【作者】 张凤秀；

【导师】 魏世强；

【作者基本信息】 西南大学 ， 农业环境保护， 2009， 博士

【摘要】 随着现代工业的高速发展,环境污染越来越严重,环境保护引起了人们的高度重视。合成酯类润滑油具有矿物型润滑油无法相比的优良的高温性和低温性,良好的粘温性和热氧化稳定性,良好的润滑性和低挥发性,极好的化学稳定性和耐辐射性,生理无毒,可生物降解等优点,在航空、航天、军事、民用等领域得到广泛的应用。酯类润滑油大量使用中不可回收损失以及传统合成方法给环境带来的污染不可忽视。因此,开展润滑油类酯的绿色合成、光降解特性以及对土壤生态的影响全面、系统的研究具有十分重要的理论和现实意义。本文采用微波无溶剂合成和生物合成两种绿色合成方法合成润滑油类多元醇酯、双酯和癸酸十二酯。并选用部分合成产物为代表研究其光解特性和对土壤生态的影响。主要研究结果如下:用三甲醇丙烷（TMP）、季戊四醇（PE）和双季戊四醇（di-PE）分别与C₅～C₉直链一元羧酸在无溶剂条件下微波催化合成润滑油羧酸类多元醇酯结果显示:与传统合成方法对比,三甲醇丙烷羧酸三酯反应时间缩短10～15倍,三甲醇丙烷辛酸三酯、三甲醇丙烷壬酸三酯的产率分别提高了11%和13%。季戊四醇羧酸四酯的反应时间缩短为10～11倍,季戊四醇辛酸四酯、季戊四醇壬酸四酯的产率分别提高了12%和10%。优化了微波无溶剂合成条件,三甲醇丙烷羧酸酸三酯微波合成的最佳条件:功率为280 W～320 W,反应时间为6～10min,产率为81%～96%。季戊四醇羧酸四酯微波合成的最佳条件:300 w～320w,反应时间为8.5～11min,产率为85%～98%。探讨了微波辐射下C₅～C₈一元羧酸与双季戊四醇（di-PE）无溶剂合成的最佳条件:C₅～C₈一元羧酸:di-PE的摩尔比为8:1;微波功率为300W～320W;筛择了最佳复合催化剂,其比值范围（浓硫酸:对甲基苯磺酸）为1:2.5～1:3.0;均得93%以上产率,反应时间为5～10 min;用乌氏粘度计测定了产物的粘度。随着羧酸碳原子的递增,其酯化温度和粘度都呈上升趋势。用己二酸、壬二酸、葵二酸、邻苯二甲酸分别与异辛醇、正十二醇微波无溶剂合成润滑油类羧酸双酯,研究结果表明:反应最佳微波功率为300 w～320 w。二元羧酸二异辛酯反应时间为8～9 min,产率为91%～95%。二元羧酸二正十二酯的反应时间为4～6 min,产率为95%～97%。首次测定了二元羧酸二正十二酯的结晶点。用¹H NMR、¹³C NMR和IR光谱对所有多元醇酯和双酯的产物结构进行了表征。测定了它们的色泽、粘度、折射率。微波无溶剂合成润滑油类多元醇酯和双酯,与酯交换法和传统工业法相比,具有反应速度加快、能耗少,产率高、原料的利用率高、副反应少,产物颜色好、质量高,减少因有机溶剂带来的环境污染等优点,是一种理想的绿色合成方法,为酯类润滑油的传统合成工艺改进提供新的研究方向。研究了乙烯对脂肪酶水解活力的直接作用及其机理。结果表明:低浓度乙烯能使脂肪酶催化三油酸甘油酯的水解活力提高;当乙烯浓度为0.9834 mmol·L^-1时,酶活力提高13.0%。高浓度乙烯降低脂肪酶活力;当乙烯浓度为7.9669 mmol·L^-1时,酶活力下降24.5%.加入乙烯的酶最适温度向高温偏移10～15℃,而酶的最适pH值不变。在pH=7.9时,乙烯使酶活力升高较大,pH为4.5～7.5,8.5,9.5～11时酶的活力降低。加入乙烯的酶与对照相比,其紫外吸收和荧光发射强度均有较大幅度增加;荧光偏振度、比旋光度和粘度显著下降。DSC分析表明:在低温范围内酶的可逆吸热峰值温度明显高于对照,而热焓变低于对照;在高温范围内酶的不可逆吸热峰值温度和热焓变都低于对照。以猪胰腺脂肪酶合成癸酸十二酯为例,研究乙烯对有机溶剂中离体脂肪酶酯化活力和构象的影响,并初步探讨其作用机理。结果表明:低浓度乙烯使脂肪酶的酯化活力提高,当乙烯浓度为247.93 nmol.L^-1时酶的酯化活力提高了39.23%。高浓度乙烯降低酶的酯化活力,当乙烯浓度为14644.23 nmol.L^-1时酶的酯化活力降低了27.64%。乙烯使环己烷和正己烷溶剂中酶的酯化活力提高,在异辛烷溶剂中降低酶的酯化活力。在乙烯的作用下酶的最适温度向低温方向偏移15℃。乙烯在底物低浓度时对酶有激活作用,在底物高浓度对酶产生抑制作用,这种激活或抑制作用是一个可逆过程。该酯化反应存在双底物抑制现象,反应动力学遵循双底物抑制的乒乓机制。与对照相比,乙烯使酶溶液的粘度、比旋光度、荧光偏振度明显降低;旋光方向改变;荧光发射强度、二阶导数谱的振幅显著增强,且峰位改变。DSC分析显示:加入乙烯的脂肪酶不可逆吸热峰值温度和热焓变均高于对照。这些结果表明乙烯对脂肪酶的水解活力、酯化活力以及酶的构象有明显的影响,证实了乙烯可以直接影响酶的微环境和构象。作用机理可能是乙烯通过改变酶的微环境以及嵌入酶分子内部改变酶的构象而引起脂肪酶水解活力和酯化活力的变化。同时也证实了有机气态小分子在酯类化合物的生物合成中有一定的影响,拓宽了生物合成的研究领域,具有非常重要的科学价值。以锐钛型纳米TiO₂作为光催化剂研究不同光解因素对双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯的光解效果的影响及双季戊四醇庚酸六酯、三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯的光解动力学规律。不同光解因素研究结果显示:与对照相比,纳米TiO₂对双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯的光降解有显著促进作用。在双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯浓度在纳米TiO₂的浓度分别为1.26 g·L^-1和1.24 g·L^-1时,光解20 min双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯的光解效果最佳。其光解率分别为93.07%和95.8%,比对照分别提高了61%和48%。pH值对双季戊四醇庚酸六酯的降解影响较大。在强酸性、中性条件下,有利于双季戊四醇庚酸六酯光降解。而在弱酸性、弱碱性条件下对双季戊四醇庚酸六酯的降解效果较差。三甲醇丙烷庚酸三酯在中性至弱碱性条件下,光降解效果最好。不同浓度的H₂O₂对双季戊四醇庚酸六酯的降解有较大影响。在试验条件下,当H₂O₂浓度为2.0mol·L^-1～3.0 mol·L^-1时,双季戊四醇庚酸六酯的光降解效率急剧上升,产生一个突变,光降解率达到95.92%。和对照相比,其光解率提高了23%。超过3.0 mol·L^-1时,光降解率提高幅度不大。三甲醇丙烷庚酸三酯在H₂O₂浓度为3 mol·L^-1降解率达到最高。与对照比较,其光解率提高了9%。有机溶剂对双季戊四醇庚酸六酯的光降解效果次序为:异辛烷＞丙酮＞无水乙醇＞二氯甲烷,异辛烷是双季戊四醇庚酸六酯光降解的最佳有机溶剂。而有机溶剂对三甲醇丙烷庚酸三酯的光降解效果次序为:丙酮-醇水溶液＞甲醇＞异辛烷＞二甲苯,三甲醇丙烷庚酸三酯光降解的最佳溶剂为丙酮和醇水溶液。光解动力学研究结果表明:纳米TiO₂浓度、pH值、H₂O₂浓度和有机溶剂对双季戊四醇庚酸六酯、三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯的光解动力学均遵循一级反应动力学规律。高浓度的纳米TiO₂对双季戊四醇庚酸六酯、三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯光解动力速率均有一定的抑制作用。双季戊四醇庚酸六酯、三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯分别在纳米TiO₂浓度为1.49 g·L^-1、2.98 g·L^-1和1.49 g·L^-1时,其光降解速率常数最大,半衰期最短。对照相比,其半衰期分别缩短了的3倍、30倍和4倍。双季戊四醇庚酸六酯在酸性条件下,速率常数大。