改性ZSM-5分子筛上乙醇胺催化胺化合成乙撑胺

研究了改性的ZSM-5沸石分子筛：F-ZSM-5、NiO-ZSM-5以及普通的H-ZSM-5沸石分子筛,在乙醇胺(MEA)催化胺化合成乙撑胺的反应中的催化性能。重点考察了催化剂酸性以及反应温度对反应的影响。F-ZSM-5与H-ZSM-5相比,有较高的酸中心密度和强度,反应中有利于生成乙二胺(EDA)。而NiO-ZSM-5含有大量中等强度的酸中心,有利于三乙烯二胺(TEDA)生成。以F-ZSM-5和NiO-ZSM-5为催化剂,在t=340℃、重量时空速度WHSV：1．1h～、NH3：MEA：H20=4．5：1．0：1．0的反应条件下,原料MEA的转化率分别为52-31％和96．40％：产物EDA、PIP、TEDA的选择性分别为8．60％、20．49％、46．99％和2．98％、13．24％、66．10％。当温度大于340℃时,MEA的转化率略有提高,但上述所希望的三种产品的选择性由于副反应的增多而很快下降。     

无毒增塑剂乙酰柠檬酸三丁酯的合成

用氨基磺酸两步法催化合成乙酰柠檬酸三丁酯。实验确定了最佳工艺条件 :(1 )酯化反应 :以 0 2mol柠檬酸为基准 ,n (柠檬酸 )∶n (正丁醇 ) =1 0∶4 0 ,m(催化剂 ) =1 5g ,t =1 1 0～1 6 0℃ ,t=2 5h ,转化率为 98 2 % ;(2 )乙酰化反应 :以 0 2mol柠檬酸三丁酯为基准 ,n (柠檬酸三丁酯 )∶n (乙酸酐 ) =1 0∶1 5 ,m(催化剂 ) =2 0g ,t =85℃ ,t=1 5h ,乙酰化收率为 91 3%。催化剂易回收 ,可循环使用 ,不污染环境。     

3,3′-二氯联苯胺的合成

以邻硝基氯苯 (Ⅰ)为起始原料 ,经过三步化学反应合成 3,3′ 二氯联苯胺 (Ⅳ ) :Ⅰ在 0 .2g 1,4 萘醌催化下与CH2 O NaOH[m(NaOH)∶m(CH2 O) =0 .95∶1 0 0 ]在 5 6～ 5 7℃反应 7h ,得到 2 ,2′ 二氯氧化偶氮苯 (Ⅱ) ,产率 91.0 % ;Ⅱ在 0 .5gAl-Ni合金及 0 .3g 1,4 萘醌催化下与水合肼在 5 6～ 5 7℃反应 7.5h ,得到 2 ,2′ 二氯氢化偶氮苯 (Ⅲ) ,产率 97.0 % ;Ⅲ在盐酸中分别于 5℃反应 2h、于 10℃反应 11h、于 2 3～2 4℃反应 11h ,得到Ⅳ ,产率 96 .9%。Ⅳ的总产率可达 85 .5 % ,纯度w (Ⅳ) =97.7%     

一锅法合成苯甲醛缩氨基脲

以水合肼、尿素和苯甲醛为原料 ,一锅法合成苯甲醛缩氨基脲 ,该工艺中间产物氨基脲不以氨基脲盐酸盐形式分离 ,直接与苯甲醛进行缩合反应 ,且不产生含肼废水。适宜的反应条件为 :n (H2 NNH2 ·H2 O)∶n (H2 NCONH2 )∶n (C6H5CHO) =1 0∶2 0∶0 8,氨基脲合成反应温度 98～ 10 1℃ ,反应时间 3～ 4h ;缩合反应pH =3～ 4 ,滴加时间 1 5h ,室温搅拌 2h ,回流 1h ,产物收率为 98.0 %。     

