不同干燥法对VPO催化剂物性的影响

以两种不同方法制备VPO催化剂, 分别采用超临界流体干燥法(SCFD)和常规干燥法干燥。用BET和XRD等测试手段考察了催化剂在400℃下焙烧后的粒子比表面大小和晶相组成。实验结果表明, 采用超临界流体干燥法比采用常规干燥法所制得的催化剂比表面大得多, 且对催化剂晶相组成也有一定的影响。     

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%.     

碱土金属醇类低共熔溶剂强化钒磷氧催化剂的制备及催化性能研究

钒磷氧(VPO)催化剂是目前实现正丁烷选择性氧化的唯一工业催化剂。利用金属助剂掺杂以及有机助剂强化是提高VPO催化剂性能的有效手段。本工作通过加入氯化镁醇类金属低共熔溶剂,实现了有机-金属助剂同时对VPO催化剂性能的调控。利用扫描电子显微镜(SEM)、BET全自动比表面与孔隙度分析仪(BET)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)等表征手段,深入探讨了合成过程中加入不同氢键供体乙二醇(EG)、1-4丁二醇(BDO)和甘油(GL)的低共熔溶剂对VPO催化剂微观形貌、比表面积、物相、表面性质和晶相转变温度的影响,同时利用固定床反应器对VPO催化剂催化正丁烷氧化制备顺酐的性能进行了评价。结果表明,氯化镁乙二醇低共熔溶剂调控制备的VPO催化剂具有分散性良好、比表面积大、活性面(020)的数量多、表面P原子富集和表面V平均价态低等特点,在丁烷氧化选择性制顺酐反应中表现出了良好的催化性能,为VPO催化剂的制备提供了新思路。     

掺杂铋助剂对钒磷氧催化剂性能的影响

通过在有机相法制备钒磷氧催化剂前体的过程中引入铋助剂,考察了不同n(Bi)/n(V)催化剂的催化性能。结果表明,当n(Bi)/n(V)=0.01时,催化剂(Bi0.01-VPO)的收率达到最大(42.6%),与没有掺杂铋助剂的催化剂(VPO)相比其转化率由31%提高到71%。采用BET、XRD、SEM、XPS分析手段,对催化剂(Bi0.01-VPO)与(VPO)进行比较分析,发现添加铋助剂改变了催化剂物相组成和微观形貌,使催化剂表面钒的平均氧化态和表面n(P)/n(V)比都有所升高,略微增大了催化剂的比表面积。     

CrF3基催化剂的热稳定性及其对气相氟化反应的催化性能

研究了CrF₃基催化剂前驱体的热行为、催化剂的晶相和比表面积、孔容对催化剂活性的影响。结果表明，惰性气氛以及向前驱体中添加微量助剂可以提高其热稳定性；CrF₃基催化剂的活性相以非晶态存在；随着比表面积和孔容的增大，催化剂的活性提高。考察了CrF₃基催化剂对氟化HCFC-123合成HFC-125反应的催化性能。     

超临界流体干燥法制备TiO2柱撑膨润土及光催化性能研究

采用溶胶-凝胶法结合超临界流体干燥技术制备了TiO2柱撑膨润土复合光催化剂，通过XRD、BET和FT-IR等分析方法对复合催化剂的物相组成、比表面积和键合状况等物化性能进行了表征，并以Cr(Ⅵ)的光催化还原反应考察其光催化性能。结果表明，用超临界法制备的复合催化剂具有大孔、锐钛矿晶型和沉降性能好等特点，且可实现晶化、干燥一步完成；该复合催化剂的光催化活性接近P25 TiO₂，且明显比空气干燥法制备的高。对于初始浓度为25 mg·L^－1的Cr(Ⅵ)离子，在最佳反应条件2.5 g·L^－1 TiO₂ 柱撑膨润土、溶液初始pH为3.0时，其光催化还原率达到77.6%。     

不同P与V比的Mo/VPO催化剂物相组成及其催化性能

采用有机相法制备了不同P与V物质的量比的Mo掺杂VOHPO₄·0.5H₂O前驱体,并通过体积分数为50%空气-40%氮气-10%水蒸汽混合气氛活化得到Mo/VPO催化剂,采用固定床反应器评价其催化正丁烷氧化制顺酐的性能。结果表明,Mo/VPO催化剂催化活性随P与V物质的量比的增大而降低,但顺酐选择性与P与V物质的量比并不呈线性关系,P与V物质的量比为0.9的Mo/VPO催化剂具有最佳的催化性能。XRD分析表明,Mo/VPO催化剂催化正丁烷氧化制顺酐的主要活性物相为(VO)₂P₂O₇和钒磷云母相,形成的主要因素不是P与V物质的量比,而是由焙烧条件决定。低P与V物质的量比的Mo/VPO中存在的少量V₂O₅物相能够提升催化剂的活性和顺酐选择性,但含量过高会因深度氧化降低催化性能。催化剂中存在的钒磷云母相有利于缩短催化剂稳定时间并提升催化性能。     