三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯在碱性条件下,光降解速率常数较大。H₂O₂对三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯的光解动力学有双重效应。在H₂O₂浓度为0.65 mol·L^-1时,对三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯有强的光敏化,而随着浓度升高,光敏化作用减弱。高浓度H₂O₂有明显的光淬灭作用。对于双季戊四醇庚酸六酯在试验浓度范围内(0～2.61 mol·L^-1),随着H₂O₂浓度升高光敏化作用增强。三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯在丙酮溶剂中的光降解速率常数最大,半衰期最短。通过双季戊四醇庚酸六酯、三甲醇丙烷庚酸三酯和邻苯二甲酸异辛酯光解产物的紫外吸收光谱和红外光谱初步分析:加入纳米TiO₂和未加入纳米TiO₂两组的光解机理不同,但光解产物中均有氢化过氧化羟基和小分子的过氧物中间体。对于双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯,未加入纳米TiO₂一组的光解机理可能是:酯基先断键,生成醇和羧酸以及少量的含过氧化物的中间体,然后进一步氧化生成含较多过氧键的中间体,最后断键生成小分子的醇和醚类化合物。而加入纳米TiO₂一组的光降解机理可能是:在纳米TiO₂催化下,光解反应物先氧化生成过氧化合物,然后再断过氧键和酯键,生成小分子的过氧化合物和小分子的醇以便进一步降解。对于邻苯二甲酸异辛酯在未加入纳米TiO₂和加入纳米TiO₂两种情况下的降解机理刚好与双季戊四醇庚酸六酯和三甲醇丙烷庚酸三酯相反。用纳米ZnO为光催化剂研究不同光解因素对邻苯二甲酸异辛酯和季戊四醇戊酸四酯光解效果的影响及季戊四醇庚酸六酯的光解动力学规律。不同光解因素研究结果表明:纳米ZnO对邻苯二甲酸异辛酯和季戊四醇戊酸四酯的光解有明显光催化效果。从光解率和经济角度考虑,纳米ZnO最佳浓度为14.23 g·L^-1。pH对邻苯二甲酸异辛酯和季戊四醇戊酸四酯的光解效果有不同的影响。邻苯二甲酸异辛酯由强酸性至弱酸中性范围,其光解率随pH值得增加而逐渐增高。pH为6.5光解效果最佳。而季戊四醇戊酸四酯随pH增加,光解效果变化规律呈单调递减性,在强酸性条件下其光解率高。H₂O₂对季戊四醇戊酸四酯光解起光敏化效果。当H₂O₂浓度为2.9382 mol·L^-1时,季戊四醇戊酸四酯光解率达到最高值,比对照提高了87.9%。而H₂O₂对邻苯二甲酸异辛酯的光解有双重作用。H₂O₂在0.9794 mol·L^-1～1.958 mol·L^-1浓度范围,产生光敏化效应。当H₂O₂浓度为0.9794 mol·L^-1时,其光解率最高,比对照提高了43.96%。当H₂O₂浓度为4.897 mol·L^-1时,H₂O₂对邻苯二甲酸异辛酯光解有淬灭作用。光催化剂与光解有机物初浓度达到一个最佳的浓度比时,光解率最高。季戊四醇戊酸四酯在纳米ZnO浓度为11.66g·L^-1时,初浓度在668.0 mg·L^-1～1002.0 mg·L^-1范围的降解率较高。邻苯二甲酸异辛酯在纳米ZnO浓度为11.53 g·L^-1时,初浓度在75.2 mg·L^-1～150.2 mg·L^-1范围出现降解率较高值。随着光照时间的延长,邻苯二甲酸异辛酯和季四戊醇戊酸四酯的降解率逐渐增大。邻苯二甲酸异辛酯光10 min,光解率达到97.3%。季戊四醇戊酸四酯光解时间大20 min时,光解率为35.03%～38.59%,其光解率就趋于平稳。季四戊醇戊酸四酯光解动力学研究结果显示:纳米ZnO浓度、pH值、H₂O₂浓度对季四戊醇戊酸四酯的光解动力学均遵循一级反应动力学规律。pH对季四戊醇戊酸四酯光解动力学有明显影响。在酸性条件下,速率常数最大。在碱性条件下,其光降解速率常数小,半衰期比酸性条件下延长了4倍。纳米ZnO浓度对季戊四醇戊酸四酯光降解动力学有明显影响。随着纳米ZnO浓度增加,光降解速率逐渐增大,并大于对照。当纳米ZnO浓度为12.94 g·L^-1时,光降解速率常数达到最大值,半衰期最短。浓度H₂O₂对季戊四醇戊酸四酯光降解动力学影响明显。在试验浓度范围内(1.1～5.8 mol.L^-1),加入H₂O₂的光解反应速率常数均大于对照。H₂O₂对季戊四醇戊酸四酯光解起到光敏化作用。当H₂O₂浓度为3.2625 mol.L^-1时,半衰期最短,比对照缩短约4倍。继续增加H₂O₂浓度,半衰期又延长。通过季戊四醇戊酸四酯光解产物的紫外吸收光谱和红外光谱,可以初步看出季戊四醇戊酸四酯没有光催化剂的作用下光解可能途径:在光解反应先氧化生成过氧化合物,然后再断过氧键和酯键,生成小分子的过氧化合物以便进一步降解。以润滑油类三甲醇丙烷庚酸三酯为润滑油污染物代表,研究其在矿子黄泥和灰棕紫泥两种土壤中的吸附特征及对钙质紫泥土的微生物数量和微生物生物氮量的影响。吸附动力学和热力学研究结果:矿子黄泥和灰棕紫泥对三甲醇丙烷庚酸三酯的吸附是一个快速过程。吸附过程可分为两个阶段,前20 min为快速反应阶段,吸附量分别达到最大吸附量的75.61%和69.37%;之后为慢速反应阶段,40 min左右基本达到吸附平衡。整个吸附反应达到平衡所需时间短,表明该类润滑油酯进人土壤后,其中一部分能迅速为土壤吸附固定,对其后期的迁移及生物降解转化有着重要的影响。采用Langmuir和Freundlich方程拟合等温吸附曲线,比较结果发现Langmuir方程拟合效果较好,表明矿子黄泥和钙质紫色土对三甲醇丙烷庚酸三酯的等温吸附特征更符合Langmuir吸附规律,其最大吸附量分别为12.99 mg·g^-1和17.45 mg·g^-1。三甲醇丙烷庚酸三酯对钙质紫泥土的微生物数量和微生物生物氮量的影响研究结果表明:三甲醇丙烷庚酸三酯对土壤中微生物数量有显著的影响。不同的处理时间、不同的三甲醇丙烷庚酸三酯浓度对土壤细菌、真菌和放线菌的影响差异大。与对照相比,细菌在前15天,各浓度是随时间增加细菌数量呈现出不同程度的上升趋势。细菌数量随时间的延长,浓度为10.0mg·kg^-1的土样,则出现激活-抑制-激活交替性的变化规律。浓度为100 mg·kg^-1的土样有一定的抑制作用。浓度为502.0 mg·kg^-1的土样,表现出激活作用。处理15天～30天,除了502.0 mg·kg^-1浓度继续出现激活、呈上升趋势以外,其余浓度细菌数量均有不同程度的下降。真菌在28天以前,三甲醇丙烷庚酸三酯各浓度对真菌均起抑制作用。特别是前5天,随浓度的增高抑制作用越强。5～30天,随着时间的延长,三甲醇丙烷庚酸三酯各浓度的土壤真菌数量上升速度快。28天～30天,0.0 mg·kg^-1和502.0 mg·kg^-1浓度的土壤真菌数量高于对照,有激活作用。与对照相比,在15天以前,10.0 mg·kg^-1浓度的土样随着时间的增加放线菌数量逐渐增加,先抑制后激活,最高激活率为33.7%。100.0 mg·kg^-1浓度的土样则是激活、抑制、再激活的变化。在第1天的激活率最高;第5天的抑制率最大。502.0 mg·kg^-1浓度的土样是先抑制后激活,放线菌数量出现先下降后升高的趋势。15～30天,各浓度出现不同程度的激活。三甲醇丙烷庚酸三酯对土壤微生物生物氮量有明显的影响。与对照相比,前15天,除了10.0 mg·kg^-1浓度的土样在前2天的微生物氮量高于对照外,其余均低于对照。15天以后,各浓度的微生物氮量均高于对照。更多还原

