Ir基催化剂用于CO选择性催化还原NO的研究进展

针对具有烟温低、氧含量高和CO浓度大等特征的固定源烟气（钢铁烧结/球团烟气和焦化烟气等）脱硝领域,CO选择性催化还原NO _x （CO-SCR）技术具有良好的发展前景。Ir基贵金属催化剂因其在CO-SCR反应体系中表现出了良好的抗氧能力和较高的催化活性成为催化脱硝领域研究的热点之一。本文重点总结了单一载体、复合载体与复合活性组分三类Ir基催化剂在CO-SCR脱除NO _x 中的催化性能,同时从制备条件和反应条件两大方面归纳了其对Ir基催化剂的CO-SCR脱硝性能的影响,简要阐述了Ir基催化剂表面反应机理,并对未来研究工作进行了展望,指出采用多种手段对催化剂进行改性,并通过降低Ir负载量、反应温度窗口以及提升其催化活性等方式来降低成本,为实现Ir基催化剂CO-SCR工业化应用提供借鉴。     

钒磷氧复合氧化物及其在催化领域的应用

钒磷氧（VPO）是一种重要的复合氧化物,在低链烷烃选择性氧化及氨氧化等反应中表现出优异的催化性能。VPO催化剂组成结构十分复杂,其晶相组成、表面形貌、酸强度等与制备方法有很大的关系,催化剂的制备方法也很大程度上影响着其催化性能。综述了VPO的不同制备方法;并对其主要晶型及特征、晶相之间的转化进行了系统分析,重点探讨了对该催化剂性能强化方法和方式的研究进展,对VPO催化剂的主要应用做了全面的概述,指出了VPO催化剂研究中存在的问题以及今后发展的方向和目标。采用先进的原位表征手段结合理论模拟计算揭示了VPO催化的构效关系,探索了VPO催化剂的新型合成方法,结合现代纳米材料理论,开发了高性能的纳微结构VPO催化剂。     

Modification of vanadium phosphorus oxides used for n-butane oxidation to maleic anhydride by interaction with niobium phosphate

A new family of vanadium phosphorus oxides (VPO) catalysts has been identified. It consists in a mixture of VPO with niobium phosphate (NbPO). The amorphous NbPO material is introduced during the preparation of the VOHPO₄·0.5H₂O precursor. It is observed that the VPO–NbPO catalyst is more rapidly activated and gives better performances (n-butane conversion and maleic anhydride selectivity) for mild oxidation of n-butane to maleic anhydride. VPO phases and the NbPO material have been identified in the VPO–NbPO precursor and in the VPO–NbPO catalyst. Nb in VPO crystals and V in NbPO particles have been respectively observed by EDX-STEM. No other VPO crystals than the VOHPO₄, 0.5H₂O precursor, and (VO)₂P₂O₇ for the catalyst, have been identified by XRD and ³¹P NMR. ³¹P NMR by spin echo mapping and ³¹P MAS NMR have confirmed an interaction of the VPO precursor with Nb and of the NbPO amorphous material with V, as evidenced by EDX-STEM. This should be the reason for the observed improvement of the catalytic results by a redox effect of niobium on the VPO catalyst modifying the V⁵⁺/V⁴⁺ balance in a favourable way.     

Ti/Zr助剂掺杂VPO催化正丁烷选择性氧化制顺酐

采用有机相法制备钒磷氧(VPO)催化剂,并在合成过程中加入Ti/Zr助剂,使用微型固定床反应器评价其催化正丁烷选择性氧化制顺酐的性能,考察了不同助剂元素及其化合物形式和添加量对催化剂性能的影响,分析了添加助剂对催化剂晶相及微观形貌的影响. 结果表明,加入助剂未改变催化剂的晶相结构,但促进了活性相(VO)2P2O7生成,且使反应后催化剂微观形貌发生改变,片层更破碎,活性相暴露,同时生成了利于反应的微量V5+;助剂金属Ti和Zr与V元素间的相互作用对催化剂表面P浓度及V价态都有一定影响;与不加助剂的VPO催化剂相比,相同反应条件下,Ti/Zr助剂修饰的VPO催化性能显著提高,摩尔比Zr/V为1.5%的Zr(NO3)4为助剂的催化剂的催化性能最佳,稳定状态下正丁烷的转化率高达99.1%,顺酐收率为54.4%.     

