热化学清洗法洗涤油泥-回收石油的工艺条件研究

以辽河油田落地油泥为样品,采用热化学清洗法洗涤油泥,净化土壤,回收石油,并获取工程所需的必要参数.通过筛选、复配,确定十二烷基苯磺酸钠(LAS):NazSiO3=1:2(质量比)为最佳清洗剂配比.考察了清洗温度、清洗液pH、液固比(即清洗剂与落地油泥的质量比)和清洗剂投加量等因素对清洗效率的影响,通过正交实验优化工艺参数,实验表明,当清洗时间为30min、清洗温度为75℃、搅拌器转速为200 r/min、液固比为8:1、清洗液pH为11、LAS Na2SiO3投加量为2.8 g/L时,含油率为21.2%(质量分数)的落地油泥样品经一级清洗,油泥残油率降为0.8%(质量分数,下同);经二级清洗,油泥残油率降为0.3%.清洗后,石油浮于水面,无明显乳化,易于分离.     

Remediation of arsenic-contaminated soils and washing effluents

Laboratory experiments were conducted to determine the distribution of various arsenic species in tailings and soils. Other specific goal of the tests were to evaluate the extraction efficiency of arsenic using alkaline or acid washing, to determine optimum operational parameters of alkaline washing, and to evaluate the arsenic precipitation of washing effluents by pH adjustment or ferric chloride addition. Alkaline washing using sodium hydroxide was found to be favorable in removing arsenic from tailings or soils having a higher portion of arsenic in the operationally defined crystalline mineral fraction of crystalline oxide and amorphous aluminosilicates. This is due to the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic because predominant negatively charged crystalline oxides do not attract the negatively charged oxyanions. For tailings, sodium hydroxide had 10-20 times higher extraction efficiencies than hydrochloric- or citric acid. The optimum concentration of sodium hydroxide for soil washing was determined to be 200 mM for all samples, while the optimum ratios were 10:1 and 5:1 for tailings and field/river sedimentary soils, respectively. The washing effluent of river soil was effectively treated by adjusting pH to 5-6 with hydrochloric acid, resulting in arsenic concentrations of <50 microgl(-1). In the case of field soil effluent, an addition of ferric chloride with a minimum mass ratio of 11 (Fe/As) was needed to reduce the arsenic below 50 microgl(-1).     

Remediation of cadmium-contaminated paddy soils by washing with calcium chloride: verification of on-site washing

We developed a new, three-step soil-wash method to remediate Cd-contaminated paddy fields. The method comprises (1) chemically washing the field soil with a CaCl2 solution; (2) washing the treated soil with water to eliminate residual Cd and CaCl2; and (3) on-site treatment of wastewater using a portable wastewater treatment system. Cd concentrations in the treated water were below Japan's environmental quality standard (0.01 mg Cd L-1), and the removal of Cd from the exchangeable fraction was 55% and from the acid-soluble fraction 15%. While soil fertility properties were affected by the soil washing, adverse effects were not crucial and could be corrected. The washing had no affect on rice growth, and reduced the average Cd concentration in rice grains by about two-thirds compared to a control plot. These results confirmed the effectiveness of the soil-wash method in remediating Cd-contaminated paddy fields.     

Remediation of cadmium contamination in paddy soils by washing with chemicals: selection of washing chemicals

The efficiencies of neutral salts, strong acids, and chelates were tested for extracting cadmium (Cd) from three paddy soils. The higher the selectivity of the cations of the added neutral salts toward soil adsorption sites, the lower the pH in the extracts and the more soil Cd could be extracted. In addition, soil carbon and nitrogen contents and mineral composition were closely associated with the amount of Cd extracted. Calcium chloride and iron(III) chloride were selected as wash chemicals to restore Cd-contaminated paddy soils in situ. Washing with calcium chloride led to the formation of Cd chloride complexes, enhancing Cd extraction from the soils. The washing also substantially decreased soil levels of exchangeable and acid-soluble Cd, which are the major forms of bioavailable Cd for rice (Oryza sativa L.). The optimum conditions for in situ soil washing were also determined for calcium chloride.     