【Abstract】 Along with the rapid development of modern industry,the environmental pollution is more and more serious,so people attach highly importance to environmental protection.Compared with mineral lubrication oil,synthesized ester lubrication oil has many excellent properties,i.e.the property of high temperature and low temperature,high viscosity index,heat-oxidation stability,fine lubricant characteristic,low volatility,excellent thermal stability,radiation-resistant characteristic, physiological harmlessness and easy biodegradability in the natural environment,therefore,it is widely used in all kinds of aviation,spaceflight,military affairs and civilian.Environmental pollution isn’t ignorable because a great deal of used ester lubrication oil can’t be reclaim and conventional synthesis method brings outgrowth and organic solvent.Thereby,the comprehensive systemic studies about green synthesis photodegradation and influence of ester lubrication oil on soil zoology are of vital importance to theory and realism.The microwave synthesis of polyol esters,di-esters without organic solvent and the biosynthesis of dodcanol capriate and the photodegradation and influence of them on soil zoology were investigated in the dissertation.Under microwave irradiation the polyol esters of lubricating oil were synthesized without organic solvent by the reaction of trimethylolpropane（TMP） or pentaerythritol（PE） or dipentaerythritol（di-PE） with C₅ to C₉ carboxylic acids.By comparing with the conventional synthetic method,the results show that the reaction time under microwave irradiation is largely shortened and the reacting velocity increases ten to fifteen times for TMP tri-ester,and the yields of TMP tri- caprylate and TMP tri- nonanoate are respectively increased 11%and 13%.For PE esters the reaction time under microwave irradiation also is largely shortened and the reacting velocity increases ten to eleven times.The yields of PE quadri-caprylate and PE quadri- nonanoate are respectively increased 12%and 10%.Optimizations of a series of reactions about PE and TMP with C₅-C₉ straight-chain fatty acid were investigated without organic solvent under microwave irradiation.For TMP esters,the best microwave power was between 280 W and 320 W.The reaction time was 6～10 min and the yields were 81%～96%.For PE esters,the best microwave power was 300 W～320 W.The reaction time was 8.5～11 min and the yields were 85%～98%.The best synthetical conditions of di-PE with C₅ to C₈ carboxylic acids were investigated without organic solvent under microwave radiation.The best molar ratio of C₅ to C₈ carboxylic acids vs di-PE was 8: 1.The best microwave power was 300W～320W.The best composite catalyst was selected,and the ratio of composite catalyst（vitriol oil vs p-toluene sulphonic acid） was from 1:2.5 to1:3.0.The yields were at least 93%within 9～10min.Their viscosity coefficients were determined by Ubbelohde viscosimeter.With the increase of carbon atom number of carboxylic acids,their esterifiable temperatures and viscosities gradually went up.Under microwave irradiation the di-ester of lubricating oil were synthesized without organic solvent by the reaction of hexane diacid or azelaic acid or sebacic acid or o-phthalic acid with isooctyl alcohol or dodecanol.The results showed that the best microwave power was 300W～3320W,the reaction time of diisooctyl adipate,diisooctyl azelate and diisooctyl sebacate was 8～9 minute and the yields were 91%～95%.The reaction time of didodecyl adipate,didodecyl azelate and didodecyl sebacate was 4～9 minute and the yields were 95%～97%.Their crystal points have been determined first.All structures of di-ester and polyol ester have been characterized by ¹H NMR、¹³C NMR and