甲醇羰基化合成乙酸催化剂的研究

乙酸作为化工生产中重要的原材料之一,主要的生产流程较为复杂,而且,对工艺技术的要求相对较高。并且,在乙酸生产的过程中,需要合理使用添加剂,如果在使用添加剂过程中稍有不慎,就会对最终生产的产品质量造成严重影响。基于此,通过对现阶段催化剂主体金属、助剂金属、载体材料三个方面进行分析,确保能够对现阶段甲醇羰基化合成乙酸的催化剂进行研究,详细介绍不适用碘甲烷促进催化剂的情况下,甲醇羰基化合成乙酸的研究成果,希望能为今后甲醇羰基化合成乙酸催化剂的流程进行优化和创新。

甲醇羰基化制乙酸催化剂的共聚物配体交替结构的理论研究(Ⅱ)

选定单体A为4-乙烯基吡啶，B分别为丙烯酸甲酯和丁烯酮，采用以ASED-MO（含原子对排斥的EHMO法）为基础的结构自动优化的EHTOPT法及Monte-Carlo法对甲醇羰基化制乙酸催化剂的共聚物配体交替结构进行了理论研究．研究了改变温度及单体浓度对共聚物配体交替结构的影响，并比较不同共聚物配体对活性的影响．

乙酸乙烯酯催化剂的工业应用研究

对数批乙烯气相法合成乙酸乙烯酯催化剂的使用数据进行对照和研究。结果表明 ,采用相同载体催化剂的升温特性和选择性相似。每批催化剂都有其最佳的温度段。在最佳的温度段内的催化剂运行时间大约为催化剂寿命的一半 ,且显示出高活性和高选择性。研究表明反应初期升温速率的快慢并不影响整个催化剂的使用寿命 ,加快升温速率是提高催化剂活性和选择性的方法之一。

Pd-Au分布状态对乙酸乙烯催化剂性能的影响

考察活性组份 Pd- Au在载体上呈不同分布状态时对乙烯法乙酸乙烯催化剂动力学参数、反应活性与选择性、活性组份表面形貌以及程序升温还原 TPR等方面的影响。通过对不同催化剂的研究发现 ,表层分布的蛋壳型催化剂其活性组份的表面分散性能更好 ,主反应活化能低 ,副反应活化能高 ,与蛋白型及均匀型催化剂相比 ,活性与选择性更高。TPR结果表明 ,非均匀分布催化剂有两个还原峰 ,而均匀分布催化剂只有一个还原峰。

合成甲苯二氨基甲酸甲酯用负载催化剂的制备

采用等体积浸渍法制备了负载型乙酸锌催化剂。当采用活性炭(AC)为载体,反应温度170℃,反应时间3 h时,催化碳酸二甲酯(DMC)与2,4-二氨基甲苯(TDA)反应制备2,4-甲苯二氨基甲酸甲酯(TDC)的效果最好,TDC的产率达86％。用TiO2对活性炭表面进行了改性,制备了TiO2包覆活性炭负载乙酸锌催化剂,170℃下反应1 h,TDC的产率较使用未改性载体的催化剂提高7％。TiO2的生成方式不同,对催化剂活性影响很大。采用XRD、XPS对各种催化剂进行表征。结果表明,造成活性炭负载乙酸锌催化剂失活及其与表面改性载体负载催化剂活性差异的原因是由于表面Zn所处的化学环境发生了改变,从而影响了TDC合成反应的催化活性,即随着Zn2p结合能的增加,Zn周围电子云密度降低,催化剂活性降低。

从苯乙酸废催化剂中回收钴

羰基化法生产苯乙酸工艺中生成的废催化剂,含有大量有价值的钴元素。介绍一种从废催化剂中,采用黄钠铁矾沉淀法将铁除去,用萃取法将锰、钻分离,制备得到含结晶水的氯化钴,钴的回收率达90％以上。

催化剂用量对聚苯醚改性氰酸酯树脂固化及性能的影响

以乙酰丙酮钴为催化剂,对质量比为1:1的低相对分子质量双端羟基聚苯醚与双酚A型氰酸酯树脂进行热固化反应,研究了催化剂质量分数(0~0.05%)对改性树脂固化及性能的影响。结果表明:改性树脂的凝胶时间随着催化剂含量的增加或温度的升高而缩短,当温度高于180℃时,凝胶时间随温度的变化不明显;固化反应温度随着催化剂含量的增加而降低;催化剂含量越高,改性树脂的初始储能模量越大,交联密度越大,玻璃化温度越高;随着催化剂含量的增加,改性树脂的介电常数和介电损耗呈先降低后升高的趋势,吸水率降低;当催化剂质量分数为0.03%时,改性树脂的固化反应温度为160℃,玻璃化温度为210℃,吸水率为0.48%,介电常数为3.51,介电损耗为5.20×10-3,性能最佳。

