絮凝-白土复合再生废润滑油.pdf

絮凝 - 白土复合再生废润滑油 ＊ 张贤明 焦昭杰 李 川 贾玉梅 张春媚 重庆工商大学废油资源化与技术装备教育部工程研究中心, 重庆 400067 摘要 结合国内外废润滑油再生技术的研究与现状, 提出以絮凝为主白土精制相结合的无污染、低成本的再生工艺技 术。在前期絮凝剂脱色再生试验的基础上, 重点考察白土精制的最佳再生参数, 结果表明, 在白土添加量 8～ 11、 白土接触反应温度130℃左右、搅拌时间 20 min、恒温沉降温度 80℃、沉淀 3 h 的条件下有最佳的再生效果 。 试验表 明, 在该复合再生条件下, 经过再生处理后的废油基本上达到了该级别新油的标准。 关键词 废润滑油 絮凝剂 活性白土 再生 ＊重庆市自然科学基金资助项目 CSTC,2006BB2251, 2006BB3248 。 0 引言 由于世界石油资源供需形势的紧张 ,对废润滑油 的回收再生利用已引起各国的广泛关注 。一般可供 回收的废润滑油量应为消费量的 40～ 45, 然而 目前的回收率非常低 ,每年回收再生利用的油品仅有 20～ 30 万 t , 其中一部分排入了环境而造成污染 [ 1] 。 废润滑油的再生根据其劣化程度有以物理方法为主 的再净化工艺和以化学方法为主的再精制工艺 [ 2] 。 如国内开发的各种系列的真空滤油机, 对于劣化程度 不是很深的废润滑油能得到很好地再生 [ 3] ,但对于劣 化严重的废润滑油并没有很好的效果 。为此本研究 通过大量的试验选取了一种效果比较好的絮凝剂 ,结 合白土精制开发出了一种成本低廉 、 操作简单的再生 工艺 。试验研究表明 ,该絮凝剂结合白土精制对磨合 机械油具有良好的再生效果, 通过试验废磨合机械油 基本上达到了再生。 1 试验 1. 1 试验原理 絮凝剂作用原理 该絮凝剂除具有一般絮凝剂的 作用外 ,关键是其特殊的氨基基团, 能够使废油中的 氧化物钝化 ,同时通过其吸附架桥、网捕作用把废油 中的积炭 、 颗粒 、 胶泥等缠绕包裹起来, 在外界提供的 动力情况下脱稳沉淀下来 [ 4] ; 白土精制作用原理 活 性白土的作用除了其强大的物理、化学吸附和一定的 脱色能力外还能进一步改善油品的性能 ,使油品的颜 色、 安定性和电气性能都有明显的提高 [ 2] 。 1. 2 试验材料 磨合机械油样 SC40; 具有氨基结构的絮凝剂 NH2CH2CH2NH CH2CH2NH2含量 99;CS-1060活性白土, 安徽芜湖飞尚矿业发展有限 公司生产。 1. 3 试验过程 量取 150 mL 的废油样于试管中, 置于一定温度 的恒温水浴或加热炉上。加入一定体积的絮凝剂 ,搅 拌适当时间后移入恒温烘箱中自然沉降一定的时间。 取经沉降后的油样 ,用石油醚稀释一定的倍数, 以石 油醚做参比在一定的波长下测定其透光率 透光率粗 略的反映油品再生效果 ,以获取絮凝处理的最佳参 数。取经絮凝处理后的油样, 在一定温度下加入适量 的活性白土,搅拌反应一定时间,恒温沉降一定时间后 经真空抽滤, 获得再生油。取经白土精制后的油样用 石油醚稀释一定的倍数,以石油醚做参比在一定的波 长下测定其透光率,以确定白土精制的参数 。白土精 制单因素试验步骤 白土添加量 10、接触反应温度 130℃,搅拌时间20 min 、 恒温沉降温度 80℃、沉淀 3 h , 讨论某单因素影响时其他因素不变,变动该因素。 2 结果与讨论 2. 1 波长的确定 不同油品的特征吸收峰不同,石油及其产品在紫 外光区有特征吸收 ,带有苯环的芳香族化合物, 主要 吸收波长为 250～ 260 nm ; 带有共轭双键的化合物主 要吸收波长为 215～ 230 nm 。一般原油的两个主要吸 收波长为 225 nm 和 254 nm 。石油产品中 ,如燃料油、 润滑油等的吸收峰与原油相近 。以石油醚做参比 ,测 得油样的最大吸收波长为 245 nm [ 5] 。 2. 2 絮凝剂对再生效果影响 通过大量的试验得出絮凝剂对废油再生的最佳 47 环 境 工 程 2008年 4 月第26 卷第2 期 参数 ,其试验数据如表 1 [ 4] 。 表 1 絮凝剂对废润滑油再生效果最佳参数 絮凝剂 添加量 搅拌时间 min 反应温度 ℃ 恒温沉降 温度 ℃ 沉淀时间 h 1. 2570～ 80802 2. 3 白土添加量对再生效果影响 白土主要是把絮凝处理后的杂质吸附沉淀下来, 同时吸附一定的色素从而达到净化再生的效果。试 验结果如图1 所示。 图 1 白土添加量对再生效果影响 由图 1 可以看出 ,当白土的添加量为废油重量的 8～ 11时有较好的再生效果 ,当白土添加量超过 11,再生效果并没有多大的改变 ,反而增加了成本, 同时过量的白土还会吸附掉大部分的油品减少再生 产量 。由此看出 8～ 11是比较理想的添加量 。 2. 4 白土反应温度对再生效果影响 通过试验发现再生效果的好坏并不会因为采用 了絮凝剂而对白土接触反应温度的要求而有所下降。 试验结果如图 2 所示 。 图 2 白土反应温度对再生效果的影响 从图2 可以看出,当白土接触反应温度低于 120℃ 时,再生效果比较差,从试验当中可以看到油品颜色有 明显的发红。当反应温度为 130℃ 左右时效果明显变 好,发红现象消失而呈现浅黄色。但当温度继续升高 时,效果却没有进一步的提高的趋势, 从图 2可以看 出,当温度在 145℃ 和 160℃时效果相差不大,因此从经 济的角度看 130℃ 左右是最佳的反应温度。 2. 5 搅拌时间对再生效果的影响 白土接触反应中需要充分的搅拌,便于白土和油 中的杂质等充分的接触。如果反应接触时间过短 ,白 土颗粒分布不均 ,其有效吸附面积不能充分展开从而 导致反应不充分 ,时间太长也会影响已经形成的胶体 或絮体变成小胶体或微粒絮体 , 而降低吸附沉淀效 果。同时反应时间太长, 油品在高温条件下也会加速 其氧化的过程, 进一步增加油品的老化率 。试验结果 如图 3 所示 。 图 3 白土搅拌时间对再生效果影响 图3 可见 ,当搅拌时间在 15min 以下时再生效果 明显比较差 ,从目测来看再生油品颜色明显发红。当 搅拌时间从 20～ 25 min 时再生效果并没有明显的变 化,目测来看颜色都很接近,试验数据表明,当搅拌反 应时间为 20 min 时有最大的透光率。当搅拌时间继 续增加并超过 30 min 后再生效果开始出现下降的趋 势,从目测来看油品颜色有趋红的趋势。由此看出白 土搅拌反应接触时间以 20 min 为最佳 。 2. 6 恒温沉降温度对再生效果的影响 白土接触反应后如果不沉淀就直接过滤会增加 过滤的难度 ,同时会造成严重的堵塞, 因此需要进行 一定时间的沉淀。鉴于油品黏度特性对其进行恒温 沉淀 。试验发现恒温沉淀对再生效果的提高是有一 定作用的。