A comparative study on direct production of ethyl levulinate from glucose in ethanol media catalysed by different acid catalysts

Direct production of ethyl levulinate (EL) from glucose catalysed by a liquid acid catalyst (sulfuric acid) and a solid acid zeolite catalyst USY NKF-7 (USY) in ethanol media was investigated in this study. Effects of the initial glucose concentration (C _G0), reaction temperature (T), amount of acid catalyst, and water addition on the yields of EL were compared, respectively. The results show that higher yield of EL can be obtained at lower C _G0. Higher temperature and acid concentration can accelerate the reaction rate, but the formation rate of the by-products increases more quickly than that of EL. Water addition also can result in the decrease of the yield of EL. Although sulfuric acid is efficient in the production of EL, the USY is more efficient in converting glucose to 5-ethoxymethyl-2-furaldehyde. Moreover, the use of USY can limit the diethyl ether production, and it can be reused for multiple times.     

Reactivity of Extra‐framework Species of USY Zeolites in Alkaline Medium

Zeolites of type USY (ultra‐stable Y) were obtained by steaming of NH₄NaY modification. Samples were modified by subsequent alkaline treatment in KOH solution. USY and USY‐KOH were characterised by chemical element analysis, XRD, IR, ²⁹Al and ²⁹Si MAS NMR spectroscopic measurements. Correct silicon to aluminium ratios (Si/Al) were determined by XRD and IR (double ring vibration w_DR) data whereas values calculated according to data of ²⁹Si MAS NMR and IR spectroscopy (asymmetrical TOT valence vibration w_TOT) appeared to be too high., In the latter case, the signals of the zeolite framework were strongly superimposed by that of extra‐framework silica gel (EFSi) formed during steaming. It was found that alkaline leaching induces desilication of silicon‐rich area of the zeolite framework and partial dissolution of EFSi. Silicate ions of both react with likewise dissolved extra‐framework aluminium (EFAl) to form X‐ray amorphous aluminosilicate. Consequently, the superposition of the ²⁹Si MAS NMR signals of the zeolite framework by silica gel was reduced for Q⁴(0Al) but increased for Q⁴ (2Al) and Q⁴(3Al) structure units. A reinsertion of EFAl into the zeolite framework has not been observed.     

Hydroisomerization of n-heptane over bimetal-bearing H3PW12O40 catalysts supported on dealuminated USY zeolite

The bimetal-bearing (CePt or LaPt) 12-tungstophosphoric acid (H₃PW₁₂O₄₀ (PW)) catalysts supported on dealuminated USY zeolite (DUSY) were prepared by impregnation and characterized by XRD, BET, IR, and H₂-chemisorption. Their catalytic activities were tested in the hydroisomerization of n-heptane with a continuous atmospheric fixed-bed reactor. After the steam treatment combined with the acid leaching, as well as the supporting with PW and the bimetals, the DUSY support retains the Y zeolite porosity and the PW well keeps its Keggin structure in catalysts. The doping of Ce into the catalysts enhances the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Ce or La, especially Ce, exhibit much higher catalytic activity and selectivity than the catalysts without dopants at lowered reaction temperatures. At the optimal reaction conditions, i.e., the reaction temperature of 250°C and WHSV of 1.4 h^?1, the catalyst with a Pt loading of 0.4%, PW loading of 10% and a molar ratio of Ce to Pt of 15:1 shows a conversion of n-heptane of 70.3% with a high selectivity for isomerization products of 94.1%.     

Cr改性USY分子筛提高裂化催化剂的异构化性能

在催化裂化过程中,烷烃分子在酸性催化剂表面进行一系列的反应,其中氢转移反应能导致汽油中的烯烃质量分数降低,而异构化、环化、芳构化反应则改善裂化产品的分布,对提高裂化汽油的辛烷值有明显的效果。为了解决我国裂化汽油中烯烃质量分数过高的问题,目前大多数催化裂化装置都采用了降烯烃裂化催化剂,以氢转移反应活性高的REUSY分子筛作为裂化催化剂的活性组分。但由于REUSY分子筛的异构化活性较低,因此裂化汽油的辛烷值有所下降,需要对裂化汽油进行加氢异构化处理。若直接对裂化催化剂进行改性,提高其异构化反应活性,     

Oxidation of benzyl alcohol by K<Subscript>2</Subscript>FeO<Subscript>4</Subscript> to benzaldehyde over zeolites

A novel and green procedure for benzaldehyde synthesis by potassium ferrate oxidation of benzyl alcohol employing zeolite catalysts was studied. The prepared oxidant was characterized by SEM and XRD. The catalytic activity of various solid catalysts was studied using benzyl alcohol as a model compound. USY was found to be a very efficient catalyst for this particular oxidation process. Benzaldehyde yields up to 96.0% could be obtained at the following optimal conditions: 0.2 mL of benzyl alcohol, 4 mmol of K₂FeO₄, 0.5 g of USY zeolite; 20 mL of cyclohexene, 0.3 mL of acetic acid (36 wt %), 30°C temperature, 4 h reaction time.     

