Removal of COD,aromaticity and color of a pretreated chemical producing industrial wastewater: a comparison between adsorption,ozonation, and advanced oxidation processes

A wide range of products are produced in the chemical producing industry such as textile dyes, chemicals, printing dyes and chemicals, paper chemicals, electrostatic powder dyes, and optical brighteners. The aim of this study is to investigate the treatability of chemical oxygen demand (COD), aromaticity, and color in the wastewater of this sector, where highly complex chemicals are used. Most of the studies in the literature are related to the treatment of synthetically prepared dyed wastewater. This study is important as it is carried out with real wastewater and gives results of many treatment methods. In the study, COD, UV-vis absorbance, and color values were attempted to be removed from the wastewater of a chemical producing industry that was pretreated by coagulation-flocculation. The COD value of the pretreated wastewater discharged to the central treatment system was restricted as 1000 mg/L. Pretreated wastewater characterization is as follows: COD: 2117 mg/L, UV-vis absorbance values at; 254 nm: 9.91, 280 nm: 8.65, 341 nm: 12.77, 436 nm: 5.01, 525 nm: 2.24, and 620 nm: 1.59. In the study, adsorption, ozonation, and advanced oxidation processes (Fenton and persulfate oxidation) were used to remove COD and UV-vis absorbance values (aromaticity, organics, and color). The method by which the best removal efficiency was obtained for all parameters was the adsorption process using powdered activated carbon (PAC). The equilibrium PAC dose was found as 6 g/L. At this adsorbent dose, the removal efficiencies of UV-vis absorbance values were all around 99% and the efficiency of COD removal was 77%. The Langmuir isotherm constants were found to be q_max= 30.4 mg/g and K_L = 487.9 (L/mg). The COD concentration at this adsorbent dose was 486 mg/L and wastewater was suitable for discharge to the central wastewater treatment plant in that region.     

Determination of Benzidine and its Congeners by Liquid Chromatography with Electrochemical Detection

High performance liquid chromatography coupled with electrochemical detection (HPLC-EC) method has been developed for the determination of benzidine and its related congeners in wastewater at the low ng/mL level. With a µ-Bondapak C₁₈ column, 53% acetonitrile (pH 4.7), and electrochemical detection at +1.0 V applied potential, the detection limits range from 3 ng/mL for benzidine to 10 ng/mL for 3,3′-dichlorobenzidine, assuming a 100 µL injection. The detection limits can be further lowered to the sub-ng/mL level by incorporating a short precolumn into the HPLC system for on-line sample enrichment. Recoveries are generally greater than 80% — except for benzidine and 3,3′-diaminobenzidine which give 50–70% recoveries. Industrial wastewater samples from a coke-plant and a plant producing 3,3′-dichlorobenzidine based dyes were successfully studied via this method.     

Adsorption studies of tannic acid by commercial ester resin XAD-7

<正>Tannic acid and its related compounds are known as refractory organic pollutants,and it can create serious problems for the environment.The adsorption and desorption studies of tannic acid on commercial resins XAD-7 and D-201 are performed,and all data indicates resin XAD-7 can be used as an effective adsorbent for removing tannic acid during water/wastewater treatment.Furthermore,adsorption thermodynamics studies indicate different adsorption mechanisms for TA on XAD-7 and D-201.FT-IR and solid state ~(13)C-NMR spectroscopy are used to explain the adsorption force between XAD-7 and TA.It suggests that hydrogen bonding is the main adsorption force for TA.Finally,XAD-7's adsorption capacity in the presence of different metal ions is investigated,which indicates that heavy metal ions in solutions can decrease the adsorption capacity for TA on ester resin XAD-7.     