试验结果如图 4 所示 。 图 4 恒温沉降温度对再生效果影响 48 环 境 工 程 2008年 4 月第26 卷第2 期 图 4 可见 ,当恒温温度在 70℃以下时 ,透光率明 显的较低 。目测可以看出再生油具有明显的浅红色, 同时略微呈现糊状, 主要原因是由于白土细小粉状颗 粒溶于油中所致。当温度高于 90℃时再生效果下 降,其中主要的原因是温度高导致的氧化 ,当然可能 也与某些色素的脱稳有关。 试验发现如果在低于 50℃下沉淀,再生效果相当差而且由于温度低, 油的 黏度低,白土和油及油中的胶质、 杂质等混溶在一起, 过滤困难且颜色差。当恒温温度为 80℃左右时再生 效果明显比较好 ,过滤后的油品透明且澄清 ,颜色也 接近新油的颜色甚至较新油颜色要浅。为此 ,当恒温 温度为80℃左右时有比较好的再生效果 。 通过絮凝-白土复合工艺处理后废油品质有了 相当大的改观, 其颜色接近或达到新油颜色 ,一些主 要的理化参数接近或达到新油标准。对于要求不是 很高的比如汽车摩托车磨合生产线上用油,经过复合 再生后完全可以重复利用 ,或者配以新油循环注入使 用,对于要求比较高的机械用油可以作为基础油加以 调和根据使用场合的不同调配不同品质的机械油使 用。其基本理化参数如表 2 所示 。 表 2 絮凝-白土处理后理化参数 理化参数 废磨 合油 絮凝 处理后 白土 精制后 SC40 新油 酸值 mgg - 1 0. 39390. 08720. 07090. 0788 黏度 mm2s- 274. 8102. 5109. 2168. 5 残炭 0. 16170. 12880. 07050. 4489 微水 10- 656403639 机械杂质 0. 1132无无无 闪点 ℃136199211248 由表 2 数据可以看出, 经絮凝白土精制过滤后润 滑油的理化指标得到提高 ,劣化因子及杂质明显的降 低,如水分 、 残炭 、 酸值甚至比新油指标都要好, 再生 效果基本上达到该级别新油标准。 3 结论 试验表明,该复合再生工艺最佳再生条件为 絮 凝剂 1. 2 的添加量 、反应温度 75℃左右 、搅拌反应 时间 5 min、 恒温沉降温度 80℃、沉淀 2 h、 白土添加量 8～ 11、 白土接触反应温度 130℃左右 、搅拌时间 20 min、恒温沉降温度 80℃左右。经絮凝 - 白土精制 处理后油品理化指标得到较大改善 ,油品基本上达到 或接近该级别新油标准。相比传统的硫酸 -白土工 艺可以从根本上解决其腐蚀设备 、产生大量的酸渣、 酸水 、 二氧化硫等二次污染问题。同时和国外加氢精 制工艺要求苛刻的操作及反应条件相比, 具有成本 低、 操作简单等优点 。 参考文献 [ 1] 董志学, 贾丽, 王军, 等. 废油再生技术的研究进展. 工业催化, 2003, 12 12 33 -35 [ 2] 王毓敏, 王恒. 润滑材料与润滑技术. 北京 化学工业出版社, 2005 [ 3] 张贤明. 油处理方法和高效真空滤油机. 中国电力, 1994, 5 3 64 -66 [ 4] 张贤明, 焦昭杰, 李川, 等. 废润滑油絮凝脱色试验研究. 环境污 染与防治, 2007 11 [ 5] 奚旦立, 孙裕生,刘秀英. 环境监测. 北京 高等教育出版社,2003 作者通信处 张贤明 400067 重庆工商大学废油资源化与技术装 备教育部工程研究中心 E -mail zxm215126. com 2007- 10-13 收稿 上接第 90页 [ 6] Cossu R,Raga R,Rossetti D .The PAF modelan integrated approach for landfill sustainability . Waste Management, 2003 23 37 -44 [ 7] 董路, 王琪, 李, 等. 填埋场加速稳定技术的研究. 中国环境 科学, 2000, 20 5461 -464 [ 8] 邹庐泉, 何品晶, 李国建, 等. 利用填埋层内微生物代谢控制 生活垃圾填埋场渗滤液污染. 环境污染治理技术与设备, 2003, 4 6 70-73 [ 9] 田艳锦, 黄启飞, 魏世强, 等. 填埋结构对渗滤液中氨氮脱除 的影响. 环境污染治理技术与设备, 2006, 7 6 35 -38 [ 10] 杨玉飞, 黄启飞, 董路, 等. 填埋结构对填埋场稳定化的影响. 中国环境科学, 2005, 25 6 710 -713 [ 11] 中华人民共和国建设部. C. JJ17-88 城市生活垃圾卫生填埋标 准 作者通信处 呼世斌 712100 陕西省西安西北农林科技大学 E -mail lxw328 gmail. com 2007- 10-31 收稿 49 环 境 工 程 2008年 4 月第26 卷第2 期 THE ENERGY-SAVING OF BGBS DESULFURIZATIONDuJijun Shi Yingjie Zhang Fan 30 Abstract The half dry and half wet de -sulfurization BGBStechnology used in coal power plant was investigated.The measures and potential of BGBS for energy -saving were analyzed. The results showed that the BGBS technology could corporate the de -sulfurization agents and the de -sulfurization ash digesting, activation, oxidation and transportation after the steam jet flow technology applied in this technology.As a result, the energy consumption and the operation cost were saved.In contrast, the power driving way which is applied in power plant currently stays in the end of energy transportation chain. It is quite energy consumable. Keywords thermal power plant, BGBS technology, steam jet flow and energy -saving STUDY ON PURIFICATION OF HYDROGEN SULFIDE ODOR BY BIO-TRICKLING FILTER INOCULATED WITH DENITRIFYING THIOBACILLUS Zhang Chengzhong Xing Yi Guo Mingfei et al 33 Abstract A strain of denitrifying Thiobacilluswas isolated from soil, which isinoculated in the bio -trickling filter to purify hydrogen sulfide. Removalefficiency can reach above 92 under following conditions the concentration of inlet 1 453 mg m3, HRT 78 s, pH 6. 