甲醇气相羰基化Ni/AC催化剂的失活行为

采用连续流动固定床反应装置,Ni/AC作为催化剂,在533 K、1.5 MPa、CO/CH3OH/CH3I摩尔比20/19/1、7.5 gcat·h·mol－1下考察了催化剂的稳定性,并通过XPS、ICP和XRD等技术对甲醇气相羰基化反应前后Ni/AC催化剂进行了表征。结果表明,长时间运转催化剂表面形成NiI2,使具有催化活性的Ni0活性中心数量减少,活性降低。XPS结果显示羰基化活性中心Ni不断迁移并在催化剂表面富集,导致积炭效应,堵塞催化剂孔道,使催化剂失活。进一步对积炭类型研究,发现形成的碳物种主要是石墨型碳。Ni向催化剂表面迁移富集,并与CO形成可挥发的Ni(CO)4,造成金属镍的大量流失由ICP所证实。     

A catalyst for the carbonylation of methanol to acetic acid in gaseous phase

A novel Rh/Ys catalyst for the carbonylation of methanol to acetic acid in gaseous phase is reported. The porous carbon beads (Ys) prepared from the carbonation of poly(vinylidene chloride) were used as the support. This catalyst has a specific surface area of 1 000 m2/g, high mechanical strength and thermal stability. The average diameter of the pore is in the range of 0.8 - 1.2nm. Experimental evidence showed that this catalyst was of high activity and selectivity, which could compare to those of the homogeneous catalyst from Monsanto. The catalytic rate could get to 900 g AcOH/g Rh·h during the carbonylation of methanol to acetic acid. The fine spreading of Ph over the Ys surface is the key factor for the activity.     

醋酸溶液中Pd-CuPc/Y催化甲烷选择氧化制甲醇

以氯化铜、钼酸铵、苯酐、氯化铵、尿素和NaY分子筛为原料,采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y.采用等体积浸渍法将金属钯担载在CuPc/Y上制备了Pd-CuPc/Y催化剂,并在醋酸水溶液中考察了其催化甲烷选择氧化合成甲醇反应的性能,结果表明,催化性能与反应温度、溶剂中CH₃COOH与H₂O的混合比例、对苯醌用量、反应时间等因素有关,在0.5%Pd-0.5%CuPc/Y添加量0.5 g、CH₃COOH与H₂O体积比4∶1、对苯醌用量1 000 μmol、反应时间3 h、反应温度150 ℃的条件下,甲醇的最佳生成量为1 840 μmol.Pd-CuPc/Y催化剂可以多次循环使用,但由于催化剂流失和催化剂表面的钯粒子聚集的原因,循环使用后的催化剂催化活性有所下降.Pd-CuPc/Y在醋酸溶液中催化甲烷选择氧化合成甲醇是亲电取代反应和活性氧物种氧化共同作用的结果.     

Relationship between surface microstructure and properties of supported catalyst Rh/Ys

The inner structure of Rh/Ys,a novel high efficiency supported catalyst,and the spreading of Rh on the Ys surface were analyzed through electron transmission microscopy and scanning tunnel microscopy.The relationship between the distribution of Rh over the support and the preparation temperature of th catalyst was determined.The formation of Rh-C bond was confirmed by XPS and far-IR spectra.The loss of Rh from the surface of the support and the catalytic activity under different preparation conditions have been compared.The internal factors for the high activity and high stability of the novel Rh/Ys catalyst have been discussed.     

