Chemical Wastewater Research Articles

Study of molecular mechanism and extraction performance evaluation for separation of phenolics from alkaline wastewater through synergistic extraction

ABSTRACT Phenols were a kind of pollutant in coal chemical wastewater with high concentration and difficult to decompose and have a significant impact on the subsequent biochemical treatment of the wastewater. In addition, phenols were a kind of weak electrolytes that partially dissociation oxidation under weakly alkaline conditions, making recovery more difficult. In order to solve this problem, phenols were extracted from weak alkaline wastewater with a synergistic solvent. First, the interaction between solvents and phenols and the solvent effect of solvents were calculated by quantum chemistry and the synergistic extractant cyclohexanone/1-pentanol was determined to have significant advantages. Moreover, the synergistic extractant was further analyzed through independent gradient model based on Hirshfeld partition analysis, atoms in molecule topology analysis, electrostatic potential analysis. Results indicated that the synergistic extract can provide multiple hydrogen bond interactions with phenol due to the double action sites of the C=O group of ketone and the -OH group of alcohol. In addition, the efficacy of the extractant was validated by multistage extraction, indicating partial dissociation oxidation of hydroquinone to benzoquinone under weakly alkaline conditions, with removal rates of 99.5% and 99.2% for phenol and hydroquinone, respectively. In general, the synergistic extractant can effectively remove phenols.

Selective separation characteristics and mechanism of oil substances with different occurrence states in coal chemical wastewater

In response to the complex nature of oil substances in coal chemical wastewater (CCW), and the challenges they pose in separation and removal, this study conducted a detailed analysis of the occurrence, composition, and content of oil substances in CCW. The selective separation characteristics and mechanisms of various materials for oil substances in different occurrence states were explored. The results revealed four main states of oil substances in CCW: suspended oil, dispersed oil, emulsified oil, and dissolved oil, with respective contented of 37.17 %, 27.82 %, 17.79 %, and 17.22 %. These oil substances primarily consisted of alkanes, aromatic hydrocarbons, benzene series, and phenolic compounds, with a total concentration of 2942.18 mg/L. Based on the investigation of the characteristics of oil substances and relevant characterization analyses, the study further explored the selective separation characteristics and mechanisms of different materials for oil substances in various occurrence states. The results indicated that activated carbon, resin, fiber balls, and oil-absorbing felt exhibited excellent selective removal efficiency for dissolved oil, emulsified oil, suspended oil, and dispersed oil, with removal rates of 79.28 %, 63.33 %, 66.89 %, and 55.54 %, respectively. These findings provide theoretical support for the selective separation and recovery of oil substances in CCW, showcasing significant practical applications.

Operational analysis of the biological treatment unit's ultraviolet-wave disinfection method for wastewater outflow

Wastewater can be contaminated with all kinds of microorganisms and small organisms, including bacteria, parasites, fungi and viruses. Therefore, it can be said that biological pollution is one of the most dangerous pollutions. These types of pollution can endanger human health and the environment. In this study, industrial wastewater disinfection has been investigated in a laboratory pilot. In this study, ultraviolet waves have been used for wastewater disinfection. In this research, treatment indicators such as wastewater pH, phosphate, nitrate, biological oxygen and chemical oxygen, organic carbon, and wastewater turbidity have been investigated. The results of this research show that if 4.5 g of dry ice is added to the wastewater entering the disinfection unit, the pH of the wastewater will decrease to about 7.9. The results presented from the disinfection unit show that the amount of chemical oxygen demand and biological oxygen demand have decreased by about 35% and 20.3%, respectively. The results of this unit show that the amount of phosphate and nitrate has decreased by 61.3 and 71.9%, respectively. Laboratory results show that the TDS of wastewater has decreased from 600 to 451 mg/l.

Critical role of zero-valent iron in the efficient activation of H2O2 for 4-CP degradation by bimetallic peroxidase-like.

