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PYROLYTIC PROCESSING OF MUNICIPAL SOLID WASTE

Gennady Gerasimov

One of the most urgent environmental problems in the modern world is the problem of municipal solid waste (MSW) management. There are numerous methods available for MSW disposal, some of which are already in operation and others that are still under development. This article provides a brief overview of the current state of research on pyrolytic methods of MSW processing. The bulk of the cited literature consists of references to review articles.

1. DESCRIPTION OF THE PROBLEM

The simplest solution to the problem of municipal solid waste (MSW) disposal is to deposit it in landfills (He et al., 2019). However, this leads to environmental pollution, irretrievable loss of valuable types of raw materials suitable for recycling, and removal of a significant amount of land from economic circulation. The practice of MSW management in developed countries shows that the most promising methods of waste disposal involve finding ways to reuse MSW (Huang et al., 2018).

The most rational way to reuse MSW is as an alternative energy source (Kumar and Samadder, 2017). The practice of MSW incineration is widespread throughout the world, which not only allows obtaining energy from untreated or unsorted waste but also reduces its volume by almost 90% and decreases the need for landfills (Mukherjee et al., 2020). On the other hand, waste incineration produces solid residues (ash) and gaseous substances, which are often even more dangerous from an environmental point of view. To reduce harmful emissions at modern waste incineration plants, multistage gas cleaning systems are used, the cost of which as a rule exceeds the cost of the main equipment (Wyrzykowska-Ceradini et al., 2011).

Technologies based on the thermal decomposition (pyrolysis) of MSW can be considered as innovative alternatives to the direct combustion of MSW (Sipra et al., 2018; Jahiral et al., 2022). Pyrolytic methods of solid waste thermal processing can reduce the volume of harmful emissions (Gerasimov, 2019). In addition, they do not require expensive fuel preparation and can be adapted for processing wastes of various compositions (Czajczyńska et al., 2017). It should be noted that liquid pyrolysis products (pyrolytic oil) contain a large number of oxidized compounds that are not suitable for direct combustion in power plants. Therefore, two-stage methods of thermal processing of MSW have been intensively developed recently (Khaskhachikh et al., 2021b). In these methods, pyrolytic oil is subjected to further processing in a catalytic cracking reactor to obtain synthesis gas, which can serve as fuel for autonomous power generating power plants or feedstock for the production of liquid motor fuels (Lavrenov et al., 2016).

2. REGULARITIES OF THE PYROLYSIS PROCESS

Pyrolysis is an endothermic process, which is associated with the thermal decomposition of organic components of MSW in inert atmosphere. Compared to combustion, pyrolysis has a lower process temperature, and accordingly lower emissions of harmful substances into the atmosphere (Chen et al., 2014). One of the significant advantages of this process is the ability to process various types of raw materials, including industrial, municipal, and medical waste products (Martinez et al., 2013).

The process of thermal decomposition of hydrocarbon material included in MSW can be represented by three separate stages. In the first stage, the initial mixture is dried and a dry residue is formed. Next, pyrolysis of the residue occurs with the release of volatile pyrolysis products into the gas phase. The pyrolysis process is accompanied by fragmentation and shrinkage of the processed material. In the final stage of the process, the pyrolysis products undergo further transformation through secondary chemical reactions, which include reforming, cracking, dehydration, polymerization, gasification, and others (Neves et al., 2011; Mangesh et al., 2022).

MSW contains a wide range of dissimilar materials. A typical MSW mixture mainly consists of food, garden, paper, cardboard, glass, and plastic waste materials (Czajczyńska et al., 2017). Due to the large uncertainty in the composition of MSW, it is difficult to predict the composition of their pyrolysis products. Therefore, MSW pyrolysis products are usually divided into three groups: char, tar (pyrolytic oil), and non-condensable gas.

