Catalysts in Thermo-Chemical Upcycling Solid Wastes to High-Value Products

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (31 October 2022) | Viewed by 20281

Special Issue Editors

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029, China
Interests: heterogeneous catalysis; ozone conversion; waste to carbon; waste to syngas; environmental sustainable processes
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Guest Editor
Department of Energy and Power Engineering, Tsinghua University, Beijing, China
Interests: photocatalytic technology in the environment and energy conversion; flue gas purification; clean energy conversion and utilization; resource utilization of solid waste
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Thermochemical upcycling solid wastes, such as municipal solid wastes, waste plastics, and biomass, to high-value products helps to address the global solid waste crisis, reduce the climate impacts, and realize circular economy by resources recovery. Fundamental breakthroughs in strategy, technology, process, and catalysts are urgently needed to accelerate developments in this emerging area.

We invite contributions related to the use of solid wastes of different types (household, industrial, etc.) into high-value products (oil, syngas, carbon, etc.) via various technologies (pyrolysis, gasification, catalytic reforming, catalytic decomposition, catalytic partial oxidation, etc.). Specially, contributions related to catalyst design, preparation, performance, lifetime, stability, and regeneration during the catalytic processes for upcycling solid wastes are welcome.


Dr. Jingbo Jia
Dr. Haiming Wang
Guest Editors

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Keywords

  • Solid wastes to carbon materials
  • Solid wastes to energy
  • Solid wastes to syngas
  • Solid wastes to oil
  • Solid wastes to chemicals
  • Pyrolysis of solid wastes
  • Gasification of solid wastes
  • Catalytic reforming
  • Yield and selectivity

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Published Papers (10 papers)

