Tert-butylation of Toluene with Tert-butyl Alcohol over Realuminated H-mordenite Zeolite

The realuminated H-mordenite catalysts(HM1-4) treated with different concentrations of NaOH and NaAlO2 aqueous solutions were prepared,and characterized by inductively coupled plasma(ICP),X-ray diffraction(XRD),Fourier transform-infrared spectroscopy(FT-IR) and temperature-programmed desorption of ammonia,They are of lower Si/Al ratio and higher acid amount while keeping a high relative crystallinity.Their catalytic per-formances were evaluated with the liquid-phase tert-butylation of toluene with tert-butyl alcohol in a 100 ml stainless steel batch reactor equipped with a stirrer.HM2 zeolite catalyst,obtained by treating HM in 0.1 mol·L-1 NaOH followed by 0.05 mol·L-1 NaAlO2 aqueous solution,shows a higher catalytic activity because of its highest acid amount.For HM2 catalyst the influences of reaction conditions on catalytic performance were investigated.The conversion of toluene is 50.3% and the selectivity of p-tert-butyltoluene is 74.7% at a temperature of 180°C,2 of molar ratio of tert-butyl alcohol to toluene,4h of reaction time and 0.2 of M(catalyst)/M(toluene).

The Inhibition Effect of Tert-Butyl Alcohol on the TiO_2 Nano Assays Photoelectrocatalytic Degradation of Different Organics and Its Mechanism

The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was reported. The adsorption performance of these organics on the TNA photoelectrode was investigated by using the instantaneous photocurrent value, and the degradation property was examined by using the exhausted reaction. The results showed that glucose exhibited the poor adsorption and easy degradation performance, phthalate showed the strong adsorption and harddegradation, but TBA showed the weak adsorption and was the most difficult to be degraded. The degradation of both glucose and phthalate could be inhibited evidently by TBA. But the effect on glucose was more obvious. The different inhibition effects of TBA on different organics could be attributed to the differences in the adsorption and the degradation property. For instance, phthalate of the strong adsorption property could avoid from the capture of·OH radicals by TBA in TNA photoelectrocatalytic process.

Isobaric Vapor–Liquid Equilibrium for tert-Butyl Alcohol + Water + Propane-1,3-Diol + 1-Ethyl-3-Methylimidazolium Chloride at 101.3 kPa

In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.

Effect of Different Salts on the Solubilities of Benzene and Diphenyl in t-Butyl Alcohol-Water Mixture and Hydrophobic Interaction

The solubilities of benzene and diphenyl in mixed solvents of t-butyl alcohol(TBA) and water with different salts have been determined at T = 298.15, 303.15, 308.15 and 313.15K. The molar fraction of TBA [x(TBA)] in mixed solvent is 0.045, and the molality of the salts (m_s)in mixed solvents are 0.000, 0.250, 0.500, 0.750 and 1.000 mol/kg, respectively. The standard Gibbsenergies of solution of benzene and diphenyl in the mixed solvents have also been calculated basedon the solubility data. The effects of different salts on the hydrophobic interaction (HI) forbenzene-benzene pair in the systems were discussed.

Solubilities of benzene, toluene and diphenyl in the t-butyl alcohol+water mixtures and hydrophobic interaction

The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100, respectively. The standard Gibbs energies of solution of benzene, toluene and diphenyl in the mixed solvent have also been calculated based on the solubility data. The hydrophobic interactions (HI) for the pairs of benzene-benzene, methane-benzene and methane-methane in the mixed solvent were calculated and discussed.

Heteropolyacids Catalysis in Synthesizing Butylacrylate

The catalytic activities of some heteropolyacids(HPAs) in synthesizing butyl acrylate are reported. It has been demonstrated that 12 tungstophosphoric acid is the most effective catalyst among more than 20 HPA(salts). Various factors concerned in this reaction have been investigated. The optimum conditions have been found, that is, the molar ratio of alcohol to acid is 1.2∶1.0 , the catalyst concentration 1%(mass fraction), the reaction time 2 h, the temperature 98—124 ℃ and a certain amount of polymerization inhibitor exists.