An important parameter in the MSW pyrolysis process is the yield of liquid pyrolysis products, which can be used for energy purposes as well as in the production of motor fuels. The yield of liquid products increases with increasing temperature, reaches a maximum, and then begins to decrease (Neves et al., 2011). The maximum yield of liquid products at high heating rates reaches 45%–75%, while at slow heating rates this value lies in the range of 35%–55%. The maximum output temperature is about 500°C. This decrease in the yield of liquid pyrolysis products at higher temperatures is explained by the secondary chemical reactions of pyrolytic oil decomposition into lighter components and non-condensable gas. This process occurs in the free space at the reactor outlet (Morf et al., 2002).

The most valuable product of MSW pyrolysis is tar, the elemental composition of which contains up to 50% oxygen. This chemical element is found in several hundred types of organic compounds that make up the tar, such as acids, ketones, aldehydes, phenols, and anhydrous sugars (Mohan et al., 2006). The high content of acids and water in pyrolytic oil also makes it incompatible with traditional fuel infrastructure (Miskolczi et al., 2013). All of this gives grounds for further processing of liquid pyrolysis products in order to obtain high-quality boiler or transport fuel. This problem is currently solved using catalytic pyrolysis techniques (Kasar et al., 2020; Peng et al., 2022).

Catalytic pyrolysis can be divided into two types depending on the method of the catalyst contact with the gas–vapor mixture formed during MSW pyrolysis (Wang et al., 2017a). The first type is called in situ catalytic pyrolysis, in which the catalyst is mixed with the feedstock and fed into the pyrolysis reactor (Galadima and Muraza, 2015); the second type is called ex situ catalytic pyrolysis, in which the gas–vapor mixture formed during pyrolysis is fed into a separate catalyst bed downstream (Wan and Wang, 2014).

One of the widely used catalysts for improving the quality of liquid pyrolysis products is coke residue (Wang et al., 2017b). It is the cheapest reagent, since it is formed during the pyrolysis process; therefore, no external catalyst input into the pyrolysis reactor is required. Another inexpensive catalyst widely used to reform pyrolysis products is calcium oxide (CaO), which has fairly high catalytic activity (Song et al., 2018). This catalyst can act as an absorbent, reactant, and catalyst depending on the conditions of the pyrolysis process. Studies have shown that the addition of CaO to raw materials contributes to the decomposition of the high-molecular components in tar, which leads to a decrease in the yield of the tar and an increase in the yield of gas (Chen et al., 2017).

3. TWO-STAGE PYROLYSIS

An alternative to the traditional pyrolytic processing of MSW is a two-stage process in which the pyrolysis products in the second stage of the process undergo high-temperature catalytic cracking during the formation of synthesis gas (Lavrenov et al., 2016; Lu et al., 2019; Veses et al., 2020). The final processing product does not contain a liquid fraction, which indicates the complete thermal decomposition of the high-molecular compounds that belong to the volatile pyrolysis products (Penney et al., 2022). On the one hand, this increases the efficiency of the source material converting into high-calorie fuel; on the other hand, this allows solving the environmental problem of MSW disposal with a minimum level of emissions of harmful substances into the environment.

The principal possibility of two-stage pyrolytic conversion of MSW components into synthesis gas has been demonstrated in a number of studies (Lavrenov et al., 2016; Saad and Williams, 2016). The technological scheme of the method includes the following stages. During the first stage, the feedstock is prepared for subsequent processing with the selection of valuable fractions of the raw material (paper, glass, metal, plastic, etc.) on the sorting line and grinding the rest of the raw material in a shredder. During the second stage, the raw material prepared for processing enters the pyrolysis reactor, where the thermal decomposition process takes place at a temperature of about 500°C with the formation of a solid residue and volatile pyrolysis products. During the third stage, the gas–vapor mixture is sent to the cracking reactor, where it is thermally and catalytically converted at a temperature of about 1000°C into synthesis gas that mainly consists of carbon monoxide and molecular hydrogen. The coal residue obtained by pyrolysis of the feedstock can be used as a catalyst in the cracking reactor. The resulting synthesis gas formed during the fourth stage of the process is cooled in a heat exchanger and purified from hydrochloric acid (HCl).