丁烷氧化制顺酐VPO催化剂前躯体的研究进展

综述了正丁烷选择性氧化制顺酐VPO催化剂的制备方法和催化机理的研究进展,分析了制备过程中溶剂和还原剂种类、磷钒原子比、还原温度及时间、添加助剂、老化条件、干燥条件及载体添加对催化剂性能的影响,介绍了VPO催化剂选择氧化丁烷制顺酐的反应机理,并展望了VPO催化剂未来的发展方向。     

正丁烷氧化制顺酐催化剂的制备及其催化性能

采用有机相法制备了具有优异催化性能的正丁烷氧化制顺酐钒磷氧(VPO)催化剂。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、扫描电镜(SEM)、氮气吸附脱附、X射线光电子能谱(XPS)、热重分析(TG)等方法对催化剂的制备过程进行了研究,分析了催化剂在整个制备过程中物相、价态、形貌和比表面积的变化。在固定床反应器上对正丁烷氧化制顺酐的反应条件进行研究,考察了反应温度、正丁烷浓度和反应空速等条件对催化剂性能的影响。结果表明,催化剂前驱体的主要物相为VOHPO4·0.5H2O。经活化后的催化剂活性相包括(VO)2P2O7(V4+)、VOPO4(V5+)和钒磷云母相(V4+和V5+混合相)。催化剂呈规则的片层结构,具有较高的比表面积,可以达到24.08 m2/g。催化剂在制备过程中需要经过干燥、焙烧和气氛活化,对催化剂的形成具有至关重要的作用。最佳的反应条件:反应温度为395℃,正丁烷摩尔分数为1.4%~1.5%,反应空速为2 000 h-1,此时正丁烷转化率为85%~87%,顺酐收率可达到59%~60%。     

V4+和V5+比例对钒磷氧催化NO2氧化环己烷性能的影响

采用浸渍法制备不同钒价态结构的钒磷氧(VPO)复合氧化物催化剂,测试其对NO₂氧化环己烷制备己二酸的催化性能,并采用XRD、XPS、H₂-TPR和UV-Vis DRS等手段进行表征,考察不同过渡金属掺杂对VPO中钒价态结构的影响,以及催化氧化环己烷性能的影响。研究结果表明,过渡金属的引入能够改变VPO中β-VOPO₄和(VO)₂P₂O₇两种晶相结构,从而调变V⁵⁺和V⁴⁺的比例,且钒的价态比例对NO₂氧化环己烷反应具有重要影响。同时含有V⁵⁺和V⁴⁺的M/AlVPO催化剂的催化性能明显高于纯V⁵⁺的β-VOPO₄和纯V⁴⁺的(VO)₂P₂O₇催化剂。其中,以V⁴⁺/V⁵⁺为0...     

Ammoxidation of 3-picoline to nicotinonitrile over vanadium phosphorus oxide-based catalysts

Ammoxidation of 3-picoline to nicotinonitrile was investigated on vanadium phosphorus oxide (VPO), VPO/SiO₂ and additive atom (Cu, Zr, Mn and Co) incorporated VPO catalysts under atmospheric pressure and at 673 K. For the purpose of comparison a conventional V₂O₅–MoO₃/Al₂O₃ catalyst was also studied under identical conditions. These catalysts were characterized by means of X-ray diffraction, electron spin resonance, infrared, ammonia chemisorption and BET surface area methods. The VPO-based catalysts show better performance than the V₂O₅–MoO₃/Al₂O₃ catalyst. Further, the VPO/SiO₂ and VPO catalysts exhibit better conversion and product selectivities than the additive-containing VPO catalysts. Better activity of VPO and VPO/SiO₂ catalysts was related to their high active surface area, higher surface acidity and lower oxidation state of vanadium. The redox couple between (VO)₂P₂O₇ (V⁴⁺) and α_I-VOPO₄ (V⁵⁺) phases appears to be responsible for the ammoxidation activity of VPO catalysts. © 1998 SCI.     

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%。     

Influence of Rare-Earth and Bimetallic Promoters on Various VPO Catalysts for Partial Oxidation of n-Butane

