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1.
钛酸酯催化碳酸二甲酯与苯酚酯交换反应 总被引:15,自引:0,他引:15
The transesterification of phenol and dimethyl carbonate (DMC) to diphenyl carbonate (DPC) was studied using tetrabutyl titanate and tetraphenyl titanate as catalysts. The main product was found to be methyl phenyl carbonate (MPC) which is an intermediate of the reaction. The selectivity for DPC was improved when increasing the phenol/DMC molar ratio or prolonging the reaction time. The phenol conversion, selectivity for MPC and DPC were 47 4%, 90 9% and 9 14%, respectively, when the transesterification reaction approached equilibrium under the conditions of 175 ℃, 25 h and DMC∶phenol∶ Ti(OBu) 4 molar ratio of 1 5∶1∶0 05. The selectivity for DPC could reach 12.2% when the reaction time was 30 h. The tetrabutyl titanate catalyst showed a higher catalytic activity than tetraphenyl titanate. 相似文献
2.
乙醇热法制备纳米二氧化钛及其对酯交换反应合成碳酸二丁酯的催化性能 总被引:1,自引:0,他引:1
The preparation of nano-TiO2 powder by the alcohol-thermal method at atmospheric pressure using ethanol as the solvent, H2TiO3 as the precursor, and KOH, NaOH or NH3·H2O as the mineralizer has been presented. XRD result showed that the structure of TiO2 is anatase, and with the increase of mineralizer alkalinity, the average diameter of TiO2 becomes smaller, and the crystallinity of TiO2 becomes higher. The diameter and the crystallinity of TiO2 affect the catalytic activity of TiO2 for the synthesis of dibutyl carbonate (DBC) from dimethyl carbonate (DMC) and butyl alcohol. The anatase TiO2 obtained from KOH exhibits high catalytic activity, giving 61.9% conversion of DMC, 100% selectivity for DBC, and 61.9% yield of DBC. The conversion of DMC, selectivity and yield of DBC remain almost unchanged through four reuses. 相似文献
3.
Dimethyl carbonate synthesis via transesterification catalyzed by quaternary ammonium salt functionalized chitosan 总被引:2,自引:0,他引:2
Yuan Zhao~ 《中国化学快报》2008,19(3):286-290
A quaternary ammonium salt covalently linked to chitosan was first used as a catalyst for dimethyl carbonate (DMC) synthesis by the transesterification of propylene carbonate (PC) with methanol. The effects of various reaction variables like reaction time, temperature and pressure on the catalytic performance were also investigated. 54% DMC yield and 71% PC conversion were obtained under the optimal reaction conditions. Notably, the catalyst was able to be reused with retention of high catalytic activity and selectivity. Consequently, the process presented here has great potential for industrial application due to its advantages such as stability, easy preparation from renewable biopolymer, and simple separation from products. 相似文献
4.
Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol 下载免费PDF全文
Tong Chen Huajun Han Zhiping Du Jie Yao Gongying Wang Dachuan Shi Desheng Zhang Zhiming Chen 《天然气化学杂志》2006,15(4):303-306
The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1. 相似文献
5.
PdCl2/ O-MCM-41催化剂制备及其在苯酚氧化羰化反应中的应用 总被引:1,自引:0,他引:1
Hybrid mesoporous silica MCM-41 (O-MCM-41) was prepared using γ-aminopropyltriethoxysilane (APTES) as spacer, tetraethoxysilane as precursor and 2-acetylpyridine as organic moiety. The heterogeneous palladium catalyst (PdCl2/ O-MCM-41) was then prepared by reaction of the hybrid MCM-41 with PdCl2(PhCN)2. The products were characterized by means of IR, XRD, XPS and N2 adsorption-desorption isotherms. The catalytic properties of the supported catalyst in the oxidative carbonylation of phenol to diphenyl carbonate (DPC) were investigated. The yield of DPC and turnover number (TON) reached 5.8% and 29 mol DPC·mol Pd-1, and Pd loss was only 2.7% at 110 ℃, 4.4 MPa for catalytic reaction of 5 h with 4.2wt% Pd loading, and molar ratio of phenol to Pd being 1000 in the presence of Cu2O and terahydrofuran (THF). 相似文献
6.