The considered method of MSW thermal processing makes it possible to obtain high-calorific synthesis gas that, according to its characteristics, is suitable for use both as fuel in power plants and raw material in the synthesis of liquid motor fuels (Yan et al., 2013). The absence of chlorine-containing components in the purified synthesis gas creates conditions that prevent the formation of chlorinated dioxins during its further use (Altarawneh et al., 2009).

4. TYPES OF PYROLYSIS REACTORS

Various reactors are used in pyrolytic processing of MSW (Bridgwater, 2012). They can be subdivided according to the heat supply method used to process the material. The first group of reactors, in which the source material is heated through the reactor walls, includes fixed-bed reactors (Khaskhachikh et al., 2021a), rotary kiln-type drum reactors (Gikas et al., 2018), screw reactors (Haydary et al., 2013), and others. The main advantages of these types of reactors are reliability and stability in operation, as well as good reproducibility of results. On the other hand, this heating technology is characterized by the relatively low intensity of heat transfer, and accordingly low productivity (Martinez et al., 2013).

The principle of the heat exchange between the gas heat carrier and the crushed MSW feedstock is at the heart of fluidized bed reactors. Fluidized bed reactors are characterized by high heating rates of solid waste particles, as well as good mixing of the components of the mixture being processed. Reactors of this type are simple in design, easy to operate, and have great potential for transition to large scale reactors (Bridgwater, 2012). Pyrolysis in reactors of this type is characterized by the high yield of liquid pyrolysis products. In particular, during the thermal processing of biomass and plastic waste, the tar yield reaches 70 wt.% in terms of dry ash-free mass (Xue et al., 2015).

The third type of heating of crushed solid waste is based on the use of a solid heat carrier. Internal heat exchange between solid particles in the reactor significantly increases the heating rate of solid waste particles compared to external heat exchange through the reactor walls (Gerasimov et al., 2019). An important advantage of reactors with solid heat carriers compared to fluidized bed reactors is the absence of a large volume of fluidizing gases, which significantly reduces energy consumption during rapid cooling and subsequent condensation of liquid products. Solid heat carriers are used in high-performance screw reactors (Campuzano et al., 2019), as well as in drum-type pyrolysis reactors (Ma et al., 2014). The use of solid heat carriers in the thermal treatment of low-grade fuels is the basis of the Galoter technology, which is currently the most efficient technology widely used in commercial applications (Gerasimov and Volkov, 2015). This technology is based on the rapid heating of fine-grained solid fuel with a solid heat carrier (ash formed during fuel pyrolysis) in a rotating drum reactor.

5. ENVIRONMENTAL ASPECTS

The use of pyrolytic methods in the thermal processing of MSW products significantly improves the environmental performance of their disposal. The pyrolysis process reduces the amount of thermal nitrogen oxide (NOx) due to lower temperatures and the reducing environment implemented in pyrolysis reactors (Chen et al., 2014). In addition, the smaller volume of pyrolysis gas requires smaller scrubbers to remove NOx, ammonia, sulfur dioxide, and HCl, which reduces investment and operating costs. One of the advantages of pyrolytic processing of MSW products compared to their direct combustion is the significant reduction in heavy metals emissions into the environment due to their retention in the solid residue (Bernardo et al., 2010).

Thermal methods of MSW processing, including pyrolysis, lead to the formation of a large number of incomplete combustion products, which include toxic and persistent organic substances (Zhou et al., 2015). Pyrolytic methods can reduce the amount of harmful emissions—in particular, extremely toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) (Gerasimov, 2019). In this regard, the most attractive method from an environmental point of view is two-stage pyrolytic conversion of MSW. Pyrolysis of the processed organic mass of MSW during the first processing stage is accompanied by the release of chlorine into the gas phase in the form of HCl. In this case, the gas-phase formation of PCDD/Fs is possible in the vapor–gas mixture due to condensation and the subsequent chlorination of the phenolic structures contained in the tar (Gerasimov, 2015). During the next stage, the gas–vapor mixture enters the thermal catalytic cracking reactor for processing into synthesis gas. At a cracking temperature of about 1000°C, complete decomposition of the tar components occurs, including phenols and PCDD/Fs formed during the pyrolysis stage (Hu et al., 2019). The cooled synthesis gas, which is supposed to be used to generate thermal and/or electrical energy or to synthesize components of liquid motor fuels is purified from HCl during the next stage. The absence of chlorine-containing components in the purified synthesis gas creates conditions that prevent the formation of chlorinated dioxins during its further use.