高碳脂肪醇磷酸酯合成的~(31)P-NMR波谱研究

采用 3 1　P NMR波谱对高碳脂肪醇与五氧化二磷的反应进行了研究 ,定量地表征了产物混合物中的各组分。结果表明 :单酯 (MAP)、双酯 (DAP)、聚酯 (PAP)和磷酸盐 (PA)在 3 1　P NMR波谱上的化学位移分别为 :3 5～ 4 6 ,0 8～ 1 1,- 9 0～ - 10 0和 3 0～ 3 5 (当pH =9时 )。同时为不同用途的脂肪醇磷酸酯盐提供了可选择的和稳定的合成条件 ,即 :在n(ROH)∶n(P2 O5) =(2 3∶1 0 )～ (3 1∶1 0 ) ,反应时间 2～ 3h ,反应温度不大于 10 0℃条件下 ,P2 O5的转化率大于 95 % ,MAP、DAP和PAP的选择性分别为 4 0 %～ 6 5 % ,2 5 %～ 33%和 10 %～ 30 %。     

2,4-二氟联苯的Friedel-Crafts乙酰化工艺研究

研究了 2 ,4 二氟联苯的Friedel Crafts酰化反应的特性。确定了该反应的最佳条件为 :t=2 0℃ ,n(AlCl3)∶n(2 ,4 二氟联苯 ) =2 5∶1 0 ,t=2 5～ 3.0h。在最佳反应条件下 ,收率≥ 93% ,w〔4 (2′,4′ 二氟苯基 ) 苯乙酮〕 =98%。     

乙醇胺催化合成乙撑胺的研究

以乙醇胺（MEA）为原料,ZSM-5分子筛为催化剂,采用缩合工艺合成了乙撑胺。考察了反应温度、n（NH3）∶n（MEA）及空速LHSV（MEA）对乙醇胺的影响。反应所用原料为质量分数50%的乙醇胺溶液。为增加乙二胺（DEA）和哌嗪（PIP）的选择性,适宜的条件为：n（NH3）∶n（MEA）=13,LHSV（MEA）=0.300 h-1,反应温度350℃,选择性S（DEA）=17.78%,S（PIP）=20.46%,S（TE-DA）=21.99%,转化率约为70%。     

青霉素制备青霉素亚砜的研究

以青霉素G钾盐与低质量分数过氧乙酸为原料氧化制备青霉素亚砜 ,其最佳工艺条件为 :n(C16 H18N2 O4 SK)∶n(CH3CO3H) =1 .0∶( 1 1～ 1 2 ) ,反应温度 0～ 5℃ ,反应时间 2 .0～ 2 5h ,w(CH3CO3H) =8 5% ,w(CH3CO2 H) =1 0 %。青霉素亚砜收率达 96 8%。同时建立了青霉素亚砜的半定量分析方法 ,以硅胶G为固定相 ,以V(CH3CO2 C4 H9 n)∶V(CH3CO2 H)∶V(NaH2 PO4 -H2 O)∶V(C4 H9OH n) =6.0∶2 .0∶1 .0∶0 5为流动相 ,用TLC法对产品进行半定量分析检测 ,并经IR、MS谱图验证了产品结构。     

间苯二甲酸二甲酯-5-磺酸钠的合成

以w(SO3) =3 0 %的发烟硫酸为磺化剂 ,间苯二甲酸 (IPA)为反应原料制备间苯二甲酸二甲酯 5 磺酸钠(SIPM)。运用正交实验设计 ,确定了最佳磺化反应条件为 :反应温度 185℃ ,反应时间 4 5h ,反应原料配比n(IPA)∶n(SO3) =1 0 0∶1 15。通过高效液色谱 (HPLC)法确定中和深度控制在pH =5 0。SIPM制备收率达到85 2 % ,w(SIPM ) =99 5 % ,各项指标符合美国杜邦公司 2 0 0 0年标准     

连续加压炔化反应合成脱氢芳樟醇

研究了以液氨为溶剂 ,在反应温度 35～ 4 0℃ ,压力 2 0～ 2 5MPa的条件下 ,6 甲基 5 庚烯 2 酮连续加压乙炔化反应制备脱氢芳樟醇工艺 ,考察了反应时间、物料量比对反应的影响 ,并对反应机理作了初步探讨。实验表明 ,反应温度 35～ 4 0℃ ,压力 2 0～ 2 5MPa ,n (6 甲基 5 庚烯 2 酮 )∶n (催化剂 )∶n(乙炔 )∶n(液氨 ) =7∶1∶5 1∶15 3,反应时间为 2 1h ,脱氢芳樟醇收率为 92 %～ 94 % ,产品经减压精馏后 ,脱氢芳樟醇质量分数大于 98%     

