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1.
The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones(PK)was studied in the N-valeronitrile-N'-methylimidazolium hexafluorophosphate([C4CNmim]+PF-6) medium. The synthesized PK was characterized by Fourier transform infrared(FTIR), elemental analysis, 13C-nuclear magnetic resonance(13C-NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and gel permeation chromatography(GPC). The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%(0.1 g ionic liquid / 1 g active carbon carrier) and the theoretical content of Pd2+ is 5wt%(0.05 g Pd2+/ 1 g active carbon carrier), the highest catalytic activity 2 963.64 gSTCO/(gPd·h) is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw /Mn=1.389.  相似文献   

2.
The process of synthesis of dimethyl-2,6-naphthalene dicaboxylate from esterification of 2,6-naphthalene dicarboxylic acid (2,6-NDCA) by methanol using sodium tungstate as catalyst was investigated. The orthogonal tests method was used for optimizing the process factors. The effects of reaction temperature, mass percentage of catalyst, reaction time and mass ratio of methanol to 2,6-NDCA on the 2,6-NDCA conversion were investigated. It was found that all the four factors had significant effect on the conversion. The optimum reaction conditions were reaction temperature 215℃ ,mass percentage of catalyst 356, reaction time 3 h, mass ratio of methanol to 2,6-NDCA 6: 1. The 2,6-NDCA conversion at above condition was 92. 80％.  相似文献   

3.
Fluidized-bed reactor is a candidate for dimethyl ether （DME） synthesis from syngas because of its excellent heat removal capability. In order to improve the attrition resistance of catalyst, an amount of silica sol as binder was added to the catalyst composed of methanol synthesis component CuO/ZnO/Al2O3 and methanol dehydration component HZSM-5, which was prepared by coprecipitation and shaped by spray drying to get spherical particles. The effect of silica sol on the catalytic activity was investigated in a fixed-bed flow microreactor. Based on the experiment results, silica sol in the range of 0-20wt% had small effect on the catalytic activity. Generally, the CO conversion and DME yield decreased with the increase in concentration of silica sol, while the attrition resistance of catalysts increased with increasing silica sol, indicating that it was feasible to improve the attrition resistance without greatly sacrificing the activity of catalyst. In addition, the characterizations of catalysts were carried out using Brunauer-Emmett-Teller （BET）, X-ray powder diffraction （XRD） and temperature programmed reduction （TPR）.  相似文献   

4.
The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst(Pd/CNT) for the copolymerization of carbon monoxide(CO) and styrene(ST) towards the formation of polyketone(PK).The Pd/CNT was characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM).The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy(FTIR),13C-nuclear magnetic resonance(NMR) and XRD,respectively.The catalyst showed excellent activity and reusability in promoting the fabrication of PK.It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%.The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene.  相似文献   

5.
The acidities of different SiO2/Al2O3 ratio ZSM-5 zeolites, CBV3024E, CBV5524G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spectroscopy, and their catalytic performances were evaluated to screen the optimal CBV8014 catalyst for ethylene oligomerization. The mesoporosity development in CBV8014 zeolite was conducted by desilication in alkaline medium. The porous characteristics, structural properties and acidic properties of parent and alkali-treated CBV8014 zeolites were studied, and their catalytic performances were evaluated, indicating that CBV8014 treated by 0.2 mol/L NaOH solution has an appropriate mesoporosity development, well preservation of catalyst acidity and crystallinity, good catalytic activity and stability, and high liquid fuel yield for ethylene oligomerization. The effect of reaction pressure on ethylene oligomerization over 0.2HZ catalyst was also investigated, and JP-8 likely hydrocarbon jet fuel was obtained by using 0.2HZ catalyst at 0.344 75 MPa with a high catalyst stability and high liquid yield.  相似文献   

