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Liu, X.; Wang, S.; Liu, N.; Wei, B.; An, T. Progress of Dispersants for Coal Water Slurry. Encyclopedia. Available online: https://encyclopedia.pub/entry/52239 (accessed on 21 May 2024).
Liu X, Wang S, Liu N, Wei B, An T. Progress of Dispersants for Coal Water Slurry. Encyclopedia. Available at: https://encyclopedia.pub/entry/52239. Accessed May 21, 2024.
Liu, Xiaotian, Shan Wang, Ning Liu, Bo Wei, Tian An. "Progress of Dispersants for Coal Water Slurry" Encyclopedia, https://encyclopedia.pub/entry/52239 (accessed May 21, 2024).
Liu, X., Wang, S., Liu, N., Wei, B., & An, T. (2023, November 30). Progress of Dispersants for Coal Water Slurry. In Encyclopedia. https://encyclopedia.pub/entry/52239
Liu, Xiaotian, et al. "Progress of Dispersants for Coal Water Slurry." Encyclopedia. Web. 30 November, 2023.
Progress of Dispersants for Coal Water Slurry
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This entry is adapted from the peer-reviewed paper 10.3390/molecules28237683

This article provides a comprehensive review of existing coal water slurry dispersants, and points out the existing problems and possible future development directions.

coal water slurry dispersant dispersant type three-dimensional structure dispersant adsorption performance

1. Classification and Characteristics of CWS Dispersants

Dispersants denote the surfactants added to CWS that enable stable dispersion of coal particles in water, preventing stratification and precipitation over extended periods [1]. As significant additives in CWS preparation, dispersants can adhere to the coal surface, altering its properties and thereby enhancing CWS performance [2].
Dispersants possess unique structural characteristics. One-dimensional dispersants encompass a linear hydrophobic end, while two-dimensional comb-like dispersants incorporate numerous hydrophilic and hydrophobic groups. Both types adhere to the coal surface via their hydrophobic ends. To enhance the adsorption capacity, a third type of dispersant, known as three-dimensional structure dispersants, has been developed. These typically comprise linear and comb structures to cater to the polar groups of coal [3][4]. The hydrophobic end and the hydrophilic end of the one-dimensional linear structure dispersant are in a straight line, such as naphthalene sulfonate formaldehyde condensate (NSF) [5][6], sodium dodecyl benzene sulfonate, and sodium dodecyl sulfate (SDS) [7], while the two-dimensional structure dispersant contains a large number of hydrophobic and polar groups, such as comb polymer sodium polystyrene sulfonate (PSS) [8]. The latter is formed by copolymerization of polymer monomer, polyethylene glycol acrylate monoester, sodium p-Phenylethane sulfonate, and acrylamide [9][10]. Preparation of these comb-like polymers involves initiation and copolymerization between diverse unsaturated monomers, which can facilitate a high coal content and low apparent viscosity via the use of super-performance one-dimensional or two-dimensional dispersants [11][12]. However, apart from the coal surface’s abundance of hydrophobic groups, it also hosts polar groups, including substances containing O, S, and N [13][14]. Therefore, the three-dimensional structure dispersant developed for this situation has more polar groups. Zhang [15] utilized renewable resources, such as tannic acid and acrylic acid, to formulate an eco-friendly polymer dispersant that possesses a jellyfish-like three-dimensional structure. Tannic acid, which comprises both hydrophobic aromatic rings and polar hydroxyl groups, closely resembles the surface properties of coal. Hence, long side chains were grafted onto the tannic acid’s plane structure, and under electrostatic repulsion and steric hindrance, aligned in parallel. This led to the formation of a hydration film on the surface of the coal particles, substantially improving the stability and reducing the viscosity of CWS. Consequently, these studies significantly reduced the production cost of dispersants, and achieved environmental sustainability during the production and use of dispersants.
Dispersants can be obtained by modifying or synthesizing natural products. Natural products such as lignin, starch, and cellulose are widely available and are indeed very low-cost and environmentally friendly. Synthetic dispersants such as naphthalene sulfonate dispersants have good performance but relatively higher costs [16]. Starch, owing to its abundance and eco-friendliness, is a frequently employed natural raw material for dispersants. However, due to its high molecular weight, starch is not chemically stable and requires degradation. This necessitates the introduction of certain groups to elevate starch’s efficacy as a dispersant, fulfilling the pulping requirements of CWS [17]. Generally, the dispersants obtained by modification are starch sulfonate, starch xanthin compound, and starch phosphate [18]. For instance, a comb-like CWS dispersant can be synthesized by polymerizing starch, acrylic acid, and styrene (SAS), which boasts numerous hydroxyl groups contributing to the hydrophilic segment [19]. These hydroxyl groups interact with water via hydrogen bonding. The hydrophobic component, the phenyl from the grafted polystyrene chains, influences the dispersant’s adsorption on coal. The molecular structure of the SAS dispersant facilitates connections between the hydrophobic groups on the coal surface and the hydrophilic groups in the water, enabling the even dispersion of coal particles in water. Natural products like starch and cellulose, which are sourced widely, are advantageous due to their low cost, renewability, eco-friendly nature, natural biodegradability, chemical stability, and biocompatibility [20][21]. Dispersants produced from these raw materials are cost-effective, cause minimal environmental pollution, and demonstrate exceptional performance. This expands the selection of dispersants, making them a prime candidate for extensive industrial application in future research [22].

