Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste

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Environmental and Carbon Dioxide Issues

Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste Components and Their Mixture: An Analytical TG-FTIR Study Yingyun Qiao, Fanfan Xu, Shili Xu, Dan Yang, Bo Wang, Xue Ming, Junhui Hao, and Yuanyu Tian Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b02571 • Publication Date (Web): 25 Sep 2018 Downloaded from http://pubs.acs.org on September 29, 2018

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Energy & Fuels

Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste Components and Their Mixture: An Analytical TG-FTIR Study

Yingyun Qiao a, Fanfan Xu a, Shili Xu b, Dan Yang c, Bo Wang a, Xue Ming a, Junhui Hao a, Yuanyu Tian a, d, * a

State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East

China), Qingdao 266580, RP China b

Shandong Hengyuan Petrochemical Co., Ltd., Linyi 251500, RP China

c

College of Science, China University of Petroleum (East China), Qingdao 266580,

RP China d

Key Laboratory of Low Carbon Energy and Chemical Engineering of Shandong

Province, Shandong University of Science and Technology, Qingdao 266580, RP China

* Corresponding Author. E-mail: [email protected] (Y Tian) Address: State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, RP China

ACS Paragon Plus Environment

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Abstract: Recently, the renewed interest in the pyrolysis of municipal solid waste has

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been aroused. In this investigation, the pyrolysis behaviors and kinetics of typical

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municipal solid waste components and their mixture at high heating rates are studied

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by using Thermogravimetry-Fourier Transform Infrared spectrometer (TG-FTIR). The

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TG/DTG results presented the different pyrolysis behaviors of each components and

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their mixture. The main volatiles were generated from 250 °C to500 °C obtained by

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FTIR results. Moreover, the consistency between volatiles release and pyrolysis

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behavior was found through FTIR and TG. By comparing the experimental and

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calculated TG/DTG curves and volatiles released curves of mixed MSW, the

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interactions between individual components has been found, which performed as the

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interactions could accelerate the first pyrolysis reaction stage and postpone the second

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and third pyrolysis reaction stage. Based on the distributed activation energy model,

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the values of activation energy of individual components and their mixture were

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distributed between 123.73 kJ·mol-1 to 312.56 kJ·mol-1. Meanwhile, the frequency

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factor of them increased along with the activation energy. Overall, those findings can

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enrich a better comprehension of the MSW pyrolysis process.

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Keywords: Municipal solid waste; pyrolysis behavior; volatiles released; TG-FTIR;

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kinetic analysis

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1. Introduction In recently years, the alternate energy sources such as biomass and municipal


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solid waste (MSW) have been widely investigated due to the increasing depletion of

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fossil fuels. MSW mainly refers to the solid wastes produced in the daily life or in

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activities that provided services for daily life, which typically made up of polymer

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wastes, biomass wastes, kitchen wastes and other inorganic materials 1. With the

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growth of economy and expansion of urbanization, the amount of MSW has increased

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year by year. The World Bank estimated that by 2025, China’s solid waste generation

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will double to more than 500 million tons annually 2. Generally, MSW has a great

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potentiality in producing syngas, tar and char that are known as bioenergy since its

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heating value can be achieved 20.57 MJ·kg-1 3. Therefore, it can be used as the source

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of heat for power generation in waste incineration power plants. Alternatively, MSW

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can also be converted to petrochemical products or high value-added chemicals by

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thermochemical treatment.

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Incineration is the main traditional thermochemical treatment for MSW in the

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past two decades because of the mature technology. However, for some reasons such

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as the dioxins (PCDD/Fs) emission and the fly ash as by-products, the incineration

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has caused opposition by public 4. Several environment-friendly treatments for MSW

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have been received extensive attention from researchers and governments all over the

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world, where pyrolysis is the most effective and clean method to retrieve energy and

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produce chemicals from wastes. According to the definition, pyrolysis is a thermal

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conversion process which is commonly carried out in the inert atmosphere (absence of

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oxygen) 5. The advantages of pyrolysis are lower pollutant emissions, higher

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recycling rates and higher economic benefits when compared to incineration. In


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addition, there is almost no waste generated during pyrolysis process because that all

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components can convert into gases, liquid (bio-oil, tar) and solid (char). However, it is

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worth noting that the pyrolysis process is affected by various factors including

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material properties, experimental conditions and apparatuses. Hence, it is important to

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be aware of the thermal decomposition behaviors of all individual components and

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their mixture to further understand the MSW pyrolysis process. Several attempts have

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been made to study the pyrolysis behavior of MSW or typical MSW components at

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laboratory-scale 6-9. The common reactors or apparatuses used in laboratory-scale

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experiments are fluidized bed, fixed bed and thermogravimetric analyzer (TGA).

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However, the main purpose of the fluidized bed or fixed bed experiments is to obtain

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the products yield of gases, oil and char. That information provided is not sufficient

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for in-depth understanding and further study of MSW pyrolysis. Moreover, the critical

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information gained from TGA analysis is also limited, which could only explain the

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pyrolysis behavior such as weight loss and pyrolysis temperature interval 10. The

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volatile products of the MSW or typical components pyrolysis process is essential to

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investigate the pyrolysis characteristics. Recently, the hyphenated TGA techniques

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which can extract further information from thermal degradation process have attracted

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widespread interest. The Thermogravimetry coupled with Fourier Transform Infrared

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spectrometer (TG-FTIR) has been widely used in analyzing the solid wastes pyrolysis

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process due to its unique advantages 11. The composition of the volatile products

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(small molecular gases and typical functional groups of large gaseous products)

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released can be detected while the thermal weight loss behavior are also recorded at


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the same time. Thus, the pyrolysis characteristics and major volatile species can be

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acquired and the weight loss change can also be associated with the emission of

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specific volatiles. In this sense, the pyrolysis study of MSW or individual components

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can be conducted on TG-FTIR.

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Kinetic study is another important aspect of MSW pyrolysis process because the

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kinetic parameters can provide guidance for design and optimization of reactors 12.

