富镧稀土镍-苯浆液体系中液相苯加氢反应动力学研究

The kinetics of liquid-phase hydrogenation of benzene in misch metal nickel-five (MlNi5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi5-C6H6 slurry system is 42.16 kJ.mol-1.     

炭基固体酸催化废油脂合成生物柴油动力学研究(英文)

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller(BET)surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.     

Kinetics of Liquid-Phase Hydrogenation of Benzene in a Metai Hydride Slurry System Formed by MlNi_5 and Benzene

The kinetics of liquid-phase hydrogenation of benzene in misch metai nickel-five (MINi5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic modei obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MINi5-C6H6 slurry system is 42.16kJ·mol-1.     

羧基功能化聚乙二醇负载铂高效催化烯烃硅氢加成反应(英文)

A series of carboxylated long chain polyethylene glycols(abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.     

非均相羰基氧化一步合成碳酸二苯酯的研究(Ⅴ)筛选催化剂及优化合成条件

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the     

An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:An indirect utilization of CO2

The utilization of CO2 as rawmaterial for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate (HDI). In this work, a green route was developed for the synthesis of HDI by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as lowboiling point solvent. Different metal oxide supported catalysts were prepared by incipientwetness impregnation (IWI), PEG-additive (PEG) and deposition precipitation with ammonia evaporation (DP) methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-525(PEG) N Co3O4/ZSM-525(IWI) N Co3O4/ZSM-525(DP). The physicochemical properties of Co3O4/ZSM- 525 catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-525(PEG) catalyst was attributed to its relative surface content of Co3+, surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525(PEG) catalyst, 250 °C temperature, 2.5 h time, 800 ml·min?1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525(PEG) catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-525 catalysts.     

用自热式高温好氧消化工艺预处理肺炎杆菌生物降解动力学研究(英文)

Biodegradation parameters and kinetic characteristics for pre-treating waste strains of Klebsiella pneu-moniae were studied in laboratory scale with an insulated reactor by an innovative technique,autothermal thermo-philic aerobic digestion(ATAD) . Based on an Arrhenius-type equation,an empirical model was developed to corre-late the removal of total suspended solid(TSS) with the initial TSS concentration,influent reaction temperature,aeration rate and stirring rate. The reaction temperatures of the ATAD system could be raised from the ambient temperatures of 25 °C to a maximum temperature of 65 °C. The exponentials for the initial TSS concentration,aeration rate and stirring rate were 1.579,-0.8175 and-0.6549,respectively,and the apparent activation energy was 6.8774 kJ·mol-1. The correlation coefficient for the pre-exponential factor was 0.9223. The TSS removal effi-ciency predicted by the model was validated with an actual test,showing a maximum relative deviation of 10.79%. The new model has a good practicability.     

离子交换树脂催化乳酸与异丁醇及正丁醇酯化反应的动力学研究

The esterification reactions of lactic acid with isobutanol and n-butanol have been studied in the presence of acid ion-exchange resin Weblyst D009. The influences of catalyst loading, stirrer speed, catalyst particle size, initial reactant molar ratio and temperature on the reaction rate have been examined. Experimental kinetic data were correlated by using the Pseudo-homogeneous, Langmuir-Hinshelwood and Eley-Rideal models. Nonideality of the liquid phase was taken into account by using activities instead of molar fractions. The activity coefficients were calculated according to the group contribution method UNIFAC. Provided that the nonideality of the liquid is taken into account, the esterification kinetics of lactic acid with isobutanol and n-butanol catalyzed by the acid ion-exchange resin can be described using all three models with reasonable errors.     

反应条件对钌催化剂和铁催化剂的氨合成性能影响

Activated carbon-supported Ru-based catalyst and A301 iron catalyst were prepared,and the influences of reaction temperature,space velocity,pressure,and H2/N2 ratio on performance of iron catalyst coupled with Ru catalyst in series for ammonia synthesis were investigated.The activity tests were also performed on the single Ru and Fe catalysts as comparison.Results showed that the activity of the Ru catalyst for ammonia synthesis was higher than that of the iron catalyst by 33.5%-37.6% under the reaction conditions:375-400 °C,10 MPa,10000 h-1,H2︰N2 3,and the Ru catalyst also had better thermal stability when treated at 475 °C for 20 h.The outlet ammonia concentration using Fe-Ru catalyst was increased by 45.6%-63.5% than that of the single-iron catalyst at low tem-perature (375-400 °C),and the outlet ammonia concentration increased with increasing Ru catalyst loading.     

