十二烷基苯磺酸钠对2-甲基吡啶电氧化的影响

通过恒电位电解实验,在以质子交换膜为隔膜的电解槽内,将十二烷基苯磺酸钠(SDBS)添加于2-甲基吡啶电氧化的有机合成体系中,研究了2-甲基吡啶在PbO2电极上的电氧化行为。通过实验确定最佳条件为:2-甲基吡啶浓度为0.5mol·L-1,H2SO4浓度为1.0mol·L-1,丙酮/水(3∶1)为溶剂,阳极电位为1.8V,反应温度为30℃,SDBS浓度为1.6×10-3mol·L-1,电解理论电量的20%,其选择性为81.98%,电流效率为59.32%。在该实验环境下,SDBS对2-甲基吡啶电氧化有明显的促进作用,选择性和电流效率都有明显的提高。     

三步法制备2-吡啶甲醇的研究

研究以2-甲基吡啶等为原料,经过氧化、酰化重排、水解反应合成2-吡啶甲醇。探讨了反应时间、反应温度、原料配比等对氧化反应过程的影响,氧化反应的最佳工艺条件是:反应时间,15h;反应温度,75℃;原料摩尔配比为n(2-甲基吡啶)∶n(冰乙酸)∶n(双氧水)=1∶4∶3,2-甲基吡啶N-氧化物的收率为88.12%。对2-甲基吡啶N-氧化物进行酰化重排和水解反应,并对最终产物进行FT IR、1 H NMR表征和HPLC检测,结果表明:最终产物为2-吡啶甲醇,纯度为98.94%。     

卢帕他定中间体5-甲基烟酸的合成

以3,5-二甲基吡啶为原料,用高锰酸钾选择性氧化,合成抗过敏性药物卢帕他定中间体5-甲基烟酸。经正交化试验,其合成最佳工艺是:n(3,5-二甲基吡啶)∶n(KM nO4)=1∶1.8,反应温度45℃,反应时间3h。反应收率62%,HPLC大于99%,产物经IR表征。     

4-甲基吡啶直接电氧化合成异烟酸工艺条件的研究

以Ti/PbO2为阳极,Pb为阴极,硫酸溶液为电解质,在阳离子交换膜为隔膜的H型电解槽中,直接电氧化4-甲基吡啶合成异烟酸,并考察了阳极电解液中4-甲基吡啶及硫酸浓度,通电量,电流密度和温度对异烟酸收率和电流效率的影响,得到的工艺条件为阳极电解液中4-甲基吡啶和硫酸的质量分数分别为10%和25%,通电量18.65(A.h),电解电流密度60 mA/cm2,60℃,在此条件下重复试验,异烟酸平均收率达到92.2%,平均电流效率50.9%。     

合成2-氰基吡啶的新型催化剂开发

采用捏合法制备了以铬为主,银、铈为助剂的钒钛催化剂,并在固定床反应器中考察其催化2-甲基吡啶氨氧化合成2-氰基吡啶.结果表明,在反应温度374℃,物料n(2-甲基吡啶):n(氨):n(空气)=1:2.5:45和空速1.2 h-1的最佳反应条件下,2-甲基吡啶转化率为99.6％,2-氰基吡啶收率为88.4％.     

2-氯甲基-3-甲基-4-(2,2,2-三氟乙氧基)-吡啶的合成研究

以2,3-二甲基吡啶为原料,经过氧化、硝化、取代、酰化以及氯化反应,合成目标产物2-氯甲基-3-甲基-4-(2,2,2-三氟乙氧基)-吡啶,5步总收率为35.6%。对中间体2,3-二甲基-4-(2,2,2-三氟乙氧基)-吡啶-N-氧化物的合成条件进行了优化选择,其较佳的合成条件:甲基异丁基甲酮作为溶剂,四丁基溴化铵为相转移催化剂,n(三氟乙醇)∶n(K2CO3)∶n(2,3-二甲基-4-硝基吡啶-N-氧化物)=4.5∶1.2∶1,反应时间12 h,反应温度95℃,所得中间体收率91.9%,所得中间体结构经1HNMR表征,确定为2,3-二甲基-4-(2,2,2-三氟乙氧基)-吡啶-N-氧化物。     

