VOCs热催化氧化技术中整体式催化剂的研究进展

热催化氧化法是目前最具发展前景的挥发性有机化合物(VOCs)处理技术之一。其中作为技术核心的整体式催化剂具有优异的传质、传热性能和热稳定性,因而备受关注。本文梳理了不同类型整体式催化剂的研究现状,展望了其发展趋势。指出:开发低成本、高抗水性和高抗毒性的整体式催化剂是其未来的发展方向;如何维持催化剂的再生循环性能,提高催化剂的使用寿命,也是整体式催化剂发展过程中迫切需要解决的重要问题。

钙类质同像置换对钙钛矿型La1-xCaxCoO3热催化氧化甲苯性能的制约机制

挥发性有机物(VOCs)是大气光化学臭氧(O3)和细颗粒物(PM2.5)的重要前驱体,其有效减排是治理大气污染的重要环节。钙钛矿型复合氧化物具有催化氧化活性好、化学组成可控、热稳定性高等优点,在热催化氧化VOCs中具有较好的前景。本研究采用溶胶-凝胶法合成不同钙置换量的钙钛矿型钴酸镧(La1-xCaxCoO3),并以甲苯作为目标VOC,考查钙置换对钴酸镧(LaCoO3)热催化氧化甲苯性能的制约机制,结果表明,钙置换没有明显改变钴酸镧的晶体结构,但显著增强其热催化氧化活性。钙置换使钴酸镧颗粒尺寸减小,比表面积和堆积孔容增加,有利于减少气体扩散阻力。以甲苯降解率为50%所对应的温度(T50),以及反应温度为200℃时的比表面积标化CO2生成速率作为评价指标,系列样品的催化活性强弱为:LaCoO3(260℃,0.094μmolm-2s-1)<La0.9Ca0.1CoO3(232℃,0.114μmol m-2 s-1)<La0.7Ca0.3CoO3(225℃,0.118μmol m-2 s-1)<La0.8Ca0.2CoO3(212℃,0.135μmolm-2s-1)。随钙置换量增加,钴酸镧的单位比表面积催化活性呈现先增强后轻微减弱的趋势。系列样品的阳离子空位吸附氧密度未发生明显改变,但晶格氧释放速率显著提高,有利于催化氧化甲苯为CO2和H2O。随着钙置换量增加,晶格氧活性呈先增加后减少的趋势,从而导致催化活性也表现出类似的变化。

MnO_2催化剂的制备及其催化氧化挥发性有机污染物的研究进展

挥发性有机污染物(VOCs)由于其危害大、来源广,因此受到人们的普遍关注.热催化氧化技术在催化降解挥发性有机污染物方面具有独特的优势,而催化剂二氧化锰(MnO_2)由于其在室温下相对于其他催化剂具有较高的处理效果以及易制备等优点而被广泛研究和使用.本文作者着重讲述了催化剂MnO_2的特点、制备工艺、降解挥发性有机污染物效率的影响因素及其负载方式等在国内外的研究现状.

5-羟甲基糠醛路线合成2,5-呋喃二甲酸的研究进展

2,5-呋喃二甲酸(FDCA)是一种能够合成生物基聚酯的重要单体,目前在新型可降解塑料等领域具有广阔的应用前景,如何高效且低廉地制备FDCA已经逐步成为了热点问题。本文系统地综述了近年来通过5-羟甲基糠醛(HMF)路线合成FDCA的主要研究进展,首先介绍了HMF路线和其他路线的联系和区别,解释了HMF路线的优点。其次,详细介绍和分析了由HMF合成FDCA的方法,包括直接氧化法、贵金属催化法、过渡金属催化法、光电催化氧化法、酶催化法和全细胞生物催化法。此外,在介绍上述方法的基础上,说明了这些方法的优缺点,总结了HMF路线制备FDCA目前仍面临的挑战,包括催化剂的选择、改善与开发,反应条件优化和对中间产物的处理,还对未来由HMF路线来制备FDCA的前景进行展望。

气相分子吸收光谱法在线氧化消解测定水质总氮研究

总氮是衡量水质富营养化程度的主要指标之一。研究热复合-紫外光催化氧化在线消解气相分子吸收光谱法分析测定水和废水中总氮,实现了在较低温度和常压条件下水质中总氮快速、安全和稳定的自动化批量分析。该文围绕热复合-紫外光催化氧化,提出了利用热复合-紫外光催化氧化在线消解气相分子吸收光谱法分析测定水中总氮的的方法,并从环境水质分析中的运用,对其作用原理、装置设计及实验对比结果等几个方面进行论述,以期可以获得更好的测定效果。

