巯基化条件对巯基乙酰壳聚糖除镉性能的影响

为有效处理含镉废水,同时进一步拓展天然高分子絮凝剂壳聚糖(CTS)的应用范围,通过正交实验得到了一种可用于除镉的高分子絮凝剂——巯基乙酰壳聚糖(MAC)的最佳制备条件。实验结果表明,在该条件下得到的MAC对废水中镉的去除率最高可达99.96%,水中镉的残余量为0.01 mg/L,远低于我国废水排放标准(0.1 mg/L);同时巯基乙酰壳聚糖与壳聚糖相比水溶性大大增强,可溶于pH值11以下的废水。     

改性壳聚糖-凹凸棒石复合絮凝剂絮凝采收小球藻

用3-氯-2-羟丙基氯化铵(CTA)季铵化改性壳聚糖(CTS),制备了季铵化改性壳聚糖(CTS-CTA);将壳聚糖(CTS)、阳离子淀粉(CS)、二甲基二烯丙基氯化铵(DMDAAC)进行三元接枝共聚,制备了三元接枝改性壳聚糖(CTS-DMDAAC-CS)。并且比较了壳聚糖(CTS)、季铵化改性壳聚糖(CTS-CTA)、三元接枝改性壳聚糖(CTS-DMDAAC-CS)对小球藻的絮凝效果,选择三元接枝改性壳聚糖与凹凸棒石进行复配,确定了最佳絮凝条件为:p H=8,絮凝剂与凹凸棒石的比例为1∶14,沉降时间为20 min,絮凝剂投加量为0.4 g。在该条件下进行了重复实验,得出小球藻的絮凝率为98.8%,并且絮体紧密、沉降速度快,不需要再次分离,具有很好的应用前景。     

响应曲面法中BBD和CCD在优化巯基乙酰化壳聚糖制备条件中的比较

以壳聚糖(CTS)和巯基乙酸为主要原料,通过酰胺化反应将巯基引入到CTS高分子链上,制备出高分子重金属絮凝剂巯基乙酰化壳聚糖(MACTS)。以含Cd(II)水样为考察目标,采用响应曲面法中的BBD和CCD实验对MACTS的制备条件进行优化,从残差分析、方差分析、响应面分析和优化条件等方面对BBD法和CCD法进行比较。结果表明,BBD法和CCD法建立的二次多项式模型回归性分别为显著和非常显著,模型选择均合理;BBD法和CCD法拟合模型的决定系数R2分别为0.871 0、0.919 7,模型相关性均较好;通过BBD法和CCD法优化制备条件后的MACTS处理含Cd(II)水样,Cd(II)的最低剩余浓度分别为0.83、0.76 mg·L-1。在优化MACTS的制备条件上采用CCD法更优于BBD法。     

有机改性蒙脱石负载巯基修复汞污染土壤

以蒙脱石作为原始材料,对其进行有机改性,将巯基基团负载在有机改性的蒙脱石上制备出重金属汞的稳定剂以稳定化修复汞污染土壤。考察稳定化时间、稳定剂添加量、浸出液pH及有机质含量对稳定化效果的影响,探究稳定化前后土壤汞形态变化。通过XRD、FTIR和SEM分析了蒙脱石、有机改性蒙脱石(Mont-OR)和负载巯基有机改性蒙脱石(Mont-OR-SH)的物理化学特征,通过原子吸收法测定汞浓度。稳定化修复结果表明,稳定化时间为30 d,稳定剂添加量为9%时,汞浸出浓度为0.066 mg·L~(-1),稳定率为98.3%,达到GB 5085.3-2007规定的汞限值0.10 mg·L~(-1)。添加不同质量的小麦秸秆作为有机质的来源,均对整个稳定化有促进作用,其中添加量为6%时,促进作用最明显,改变浸出液pH,在强酸性和强碱性条件下,利用此稳定剂对汞的稳定作用降低。TESSIER五步提取法结果表明,负载巯基的有机改性蒙脱石的添加导致可交换态汞、碳酸盐结合态汞、铁锰氧化物结合态汞含量下降,而有机结合态汞、残渣态汞含量增加。实验结果证明有机改性蒙脱石负载巯基能够有效地应用于汞污染土壤修复。     

壳聚糖接枝共聚物的合成及应用研究

在N2保护下,以浓度为0.8 mmol/L硝酸铈铵为引发剂,控制壳聚糖(CTS)和丙烯酰胺(AM)质量比为mCTS∶mAM=1∶6,于50℃下接枝共聚反应3 h,得改性的壳聚糖衍生物(CAM).用IR对产物进行表征.通过对废水的处理,研究了共聚产物在絮凝、COD去除、脱色上的应用.结果表明:CAM的絮凝效果好于聚丙烯酰胺和壳聚糖,CAM对COD的去除率达到84.7%,并有较好的脱色效果.     

