氯化氢催化氧化制氯气达到化学平衡前后的反应行为

采用氧化铝为载体的铜基复合催化剂在固定床与无梯度组合反应器上考察了氯化氢催化氧化制氯气的反应行为。在反应温度T=360~400℃、进料摩尔配比nHCl/nO2=1~4、HCl空速W/FHCl0=0.01~60h-1以及常压条件下考察了反应温度、进料摩尔比、HCl空速等工艺条件对HCl转化率与反应速率的影响。结果表明:在到达化学平衡以前,HCl转化率和反应速率随着反应温度的升高或反应气体摩尔配比nHCl/nO2的降低而升高;随着反应空速FHCl0/W的降低,HCl转化率先逐渐升高,而HCl反应速率逐渐降低。在达到化学平衡以后,转化率随着反应温度的升高或反应气体摩尔配比nHCl/nO2的升高或反应空速FHCl0/W的降低而降低,反应速率为零。控制反应温度在390~400℃范围内,原料气摩尔比nHCl∶nO2为(4∶3)^(4∶2),HCl空速W/FHCl0在2.5h-1左右,此时的HCl转化率可达到60%~70%,且HCl反应速率保持在(0.2~0.25)mmol/(g·min)。本文采用的联合实验装置对于化学平衡前后的反应行为均能较好地考察,为考察与研究同类反应的反应行为开辟了新思路。

氯化氢催化法合成氨基酸酯盐酸盐

以氨基酸与苯甲醇的酯化反应为模型反应,研究了氯化氢催化下的氨基酸酯化工艺。采用1,2-二氯乙烷作为溶剂,共沸蒸馏带出生成的水,以促进酯化反应完成,再经重结晶后得到目标产物氨基酸苄酯盐酸盐。当氨基酸与苯甲醇物质的量之比为1.00:1.08,反应温度83℃,反应时间4~6 h时,收率可达65%左右。此外,在氨基酸与甲醇等低沸点醇进行酯化时,采用醇同时作为反应物和带水剂的方法,提高反应的平衡转化率,并将蒸馏出的醇经过除水处理后重新加入反应体系中,氨基酸酯盐酸盐收率在75%~85%。利用反应-分离耦合技术提高了产物的收率与纯度,缩短了反应时间,减少了原料的用量。

氯化氢催化氧化制氯气在无梯度反应器上的反应行为考察

针对氯化氢催化氧化制氯气工艺,使用以氧化铝为载体的铜基复合催化剂,在无梯度反应器上进行反应行为考察。在常压条件下考察反应温度、进料摩尔比、HCl空速等工艺条件对HCl转化率和HCl反应速率的影响。结果表明,在考察范围内,HCl转化率和反应速率均随着反应温度T的升高,或反应气体摩尔配比nHCl/nO2的降低而升高;随着反应空速FHCl0/W的降低,HCl转化率先升高后降低,在HCl空速为5 h-1时达到最大,而HCl反应速率逐渐降低。优化工艺条件为:反应温度400℃,原料气摩尔比nHCl∶nO2=4∶4,HCl空速FHCl0/W=5 h-1时,此时HCl转化率接近60%,且HCl反应速率在0.5×10-3 mol/(g·min)左右,反应效率较高。但由于在考察范围内无法达到化学平衡状态,达到化学平衡后的反应行为仍需进一步考察。

邻氯苯甘氨酸甲酯的绿色合成工艺研究

以邻氯苯甘氨酸为原料,在乙酰氯与甲醇制成的氯化氢甲醇溶液中,进行原位氯化氢催化酯化,绿色合成了标题化合物。通过正交实验研究各因素(物料比、反应温度、反应时间)对产率的影响,找到了最佳合成工艺条件。该反应最佳工艺条件是:物料比为1∶3,反应温度为45℃,反应时间为10 h,收率高达95.6%。与文献相比,该反应条件温和,环境友好,收率较高。目标产物通过MS和1H NMR进行了结构表征。

M/C_(3)N_(4)/AC(M=Au,Pt,Ru)‐catalyzed acetylene coupling with ethylene dichloride:How effective are the bifunctionalities?

Acetylene coupling with ethylene dichloride,which uses both coal and oil resources,is attractive for sustainable PVC manufacturing.Herein,highly active and stable carbon nitride‐based catalysts were developed by a novel pre‐oxidation‐pyrolysis process,affording unprecedented dehydrochlorination activity with good durability.The best‐performing system was further modified with different precious metals(Au,Pt,and Ru)to promote the hydrochlorination chemistry between the in‐situ formed hydrogen chloride and acetylene co‐feed.The presence of metal centers intensifies the hydrochlorination activity but weakens the dehydrochlorination ability due to competitive adsorption between the two reactants at the metal sites.Superior coupling performance was achieved over C_(3)N_(4)/AC and single‐atom Au/C_(3)N_(4)/AC catalysts in cascade reactors.Our results strongly suggest that dehydrochlorination is an essential step in the coupling reaction,and the activation of acetylene and ethylene dichloride molecules requires different active sites that should be engineered in future work.

