Journal Pre-proof

Influence of ultrasonic pretreatment on the co-pyrolysis characteristics and kinetic

parameters of municipal solid waste and paper mill sludge

Shiwen Fang, Yousheng Lin, Yan Lin, Shu Chen, Xiangyang Shen, Tianming
Zhong, Lixing Ding, Xiaoqian Ma

PII: S0360-5442(19)32005-5
DOI: https://doi.org/10.1016/j.energy.2019.116310
Reference: EGY 116310

To appear in: Energy

Received Date: 05 August 2019

Accepted Date: 08 October 2019

Please cite this article as: Shiwen Fang, Yousheng Lin, Yan Lin, Shu Chen, Xiangyang Shen,
Tianming Zhong, Lixing Ding, Xiaoqian Ma, Influence of ultrasonic pretreatment on the co-pyrolysis
characteristics and kinetic parameters of municipal solid waste and paper mill sludge, Energy
(2019), https://doi.org/10.1016/j.energy.2019.116310

This is a PDF file of an article that has undergone enhancements after acceptance, such as the
addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive
version of record. This version will undergo additional copyediting, typesetting and review before it
is published in its final form, but we are providing this version to give early visibility of the article.
Please note that, during the production process, errors may be discovered which could affect the
content, and all legal disclaimers that apply to the journal pertain.

© 2019 Published by Elsevier.

 Journal Pre-proof

Influence of ultrasonic pretreatment on the co-pyrolysis characteristics and kinetic

parameters of municipal solid waste and paper mill sludge

Shiwen Fanga, Yousheng Linb, Yan Linc, Shu Chena*, Xiangyang Shena, Tianming

Zhonga, Lixing Dinga, Xiaoqian Mad

aCollege of Mechanical and Electrical Engineering, Zhongkai University of Agriculture

and Engineering, 510225, Guangzhou, China

bGuangdong Provincial Key Laboratory of Distributed Energy Systems, School of

Chemical Engineering and Energy Technology, Dongguan University of Technology,

523808, Dongguan, China
cGuangzhou Institute of Energy Conversion, Chinese Academy of Sciences, 510640,

Guangzhou, China
dSchool of Electric Power, South China University of Technology, 510640, Guangzhou,

China
Abstract

In this study, through orthogonal experiments design, the influences of ultrasonic

pretreatment (frequency, power and treatment time) on co-pyrolysis and catalytic

pyrolysis of municipal solid waste and paper mill sludge were explored. The differential

thermogravimetry curves became steeper and the peak values were larger after

pretreatment, which made the pyrolysis reaction rapidly and the volatile separated out

timely. However, the change of pyrolysis characteristics was not obvious after adding

MgO. The catalytic effect of MgO increased with the increase of sludge ratio. After

pretreatment, the average activation energy of the samples had an overall increasing

trend, but the change was small. MgO had a decreasing effect on activation energy, and

with the increasing proportion of sludge the degree of reduction became significant. In

* Corresponding author.
Tel.: +86 20 36076161; fax: +86 20 36076161.
Email: weilachen@163.com. (Shu Chen).
1
 Journal Pre-proof

addition, high ultrasonic frequency had a negative effect on reducing activation energy.

Keywords： Ultrasonic pretreatment; Orthogonal; DAEM; Co-pyrolysis; MgO;

Municipal solid waste.

Nomenclature

MSW Municipal Solid Waste

PVC Polyvinyl Chloride

PMS Paper Mill Sludge

SEM Scanning Electron Microscope

TG Thermogravimetry

DTG Differential Thermogravimetry

Ti The initial temperature

Tf The terminated temperature

DTG1, DTG2, DTG3 The mass loss rate of the first, second and the thi rd peak

T1, T2, T3 The temperature of the first, second and the third peak

Mf The pyrolysis residue mass

D The pyrolysis characteristic index

Emean The average activation energy

DAEM Distributed Activation Energy Model

1 Introduction

Presently, the energy crisis caused by the depletion of fossil resources and

continual environmental deterioration as a result of overdependence on fossil fuels has

made biomass-based energy a particularly attractive research object. Municipal solid

2
 Journal Pre-proof

waste (MSW) consisted of paper, fruit and kitchen waste etc [1], is a kind of constantly

increased biomass. As for MSW contained a large portion of organic materials, it can

be considered as an energy source [2]. Meanwhile, annual generation of MSW in China

was expected to reach 200 million tons by 2016, an increase of 5.3% over the total

amount in 2015. The global waste production will be as high as 2200 and 4200 million

tons per year in 2025 and 2050, respectively. According to directive of the European

Union regulations on the renewable, sludge is defined as a special type of biomass due

to its near-zero emission of carbon dioxide [3]. Paper mill sludge (PMS) from paper

mill papermaking wastewater is a great issue risking the environment and human health

[4]. In general, about 40-50 kg of sludge is generated in the production of 1 ton of paper

[5]. Biochemical sludge of fine fiber, undissolved wood fiber, plastic sheet, nylon and

resin are the main components of PMS, which have higher organic components and can

reach more than 1000 kcal/kg (water content less than 50%). Therefore, to find a proper

waste treatment is hence an urgent and important task for the continued development

of cities.

Up to now, plenty of researchers hold interests in biomass treatment by means of

chemical, biochemical, and thermochemical processes including pyrolysis [6].

Pyrolysis, the thermal destruction lack of oxygen, is significant when it comes to the

value-added utilization of biomass [7]. And bio-oil, bio-char, and non-condensable gas

could be produced, all of which have a wide range of uses across numerous fields [8].

Additionally, co-pyrolysis, a biomass mixed with one or more other fuels, can improve

the pyrolysis characteristics and the quality and quantity of the liquid products can also

3
 Journal Pre-proof

be promoted. [9]. In recent years, with the increasing of solid waste, the co-pyrolysis

of biomass and solid waste has attracted the attention of scholars. Minquan Dai et al.

studied the behaviors, product characteristics and kinetics of catalytic co-pyrolysis

spirulina and oil shale throgh TG and Py-GC/MS [10]. Results indicated that oil shale

delayed the thermal decomposition of organic matters in spirulina. Juan D. Martinez et

al. [11] studied the co-pyrolysis of forestry waste and tires. And the quality of the bio-

oil with the add of the tire had a certain degree of improvement. Zhao Jun et al. explored

the co-pyrolysis of municipal solid waste and wheat straw to produce hydrogen-rich

syngas [12]. Yousheng Lin et al. investigated the thermochemical behavior of co-

pyrolysis beeen oil-palm solid waste and paper sludge. The lowest average activation

energy was achieved when the percentage of oil-palm solid wastes was 70% [13].