IR spectra,and their refractive indexes,viscosity coefficients and colors and luster have been determined.In comparison with the conventional and industrial method,microwave-synthesized method has many advantages of fast reacting velocity,high yield,low energy consuming,few outgrowth,good colors and quality and decreasing environmental pollution by reason of organic solvent.Thereby,it is a perfect green synthetical method and it may provide a new research orientation for traditional technology improvement of ester lubricating oil.The mechanism and direct effect of ethylene on lipase activity have been studied.The results showed that the lipase activity increased in ethylene of lower concentrations and the highest percent was 13.0%when the ethylene concentration was 0.9834 mmol·L^-1.The lipase activity decreased in ethylene of higher concentrations and the highest percent was 24.50%when the ethylene concentration was 7.9669 mmol·L^-1.The optimum temperature of the lipase in the presence of ethylene increased by10～15℃compared to that in the absence of ethylene.The optimum pH of the lipase was 7.5 in the presence or absence of ethylene.When pH was 7.9 the lipase activity in the presence of ethylene increased greater and reduced when pH was 4.5～7.5,8.5 and 9.5～11.To compare with contrast,the UV absorption and fluorescence emission intensities of the lipase in the presence of ethylene were enhanced markedly,and its fluorescence polarization,specific rotatory power at 30℃and the viscosity at 14℃in the presence of ethylene declined obviously.Differential scanning calorimetry was adopted for studying conformational transition of the lipase in the presence or absence of ethylene.The results revealed that the peak temperature of reversible endotherm of the lipase in the presence of ethylene was higher than that of the contrast and the enthalpy was lower than that of the contrast at a lower temperature,and the peak temperature of nonreversible endotherm and the enthalpy in the presence of ethylene were lower than that of the contrast at a higher temperature.The mechanism and effect of ethylene on esterifiable activity of lipase and its conformation have been investigated in organic solvents,taking the example of lipase-catalyzed esterification of capric acid and dodcanol.The results showed that the lipase activity increased in the presence of ethylene of lower concentrations and the highest percent was 39.23%when the ethylene concentration was 247.93nmol.L^-1.The lipase activity decreased in the presence of ethylene of higher concentrations and the highest percent was 27.64%when the ethylene concentration was 14644.23nmol.L^-1.The lipase activity in cyclohexane and n-hexane increased and decreased in isooctane in the presence of ethylene.The optimum esterifiable temperature of the lipase in the presence of ethylene decreased by 15℃compared to that in the absence of ethylene.The lipase activity was activated by ethylene in lower substrate concentration and inhibited by ethylene in higher substrate concentration.These actions were reversible.The esterification reaction had the inhibition effects of both substrates.The kinetics of the reaction was consistent with the Ping-Ping Bi-Bi mechanism,which is characterized by inhibition by both acid and alcohol.To compare with contrast,the viscosity at 14℃,and specific rotatory power at 25℃and fluorescence polarization of the lipase in the presence of ethylene declined obviously;and