Recovery of Acid and Alkaline from Industrial Saline Wastewater by Bipolar Membrane Electrodialysis under High-Chemical Oxygen Demand Concentration

Actual high saline wastewater containing concentrated organics and sodium chloride is a bioenergy and renewable resource. This study compared two different bipolar membrane electrodialysis membranes from two companies’ stacks to recover HCl and NaOH from sodium chloride solution and actual chemical wastewater. The results demonstrated that the electrolysis rates were around 1.5 kg/m²h, the HCl and NaOH production rates were about 0.9 kg/m²h, energy consumption was in the range of 1.05–1.27 kWh/kg, and the economic benefits were above 1 yuan/h in BMED systems. From analyzing the performance of seven different BMED membrane stacks, the B2 stack was chosen for electrolyzing actual high salt wastewater to observe the effect of chemical oxygen demand on BMED systems, where electrolytic salt performance, HCl-NaOH alkali production rates, and energy consumption show linear dependence on time for 5000 mg/L chemical oxygen demand wastewater. It illustrated chemical oxygen demand can enhance energy consumption and reduce electrolytic salt performance and the acid and alkali production rates, due to improving the membrane area resistance. In this study, the effect of high COD saline wastewater on the performance of a BMED membrane stack was clarified and the mechanism was analyzed for its practical application in treating chemical high salt wastewater.     

Entrapped mixed microorganisms to treat organic wastewater from food industry

Limited land and insufficient technicians to operate a wastewater treatment system are main restrictions for many factories. Therefore, an ideal wastewater treatment method for a small or land-limited factory must possess merits such as high performance efficiency, high organic loading rate, little odor, simple operation, easy maintenance, and little land required (simultaneously). An entrapment technique to immobilize mixed microorganisms to treat organic wastewater, which was developed in the present work, possesses these characteristics. This project was done on a laboratory scale. The microorganisms were activated sludge (an undefined mixture of microorganisms obtained directly from a domestic wastewater treatment plan) and the mixed microorganisms were immobilized in cellulose triacetate by means of an entrapment technique to treat organic wastewater from food industry. After wastewater was treated by this system, the SCOD (soluble COD) removal efficiency of 81% evaluated samples exceeded 80% in 1.5 ± 0.9 g SCOD/L/d of the volumetric loading rate and 7–10 h for the hydraulic retention time. This wastewater treatment method can be applied to other organic industrial wastewater.     

Analysis of sulphonated polyphenols, synthetic tanning agents in heavily polluted tannery wastewaters

A method is presented for the analysis of sulphonated polyphenols, acting as synthetic tanning agents, in heavily polluted tannery wastewater. It consists of ion-pair solid-phase extraction (RP-18) with tetrabutylammonium bromide followed by reversed-phase ion-pair liquid chromatography on a C₁₈ stationary phase with UV detection. The detection limit is 15 μg/1. The influence of the wastewater matrix on extraction and the effects of pH and temperature on the HPLC separation are discussed. The procedure is not affected by the high contents of dissolved organic carbon and inorganic salts of tannery wastewater. The tannery effluents investigated contained around 40 mg/1 of sulphonated polyphenols. These compounds appear to be refractory against both anaerobic and aerobic biological wastewater treatment. They might, thus, contribute to the dissolved organic sulphur content of surface waters.     

Rapid simultaneous determination of 14 sulfonamides in wastewater by liquid chromatography tandem mass spectrometry

This paper describes a rapid method for the determination of 14 kinds of sulfonamides (SAs) in wastewater using SPE, and LC-MS/MS with positive ESI (ESI(+)) and selected reaction monitoring (SRM) mode. The SPE was performed on an Oasis hydrophilic-lipophilic-balanced (HLB) cartridge. Chromatographic separation on a C18 column was achieved using a binary eluent containing methanol and water with 0.2% formic acid. Typical recoveries of the analytes ranged from 22.3 to 87.0% at a fortification level of 100 ng/L. The LODs in wastewater except sulfathiazole (3 ng/L) could be detected and quantified at levels as low as 1 ng/L. Finally, the method was applied to water from the municipal outlet and the aquaculture wastewater effluent. Sulfamethazine (SM(2)), sulfamethoxypyridazine (SMP), and sulfamethoxazole (SMZ) were most frequently found in wastewater in a concentration range between 1.2 and 31.7 ng/L.     