A novel flower-like hydrated magnesium carbonate hydroxide,Mg_5(CO_3)_4(OH)_2·4H_2O,with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant.Reaction time has an important effect on the final morphology of the product.The micro-structure and morphology of Mg_5(CO_3)_4(OH)_2·4H_2O were characterized by means of X-ray diffractometry(XRD),field-emission scanning electron microscopy(FE-SEM).Brunauer-Emmett-Teller(BET)surface areas of the samples were also measured.The probable formation mechanism of flower-like micro-structure was discussed.It was found that Mg_5(CO_3)_4(OH)_2·4H_2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate(DPC)by transesterification of dimethyl carbonate(DMC)with phenol. 相似文献
7.
《高分子科学》2017,(1)
Mg-Al mixed oxides with different Mg/Al molar ratio were prepared by thermal decomposition of hydrotalcitelike precursors at 500℃ for 5.0 h and used as catalysts for the transesterification of diphenyl carbonate with 1,4-butanediol to synthesize high-molecular-weight poly(butylene carbonate)(PBC). The structure-activity correlations of these catalysts in this transesterification process were discussed by means of various characterization techniques. It was found that the chain growth for the formation of PBC can only be obtained through connecting ―OH and ―OC(C)OC_6H_5 end-group upon removing the generated phenol, and the sample with Mg/Al molar ratio of 4.0 exhibited the best catalytic performance, giving PBC with M_w of 1.64 × 10~5 g/mol at 210 ℃ for 3.0 h. This excellent activity depended mainly on the specific surface area and basicity rather than pore structure or crystallite size of MgO. 相似文献
8.
Ordered mesoporous Ba CO3/C composites were synthesized by a multi-component co-assembly method combined with a carbonization process using phenolic resol as carbon source, barium nitrate as barium precursor, and triblock copolymer Pluronic F127 as template. The synthesized materials were characterized by X-ray diffraction, transmission electron microscopy, N2 physical adsorption, thermogravimetric analysis, and temperature-programmed desorption of CO2. When Ba CO3 contents were increased from 9.1 wt% to 44.7 wt%, pore size increased from 3.1 to 4.3 nm and the BET(Brunauer-Emmett-Teller) surface area initially increased to a maximum value of 390 m2 g-1(at a Ba CO3 content of 18.5 wt%) before subsequently decreasing. Ba CO3 was well dispersed in the amorphous carbon framework, and no phase separation was observed. The mesoporous BaCO3/C composites exhibited high catalytic activities toward the transesterification of glycerol and dimethyl carbonate into glycerol carbonate. A glycerol conversion of 97.8% and a glycerol carbonate selectivity of 98.5% were obtained under the optimized reaction conditions. 相似文献
9.
Copper oxides were prepared by direct heating and decomposing copper(Ⅱ) salts, such as Cu 2(OH) 2CO 3, Cu(NO 3) 2·3H 2O, Cu 2C 6H 4O 7·2 5H 2O, CuC 2O 4·2H 2O and CuAc 2·H 2O. The phase, surface area and catalytic activity of the oxides for H 2O 2 decomposition were investigated by means of XRD and BET measurements. It has been demonstrated that the characteristics of copper oxides obtained from different precursors are much different from each other. Monocomponent nano CuO, which has higher catalytic activity for H 2O 2 decomposition, can be prepared by direct heating and decomposing Cu 2(OH) 2CO 3. On the other hand, CuO in the decomposition products of the organic acid copper can be partially reduced to Cu 2O and Cu in the reducing atmosphere, and the Cu 2O component in the products has higher catalytic activity for H 2O 2 decomposition. 相似文献
10.
