Experimental investigation and theoretical modeling on scale behaviors of high salinity wastewater in zero liquid discharge process of coal chemical industry

Zero liquid discharge(ZLD)treatment and reuse equipment of high salinity wastewater in coal-chemical industry often occur in various types of blockage problems because of high salt content,affecting the long-term stability of the device.In this study,the effects of solution temperature,steel,reaction time and wall roughness on fouling were investigated.The changes in the contents of fouling and fouling substances were qualitatively and quantitatively analyzed by XRD and EDS respectively,and the formation of scale was observed by SEM.The results show that with temperature increasing,Q235 steel is the most difficult to scale.Scaling rate of all salt scales reaches a maximum after 12 h,and the fouling rate decreases significantly from 12 to 48 h.It gradually stabilizes at 48 to 96 h.With the roughness increasing,the thickness of fouling layer increases,and a linear relationship is presented for 1 to 10 h.By comparing actual and simulated wastewater scaling rates,the relationship between actual and simulated wastewater scaling rates is y=ax-0.494.The composition of the scale was analyzed,calcium carbonate is the main product and increases with fouling time.Based on the above-mentioned results combining literatures,the hybrid prediction model with calcium carbonate as the main product is put forward.It is discussed microscopically that calcium carbonate is converted from aragonite and vaterite in a thermodynamically metastable state to calcite in a thermodynamically stable state.

Utilizing 3D DOSY NMR in the characterization of organic compounds in coal chemical wastewater

Coal chemical wastewater(CCW)with the features of high toxicity and poor biodegradability is a big issue in environmental remediation,posing a great threat to aquatic ecosystems and to human beings.Such complex molecular mixtures are notoriously difficult to characterize without initial physical separation.Herein,we present the 3D diffusion ordered spectroscopy(DOSY)analysis for CCW using DOSY-COSY and DOSY-HSQC methods,the advantages of this strategy have been demonstrated in the analysis of mixtures of aliphatic oxygenates and aromatic compounds,before being implemented on a genuine CCW sample in this study.The results showed that 3D DOSY is a robust and reliable tool for providing superior resolution and virtual separation of complex pollutants,and can be used as a general approach for structural elucidation.

Application of Air Separation Unit in SINOPEC's Coal Chemical Business

With the rapid growth of coal chemical industry in China, the selection and application of Air Separation Unit(ASU) became very important. As the core unit in coal chemical industry, ASU will greatly impact the engineering construction and operation/production of coal chemical business. In this paper, major suppliers of ASU at home and abroad were reviewed, and the major supplying status of ASU in China was introduced. The ASUs in operation of SINOPEC were listed and discussed. On this basis, some suggestions of ASU selection strategies were provided on localization, standardization and operation methods.

Overview of enhancing biological treatment of coal chemical wastewater:New strategies and future directions

Coal chemical wastewater(CCW)is a type of refractory industrial wastewater,and its treatment has become the main bottleneck restricting the sustainable development of novel coal chemical industry.Biological treatment is considered as an economical,effective and environmentally friendly technology for CCW treatment.However,conventional biological process is difficult to achieve the efficient removal of refractory organics because of CCW with the characteristics of composition complexity and high toxicity.Therefore,seeking the novel enhancement strategy appears to be a favorable solution for enhancing biological treatment efficiency of CCW.This review focuses on presenting a comprehensive picture about the exogenous enhancement strategies for CCW biological treatment.The performance and potential application of exogenous enhancement strategies,including co-metabolic substrate enhancement,biofilm filler enhancement,adsorption material enhancement and conductive mediator enhancement,were expounded.Meanwhile,the enhancing mechanisms of different strategies were comprehensively discussed from a biological perspective.Furthermore,the prospects of enhancement strategies based on the engineering performance,economic cost and environmental impact(3E)evaluation were introduced.And novel enhancement strategy based on“low carbon emissions”,“resource recycling”and“water environment security”in the context of carbon neutrality was proposed.Taken together,this review provides technical reference and new direction to facilitate the regulation and optimization of typical industrial wastewater biological treatment.