Despite many researches of pyrolysis in MSW or PMS with other fuel, only a few have

been conducted on co-pyrolysis of MSW and PMS. Catalytic pyrolysis technology

combines the pyrolysis process with the catalytic upgrading process of primary

pyrolysis steam to obtain liquid fuels with lower oxygen content or liquid products with

more abundant target products [14]. Basic metal oxides are highly active catalysts for

ketoylation and hydroxyl aldehyde condensation of carboxylic acids and carboxylic

compounds, which can effectively improve the quality of bio-oils, such as CaO and

MgO (non-toxic, economical and environmentally friendly materials) [15]. According

to the previous researches, compared to ZnO, Al2O3, ZnCl2, AlCl3, MgCl2 and activated

carbon, MgO could improved the pyrolysis thermal characteristics and declined the

activation energy. Hence, MgO was used as additive in this paper.

4
 Journal Pre-proof

Biomass pretreatment refers to the use of physical, chemical or microbial means

to optimize the treatment of raw materials. It could destroy the connection between

cellulose-hemicellulose-lignin structurea and remove lignin, so that better quality

biological oil products can be produced in the pyrolysis process. By definition,

ultrasound is an acoustic and emerging green energy at a frequency higher than the 20

kHz and is normally limited up to 1 MHz [15]. Ultrasonic can generate high shear forces

through acoustic cavitation [16] that can provide mixing, accelerate mass transfer, and

break up particulates [17]. It has been widely applied in various biological and chemical

processes. Lucie Cherpozat et al. [18] discussed the application of ultrasonic

pretreatment technology in producing bio-oil from pyrolysis wood. In this study, 0.5 h

at 170 kHz frequency and 1.5 h at 40 kHz frequency were found to increase the

production of bio-oil by 12% compared with that without pretreatment. Sridhar Pilli et

al. [19] studied the effect of ultrasonic on anaerobic degradation of sludge, indicating

that sludge reduction and methane gas production after treatment had been improved to

a large extent. From the perspective of dynamics, the influence order of each parameter

was: PH value > sludge concentration > ultrasonic intensity > ultrasonic density.

However, the work on ultrasonic pretreatment on the mixture of MSW and PMS was

hardly found.

Many scholars believe that the kinetics of biomass pyrolysis consists of an infinite

number of parallel first-order reactions, and its activation energy presents a certain

continuous distribution, which is called distributed activation energy (DAEM) [20].

Therefore, the model has two assumptions: firstly, the reaction system has many

5
 Journal Pre-proof

parallel reactions; secondly, each reaction is described by first-order kinetic mechanism

function. Nowadays, this model has become the most widely used model in the research

of pyrolysis process. Qung-vu Bach et al. studied the combustion kinetics of wet-

torrefied forest residues using DAEM [21]. Anjireddy Bhavanam et al. also used

DAEM to explore the kinetics of solid waste pyrolysis and found that the activation

energy decreased with the addition of agricultural residues [20]. Jinzhi Zhang et al. first

applied the multi-Gaussian-DAEM-reaction model for thermal decompositions

cellulose, hemicellulose and lignin [22]. Nevertheless, the study on co-pyrolysis of

MSW and PMS through DAEM was scarce.

In this paper, the ultrasonic system through orthogonal test operated at various

frequency, power, mixing ratios, treatment time for pretreatment of MSW and PMS.

Afterwards, TG was used to explore the characters of co-pyrolysis of MSW and PMS,

as well as the differences in addition of additive (MgO) pro or post pretreatment. The

differences of samples after pretreatment and the kinetics behaviors investigated by

distributed activation energy model (DAEM) were also examined in the research.

Furthermore, this work presented the value of the ultrasonic pretreatment for MSW and

PMS and provide very usefully information for system optimizing.

2 Materials and methods

2.1 Materials

The municipal solid waste (MSW) was a complex mixture. According to Hui Zhou

[23], food and fruit waste, wood, paper and PVC were consisted and the percentages as

received basis of which was 46.4%, 4.7%, 18.2% and 30.7%, respectively. In a paper

6
 Journal Pre-proof

mill in Guangdong Province China, the paper mill sludge (PMS) was gained. A series

of pre-treatments of MSW and PMS were required before the experiments. Above all,

the samples were dried at 105°C for 24 h in an oven. Then, mechanically crushed in a

grinder and sieved to obtain uniform fractions with particle size, less than 178 µm.

The pyrolysis characteristic indexes with 70%, 90% percentage of sludge were too

low and the characteristics were close to sludge which had almost no utility value. At

the same time, the pyrolysis products with high content of sludge had high content of

oxygenated compounds. It would reduce the quality of the pyrolysis products.

Therefore, MSW and PMS were mixed through a micro rotary mixer for 2 h with 90%,

70% and 50% sludge ratio, which were named as 90M10P, 70M30P and 50M50P,

respectively. Afterwards, the mixtures were dried at 105°C for 24 h in an oven. On the

basis of GB/T212-2008, GB211-84 and ASTM D5373-08, the ultimate analysis and

proximate analysis of MSW and PMS on dry basis were measured, and displayed in

Table 1. The high heating value (HHV) was calculated by Dulong equation based on

ultimate analyses:

QGVC =338.2C+1442.8  H  O / 8  (1)

C, H, and O were the mass fractions of carbon, hydrogen and oxygen. MgO, a

nontoxic economical and environment-friendly material, was purchased from a shop

and it was already widely used for solid waste treatment. It was produced by a chemical

reagent factory in Tianjing, China, and the purity was more than 98%. According to the

former and other scholar’s researches, 5% mass ratio of MgO had a greater degree to

reduce initial temperature and increase the pyrolysis characteristic index [24]. Finally,

7
 Journal Pre-proof

5% mass ratio of MgO was added into the mixture and the samples were placed in the

dry dish for the following experiments.