How the Yield of Maleic Anhydride in n-Butane Oxidation,Using VPO Catalysts,was Improved Over the Years

Key patents for the oxidation of n-butane to maleic anhydride (MA) using V/P mixed metal oxides (VPO) have been analyzed to evidence the important parameters needed to optimize the catalytic behaviour. The important aspects for the optimization of the catalyst performance are the preparation of the precursor (VO)HPO₄·0.5H₂0, its activation to form the active catalyst VO₂P₂O₇ and a small amount of VOPO₄, the methodology of the addition of promoters, and the shaping of the catalyst. Even small, sustainable improvements in the MA yield (>1 %) achieved by improved, modified or optimized catalysts are significant on an industrial scale with the world production of MA being a respectable 2.7 Million tons/year. Although substantial improvements in MA yield have been achieved industrially over the past 40 years by improving the VPO catalyst composition and by optimizing process operations; the MA process remains, as practiced today, one of the least efficient industrial selective oxidation processes. Therefore, a huge incentive exists in the field to improve the MA catalyst and process, which led us to search for clues towards this end by analyzing the pertinent patent literature, as reported here.     

活化气氛对正丁烷选择性氧化制顺酐催化剂性能的影响

研究了正丁烷选择性氧化制顺酐钒磷氧催化剂的前驱体分别在空气、水蒸汽-空气、正丁烷-空气以及氮气4种活化气氛活化对催化剂性能的影响,采用BET、XRD和XPS等对活化后的催化剂进行表征。结果表明,采用水蒸汽-空气活化的VPO-2催化剂晶相组成较好,钒平均价态为4.19。丁烷氧化评价试验结果表明,VPO-2催化剂的催化性能较好,正丁烷转化率达92.47%,顺酐选择性达60.48%。     

Water modification of PEG-derived VPO for the partial oxidation of propane

In this study, the PEG-derived VPO precursors were subject to water refluxing (90 °C, 8 h) and in situ activation in a steam-containing environment. For comparison, the VPO precursors without water refluxing were also activated in a similar manner. The IR measurement indicated that the majority of PEG in the precursor has been removed during water refluxing, and the VPO is essentially unenwrapped by PEG. The consequence is an increase of particle size and crystallinity of VPO as well as decreases in surface acidity and site density. The activation of catalysts in a stream-containing environment has an influence on the content of V⁵⁺ species and on the reduction behavior of the VPO catalysts. The VPO catalyst activated with 20% water vapor (by volume) in the feed shows the highest crystallinity. Compared with the non-PEG-derived VPO precursor, the PEG-derived one undergoes structure changes of higher severity during the water/steam treatments. The VPO catalyst generated from the PEG-derived precursor with water refluxing and activated with steam (20%) exhibited a propane conversion of 25% and a (AA + HAc) selectivity of 70%. The superior catalyst behavior can be interpreted in terms of the higher crystallinity of the (VO)₂P₂O₇ phase, the lower content of V⁵⁺ species, and the milder surface acidity as caused by the water/steam treatments.     

负载型Mn基低温NH3-SCR脱硝催化剂研究综述

MnO_x以其良好的低温催化活性成为当前低温NH₃-SCR脱硝催化剂研究的热点,负载型Mn基低温脱硝催化剂较好地解决了非负载型低温N₂选择性差、易中毒等难题,具有良好的工业应用前景.本文综述了负载型Mn基低温脱硝催化剂的研究现状,从活性组分、载体、制备方法、机理和动力学以及抗H₂O、SO₂性能5个方面介绍了负载型Mn基低温脱硝催化剂的研究现状,着重阐述了金属氧化物、分子筛、炭基等人工和天然载体负载MnO_x在制备方法和脱硝活性方面的最新研究成果,简述了Mn基低温脱硝催化剂的催化机理以及动力学研究进展,分析了Mn基低温脱硝催化剂的H₂O和SO₂中毒机理.指出提高负载型Mn基低温脱硝催化剂的抗中毒性能和再生是今后研究的重点.     