老化石油污染土壤的清洗处理

以华北油田老化长达1年以上的石油污染土壤为研究对象,采用自行选配的清洗剂对该污染土壤进行了一次清洗和二次清洗处理.实验结果表明,一次清洗后,污染土壤样品的含油率从26.34%～29.90%降到6.34%～7.84%,洗油率达80.06%～81.06%;经二次清洗处理后,污染土壤样品的含油率从26.34%～29.90%降到4.05%～4.85%,洗油率达88.06%～88.19%.在一次清洗和二次清洗的基础上,通过模拟实验确定了洗油污水回用的最佳回用率为80%,最佳加药质量浓度为0.4 g/L,该条件下污水的最终产生量也较少.按照该参数对华北油田的石油污染土壤进行了清洗实验,洗油率达79.20%～80.51%.     

Remediation of cadmium-contaminated paddy soils by washing with chemicals: effect of soil washing on cadmium uptake by soybean

We conducted a pot experiment to evaluate the effect of soil washing with CaCl(2) on Cd absorption by two soybean cultivars. The results were as follows: (1) Soybean growth was not significantly different in washed and unwashed soils, but the seed Cd concentration for both cultivars decreased significantly, up to 25%, in the washed soils compared with the unwashed soils. (2) In the washed soils, the Cd concentration in the soil solution indicated an obviously lower value from sowing to the flowering stage; however, the change in Cd speciation was not evident in the CaCl(2)-washed soil solution. Consequently, the effect of soil washing using CaCl(2) on Cd-contaminated paddy soils can be expected to continue after a CaCl(2)-washed paddy field is converted to an upland field.     

表面活性剂清洗处理重度石油污染土壤

为了优化表面活性剂清洗处理重度石油污染土壤的方法和具体洗脱条件参数，采集山东省东营市胜利油田污染土壤，研究了阴离子-非离子混合表面活性剂对该土壤中石油类污染物的去除效果。应用化学热洗原理，主要考查了表面活性剂配比、投加量、清洗温度及清洗助剂对去除效果的影响。实验得到的清洗处理最佳条件为：使用LAS与TX-100质量比为8∶2的组合表面活性剂，总表面活性剂浓度为3 g/L，助剂硅酸钠浓度为5 g/L，75℃条件下搅拌1 h。清洗后土壤含油量从20%下降到4.6%，去除率达到76.9%。废水回用实验表明，清洗处理的废水对土壤中石油烃类物质仍有一定的去除效果。废水回用比从30%到100%时，对土壤中石油烃的去除率都可达到55%以上。对废水进行二次回用时仍能去除18.8%的污染物。     

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.     

Chelator induced phytoextraction and in situ soil washing of Cu

In a soil column experiment, we investigated the effect of 5 mmol kg(-1) soil addition of citric acid, ethylenediamine tetraacetate (EDTA), diethylenetriamine-pentaacetate (DTPA) and [S,S]-stereoisomer of ethylenediamine-disuccinate (EDDS) on phytoextraction of Cu from a vineyard soil with 162.6 mg kg(-1) Cu, into the test plant Brassica rapa var. pekinensis. We also examined the use of a horizontal permeable barrier, composed of layers of nutrient enriched sawdust and apatite, for reduction of chelator induced Cu leaching. The addition of all chelators, except citric acid, enhanced Cu mobility and caused leaching of 19.5-23% of initial total Cu from the soil column. However, Cu plant uptake did not increase accordingly; the most effective was the EDDS treatment, in which plant Cu concentration reached 37.8 +/-1.3 mg kg(-1) Cu and increased by 3.3-times over the control treatment. The addition of none of the chelators in the concentration range from 5 to 15 mmol kg(-1) exerted any toxic effect on respiratory soil microorganisms. When EDDS was applied into the columns with horizontal permeable barriers, only 0.53 +/- 0.32% of the initial total Cu was leached. Cu (36.7%) was washed from the 18 cm soil layer above the barrier and accumulated in the barrier. Our results indicate that rather than for a reduction of Cu leaching during rather ineffective chelate induced Cu phytoextraction, horizontal permeable barriers could be more effective in a new remediation technique of controlled in situ soil washing of Cu with biodegradable chelates.     

