Home Physical Sciences Effect of transition metal chloride (ZnCl2) on low-temperature pyrolysis of high ash bituminous coal
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Effect of transition metal chloride (ZnCl2) on low-temperature pyrolysis of high ash bituminous coal

  • Deepak Singh Panwar , Ram Chandra Chaurasia , Bhupendra Singh Ken , Balraj Krishnan Tudu , Vishal Shah , Jigesh Mehta , Abhinav Kumar , Mushtaq Ahmad Ansari , Lakshmaiya Natrayan and Ishfaq Ahmed Malik EMAIL logo
Published/Copyright: August 30, 2024
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Open Chemistry
From the journal Open Chemistry Volume 22 Issue 1

Abstract

Concerns about pollution and global warming have grown in recent years. Efficient coal use is critical for reducing the environmental toll of fossil fuel consumption. This study aims to examine how transition metal chlorides affect the burn-off rate and thermal conversion efficiency of bituminous coal with a high ash content. The analytical methods used include proximate, thermo-gravimetric, morphological, and pyrolysis analyses. This research examined the effect of change in the carbonization temperature, carbonization time, and catalyst concentration on the thermal degradation of high-ash bituminous coal impregnated with ZnCl2. At various ratios, zinc chloride solution was adsorbed onto the coal surface. The treated coal was then heated at different temperatures ranging from 510 to 710°C, under atmospheric pressure, in a furnace without air. This process was carried out to enhance the rate of burnout or pyrolysis. The response surface approach reveals that the carbonization time is a crucial input parameter, followed by the carbonization temperature and catalyst concentration. The response surface methodology analysis yielded a coefficient of determination of 0.9734.

Keywords: thermal conversion; high ash bituminous coal; low-temperature pyrolysis; impregnation; response surface methodology

1 Introduction

Coal is the predominant source of energy generation in several nations, even in the present day. The need for coal is rising due to the intricacy of using other energy sources such as petroleum, gaseous fuels, and nuclear power. The release of substantial CO2 and other greenhouse gases is a significant environmental concern associated with using fossil fuels [1]. Catalytic pyrolysis of coal leads to the formation of char, which has a large surface area and exhibits significant reactivity toward oxidizing gases. Additionally, this process reduces the fluidity of coal at high temperatures and increases its molecular weight. Coal pyrolysis and gasification yield both gaseous and liquid fuels; however, it requires significant investment due to the requirement for complex and costly equipment to reach high temperatures [2,3,4,5,6,7,8,9,10,11,12,13]. Like the direct burning of solid fuel, the “burn off” process demonstrates high reactivity with oxygen, producing gaseous byproducts. Although many studies have used kinetic analysis to support the presence of the “burn-off” response [14,15,16,17,18,19,20], detecting this reaction may be difficult for many reasons.

An intriguing component of the issue may be explored by exploring the mechanism of this reaction and how it relates to the oxygen adsorption process. Coal gasification, pyrolysis, and oxidation were facilitated by the abundance of free radicals on coal particle surfaces and in newly formed coal fissures [21,22]. As highlighted by Zhan et al. [23], the level of free radicals plays a crucial role in primarily influencing the “burn-off” response. Coal typically has three types of pores: macro-porous, meso-porous, and micro-porous. These pores have a role in the absorption and adsorption of fluids on the surface of coal [24,25]. Zinc chloride (ZnCl2) and tin chloride (SnCl2) are effective Lewis acids for activating carbonaceous materials like coal. When these acids are dissolved in a liquid and come into contact with coal, they are absorbed onto the surface and into the coal. Prior research indicates that Lewis acids enhance the production of char and gaseous byproducts while reducing the development of tar [26,27,28]. When coal is treated with Lewis acids and heated without air or oxygen, it undergoes gasification, resulting in the liberation of gaseous products and decreased weight/mass [8,27,29]. The primary determinant of the gasification or combustion rate is the rate of weight loss over time [30,31].

Determining how different process variables affect the process’s reaction has recently become possible using multivariate statistical tools. An experimental design is used to study the main and combined impacts of process variables using a small number of experiments. One statistical method that may be used to construct functional linkages between dependent and independent variables is response surface methodology (RSM).

Coal is an essential and crucial energy source on a global scale, particularly in regions that have substantial coal reserves and well-established coal-fired power infrastructure. Nevertheless, the burning of high-ash bituminous (HAB) coal is inherently restricted, which hampers its efficient use and adds to environmental harm. The novelty of this research is to gather information on the effect and mechanism of transition metals on improving the heat release efficiency of coal pyrolysis. Catalytic experiments often use ZnCl2, a low-cost transition metal chloride. Thermal analyses select ZnCl2 to explore its effects on the “burn-off” reaction and heat release of HAB coal. However, very few scholars have focused on the effect and mechanism of transition metals on improving the heat release efficiency of coal pyrolysis. Thermal analyses (TG-DSC), proximate analysis, FESEM, and EDX analyses specifically discuss the mechanism and key factor of the pyrolysis reaction, potentially offering a new approach to the efficient use of HAB materials. The effect of carbonization temperature, carbonization time, and catalyst (ZnCl2) concentration was analyzed utilizing RSM.