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Bernardo, M., Lapa, N., Gonçalves, M., Barbosa, R., Mendes, B., and Pinto, F. (2010) Toxicity of Char Residues Produced in the Co-Pyrolysis of Different Wastes, Waste Manage., 30: 628–635.

Bridgwater, A.V. (2012) Review of Fast Pyrolysis of Biomass and Product Upgrading, Biomass Bioenergy, 38: 68–94.

Campuzano, F., Brown, R.C., and Martinez, J.D. (2019) Auger Reactors for Pyrolysis of Biomass and Wastes, Renew. Sustain. Energy Rev., 102: 372–409.

Chen, D., Yin, L., Wang, H., and He, P. (2014) Pyrolysis Technologies for Municipal Solid Waste: A Review, Waste Manage., 34: 2466–2486.

Chen, X., Chen, Y., Yang, H., Chen, W., Wang, X., and Chen, H. (2017) Fast Pyrolysis of Cotton Stalk Biomass Using Calcium Oxide, Bioresour. Technol., 233: 15–28.

Czajczyńska, D., Anguilano, L., Ghazal, H., Krzyzynska, R., Reynolds, A.J., Spencer, N., and Jouhara, H. (2017) Potential of Pyrolysis Processes in the Waste Management Sector, Therm. Sci. Eng. Prog., 3: 171–197.

Galadima, A. and Muraza, O. (2015) In Situ Fast Pyrolysis of Biomass with Zeolite Catalysts for Bioaromatics/Gasoline Production: A Review, Energy Convers. Manage., 105: 338–354.

Gerasimov, G. (2015) Modeling Study of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans Behavior in Flue Gases under Electron Beam Irradiation, Chemosphere, 158: 100–106.

Gerasimov, G., Khaskhachikh, V., Potapov, O., Dvoskin, G., Kornileva, V., and Dudkina, L. (2019) Pyrolysis of Sewage Sludge by Solid Heat Carrier, Waste Manage., 87: 218–227.

Gerasimov, G. and Volkov, E. (2015) Modeling Study of Oil Shale Pyrolysis in Rotary Drum Reactor by Solid Heat Carrier, Fuel Process. Technol., 139: 108–116.

Gerasimov, G.Y. (2019) Comparative Analysis of PCDD/Fs Formation during Pyrolysis and Incineration of Medical Waste, IOP Conf. Series: Earth Environ. Sci., 272: 022116.

Gikas, P., Zhu, B., Batistatos, N.I., and Zhang, R. (2018) Evaluation of the Rotary Drum Reactor Process as Pretreatment Technology of Municipal Solid Waste for Thermophilic Anaerobic Digestion and Biogas Production, J. Environ. Manage., 216: 96–104.

Haydary, J., Susa, D., and Dudáš J. (2013) Pyrolysis of Aseptic Packages (Tetrapak) in a Laboratory Screw Type Reactor and Secondary Thermal/Catalytic Tar Decomposition, Waste Manage., 33: 1136–1141.

He, P., Chen, L., Shao, L., Zhang, H., and Lü, F. (2019) Municipal Solid Waste (MSW) Landfill: A Source of Microplastics? – Evidence of Microplastics in Landfill Leachate, Water Res., 159: 38–45.

Hu, B., Huang, Q., Chi, Y., and Yan, J. (2019) Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans in Three-Stage Municipal Solid Waste Gasifier, J. Cleaner Prod., 218: 920–929.

Huang, B., Wang, X., Kua, H., Geng, Y., Bleischwitz, R., and Ren, J. (2018) Construction and Demolition Waste Management in China through the 3R Principle, Resour. Conserv. Recycl., 129: 36–44.