Developing an Efficient Processing System Treatment for the High Concentration of Eucalyptus Chemical Mechanical Pulp Wastewater

The current wastewater treatment method shows low efficiency in treating wastewater with high concentrations of chemical mechanical pulp (CMP). Therefore, a chlorine dioxide Pretreatment Anaerobic Treatment (DPAT) was developed and applied to treat the CMP wastewater to obtain higher efficiency, obtaining the following results: The biodegradability of CMP wastewater improved after chlorine dioxide pretreatment. The COD of wastewater treated with chlorine dioxide was reduced from 5634 mg/L to 660 mg/L. The removal rate for chemical oxygen demand (COD) was 88.29%, 29.13% higher than the common anaerobic treatment. The reasons for the high efficiency of the DPAT treatment were that chlorine dioxide pretreatment removed the toxic substances in the original wastewater and thereby promoted the proliferation and growth of the anaerobe. The results show that pretreatment with chlorine dioxide can effectively enhance the biodegradability of high-concentration CMP wastewater. Therefore, DPAT treatment of high-concentration CMP wastewater is beneficial to environmental protection.     

大孔树脂吸附法处理模拟邻苯二酚生产废水的研究

本文采用ＮＫＡ－２大孔径树脂吸附法处理模拟邻苯二酚废水,室温下以６ＢＶ／ｈ流速吸附便能达到国家的排放标准。废水中酚的含量≤５．０ｍｇ／Ｌ;系统地研究了温度、流速、废水ｐＨ值等因素对树脂吸附性能的影响;提出分析废水中邻苯二酚含量的高效液相色谱（ＨＰＬＣ）法。     

竹炭为高效吸附剂的固相萃取分析环境水样中的痕量三氯生

建立了一种由竹炭作为固相萃取高效吸附剂富集环境水样中痕量三氯生的新方法. 研究并优化了几个影响富集效率的参数. 在优化条件下, 三氯生的检测限为0.08 μg/L, 在1～100 μg/L 范围内有良好的线性关系, 相对标准偏差为2.9% (n=7). 方法可应用于实际废水样品的分析.     

Chemometric data analysis of pollutants in wastewater—a case study

In this study, chemometric techniques such as cluster analysis (CA), discriminant analysis (DA), principal component analysis (PCA) and partial least squares (PLS) were used to analyse the wastewater dataset to identify the factors which affect the composition of sewage of domestic origin, spatial and temporal variations, similarity/dissimilarity among the wastewater characteristics of cis- and trans-drains and discriminating variables. Samples collected from 24 wastewater drains in Lucknow city and from three sites on Gomti river in the month of January/February, May, August and November during the period of 5 years (1994-1999) were characterized for 32 parameters. The multivariate techniques successfully described the similarities/dissimilarities among the sewage drains on the basis of their wastewater characteristics and sources signifying the effect of routine domestic/commercial activities in respective drainage areas. Spatial and seasonal variations in wastewater composition were also determined successfully. CA generated six groups of drains on the basis of similar wastewater characteristic. PCA provided information on seasonal influence and compositional differences in sewage generated by domestic and industrial waste dominated drains and showed that drains influenced by mixed industrial effluents have high organic pollution load. DA rendered six variables (TDS, alkalinity, F, TKN, Cd and Cr) discriminating between cis- and trans-drains. PLS-DA showed dominance of Cd, Cr, NO₃, PO₄ and F in cis-drains wastewater. The results suggest that biological-process based STPs could treat wastewater both from the cis- as well as trans-drains, however, prior removal of toxic metals will be required from the cis-drains sewage. Further, seasonal variations in wastewater composition and pollution load could be the guiding factor for determining the STPs design parameters. The information generated would be useful in selection of process type and in designing of the proposed sewage treatment plants (STPs) for safe disposal of wastewater.     

