真空紫外光化学反应器的研究

设计了能产生波长小于200 nm的真空紫外光化学反应器,通过工作气体氮气进行光强标定表明,其主要产生109 nm,120 nm,149 nm,174 nm波长的光(N原子谱线)。首次在该光化学反应器中进行了CO2光解反应的研究,实验结果表明该实验条件下CO2光解后生成产物CO,当光源电流300 mA时,生成CO的相对量与光源内工作气体的真空度相关。提出了光化学反应器设计时存在的问题、影响因素及考虑因素,为光化学反应器设计放大和操作条件优化提供实验依据和理论思路。     

光化学反应器

光化学反应过程由于具有选择性好且可在常温常压下进行等特点而在施工领域有着良好的应用前景，光化学反应器作为光化学生产过程的核心设备，在光化学工艺的应用中具有十分重要的地位。本文从工程应用的角度出发，介绍了常见的光化学反应器的类型，总结了描述光化学反应器行为的模型，并讨论了有关光化学反应器的设计计算及放大等问题。     

光化学反应工程

光化学反应工程是化学反应工程的一个分支，本文在概述光化学反应工程的发展基础上，对光化学反应速率方程的建立，光化学反应器的设计原理和特点进行了介绍。     

多相光化学反应器的辐射能传递模型

以双通量模型为基础模拟多相光化学反应器中的辐射能传递行为 ,考虑透过光催化剂颗粒的光子总数修正了双通量模型 ,采用比较简单的模型说明了多相光化学反应器内量纲 1光辐射能分布和光催化剂的量纲 1吸收光子总数分布 ,举例讨论了半导体超细粉末二氧化钛为光催化剂的气固相光化学反应器在不同光催化剂粒径、不同反应器厚度条件下反应器内量纲 1光辐射能分布和光催化剂的量纲 1吸收光子总数分布     

三唑磷的光解特性及其影响因素

以氙灯与太阳光为光源,研究了三唑磷的光解特性及其影响因子.结果表明,太阳光下,三唑磷在水溶液中的光解半衰期约为19 d,氙灯下25℃时为6.56 h,35℃时为3.65 h.氙灯下,三唑磷在石油醚、甲苯和丙酮3种介质中的光解速率次序为石油醚＞甲苯＞丙酮.应用气相色谱-质谱法确定了三唑磷的光解中间产物分别为1-苯基-3-羟基-1,2,4-三唑和O,O-二乙基硫代磷酸,同时该产物能较快地进一步光解.     

新型含硫化合物的荧光光谱及其光解机理

本工作合成了硫代ａ－萘甲酸－ｓ－苯酯和硫代苯甲酸－ｓ－苯并噻唑酯，对其光化学和光物理行为进行了研究。由于萘基和苯并噻唑基的引入，有效地增加了该类化合物的最大吸收光谱范围，并在受光激发后，可观察到有荧光发射。工作中发现，硫代ａ－萘甲酸－ｓ－苯酯荧光发射强度会随光照时间的增加而加强，这是因该化合物光解时生成了有高荧光量子产率的ａ，ａ’－联苯；但在硫代苯甲酸－ｓ－苯并噻唑酯的光解中观察不到上述现象，文章     

煤焦与水蒸气及二氧化碳的气化反应动力学

本文应用恒速升温热重法对6种中国煤焦与二氧化碳和水蒸气的气化反应进行研究。采用下面二个动力学方程来求算气化反应动力学参数。计算机处理实验数据结果表明n=1的相关系数及计算值与实验结果的一致性都比n≠1的好。 K_2CO_3用作催化剂能明显加速义马长焰煤焦与二氧化碳和水蒸气气化反应速率,可预测K_2CO_3对其他5种中国煤焦亦有较明显的催化气化能力。     

半导体Z反应光解水制氢的光能转换效率及研究进展

通过介绍人工半导体Z反应的原理,综述该类型反应体系,包括模拟PSI催化剂（PS1[H2]）、模拟PSII催化剂（PS2[O2]）和介体（mediator） 应用于人工模拟光解水制氢的研究进展,重点阐述此三者在Z反应中所起的作用及其电子传递机理的发展现状,并通过估算不同介体的光能转换效率比较各反应系统的优缺点,指出无介体Z反应系统的电子传递机理、非贵金属助剂的制备、在光催化还原二氧化碳和光电催化中的应用是未来Z反应研究的重点。     