Peroxidase-like based on double transition metals have higher catalytic activity and are considered to have great potential for application in the field of pollutant degradation. First, in this paper, a novel Fe0-doped three-dimensional porous Fe0@FeMn-NC-like peroxidase was synthesized by a simple one-step thermal reduction method. The doping of manganese was able to reduce part of the iron in Fe-Mn binary oxides to Fe0 at high temperatures. In addition, Fe0@FeMn-NC has excellent peroxidase-like mimetic activity, and thus, it was used for the rapid degradation of p-chlorophenol (4-CP). During the degradation process, Fe0 was able to rapidly replenish the constantly depleted Fe2+ in the reaction system and brought in a large number of additional electrons. The ineffective decomposition of H2O2 due to the use of H2O2 as an electron donor in the reduction reactions from Fe3+ to Fe2+ and from Mn3+ to Mn2+ was avoided. Finally, based on the experimental results of LC-MS and combined with theoretical calculations, the degradation process of 4-CP was rationally analyzed, in which the intermediates were mainly p-chloro-catechol, p-chloro resorcinol, and p-benzoquinone. Fe0@FeMn-NC nano-enzymes have excellent catalytic activity as well as structural stability and perform well in the treatment of simulated wastewater containing a variety of phenolic pollutants as well as real chemical wastewater. It provides some insights and methods for the application of peroxidase-like enzymes in the degradation of organic pollutants.

Electrocatalytic mechanism of titanium-based anodes and research progress of chemical saline wastewater treatment: A short review

Electrocatalytic treatment of chemical saline wastewater showed great technical advantages due to its characteristics of simple operation, high catalytic efficiency and little secondary pollution. The review takes the classification and composition of titanium-based anodes as the starting point. Typical studies of wastewater treatment by electrocatalytic technology based on free radicals and non-free radicals were also discussed. Combined with the previous researches about electrocatalytic mechanisms in recent years, the mechanisms of titanium-based anodes were analyzed in terms of ·OH, active chlorine and others. The studies on titanium-based anodes in chemical wastewater containing different salt concentrations, such as dye wastewater, coal chemical wastewater, landfill leachate wastewater, fertilizer and pesticide production wastewater, etc., were thoroughly examined. According to the amount of electricity required for the removal of organic matter per unit, the energy consumption of titanium-based anodes for wastewater treatment by electrochemistry was described. The review would provide theoretical basis and technical support for electrocatalytic treatment of chemical saline wastewater.

Construction of aldehyde-based, ester-based hyper-cross-linked polar resin and its selective adsorption mechanism for phenol in coal chemical wastewater

Efficient and precise recovery of phenol from coal chemical wastewater (CCW) poses a significant challenge, prompting the development of a novel aldehyde-based, ester-based hyper-cross-linked polar resin (DES–COOC–CHO) in this study. Two distinct functional group modification methods were employed to enhance the screening effect of the resin. SEM, FT-IR, NMR, XPS, and BET characterizations confirmed the successful construction of the hyper-cross-linked polar resin, incorporation aldehyde and ester groups, exhibiting a special surface area of 627.2 m2/g and a microporous specific surface area percentage of 29.94%. DES–COOC–CHO adhered to the pseudo-second-order kinetic model and Langmuir model (maximum adsorption capacity of 118.0 mg/g). Its adsorption of phenol was spontaneous chemisorption, monolayer adsorption. Notably, even after undergoing 20 adsorption–desorption cycles, the resin maintained a stable adsorption capacity, showcasing excellent recoverability. In the presence of phenols sharing similar properties, DES–COOC–CHO exhibited superior selectivity for phenol. In real CCW, it achieved a remarkable 90% selective removal rate of phenol. The primary selective mechanism relied on the hydrogen bonding effect facilitated by aldehyde and ester groups, coupled with microporous sieving of appropriate size. In comparison with other adsorbent materials, DES–COOC–CHO exhibited superior adsorption properties, coupled with a cost-effective preparation process, presenting significant potential for practical applications.

Safe Disposal of Accident Wastewater in Chemical Industrial Parks Using Non-Thermal Plasma with ZnO-Fe3O4 Composites.