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Research

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18 pages, 8096 KiB  
Article
Hydrodeoxygenation of Bio-Oil over an Enhanced Interfacial Catalysis of Microemulsions Stabilized by Amphiphilic Solid Particles
by Kuan Du, Beichen Yu, Yimin Xiong, Long Jiang, Jun Xu, Yi Wang, Sheng Su, Song Hu and Jun Xiang
Catalysts 2023, 13(3), 573; https://doi.org/10.3390/catal13030573 - 12 Mar 2023
Cited by 1 | Viewed by 1418
Abstract
Bio-oil emulsions were stabilized using coconut shell coke, modified amphiphilic graphene oxide, and hydrophobic nano-fumed silica as solid emulsifiers. The effects of different particles on the stability of bio-oil emulsions were discussed. Over 21 days, the average droplet size of raw bio-oil increased [...] Read more.
Bio-oil emulsions were stabilized using coconut shell coke, modified amphiphilic graphene oxide, and hydrophobic nano-fumed silica as solid emulsifiers. The effects of different particles on the stability of bio-oil emulsions were discussed. Over 21 days, the average droplet size of raw bio-oil increased by 64.78%, while that of bio-oil Pickering emulsion stabilized by three particles only changed within 20%. The bio-oil Pickering emulsion stabilized by Ni/SiO2 was then used for catalytic hydrodeoxygenation. It was found that the bio-oil undergoes polymerization during catalytic hydrogenation. For raw bio-oil hydrodeoxygenation, the polymerization reaction was little affected by the temperature below 200 °C, but when the temperature raised to 250 °C, it was greatly accelerated. However, the polymerization of monocyclic aromatic compounds in the reaction process was partially inhibited under the bio-oil Pickering emulsion system. Additionally, a GC-MS analysis was performed on raw bio-oil and hydrodeoxygenated bio-oil to compare the change in GC-MS-detectable components after hydrodeoxygenation at 200 °C. The results showed that the Pickering emulsion catalytic system greatly promoted the hydrodeoxygenation of phenolic compounds in bio-oil, with most monocyclic phenolic compounds detected by GC-MS converting to near 100%. Full article
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14 pages, 2146 KiB  
Article
Heterogenization of a Tungstosilicic Acid Catalyst for Esterification of Bio-Oil Model Compound
by Prapaporn Prasertpong, Jeremiah Lipp, Anhua Dong, Nakorn Tippayawong and John R. Regalbuto
Catalysts 2023, 13(1), 38; https://doi.org/10.3390/catal13010038 - 25 Dec 2022
Viewed by 1762
Abstract
Based on a prior demonstration of the high activity of a homogeneous tungstosilicic acid catalyst for the esterification of acetic acid as bio-oil model compound, a further study has been undertaken in an attempt to heterogenize the catalyst. Tungsten oxide was supported on [...] Read more.
Based on a prior demonstration of the high activity of a homogeneous tungstosilicic acid catalyst for the esterification of acetic acid as bio-oil model compound, a further study has been undertaken in an attempt to heterogenize the catalyst. Tungsten oxide was supported on amorphous silica (W/A150) using incipient wetness impregnation and incorporated into the structure of structured silica (W-KIT-5) via a one-step hydrothermal synthesis. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), physisorption (BET), and temperature-programmed desorption of ammonia (NH3-TPD). Both series were evaluated for the esterification of acetic acid with ethanol and compared with the homogeneous 12-tungstosilicic acid catalyst. The result of XRD analysis suggests the average crystallite size of the W oxide nanoparticles on both supports to be less than 2 nm, while XPS analysis revealed that all W existed in the W 6+ oxidation state. From the BET and NH3-TPD analyses, it was shown that the KIT-5 series had higher surface area and acidity than the W/A150 catalyst. The 10% W-KIT-5 was shown to be the best heterogeneous catalyst with the highest activity and acid conversion of about 20% and 93% of the homogeneous catalyst. Significant leaching of tungsten from both the supports occurred and will have to be solved in the future. Full article
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13 pages, 2779 KiB  
Article
Synthesis of Sulfonated Carbon from Discarded Masks for Effective Production of 5-Hydroxymethylfurfural
by Hengyu Hao, Feng Shen, Jirui Yang, Mo Qiu, Haixin Guo and Xinhua Qi
Catalysts 2022, 12(12), 1567; https://doi.org/10.3390/catal12121567 - 02 Dec 2022
Cited by 4 | Viewed by 1284
Abstract
5-hydroxymethylfurfural (HMF), as one of the top ten important platform chemicals, can be used to produce 2,5-furandicarboxylic acid (FDCA), 2,5-dimethyl furan (DMF), levulinic acid, and other chemicals. An environmentally friendly system for the synthesis of sulfonated carbon materials from discarded masks has been [...] Read more.
5-hydroxymethylfurfural (HMF), as one of the top ten important platform chemicals, can be used to produce 2,5-furandicarboxylic acid (FDCA), 2,5-dimethyl furan (DMF), levulinic acid, and other chemicals. An environmentally friendly system for the synthesis of sulfonated carbon materials from discarded masks has been proposed. A series of mask-based solid acid catalysts (bMC-SO3H) were prepared by a simple two-step process. Mechanochemical pretreatment (ball milling) of waste mask and sulfonated group precursor, followed by thermal carbonization under nitrogen gas, were used to synthesize sulfonated porous carbon. The total acid amount of the prepared bMC-SO3H was measured by the Boehm method, which exhibited 1.2–5.3 mmol/g. The addition of the sulfonated group precursor in the mechanochemical treatment (ball milling) process caused intense structure fragmentation of the discarded masks. These sulfonated porous carbons (bMC(600)-SO3H) as solid acid catalysts achieved fructose conversion of 100% and HMF yield of 82.1% after 120 min at 95 °C in 1-butyl-3-methylimidazolium chloride. The bMC-SO3H could be reused five times, during which both the HMF yield and fructose conversion were stable. This work provides a strategy for the synthesis of sulfonated carbon from discarded masks and efficient catalyzed fructose upgrading to HMF. Full article
