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Waste Disposal & Sustainable Energy

, Volume 1, Issue 2, pp 91–98 | Cite as

Study on the relationship between waste classification, combustion condition and dioxin emission from waste incineration

  • Xiaodong Li
  • Yunfeng Ma
  • Mengmei Zhang
  • Mingxiu Zhan
  • Peiyue Wang
  • Xiaoqing Lin
  • Tong Chen
  • Shengyong Lu
  • Jianhua YanEmail author
Review
  • 81 Downloads

Abstract

Domestic waste in China is mainly collected as a combination of different types of materials. The components are variable and complex, with very different combustion characteristics making it difficult to optimize the burning to reduce pollution. There are still some controversies about the accuracy of using carbon monoxide (CO) emission to characterize waste incineration performance. Here, we investigated the relationship between waste classification, incineration conditions and dioxin emission and concluded that the concentration of CO in flue gas could not be used as the only criterion of combustion efficiency and safety. Considering the close relationship between the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and products of incomplete combustion, the relatively low concentrations of CO are not a reliable indicator that an incinerator equipped with an activated carbon injection system and fabric filter could achieve the national standards for PCDD/F emission. The goal, therefore, is not only to lower the emission of PCDD/Fs and other pollutants through classifying the waste components at the source, but also to reduce the need for the treatment of incinerated waste to protect the environment and to increase the power generation efficiency of municipal solid waste incineration (MSWI) plants. As the demand for waste disposal continues to rapidly increase, the need for a safe waste incineration system with dioxin emission controls makes the classification of waste an indispensable part of future MSWI systems.

Keywords

Incineration Waste classification CO Dioxin Emission 

Introduction

Municipal waste collected in China for disposal by burning has heretofore not been required to be classified according to materials as it is in some countries. This presents a multitude of problems because of the great variety of waste items that require very different combustion conditions to be incinerated completely and safely. Efficiency has been characterized by CO concentration in flue gas, but this has proven inadequate for indicating levels of hazardous pollutants such as dioxins and furans. Low CO emissions do not necessarily correspond to dioxin levels below the standard 0.1 ng I-TEQ/Nm3. It is also unknown about the effect of waste composition and classification on dioxin emission from waste incineration. This paper is expected to contribute to a better understanding of the relationship between waste classification, incineration conditions and dioxin emissions.

Domestic waste composition and combustion characteristics

The composition of domestic waste in China is complex, and can sometimes include illegally dumped industrial waste and biohazardous medical waste. This uncertain combination of components makes optimizing incineration impossible and pollutant control very difficult. Researchers at Zhejiang University and Tsinghua University have studied the ignition temperatures, burnout temperatures and average burning rates of different waste components by thermogravimetric analysis [1, 2, 3]. The combustion characteristics of different waste components such as kitchen scraps, paper, fabric, chlorine-containing plastics and chlorine-free plastics are vastly different. Table 1 shows the industrial analysis, calorific value and combustion characteristics of a variety of waste items arranged in descending order according to ignition temperature: kitchen waste < paper < fabric < plastic, and according to the burnout temperature: fabric < plastic < paper < kitchen waste. Paper and fabric play an important role in the early stages of waste combustion, but when the combustion temperature rises to a certain point, the burning of plastics becomes the main chemical reaction. The burning time of kitchen waste is the longest.
Table 1

Industrial analysis and combustion characteristics of waste components [4]

Waste components

Industrial analysis

Calorific value

Combustion characteristics

Moisture (%)

Ash (%)

Combustible basis (%)

Low calorific value (kJ kg−1)

Ignition temperature (°C)

Burnout temperature (°C)

Kitchen waste

90.77

0.71

8.52

− 1034

168

780

Paper

4.85

7.56

87.60

11,113

299

688

Chlorine-containing plastics

0.29

0.14

99.56

38,295

424

499

Chlorine-free plastics

0.32

0.42

99.26

36,871

430

503

Fabric

6.19

0.56

93.25

14,559

331

406

Volatile and fixed carbon are merged into ‘combustible’