二氧化碳的氨化反应研究进展

论述了减排CO2的重要性,概述了CO2化学利用的主要方法,综述了CO2的3种氨化反应,即氨化反应生成碳酸氢铵、尿素和三聚氰酸,重点介绍了CO2氨化反应生成三聚氰酸,对该反应进行了热力学分析,叙述了其反应的特点,得出CO2氨化合成三聚氰酸等固体产品是一条比较可行的CO2化学利用路线。氨化合成三聚氰酸不仅可以实现CO2的封存,而且能够实现CO2的高值有效利用,对解决CO2减排具有重要意义。认为将氨化反应与煤化工产业相结合,可以有效减少二氧化碳的排放强度,具有广阔的发展前景。     

Heterogeneous catalysts,reaction kinetics,and reactor designs for methanol production from carbon dioxide: A critical review

The process of preparing methanol from carbon dioxide is one of the ways to solve the environmental problems caused by greenhouse gases, the problem of fossil energy depletion, and the problem of fuel exhaust emissions. However, after decades of development, the process of preparing methanol from carbon dioxide is still unable to achieve large-scale industrialization. This critical review sharply points out the problems and obstacles that need to be solved urgently on the industrialization road of carbon dioxide methanol preparation process and summarizes its progress. The problems faced by the methanol production industry from carbon dioxide are first the thermodynamic constraints, second the lower reaction rate and conversion effect, and finally the energy loss. In order to solve these problems, this paper first introduces the active sites, structural effects, and dynamic changes of copper-based catalysts, as well as the unique reaction mechanism and doping modification of indium-based catalysts. Zinc and zirconium promoters and some metal oxide supports can form unique interactions with active components to improve the catalytic performance of the catalyst. Next, various kinetic models and applications of methanol production from carbon dioxide are summarized, which is an important bridge linking laboratory and industrialization; the advantages and disadvantages of fixed bed reactor and paddle reactor were compared. Finally, the full text is summarized and prospected.     

紫外光辐照ABS/碳纳米管的研究

丙烯腊—丁二烯—苯乙烯共聚物(ABS)在室温、氮气环境下，通过紫外光辐照，在其分子链上引入了碳纳米管(CNTs)。通过荧光光谱分析，ABS／CNTs在418nm处有强的荧光发射峰；透射电子显微镜观察发现，CNTs在端头处打开及转弯处打断，被ABS包覆，ABS/CNTs的体积电阻率随CNTs的加入量增多而降低；紫外光辐照ABS/CNTs的导电性显著优于熔融共混ABS/CNTs；扫描电子显微镜表明，CNTs在紫外光辐照ABS基体中均匀分布。     

浆态床中CO2加氢直接合成二甲醚的双功能催化剂

采用共沉淀沉积法制备了CuO-ZnO-Al2O3-ZrO2/HZSM-5双功能催化剂,利用XRD、BET、H2-TPR、NH3-TPD等手段进行表征。在连续流动加压浆态床反应器中,以医用石蜡为惰性液相介质,研究了其对CO2加氢直接合成二甲醚的催化反应,考察了不同温度、不同压力、不同氢碳比和不同空速对反应结果的影响。研究表明,提高反应温度有利于提高CO2转化率,但使二甲醚的选择性降低;增大压力和氢碳比有利于提高CO2转化率和二甲醚的选择性;增大空速会使CO2转化率和二甲醚选择性均呈现下降趋势。     

Enhanced weathering to capture atmospheric carbon dioxide: Modeling of a trickle-bed reactor

Enhanced weathering (EW) of alkaline minerals can potentially capture CO₂ from the atmosphere at gigaton scale, but the reactor design presents great challenges. We model EW with fresh water in a counter-current trickle flow packed bed batch of 1–10 mm calcite particles. Weathering kinetics are integrated with the mass transfer of CO₂ incorporating transfer enhancement by chemical reaction. To avoid flooding, flow rates must be reduced as the particles shrink due to EW. The capture rate is mainly limited by slow transfer of CO₂ from gas to liquid although slow dissolution of calcite can also play a role in certain circumstances. A bed height of at least 7–8 m is required to provide sufficient residence time. The results highlight the need to improve capture rate and reduce energy and water consumption, possibly through enriching the feed with CO₂ and further chemical acceleration of the mass transfer.     