Study on extraction kinetics of α-cyclopentylmandelic acid enantiomers with hydroxyethyl-β-cyclodextrin as chiral selector

In this work,the kinetic study on reactive extraction ofα-cyclopentylmandelic acid(α-CPMA)enantiomers was performed in a Lewis cell using hydroxyethyl-β-cyclodextrin(HE-β-CD)as chiral selector.The enantioselective complexation equilibrium between HE-β-CD andα-CPMA enantiomers was studied by phase solubility method.The important process parameters affecting the initial extraction rate were separately studied and the reaction rate equations were deduced.The optimal conditions for kinetic study were as follows:stirring speed of 75 r·min~(-1),interfacial area of 12.56 cm~2,pH of 2.5,initial HE-β-CD concentration of 0.05 mol·L~(-1),initialα-CPMA concentration of 5 mmol·L~(-1),and temperature of 278 K.The reaction has been found to be first order inα-CPMA and second order in HE-β-CD with the forward rate constants of 2.056×10~(-3)m~6·mol~(-2)·s~(-1)and 1.459×10~(-3)m~6·mol~(-2)·s~(-1)for(S)-α-CPMA and(R)-α-CPMA,respectively.The complexation equilibrium constants were evaluated as 61 L·mol~(-1) and 117 L·mol~(-1)for(S)-α-CPMA and(R)-α-CPMA,and the intrinsic enantioselectivity is estimated as 1.92.     

Mechanism and kinetics of esterification of adipic acid and ethylene glycol by tetrabutyl titanate catalyst

An eight-step mechanism of esterification reaction between adipic acid (AA) and ethylene glycol (EG) catalyzed by tetrabutyl titanate [Ti(OBu)₄] was studied in detail. The kinetic data for the esterification reaction between AA and EG catalyzed by tetrabutyl titanate [Ti(OBu)₄] were measured in the temperature range of 403 K-433 K. A second-order kinetic model was established, and the model parameters were obtained through an optimization procedure by minimizing the value differences between the simulated component concentrations in the reaction system with the experimental ones. The results demonstrate that the model is suitable for the esterification reaction between AA and EG catalyzed by tetrabutyl titanate [Ti(OBu)₄]. Furthermore, the esterification reaction rate increases with the increase of reaction temperature, concentration of catalyst and the initial reactant ratio of EG to AA.     

间苯二甲酸丙二醇酯-5-磺酸钠的合成工艺

以间苯二甲酸二甲酯-5-磺酸钠(SIPM)、1,3-丙二醇(1,3-PDO)为原料,采用酯交换法合成了间苯二甲酸丙二醇酯-5-磺酸钠(SIPP),并研究了催化剂种类及浓度、原料配比和反应温度对酯交换反应的影响。结果表明:通过工艺优化,当选择以钛酸四丁酯作为催化剂,其摩尔分数为0.1%(相对原料中SIPM的摩尔分数),1,3-PDO与SIPM的摩尔分数比为10.14∶1,反应温度为173℃时,酯交换反应速率较快且产物色泽良好。     

有机钛酸酯催化制备聚碳酸酯二元醇的工艺研究

以有机钛酸酯（Ti（OBu）4）为催化剂,考察了反应物碳酸二乙酯（DEC）和1,4-丁二醇（BDO）摩尔比、减压时间及温度、精馏柱塔板数等对酯交换反应的影响,制备出了相对分子质量在2000左右的聚碳酸酯二元醇（PCDL）。采用IR和1H—NMR表征了产物PCDL的分子结构,气相色谱法分析了馏分的组成。结果表明,常压阶段馏分为乙醇,与反应物的摩尔比无关;减压阶段,当反应物摩尔比〉1．0时,DEC与乙醇形成共沸物一起被蒸出。当反应物摩尔比≥1．0时,所得产物的相对分子质量能够稳定地控制在2000左右。随着减压反应时间的延长和温度的升高,PCDL的相对分子质量诼渐增大．羟值则逐渐降低。     

脂肪-芳香族共聚酯PBST合成的共酯化工艺

为利用现有的三釜工业聚酯装置合成脂肪-芳香族共聚酯(PBST),对其共酯化动力学及工艺进行了研究。结果表明,共酯化前期主要是丁二酸(SA)的酯化,后期主要是对苯二甲酸(TPA)的酯化,具有与"平行"酯化相接近的动力学特点;采用共酯化-共缩聚工艺合成PBST具有可行性。温度、醇酸物质的量之比(醇酸比)、催化剂用量对共酯化反应有明显的影响。采用钛酸四丁酯-乙酰丙酮镧[TBT-La(acac)3]双组份催化剂(Ti与La的物质的量比为1),在共酯化温度210℃、醇酸比2、催化剂用量0.1%(摩尔分数)的条件下,共酯化2 h、共缩聚1 h,可制得特性粘数1.2 d L/g、色泽良好的PBST共聚酯树脂。     