Due to the rapid release of volatiles from combusted waste, the excess air coefficient (the ratio of actual air supply to theoretical air supply) is particularly important for efficient combustion. The composition of domestic waste from different regions of China can be quite different, and the difference between the calorific value of the waste and the corresponding amount of air required for theoretical combustion is also large (Table 2). The calorific value of waste from Macao and the corresponding theoretical air volumes are almost twice as much as those for waste collected at the same time from Qingdao, Beijing and Hangzhou. Figure 1 shows the effect of excess air coefficient on the combustion of wood and cardboard in an incinerator with a bed temperature of 850 °C. When the excess air coefficient for wood is lower than 60% or for cardboard is below 100%, the concentration of emitted CO increase substantially. Therefore, to ensure the efficient combustion of waste components and to reduce CO concentration, a reasonable excess air coefficient needs to be maintained [5]. By analyzing the combustion characteristics of various substances in waste [6], the shapes of the exothermic curves of different components were found to vary significantly, separated or partly overlapped, reflecting their basic chemical composition. For mixed waste, incomplete combustion was inevitable, resulting in the elevated emission of CO and other combustion products. Only when the ignition conditions, oxygen demand and burnout time are optimized, could the waste components be efficiently incinerated and a reduction in the emissions of CO and other incomplete combustion products be achieved.
Table 2

Industrial analysis, calorific value and theoretical air measurement value of waste samples [5]

City

Industrial analysis (%)

Calorific value (kJ kg−1)

Theoretical air measurement value (kg kg−1)

Moisture

Volatile

Fixed carbon

Ash

Qingdao

42.4

18.6

2.8

36.3

4204

1.78

Xi’an

25.0

15.0

2.4

57.6

3363

1.35

Beijing

26.2

18.9

2.8

52.2

4624

1.77

Macao

39.2

42.9

5.4

12.5

9436

3.67

Hangzhou

51.6

18.9

3.0

26.5

3569

1.69

Guangzhou

53.5

21.4

3.4

21.8

4326

1.93

Shenzhen

40.9

31.2

4.1

23.7

7403

2.94

Fig. 1

The effect of excess air coefficient on the combustion efficiency [5]

A lower CO concentration does not correspond to complete combustion of complex waste components

Although waste and coal are both solid fuels, there are differences in the calculation methods for their combustion efficiencies. In the waste incineration industry, the method of calculating combustion efficiency of fuel oil or gas is still used (shown as formula 1). This calculation method is inadequate for waste incineration because it represents the combustion efficiency of all materials only as gaseous components,
$$ \eta_{\text{c}} = \frac{{\left[ {{\text{CO}}_{ 2} } \right]}}{{\left[ {{\text{CO}}_{ 2} } \right] + \left[ {\text{CO}} \right]}} $$
(1)
where \( \eta_{\text{c}} \) represents the combustion efficiency; \( \left[ {{\text{CO}}_{ 2} } \right] \) and \( \left[ {\text{CO}} \right] \) represent the volume concentration of CO2 and CO in the flue gas, respectively.
In the power generation industry, formula (2) is used to calculate the combustion efficiency of coal, which takes into account the burnout situation of both the gaseous and solid components of the fuel. This calculation is more comprehensive and reasonable for the calculation of the combustion efficiency of solid fuels,
$$ \eta_{\text{c}} = 100 - \left( {q_{3} + q_{4} } \right)\% $$
(2)
where \( \eta_{\text{c}} \) represents the percent combustion efficiency; q3 is the heat loss from the incomplete combustion of gaseous compounds, mainly CO; and q4 is the heat loss from incomplete combustion of solids, furnace bottom slag and tail fly ash.

The results show that although CO concentration can reflect the combustion of gaseous components of waste, it cannot fully represent the concentration of incomplete combustion products emitted from waste incineration. When CO concentration from waste incineration is high, it indicates poor combustion. At this time, the concentration of incomplete combustion products represented by polycyclic aromatic hydrocarbons (PAHs) correlates well with CO concentration. However, when CO in the flue gas is low, the correlation between CO and the concentration of products of incomplete combustion (PICs) is poor [7, 8, 9]. The loss due to unburned solid ash and fly ash is not considered, so low CO levels during incineration do not correspond to lower concentrations of incomplete combustion products or the overall efficiency of waste incineration. When non-combustible components such as rubber products and industrial waste are mixed with household waste, it is much more difficult for the solid components to be fully burned than the gaseous components. When the CO concentration is low in the process of waste combustion, only the gas phase component burns sufficiently, which cannot represent the full combustion of a complex mix of waste components; therefore, adequate waste incineration cannot be achieved by only ensuring low CO emissions.