2.2 Experimental facility

Ultrasonic instrument KQ-500VGV, was purchased from Kunshan Ultrasonic

Instrument co., LTD China. The schematic diagram of the ultrasonic cleaning machine

was described in Fig. 1. The system is composed of: (1) heat shield, (3) water tank, (4)

controller, (5) bottom pad, (6) beaker and (8) glass cover to ensure that the samples do

not overflow. Moreover, (2) and (7) represent the water level of the water tank and

beaker, respectively. To ensure samples can all be affected by ultrasonic wave, the (2)

should be higher than (7). The factory settings of the device have three optional

frequencies of 45, 80 and 100 kHz, four adjustable powers of 200, 300, 400 and 500

W, and the operating time span is from 1 minute to 480 minutes.

The electron microscope used in this paper was S-3700N tungsten filament

scanning electron microscope (SEM) produced by Hitachi company in Japan and

equipped with Bruker energy spectrometer in Germany. The acceleration voltage is 0.3

kV-30.0 kV and the resolution is up to 3 nm. Furthermore, the magnification rate is 5-

300,000 times.

In this study, the thermogravimetric simultaneous thermal analyzer (METTLER

TOLEDO TGA/DSC1) was examined for co-pyrolysis. The main performance indexes

of the instrument are as follows: (1) the temperature accuracy is ±0.5°C, the temperature

measurement accuracy is ±0.3°C, and the linear heating rate (room temperature-

maximum temperature) is 0.1-100 °C/min. (2) during the pyrolysis process, sample

8
 Journal Pre-proof

quality measurement can be achieved at the same time with a mass measurement

sensitivity of 0.1 ug.

2.3 Experiments methods

The results of orthogonal experiment were analyzed by range analysis. Kjm was

named as sum of the corresponding experiments of the m level of column j factor. The

number could determine the quality of the level of j factor. In addition, kjm was the

average of the Kjm (kjm=Kjm/3). Rj was the range of column j factor, which responded

the fluctuation of each level. That was to say, Rj=kjmax-kjmin. According to the size of Rj,

the primary and secondary order of factors could be judged. The main working

parameters of ultrasonic were ultrasonic power, ultrasonic frequency and treatment

time [25]. Low frequencies promoted mechanical and physical phenomena and more

efficient solubilization [26]. A L9(34) [27] orthogonal test on the ultrasonic frequency

(45, 80 and 100 kHz) named as A, the ultrasonic power (200, 300 and 400 W) named

as B, the mixing ratios of MSW:PMS (9:1, 7:3 and 5:5) named as C and the treatment

time (1, 2 and 3 h) named as D was designed and displayed in Table 2.

For each ultrasonic treatment, the samples with 10 g were put into a beaker and

poured into deionized water 700 ml with constantly stirring. Afterwards, the beaker was

covered and placed into the water tank. In accordance with the orthogonal test, the

corresponding frequency, power and treatment time were set. Next, the beaker with

samples air-dried for 48 h. Finally, the samples were fetched and placed in the dry dish.

The temperature range for TG of co-pyrolysis process was from 110°C to 900°C

with 30 °C/min heating rate and the flow rate of N2 atmosphere was 80 ml/min. As for

9
 Journal Pre-proof

consistent comparison, the mass of samples was 5±0.1 mg for each experiment and all

the experiments were repeated to guarantee the correctness.

The intersection of the horizontal line on TG curve and the tangent line on DTG

curve at the maximum weightlessness rate can be defined as the initial temperature (Ti)

[24]. The corresponding temperature when the mass loss of materials in the pyrolysis

experiment reaches 98% of the total loss is defined as the terminated temperature (Tf).

The pyrolysis characteristic index (D) is determined by the fastest reaction speed and

the duration of reaction, which is used to characterize the degree of difficulty of the

pyrolysis reaction of components. The index D could be calculated by Eq. (2) [28]:

D   dw / dt max  dw / dt mean M   / TT

i max T1/2  (2)

where (dw/dt)max for the maximum mass loss rate (%/min); (dw/dt)mean for the average

mass loss rate (%/min); M∞=1-Mf/100, for the pyrolysis mass loss (%); Ti for the initial

temperature (°C); Tmax for the temperature according to the (dw/dt)max and △T1/2 for the

temperature range of the (dw/dt)/(dw/dt)max=0.5(half-peak width).

Because the pyrolysis is composed of a series of stage, the characteristic index

can be rewritten as Eq. (3):

D   i i  Di (3)

where βi is the mass loss percentage of each step in the total mass loss (%); Di is the

pyrolysis characteristic index D of each step; D is the comprehensive pyrolysis

characteristic index of all steps.

According to the Arrhenius equation (k(T)=Aexp(-ER/RT)), the pyrolysis process

of all the samples could be described by Eq. (4) [29]:

10
 Journal Pre-proof

d / dt  k T  f    A exp   E /  RT   f   (4)

where dα/dt stands for the rate of conversion, k for the rate constant, f(α) for the reaction

model, α for conversion degree in the process, %, A for the pre-exponential Arrhenius

factor, s-1, Eα for the apparent activation energy, kJ/mol, R for the universal gas constant,

kJ/mol, and T for the reaction temperature, K. Moreover, α, the conversion rate can be

defined as follows:

 =  m0  mt  /  m0  m  (5)

where m0, mt and m∞ respect the initial mass, time t and final mass of the samples,

respectively. For the non-isothermal is conversional experiments at constant heating

rate, β=dT/dt. Eq. (4) and Eq. (5) can be written as Eq. (6):

d / dT  ( A /  )exp( E / RT ) f ( ) (6)

At the same time, the integral form of Eq. (6) is shown as Eq. (7):
 T
 d / f    G    1 /   A exp   E / RT  dT (7)
0 0

The distributed activation energy model (DAEM), an effective method to conduct

a set of irreversible single (first-order) reactions, in this paper is expressed as Eq. (8)

[30]:


 t

1     exp k0  e  E / RT dt f  E  dE
0 0
(8)

where α is on the behalf of extent of conversion, k0 is the pre-frequency factor, t is the

time, R is the universal gas constant, 8.314 kJ/mol·K, T is the reaction temperature and

f(E) is the activation energy distribution, indicating the variation of the activation

energy of the first-order irreversible reaction.