Efficient and stable Ru(Ⅲ)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination

Herein,we report an excellent,supported Ru(III)‐ChCl/AC catalyst with lower Ru content,where the ionic complex ChRuCl4 serves as the active component for acetylene hydrochlorination.The prepared heterogeneous Ru‐10%ChCl/AC catalyst shows excellent activity and long‐term stability.In this system,ChCl provides an environment for the ChRuCl4 to be stabilized as Ru(III),thus suppressing the reduction of the active species and the aggregation of ruthenium species during the reaction.The interaction between reactants and catalyst species was investigated by catalyst characterizations in combination with DFT calculations to disclose the effect of the ChRuCl4 complex and ChCl on the catalytic performance.This inexpensive,efficient,and long‐term catalyst is a competitive candidate for application in the hydrochlorination industry.

Wheat flour-derived N-doped mesoporous carbon extrudes as an efficient support for Au catalyst in acetylene hydrochlorination

We recently reported an N‐doped mesoporous carbon(N‐MC)extrudate,with major quaternary N species,prepared by a cheap and convenient method through direct carbonization of wheat flour with silica,which has excellent catalytic performance in acetylene hydrochlorination.Herein,we examined the activity of Au supported on N‐MC(Au/N‐MC)and compared it with that of Au supported on nitrogen‐free mesoporous carbon(Au/MC).The acetylene conversion of Au/N‐MC was 50%at 180°C with an acetylene space velocity of 600 h–1 and VHCl/VC2H2 of 1.1,which was double the activity of Au/MC(25%).The introduced nitrogen atoms acted as anchor sites that stabilized the Au3+species and inhibited the reduction of Au3+to Au0 during the preparation of Au/N‐MC catalysts.

Oxygen and nitrogen-doped metal-free carbon catalysts for hydrochlorination of acetylene

Activated carbon was tested as metal-free catalyst for hydrochlorination of acetylene in order to circumvent the problem of environment pollution caused by mercury and high cost by noble metals. Oxygen-doped and nitrogen-doped activated carbons were prepared and characterized by XPS, TPD and N2 physisorption methods. The influences of the surface functional groups on the catalytic performance were discussed base on these results. Among all the samples tested, a nitrogen-doped sample, AC-n-US00, exhibited the best performance, the acety- lene conversion being 92% and vinyl chloride selectivity above 99% at 240 ~C and C2H2 hourly space velocity 30 h- 1. Moreover, the AC-n-US00 catalyst exhibited a stable performance during a 200 h test with a conversion of acetylene higher than 76% at 210 ~C at a C2H2 hourly space velocity 50 h 1. In contrary, oxygen-doped catalyst had lower catalytic activities. A linear relationship between the amount of pyrrolic-N and quaternary-N species and the catalytic activity was observed, indicating that these nitrogen-doped species might be the active sites and the key in tuning the catalytic performance. It is also found that the introduction of nitrogen species into the sample could significantly increase the adsorption amount of acetylene. The deactivation of nitrogen- doped activated carbon might be caused by the decrease of the accessibility to or the total amount of active sites.

Catalytic Hydrogenation of Aromatic Compounds in the Liquid Phase

Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.

A Pd-Fe-B/γ-Al2O3 Amorphous Alloy Catalyst for Hydrogenation of Chloronitrobenzene to Chloroaniline

A Pd-Fe-B/γ-Al2O3 amorphous alloy catalyst was prepared by impregnation and chemical reduction with borohydrine aqueous solution. The catalyst was characterized by X-ray diffraction（XRD）, scanning electron microscope（SEM）, differential scanning calorimetry（DSC） and elecdes design suite（EDS） and was used for catalytic hydrogenation of 5-nitro-2-chloro-2＇, 4＇-dimethylbenzenesulfonanilide （NCD）. The amorphous alloy catalyst shows significantly high activity and selectively for hydrogenation of NCD to 5-Amino-2-chloro- 2＇, 4＇-dimethyibenzenesuifonanilide （ACD）.

Synthesis and characterization of a tetradentate PNCP iridium complex for catalytic alkane dehydrogenation

A novel hydrido iridium chloride complex supported by a tetradentate PNCP ligand has been synthesized and characterized. Upon activation with NaOtBu, the PNCP-IrHC1 complex is active for transfer dehydrogenation of cyclic and linear alkanes.