The industrial hydroformylation of olefins with a rhodium-based supported liquid phase catalyst: I: Description of the catalyst system,catalyst characterization and preparation,together with some orienting hydroformylation experiments with propyl

Hydridocarbonyltris(triphenylphosphine)-rhodium(I) (RhHCO(PPh₃)₃), dissolved in liquid triphenylphosphine and immobilized in a porous support b The hydroformylation reaction proceeds in the following way for propylene: CH₃CHCH₂ + CO + H₂ → CH₃CH₂CH₂CHOIn order to assess the industrial applicability of the above-mentioned catalyst a number of support materials were investigated. The influence of the rIt is concluded that supports based on α-alumina show the best results if these are pure and have an inert surface. SCS9 and SA5202 and also an experIn the range 25 – 100 (mol Rh) (m³ PPh₃)⁻¹ the reaction rate is first order with respect to the rhodium concentration. The selectivityThe degree of propylene conversion can be as high as 16.8% without an adverse effect on the catalyst performance. In this range of degrees of conversio     

The industrial hydroformylation of olefins with a rhodium-based supported liquid phase catalyst (SLPC): II. Influence of the degree of liquid loading on the catalytic performance of the rhodium-based supported liquid phase catalyst

Ethylene was hydroformylated with a rhodium-based liquid phase catalyst supported on α-Al₂O₃. Triphenylphosphine was the ligand in the catalyst. The effect of the degree of liquid loading on the catalytic performance was investigated for the range δ = 0.05 – 0.80. A stable activity level, which was highly dependent on the type of α-Al₂O₃, was reached in 24 h on-stream time. The experiments were carried out at relatively large Rh concentrations of up to 100 mol Rh m⁻³. For some supports the maximum value led to deactivation. A concentration of 50 mol Rh m⁻³ resulted in better stability. The deactivation was probably caused by the formation of aldol products which leached out the catalyst.     

Alternating cooligomerization of isoprene and propylene with vanadium catalyst

Alternating cooligomerization of isoprene with propylene has been investigated between ?30 and 0°C, VO(acac)₂–Et₃Al–Et₂AlCl being used as catalyst. In the presence of an excess of propylene, 2,4,7-trimethyl-1,4-octadiene and 2,4-dimethyl-1,4-nonadiene are selectively formed. The formation is explained by the alternating coordination of isoprene and propylene to the vanadium. When triphenylphosphine or pyridine is added to the catalyst, the cooligomerization is suppressed while the formation of the dimer and trimer of isoprene is high.     

Low pressure,highly active rhodium catalyst for the homogeneous hydroformylation of olefins

Hex-1-ene hydroformylation was examined at pressures of 1–11 atm and 40 °C, using Rh(acac)[P(OPh)₃]₂ + P(OPh)₃ as catalyst. The highest efficiency of aldehydes was achieved employing a small P(OPh₃)₃ excess-[P(OPh)₃]:[Rh] = 2:1. For reactions carried out at 1 atm, very high n/iso ratios i.e. 10–80 were obtained. Pressure increase caused a systematic drop of the n/iso ratio to ca. 5 at 11 atm. Simultaneously with hydroformylation, isomerisation of hex-1-ene to hex-2-ene occurs, but the contribution of the latter declines with increasing pressure. IR examination of the reaction mixture revealed that HRh(CO)[P(OPh)₃]₃ was the active form of the catalyst.The same catalytic system was applied in propylene hydroformylation at 5–10 atm pressure and 40 °C. In such conditions the yield of aldehydes was 10–70%, with a n/iso selectivity of 2–10.     

Effective tri-metallic TiO2 supported catalyst for hydrocarbon production from carbon dioxide

The current socio-economic issues with concerns on environmental quality and global warming are attributed to high concentrations of atmospheric carbon dioxide due to extensive usage of fossil fuels. Thus, over the last two decades, comprehensive work has been reported on carbon capture and storage and catalytic conversion of carbon dioxide to hydrocarbons. Among these, the reactions with hydrocarbons to form value-added products have been in focus. In this work, an attempt was made to identify the feasibility of the reaction: carbon dioxide and steam to form hydrocarbons of fuel value. After reviewing the literature on the development of various catalysts and their mechanism, a multi-metallic catalyst supported by TiO₂ Nano-needles was explored. The reaction mechanism is expected to proceed with activated CO₂ complex and hydroxyl groups over the metal oxide catalyst. Current reported work on CO₂ and Hydrogen proceeds with activated CO₂ and protons over the catalyst. The characterization techniques mainly XPS, XRD, TGA, FESEM-EDAX, FTIR, and NMR were used to analyze the catalyst activity and to confirm the products formed. The reaction is found to yield methanol and oxygen only. However, the conversion is found to be 0.4% - 3.8% in the temperature range 350°C to 550°C. The reaction of CO₂ with hydroxyl groups from water vapor can be effective as an alternative to the reaction with protons from hydrogen.     

Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO2 methanation: cooperative effect between Ni nanoparticles and a basic support

Ni-Al hydrotalcite derived catalyst (Ni-Al₂O₃-HT) exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO₂ over this catalyst initiated at 225 °C and reached 82.5% CO₂ conversion with 99.5% CH₄ selectivity at 350 °C, which was much better than its impregnated counterpart. Characterizations by means of CO₂ microcalorimetry and ²⁷Al NMR indicated that large amount of strong basic sites existed on Ni-Al₂O₃-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO₂ and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction.     

Highly active supported catalysts for olefin polymerization: Preparation and characterization of the catalyst

With use of the support prepared by the reaction¹ of a Grignard reagent with reaction mixture of AlCl₃ and CH₃Si(OC₂H₅)₃, an immobilized active stereospecific titanium catalyst was prepared by the three-step treatment of the support, first with TiCl₄, second with ethylbenzoate, and third with TiCl₄ again. The catalyst was also prepared by the two-step treatment of the support, with the mixture of TiCl₄ and ethylbenzoate, and with TiCl₄. Solids obtained in each step of the catalyst preparation were characterized by elemental and IR analysis, and their activities for propylene polymerization were determined with triethylaluminum as a cocatalyst under an atmospheric propylene pressure for 1 h at 60°C. The experimental data support the idea that both TiCl₄ and ethylbenzoate as donors are immobilized on the surface of the active stereospecific catalyst without any interaction between them.     

Effect of the ligand nature in cobalt complexes on the selectivity of the reaction of carbon dioxide and propylene oxide

The reaction of carbon dioxide with propylene oxide in the presence of the (salen)CoCl or (TPP)CoCl (salen = bis(3,5-di-tert-butyl-salicylidene)-1,2-diaminocyclohexane, TPP = 5,10,15,20-tetraphenylporphyrin) catalyst and the PPNCl (bis(triphenylphosphine)iminium chloride) cocatalyst has been carried out at 20–60°С and a СО₂ pressure of 0.6 MPa to investigate the effect of the ligand nature on the reaction rate and selectivity. The change in the reaction rate and selectivity in relation to the temperature and cocatalyst/catalyst ratio has been studied. The activation energy of the copolymerization of СО₂ with propylene oxide catalyzed by the (salen)CoCl complex have been obtained.     

The influence of reagent concentration on the kinetics of carbon dioxide-propylene oxide copolymerization in the presence of a cobalt complex

The effect of the concentrations of propylene oxide and the catalyst (salen)CoDNP/[PPN]Cl ((salen)CoDNP: [PPN]Cl = 1: 1, mol/mol) on the kinetics of the copolymerization of CO₂ and propylene oxide at 0.5 MPa and 20°C has been studied. The reaction proceeds at a constant rate after an induction period, and the value of this period varies with the reagent concentrations. The steady-state reaction rate increases linearly with the propylene oxide concentration in the range 5.0–14.3 mol/L. At high catalyst concentrations, such as (5.2–7.3) × 10^?3 mol/L, the reaction rate is first order in the catalyst; at concentrations below 5 × 10^?3 mol/L, the reaction rate is second order in the catalyst. Molecular mass increases in proportion to the propylene oxide conversion, that is consistent with a living polymerization process. A regioregular copolymer with 96% head-to-tail (HT) connectivity of propylene oxide has been obtained.     