11
 Journal Pre-proof

Moreover, considering that the frequency factor A is not a constant, but A=A0Tm,

combined with Eq. (7) and Eq. (8), the improved DAEM equation is as follows:

  1   exp   A0 /  m  E , T   f  E0 ,  dE (9)
0

ψ(E,T) is the general Boltzman integral factor, as named as the general temperature

integral, can be expressed as Eq. (10) [31]:

exp  u '   a1  u '  b1  m  c1 

 m  E,T    E / R 
m 1
exp  '  (10)
u ' m 2  u  b2  m  c2 
where a1=0.000382356836470987, b1=-0.980711097079693, c1=-1.96306290504183,

b2=0.361953838478452, c2=1.47704119261266.

To obtain a higher goodness of fit, the evaluation function (O.F.) of model

optimization is shown as Eq. (11):

SSE / dof Error   e   c  /  n  p  1

2

O.F .  1  adjR  2
 (11)
SST / dofTotal   e   emean 2 /  n  1

where SSE is the sum of squares for error; SST for the sum of squares for total; n is the

number of scatters, decomposed by curves; p is the number of independent variables

for the fitting model; dofError is the degrees of freedom for SSE; dofTotal is the degrees

of freedom for SST; αe, αe-mean and αc stand for the conversion experiment value, average

value and fitting value, respectively. The closer the value of O.F. is to zero, the higher

the goodness of fit of the model is.

3 Results and discussions

3.1 The differences before and after pretreatment

The SEM images of samples before and after pretreatment were shown in Fig. 2

and Fig. 3. Moreover, the magnification was 5000 times. In Fig. 2, with the increasing

12
 Journal Pre-proof

of PMS ratio, the powdery substances increased. And it could be found that the fiber

had a complete structure without fracture and powder particles were attached to the

surface. An interesting phenomenon was showed in Fig. 3 that ultrasonic pretreatment

did not change the structure of the mixed samples to a large extent. As we know, at the

high frequency stage (100-1000 kHz), the acoustic chemical effect was mainly

manifested to stabilize bubble formation. When the bubble imploded, it could eject

violent substances and form greater energy, which could increase the contact and

reaction between liquid and solid particles [15]. High power also caused significant

cavitation phenomenon and induced the change of biomass structure. Thus it can be

seen that the energy was not enough to cause the changes in the morphology of the

samples. However, the surface of the treated samples was relatively rough.

A Van Krevelen diagram consisted of the horizontal and vertical coordinates of

O/C and H/C respectively (H/C vs O/C), which could allow for delineation of the

reaction pathways [32]. The Van Krevelen diagram of the samples before and after

pretreatment was exhibited in Fig. 4. The H/C ratio and O/C ratio respectively increased

and decreased with the increasing of PMS. It meant that the adding sludge could

promote the quality of bio-oil pyrolyzed by samples. In especial, 70M30P had the most

effectiveness. According to Table 2, the numbers of 1, 6 and 8 represented the mixed

proportion of 90M10P; 2, 4 and 9 represented 70M30P; and 3, 5 and 7 represented

50M50P. Not all the ultrasonic conditions could improve the elements of the samples,

only number 6 (80 kHz, 400 W, 2h) and 5 (80 kHz, 300 W, 1h) had the upgraded effects.

As can be seen from some researches [33], the carbon content would decrease after

13
 Journal Pre-proof

ultrasonic treatment. The conditions of 6 and 8, both under 80 kHz, could reduce

oxygen content substantially. An upgrade process at a frequency of 80 kHz might be

imagined.

3.2 The different effects on pyrolysis characteristics of materials

Thermogravimetric data (TG) and differential thermogravimetry (DTG) of

samples under heating rate of 30 °C/min were given in Fig. 5a and b, respectively.

Furthermore, the pyrolysis characteristic parameters and index were listed in Table 3.

The numbers of “1+” to “9+” respected for the pretreated samples (1 to 9) with MgO,

in order to ensure the effects of additive.

As illustrated in the Fig. 5b, the pyrolysis process of MSW included two main

stages. The first stage was corresponding to the decomposition of cellulose,

hemicellulose, pectin, starch and PVC. Due to the charring stage of hemicellulose, the

degradation of remaining hydrocarbons of PVC and the decomposition of lignin, the

second stage appeared [34, 35]. The pyrolysis process of PMS also could be divided

into two stages: corresponding to the decomposition of hemicellulose, cellulose and

lignin for the first stage and the tar, coke, calcium carbonate and other minerals for the

second stage [36].

For the PMS proportion was 10%, compared with 90M10P, the pyrolysis

characteristics parameters after pretreatment significantly improved. And the peak

values of the first and second peaks increased sharply, indicating that ultrasonic

pretreatment could promote the pyrolysis reaction in the first and second stages, so that

volatiles precipitated rapidly in the first stage. Among them, the experimental

14
 Journal Pre-proof

conditions corresponded to the 6 (80 kHz, 400 W, 2 h) and 8 (100 kHz, 300 W, 3 h)

had the most significant effects, which increased the value of first peak by 189.63 and

244.75 %/min, respectively. Compared with the samples without pretreatment, the

samples under number 6, reduced the initial temperature and raised the terminated

temperature which expanded the temperature range of the whole pyrolysis reaction.

However, the samples (with 8) appeared the opposite effect, that increasing the initial

temperature, lowering the terminated temperature and shortening the temperature range

of the reaction. The comprehensive pyrolysis characteristic index of samples generally

promoted after pretreatment, which concluded that the ultrasonic was helpful to reduce

the pyrolysis difficulty of samples. Adding MgO could reduce the initial temperature

and the terminated temperature of blends and moved the reaction to low temperature.

At the same time, the addition of additives did not signification promote the

optimization of the peak value, but hampered the pyrolysis reaction. It might be because

MgO as a substance not involved in the reaction, covered the surface of the sample, so

that volatiles could not be precipitated in time. Meanwhile, MgO had the possibility of

reacting with volatiles [37]. Hence, the peak value reduced. The pyrolysis index also

did not increase further due to the catalytic effect of additive. In conclusion, the working

condition corresponding to serial No.8 was the one with the optimal pyrolysis

characteristics when the sludge ratio was 10%.