6.
SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions have also been found, mole ratio of n（La^3＋）：n（Ti^4＋） is 1：34, the soaked consistency of H2SO4 is 0.8 tool/L, the soaked time of HESO4 is 24 h, the calcining temperature is 480 ℃, the calcining time is 3 h. Then it was applied in the catalytic synthesis often important ketals and acetals as catalyst and revealed high catalytic activity. Under these conditions on which the molar ratio of aldehyde/ketone to glycol is l： 1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 41.4%-95.8%.  相似文献   

7.
To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copoiymerization of carbon monoxide (CO) and styrene (ST) to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2'-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectrosco py respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copoiymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copoiymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/(mol·h).  相似文献   

8.
The complex heat of BF_3 with methanol was measured by utilizing the principle of the Bunsen ice calorimeter. The complex heat of BF_3 –methanol was found to be 49.2 and 58.1 kJ/mol when the molar ratio of BF_3 to methanol was 1:2 and 1:1,respectively. In addition,the complex heat of BF_3 –anisole was also measured to test the apparatus error. The BF_3 –anisole result showed a calorimeter value of 53.1 kJ/mol with a system error of 2.3% as compared with the value reported in the literature. The mechanism of the reaction of BF_3 and methanol was interpreted based on our obtained results. This apparatus is useful and suitable for measuring the heat of other liquid–gas and liquid–liquid reactions.  相似文献   

9.
We studied the esterification of free fatty acids （FFA） in tung oil with methanol by using activated carbon treated with sulfuric acid as a catalyst, and investigated the effect of different temperatures, methanol/oil mole ratio and catalyst amount on the conversion of FFA. Results show that the optimal reaction condition is when the reaction time is 2 h, the mass fraction of the catalyst to total material is 5%, the molar ratio of menthol to FFA is 15 ： 1, and the reaction temperature is 368.15 K. We also investigated the kinetics of estefification at various temperatures. Results indicate that the rate-control step could be attributed to the surface reaction, and within the range of the experimental conditions, the as-calculated kinetics formula can depict the esterification processes well.  相似文献   

10.
A series of 4,4'-disubstituted-[2,2']-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been synthesized and employed in the copolymerization of carbon monoxide(CO)and styrene. The available bipyridine and its derivatives were coordinated with palladium(Ⅱ)acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of 13 C NMR, FTIR, differential scanning calorimetry(DSC)and element analysis techniques concerning its structure and thermal performance. The effect of different electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of copolymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composition, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2'-bipyridine ligand(1 356 g STCO/(g Pd · h)), when the molecular weight and polydispersity index of the polyketone are M n=8 502,M w=1 3440 and M w/M n=1.581, respectively.  相似文献   

11.
Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated.[Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2'-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied.  相似文献   

12.
Cucumber and rice plants with varying ammonium (NH4 +) sensitivities were used to examine the effects of different nitrogen (N) sources on gas exchange, chlorophyll (Chl) fluorescence quenching, and photosynthetic electron allocation. Compared to nitrate (NO3 −)-grown plants, cucumber plants grown under NH4 +-nutrition showed decreased plant growth, net photosynthetic rate, stomatal conductance, intercellular carbon dioxide (CO2) level, transpiration rate, maximum photochemical efficiency of photosystem II, and O2-independent alternative electron flux, and increased O2-dependent alternative electron flux. However, the N source had little effect on gas exchange, Chl a fluorescence parameters, and photosynthetic electron allocation in rice plants, except that NH4 +-grown plants had a higher O2-independent alternative electron flux than NO3 −-grown plants. NO3 − reduction activity was rarely detected in leaves of NH4 +-grown cucumber plants, but was high in NH4 +-grown rice plants. These results demonstrate that significant amounts of photosynthetic electron transport were coupled to NO3 − assimilation, an effect more significant in NO3 −-grown plants than in NH4 +-grown plants. Meanwhile, NH4 +-tolerant plants exhibited a higher demand for the reduced form of nicotinamide adenine dinucleotide phosphate (NADPH) for NO3 − reduction, regardless of the N form supplied, while NH4 +-sensitive plants had a high water-water cycle activity when NH4 + was supplied as the sole N source.  相似文献   