3-甲基苯丙酮的合成方法研究

以溴乙烷和镁屑为原料,四氢呋喃为溶剂制备乙基溴化镁格氏试剂。格氏试剂和间甲基苯甲醛反应得到3′-甲基苯丙醇,随后采用氯铬酸吡啶鎓盐(Pcc)氧化得到产品3′-甲基苯丙酮。收率为72%,纯度为98%(HPLC)。优化反应条件为:n(溴乙烷)∶n(镁屑)∶n(间甲基苯甲醛)=1.2∶1.1∶1.0,氧化反应温度为40℃。     

2-(4′-羟基苯氧基)-3-氯-5-三氟甲基吡啶的合成

以对苯二酚与2,3-二氯-5-三氟甲基吡啶单醚化合成精吡氟氯禾灵的重要中间体2-(4′-羟基苯氧基)-3-氯-5-三氟甲基吡啶。探讨并得到了反应的最佳工艺条件:K2CO3为缚酸剂,二甲基亚砜和甲苯为溶剂,n(2,3-二氯-5-三氟甲基吡啶)∶n(对苯二酚)∶n(K2CO3)=1∶2∶1.08,不需要脱水。在回流条件下加入2,3-二氯-5-三氟甲基吡啶并反应5 h。在此条件下,2,3-二氯-5-三氟甲基吡啶的转化率100%,产品的选择性大于98%。     

2,3-二甲氧基-5-甲基-1,4-苯醌的合成

以3,4,5-三甲氧基甲苯(TMT)为原料,先由V ilsm e ier-Haack反应合成6-甲基-2,3,4-三甲氧基苯甲醛,然后在对甲基苯磺酸催化下经Dak in反应将其氧化为6-甲基-2,3,4-三甲氧基苯酚,最后用重铬酸钠催化氧化合成了辅酶Q0,过程总收率达到72.3%。经正交实验得V ilsm e ier-Haack反应的最佳工艺为:n(TMT)∶n(POC l3)∶n(DMF)=1∶1.8∶2.2,反应温度70℃,反应时间7 h。在此工艺条件下,此步反应收率可达93.2%,w(6-甲基-2,3,4-三甲氧基苯甲醛)=98.5%;在Dakin反应中,以w(H2O2)=30%为氧化剂,30℃为最佳反应温度,反应时间1.5 h。     

3-氰基吡啶的合成工艺优化

以Al2O3为载体,负载Cu、Na制备得到氨氧化催化剂,以固定床为反应器,将3-甲基吡啶和氨气、空气氧化,合成得到3-氰基吡啶.考查了Cu、Na含量,催化剂用量、原材料摩尔比、反应温度的影响.反应的最优条件为Cu含量2.5％,Na含量0.9％,反应温度340℃,催化剂用量6％,3-甲基吡啶/氨气(n/n)=1.05:1,氨气/空气(n/n)=1:9,此时3-甲基吡啶的收率高于92％.     

防垢功能纳米乳液制备与性能研究

以表面活性剂Span 80和Tween 80与正构烷烃为主要原料,应用正交设计实验方法优化出微乳液形成的最佳条件:油相选正庚烷或正辛烷,Span 80与Tween 80质量比(1∶1.5)～(1∶2),Span 80浓度3.9%～4.2%,正丁醇浓度7.0%～9.0%。将3种防垢成分FG-1、FG-2和FG-3分散于微乳液水相中,形成稳定均相的防垢纳米乳液。性能评价结果表明,含有防垢剂FG-1和FG-2的纳米乳液防垢率分别为90.1%和89.6%,与地层水接触后无絮凝物;含有FG-2的纳米乳液防垢剂吸附性好,解吸速率慢,并且高矿化度下仍有较好的防垢性能。与现用防垢剂商品相比,纳米乳液的防垢率随时间变化具有一个峰值,大大增加了防垢剂作用时间,提高了防垢效果,并对岩石渗透率有一定的修复能力。     