Copolymerization of propylene oxide and CO2 using achiral salophen Co(III) penta-florobenzoate as catalyst and tetrabutyl ammonium bromide as co-catalyst

Copolymerization of racemic propylene oxide with carbon dioxide is investigated in the presence of economically inexpensive and effective achiral salophenCo(III)X [salophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-phenylenediimine, X = pentaflorobenzoate] catalyst and tetrabutyl ammonium bromide as co-catalyst. Effects of different variables like monomer to catalyst ratio, catalyst/co-catalyst ratio, temperature, pressure of CO₂ on molecular weight, yield and selectivity of poly(propylene carbonate) [PPC] have been investigated. The maximum M_w of 25.8 g/mol has been obtained at 15 bar and 50°C. All the samples were found to have excellent polydispersity near to 1.     

Promotion effect of additive Fe on Al2O3 supported Ni catalyst for CO2 methanation

In this paper, the effect of additive Fe on Ni/Al₂O₃ catalyst for CO₂ methanation was studied. A series of bimetallic Ni–Fe catalysts with different Ni/Fe ratios were prepared by impregnation method. For comparison, monometallic Fe‐based and Ni‐based catalysts were also prepared by the same method. The characterization results showed that adding Fe to Ni catalyst on the premise of a low Ni loading(≦12 wt.%) enhanced CO₂ methanation performance. However, when the Ni loading reached 12 wt.%, the catalytic activity decreased with the increase of Fe content, but still higher than the corresponding Ni‐based catalyst without Fe. Among them, the 12Ni3Fe catalyst exhibited the highest CO₂ conversion of 84.3 % and nearly 100% CH₄ selectivity at 50000 ml g^‐1 h^‐1 and 420 °C. The enhancement effect of adding Fe on CO₂ methanation was attributed to the dual effect of suitable electronic environment and increased reducibility generated by Fe species.     

Synthesis and characterization of high molecular weight poly(1,2-propylene carbonate-<Emphasis Type="Italic">co</Emphasis>-1,2-cyclohexylene carbonate) using zinc complex catalyst

Using supported multi-component zinc dicarboxylate catalyst,poly（1,2-propylene carbonate-co-1,2-cyclohexylene carbonate）（PPCHC） was successfully synthesized from carbon dioxide（CO₂） with propylene oxide（PO） and cyclohexene oxide（CHO）.The conversion of epoxides dramatically increased up to 89.7%（yield:384.2 g of polymer per g of Zn） with increasing reaction temperature from 60℃to 80℃.The optimized reaction temperature is 80℃.The chemical structure,the molecular weight,as well as thermal and mechanical properties of the resulting terpolymers were investigated extensively. When CHO feed content（mol%） is lower than 10%,the PPCHC terpolymers have number average molecular weight（M_n） ranging from 102×10³ to 202×10³ and molecular weight distribution（MWD） values ranging from 2.8 to 3.5.In contrast to poly（propylene carbonate）（PPC）,the introduction of small amount of CHO leads to increase in the glass transition temperature from 38.0℃to 42.6℃.Similarly,the mechanical strength of the synthesized terpolymer is greatly enhanced due to the incorporation of CHO.These improvements in mechanical and thermal properties are of importance for the practical application of PPC.     

Polymeric ionic liquid as novel catalyst for the Prins reaction

A series of micro-mesoporous polymeric ionic liquids (PILs) have been successfully synthesized by the method of anion and cation copolymerization. Then use FT-IR, N₂ adsorption–desorption isotherms, SEM, and TG to characterize them. Furthermore, the catalytic performance of the synthesized PILs was investigated for the Prins reaction of propylene with 1, 3, 5-trioxane. Among the four PILs synthesized, VIMBs-DVB-SSA has better catalytic activities for the Prins reaction. Under the optimal conditions, 100 °C, 8 wt%, 4 h and n (propylene)/n (1, 3, 5-trioxane) = 4:1, the conversion of formaldehyde (99.8%) and selectivity (81.7%) for 4-methyl-1, 3-dioxane. In addition, the effects of reaction time, catalyst dosage, and reaction temperature and mole ratio of reaction substrates on the reaction were also investigated. The prepared catalyst had good thermal stability and can be reused easily.     

