Application status and comparison of dioxin removal technologies for iron ore sintering process



The emission of dioxins from the iron ore sintering process is the largest emission source of dioxins, and the reduction in dioxin emission from the iron ore sintering process to the environment is increasingly important. Three approaches to control the emission of dioxins were reviewed: source control, process control, and terminal control. Among them, two terminal control technologies, activated carbon adsorption and selective reduction technology, were discussed in detail. Following a comparison of the reduction technologies, the terminal control method was indicated as the key technology to achieve good control of dioxins during the sintering process. For the technical characteristics of the sintering process and flue gas, multiple methods should be collectively considered, and the most suitable method may be addition of inhibitors + ultra-clean dust collection (electrostatic precipitation/bag filter) + desulphurization + selective catalytic reduction to sufficiently remove multiple pollutants, which provides a direction for the cooperative disposal of flue gas pollutants in future.


Iron ore sintering process Dioxins Removal technology Activated carbon adsorption Selective catalytic reduction 

1 Introduction

Dioxins and benzofurans are obtained from the homologues of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), which are generically termed as dioxins. Out of a total of 210 congeners, 75 belong to PCDDs and 135 to PCDFs. The most toxic congener is 2, 3, 7, 8-tetrachlorodibenzo-dioxin with a toxicity equivalent to 1000 times that of potassium cyanide (KCN). The hazard it presents is close to a nuclear disaster [1, 2]. Dioxins exhibit complex structures, and even a very low content of them is significantly harmful. They form strong bonds with soil or other particulate matter, thereby making their elimination from the environment difficult. Dioxins are extremely lipophilic and accumulate in fat, thereby causing skin acne, lymphoma, hyperlipidaemia and immune system and nervous system lesions. In the most severe cases, they are an irreversible carcinogen, a teratogen and a mutagen [3, 4, 5, 6]. Hence, dioxins are included in the first 12 types of persistent organic pollutants.

China submitted ‘The National Plan of Action for the Implementation of the Stockholm Convention on Persistent Organic Pollutants in the People’s Republic of China’ in April 2007 to the Secretariat of the Stockholm Convention. According to this, the total annual emission of dioxins from all industries was 10,237.03 g, and the total emission of dioxins in the iron ore sintering process alone was 4666.90 g, which accounted for approximately 46% of the total annual emission of various industries, and hence it is the highest source of pollutants [7]. With an increase in the iron ore sintering production, the emission of dioxins continues to grow, becoming one of the main pollutants for national priority control for a long period.

The National Environmental Protection 12th Five-Year Plan required iron and steel, nonferrous metals and other key industries to reduce the content of dioxin emission by 10% during the 12th Five-Year Plan period. Moreover, the National Environmental Protection 13th Five-Year Plan demanded an increase in the environmental governance effort to implement the most stringent environment protection system. The iron and steel industry that involves significant pollutant discharge faces several challenges to reduce pollution and is responsible for the same [8, 9].

According to Chinese standard GB 28662-2012, China has implemented more stringent pollutant discharge standards from 1 January 2015, including a new dioxin emission limiting value of 0.5 ng TEQ/m3 (TEQ is short for toxic equivalent quantity). In future, dioxin emission limiting value will correspond to 0.1–0.2 ng TEQ/m3 in a few vulnerable areas. Dioxins will be one of the primarily controlled pollutants given the increasingly stringent environmental requirements from the Chinese government in future. Therefore, it is important to fully understand and acknowledge the current application situation and comparison of dioxin removal technologies, which will benefit not only the development of economically efficient reduction technology but also the clean and sustainable development of sintering processes.

