Multifactorial analysis in the study of hydroformylation of oct-1-ene using supported aqueous phase catalysis

The influence of the hydration and the surface characteristics of five supports in the hydroformylation of oct-1-ene by supported aqueous phase catalysis (SAPC) using [Rh₂(μ-S^tBu)₂(CO)₂(TPPTS)₂] as catalyst was studied. The results confirm that the size of the pores and the amounts of water were found to be the determining factors contributing to the SAPC. According to the size of pores there is a critical value for which the SAPC takes place either in the classical model or in conditions where the pores are filled. When the pores are fully filled the SAPC can operate efficiently onto the external surface, stabilising the conversion in a relatively wide range of support hydration.     

Wacker oxidation catalysis in a supported aqueous phase

Adsorption of palladium (II) and copper (II) salts onto the controlled pore glass CPG-240, in the presence of water, yields a supported aqueous phase Wacker oxidation catalyst. Conversions of 1-heptene to 2-heptanone of up to 24% under batch conditions are observed. The activity and selectivity of the catalysts are sensitive to water content, oxygen pressure and temperature.     

Allylic substitution catalysed by silica-supported aqueous phase palladium(0) catalysts

The supported aqueous phase methodology was applied to the catalytic system Pd(OAc)₂/5TPPTS, a catalyst precursor of the Trost–Tsuji reaction. The characterization of the solid by ³¹P MAS NMR spectroscopy confirms the reduction by the phosphines of Pd(II) to Pd(0) as Pd(TPPTS)₃. The catalytic properties of this solid were determined for the allylic substitution of (E)-cinnamyl ethyl carbonate by nucleophiles such as ethyl acetoacetate, dimethyl malonate, morpholine, phenol and 2-mercaptopyridine and were compared to those of the same catalytic system in a biphasic water/nitrile medium. Having demonstrated the absence of palladium leaching and having solved the problem of water leaching from the solid into the organic solvent, the SAP Pd catalyst was engaged with success in a continuous flow experiment, demonstrating the possibility to reach a productivity superior to 2200 moles of carbonate selectively converted per mole of palladium within 11 h. This revised version was published online in June 2006 with corrections to the Cover Date.     

Substrate-selective catalysis in an aqueous biphasic system with per(2,6-di-O-methyl)-β-cyclodextrin

The biphasic palladium-catalysed cleavage of water-insoluble allylic substrates in the presence of methylated cyclodextrins has been investigated with the aim of performing substrate-selective catalytic reactions. While no substrate selectivity was observed in control experiments in which acetonitrile was used as mass transfer promoter, the use of DMCyD led in some cases to high substrate selectivities. For instance, a 97:3 product ratio was observed during the cleavage of a 50:50 mixture of N-dodecyl-O-allyl urethane and N,N-dihexyl-O-allyl urethane. The whole results demonstrate that the size-fit concept which postulates the highest reactivity for the best size-matched host–guest pair is limited to predict the substrate selectivity.     

Deep oxidation of aqueous organics over a silicon carbide-activated carbon supported platinum–ruthenium bimetallic catalyst

In previous work, we developed a highly active bimetallic platinum–ruthenium catalyst supported on a very high surface area activated carbon substrate. In fixed bed reactors, this catalyst proved capable of the continuous long-term deep oxidation of a variety of aqueous organic contaminants associated with spacecraft wastewater streams at 121 °C. This work was extended to the mineralization of more typical environmental contaminants, including halocarbons and aromatics. The primary weakness of this catalyst was the tendency toward relatively high rates of chemical decomposition. To overcome this limitation, methods were developed for the production of a silicon carbide coating over the surface of the activated carbon, yielding a reasonable trade-off between increasing resilience and decreasing surface area. Here we report the catalytic decomposition of dissolved organic contaminants at 130 °C using this silicon carbide/activated carbon supported bimetallic catalyst.     