四氯化锡催化乙酸酯的合成研究

四氯化锡取代浓硫酸作为酯化催化剂 ,在乙酸异戊酯、乙酸正戊酯、乙酸正丁酯的合成中显示出很好的催化效果 ,反应 1h产率都可达 90 %以上。而催化乙酸仲丁酯的合成效果不理想 ,当酸、醇和催化剂的摩尔比为 1∶0 8∶0 0 1时 ,130℃反应 2h产率仅达 6 0 8%。

负载型乙酸锌催化1,2-丙二醇与二氧化碳合成碳酸丙烯酯反应性能

采用浸渍法制备了负载量15%的Zn(OAc)2/SiO2催化剂,并对其催化CO2与1,2-丙二醇(PG)合成碳酸丙烯酯(PC)的反应性能进行了研究。在反应温度160℃、反应时间4h、CO2初始压力3.0MPa、催化剂用量2.5%、乙腈/PG摩尔比为1.8∶1条件下,PG转化率为18.2%,PC收率为10.2%,选择性为56.0%。通过GC-MS定性分析确定主要副产物为乙酰胺、1,2-丙二醇-2-乙酸酯和1,2-丙二醇二乙酸酯。XRD和BET分析和活性评价表明:Zn(OAc)2/SiO2存在一定程度的活性组分流失。

相转移催化合成2,4-二氯苯氧乙酸新工艺研究

以2,4-二氯苯酚和氯乙酸为原料,在碳酸钾作用下筛选相转移催化剂(四丁基溴化铵、四乙基溴化铵和PEG-600)进行醚化反应,制备2,4-二氯苯氧乙酸。所获得的最佳工艺条件是:催化剂选PEG-600/KI为最佳,二氯苯酚和氯乙酸原料物质的量比1∶2,相转移催化剂PEG-600用量为二氯苯酚的6%,KI用量为二氯苯酚量的10%。在此合成条件下,2,4-二氯苯氧乙酸收率达94.2%。

KOAc/NaY催化DMC合成邻甲基苯甲醚稳定性考察

通过连续流动固定床反应器考察了真空浸渍制备的负载型固体碱催化剂KOAc/NaY(2mmol/g)的稳定性。结果表明,该催化剂在30h内具有较好的稳定性,但随后活性逐渐下降;热重分析表明催化剂在450K～600K的温度范围内有较好的热稳定性;X射线衍射(XRD)、CO2程序升温脱附(CO2-TPD)、BET和扫描电镜(SEM)等表征结果表明,碳酸二甲酯(DMC)在高温下的分解造成的积炭堵塞催化剂的孔道导致催化剂表面碱中心大量减少是其活性降低的原因。

离子液体在碳酸丙烯酯合成中的作用

简要阐述了离子液体的概念和用途。将四氟硼酸-1-甲基-3-丁基咪唑离子液体[Bmim]BF4应用于碳酸丙烯酯的合成,以此来探讨离子液体在合成中的作用。研究结果表明,在碳酸丙烯酯的合成中用负载型乙酸锌作催化剂有良好的催化活性,结合使用离子液体[Bmim]BF4作溶剂,不仅可以得到很好的产率,而且与传统方法相比,具有两个明显优势:离子液体在合成碳酸丙烯酯的工艺中起了一定的促进作用,并且经过减压蒸馏,离子液体很容易的分离出来,可以重复使用;离子液体不易挥发,是很好的绿色溶剂。

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Catalytic Esterification of Methyl Alcohol with Acetic Acid

Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reaction rate increased with increase in catalyst concentration and reaction temperature, but decreased with an increase in water concentration. Stirrer speed had virtually no effect on the rate under the experimental conditions. The rate data were correlated with a second-order kinetic model based on homogeneous reaction. The apparent activation energy was found to be 22.9kJ mol-1 for the formation of methyl acetate. The methyl acetate production was carried out as batch and continuous in a packed bed reactive distillation column with high purity methyl acetate produced.

Recovery of Dilute Acetic Acid by Catalytic Distillation Using NKC-9 as Catalyst

The reaction kinetics of dilute acetic acid with methanol using NKC-9 as catalyst was studied at temperatures of 308 K, 318 K, 323 K, 328 K. The kinetic model based on Langmuir-Hinshelwood rate model was derived and the activation energy was 6.13 × 10^4 kJ/kmol. The experiment of recovery of dilute acetic acid was conducted in a packed bed catalytic distillation column. The optireal process parameters and operational conditions determined to make up to 85.9% conversion of acetic acid are as follows：the height of catalyst bed is 1 100 mm, reflux ratio is 4： 1, and the ratio of methanol to acetic acid is 2： 1. The method can be used as a guide in industrial scale recovery of 15% 30% dilute acetic acid.