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Since the multiple integral or differential formulas, there are various methods to

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calculate the kinetic parameters, which including model-fitting methods, model-free

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methods and distributed activation energy model (DAEM) method. Several kinetics

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studies on the pyrolysis of MSW or individual components have been investigated,

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but the parameters obtained are not quite consistent 13-16. Generally, model-fitting

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methods are more complicated than model-free methods since the kinetic parameters

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obtained with an assumption of reaction mechanism function. However, the activation

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energy is the only kinetic parameter that can be gained by using the model-free

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methods. The DAEM method is another poplar kinetic method in the calculation of

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kinetic parameters for coal, biomass and solid waste because its capability to describe

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the complicated pyrolysis process 11. It is well know that the DAEM method assumes

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that there are multiple independent parallel reactions occurred simultaneously in the

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pyrolysis process, while the kinetic parameters are not the same. Furthermore, all

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parallel reactions are regarded as irreversible first-order reaction in this method. This

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assumption is reasonable here because of the diversity and complexity of MSW or

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individual components. Therefore, DAEM method has been chosen to calculate and


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evaluate the kinetic of MSW or individual components during pyrolysis process. The principal objective of this work is to study the pyrolysis behaviors and

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kinetics of typical MSW components (plastics, rubber, textile, paper, poplar wood and

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kitchen wastes) and mixed MSW at high heating rates by means of TG-FTIR. Firstly,

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pyrolysis characteristics of individual components and mixed MSW were analyzed by

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TG analysis. Then, the composition and releasing characteristics of gas-phase

95

products and functional groups were identified through infrared spectrum. By

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comparing the experimental and calculated values of mixed MSW, the interactions

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between the individual components were explored. Finally, the kinetic parameters and

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compensation effect were obtained by using DEAM method, which should be

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instructive for the design and optimization of MSW pyrolysis reactors.

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2. Materials and methods

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2.1. Materials

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Plastics (PE, PP and PVC), rubber, textile, paper, poplar wood and kitchen wastes

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(pork and rice) were chosen in this study. The plastics were purchased from Sinopec,

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China. The rubber was obtained from waste bicycle tires, the paper and textile were

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bought from market. In addition, the poplar wood was gathered from poplar trees in

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campus and the kitchen wastes were gained from canteen. The MSW sample were

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mixed by the ratio (plastics: rubber: textile: paper: poplar wood: kitchen wastes= 2: 1:

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1: 1: 1: 4) according to related literature 17. Some pre-treatments needed to be

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completed before the experiment starts. First, all samples were milled and sieved by


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grinder and sieve, which the particle size is less than 150 µm to prevent heat transfer

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effect in dynamic pyrolysis. Then, the samples were placed in oven with the

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temperature of 110 ℃ for 24h to eliminate the effects of moisture.

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2.2. Experiments

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The pyrolysis experiments of individual components and mixed MSW were

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carried out on the thermogravimetric analyzer (STA449 F3, NETZSCH, Germany)

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with a high-speed heating furnace, of which the heating rate is from 0 ℃·min-1

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to1000 ℃·min-1 and the maximum temperature is 1250 ℃. All samples were heated

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from 30 to 1000 ℃ under nitrogen (99.999% N2) atmosphere with 120 ml·min-1 (100

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ml·min-1 carrier gas and 20 ml·min-1 protective gas) at different heating rates of 50,

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100, 300, 500 and 700 ℃·min-1, respectively. In order to reduce heat transfer

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limitation, all samples were taken in platinum crucible for about 5 mg in this study.

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The release of volatiles during the entire pyrolysis process was detected by

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Fourier Transform Infrared spectrometer (TENSOR II, Bruker Optics, Germany). The

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output products from TGA were collected by FTIR through capillary bundle in

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transfer line with a constant temperature of 200 ℃ to prevent the volatiles

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condensation. In addition, FTIR analysis was conducted by the resolution of 4 cm-1

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with the spectrum at the range of 4000-440 cm-1. In order to eliminate the effect the

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background signal, it is necessary to measure the blank experiments before loading

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samples. However, the symmetrical molecules (N2, H2 and Cl2) and compounds with

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similar functional groups cannot be accurately identified by FTIR.

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2.3. Kinetic model (DAEM)


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The distributed activation energy model (DAEM) has been widely used in

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analyzing the activation energy and frequency factor of complicated reactions

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occurred in the entire pyrolysis process of fossil fuels 18, and later successfully applies

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to various raw materials such as coal, biomass and solid wastes 19. This model

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assumes that the pyrolysis of solid wastes include number of parallel first order

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irreversible reactions, which is written as follow:

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1 − / ∗ = (− ⁄ )() (1)

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Where V represents the volatile matter at time t and V* represents the effective

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volatile matter, T is the pyrolysis temperature as a function of time t. E and A are the

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activation energy and frequency factor, respectively.. Moreover, f(E) is the function of

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activation energy distribution curve and it satisfies the normalized condition as

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follow:

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( ) = 1

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(2)

The calculation of pyrolysis temperature T at any time t with the heating rate β is

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written as:

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= + t

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(3)

The Eq. (1) is simplified by an estimated method for f(E) and A provided by

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Miura and Maki 20, which is shown as:

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( ⁄ ! ) = ln( $⁄ ) + 0.6075 − ⁄$

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(4)

Thus, the kinetic parameters (E and A) can be obtained by plotting ln(β/T2) as a

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function of 1000/T with the specified values of V/V* under different heating rate

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conditions, of which the slope and intercept represent the value of E and A,


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respectively.

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3. Results and discussion

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3.1. Physicochemical parameters of materials

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The proximate and ultimate analysis of six kinds of components and mixed MSW

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are presented in Table 1. The proximate analysis was conducted based on the Chinese

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National Standards of GB/T 212-2008 and the ultimate analysis was done by using an

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elemental analyzer (Vario EL cube, Elementar, Germany). Moreover, the higher

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heating value (HHV=33.5C+142.3H-15.4O-14.5N) 21 and lower heating value

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(LHV=81C+342.5H-O/8+22.5S-6(9H+W)) 22 of components and their mixture are

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also given in Table 1.