2 Materials and methods

An HAB coal sample was supplied by Geocoal Engineering Private Limited (Dhanbad district, India). The collected coal sample was processed by various methods to meet our desired size (1.5 mm) for analysis. The feed sample utilized for catalytic decomposition is analyzed in both proximate and ultimate analyses, as shown in Table 1. The methods involve making ZnCl2 solutions with varying mass percentages (3, 6, and 9%). Then, this solution is poured into the 10 g coal sample in the beaker and left for some time (30 min) so that ZnCl2 can adequately adsorb on the coal. The coal sample was dried in an air drier set at 100 ± 10°C after 30 min to eliminate any water absorbed onto the coal’s surface. Coal samples of known mass are placed in a silica crucible and placed in a close-mouth muffle furnace maintained at three different temperatures: 510, 610, and 710°C. To determine burn-off%, the crucible is taken out after 10, 20, and 30 min, and weight loss is measured with respect to time given for burn-off%.

Table 1

Proximate and ultimate analyses of HAB coal sample

Proximate analysis (%) Ultimate analysis (%)
Moisture 0.56 Carbon 37.92
VM 13.12 Hydrogen 1.79
Ash 52.53 Nitrogen 1.46
FC 33.79 Sulfur 0.62
GCV (cal/g) 3631.00 Ash 52.53
Oxygen 5.68

Instantaneous reactivity (R t ) at different reaction times is calculated from the following equation:

(1) R t = ( 1 / W t ) × ( d w / d t ) ,

where W t is the weight of the unreacted char and the (dw/dt) slope of the burn-off vs time t, respectively.

2.1 Proximate analysis

Following the method outlined by the Bureau of Indian Standards, proximate analysis was carried out [32]. Coal with a particle size of −212 μm was produced to carry out the analysis. Then, coal ash content, moisture, and volatile matter (VM) were measured using 1 g of coal for each study.

2.2 Thermo-gravimetric analysis (TGA)

TGA tests were conducted using the Mettler Toledo and Netzsch equipment at the CSIR-CSMCRI facility in Bhavnagar. A 10 mg coal sample in powdered form was heated at 10°C per minute in the presence of nitrogen gas until it reached a temperature of 1,000°C.

2.3 Morphological analysis

To determine if the surface morphology of the coal particles changed after ZnCl2 treatment, FE-SEM and EDX analyses were performed. A platinum-coated evacuated die was used to compress −212 μm samples of HAB coal into conductive pellets. The pellets were examined using an airtight chamber and a JEOL JSM 7100F at CSIR-CSMCRI, Bhavnagar.

2.4 Pyrolysis analysis

Precise amounts of HAB coal samples and impregnated coal samples were weighed in silica crucibles. These crucibles were placed in a sealed Muffle furnace at 510, 610, and 710°C. During the burn-off process, the crucible was removed after 10 min, and the weight lost was determined to calculate the percentage of burn-off over time. This process is iterated until the weight is consistently measured.

2.5 RSM

The Box–Behnken design (BBD) is a popular statistical experimental design in RSM [33]. Modeling, experiment design, and workflow optimization are all made easier by RSM, a collection of statistical and mathematical tools. When looking at the impact of several factors on a response, the BBD is a great tool. Due to its factorial nature, the BBD allows the simultaneous manipulation of several parameters to ascertain their influence on the final outcome. To conduct a more comprehensive analysis of the variable, this technique often incorporates three levels of each component: low, middle, and high. The BBD is believed to be efficient when evaluating the amount of trials required to get precise data on the components and their interactions. The primary goal of the BBD is to create a mathematical model that translates the input feed components into a response variable. Researchers may use it to analyze experimental data using analysis of variance (ANOVA), which helps identify key factors and interactions. The BBD is widely used by researchers to optimize processes with many variables in many fields, including medicine, chemistry, engineering, and manufacturing.

The association between the variables was established using a best-fitting second-order polynomial equation. The equation based on the fitted model is as follows:

(2) y = β 0 + ∑ i = 1 k β i x i + ∑ j = 1 k β j j x j 2 + ∑ ∑ i j k β i j x i x j + ε ,

where Y is the predicted response, β 0 is a constant, and the coefficients for linear, interaction, and quadratic effects are represented by β i , β ij , and β jj , respectively. In the equation, ε represents the residual. Our ANOVA was used to determine the model’s significance, with a confidence level of α = 0.05. The lack of fit, F- and p-values are some of the methods employed by statisticians to determine the relative importance of each parameter. The experiment design, statistical analysis, and response surface studies were all conducted using Design-Expert 13.

3 Results and discussion

3.1 Structure characteristics of ZnCl2-loaded HAB coal samples

SEM imaging was used to identify changes in the surface morphology of coal particles after ZnCl2 treatment. This method may involve differences in the particle size, shape, and surface roughness relative to untreated coal particles. HAB coal samples were activated using the salt impregnation method to analyze the catalytic effects of ZnCl2 salts on the surface of HAB coal during combustion and gasification. Under the treatment of ZnCl2 salts in an aqueous solution, fragments and various sizes of holes occur on the surface of HAB coal, while the reaction of ZnCl2 salts on coal mainly results in the creation of tiny fragments. These findings indicate the depolymerization or rebuilding of coal surface structure after ZnCl2 salt impregnation. ZnCl2 loading could lead to agglomeration, which results in the development of more extensive clusters or aggregates of coal particles. The existence of pits, fissures, or protrusions on the coal particle surface could influence surface reactivity and interaction with other components during combustion or gasification processes. The SEM images of HAB coal and Zn-loading samples are shown in Figure 1.

Figure 1 SEM micrographs of raw and impregnated coal samples: (a) coal, (b) coal–3%_ZnCl2, (c) coal–6%_ZnCl2, and (d) coal–9%_ZnCl2.
Figure 1

SEM micrographs of raw and impregnated coal samples: (a) coal, (b) coal–3%_ZnCl2, (c) coal–6%_ZnCl2, and (d) coal–9%_ZnCl2.

