Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

降水中甲酸、乙酸和草酸的离子色谱法测定及样品保存研究

甲酸、乙酸和草酸是降水中有机酸的主要成分。研究选用离子色谱法同时测定降水中的甲酸、乙酸和草酸,并对降水样品中3种有机酸的保存条件进行了研究。优化后的色谱条件为4. 0 mmol/L Na_2CO_3和1. 2 mmol/L NaHCO_3混合淋洗液,淋洗液流速为1. 0 m L/min,进样体积为200μL,电导池温度为30℃,柱温为室温。甲酸、乙酸和草酸的检出限分别为0. 002、0. 005、0. 005 mg/L,实际降水样品测定时平行样的相对标准偏差为1. 4%～12%,加标回收率为95%～118%。样品采集后需尽快用0. 45μm聚醚砜微孔滤膜过滤,4℃以下冷藏密封保存,2 d内测定。若用氢氧化钠溶液调节p H至8～10,样品可保存7 d。     

茅草添加与温度变化对餐厨垃圾厌氧水解产酸的影响

比较了茅草添加在温度变化条件下对餐厨垃圾厌氧水解过程小分子有机酸产量的影响，提出一种新型餐厨垃圾的资源化方式。研究结果显示，餐厨垃圾在55℃条件下厌氧水解主要产物为乳酸，达到25．7g／L，其干物质转化率可以达到32．1％（gTS），而餐厨＋茅草处理在同样条件下的乳酸产量为20．1g／L，干物质转化率为25．1％。温度下降为37℃后继续进行的的厌氧水解，得到的主要产物是乙酸、丙酸和丁酸，餐厨处理和餐厨＋茅草处理这两者的峰值分别为6．5、2．8、8．0和6．1g／L、2．7g／L和5．9g／L。结果显示茅草添加可以在一定程度上调节水解产物的比例，而温度变化可以调控小分子有机酸的产量。本研究结果表明，厌氧水解是一种有潜力的小分子有机酸生产与餐厨垃圾资源化处理途径。     

COD组分分析的实验条件及结果可靠性分析

本研究尝试用SF(OURmax/OURen)代替S(0)/X(0)来作为呼吸法确定COD组分最优实验条件的参数,从而简化测量过程且可实现自动化操作.另外由生长消耗COD与生物量的比值来判断测量结果的可靠性.结果表明,获得可靠的RBCOD组分分析结果的实验条件为:1对于易生物降解含量较高的水质(如由乙酸钠配制的污水),SF在2.8~5.3范围内,生长消耗COD与生物量比值在30%以内;2对于易生物降解和难生物降解物质适中的水质(如典型生活污水),SF应在5.8~6.4左右,生长消耗COD与生物量比值在30%以内;3而对于含有大量难生物降解物质的工业废水(垃圾渗滤液),SF在15以下,且生长消耗COD与生物量的比值在40%以内.由此可见,采用呼吸法确定COD组分,其最优条件SF范围随碳源的复杂程度的上升而上升.     

β-环糊精/醋酸纤维素纳米纤维的制备及对染料废水的处理

制备了不同β-环糊精(β-CD)含量的醋酸纤维素(CA)纳米纤维膜,并对纤维膜的结构形貌、尺寸分布、孔隙率、比表面积以及纤维膜的力学性能进行表征分析。随后研究了不同β-CD含量、初始浓度、吸附时间下,纳米纤维膜对甲基红染料的截留性能和吸附性能。结果表明:过量(≥30%)的β-环糊精会使纳米纤维产生珠节,纤维的形貌和力学性能变差;吸附试验表明,β-CD的加入提高了CA纳米纤维膜对染料的吸附,MR吸附率可达93.48%,最大平衡吸附量可达181.74 mg/g,比纯CA纳米纤维膜提高了将近40%;此外,染料的截留实验表明,纳米纤维膜对染料的截留效果较差,最大截留率为50.35%。     

不同类型填料的三维电极/Fenton试剂法处理苯酚废水

采用不同类型填料对三维电极/Fenton试剂法处理苯酚模拟废水进行研究.结果表明.不同类型活性炭填料对苯酚去除率有很大影响,粒炭不适合做粒子电极,采用5.0 mm柱炭处理效果较好;采用石英砂与活性炭混合填料的处理效果比单一活性炭填料好,但苯酚去除率提高不明显;电解槽反应器中按比例投加涂膜活性炭和活性炭混合填料能明显提高苯酚去除率;当涂膜活性炭与活性炭体积比为1,2时,苯酚去除率最高,达96.8%.     