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The rubber has the highest ash content and fixed carbon content among all

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components, while the plastics (PE, PP and PVC) have the highest volatile matter

168

content. In addition, the ash content is relatively low of all components and mixed

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MSW when compared to other fractions of proximate analysis. It is well accepted that

170

low ash content and high volatile matter content are suitable for pyrolysis due to the

171

potential available energy is high 23. The carbon element content of PE and PP is more

172

than 80%, other components are nearby 40% except rubber. Meanwhile, PE and PP

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has the highest hydrogen element content, while others are less than 9%. The nitrogen

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and sulfur content of all components are quite low except pork, which has the highest

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nitrogen element reach to 9.90%. It is worth mentioning that the chlorine content of

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PVC cannot be discovered due to the limitation of apparatus. The value of oxygen


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content of PVC in Table 1 contains a large amount of chlorine. Since the bond energy

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of C−O and C-H is lower than C-C, higher ratios of oxygen and hydrogen content

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compared with carbon in ultimate analysis could reduce the potential energy value 24.

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The definition of heating value is the energy or heat released by a unit of volume or

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mass of fuel when it is completely burned. The difference of higher heating value

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(HHV) and lower heating value (LHV) is whether to consider the latent heat of

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vaporization. As shown in Table 1, the HHV and LHV of all samples varies from 15

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to 50 MJ·kg-1. The heating values of PE, PP, rubber and mixed MSW are very high

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(more than 20 MJ·kg-1), while other components are distributed within the scope of

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15-20 MJ·kg-1. The heating value requirement for MSW incineration or pyrolysis is

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no less than 6500 KJ·kg-1 17, so all samples in this study meet the requirements of

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application.

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3.2. Pyrolysis analysis

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3.2.1. Pyrolysis analysis of individual components

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The TG and DTG curves obtained from TGA experiments of nine individual

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components at different heating rates (50, 100, 300, 500 and 700 ℃·min-1) are given

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in Fig. 1 and 2, respectively. Table S1 (Supporting Information) lists the pyrolysis

195

characteristic parameters of individual components under different heating rate

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conditions.. The pyrolysis behavior of PE and PP are similar because of their similar

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chemical structure, of which are saturated straight-chain polymer. These was only one

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major pyrolysis reaction stage can be observed during the pyrolysis process of PE and


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PP from the TG/DTG curves. The pyrolysis interval of them was about 200 ℃, which

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is relatively narrow compared to other components. Another plastic component PVC

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had a distinct difference of pyrolysis characteristics because it was manufactured from

202

the mixture of about 57% chlorine. There were two main reaction stages occurred in

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the pyrolysis process of PVC, which were the dehydrochlorination process in

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227-306 ℃ and the degradation process of remaining hydrocarbons in 399-683 ℃ 25. It

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can be observed that a significant peak at 204-660 ℃ and a weak peak at 665-998 ℃

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appeared in DTG curves of rubber component. According to the previous

207

investigation 26, the primary pyrolysis of rubber was the main stage of the entire

208

process, of which were the decomposition of plasticizer, natural rubber and synthetic

209

rubber. The second stage was the secondary cracking reactions of products under high

210

temperature condition. The pyrolysis process of textile showed that there was only

211

one pyrolysis reaction that took place from 261 ℃ to 641 ℃. The main reaction of

212

entire pyrolysis process was the decomposition of cellulose fibers and then the

213

dewater and decarboxylation process occurred at about 450 ℃ 27. It is obviously that

214

the pyrolysis of paper was two stage processes obtained from TG/DTG. The main

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weight loss occurred at 269-557 ℃ was the thermal decomposition reactions of plant

216

fibers, which including cellulose, hemicellulose and lignin. The second stage from

217

694 ℃ to 899 ℃ was the decomposition of the calcite and other additives which added

218

in the papermaking process 28. There were two peaks can be found in DTG curves that

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the main pyrolysis reactions proceed from 230 ℃ to 669 ℃ for poplar wood, which is

220

shown to be the decomposition of hemicellulose and cellulose, while the lignin


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thermal decomposition interval was wide without significant characteristic peaks. The

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pyrolysis of pork had only one reaction stage occurred at 190-647 ℃. At the initial of

223

pyrolysis, low molecular weight compounds evaporated. With the temperature

224

increased, the main degradation reactions occurred at about 360 ℃, which was the

225

thermal decomposition of organic intermediates 29. It was only one main DTG peak

226

can be found during the pyrolysis process of rice. The main reactions occurred at

227

258-618 ℃ was the decomposition of starch and a small amount of protein.

228

It is significant that there was a lateral offset in TG/DTG curves of Fig. 1 and

229

2when the heating rates increased. The reason for this displacement can be attributed

230

to the thermal lag, which is shown as a large difference between the temperatures of

231

furnace samples under high heating rate conditions. Moreover, the heat transfer

232

limitations was another factor for the lateral offset. With the increasing of heating

233

rates, the reaction time became short, which directly lead to the difficult in the heat

234

transfer from the boundary layer to the reacting surface 30. There also had a

235

phenomenon that the residues after pyrolysis decreased with the heating rates

236

increased except plastics and rubber component. High heating rates can result in rapid

237

fragmentation of biomass and enhance the yield of volatiles. It can be explained that

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the increase of heating rates would shorten the pyrolysis reaction time, thus

239

minimized the time available for secondary reactions such as tar cracking or

240

repolymerization 31. Therefore, the weight loss of biomass pyrolysis process was

241

higher under high heating rate conditions. Plastics and rubber basically have no tar

242

generated under high temperature pyrolysis, so the weight loss is not affected by the


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heating rates.

244 245

3.2.2. Pyrolysis analysis of mixed MSW

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In this study, biomass and polymers are two main categories based on the

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complex composition of MSW. Paper, poplar wood and kitchen wastes belong to

248

biomass, of which the main ingredients can be divided into cellulose, hemicellulose,

249

lignin, starch and protein. Plastics, rubber and fibers are polymers, which consist of

250

macromolecular compounds contained a high amount of hydrocarbons 16. Fig.3 shows

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the experimental and calculated TG/DTG curves for the mixed MSW pyrolysis

252

process under different heating rates, of which the calculated curves was obtained

253

from the linear combination of individual components. Table S2 in Supporting

254

Information lists the comparison of experimental and calculated values for mixed

255

MSW pyrolysis characteristic parameters. Two obvious peaks and one inconspicuous

256

peak were presented in DTG curves at all heating rates, so it can be inferred that the

257

pyrolysis process of mixed MSW could be distinguished into three reaction stages.