Complete waste incineration requires stable, homogeneous component characteristics

Because of the complex composition of domestic waste, there will always be some interaction between the different components when incinerated. For example, the combustion rate of a mixture of kitchen waste and bamboo waste is significantly higher than that of the linear superposition of the two components, which indicates that the two components interact to promote the combustion process [10]. The combustion characteristics of waste also change with variation in the size, shape and moisture content of the components. Taking fuel shape as an example, the differences in specific surface area (mass basis) result in different reaction rates, which further leads to differences in ignition time, combustion time, combustion temperature, flue gas components and carbon content in fly ash. Generally speaking, the larger the specific surface area of the fuel, the faster it ignites and the quicker it burns.

When domestic waste has been classified (if it can be further made into homogeneous fuel, the effect will be better), the overall size, shape and moisture content remain relatively stable. Therefore, the interaction of various components in the mixed combustion process is relatively controllable; the air distribution and pollutant levels in the incinerator can be more easily regulated; the distribution of flow field and temperature field is relatively stable. Ultimately, more complete waste incineration is achieved. As an example, since 2013 in the Shibuya District, Tokyo, Japan, it has been stipulated that waste should be divided into four categories: combustible waste, non-combustible waste, coarse waste and resource waste. Each category was subdivided into several sub-types. For example, branches less than 50 cm in length were classified as ‘combustible waste’. It was recognized that the stability of waste components allows for more efficient waste incineration.

Incomplete combustion products increase the dioxin emissions from waste incineration

Unstable combustion is one of the results caused by the variability in the components and fuel characteristics of waste, which is not conducive to optimal operation of incinerators [10]. The calorific value of waste in most parts of China ranges from 4000 to 6000 kJ/kg, and the components are complex and variable. Sharp changes in the calorific value of waste cause unstable combustion, which makes it necessary to adjust the combustion conditions to maintain combustion efficiency [11]. In China, kitchen waste makes up a large proportion of municipal solid waste (MSW), and the moisture content of such waste is high. This results in delayed or unstable ignition of waste, which would further cause unstable and incomplete combustion [12]. The ash content also influences the fuel characteristics of waste. In extreme cases, when the ash content reaches 57% and the calorific value is low [13], the waste can hardly be burned.

In recent years, advances in waste incineration technology and improvements in efficiency prompted China to adopt incineration as a primary method for waste disposal. Closer control and monitoring of combustion conditions using the principle of ‘3T + E’ (time, turbulence, temperature and excess oxygen) have achieved the destruction of dioxin contamination in the waste feed, but dioxin can also be generated in the post-combustion areas of an incinerator. Figure 2 summarizes the main pathways for dioxin formation in waste incineration, and there are two widely recognized theories about how dioxins form during waste incineration [14, 15]: (a) homogeneous reactions in the higher temperature range of 400–800 °C, at which point the main process of homogeneous formation is the rearrangement reactions of chlorinated precursors in the flue gas, such as chlorophenols (CPs) and chlorobenzenes (CBz); (b) heterogeneous reactions in the lower temperature region of 200–400 °C, with PCDD/Fs that are heterogeneously formed from precursor compounds such as CPs and CBzs or via de-novo synthesis from carbon matrices existing on fly ash surface. The latter requires transition metals or their compounds acting as catalysts. In the actual waste incineration process, the contribution of heterogeneous catalytic synthesis to dioxin formation is often much higher than that of homogeneous reactions [16]. Wang et al. [17] and Zhang et al. [18] found that the economizer region is generally the largest dioxin producer because its working temperature is within the window of the dioxin phase-out in the low temperature synthesis range of 200–500 °C. For MSW incinerators, the post-combustion regeneration area is the main source of dioxins, both in grate furnaces and fluidized bed furnaces.
Fig. 2

The pathways of PCDD/F formation from municipal solid waste incineration [19]

