis of the examined samples, mass range of CO2, CO and H2O

products. The heating rate for all TG/MS experiments was 10oC/min, while mass and

particle size of the initial samples were kept the same as in the TGA experiments.

The ion source operated at 70eV and the ions were detected by a Secondary Electron

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Multiplier (SEM), properly calibrated. The data acquisition was performed by the Pyris

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TGA and Quadstar MS software. The mass to charge ratios m/z= 2, 15, 17, 18, 24-27

and 41, 28, 35, 44 accounting for H2, CH4, NH3, H2O, C2-HCN and C3, CO, HCl, CO2

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respectively, were continuously monitored. The contribution of fragments from more

than one compound to the intensity of a specific m/z ratio was taken into account, by

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determining all the compound calibration factors for each m/z ratio that this compound
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contributes, using standard two components gas mixtures of known concentration of
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the single compound in Argon. The quantitative analysis of the evolved gases (except
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for NH3, HCl and HCN) was completed by determining the CO2, CO and H2O

calibration factors from the experiments of calcium oxalate monohydrate pyrolysis. The
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calibration was validated by comparing with standard gas mixtures of known

concentrations in Argon, other than the ones used in the calibration procedure.
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2.3 Deconvolution of DTG thermograms using a pyrolysis kinetic model

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According to the Independent Parallel Reaction model (IPR), thermal decomposition

of biomass materials can be described as the sum of parallel devolatilization reactions

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of three or more pseudocomponents that constitute biomass [30,31]. The rate of

decomposition of each pseudocomponent for first order reactions can then be expressed

as:

𝐸
𝑑𝑎𝑖 −𝑅𝑇𝑖 (1−𝑎𝑖 )
= 𝐴𝑖 ∙ 𝑒 (1)
𝑑𝑡
 𝐸
𝐴𝑖 𝑇 − 𝑖
− ∙∫𝑇𝑜 𝑒 𝑅𝑇 𝑑𝑇
𝑎𝑖 = 1 − 𝑒 𝑏 (2)

The overall rate for biomass (sum of n pseudocomponents) equals:

𝑚
𝑑(𝑚𝑜) 𝑑𝑎𝑖
= − ∑𝑛𝑖=1 (3)
𝑑𝑡 𝑑𝑡

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where: m is mass at time t, ci is the fraction of volatiles produced by the i-th component:

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i i
m o
 m char
ci= , mo is the initial dry mass, mchar is the final mass at the end of the
m

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o

pyrolysis, Ai is the pre-exponential factor, i is the component index, Ei is the activation

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energy, ai is the conversion (0<ai<1), T is the temperature, b is the non-zero heating rate

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and R is the universal gas constant. The IPR model was modified to include the pre-
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exponential factor dependence on heating rate, as described in detail in a previous work
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[32]. The kinetic parameters were determined by simultaneous fitting to all TGA
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experiments carried out at the five linear heating rates. Minimization of the Objective

Function was performed under constraints using fmincon routine of Matlab®. Goodness
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of fit was estimated for each experiment at a specified heating rate, through deviation

between experimental and model values:

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√𝑂.𝐹.∙(𝑍−𝑁)
Deviation (%) = 100 ∙ 𝑑𝑚𝑒𝑥𝑝
(4)
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max(− 𝑑𝑡 )
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where Z is the number of data points, N is the number of parameters employed in the
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model and O.F. the Objective Function.

2. Results and Discussion

2.1 Characterization of Samples

Ultimate analysis, calorific value and proximate analysis of the studied samples are

given in Table 1. Olive kernel and MSW have a high volatile content of 73.6%wt, a

typical, however, value for lignocellulosic materials.Sewage sludge has a lower value

but inside the anticipated range for such kind of biomass material [33]. The calorific

value of the examined samples is appreciable, with the one of olive kernel being in the

range of a sub-bituminous coal, while the values for the other samples are in the range

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of a medium quality lignite. The nitrogen content of all the samples and especially of

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sewage sludge is considered to be high and some relevant N-emissions during pyrolysis

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will be a matter of examination in this work. Regarding sulfur, only sewage sludge has

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an appreciable content, so that SO2 emissions especially during combustion processes

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is a matter of concern for this biomass material. Furthermore, emission and corrosion
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problems from Cl content are not anticipated during OK and SS thermochemical
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processes, while for MSW the Cl content is somehow marginal. It is additionally worth
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mentioning, as a benchmark, that the Cl content of the examined MSW fraction is below

the lower limit included in the EURITS technical specifications for RDF fractions, or
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the corresponding standards for SRF fractions of class 2 [34].