污染土壤的淋洗法修复研究进展

污染土壤淋洗技术是修复污染土壤的一种新方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法主要使用淋洗剂清洗土壤 ,使土壤中污染物随淋洗剂流出 ,然后对淋洗剂及土壤进行后续处理 ,从而达到修复污染土壤的目的。因为淋洗剂的种类和淋洗方式的不同 ,土壤淋洗法可分为许多种类。土壤淋洗法主要受土壤条件、污染物类型、淋洗剂的种类和运行方式等因素影响。综合考虑多方面因素 ,就有潜力设计出经济高效的土壤淋洗系统。土壤淋洗法有很多优点 ,尽管也存在一些问题 ,但其技术上的优势也是其他方法难以取代的 ,所以有良好的应用前景。     

洗车废水处理技术现状与展望

洗车废水中含有泥砂、油乳化液、有机物及洗涤剂类污染物质。在分析中 ,对洗车废水的水质进行了分类 ,并针对不同的水质 ,对国内的大型洗车场的处理工艺和小型洗车行的洗车废水回用工艺进行了介绍和分析 ,对国外采用膜工艺处理洗车废水的相关研究也进行了简要的介绍 ,同时提出了洗车废水的污泥处理问题。从社会、经济效益来看 ,洗车废水回用是必然趋势。现行的洗车废水回用处理工艺回用率低、处理效果不理想 ,采用高效、简单、实用、经济的原则进行设计 ,满足社会对洗车水回用的需求是未来洗车废水处理技术发展的要求     

膜生物反应器中膜的清洗方法和机理研究

研究了膜生物反应器处理盥洗废水时 ,水力清洗、酸洗、碱洗等不同组合形式对膜的清洗效果。结果表明 ,水力清洗可以较彻底地去除运行初期的膜表面沉积物 ,使膜通量有较大程度的恢复。对运行时间较长的膜来说 ,有机物和微生物是造成膜污染的主要原因。清水冲洗后用 0 0 5 %NaClO浸泡 1h ,再用 0 5 %的H2 SO4浸泡 1h是盥洗废水处理用膜有效的清洗方法 ,清水膜通量可恢复至 1 0 0 %。     

Evaluation of biosurfactants for crude oil contaminated soil washing

An evaluation of the ability of aqueous biosurfactant solutions (aescin, lecithin, rhamnolipid, saponin and tannin) for possible applications in washing crude oil contaminated soil was carried out. The biosurfactants behaviour in soil-water, water-oil and oil-soil systems (such as foaming, solubilization, sorption to soil, emulsification, surface and interfacial tension) was measured and compared with a well-known chemical surfactant (sodium dodecyl sulphate, SDS) at varying concentrations. Results showed that the biosurfactants were able to remove significant amount of crude oil from the contaminated soil at different solution concentrations for instance rhamnolipid and SDS removed up to 80% oil and lecithin about 42%. The performance of water alone in crude oil removal was equally as good as those of the other biosurfactants. Oil removal was due to mobilization, caused by the reduction of surface and interfacial tensions. Solubilization and emulsification effects in oil removal were negligible due to the low crude oil solubilization of 0.11%. Therefore, these studies suggest that knowledge of surfactants' behaviour across different systems is paramount before their use in the practical application of oil removal.     

木质素盐在原油污染土壤清洗中的应用

木质素磺酸盐价格低廉,容易获得,若将其作为洗油剂中的牺牲剂,可较大幅度地降低洗油成本.以华北油田原油、华北平原典型表层土壤为模拟原料,配制了石油污染土壤,探讨木质素磺酸铵和木质素磺酸钠的洗油性能,以及木质素磺酸盐与壬基酚聚氧乙烯醚、曲拉通和平平加的复配效果.实验以碳酸钠和硅酸钠为助剂,经反复实验筛选,确定了4组最佳洗油剂配方:(Ⅰ)6(曲拉通):6(平平加):8(木素钠):40(硅酸钠):40(碳酸钠);(Ⅱ)6(曲拉通):6(壬酚聚醚):8(木素钠):35(硅酸钠):45(碳酸钠);(Ⅲ)9(曲拉通):3(壬酚聚醚):8(木素钠):50(硅酸钠):30(碳酸钠);(Ⅳ)6(曲拉通):6(壬酚聚醚):3(木素铵):5(木素钠):35(硅酸钠):45(碳酸钠).以此配方为基础,利用正交实验设计对搅拌温度、时间、固液比和加药浓度等工艺条件进行了优化.结果表明:当搅拌温度75℃、搅拌时间50 min、固液比1:15、加药总浓度为0.3g/L时,洗油率可达92.25%.清洗后污油无明显乳化现象,且浮于液面,只须简单刮油即可回收.     