6-氨基青霉烷酸生产废水厌氧和深度处理实验研究

针对6-氨基青霉烷酸生产废水高污染物浓度,高硫酸根,难降解物质多的特点对废水经过硫酸根预处理,稀释3倍和6倍后,废水对厌氧污泥没有急毒性,厌氧污泥可以逐步适应废水环境。经过厌氧处理以及后续的Fenton深度处理,高浓度的6-氨基青霉烷酸生产废水COD_cr可由45450 mg/L 降到255 mg/L。出水COD_cr可达到污水三级排放标准。     

改性竹炭对含铅废水吸附处理的效果研究

研究了商用竹炭和改性竹炭对含铅废水的吸附处理的实验条件及效果。结果表明,对一定质量浓度及一定量含铅废水处理时,只要条件和吸附剂竹炭的投放量合适,铅的去除率均可达99.9%以上。以我国饮用水卫生标准中铅含量≤0.05mg/L为标准,根据废水中铅的含量,给出了吸附处理所需吸附剂投料量的估算方法和实验验证结果,为竹炭在含铅废水处理中的应用提供理论依据。     

Automated determination of aliphatic primary amines in wastewater by simultaneous derivatization and headspace solid-phase microextraction followed by gas chromatography–tandem mass spectrometry

This paper presents a fully automated method for determining ten primary amines in wastewater at ng/L levels. The method is based on simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to ion trap tandem mass spectrometry (GC–IT-MS–MS). The influence of main factors on the efficiency of derivatization and of HS-SPME is described in detail and optimized by a central composite design. For all species, the highest enrichment factors were achieved using a 85 μm polyacrylate (PA) fiber exposed in the headspace of stirred water samples (750 rpm) at pH 12, containing 360 g/L of NaCl, at 40 °C for 15 min. Under optimized conditions, the proposed method achieved detection limits ranging from 10 to 100 ng/L (except for cyclohexylamine). The optimized method was then used to determine the presence of primary amines in various types of wastewater samples, such as influent and effluent wastewater from municipal and industrial wastewater treatment plants (WWTPs) and a potable water treatment plant. Although the analysis of these samples revealed the presence of up to 1500 μg/L of certain primary amines in influent industrial wastewater, the concentration of these compounds in the effluent and in municipal and potable water was substantially lower, at low μg/L levels. The new derivatization–HS-SPME–GC–IT-MS–MS method is suitable for the fast, reliable and inexpensive determination of primary amines in wastewater in an automated procedure.     

Direct aqueous injection with backflush thermal desorption for wastewater monitoring by online GC-MS

A gas chromatography—mass spectrometry system with a novel injector type, which is designed for direct aqueous injection of wastewater, is presented. The system is used for online monitoring of the influent of the wastewater treatment plant at BASF’s main chemical production site in Ludwigshafen, Germany. The purpose of monitoring is to protect the biological treatment process and the receiving water body, the Rhine. The modular system is primarily based on commercial equipment, but utilizes a special injection system, which is connected to a Deans switch. The two-stage injector consists of a programmable temperature vaporizer (PTV) injector with a small volume insert for vaporization and a dual sorbent packed second PTV for analyte adsorption/desorption. The Deans switch allows a backflush/thermal desorption operation which enables the direct injection of filtered, crude wastewater. About 170 volatile and semivolatile compounds are calibrated with approximate detection limits of 1 mg/L, which are sufficient for the analysis of untreated wastewater. The quantitative results are transferred to a database which is connected to a process control system. If the wastewater does not meet the required specification, an alarm is generated and the wastewater is diverted into a storage basin. Special software programs and routines allow for reliable, unattended operation and remote instrument control. Data quality is automatically controlled in each run and through the daily analysis of quality control samples. The current design allows for analysis of volatile compounds, such as methanol, whereas an earlier injector setup restricted the range of analytes to less volatile compounds (of size C₄ or greater).     

Determination of 76 pharmaceutical drugs by liquid chromatography–tandem mass spectrometry in slaughterhouse wastewater