2.2 Additivity investigation and deconvolution curves from kinetic analysis

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The experimental DTG pyrolysis thermograms of mixtures of the examined samples

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OK with SS and OK with MSW at the specified ratio (7:3, respectively) are presented
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in Figure 1 together with the calculated ones taking into account the simple

𝑑𝑚𝑐𝑎𝑙𝑐 𝑑𝑚𝑗
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mixing/additive rule: 𝑑𝑡
= ∑2𝑗=1 𝑥𝑗 ∙ 𝑑𝑡
(5)
𝑚𝑜 𝑚𝑜𝑗

where j=1,2 is the mixture component indice. For an easier comparison of the weight

loss dynamics of the mixtures and the single components, the measured DTG curves of
OK, SS and MSW sample are also included. The corresponding DTG characteristics

are given in Table 2. These parameters include the maximum degradation rates Rmax

and the temperature of maximum rate Tmax, the yield at maximum rate, the initial

degradation temperature (at 1% conversion) Tin, as well as the full width of the rate

curve at half maximum FWHM, representing temperature interval of the degradation

process [35]. Slight or near zero differences between these characteristic values of the

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experimental and theoretical DTG curves of the mixtures are observed. Τaking

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additionally into account the deviation value between calculated and experimental

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values which is 4.0% maximum (calculated based on equation (4) and shown in Figure

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1), additivity behavior can be deduced for both mixtures. Consequently, there exists the

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possibility of predicting with good approximation the DTG curves of mixtures, by a
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simple additive mixing rule (equation 5) of the thermogravimetric signals of the
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components that constitute the mixture. The additivity was consequently extended for
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the final biochar percentage, as for the OK/SS mixture the experimental value was

determined at 29.0% of (at 850oC and 7 min residence time) and the calculated from
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the mixing rule was 29.4%, while for the OK/MSW the values were 26.6 and 26.4%

respectively.
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The modified IPR model was successfully applied for the kinetic evaluation of
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pyrolysis of all the examined samples. Simultaneous fitting to the experimental results
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of pyrolysis at all heating rates proved to be very good with the deviation ranging from

1.8-3.7%. The deconvolution curves of the samples for each pseudo-component at

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heating rate of 10oC/min, are presented in Figure 2a-c. Despite the fact that the

examined samples are of course not “pure” lignocellulosic materials like wood, kinetic

analysis demonstrates lignocellulosic nature and properties of their pseudocomponents.

This fact can be supported by the pseudocomponent profile shape and range of
degradation, with the characteristic narrow degradation range of hemicellulose,

cellulose and the broad one of lignin, as well as the corresponding kinetic values (Table

3). Regarding olive kernel, its chemical inhomogeneity could be well described

kinetically only with the adoption of a fourth pseudocomponent with broad degradation

range, probably attributed to organic compounds, such as oil and phenols. The

holocellulosic nature of the first two pseudocomponents of sewage sludges was also

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found by Thipkhunthod et.al. [36], who linked chemically complex proteins of sludge

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bacterias with first pseudocomponent of hemicellulosic nature and carbohydrates with

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second degradation zone of cellulosic nature. Chen et.al. [37] also found that proteins

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and carbohydrates of microalgae species approximately degraded in the hemicellulosic

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and cellulosic range. The lipids content degraded in the range of approximately 200-

600oC, which is the devolatilization range of the third pseudocomponent of the

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A
examined sewage sludge. However, although lipids is a common organic constituent of
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sewage sludges, further experimentation would be required to confirm or clarify the

exact nature of the third pseudocomponent. Regarding MSW pyrolysis, as shown in

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Figure 2c, the dynamics of this process could be well described by the adoption of only

three pseudocomponents, despite chemical complexity of this sample. Moreover, as

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mentioned in Section 2.1, lignocellulosic materials like paper, woody materials and

others dominate in MSW composition, while plastics have been removed and that is
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why the characteristic degradation zone between 400-500oC attributed to degradation

of fractions of plastics [38], is missing.