Recycling of methylaluminoxane (MAO) cocatalyst in ethylene polymerization with supported metallocene catalyst

The economy of the metallocene catalyst system in olefin polymerization depends more on the cost of methylaluminoxane (MAO) cocatalyst rather than on the catalyst cost since high ratio of cocatalyst to catalyst is required to have sufficient activity. The conditions to minimize the consumption of MAO have been studied for the ethylene polymerization with supported metallocene catalyst. By introducing the prepolymerization step, in which the supported metallocene catalyst is activated at high MAO concentration before polymerization, the MAO could be recovered after the prepolymerization and recycled repeatedly for the subsequent activation with marginal decrease in activity. No extra MAO was needed during the main polymerization. The addition of small amount of MAO or less expensive alkylaluminum at each recycle step kept the catalyst activity to the initial level. It compensates the MAO losses occurring both by the incomplete decantation of MAO solution and by the reaction with metallocene complex or impurities. As a result, the actual consumption ratio of Al/Zr in moles in commercial applications could be reduced to about 30 without sacrificing the activity. This value is significantly low considering that conventionally an Al/Zr ratio of 1,000 is required for sufficient activity. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Multiple steady-states for the oxidation of aqueous ethanol with oxygen on a carbon supported platinum catalyst

The selective oxidation of aqueous ethanol by dioxygen over a platinum on carbon catalyst was investigated in a three-phase continuously stirred tank reactor at a total pressure of 600 kPa, a temperature of 323 K, a pH of 8.4, and a catalyst concentration of 2.3 kg m^–3. Multiple steady-states were obtained by systematic changes in the start-up procedure and variation of the feed concentration of ethanol and partial oxygen pressure in the reactor. The ethanol feed concentration was varied from 100 to 2500 mol m^–3 and the partial oxygen pressure from 8 to 120 kPa. On the time scale of the experiments, i.e. 21 ks, two steady-states of the net disappearance rate of ethanol are observed in the ethanol feed concentration range from 500 to 2500 mol m^–3 at a partial oxygen pressure of 58 kPa and in the range of partial pressure of oxygen from 8 to 120 kPa at an ethanol feed concentration of 500 mol m^–3. Three steady-states are observed in the feed ethanol concentration range from 200 to 400 mol m^–3 and a partial oxygen pressure of 58 kPa.     

Iodination of plasticized poly(vinyl chloride) in aqueous media via phase transfer catalysis

Nucleophilic substitution of chlorine on plasticized poly(vinyl chloride) (PVC) was carried out using potassium iodide (KI) in the presence of a phase transfer catalyst (PTC) in aqueous media. Iodination was confirmed using energy dispersive X‐ray analysis (EDAX). The extent of iodination was studied with respect to time, temperature, concentration of the reactants, as well as different PTCs. Among the different PTCs examined, tetrabutylammonium bromide (TBAB) and tetrabutylammonium hydrogen sulfate (TBAH) were found to be highly efficient for the reaction. About 25% increase in weight was observed for PVC sheets iodinated under optimal reaction conditions. The thermal stability of the modified PVC was found to be impaired upon iodination. The iodinated PVC released iodide ions when kept in distilled water, as evidenced by UV spectroscopy. Sustained release of iodide ion in distilled water was followed up for about 30 days. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 493–499, 2002; DOI 10.1002/app.10176     

Separation of catalase from Amsonia orientalis with single step by aqueous two-phase partitioning system (ATPS)

Catalase from Amsonia orientalis was purified by ATPS, and its efficiency was compared against hydrophobic interaction chromatography. Activity recovery and purification fold of purified catalase by ATPS were examined under varying experimental conditions. The effects of various factors such as type of phase-forming salts, (PEG) mass, with their different concentrations, pH and temperature effects on partitioning were investigated. The highest activity recovery (156%) and purification fold (8.67) of catalase were obtained in the ATPS system containing 10% (g/g) PEG4000, 15% (g/g) Na₂SO₄ at pH 6.0 and room temperature. In hydrophobic interaction chromatography, the enzyme has been purified 12.54-fold with 57.5% recovery. The molecular weight of catalase was determined as 75 kDa by SDS-PAGE.     