富氧条件下氢气选择催化还原汽车尾气氮氧化物的研究进展

汽车尾气中的氮氧化物（NO _x ）是大气主要污染物之一,严重危害了环境和人类健康。选择催化还原（SCR）消除技术是一种在富氧条件下能够高选择性消除NO _x 的技术。氢气选择催化还原氮氧化物（H₂-SCR）由于其低温高活性的优势备受关注。目前H₂-SCR研究中以Pt和Pd作活性组分催化剂使用较多,其中Pt基催化剂的研究最为广泛,本文介绍了催化剂载体类型、载体性质（如酸碱性、比表面积、孔道结构）、助剂和预处理方式等对催化活性的影响及影响机制,综述了反应条件参数（如反应气中O₂和NO₂浓度,杂质气体H₂O和SO₂）对催化剂催化活性的影响,认为反应气组分的影响在于各组分在催化剂上的竞争吸附以及对催化剂活性位的影响,最后展望了面向实际应用H₂-SCR技术未来的研究方向。     

低温脱硝催化剂研究进展

在传统选择性催化还原技术（SCR）催化剂的基础上,分别以钒-钛系催化剂、固溶体催化剂和新型MnO _x 催化剂为重点介绍了近些年低温SCR催化剂的研究进展,综述了不同活性组分的复合型催化剂的制备方法、元素掺杂、反应机理和抗性等,并通过分析不同复合型催化剂的表征总结了催化剂的性能状况以及低温脱硝效率,着重阐述了新型MnO _x 催化剂所具有的优异脱硝特性,认为通过改性提高新型MnO _x 的抗水抗硫性将会成为该领域未来的发展方向和研究热点,最后介绍了不同负载体对新型MnO _x 催化剂的催化效率的影响规律,发现二氧化钛负载体具有良好的抗水性,三氧化二铝负载体能显著增强催化活性,二氧化铈负载体的热稳定性较好。     

硬脂醇改性的氧化石墨烯/正十八烷复合相变材料的热物性研究

向正十八烷中加入高导热填充物形成复合相变材料（PCM）,可以很好地提升其导热性能,同时,为了保证符合相变材料的高热导率、分散性和再循环可靠性,利用硬脂醇修饰氧化石墨烯（GO）,形成改性石墨烯（MG）与正十八烷的复合相变材料。分别制备了改性石墨烯质量分数为0、1%、2%、3%、4%（质量）的改性石墨烯/正十八烷复合相变材料,并经过扫描电镜测试、红外光谱分析、差示扫描量热实验及导热分析等测试对其形貌结构及热物性进行表征和研究。实验表明制备的改性石墨烯/正十八烷复合相变材料具有很好的分散性;当纳米石墨烯片的质量分数达到4%时,复合相变材料的热导率相对于纯正十八烷高出了131.9%。     

乙酸(酯)-甲醛缩合制丙烯酸(酯)研究进展

近年来,通过乙酸（酯）和甲醛缩合制备丙烯酸的新路线吸引了学术界和工业界的广泛关注。此新路线的优点是过程简单,原料可从天然气、煤化工产品中获得,成本低廉,对可持续生产丙烯酸具有十分重要的意义。国内外研究者针对这一反应开发了多种类型的催化剂,包括钒磷氧（VPO）类催化剂、负载型碱金属/碱土金属以及离子液体等。本文综述了不同种类催化剂近期的研究成果,总结了三类催化剂的优缺点。指出均相的离子液体催化剂具有反应温度低、能耗少、选择性高的特点,但反应为间歇操作,产物分离困难、催化剂较难重复利用,催化效率偏低。VPO类催化剂和碱金属/碱土金属类催化剂,反应温度较高（320～400℃）,但可实现连续反应,产物分离方便,催化效率较高。相比于VPO类催化剂,碱金属/碱土金属类催化剂涉及的反应较少,对目标产物的选择性较高,但整体催化效能低于VPO类催化剂,且失活催化剂再生困难。最新的研究结果表明,经典的有机相法制备VPO前体可以被更加简便、经济与环境友好的一锅水相法取代。空气氛中简单焙烧即可完成催化剂前体的活化。不仅大大简化了催化剂制备,而且所得催化剂的小试性能优异,从而为后续应用奠定了重要基础。     

Controlling factors in the selective conversion of n-butane over promoted VPO catalysts at low temperature

Unpromoted and 1.2, 2.3 and 4.3 molar % Co:V cobalt-promoted vanadium-phosphorous-oxide (VPO) catalysts were synthesized via an organic route. The catalyst precursors were calcined and then conditioned in a reactor, forming the active vanadyl pyrophosphate (VO)₂P₂O₇ phase, which was confirmed via X-ray diffraction studies (XRD). The effect of co-promotion on the yield of maleic anhydride (MA) from n-butane oxidation was examined at different temperatures and gas hourly space velocities (GHSV). 2.3% Co:V was the optimum promoter loading for a high yield towards MA. Higher GHSV's proved to enhance the selectivity towards MA.