2 Dioxins in iron ore sintering process

2.1 Detection of dioxins in iron ore sintering process

Compared with Europe, Canada, the USA, Japan and several other countries, it is relatively late for China to establish a list of dioxin emissions. The estimation of dioxin emission in China in 2014 was primarily based on the United Nations Environment Programme (UNEP) ‘Dioxin Inventory Estimation Standard Toolkit’. The sampling and analysis of dioxins are keys to achieving a reduction in dioxin emission. Presently, the most common method used to detect dioxins in the iron ore sintering process involves digging a hole on the gas flue between the fan and the chimney in the sintering site and then pumping the gas sample into a sealed beaker. The gas samples are extracted with toluene, concentrated to 3 mL by a rotary evaporator and then purified by multiple layers of silica gel. Finally, the samples are concentrated to 20 μL using a nitrogen blowing instrument and analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) [10].

2.2 Formation of dioxins in iron ore sintering process

Three mechanisms contribute to the formation of dioxins during the sintering process: precursor synthesis, de novo synthesis and residual dioxin. In general, the dioxins formed in the sintering process are mainly generated by the precursor and de novo synthesis routes in the sintered material layer and in the gas pipeline.

The precursor synthesis refers to the generation of PCDD/Fs by chlorine-containing precursor compounds, such as chlorobenzenes and polychlorinated biphenyls, by the Ullmann reaction in an alkaline environment or by a direct catalytic reaction on a fly ash surface [11]. The de novo synthesis involves the generation of an acid chloride (halide) by a macromolecular residual carbon or chlorine source on a fly ash surface under certain temperature conditions through metal catalysis, and the subsequent oxidization of the acid chloride to generate PCDD/Fs [12, 13].

During the iron ore sintering process, PCDD/Fs are generated by both the precursor and de novo synthesis routes under the conditions of suitable temperature on the sintered bed, in the presence of sufficient important ingredients such as oxygen, carbon and chlorine sources, and sufficient catalytic activity of copper, iron and other transition metals. Figure 1 shows that several PCDDs are generated by the Ullmann reaction when the temperature of the sinter zone is 300–400 °C [14, 15]. Moreover, a significant amount of PCDFs are generated by de novo synthesis at 250–450 °C [16, 17]. Therefore, this temperature range can be considered the zone of dioxin primary formation. Part of PCDD/Fs decomposes when the temperature exceeds 500 °C in the combustion zone because of the decomposition of PCDD generated by the Ullmann reaction [18]. Yang et al. [19] indicated the ratio of PCDF/PCDD in the flue gas to be approximately 10. In addition, changes in the ratio of coke powder, hot air temperature or hot air oxygen content evidently changed the concentration of PCDFs although that of PCDDs remained almost constant. Thus, it is determined that the dioxins in the sintering process are mainly PCDFs that are generated by the de novo synthesis route.
Fig. 1

Unified PCDD/Fs formation pathway in iron ore sinter zones [14, 16]

2.3 Emission of dioxins in iron ore sintering process

There is an increasing focus on the emission of dioxins in the process of sintering. Most steel enterprises are still in the stage of electrostatic dusting and desulphurization. We invested in three representative sintering plants in China to obtain the information as detected by professional testing agencies, which is given in Table 1. The emissions of dioxins from sintering plants are predominantly gaseous with a maximum concentration of 0.73 ng TEQ/m3 and a minimum of 0.51 ng TEQ/m3, both of which exceed the national standard of China. The emission of PCDD/Fs from a pellet sintering plant is 0.088 ng TEQ/m3, which satisfies the national standard of China. Figure 2 shows the concentration of components of dioxin-like homologues and the concentration of toxicity equivalent conversion. Among the dioxin-like homologues emitted from the three sintering plants, PCDFs constitute the largest proportion and have the highest toxicity. This is in accordance with the formation mechanism of dioxins in the sintering process.
Table 1

Dioxin emissions in iron ore sintering plants



Detection position

Concentration/(ng TEQ m−3)