Biotoxicity dynamic change and key toxic organics identification of coal chemical wastewater along a novel full-scale treatment process

It is particularly important to comprehensively assess the biotoxicity variation of industrial wastewater along the treatment process for ensuring the water environment security.However,intensive studies on the biotoxicity reduction of industrial wastewater are still limited.In this study,the toxic organics removal and biotoxicity reduction of coal chemical wastewater(CCW)along a novel full-scale treatment process based on the pretreatment process-anaerobic process-biological enhanced(BE)process-anoxic/oxic(A/O)process-advanced treatment process was evaluated.This process performed great removal efficiency of COD,total phenol,NH_(4)^(+)-N and total nitrogen.And the biotoxicity variation along the treatment units was analyzed from the perspective of acute biotoxicity,genotixicity and oxidative damage.The results indicated that the effluent of pretreatment process presented relatively high acute biotoxicity to Tetrahymena thermophila.But the acute biotoxicity was significantly reduced in BE-A/O process.And the genotoxicity and oxidative damage to Tetrahymena thermophila were significantly decreased after advanced treatment.The polar organics in CCW were identified as the main biotoxicity contributors.Phenols were positively correlated with acute biotoxicity,while the nitrogenous heterocyclic compounds and polycyclic aromatic hydrocarbons were positively correlated with genotoxicity.Although the biotoxicity was effectively reduced in the novel full-scale treatment process,the effluent still performed potential biotoxicity,which need to be further explored in order to reduce environmental risk.

Effect of demineralization on pyrolysis characteristics of LPS coal based on its chemical structure

The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.

Effect of alkalinity on nitrite accumulation in treatment of coal chemical industry wastewater using moving bed biofilm reactor

Nitrogen removal via nitrite （the nitrite pathway） is more suitable for carbon-limited industrial wastewater. Partial nitrification to nitrite is the primary step to achieve nitrogen removal via nitrite. The effect of alkalinity on nitrite accumulation in a continuous process was investigated by progressively increasing the alkalinity dosage ratio （amount of alkalinity to ammonia ratio, mol/mol）. There is a close relationship among alkalinity, pH and the state of matter present in aqueous solution. When alkalinity was insufficient （compared to the theoretical alkalinity amount）, ammonia removal efficiency increased first and then decreased at each alkalinity dosage ratio, with an abrupt removal efficiency peak. Generally, ammonia removal efficiency rose with increasing alkalinity dosage ratio. Ammonia removal efficiency reached to 88% from 23% when alkalinity addition was sufficient. Nitrite accumulation could be achieved by inhibiting nitrite oxidizing bacteria （NOB） by free ammonia （FA） in the early period and free nitrous acid in the later period of nitrification when alkalinity was not adequate. Only FA worked to inhibit the activity of NOB when alkalinity addition was sufficient.

Synthesis and evaluation of cationic flocculant P(DAC-PAPTAC-AM) for flocculation of coal chemical wastewater

In this study,a high-efficiency cationic flocculant,P(DAC-MAPTAC-AM),was successfully prepared using UV-induced polymerization technology.The monomer Acrylamide(AM):Acryloxyethyl Trimethyl ammonium chloride(DAC):methacrylamido propyl trimethyl ammonium chloride(MAPTAC)ratio,monomer concentration,photoinitiator concentration,urea content,and cationic monomer DAC:MAPTAC ratio,light time,and power of highpressure mercury lamp were studied.The characteristic groups,characteristic diffraction peaks,and characteristic proton peaks of P(DAC-MAPTAC-AM)were confirmed by fourier transform infrared spectroscopy(FTIR),X-Ray diffraction(XRD),1H nuclear magnetic resonance spectrometer(1H NMR),and scanning electron microscopy(SEM).The effects of dosage,pH value,and velocity gradient(G)value on the removal efficiencies of turbidity,COD,ammonia nitrogen,and total phenol by poly aluminum ferric chloride(PAFC),P(DACMAPTAC-AM),and PAFC/P(DAC-MAPTAC-AM)in the flocculation treatment of coal chemical wastewater were investigated.Results showed that the optimal conditions for the flocculation of coal chemical wastewater using P(DAC-MAPTAC-AM)alone are as follows:dosage of 8-12 mg/L,G value of 100-250 s^-1,and pH value of 4-8.The optimal dosage of PAFC is 90-150 mg/L with a pH of 2-12.The optimal dosage for PAFC/P(DAC-MAPTAC-AM)is as follows:PAFC dosage of 90-150 mg/L,P(DAC-MAPTAC-AM)dosage of 8-12 mg/L,and pH range of 2-6.When P(DAC-MAPTAC-AM)was used alone,the optimal removal efficiencies of turbidity,COD,ammonia nitrogen,and total phenol were 81.0%,35.0%,75.0%,and 80.3%,respectively.PAFC has good tolerance to wastewater pH and good pH buffering.Thus,the flocculation treatment of coal chemical wastewater using the PAFC/P(DAC-MAPTAC-AM)compound also exhibits excellent resistance and buffering capacity.