For PMS ratio of 30%, the pretreatment could greatly optimize the pyrolysis

characteristics parameters of samples. The pretreated samples all could reduce the

initial temperature and the terminated temperature. It resulted that the reaction moved

15
 Journal Pre-proof

to a lower temperature section, which had the potential to save input energy. The values

of first peak increased by 31.79 %/min (2), 59.57 %/min (4) and 77.39 %/min (9),

respectively. In addition, the value of second peak was significantly enhanced under

numbers of 9, 4, 2+ and 2. The pyrolysis characteristic index increased by 6.617×10-07

(2), 14.255×10-07 (4) and 22.485×10-07 (9), respectively. After the addition of MgO, the

initial temperature raised, which might because of the energy absorption required by

the catalytic action of additive. Nevertheless, due to the catalytic effect, the terminated

temperature reduced and the reaction ended prematurely. Except for the first peak value

of the samples under number 9+, the first and second peak values of the samples all

increased compared with those before pretreatment. The first and second peaks

increased by 57.44 %/min, 14.29 %/min (2+), 5.02 %/min, 1.19 %/min (4+) and

0.65 %/min (9+), respectively. The pyrolysis characteristic index of 2+ (16.134×10-07)

and 4+ (2.757×10-07) were higher than that of 2.264×10-07 before pretreatment, and the

index of 2+ was higher than that of 8.881×10-07 under No.2. Based on the aboved

mentioned conditions, the working condition corresponding to serial number 9 was the

best working condition with 30% sludge ratio.

Ultrasonic pretreatment also played a positive role in improving the pyrolysis

characteristics of 50% ratio of PMS. All experimental conditions under this ratio could

increase the initial temperature and reduce the terminated temperature. Also be able to

increase the peak value and promote the separated of volatiles. Among them, the third

peak (-19.80 %/min) appeared under 7, which demonstrated that the pyrolysis reaction

at high temperature was promoted. And the values of increased pyrolysis index

16
 Journal Pre-proof

were 10.053×10-07 (3), 4.932×10-07 (5), 5.103×10-07 (7), 13.921×10-07 (3+), 1.594×10-07

(5+) and 0.533×10-07 (7+), respectively. A conclusion could be drawn that with the

increase of PMS ratio, the catalytic effect of MgO became more significant. The most

obvious superposition promoting effect of pretreatment and additives was the working

condition of 45 kHz, 400 W and 3 h. In summary, the 100 kHz, 200 W, 2 h with MgO

operating conditions corresponding to serial number 3+ was the best operating

condition under this ratio.

The results of the orthogonal experiment analysis for comprehensive pyrolysis

characteristic index were listed in Table 4. It could be seen that the values of KA3, KB2,

KC1 and KD3 were the largest without additive. Therefore, to obtain the better pyrolysis

characteristic index, the working condition was 100 kHz、300 W、90M10P、3 h. On

the basis of the range, the order of influence of these four influencing factors from large

to small was judged as follows: mixing ratio > ultrasonic frequency > treatment time >

ultrasonic power. After adding MgO, the optimal condition was 45 kHz、 300 W、

7:3、 3 h with KA1、 KB2、 KC2 and KD3. At the same time, the order was ultrasonic

frequency > mixing ratio > treatment time > ultrasonic power.

The differences of the orthogonal experiment analysis for comprehensive

pyrolysis characteristic index with or without MgO were listed in Table 6. MgO could

improve the pyrolysis characteristic index of samples only at the ultrasonic frequency

of 45 kHz. When the ratio of PMS was 10%, the inhibition effect on the lifting index

was the strongest. Under the working conditions of 45 kHz, 200 W, 50M50P and 1 h,

the catalytic effect of MgO was the most significant. In the meanwhile, the catalytic

17
 Journal Pre-proof

effect on the four factors from strong to weak order was mixing ratio, ultrasonic

frequency, treatment time and ultrasonic power.

3.3 kinetics analysis

The average activation energy of samples calculated by DAEM was shown in

Table 3, and the correlation coefficients of all samples were greater than 0.99. It could

be concluded that the activation energy increased with the increasing of PMS

proportion, and the values of activation energy were between 201.545 kJ/mol (MSW)

and 237.202 kJ/mol (PMS), indicating that ultrasonic pretreatment and subsequent

catalytic action had a weak impact on the change of activation energy. The samples

were arranged according to the mixing ratio of MSW and PMS, and the average

activation energy was showed in Fig. 6. So as to compare the variation range of

activation energy clearly, a black dotted line took untreated samples as the reference

was used. After ultrasonic pretreatment, the activation energy had an upward trend.

This phenomenon was consistent with the research studied by Zhenyu Wang et. al [33].

It might be due to the links between lignin and carbohydrates and the links of some

amorphous carbohydrates were damaged by ultrasonic. Hence, the regularity of

compounds was increased [38, 39]. Also might as the alkali metals in ash were removed

through ultrasonic and the catalytic effect on pyrolysis reduced [40, 41]. The addition

of MgO had the ability to reduce the activation energy of samples after pretreatment,

except for 1+ and 6+. For 90M10P, the activation energy with number of 1, 6 and 8+,

were lower than that of untreated samples. However, the energies with 1+, 6+ and 8

were higher, but the range of change was within 3 kJ/mol. In the case of serial No.8,

18
 Journal Pre-proof

the activation energy descended by 1.32 kJ/mol through catalytic activity of MgO. The

activation energies with 8 and 1+ were the largest, while the energy was the lowest with

8+ (204.45 kJ/mol). For 70M30P, except for 4+ (207.98 kJ/mol), the activation energies

of samples in other conditions were higher than those in untreated conditions.

Meanwhile, the catalytic effect of MgO was obvious under the serial No.4 condition

(80 kHz, 200 W, 3 h), which reduced energy of 7.866 kJ/mol. The value of activation

energy under serial No. 9 condition was the largest (220.19 kJ/mol) and the lowest

under No.4+. For 50M50P, under the working conditions of 5 and 7 (the maximum

value of activation energy), the activation energies were higher than that of untreated.

Additionally, the value of activation energy with 5+ was the lowest (209.12 kJ/mol),

and the values were reduced by 9.90 kJ/mol (compared with untreated) and 16.18

kJ/mol (compared with 5), respectively. A rule could be discovered that the

experimental serial numbers of high activation energy values in three proportions were

7, 8 and 9 respectively, and the frequencies were all 100 kHz. It indicated that high

frequencies had the ability to increase activation energy.