Chemical wastewater has a high concentration of toxic and hazardous antibiotic pollutants, which not only devastates the ecological environment and disrupts the ecological balance, but also endangers human health. This research proposed a non-thermal plasma (NTP) combined with a ZnO-Fe3O4 nano-catalyst system to achieve the efficient degradation of ciprofloxacin (CIP) in chemical wastewater. Firstly, ZnO-Fe3O4 composite materials were prepared using hydrothermal method and characterized with scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), etc. With the sole NTP, NTP/ZnO, and NTP/ZnO-Fe3O4 systems, the removal efficiency of CIP can reach 80.1%, 88.2%, and 99.6%, respectively. The optimal doping amount of Fe3O4 is 14%. Secondly, the capture agent experiment verified that ·OH, ·O2-, and 1O2 all have a certain effect on CIP degradation. Then, liquid chromatography-mass spectrometry (LC-MS) was used to detect the intermediate and speculate its degradation pathway, which mainly included hydroxyl addition, hydroxyl substitution, and piperazine ring destruction. After treatment with the NTP/ZnO-Fe3O4 system, the overall toxicity of the product was reduced. Finally, a cyclic experiment was conducted, and it was found that the prepared ZnO-Fe3O4 catalyst has good reusability. The NTP/ZnO-Fe3O4 was also applied in practical pharmaceutical wastewater treatment and has practical applicability.

Analysis and standardization of coal chemical wastewater treatment and reuse systems

To meet the practical needs of classified collection, graded treatment, and quality recycling of coal chemical wastewater, and in accordance with the standardization requirements of wastewater resource utilization, the Standardization Administration of China released the national standard GB/T 42,866-2023 ″Guidelines for Coal Chemical Wastewater Treatment and Recycling Technology” on August 6, 2023, for the first time. Based on the standard, this paper comprehensively and systematically sorts out and analyzes the characteristics, processes, water circulation systems, and standardization paths of units such as coal chemical wastewater collection and treatment, recycling, and the treatment of concentrated brine water, through extensive industry research. Furthermore, by integrating typical engineering case practices, this paper explains the feasibility of the paths, which provides technical guidance and experience for relevant cases of coal chemical wastewater treatment and recycling. It is also of great importance for promoting the standardized management and development of coal chemical wastewater treatment and recycling worldwide.

Pilot-scale evaluation of the sustainability of membrane desalination systems for the concentrate volume minimization of coal chemical wastewater

5 stars represents the best technical performance/highest cost.

Case Study on the Design Engineering of Deodorization System in Coal Chemical Wastewater Treatment Plants in the New Era

Case Study on the Design Engineering of Deodorization System in Coal Chemical Wastewater Treatment Plants in the New Era

Electrochemical oxidation of reverse osmosis concentrate using a pilot-scale reactive electrochemical membrane filtration system: Performance and mechanisms

Scale-up treatment of real wastewater holds the key to promoting the practical application of electrochemical filtration technology. This work used a pilot-scale Ti/Pd reactive electrochemical membrane (REM) system (12 REM modules with a total REM area of 0.144 m2) to treat high-salinity reverse osmosis concentrate (ROC) from a chemical industry park. The pilot-scale Ti/Pd REM system demonstrated effective electrochemical degradation of ROC wastewater, achieving removal efficiencies of 82.3 ± 1.9% for COD and 46.7 ± 5.6% for TN at a membrane flux of 90 L/(m2·h) and a cell voltage of 5 V, with an energy consumption of 0.045 kWh/g-COD. Singlet oxygen (1O2) and reactive chlorine species were identified as the two primary reactive oxygen species generated in the Ti/Pd REM system. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis indicated that the pilot-scale Ti/Pd REM treatment effectively oxidized humic acid-like substance and unsaturated aromatic compounds. Overall, the Ti/Pd REM technology shows a promising application potential for the treatment of high-salinity ROC from the chemical industry.