its fluorescence emission intensities and the distance between extremum value of ultraviolet second-derivative spectroscopy were enhanced markedly,and their peak locations changed in the presence of ethylene.The DSC revealed that the peak temperature of nonreversible endotherm and its enthalpy of the lipase in the presence of ethylene were higher than that of the contrast.These results prove adequately that ethylene can directly influence not only the esterifiable and hydrolytic activity of the lipase but also the microcosmic environment and conformation of the lipase.The mechanism that ethylene acts on the lipase probably is that ethylene changes the microcosmic environment of the lipase and embeds the lipase inside to drive the conformational transition of the lipase.This also prove organic gaseous small molecule can effect on the biosynthesis of ester and extend its study scope.The result is the very significance for chemistry biology science.The photodegradation of di-PE hexa-heptylate,TMP tri-heptylate and diisooctyl o-phthalic ester under UV were investigated,using anatase nano-TiO₂ as photocatalyst.The photodegradation results of the concentration of nano-TiO₂ and H₂O₂,PH,organic solvents,and the analysis of reaction kinetics as follows:Compared with the comparison,anatase nano-TiO₂ can markedly accelerate the photo -degradation of di-PE hexa-caproate and TMP tri-heptylate.When nano-TiO₂ concentrations were respectively 1.26g·L^-1 and 1.24 g·L^-1 and ultraviolet radiation time was 20 min,their degradation effects were the best,and the degradation percents of di-PE hexa-caproate and TMP tri-heptylate were respectively 93.07%and 95.8%and respectively increased about 61%and 48%than their contrasts.Effect of pH on the photodegradation of di-PE hexa-caproate was obvious and was the best in acidity and neutral conditions,but weak acidity and alkaline conditions was not advantageous for its photodegradation.For TMP tri-heptylate,the most suitable pH was neutral and weak alkaline. The effect was the best.Peroxide of hydrogen（H₂O₂） can promote photodegradation of di-PE hexa-caproate and TMP tri-heptylate.When the concentration of H₂O₂ was 2mol·L^-1～3 mol·L^-1,the photodegradation percent sharp rose and reached 95.92%and the photodegradation percent increased about 23%than the contrast.When the concentration of H₂O₂ was higher than 3 mol·L^-1, the increase of photodegradation percent was slow.For TMP tri-heptylate,when the concentration of H₂O₂ was 3 mol·L^-1,the degradation effect was the best and the percent increased about 9%by comparing with the contrast.Effect of organic solvent on the photodegradation of di-PE hexa-caproate and TMP tri-heptylate was significantly.For di-PE hexa-caproate,the order of the best photodegradation effect in four organic solvents was:isooctane＞acetone＞anhydrous ethanol＞dichloromethane.Thus,the best solvent of photodegradation was isooctane.For TMP tri-heptylate,the order of the best photodegradation effect in five organic solvents was:acetone alcohol- water solution＞methanol＞isooctane＞xylene＞.The best solvents of photodegradation were acetone and alcohol -water solution.The experimental results of the dynamics show that the kinetic equation of photodegradation of the concentration of nano-TiO₂ and H₂O₂,PH,organic solvents for di-PE hexa-caproate,TMP tri-heptylate and diisooctyl o-phthalic ester conform to a one-order dynamics rule.Higher concentration of nano-TiO₂ can