258

From Fig. 3, the first stage occurred at about 240-390 ℃ was the main stage due to the

259

absolute value of DTG is much high than that of other two stages. The thermal

260

decomposition of biomass ingredients and textile was the main pyrolysis reaction in

261

this stage. According to related literatures 32-34, the pyrolysis temperature interval for

262

hemicellulose was 225-350 °C, cellulose was 325-375 °C, lignin was 250-600 °C,

263

starch was 269-345 °C and protein was 220-500 °C respectively. At the initial of the

264

first pyrolysis reaction stage, the hemicellulose first began to decompose because of


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the low polymerization degree. Meanwhile, the first pyrolysis reaction of protein also

266

occurred in this stage. With the temperature increased, several primary polymerization

267

reactions of cellulose and starch began. The peaks of DTG curves reached a

268

maximum temperature values under different heating rates, then the decomposition of

269

starch and cellulose became more intensified. In addition, the primary decomposition

270

of rubber and dechlorination of PVC also happened. The second reaction stage was

271

not prominent in TG/DTG curves owing to the components pyrolysis in this stage was

272

not abundant. Lignin began to decompose in this stage due to the decomposition rate

273

of lignin is relatively slow than that of cellulose and hemicellulose. At the same time,

274

the second pyrolysis reaction stage of protein also took place. At the final of this stage,

275

the initial chain scission reactions of plastics started. In the third pyrolysis reaction

276

stage within the pyrolysis interval of 440-608 °C, the thermal decomposition of PE

277

and PP was the major reactions. The thermal cracking or decomposition of the

278

dehydrochlorinated PVC also occurred in this stage. However, there had slight

279

fluctuations in TG/DTG curves when the pyrolysis temperature above 750 °C, this

280

phenomenon resulted from the thermal decomposition of inorganic minerals

281

contained in paper and rubber.

282

There are obvious deviations between the experimental and calculated results of

283

TG/DTG curves at different heating rates can be observed in Fig. 3. The peaks of

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experimental DTG curves in the first stage were observed to offset to the low

285

temperature compared to calculated curves. And the corresponding DTG peak values

286

of experimental were low than that of linear calculation. It meant that the individual


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components interacted during the pyrolysis process of mixed MSW in this stage, and

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this interaction had a positive effect on the reaction. Yang et al.35 conducted an

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in-depth investigation of hemicellulose, cellulose, and lignin in biomass, which had

290

demonstrated that they have no apparent interaction during pyrolysis. Thus, the

291

acceleration effect can be attributed to the generation of HCl during the

292

dehydrochlorination process of PVC 36. The hydrogen chloride (HCl) could affect the

293

decomposition of hemicellulose, cellulose and lignin through catalytic effect as a

294

Lewis acid. It can not only make the reaction proceed at lower temperatures, but also

295

enhance the reaction intensity. Analogously, the difference between the experimental

296

and calculated results at the second reaction stage was similar to that of first stage.

297

This phenomenon can also be explained by the dehydrochlorination of PVC, which

298

can promote the reaction under the catalytic effect of HCl. However, as the pyrolysis

299

temperature increased, the dehydrochlorination process ended and the reaction leveled

300

off. The peaks of the third stage in experimental curves moved to the right

301

significantly compared to that of the calculated curves in Fig. 3. The main reactions

302

were the thermal degradation of plastics (PE, PP and PVC) in this stage according to

303

the pyrolysis characteristic parameters. Wu et al. 37 stated that the pyrolysis process of

304

PE/PVC blends were postponed than that of single component. Meanwhile, the same

305

retardation of PP in PVC/PP blends was found by Miranda et al. 38. Therefore, the

306

peak temperature of DTG curves would be delayed during the co-pyrolysis process of

307

mixed plastics. Similar to the individual components, the TG/DTG curves moved

308

toward higher temperatures zone along with the heating rates due to thermal lag and


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

309

heat transfer limitations. The higher the heating rate is, the less obvious the second

310

pyrolysis stage will be. It is attributed to that the high heating rates would lead to the

311

decrease of reaction time, so the reaction of each component were not obvious or even

312

simultaneous.

313 314

3.3. FTIR analysis

315

3.3.1. FTIR analysis of individual components

316

TG-FTIR is commonly used to detect the gaseous products and typical functional

317

groups in volatiles from the pyrolysis process in real time. It can provide a judgment

318

to determine the species of pyrolysis products and deepen the understanding of

319

pyrolysis behaviors. A summary for infrared bands of gaseous products and typical

320

functional groups investigated in this study are presented in Table 2. Fig. 4 shows the

321

intensity via temperature profiles of the evolution of products during pyrolysis

322

process of individual components at 100 ℃·min-1. The absorption spectrum at a

323

particular wavenumber are linear depending on the concentration of volatiles

324

according to Lambert-Beer law, so the variation of absorbance intensity could reflect

325

the evolutionary tendency of gaseous products and typical functional groups.

326

As shown in Fig. 4 (a), there were several peaks of CO2 absorbance can be

327

observed in all individual components profiles. The main reactions for the formation

328

of CO2 occurred at around 250-450 °C, which were resulted from the destruction and

329

reforming of −C=O, −COOH and R−O−R 39. When the temperature reached 700 °C,

330

there had several significant peaks of paper and rubber. It can be owing to the


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Energy & Fuels

331

decomposition of inorganic minerals (mainly CaCO3) or secondary cracking reactions

332

under high temperature conditions. Carbon dioxide is considered as one major

333

products during the biomass pyrolysis process, but there almost no release during

334

plastics pyrolysis. In addition, the generation of CO had a similar tendency with CO2

335

from 250 °C to 500 °C, but the intensity of individual components was quite different.

336

Since the secondary thermochemical decomposition of carbonyls and other volatiles,

337

there was only one obvious CO absorbance peak 40. The intensity of CO release of

338

paper, textile and poplar wood were slightly higher than other components. Fig. 4 (c)

339

depicts the intensity of CH4 release and two absorbance peaks at different temperature

340

range can be found. The first absorbance peak of CH4 release occurred at 300-500 °C.