用于净化除菌的新型净化型光伏Trombe墙性能研究

PV-Trombe墙是一种太阳能利用系统,能实现室内采暖和产电双重功能,但其对太阳热的利用非常有限.热催化氧化和热杀菌是两种先进的空气净化技术,利用太阳热能进行热脆化氧化和除菌杀毒具有巨大的应用潜力.基于此,提出了一种新型的净化PV-Trombe墙,能实现产电、室内采暖、甲醛降解和除菌.首先,建立了净化PV-Trombe墙的传热传质模型,并通过实验数据进行了验证.其次,分析了光伏覆盖率为0时的综合性能.最后,研究了光伏覆盖率对系统性能的影响.结果表明:①PV覆盖率为0时,平均日空气热效率为0.46,甲醛单通率为0.35;甲醛降解产生的洁净空气总量为93.4 m3;五种细菌被完全热灭活了几个小时.大肠杆菌、单核增生杆菌、植物杆菌、森夫滕伯格菌和酿酒酵母失活产生的洁净空气总生成量分别为188.3、173.0、201.4、189.9和200.2 m3.②光伏覆盖率对系统综合性能的影响不同.就特定性能而言,光伏覆盖率仅对电性能有正向影响,对其他性能如热性能、甲醛降解性能和除菌性能有负面影响.但考虑到系统的综合性能,建议电能为附加产品,光伏覆盖率较低.③系统可为新冠肺炎疫情防控提供支持.

Numerical simulation of diffusion process for oxidative dehydrogenation of butene to butadiene

A comprehensive single particle model which includes the mesoscale and microscale models was developed to study the influence of particle diameter on mass and heat transfer occurring within a ferrite catalyst during the oxidative dehydrogenation of butene to butadiene process. The verified model can be used to investigate the influence of catalyst diameter on the flow distribution inside the particle. The simulation results demonstrate that the mass fraction gradients of all species, temperature gradient and pressure gradient increase with the increase of the particle diameter. It means that there is a high intraparticle transfer resistance and strong diffusion when applying the large catalysts. The external particle mass transfer resistance is nearly constant under different particle diameters so that the effect of particle diameter at external diffusion can be ignored. A large particle diameter can lead to a high surface temperature, which indicates the external heat transfer resistance. Moreover, the selectivity of reaction may be changed with a variety of particle diameters so that choosing appropriate particle size can enhance the production of butadiene and optimize the reaction process.

Visible light-enhanced photothermal CO2 hydrogenation over Pt/Al2O3 catalyst

Light illumination has been widely used to promote activity and selectivity of traditional thermal catalysts. Nevertheless, the role of light irradiation during catalytic reactions is not well understood. In this work, Pt/Al2 O3 prepared by wet impregnation was used for photothermal CO2 hydrogenation, and it showed a photothermal effect. Hence, operando diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculations were conducted on Pt/Al2 O3 to gain insights into the reaction mechanism. The results indicated that CO desorption from Pt sites including step sites(Ptstep) or/and terrace site(Ptterrace) is an important step during CO2 hydrogenation to free the active Pt sites. Notably, visible light illumination and temperature affected the CO desorption in different ways. The calculated adsorption energy of CO on Ptstep and Ptterrace sites was-1.24 and-1.43 e V, respectively. Hence, CO is more strongly bound to the Ptstep sites. During heating in the dark, CO preferentially desorbs from the Ptterrace site. However, the additional light irradiation facilitates transfer of CO from the Ptstep to Ptterrace sites and its subsequent desorption from the Ptterrace sites, thus promoting the CO2 hydrogenation.

气体苯系物污染治理方法研究进展

苯系物(BTEX)是苯及其衍生物的总称,代表化合物包括苯、甲苯、乙苯、二甲苯等,其具有神经毒性、遗传毒性和致癌性,会造成环境污染和危害人体健康,苯系物的广泛应用已经使其成为危害大气环境的主要污染物之一,因此对大气苯系物污染的治理也越发重要.本文对气体苯系物处理的两种方法回收法和消除法的研究现状进行了综述,回收法包括吸收法、吸附法、冷凝法、膜分离法等,消除法包括(热)催化氧化法、生物处理法、低温等离子和光催化氧化法等,主要从原理、应用及优缺点等方面对这些方法进行了分析和对比,并对多种技术联合处理苯系物的方法做出研究展望.在目前的技术中,吸附法和催化氧化法是最受欢迎的,同时也是最具发展前景的,但对吸附法和催化氧化法还需要进一步探索有效的双功能吸附-催化剂,以及现实条件下与废气排放系统的兼容性问题.

