The role of zinc oxide in Cu/ZnO catalysts for methanol synthesis and the water–gas shift reaction

All commercial catalysts for methanol synthesis and for the water–gas shift reaction in the low temperature region contain zinc oxide in addition to the main active component, copper. The varied benefits of zinc oxide are analysed here. The formation of zincian malachite and other copper/zinc hydroxy carbonates is essential in the production of small, stable copper crystallites in the final catalyst. Further, the regular distribution of copper crystallites on the zinc oxide phase ensures long catalyst life. Zinc oxide also increases catalyst life in the water–gas shift process by absorbing sulphur poisons but it is not effective against chloride poisons. In methanol synthesis, zinc oxide (as a base) removes acidic sites on the alumina phase which would otherwise convert methanol to dimethyl ether. Although bulk reduction of zinc oxide to metallic zinc does not take place, reduction to copper–zinc alloy (brass) can occur, sometimes as a surface phase only. A new interpretation of conflicting measurements of adsorbed oxygen on the copper surfaces of methanol synthesis catalysts is based on the formation of Cu–O–Zn sites, in addition to oxygen adsorbed on copper alone. The possible role of zinc oxide as well as copper in the mechanisms of methanol synthesis is still the subject of controversy. It is proposed that, only under conditions of deficiency of adsorbed hydrogen on the copper phase, hydrogen dissociation on zinc oxide, followed by hydrogen spillover to copper, is significant. This revised version was published online in June 2006 with corrections to the Cover Date.     

The effect of SiO_2 particle size on iron based F–T synthesis catalysts

The effect of particle size of silica, as catalyst binder, on the chemical and mechanical properties of iron based FT catalyst was studied in this work. The samples were characterized using XRD, BET, TEM, FT-IR, and H2-TPR, respectively. The attrition resistance and the FT activity were tested. Si-8–Si-15 catalysts prepared with 8–15 nm silica sol show good attrition resistance(attrition loss b 4%), especially Si-13 with an attrition loss of 1.89%. Hematite appeared in XRD patterns when silica sol above 15 nm is used. TEM micrographs show that no obvious Si O_2 particles appear when silica sol particle with size less than 8 nm was used, but Si O_2 particles coated with small ferrihydrite particles appear when silica sol above 8 nm was used. Si–O–Si vibration peak in FT-IR spectra increases with increasing silica sol size. Samples prepared with silica sol show good stability of FT reactions, and the average molecular weight of FT products increases with the increase of Si O_2 particle.     

Pd/polyaniline as the catalysts for 2‐ethylanthraquinone hydrogenation. The effect of palladium dispersion

By doping of polyaniline (PANI) in PdCl₂ aqueous and ethanol solutions the catalysts containing crystalline and colloidal Pd particles of different sizes were prepared. The size of palladium particles present in Pd/PANI catalysts (characterised by SEM and XRD methods) influenced the course of 2‐ethylanthraquinone (eAQ) hydrogenation, a key step in the industrial production of H₂O₂. The presence of large palladium particles promotes reactions leading to the formation of the so‐termed “degradation products” not capable of hydrogen peroxide formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

The function of zeolite on Pt autoreduction and dispersion in Pt/L and Pt/β catalysts

TPR, CO-FTIR and¹²⁹Xe NMR spectroscopic techniques were used to measure the distribution of platinum species after the calcination of Pt/L and Pt/ zeolites. Autoreduction which occurred in Pt/ zeolite was avoided in the channel of L zeolite. Pt particles dispersed well and exhibited excellent reactivity for the aromatization ofn-hexane in L zeolite.     

Correlation of activity and stability of CuO/ZnO/Al2O3 methanol steam reforming catalysts with Cu/Zn composition obtained by SEM–EDAX analysis

A series of CuO/ZnO/Al₂O₃ catalysts were prepared and characterized by TPR, surface area, metal area, XRD and SEM–EDAX analysis. These systems were evaluated in the development of a methanol steam reforming catalyst (MSR). A correlation of activity and stability of MSR catalysts with the Cu/Zn ratio derived by SEM–EDAX analysis is observed. The stable activity of these catalysts is also supported by the method of preparation, low temperature reducibility and the presence of reversibly oxidizable Cu species observed by TPR of fresh and used catalysts.     

The effect of copper valence on catalytic combustion of styrene over the copper based catalysts in the absence and presence of water vapor☆

Catalysts Cu Ox/γ-Al_2O_3-IH and Cu Ox/γ-Al_2O_3-IM were prepared, characterized, and tested for styrene combustion in the absence and presence of water vapor. The effect of copper valence of the catalysts on the catalytic activity for styrene combustion was discussed using the theory of hard soft acids and bases(HSAB).The results showed that the existence of water vapor in feed stream inhibited the catalytic activity for styrene combustion due to the competition adsorption of water molecule. HSAB theory confirmed that the local soft acidity of the catalyst Cu Ox/γ-Al_2O_3-IH was much stronger than that of the catalyst Cu Ox/γ-Al_2O_3-IM because of the higher content of soft acid Cu+on its surface, which increased the adsorption ability toward soft base of styrene and reduced the adsorption toward hard base of water vapor, and thus increased the catalytic activity for styrene combustion and weakened the negative influence of water vapor.     