341

This was caused by the decomposition of paper, textile, food wastes, poplar wood,

342

rubber and the first stage of PVC, of which the C-R bonds cracking and

343

recombination. Moreover, the demethylation of the methoxy groups (−O−CH3) can

344

also result in the formation of CH4 when the pyrolysis temperature above 400 °C. The

345

second absorbance peak main caused by the thermal cracking of PE and PP. The C−H

346

and C−R bonds generated from the depolymerization of PE, PP and PVC were broken

347

to form free radicals, which can undergo further recombination to form low molecular

348

gas such as methane 41. PE and PP had a much stronger intensity of CH4 release than

349

other components because of the high carbon and hydrogen content. As shown in Fig.

350

4 (d), one obvious absorbance peak of O−H was observed and it occurred in the range

351

of 260-500 °C. The O−H stretching vibration at the wavenumber of 3387 cm-1 related

352

to H2O, which was mostly generated by the cracking reaction of oxygen-containing or


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

353

hydroxyl-containing functional groups 42. Fig. 4 (e) and (f) shows the absorbance

354

curves of C=O (mainly in aldehydes, ketones, esters) and C−O (mainly in alcohols,

355

ethers, phenols), and the similar trends occurred from 250 °C to 460 °C can be found.

356

Those two functional groups mainly appeared in the pyrolysis process of

357

hemicellulose and cellulose 43. Meanwhile, the release intensity of C=O and C−O of

358

individual components were slightly similar. The intensity of poplar wood was the

359

highest, whereas plastics and rubber almost no release. Overall, the evolution of

360

volatiles release were similar among biomass but quiet different between biomass and

361

plastics. Furthermore, the evolution of gaseous products and functional groups had

362

good consistency with pyrolysis characteristics of individual components, the main

363

functional groups generated from 250°C to 500 °C corresponded to all samples

364

pyrolysis between 200-600 °C.

365 366 367

3.3.2. FTIR analysis of mixed MSW The gaseous products and typical functional groups of volatiles in the mixed

368

MSW pyrolysis process at 100 ℃·min-1 are also detected by FTIR. Fig.5 gives the

369

comparison of products release with temperature of mixed MSW by experimental and

370

calculated data. It was not hard to find that the temperature of products release

371

corresponded to the temperature mentioned in mixed MSW pyrolysis process. As

372

shown in Fig. 5 (a), there were one main absorbance peak appeared before 400 ℃ and

373

two small absorbance peaks appeared after 400 ℃ of CO2 release, which can be

374

observed both in experimental and calculated profiles. The CO2 generated from mixed


Page 18 of 37

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Energy & Fuels

375

MSW pyrolysis was more than superposition result and the released temperature was

376

shifted to earlier. The main peak of CO absorbance occurred at about 300 ℃ from

377

experimental data, of which the calculated occurred at around 370 ℃ in Fig. 5(b),

378

which was contributed to the acceleration effect by interactions However, a small

379

obvious absorbance peak appeared at 505 ℃ was only found in experimental profile.

380

This phenomenon can be explained as the interaction between the various components

381

resulted in the pyrolysis reaction for CO generation in this stage. As presented in Fig.

382

5 (c)-(f), the evolution of other products release had a good consistency between

383

experimental and calculated profiles. However, the product concentration and release

384

temperature were slightly different. For CH4, the initial release temperature of first

385

pyrolysis stage was advanced and the third stage pyrolysis temperature was postponed

386

during mixed MSW pyrolysis when compared to calculated results. In addition, the

387

intensity of CH4 release was low than calculated result at the third stage of entire

388

pyrolysis process, which was caused by the interactions among plastics. Compared

389

with the calculated results, the initial release temperature of O−H,

390

was advanced from experimental results. The O−H and C=O concentration of

391

experimental results was slightly high than calculated results, while the C−O

392

concentration is low when compared to calculated result. Therefore, it can be inferred

393

that the interactions between the individual components were able to strengthen the

394

release of CO2, CH4, O−H and C=O, and they can inhibit the generation of CO and

395

C−O at the same time.

396


C−O and C=O

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

397 398

3.4 Kinetic analysis Distributed activation energy model (DAEM) method has been widely applied in

399

calculating the kinetic parameters (activation energy Ea and frequency factor A) of the

400

pyrolysis process for solid wastes. Meanwhile, the iso-conversional method is one of

401

the most reliable way in accurate calculation of kinetic parameters 44, 45. In this study,

402

the conversion range 0.05-0.95 with the step size of 0.05 at different heating rates has

403

been chosen to investigate the kinetic.. Fig. 6 (a) displays the linear fit by plotting

404

ln(β/T2) vs 1/T for mixed MSW, Fig. 6 (b) shows the activation energy for all

405

components at different conversions and Fig 6 (c) and (d) exhibits the kinetic

406

compensation effect for rice and mixed MSW, respectively. In addition, the

407

compensation effect of other components are given in Fig. S1 (Supporting

408

Information). The kinetic parameters and compensation effect of different

409

components are listed in Table 3.

410

From Fig. 6 (a), all data points in the same conversion showed good correlation

411

with the fitting line except 0.05, 0.90 and 0.95. Obviously, the slopes and intercepts at

412

different conversions were not quite the same, which meant that the values of Ea and

413

A were mutative during the entire pyrolysis process. It might be attributed to the

414

complexity and diversity of MSW composition and the interaction between

415

components in the pyrolysis process. The same phenomenon also existed in individual

416

components, it can be explained that there were more than one single reaction

417

mechanisms during pyrolysis. And the competitive relations of those mechanisms

418

resulted in the decrease or increase of activation energy 46. As shown in Fig. 6 (b), the


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Energy & Fuels

419

values of activation energy of most components was abnormal at low (V/V* < 0.1)

420

and high (V/V* > 0.9) conversion conditions. This was because that the minor errors

421

occurred in the baseline determination can greatly affect these parameters by using

422

iso-conversion model 47. All activation energy in the conversion range of 0.2~0.8 was

423

concentrated between the values of 100~300 kJ·mol-1 except PE, PP and part of pork.