Study on material structure design, selective adsorption mechanism, and application for adsorption recovery of oil substances in coal chemical wastewater

In response to the problem of high emulsified and dissolved oils being difficult to recovery from coal chemical wastewater (CCW), this study specifically constructed a non-polar, macropore, and hydrophobic adsorption material (pSt-X) based on the main components of these two oils (aromatics and phenols) for selective recovery. The results revealed that pSt-X had an adsorption capacity of 215.52 mg/g, which had remained stable for multiple recycling sessions, with an adsorption capacity constantly above 95 %. The pSt-X has significantly larger particle size (0.7 mm–1.2 mm), which simplifies the process of adsorption regeneration and effectively prevents the loss of the adsorbent powder problem. The pSt-X adsorbent demonstrated remarkable selectivity towards dissolved and emulsified oils, exhibiting removal rates of 90.2 % and 81.7 %, respectively. Moreover, pSt-X proved remarkable selectivity in removing aromatic hydrocarbons (AHs) and phenols, with impressive removal rates of 77.8 % and 85.9 %, respectively. The selective separation mechanism of pSt-X for oil substances was further analyzed, indicating that its selective adsorption of oils was primarily driven by hydrophobic, π-π, and hydrogen bonding interactions owing to its non-polar and macropore structure and hydrophobic properties. The results of this study provide solid theoretical support for green and low-carbon recovery of oil substances in CCW and are of positive practical importance for clean production in the coal chemical industry.

Membrane fouling and influencing factors of a submerged commercial ceramic flat membrane bioreactor in treatment of coal chemical wastewater

An anoxic/oxic (A/O) treatment unit was upgraded using a submerged commercial ceramic flat-membrane bioreactor. The upgraded bioreactor effectively treated coal chemical wastewater. However, the factors influencing membrane fouling remain unclear. Thus, this study explored the mechanisms of membrane fouling of a commercial ceramic flat membrane bioreactor. With increasing duration of backwash, the rate of growth of transmembrane pressure (TMP) gradually increased. The proportions of concentration polarization resistance Rp and cake layer resistance Rf were 48.87% and 50.08%, respectively. Under the action of static electricity, negatively charged particles in the mixed liquid do not easily adhere to the membrane. Under conditions of high mixed liquid suspended solids (＞12 000 mg/L), an increase in the suspended solid content in the mixture caused membrane fouling and pore blockage. When the flux exceeded 58 L·m−2·h−1, the TMP increased sharply. When the aeration rate exceeded 200 mL/min, the impact of membrane erosion on fouling was no longer significant. The optimal suction/cessation ratio was 7:3. After cleaning with NaOH and NaClO, surface fouling of the membrane was significantly reduced.

Pilot study on ceramic flat membrane bioreactor in treatment of coal chemical wastewater

Some toxic and refractory pollutants in coal chemical wastewater can penetrate the biochemical treatment systems and cause high concentrations of suspended solids in the effluent, which may obstruct the subsequent advanced treatment. In this project, a submerged ceramic plate membrane system was integrated to the last oxic corridor of an existing multistage anoxic/oxic tank. In the ceramic flat membrane bioreactor, the influent chemical oxygen demand (COD) was 102.24–178.88 mg/L, with a removal ratio of approximately 30%. The NH3–N concentration in the effluent was relatively stable with an average value of 1.76 mg/L. The turbidity of the effluent was in the range of 0.235–0.852 NTU and was stable below 1 NTU. A flux of 30 L m−2·h−1 could meet the requirements of the pilot test. A gas-water ratio of 50:1 was found optimal. When the concentration of mixed liquor suspended solids (MLSS) was >3769 mg/L, the extracellular polymeric substance in the mixed solution was utilized by microorganisms as a substrate. High MLSS decreased membrane fouling rate. NaClO backwashing can effectively remove pollutants without adversely affecting the treatment efficiency of membrane bioreactors.