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2.3 TG-MS analysis of the evolved volatiles from the samples and additivity assessment

of pyrolysis light gases from blends of the samples

The TG/MS profile of CO2 and CO light gases evolved from the pyrolysis of each of

the examined samples is illustrated in Figure 3a-c, together with the corresponding

DTG curve. By comparing with the DTG profile, as well as with the profile of the

deconvolution curves (Figure 2), it can be deduced that CO2 evolution arise from the

contribution of all pseudocomponents for all three samples. On the contrary, CO seems

to be the result of all the components degradation that constitute the initial raw material

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only for OK sample, while for SS and MSW this is not the case, judging by the existing

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difference between CO and DTG profiles. It is telling to note that in the case of SS not

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only CO is much less than CO2 evolution, comparing with the other two samples, but

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also CO evolves mainly from the contribution of the third and fourth degradation zone

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and much less from the second. Moreover, the degradation of second pseudocomponent
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of cellulosic nature, is mainly responsible for CO evolution in the case of MSW sample.
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The evolution profiles of CH4 and H2, illustrated in Figure 4a,b, were differentiated
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from the corresponding DTG curves, a fact that had been also noted in a previous

research regarding pyrolysis of other kind of biomass samples [31]. While the
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characteristic shoulder in the range of 420-440oC, attributed to –OCH3 functional group

cracking, mainly from lignin, is present for the examined OK sample as well as other
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woody biomass samples or energy crops in the literature, [10,31,39] it is absent from

the CH4 profile of SS and MSW. However, all three samples exhibit the characteristic
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peak of higher temperatures at a maxima of about 515-535oC, depending on the sample.

This peak may also appear at slightly higher temperatures for other biomass samples
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and it is due to charring processes that include demethylation with the creation of a

solid with more reticulated structure [40]. H2 production, which initiate above 480oC

for the examined samples, is also the result of charring processes with the creation of a

more condensed aromatic structure, due to hydrogenation reactions [41]. The profile
production of NH3 and HCN, known to be precursor compounds for NOx emissions

during combustion processes [42], is illustrated in Figures 5a,b. Regarding NH3 profile,

all samples present a peak with a maximum at around 340oC (±7oC). Comparing the

quantity of NH3 emitted in this zone between the three examined samples, this seems

to be nearly linked to nitrogen content differences of the raw materials proximate

analysis. The slight second peak in the 600-800oC temperature zone for OK, may be

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attributed to charring transformation processes [43], while appreciable NH3 evolution

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from the SS sample is present between 600-750oC and can be linked to the

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4thpseudocomponent of the kinetic evaluation (Figure 2b). The origin of nitrogen

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compounds evolution in sewage sludges is mainly attributed to proteins and amino

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acids present in bacterial matter of microorganisms [44,45]. The other precursor N-
N
compound HCN, presents a characteristic delayed evolution as its emission initiates

above 300oC, as well as a peak at higher temperatures (470±10oC), a fact that can be
A
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observed for all three examined samples. The HCN profile of MSW and OK almost

coincides, while the one of SS has a different pattern with greater HCN quantities
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released. An additional peak at higher temperatures at about 620oC and a continuous

release up to 765oC (contrary to other two samples) can be observed in relation to NH3
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origin of evolution. The evolution of another important emission and corrosion

compound HCl, is shown in Figure 5c. As expected, MSW with greater Cl content
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presents the highest peak (around 340oC) while the corresponding signal from the SS

sample is negligible and almost related to background noise. However, notable HCl
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emission can be observed from OK sample if one compares Cl content of MSW and

OK proximate analysis, leading to the conclusion that the last value may not be

determinant for HCl emissions during pyrolysis.