Preparation and characterization of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/ZrO<Subscript>2</Subscript> catalyst for carbonation of methanol into dimethyl carbonate

A H₃PW₁₂O₄₀/ZrO₂ catalyst for effective dimethyl carbonate (DMC) formation via methanol carbonation was prepared using the sol–gel method. X-ray photoelectron spectra showed that reactive and dominant (63%) W(VI) species, in WO₃ or H₂WO₄, enhanced the catalytic performances of the supported ZrO₂. The mesoporous structure of H₃PW₁₂O₄₀/ZrO₂ was identified by nitrogen adsorption–desorption isotherms. In particular, partial sintering of catalyst particles in the duration of methanol carbonation caused a decrease in the Brunauer–Emmett–Teller surface area of the catalyst from 39 to 19 m²/g. The strong acidity of H₃PW₁₂O₄₀/ZrO₂ was confirmed by the desorption peak observed at 415 °C in NH₃ temperature-programmed desorption curve. At various reaction temperatures (T?=?110, 170, and 220 °C) and CO₂/N₂ volumetric flow rate ratios (CO₂/N₂?=?1/4, 1/7, and 1/9), the calculated catalytic performances showed that the optimal methanol conversion, DMC selectivity, and DMC yield were 4.45, 89.93, and 4.00%, respectively, when T?=?170 °C and CO₂/N₂?=?1/7. Furthermore, linear regression of the pseudo-first-order model and Arrhenius equation deduced the optimal rate constant (4.24?×?10^?3 min^?1) and activation energy (E_a?=?15.54 kJ/mol) at 170 °C with CO₂/N₂?=?1/7 which were favorable for DMC formation.     

基于两性离子型季铵盐-KI的温度控制自分离离子液体(IL)催化体系用于二氧化碳固定反应（英文）

随着在世界各国工业化进程不断加快,人类对煤、石油、天然气等化石燃料的需求越来越大,既加速了能源短缺,又排放了大量CO_2.CO_2又成为分布最广、价格便宜和储量丰富的碳资源.人类除了努力做到CO_2减排,又可将其转化为能源、材料和各种化工产品.CO_2与环氧化合物发生偶联反应生成环碳酸酯,具有原子经济性,符合绿色化学的观点,是最有前景的方法之一.CO_2可以与三元环氧化合物发生偶联反应生成五元环状碳酸酯,它是当今合成环碳酸酯比较成熟的方法.已经被设计合成并应用的高效催化体系有离子液体催化剂、金属盐或氧化物催化剂、有机催化剂、希夫碱金属配合物催化剂以及大环金属配合物催化剂等等,但最有效的催化剂还是均相催化剂,其最大的缺点在于催化剂和产物分离困难.既有均相催化剂高的催化活性,又能像多相催化剂易于分离,是人们设计新催化剂的目标.本文设计合成了一系列含有不同烷基链长度的两性离子型季铵盐(ZTQAs),可以与KI协同催化CO_2与环氧化合物偶联反应.随着烷基链的增长,ZTQAs在碳酸丙烯酯中表现出温度调控的自分离特性.通过X射线光电子能谱和量子化学计算证实,ZTQAs与KI之间存在明显的相互作用,从而增强了碘离子的亲核能力.当反应条件为125 ℃,CO_2压力1.5 MPa以及1mol%催化剂用量下,DTPS/KI催化剂取得了良好的收率(95.1%).并且该催化剂可以从催化系统中自发的析出,因而既表现出均相催化剂的高活性,又可以像非均相催化剂那样循环使用.该催化剂催化各种环氧化合物与CO_2偶联反应中均显示出良好的催化性能     

(Salan)CrCl,an effective catalyst for the copolymerization and terpolymerization of epoxides and carbon dioxide

The selective transformation of CO₂ and epoxides to afford completely alternating copolymers remains a topic of much interest for the potential utilization of carbon dioxide in chemical synthesis. The use of salicylaldimine (salen)‐metal complexes and their saturated (salan)‐metal versions have proven to be the most effective and robust single‐site catalyst for these processes. Herein, we report on mechanistic aspects of the copolymerization of alicyclic and aliphatic epoxides with CO₂ in toluene solution and in neat epoxides in the presence of a (salan)CrCl/onium salt catalyst system. The activation barriers for both cyclohexene oxide(CHO)/CO₂ and propylene oxide(PO)/CO₂ were shown to be significantly higher in toluene solution than those previously reported for reactions carried out under solventless conditions. Terpolymerization of CHO/vinylcyclohexene oxide/CO₂ was shown via Fineman‐Ross analysis at 60 °C to proceed with little monomer selectivity, for example, r_CHO = 1.03 and r_VCHO = 0.847. On the other hand, terpolymerization of CHO/PO/CO₂ occurred at 25 °C with a propensity for incorporation of PO in the polymer. However, at 40 °C, Fineman‐Ross analysis revealed r_CHO and r_PO values of 0.869 and 1.49, thereby affording a terpolymer with a more equal distribution of monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Multidisciplinary green approaches (ultrasonic,co-precipitation,hydrothermal, and microwave) for fabrication and characterization of Erbium-promoted Ni-Al2O3 catalyst for CO2 methanation