The results of the orthogonal experiment analysis for average activation energy

were displayed in Table 5. The values of KA1, KB3, KC1 and KD3 were the maximum

without MgO. Therefore, the working condition for obtaining better pyrolysis

characteristic index was 45 kHz, 400 W, 90M10P and 3 h. According to the rage, the

order of these four factors was mixing ratio > ultrasonic frequency > treatment time >

ultrasonic power. While after adding MgO, the optimal condition was 80 kHz、300 W、

90M10P、3 h and the order was mixing ratio > ultrasonic frequency > ultrasonic power

19
 Journal Pre-proof

>treatment time. The activation energies subtracted by the values before and after

adding MgO, were shown in Table 6. MgO had a positive effect on reducing activation

energy. Moreover, the minimum (-0.73) and maximum (11.08) values for △kC1 and

△kC3 respectively, indicated that MgO had a more significant catalytic effect on sludge.

Under the working condition of 80 kHz, 200 W, 50M50P and 1 h, MgO possessed the

most significant catalytic effect. At the same time, catalytic effect on the four factors

from strong to weak order was mixing ratio > frequency> power > treatment time.

4. Conclusion

The differences of samples pro and post pretreatment, the characteristics

parameters of co-pyrolysis and catalytic pyrolysis, and the kinetic parameters were

obtained through the orthogonal experimental of ultrasonic pretreatment. After

ultrasonic pretreatment, the DTG curves became steeper and the values of peak got

larger. It accelerated pyrolysis reaction and precipitate volatile components in time. The

catalytic effect of MgO enhanced with the increasing of sludge ratio. In order to get

higher pyrolysis characteristics index, the optimal condition was 100 kHz, 300 W, 9:1,

3 h and 45 kHz, 300 W, 7:3, 3 h respectively for the case without and with MgO. MgO

could improve the pyrolysis index of samples only at the 45 kHz frequency. And under

the condition of 45 kHz, 200 W, 5:5, 1 h, the catalytic effect of MgO was most

significant.

After pretreatment, the average activation energy of samples increased slightly.

MgO had a decreasing effect on activation energy, and the change range increased with

the increase of sludge proportion. High ultrasonic frequency had a negative effect on

20
 Journal Pre-proof

reducing activation energy. In the absence of additives, the optimal condition for

obtaining the lowest average activation energy was 45 kHz, 400 W, 9:1, 3 h. After MgO

was added, the optimal working condition was as follows: 80 kHz, 300 W, 9:1, 3 h. At

80 kHz, 200 W, 50M50P and 1 h, the catalytic effect of MgO was the most significant.

At the same time, the influence of catalysis on the four factors from strong to weak in

the order was mixing ratio, frequency, power and action time.

Acknowledgements

This work was supported by the National Natural Science Foundation of China

(51606227); the Guangdong Natural Science Foundation (2018A030310026).

5. References
[1] Fang S, Yu Z, Lin Y, Hu S, Liao Y, Ma X. Thermogravimetric analysis of the co-pyrolysis of paper
sludge and municipal solid waste. Energy Conversion and Management. 2015;101:626-31.
[2] Psomopoulos CS, Bourka A, Themelis NJ. Waste-to-energy: A review of the status and benefits in
USA. Waste Manag. 2009;29(5):1718-24.
[3] Urych B, Smoliński A. Kinetics of Sewage Sludge Pyrolysis and Air Gasification of Its Chars. Energy
& Fuels. 2016;30(6):4869-78.
[4] Fang S, Yu Z, Ma X, Lin Y, Chen L, Liao Y. Analysis of catalytic pyrolysis of municipal solid waste
and paper sludge using TG-FTIR, Py-GC/MS and DAEM (distributed activation energy model). Energy.
2018;143:517-32.
[5] Cho D-W, Kwon G, Yoon K, Tsang YF, Ok YS, Kwon EE, et al. Simultaneous production of syngas
and magnetic biochar via pyrolysis of paper mill sludge using CO 2 as reaction medium. Energy
Conversion and Management. 2017;145:1-9.
[6] FitzPatrick M, Champagne P, Cunningham MF, Whitney RA. A biorefinery processing perspective:
treatment of lignocellulosic materials for the production of value-added products. Bioresour Technol.
2010;101(23):8915-22.
[7] Imam T, Capareda S. Characterization of bio-oil, syn-gas and bio-char from switchgrass pyrolysis at
various temperatures. Journal of Analytical and Applied Pyrolysis. 2012;93:170-7.
[8] Czernik S, Bridgwater AV. Overview of Applications of Biomass Fast Pyrolysis Oil. Energy & Fuels.
2004;18(2):590-8.
[9] Krerkkaiwan S, Fushimi C, Tsutsumi A, Kuchonthara P. Synergetic effect during co-
pyrolysis/gasification of biomass and sub-bituminous coal. Fuel Processing Technology. 2013;115:11-
8.
[10] Dai M, Yu Z, Fang S, Ma X. Behaviors, product characteristics and kinetics of catalytic co-pyrolysis
spirulina and oil shale. Energy Conversion and Management. 2019;192:1-10.
21
 Journal Pre-proof