Removal of Hg0 from containing‐SO2/NO flue gas by ultraviolet/H2O2 process in a novel photochemical reactor

A novel photochemical spray reactor is first developed and is used to remove Hg⁰ and simultaneously remove Hg⁰/SO₂/NO from flue gas by ultraviolet (UV)/H₂O₂ process. The effects of several parameters (UV wavelength, UV power, H₂O₂ concentration, Hg⁰ inlet concentration, solution temperature, liquid–gas ratio, solution pH, SO₂ concentration, NO concentration, and O₂ concentration) on removal of Hg⁰ by UV/H₂O₂ process were investigated. Removal mechanism of Hg⁰ is proposed and simultaneous removal of Hg⁰, NO, and SO₂ is also studied. The results show that the parameters, UV wavelength, UV power, H₂O₂ concentration, liquid–gas ratio, solution pH, and O₂ concentration, have significant impact on removal of Hg⁰. However, the parameters, Hg⁰ inlet concentration, solution temperature, SO₂ concentration, and NO concentration, only have small effect on removal of Hg⁰. Hg²⁺ is the final product of Hg⁰ removal, and Hg⁰ is mainly removed by oxidations of H₂O₂, ·OH, · O, O₃, and photoexcitation of UV. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2275–2285, 2014     

单,双核络合物催化二氧化碳与环氧乙烷反应研究

报道了１０个含Ｐ配体的单,双核络合物在二氧化碳和环氧乙烷反应中的均相催化活性,分析了活性差异的原因。     

Development of a continuous reactor for the electro-reduction of carbon dioxide to formate – Part 1: Process variables

This paper reports an experimental investigation into the effects of five process variables on the performance of a bench-scale continuous electrochemical reactor used in the reduction of CO₂ to potassium formate, and interprets the data in terms of reactor engineering for a (speculative) industrial process for electro-reduction of CO₂. The process variables: temperature, catholyte species, catholyte conductivity, cathode specific surface area and cathode thickness were studied, along with CO₂ pressure and current density, in a set of factorial and parametric experiments aimed to unravel their main effects and interactions. These variables showed complex interdependent effects on the reactor performance, as measured by the current efficiency and specific energy for generation of formate (HCO₂⁻). The “best” result has a formate current efficiency of 86% at a superficial current density of 1.3 kA m⁻², with a product solution of 0.08 m KHCO₂ and specific electrochemical energy of 260 kWh per kmole formate. The combined results indicate good prospects for process optimization that could lead to development of an industrial scale reactor.     

环氧环己烷与二氧化碳合成碳酸环己烯酯的化学反应动力学

引言由于CO2排放量的急剧增加,“温室效应”已成为当今世界性的难题,固定CO2并综合利用CO2的研究显得越来越重要。CO2和环氧化合物经过环加成反应制备环状碳酸酯的工艺路线,为固定和利用CO2提供了一条有效途径。环状碳酸酯不仅是一种性能优良的高沸点、高极性的有机溶剂,而且在     

Effects of process conditions and electrode material on reaction pathways for carbon dioxide electroreduction with particular reference to formate formation

This paper reviews the most common reaction pathways for CO₂ electroreduction proposed by various workers in recent years. Each pathway involves certain intermediate compounds and certain end products and thus the pathways promoted, within a specific process, can be deduced from which of these have been detected. There are considered to be four principal pathways, each based on one of the following reactions: (1) CO(g) formation via disproportionation, (2) CO₂ ^– radical formation, (3) COOH(ad) formation and (4) the formation of reduced CO _x ^y–(ad) species giving a range of reduced CO₂ end products. This paper places particular emphasis on the formation of HCOOH. The effects of electrocatalyst and process conditions on reaction pathways is also reviewed.