Catalytic properties of Ni/ceria-yttria electrode materials for partial oxidation of methane 下载免费PDF全文
The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ (x = 0.05, 0.10, 0.15 and 0.20) were investigated for partial oxidation of methane (POM). The CeO2-Y2O3 solid solutions were prepared by co-precipitaion method. The Ni-based catalysts supported on the solid solutions were obtained using the impregnation method. Structural, surface and redox characteristics of the prepared catalysts were systematically examined by means of X-ray diffraction (XRD), N2 adsorption-desorption (Brunauer-Emmet-Teller BET method), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) methods. The results indicated that yttria doped in the ceria system, forming a good solid solution, readily induced more defects and oxygen vacancies that favored the improvement of catalytic activity and coking resistance. In the temperature range of 600-850 ℃, Ni/Ce0.90Y0.10O1.95 catalyst exhibited the best catalytic activity among the four tested catalysts, with the CH4 conversion, CO selectivity and H2 selectivity of 78.8%, 90.6% and 89.8%, respectively, at 850 ℃. And the H2/CO molar ratio in products of Ni/Ce0.90Y0.10O1.95 catalyst was closer to the theoretical value of 2.0. The excellent coking resistant behaviors for all catalysts were clearly manifested by Thermal Analysis. 相似文献
11.
Zn-Al水滑石催化碳酸二甲酯与苯酚酯交换反应的研究 总被引:7,自引:0,他引:7
用共沉淀法制备了Zn-Al水滑石,并用于多相催化酯交换合成碳酸二苯酯的反应.研究了不同n(Zn)/n(Al)比的水滑石及其焙烧产物等对酯交换反应的催化活性.结果表明,Zn-Al水滑石催化剂对该反应的催化活性和选择性很高,当n(Zn)/n(Al)=3时,在150~180℃,n(PhOH)/n(DMC)=2,催化剂用量为反应物总质量的1.5%,在反应时间为12h的条件下,DMC的转化率达到55.9%,DPC和MPC的收率分别为25.3%和27.0%,酯交换产物的选择性达到93.6%.利用XRD,TG-DTA和TEM等手段对催化剂进行了表征. 相似文献
12.
碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的热力学性质及均相催化剂 总被引:6,自引:0,他引:6
在298.15K,101.325kPa条件下,液态碳酸二甲酯(DMC)的标准Gibbs自由能和熵分别估算为-472.3kJ*mol-1和245.2J*mol-1*K-1.在298K~523K计算了由DMC和苯酚生成碳酸二苯酯(DPC)和苯甲醚反应的热力学性质(ΔrH0m,ΔrS0m,ΔrG0m和平衡常数).计算出的热力学性质表明,DMC和苯酚酯交换合成DPC反应是吸热的,并且在热力学上是不利的.研究了n-Bu2SnO,
Ti(OC4H9)4, AlCl3和ZnCl2四种酯交换法合成DPC反应的催化剂,其中n-Bu2SnO具有最高的催化活性.热力学计算和实验结果均表明,合成DPC反应的最佳温度为453K.当以n-Bu2SnO为催化剂,n(苯酚)∶n(DMC)=4∶1时,DPC的产率和选择性分别为43.0%和88.7%. 相似文献
13.