Vanadium phosphorous oxide (VPO) catalyst was prepared using dihydrate method and tested for the potential use in selective oxidation of n-butane to maleic anhydride. The catalysts were doped by La, Ce and combined components Ce + Co and Ce + Bi through impregnation. The effect of promoters on catalyst morphology and the development of acid and redox sites were studied through XRD, BET, SEM, H₂-TPR and TPRn reaction of n-butane/He. Addition of rare-earth element to VPO formulation and drying of catalyst precursor by microwave irradiation increased the fall width at half maximum (FWHM) and reduced the crystallite size of the Vanadyl hydrogen phosphate hemihydrate (VOHPO₄ · 1/2 H₂O, VHP) precursor phase and thus led to the production of final catalysts with larger surface area. The Ce doped VPO catalyst which, assisted by the microwave heating method, exhibited the highest surface area. Moreover, the addition of promoters significantly increased catalyst activity and selectivity as compared to undoped VPO catalyst in the oxidation reaction of n-butane. The H₂-TPR and TPRn reaction profiles showed that the highest amount of active oxygen species, i.e., the V⁴⁺–O^? pair, was removed from the bimetallic (Ce + Bi) promoted catalyst. This pair is responsible for n-butane activation. Furthermore, based on catalytic test results, it was demonstrated that the catalyst promoted with Ce and Bi (VPOD1) was the most active and selective catalyst among the produced catalysts with 52% reaction yield. This suggests that the rare earth metal promoted vanadium phosphate catalyst is a promising method to improve the catalytic properties of VPO for the partial oxidation of n-butane to maleic anhydride.     

磷酸氧钒催化剂制备及其催化氧化性能研究进展

综述磷酸氧钒(VPO)催化剂制备方法及其对烷烃类物质催化氧化反应的研究进展,分析催化剂制备过程中载体、助剂、还原剂、分散剂、磷钒原子比以及在醇类溶液中回流时间等对VPO催化剂性能的影响。介绍VPO催化剂对烷烃类物质选择性氧化反应的反应机理,并展望VPO催化剂未来发展方向。     

Synthesis of 2,6-dichlorobenzonitrile from 2,6-dichlorotoluene by gas phase ammoxidation over VPO catalysts

Ammoxidation of 2,6-dichlorotoluene to 2,6-dichlorobenzonitrile is indeed an industrially important reaction for producing various commercially useful chemicals. In this contribution, differences in the catalytic performance of bulk, supported and promoted VPO samples are described. The choice of P/V ratio is found to play a key role on the catalytic properties of the catalysts. Activity is observed to decrease with increase in P/V ratio of the catalysts. About 55% yield of DCBN and ca. 95% conversion of DCT is obtained over bulk VPO solids having low P/V ratios (≤1). However, the catalytic performance of these bulk VPO solids is considerably improved when they are supported on γ-Al₂O₃ (Y-DCBN = 70% and X-DCT = >90%). In the direction of further enhancing the yield of DCBN, some selected transitional metal ions (Cr, Fe, Co and Mo) are also used as promoters for the present VPO solids. These promoted catalysts displayed superior performance compared to bulk and supported VPO catalysts. Amazingly, the yield of DCBN is significantly enhanced from 55% (on bulk VPO solids) to ca. 80% on the promoted VPOs, which is indeed a remarkable outcome of this study. This increase in the catalytic performance can be attributed to the surface enrichment of phosphorus in the supported and promoted catalysts compared to their corresponding bulk VPOs. Additionally, the influence of calcination temperature on the distribution of oxidation states of vanadium is presented.     

Partial Oxidation of Isobutane over Vanadium Phosphorus Oxides

A series of vanadium phosphorus oxides (VPO) were prepared by using dodecyl amine as surfactant and tested for the partial oxidation of isobutane and isobutene. Characterization results showed that their structure and properties depend on the content of dodecyl amine. Catalytic tests showed that relatively high isobutane conversion and desired product selectivity can be achieved over a proper dodecyl amine doping VPO catalyst. It is also found that higher isobutane conversion can be achieved over V⁴⁺-containing phases as compared to V⁵⁺-containing phases, while proper surface V⁵⁺/V⁴⁺ ratio may be propitious to obtain high selectivity to methacrylic acid for the selective oxidation of isobutane. In addition, the content of dodecyl amine in the preparation of the VPO catalysts appears to be more important in determining the surface P/V ratio of the catalysts.     

The selective oxidation of η‐butane to maleic anhydride: comparison of bulk and supported V–P–O catalysts

V–P–O catalysts supported on the surface of silica and titania particles were studied and compared with bulk V–P–O. The catalytic performance was tested in the η‐butane oxidation reaction to maleic anhydride, and the structure of the equilibrated catalysts was characterised with X‐ray absorption spectroscopy (EXAFS) and (low‐temperature) ESR spectroscopy. Our results show considerable differences in catalytic performance between VPO/TiO₂ on the one hand, and VPO/SiO₂ and VPO/bulk on the other hand, the yield to maleic anhydride being comparable for VPO/bulk and VPO/SiO₂. The differences in catalytic behaviour are attributed to differences in the local structure around vanadium (EXAFS). Furthermore, different spin exchange interactions between vanadium atoms in the three samples have been observed (ESR). The combination of characterisation methods suggests that the structure of the supported V–P–O phase is amorphous and differs considerably from that of bulk crystalline vanadylpyrophosphate. We therefore propose that the oxidation of η‐butane to maleic anhydride takes place over an amorphous surface V–P–O phase. This finding has high relevance for our understanding of the catalytic activity of bulk crystalline V–P–O catalysts as well. This revised version was published online in July 2006 with corrections to the Cover Date.