Study of phase behavior and Congo red dye partitioning in aqueous two-phase systems composed of hydrophilic alcohols (1-propanol/ 1-butanol) and sodium salts

ABSTRACT

The partitioning of the Congo red dye in ATPSs formed by alcohols (1-butanol, 1-propanol)/sodium salts was considered. Binodal and the LLE data were experimentally determined at 298.15 K. The salting-out abilities of the salts follow the order Na₃C₆H₅O₇ > NaH₂PO₄ > C₂H₃ O₂Na. The phase-forming abilities of the alcohols follow the order: 1-butanol > 1-propanol. The four-parameter equation was applied to correlate the binodal curves data. Therefore, The Bancroft and Othmer-Tobias equations were used to prove the reliability of the corresponding LLE data. ATPS composed of 6.5% of 1-butanol and 20% of Na₃C₆H₅O₇ had the highest values of extraction by the yield of 98.54%.     

Enzyme mass transfer coefficient in aqueous two phase system using a packed extraction column

Fractional dispersed phase hold-up and dispersed side mass transfer coefficients for amyloglucosidase were measured in a 56 mm i.d. packed extraction column using a sodium sulphate-polyethylene glycol 4000 system. Raschig rings (3 to 13.3 mm), Berl saddles (12 mm), Pall rings (12.6 mm), glass spheres (5.2 mm) and structured wire gauze were used as packings. The effect of packing size was investigated in the case of ceramic Raschig rings. The effect of phase composition of the aqueous phase system also was studied. Correlations have been developed for fractional dispersed phase hold-up and volumetric mass transfer coefficient with packing voidage, dry surface area of packings, superficial dispersed phase velocity and the liquid phase physical properties.     

Mercapto-Functionalized MCM-41 Anchored Palladium(0) Complex as an Efficient Catalyst for the Heterogeneous Suzuki Reaction

Mercapto-functionalized MCM-41 anchored palladium(0) complex is an efficient catalyst for the heterogeneous Suzuki reaction of arylboronic acids with aryl halides. Our system not only solves the basic problems of catalyst separation and recovery but also avoids the use of phosphine ligands.     

Extraction of Cu(II) ions from aqueous media using PEG/Sulphate salt aqueous two-phase system

A simple ATPS of polyethylene glycol/sulphate salt was proposed for the extraction of Cu(II) ions from aqueous media. Maximum extraction efficiency of Cu ions was obtained in the aqueous PEG2000/ sodium sulphate two-phase system. In the following, design of experimental methodology using Taguchi orthogonal array was applied to evaluate the effects of four independent variables on the partitioning behavior of Cu ions from aqueous media. The results indicated that the temperature and pH of the system were the major contributory factors for Cu ions partitioning. The maximum extraction efficiency of Cu ions was determined to be 77.89% under the optimal conditions.     

小分子双水相浮选高效液相色谱法测定污水中痕量氯霉素

用乙醇/磷酸氢二钾双水相体系浮选污水中的氯霉素,通过对盐的质量分数、有机溶剂的体积、气体流速和浮选时间的选择和优化,在理想条件下,氯霉素的平均浮选效率可以达到94%。该方法用于河水和鱼塘水样品中氯霉素的检测,检出限为0.5 ng/mL,加标回收率为89.44%～100.16%,相对标准偏差RSD为1.1%～2.1%,适用于污水中痕量氯霉素的分离/富集及分析测定。     

小分子醇/盐二元双水相体系中盐酸土霉素的分配行为

在双水相体系研究的基础上,建立了乙醇与正丙醇和磷酸二氢钠形成的二元双水相体系萃取盐酸土霉素的新方法,考察了小分子醇的用量、盐种类和浓度、pH值、温度以及静置时间对盐酸土霉素分配行为的影响。结果表明,小分子醇/盐二元双水相体系可用于抗生素分配行为的研究,其中体系组成为乙醇和正丙醇,磷酸二氢钠浓度在48%,pH值在4～5,温度25℃,以及静置12 h左右,盐酸土霉素在该二元双水相体系中的分配系数达到21.95,萃取率达86.09%。     

Processing of soybean (Glycine max) extracts in aqueous two‐phase systems as a first step for the potential recovery of recombinant proteins