3.2 Thermogravimetric (TG)-Differential thermogravimetric (DTG) analysis of ZnCl2-loaded HAB coal samples

Figure 2(a) and (b) displays the thermal analysis curves of TG-DTG for the untreated and ZnCl2-treated coal samples. The TGA curve shown in Figure 2(a) demonstrates slight fluctuations in weight loss in the temperature range of 25–160°C, suggesting a low level of moisture. In addition, the process of weight loss caused by the production of VM starts after reaching a temperature of 350°C for all the samples. The pyrolysis process is initiated after reaching a temperature of 480°C, resulting in a significant and fast reduction in weight. Once the temperature reaches 600°C, the coal samples experience a minimal decrease in weight, indicating that no more substances are available for combustion and that the pyrolysis process has concluded. The delay in pyrolysis is due to the sample’s elevated burnout temperature and diminished porous structure [34].

Figure 2 (a) TGA of raw coal and different ZnCl2-treated samples. (b) DTG of raw coal and different ZnCl2-treated samples.
Figure 2

(a) TGA of raw coal and different ZnCl2-treated samples. (b) DTG of raw coal and different ZnCl2-treated samples.

The temperatures that define specific properties, such as the temperature at which ignition occurs (T i), peak temperature (T p), and burnout temperature (T f) during the pyrolysis process, may be identified using DTG analysis, as shown in Figure 2(b). The pyrolysis behavior of raw coal and ZnCl2-treated samples requires a thorough understanding of these characteristics. An evident disparity in the pyrolysis profile is seen between the raw sample and those with varying concentrations of ZnCl2, namely 3, 6, and 9%. Based on the information shown in Figure 2(b), it can be deduced that the raw coal to 9% ZnCl2 samples have a lower ignition temperature, namely approximately 395–380°C. Nevertheless, there is a decrease in the ignition temperature (T i) as the concentration of ZnCl2 increases, ranging from 3 to 9%. The change observed may be related to the increased prevalence of VM release in ZnCl2 samples with lower concentrations (3, 6, and 9%). This facilitates the coal samples’ pyrolysis and combustion process. A solitary peak in all samples suggests a step-by-step and uninterrupted decomposition process characterized by the elimination of water and the depletion of complex hydrocarbon compounds from the sample [35]. The burnout temperatures for all samples fall within the range of 511–720°C. Nevertheless, a higher concentration of ZnCl2 leads to an elevation in the burnout temperature, causing a decrease in the pyrolysis rate and increasing the time needed for the pyrolysis process to be fully completed [34,35,36,37,38].

3.3 Kinetic analysis of ZnCl2-loaded HAB coal samples

The Coats–Redfern (C–R) method was used for kinetic analysis, but other models were not considered. The C–R method [36] is a first-order reaction with an integral rate equation mainly used for the calculation of activation energy (E) and pyrolysis kinetic parameters like the pre-exponential factor (A) and regression coefficient (R 2), compared to other methods. In this method, E is calculated from the linearized plot pyrolysis data attained through TGA as ln − ln ( 1 − x ) T 2 vs 1/T from equation (1) [36] as follows:

(3) ln − ln ( 1 − x ) T 2 = ln A R H E 1 − 2 R T E − E R T ,

where x is the proportion of coal that is burnt at a certain time t, n is the order of the pyrolysis process, H is the heating rate in °C/min, E is the activation energy of coal in kJ/mol, A is the frequency factor in min-1, T is the temperature in K, and R is the universal gas constant (= 8.314 J/K mol).

Table 2 demonstrates a negative correlation between the pyrolysis efficiency (E) and the concentration of ZnCl2, indicating that as the concentration of ZnCl2 increases, the pyrolysis efficiency decreases. Similarly, a decrease was seen in the value of A from 26.19 to 4.16 per minute. The activation energy (E) decreases from 42.91 to 31.92 kJ/mol. The decrease in noncombustible material in the porous structure of coal is responsible for this drop. The activation energy decreases more. The pyrolysis process can explain this trend, which generates numerous active sites within the coal structure. These active sites facilitate easier and smoother pyrolysis, leading to decreased activation energy [34,35,36,37,38].

Table 2

Pyrolysis characteristic profile and kinetic analysis of raw and treated coal samples

Sample no. T i (°C) T p (°C) T f (°C) DTGmax (%/min) Mass loss (%) R 2 A (min−1) E (kJ/mol)
Raw coal 393.88 511.87 718.89 −7.42 12.51 0.899 26.1965 42.9152
3% ZnCl2 388.16 499.17 719.17 −6.736 12.22 0.922 18.3237 40.3986
6% ZnCl2 386.93 493.93 719.93 −6.865 12.09 0.922 15.2531 39.2945
9% ZnCl2 384.05 493.20 782.00 −6.501 11.50 0.897 4.16582 31.9258

3.4 Effect of carbonization time on HAB coal samples

This work indicates that impregnated coal becomes more reactive as carbonization time increases. Up to 30 min at 510°C, there was a significant increase in weight loss, but the change in reactivity slowed beyond that point. Coal’s reactivity increases with carbonization time at a constant temperature. The carbonization temperature of 610°C resulted in a significant increase up to 30 min, followed by a steady weight decrease. A similar trend was seen at 710°C, as shown in Figure 3(a)–(c). Weight loss was lower at 510°C compared to that at 610 and 710°C. Reducing surface area and micropore volume caused by carbon shrinkage at higher temperatures leads to significant weight loss in HAB coal.