The synthesis of new chiral salen complexes immobilized on MCM‐41 by grafting and their catalytic activity in the asymmetric borohydride reduction of ketones

The new chiral salen complexes were synthesized and supported on mesoporous MCM‐41 through the condensation of 3‐aminopropyltrimethoxysilane and 2,6‐diformyl‐4‐tert‐butylphenol by the multi‐grafting method. The immobilized optically active Co(II) salen complexes showed a very high enantioselectivity in the asymmetric borohydride reduction of aromatic ketones. The chiral salen Co(II) complexes immobilized over MCM‐41 were stable during the reaction and exhibited a relatively high enantioselectivity for the reduction of ketones as compared with the homogeneous salen catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of heat treatment conditions on the textural and catalytic properties of nickel–titania composite aerogel catalysts

Highly dispersed nickel–titania composite aerogel catalysts have been prepared by CO₂ supercritical drying of alcogels obtained by the sol–gel process. The effect of heat treatment conditions on the textural and structural properties of the resulting aerogels was investigated by nitrogen adsorption–desorption, TG/DTA, XRD and TEM. The nickel–titania composite aerogel calcined and reduced under carefully controlled conditions exhibited an excellent catalytic performance for the liquid-phase hydrogenation of benzophenone to benzhydrol.     

The effect of CuO–ZnO–Al2O3 catalyst structure on the ethanol synthesis from syngas

CuO–ZnO–Al₂O₃ catalysts were prepared by complete liquid phase technology with different addition sequences. The results indicated that the catalyst prepared by the addition of (C₃H₇O)₃Al to Cu(NO₃)₂ and Zn(NO₃)₂ solutions shows excellent ethanol selectivity at the initial stages of reaction, reaching approximately 40%. X-ray photoelectron spectroscopy results showed that ethanol synthesis requires a higher Cu⁺ content and higher Cu/Zn ratio on the catalyst surface. The temperature-programmed reduction test revealed strong interactions between Cu species and zinc or aluminum oxide. The increase in the difficulty of catalyst reduction indicated higher ethanol selectivity.     

The effect of ultrasound in combination with thermal treatment on the germinated barley’s alpha-amylase activity

The effects of ultrasound as emerging technology along with thermal treatment were investigated on the activity of barley’s alpha-amylase after germination. All experiments were carried out at 20 kHz on an ultrasonic generator by considering the three effective factors, temperature (30, 50 and 70°C) and ultrasonic intensities (20, 60 and 100% setting from total power of device (460 W)) in different time intervals (5, 10 and 15 min). For determining the effects of these parameters, the enzymatic activity was assayed by measuring the reducing sugars released as a result of the alpha-amylase action on soluble starch using 3,5-dinitrosalicylate regent (DNS). The results of these assays were analyzed by Qualitek4 software by using the Taguchi statistical method to evaluate the factor’s effects on the enzyme activity. Consequently, the results of assays showed that the activity of this enzyme from germinated barley was reduced after thermosonication by comparing to the blank.     

The effect of scale and interfacial tension on liquid–liquid dispersion in in-line Silverson rotor–stator mixers

The effect of scale, processing conditions, interfacial tension and viscosity of the dispersed phase on power draw and drop size distributions in three in-line Silverson rotor–stator mixers was investigated with the aim to determine the most appropriate scaling up parameter. The largest mixer was a factory scale device, whilst the smallest was a laboratory scale mixer. All the mixers were geometrically similar and were fitted with double rotors and standard double emulsor stators. 1 wt.% silicone oils with viscosities of 9.4 mPa s and 339 mPa s in aqueous solutions of surfactant or ethanol were emulsified in single and multiple pass modes. The effect of rotor speed, flow rate, dispersed phase viscosity, interfacial tension and scale on drop size distributions was investigated.     

The influence of thermal pretreatment of Re/γ-alumina catalysts in hydrogen on their activity for hydrogenation and hydrogenolysis of benzene

The specific activity of Re/-alumina catalysts (10.4 and 1.04 wt% Re) preheated in hydrogen at 550–800°C for benzene hydrogenation and hydrogenolysis at 80–300°C has been found to not change or to increase with increasing pretreatment temperature, respectively. The results are discussed in relation to the metal dispersion.     

The effects of promoters on catalytic properties and deactivation–regeneration of the catalyst in the synthesis of dimethyl carbonate

The effects of different alkali metal promoters in PdCl₂-CuCl₂/activated carbon (a.c.) catalyst on the reaction performance for synthesizing dimethyl carbonate (DMC) by gas-phase oxidative carbonylation of methanol were studied. The bulk and surface properties of catalyst PdCl₂-CuCl₂-CH₃COOK/a.c. were characterized by XRD, XPS, and AAS techniques. On the basis of catalyst characterization and activity evaluation, the functions of promoters were further investigated, and the deactivation–regeneration of catalyst PdCl₂-CuCl₂-CH₃COOK/a.c. was also discussed. The results show that the space time yield (STY) of DMC on catalysts with different alkali metal promoters ranks in the following order: K>Na>Li. The main reason for catalyst deactivation is the loss of chlorine. Fortunately, during the preparation of the catalyst, the interaction between CH₃COOK and PdCl₂ or CuCl₂ that results in the formation of KCl limits the loss of chlorine. An obvious increase of the catalyst lifetime and catalytic activity is observed by treating fresh catalyst with a methanol solution of methyl chloroacetate. If deactivated catalyst is treated with a methanol solution of methyl chloroacetate in N₂ stream at 200 °C for 4 h and then treated in N₂ stream at 200 °C for 2 h, the catalytic activity can be restored effectively and the regeneration induction period can be shortened. The catalytic activity after two times of regeneration can still be restored to 93% of the fresh catalyst. The run time of this catalyst is up to 300 h.