P204-P507-HCl体系回收废FCC催化剂中稀土的优化

针对废流化催化裂化(FCC)催化剂的资源化利用问题,采用溶剂萃取法从废FCC催化剂中高效回收稀土。对无机酸浸出过程、二(2-乙基己基)磷酸(P204)和2-乙基己基膦酸单2-乙基己基酯(P507)单独萃取稀土过程以及P204-P507复合萃取稀土过程分别进行了研究。结果表明,盐酸为最佳浸出剂,在最佳浸出条件(4 mol·L⁻¹盐酸溶液、浸出时间为4 h、60 ℃、固液比为1∶15)下,Ce和La的浸出率分别为99.7%和97.7%。萃取过程的最佳条件为萃取剂浓度1.5 mol·L⁻¹、浸出液初始pH=2.5,P204和P507对Ce和La的萃取率均较高,而P507对杂质铝的萃取率远低于P204。P204-P507复合萃取体系中P507体积比为0.2时,Ce和La的回收率分别达到80.4%和75.3%,略低于纯P204萃取体系,而杂质铝的回收率小于10.0%。P204-P507复合萃取体系能有效降低回收稀土中杂质铝的萃取量。本研究可为从废FCC催化剂中回收高纯度稀土提供参考。     

V2O5/CeO2催化剂用于低温NH3-SCR的性能研究

采用浸渍法制备了系列V2O5/CeO2催化剂,用于低温NH3选择性催化还原(NH3-SCR)NO.同时,考察了催化剂中V2O5负载量和煅烧温度对催化活性的影响,并运用SEM,BET和XRD物理化学技术对催化剂进行了表征.结果表明,V2O5/CeO2催化剂对模拟烟气中的NO转化呈现出较高的活性,但是V2O5负载量和催化剂的催化活性并不呈线性递增的关系.当V2O5负载量超过10%时,催化剂的催化活性开始下降.随着煅烧温度的升高,由于钒酸铈的生成,催化剂的催化活性下降.400℃为最佳煅烧温度.     

Regeneration of commercial selective catalyst reduction catalysts deactivated by Pb and other inorganic elements

The regeneration of commercial SCR(Selective Catalyst Reduction) catalysts deactivated by Pb and other elements was studied.The deactivated catalyst samples were prepared by chemical impregnation with mixed solution containing K_2SO_4,Na_2SO_4,CaSO_4,Pb(NO_3)_2and NH_4H_2PO_4.A novel method combining Ethylenediaminetetraacetic acid disodium salt(EDTA-2Na) and H_2SO_4solution(viz.catalysts treated by dilute EDTA-2Na and H_2SO_4 solution in sequence) was used to recover the activity of deactivated samples,and the effect was compared with single H_2SO_4,oxalic acid,acetic acid,EDTA or HNO_3 solutions.The surface structure,acidity and reducibility of samples were characterized by N_2adsorption–desorption,inductively coupled plasma optical emission spectrometer(ICP-OES),scanning electron microscopy(SEM),X-ray diffraction(XRD),X-ray fluorescence(XRF),H-2-temperature programmed section(H_2-TPR),NH3-temperature programmed desorption(NH3-TPD) and in situ DRIFTS.Impurities caused a decrease of specific surface area and surface reducibility,as well as Br?nsted acid sites,and therefore led to severe deactivation of the SCR catalyst.The use of an acid solution alone possibly eliminated the impurities on the deactivated catalyst to some extent,and also increased the specific surface area and Br?nsted acid sites and promoted the surface reducibility,thus recovered the activity partially.The combination of EDTA-2Na and H_2SO_4 could remove most of the impurities and improve the activity significantly.The removal of Pb should be an important factor for regeneration.Due to a high removal rate for Pb and other impurities,the combination of EDTA-2Na and H_2SO_4 solutions provided the best efficiency.     

废弃SCR脱硝催化剂无害化处理的研究进展

鉴于废弃SCR脱硝催化剂中含有多种痕量重金属以及可回收利用物质,从处理工艺包括重金属的去除、有价金属的回收等方面综述了废弃SCR脱硝催化剂无害化处理的现状,总结了现阶段的研究重点以及工业化应用的瓶颈。目前主要关注废弃SCR脱硝催化剂中钒、钨、钛的回收工艺,但工业化成本昂贵,难以实现效益均衡化。根据现行废弃SCR脱硝催化剂的处置规范,烟气飞灰中重金属的存在是废催化剂处置工艺复杂化的关键。研究重金属的去除以及有价金属的回收,方能最终实现针对废弃SCR脱硝催化剂无害化处理工艺的综合研发。     

非均相高效催化剂在餐厨废油转化生物柴油中的应用

近年来,非均相催化剂在酯化和转酯化催化制备生物柴油中备受关注。综述了固体碱、固体酸、固定化酶等非均相高效催化剂在生物柴油制备中的研究进展,并展望了新型非均相催化剂在餐厨废油转化制备生物柴油的应用前景。     

碳包覆Pd/Al2O3催化剂催化4-溴苯酚加氢脱溴的活性和稳定性调控研究

在污染物液相催化加氢脱卤过程中,提高催化剂的稳定性至关重要.以水热合成法制备了不同碳包覆量的Pd/Al₂O₃@C催化剂,对催化剂进行了系列表征,并将催化剂应用于4-溴苯酚(4-BP)污染物的催化加氢脱溴反应.表征结果显示碳层提高了Pd/Al₂O₃的表面疏水性,有利于4-BP在催化剂上的吸附.并且在Pd/Al₂O₃@C催化剂的碳化过程中,碳还原部分Pd颗粒,并保留部分正价态Pd活性位,增强了4-BP中C-Br键的活化.与Pd/Al₂O₃相比,碳涂层提高了催化剂的催化活性.但当碳包覆量超过最佳包覆量后,暴露的Pd粒子随碳包覆量的增加而减少,导致活性下降.此外,碳层修饰后,催化剂的稳定性显著提高,从而大大抑制了Pd粒子的团聚和损耗.Pd/Al₂O₃@C表面的碳涂层对卤素具有较高的耐受性,从而减轻了液相催化加氢脱卤反应中活性中心的中毒.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni(NO3)2和Fe(NO3)3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO+NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

铁炭复配修复地下水中NO_3~- -N的条件研究

采用了铁炭复配修复地下水中NO3--N,探讨了实验条件对修复效果的影响。结果表明,在pH值近中性条件(初始pH 6.42)下,反应时间为1 h时NO3--N修复率达到60.85%;Fe/C=1∶1时介质最佳用量分别为4~5 g;Fe/C=1/1.5时修复率为72.80%;反应速率在高振荡强度下大于低振荡强度;氧化铜的催化效果最好,可使修复率提高7.5个百分点。铁炭复配介质修复地下水中NO3--N是有效可行的,修复率随反应时间的增加而提高,在Fe/C=1∶1时修复率与介质用量呈正相关,无限减小Fe/C比并不能无限提高修复率,振荡强度对修复具有显著影响,低振荡强度下的修复过程较高强度存在滞后现象,并非所有金属氧化物催化剂对铁炭修复NO3--N均有促进作用。     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.