Probing the Brønsted Acidity of the External Surface of Faujasite-Type Zeolites

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or ³¹P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.     

Cu-loaded dealuminated Y zeolites active in selective catalytic reduction of nitric oxide with ammonia

The selective catalytic reduction of NO with ammonia in the presence of oxygen has been carried out on Cu-loaded dealuminated Y zeolite catalysts. Copper was introduced by the usual ion-exchange procedure with an aqueous solution of cupric acetate. On deeply dealuminated USY zeolites, Cu²⁺ was supported in the amount larger than 2Cu/Al = 2, resulting in the formation of CuO fine particles in addition to the isolated and dimer Cu²⁺ species. The specific catalytic activity per surface copper on the CuO particles was very high compared with these Cu²⁺ species. NO adsorption measurement revealed the higher dispersion of CuO on the deeply dealuminated USY than on SiO₂, which made Cu/USY a better catalyst for the reduction of NO. The reaction intermediates were investigated through the IR spectra of adsorbed species.     

Controllably Confined ZnO on USY Zeolites (USY@ZnO/Al2O3) as Efficient Lewis Acid Catalysts for Baeyer–Villiger Oxidation

A ZnAl‐LDHs (layered double hydroxides) phase was readily formed on the surface of a USY zeolite through a distinctive in situ growth method that benefitted from the interaction of the added Zn source and aluminum species extracted from the Al‐rich USY zeolite crystals. The migration of aluminum and simultaneous interaction with the external Zn source took place in one pot to form a ZnAl‐LDHs phase coated on the surface of the USY crystals. Upon calcination, the ZnAl‐LDHs phase was transformed into a ZnO/Al₂O₃ composite that was still firmly anchored on the USY zeolite, without sacrificing the core–shell structure. The resultant USY@ZnO/Al₂O₃ materials gave rise to unique Lewis acidity and hierarchical porosity, which endowed the catalyst with promising performance in the Baeyer–Villiger oxidation of ketones with H₂O₂ or bulky tert‐butyl hydroxide as an oxidant.     

Cu-loaded dealuminated Y zeolites active in selective catalytic reduction of nitric oxide with ammonia

The selective catalytic reduction of NO with ammonia in the presence of oxygen has been carried out on Cu-loaded dealuminated Y zeolite catalysts. Copper was introduced by the usual ion-exchange procedure with an aqueous solution of cupric acetate. On deeply dealuminated USY zeolites, Cu²⁺ was supported in the amount larger than 2Cu/Al=2, resulting in the formation of CuO fine particles in addition to the isolated and dimer Cu²⁺ species. The specific catalytic activity per surface copper on the CuO particles was very high compared with these Cu²⁺ species. NO adsorption measurement revealed the higher dispersion of CuO on the deeply dealuminated USY than on SiO₂, which made Cu/USY a better catalyst for the reduction of NO. The reaction intermediates were investigated through the IR spectra of adsorbed species.     

Cu-MgO/USY催化甘油氢解制丙二醇(英文)

以USY为载体制备了一系列不同Cu和MgO负载量的酸碱双功能催化剂Cu-MgO/USY用于甘油氢解制丙二醇反应,并采用X射线粉末衍射、透射电镜、傅里叶红外光谱、NH3程序升温脱附等手段对该催化剂进行了表征.结果表明,负载后的USY载体其Y沸石特征峰保持完整,且MgO的加入提高了Cu在载体表面的分散度.在200 oC,3.5 MPa H2下反应10 h以及6%催化剂0.2Cu-MgO/USY(0.2 g Cu与1.0 g MgO负载于1.0 g USY上面)用量的条件下,甘油转化率达到83.6%,1,2-丙二醇及1,3-丙二醇的选择性分别为40%和19.4%.     

ScIII‐Doped Zeolites as New Heterogeneous Catalysts: Mukaiyama Aldol Reaction

Sc^III‐doped solids based on zeolite materials have been investigated for the first time as catalysts in organic synthesis. Sc^III–USY zeolite proved to be a novel and very efficient heterogeneous catalyst for the Mukaiyama aldol reaction. This easy‐to‐prepare catalyst exhibited wide scope and compatibility with functional groups and is very simple to use, easy to remove (by simple filtration), and is recyclable (up to three times without loss of activity).     