Decontamination of electronic waste-polluted soil by ultrasound-assisted soil washing

Laboratorial scale experiments were performed to evaluate the efficacy of a washing process using the combination of methyl-β-cyclodextrin (MCD) and tea saponin (TS) for simultaneous desorption of hydrophobic organic contaminants (HOCs) and heavy metals from an electronic waste (e-waste) site. Ultrasonically aided mixing of the field contaminated soil with a combination of MCD and TS solutions simultaneously mobilizes most of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and the analyte metal (Pb, Cu, and Ni) burdens. It is found that 15 g/L MCD and 10 g/L TS is an efficient reagent combination reconciling extraction performance and reagent costs. Under these conditions, the removal efficiencies of HOCs and heavy metals are 93.5 and 91.2 %, respectively, after 2 cycles of 60-min ultrasound-assisted washing cycles. By contrast, 86.3 % of HOCs and 88.4 % of metals are removed from the soil in the absence of ultrasound after 3 cycles of 120-min washing. The ultrasound-assisted soil washing could generate high removal efficiency and decrease the operating time significantly. Finally, the feasibility of regenerating and reusing the spent washing solution in extracting pollutants from the soil is also demonstrated. By application of this integrated technology, it is possible to recycle the washing solution for a purpose to reduce the consumption of surfactant solutions. Collectively, it has provided an effective and economic treatment of e-waste-polluted soil.

     

木质素盐在原油污染土壤清洗中的应用

木质素磺酸盐价格低廉,容易获得,若将其作为洗油剂中的牺牲剂,可较大幅度地降低洗油成本.以华北油田原油、华北平原典型表层土壤为模拟原料,配制了石油污染土壤,探讨木质素磺酸铵和木质素磺酸钠的洗油性能,以及木质素磺酸盐与壬基酚聚氧乙烯醚、曲拉通和平平加的复配效果.实验以碳酸钠和硅酸钠为助剂,经反复实验筛选,确定了4组最佳洗油剂配方：（Ⅰ）6（曲拉通）：6（平平加）：8（木素钠）：40（硅酸钠）：40（碳酸钠）;（Ⅱ）6（曲拉通）：6（壬酚聚醚）：8（木素钠）：35（硅酸钠）：45（碳酸钠）;（Ⅲ）9（曲拉通）：3（壬酚聚醚）：8（木素钠）：50（硅酸钠）：30（碳酸钠）;（Ⅳ）6（曲拉通）：6（壬酚聚醚）：3（木素铵）：5（木素钠）：35（硅酸钠）：45（碳酸钠）.以此配方为基础,利用正交实验设计对搅拌温度、时间、固液比和加药浓度等工艺条件进行了优化.结果表明：当搅拌温度75℃、搅拌时间50 min、固液比1：15、加药总浓度为0.3g/L时,洗油率可达92.25%.清洗后污油无明显乳化现象,且浮于液面,只须简单刮油即可回收.     

Scavenging of BHCs and DDTs from soil by thermal desorption and solvent washing

Intensive remediation of abandoned former organochlorine pesticides (OCPs) manufacturing areas is necessary because the central and surrounding soils contaminated by OCPs are harmful to crop production and food safety. Organochlorine and its residues are persistent in environments and difficult to remove from contaminated soils due to their low solubility and higher sorption to the soils. We performed a comprehensive study on the remediation of OCPs-contaminated soils using thermal desorption technique and solvent washing approaches. The tested soil was thermally treated at 225, 325, 400, and 500 °C for 10, 20, 30, 45, 60, and 90 min, respectively. In addition, we tested soil washing with several organic solvents including n-alcohols and surfactants. The optimal ratio of soil/solvent was tested, and the recycling of used ethanol was investigated. Finally, activities of polyphenol oxidase (PPO), urease (URE), alkaline phosphatase, acid phosphatase (ACP), and invertase (INV) were assayed in the treated soils. The tested soil was thermally treated at 500 °C for 30 min, and the concentration of contaminants in soil was decreased from 3,115.77 to 0.33 mg kg^?1. The thermal desorption in soil was governed by the first-order kinetics model. For the chemical washing experiment, ethanol showed a higher efficiency than any other solvent. Using a 1:20 ratio of soil/solvent, the maximum removal of OCPs was achieved within 15 min. Under this condition, approximately 87 % of OCPs was removed from the soils. More than 90 % of ethanol in the spent wash fluid could be recovered. Activities of some enzymes in soils were increased after ethanol treatment. But ALP, ACP, and INV activities were decreased and PPO and URE showed slightly higher activities following remediation by thermal treatment. Both heating temperature and time were the key factors for thermal desorption of OCPs. The n-alcohol solvent showed higher removal of OCPs from soils than surfactants. The highly efficient removal of OCPs from soil was achieved using ethanol. More than 90 % of ethanol could be recovered and be reused following distillation. This study provides a cost-effective and highly efficient way to remediate the OCPs-contaminated soils.     