SYNTHESIS AND PROPERTIES OF SULFHYDRYL CHITOSAN

A new adsorbent for heavy metal ions, sulfhydryl chitosan (S chitosan), was produced by treatment of chitosan with sulhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confirmed by elemental analysis and FT IR spectra analysis. The adsorption properties of sulfhydryl chitosan for Cu(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Cr(Ⅲ) and Ni(Ⅱ) were investigated, and the effect of pH value on adsorption, adsorption kinetics, and selective adsorption was examined. It was shown that S chitosan has good adsorption for Pb(Ⅱ), Cu(Ⅱ) and Cd(Ⅱ) like chitosan, is also insoluble in acid solution; has good adsorption kinetic properties for heavy metal ions; and can be used in acid solution. The adsorption capacities of S chitosan can be affected by media acidity. The adsorbed Cu(Ⅱ) Cd(Ⅱ)and Pb(Ⅱ) could be eluted by diluted chlorhydric acid.

Enhanced catalytic performance of Cu-and/or Mn-loaded Fe-Sep catalysts for the oxidation of CO and ethyl acetate

The Fe-modi fied sepiolite-supported Mn–Cu mixed oxide(Cux Mny/Fe-Sep) catalysts were prepared using the co-precipitation method.These materials were characterized by means of the XRD,N_2 adsorption–desorption,XPS,H_2-TPR,and O_2-TPD techniques,and their catalytic activities for CO and ethyl acetate oxidation were evaluated.The results show that catalytic activities of the Cux Mny/Fe-Sep samples were higher than those of the Cu1/Fe-Sep and Mn2/Fe-Sep samples,and the Mn/Cu molar ratio had a distinct in fluence on catalytic activity of the sample.Among the Cux Mny/Fe-Sep and Cu1Mn2/Sep samples,Cu1Mn2/Fe-Sep performed the best for CO and ethyl acetate oxidation,showing the highest reaction rate and the lowest T50 and T90 of 4.4×10^(-6) mmol·g-1·s-1,110,and 140 °C for CO oxidation,and 1.9×10^(-6) mmol·g-1·s-1,170,and210 °C for ethyl acetate oxidation,respectively.Moreover,the Cu1Mn2/Fe-Sep sample possessed the best lowtemperature reducibility and the lowest temperature of oxygen desorption as well as the highest surface Mn^(4+)/Mn^(3+) and Cu^(2+)/CuO atomic ratios.It is concluded that factors,such as the strong interaction between the Cu or Mn and the Fe-Sep support,good low-temperature reducibility,and good mobility of chemisorbed oxygen species,might account for the excellent catalytic activity of Cu1Mn2/Fe-Sep.

In_2O_3-modified Cu/SiO_2 as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol

A series of indium oxide‐modified Cu/SiO2catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation.In‐Cu/SiO2catalyst containing1.0wt%In2O3exhibited the best catalytic activity and stability.The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO2increased the copper dispersion,diminished the copper crystallite size,and enriched the surface Cu+concentration.Furthermore,the Cu/SiO2catalyst gradually deactivated during the stability test,which was mainly attributed to copper sintering and the valence change in surface copper species.In contrast,indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

An efficient and reusable bimetallic Ni_3Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid toγ-valerolactone

Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity,selectivity and stability in catalytical conversion.Herein,we report a facile one‐pot carbothermal route to in‐situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst.The X‐ray diffraction,transmission electron microscopy,X‐ray photoelectron spectroscopy and N2 adsorption‐description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in carbon matrix.The as‐prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid(LA)toγ‐valerolactone(GVL)via both direct hydrogenation(DH)and transfer hydrogenation(TH).In DH of LA,the bimetallic catalyst achieved a 93.8%LA conversion efficiency with a 95.5%GVL selectivity and 38.2 mmol g–1 h–1 GVL productivity(under 130°C,2MPa H2 within 2 h),which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts,respectively.In addition,the identical catalyst displayed a full conversion of LA with almost 100%GVL selectivity and 167.1 mmol g–1 h–1 GVL productivity at 180°C within 0.5 h in TH of LA.Under optimal reaction conditions,the DH and TH catalytic performance of 500‐Ni3Fe NPs@C(3:1)catalyst for converting LA to GVL is comparable to the state‐of‐the‐art noble‐based catalysts.The demonstrated capability of bimetallic catalyst design approach to introduce dual‐catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.

Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation

A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source.Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites.The special complexing capability of EDTA^(2–)plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process,thus leading to a uniform distribution of Mo in the MFI framework.In addition,a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites.The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H_(2)O_(2)as the oxidant.The composition-optimized catalyst,Mo-MFI-50,efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion(93%)and epoxide selectivity(82%)at 75℃after 9 h of reaction.Moreover,the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.