Ni-Sn-Cr/AC催化剂上乙酸甲酯气相羰基化合成醋酐反应的研究

以活性炭为载体,采用浸渍法制备Ni-Sn-Cr/AC催化剂,在连续流动固定床反应器上研究其对乙酸甲酯气相羰基化合成醋酐反应的催化性能。分别考察了Ni、Sn、Cr三种金属组分的负载量对催化活性的影响,进一步考察了反应压力、反应温度、反应时间对反应的影响。实验结果表明,在Ni9%-Sn12%-Cr6%/AC催化剂上,当反应温度205℃,压力5.5MPa,催化剂焙烧温度600℃,催化剂焙烧时间为4h的条件下,乙酸甲酯的转化率为38.8%,醋酐的选择性为81.1%。采用X射线衍射和元素分析技术分别对反应前和不同反应时间后的催化剂进行了表征。分析结果表明,Ni⁰是催化剂的主要活性中心,随着反应时间的延长,活性组分镍的流失现象比较严重,同时催化剂上出现积炭及载体骨架遭到破坏,是导致催化剂失活的主要原因。     

Gas-phase oxidative carbonylation of methane to acetic acid over zeolites

Gas-phase oxidative carbonylation of methane was first performed on ZSM-5 zeolites. The addition of water vapor to a mixture of carbonylation gases leads to a multiple (by two orders of magnitude) increase in acetic acid yield. Zeolites with high acidity, primarily Brønsted acidity, favor the target product formation.     

Kinetics of esterification of acetic acid with n-butanol over different homogeneous acid catalysts

The esterification reaction of n-butanol and acetic acid has been performed in batch reactor in the presence of different homogeneous acid catalyst, namely sulfuric acid, nitric acid, and para toluene sulfonic acid (p-TSA). The objective of present research work is to investigate kinetic behavior of esterification reaction over the temperature range of 60°C–80°C. The effect of reaction parameter such as catalyst loading varied from 1% to 5% v/v and acid to alcohol molar ratio of 1:1, 1:3, and 1:5 has been observed. A pseudo homogeneous kinetic model has been applied. Kinetic parameters such as equilibrium constant, reaction rate constant, enthalpy, activation energy, and entropy were calculated by the experimental data for different acid catalyst system. It was observed that sulfuric acid gives higher conversion 73% than p-TSA 68.5% and nitric acid 66.25% at temperature of 80°C, 1:1 molar ratio and 3% catalyst concentration. The activation energy was estimated 36448.49, 23324.31 and 19060.156 J/mol K for three different catalyst sulfuric acid, nitric acid and p-TSA respectively. The enthalpy and entropy of the esterification reaction of acetic acid with n-butanol over three different catalysts has been calculated (Enthalpy: 25.788 KJ/mol, 12.256 KJ/mol, 28.320 KJ/mol, Entropy: 88.1 J/mol K, 45.298 J/mol K, 91.44 J/mol K) and found enthalpy is having positive value that shows reaction is endothermic.     

Kinetics of methanol steam reforming over COPZr-2 catalyst

The COPZr-2 catalyst, which was prepared in our prophase research, showed good catalytic performance in methanol steam reforming reaction. In this article, the best one was chosen as an example to study the reaction kinetics of methanol steam reforming over this type of catalyst. First, the effects of methanol conversion to outlet CO2 and methanol conversion to outlet CO on methanol pseudo contact time W/FMeOH were investigated. Then by applying the reaction route that methanol direct reforming （DR） and methanol decomposition （DE） were carried out in parallel, the reaction kinetic model with power function type was established. And the parameters for the model were estimated using a non-linear regression program which computed weighted least squares of the defined objects function. Finally, the kinetic model passed the correlation test and the F-test.     

甲醇气相羰基化Ni-Pd/AC催化剂失活机理的研究

采用连续流动固定床反应装置,Ni Pd/AC为催化剂,在260℃、1.5MPa、CO/CH3OH/CH3I摩尔比为20/19/1、W/F为7.5g·h·mol－1下考察了催化剂的稳定性,并对失活前、后Ni-Pd/AC催化剂进行了比表面积、热解-红外分析（Py FTIR）和XPS表征。结果表明,反应初期反应产物乙酸或乙酸甲酯与催化剂之间强吸附堵塞了催化剂孔道,导致扩散受到限制。随着反应时间的延长,羰基化活性中心Ni不断迁移并富集在催化剂表面上,使Ni晶粒增大,成为积炭的活性中心,积炭堵塞了催化剂孔道,导致催化剂失活。进一步对积炭类型进行研究,发现形成的碳物种主要是类石墨型碳。     