The dispersion of nickel catalysts is crucial for the catalytic ability of CO₂ methanation, which can be influenced by the fabrication method and the operation process of the catalysts. Therefore, a series of fabrication methods, including ultrasonic, hydrothermal, microwave, and co-precipitation, have been applied to prepare 25Ni-5Er-Al₂O₃ catalysts. The fabrication method can partially influence the structural and catalytic activity of the nickel aluminate catalysts. Among the catalysts modified by Erbium prepared with various methods, the catalyst fabricated by ultrasonic pathway exhibited better catalytic performance and CH₄ selectivity especially, at a temperature (400 ℃). The impact of the temperature of the reaction (200–500 °C) was examined under a stoichiometric precursor ratio of (H₂:CO₂) = 4: 1, atmospheric pressure, and space velocity (GHSV) of 25000 mL/gcath. The results demonstrate that the ultrasonic method is strongly efficient for fabricating Ni-based catalysts with a high BET surface area of about 190.33 m²g^?1. The catalyst composed via the ultrasonic technique has 69.38 % carbon dioxide conversion and 100 % methane selectivity at 400 °C for excellent catalytic performance in CO₂ methanation reactions. The fabrication effect can be associated with its high surface area, which is achieved via the hot spot mechanism. Besides, the addition of Erbium promotes the Ni dispersion on the supports and stimulates the positive reaction because of the erbium oxygen vacancies.     

Titanocene dichloride/KI: an efficient catalytic system for synthesis of cyclic carbonates from epoxides and CO2

Titanocene dichloride (Cp₂TiCl₂)/KI was developed to be an efficient catalytic system for the cycloaddition of CO₂ to epoxides to synthesize relevant cyclic carbonates from epoxides and CO₂. Various influencing factors on the coupling reaction, such as co‐catalyst, temperature, CO₂ pressure and reaction time, were investigated. The optimal reaction conditions were KI as co‐catalyst, 150 °C reaction temperature, 12 atm CO₂ pressure and 4 h reaction time using THF as solvent for the synthesis of propylene carbonate in 98% yield. Copyright © 2013 John Wiley & Sons, Ltd.     

Palladium supported on silica–chitosan hybrid material (Pd‐CS@SiO2) for Suzuki–Miyaura and Mizoroki–Heck cross‐coupling reactions

Palladium supported on silica–chitosan hybrid material was prepared and characterized using thermogravimetric and differential thermogravimetric analyses, scanning electron microscopy, and Fourier transform infrared, energy‐dispersive X‐ray and X‐ray photoelectron spectroscopies. The prepared Pd‐CS@SiO₂ catalyst (1 mol%) was used for the Suzuki–Miyaura cross‐coupling reaction of various aryl halides and arylboronic acids in 95% ethanol at 80 °C and the Mizoroki–Heck reaction in dimethylformamide at 110 °C using K₂CO₃ as a base. The developed catalyst is well suitable for the 3R approach (recoverable, robust, recyclable) for cross‐coupling reactions without appreciable loss of its activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Kinetics of hydroformylation of camphene using rhodium-phosphite catalyst

Kinetics of hydroformylation of camphene was investigated in the presence of [Rh(CO)₂(acac)]/P(OPh)₃ catalyst in a temperature range of 363–383 K. The influence of parameters such as stirring speed, camphene, catalyst, ligand concentrations, and partial pressures of H₂ and CO on the activity and selectivity of the catalyst has been studied. The rate showed a first-order dependence with respect to catalyst and camphene concentrations. The effect of partial pressure of hydrogen showed fractional order dependence. The plots of rate versus excess ligand, that is, (P(OPh)₃) concentration and rate versus CO partial pressure passed through maxima and showed typical substrate/ligand inhibited kinetics. An empirical rate equation has been proposed and found to be in good agreement with the observed rate data. The kinetic parameters and activation energy were also evaluated.