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17 pages, 49033 KiB  
Article
Acid Gas and Tar Removal from Syngas of Refuse Gasification by Catalytic Reforming
by Guoan Yuan, Wei Zhou, Rui Yang, Yuru Liu, Jingyu Zhu, Ke Yin and Dezhen Chen
Catalysts 2022, 12(12), 1519; https://doi.org/10.3390/catal12121519 - 25 Nov 2022
Cited by 2 | Viewed by 1391
Abstract
The existence of acid gas and tar in syngas of municipal solid waste gasification limits its downstream utilization as a clean energy source. Here, we investigated the catalytic removal of HCl and tar. The key parameters affecting the catalytic reaction, including space velocity, [...] Read more.
The existence of acid gas and tar in syngas of municipal solid waste gasification limits its downstream utilization as a clean energy source. Here, we investigated the catalytic removal of HCl and tar. The key parameters affecting the catalytic reaction, including space velocity, temperature, the amounts of active metals in the catalyst and the carrier material, were studied, targeting optimized operating conditions for enhanced syngas purification. The morphology, mineral phases, surface area and pore size before and after the reaction were investigated to understand the mechanism to dominate the reaction. The results showed that the removal rate of CaO adsorbent and HCl reached 96% at 400 °C. When the space velocity ratio was 1.0 and the temperature was 400 °C, HCl removal (97%) by NaAlO2 was even better. Nevertheless, clogging was observed for NaAlO2 via the BET test after reaction to jeopardize its durability. A level of 25% Ni doping on Zr1-x(Cex)O2 support provides high stability for tar removal. This is because the Zr1-x(Cex)O2 carrier has higher carbon deposition resistivity than the Al2O3 carrier. The EDX results confirmed that a large amount of C (79.3%) was accumulated on the commercial catalyst surface supported by Al2O3 (25% Ni-based). As for the temperature, a temperature higher than 800 °C could not enhance the efficiency of tar removal, likely due to catalyst deactivation. Carbon deposition and agglomeration are the two main causes of catalyst deactivation. At 800 °C, 25% Ni-based synthetic catalyst can convert 48.5 ± 19.4% tar to low molecular weight organic compounds. By contrast, such a conversion rate under the same temperature only accounted for 5.0 ± 6.8% based on a commercial catalyst. These insights point to the important role of catalyst support materials. Full article
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24 pages, 4538 KiB  
Article
Upgrading Mixed Agricultural Plastic and Lignocellulosic Waste to Liquid Fuels by Catalytic Pyrolysis
by Farid Sotoudehnia and Armando G. McDonald
Catalysts 2022, 12(11), 1381; https://doi.org/10.3390/catal12111381 - 07 Nov 2022
Cited by 4 | Viewed by 2209
Abstract
Agriculture generates non-recyclable mixed waste streams, such as plastic (netting, twine, and film) and lignocellulosic residues (bluegrass straw/chaff), which are currently disposed of by burning or landfilling. Thermochemical conversion technologies of agricultural mixed waste (AMW) are an option to upcycle this waste into [...] Read more.
Agriculture generates non-recyclable mixed waste streams, such as plastic (netting, twine, and film) and lignocellulosic residues (bluegrass straw/chaff), which are currently disposed of by burning or landfilling. Thermochemical conversion technologies of agricultural mixed waste (AMW) are an option to upcycle this waste into transportation fuel. In this work, AMW was homogenized by compounding in a twin-screw extruder and the material was characterized by chemical and thermal analyses. The homogenized AMW was thermally and catalytically pyrolyzed (500–600 °C) in a tube batch reactor, and the products, including gas, liquid, and char, were characterized using a combination of FTIR, GC-MS, and ESI-MS. Thermal pyrolysis wax products were mainly a mixture of straight-chain hydrocarbons C7 to C44 and oxygenated compounds. Catalytic pyrolysis using zeolite Y afforded liquid products comprised of short-chain hydrocarbons and aromatics C6 to C23. The results showed a high degree of similarity between the chemical profiles of catalytic pyrolysis products and gasoline. Full article
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8 pages, 1910 KiB  
Article
Catalytic Degradation of Bisphenol A in Water by Poplar Wood Powder Waste Derived Biochar via Peroxymonosulfate Activation
by Haiqin Lu and Lu Gan
Catalysts 2022, 12(10), 1164; https://doi.org/10.3390/catal12101164 - 02 Oct 2022
Cited by 8 | Viewed by 1256
Abstract
A series of biochar materials was prepared through pyrolyzing poplar wood powder waste under different pyrolyzing temperatures, which were afterwards characterized in detail. Then, the poplar powder biochar (PPB) was used to degrade bisphenol A (BPA) in water via activating peroxymonosulfate (PMS). The [...] Read more.