磷化过程对MoP催化剂醋酸加氢合成乙醇性能的影响

制备了系列磷化钼催化剂用于醋酸加氢合成乙醇活性评价,并采用XRD、XPS和SEM等技术对催化剂进行表征。结果表明,催化剂除含有MoP外,还有MoP_2O_7和MoO_2等物种,催化醋酸生成乙醇的活性物种是MoP,或者是MoP与MoP_2O_7、MoO_2协同起催化作用。磷化温度一定程度上影响催化剂的形成和活性组分的分布,磷化温度太低,MoP形成量少,磷化温度太高,MoP发生团聚和烧结,磷化温度为650℃时制备的催化剂活性最高。磷钼物质的量比为1.0时催化剂的乙醇合成性能最高。     

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-Ox catalysts

Alkaline earth metal (Mg, Ca, Sr and Ba)-doped Mo-V-Sb-Ox catalysts, prepared by a dry-up method, have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions. The catalysts have been characterized by N2 adsorption-desorption, temperature-programmed desorption (TPD) of NH3, SEM and XRD. Influence of water vapor on the catalytic performance, particularly on the selectivities to acetic acid and acrylic acid, has also been studied. The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-Ox catalysts. The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals, which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid. The catalytic activity and product selectivities were found to be influenced by the reaction temperature, C3H8/O2 ratio and space velocity. A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.     

Synthesis of dimethyl carbonate by vapor phase oxidative carbonylation of methanol over Cu-based catalysts

Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities were intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological analysis by X-ray diffraction and SEM was also conducted in order to characterize the emloyed catalysts. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120–130°C. The reaction rate was too slow below 100°C, while too much by-products was produced above 150°C. Among the various catalysts employed, CuCl₂/NaOH/AC catalyst with the molar ratio of OH/Cu=0.5–1.0, has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu₂(OH)₃Cl.     

Iodide and acetate promotion of carbonylation of methanol to acetic acid: Model and catalytic studies

Iodide and acetate salts increase the rate of reaction of Li[RhI₂(CO)₂] with MeI at 25° C in acetic acid solution, a model of the rate-determining step in catalytic methanol carbonylation. The effects of water, LiBF₄, and other additives are also reported. Iodide salts also promote catalytic methanol carbonylation at low water concentrations. In the case of LiI promoter, lithium acetate is produced in catalytic solutions via the reaction of LiI with methyl acetate. The promotional effects of iodide and acetate on both the model and catalytic systems are rationalized in terms of iodide or acetate coordination to [RhI₂(CO)₂]⁻, to yield five-coordinate Rh^I anions as reactive intermediates for rate-determining reactions with MeI.     

Novel mild synthesis of high-added-value p-hydroxyphenyl acetic acid and 3,4-dihydroxyphenyl acetic acid using the acidic clay/hydrogen peroxide catalytic system

Acid-activated clays KSF and KSF/0 were successfully used in the hydrogen peroxide conversion of phenyl acetic acid to high-added phenolic compounds: p-hydroxyphenyl acetic acid and 3,4-dihydroxyphenyl acetic acid, endowed with a powerful antioxidant capacity. The catalytic conversion enhancement could be correlated to the total surface acidity and the high iron content of the catalysts KSF/0 and KSF, respectively. The synthetic route described here was conducted under mild conditions with very low degree of mineralization and without significant Fe ion leaching observations. The synthesis reaction is operationally simple and could find application for industrial purposes.     

Oxidative interactions of propene with acetic acid on a Pd-zeolite catalyst

The interactions between C₃H₆, AcOH and O₂ were investigated on 1.5 % Pd/TsVM catalysts prepared with and without addition of 15 % AcOK. Three states for surface oxygen on the promoted catalyst were distinguished. Two of them are involved in the oxidation of AcOH and C₃H₆ to CO₂ and H₂O, whereas the adsorbed species of the third type participates in the formation of allyl acetate. The O/Pd ratios for the promoted catalyst fall in the range from 3 to 4, the nonpromoted system is characterized by an O/Pd value of 0.5. IR-spectral data are used to discuss the reaction scheme for the formation of allyl acetate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1721–1726, October, 1993.     