非均相湿式过氧化氢氧化H-酸废水的研究

为研究催化剂对湿式过氧化氢氧化印染废水效果的影响,采用共沉淀法制备了TiO2-CeO2催化剂,并用浸渍法制备了不同铁负载量的Fe/TiO2-CeO2系列催化剂。以过氧化氢湿式催化氧化法处理COD=10 125 mg/L的H-酸模拟印染废水,结果表明:以TiO2-CeO2催化剂处理水样,当催化剂质量浓度为4 g/L,n(Ti)∶n(Ce)=9∶1,水样初始pH=5,反应温度80℃,反应时间2 h,COD去除率达44.3%;以Fe/TiO2-CeO2处理水样,当催化剂质量浓度为4 g/L,n(Ti)∶n(Ce)=9∶1,w(Fe)=2.0%,在水样初始pH=5,反应温度100℃,反应时间1.5 h的条件下,COD去除率可达86.9%。     

Titanium-based solid catalysts for transesterification of methyl-methacrylate by 1-butanol: the homogeneous catalysis contribution

Titanium-based solid catalysts were prepared according to two different procedures. In order to improve the stability of the SiOTi bond in the titanium grafted silica catalysts, the surface remaining hydroxyl groups were passivated to prevent the titanium leaching by SiOTi bond solvolysis. This was performed by grafting trimethoxy-silane groups on isolated silanols of silica, after or before metal grafting. The synthesised materials were characterised by FT-IR spectroscopy, and their catalytic properties evaluated in the reaction of transesterification of methyl-methacrylate (MMA) with 1-butanol (BuOH) in liquid phase to produce butyl-methacrylate (BuMA). An important titanium leaching (18–35%) was always detected with all the solid catalysts.

Investigation of the behaviour of Ti(OBu)₄ as homogeneous catalyst for very small concentrations of titanium was carried out in order to evaluate the catalytic contribution of the active dissolved species. We demonstrate here that the catalytic activity is mainly due to the homogeneous catalysis.     

Preparation of novel titania supported palladium catalysts for selective hydrogenation of acetylene to ethylene

Novel titania supports have been designed and elaborated with the hydrolysis precipitation method, by adjusting and controlling of the main preparation parameters, such as pH value, adding rate of tetrabutyl titanate Ti(OBu)₄, and calcining temperature of precursor during support preparation. The new titania supported Pd catalysts were prepared and investigated for selective hydrogenation of acetylene to ethylene. The catalyst samples have been characterized by temperature programmed reduction (TPR), XRD and BET techniques. The experimental results indicated that with MgO modification, the improved catalyst (0.5%Pd–MgO/TiO₂) showed better performance of high and stable activity.     

Ti(OBu)_4/TiO_2-Al_2O_3催化合成聚(己二酸-1,4-丁二醇)酯

用Ti(OBu)4/TiO2-Al2O3催化剂合成了聚(己二酸-1,4-丁二醇)酯。Ti(OBu)4/TiO2-Al2O3合成聚(己二酸-1,4-丁二醇)酯的最佳反应条件:催化剂载体焙烧温度为750℃,焙烧时间为4 h,催化剂加入量为1.5%,n(己二酸)/n(1,4-丁二醇)=1∶(1.2~1.3),反应温度为165~170℃,反应时间4 h,在此条件下得到聚酯,酯化率为93.02%,Mn=3 080,Mn/Mw=1.206,催化剂可反复使用5次。     

Alkoxysilane modification of a Ti‐based catalyst system for ethylene dimerization: A step forward in enhancing productivity and selectivity

Alkoxysilanes were used as novel enhancing agents in the Ti‐based catalyst for the highly selective ethylene dimerization to butene‐1. The dimerization of ethylene was carried out using the homogeneous Ti(OBu)₄/THF/TEA/alkoxysilane catalyst system, where Ti(OBu)₄, THF (tetrahydrofuran), TEA (triethylaluminum), and alkoxysilane were used as catalyst, additive, activator, and modifier, respectively. The nature and concentration of alkoxysilanes on the dimerization rate, catalyst yield, by‐products production, and selectivity to butene‐1 were investigated in detail. It was found that the performance of alkoxysilanes assisted with the class of the Ti‐based catalyst system, developed in this work, has been furthered by high productivity and selectivity with respect to the bare catalyst system. It proved that alkoxysilanes could play an excellent improving role in the selective ethylene dimerization process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44615.     

La／B共掺杂Ti02光催化降解苋菜红的研究

采用溶胶-凝胶法制备La/B共掺杂Ti O2催化剂和纯TiO2催化剂。以苋菜红溶液为降解目标物,研究了La/B共掺杂TiO2为催化剂的紫外光催化反应。重点考察了La/B共掺TiO2催化剂的掺杂比、催化剂的煅烧温度、光照时间、催化剂的添加量、溶液初始浓度、溶液p H值对降解率的影响。实验结果表明：单纯只靠紫外光光照或催化剂并不能快速、有效地降解苋菜红溶液。在La和B掺杂比为1：2、催化剂的煅烧温度为600℃、催化剂用量为3.0g/L、溶液p H值为5.5、溶液初始浓度为10mg/L的苋菜红溶液200m L,紫外光光照60min的条件下,La/B共掺杂的TiO2催化剂和纯TiO2催化剂光催化脱色率分别可达99.60%、86.45%,TOC的去除率为60.06%。