A multi-residue method for the analysis of 76 pharmaceutical agents of nine classes of drugs (tetracyclines, macrolides, fluoroquinolones, β-agonists, β-blockers, diuretics, sedatives, sulfonamides and chloramphenicol) in slaughterhouse wastewater and a receiving river is presented. After simultaneous extraction with an Oasis HLB solid-phase extraction (SPE) cartridge and further purification using an amino SPE cartridge, analytes were detected by liquid chromatography–electrospray ionization-tandem mass spectrometry in positive or negative ion mode. Standard addition was used for quantification to overcome unavoidable matrix effects during ESI-MS analysis. Recoveries for most analytes based on matrix-matched calibration in different test matrices were >60%. The method quantification limits of 76 pharmaceuticals were in the range 0.2–30 ng/L. Nineteen compounds of 76 drugs were found in raw and treated slaughterhouse wastewater from four main slaughterhouses in Beijing. Sulfanamides (sulfanilamide, sulfameter), fluoroquenones (ofloxacin, pefloxacin, norfloxacin, ciprofloxacin, enrofloxacin), tetracyclines (tetracycline, oxytetracycline) and macrolides (kitasamycin, tylosin, erythromycin) were most frequently detected, with the highest levels up to ∼3 μg/L in slaughterhouse wastewater and ∼1 μg/L in treated wastewater. Illicit drugs for animal feeding such as clenbuterol and diazepam were commonly detected in slaughterhouse wastewater. These analytes were also observed in a river receiving slaughterhouse wastewater, with a highest level of up to 0.2 μg/L.     

Analytical method for the determination of the aminoglycoside gentamicin in hospital wastewater via liquid chromatography-electrospray-tandem mass spectrometry

A method for the determination of gentamicin residues in hospital wastewater has been developed using kanamycin as a surrogate standard. The method consists of solid-phase extraction (SPE) and detection by ion-pair chromatography with electrospray tandem mass spectrometry (LC–ES-tandem MS). The SPE was performed on a weak cation exchanger. Filtration should be avoided in the sample preparation, otherwise a significant loss of gentamicin occurs. Chromatographic separation on a C₁₈-column was achieved using a ternary eluent containing methanol, water and 20 mmol l⁻¹ heptafluorobutyric acid solution. Mean relative recoveries of the analytes in hospital wastewater varied between 107 and 111%. The limit of quantification (LOQ) was 0.20 μg l⁻¹ in hospital wastewater. Gentamicin was found in native hospital wastewater in a concentration range between 0.4 and 7.6 μg l⁻¹.     

Adsorption of Cr(VI) on ureolytic mixed culture from biocatalytic calcification reactor

Ca-rich water and wastewater have caused problems in water use, wastewater reuse and the operations of reactors treating Ca-rich wastewater. Nowadays, reuse of wastewaters is fast gaining importance as water sources have been polluted. Therefore, the concept of biocatalytic calcification reactors (BCR) based on urea hydrolysis, pH increase and calcite production has been studied to remove Ca from wastewaters. This biological process produces significant amounts of waste sludge. In the present study, Cr(VI) adsorption on the ureolytic mixed culture (UMC) waste by-product from BCR was investigated to evaluate its potential for metal removal. The biosorption process was investigated using equilibrium batch tests and the data were fit to the Langmuir, Freundlich and Temkin isotherm models. The Cr(VI) ion concentration dependence of sorption (1-100 mg/L) could be fit to the Langmuir isotherm model. Monolayer adsorption capacity, qm (mg/g), of the adsorbent was 8.67 and the Langmuir constant b (L/mg) was 0.881. Based on the obtained results, the waste UMC appears to be a potential biosorbent for the removal of Cr(VI) from wastewater, although its adsorptive capacity is lower than those of other biosorbents.     

Fe(0)/Cu双金属还原与Fenton氧化集成工艺处理印染生化尾水树脂脱附液的研究

通过比较Fe(0)和Fe(0)/Cu还原工艺处理印染生化尾水树脂脱附液的效果,发现Fe(0)/Cu双金属还原对脱附液TOC和UV254去除率均优于Fe(0)。若将Fe(0)/Cu双金属还原与Fenton氧化工艺集成可以进一步提高处理效果。该组合工艺处理后,TOC去除率高达66%,UV254去除率高于90%,脱附液的BOD5/CODcr从低于0.1升高至0.38左右。由此可见,该组合工艺对复合功能树脂碱脱附液具有良好的处理效果,处理后废水的毒性降低,可生化性显著提高,为其返回生物系统进一步生化降解提供了较好的保证。