Fuming Mei Exiang Chen Guangxing Li Aiqing Zhang 《Reaction Kinetics and Catalysis Letters》2008,93(1):101-108
Mg-Al-O-t-Bu hydrotalcite was synthesized and characterized by XRD, FT-IR and TGA-DTA. It was proved to be an active heterogeneous
catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. When the reaction was carried out over Mg-Al-O-t-Bu
hydrotalcite at 80°C, 7 h, molar ratio of ethanol to DMC 5:1, 1.0 wt.% of catalyst, the conversion of DMC was 86.4%, the selectivity
to diethyl carbonate (DEC) was 61.2%. This heterogeneous catalyst could be used 5 times without loss of its activity. 相似文献
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碳酸二苯酯(DPC)是非光气法生产聚碳酸酯(PCs)的重要原料,具有多种酯交换法合成路线,如碳酸二甲酯(DMC)与苯酚酯交换法、DMC与苯基乙酸酯(PA)酯交换法、草酸二甲酯(DMO)与苯酚酯交换法等.本文对比测定了几种金属乙酰丙酮配合物和有机钛化合物对碳酸二甲酯(DMC)与苯基乙酸酯(PA)酯交换合成DPC反应的催化性能,结果表明,乙酰丙酮氧钛[TiO(acac)2]是一种良好的酯交换催化剂,具有优良的催化性能.在反应条件θ=180℃,n(PA)=0.8 mol,n(DMC)/n(PA)=1/2,n(TiO(acac)2)/n(PA)=0.006,t=4 h下,DMC转化率可达74.9%,甲基苯基碳酸酯(MPC)和DPC的选择性分别可达56.9%和38.9%.探索并提出了TiO(acac)2催化DMC与PA酯交换合成DPC反应的机理. 相似文献
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18.
超分子结构甲基橙插层水滑石的组装及其光热稳定性研究 总被引:9,自引:0,他引:9
甲基橙是一种酸性染料,但因为它的光和热稳定性较差,使其应用范围和使用效果受到了一定限制.以Mg0.67Al0.33(OH)2(CO3)0.165·0.58H2OLDHs为前体,采用离子交换法,将甲基橙插入到LDHs层间,借助XRD,FTIR,UV-Vis和TG-DTA等手段对样品进行表征.结果表明,甲基橙阴离子可以完全取代前体层间的CO32-离子,组装得到晶体结构良好的甲基橙插层LDHs.对其结构进行研究发现,LDHs主体层板与客体甲基橙阴离子之间存在静电吸引、氢键和其它弱化学键相互作用,具有超分子结构特征.该超分子结构材料不仅保持了甲基橙本身的颜色,而且与甲基橙相比,其耐光性和耐热性均有大幅度的提高. 相似文献
19.
Transesterification of dimethyl carbonate with phenol over a bimetallic molybdenum and copper catalyst 总被引:1,自引:0,他引:1
Dongshen Tong Tong Chen Fei Ma Tao Kang Yongcheng Lei Jing Hu Yue Wang Gongying Wang 《Reaction Kinetics and Catalysis Letters》2008,94(1):121-129
Mo-Cu bimetallic oxides were found to be efficient heterogeneous catalysts for the transesterification of dimethyl carbonate
(DMC) with phenol. When the reaction was carried out between 150 and 180°C, with a molar of Mo/Cu of 1:1, molar ratio of phenol/DMC
of 1:1, 4.8 wt.% of the catalyst, 9 h, the conversion of phenol was 49.9%, and the total yield of MPC and DPC was 45.4%. Catalyst
reuse showed a gradual decline in the catalytic activity. The decrease in catalytic activity might be due to leaching out
of Mo and Cu, and/or carbon deposition. 相似文献
20.
KNO3/MCM-48催化酯交换法合成碳酸二丙酯 总被引:2,自引:0,他引:2
对KNO3/MCM-48用于丙醇和碳酸二甲酯进行酯交换合成碳酸二丙酯的催化性能进行了考察. 用X射线衍射(XRD)、红外光谱(IR)和X射线荧光法研究了催化剂的结构特征和表面性质. XRD结果表明,随着K负载量的增加,载体特征峰强度逐渐减弱,但仍保留MCM-48的晶体结构. 随着焙烧温度的升高, KNO3逐渐分解成K2O. 分别考察了活性组分负载量、焙烧温度、焙烧时间和催化剂的用量以及反应时间对反应的影响. 结果表明, KNO3/MCM-48催化剂对碳酸二丙酯的合成具有很高的催化活性. 在反应温度363 K, 反应时间6 h, 催化剂用量5%, 丙醇与碳酸二甲酯摩尔比为4的条件下,碳酸二甲酯的转化率可达99.9%, 产物碳酸二丙酯选择性93.4%, 产率93.3%. 相似文献