Thermal coupled photoconductivity as a tool to understand the photothermal catalytic reduction of CO2

Photocatalysis shows great promise in the field of solar energy conversion.One of the reasons for this is because it promotes the development of multi-field-coupled catalysis.In order to explore the principles of multi-field-coupled catalytic reactions,an in situ multi-field-coupled characterization technique is required.In this study,we obtained hydrogenated ST-01 TiO2 and observed enhanced catalytic activity by thermal coupled photocatalysis.In situ photoconductivity was employed to understand the activity enhancement.The effects of the reaction temperature,reaction atmosphere,and oxygen vacancy(Ov)on the photoconductivity of TiO2 were studied.After coupling thermal into photoconductivity measurement,highly active Ov-TiO2 displayed rapid decay of photoconductivity in a CO2 atmosphere and slow decay of photoconductivity in a N2 atmosphere.These phenomena revealed that photothermal coupling assisted the detrapping of electrons at the Ov surface and promoted electron transfer to CO2,which clearly explained the high photothermal catalytic activity of Ov-TiO2.This study demonstrated that photoconductivity is a useful tool to help understand photothermal catalytic phenomena.

Thermodynamic Study on the Catalytic Partial Oxidation of Methane to Syngas

the catalytic partial oxidation of methane to syngas (CO + H_2)has been simulated thermodynamically with the advanced processsimulator PRO/II. The influences of temperature, pressure, CH_4/O_2ratio and steam addition in feed gas on the conversion of CH_4selectively to syngas and eat duty required were investigated, andtheir effects on carbon formation were also discussed. The simulationresults were in good agreement with the literature data taken from aspouted bed reactor.

Efficient destruction of sodium cyanide by thermal decomposition with addition of ferric oxide

Efficient destruction of cyanide by thermal decomposition with ferric oxide addition was proposed. The mechanism of destruction of sodium cyanide with or without ferric oxide addition under various conditions was examined by XRD, DSC-TG, and chemical analysis technologies. In the absence of ferric oxide, sodium cyanide decomposes at 587.4 ℃ in air and 879.2 ℃ in argon atmosphere. In the presence of ferric oxide, about 60% of sodium cyanide decomposes at 350 ℃ for 30 min in argon, while almost all sodium cyanide decomposes within 30 min in air or O2 with mass ratio of ferric oxide to sodium cyanide of 1:1. The increase of ferric oxide addition, temperature, and heating time facilitates the destruction of sodium cyanide. It is believed that with ferric oxide addition, NaCN reacts with Fe2O3 to form Na4Fe(CN)6, Na2CO3, NaNO2 and Fe3O4 in argon. NaCN decomposes into NaCNO, Na4Fe(CN)6, minor NaNO2, and the formed NaCNO and Na4Fe(CN)6 further decompose into Na2CO3, CO2, N2, FeOx, and minor NOx in air or O2.

A facile one-pot hydrothermal synthesis as an efficient method to modulate the potassium content of cryptomelane and its effects on the redox and catalytic properties

Cryptomelane has been widely applied as catalyst in oxidation reactions due to its excellent redox properties and low cost.Here,a novel one-pot hydrothermal synthesis using a potassium permanganate aqueous solution as precursor and ethanol as reducing agent has successfully been developed to obtain cryptomelane nano-oxides.This synthetic route makes it possible to control the amount of potassium incorporated into the structure of the cryptomelane by selecting the appropriate synthesis temperature and ethanol initial concentration.Taking advantage of this approach,the effect of potassium concentration on the structural stability and reducibility of the cryptomelane,which are poorly discussed in the literature,has been studied.We have observed that samples with low content of potassium(~11%)show high conversions of CO to CO2 especially at low temperatures.The lower activity of the samples with high K contents(~16%)can be ascribed to the beneficial effect of K on the structural stability of cryptomelane in detriment of labile oxygen on cryptomelane surface.

Investigation of low-temperature hydrothermal stability of Cu-SAPO-34 for selective catalytic reduction of NO_x with NH_3

The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.