Sample state



Before desulphurization


Gas phase



Before desulphurization


Gas phase


10 shaft furnace

After electrostatic dust removal


Gas phase

Fig. 2

Concentration of dioxins in a sintering plant

Zhang et al. [20] studied the emission of dioxins from sintering plants No. 4 and No. 5 in Shanghai Meishan Iron and Steel Co., Ltd., which have an area of 450 m2. Table 2 shows the detection results. After adopting effective measures to reduce emissions, the dioxin emissions in the sintering plants reduced significantly. In addition, the final concentrations of dioxins at the outlet of the absorption tower satisfied the national emission standards of China.
Table 2

Detection results of dioxin emissions in Shanghai Meishan Iron and Steel Co., Ltd. (ng TEQ m−3)

Sintering plant No. 4

Sintering plant No. 5









3 Removal technologies of dioxin emission in sintering process

Based on the formation mechanism of dioxins in the sintering process, the reduction methods for dioxin emission in flue gas are divided into three types in terms of the kind of control according to the process: source control, process control and terminal control.

3.1 Source control and process control

Source control reduces the release of dioxins during the sintering process by controlling the sintering raw material components such as chlorine source elements and sensitive elements to dioxin formation (Cu, Fe, Ni and other elements or compounds of transition metal elements) [21]. Therefore, the source control method requires high-quality sintering materials.

During process control, the sintering process can be adjusted using methods such as addition of inhibitors or flue gas thermal cycle. Several studies have indicated that dioxin emission can be reduced by adjusting the sintering process such as controlling the end of sintering position [22], amount of coke, temperature of hot air, oxygen content in the wind and negative pressure of the outlet [20, 23, 24]. Dioxin release is also reduced by a flue gas thermal cycle as pyrolysis of the chemicals occurs at high temperatures. Part of the exhaust gas is allowed to re-enter the sintered layer, thus achieving reduction of the emission of dioxins by 60% using the flue gas thermal cycle technique [25, 26].

The method of adding inhibitors such as S, N or a basic component into the sintered material layer reduces the number of dioxins generated. The added inhibitor consumes chlorine sources or inactivates the catalyst. Although sulphurous inhibitors and basic components inhibit the formation of dioxin, they have certain disadvantages that S can result in a high SO2 emission in the flue gas and the basic component, such as Na or K, is not conducive to the operation of a blast furnace [27, 28]. Hence, the most frequently used inhibitors are those containing N, such as urea, ammonium hydroxide, melamine, triethylamine and ammonium hydrogen phosphate [29]. The N-containing inhibitors form a stable inert compound with the metal catalyst, weakening its catalytic activity and thereby eliminating the metal and its oxides. When an ammonia-containing inhibitor is used, NH3 produced by the inhibitor’s thermal decomposition reacts with HCl to reduce the chlorine source required for the de novo synthesis route. In addition, a nitrogen-containing inhibitor also reduces the emission of SO x in the flue gas. In Refs. [30, 31, 32, 33], 70% dioxins are reduced by adding 0.035% solid urea during the granulating process, simultaneously reducing the emission of gaseous SO2. Furthermore, the result of an industrial test conducted on the sintering plant No. 1 in Baosteel Group Ltd. indicated that a 50% reduction in dioxin release was achieved through the addition of urea.

3.2 Terminal control

Although source control and process control reduce dioxin emission, the reduction level is limited. The increasingly stringent pollutant control standards lead to the inadequacy of source control or process control by itself to satisfy higher requirements of dioxin emission standards. Despite the relatively higher costs, terminal control leads to higher environmental benefits.

The terminal control deals with the gaseous and particle phases of dioxins in the sintered flue gas. The main control techniques involve physical removal and chemical degradation. The essence of physical removal is adsorption. Hence, it is unable to destroy the chemical structure of PCDD/Fs, and it is necessary to deal with the disposal of the adsorbents containing highly concentrated PCDD/Fs. The main methods of adsorption include activated carbon adsorption, semi-dry lime powder dust removal and electrostatic dust removal. Chemical degradation destroys the PCDD/Fs molecules, and thus there is no risk of follow-up treatments. The main chemical degradation methods include bag-type catalytic and selective catalytic reduction (SCR), which only remove gaseous PCDD/Fs in flue gas [34]. Presently, the most widely applied terminal methods are activated carbon adsorption and SCR. Therefore, the present study reviews in detail these techniques to reduce PCDD/Fs.

