Catalytic activities and acid strengths of Nio-Zro2 catalysts modified with acids

A series of NiO-ZrO₂ catalysts were prepared by coprecipitation from the mixed aqueous solution of nickel chloride-zirconium oxychloride, and were modified with acids, H₂SO₄, H₃PO₄ and H₃BO₃. It was found that the NiO-ZrO₂ catalyst containing 25 mole percent of nickel oxide and evacuated at 400‡C for 1.5 hr showed maximum catalylic activities for 1-butene isomerization and ethylene dimerizalion. The catalytic activities for both isonierization and dimerizalion were correlated with the acid strengths of the catalysts. The isonierization activity of 1-butene ran parallel with the dimerization activity of ethylene, although the isomerization look place on relatively weak acid sites as compared with the dimerization.     

Low-temperature catalytic combustion on Pt/SO 4 2− /ZrO2 and Pd/SO 4 2− /ZrO2 catalysts

Low-temperature combustion of various organic compounds on Pt/SO ₄ ^–2 /ZrO₂ and Pd/SO ₄ ^–2 /ZrO₂ was studied. For these organic compounds, especially saturated hydrocarbons, the combustion activities of Pt/SO ₄ ^–2 /ZrO₂ are higher than those of Pt/ Al₂O₃. Pt/SO ₄ ^–2 /ZrO₂ combustion catalysts can be used in a wide range of space velocity and oxygen content. The catalytic activity is enhanced with an increase of Pt loading from 0.1 to 1.0 wt%. The superacidity of the support material is responsible for the improvement in activity rather than an increase in catalyst surface area or metal dispersion. Pd/SO ₄ ^–2 /ZrO₂ are less active than Pt/SO ₄ ^–2 /ZrO₂.     

SO42-/TiO2/Al2O3型固体酸制备及催化合成醋酸丁酯

以共沉淀-浸渍法制备了SO₄^2-/TiO₂/Al₂O₃型固体酸催化剂,醋酸与正丁醇酯化反应作为探针反应,考察SO₄^2-/TiO₂/Al₂O₃型固体酸催化剂的催化性能,采用响应面法对制备催化剂过程中的陈化温度、硫酸浸渍液浓度和焙烧温度因素进行优化,通过XRD和IR对制备的固体酸催化剂进行表征。结果表明,在陈化温度-4 ℃、硫酸浸渍液浓度1.48 moL·L^-1和焙烧温度586 ℃条件下制得的催化剂催化性能最高,醋酸正丁酯酯化率可达98.1%,重复使用性良好。     

SO4^2—／ZrO2—SiO2超强酸催化剂的制备及催化合成丁酸异戊酯的研究

以硝酸锆为主要原料,采用酸浸渍法制得SO4^2-/ZrO2-SiO2固体超强酸,对主要影响其催化活性的焙烧温度进行了考察,并将制得的SO4^2-/ZrO2-SiO2作催化剂,合成了丁酸异戊酯,确定了最佳工艺条件。实验表明制得的该催化剂具有较高的催化活性,用其催化合成丁酸异戊酯其收率达93％。     

Phase structure of V2O5/TiO2 catalyst and catalytic behavior with removal of NO by ammonia

V₂O₅/TiO₂ catalyst with 3% (w/w) V loading has been prepared by sol–gel method. The characterization results of the catalyst structure and catalytic activity show that VO _X state is strongly dependent on the calcination temperature. Little effect is found for phase structure of TiO₂ support on catalytic activity. High catalytic activity in wide temperature range (240–420 °C) is observed for the catalysts calcinated at different temperatures at a space velocity of 50,000 h^?1. Space velocity and alkali metal oxides strongly influence the catalytic activity of the catalyst which was calcinated at 450 °C, furthermore, the one has high tolerance to SO₂ in our test conditions.     