The cumulative production of light gases, tar, water and other volatiles in the

temperature range of pyrolysis (up to 600oC and 800oC), as well as the average higher

heating value (HHV) of the pyrolysis gas (including compounds up to C3), are shown

in Table 4. HHV was determined by calculation of the average percentage mol content

of light gases in the examined temperature range and the heat of combustion values of

each gas in the mixture. The yield of condensable products (excluding water) lies inside

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a narrow range between 29.0-36.5%wt of raw material mass for the three samples, with

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the yield of SS being the greatest. This range is a typical percentage one for evolution

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of condensables, under slow heating rate pyrolysis of biomass materials. On the

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contrary, the pyrolytic water content is obviously lower for MSW, either expressed as

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a percentage on initial material basis (5.3%) or in total condensable products (14.2%).

Τhe SS water content is also considered to be low, nevertheless even lower values have
N
A
been reported in the literature for sewage sludges [46]. Regarding the quantities of light
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gases evolved per mass of raw material, major differences between the samples are

observed for CO where OK dominates, as well as C3, where evolution from SS sample
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is greater. Total quantity of light gases including C2, C3 is greater for OK and lesser for

SS which has also lower volatiles. The gross calorific value of the mixture of pyrolysis
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light gases from OK (14.4MJ/Nm3) is considered to be satisfactory for the energy

requirement of pyrolysis units [5]. The calorific value of the light gases from the other
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two samples is even higher and especially for SS (22.4 MJ/Nm3 in the range of coke

oven gas), due to its higher C3 content with higher heat of combustion values.
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The experimental TG/MS profiles of some light gases evolved from the pyrolysis of

OK, SS and MSW samples and the mixtures of them (OK/SS and OK/MSW sample at

a ratio 7:3), are presented in Figures 6a-b and 7a-d and g (OK/SS mixture), as well as

in Figures 6c-d and 7e-f and h (OK/MSW mixture). In the same Figures the theoretical
evolution profile calculated using the TG/MS profile of gas from each sample

participating in the mixture at the specified ratio (7:3) and assuming full additivity, is

also presented for comparison. The additivity assessment picture is completed by the

data presented in Table 5, relating to the deviation between experimental and calculated

values for all light gases and water and for each examined mixture at a temperature

range up to 600oC. This deviation was calculated according to equation (4), adapted for

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MS data instead of the DTG ones. The light gases evolved from both mixtures can be

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then categorized into two groups in terms of their additivity (or synergy) behavior. As

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can be resulted from the experimental and calculated profiles in Figures 6a-d, as well

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as from the high corresponding deviation values (Table 5), the first group (CO and H2)

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presents a clear non-additive behavior, as synergy effects seem to suppress the
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evolution of these two compounds from both mixtures, when compared to the
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theoretical values. CO evolution is restrained, especially in the hemicellulose and
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secondarily in the cellulose degradation temperature range, as it starts at higher

temperature and its maximum production rate is much lower particularly for the
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OK/MSW mixture. CO inhibition due to co-pyrolysis or even a radical change of MS

profile have been also mentioned in the literature for other materials [47,48]. CO
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however seems to present more (or nearly) additive behavior for temperatures higher

than 450oC. On the contrary, H2 production synergistic behavior occurs only at higher
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temperatures, greater than 550oC, where dehydrogenation reactions of aromatic

structures during the charring processes are favored [19,40], likely due to ash
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compositional change of the mixtures affecting these reactions [49]. It is worth noting

that cases of experimental hydrogen production higher than the theoretically expected

from the mixture [9,50] or lower than the theoretically expected [48,49], as well as

cases of additivity or weak synergetic effects [15] have been recorded in the literature,
depending mainly on the compounds of the mixture, the mixing ratio and the co-

pyrolysis reactor used for each case. When a fixed bed reactor was used for co-

pyrolysis, H2 production was affected by secondary reactions and synergy was linked

to this kind of reactions resulting in higher than theoretically expected production of H2

[9,50].