羟基新戊酸的电化学合成

在质子交换膜电解槽中,以PbO2 为阳极,以羟基新戊醛为原料,利用直接电氧化方法合成羟基新戊酸。通过四因素三水平正交实验,得到最佳合成条件:pH=1,阳极电位1 65V,反应物浓度0 22mol/L,反应温度15℃。在此条件下,该反应的选择性达到91 6%,电流效率达到56 9%。研究发现,在4个影响因素中,pH对选择性和电流效率的影响最大。通过耗竭性电解实验,得到消耗电量与转化率的关系,可以由消耗电量近似地估算反应物的转化率。     

Efficient recovery of phenol from phenolic wastewater by emulsion liquid membrane

The recovery of phenol from phenolic wastewater by emulsion liquid membrane (ELM) was investigated. The W/O emulsion was prepared with kerosene, Span−80, carrier, liquid paraffin, and NaOH solution. The effects of NaOH concentration, oil–internal solution ratio, shearing speed, Span−80 concentration, and carrier type and concentration on emulsion breakage were studied. In the single factor experiments of stability of W/O emulsion, the lowest percentages of emulsion breakage were achieved at a NaOH concentration of 0.03 g/ml, an oil–internal solution ratio of 2:1, a shearing speed of 1500 r/min, a Span−80 concentration of 8%, a tributyl phosphate (TBP) concentration of 0.8%, and an ethyl acetate concentration of 0.8%, respectively. Then, the effects of nine factors on extraction efficiencies of phenol were investigated. This indicated that the effects of shearing speed, oil-internal solution ratio, emulsion-external solution ratio, liquid paraffin concentration, and mixing speed on extraction efficiencies of phenol were limited. However, the carrier concentration, NaOH concentration, Span−80 concentration, and phenol concentration had important impacts on the extraction efficiency of phenol. The extraction efficiency of phenol could reach 99.7%. Besides, the results of orthogonal experiments indicated that during the extraction of phenol by ELM, the order of importance of factors was NaOH concentration > emulsion-external solution ratio > volume fraction of Span−80 > volume fraction of TBP. After extraction, the recycled emulsion with Span−80 could not easily be effectively demulsified through heating, which only provided the highest demulsification efficiency of 18.2%. However, the recycled emulsion could be effectively demulsified through centrifugation, which could get the highest demulsification efficiency of 86% at a centrifugal rotational speed of 2000 r/min and a centrifugal time of 25 min.     

淀粉接枝共聚物微球的合成研究

用V(环己烷)∶V(淀粉溶液)=4∶1构成反相悬浮体系,m(Span60)∶m(Tween60)=2∶1复配为分散剂,在60℃下以K2S2O8-NaHSO3引发N,N’-亚甲基双丙烯酰胺(MBAA)与淀粉的接枝共聚,制备了淀粉接枝共聚物微球。正交实验表明,合成共聚微球的较优工艺条件为:淀粉液浓度20%,引发剂用量0.2 g,MBAA用量0.4 g,油水比为3∶1,乳化剂用量1.0 g。用SEM和粒度分析仪对微球形貌和粒度分布进行了研究,用FT-IR对其结构进行了表征,用XRD,TGA对其物性进行了分析。结果显示,共聚物微球形态圆整,平均粒径50.2μm,微球中存在酰氨基结构,与淀粉颗粒相比,结晶度降低,热稳定性提高。     

铜盐法分离3-甲基吡啶与4-甲基吡啶

3-甲基吡啶（3-MPD）与4-甲基吡啶（4-MPD）主要来源于吡啶、3-甲基吡啶合成的副产物以及煤焦油，但由于两者是沸点十分相近（分别为144．14℃、145℃）的同分异构体，依靠传统的分离方法，如精馏、普通的溶剂萃取，无法将其分离开来。3-甲基吡啶与4-甲基吡啶混合体系的分离技术主要有化学转化法、共沸精馏法、反应蒸馏法、吸附分离法、解离萃取法以及其他方法。其中铜盐法在常压或低压下操作，操作安全可靠。适用于工业化生产。     