SO2-4／TiO2-ZrO2固体酸催化剂催化废弃动植物油脂制备生物柴油

制备了SO2-4/TiO2-ZrO2固体酸催化剂,并以其催化废弃动植物油脂与甲醇发生酯交换反应制备生物柴油.结果表明,催化剂SO2-4-/TiO2-ZrO2表现出了较高的催化活性,在反应压力343 kPa下的最佳酯交换反应条件为:反应温度125℃、醇油摩尔比10∶1、催化剂用量5％、反应时间3h,该条件下废弃动植物油脂...     

Study on SO42−/ZrO2-MoO3 in the integrative transformation of cottonseed oil deodorizing distillate

With the integrative transformation of non α-tocopherols, glycerides, free fatty acids, and methyl alcohol in cottonseed oil deodorizing distillate as the target reaction, we prepared highly catalytic SO₄^2?/ZrO₂-MoO₃ solid acid catalyst by precipitation–wet impregnation. The optimal conditions for catalyst preparation were then determined by varying sulfuric acid concentration, MoO₃ loading factor, calcination temperature, and calcination time. The structure of SO₄^2?/ZrO₂-MoO₃ solid acid catalyst was then examined by X-ray diffraction (XRD), Brunauer–Emmett–Teller measurements, scanning electron microscopy, and other methods. Results show that the MoO₃ loading factor (percentage weight ratio of MoO₃ to ZrO₂), impregnation concentration of sulfuric acid, and calcination temperature were the most important factors that influenced catalytic activity. The optimal conditions for catalyst preparation were an MoO₃ loading factor of 20%, a sulfuric acid impregnation concentration of 0.75 mol/L, a calcination temperature of 550 °C, and a calcination time of 6 h. The obtained catalyst exhibited the highest catalytic activity under these conditions.     

Long-term stability of the V2O5/Al2O3 catalyst for the selective reduction of nitrogen oxides

Changes of the V₂O₅/Al₃O₃ catalyst aged for up to 10 years under real conditions of the selective catalytic reduction of NO _x by ammonia (SCR) at the tail gases of the nitric acid plant were characterized by⁵¹V NMR spectroscopy, porosimetry, temperature programmed reduction (TPR) and catalytic activity measurements. The catalytic activity and the redox properties of the catalyst were found intact. Only small variations of the ratio of the octahedral and tetrahedral vanadia species were documented by⁵¹V NMR on aged catalyst.     

FeVO4 nanorods supported TiO2 as a superior catalyst for NH3–SCR reaction in a broad temperature range

In this work, a catalyst with FeVO₄ nanorods supported on TiO₂ was prepared and applied for NH₃–SCR reaction. A significantly enhanced low temperature catalytic activity has been achieved in the presence of 10% H₂O with the active window shifting by 15 °C to lower temperatures, compared to the classical catalyst with FeVO₄ nanoparticles supported TiO₂. For the catalyst containing FeVO₄ nanorods, enhanced redox ability and enriched surface active oxygen species originated from its unique crystal structure and predominantly exposed reactive crystal facets (− 2 1 0) on the catalyst surface are responsible for its improved low temperature catalytic activity.     

Reactions of turpentine using Zr-MCM-41 family mesoporous molecular sieves

The mesoporous molecular sieve Zr-MCM-41 was synthesized under hydrothermal conditions. Zr-MCM-41 material was impregnated using sulfuric acid to prepare SO ₄^2-/Zr-MCM-41. The obtained materials were characterized by XRD, FT-1R, N₂ adsorption/desorption and NH₃-TPD analysis technique. The results indicated that SO ₄^2-/Zr-MCM-41 was of better mesoporous structure, long range ordering and crystallites, and that SO ₄^2-existed in the skeleton of Zr-MCM-41 and enhanced its acidity. SO₄^2-/Zr-MCM-41 were firstly used as catalyst in the esterification of terpineol. The catalytic results were compared with those obtained by using sulfuric acid (33%), HY, HZSM-5 and SO₄^2-/ZrO₂ as catalysts. It was showed that SO₄^2-/Zr-MCM-41 were not only of better catalytic activity and selectivity, but also of better regenerable performance. The effects of synthesis methods of catalysts and Si/Zr mole ratio on catalytic properties were also studied. In addition, AlCl₃ was supported on the synthesized mesoporous molecular sieves to get composite catalysts that were firstly used to catalyze the polymerization of -pinene. It was showed that the catalytic result of the composite catalyst was better than that AlCl₃ alone.*To whom correspondence should be addressed. E-mail: yushitao@elong.com     