restrain the photodegradation of di-PE hexa-caproate,TMP tri-heptylate and diisooctyl o-phthalic ester.When the concentrations of nano-TiO₂ respectively were 1.49 g·L^-1,2.98 g·L^-1 and 1.49 g·L^-1,the velocity constants of di-PE hexa-caproate,TMP tri-heptylate and diisooctyl o-phthalic ester were the highest and the half- life were the shortest. Compared with the comparison,their half lifes were respectively shortened three times,thirty times and four times.The velocity constant of dipentaerythritol hexa-caproate was the highest in acidity conditions.The velocity constants of TMP tri-heptylate and diisooctyl o-phthalic ester were the highest in alkaline condition.Peroxide of hydrogen on the photodegradation dynamics of TMP tri-heptylate and diisooctyl o-phthalic ester showed two effects.0.65 mol·L^-1 H₂O₂ showed a strong photosensitizing effect.But along with the increase of concentration of H₂O₂,the photosensitizing effect showed more and more weak.High concentration of H₂O₂ showed obvious photoquenehing effect.For di-PE hexa-caproate,when the concentration H₂O₂ is in the range of 0～2.61 mol·L^-1,the photosensitizing effect was more and more strong with the increase of concentration of H₂O₂.The velocity constants of TMP tri-heptylate and diisooctyl o-phthalic ester were the highest in acetone and the half- life were the shortest.By the primary analysis of the infrared spectra and the UV absorption spectra of the photodegradation outcomes of di-PE hexa-caproate,TMP tri-heptylate and diisooctyl o-phthalic ester,the mechanisms of their photodegradations with nano-TiO₂ or without nano-TiO₂ were different and there were intermediates of hydroxy hydrogen peroxide and small molecule peroxide in photodegradation outcomes.For di-PE hexa-caproate and TMP tri-heptylate,the photodegradation mechanism without nano-TiO₂ was possibly that the ester bond first cut and became alcohol and carboxyl acid as well as little peroxide intermediate,afterwards,they were oxidized further into a lot of peroxide intermediates,and finally cut the peroxide bond and came into being small molecule alcohol and aether.The photodegradation mechanism with nano-TiO₂ was possibly that the peroxide first was produced,then cut the peroxide bond and the ester bond and became small molecule alcohol and the peroxide so as to be oxidized further into alcohol and aether of low molecular weight. For diisooctyl o-phthalic ester,the photodegradation mechanism with nano-TiO₂ or without nano-TiO₂ was opposite with those of dip-PE hexa-caproate and TMP tri-heptylate with nano-TiO₂ or without nano-TiO₂.The photodegradations of PE quadri-valerate and diisooctyl o-phthalic ester under the UV were investigated,using nano-ZnO as photocatalyst.The research results of photocatalytic degradation of the concentration of nano-ZnO and H₂O₂,PH,reaction time,initial concentration of the ester and the analysis of reaction kinetics as follows:Compared with the comparison,nano-ZnO can markedly accelerate the photodegradation of pentaerythritol quadri-valerate and diisooctyl o-phthalic ester.Considering degradation percent and the cost,the best concentration of nano-ZnO was 14.23 mol·L^-1.The photodegradation effect of pH on PE quadri-valerate and diisooctyl o-phthalic ester was different.For diisooctyl o-phthalic ester, the degradation percent increased with pH enhancing from strong acidity to weak acidity and neutral condition.When pH was 6.5,the photodegradation effect was