2. Anionic Dispersants

Anionic dispersants are the most researched and applied CWS dispersants at present owing to their outstanding dispersing ability, wide sources, and low price. Common anionic dispersants include lignin dispersants, humic acid-based dispersants, naphthalene-based dispersants, and polycarboxylic acid-based dispersants. 

2.1. Lignin Dispersants

Lignin dispersants are mainly obtained by modifying alkali lignin or lignosulfonate, a by-product of the paper industry. In addition to having a wide range of sources and economy, lignin dispersants can be employed to prepare coal water slurry with relatively superior stability than naphthalene-based dispersants [23]. However, the CWS viscosity prepared by such dispersants is relatively high, and the performance of lignin dispersants can be improved by modification methods such as sulfonation, polycondensation modification, and graft copolymerization modification [24][25][26].
Sulfonation modification is used to improve the hydrophilic properties of dispersants and the stability of CWS by replacing the benzene ring of lignin sulfonate molecules or the hydrogen, hydroxyl, and methoxy groups on the side chain of a benzene ring with the sulfonic group [27]. The sulfonation reaction can endow alkali lignin with good water solubility, surface activity, and reactivity. Sulfated lignin can be modified by oxidation and sulfomethylation to prepare sulfomethylated lignin [28]. Oxidation and sulfomethylation can raise the carboxyl and sulfonate contents of lignin, leading to an increase in the anion charge density. Sulfomethylated lignin can be adsorbed on coal particles and improve the fluidity of slurry more effectively.
Polycondensation modification is aimed at the phenol hydroxyl, alcohol hydroxyl, and aldehyde groups, and other unit structures of lignin sulfonate molecules that are prone to polycondensation reactions of aldehydes, phenols, lipids, and other molecules. The dispersion and adsorption of lignin dispersants can be strengthened through polycondensation modification [29]. The polycondensation reaction can endow the resulting products with certain relative molecular weights and adsorption and dispersion properties [30]. Chen et al. modified horsetail pine alkali lignin into an efficient coal water slurry dispersant, ALB, by sulfomethylation polycondensation reactions using sulfomethylated alkali lignin and sulfonated acetone formaldehyde as raw materials [24]. The experiment revealed that ALB dispersants displayed a comparatively stable viscosity reduction effect, surpassing the performance of conventional lignin dispersants. Furthermore, the molecular weight and sulfonic acid group content were identified as key factors influencing the dispersion and viscosity reduction capability of CWS. Graft copolymerization leverages the properties of lignin and its derivatives. Under the initiation process, lignin molecules can react with acrylic acid, acrylamide, styrene, hydroxyethyl methacrylate, vinyl acetate, and other functional branches, thereby enhancing their dispersion and stability. Maryam et al. [31] extracted kraft lignin and sulfonated lignin from papermaking wastewater as the source of lignin and chemical structure for acrylamide graft radical copolymerization modification initiated by thermal or redox initiators. Aliphatic hydroxyl groups were identified as the active sites of graft copolymerization, and the number of these functional groups in the lignin chain caused an important influence on the progress of graft copolymerization.
Lu et al. [32] copolymerized β-cyclodextrin (β-CD) and chlorotrione epoxide into alkali lignin to synthesize a modified alkali lignin dispersant (β-CD-AL), which dramatically increased the stability of the lignin dispersant pulping and reduced the viscosity of the slurry in their study. The synthesis scheme of the dispersant is described in Figure 1. The effects of the β-CD content on the dispersibility, zeta potential, and adsorption properties of β-CD-AL were also investigated. It was found that the stability was gradually enhanced with the increase in the copolymerized β-CD dosage under the synergistic effect of electrostatic repulsion and spatial site resistance. In addition, the amount of copolymerized β-CD reached a peak value for the optimal viscosity reduction effect.
Molecules 28 07683 g001
Figure 1. Synthetic schematic diagram of β-CD-AL.