Biodegradability enhancement and sequential treatment of real chemical industry wastewater by chemical coagulation and Electro-Fenton processes

A sequential treatment with chemical coagulation in the first step and Electro-Fenton (EF) in the second step was applied to chemical industry wastewater. By coagulation using Poly Aluminum Chloride (PAC) as a coagulant, 57.5% chemical oxygen demand (COD), 96.8% total suspended solids (TSS), and 90.5% color index (CI) removal were obtained. In the EF process applied after chemical coagulation, the design parameters were optimized by the central composite design. Two quadratic models of the four factors were established with the COD and CI as two responses. Optimized conditions of the EF were pH 2.5, Fe2+ dose 5 mM, applied current 1 A, and reaction time 60 min. Under these conditions, the COD removal from the validation experiments was 63.5%. In total, 84.5% COD removal was achieved with the two-step treatment. By extending the reaction time in EF to ensure the discharge limits, 89.5% COD removal was reached, and the COD concentration decreased to 193 mg/L after 240 min. At the same time, the 5-day biochemical oxygen demand (BOD5)/COD ratio increased from 0.1 to 0.57 after 240 min. Consequently, the discharge limit was provided and the biodegradability was improved.

Study of the biofilm mechanism of C4-HSL and C6-HSL in the degradation of quinoline.

Quinoline is a hard-to-degrade organic compound widely found in coal chemical wastewater, that seriously affects the ecological environment and human health. A number of biochemical methods are already available for quinoline degradation, but the use of microbial community sensing for quinoline degradation has not been studied in depth. Therefore, this paper focuses on the enhanced mechanism of quorum-sensing signaling molecules in the biofilm formation process during quinoline degradation by functional strains of bacteria. In this paper, the effects of the signal molecules C4-HSL and C6-HSL on the adhesion ability, colony diameter, biofilm formation ability and biofilm morphology of functional strains of quinoline degrading bacteria (Ochrobactrum sp., LC-1) were investigated, and the results showed that both signal molecules promoted the biofilm formation process during the degradation of quinoline by exhibiting an efficient biofortification effect. Both signal molecules could enhance the colony diameter of strain LC-1, where C4-HSL could enhance the biomass of strain LC-1 and stimulate the secretion of extracellular polysaccharides; and C6-HSL could induce the enhancement of adhesion performance and the secretion of extracellular proteins from strain LC-1; both molecules together enhanced the biofilm formation process of strain LC-1. This study has practical application in the degradation of quinoline in coal chemical wastewater.

Regulation methods and enhanced mechanism on the efficient degradation of aromatics in biochemical treatment system of coal chemical wastewater

In order to address the problems of poor treatment effect of coal chemical wastewater (CCW) biochemical treatment system resulting in non-compliance with effluent standards and unstable operation, a combination regulation method of co-substrate metabolism and predominant flora enhancement was constructed, and the performance and mechanism of enhanced degradation of aromatics in CCW was also investigated in this study. The results showed that when the influent concentration of chemical oxygen demand (COD) and aromatics was less than 600 mg/L and 180 mg/L respectively, there was no significant effect of the combined regulation method on the enhanced treatment of aromatics, the removal rate of total organic carbon (TOC) in the system could all more than 73%; while when the influent concentration of COD increased to 800 mg/L and the aromatics concentration increased to more than 240 mg/L, the ordinary activated sludge system had collapsed. Compared with the regulation method of co-substrate metabolism alone, the combination regulation method increased the removal rate of TOC by 21%. The analysis of antioxidant enzyme activity showed that under the combination regulation method, the antioxidant enzyme activity of microorganisms was higher and their resistance to adverse environments was stronger. EPS and dehydrogenase analysis indicated that the combination regulation method was more conducive to microbial degradation of aromatics. Meanwhile, the analysis of microbial community structure showed that the aromatics degradation bacteria genera Rhodococcus, Luteococcus, etc. were enriched under the combination regulation method. The study provides a theoretical basis and technical guidance for solving the problems of unstable operation of CCW biochemical treatment systems and non-compliance with effluent standards.