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The second group of compounds consists of the rest light gases (CH4, CO2, C2, C3, NH3,

IP
HCN, HCl) and water, which generally present additive or slight synergistic behavior

at the whole experimental temperature range of co-pyrolysis, as can be observed from

R
SC
Figures 7a-h. Regarding the hydrocarbons CH4, C2, C3, the evolution of which usually

follow a similar production pathway [10], slightly non-additive behavior appears at

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lower temperatures (below 350oC) and the deviation value for both mixtures (equation
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4) and for temperature range up to 600oC does not exceed 8.8% (case of C2 for
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OK/MSW mixture). Nearly absence of synergy effects is observed for CO2 evolution
M

for the whole temperature range and for both mixtures. The corresponding deviation

does not exceed the low value of 3.5%. Synergy effects for CO2 have been found in the
ED

literature to relate with secondary reactions taking place in reactors other than

thermogravimeters, mainly in setups of fixed bed type [9,15,20,50]. However some

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cases of synergetic effects have been also reported in TGA reactors for different
E

materials than the ones examined and for some mixing ratios [46,51]. The NOx
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precursor compounds, NH3 and HCN exhibit additive behavior in co-pyrolysis, as can

be observed from the MS profiles (Figures 7e, g, h) and the deviation values of Table
A

5. It is worth mentioning that additivity of NH3 and HCN applies to the OK/SS mixture

as well, despite the high nitrogen content SS and the non-negligible one of OK, the

release of which in various types of N-compounds in gas phase could be more or less

affected by co-pyrolysis synergistic interactions. NH3 increase or inhibition have been

reported for pyrolysis of other N-containing materials with biomass in some researches,

as a consequence of this synergy [3,52,53]. On the other hand, slight synergistic effects

can be deduced from the examination of MS profile of HCl for the mixture of OK with

MSW (Figure 7f), taking also into account the corresponding deviation of 11.6% (Table

5). The additivity assessment was not carried out for the other mixture, because it was

irrelevant, due to negligible HCl evolution from the pyrolysis of single SS sample, as

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aforementioned. Strong co-pyrolysis synergistic interactions for HCl have been found

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by other researchers, but mainly for the higher temperature zone of HCl evolution, after

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400oC [47], where no evolution was observed for the examined samples.

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Quantitative data for light gases evolution, as well as higher heating value, tar and water

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yields for the pyrolysis of the examined mixtures are shown in Table 6. A decrease of
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the quantity of total light gases, comparing to the calculated value based on additive
A
rule (Table 6), was found to occur with co-pyrolysis. CO and H2 decrease dominates
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and contributes to the percentage decrease of total gas, due to their aforementioned

strong synergy behavior, while the decrease of other light gases was small or inside the
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repeatability of the measurements. That was the case for both the examined mixtures

and as char production was found to follow an additive behavior and no strong synergy
PT

effects were calculated regarding water production, a corresponding slight increase of

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condensable gases (tar and other heavier volatiles) was, on the other hand, determined
CC

(Table 6). Finally, the higher heating value of the OK/SS mixture does not practically

deviate from the theoretical one calculated on a mixing rule basis. This is due to
A

negligible mol fraction change of the components in total light gas mixture, comparing

to the theoretical ones. A small HHV decrease in the case of OK/MSW mixture was

observed and is attributed to the clear decrease of CO evolution (accompanied also by

mol fraction decrease), because of the co-pyrolysis synergy effects.

Conclusions

Co-pyrolysis of urban solid wastes with olive kernel is a promising method for the

valorization of these wastes in terms of energy and added-value products, reducing at

the same time their volume for land disposal. The TG/MS setup developed and

implemented in this work was found to be proper not only for the comprehensive study

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of thermal decomposition events and the qualitative analysis of evolved volatiles, but

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also for the quantitative determination of important light gases as well as of total gas,

char and tar yield. Thus, it provides useful information for practical applications at

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larger scale on system design, performance and environmental aspects.

