Preparation of calcium oxalate—bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters

Background, aim, and scope  Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods  On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ^2––BPR–Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results  The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 × 10⁵ M^–1. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30–50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion  The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ^2– captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions  By characterizing the C₂O₄ ^2––BPR–Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] _n ^2n–, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives  The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A simple chemical free arsenic removal method for community water supply - A case study from West Bengal, India

This report describes a simple chemical free method that was successfully used by a team of European and Indian scientists (www.qub.ac.uk/tipot) to remove arsenic (As) from groundwater in a village in West Bengal, India. Six such plants are now in operation and are being used to supply water to the local population (www.insituarsenic.org). The study was conducted in Kasimpore, a village in North 24 Parganas District, approximately 25 km from Kolkata. In all cases, total As in treated water was less than the WHO guideline value of 10 μg L⁻¹. The plant produces no sludge and the operation cost is 1.0 US$ per day for producing 2000 L of potable water.     

化学沉淀法除去废水中的氨氮及其反应的探讨

研究了化学沉淀法处理含氨氮废水，实验研究了不同操作条件，如溶液ｐＨ值、沉淀剂种类和配比、废水中的初始氨浓度等对氨的处理效率的影响，在适宜的操作条件下，可除去废水中的氨高达９９％，处理后残液中氨浓度小于１ｍｇ／Ｌ（１ｐｐｍ），探讨了化学沉淀反应过程的机理。     

我国合成洗涤剂生产废水治理技术研究

综述了近年来我国合成洗涤剂生产废水的特性;化学混凝法、泡沫分离法和生物接触氧化法处理合成洗涤剂生产废水的最佳工艺条件及其处理效果;工程应用实例及经济分析等。生产运行结果表明,处理后出水水质全面达到国家排放标准。化学混凝法,泡沫分离一混凝法其设备、流程简单、去除效率高、占地少,但运行费用较高。生物接触氧化－臭氧氧化法其出水可以回用、工艺先进、可靠、运行费用低、无二次污染。     

印染废水处理方法的研究

针对印染废水的特点 ,采用混凝沉降 -氧化法处理印染废水。根据生产实际 ,把废水分成较易处理和较难处理两种情况。经过混凝沉降、化学氧化、砂滤后 ,可达到国家印染废水的排放标准。同时 ,确定了主要技术参数和工艺流程 ,并对实验结果进行了理论和经济分析     

城市污水化学除磷的探讨

阐述了城市污水处理除磷的重要性和迫切性，而在普遍采用的生物除磷技术不能满足出水磷的排放标准时可考虑采用化学除磷技术，系统分析了化学除磷的原理，特点及影响因素，结合工程实例介绍了城市污水化学除磷的除磷效果，并指出了我国在现阶段城市的污水化学除磷技术研究与发展的目标。     

含油污泥处理技术研究

针对某炼厂难以处理的含油污泥，用正交试验法对自理含油污泥的试验条件（破乳剂用量、提取剂用量、热水用量及加药方式）进行了研究，确定了先加污泥量１．０％破乳剂ＪＰ９９８搅３０ｍｉｎ，再加污泥量３０％的８０℃热水，再缓慢加入污泥量１０％的提取剂在８０℃下反应１ｈ，最后在２０００ｒ／ｍｉｎ下离心分离２０ｍｉｎ的实验条件和化学配方；据此化学破乳加机械三相离心分离技术处理后的含油污泥的原油回收率达９０％，油回     

Improving the removal of fine particles by chemical agglomeration during the limestone-gypsum wet flue gas desulfurization process

Coal-fired power plants are considered a major source of fine particle emissions in China.Aimed to improve the removal efficiency of fine particles during the limestone-gypsum wet flue gas desulfurization(WFGD) process, a novel technology using chemical agglomeration to abate the emission of fine particles is presented herein. The relationship between fine particle emission and the proportion of fine particles in the desulfurization slurry was studied.Additionally, the influence of chemical agglomeration on fine particle size distribution, both in the flue gas and slurry was experimentally investigated. When chemical agglomeration agents were added to the desulfurization slurry, the fine particle removal performance as well as the effects of the operation parameters was also explored via the simulated experimental facility.The results revealed that the fine particles in both the desulfurization slurry and flue gas were significantly enlarged after the addition of the agglomeration agents. This was more marked in the submicron particles. Thus, the proportion of fine particles( 10 μm) in the slurry decreased from 31.1% to 22.6%. An increase in the desulfurization slurry temperature and liquid-to-gas ratio aided the reduction in fine particle emission. Moreover, the addition of an agglomeration agent in the slurry did not affect the desulfurization efficiency of the desulfurization tower and even promoted the WFGD process. Thus, the proposed chemical agglomeration technique reduced the fine particle emission of the WFGD system by ～30%, while a desulfurization efficiency 90% was maintained.     

氢氧化钙清液加氯化钙处理酸性高浓度含氟废水

研究了pH值、氯化钙投加量、搅拌时间及沉淀时间等因素对酸性高浓度含氟废水处理效果的影响;提出了采用氢氧化钙清液加氯化钙作为新型沉淀剂处理酸性高浓度含氟废水的工艺参数：pH值在8．5－9．5,按照nCa／F=0．7加入5％CaCl2溶液,搅拌45min、沉降90min;采用此工艺参数处理氟离子浓度为2600mg／L、pH值为2．97的废水,能把废水氟离子的浓度降至20mg／L以下,达到国家二级排放标准;采用本工艺取代传统工艺的好处是：沉渣中氟化钙纯度高,有利于废水中氟的回收利用。     

氨基酸型螯合树脂的合成及其吸附性能

以三乙烯四胺，环氧氯丙烷和氯乙酸为原料，合成了氨基酸结构的螯合树脂，并研究了Ｃｕ＾２＋，Ｐｂ＾２＋，Ｎｉ＾２＋，Ｚｎ＾２＋的吸附性能。结果表明，该树脂对Ｃｕ＾２＋，Ｐｂ＾２＋，Ｐｂ＾２＋，Ｎｉ＾２＋比对Ｚｎ＾２＋具有良好的吸附性能，其吸附量可达１．４０，，１．３９，１．２０及０．４ｍｏｌ／ｇ。