多产低碳烯烃及柴油用分子筛的设计

目前,催化裂化的原料大多是蜡油和减压渣油的混合油,或全部的常压渣油 .其相对分子量范围很宽,组成十分复杂 .为了分别对待大小不同的分子和不同碳氢比化合物的裂化性能,现代催化裂化催化剂应具有梯度孔结构与梯度酸中心的优化结构配置 .而目前催化裂化的主导分子筛 USY二次孔含量还不能满足原料油日趋变重的需求,并且滞留在分子筛孔 /笼内的非骨架铝限制了其选择性的进一步提高,因此有必要对其结构进一步修饰 .　　本研究在 USY基础上合成新的催化裂化多产低碳烯烃和柴油用分子筛催化剂 .新型 USY基分子筛从晶体结构、孔容及孔…     

Hydroisomerization of n-heptane over bimetal-bearing H3PW12O40 catalysts supported on dealuminated USY zeolite

The bimetal-bearing (CePt or LaPt) 12-tungstophosphoric acid (H₃PW₁₂O₄₀ (PW)) catalysts supported on dealuminated USY zeolite (DUSY) were prepared by impregnation and characterized by XRD, BET, IR, and H₂-chemisorption. Their catalytic activities were tested in the hydroisomerization of n-heptane with a continuous atmospheric fixed-bed reactor. After the steam treatment combined with the acid leaching, as well as the supporting with PW and the bimetals, the DUSY support retains the Y zeolite porosity and the PW well keeps its Keggin structure in catalysts. The doping of Ce into the catalysts enhances the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Ce or La, especially Ce, exhibit much higher catalytic activity and selectivity than the catalysts without dopants at lowered reaction temperatures. At the optimal reaction conditions, i.e., the reaction temperature of 250°C and WHSV of 1.4 h⁻¹, the catalyst with a Pt loading of 0.4%, PW loading of 10% and a molar ratio of Ce to Pt of 15:1 shows a conversion of n-heptane of 70.3% with a high selectivity for isomerization products of 94.1%. Supported by the Natural Science Foundation of China (Nos. 20306011 and 20476046), the Ph. D. Program Foundation of Chinese University (20040291002), and the Ph. D. innovation Program Foundation of Nanjing University of Technology (BSCX200506)     

Improvement in nanocomposite host (nanocavity of dealuminated zeolite Y)-guest (12-molybdophosphoric acid) catalytic activity and its application to the one-pot three-component synthesis of tetrahydrobenzo[b]pyrans

Zeolite Y was dealuminated by chemical methods (with ethylenediaminetetraacetic acid) to modify the zeolite structure for 12-molybdophosphoric acid (MPA) loading. MPA was encapsulated in the nanocavities of modified dealuminated zeolite Y (MDAZY) and characterized by Fourier transform infrared, X-ray diffraction, and atomic absorption spectroscopy. The new catalyst was applied for an efficient chemoselective synthesis of tetrahydrobenzo[b]pyran derivatives, and the corresponding products were obtained in good to excellent yields in very short reaction times. Furthermore, the catalytic activity of this new catalyst in the synthesis of tetrahydrobenzo[b]pyrans was compared with MPA encapsulated in zeolite Y dealuminated by the hydrothermal method. The catalyst (MPA–MDAZY) was recovered and reused several times without loss of its catalytic activity.     

Magnetic Field-Enhanced Electrocatalytic Oxygen Evolution on a Mixed-Valent Cobalt-Modulated LaCoO3 Catalyst

Extensive efforts to enhance the oxygen evolution reaction (OER) catalytic performance of transition metal oxides mainly concentrate on the extrinsic morphology tailoring, lattice doping, and electrode interface optimizing. Nevertheless, little room is left for performance improvement using these methods and an obvious gap still exists compared to the precious metal catalysts. In this work, a novel “mixed-valent cobalt modulation” strategy is presented to enhance the electrocatalytic OER of perovskite LaCoO₃ (LCO) oxide. The valence transition of cobalt is realized by ethylenediamine post reduction procedure at room temperature, which further induces the variation of magnetic properties for LCO catalyst. The optimized LCO catalyst with Co²⁺/Co³⁺ of 1.98 % exhibits the best OER activity, and the overpotential at 10 mA cm⁻² current density is decreased by 170 mV compared pristine LCO. Impressively, the ferromagnetic LCO catalyst can perform magnetic OER enhancement. By application of an external magnetic field, the overpotential of LCO at 10 mA cm⁻² can be further decreased by 20 mV compared to that of under zero magnetic field, which arises from the enhanced energy states of electrons and accelerated electron transfer process driven by magnetic field. Our findings may provide a promising strategy to break the bottleneck for further enhancement of OER performance.     