The complex components of unclassified waste show obvious difference in their combustion characteristics, which inevitably cause the formation of PICs, such as PAHs [20, 21, 22]. Although the concentration of CO may be low, it is inevitable to notice the presence of PICs such as PAHs, CBzs and CPs at concentrations in the mg or μg range, or even lower. PCDD/Fs can also be regenerated by the PICs of aromatic hydrocarbons formed from the waste combustion process. CBZs and CPs, which are considered the most closely related precursors of PCDD/Fs, can generate these compounds through both homogeneous and heterogeneous reactions. The concentration of CBz and CP is positively correlated with the toxic equivalent quantity (TEQ) of PCDD/Fs in flue gas, which could be used for online monitoring of PCDD/Fs [23, 24]. PAHs can directly generate PCDD/Fs through a condensation and oxychlorination pathway [25], which can also form carbon black and other macromolecule structures during the cooling of flue gases, and then generate PCDD/Fs via a de novo synthesis pathway [26]. PCDD/Fs can be synthesized in the range of ng through the above pathways from PICs at concentrations in the μg range and even lower. So even though the concentration of CO in flue gas is low, the probability of PCDD/F emissions exceeding the national standards is still high given the poor combustion efficiency in most MSW incinerators and lack of terminal air pollution control devices (APCDs) [27, 28].

Waste classification can control the components associated with PCDD/F formation

As shown in Fig. 3, in addition to the parameters of temperature and O2, the presence of Cl and heavy metals as catalysts are two other key factors influencing the formation of PCDD/Fs. The sources of these two elements are the components in the original waste subjected to incineration. The components of classified wastes are more homogeneous and stable. The classified waste also has a higher calorific value, which makes it easier to be organized for combustion. Moreover, classification can help to reduce not only the emission of PICs, but also the content of Cl and heavy metals from the waste input, substantially reducing the original concentration of PCDD/Fs. Wikström et al. [29] and Halonen et al. [30] found that the chlorine content showed a threshold value of about 1 wt% for promoting PCDD/F emission from an incinerator: below the threshold, the content of chlorine presented no obvious influence on the formation of PCDD/Fs; however, above the threshold, the formation of PCDD/Fs increased with the rising chlorine content. Further studies confirmed the role of Cl in PCDD/Fs synthesis. Hatanaka et al. [31] and Yasuhara et al. [32] studied the influence of chlorine content on PCDD/F formation through separately adding different amounts of PVC and NaCl into simulated fly ash, resulting in the concentration of PCDD/Fs increasing with increasing chlorine content during the cooling process of flue gas regardless of whether the source of chlorine was organic or inorganic. Figure 3 shows the relationship between chlorine content and concentration of PCDD/Fs at the 350 °C post-combustion zone of an incinerator [31]. Kolenda et al. [33] measured the concentration of PCDD/Fs after adding different fuels and found the highest emission of 9.8 ng TEQ/Nm3 when co-combusting PVC with plywood, which is much higher than that of incinerating biomass. The chlorine content of the input waste has been proved to show a significant influence on the formation and emission concentration of PCDD/Fs.
Fig. 3

The relationship between chlorine content and formation concentration of PCDD/Fs from 350 °C post combustion zone of incinerator [31]

The catalytic effect of heavy metals in fly ash of MSW incinerators is essential for the formation of PCDD/Fs. Many studies have shown that the commonly found metals in fly ash, such as copper, iron, chromium, nickel and zinc, all may play an important role in the formation of PCDD/Fs, and that copper (especially CuCl2) presents the strongest promoting effect [18, 34, 35]. The PCDD/F output from fly ash added with chloride or oxide of copper, iron, chromium, nickel or zinc was at 2–4 orders of magnitude higher than that from fly ash without the addition of these catalytic metals [18, 35]. The chlorine content of input waste directly influences the chlorine content of fly ash, further influencing the formation of PCDD/Fs. Hatanaka et al. [36] found that the PCDD/F yield from the incineration of waste containing copper content of 0.007% was five times higher than that from the incineration of waste without chlorine. Thus, to achieve a significant reduction in PCDD/F formation, it is necessary to reduce the content of metal catalysts in the input waste.