424

Moreover, the frequency factor increased along with the activation energy. The mean

425

of activation energy (Ea), frequency factor (A) and correlation coefficient (R2) are

426

listed in Table 3. Due to the PVC, rubber, paper and mixed MSW had more than one

427

weight loss stage, it was classified into different stages to obtain the kinetic

428

parameters for a clearer understanding. The average activation energy of pork, PP and

429

PE were relatively high, which was shown as 321.63 kJ·mol-1, 312.56 kJ·mol-1 and

430

296.80 kJ·mol-1, respectively. The average activation energy of first reaction stage of

431

PVC and third reaction stage of Mixed MSW were the lowest with the values of

432

123.73 kJ·mol-1 and 146.72 kJ·mol-1. The values of average activation energy of other

433

components were around 200 kJ·mol-1. However, the correlation coefficient of kinetic

434

parameters for plastics and mixed MSW was low, while that of other components

435

were more than 0.97. The main reason for the low value of correlation coefficient was

436

the inevitable errors under low and high conversion in calculation process. Moreover,

437

the heating rate range (50-700 ℃·min-1) in this study was broad and the conversion

438

range (from 0.05 to 0.95 with 0.05 step size) for calculation was also wide. To obtain

439

more reliable kinetic parameters, the confidence interval (µ=0.99) is summarized in

440

Table 4. And the calculation formulas of the confidence interval index in Excel are


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

441

listed in Table S3 (Supporting Information). The confidence interval is the estimated

442

interval of the population parameters constructed from the original data. Since the

443

lack of rigor, the confidence intervals can enhance the credibility of results in error

444

analysis of kinetic study 48. The 99% confidence intervals of Ea and A are selected in

445

this study are to provide the reference for related investigations.

446

Fig. 6 (c) and (d) shows the relationship between Ea and A for rice and mixed

447

MSW. Although the frequency factor A varied widely with the activation energy Ea,

448

they all demonstrated a strong linear relationship between the values of ln A and Ea,

449

which is known as “compensation effect” 49, 50. In many cases, the variation of these

450

parameters corresponds to the equation as ln A = a + bEa, of which a and b are

451

constants. Rice had only one main pyrolysis stage, so the compensation effect was

452

only one linear line. However, the compensation effect of mixed MSW seemed

453

slightly complicated and must be analyzed by the corresponding stages. This was also

454

suitable for other multi-stage reaction components such as PVC, rubber and paper

455

shown in Fig. S1. The equations obtained from compensation effect and their

456

correlation coefficient were summarized in the right column of Table 3. The existence

457

of kinetic compensation effect was confirmed by the high correlation coefficient

458

values.

459 460 461 462

4. Conclusion In this investigation, the TG/DTG curves of typical MSW components and mixed MSW at high heating rates were presented. Biomass components exhibited similar


Page 22 of 37

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Energy & Fuels

463

pyrolytic properties, which including the thermal decomposition of cellulose,

464

hemicellulose and lignin. Plastic components had the same pyrolysis tendency except

465

PVC. The pyrolysis process of mixed MSW had three different stages, of which the

466

first pyrolysis stage was the main stage. The interactions between different

467

components could promote the first pyrolysis stage, whereas the second and third

468

pyrolysis stage were suppressed. From FTIR analysis, the main volatiles generated at

469

the temperature interval of 250-500 °C. CO2 was the major gaseous product released

470

from the pyrolysis process except plastics, while CH4 released of plastics was higher

471

than other components. Moreover, the contradistinctive FTIR results suggested that

472

the interactions between the individual components can strengthen the release of CO2,

473

CH4, O−H and C=O and inhibit the release of CO and C−O. Through the calculation

474

of kinetic parameters and compensation effects, the DAEM was successfully

475

validated with experimental data. The activation energy values of individual

476

components and their mixture were distributed between 123.73 kJ·mol-1 to 312.56

477

kJ·mol-1. Such information obtained from this investigation can provide guiding

478

significance for industrial pilot or industrialization for MSW pyrolysis.

479 480 481

Acknowledgements The financial support of the National Natural Science Foundation of China

482

(21576294 and 21706287), Qingdao People's Livelihood Science and Technology

483

Project (16-6-2-51-nsh) and Independent Innovation Research Project of China

484

University of Petroleum (East China) (24720185022A) is gratefully appreciated by


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authors.

486 487

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(49)

(50)

126, 1037–1046. Ahmad, M.S.; Mehmood, M.A.; Taqvi, S.T.H.; Elkamel, A.;Liu, C.; Xu, J.; Rahimuddin, S.A.; Gull, M. Pyrolysis, Kinetics Analysis, Thermodynamics Parameters and Reaction Mechanism of Typha latifolia to Evaluate its Bioenergy Potential. Bioresour. Technol. 2017, 245, 491–501. Vyazovkin, S.; Burnham, A. K.; Criado, J. M.; Pérez-Maqueda, L. A.; Popescu, C.; Sbirrazzuoli, N. ICTAC Kinetics Committee Recommendations for Performing Kinetic Computations on Thermal Analysis Data. Thermochim. Acta 2011, 520 (1–2), 1–19. Hu, M.; Chen, Z.; Wang, S.; Guo, D.; Ma, C.; Zhou, Y.; Chen, J.; Laghari, M.; Fazal, S.; Xiao, B.; et al. Thermogravimetric Kinetics of Lignocellulosic Biomass Slow Pyrolysis Using Distributed Activation Energy Model, Fraser-Suzuki Deconvolution, and Iso-Conversional Method. Energy Convers. Manag. 2016, 118, 1–11. Pacheco, H.; Thiengo, F.; Schmal, M.; Pinto, J.C. A Family of Kinetic Distributions for Interpretation of Experimental Fluctuations in Kinetic Problems. Chem. Eng. J. 2018, 332, 1385-8947. Ye, G.; Luo, H.; Ren Z.; Ahmad, M.S.; Liu, C.; Tawab, A.; Al-Ghafari, A.B.; Omar, U.; Gull, M.; Mehmood, M.A. Evaluating the Bioenergy Potential of Chinese Liquor-industry Waste through Pyrolysis, Thermogravimetric, Kinetics and Evolved Gas Analyses. Energy Convers. Manag. 2018, 163, 13– 21. Narayan, R.; Antal, M. J. Thermal Lag, Fusion, and the Compensation Effect during Biomass Pyrolysis. Ind. Eng. Chem. Res. 1996, 35 (5), 1711–1721.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