Jahirul, M.I., Rasul, M.G., Schaller, D., Khan, M.M.K., Hasan, M.M., and Hazrat, M.A. (2022) Transport Fuel from Waste Plastics Pyrolysis—A Review on Technologies, Challenges and Opportunities, Energy Convers. Manag., 258: 115451.

Kasar, P., Sharma, D.K., and Ahmaruzzaman, M. (2020) Thermal and Catalytic Decomposition of Waste Plastics and Its Co-Processing with Petroleum Residue through Pyrolysis Process, J. Cleaner Prod., 265: 121639.

Khaskhachikh, V.V., Kornileva, V.F., and Gerasimov, G.Y. (2021a) Investigation into the Pyrolysis of Medical Waste in a Fixed-Bed Reactor, J. Eng. Phys. Thermophys., 94: 580–586.

Khaskhachikh, V.V., Larina, O.M., Sychev, G.A., Gerasimov, G.Ya., and Zaichenko, V.M. (2021b) Pyrolitic Methods of the Thermal Processing of Solid Municipal Waste, High Temp., 59: 373–383.

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Lu, P., Huang, Q., Chi, Y., Wang, F., and Yan, J. (2019) Catalytic Cracking of Tar Derived from the Pyrolysis of Municipal Solid Waste Fractions over Biochar, Proc. Combust. Inst., 37: 2673–2681.

Ma, Z., Gao, N., Xie, L., and Li, A. (2014) Study of the Fast Pyrolysis of Oilfield Sludge with Solid Heat Carrier in a Rotary Kiln for Pyrolytic Oil Production, J. Anal. Appl. Pyrolysis, 105: 183–195.

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Veses, A., Sanahuja-Parejo, O., Callén, M.S., Murillo, R., and García, T. (2020) A Combined Two-Stage Process of Pyrolysis and Catalytic Cracking of Municipal Solid Waste for the Production of Syngas and Solid Refuse-Derived Fuels, Waste Manage., 101: 171–185.

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Referências

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  2. Bernardo, M., Lapa, N., Gonçalves, M., Barbosa, R., Mendes, B., and Pinto, F. (2010) Toxicity of Char Residues Produced in the Co-Pyrolysis of Different Wastes, Waste Manage., 30: 628–635.
  3. Bridgwater, A.V. (2012) Review of Fast Pyrolysis of Biomass and Product Upgrading, Biomass Bioenergy, 38: 68–94.
  4. Campuzano, F., Brown, R.C., and Martinez, J.D. (2019) Auger Reactors for Pyrolysis of Biomass and Wastes, Renew. Sustain. Energy Rev., 102: 372–409.
  5. Chen, D., Yin, L., Wang, H., and He, P. (2014) Pyrolysis Technologies for Municipal Solid Waste: A Review, Waste Manage., 34: 2466–2486.
  6. Chen, X., Chen, Y., Yang, H., Chen, W., Wang, X., and Chen, H. (2017) Fast Pyrolysis of Cotton Stalk Biomass Using Calcium Oxide, Bioresour. Technol., 233: 15–28.
  7. Czajczyńska, D., Anguilano, L., Ghazal, H., Krzyzynska, R., Reynolds, A.J., Spencer, N., and Jouhara, H. (2017) Potential of Pyrolysis Processes in the Waste Management Sector, Therm. Sci. Eng. Prog., 3: 171–197.
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  10. Gerasimov, G., Khaskhachikh, V., Potapov, O., Dvoskin, G., Kornileva, V., and Dudkina, L. (2019) Pyrolysis of Sewage Sludge by Solid Heat Carrier, Waste Manage., 87: 218–227.
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  22. Khaskhachikh, V.V., Larina, O.M., Sychev, G.A., Gerasimov, G.Ya., and Zaichenko, V.M. (2021b) Pyrolitic Methods of the Thermal Processing of Solid Municipal Waste, High Temp., 59: 373–383.
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