Figure 3 Effect of (a) carbonization temperature with change in the catalyst concentration at 10 min, (b) carbonization temperature with change in the catalyst concentration at 20 min, and (c) carbonization temperature with change in the catalyst concentration at 30 min.
Figure 3

Effect of (a) carbonization temperature with change in the catalyst concentration at 10 min, (b) carbonization temperature with change in the catalyst concentration at 20 min, and (c) carbonization temperature with change in the catalyst concentration at 30 min.

3.5 Effect of ZnCl2 concentration on HAB coal samples

It was observed in many studies that ZnCl2 concentration significantly affects the pyrolysis, combustion, and gasification process. Figure 4(a)–(c) demonstrates that ZnCl2 concentration significantly affects burn-off%. Increasing ZnCl2 concentration leads to a considerable increase in burn-off of up to 9% and significantly decreases at a constant temperature and carbonization time at lower concentrations. Many researchers reported similar results [26,39]. The highest reduction was achieved with 9% ZnCl2-impregnated coal at 610 and 710°C.

Figure 4 Effect of (a) concentration-time with the change in the concentration temperature at 3%, (b) concentration-time with the change in the concentration temperature at 6%, and (c) concentration-time with the change in the concentration temperature at 9%.
Figure 4

Effect of (a) concentration-time with the change in the concentration temperature at 3%, (b) concentration-time with the change in the concentration temperature at 6%, and (c) concentration-time with the change in the concentration temperature at 9%.

3.6 Effect of carbonization temperature on HAB coal samples

The effect of carbonization temperature on HAB coal is shown in Figure 5(a)–(c), which illustrates that increasing the carbonization temperature leads to increased weight loss at the same catalyst concentration and time. Higher temperatures may shift the coal particle porosity from micro-porosity to macro-porosity, as shown in previous studies [40,41]. Gases (VM) evolve faster at higher temperatures of 710°C than at lower temperatures of 510°C.

Figure 5 Effect of (a) catalyst concentration with change in time at 510°C, (b) catalyst concentration with change in time at 610°C, and (c) catalyst concentration with change in time at 710°C.
Figure 5

Effect of (a) catalyst concentration with change in time at 510°C, (b) catalyst concentration with change in time at 610°C, and (c) catalyst concentration with change in time at 710°C.

3.7 RSM

In the present study, three process variables were varied: carbonization time, catalyst concentration, and carbonization temperature; the results are tabulated. The coded and uncoded levels of the process variables are shown in Table 3.

Table 3

Coded and uncoded levels of variables for the BBD

Variables Coded symbol Levels and range
−1 0 1
Carbonization time (min) A 10 20 30
Catalyst concentration (%) B 3 6 9
Carbonization temperature (°C) C 510 610 710

A BBD of 15 experiments for studying the effect of three variables on burn-off rate: carbonization time (A), catalyst concentration (B), and carbonization temperature (C), as shown in Table 4.

Table 4

BBD matrix showing observed response and predicted response

C. Time Cat. Conc. C. Temp. Observed % BO Predicted % BO
−1 −1 0 18.71 18.69
1 −1 0 57.88 52.95
−1 1 0 19.64 24.57
1 1 0 62.72 62.75
−1 0 −1 11.93 10.17
1 0 −1 32.67 35.83
−1 0 1 22.15 18.99
1 0 1 64.02 65.77
0 −1 −1 22.61 24.38
0 1 −1 34.08 30.91
0 −1 1 39.27 42.45
0 1 1 53.36 51.60
0 0 0 37.4 38.00
0 0 0 38.1 38.00
0 0 0 38.5 38.00

The different combinations of variables resulted in burn-off% varying between 11.93 and 67.68%. The predicted values using the model given by the BBD ranged between 10.17 and 74.51%. From the data presented, a relationship between the response and process variables was attained and expressed in a second-order quadratic equation as follows:

(4) BO ( % ) = 38 + 18.11 A + 3.92 B + 9.69 C − 1.45 A 2 + 3.19 B 2 − 3.86 C 2 + 0.9775 A B + 5.28 A C + 0.655 B C .

Results from the ANOVA are shown in Table 5, confirming the model’s statistical significance.

Table 5

ANOVA table of the quadratic model for the catalytic thermal conversion of coal

Source DF Seq SS Adj MS F-value P-value
Model 9 3721.25 413.47 20.32 0.002
A-Carbonization time 1 2623.05 2623.05 128.89 <0.0001
B-Catalyst concentration 1 122.7 122.7 6.03 0.0576
C-Carbonization temperature 1 750.98 750.98 36.9 0.0017
A² 1 7.76 7.76 0.3815 0.5639
B² 1 37.51 37.51 1.84 0.2326
C² 1 54.94 54.94 2.7 0.1613
AB 1 3.82 3.82 0.1878 0.6828
AC 1 111.62 111.62 5.48 0.0662
BC 1 1.72 1.72 0.0843 0.7832
Residual 5 101.75 20.35
Lack of fit 3 101.13 33.71 108.75 0.0091
Pure error 2 0.62 0.31
Total 14 3823.01

R 2 = 0.9734.

Predicting the percentage of burn-off, the model’s forecast was considered significant with a p-value of less than 0.001. With an R 2 value of 0.9734, we may conclude that the experimental variables under consideration account for all of the variation in burn-off%. The model is very relevant when the modified R 2 value is close to the R 2 coefficient. If the sign of the coefficient is positive, then the variables have an additive impact on the burn-off%. If it is negative, then the variables have an antagonistic effect. Statistical analysis revealed that there were positive linear effects of carbonization time (p < 0.000), catalyst concentration (p < 0.057), and carbonization temperature (p < 0.001) on the sample.