The catalysts were tested over a 200 h period, generally taking some 24 h to reach steady-state performance. The best performing catalyst yielded 45% MA at 275 °C and a GHSV of 7200 ml g⁻¹ h⁻¹, with an n-butane conversion of 73%, whilst all previously reported VPO catalysts produced far lower MA yields at this temperature.     

Reduction of NOx over Fe/ZSM-5 catalysts: mechanistic causes of activity differences between alkanes

Fe/ZSM-5 catalysts prepared by sublimation of FeCl₃ onto H/ZSM-5 catalyze the selective reduction of NO_x by hydrocarbons to N₂. The order of the relative rates and N₂ yields obtained with different alkanes reveals a non-trivial chemistry. The maximum yield is lower for propane than for n-butane but about the same for n- and iso-butane. However, at temperatures below this maximum, the N₂ yield is higher for propane and n-butane than for iso-butane. Deposits are formed on the catalyst that contain N atoms in a low-oxidation state which are able to react with NO₂ to form N₂. TPO and FTIR results show that the amount and also the character of the deposits depend on the nature of alkanes. The change of the oxidation state of nitrogen from a high value in NO or NO₂ to a lower value in nitrile and amino groups of the deposit is rationalized by applying mechanistic concepts of organic chemistry, including the Beckmann rearrangement and fragmentation. FTIR spectra and the observed oxygen- and nitrogen-containing compounds by GC-MS are potential clues to the reaction mechanism.     

Study on thermal properties of stearyl alcohol modified graphene oxide/ n-octadecane composite phase change materials

Adding high thermal conductivity fillers to n-octadecane to form a composite phase change material(PCM) can improve its thermal conductivity. At the same time, to ensure high thermal conductivity, dispersion stability and recycling reliability of PCM, a type of composite PCM has been fabricated by grafting stearic alcohol onto graphene oxide (GO). The modified graphene/n-octadecane composite PCMs with 0, 1%, 2%, 3% and 4%(mass) of modified graphene were prepared to characterize and study of feature structure and thermophysical properties by means of scanning electron microscope, infrared spectrum analysis, differential scanning calorimetry and thermal conductivity analysis, etc. Experiments show that the modified graphene/n-octadecane composite PCMs prepared in this paper has good dispersion stability. When the mass fraction of modified graphene reaches 4%, the thermal conductivity of composite PCMs is 131.9% higher than that of pure n-octadecane.     

A vanadium phosphorus oxide catalyst synthesized in rotating packed bed for high-efficiency selective oxidation of n-butane

Oxidation of n-butane to produce maleic anhydride (MA) by the vanadium phosphorus oxide (VPO) catalyst is important for the fine chemical industry. However, the improvement in MA yield exceeding 60% is still a big challenge. In this article, a VPO catalyst with increased MA yield originated from the tailored structure of VPO precursor prepared in a rotating packed bed (RPB) reactor with excellent micro-mixing efficiency. The activated VPO-RPB catalyst displayed the coexistence of X₁-VOPO₄ and α_I-VOPO₄ phases and enhanced reducibility of V⁴⁺ state. Remarkably, the MA yield in n-butane oxidation catalyzed by VPO-RPB reached up to 66%, showing an increment by 14% compared with VPO-STR prepared in a stirring tank reactor (STR). The VPO-RPB showed the repeatable catalytic performance and achieved a promising scale-up production. This work provides the experimental evidence of a dual-phase (X₁-VOPO₄ and α_I-VOPO₄) mechanism for n-butane oxidation, and reveals the structure–activity dependence of VPO catalyst.     