乙醇胺缩合胺化反应合成乙二胺研究进展

乙醇胺（MEA）缩合胺化反应是一种绿色、高效的乙二胺（EDA）催化合成技术。本文综述了MEA缩合胺化反应合成EDA的催化反应过程、缩合胺化催化剂及胺化产物分离纯化技术的最新研究进展和动向，重点探讨了缩合胺化反应机理、反应热力学及动力学、催化剂酸性及孔道结构对反应性能的影响、催化剂失活、胺化产物分离纯化技术等，总结了缩合胺化反应合成EDA工艺过程中存在的技术问题。提出通过制备多级孔道沸石分子筛催化剂实现择形催化与高效扩散之间的协调统一；通过强化分子筛催化剂改性方法研究，实现催化剂表面酸性的精确调控。在择形催化和酸催化的协同作用下，有望从根本上解决缩合胺化反应中存在的技术问题，加快缩合胺化反应工艺技术的工业化应用普及。     

Transesterification of rapeseed oil catalyzed by liquid organic amine in supercritical methanol in a continuous tubular‐flow reactor

The catalytic activity of four liquid organic amines, triethylamine (TEA), diethylamine (DEA), ethylenediamine (EDA) and monoethanolamine (MEA), in the transesterification reaction of rapeseed oil in supercritical methanol was studied in this paper. The results showed that the order of the catalytic activity was DEA > TEA > MEA > EDA. The effect of the molar ratio of methanol to oil on the reaction was involved. Further, with TEA as the catalyst, the effect of the reaction pressure on this reaction was investigated. Pressure had a positive effect on this reaction. Additionally, the efficiency of the co‐solvent, including ethyl acetate, propylene oxide, tetrahydrofuran and cyclohexanone, was studied, showing that ethyl acetate had a positive effect on this reaction. The overall results suggested that the methyl ester yield in a continuous reactor was inferior to that in a batch reactor, mainly because of the poor mutual solubility between the oil and methanol. Furthermore, possible mechanisms for this amine‐catalyzed reaction were proposed.     

一种含三嗪环的四臂引发核的合成与表征

以三聚氯氰(CNC)和乙二胺(EDA)为原料,通过亲核取代反应合成了含1,3,5-三嗪环的四臂引发核:N,N′-二-(4,6-二氯-[1,3,5]-三嗪基)-乙二胺。考察了反应物投料摩尔比,碱的种类和用量,加料速率和反应时间对产物收率的影响。结果表明:n(CNC)∶n(EDA)=2∶1,碱用NaOH,且n(NaOH)∶n(EDA)=2∶1,以V(二氯甲烷)∶V(水)=1∶1为溶剂,乙二胺的NaOH水溶液的滴加速率为1 mL/m in,0~5℃反应2 h,收率达95.5%。通过元素分析、质谱、核磁共振、红外光谱对目标产物的结构进行了分析表征。     

改性ZSM-5分子筛催化合成哌嗪

研究了不同金属离子改性得到的M-ZSM-5分子筛在以乙二胺(EDA)为原料合成哌嗪反应中的催化性能。通过NH3-TPD和BET法对催化剂进行表征,结果表明,经过离子交换后HZSM-5的骨架结构没有发生变化,仅仅是表面酸性发生了变化。重点考察了催化剂酸性对反应的影响,实验表明,提高弱酸和中强酸中心所占比例有利于哌嗪(PA)和三乙烯二胺(TEDA)生成。以Zn-ZSM-5和Zn/K-ZSM-5为催化剂,在常压,t=360℃,空速为0.25 g/(min.h),m(EDA)∶m(H2O)=4∶6的反应条件下,原料EDA的转化率分别为94.1%和82.6%;产物PA和TEDA的选择性分别为45.5%,42.1%和29.4%,50.1%。     

苯酚介质中双酚A缩水甘油醚/乙二胺环氧树脂降解工艺与动力学研究

以苯酚为反应介质,在温度280~340℃、时间30~300 min条件下,研究了双酚A缩水甘油醚/乙二胺(DGEBA/EDA)环氧树脂的降解反应,考察了温度、时间等因素对降解的影响。通过气相色谱-质谱联用(GC-MS)和高效液相色谱(HPLC)对液相产物进行了定性和定量分析。结果表明:降解产物为40余种C5-C20有机化合物,相对分子量为93~318,主要组分是苯酚、对异丙基苯酚、双酚A及少量酚类化合物和含氧基团有机物等;温度越高,时间越长,降解程度越大,主要单体收率越高。340℃,70 min时,主产物对异丙基苯酚和双酚A的收率总量最大,分别为25.9%和28.1%。根据反应体系压力随时间的变化曲线初步推断探讨了降解反应的机理,通过实验数据关联,得出降解反应级数为一级,降解反应活化能为100.3 kJ mol 1,对比可知双酚A缩水甘油醚/乙二胺环氧树脂在有机相苯酚中的降解能够降低其反应活化能。最后得到降解反应速率方程为d[ER]/dt=4.5×107exp(1.0×105/RT)[ER]。     