On the other hand, as their p-values were more than 0.05, the quadratic terms of carbonization time (p < 0.563), catalyst concentration (p < 0.232), and carbonization temperature (p < 0.161) were determined to be non-significant. The statistical significance of the interaction effects between concentration and time (p < 0.0682), time and temperature (p < 0.066), and concentration and temperature (p < 0.783) is shown to be insignificant. A p-value < 0.002 and an F-value of 20.32 characterize the quadratic model. The strong F-values demonstrate the model is statistically significant [33,42,43]. The carbonization time is the most important process element, contributing 68.61% of the total, followed by the catalyst concentration at 3.20% and the carbonization temperature at 19.64%. Accordingly, carbonization time is the most important factor, followed by carbonization temperature and catalyst concentration, regarding the burn-off hierarchy. A variety of process parameters were examined using the RSM 3D plots.

In RSM plots, two factors are shown to affect the response variable while the remaining variables are held at their intermediate values. Figure 6(a)–(c) shows that the pyrolysis rate significantly increases when the carbonization time increases. The optimal pyrolysis rate was seen when the catalyst concentration was low and the carbonization period was high. An analogous pattern of transformation was seen when the carbonization temperature was raised. The pyrolysis rate was greater at elevated temperatures (710°C) for both the concentration and carbonization time. The tight correspondence between the actual and anticipated values, as shown by the substantial R 2 value, confirms the importance of the model predicted by the RSM BBD, as shown in Figure 7.

Figure 6 Effect of variables on the response in a 3D surface: (a) effect of time and concentration on burn-off%, (b) effect of concentration and temperature on burn-off%, and (c) effect of time and temperature on burn-off%.
Figure 6

Effect of variables on the response in a 3D surface: (a) effect of time and concentration on burn-off%, (b) effect of concentration and temperature on burn-off%, and (c) effect of time and temperature on burn-off%.

Figure 7 Comparison between prediction with observed values for burn-off%.
Figure 7

Comparison between prediction with observed values for burn-off%.

4 Conclusions

Although ZnCl2 has been shown to improve the combustion of HAB coal, many unanswered questions and neglected research topics remain. This study focuses on the technical details of adjusting the ZnCl2 dose to ensure equal distribution, long-term stability, and compatibility with current combustion systems. This report lays forth potential avenues for research that might lead to developments in this field. Among them, there is a pressing need for scale-up studies, techno-economic evaluations, and a deeper dive into the underlying processes. The surface of HAB coal becomes speckled with pieces and holes of varying sizes when treated with a water solution of ZnCl2 salts. Tiny pieces are the main byproduct of the reaction between coal and ZnCl2 salts. Evidence from the data points to depolymerization or rebuilding of the coal surface structure after impregnation with ZnCl2 salt. Adding ZnCl2 can potentially make the coal particles agglomerate or clump together. Using TG-DTG analysis, pyrolysis tests show that HAB coal exhibits improved ignition properties when treated with ZnCl2 concentrations ranging from 3 to 9% compared to untreated coal. The activation energy of the treated coal decreased from 42.91 to 31.92 kJ/mol when treated with 9% ZnCl2, lending credence to this claim. Typically, the ignition temperature (T i) and peak temperature (T p) decrease as one moves from untreated coal to coal treated with 9% ZnCl2. The decrease in ignition temperature (from 393.88 to 384.05°C) and peak temperature (511.87 to 493.20°C) is more apparent. However, there is an increase in the burning temperature of clean coal. The reduced ash content of the coal samples causes the pyrolysis process to go into its later phases. The reduced Ti and Tp levels in the treated coal samples indicate an increase in ignitability, which is beneficial for pyrolysis operations and power plants.

Research on coal pyrolysis properties and the effects of ZnCl2 treatment has concluded that a ZnCl2 concentration of 9% is optimum for mineral removal from HAB coal. Using RSM to predict burn-off percentage is a rigorous approach, and the coefficient of determination (R 2) is 0.9734. The quadratic model showed that the predicted values were in agreement with those obtained experimentally. The developed model considered the carbonization time as the primary input, and the carbonization temperature and catalyst concentration were the secondary and most essential input parameters.

Acknowledgements

The authors acknowledge and extend their appreciation to the Researchers Supporting Project Number (RSPD2024R996), King Saud University, Riyadh, Saudi Arabia, for funding this study.

  1. Funding information: The authors acknowledge and extend their appreciation to the Researchers Supporting Project Number (RSPD2024R996), King Saud University, Riyadh, Saudi Arabia for funding this study.

  2. Author contributions: Conceptualization, Methodology, Visualization, Investigation, Writing – Original Draft, Writing – Review & Editing, Project administration – DSP, RCC; Resources Visualization – VS, JM, AK, MAA, IAM, LN; Formal analysis and Investigation – BSK, BKT. All the authors agreed on the final version of the manuscript.

  3. Conflict of interest: Authors state no conflict of interest.

  4. Data availability statement: The data used to support the findings of this study are available from the corresponding author upon request.