Phenol Tert-Butylation Catalyzed by Zeolite H-Mordenite

Para-tert-butyl phenol (p-TBP) and 2,4-di-tert-butyl phenol (2,4-DTBP) are widely used for the preparation of antioxidants. Zeolite catalysts showed good performance for the synthesis of p-TBP and 2,4-DTBP. In this work, zeolite H-mordenite (HM) catalyst was prepared and the alkylation of phenol with tert-butyl alcohol over zeolite HM catalyst was investigated at different reaction conditions. It is found that increasing temperature enhances the selectivity to p-TBP and the optimum reaction temperature for phenol conversion is 438 K. Increasing flow rate decreases phenol conversion apparently while the selectivity to p-TBP has a little increase. The suitable tert-butyl alcohol/phenol molar ratio is 2. Lower alcohol/phenol molar ratios are beneficial to p-TBP while higher ones are helpful for producing 2,4-DTBP.

正丁醇-盐酸法测定花生红衣中原花青素的方法优化

以花生红衣为原料,以原花青素含量为指标,采用优化后的正丁醇-盐酸法测定花生红衣提取物中原花青素的含量。通过单因素试验确定液料比、烘箱温度、保温时间对原花青素含量的影响。采用响应面软件,以单因素试验为基础,设计三因素三水平的响应面试验,并对试验结果进行分析。结果表明,影响花生红衣中原花青素含量的因素顺序为液料比>烘箱温度>保温时间,根据实际试验可行性,优化后的正丁醇-盐酸法的最佳条件分别为液料比65∶1(mL/g)、烘箱温度90℃、保温时间60 min,在此条件下原花青素的含量达到最高为135.003 mg/g。该方法的加标回收率为97.48%~98.78%,相对标准偏差为0.4%~1.1%。优化后的正丁醇-盐酸法具有较高的准确度和精密度,可为原花青素含量的测定方法优化提供参考。

渗透汽化膜分离技术回收废水中有机溶媒的应用探析

精细化工/医药企业废水产生量巨大,且其中往往含有高附加值有机溶媒。废水直接排放会增加企业环保部门压力,回收又苦于没有理想技术。渗透汽化是一种用于液相混合物分离的新型膜分离技术,具有绿色环保、高效节能等优点,能够实现液相中有机溶媒的高效富集,因此在废水提浓减量、有机溶媒回收等方面有着巨大应用潜力。总结了基于PDMS膜的渗透汽化技术在异丁醇-水、乙酸丁酯-水、乙腈-水体系中的应用效果及诸多优势,为该技术工程化提供理论支撑。

丁烯水合反应器床层压差的研究进展

正丁烯直接水合法合成SBA是甲乙酮生产工艺中的重要环节,直接水合法与传统的硫酸间接水合法相比具有流程短、占地省、投资少、三废排放量小、选择性好等优点。在以强酸性阳离子交换树脂为催化剂进行正丁烯水合反应工艺研究过程中,观察到随着反应时间增加,水合反应床层压差升高并伴有床层压力震荡产生。本文分析了丁烯水合反应运行过程中床层压差升高的原因,提出了降低反应器压差的方法,有效的保证了水合反应装置的正常平稳运行。

钯催化炔丙醇与叔丁基异腈选择性合成吡咯并呋喃衍生物和氨基甲酸酯

报道了钯催化下炔丙醇与叔丁基异腈反应高选择性合成吡咯并呋喃衍生物和氨基甲酸酯的新方法.在10%(摩尔分数)Pd(OAc)_(2)与110%(摩尔分数)LiBr存在下,一分子炔丙醇与三分子叔丁基异腈在水的参与下发生“有序的”异腈三重插入反应,以56%~73%的产率高选择性地生成了吡咯并呋喃衍生物;而在10%(摩尔分数)Pd(PPh_(3))_(4)和110%(摩尔分数)K_(3)PO_(4)存在下,一分子炔丙醇与一分子叔丁基异腈在空气中氧气的参与下发生简单氧化偶联反应,以51%~74%的产率生成了氨基甲酸酯.该方法仅通过简单改变钯催化剂与盐的种类就能得到不同产物,且反应选择性高,分别为吡咯并呋喃亚胺衍生物和氨基甲酸酯提供了有吸引力的合成途径.