BACKGROUND: The potential use of plants as production systems to establish bioprocesses has been established over the past decade. However, the lack of efficient initial concentration and separation procedures affect the generic acceptance of plants as economically viable systems. In this context the use of aqueous two‐phase systems (ATPS) can provide strategies to facilitate the adoption of plants as a base for bioprocesses. Among the crops, soybeans (Glycine max) represent an attractive alternative since potentially they can produce high levels of recombinant protein. In this paper the processing of fractionated soybean extracts using ATPS is evaluated as a first step to recover recombinant proteins expressed in plants, using β‐glucuronidase (GUS; E.C. 3.2.1.31) as a model protein. RESULTS: The evaluation of the effect of system parameters provided the conditions under which the contaminant proteins from fractionated soybean extracts and GUS concentrated in opposite phases. A PEG 600/phosphate system comprising 14.5% (w/w) polyethylene‐glycol (PEG), 17.5% (w/w) phosphate, a volume ratio (Vr) equal to 1.0, and a system pH of 7.0 resulted in the potential 83% recovery of GUS from the complex mixture and an increase in purity of 4.5‐fold after ATPS. CONCLUSIONS: The findings reported here demonstrate the potential of ATPS to process fractionated soybean extract as a first step to isolate and purify a recombinant protein expressed in soybeans. The proposed approach can simplify the way in which recombinant proteins expressed in plants can be recovered. Copyright © 2007 Society of Chemical Industry     

A novel aqueous micellar two-phase system composed of surfactant and mannitol for purification of polygalacturonase enzyme from Durio zibethinus Murray and recycling phase components

A novel aqueous micellar two-phase system composed of surfactant and mannitol was employed for the first time to purify polygalacturonase from Durio zibethinus Murray. The influences of different parameters such as type of surfactants, composition of surfactant/mannitol, pH and crude load on polygalacturonase partitioning were investigated. The results indicated that the polygalacturonase was recovered in 25% Tween 80 and 22% mannitol, at 68.2% of Tie line length, crude load of 30% at pH 5.0. The enzyme was successfully recovered with a high purification factor of 16.1 and yield of 97.3% while phase components were also recovered and recycled above 95%.     

The use of palladium nanoparticles supported with MCM-41 and basic (Al)MCM-41 mesoporous sieves in microwave-assisted Heck reaction

A series of supported catalysts has been obtained by grafting of chemically generated palladium nanoparticles onto basic, Cs⁺ ion-exchanged molecular sieves (Al)MCM-41 and onto the non-basic, parent material MCM-41. Catalytic activity of the catalysts has been investigated in the Heck reaction between bromobenzene and butyl acrylate under microwave irradiation. The activity of the bifunctional catalysts (Pd@Cs⁺-(Al)MCM-41) and the activity of Pd@MCM-41 combined with sodium acetate as an external base were considerably higher under microwave irradiation than activities observed for the same catalytic systems under the conventional heating. The Pd@MCM-41/NaOAc system showed higher conversions than the bifunctional catalysts presumably due to a different nature and accessible amount of the base. On the other hand, microwave irradiation seems to increase the rate of aggregation of the metallic particles and thus also catalyst deactivation as compared with the usual heating.     

Modeling of two‐phase polymerization of acrylamide in aqueous poly(ethylene glycol) solution

Two‐phase polymerization of acrylamide (AM) has been successfully carried out in aqueous poly(ethylene glycol) (PEG) solution with 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane] dihydrochloride (AIBI) as the initiator. A new heterogeneous kinetic model has been developed based on the partitioning of components between the two phases. It was found that polymerization proceeded in both the continuous and dispersed phases, even though the latter was the dominating polymerization locus. Besides the initiator, monomer concentration, and polymerization temperature, the PEG concentration also significantly influences the polymerization rate. With increasing concentration of PEG, gel effects in the aqueous PAM droplets were enhanced and more monomer preferred to polymerize inside the droplets, hence, the polymerization kinetics accelerated. The proposed model can successfully predict the composition of each phase and the polymerization kinetics during the aqueous two‐phase polymerization over a wide range of various reactions conditions. © 2010 American Institute of Chemical Engineers AIChE J, 2011