Study of induction period over K2CO3/MoS2 catalyst for higher alcohols synthesis

The K₂CO₃/MoS₂ catalyst for higher alcohols synthesis with synthesis gas as feedstock was prepared. The catalyst was characterized by TPR, in-situ XPS, XRD and SEM. Effects of pretreatment with H₂, CO or synthesis gas on activity and selectivity of the catalyst were investigated. Results showed that there was a remarkable induction period about 180 h at the initial reaction stage for the un-treated catalyst. The catalytic performances for alcohols synthesis changed notably during the induction period. The induction period was confirmed to be resulted primarily from the sulfur losing and K element dispersion on the surface of ADM catalysts. Pretreatment of the catalyst could remarkably shorten the time of induction period as well as promote the catalytic activity. Furthermore, the higher alcohols (C₂ + OH) content in the liquid products were enhanced after the catalyst pretreated by CO or synthesis gas which could be ascribed to the increasing of Mo⁴⁺ content on the surface of the catalyst.     

Effect of Cu doping on the SCR activity of CeO2 catalyst prepared by citric acid method

CeO₂–CuO catalyst prepared by citric acid method was investigated for selective catalytic reduction of NO with NH₃. The activity of the CeO₂ catalyst was enhanced about 8–27% in the temperature range of 125–225 °C at a space velocity of 28,000 h⁻¹ by the addition of Cu. It was found that the state of Cu species had great impact on the SCR performance of CeO₂–CuO catalyst. Cu²⁺ can enhance the low temperature activity of SCR reaction, while CuO would promote NH₃ oxidation before SCR reaction at high temperature, which would cause the decrease of its high temperature SCR activity.     

Ni/Al2O3催化剂对高纯HCl中微量CO2甲烷化反应的催化性能

用浸渍法制备了以Al₂O₃为载体、Ni为活性组分的Ni/Al₂O₃二氧化碳甲烷化催化剂,在等温固定床反应器中研究了在Ni/Al₂O₃催化剂作用下,高纯氯化氢中微量CO₂甲烷化反应效果,并考察了温度、压力、氯化氢体积空速以及H₂/CO₂摩尔比对CO₂转化率的影响,同时研究了催化剂活性、稳定性及其再生性能。结果表明,在温度为250℃、压力为4.0 MPa、氯化氢空速为100 h^-1、H₂/CO₂摩尔比为500:1条件下,CO₂甲烷化反应效果最好,其转化率可达到90%左右,对于高纯氯化氢中微量CO₂的脱除起到很好的效果;催化剂在温度高于300℃时,反应不久后会迅速失活;催化剂再生性能只能部分恢复到新鲜水平。     

Synthesis, characterization, and catalytic phenol hydroxylation of a novel complex oxide HxV2Zr2O9.H2O

A novel type of complex oxide H_xV₂Zr₂O_9.H _2O with V⁴⁺ and V⁵⁺ mixed valence has been hydrothermally synthesized in a V₂O₅-ZrO₂-H₂O system at 240°C for 5 days in presence of NaF. The catalytic data over these complex oxides show that these complex oxides are catalytically very active in phenol hydroxylation by 30% aqueous hydrogen peroxide, and their catalytic activity is dependent on crystal size of the catalysts. The phenol conversion over the catalyst with crystal size of 7 μm is twice that over the catalyst with crystal size of 35 μm. The V⁵⁺ species are suggested to be the catalytic active sites. Some other factors which influence the catalytic activity were also investigated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Selective ammoximation of ketones and aldehydes catalyzed by a trivanadium-substituted polyoxometalate with H2O2 and ammonia

The ammoximation of different ketones and aldehydes to their corresponding oximes catalyzed by K₆[PW₉V₃O₄₀]·4H₂O was carried out with hydrogen peroxide and ammonia in isopropanol at room temperature. High yields of oximes were obtained in this catalytic system. This catalytic system was proved to be heterogeneous by the ammoximation activity of removal of catalyst and the elemental analysis of the filtrate after reaction. A possible procedure for the ammoximation catalyzed by K₆[PW₉V₃O₄₀]·4H₂O with H₂O₂ and NH₃·H₂O was proposed. The fresh and used catalysts were characterized by IR and ³¹P MAS NMR, which revealed the good stability of the catalyst.     