The mixtures of olive kernel with sewage sludge and municipal solid wastes studied,

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reacted in the same temperature range as raw fuels, exhibiting maximum decomposition
N
rate at a slightly lower temperature than that of the principal component olive kernel.
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The quantities of tar and char of the mixtures could be well predicted on an additive
M

basis using the blending ratio of raw samples in the mixture, however the amount of

gases showed small deviation. The quantitative evolution of light gases could be
ED

predicted from parent fuels, except those of CO and H2. The amount of light gases from

the blends was somehow reduced as compared to olive kernel, nevertheless the heating
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value was increased being satisfactory for the energy requirements of pyrolysis units.
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Nitrogenous species, such as NH3, evolved during co-pyrolysis of olive kernel with
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sewage sludge, are much greater than in the case of the mixture with municipal solid

waste and should be of concern. Finally, the modified IPR model developed for the
A

kinetic evaluation and the deconvolution of DTG pyrolysis thermograms of all the

examined raw samples, fitted the experimental results with great accuracy.

Acknowledgements
The authors kindly thank Abea Anatoli S.A. olive processing plant, the municipality of

Chania and the solid waste management company (DEDISA S.A.) for providing the

raw materials of olive kernel, sewage sludge and municipal solid waste respectively.

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Figure 1: Comparison between experimental and calculated DTG thermograms

of mixtures of (a) OK with SS and (b) OK with MSW samples
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A
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RIP
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 Figure 2: Deconvolution pyrolysis curves according to modified IPR model for
(a) OK (b) SS and (c)MSW

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Figure 3: DTG, CO2 and CO profiles for (a) OK (b) SS and (c)MSW
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Figure 4: (a) CH4 and (b) H2 profiles for OK, SS and MSW samples
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Figure 5: (a) NH3, (b) HCN and (c) HCl profiles for OK, SS and MSW samples
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Figure 6: Synergistic effects in CO, H2 evolution from pyrolysis of mixture of OK

with SS (a,b) and OK with MSW (c,d)
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Figure 7: Additive or slightly synergistic behaviour of some light gases evolved

from pyrolysis of mixture of OK with SS (a-d and g) and OK with MSW (e,f
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and h)
 TABLES

Table 1.
Proximate analysis, ultimate analysis (%dry) and calorific value of the studied
samples
OK SS MSW
Volatiles 73.1 63.6 73.6
Proximate analysis Fixed Carbon 19.8 12.8 4.1
(% wt dry) Ash 7.1 23.6 22.3

C 49.0 35.0 38.6

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H 6.7 6.1 5.8
Ultimate analysis N 2.0 4.5 1.5

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(% wt dry) S 0.3 1.7 0.31
O 34.8 28.9 31.2
Cl 0.06 0.01 0.32

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Calorific value HHV 20.6 14.8 15.6

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(MJ/kg)

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Table 2: DTG characteristic parameters of pyrolysis
Rmax (1) Tmax (2) Ymax (3) FWHM (4) Tin (5)
OK 0.0583 337 0.63 78 195
SS 0.0373 290 0.84 112 183
MSW 0.0621 340 0.65 68 190
OK/SS exp. (*) 0.0458 333 0.67 94 190
OK/SS calc. (**) 0.0489 334 0.66 94 194
OK/MSW exp. (*) 0.0553 334 0.66 75 195
OK/MSW calc. (**) 0.0592 338 0.63 73 198

(*) experimental DTG curve

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(**) theoretically calculated (from mixing rule) DTG curve
(1) maximum DTG rate [min-1]

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(2) temperature at maximum DTG rate [oC]
(3) yield at maximum DTG rate

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(4) full width at half maximum [oC]
(5) temperature at 1% conversion

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Table 3: Kinetic parameters for the studied samples according to the modified IPR
model
Kinetic parameters OK SS MSW
E1(kJ/mol) 85.3 134.0 92.1