A series of biochar materials was prepared through pyrolyzing poplar wood powder waste under different pyrolyzing temperatures, which were afterwards characterized in detail. Then, the poplar powder biochar (PPB) was used to degrade bisphenol A (BPA) in water via activating peroxymonosulfate (PMS). The results indicate that the activation efficiency of the prepared PPB was correlated with its surface functional groups, which were regulated by its pyrolyzing temperature. Specifically, the biochar pyrolyzed at 600 °C (PPB-600) exhibited the optimal BPA removal activity, in which 0.5 g/L of PPB-600 could remove 0.02 mM of BPA within 120 min. From the results of scavenging tests, ESR analysis and probe pollutant degradation tests, it was inferred that the BPA was degraded by non-radical singlet oxygen in the PPB/PMS system. Since PPB consumed its surface oxygen functional groups and structural defects to activate PMS, the catalytic performance of PPB was gradually reduced after several cycles. This study can provide new insight for the design and preparation of metal-free biochar catalysts from waste wood precursor for the highly-efficient removal of refractory organic pollutants in water. Full article
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16 pages, 2165 KiB  
Article
Pyrolysis and Co-Combustion of Semi-Dry Sewage Sludge and Bituminous Coal: Kinetics and Combustion Characteristics
by Guangyang Li, Zhuoyuan Chen, Afeng Wu, Tao Shi, Xiong Zhang, Hui Li, Haiping Yang, Jingai Shao, Shihong Zhang and Hanping Chen
Catalysts 2022, 12(10), 1082; https://doi.org/10.3390/catal12101082 - 20 Sep 2022
Cited by 1 | Viewed by 1268
Abstract
To reduce the energy consumption and cost of the drying of sewage sludge (SS) and to ensure stability during combustion, the pyrolysis and co-combustion characteristics of semi-dry SS after the dehydration of flocculant and bituminous coal (BC) were studied in this work. The [...] Read more.
To reduce the energy consumption and cost of the drying of sewage sludge (SS) and to ensure stability during combustion, the pyrolysis and co-combustion characteristics of semi-dry SS after the dehydration of flocculant and bituminous coal (BC) were studied in this work. The results show that the decrease in moisture content accelerates the release of volatile substances, and the increase in heating rate can also enhance the release of water and volatile matters. Furthermore, in the co-combustion of semi-dry SS and BC, the increase in mixing ratio (from 0% to 60%) of semi-dry SS caused the ignition and burnout temperature to decrease from 481 °C to 214 °C and from 702 °C to 627 °C, respectively. During co-combustion, the infrared spectra showed that the temperature range of 300–700 °C was the main gas precipitation area, and the main gaseous products were CO2, NOx, SO2, and volatile organic pollutants (VOCs). Full article
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17 pages, 2870 KiB  
Article
A Thermal Study on Peat Oxidation Behavior in the Presence of an Iron-Based Catalyst
by Mohammed A. Khelkhal, Semen E. Lapuk, Nikita E. Ignashev, Alexey A. Eskin, Mikhail Yu. Glyavin, Nikolay Yu. Peskov, Tatiana O. Krapivnitskaia and Alexey V. Vakhin
Catalysts 2021, 11(11), 1344; https://doi.org/10.3390/catal11111344 - 09 Nov 2021
Cited by 5 | Viewed by 1665
Abstract
Peat is a resource used for heat and energy, particularly in countries where peat is abundant and conventional fuels are not available. Some countries have made extensive use of peat resources to produce electricity and heat in addition to light hydrocarbons. By doing [...] Read more.
Peat is a resource used for heat and energy, particularly in countries where peat is abundant and conventional fuels are not available. Some countries have made extensive use of peat resources to produce electricity and heat in addition to light hydrocarbons. By doing so, they were able to reduce the cost of importing fossil fuels. To the best of our knowledge, there is a lack of a detailed description of the peat oxidation process in the presence of other substances. Herein, the process of peat oxidation was studied in-depth by means of thermal analysis in the presence of iron tallate acting as a catalytic agent. Differential scanning calorimetry and thermogravimetric analysis demonstrated an oil-like oxidation behavior during the combustion of the used peat. The process of peat oxidation includes two main regions: low-temperature oxidation (LTO), which occurs during the oxidation of light hydrocarbons, followed by the so-called high-temperature oxidation (HTO), which includes the oxidation of the obtained coke-like product. Moreover, the application of non-isothermal kinetics experiments based on the isoconversional and model approach principle have confirmed the role of 2% iron tallate in peat mass by improving the oxidation rate at low- and high-temperature oxidation (HTO) regions. The results obtained from this study have proven that the added catalyst improves efficiency with regards to the energy activation in the process by leading to its significant decrease from 110.8 ± 7.8 kJ/mol to 81.8 ± 7.5 kJ/mol for LTO and from 157.8 ± 19.1 kJ/mol to 137.6 ± 9.3 kJ/mol for HTO. These findings clearly confirm the improvement in the rate of the process by shifting the LTO and HTO peaks to lower regions in the presence of the catalyst. These results further emphasize the possible impact which could be generated by the application of thermally enhanced oil recovery methods on peat development and exploitation. Full article
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Review