PWA/montmorillonite K10 catalyst for synthesis of coumarins under solvent-free conditions

12-Tungstophosphoric acid supported on montmorillonite K10 (PWA/mont-K10) catalysed Pechmann condensation reaction was reported. The catalyst was characterized by XRD, FTIR, UV–Vis DRS, surface area and pore size analysis, TGA and acidity by DRIFTS using pyridine. The morphology of the catalyst was studied by SEM. The activity of mont-K10, mont-KSF, \textSO ₄ ^{2 -} \mathord

La3+-SO2-4/TiO2催化合成衣康酸二丁酯

研究了固体超强酸La³⁺-SO^2-₄/TiO₂催化衣康酸与正丁醇合成衣康酸二丁酯的酯化反应,考察了催化剂种类,确定以La³⁺-SO^2-₄/TiO₂为催化剂,催化剂La³⁺-SO^2-₄/TiO₂的最佳焙烧温度为450 ℃。并考察反应物配比、催化剂用量和反应时间等因素对酯化反应的影响,确定最佳工艺条件：n（衣康酸）∶n（正丁醇）＝1∶3,催化剂用量为反应物总质量的4.5%,反应时间3.0 h。在该条件下,衣康酸转化率达95.7%,产物衣康酸二丁酯收率为93.3%。并对La³⁺-SO^2-₄/TiO₂的重复使用性能进行考察,结果表明,与La³⁺-SO^2-₄/TiO₂相比,La³⁺-SO^2-₄/TiO₂重复使用5次后,仍具有较高的催化活性,衣康酸转化率为92.3%,衣康酸二丁酯收率90.8%,说明稀土元素La的添加对于增加固体超强酸的寿命起了主要作用。     

Novel Pd–Au/TiO2 catalyst for the selective catalytic reduction of NOx by H2

Novel Pd–Au/TiO₂ catalyst exhibited high catalytic activity with a wide temperature window for the selective catalytic reduction of NO_x by H₂ in the presence of oxygen. The synergetic effect between Pd and Au contributes to the formation of Pd⁰ and Pd–Au alloy, thus promoting the NO_x reduction to proceed.     

Influence of the calcination temperature on the Au/FeOx/Al2O3 catalyst

The effect of calcination temperature on the electronic structure of gold catalyst was investigated in this paper. CO oxidation was employed as a test reaction to correlate the phase changes to the catalytic activity. The TPR, XPS and XRD characterization showed that the highly active Au/FeO_x/Al₂O₃ catalyst contained both gold atoms and ions. The catalytic performance of gold catalyst may depend on the Au⁰/Au³⁺ ratio. The best activity in the present work was obtained when the Au⁰/Au³⁺ ratio was about 0.89. Copyright © 2006 Society of Chemical Industry     

Ambient temperature oxidation of carbon monoxide using a Cu2Ag2O3 catalyst

The mixed copper–silver oxide, Cu₂Ag₂O₃, has been prepared by co-precipitation and tested for ambient temperature carbon monoxide oxidation. The catalyst demonstrated appreciable low temperature oxidation activity and the catalyst aged for 4 h was the most active. Carbon monoxide conversion increased with time-on-stream, reaching steady state after ca. 1000 min. Acomparison of the catalytic activity has been made with a representative sample of a high activity hopcalite, mixed copper/manganese oxide catalyst. On the basis of CO oxidation rate data corrected for the effect of catalyst surface area the Cu₂Ag₂O₃, aged for 4 h was at least as active as the hopcalite.