The chlorine in MSW is mainly from the PVC in plastics and electronics (e-)waste (organochlorine) and chlorine salts dominated by NaCl in kitchen waste (inorganic chlorine) [37]. However, the chlorine content of medical waste and partial industry waste is much higher than in MSW [38]. Strictly controlling the co-combustion of MSW with medical and industry waste, and separating the plastic, e-waste and other components with high chlorine content from MSW can notably reduce its chlorine content [39]. Taking copper and zinc as examples, the main sources of these two metals in MSW are metal fabrications, e-waste and kitchen waste, etc. [40]. Waste classification and plastic separation before incineration can reduce not only the total amount of input metal catalysts, but also the heavy metal content in bottom slag and fly ash, decreasing the total amount of PCDD/Fs produced and making it much easier to dispose of or reuse bottom slag and fly ash.

Learning from the experience of other countries, Japan in 2010 had achieved the 99% target for reducing the total PCDD/F emission since the Revised Guidelines for the Prevention of Dioxin Formation Relating to Waste Treatment (1997) was promulgated in 1977 (Fig. 4). Through waste classifying, Japan was able to control the two key components for the formation of dioxins (chlorine and heavy metals), increase the calorific value and burnout ratio of waste, and substantially reduce the original concentration of PCDD/Fs before the flue gas reached the APCDs. In addition, the Japanese government issued guidelines to prevent formation of dioxin in 1990, emphasizing that reducing PCDD/F emission from MSWI should be carried out by classifying waste from various sources, reasonably combining different types of waste for incineration and optimizing the flue gas purification system. Shi et al. [41] reported that waste classification in a full-scale grate incinerator reduced chlorine content by 43% and metal content by 86%, increased calorific significantly and improved combustion conditions. As shown in the results, after waste classification the original concentration of PCDD/Fs before APCDs was 9.3 ng TEQ/Nm3, which was only 69.4% of the concentration without waste classification. Therefore, waste classification can reduce the two key components (chlorine and catalytic metals) in the stream of incinerated waste, resulting in more stable combustion and lower emission of PCDD/Fs [19].
Fig. 4

The total amount of PCDD/F emission from MSWI in Japan

(Data source: Ministry of Environment of Japan, 2012 [42])

Waste classification is necessary for MSWI now and in the future

In summary, the concentration of CO in flue gas cannot be the only criterion for combustion performance. Although the concentration of CO can reflect the combustion conditions of the gas-phase waste components, it is not directly correlated to the optimal combustion conditions of solid-phase waste components and the formation of PICs. Considering the close relationship between the formation of PCDD/Fs and PICs, a low flue gas concentration of CO does not indicate that an incinerator equipped with activated carbon injection and a fabric filter would achieve the national standards of PCDD/F emission. Unclassified waste contains an inhomogeneous mixture of components with different combustion characteristics, and also with various amounts of metal catalysts and reactive chlorine compounds that are instrumental in the formation of PCDD/Fs. Burning unclassified waste inevitably causes large formation of PICs of aromatic hydrocarbons and the generation of PCDD/Fs in the cooling flue gases. The components of classified waste are more homogeneous and stable. The classified waste presents a higher calorific value, making it easier to be organized for efficient combustion and leading to lower emission of PICs. Classification not only lowers emission of PCDD/Fs and other pollutants through controlling the key components of waste from the source, but also reduces the pressure for environmental protection treatment of MSWI plants and increases the efficiency of power generating plants. Therefore, through the above analysis, we can draw the following conclusion: from the point of view of waste incineration demand and dioxin emission control, waste classification is not only necessary, but also an indispensable part of the future of MSWI systems.

Notes

Acknowledgements

This study was supported by the National Natural Science Foundation of China (51621005), and the National Key Research and Development Program of China (2017YFC0703100).

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Copyright information

© Zhejiang University Press 2019

Authors and Affiliations

  • Xiaodong Li
    • 1
  • Yunfeng Ma
    • 1
  • Mengmei Zhang
    • 1
  • Mingxiu Zhan
    • 2
  • Peiyue Wang
    • 1
  • Xiaoqing Lin
    • 1
  • Tong Chen
    • 1
  • Shengyong Lu
    • 1
  • Jianhua Yan
    • 1
    Email author
  1. 1.State Key Laboratory for Clean Energy Utilization, Institute for Thermal Power EngineeringZhejiang UniversityHangzhouChina
  2. 2.College of Metrology and Measurement EngineeringChina Jiliang UniversityHangzhouChina

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