Forward osmosis coupled with lime-soda ash softening for volume minimization of reverse osmosis concentrate and CaCO_(3) recovery: A case study on the coal chemical industry

Reverse osmosis(RO)is frequently used for water reclamation from treated wastewater or desalination plants.The RO concentrate(ROC)produced from the coal chemical industry(CCI)generally contains refractory organic pollutants and extremely high-concentration inorganic salts with a dissolved solids content of more than 20 g/L contributed by inorganic ions,such as Na^(+),Ca^(2+),Mg^(2+),Cl^(−),and SO_(4)^(2−).To address this issue,in this study,we focused on coupling forward osmosis(FO)with chemical softening(FO-CS)for the volume minimization of CCI ROC and the recovery of valuable resources in the form of CaCO_(3).In the case of the real raw CCI ROC,softening treatment by lime-soda ash was shown to effectively remove Ca^(2+)/Ba^(2+)(>98.5%)and Mg^(2+)/Sr^(2+)/Si(>80%),as well as significantly mitigate membrane scaling during FO.The softened ROC and raw ROC corresponded to a maximum water recovery of 86%and 54%,respectively.During cyclic FO tests(4×10 h),a 27%decline in the water flux was observed for raw ROC,whereas only 4%was observed for softened ROC.The cleaning efficiency using EDTA was also found to be considerably higher for softened ROC(88.5%)than that for raw ROC(49.0%).In addition,CaCO3(92.2%purity)was recovered from the softening sludge with an average yield of 5.6 kg/m^(3) treated ROC.This study provides a proof-of-concept demonstration of the FO-CS coupling process for ROC volume minimization and valuable resources recovery,which makes the treatment of CCI ROC more efficient and more economical.

Performance of water-based foams affected by chemical inhibitors to retard spontaneous combustion of coal

The micelle generating process of the sodium dodecyl sulfate(SDS) solution with the addition of chemical inhibitors was elucidated using phase separation model, and the descending order of the capacity for the selected chemical inhibitors to reduce the critical micelle concentrations of the solution are Mg Cl_2, Ca Cl_2,NH_4HCO_3 and NH_4Cl. The data to quantitatively describe the foam decay process, including foaming ratio,foam life and decay behaviors, was obtained by pressure measuring system. The results indicate that chemical inhibitors can improve the solution foamability. The capacity of the inhibitors to enhance the solution foamability is sorted as NH_4 Cl, NH_4HCO_3, Mg Cl2 and Ca Cl_2 which can distinctly improve the foam stability as well. The capacity of the inhibitors to enhance the SDS foam stability can be arranged as Mg Cl_2, NH_4 Cl, NH_4HCO_3 and Ca Cl_2. It is observed that the gravity drainage plays a leading role in the increase of proportion of diffusion drainage. The oxidation dynamic parameters of the coal samples treated by inhibition foams were investigated using thermal analysis technique, and their synergistic effects on inhibiting coal oxidation were explored.

Application and development status of coal gasification technology in China

Introduced the application and development status of coal gasification tech- nology in China. The most widely used coal gasification technology in China is the at- mospheric fixed-bed gasifier, its total number is about 9 000. About 30 pressurized fixed-bed gasifiers are in operation, and more than 10 atmospheric fluidized-bed gasifi- ers were used. There are 13 Texaco entrained-flow bed gasifiers are under operation, 10 Texaco and 11 Shell gasifiers that are being installed or imported. About 10 under- ground gasifiers are under running now. The present R&D of coal gasification technolo- gies are to improve the operation and controlling level of fixed-bed gasification technol- ogy, and developing or demonstration of fluidized-bed and entrained-flow bed gasifiers.

