Candida and Pseudomonas Lipase-Catalyzed Hydrolysis of Butteroil in the Absence of Organic Solvents

Candida rugosa lipase (CRL) and Pseudomonas fluorescein lipase (PFL) were used to hydrolyze a low-melting point butteroil fraction in the absence of orgaic solvents. CRL and PFL displayed pH activity optima of 6.7 and 7.8, and temperature-activity optima of 40–50°C and 35°C, respectively. Maximum activity for PFL was observed at 5% (v/v) water content. CRL showed higher specificity towards butyric acid relative to PFL after 3 hours of hydrolysis at 40°C (22.3 mol% vs 7.8 mol%, respectively). Both enzymes displayed, however, high specificities towards palmitic and oleic acids. CRL's inherent specificity towards butyric acid makes it an ideal choice for a biological catalyst to generate useful dairy flavor profiles.     

Electrocatalytic hydrogenation of cyclohexanone: Simple dynamic cell design

The electrocatalytic hydrogenation of cyclohexanone has been investigated with catalytic powder particles made of metal nanoaggregates deposited on a nonconductive material such as activated carbon and alumina. The catalytic powder particles were suspended in the solution under vigorous stirring conditions. The brief contact of the powder particles with a porous carbon cathode was sufficient to form adsorbed hydrogen on the metallic nanoaggregates through water electrolysis and initiate the electrohydrogenation process. It is demonstrated that the key parameters of the electrohydrogenation process are both the nature of the metallic nanoaggregates and the nature of the non-conductive material. The hydrodynamics of the solution under vigorous stirring conditions have also been studied for the particular cell used in the present study.     

Enzymatic degradation of esters of dichloropropanols: removal of chlorinated glycerides from processed foods

The esters of dichloropropanols from the byproduct of hydrolysates during food processing were degraded by the cell-free extracts of a dichloropropanol-assimilating bacterium of Pseudomonas sp. OS-K-29. 1-Acyloxy-2,3-dichloropropane was hydrolysed into the corresponding carbonic acid and 2,3-dichloropropanol, and then the dichloropropanol was dechlorinated. The esterase activity of the cell-free extracts was effective for the esters of the dichloropropanols and monoacylglycerides, but not for hydrolysing the lipase substrates such as triacylglycerides and Tween 60. A comparative study using a series of octanoyl glycerides and the esters of the dichlopropanols showed that the substrate specificities of the cell-free extracts were similar to the monoacylglyceride lipase from Penicillium camembertii.     

Cis–trans isomerization of olefinic alcohols promoted by Rh(I) complexes

Homogeneous hydrogenation and isomerization reaction of cis-2-butene-1,4-diol has been investigated in ethanol by using tris(triphenylphosphine)chlororhodium(I), RhCl(PPh₃)₃, and triethylamine at 303 K and 0.01–0.1 MPa partial hydrogen pressure. Under reduced H₂ pressure, the geometric isomerization reaction occurs, to a high extent, leading to trans-2-butene-1,4-diol up to 93% selectivity at 90% conversion of the cis analogous. Effects of H₂ partial pressure as well as triethylamine, added phosphine and olefin concentrations on the rate of reaction and on the products distribution were also investigated. The results obtained can be interpreted on the basis of a proposed mechanism in which RhH(PPh₃)₃ is the active species. The high selectivity towards cis-trans isomerization of cis-2-butene-1,4-diol is attributed to steric factors of the Rh(I) coordinated triphenylphosphine groups.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

超临界流体中的酶催化

与其他非水相酶催化介质相比 ,超临界流体有其独特的优越性。阐述了超临界流体的概念、对超临界流体的选择原则以及在超临界流体中酶催化的各种影响因素 ,还讨论了在此类流体中酶催化的应用和发展前景     

Study on Preparation and Application of Ti／Si Complex Zeolite

A Ti/Si complex zeolite has been prepared. X-ray diffraction and infrared spectrometry study has shown that two structures, namely the ZSM-5 and MCM-41, exist in the sample. BET tests have revealed that the complex zeolite contains regular mesopores of 2.6 nm. Ultraviolet spectrometry analysis has shown that the Ti species exist in the zeolite skeleton in the form of tetra-coordinate valence. The Ti/Si complex zeolite (TS-1/Ti-MCM-41) has apparently improved catalytic activity with respect to the macromolecular organic compound oxidation as compared to individual components of either Ti or Si containing zeolites (TS-1 and Ti-MCM-41).     

Performance of the polymer- and oxide-supported triphase catalysts and effect of ultrasound on their stabilities

In this study, several trialkylamines were immobilized on chloromethylated polystyrene (CMPS), silica gel, and alumina to prepare triphase catalysts for catalyzing the etherification reaction of allyl bromide (the organic reactant) and sodium phenolate (the aqueous reactant). The reactor was agitated mechanically or with the aid of ultrasonic vibration. Performances of the prepared catalysts were compared, and the effect of imposing ultrasound was investigated based on the activity, selectivity, and stability of the catalyst. Experimental results show that tri-n-propylamine is the best active species when CMPS is used as the support, while tri-n-butylamine is the best when SiO₂ and Al₂O₃ are employed as the supports. The CMPS-supported catalyst is far better than the SiO₂- and Al₂O₃-supported catalysts in activity and selectivity but not in stability. Imposing the ultrasound can effectively increase the reaction rate. Mechanical agitation at a low speed with the imposition of ultrasonic vibration not only results in a conversion slightly higher than the case with a high mechanical agitation speed without ultrasonic vibration, but also gives a constant stability for the CMPS-supported catalyst.     

固体超强酸S_2O_8~(2-)/SnO_2-SiO_2催化合成环己酮1,2-丙二醇缩酮

采用沉淀-浸渍法制备了固体超强酸S2O28-/SnO2-SiO2,以它为催化剂催化环己酮和1,2-丙二醇合成了环己酮1,2-丙二醇缩酮;考察了带水剂种类及用量、酮醇摩尔比、催化剂用量、反应时间对产品收率的影响,并用正交实验对反应条件进行了优化。实验结果表明,适宜的反应条件为:n(环己酮)∶n(1,2-丙二醇)=1∶1.6、催化剂用量为反应物料总质量的2.0%、带水剂环己烷用量5.0mL、反应时间50min。在此条件下,环己酮1,2-丙二醇缩酮收率达到91.47%;催化剂的稳定性良好,在重复使用5次后环己酮1,2-丙二醇缩酮收率为82.20%,活性下降的主要原因为催化剂表面积碳和吸附了有机物;经傅里叶变换红外光谱和气相色谱质谱分析表明,产物为环己酮1,2-丙二醇缩酮,纯度为100%。     

双功能加氢精制催化剂在焦化富气制氢中的应用

介绍了JT-1G／JT-4加氢精制催化剂的烯烃饱和功能和有机硫转化功能；阐述了该催化剂在中石油辽河石化分公司、浙江工程设计院共同开发的用于焦化富气制氢原料的烯烃饱和及有机硫转化的新加氢工艺——逆流-等温-绝热加氢精制工艺中的使用情况。原料中体积分数13％～16％的烯烃经过加氢精制后降至0；原料中有机硫得到充分转化；焦化富气经过加氢精制后，满足了作为制氢原料的要求，降低了制氢成本。