*2.1. Materials*

4-Phenyl-pyrazole (4-Ph-pzH) was prepared according to a procedure from the literature [14]. All other reagents were purchased from commercial sources and used as received. Solvents were purified using standard techniques [15]. [PPN]2[Cu3(μ3-Cl)2(μ-pz)3Cl3] and [PPN]2[Cu3(μ3-O)(μ-pz)3Cl3] were prepared according to published procedures [12]; PPN<sup>+</sup> = bis(triphenylphosphine)iminium.


**1. Introduction**

Recently, the need for waste to be converted to energy has emerged globally. Waste sewage sludge is one of the renewable energy resources, and the amount of it has gradually increased over the years in Korea, where it reached up to 20 million tons in 2020. Since ocean dumping was prohibited after the international prohibition of waste sludge was announced in 2012, technology to convert waste sludge to energy has developed as an alternative disposal option.

The capacity of commercial fluidized bed combustion (FBC) plants for waste sludge is between 50 and 300 tons per day.

However, GHGs have become a worldwide issue, and converting waste, such as sludge, biomass, and municipal solid waste, to energy has been identified as a secondary source of GHG emissions, with fossil fuel combustion deemed a primary emission source. To mitigate global warming, carbon capture and storage (CCS) technology was developed to reduce GHGs, such as carbon dioxide, from anthropogenic emission sources. The effects of GHGs on global warming are acknowledged worldwide; therefore, GHG emission reduction has increased in importance.

Oxy-fuel combustion consumes a combination of oxygen greater than 95% in purity and recycles flue gas, which is enriched with carbon dioxide. During oxy-fuel combustion, a gas consisting primarily of carbon dioxide is generated that is ready for sequestration without stripping of the carbon dioxide from the flue gas. Due to the different surroundings

**Citation:** Jang, H.-N.; Yoo, H.-M.; Choi, H.S. Particle Size Distribution and Enrichment of Alkali and Heavy Metals in Fly Ash on Air and Oxy-Fuel Conditions from Sludge Combustion. *Energies* **2023**, *16*, 145. https://doi.org/10.3390/en16010145

Academic Editors: Tomasz Czakiert and Monika Kosowska-Golachowska

Received: 7 October 2022 Revised: 14 November 2022 Accepted: 26 November 2022 Published: 23 December 2022

**Copyright:** © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).

during combustion, the flue gas composition of oxy-fuel combustion should be different than it is with air combustion [1].

In waste sludge combustion, the flue gas includes various air pollutants, such as ash, heavy metals, sulfur oxide, and nitrogen oxide. Among these air pollutants, the behaviors of ash and heavy metals are especially important because these compounds incur adverse health effects and prevent economical operation by causing fouling of, and deposition on, the boiler tube. There are numerous studies about the behavior of ash and heavy metals during conventional waste sludge combustion [1,2]. Rink et al. [3] studied the behavior of ash during sewage sludge combustion using a 300 kW bubbling fluidized bed (BFB) combustor. According to this study, particle size distribution was different along the height of the BFB combustor. This might have occurred because of different particle formation mechanisms in each temperature region. In addition, particle shapes were different at each sampling location, which were related to the particle formation mechanism of heavy metals. Cenni et al. [4] investigated the recovery rate of heavy metals in bottom ash, cyclone ash, and filter ash by blending sewage sludge with coal using a 500 kW pulverized fuel combustion chamber. This study indicated that the recovery rate of metals tended to increase when the blending rate of sewage sludge increased due to a flame temperature difference, in comparison with coal combustion. Latva-Somppi et al. [5] studied ash deposition and size distribution from the combustion of sewage sludge with wood by comparing BFB and CFB combustors. According to this study, sewage sludge contained a high proportion of alkali metals, such as Al, Ca, Si, and K, which caused ash deposition in the refractory liners and boiler tube. It was found that ash deposition did not occur in the CFB combustor, due to the advantageous heat distribution of the CFB. In addition, ash size in the CFB was smaller than it was in the BFB because the time for particle growth from metals, which was the main cause of ash deposition, was shorter than it was for the BFB. Lopez et al. [6] investigated metal partitioning in bottom ash and fly ash in accordance with their volatility with variation in sludge mixture with coal using a 90 kW BFB pilot plant. According to the study, Hg, Cd, Cu, and Pb in the fly ash increased more significantly in the mixture of sludge with coal than in the coal alone, whereas Cr, Ni, Mn, and Zn in the fly ash were less significant. In addition, Hg, Cd, Pb, and Zn increased more in the fly ash than in the bottom ash, whereas Mn, Cu, Ni, and Cr were not as significant, which was likely related to the volatility of the metals. Marani et al. [7] studied the enrichment factor of metals, such as Cd, Cr, Mn, Ni, Pb, Ti, and Zn, in cyclone ash and fly ash from sewage sludge combustion by chlorine content using a 250 kg/h CFB pilot plant. According to the study, the concentrations of those metals were enriched more in the fly ash than they were in the cyclone ash. Regarding the enrichment factor, Cd and Cr increased as chlorine content increased, whereas other metals were not as significant, likely due to the difference in the volatility of metals and formation of metal chloride compounds. Amand and Leckner [8] studied mass balance of trace metals from co-combustion of sludge, with coal or wood as the base fuel, by using a 12 MWth CFB boiler. The study indicated that the trace metals in ash increased when wood was the base fuel as the sludge mixing rate increased, whereas this trend was not present when coal was the base fuel. Regarding the mass balance of trace metals in ash, volatile matter, such as Hg and Cd, was enriched in the fly ash from a second cyclone and bag filter, but non-volatile matter, such as Mn, was evenly enriched in the bottom ash and fly ash during co-combustion of coal and sludge. However, non-volatile matter was enriched in the finest fly ash during co-combustion of wood and sludge. Elled et al. [9,10] studied relative enrichment of volatile matter and non-volatile matter at different sampling points, such as the bed ash, second cyclone ash, and bag-filter ash, from co-combustion of wood and sludge. The study indicated that as the sludge mixing rate increased, the enrichment rate of volatile matter increased more in the fly ash than it did for the non-volatile matter in the fly ash. As mentioned above, there has been numerous research works related to the behavior of ash and heavy metals during FBC incineration. In summary, the studies concluded that the fate of trace elements was influenced by fuel type, combustion facility type, and operating conditions (temperature, pressure, oxidizing