Effects of different acclimations on high solution bacteria in coal-gas wastewater degradation

To make microbial community be applied more easily in practical biotreatment engineering,three acclimation processes were carried out in lab scale. Three kinds of mixed microorganism cultures with degradability for a gas-making plant wastewater were obtained. The degradation experiments results of coal-gas wastewater indicated that different acclimation processes had obviously impacted on degradability of microbial community,and under high sludge loading rate,mixed microorganism cultureⅠ(obtained by H.S.B as bacteria source and raw wastewater as alone carbon and energy source)presented stronger degradability for coal gasification wastewater than the others. COD removal rate of mixed cultureⅠcan reach 57.6% under very low MLSS when the influent COD is 900 mg/L. Meanwhile,the results of microscopic examination showed that Protozoa,mainly epistylis and Vorticella species,were stronger activity and larger quantities in mixed cultureⅠ.

Reviews of clean coal conversion technology in China:Situations & challenges

It is important to develop the advanced coal to chemicals industry(ACCI)against a backdrop of coal-based energy structures,excessive imported oil and natural gas,and strict environmental constraints in China.In this study,the technology and industry of China’s ACCI are reviewed to explain the effect of using coal to replace oil and natural gas,and the corresponding resource and environmental burdens that this will create.Development trends in technology and industry are also proposed to explore future scenarios.The review shows that although excellent progress has been made on an industrial scale,demonstrative level,and in terms of technology and equipment,the lack of strategic understanding,severe external constraints,partly underdeveloped technologies,and weak foundations must be immediately addressed.Therefore,it is necessary to clarify the importance that the ACCI has on the energy revolution and energy system.Based on technological innovation,a variety of external factors should be considered as a whole with emphasis on filling the knowledge gap of theoretical foundations and industry standards to support high-quality development for ACCI.

Capability of phenol-degrading biofilm

The degradation rate of phenol-degrading biofilm was studied.The biofilm of the biofilm was a kind of phenol-degrading bacteria.The bacteria was separated from coal chemical industry wastewater.The carbon source adopted four kinds of phenols,including phenol,methyl phenol,2-methyl phenol and resorcinol.Stenotrophomonas maltophilia K279a was gained.Twelve ratio of artificial phenol mixture was designed.The degradation rate of the twelve groups was all 99.9% in 16 h.The degradation rate from high to low was phenol,resorcinol,methyl phenol,2-methyl phenol.Phenol improved the degradation of the other phenols.The coal chemical wastewater contained 980 mg/L COD and 805 mg/L phenol.The degradation rate of COD and phenol was 70% and 77%,respectively.The domesticated biofilm (D) and the biofilm without domestication (WD) respectively used 45 h and 56 h.The results showed that the biofilm can be applied to the aerobic treatment process with high proportion of total phenol.

Recent Advances in Precombustion Coal Cleaning Processes

The mineral matter in coal constitutes a major impediment to the direct use of coal in power plants.A concerted effort has been mounted to reduce the ash/sulfur contents in product coal to meet theever mcre stringent environmental regulations. In recent years, significant advances have taken placein fine coal cleaning technologies. A review of recent developments in advanced physical, chemical andbiological processes for deep-cleaning of fine coal is presented.

Hybrid peroxi-coagulation/ozonation process for highly efficient removal of organic contaminants

Aromatic compounds such as phenols presented widely in coal chemical industry wastewater(CCW)render the treatment facing great challenge due to their biorefractory characteristics and potential risks to the environment and human health.Ozone-based advanced oxidation processes show promising for these pollutants removal,but the mineralization via ozonation alone is unsatisfactory and not cost-effective.Herein,a hybrid peroxi-coagulation/ozonation process(denoted as PCO)was developed using sacrificial iron plate as an anode and carbon black modified carbon felt as cathode in the presence of ozonation.An enhanced phenol removal of∼100%within 20 min and phenol mineralization of∼80%within 60 min were achieved with a low energy consumption of 0.35 kWh/g TOC.In this novel process,synergistic effect between ozonation and peroxi-coagulation was observed,and beside O_(3) direct oxidation,peroxone played a dominant role for phenol removal.In the PCO process,the hydrolyzed Fe species enhanced the generation of reactive oxygen species(ROS),while•OH was dominantly responsible for pollutant degradation.This process also illustrated high resistance to high ionic strength and better performance for TOC removal in real wastewater when compared with ozonation and peroxi-coagulation process.Therefore,this process is more cost-effective,being very promising for CCW treatment.