仲丁醇脱氢制甲乙酮催化剂的研究

采用BC-DH2004催化剂进行仲丁醇脱氢合成甲乙酮的研究.考察不同催化体系的热稳定性,并考察催化剂的堆密度、助剂含量和仲丁醇的原料组成对BC-DH2004催化剂性能的影响及BC-DH2004催化剂多周期运行的稳定性.实验结果表明,BC-DH2004催化剂的热稳定性好;在反应温度250～270℃、液态空速4 h-1的条件下,仲丁醇脱氢产物中甲乙酮的质量分数大于80%,碳八酮的质量分数小于3%;具有适当的堆密度和助剂含量的催化剂性能较好;经再生后催化剂的性能稳定,操作周期大于1 250 h.

H型丝光沸石催化剂催化甲苯与叔丁醇的烷基化反应

针对合成对叔丁基甲苯传统工艺中存在的缺点,采用环境友好、可重复利用的H型丝光沸石催化剂(以下简称催化剂)进行了甲苯与叔丁醇的烷基化反应,并用X射线衍射和氨程序升温脱附等方法对不同焙烧温度下得到的催化剂的物相结构和酸性质进行了表征,研究了各种反应条件对催化剂的催化性能的影响。实验结果发现,在适宜的操作条件下,即催化剂的焙烧温度823K、反应温度180℃、反应时间3h、初始压力1.0MPa、原料与催化剂的质量比为8、叔丁醇与甲苯的摩尔比为4、溶剂环己烷与甲苯的摩尔比为5时,甲苯转化率达42.73%,叔丁基甲苯的选择性为96.30%,对叔丁基甲苯的选择性为80.37%。

SO_3H—离子液体催化苯酚和叔丁醇选择性烷基化反应

研究了SO3 H—功能化离子液体催化苯酚与叔丁醇的烷基化反应。考察不同的功能化离子液体、反应时间、反应温度、苯酚与叔丁醇的摩尔比以及离子液体的用量等反应条件对烷基化反应的影响,并考察了离子液体的循环使用。研究结果表明在优化的反应条件(n(苯酚) /n(叔丁醇) =1∶2 ,15mmol离子液体,10mmol苯酚,70℃,8h)下,苯酚的转化率和选择性分别为80 .4 %和6 0 .2 % ;离子液体重复使用三次,其催化活性不变。此外根据产物的分布,讨论了烷基化的反应机理。

硫酸氢钠催化合成尼泊金丁酯

应用一水硫酸氢钠催化正丁醇与对羟基苯甲酸的酯化反应,合成了尼泊金丁酯。研究结果表明,硫酸氢钠具有较高的催化活性。考察了对羟基苯甲酸/正丁醇摩尔比、催化剂用量及反应时间对酯产率的影响。在典型反应条件(对羟基苯甲酸/正丁醇/硫酸氢钠的摩尔比=1∶2∶0.072回流分水5h)下,所得尼泊金丁酯的产率为92.8%。该催化剂易于回收,且可重复使用。

广西产美味猕猴桃根正丁醇部位化学成分研究

目的：研究广西产美味猕猴桃根正丁醇部位的化学成分。方法：应用色谱技术分离纯化，根据理化性质和波谱数据鉴定化合物结构。结果：从美味猕猴桃根正丁醇部位中分离并鉴定了6个化合物，分别为毛花猕猴桃酸B（1），2a，3β，24-三羟基-12-烯-28-乌苏酸（2），2a，3a，24-三羟基-12-烯-28-乌苏酸（3），2a，3a，23-三羟基-12，20（30）-二烯-28-乌苏酸（4），2α，3α，24-三羟基-12，20（30）-二烯-28-乌苏酸（5），正丁基-O-β-D-吡喃果糖苷（6）。结论：化合物1—4，6均为首次从该植物中分离得到，其中化合物6为首次从猕猴桃属植物中分得。