environment, and ash formation). However, these studies were conducted mainly under air combustion conditions and focused on co-combustion of sludge with coal or wood as the base fuel using BFB combustion technology [11–15].

CFB combustion technology has many advantages for heat recovery, so waste sewage sludge combustion should be retrofitted to, or newly commercialized for, CFB combustion facilities. In addition, a commercial FBC should be retrofitted to a carbon dioxide reduction facility. Only a few studies have been conducted on oxy-fuel combustion technology using CFB combustion technology for sludge combustion. When these technologies are applied to sludge combustion, combustion performances and the behavior of ash and heavy metals should be different under different combustion conditions. In this study, the particle size distributions composed of affluent metal components and the chemical reaction of aluminum, calcium, and potassium as alkali metals and chrome, copper, nickel, and zinc as tract metals from sludge combustion under the conditions of oxygen with nitrogen as the air combustion and oxygen with carbon dioxide as the oxy-fuel combustion were demonstrated, using a 30 kW CFB reactor.

#### **2. Test Facility and Experimental Methods**

#### *2.1. Test Facility and Fuel Characteristics*

Figure 1 shows a schematic stream of the test facility of the 30 kW CFB oxy-fuel reactor. The demonstration test was conducted in the facility, which consisted of a riser, a cyclone, a down-comer, and a loop-seal. The facility had a riser with an inner diameter of 0.15 m and a height of 6.4 m. The combustion temperature for the sludge fuel combustion was optimized at 800 ◦C. The feeding rate of the sludge was determined at 13 kg/h. Table 1 shows the summary of experimental conditions using the 30 kW CFB oxy-fuel reactor [16].

**Figure 1.** Schematic diagram of the 30 kW CFB oxy-fuel pilot test bed.

**Table 1.** Experimental conditions used during oxy-fuel combustion in the 30 kW CFB oxy-fuel pilot test bed.


*Article* **Distribution of the Water-Soluble Astaxanthin Binding Carotenoprotein (AstaP) in Scenedesmaceae**

**Hiroki Toyoshima 1, Ami Miyata 1, Risako Yoshida 1, Taichiro Ishige 2, Shinichi Takaichi 3 and Shinji Kawasaki 1,3,\***

**Abstract:** Photooxidative stress-inducible water-soluble astaxanthin-binding proteins, designated as AstaP, were identified in two Scenedesmaceae strains, *Coelastrella astaxanthina* Ki-4 and *Scenedesmus obtusus* Oki-4N; both strains were isolated under high light conditions. These AstaPs are classified as a novel family of carotenoprotein and are useful for providing valuable astaxanthin in water-soluble form; however, the distribution of AstaP orthologs in other microalgae remains unknown. Here, we examined the distribution of AstaP orthologs in the family Scenedesmaceae with two model microalgae, *Chlamydomonas reinhardtii* and *Chlorella variabilis*. The expression of AstaP orthologs under photooxidative stress conditions was detected in cell extracts of Scenedesmaceae strains, but not in model algal strains. Aqueous orange proteins produced by Scenedesmaceae strains were shown to bind astaxanthin. The protein from *Scenedesmus costatus* SAG 46.88 was purified. It was named ScosAstaP and found to bind astaxanthin. The deduced amino acid sequence from a gene encoding ScosAstaP showed 62% identity to Ki-4 AstaP. The expression of the genes encoding AstaP orthologs was shown to be inducible under photooxidative stress conditions; however, the production amounts of AstaP orthologs were estimated to be approximately 5 to 10 times lower than that of Ki-4 and Oki-4N.