13.
The central composite design in the modeling and optimization of catalytic dehydration of ethanol to ethylene was performed to improve the ethylene yield. A total of 20 experiments at random were conducted to investigate the effect of reaction temperature, Si/Al ratios of H-ZSM-5 catalyst and liquid hourly space velocity (LHSV) on the ethylene yield. The results show that the relationship between ethylene yield and the three significant independent variables can be approximated by a nonlinear polynomial model, with R-squared of 99.9% and adjusted R-squared of 99.8%. The maximal response for ethylene yield is 93.4% under the optimal condition of 328 °C, Si/Al ratio 85, and LHSV 3.8 h−1.  相似文献   

14.
The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH3) and isocyanic acid (HNCO) whereas at higher temperatures the oxidation processes take effect and the products include a low concentration of nitric oxide (NO) and nitrous oxide (N2O). The gas HNCO is quite stable and a high yield of HNCO is observed. The ratio of NH3 to HNCO increases from approximately 1.2 to 1.7 with the temperature. The chemical analysis shows that H radical is in favor of HNCO hydrolysis by instigating the reaction HNCO+H·→·NH2+CO and high temperature has positive effect on H radical. The hydrolysis of HNCO over an alumina catalyst made using a sol-gel process (designated as γ-Al2O3) is investigated. The conversion of HNCO is high even at the high space velocities (6×105 h-1) and low temperatures (393–673 K) in the tests with catalysts, which enhances HNCO hydrolysis and raises the ratio of NH3 to HNCO to approximately 100. The pure γ-Al2O3 shows a better catalytic performance than CuO/γ-Al2O3. The addition of CuO not only reduces the surface area but also decreases the Lewis acid sites which are recognized to have a positive effect on the catalytic activity. The apparent activation energy of the hydrolysis reaction amounts to about 25 kJ/mol in 393–473 K while 13 kJ/mol over 473 K. The overall hydrolysis reaction rate on catalysts is mainly determined by external and internal mass-transfer limitations.  相似文献   

15.
Chemically processed Nb-doped SrTiO3 films and properties   总被引：1，自引：0，他引：1  
Homogeneous, crack-free SrNbxTi1−x O3 thin films on (110) silicon substrates were successfully fabricated by sol-gel processing. The optimum route and conditions were systematically investigated. Sr(OAc)2 glacial acctic acid solution, after being refluxed and reacted with tartrate, formed Sr(OAc)2(C4H6O6)2; Ti(OBu)4 formed Ti(OAc)4−x (AcAc)x after having the ligand partially exchanged with AcAc, while Nb(OC2H5)5 formed (OAc)2Nb(AcAc) (C4H6O6) by exchanging of ligand in glacial acetic acid with (CH3CO)2O. All the metal species after undergoing partial hydrolysis and polymerization with hydroxyl or oxygen, formed SrNbxTi1−x O13 cluster sol. Methyl cellulose (MCL) caused SrNbxTi1−x O3 sol to have polymeric structure and easily form films. SrNbxTi1−x O3 films with perovskite were subsequently formed after being annealed at 650∼750 °C for 60 min in 25% N2+75% H2 (volume ratio) atmosphere. Resistivity of the SrNb0.1Ti0.9O3 films at room temperature was 64 μω·cm, a particular T 2 temperature dependence of the resistivity, from 25 K up to room temperature, was observed. Project (No. 2002CB613305) supported by the National Basic Research Program (973) of China  相似文献   

16.
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17.
Ethene/norbornene copolymerization by the catalyst system [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO was investigated in detail at 30 °C, 60 °C, and 90 °C. A mass flow controller was used in this work to obtain kinetic data and investigate temperature's effects on activity, norbornene incorporation, copolymerization parameter, microstructure, glass transition temperature, and molar masses were described. High copolymerization valuesr ξ and high alternation are determined. The number of isotactic alternating sequences is much higher than that of the syndiotactic alternating sequences.  相似文献   

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