the best.For PE quadri-valerate,the degradation percent monotonously descended with pH enhancing from strong acidity to alkalescence. Thus,the degradation percent was the highest in strong acidity condition.Peroxide of hydrogen on the photodegradation of PE quadri-valerate showed obvious photosensitizing effect.When the concentration of H₂O₂ was 2.9382 mol·L^-1,the degradation percent was 60.48%and increased 87.9% than the contrast.Moreover,the photodegradation of peroxide hydrogen on diisooctyl o-phthalic ester has two effects.When the concentration of H₂O₂ was in the range of 0.9794 mol·L^-1～1.96mol·L^-1,it showed obvious photosensitizing effect.When the concentration of H₂O₂ was 0.9794 mol·L^-1,the degradation percent was the highest and increased 43.96%than the contrast. When the concentration of H₂O₂ was 4.897 mol·L^-1,it showed obvious photoquenehing effect.The best concentration ratio of photocatalyst and reactant could make that the degradation percent was the highest.When the concentration of nano-ZnO was11.66 g·L^-1 and the concentration of PE quadri-valerate was in the range of 668 mg·L^-1～1002.0mg·L^-1,the degradation percent was the highest.When the concentration of nano-ZnO was11.53 g·L^-1 and the concentration of diisooctyl o-phthalic ester was in the range of 75.2 mg·L^-1～150.2mg·L^-1,the the degradation percent was the highest Along with the photodegradation time prolonging,the degradation percent of PE quadri-valerate and diisooctyl o-phthalic ester gradually increased.The degradation percent of diisooctyl o-phthalic ester reached 97.35%in 10min.And when the photodegradation time exceeded 20min,the degradation percent of PE quadri-valerate was 35.03%～38.59%and it was reposeful.The results of the dynamics show that the kinetic equations of the photodegradation of the concentration of nano-ZnO and H₂O₂,PH for PE quadri-valerate conform to a one-order dynamics rule.Effect of pH on the photodegradation dynamics of PE quadri-valerate was remarkable.The velocity constant in acidity conditions was the highest.The velocity constant in alkaline conditions was small and the half life was prolonged four times than that in acidity conditions.Effect of nano-ZnO concentration on the photodegradation dynamics of PE quadri-valerate was also notable. Along with the increase of nano-ZnO concentration,the velocity constant also increased and it was higher than its contrast.When nano-ZnO concentration was 12.49 g·L^-1,the velocity constant was the highest and the half life was the shortest.In the testing concentration of 1.1 mol·L^-1～5.8 mol·L^-1 H₂O₂,the velocity constant was higher than its contrast.This indicated that H₂O₂ on the photodegradation of PE quadri-valerate had obvious photosensitizing effect.When the concentration of H₂O₂ was 3.2625 mol·L^-1,the half life was the shortest and it was shortened four times than the contrast.But going on the increase of H₂O₂ concentration,the half life prolonged.By the primary analysis of the infrared spectra and the UV absorption spectra of the photodegradation outcomes of PE quadri-valerate,the mechanisms of their photodegradations without photic-catalyzer was likely to the peroxide first was produced,then cut the peroxide bond and the ester bond and became small molecule alcohol and the peroxide so as to be oxidized further into alcohol and aether of low molecular weight. The adsorption properties in mineral flavicant soil and gray-brown purple soil,and the