**Keywords:** astaxanthin; *Scenedesmus*; *Coelastrella*; carotenoprotein; astaxanthin-binding protein


Brian Albert Robson

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75662

#### Abstract

Several astronomical observations concerning the structure of galaxies, the rotation of stars in spiral galaxies, the motions of galaxies within a cluster of galaxies, and so on, cannot be understood in terms of Newton's universal law of gravitation and the visible atomic matter within the galactic systems. This chapter reviews the progress made over many decades in the understanding of these cosmological observations that indicate a serious breakdown of Newton's universal law of gravitation unless there exists additional unseen matter, named "dark matter." The only alternative to "dark matter" is to modify Newtonian gravity. The chapter presents a critical review of the two main approaches to providing the additional gravity required to understand the puzzling astronomical observations: (1) the "dark matter" hypothesis providing additional unseen mass and (2) modification of Newton's universal law of gravity such that there is a stronger gravitational field at larger distances. Both Milgrom's modified Newtonian dynamics (MOND) theory and Robson's recent quantum theory of gravity provided by the generation model (GM) of particle physics are discussed.

Keywords: gravity, dark matter, MOND theory, generation model

## 1. Introduction

The notion of "dark matter" emerged from several astronomical observations concerning the structure of galaxies, the rotation of stars and neutral hydrogen gas in spiral galaxies, the motions of clusters of galaxies, and so on. These observations could not be described in terms of Newton's universal law of gravitation and the visible ordinary atomic matter within the galactic systems. This chapter reviews the progress made over many decades in the understanding of these cosmological observations that indicated a serious breakdown of Newton's universal law of gravitation unless there existed additional unseen matter that was named "dark matter." The only alternative to "dark matter" was to modify Newtonian gravity.

© 2018 The Author(s). Licensee IntechOpen. Distributed under the terms of the Creative Commons Attribution-NonCommercial 4.0 License (https://creativecommons.org/licenses/by-nc/4.0/), which permits use, distribution and reproduction for non-commercial purposes, provided the original is properly cited.

This chapter presents a critical review of the two main approaches to providing the additional gravity required to understand the puzzling astronomical observations: (1) the "dark matter" hypothesis providing additional unseen mass and (2) modification of Newton's universal law of gravity such that there is a stronger gravitational field at larger distances. Both Milgrom's modified Newtonian dynamics (MOND) theory and Robson's recent quantum theory of gravity provided by the generation model (GM) of particle physics are discussed.


**7. Conclusions and Future Work**

Games in the digital era promote cultural heritage by relying on several affective capabilities. This article has a twofold focus. First, a template Simon–Ando iterative scheme is developed for clustering player profiles consisting of attributes with affective content. Certain schemes deriving from this template are evaluated based on inter- and intra-clustering distances as well as on the number of iterations and the number of floating point operations required. The former are indicators of clustering quality, while the latter of scalability. The results are interpreted in light of the Bartle taxonomy. Understanding the player base in this way can lead to recommendations about placing emphasis on specific game elements. Second, the role of user annotations on clustering is evaluated by deriving versions using weight matrices based on them. Experiment results clearly show that in every case the inclusion of user annotations had a distinct positive effect.

Concerning future research directions, the algorithmic aspect of the proposed methodology can be improved by examining alternative combinations of attributes and tensors utilizing them. Moreover, the stability properties as well as its complexity should be carefully evaluated through extensive simulations. Another possible research direction lies in constructing more datasets from diverse player audience. This will lead to better evaluation of alternative player clustering methodologies.

**Author Contributions:** G.D. did the coding and developed the algorithmic strategy; Y.V. contributed to the algorithmic approach and did the bibliographic search; and P.M. provided guidance and oversight. All authors have read and agreed to the published version of the manuscript.

**Funding:** This research was co-financed by the European Union and Greek national funds through the Competitiveness, Entrepreneurship and Innovation Operational Programme, under the Call "Research-Create-Innovate"; project title: "Development of technologies and methods for cultural inventory data interoperability—ANTIKLEIA"; project code: T1EDK-01728; MIS code: 5030954.

**Conflicts of Interest:** The authors declare no conflict of interest.

#### **References**

**Publisher's Note:** MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).