A1(min-1)* 8.66.107 8.05.1011 1.24.108

C1 0.12 0.12 0.15

E2(kJ/mol) 132.9 133.7 152.5

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A2(min-1) * 2.69.1011 1.27.1011 6.98.1012

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C2 0.24 0.14 0.25

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E3(kJ/mol) 46.2 33.9 31.8

A3(min-1) * 3.94.102 6.24.101 2.51.100

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C3 0.24 0.27 0.20
E4(kJ/mol) 47.9 44.8 -

A4(min-1) * 9.56.101 U
2.04.101 -
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C4 0.08 0.13 -
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Table 4: Cumulative production of volatiles from pyrolysis and average higher heating
value of light gases at temperature range up to 600oC and 800oC
OK SS MSW
(600/800oC) (600/800oC) (600oC)
H2 (Nm3/t biom.) 14.9/96 9.3/49 31.1
CO (Nm3/t biom.) 55.8/76 13/38 23.2
CH4 (Nm3/t biom.) 22.3/25 18/22 22.0
CO2 (Nm3/t biom.) 89.2/94 54/72 83.4

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C2 (Nm3/t biom.) 10.2/11.4 7.1/8.0 12.1

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C3 (Nm3/t biom.) 3.8/4.3 11.2/13.4 6.7
Sum of light

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196/309 113/204 179
gases (Nm3/t biom,)

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Gas HHV
(MJ/Nm3, 14.4 22.4 16.8
(600oC)
Tar and other
volatiles (*)
29.0 U
36.5 32.1
N
H2O (**) 10.0--25.6 7.5--17.0 5.3--14.2
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(*) %w/w dry biomass at 600oC
(**) %w/w dry biomass -- % in tar and other condensables at 600oC
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Table 5: Deviation between experimental and calculated values assuming an additive
mixing rule
Deviation (%) Deviation (%)
OK/SS OK/MSW
(up to 600oC) (up to 600oC)
H2 25.7 19.6
CO 18.1 29.4
CH4 4.0 5.7

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CO2 3.5 2.5

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C2 8.5 8.8
C3 4.8 5.0

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NH3 4.3 3.7

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HCN 6.5 3.9
HCl - 11.6
H2 O 5.0
U 5.4
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Table 6: Quantitative TG/MS data for OK/SS and OK/MSW mixtures at 600oC

OK/SS OK/SS OK/MSW OK/MSW

additivity additivity
experimental rule experimental rule
(600 oC) (600oC) (600oC) (600oC)
H2 (Nm3/t 11±0.6 / 13.2±0.5 / 17.4±0.9 19.8±0.7
biom.) 44(800oC) 81.9(800oC)
CO (Nm3/t
27.7±0.8 43.0±1.1 27.7±0.8 46.0±1.1
biom.)

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CH4

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(Nm3/t 20.7±0.6 21.0±0.5 20.6±0.6 22.2±0.5
biom.)

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CO2
(Nm3/t 73.6±1.7 78.6±1.5 86.0±2.0 87.5±1.5

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biom.)

C2 (Nm3/t
9.7±0.3 9.3±0.2 9.1±0.3 10.8±0.2
biom.)

C3 (Nm3/t
biom.)
5.9±0.2 6.0±0.1 U 4.3±0.1 4.7±0.1
N
Sum of
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light gases
149±2.1 171.1±2.0 165.1±2.4 190.9±2.1
(Nm3/t
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biom,)

Gas HHV
16.9±0.3 16.8±0.3 14.5±0.2 15.1±0.2
(MJ/Nm3)
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Tar and
rest
volatiles 34.4±1.1 31.3±1.0 31.1±1.2 29.9±1.0
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(% wt
dry)
H2O (%
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wt dry/ % 8.8±0.2/20.4 9.3±0.2/22.9 8.1±0.2/20.7 8.6±/22.3

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in tar)
Char (%
34.9±1.1 34.7±1.1 36.7±1.1 36.0±1.1
dry)
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(*) statistics of total Gas, tar and HHV are based on errors of measurements of
individual gases (with 95% confidence) and the error propagation theory