Kinetic studies for the esterification of acetic acid with epichlorohydrin over an anion exchange resin catalyst

The kinetics of the esterification reaction between acetic acid and epichlorohydrin catalysed by Purolite A-520E strong basic anion exchange resin was studied. The effects of certain parameters such as stirring speed, particle diameter, temperature, catalyst amount and molar ratio between reactants were experimentally determined. It was found that the overall reaction rate is intrinsically kinetically controlled. The partial orders of reaction with respect to catalyst, acetic acid and epichlorohydrin were determined. A reaction mechanism is proposed. Based on chromatographic data and taking into account the partial orders of reaction, a more detailed kinetic model is suggested.      

Ab initio study on the mechanism of rhodium-complexcatalyzed carbonylation of methanol to acetic acid

The whole catalytic cycle of the carbonylation of methanol to acetic acid catalyzed by Rh complex is theoretically studied. All structural geometries of reactant, intermediates, transition states and product are optimized at HF/LANL2DZ level under the ECP approximation. The potential energy profiles for elementary reactions of carbonylation are calculated respectively. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The results indicate that the activation energy values of CHin₃I oxidative addition, carbonyl insertion and CH₃COI reductive elimination fundamental steps are 216.03, 128.10 and 126.55 kJ/mol, respectively; and that the CH₃I oxidative addition step is predicted to be the rate-determining one.     

Study on Ni/C catalysts for vapor phase carbonylation of ethanol

Activated carbon-supported Ni catalysts for vapor phase carbonylation of ethanol to propionic acid in the presence of ethyl iodide as promoter were investigated. Under optimum reaction conditions, the conversions of carbon monoxide and ethanol were measured to be 81.4% and 98.4%, respectively, while the selectivity for propionic acid was found to be 98.65%. The catalyst was stable within 48 h on stream. XRD and XPS methods were used to characterize the structures and surface properties of the fresh and tested catalysts. The characterization results indicated that aggregation of nickel particles and formation of nickel iodide on the catalyst surface should be responsible for the deactivation of the catalysts.     

乙烯直接氧化制乙酸催化剂Pd-H3PO4-Cu/Al2O3的研究

以浸渍法制备了一系列不同Pd担载量的Pd-H3PO4-Cu／Al2O3催化剂，采用微型固定床反应器对乙烯直接氧化合成乙酸工艺进行了活性评价．考查了Pd含量、不同助剂的添加、Cu氧化物含量等对催化剂性能的影响并采用TPR，SEM等方法进行了结构表征．实验结果表明：各组分含量为ωpd=3％，ωH3PO4=50％，ωCu=9．5％时，该催化剂具有较理想的活性与选择性．在反应温度为200℃、压力为0．8Mpa、原料气物质的量比为n(C2H4)：n(O2)：n(N2)：n(H2O)=50：6：14：30的条件下，乙烯的转化率与乙酸的选择性分别达3．8％和86．3％。在Pd-H3PO4／Al2O3催化剂中引入Cu的化合物后，不仅提高了催化剂的活性，而且催化剂的稳定性也有显提高．     

Ab initio study on the mechanism of rhodium-complex- catalyzed carbonylation of methanol to acetic acid

The whole catalytic cycle of the carbonylation of methanol to acetic acid catalyzed by Rh complex is theoretically studied. All structural geometries of reactant, intermediates, transition states and product are optimized at HF/LANL2DZ level under the ECP approximation. The potential energy profiles for elementary reactions of carbonylation are calculated respectively. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The results indicate that the activation energy values of CH3I oxidative addition, carbonyl insertion and CH3COI reductive elimination fundamental steps are 216.03, 128.10 and 126.55 kJ/mol, respectively; and that the CH3I oxidative addition step is predicted to be the rate-determining one.