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29 pages, 2715 KiB  
Review
Current Challenges and Perspectives for the Catalytic Pyrolysis of Lignocellulosic Biomass to High-Value Products
by Wenli Wang, Yaxin Gu, Chengfen Zhou and Changwei Hu
Catalysts 2022, 12(12), 1524; https://doi.org/10.3390/catal12121524 - 26 Nov 2022
Cited by 12 | Viewed by 2971
Abstract
Lignocellulosic biomass is an excellent alternative of fossil source because it is low-cost, plentiful and environmentally friendly, and it can be transformed into biogas, bio-oil and biochar through pyrolysis; thereby, the three types of pyrolytic products can be upgraded or improved to satisfy [...] Read more.
Lignocellulosic biomass is an excellent alternative of fossil source because it is low-cost, plentiful and environmentally friendly, and it can be transformed into biogas, bio-oil and biochar through pyrolysis; thereby, the three types of pyrolytic products can be upgraded or improved to satisfy the standard of biofuel, chemicals and energy materials for industries. The bio-oil derived from direct pyrolysis shows some disadvantages: high contents of oxygenates, water and acids, easy-aging and so forth, which restrict the large-scale application and commercialization of bio-oil. Catalytic pyrolysis favors the refinement of bio-oil through deoxygenation, cracking, decarboxylation, decarbonylation reactions and so on, which could occur on the specified reaction sites. Therefore, the catalytic pyrolysis of lignocellulosic biomass is a promising approach for the production of high quality and renewable biofuels. This review gives information about the factors which might determine the catalytic pyrolysis output, including the properties of biomass, operational parameters of catalytic pyrolysis and different types of pyrolysis equipment. Catalysts used in recent research studies aiming to explore the catalytic pyrolysis conversion of biomass to high quality bio-oil or chemicals are discussed, and the current challenges and future perspectives for biomass catalytic pyrolysis are highlighted for further comprehension. Full article
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30 pages, 34347 KiB  
Review
Value-Added Products from Catalytic Pyrolysis of Lignocellulosic Biomass and Waste Plastics over Biochar-Based Catalyst: A State-of-the-Art Review
by Peng Li, Kun Wan, Huan Chen, Fangjuan Zheng, Zhuo Zhang, Bo Niu, Yayun Zhang and Donghui Long
Catalysts 2022, 12(9), 1067; https://doi.org/10.3390/catal12091067 - 19 Sep 2022
Cited by 13 | Viewed by 3947
Abstract
As the only renewable carbon resource on Earth, lignocellulosic biomass is abundant in reserves and has the advantages of environmental friendliness, low price, and easy availability. The pyrolysis of lignocellulosic biomass can generate solid biochar with a large specific surface area, well-developed pores, [...] Read more.
As the only renewable carbon resource on Earth, lignocellulosic biomass is abundant in reserves and has the advantages of environmental friendliness, low price, and easy availability. The pyrolysis of lignocellulosic biomass can generate solid biochar with a large specific surface area, well-developed pores, and plentiful surface functional groups. Therefore, it can be considered as a catalyst for upgrading the other two products, syngas and liquid bio-oil, from lignocellulosic biomass pyrolysis, which has the potential to be an alternative to some non-renewable and expensive conventional catalysts. In addition, as another carbon resource, waste plastics can also use biochar-based catalysts for catalytic pyrolysis to solve the problem of accumulation and produce fuels simultaneously. This review systematically introduces the formation mechanism of biochar from lignocellulosic biomass pyrolysis. Subsequently, the activation and modification methods of biochar catalysts, including physical activation, chemical activation, metal modification, and nonmetallic modification, are summarized. Finally, the application of biochar-based catalysts for lignocellulosic biomass and waste plastics pyrolysis is discussed in detail and the catalytic mechanism of biochar-based catalysts is also investigated. Full article
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