[11] Martínez JD, Veses A, Mastral AM, Murillo R, Navarro MV, Puy N, et al. Co-pyrolysis of biomass
with waste tyres: Upgrading of liquid bio-fuel. Fuel Processing Technology. 2014;119:263-71.
[12] Jun Z, Shuzhong W, Zhiqiang W, Haiyu M, Lin C. Hydrogen-rich syngas produced from the co-
pyrolysis of municipal solid waste and wheat straw. International Journal of Hydrogen Energy.
2017;42(31):19701-8.
[13] Lin Y, Ma X, Yu Z, Cao Y. Investigation on thermochemical behavior of co-pyrolysis between oil-
palm solid wastes and paper sludge. Bioresour Technol. 2014;166:444-50.
[14] Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy.
2012;38:68-94.
[15] Fang S, Gu W, Chen L, Yu Z, Dai M, Lin Y, et al. Ultrasonic pretreatment effects on the co-pyrolysis
of municipal solid waste and paper sludge through orthogonal test. Bioresource Technology. 2018;258:5-
11.
[16] Khanal SK, Montalbo M, Leeuwen Jv, Srinivasan G, Grewell D. Ultrasound enhanced glucose
release from corn in ethanol plants. Biotechnology & Bioengineering. 2010;98(5):978-85.
[17] Li X, Mettu S, Martin GJO, Ashokkumar M, Lin CSK. Ultrasonic pretreatment of food waste to
accelerate enzymatic hydrolysis for glucose production. Ultrasonics sonochemistry. 2019;53:77-82.
[18] Cherpozat L, Loranger E, Daneault C. Ultrasonic pretreatment effects on the bio-oil yield of a
laboratory-scale slow wood pyrolysis. Journal of Analytical and Applied Pyrolysis. 2017;126:31-8.
[19] Pilli S, Bhunia P, Yan S, LeBlanc RJ, Tyagi RD, Surampalli RY. Ultrasonic pretreatment of sludge:
a review. Ultrasonics sonochemistry. 2011;18(1):1-18.
[20] Bhavanam A, Sastry RC. Kinetic study of solid waste pyrolysis using distributed activation energy
model. Bioresour Technol. 2015;178:126-31.
[21] Bach Q-V, Tran K-Q, Skreiberg Ø. Combustion kinetics of wet-torrefied forest residues using the
distributed activation energy model (DAEM). Applied Energy. 2017;185:1059-66.
[22] Zhang J, Chen T, Wu J, Wu J. Multi-Gaussian-DAEM-reaction model for thermal decompositions
of cellulose, hemicellulose and lignin: comparison of N(2) and CO(2) atmosphere. Bioresour Technol.
2014;166:87-95.
[23] Zhou H, Meng A, Long Y, Li Q, Zhang Y. An overview of characteristics of municipal solid waste
fuel in China: Physical, chemical composition and heating value. Renewable and Sustainable Energy
Reviews. 2014;36:107-22.
[24] Fang S, Yu Z, Lin Y, Lin Y, Fan Y, Liao Y, et al. A study on experimental characteristic of co-
pyrolysis of municipal solid waste and paper mill sludge with additives. Applied Thermal Engineering.
2017;111:292-300.
[25] Rasapoor M, Ajabshirchi Y, Adl M, Abdi R, Gharibi A. The effect of ultrasonic pretreatment on
biogas generation yield from organic fraction of municipal solid waste under medium solids
concentration circumstance. Energy Conversion and Management. 2016;119:444-52.
[26] Rasapoor M, Adl M, Baroutian S, Iranshahi Z, Pazouki M. Energy performance evaluation of
ultrasonic pretreatment of organic solid waste in a pilot-scale digester. Ultrasonics sonochemistry.
2019;51:517-25.
[27] Zhang Z, Fang H, Yan H, Jiang Z, Zheng J, Gan Z. Influencing factors of GaN growth uniformity
through orthogonal test analysis. Applied Thermal Engineering. 2015;91:53-61.
[28] Zheng J, Jin YQ, Chi Y, Wen JM, Jiang XG, Ni MJ. Pyrolysis characteristics of organic components
of municipal solid waste at high heating rates. Waste Manag. 2009;29(3):1089-94.
[29] Jaroenkhasemmeesuk C, Tippayawong N. Thermal degradation kinetics of sawdust under
22
 Journal Pre-proof

intermediate heating rates. Applied Thermal Engineering. 2016;103:170-6.

[30] Lin Y, Chen Z, Dai M, Fang S, Liao Y, Yu Z, et al. Co-pyrolysis kinetics of sewage sludge and
bagasse using multiple normal distributed activation energy model (M-DAEM). Bioresour Technol.
2018;259:173-80.
[31] Lin Y, Tian Y, Xia Y, Fang S, Liao Y, Yu Z, et al. General distributed activation energy model (G-
DAEM) on co-pyrolysis kinetics of bagasse and sewage sludge. Bioresour Technol. 2019;273:545-55.
[32] Lin Y, Ma X, Peng X, Yu Z. Hydrothermal carbonization of typical components of municipal solid
waste for deriving hydrochars and their combustion behavior. Bioresour Technol. 2017;243:539-47.
[33] Wang Z, He Z, Zhao Z, Yi S, Mu J. Influence of ultrasound-assisted extraction on the pyrolysis
characteristics and kinetic parameters of eucalyptus. Ultrasonics sonochemistry. 2017;37:47-55.
[34] Sørum L, Grønli MG, Hustad JE. Pyrolysis characteristics and kinetics of municipal solid wastes.
Fuel. 2000;80(9):1217-27.
[35] Peng H, Wang N, Hu Z, Yu Z, Liu Y, Zhang J, et al. Physicochemical characterization of
hemicelluloses from bamboo (Phyllostachys pubescens Mazel) stem. Industrial Crops and Products.
2012;37(1):41-50.
[36] Yanfen L, Xiaoqian M. Thermogravimetric analysis of the co-combustion of coal and paper mill
sludge. Applied Energy. 2010;87(11):3526-32.
[37] Aboulkas A, El harfi K, El Bouadili A. Thermal degradation behaviors of polyethylene and
polypropylene. Part I: Pyrolysis kinetics and mechanisms. Energy Conversion and Management.
2010;51(7):1363-9.
[38] Alvira P, Tomas-Pejo E, Ballesteros M, Negro MJ. Pretreatment technologies for an efficient
bioethanol production process based on enzymatic hydrolysis: A review. Bioresour Technol.
2010;101(13):4851-61.
[39] Koutsianitis D, Mitani C, Giagli K, Tsalagkas D, Halasz K, Kolonics O, et al. Properties of
ultrasound extracted bicomponent lignocellulose thin films. Ultrasonics sonochemistry. 2015;23:148-55.
[40] Olsson JG, J?glid U, Pettersson JBC, Hald P. Alkali Metal Emission during Pyrolysis of Biomass.
Energy & Fuels. 1997;11(4):779-84.
[41] Raveendran K, Ganesh A, Khilar KC. Influence of mineral matter on biomass pyrolysis
characteristics. Fuel. 1995;74(12):1812-22.

23
 Journal Pre-proof

Highlights
 Study on the co-pyrolysis of municipal solid waste and paper mill sludge.

 The differential thermogravimetry curves became steeper after pretreatment.

 Distributed activation energy model was used to calculate the kinetic parameters.

 The average activation energy had a minor increasing trend after pretreatment.

 High ultrasonic frequency had a negative effect on reducing activation energy.

Table 1

The ultimate analyses and proximate analyses of MSW and PMS on dry basis.