3.2.1 Activated carbon adsorption

In 1991, activated carbon adsorption technology was utilized to treat waste incineration flue gas in Japan, Europe and a few other countries across the world. Subsequently, the technology was gradually applied to reduce pollutants from sintering flue gas. Currently, the method is used in Japanese steel mills, South Korean Pohang, Chinese TISCO and several other steel companies [35, 36]. Dioxins in flue gas are adsorbed and removed by porous substances. Widely used adsorbents include activated carbon, coke and lignite. Among these, activated carbon has optimal adsorption effect, is cheap and is easy to find. Therefore, it is widely used in fixed beds, moving beds and injection bed-bag filters. Table 3 lists three different adsorption modes of activated carbon. The adsorption rate increases by approximately 98% when the flue gas temperature is approximately 150 °C. An increase in the temperature decreases the removal efficiency of dioxins. When activated carbon adsorption technology is used, the temperature of flue gas should not exceed 200 °C, which is the most suitable temperature for sintering flue gas pollutant treatment.
Table 3

Removal efficiencies of dioxins by three absorption methods with respect to various temperatures

Adsorption method


Adsorption rate/%





Moving bed




Recycling after specific treatment, such as thermal desorption

Suitable for small incinerator




Fixed bed





Injection bed-bag filter



Powder 0.2–0.4

Incineration and landfill

Suitable for large incinerator










The dioxins in the sintered flue gas are in gaseous and particle phases. Generally, the gaseous dioxins are adsorbed by the activated carbon, and the particle dioxins adhere to the surface of the fine particles such as fly ash. Subsequently, these particle dioxins are finally removed by the bag filter [40]. Studies indicated that activated carbon used in fixed beds effectively reduces only gaseous dioxin emission, whereas injection bed-bag filters simultaneously reduce both gaseous and particle dioxins [41]. As reported in Ref. [42], the removal rate of PCDD/Fs at the exit site reaches 97.36% when the activated carbon injection-circulating fluidized bed (ACI-CFB)-bag filter technique is used in the sintering plant. The removal rate of gaseous dioxins was 99.47%, and that of particle dioxins was 96.93%. The process flow chart of the ACI-CFB-bag filter technique is shown in Fig. 3. Following injection, the activated carbon mixes with fly ash and the mixture is collected by the dust collector. It is important to focus on the problems of post-treatment of saturated activated carbon. High concentrations of dioxins are adsorbed by the activated carbon, which result in a complex post-treatment. The post-treatment can increase the cost and may lead to secondary pollution if performed improperly. Presently, there are two main methods to solve this problem. The first method is landfill or high-temperature incineration. However, it causes the secondary release of mercury or other pollutants. The second method is catalytic degradation. Porous carbon material is also an extremely suitable carrier for promoting a catalytic reaction [32].
Fig. 3

Process flow diagram of ACI-CFB-bag filter technique [42]

3.2.2 Selective catalytic reduction

Selective catalytic reduction is originally used for denitrification of flue gas, and it exhibits an excellent performance in the catalytic degradation of dioxins. Under the action of the catalyst, the gaseous dioxins are chemically degraded at low temperatures, and the final product is CO2, H2O and HCl. The reaction procedure is as follows:
$${\text{C}}{1_2}{{\text{H}}_n}{\text{C}}{{\text{l}}_8}{ - }n{{\text{O}}_2} + \left( {9 + 0.5n} \right){{\text{O}}_2} \to \left( {n - 4} \right){{\text{H}}_2}{\text{O}} + 12{\text{C}}{{\text{O}}_2} + \left( {8 - n} \right){\text{HCl}}$$
$${\text{C}}{1_2}{{\text{H}}_n}{\text{C}}{{\text{l}}_8}{ - }n{\text{O}} + \left( {9.5 + 0.5n} \right){{\text{O}}_2} \to \left( {n - 4} \right){{\text{H}}_2}{\text{O}} + 12{\text{C}}{{\text{O}}_2} + \left( {8 - n} \right){\text{HCl}}$$