交联壳聚糖对铀的吸附研究

以壳聚糖(CTS)为原料,在碱性条件下用环氧氯丙烷对壳聚糖进行化学改性,制得不溶水的交联壳聚糖(CCTS)。利用CCTS吸附铀(UO22+),探讨吸附动力学规律以及初始浓度,pH值的影响。实验结果表明,CCTS对UO22+的吸附符合Langmu ir吸附等温模型,并能用准二级速率方程对吸附动力学加以描述。当在CCTS为10 mg,pH为3,UO22+初始浓度为50μg/mL条件下,CCTS对UO22+的吸附去除率为98%以上。     

巯基酯化壳聚糖的合成及对Cd~(2+)的去除性能研究

采用化学方法,研究了以巯基甲壳质制备巯基酯化壳聚糖的最佳合成方案。研究表明,巯基甲壳质的脱乙酰条件(包括时间、温度、氢氧化钠浓度)影响其产物巯基酯化壳聚糖对重金属镉离子的吸附效果。当脱乙酰时间为2 h,温度为160℃,氢氧化钠浓度为20%时,20 mg的合成产物对30 mL Cd2+浓度为20 mg/L水样的去除率最高,达到85.46%,其对镉离子的吸附量达到28.5 mg/g。通过对产物进行红外分析发现,巯基甲壳质中出现脂基特征峰值,脱乙酰后脂基并没有消失,证明最后的产物为巯基酯化壳聚糖。     

新型高分子絮凝剂黄原酸化壳聚糖的制备及除铜性能

以壳聚糖(CTS)为原料,先用苯甲醛保护其C_2位上的氨基生成Schiff碱壳聚糖,再将二硫代羧基通过黄原酸化反应接枝到CTS C_6位羟基上,制备出一种新型高分子絮凝剂——黄原酸化CTS(XCTS)。采用单因素实验法考察了XCTS制备的影响因素及其制备条件,并探讨了水样中Cu~(2+)初始浓度、pH对XCTS除铜性能的影响。结果表明,当XCTS制备条件为CS_2用量2.0mL、NaOH浓度5.0%(质量分数)、预反应温度30℃、预反应时间30min、主反应温度60℃、主反应时间240min时,制得的XCTS除铜性能最好,Cu~(2+)的最高去除率可达97.7%。XCTS最佳投药量随着水样中Cu~(2+)初始质量浓度的增加而增加;Cu~(2+)的去除率随着水样pH(pH不为7.0时)升高而先增大后减小,水样pH为6.0时,Cu~(2+)去除效果最佳。     

络合-陶瓷膜耦合技术资源化处理模拟低浓度含铜废水

以聚丙烯酸(PAA)和壳聚糖(CTS)作为络合剂,耦合孔径200 nm的陶瓷膜处理模拟低浓度含铜废水,采用ICP-MS、TOC、SEM表征与Darcy膜污染模型对处理效果和膜污染情况进行表征;对比研究不同络合剂对Cu~(2+)截留效果与资源化回用效率的影响;并探讨对应的膜污染机理。结果表明:溶液pH通过影响聚合物络合活性位点对Cu~(2+)截留率起决定性作用;在pH=6、P/M≥5或C/M=10的优化条件下,Cu~(2+)截留率接近100%;PAA相对于CTS对Cu~(2+)的络合效率更高,而CTS具备更好的抗杂质离子干扰能力;酸解、循环回用的PAA与CTS对Cu~(2+)截留率稳定在99%以上。膜污染阻力分布计算和SEM、EDX微观表征表明,滤饼污染为膜污染主要形式,CTS更易造成不可逆的膜孔堵塞污染。     

巯基酯化壳聚糖的合成及对 Cd2 +的去除性能研究简

采用化学方法，研究了以巯基甲壳质制备巯基酯化壳聚糖的最佳合成方案。研究表明，巯基甲壳质的脱乙酰条件（包括时间、温度、氢氧化钠浓度）影响其产物巯基酯化壳聚糖对重金属镉离子的吸附效果。当脱乙酰时间为2 h，温度为160℃，氢氧化钠浓度为20%时，20 mg的合成产物对30 mL Cd²⁺浓度为20 mg/L水样的去除率最高，达到85.46%，其对镉离子的吸附量达到28.5 mg/g。通过对产物进行红外分析发现，巯基甲壳质中出现脂基特征峰值，脱乙酰后脂基并没有消失，证明最后的产物为巯基酯化壳聚糖。     