丙烯酰胺反相微乳液体系的制备、聚合及表征

本论文探讨了用Span80,Tween60为复合乳化剂,煤油为分散介质,制备丙烯酰胺的反相微乳液,并研究了所形成微乳兴的微观结构和影响该微乳液体系聚合反应的因素,本文重点研究了复合乳化剂的配比,丙烯酰胺反相微乳液体系的形成机理,并通过紫外分光光度计,旋转粘度计等对微乳液体系可能形成的微观结构和特性进行了分析探讨。其后,采用氧化还原引发剂体系进行了微乳液聚合,并对聚丙烯酰胺的物理性能,化学结构,相对分子质量等进行了测定和表征。     

Effect of pyridine and its derivatives on the electrodeposition of nickel from aqueous sulfate solutions. Part II: Polarization behaviour

The electrochemical reactions occurring during electrodeposition of nickel from acidic sulfate solutions were examined by cyclic and linear sweep voltammetry techniques. The effect of pyridine, 2-picoline and 4-picoline on the electrode polarization behaviour and electron transfer parameter of the cathodic reduction process was also investigated. Strongest electrode polarization was seen with 4-picoline. The order of cathodic polarization was 4-picoline > 2-picoline > pyridine. Kinetic parameters such as Tafel slope, transfer coefficient and exchange current density were determined to analyse the nature of the electrode reactions. The exchange current density for nickel deposition on nickel and stainless steel substrates was in the order 4-picoline < 2-picoline < pyridine.     

Treatment of Biodiesel Wastewater by Combined Electroflotation and Electrooxidation Processes

The objective of this research was to determine the optimum conditions for biodiesel wastewater treatment using a combined electroflotation and electrooxidation process in a bench-scale reactor. The effects of current density, conductivity, and reaction time were studied and optimized. The experimental results show that electroflotation (pre-treatment) could effectively remove turbidity, total solids, oils and greases, chemical oxygen demand and methanol by 92%, 98%, 100%, 57%, and 23%, respectively, using aluminum electrodes and applying a current density of 8.0 mA cm^?2 for a reaction time of 60 min. After pre-treating, the effluent was subjected to electrooxidation using Ti/RuO₂ anodes. The efficiency of the applied current density and reaction time were evaluated and optimized. The experimental results shows that electrooxidation could effectively remove the residual methanol and chemical oxygen demand by 68% and 95%, respectively, by applying a current density of 40.0 mA cm^?2 for a reaction time of 240 min.     

Comparative Study of Electrocoagulation and Electrooxidation Processes for the Degradation of Ellagic Acid From Aqueous Solution

A comparative study of electrocoagulation and electrooxidation processes for the degradation of ellagic acid from aqueous solution was carried out. For the electrocoagulation process, metallic iron was used as electrodes whereas graphite and RuO₂/IrO₂/TaO₂ coated titanium electrodes were used for the electrooxidation processes. The effect of the process variables such as initial pH, concentration of the supporting electrolyte, applied current density, electrolysis time, and anode materials on COD removal were systematically examined and discussed. Maximum COD removal of 93% was obtained at optimum conditions by electrocoagultion using an iron electrode. The ellagic acid was degraded completely by electrooxidation using graphite electrodes under the optimum conditions. During electrooxidation, the chloride ion concentration was estimated and the effect of the Cl^? ion was discussed. The finding of this study shows that an increase in the applied current density, NaCl concentration, and electrolysis time enhanced the COD removal efficiency. The UV–Vis spectra analysis confirms the degradation of ellagic acid from aqueous solution.     

反相微乳液法制备陶瓷彩喷墨水(Ⅰ)

系统地研究了Span80-Tween60/助乳化剂/油/FeCl3反相微乳液体系。通过正交实验,进行方差分析,得出最佳反相微乳液体系。通过均匀实验和全面实验,绘制出体系的拟三元相图,并由相图得出体系的最佳比例。绘制出最大溶水量与温度的曲线,从而确定最佳乳化温度。在最佳温度、最佳比例下,配制出两种墨水,并测定了墨水的表面张力、粘度、电导率和稳定性等性能。