Maximum Hydrogen Production by Autothermal Steam Reforming of Bio-oil With NiCuZnAI Catalyst

Autothermal steam reforming （ATR） of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effective production of hydrogen through ATR of bio-oil was performed at lower temperature with NiCuZnAl catalyst. The highest hydrogen yield from bio-oil reached 64.3% with a nearly complete bio-oil conversion at 600℃, the ratio of steam to carbon fed （S/C） of 3 and the oxygen to carbon ratio （O/C） of 0.34. The reaction conditions in ATR including temperature, O/C, S/C and weight hourly space velocity can be used to control both hydrogen yield and products distribution. The comparison between the ATR and common steam reforming of bio-oil was studied. The mechanism of the ATR of bio-oil was also discussed.

Highly photoreactive TiO_2 hollow microspheres with super thermal stability for acetone oxidation

TiO2hollow microspheres(TiO2‐HMSs)have attracted much attention because of their high photoreactivity,low density,and good permeability.However,anatase TiO2‐HMSs have poor thermal stability.In this study,surface‐fluorinated TiO2‐HMSs were assembled from hollow nanoparticles by the hydrothermal reaction of the mixed Ti(SO4)2–NH4HF–H2O2solution at180°C.The effect of the calcination temperature on the structure and photoreactivity of the TiO2‐HMSs was systematically investigated,which was evaluated by photocatalytic oxidation of acetone in air under ultraviolet irradiation.We found that after calcination at300°C,the photoreactivity of the TiO2‐HMSs decreases from1.39×10?3min?1(TiO2‐HMS precursor)to0.82×10?3min?1because of removal of surface‐adsorbed fluoride ions.With increasing calcination temperature from300to900°C,the building blocks of the TiO2‐HMSs evolve from truncated bipyramidal shaped hollow nanoparticles to round solid nanoparticles,and the photoreactivity of the TiO2‐HMSs steady increases from0.82×10?3to2.09×10?3min?1because of enhanced crystallization.Further increasing the calcination temperature to1000and1100°C results in a decrease of the photoreactivity,which is ascribed to a sharp decrease of the Brunauer–Emmett–Teller surface area and the beginning of the anatase–rutile phase transformation at1100°C.The effect of surface‐adsorbed fluoride ions on the thermal stability of the TiO2‐HMSs is also discussed.

Thermal catalysis under dark ambient conditions in environmental remediation:Fundamental principles, development, and challenges

Thermal catalytic degradation of organic pollutants conducted in the dark at room temperature under atmospheric pressure without the need of external chemicals and energy sources has attracted a lot of attention over the last two decades. It provides unparalleled advantages over other advanced oxidation processes (AOPs) in treating domestic and industrial contaminated wastewater from the viewpoint of energy/chemical conservation and ease of operation. Rich knowledge has been accumulated in terms of the synthesis and application of thermal catalysts though controversies remain regarding their underlying mechanisms. This review sheds light on the proposed thermo- catalysis mechanism for the first time and presents the development of thermal catalysts under dark ambient conditions with a focus on catalyst materials, catalytic activity, and mechanism. The present review aims to provide mechanistic insights into the rational design of novel and efficient catalysts, and their underlying mechanisms as well as the emerging challenges and perspectives in thermo-catalysis under dark ambient conditions used for the practical and efficient treatment of contaminated wastewater.

Iron Arene Salts as Initiators for Thermal Curing of Epoxides by Photo-catalysis

[Cyclopentadien-Fe-naphthalene]BF4(CFN) and [cyclopentadien-Fe-anisole]BF4(CFA) as thermal cationic initiators for the curing of epoxide E44 and GGE were investigated. CFN brought out the curing of E44 at 89.1℃ and that of GGE at 148.7℃. However, CFA had much less thermal initiating activity under 300℃. Under UV radiation for short time, the thermal initiating activities of CFN and CFA were enhanced obviously. It was observed that the initiating onset temperature decreased and the evolved heat of the curing increased. Both CFN and CFA can carry out the polymerization of E44 and GGE near 85℃ and 112℃ by UV radiation.

In situ Fourier Transform Infrared Spectroscopy Diagnostic for Characterization and Performance Test of Catalysts

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior （temperature-programmed reduction/temperatureprogrammed re-oxidation） as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 （υ1） and 650 cm-1 （υ2） respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.