0, The strain bacterium can endure the high pollution load and possess the larger buffer capacity and removing efficiency of hydrogen sulfide, which offered a basis for treating H2S in the industrial application. Keywords hydrogen sulfide, denitrifying Thiobacillus and bio -trickling filter NEW TECHNOLOGY OF DUST REMOVAL AND DESULFURIZATION FOR SMALL-SIZED BOILERSNiu Taotao Wang Jiangen Li Zhenyu et al 36 Abstract In this paper, the process composition and principle of double -alkali of sodium calcium multi-polar spray strong swirl process were introduced. Combining the project design, the environmental and economic benefits were analyzed. The results show that this process features less investment low running cost and good effect, it has broad development prospects. Keywords flue gas, double -alkali of sodium calcium and dust removal desulfurization STUDY ON LOW-TEMPERATURE ADSORPTION OF NO IN FLUE GAS BY MODIFIED ACTIVATED CARBON FIBERWang Xiaoming Xu Lusi Shu Zhan 39 Abstract A pilot study was done by micro -reactor of rayon-based R -ACF for denitration. The results showed if ACF immersed into sulfuric acid before impregnated with ammonia solution.it can efficiently increase the oxygen functional groups, and nitrogen functional groups, and is feasible for oxygenating removal NOXat low temperature. Through successive test record the amount ofNO adsorption, the adsorption efficiency of R -ACF before and after desorption of NO reached 15. 2 and 11. 5 respectively.In addition, through negative air desorption the R -ACF removal efficiency can reach 78. 7.It wasverified that R -ACF has good desorption cycle efficiency and renewable NO perance, which has a value of industrial application aswell. Keywords rayon -based activated carbon fiber R -ACF, denitration, modified and analytic test DISCUSSION ONCALCULATING THE GROUND MAXIMUM CONCENTRATION AND MAXIMUM DISTANCE OF ATMOSPHERIC POLLUTIONWang Feng Cheng Xiaoquan Chen Fei 42 Abstract It is analysed that the limitations and problems in calculating model for calculation of the ground maximum concentration and maximum distance of Technical Guidelines for Environmental Impact Assessment on Atmospheric Environment. At the same time, a simple substitution is given. It maybe a referrence to the work of EIA . Keywords point source, maximum ground concentration and distance THE RECYCLING TECHNOLOGY OF WASTED CRT DISPLAY UNITS Yin Fengfu Wang Hailong Liu Zhenyu et al 44 Abstract The harm to the environment of cathode