Novel membrane contactor-like bioreactor for selective separation and biodegradation of phenol and ammonium from coal chemical wastewater

The development of coal chemical industry usually generates high-concentrated wastewater containing phenol and ammonium, which requires deep treatment before disposal. Herein, a novel combined process of membrane contactor and bioreactor (MCBR) was established for the efficient treatment of phenol-ammonium wastewater for the first time. When pH was in the range of 8–13, the increase of pH weakened the transmembrane mass transfer of phenol and enhanced the mass transfer of ammonia, owing to their different existing forms at different pH values. At a temperature of 20–30 ℃, the transmembrane mass transfer of phenol and ammonia both increased with temperature increasing. Meanwhile, the established transmembrane mass transfer model reflected the same tendencies of phenol and ammonium recovery rates between experiment and theory. The precise control of concentrations of phenol and ammonium by membrane contactor ensured the safety and effectiveness of subsequent biodegradation process. After biodegradation, the concentrations of phenol and ammonium reduced from 120.1 and 78.9 mg/L to 7.8 and 2.5 mg/L, respectively. The volatile solid content of activated sludge remained relatively constant, while the settling ratio decreased from 39 % to 29 %. Overall, this study established a novel MCBR system for green and cost-effective treatment of high-concentrated coal chemistry wastewater.

Eminent destruction of organics and pathogens concomitant with power generation in a visible light-responsive photocatalytic fuel cell with NiFe2O4/ZnO pine tree-like photoanode and CuO/Cu2O nanorod cathode

Environmental conservation and energy scarcity have become two core challenges with the ever-increasing advancement of industry, particularly chemical energy rich wastewater comprising refractory organics and pathogenic microbes. Here, a multifunctional photocatalytic fuel cell (PFC) was devised using NiFe2O4 nanoparticle-loaded on pine tree-like ZnO/Zn (NiFe2O4/ZnO/Zn) photoanode and CuO/Cu2O nanorods-loaded on Cu (CuO/Cu2O/Cu) cathode for extracting electricity upon wastewater treatment. When fed with Rhodamine B (RhB) dyestuff, the NiFe2O4/ZnO/Zn-PFC provided the maximum power density (Pmax) of 0.539 mW cm−2 upon visible light irradiation with an average RhB degradation of 85.2%, which were 2.8 and 2.7 times higher than ZnO/Zn, respectively. The remarkable enhanced NiFe2O4/ZnO/Zn-PFC performance was owing to the synergistic effect of pine tree-like structure and Z-scheme heterostructure. The pine tree-like with high surface area was not only for effective harnessing photon energies but also provided more directional routes for rapid segregation and transport of carriers and higher interface contacting areas with electrolyte. Through a series of systematic characterizations, the Z-scheme heterostructure mechanism of the system and organics degradation pathway were also speculated. Additionally, the performance of the NiFe2O4/ZnO/Zn-PFC in industry printing wastewater showed Pmax of 0.600 mW cm−2, which was considerably impressive as real wastewater was challenging to accomplish. The phytotoxicity outcome also manifested that the comprehensive toxicity of RhB was eradicated after PFC treatment. Lastly, the excellent recyclability and the pronounced bactericidal effect towards Escherichia coli and Staphylococcus aureus were other attributions which enabled the NiFe2O4/ZnO/Zn-PFC for possible practical application.

Mechanism of organic fouling in the reverse osmosis process of coal chemical wastewater

With the development and utilization of coal on a large scale, the treatment of coal chemical wastewater (CCW) had received extensive attention. This study utilized CCW from a coal liquefaction wastewater treatment plant to investigate the mechanism of organic fouling in the reverse osmosis (RO) process. CCW, which possessed high levels of organic matter, underwent RO process and resulted in significantly improved water quality, with a decrease in total organic carbon from 173.70 mg/L to 2.36 mg/L. However, the membrane surface was fouled by organic matter after continuous filtration for 14 h, causing a substantial reduction in the membrane flux, which decreased to 69.0 % normalized membrane flux. High molecular weight humic acid, the primary organic matter present in CCW, was found to be responsible for the organic fouling on the membrane surface, consistent with the main organic component of CCW. Moreover, organic foulants, including nitrogen heterocyclic compounds, alcohols, and lipids, were detected on the membrane surface. The study presented herein provides a comprehensive understanding and analysis of organic fouling in a RO system, offering crucial data support for the development of effective strategies to prevent and control RO membrane fouling in water treatment processes.