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Received: 2024-05-11
Revised: 2024-06-18
Accepted: 2024-07-24
Published Online: 2024-08-30

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/chem-2024-0077
Keywords for this article
thermal conversion; high ash bituminous coal; low-temperature pyrolysis; impregnation; response surface methodology
Creative Commons
BY 4.0

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  29. Metformin inhibits knee osteoarthritis induced by type 2 diabetes mellitus in rats: S100A8/9 and S100A12 as players and therapeutic targets
  30. Effect of silver nanoparticles formulated by Silybum marianum on menopausal urinary incontinence in ovariectomized rats
  31. Synthesis of new analogs of N-substituted(benzoylamino)-1,2,3,6-tetrahydropyridines
  32. Response of yield and quality of Japonica rice to different gradients of moisture deficit at grain-filling stage in cold regions
  33. Preparation of an inclusion complex of nickel-based β-cyclodextrin: Characterization and accelerating the osteoarthritis articular cartilage repair
  34. Empagliflozin-loaded nanomicelles responsive to reactive oxygen species for renal ischemia/reperfusion injury protection
  35. Preparation and pharmacodynamic evaluation of sodium aescinate solid lipid nanoparticles
  36. Assessment of potentially toxic elements and health risks of agricultural soil in Southwest Riyadh, Saudi Arabia
  37. Theoretical investigation of hydrogen-rich fuel production through ammonia decomposition
  38. Biosynthesis and screening of cobalt nanoparticles using citrus species for antimicrobial activity
  39. Investigating the interplay of genetic variations, MCP-1 polymorphism, and docking with phytochemical inhibitors for combatting dengue virus pathogenicity through in silico analysis
  40. Ultrasound induced biosynthesis of silver nanoparticles embedded into chitosan polymers: Investigation of its anti-cutaneous squamous cell carcinoma effects
  41. Copper oxide nanoparticles-mediated Heliotropium bacciferum leaf extract: Antifungal activity and molecular docking assays against strawberry pathogens
  42. Sprouted wheat flour for improving physical, chemical, rheological, microbial load, and quality properties of fino bread
  43. Comparative toxicity assessment of fisetin-aided artificial intelligence-assisted drug design targeting epibulbar dermoid through phytochemicals
  44. Acute toxicity and anti-inflammatory activity of bis-thiourea derivatives
  45. Anti-diabetic activity-guided isolation of α-amylase and α-glucosidase inhibitory terpenes from Capsella bursa-pastoris Linn.
  46. GC–MS analysis of Lactobacillus plantarum YW11 metabolites and its computational analysis on familial pulmonary fibrosis hub genes
  47. Green formulation of copper nanoparticles by Pistacia khinjuk leaf aqueous extract: Introducing a novel chemotherapeutic drug for the treatment of prostate cancer
  48. Improved photocatalytic properties of WO3 nanoparticles for Malachite green dye degradation under visible light irradiation: An effect of La doping
  49. One-pot synthesis of a network of Mn2O3–MnO2–poly(m-methylaniline) composite nanorods on a polypyrrole film presents a promising and efficient optoelectronic and solar cell device
  50. Groundwater quality and health risk assessment of nitrate and fluoride in Al Qaseem area, Saudi Arabia
  51. A comparative study of the antifungal efficacy and phytochemical composition of date palm leaflet extracts
  52. Processing of alcohol pomelo beverage (Citrus grandis (L.) Osbeck) using saccharomyces yeast: Optimization, physicochemical quality, and sensory characteristics
  53. Specialized compounds of four Cameroonian spices: Isolation, characterization, and in silico evaluation as prospective SARS-CoV-2 inhibitors
  54. Identification of a novel drug target in Porphyromonas gingivalis by a computational genome analysis approach
  55. Physico-chemical properties and durability of a fly-ash-based geopolymer
  56. FMS-like tyrosine kinase 3 inhibitory potentials of some phytochemicals from anti-leukemic plants using computational chemical methodologies
  57. Wild Thymus zygis L. ssp. gracilis and Eucalyptus camaldulensis Dehnh.: Chemical composition, antioxidant and antibacterial activities of essential oils
  58. 3D-QSAR, molecular docking, ADMET, simulation dynamic, and retrosynthesis studies on new styrylquinolines derivatives against breast cancer
  59. Deciphering the influenza neuraminidase inhibitory potential of naturally occurring biflavonoids: An in silico approach
  60. Determination of heavy elements in agricultural regions, Saudi Arabia
  61. Synthesis and characterization of antioxidant-enriched Moringa oil-based edible oleogel
  62. Ameliorative effects of thistle and thyme honeys on cyclophosphamide-induced toxicity in mice
  63. Study of phytochemical compound and antipyretic activity of Chenopodium ambrosioides L. fractions
  64. Investigating the adsorption mechanism of zinc chloride-modified porous carbon for sulfadiazine removal from water
  65. Performance repair of building materials using alumina and silica composite nanomaterials with electrodynamic properties
  66. Effects of nanoparticles on the activity and resistance genes of anaerobic digestion enzymes in livestock and poultry manure containing the antibiotic tetracycline
  67. Effect of copper nanoparticles green-synthesized using Ocimum basilicum against Pseudomonas aeruginosa in mice lung infection model
  68. Cardioprotective effects of nanoparticles green formulated by Spinacia oleracea extract on isoproterenol-induced myocardial infarction in mice by the determination of PPAR-γ/NF-κB pathway
  69. Anti-OTC antibody-conjugated fluorescent magnetic/silica and fluorescent hybrid silica nanoparticles for oxytetracycline detection
  70. Curcumin conjugated zinc nanoparticles for the treatment of myocardial infarction