2.2. Humic Acid-Based Dispersants

Low-rank coal, such as lignite, contains a large amount of humic acid. Humic acid dispersants, extracted from low-rank coal such as lignite, present good dispersion performance and can be used alone [33]. It has been confirmed that the lower the maturity of raw coal, the better the viscosity reduction effect of the prepared dispersants for CWS. However, the disadvantages are that these dispersants are sensitive to metal ions, propensity form precipitates, lead to prepared slurry with poor stability, and propose correspondingly higher requirements for pulping water quality [34][35].
Humic acid is rich in condensed aromatic units, which are similar to the structure of coal, and thus can be tightly adsorbed on the coal surface [36][37]. In addition, humic acid encompasses active groups, such as hydroxyl and carboxyl groups, providing the possibility for chemical modification of humic acid [38]. Currently, studies on the modification of humic acid as a dispersant focus on the sulfonation, nitration, sulfomethylation, and graft copolymerization of humic acid molecules. The purpose is to introduce functional groups with strong hydrophilicity into humic acid molecules [39][40]. Zhang et al. [35] fabricated a novel humic acid-based dispersant, humic acid-grafted sodium polystyrene sulfonate (HA-g-pssNa). This dispersant possesses a hydrophobic humic acid core and a hydrophilic sodium polystyrene sulfonate side chain, synthesized through a surface acylation reaction and atom transfer radical polymerization of humic acid. Various properties of HA-g-pssNa, pssNa, and naphthalene sulfonate formaldehyde condensate (NSF) as dispersants for the preparation of CWS were compared. The results revealed that the pulping properties of HA-g-pssNa were reinforced with the increase in pssNa side chain length. In the case of the appropriate chain length of HA-g-pssNa, the CWS prepared with this dispersant achieved good apparent viscosity and static stability, with superior performance than pssNa and NSF.
Kang et al. [34] modified sodium humate solution by sulfomethylation to prepare sulfomethylated humic acid dispersant (LSHA dispersant) and determined the optimal process conditions for modification through orthogonal experiments. Compared with the slurry-forming performance of commercial sodium naphthalenesulfonate dispersants, both of them can meet the requirements of CWS gasification, but the LSHA dispersant is better in terms of stability.
A humic acid-based polycarboxylate dispersant for CWS can be synthesized by copolymerizing humic acid, acrylic acid, and maleic acid, and its dispersion performance is much better than that of humic acid before copolymerization modification. The synthesis scheme of the dispersant is described in Figure 2 [41]. When the dosage of the dispersant reached 0.5 wt%, the apparent viscosity of the CWS was 505 mPa·s, while the permeability reached 85.45% after 96 h. The stability of the CWS was 12.87% higher than that of CWS prepared directly with humic acid as a dispersant. And the maximum concentration of the coal water slurry could reach up to 70 wt%. Overall, the aforementioned studies have greatly broadened the application scope of humic acid dispersants.
Molecules 28 07683 g002
Figure 2. Humic acid-based dispersant polymerization reaction scheme.

2.3. Naphthalene-Based Dispersants

Naphthalene-based dispersants, primarily comprised of naphthalene sulfonic acid polymers, are the most prevalent dispersants on the market. The structure of typical naphthalene dispersants is depicted in Figure 3. These dispersants offer superior dispersion performance, viscosity reduction, and slurry fluidity when compared with lignin-based dispersants. However, they also have notable disadvantages including high cost, suboptimal slurry stability, and a propensity for precipitation [23][42].
Molecules 28 07683 g003
Figure 3. Structural formula of sodium methylene naphthalene sulfonate.
The dispersion performance of naphthalene-based dispersants can primarily be adjusted by varying the degree of condensation and sulfonation [43]. An increased degree of condensation correlates positively with the binding strength and slurry effect of coal. However, for coal molecules with medium and low degrees of metamorphism, there exists a significant steric hindrance effect. This results in a weakened bond between the dispersant and the coal, despite an increase in the molecular chain length of the dispersants concurrent with the condensation degree. This suggests an optimal value for the coagulability of coal water slurries derived from medium and low-grade coals exists [44][45]. Another strategy for improving the performance of naphthalene dispersants is graft modification. Modifying the branch chain length through graft copolymerization can produce modified naphthalene dispersants with varying chain lengths. This can be achieved by adjusting the ratio of ethylene oxide to aromatic monomer.
Currently, naphthalene sulfonate formaldehyde condensate (NSFC) has emerged as a widely used dispersant in CWS applications due to its effective viscosity reduction properties. At present, scholars mainly study the effects of the reaction conditions, sulfonation quality, and degree of polymerization on its dispersion performance [16]. Upon the addition of NSFCs to CWS, the coal surface’s hydrophobicity decreases while the conversion of weakly bound water to free water is facilitated, thereby enhancing water fluidity. Consequently, the hydrophilicity of the coal surface is increased and the viscosity is significantly reduced [46]. Due to its cost-effectiveness and superior viscosity control characteristics, NSFC holds potential for broader industrial applications compared to other dispersants [47].