直接氧化法制备2,5-二氯苯酚

2,5-二氯苯酚是重要的酚类化合物，工业上常用的2,5-二氯苯酚的制备方法大多存在生产流程长、污染严重等问题。针对这些问题，本文提出了以对二氯苯为原料、H₂O₂为氧化剂的直接氧化制备2,5-二氯苯酚的工艺，并对催化剂和溶剂进行初步筛选，探讨了不同催化体系对反应的影响，确定以铁粉作催化剂、乙酸为溶剂的反应体系下，通过对氧化剂用量、反应温度、反应时间、催化剂用量等工艺条件的考察，获得最佳工艺条件。实验结果表明，当工艺条件为n(对二氯苯)∶n(50%H₂O₂)∶n(Fe)=1∶3∶0.10、反应温度60℃、反应时间2.5h时，反应效果最佳；产物经GC-MS和¹HNMR分析确定为2,5-二氯苯酚，经气相色谱分析，2,5-二氯苯酚选择性达83.4%，收率达42.6%。     

低温等离子体协同Mn基催化剂降解氯苯研究

以氯代挥发性有机物（CVOCs）中的典型代表氯苯为研究对象,分别采用硝酸锰（MN）和乙酸锰（MA）为前体,通过浸渍法制备Mn基催化剂,考察了低温等离子体协同Mn基催化剂降解氯苯性能以及抑制反应副产物臭氧生成的影响。研究发现对于不同反应系统,提升电压可以提高氯苯降解效率;催化剂引入能够大幅度提高氯苯降解性能,与MnO _x （MN）/γ-Al₂O₃相比,MnO _x （MA）/γ-Al₂O₃引入对氯苯降解效果更好,对臭氧生成的抑制性能更高。利用N₂吸附-脱附、扫描电镜（SEM）、X射线衍射（XRD）、傅里叶红外光谱（FT-IR）和X射线光电子能谱（XPS）等手段对反应前后催化剂进行表征分析,发现放电并未对催化剂的孔径及晶相结构产生影响;通过无机氯选择性和尾气质谱结果分析氯苯降解过程中氯元素变化;与MnO _x （MN）/γ-Al₂O₃催化剂相比,MnO _x （MA）/γ-Al₂O₃催化剂的比表面积相对较大,活性组分分散性更高、更均匀,从而导致反应系统内更多的臭氧在催化剂表面分解为活性氧原子,提高了氯苯的降解性能并抑制了反应系统内臭氧的生成。     

低温等离子体协同Mn基催化剂降解氯苯研究

以氯代挥发性有机物（CVOCs）中的典型代表氯苯为研究对象,分别采用硝酸锰（MN）和乙酸锰（MA）为前体,通过浸渍法制备Mn基催化剂,考察了低温等离子体协同Mn基催化剂降解氯苯性能以及抑制反应副产物臭氧生成的影响。研究发现对于不同反应系统,提升电压可以提高氯苯降解效率;催化剂引入能够大幅度提高氯苯降解性能,与MnO _x （MN）/γ-Al₂O₃相比,MnO _x （MA）/γ-Al₂O₃引入对氯苯降解效果更好,对臭氧生成的抑制性能更高。利用N₂吸附-脱附、扫描电镜（SEM）、X射线衍射（XRD）、傅里叶红外光谱（FT-IR）和X射线光电子能谱（XPS）等手段对反应前后催化剂进行表征分析,发现放电并未对催化剂的孔径及晶相结构产生影响;通过无机氯选择性和尾气质谱结果分析氯苯降解过程中氯元素变化;与MnO _x （MN）/γ-Al₂O₃催化剂相比,MnO _x （MA）/γ-Al₂O₃催化剂的比表面积相对较大,活性组分分散性更高、更均匀,从而导致反应系统内更多的臭氧在催化剂表面分解为活性氧原子,提高了氯苯的降解性能并抑制了反应系统内臭氧的生成。     

Preparation of Novel Composite VPO/Fumed Silica Catalyst for Partial Oxidation of n-Butane

By applying fumed SiO₂ and the deposition–precipitation method based on organic medium, the composite VPO/fumed SiO₂ catalysts were first prepared and tried for partial oxidation of n-butane to maleic anhydride. In the temperature range of 653–693 K the fumed SiO₂-based catalysts not only showed good activity but also maintained sufficiently high MA selectivity in comparison to some conventional supported VPO catalysts. As an example, the catalyst with 30% VPO content showed butane conversion of 60% and MA selectivity of 58 mol% at 673 K. The turnover rates of low loading samples are found to be higher than that of high loading sample as well as unsupported catalyst. Besides the unique interaction which may exist between VPO component and the fumed SiO₂ material, co-existence of dominant (VO)₂P₂O₇ and minor VOPO₄ in these non-equilibrated catalysts may be favorable for MA formation. Moreover, introducing the additive of polyethylene glycol (PEG) in the preparation medium can obviously enhance the dispersion of VPO component and hence lead to a more selective catalyst.