  71. Identification and in silico screening of natural phloroglucinols as potential PI3Kα inhibitors: A computational approach for drug discovery
  72. Exploring the phytochemical profile and antioxidant evaluation: Molecular docking and ADMET analysis of main compounds from three Solanum species in Saudi Arabia
  73. Unveiling the molecular composition and biological properties of essential oil derived from the leaves of wild Mentha aquatica L.: A comprehensive in vitro and in silico exploration
  74. Analysis of bioactive compounds present in Boerhavia elegans seeds by GC-MS
  75. Homology modeling and molecular docking study of corticotrophin-releasing hormone: An approach to treat stress-related diseases
  76. LncRNA MIR17HG alleviates heart failure via targeting MIR17HG/miR-153-3p/SIRT1 axis in in vitro model
  77. Development and validation of a stability indicating UPLC-DAD method coupled with MS-TQD for ramipril and thymoquinone in bioactive SNEDDS with in silico toxicity analysis of ramipril degradation products
  78. Biosynthesis of Ag/Cu nanocomposite mediated by Curcuma longa: Evaluation of its antibacterial properties against oral pathogens
  79. Development of AMBER-compliant transferable force field parameters for polytetrafluoroethylene
  80. Treatment of gestational diabetes by Acroptilon repens leaf aqueous extract green-formulated iron nanoparticles in rats
  81. Development and characterization of new ecological adsorbents based on cardoon wastes: Application to brilliant green adsorption
  82. A fast, sensitive, greener, and stability-indicating HPLC method for the standardization and quantitative determination of chlorhexidine acetate in commercial products
  83. Assessment of Se, As, Cd, Cr, Hg, and Pb content status in Ankang tea plantations of China
  84. Effect of transition metal chloride (ZnCl2) on low-temperature pyrolysis of high ash bituminous coal
  85. Evaluating polyphenol and ascorbic acid contents, tannin removal ability, and physical properties during hydrolysis and convective hot-air drying of cashew apple powder
  86. Development and characterization of functional low-fat frozen dairy dessert enhanced with dried lemongrass powder
  87. Scrutinizing the effect of additive and synergistic antibiotics against carbapenem-resistant Pseudomonas aeruginosa
  88. Preparation, characterization, and determination of the therapeutic effects of copper nanoparticles green-formulated by Pistacia atlantica in diabetes-induced cardiac dysfunction in rat
  89. Antioxidant and antidiabetic potentials of methoxy-substituted Schiff bases using in vitro, in vivo, and molecular simulation approaches
  90. Anti-melanoma cancer activity and chemical profile of the essential oil of Seseli yunnanense Franch
  91. Molecular docking analysis of subtilisin-like alkaline serine protease (SLASP) and laccase with natural biopolymers
  92. Overcoming methicillin resistance by methicillin-resistant Staphylococcus aureus: Computational evaluation of napthyridine and oxadiazoles compounds for potential dual inhibition of PBP-2a and FemA proteins
  93. Exploring novel antitubercular agents: Innovative design of 2,3-diaryl-quinoxalines targeting DprE1 for effective tuberculosis treatment
  94. Drimia maritima flowers as a source of biologically potent components: Optimization of bioactive compound extractions, isolation, UPLC–ESI–MS/MS, and pharmacological properties
  95. Estimating molecular properties, drug-likeness, cardiotoxic risk, liability profile, and molecular docking study to characterize binding process of key phyto-compounds against serotonin 5-HT2A receptor
  96. Fabrication of β-cyclodextrin-based microgels for enhancing solubility of Terbinafine: An in-vitro and in-vivo toxicological evaluation
  97. Phyto-mediated synthesis of ZnO nanoparticles and their sunlight-driven photocatalytic degradation of cationic and anionic dyes
  98. Monosodium glutamate induces hypothalamic–pituitary–adrenal axis hyperactivation, glucocorticoid receptors down-regulation, and systemic inflammatory response in young male rats: Impact on miR-155 and miR-218
  99. Quality control analyses of selected honey samples from Serbia based on their mineral and flavonoid profiles, and the invertase activity
  100. Eco-friendly synthesis of silver nanoparticles using Phyllanthus niruri leaf extract: Assessment of antimicrobial activity, effectiveness on tropical neglected mosquito vector control, and biocompatibility using a fibroblast cell line model
  101. Green synthesis of silver nanoparticles containing Cichorium intybus to treat the sepsis-induced DNA damage in the liver of Wistar albino rats
  102. Quality changes of durian pulp (Durio ziberhinus Murr.) in cold storage
  103. Study on recrystallization process of nitroguanidine by directly adding cold water to control temperature
  104. Determination of heavy metals and health risk assessment in drinking water in Bukayriyah City, Saudi Arabia
  105. Larvicidal properties of essential oils of three Artemisia species against the chemically insecticide-resistant Nile fever vector Culex pipiens (L.) (Diptera: Culicidae): In vitro and in silico studies
  106. Design, synthesis, characterization, and theoretical calculations, along with in silico and in vitro antimicrobial proprieties of new isoxazole-amide conjugates
  107. The impact of drying and extraction methods on total lipid, fatty acid profile, and cytotoxicity of Tenebrio molitor larvae
  108. A zinc oxide–tin oxide–nerolidol hybrid nanomaterial: Efficacy against esophageal squamous cell carcinoma
  109. Research on technological process for production of muskmelon juice (Cucumis melo L.)
  110. Physicochemical components, antioxidant activity, and predictive models for quality of soursop tea (Annona muricata L.) during heat pump drying
  111. Characterization and application of Fe1−xCoxFe2O4 nanoparticles in Direct Red 79 adsorption
  112. Torilis arvensis ethanolic extract: Phytochemical analysis, antifungal efficacy, and cytotoxicity properties