煤燃烧过程中有机钙固氟效果研究

选择醋酸钙镁、醋酸钙2种有机钙为固氟剂,在固定床管式炉上对它们的固氟效果进行了初步研究,并分析了粒径、温度、钙硫比等对试验结果的影响.通过与传统固氟剂碳酸钙的固氟效果进行比较发现:在相同实验条件下,这2种有机钙具有良好的固氟效果,高温阶段效果更加明显,温度为1 000～1 100℃时,醋酸钙镁的固氟率是碳酸钙的1.68～1.74倍,醋酸钙的固氟率为碳酸钙的1.28～1.37倍.     

醋酸酯生产线物料输送泵的选型与污染物排放量的关系

以钱塘江上游某化工企业的醋酸酯生产线为例,通过分析物料输送泵优化技改前后的工艺流程和污染物排放情况,从而佐证化工行业物料输送泵的选型与污染物排放量是密切相关的,可以达到指导该类项目的环境影响评价和清洁生产审核,同时也能为企业的节能减排提供一定的技术依据。     

Combination effect of pH and acetate on enzymatic cellulose hydrolysis

The productivity and efficiency of cellulase are significant in cellulose hydrolysis. With the accumulation of volatile fatty acids (VFAs), the pH value in anaerobic digestion system is reduced. Therefore, this study will find out how the pH and the amount of acetate influence the enzymatic hydrolysis of cellulose. The effects of pH and acetate on cellulase produced from Bacillus coagulans were studied at various pH 5-8, and acetate concentrations (0-60 mmol/L). A batch kinetic model for enzymatic cellulose hydrolysis was constructed from experimental data and performed. The base hypothesis was as follows: the rates of enzymatic cellulose hydrolysis rely on pH and acetate concentration. The results showed that the suitable pH range for cellulase production and cellulose hydrolysis (represents efficiency of cellulase) was 2.6-7.5, and 5.3-8.3, respectively. Moreover, acetate in the culture medium had an effect on cellulase production (K1= 49.50 mmol/L, n=1.7) less than cellulose hydrolysis (K1=37.85 mmol/L, n=2.0). The results indicated that both the pH of suspension and acidogenic products influence the enzymatic hydrolysis of cellulose in an anaerobic environment. To enhance the cellulose hydrolysis rate, the accumulated acetate concentration should be lower than 25 mmol/L, and pH should be maintained at 7.     

包埋类脂的吸附剂制备及吸附POPs性能

用丙酮作溶剂将三油酸甘油酯分散到醋酸纤维(CA)基体中,采用悬浮聚合的方法制备出了一种兼具亲水性,又能高倍富集持久性有机污染物的球形复合吸附剂。通过对分散剂的种类及其用量、悬浮介质的种类及其用量的研究,获得了球形复合吸附剂的最佳合成路线与工艺.球形吸附剂粒径为1～2mm。通过荧光分析和电镜扫描分析,表明三油酸甘油酯已被包埋到醋酸纤维基体中,并得到了均匀分散。采用七氯、狄氏剂、异狄氏剂、灭蚁灵为代表性的持久性有机污染物(POPs)。动力学吸附实验表明,当初始浓度为1μg/L时,在快速吸附阶段,溶液中80%的氯、狄氏剂、异狄氏剂可得到有效去除,但并没有达到吸附平衡。快速吸附完后,还在持续地进行慢速吸附。而对于灭蚁灵,吸附速度远远低于其他几种POPs。实验证明了吸附速度不仅与辛醇/水系数有关,而且还与有机污染物的分子结构有关。