Ultimate analyses (wt.%) Proximate analyses (wt.%)

Samples HHV (kJ/kg)
C H O N S Volatile Fixed carbon Ash

MSW 40.66±0.15 5.45±0.06 43.80±0.12 0.54±0.001 0.18±0.002 76.51±0.12 14.12±0.33 9.37±0.213 13715.14±57.48

PMS 18.92±0.10 1.79±0.009 16.71±0.09 1.89±0.01 0.68±0.06 39.15±0.15 0.84±0.09 60.01±0.249 5967.71±30.57

Table 2

The L9(34) orthogonal test used for study.

Factors
Numbers
A/kHz B/W C D/h

1 45 200 9:1 1

2 45 300 7:3 2

3 45 400 5:5 3
 4 80 200 7:3 3

5 80 300 5:5 1

6 80 400 9:1 2

7 100 200 5:5 2

8 100 300 9:1 3

9 100 400 7:3 1

Table 3 The pyrolysis characteristics parameters and average activation energy of samples

Tia Tfb Mf c DTG1 d T1 e DTG2 d T2 e DTG3 d T3 e D Emean R2

Samples
(°C) (°C) (%) (%/min) (°C) (%/min) (°C) (%/min) (°C) （10-07） (kJ/mol)

MSW 269.4 890.0 15.07 -31.26 309.9 -6.45 469.1 - - 3.049 201.545 0.9998

90M10P 272.1 887.0 24.66 -29.74 303.8 -6.35 477.1 - - 2.706 204.877 0.9996

70M30P 276.2 884.0 31.36 -27.42 307.5 -3.19 474.6 - - 2.264 208.171 0.9995

50M50P 275.2 878.0 46.36 -12.32 313.7 -2.75 462.2 -2.48 692.5 0.391 219.021 0.9991
PMS 676.7 863.0 61.77 -3.61 329.0 - - -4.64 716.0 0.016 237.202 0.9986

1 271.6 888.0 22.04 -56.89 307.9 -16.18 475.8 - - 10.157 204.557 0.9997

2 276.0 878.0 40.21 -59.21 308.1 -16.64 475.8 - - 8.881 212.138 0.9996

3 277.4 876.0 45.80 -64.59 311.7 -19.01 473.8 - - 10.444 216.010 0.9995

4 275.4 881.0 41.72 -86.99 310.2 -28.89 476.5 - - 16.519 215.856 0.9996

5 276.4 870.0 54.28 -49.20 313.5 -20.71 468.1 - - 5.323 225.301 0.9994

6 271.5 888.0 18.43 -219.37 307.1 -57.03 476.1 - - 122.091 204.567 0.9997

7 275.9 863.0 57.78 -48.35 318.1 -23.18 458.6 -19.80 693.5 5.494 228.816 0.9997

8 274.7 879.0 31.74 -274.49 308.2 -69.09 475.5 - - 190.432 205.776 0.9998

9 275.4 875.0 50.32 -108.41 312.0 -39.62 473.0 - - 24.749 220.187 0.9993

1+ 272.4 883.0 31.10 -46.61 307.8 -13.78 475.0 - - 5.948 207.318 0.9997

2+ 278.2 876.0 40.27 -84.86 310.5 -17.48 474.1 - - 16.134 211.043 0.9996

3+ 275.4 873.0 42.64 -80.57 313.1 -30.52 475.1 - - 14.212 213.398 0.9997
 4+ 285.6 877.0 33.77 -32.44 309.5 -4.38 480.7 - - 2.757 207.989 0.9997

5+ 281.4 878.0 36.29 -30.18 312.4 -4.47 472.0 - - 1.985 209.121 0.9997

6+ 271.3 880.0 28.15 -23.91 310.9 -7.97 475.1 - - 1.357 205.328 0.9998

7+ 282.7 874.0 44.33 -18.60 216.2 -3.82 470.6 - - 0.924 214.362 0.9996

8+ 271.3 881.0 25.52 -26.88 309.8 -7.88 475.1 - - 1.726 204.454 0.9998

9+ 278.2 873.0 46.35 -15.98 313.0 -3.84 472.5 - - 0.502 215.288 0.9996

aT , the initial temperature.

i

bT , the terminated temperature.

f

cM , the pyrolysis residue mass.

f

dDTG
1, DTG2, DTG3, the mass loss rate according to the first peak, the second peak and the third peak.

eT
1, T2, T3, the temperature according to the first peak, the second peak and the third peak.

D, the comprehensive pyrolysis characteristics index.

Emean, the average activation energy.

R, the correlation coefficients.

Table 4 The results of the orthogonal experiment analysis for comprehensive pyrolysis characteristic index

Comprehensive pyrolysis characteristic index

None MgO

A B C D A B C D

K1 29.48 32.17 322.68 40.23 36.29 9.63 9.03 8.43

K2 143.93 204.64 50.15 136.46 6.09 19.84 19.39 18.41

K3 220.67 157.28 21.26 217.39 3.15 16.07 17.12 18.69

k1 9.83 10.72 107.56 13.41 12.09 3.21 3.01 2.81

k2 47.98 68.21 16.72 45.49 2.03 6.61 6.46 6.14

k3 73.56 52.43 7.09 72.46 1.05 5.36 5.71 6.23

R 63.73 57.48 100.47 59.05 11.05 3.41 3.45 3.42

 Table 5 The results of the orthogonal experiment analysis for average activation energy

Average activation energy

None MgO

A B C D A B C D

K1 632.70 649.23 614.90 650.05 631.76 629.67 617.10 631.73

K2 645.72 643.22 648.18 645.52 622.44 624.62 634.32 630.73

K3 654.78 640.76 670.13 637.64 634.10 634.01 636.88 625.84

k1 210.90 216.41 204.97 216.68 210.59 209.89 205.70 210.58

k2 215.24 214.41 216.06 215.17 207.48 208.21 211.44 210.24

k3 218.26 213.59 223.38 212.55 211.37 211.34 212.29 208.61

R 7.36 2.82 18.41 4.13 3.89 3.13 6.59 1.96

Table 6 The differences of the orthogonal experiment analysis for comprehensive pyrolysis characteristic index and average activation energy

with or without MgO

Comprehensive pyrolysis characteristic index Average activation energy

A B C D A B C D

△k1 -2.26 7.51 104.55 10.60 0.31 6.52 -0.73 6.11

△k2 45.95 61.60 10.26 39.35 7.76 6.20 4.62 4.93

△k3 72.51 47.07 1.38 66.23 6.89 2.25 11.08 3.93

R 74.77 54.09 103.17 55.63 7.45 4.27 11.82 2.17