ray tubes CRTdisplay units and their dismantling s are discussed. The physical seperating s like heated-ring , heat-deation, seperating at melten status, laser cutting and diamand cutting, and the chemical seperating s like hot acid ejecting and hot acid in dipping are analyzed. According to the local situation, material reusing status in China is analyzed after the CRT have been seperated. It is posed that different trends of seperating CRT in both the developed and developing countries. Keywords CRT display unit, seperating technology, lead glass and material reusing REGENERATION OF WASTE LUBRICATING OIL BY FLOCCULATION -CLAY PROCESS Zhang Xianming Jiao Zhaojie Li Chuan et al 47 Abstract Based on the research of regeneration and recycling technology at home and abroad, the non-pollution, low-cost regeneration technology which is on the basis of flocculation and combinedwith activated-clay wasproposed. Depending on the earlier experimentof flocculants decoloring and regeneration, it was emphasizedthat the best parameterson activated-clay refining the waste oil was thatwhen the clay dosage was 8～ 11、 the clay contact reaction temperature wasabout 130℃、stirting time was20 min and the constant temperature subsidence temperature 3 ENVIRONMENTAL ENGINEERING Vol. 26, No. 2,Apr. ,2008 is 80℃ with a settling time of 3 h the regeneration effect is best. Under these regeneration conditions, the used oil basically reached the fresh oil standard. Keywords waste lubricating oil, flocculant, activated clay and regeneration A NEW OF ENERGY TRANSATION IN SUPERCRITICAL WATER INTERNAL- COMBUSTIONYi Baokui Ma Chunyuan Lu Shenqing et al 50 Abstract Supercritical water thermal decomposition technology is a new type of energy -efficient treatment of organic wastes. It s a new type of waste disposal and recycling of energy.It is introduced the application of this technology in the field of energy use.It is also discussed the thermal decomposition of biomass andwaste tires in supercritical water. Keywords supercrilical water, organic waste and thermal decomposition ENERGY -SAVING OPTIMUM DESIGN AND APPLICATION OF WASTEWATER CYCLONE SEPARATIONSYSTEM IN FGDWang Fangqun Yin Mingyang DuYungui et al 53 Abstract The wastewater cyclone separation system in FGD has been optimally designed.Two optimization schemes were provided according to whether the static pressure produced by the elevation difference betweeen the overflow of gypsum slurry cyclone separator and inlet of wastewater cyclone separator meets the needof the sum of inlet pressure of wastewater cyclone separator and head lossin pipelines. The beneficial effect of the optimum design is simplifying design, decreasing equipment costs and operating costs.The optimum design has been successfully applied to more than 10 FGD projects. Keywords FGD, wastewater cyclone separation system, energy -saving, optimum design and application THE TREATING COST ANALYSIS OF SEWAGE TREATMENT PLANTYuan Peisheng 55 Abstract This paper analyzed and discussed the concept and composition of sewage treating cost. It has confirmed composition of running cost, surveyed running cost and treating cost of a sewage treatment plant 30 000 t d. The measures for reducing treating cost were posed. Keywords town, sewage treatment, treating cost and running cost RESEARCH ON DEGRADATION OF OILY WASTEWATER BY HIGH EFFICIENT MICROFLORA Zhang Shiping Zheng Guanghong Wang Lei 58 Abstract The bacteria that could use crude oil as carbon source have been screened from the oil-contaminated soil. They could degrade high concentration oilwastewater effectively. When preliminary concentration is 2 g L, and 10 bacteria are inoculated in the wastewater, the concentration is only 420 mg L after 7d.The efficiency of degradation could be 80.If glycerin is entered in the oil wastewater and the concentration is more than 100 mg L, the efficiency of degradation is retrained. In the condition of high-salinity, if the concentration of seaweed mix salt is more than 1. 0 g L, the growth of bacteria are restrained. Keywords bacteria, oil wastewater and biodegradation ADSORPTION OF HEXAVALENT CHROMIUM IN CLAY BY TP Tan Xiao Yu Yongxian Yang Qing et al 61 Abstract Influence of TP on adsorption of hexavalent chromium in the clay was investigated.Effects of reaction time, pH, concentrations of TP and adding amount were studied. The reduction of Cr Ⅵ was examinedwhile the optimum reaction conditionswere determined. TP could enhance the adsorption of Cr Ⅵ because of the complexion reaction between TP and CrⅥ .The reaction mechanisms of TP with chromium and clay surfaces were certified. Keywords TP, hexavalent chromium, clay, complexion and adsorption POSSIBILITY OF COKING SEWAGE TREATMENTBYUSING COAL -WATER SLURRY TECHNOLOGYGuo Jiping Fang Huibin Liu Shuping 64 Abstract The properties of coking sewage and the domestic treatment process for coking sewage were introduced, the possibility of the coking sewage treatment by using coal-water slurry technology was expounded from water quality、water volume and coal -water slurry . Keywords coal-water slurry, coking sewage and treatment process ANALYSIS THE RESISTIVITY CHARACTERISTICS OF CONTAMINATED SOIL Bai Lan Zhou Zhonghua Zhang Huyuan et al 66 Abstract This paper analyses all the possible factors that could influence electrical resistivity.In the series of experiments, contaminated loess was made by mixing loess separately with NaCl, gasoline and leachate. And finally substantiate thatwe could distinguish contaminated loess and normal loess from their different electrical resistivity. Whichwill also offer significant reference for the future uation and reusing of those contaminated sites. Keywords contaminated soil, loess, electric