热化学清洗与溶剂萃取法处理页岩油泥

对吉林桦甸页岩油泥采用热化学清洗、溶剂萃取、热化学清洗-溶剂萃取组合3种方法进行处理,回收页岩油。萃取液浓缩后进行气相色谱-质谱分析(GC-MS),油泥进行电镜扫描(SEM)。结果表明,热化学清洗获得最佳工况为搅拌频率250 r/min、清洗温度80℃、液固比为8∶1、清洗时间30 min、浓度6 g/L,在此工况下Na2Si O3和SDS(十二烷基硫酸钠)可使油泥残油率降为26%和27.6%。二甲苯萃取脱油效果优于热化学清洗。组合处理阶段,Na2Si O3清洗对后续萃取起促进作用,可获得96.3%的脱油率,而SDS清洗对后续萃取起抑制作用,仅获得42.7%的脱油率。SEM分析知经Na2Si O3清洗后油泥呈分散结构,增大了后续萃取油泥与溶剂接触面积。GC-MS分析知,Na2Si O3清洗对于后续二甲苯萃取轻质烃、重质烃溶出行为均起促进作用,而SDS清洗对后续二甲苯萃取轻质烃溶出行为起抑制作用。Na2Si O3清洗-二甲苯萃取是一种很好的油回收方法,具有经济价值,同时可减少石油烃对环境污染。     

不同类型清洗剂对含聚油泥清洗效果及界面性质的影响

为解决聚驱采出液中产生的大量含聚油泥造成石油资源浪费和环境污染问题,选用化学清洗法对含聚油泥进行处理。不同类型化学清洗剂对含聚油泥清洗效果的规律是:无机型和非离子型清洗剂对含聚油泥清洗效果最好,阴离子型清洗剂次之,阳离子型清洗剂最差。优化了无机清洗剂Na2SiO3和非离子型清洗剂EL100的脱油条件,脱油率分别达到91.12%和85.59%。不同类型清洗剂清洗含聚油泥的脱油率与油水界面性质具有明显的关联性,即脱油率越高,水相电导率越小,油滴Zeta电位绝对值越小,油滴中值粒径越大,油水界面张力越小。     

含油污泥热化学清洗剂的研制与清洗效果实验分析

含油污泥是严重影响油田生产环境的一大危险废物,不仅含有大量原油资源,且处理难度大。本文针对吉林油田含油污泥,筛选几种有利于油、水和泥分离的药剂进行复配,通过正交实验确定OP-10(D)∶SDS(B)∶PAC(G)=2∶3∶3的最佳清洗剂配比,运用热化学清洗法从含油污泥中回收原油。利用单因素实验法分别考察了热洗温度、液固比、搅拌强度、搅拌时间、热洗次数及pH值单一因素对样品含油污泥清洗效果的影响。实验结果表明,最佳工艺条件为:选取热洗温度80℃,液固比为4∶1,药剂量为1%,搅拌强度为120 r·min-1,搅拌时间为30 min,pH为8,热洗后的清洗废液经处理调整至初次清洗浓度可循环利用。在最佳工况下,将含油率为51.13%的污泥样品洗至脱油率为96.75%,较好的回收了污泥中的原油,达到了保护环境的目的,具有经济价值。     

含油污泥化学清洗处理实验研究与工艺参数优化

以大庆采油一厂的含油污泥为研究对象,采用化学清洗方法,以处理后底泥残油率为评价指标,优化影响含油污泥清洗效率的参数。根据单因素实验,确定清洗温度、化学药剂浓度、液固比的取值范围;采用Design-Expert响应曲面法,考察单独变量作用及交互作用对含油污泥残油率的影响。选择软件中二次多项式模型进行模拟可知,单因素变量、清洗温度与化学药剂浓度的交互项均对含油污泥残油浓度具有显著影响;模型优化结果显示,化学法处理含油污泥的最佳工艺条件为清洗温度78.68℃、化学药剂浓度0.84 g·L~(-1)、液固比9.40∶1,模型预测底泥残油率为3.85%,实验验证结果的平均值是3.96%,测定值与预测值之间相对误差为2.78%,证明该模型的可靠性。     