TS-1分子筛催化O_3/H_2O_2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系（O3/H2O2/TS-1）对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸（初始浓度为100 mg/L）的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

TS-1分子筛催化O3/H2O2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系(O3/H2O2/TS-1)对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸(初始浓度为100 mg/L)的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

The long-term effect of initial pH control on the enrichment culture of phosphorus- and glycogen-accumulating organisms with a mixture of propionic and acetic acids as carbon sources

In most studies on phosphorus- and glycogen-accumulating organisms (PAO and GAO), pH was controlled constantly throughout the entire anaerobic and aerobic periods, and acetic acid was used as the carbon source. In this paper, the effect of long-term initial pH values on PAO and GAO was investigated with mixed propionic and acetic acids as carbon sources. It was observed that with pH increasing from 6.4 to 8.0, the anaerobic propionic acid uptake rate by PAO linearly increased but that by GAO proportionally decreased. At pH 6.70 and pH 7.51, PAO and GAO exhibited the same acetic and propionic acid uptake rates, respectively. The acetic acid uptake rate by PAO was greater than that by GAO at pH > 6.70, and the propionic acid uptake rate by PAO was higher than that by GAO at pH > 7.51, which indicated that PAO would take predominance over GAO at pH > 7.51. Poly-3-hydroxybutyrate, poly-3-hydroxyvalerate and poly-3-hydroxy-2-methylvalerate shared 7%, 62% and 31%, respectively in the PAO system, and 11%, 44% and 45% respectively in the GAO system, and these fractions were observed independent of pH either in the PAO or in the GAO system. In the PAO system, with the increase of pH, the phosphorus removal efficiency was improved greatly, and a phosphorus removal efficiency of 100% was achieved at 8.0. Further investigation showed that the higher phosphorus removal efficiency at higher pH was mainly caused by a biological effect instead of chemical one.     

Electrokinetic remediation of a Cu contaminated red soil by conditioning catholyte pH with different enhancing chemical reagents

The effect of enhancement reagents on the efficiency of electrokinetic remediation of Cu contaminated red soil is evaluated. The enhancement agents were a mix of organic acids, including lactic acid+NaOH, HAc-NaAc and HAc-NaAc+EDTA. The soil was prepared to an initial Cu concentration of 438 mgkg(-1) by incubating the soil with CuSO4 solution in a flooded condition for 1 month. Sequential extraction showed that Cu was partitioned in the soil as follows: 195 mgkg(-1) as water soluble and exchangeable, 71 mgkg(-1) as carbonate bound and 105 mgkg(-1) as Fe and Mn oxides. The results indicate that neutralizing the catholyte pH maintains a lower soil pH compared to that without electrokinetic treatment. The electric currents varied depending upon the conditioning solutions and increased with an increasing applied voltage potential. The electroosmotic flow rate changed significantly when different conditioning enhancing reagents were used. It was observed that lactic acid+NaOH treatments resulted in higher soil electric conductivities than HAc-NaAc and HAc-NaAc+EDTA treatments. Ultimately, enhancement by lactic acid+NaOH resulted in highest removal efficiency (81% Cu removal) from the red soil. The presence of EDTA did not enhance Cu removal efficiencies from the red soil, because EDTA complexed with Cu to form negatively charge complexes, which slowly migrated toward the anode chamber retarding Cu2+ transport towards the cathode.     

Acid washing and stabilization of an artificial arsenic-contaminated soil.

An acid-washing process was studied on a laboratory scale to extract the bulk of arsenic(V) from a highly contaminated Kuroboku soil (Andosol) so as to minimize the risk of arsenic to human health and the environment. The sorption and desorption behavior of arsenic in the soil suggested the possibility of arsenic leaching under acidic conditions. Artificially contaminated Kuroboku soil (2830 mg As/kg soil) was washed with different concentrations of hydrogen fluoride, phosphoric acid, sulfuric acid, hydrogen chloride, nitric acid, perchloric acid, hydrogen bromide, acetic acid, hydrogen peroxide, 3:1 hydrogen chloride-nitric acid, or 2:1 nitric acid-perchloric acid. Phosphoric acid proved to be most promising as an extractant, attaining 99.9% arsenic extraction at 9.4% acid concentration in 6 h. Sulfuric acid also attained high percentage extraction. The arsenic extraction by these acids reached equilibrium within 2 h. Elovich-type equation best described most of the kinetic data for dissolution of soil components as well as for extraction of arsenic. Dissolution of the soil components could be minimized by ceasing acid washing in 2 h. The acid-washed soil was further stabilized by the addition of lanthanum, cerium, and iron(III) salts or their oxides or hydroxides which form insoluble complex with arsenic. Both salts and oxides of lanthanum and cerium were effective in immobilizing arsenic in the soil attaining less than 0.01 mg/l As in the leaching test.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