Removal of Pb and MDF from contaminated soils by EDTA- and SDS-enhanced washing

Heavy metal- and organic-contaminated sites are ubiquitous, but few studies have been conducted to address such an issue. EDTA- and SDS-enhanced washing was studied for remediation of Pb- and/or marine diesel fuel (MDF)-contaminated soils. The feasibility of recovery and reuse of EDTA and SDS, as well as the physicochemical interactions among the chemical agents, contaminants and soils were extensively investigated using batch experiments. The optimal washing sequence was then determined. The experimental results showed that EDTA could be recovered and reused for four cycles without significant loss of its chelating capacity, while the extraction capability of SDS was noticeably reduced after each reuse cycle. The free phase of marine diesel fuel (MDF) in soils physically isolated the sorbed Pb on soils and thus reducing its extraction by EDTA. The presence of SDS alone or together with low concentration of EDTA was found to enhance Pb removal probably via electrostatic interaction and dissolution of soil organic matter. However, it hindered Pb extraction by high concentration of EDTA, because of the potential formation of complexes between some strongly-bound Pb and SDS, that are more resistant to desorption. Therefore, EDTA washing followed by SDS achieved the highest Pb removal efficiency. On the other hand, MDF removal by SDS was significantly hindered by coexisting Pb in soils, probably because the formation of Pb-dodecyl sulfate (DS) complex would decrease the effective amount of SDS available for forming micelles in solution and enhance MDF sorption. EDTA alone or together with SDS could enhance MDF removal, but the residual MDF after EDTA-washing became more resistant to SDS removal. Consequently, SDS washing followed by EDTA is considered as the optimal washing sequence for MDF removal.     

Removal of alkylphenols from polluted sites using surfactant-assisted soil washing and photocatalysis

Background and purpose  

Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4–tert-butylphenol in the presence of nonionic (C₁₂E₈ and C₁₂E₂₃) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO₂ dispersions irradiated with simulated solar light.     

Effects of walnut husk washing waters and their phenolic constituents on horticultural species

INTRODUCTION: The reuse of wastewaters for agricultural purposes is a common practice in many countries and is increasingly recommended by organizations that promote sustainable development. Yet, it is restricted by the potential negative impact of these materials on soil and crops. The aim of this study was therefore to evaluate the environmental impact of walnut husk washing waters (WHWW) and their organic fractions, in order to conceive their agricultural exploitation. DISCUSSION: Phytotoxicity tests and morphological investigations on representative plant species of horticultural interest indicated that WHWW and their organic fractions can elicit a concentration-dependent stimulating effect on the growth of radish, lettuce cv. cavolo Napoli with effects up to 165 %. An opposite inhibitory effect up to 70 % was observed on spinach and lettuce cv. Gentilina. Proapoptotic effects were observed by acridine orange/ethidium bromide assay in the species inhibited by WHWW treatment. High-performance liquid chromatography-mass spectrometry analysis of the WHWW revealed the presence of a main component which was extracted selectively in organic solvents and purified by preparative chromatography. Complete spectral analysis allowed identification as 4,8-dihydroxy-1-tetralone, commonly known as regiolone. Regiolone exhibited the same concentration-dependent activity on root elongation with a stimulation in the case of radish up to 135 % with respect to control. These results open perspectives in the exploitation of WHWW and the main phenolic constituent readily available by a straightforward isolation procedure as a natural fertilizer for specific crops.