  113. Magnetite–poly-1H pyrrole dendritic nanocomposite seeded on poly-1H pyrrole: A promising photocathode for green hydrogen generation from sanitation water without using external sacrificing agent
  114. HPLC and GC–MS analyses of phytochemical compounds in Haloxylon salicornicum extract: Antibacterial and antifungal activity assessment of phytopathogens
  115. Efficient and stable to coking catalysts of ethanol steam reforming comprised of Ni + Ru loaded on MgAl2O4 + LnFe0.7Ni0.3O3 (Ln = La, Pr) nanocomposites prepared via cost-effective procedure with Pluronic P123 copolymer
  116. Nitrogen and boron co-doped carbon dots probe for selectively detecting Hg2+ in water samples and the detection mechanism
  117. Heavy metals in road dust from typical old industrial areas of Wuhan: Seasonal distribution and bioaccessibility-based health risk assessment
  118. Phytochemical profiling and bioactivity evaluation of CBD- and THC-enriched Cannabis sativa extracts: In vitro and in silico investigation of antioxidant and anti-inflammatory effects
  119. Investigating dye adsorption: The role of surface-modified montmorillonite nanoclay in kinetics, isotherms, and thermodynamics
  120. Antimicrobial activity, induction of ROS generation in HepG2 liver cancer cells, and chemical composition of Pterospermum heterophyllum
  121. Study on the performance of nanoparticle-modified PVDF membrane in delaying membrane aging
  122. Impact of cholesterol in encapsulated vitamin E acetate within cocoliposomes
  123. Review Articles
  124. Structural aspects of Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se) derivatives
  125. Biosurfactants in biocorrosion and corrosion mitigation of metals: An overview
  126. Stimulus-responsive MOF–hydrogel composites: Classification, preparation, characterization, and their advancement in medical treatments
  127. Electrochemical dissolution of titanium under alternating current polarization to obtain its dioxide
  128. Special Issue on Recent Trends in Green Chemistry
  129. Phytochemical screening and antioxidant activity of Vitex agnus-castus L.
  130. Phytochemical study, antioxidant activity, and dermoprotective activity of Chenopodium ambrosioides (L.)
  131. Exploitation of mangliculous marine fungi, Amarenographium solium, for the green synthesis of silver nanoparticles and their activity against multiple drug-resistant bacteria
  132. Study of the phytotoxicity of margines on Pistia stratiotes L.
  133. Special Issue on Advanced Nanomaterials for Energy, Environmental and Biological Applications - Part III
  134. Impact of biogenic zinc oxide nanoparticles on growth, development, and antioxidant system of high protein content crop (Lablab purpureus L.) sweet
  135. Green synthesis, characterization, and application of iron and molybdenum nanoparticles and their composites for enhancing the growth of Solanum lycopersicum
  136. Green synthesis of silver nanoparticles from Olea europaea L. extracted polysaccharides, characterization, and its assessment as an antimicrobial agent against multiple pathogenic microbes
  137. Photocatalytic treatment of organic dyes using metal oxides and nanocomposites: A quantitative study
  138. Antifungal, antioxidant, and photocatalytic activities of greenly synthesized iron oxide nanoparticles
  139. Special Issue on Phytochemical and Pharmacological Scrutinization of Medicinal Plants
  140. Hepatoprotective effects of safranal on acetaminophen-induced hepatotoxicity in rats
  141. Chemical composition and biological properties of Thymus capitatus plants from Algerian high plains: A comparative and analytical study
  142. Chemical composition and bioactivities of the methanol root extracts of Saussurea costus
  143. In vivo protective effects of vitamin C against cyto-genotoxicity induced by Dysphania ambrosioides aqueous extract
  144. Insights about the deleterious impact of a carbamate pesticide on some metabolic immune and antioxidant functions and a focus on the protective ability of a Saharan shrub and its anti-edematous property
  145. A comprehensive review uncovering the anticancerous potential of genkwanin (plant-derived compound) in several human carcinomas
  146. A study to investigate the anticancer potential of carvacrol via targeting Notch signaling in breast cancer
  147. Assessment of anti-diabetic properties of Ziziphus oenopolia (L.) wild edible fruit extract: In vitro and in silico investigations through molecular docking analysis
  148. Optimization of polyphenol extraction, phenolic profile by LC-ESI-MS/MS, antioxidant, anti-enzymatic, and cytotoxic activities of Physalis acutifolia
  149. Phytochemical screening, antioxidant properties, and photo-protective activities of Salvia balansae de Noé ex Coss
  150. Antihyperglycemic, antiglycation, anti-hypercholesteremic, and toxicity evaluation with gas chromatography mass spectrometry profiling for Aloe armatissima leaves
  151. Phyto-fabrication and characterization of gold nanoparticles by using Timur (Zanthoxylum armatum DC) and their effect on wound healing
  152. Does Erodium trifolium (Cav.) Guitt exhibit medicinal properties? Response elements from phytochemical profiling, enzyme-inhibiting, and antioxidant and antimicrobial activities
  153. Integrative in silico evaluation of the antiviral potential of terpenoids and its metal complexes derived from Homalomena aromatica based on main protease of SARS-CoV-2
  154. 6-Methoxyflavone improves anxiety, depression, and memory by increasing monoamines in mice brain: HPLC analysis and in silico studies
  155. Simultaneous extraction and quantification of hydrophilic and lipophilic antioxidants in Solanum lycopersicum L. varieties marketed in Saudi Arabia
  156. Biological evaluation of CH3OH and C2H5OH of Berberis vulgaris for in vivo antileishmanial potential against Leishmania tropica in murine models
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