638 639

Page 28 of 37

Table 1 Proximate and ultimate analysis of all samples. Samples

Plastics PE

Rubber PP

Textile

Paper

PVC

Poplar

Kitchen wastes

Mixed

wood

Pork

Rice

MSW

Proximate analysis (wt.%) Ad

-

-

-

18.74

2.70

12.59

2.70

3.70

2.38

4.32

Vd

99.98

99.97

97.23

59.52

87.55

73.84

79.81

90.56

81.33

84.55

FCd

0.02

0.03

2.77

21.74

10.21

13.57

17.49

5.74

16.29

14.13

84.13

38.64

69.94

44.51

41.05

45.39

43.63

44.17

53.76

Ultimate analysis (wt.%) C

85.47

H

14.21

14.96

4.77

5.78

6.73

6.16

6.24

8.30

6.92

8.77

N

0.08

0.23

0.14

0.40

0.37

0.04

0.18

9.90

1.24

2.01

0.24

0.24

0.11

1.42

0.91

0.35

1.99

0.96

1.07

0.98

3.72

44.78

39.81

43.50

33.51

44.22

30.16

S O

a

0.13

0.43

56.34

*

Heat value (MJ·kg-1)

640 641 642

HHV

48.84

49.37

19.64

31.02

17.54

16.38

17.36

19.84

17.65

25.55

LHV

43.64

43.91

17.97

29.41

17.23

15.95

17.28

19.79

17.39

24.08

A: ash; V: volatile matter; FC: fixed carbon; HHV: higher heating value; LHV: Lower heating value a d dry basis; by difference; * the result contains Cl.


Page 29 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

643 644

Table 2 The IR bonds for gaseous products and functional groups. Wavenumber/cm-1

Assignment

Possible compounds

2384 2180 3014 3200-3600 1650-1900 1080-1300

CO2 CO CH4 O−H Stretching C=O Stretching C−O Stretching

/ / / Water Carbonyl compounds Alcohols, phenols, esters


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

645 646

Page 30 of 37

Table 3 Kinetic parameters and compensation effect of components. Components

Stage

Kinetic parameters Ea/kJ·mol

-1

A/min

Kinetic compensation effect -1

2

R

Equation

R2

Plastics PE

/

296.80

3.49E20

0.9347

ln A=0.1794Ea−5.9437

0.9985

PP

/

312.56

1.26E22

0.9456

ln A=0.1764Ea−4.2510

0.9995

PVC

1st

123.73

2.01E16

0.9457

ln A=0.2302Ea+9.0563

0.9981

2nd

206.70

1.13E22

0.9561

ln A=0.1152Ea+26.9677

0.9651

1st

183.28

1.13E14

0.9905

ln A=0.1475Ea+5.3247

0.9884

Rubber

2nd

203.55

4.93E10

0.9742

ln A=0.1978Ea−15.6413

0.9996

Textile

/

201.54

9.59E22

0.9726

ln A=0.2354Ea+5.4755

0.9990

Paper

1st

205.69

7.01E12

0.9695

ln A=0.2152Ea−5.0756

0.9993

2nd

198.43

1.87E12

0.9710

ln A=0.1680Ea−8.9273

0.9943

Poplar wood

/

186.95

1.38E15

0.9733

ln A=0.2305Ea−8.2324

0.9950

Pork

/

321.63

2.55E26

0.9738

ln A=0.1506Ea+12.3665

0.9972

Rice

/

234.57

1.08E21

0.9751

ln A=0.2312Ea−5.8004

0.9949

1st

163.30

3.15E15

0.9571

ln A=0.6211Ea−65.7391

0.9817

2nd

187.75

6.98E16

0.9357

ln A=0.1477Ea+11.0539

0.9681

3rd

146.72

9.98E10

0.9287

ln A=0.1317Ea+6.0037

0.9625

Kitchen wastes

Mixed MSW


Page 31 of 37 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

647 648

Table 4 The activation energy and frequency factor at the confidence interval of 0.99. Components

Stage

Kinetic parameters (µ=0.99) Ea/kJ·mol-1 A/min-1

/ / 1st 2nd 1st 2nd / 1st 2nd /

279.51−314.40 286.05−339.07 111.90−135.56 196.70−213.58 169.87−196.69 193.19−213.92 175.25−227.82 164.55−246.83 195.13−200.39 150.82−218.26

1.57E19−8.21E21 1.17E20−1.35E24 1.32E15−3.06E17 3.57E21−2.50E22 1.56E13−8.17E14 6.35E9−3.83E11 1.97E20−4.66E25 1.49E13−7.32E20 2.29E10−5.54E10 3.33E11−1.18E18

/ /

223.40−419.87 212.32−256.81

9.59E19−6.80E32 6.31E18−1.85E23

1st 2nd 3rd

160.40−166.20 166.59−208.91 136.47−156.97

5.21E14−1.94E16 3.07E15−1.59E18 2.59E10−3.85E11

Plastics PE PP PVC Rubber Textile Paper Poplar wood Kitchen wastes Pork Rice Mixed MSW


Energy & Fuels

50 °C•min-1

100 °C•min-1

300 °C•min-1

LDPE

PP

80

60

60

TG/%

80

60

40

40

20

0 400

600

800

1000

400

600

800

1000

200

Rubber

Textile

100

60

60

TG/%

60

TG/%

80

20

40

20

0 800

1000

40

400

600

800

1000

200

Poplar wood

Pork

100

60

TG/%

60

TG/%

60

20

40

20

0 800

1000

Rice

40

0 200

400

600

800

1000

Temparature/°C

200

400

600

Temparature/°C

650 651

1000

20

0 600

Temparature/°C

800

100

80

40

600

Temparature/°C

80

400

400

Temparature/°C

80

200

Paper

0 200

Temparature/°C

100

1000

20

0 600

800

100

80

40

600

Temparature/°C

80

400

400

Temparature/°C

100

TG/%

40

0 200

Temparature/°C

200

PVC

20

0 200

700 °C•min-1

100

80

20

649

500 °C•min-1

100

TG/%

TG/%

100

TG/%

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 37

Fig.1. TG curves of individual components pyrolysis at different heating rates.