Currently, the catalysts mainly used are precious metals and transition metal oxides. Precious metals are not suitable for large-scale industrial application since they are costly and are easily susceptible to SO x and HCl [43]. Transition metal oxides are cheap and exhibit good catalytic activity [44]. In addition, introduction of a transition metal into a vanadium-based catalyst as a second-phase catalyst improves the catalyst activity [45]. The degradation effect of catalyst was studied under various metal oxide catalysts and V-containing composite metal oxide catalysts in laboratory [46]; the optimal effect on catalytic degradation was found for nano-TiO2 on the loading of V (VO x /TiO2), which was followed by CeO x , MnO x , WO x and MoO x . The effect of catalytic degradation of VO x -CeO2/TiO2 is optimal in composite metal oxide catalysts.

The research status of degradation of PCDD/Fs by different metal oxide catalysts is shown in Table 4. As shown in Table 4, temperature significantly affects the activity of V-based catalysts. The V-based catalyst exhibits excellent catalytic oxidation of PCDD/Fs when the temperature exceeds 300 °C. The catalytic activity decreases when the temperature decreases, especially lower than 200 °C. In such low temperature range, metal elements (including W, Mo and Ce), new carbon materials (including carbon nanotubes and graphene) and other active ingredients are required. Nowadays, several scholars [46, 47, 48, 49, 50, 51, 52, 53] worldwide have developed highly efficient and stable SCR catalysts. These studies mainly focus on catalyst selection and preparation methods. Given the complex detection methods and high toxicity of PCDD/Fs, o-dichlorobenzene is typically used to replace dioxins in laboratory, as they possess the same structure as dioxins and correspond to the precursor of dioxins.
Table 4

Degradation of PCDD/Fs under various metal oxide catalysts



Remove rate/%


V2O5-WO3/TiO (honeycomb)

280 °C



V2O5-WO3/TiO2 (honeycomb)

220 °C




200 °C




150 °C, 20,000 h−1 space velocity




300 °C, 7000 h−1 space velocity

11% O2, 5% H2O




150–350 °C, 8200 h−1 space velocity



VO x /CeO2

345 °C



VO x -CeO2/TiO2 (nanometre)

200 °C



Ce-V x O y /TiO2

280 °C



Recently, several countries have begun using SCR technology to control flue gas pollutants. There are four sintering plants with SCR reactors in Pohang Iron and Steel Company. The measurement results for these plants indicate that the removal rate of SO x and NO x is 80% and that of dioxin is ≤ 0.1 ng TEQ/m3 [34]. China Steel Corporation in Taiwan uses a dual-effect catalyst that is independently developed. Their major components of catalysts are V2O5/WO3/TiO2 with an optimum working temperature of 250–320 °C, within which the reduction rates for both dioxins and NO x considerably exceed 80%. A plate-type catalyst possesses a higher resistance to ash corrosion and lowers the possibilities of clogging and decreases in pressure [54]. In Belgium, the concentration of dioxins in flue gas is 0.001 ng TEQ/m3 and the concentrations of NO x and CO are reduced by 90 and 20%, respectively, following treatment with the SCR unit [55].