Selective Removal of Carbon Dioxide from Wet CO2/H2 Mixtures via Facilitated Transport Membranes containing Amine Blends as Carriers

The selective separation of carbon dioxide (CO₂) from a wet gaseous mixture of CO₂/H₂ through facilitated transport membranes containing immobilized aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), ethylenediamine (EDA) and monoprotonated ethylenediamine (EDAH⁺) and their blends was experimentally investigated. The effect of CO₂ partial pressure, amine concentration, feed side pressure and amine species on the CO₂ and H₂ permeances were studied. The CO₂ permeability through amine solution membranes decreased with increasing CO₂ feed partial pressure but the H₂ permeance was almost independent of the H₂ partial pressure. A comparison of experimental results showed that single or blended amines with low viscosity and a moderate equilibrium constant, i.e., large forward and reverse reaction rate of CO₂‐amine, are suitable for effective separation of CO₂. The permeability of CO₂ generally increased with an increase in amine concentration, although this increase may be compromised by the salting out effect and decrease in diffusivities of species. The results obtained indicated that CO₂ permeance across a variety of amines are in the order of DEA (2 M) > MD (2 M) > MD (1 M) > MEA (2 M) > MEA (4 M) > MD (4 M) > DEA (1 M) > DEA (4 M) > MEA (1 M) for various concentrations of MEA + DEA blend and are in the order of EDAH⁺ (2 M) > DEA (2 M) > MH (2 M) > DH (2 M) > ED (2 M) > EDA (2 M) > MEA (2 M) for various blends of amine.     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

Interfacial turbulence accompanying chemical absorption

Absorption rates for carbon dioxide into aqueous solutions of EDA and MEA with and without adding surface active agent were measured in a laminar liquid-jet apparatus to check and verify the Marangoni effect. In addition, experiments were conducted for the tracer desorption of ethylene from aqueous EDA and MEA solutions into carbon dioxide or nitrogen stream. It has been concluded that the Marangoni effect cannot be neglected for such short contact times as in a laminar liquid-jet. The Marangoni instability accompanying the present chemical absorptions is attributed to combinated effects of the presence of ionic products, the depletion of the reactant liquid near the interface and an increase in interfacial temperature.     

Fe-Cu/ZSM-5催化剂及其胺化催化性能研究

制备了一种Fe-Cu/ZSM-5胺化催化剂,考察其在乙醇胺选择性合成哌嗪、三乙烯二胺反应中的催化活性。结果表明,随着Fe、Cu负载量的增加,催化剂表面酸性逐渐向强酸方向位移,总酸量增加,反应转化率提高;Cu负载量对反应转化率及乙二胺选择性的影响相对较弱,但对哌嗪的生成有明显的促进作用;催化反应性能不仅受催化剂酸性的影响,还与负载组分的性质及负载组分与载体间的相互作用有关。     

羟乙基乙二胺的连续流制备工艺研究

以乙二胺和环氧乙烷为原料,在具有特殊微结构的连续流微反应器内发生乙氧基化反应合成羟乙基乙二胺。考察了原料物质的量比、乙二胺含水量、反应温度、停留时间等对反应的影响。确定了最佳工艺条件为：n(乙二胺) : n(环氧乙烷) = 3:1、乙二胺含水量控制在5%（质量分数）以内、反应温度为80 ℃、停留时间为60 s。在此条件下,环氧乙烷转化率接近100%,羟乙基乙二胺的选择性为87.4%,二羟乙基乙二胺的选择性为9.2%。间歇釜式反应工艺在相同物料比和反应温度条件下,羟乙基乙二胺的选择性为83.5%,二羟乙基乙二胺的选择性为15.9%,与之相比,连续流微反应器能有效提高羟乙基乙二胺的选择性,降低副反应的发生,同时大大缩短了反应时间,提高了反应效率。