叔丁醇基凝胶注模工艺制备轻质、高强莫来石多孔陶瓷

以叔丁醇为成型溶剂,莫来石粉为起始原料,采用凝胶注模成型方法制备出轻质、高强莫来石多孔陶瓷.莫来石多孔陶瓷中的孔隙形成于干燥过程中叔丁醇的快速挥发,孔隙分布均匀且相互连通.随烧结温度升高,气孔率、开气孔率和比表面积分别由77.8%、76.0%和10.39m2/g下降到67.6%、65.5%和4.26m2/g,而抗压强度则由3.29MPa显著提高到32.36MPa,材料孔径大小受烧结温度影响较小,孔径尺寸呈单峰分布,且几乎所有的气孔都为开口气孔,透气度与孔径尺寸具有一致的变化关系.莫来石多孔陶瓷在高气孔率条件下仍然保持高强度的主要原因是材料中均匀的孔隙结构、孔径尺寸小且相对集中、以及因烧结颈的形成在空间上所表现出的一种颗粒搭接骨架结构.

叔丁醇共溶剂用于制备生物柴油的研究

利用叔丁醇作为共溶剂可使棕榈油、甲醇和催化剂形成均相体系,用于酯交换反应制备生物柴油,可以缩短反应时间。实验以棕榈油为原料,氢氧化钠为催化剂,在带夹套的玻璃反应器内进行反应。考察了共溶剂质量分数、催化剂质量分数、反应温度、醇油摩尔比等因素对生物柴油产率的影响,获得了最佳反应条件。实验结果表明,当叔丁醇质量为棕榈油质量的11.6%,催化剂质量为油质量的1.0%,反应温度为60℃,醇油摩尔比为6∶1时,反应2 m in后生物柴油产率达到了90%。

生物滴滤塔处理药厂含醋酸丁酯、正丁醇和苯乙酸的挥发性混合废气

研究采用装有特制ZX0 2型填料的生物滴滤塔 ,对某药厂青霉素车间现场发生的主要含醋酸丁酯、正丁醇和苯乙酸等混合废气进行了 3个多月的连续处理中试试验 .主要考察了醋酸丁酯、正丁醇和苯乙酸的进气污染物质量负荷 (Nw)、停留时间和喷淋水量对各自去除率的影响及生物降解性能 .实验运行结果表明 ,当醋酸丁酯、正丁醇和苯乙酸的最大Nw 为 2 2 9 5g/ (m3 ·h)、2 75 . 4 g/ (m3 ·h)和 4 2. 5 g/ (m3 ·h)时 ,其去除率分别为 96 %、95 %和 10. 0 % .说明本生物滴滤塔能有效去除该厂混合废气 ,其最佳运行参数为 :停留时间 31 .2s ,喷淋水量为 4L/ (L·d) .该滴滤塔抗冲击负荷能力强 ,无堵塞现象 ,无需经常进行反冲洗 ,可长期稳定运行 .

隔离壁精馏塔萃取精馏制无水叔丁醇研究

用隔离壁精馏塔萃取精馏制无水叔丁醇,在溶剂比为1.5,回流比为2∶1,叔丁醇原料进料速度为1.7 mL/min时,塔顶叔丁醇的质量分数达到99.6%;塔釜乙二醇的质量分数达到97.7%,可直接作萃取剂循环利用。用AspenPlus对该工艺和二塔萃取精馏工艺对比,结果与实验相一致,塔顶叔丁醇质量分数的相对误差为0.4%,塔釜乙二醇质量分数的相对误差1.3%。结果显示,该工艺比现有工艺省了1个塔、1个再沸器和1个冷凝器,节能27%,降低了能耗和设备投资。