孤岛落地油泥制备改性沥青及其性能

以油田油泥与基质沥青为实验原材料,采用高速剪切方法制备油田油泥改性沥青,通过针入度、软化点、延度、运动黏度和离析软化点差等表征方法,研究孤岛落地油泥对沥青高低温性能、加工性能和储存稳定性的影响。结果表明:活性中间体与苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)添加量(质量分数)分别为15%与4%时,孤岛落地油泥改性沥青的针入度比基质沥青降低0.4 mm,软化点比基质沥青提高24℃,运动黏度为0.28 Pa·s,离析软化点差(165℃,48 h)为0.3℃,其各项指标均同时满足橡胶沥青评价指标要求和SBS沥青评价指标要求;加入适量的油泥可提高沥青的低温抗裂性能,改善加工性能,而对沥青储存稳定性无明显影响。     

含油污泥清洗剂的制备与研究

以异丙醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,甲基丙烯酸(MAA)、丙烯酸丁酯(BA)和苯乙烯(St)为混合单体,通过溶液聚合的方法制备一种含油污泥清洗剂.介绍了该清洗剂的制备方法,考察了单体用量及清洗条件对清洗剂脱油性能的影响,探讨了清洗剂对含油污泥中原油不同组分的去除效率,并用红外光谱证实了所制备共聚物结构的官能团.清洗剂性能评价表明:单体用量和清洗条件均有最佳值,其中单体最佳质量比为MAA:BA:St=21:62:17,最佳清洗条件分别是:加药浓度为250 mg/L,水洗温度为60℃,反应时间为40 min;清洗剂对含油污泥中芳烃去除率最高,达93.0%.     

用钛白废酸和副产锌泥制备活性氧化锌

以次硫酸氢钠甲醛副产锌泥和钛白废酸为原料,经高剪切乳化、酸浸、锌粉置换、除杂、碱锌合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备活性氧化锌。考察了浸取工艺液固比(硫酸与副产锌泥的质量比)和硫酸质量分数对锌浸出率的影响,以及煅烧温度和时间对活性氧化锌质量的影响。实验结果表明,锌泥酸浸工艺的最佳液固比4,硫酸质量分数30%,在此工艺条件下,锌浸出率达95%。活性氧化锌的最佳煅烧温度为600℃,煅烧时间为240 min,在此条件下测定产品质量,氧化锌质量分数大于96%,比表面积大于50 m2/g,堆积密度小于0.35 g/m L。     

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%.     

响应面法优化UV/H_2O_2光氧化法处理高浓度LAS废水

采用响应面法对UV/H2O2光氧化法处理高浓度LAS废水的工艺参数进行了系统研究。根据Box-Behnken Design(BBD)设计原理,以初始pH与H2O2投加量、反应时间和温度为主要影响因素,设计4因素3水平共29个实验点的实验方案,并建立了二次响应面拟合模型。方差分析表明,初始pH与H2O2投加量、反应时间和温度以及初始pH和H2O2投加量、H2O2投加量和温度之间的交互作用,对实验结果具有显著性影响。实验得到的光氧化高浓度LAS废水最佳工艺条件,pH为4.0,H2O2投加量为40 mmol/L,反应时间为90 min,温度为25℃,在此条件下,LAS的平均去除率为98.1%。     

炼厂"三泥"的生物处理研究

从大港油田筛选和分离出3株以原油为碳源的石油降解菌,初步鉴定为假单胞菌属(Pseudomonas sp.),用这3株菌混合处理某炼厂的"三泥",在适宜的降解条件下,仅需投加混合菌液,无需添加营养物(N,P),可使含油污泥A的残油量从67g/kg降至7.7g/kg,混合油泥试样AB的残油量从19.7g/kg降至3.1g/kg,平均去除率为84%以上,可以实现含油污泥的较为经济的、有效的处理.经生物处理后含油污泥的恶臭味完全消失.     

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.     

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。     

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 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.     

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.     

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。     

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.     

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.