W-Ni/Al2O3-USY催化剂中USY的作用

采用ＥＳＣＡ，ＴＰＲ及高压连续流动反应色谱等技术研究了在Ｗ－Ｎｉ／Ａｌ２Ｏ３中引入超稳Ｙ型分子筛对载体表面性质及催化剂加氢脱氮活性的影响。结果表明：ＵＳＹ可明显改善Ｗ和Ｎｉ的分散状态，提高催化剂的总酸，并可调变Ｂ酸和Ｌ酸的分布；加入ＵＳＹ可提高催化剂的比表面积，但不利于发挥Ｎｉ的助剂作用；加入适宜量的ＵＳＹ，可明显提高催化剂的加氢脱氮活性。     

Analysis of Acidic Properties of Zeolitic and Non-Zeolitic Solid Acid Catalysts Using Temperature-Programmed Desorption of Ammonia

A method of ammonia temperature-programmed desorption (TPD) for analysis of acidic property of a solid was improved by introduction of a water vapor treatment method and development of a theory for calculation of ammonia adsorption heat from the TPD profile. The improved method was applied to various solid acid catalysts to establish relationships between the acidic properties and catalytic performances for various acid-catalyzed reactions. Here, examples of the applications to some important acid catalysts are reviewed. The exact analysis of acidic property of Y zeolite and its change by such modifications as steaming and ethylenediaminetetraacetic acid (EDTA) treatment gave a new interpretation on the generation of alkane (paraffin) cracking activity on an ultra stable Y (USY) zeolite. The surface density and strength of acid sites on WO₃/ZrO₂ and SO₄ ^2–/ZrO₂ catalysts were determined, and their relations with catalytic activities for Friedel–Crafts type alkylation and skeletal isomerization of alkane were found.     

Effects of binder, coking and regeneration on acid properties of H-mordenite during TDP reaction

The effects of binder, coking and regeneration on the acid properties of H-mordenite zeolite during toluene disproportionation reaction (TDP) have been investigated by solid-state ³¹P-MAS-NMR of various adsorbed phosphorous probe molecules in conjunction with elemental analysis by ICP-MS technique. A series of fresh, spent and regenerated mordenite-based commercial catalysts were examined and the results were also compared with binder-free H-mordenite zeolite and unformulated γ-alumina binder. It is found that parent H-mordenite zeolite possessed only Brønsted acidity, which is responsible for the observed catalytic activity. In contrast, the γ-Al₂O₃ binder exhibited only Lewis acidity and plays a minor role during the catalytic reaction. While the amount of strong Brønsted acid sites decreased rapidly during initial coking, it reached a plateau at a total coke content of ca. 7 wt%, corresponding to ca. 80% decrease in total acidity. That the catalyst remained active even under deep coke deposition (>7 wt%) condition indicated catalytic activity may be invoked by subsequent coking taking place on the external surface rather than intracrystalline channels of the zeolite catalyst. Furthermore, upon catalyst regeneration treatment, ca. 75% of the total acidity could be effectively recovered.     

脱铝超稳Y沸石催化合成乙酸正丁酯研究

研究了脱铝超稳Y沸石催化乙酸与正丁醇的酯化反应。考察了催化剂硅铝比，催化剂用量，反应物配比，反应时间等因素对反应的影响。在适宜的反应条件下乙酸酯化率可达98．0％，且催化剂可重复使用。     

草酸脱铝改性USY的表征及加氢裂化性能

采用草酸脱铝对USY分子筛进行了改性,考察了草酸加入量对USY相对结晶度(CRX)、硅铝比(nS iO2/nA l2O3)、比表面积、孔结构及加氢裂化性能的影响,并采用程序升温脱附和原位红外光谱技术对改性USY型分子筛的酸性进行了表征。结果表明,随草酸加入量的增加,在脱除USY中非骨架铝的同时,骨架铝被脱除的量也逐渐增多,致使USY的相对结晶度先提高而后降低、硅铝比提高、酸强度和酸量降低。正癸烷的加氢裂化结果表明,当草酸的加入质量比为0.2时,正癸烷的转化率和一次裂化产物的选择性分别为68.5%和80.1%。草酸改性USY具有高催化活性是因为该分子筛具有空旷的介孔结构和较多的可接近的酸性位;一次裂化产物选择性高是因为空旷的介孔结构使裂化产物快速离开酸性位而避免了二次裂化。