change of soil microbes and microbial biomass nitrogen（MBN） in calcic-purple soil were studied by selecting TMP tri-heptylate as the representative of lubrication oil contamination.Adsorption kinetics and thermodynamic experiments showed that the adsorption in them was a fast process, 75.61%and 69.37%of the maximum adsorption in the two soils were respectively completed in the first twenty minutes,followed by a gradual decline,and an equilibrium was eventually reached in about 40 minutes.Thus the adsorption equilibrium time was short.This revealed that after TMP tri-heptylate went into the soil,the part of TMP tri-heptylate was fleetly fixed on the soil.This adsorption was of vital importance to late transfer and biodegradability.The isothermal adsorption data were fitted by both Freundlich equation and Langmuir equation and the results showed that Langmuir equation described the adsorption characteristics better than the Freundlich equation.The maximum adsorption capacities were obtained from the Langmuir equation,which were 12.99mg.g ^-1and 17.45 mg.g^-1 respectively for flavicant soil and gray-brown purple soil.The result of soil microbe quantity and microbial biomass nitrogen（MBN） in calcic-purple soil indicated that the effect of TMP tri-heptylate on soil microbe quantity and MBN was very remarkable.The effect was different with different time and different concentration of TMP tri-heptylate.Compared with the comparison,the bacteria quantity rose with time at each concentration tested before 15 day.Along with test time prolonging,the bacteria quantity in the soil treated with 10.0 mg.kg^-1 revealed stimulation-inhibition- stimulation effect,while that treated with 100.0mg.kg^-1 had certain inhibitory effect,and that treated with 502.0mg.kg^-1 became stimulatory. During 15 day～30 day,exception for that treated with 502.0mg.kg^-1 keeping the rise and having stimulation effect,the bacteria quantity at the other concentration all descended.Before 28 day tested,the effect of TMP tri-heptylate at each concentration tested on fungi population was inhibition.In particular,before 5 day tested,the inhibitory effect was more and more strong with the concentration increase of TMP tri-heptylate.During 5 day～30 day,the rise speed of fungi population was fast with time prolonging.During 28 day～30 day,fungi population treated with the concentration of 10.0mg.kg^-1 and 502.0mg.kg^-1 was higher than its contrast and showed stimulation effect.Compared with the comparison,the actinomyce population treated with 10.0mg.kg^-1 gradually increased with test time prolonging before 15 day,and the effect was firstly inhibition and then stimulation.The highest percent of stimulation was 33.7%.The effect of TMP tri-heptylate on the soil actinomyce population treated with 100.0mg.kg^-1 was stimulation-inhibition- stimulation. The stimulation percent was the highest in first day.But the inhibition percent was biggest in fifth day.The effect of treated with 502.0 mg.kg^-1 was inhibition at the beginning and stimulation later. During 15 day～30 day,the effects at each concentration on actinomyce population were stimulation. Compared with the comparison,exception for that treated with the concentration of 10.0mg.kg^-1 was higher than its contrast before two days,microbial biomass nitrogen（MBN） at the other concentration tested was lower than its contrast.After 15 day tested,MBN at each tested concentration was higher than its contrast.更多还原