2.4. Polycarboxylic Acid Dispersants

The molecular structure of polycarboxylate-based additives consists of comb-shaped surfactants with graft copolymers. The main chain is polymerized by active monomers comprising functional groups, and the side chain is grafted onto active monomers containing functional groups and the main chain [9][48]. The structure is easy to design and can be modified according to different needs. Therefore, the viscosity reduction effect of polycarboxylate-based dispersants is stronger than that of traditional lignin dispersants and naphthalene dispersants. Combined with the advantage of low pollution, such dispersants enjoy a wider range of applications [49][50]. The structure of common polycarboxylate dispersant is shown in Figure 4 [51].
Molecules 28 07683 g004
Figure 4. Structure of polycarboxylate dispersant.
Polycarboxylate dispersants are easy to prepare because they can regulate the adsorption capacity on coal surfaces and improve the chemical properties of coal surfaces by introducing polycarboxylate. Zhu [49] and others adopted ammonium persulfate sodium bisulfite as a redox catalyst to synthesize a new amphoteric polycarboxylate dispersant for CWS by using sodium p-phenylethylsulfonate, polyethylene glycol acrylate monoester, and ethyl trimethyl ammonium methacrylate. When the dosage of the dispersant was 0.3 wt%, the maximum concentration of CWS could reach 65.0 wt%. Polycarboxylate dispersants containing anionic and cationic groups lead to a better anchoring effect on coal through ion adsorption.
In recent years, it is a research hotspot to adjust the synthesis scheme of polycarboxylate dispersants to obtain better-performing dispersants, such as controlling the ratio of acrylic acid to sodium phenylene sulfonate, initiator composition, and temperature. The most suitable PC dispersants for pulping were selected according to the viscosity of each type of CWS at 100 s−1, shear thinning behavior, static stability (>14), and maximum solid loads (>55 wt%). Polycarboxylate dispersants are effectively adsorbed on the surface of coal particles through horizontal multipoint adsorption, mainly through the interaction between the hydrophobic groups of dispersant molecules and the hydrophobic regions of coal particles, finally intensifying the hydrophilicity of coal particles and the stability of the hydration membrane [52].

3. Cationic Dispersants

The molecular structure of cationic dispersants typically comprises two components: positively charged non-polar hydrophilic groups and lipophilic hydrocarbon chains. Unlike anionic types, cationic dispersants facilitate the dispersion of particles in water into a colloidal solution via interaction between the positively charged molecular groups and the negatively charged particle surface. Currently, quaternary ammonium salts, heterocycles, and octadecenylamine acetate represent some of the widely used cationic dispersants on the market [53]. Figure 5 presents a typical molecular structure diagram of a quaternary ammonium salt dispersant.
Molecules 28 07683 g005
Figure 5. Structure diagram of cetyltrimethylammonium bromide.

4. Non-Ionic Dispersants

The primary types of non-ionic CWS dispersants are polyoxyethylene ether and polyoxyethylene block polyether surfactants, with the former attracting more attention. Characterized by their non-ionization in water, non-ionic dispersants can control both hydrophilic and hydrophobic groups, making them less susceptible to the influence of water quality and the substances in coal on the dispersion effect compared to other dispersants. At the same time, there is no need for a stabilizer when using non-ionic dispersants. They are also the most expensive dispersants for CWS [54]. A CWS dispersant prepared by non-ionic surfactants extracted from natural plants is a relatively low-cost, environment-friendly, and strong non-ionic dispersant. Figure 6 illustrates the structure of a typical non-ionic dispersant.
Molecules 28 07683 g006
Figure 6. Molecular structure of alkylphenol polyoxyethylene ether.
The minimum apparent viscosity that CWS can achieve with polyoxyethylene ether as a dispersant is closely related to the polyoxyethylene adduct number [55]. Alkyl polyoxyethylene ethers with more alkyl carbon atoms have an optimal addition number. Li [56] utilized two non-ionic dispersants, polyoxyethylene dodecyl phenol ether (PDPE) and polyoxyethylene lauryl ether (PLE), as CWS dispersants and compared their slurry forming performance. Both dispersants contained 30% ethylene oxide. At a CWS viscosity of 1000 mPa·s, the maximum concentrations of PDPE and PLE were 67.60% and 62.95%, respectively. PDPE displayed easier adsorption onto coal than PLE and formed more stable bonds due to the P-P stacking effect, leading to more uniform coal dispersion in the solution.

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Subjects: Chemistry, Applied; Engineering, Chemical
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Xiaotian Liu
,
Shan Wang
,
Ning Liu
,
Bo Wei
,
Tian An
View Times: 234
Revisions: 2 times (View History)
Update Date: 12 Dec 2023
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