柠檬酸浸出土壤中铜、锌的优化设计

以某工业废弃地土壤为供试材料,采用批次实验方法,研究了柠檬酸对重金属Cu、Zn的浸出效果。并在单因素实验基础上,探讨不同pH值、柠檬酸浓度、固液比和浸提时间等对浸出效果的影响,进而对实验条件进行正交优化组合,确定优化工艺参数为：pH值为3.2,柠檬酸浓度为0.4 mol/L,壤土固液比为1/10,土壤中Cu、Zn接近平衡的时间分别为1 h和1.5 h。结果表明,在此条件下,对这2种金属来说,Cu较Zn易释放,Cu、Zn的最大浸出率分别为74.8%和65.3%。柠檬酸浸提前后,土壤中有机质含量下降范围为0.61%~3.16%。单从土壤有机质含量来看,柠檬酸对土壤质量影响较小,具有较好的应用前景。     

Effects of remediation train sequence on decontamination of heavy metal-contaminated soil containing mercury

When a contaminated site contains pollutants including both nonvolatile metals and Hg, one single remediation technology may not satisfactorily remove all contaminants. Therefore, in this study, chemical extraction and thermal treatment were combined as a remediation train to remove heavy metals, including Hg, from contaminated soil. A 0.2 M solution of ethylenediamine tetraacetic acid (EDTA) was shown to be the most effective reagent for extraction of considerable amounts of Cu, Pb, and Zn (>50%). Hg removal was ineffective using 0.2 M EDTA, but thermogravimetric analysis suggested that heating to 550°C with a heating rate of 5°C/min for a duration of 1 hr appeared to be an effective approach for Hg removal. With the employment of thermal treatment, up to 99% of Hg could be removed. However, executing thermal treatment prior to chemical extraction reduced the effectiveness of the subsequent EDTA extraction because nonvolatile heavy metals were immobilized in soil aggregates after the 550°C treatment. The remediation train of chemical extraction followed by thermal treatment appears to remediate soils that have been contaminated by many nonvolatile heavy metals and Hg.

ImplicationsA remediation train conjoining two or more techniques has been initialized to remove multiple metals. Better understandings of the impacts of treatment sequences, namely, which technique should be employed first on the soil properties and the decontamination efficiency, are in high demand. This study provides a strategy to remove multiple heavy metals including Hg from a contaminated soil. The interactions between thermal treatment and chemical extraction on repartitioning of heavy metals was revealed. The obtained results could offer an integrating strategy to remediate the soil contaminated with both heavy metals and volatile contaminants.     

The long-term effect of initial pH control on the enrichment culture of phosphorus- and glycogen-accumulating organisms with a mixture of propionic and acetic acids as carbon sources

In most studies on phosphorus- and glycogen-accumulating organisms (PAO and GAO), pH was controlled constantly throughout the entire anaerobic and aerobic periods, and acetic acid was used as the carbon source. In this paper, the effect of long-term initial pH values on PAO and GAO was investigated with mixed propionic and acetic acids as carbon sources. It was observed that with pH increasing from 6.4 to 8.0, the anaerobic propionic acid uptake rate by PAO linearly increased but that by GAO proportionally decreased. At pH 6.70 and pH 7.51, PAO and GAO exhibited the same acetic and propionic acid uptake rates, respectively. The acetic acid uptake rate by PAO was greater than that by GAO at pH > 6.70, and the propionic acid uptake rate by PAO was higher than that by GAO at pH > 7.51, which indicated that PAO would take predominance over GAO at pH > 7.51. Poly-3-hydroxybutyrate, poly-3-hydroxyvalerate and poly-3-hydroxy-2-methylvalerate shared 7%, 62% and 31%, respectively in the PAO system, and 11%, 44% and 45% respectively in the GAO system, and these fractions were observed independent of pH either in the PAO or in the GAO system. In the PAO system, with the increase of pH, the phosphorus removal efficiency was improved greatly, and a phosphorus removal efficiency of 100% was achieved at 8.0. Further investigation showed that the higher phosphorus removal efficiency at higher pH was mainly caused by a biological effect instead of chemical one.     

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.