800

1000

Page 33 of 37

50 °C•min-1

100 °C•min-1

0

0

-300

-300

300 °C•min-1

500 °C•min-1

700 °C•min-1

0

-900

-1

-600

DTG/%⋅min

-1

-600

DTG/%⋅min

DTG/%⋅min

-1

-100

-900

-200

-300 -1200

-1200

LDPE

-1500 200

400

600

800

-400

PP

-1500

1000

200

400

Temparature/°C

600

800

1000

PVC 200

400

Temparature/°C

600

800

1000

Temparature/°C 0

0

0

-150

DTG/%⋅min

-1

DTG/%⋅min

-1

DTG/%⋅min

-200

-1

-200

-100

-400

-300

-450 -300

-600

Rubber 200

400

600

800

1000

Textile 200

400

Temparature/°C

600

800

Paper

1000

200

400

Temparature/°C

600

800

1000

Temparature/°C

0

0

0

-100 -300

-300

-1

-200

DTG/%⋅min

-1

DTG/%⋅min

-1

-150

DTG/%⋅min

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

-300

-400

-600

-900

-450 -500

Poplar wood

652

200

400

600

Temparature/°C

800

Pork

1000

200

400

600

800

Temparature/°C

1000

-1200

Rice 200

400

600

Temparature/°C

653 654

Fig.2. DTG curves of individual components pyrolysis at different heating rates.


800

1000

Energy & Fuels

Experimental Calculated

100

50

0

-20

2nd 3rd

0

0 -25

-40

-1

-25

1st

TG/%

TG/%

2nd 3rd

0

40

25

DTG/%⋅min

25

1st

80

75 20

50


100 40

75

DTG/%⋅min -1

-50

-50 -40

-75

50 °C•min 200

400

600

800

200

1000

400


800

1000


100 300

75

400

75

50

50

150

2nd

3rd

0

-25

2nd

3rd

0

0 -25

-200

-50

-1

-1

-150

1st

TG/%

1st 0

200

25

DTG/°C⋅min

25

TG/%

600

Temperature/°C

Temperature/°C

100

-50 -300

-75

300 °C•min

-75

-1

-1

-100

656

-1

100 °C•min

-100

-100

655

-80

-75

-1

DTG/°C⋅min

200

400

600

800

1000

-400

500 °C•min

-100 200

400

600

800

1000

Temperature/°C

Temperature/°C


100

600

75 300

50

TG/%

25

1st

0

2nd

3rd

0

-25

-1

DTG/°C⋅min

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 37

-300 -50 -75

700 °C•min

-100

657 658 659

200

400

600

800

-1 -600

1000

Temperature/°C

Fig.3. The experimental and calculated TG and DTG curves of mixed MSW pyrolysis at different heating rates.


Page 35 of 37

PE PP PVC Rubber Textile Paper Poplar wood Pork Rice

Intensity

0.16

0.12

0.08

0.06

(b) CO


0.04

Intensity

(a) CO2 0.20

0.02

0.04

0.00

0.00

200

660

400

600

800

1000

200

400

Temerature/°C

(c) CH4


0.050

Intensity

0.3

0.025

0.000

0.2

300

350

400

450

500

550

600

800

1000

Temerature/°C PE PP PVC Rubber Textile Paper Poplar wood Pork Rice

(d) O−H 0.06

Intensity

0.4

0.03

0.1

0.0

0.00

200

661

400

600

200

1000

400

0.04

0.04

0.02

0.02

0.01

0.00

0.00 200

400

600

Temerature/°C

800

1000

800

1000


(f) C–O

0.03

Intensity

0.06

600

Temerature/°C PE PP PVC Rubber Textile Paper Poplar wood Pork Rice

(e) C=O

662 663 664

800

Temerature/°C

Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

200

400

600

800

1000

Temerature/°C

Fig.4. The evolution of products with temperature in the pyrolysis process of individual components at heating rate of 100 ℃·min-1.


Energy & Fuels

0.16


(a) CO2

0.05


(b) CO

0.04 0.12

Intensity

Intensity

0.03 0.08

0.02

0.04

0.01

0.00

0.00

200

665

400

600

800

200

1000

400


(c) CH4 0.05

600

800

1000

Temperature/°C

Temperature/°C

(d) O−H


0.03

0.04

0.03

Intensity

Intensity

0.02

0.02

0.01

0.01 0.00

0.00 200

666

400

600

800

1000

200

Temperature/°C

0.020

600

800

1000

Temperature/°C Experimental Calculated

(f) C−O


(e) C=O

400

0.009

0.015

Intensity

0.006

Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 37

0.010

0.003 0.005

0.000

667 668 669

0.000 200

400

600

Temperature/°C

800

1000

200

400

600

800

1000

Temperature/°C

Fig. 5. The comparison of products release with temperature of mixed MSW by experimental and calculated data at heating rate of 100 ℃·min-1.


Page 37 of 37

(a) -6.0

700 °C⋅min

600

-1

(b)

-1

500 °C⋅min

300 °C⋅min 100 °C⋅min

-1

2

ln(β/T )

-7.5

500

-1

-1

-7.0

Ea (kJ⋅mol )

-6.5

-8.0

50 °C⋅min

-8.5

-1

v/v*=0.05

-9.0

PE PP PVC Rubber Textile

Paper Poplar wood Pork Rice MSW

400

300

200

0.3 0.7

-9.5

100

0.95 -10.0 1.1

670

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

0.0

2.0

0.2

0.4

0.6

0.8

1.0

V/V*

1000/T

(d) Mixed MSW

(c) Rice

40

56

2nd Stage 36

1st Stage

52

32 48

ln A

ln A

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

ln A=0.2312Ea-5.8004

ln A=0.6211Ea-65.7391 2 R =0.9817

28

3rd Stage

2

R =0.9945

44

ln A=0.1317Ea+6.0037 2 R =0.9625

24

20

40

200

671 672 673 674

ln A=0.1477Ea+11.0539 2 R =0.9681

220

240

260

280

100

120

140

160

180

200

220

-1

-1

Ea(kJ⋅mol )

Ea(kJ⋅mol )

Fig.6. Kinetic study by DAEM: (a) Arrhenius plots for mixed MSW, (b) Activation energy values, (c) Kinetic compensation effect for rice, (d) Kinetic compensation effect for mixed MSW.


240

Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste

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