Both activated carbon adsorption technology and SCR technology simultaneously remove SO x , NO x and PCDD/Fs in flue gas, thus satisfying the future development of flue gas pollutant control technology, especially in focused emission source industries such as iron ore sintering. A previous study [56] outlined four simultaneous control technologies for multiple pollutants by analysing the statistics of the emission characteristics of multiple pollutants in flue gas from an iron ore sintering plant. Table 5 shows a comparison of the four simultaneous control technologies. Multiple pollutants in flue gas are removed by dust and desulphurization devices combined with activated carbon and SCR technology. Among them, multiple pollutants in sintering gas are removed by dust collection + SCR + desulphurization, wherein the operational costs are the lowest.
Table 5

Comparison of four simultaneous control technologies [56]

Technology No.

Technological route


Operational costs/(RMB t−1)

SO x

NO x




Dust collection + activated carbon injection + wet desulphurization






Dust collection + activated carbon injection + semi-dry desulphurization






Dust collection + activated carbon injection






Dust collection + SCR + desulphurization





4 Comparison of dioxin removal technologies

A review of the emission and reduction of PCDD/Fs from iron ore sintering processes in China indicates that the following factors should be considered: (1) Technical factors include suitability, reliability, advance, pollutant removal and energy consumption. (2) Economic factors include investment and operating expenses. (3) Environmental factors include both positive effects (pollution reduction) and negative effects (secondary pollution) of reduction technology on the environment and must be considered at the initial stage. Table 6 shows a comparison of different technologies of dioxin reduction.
Table 6

Comparison of different technologies of dioxin reduction


Activated carbon adsorption [57]

SCR [58]

Flus gas hot cycle [59]

Dust collection [60, 61]

Adding inhibitors [62, 63]

Wet dust extraction

Electrostatic precipitation

Bag filter

Nitrogen inhibitor

Sulphurous inhibitor

Technology maturity







Relatively mature

Removal efficiency/%
















Generally small

Generally small

Occupied area







Generally small

Generally small

Secondary pollution

Saturated activated carbon






Ammonia leakage


Suitable flue gas


Large and continuous

Large and continuous

Large and continuous





Type of pollutants

SO x , NO x , PCDD/Fs

NO x , PCDD/Fs

SO x , NO x , PCDD/Fs


SO x , PCDD/Fs

NO x , PCDD/Fs

Thus, the study of the dioxin removal technologies indicates that a single removal technology is insufficient. Therefore, multiple methods should be collectively considered to ensure that the final dioxin emission is below the limiting value. Given the above factors, the most suitable method may be addition of inhibitors + ultra-clean dust collection (electrostatic precipitation/bag filter) + desulphurization + SCR to sufficiently remove multiple pollutants. Although this method gives the best removal efficiency, it has higher requirements for desulphurization and dust collection. Hence, an efficient catalyst with low-temperature activity corresponds to the direction and hot spot for future research that holds the key to SCR technology.

5 Conclusions

To more effectively control the dioxin emission from industrial production, it is necessary to first accurately measure the emissions of dioxins. A unified regulatory and testing method must be developed and further improved to constantly update detection technology.

Terminal control is an efficient dioxin removal technology that satisfies the requirements of reducing dioxin emission from the large-scale iron ore sintering process and simultaneously corresponds to synergistic denitrification.

Flue gas treatment is a method of terminal control to reduce dioxins in flue gas although it is expensive. A future direction may involve addition of inhibitors + ultra-clean dust collection + desulphurization + SCR with the development of appropriate catalyst and the exploration of advanced preparation methods. High-efficiency catalysts resist water and sulphur and simultaneously remove NO x in flue gas at low temperatures.



The authors acknowledge financial support from the Key Project of National Natural Science Foundation of China (U1660206) and General Program of National Natural Science Foundation of China (51674002).


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Copyright information

© China Iron and Steel Research Institute Group 2018

Authors and Affiliations

  1. 1.Key Laboratory of Metallurgical Emission Reduction & Resources Recycling, Ministry of EducationAnhui University of TechnologyMa’anshanChina
  2. 2.School of Metallurgical EngineeringAnhui University of TechnologyMa’anshanChina

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