异丁烯制备甲基丙烯醛催化剂的研究进展

异丁烯选择氧化制备甲基丙烯醛是异丁烯法制备甲基丙烯酸甲酯的关键步骤.本文综述了异丁烯选择氧化生成甲基丙烯醛催化剂,其中包括复合氧化物催化剂和杂多化合物催化剂等的研究现状,讨论了在Mo-Bi催化剂上异丁烯选择氧化生成甲基丙烯醛的反应机理.     

甲基丙烯醛氧化酯化制备甲基丙烯酸甲酯

引言 甲基丙烯酸甲酯（MMA）是重要的有机化工原料．目前主要采用丙酮氰醇法（ACH法）生产,该法存在原料剧毒、使用高腐蚀性硫酸、原子利用率低等缺点．异丁烯（IB）氧化法以其原料广泛、过程无废物排放、原子利用率高等优点,被工公认为生产MMA的清洁工艺技术．     

甲基丙烯醛一步法制甲基丙烯酸甲酯催化剂研究进展

介绍了目前生产甲基丙烯酸甲酯(MMA)的几种工业化合成路线,其中甲基丙烯醛直接氧化酯化法因其环境友好而得到更多的关注。列举了甲基丙烯醛一步法制备MMA的几类催化剂,包括其制备方法、催化性能、使用条件等,指出钯系催化剂的研制将成为今后的主要发展方向,在改进催化剂性能的同时更应加强基础理论方面的研究。     

AN OVERVIEW OF HYDROPHOBIC CATALYST OVER STYRENE-DIVINYLBENZENE COPOLYMER

Recently developed catalytic processes with hydrophobic catalysts supported over styrene-divinylbenzene copolymer (SDB) were reviewed. Applications of such catalytic processes in commercial chemicals production and environmental management were examined in great detail. Based on this research work, the feasibility of hydrophobic catalysts over SDB utilized in the synthesis of methyl methacrylate (MMA) from methacrolein (MAL) in molecular O₂ was evaluated.     

MgO-SBA-15 Supported Pd-Pb Catalysts for Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate☆

Novel MgO–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein (MAL) with methanol to methyl methacrylate (MMA). The MgO–SBA-15 supports were synthesized with different...     

甲基丙烯酸甲酯的绿色催化合成进展

合成甲基丙烯酸甲酯(MMA)的传统方法丙酮氰醇法(ACH法)存在着原料毒性大、副反应 多,工艺流程复杂、原子利用率低的缺点。绿色催化合成MMA的方法主要有改进的ACH法、异丁烯 法、丙炔法、丙烯法、甲基丙烯醛氧化酯化法等,这些方法均符合绿色化学的要求。笔者对这几种绿色合 成工艺以及所用催化剂的研究概况进行了综述。     

异丁烯为原料制备甲基丙烯酸甲酯的催化剂

The catalysts used for manufacturing methyl methacrylate (MMA) by two-step conversion of isobutylene via methacrolein (MAID were studied. The selective oxidation of isobutylene to MAL was carried out in a fixed-bed flow microreactor using a series of Mo-Bi-containing catalysts and the oxidative esterification of MAL to MMA was carried out in a slurry-bed reactor using a series of palladiumcontaining catalysts. By means of BET and XPS, the properties of the catalysts were characterized. It was found that the performance of Mo-Bi-Co-Fe-Ce-O catalyst was improved distinctly when Cs was added for the selective oxidation of isobutylene to MAL, and the Pd5Bi2PbFe/CaCO3 catalyst with the loading sequence of Pd, Pb and Bi, Fe showed the best performance for the oxidative esterification of MAL to MMA.     

Preparation and morphology study of microporous poly(HEMA–MMA) particles

Porous poly(2‐hydroxyethyl methacrylate‐methyl methacrylate) particles crosslinked with ethylene glycol dimethacrylate were synthesized by free‐radical suspension copolymerization in an aqueous phase initiated by an oil‐soluble initiator, 2,2‐azobisisobutyronitrile. 1‐octanol was used as a pore forming agent (porogen). The porous structures, the particle morphology, and the swelling capacity of the resultant polymer in water at room temperature were studied at different crosslink densities and under various porogen concentrations. The analysis via Scanning Electronic Microscopy (SEM) indicated that permanent pores remained in the dried polymeric particles prepared in the presence of the porogen at certain crosslink densities. According to the studies via the SEM pictures and the pore size distributions, higher porogen concentration promotes the formation of more pores, and higher crosslink density results in narrower pore size distribution. The swelling capacity of the particles in water at room temperature decreases with an increase in the crosslink density, and the existence of the highly porous structures enhances the swelling capacity of the porous particles of poly(2‐hydroxyethyl methacrylate‐methyl methacrylate). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 707–715, 2007     

甲基丙烯醛氧化酯化整体式催化剂制备及评价

针对甲基丙烯醛氧化酯化浆态床反应过程中颗粒催化剂易破碎、活性组分易流失等缺点,采用浸渍法在电沉积到泡沫镍合金表面的氧化铝-氧化镁涂层上负载活性组分,制备了Pd_xPb_y/Al₂O₃-MgO/泡沫镍合金整体式催化剂。研究分析了铝溶胶含量、Al₂O₃含量、沉积电压和沉积时间等条件对涂层负载的影响,并对载体和催化剂进行了BET、XRD、SEM、ICP和TEM表征和气-液-固固定床反应性能评价。结果表明,当铝溶胶的体积含量为35%～40%,Al₂O₃含量为25～30 g·L^-1,沉积电压为10～12 V,沉积时间为8～12 min,搅拌速度为200～250 r·min^-1时可得到稳定的涂层。在温度为80℃、压力为0.3 MPa、醇醛摩尔比为8:1、液相物料进口流量为0.5 ml·min^-1、氧气进口流量为35 ml·min^-1、反应时间为2 h条件下,整体式催化剂上甲基丙烯醛转化率最高为76.1%,甲基丙烯酸甲酯选择性为81.2%。研究结果可为甲基丙烯醛氧化酯化制甲基丙烯酸甲酯的生产工艺优化提供科学数据。     

甲基丙烯醛氧化酯化制甲基丙烯酸甲酯

制备了用于甲基丙烯醛(MAL)一步氧化酯化为甲基丙烯酸甲酯(MMA)的新型催化剂;考察了反应温度、催化剂在反应体系中的质量分数对MAL转化率和产物选择性的影响;将离子液体[bmim]PF6用于该反应中,不仅提高了产物的选择性,还能有效防止产物的聚合。反应温度θ=50℃,催化剂在反应体系中质量分数为2 4%,pH=10 5,O2流量6mL/min,反应时间6h时,在反应体系中添加1mL离子液体[bmim]PF6,MAL的转化率为96 2%,MMA单体的选择性可达98 7%。     

纳米CeO_2载体对Au-Pd催化剂性能的影响

采用十六胺和不同铈前驱体(硝酸铈铵或硝酸亚铈)分别合成了纳米CeO2(H4和H3),考察了纳米CeO2载体的织构性质对Au-Pd催化剂甲醇部分氧化制氢(POM)性能的影响,用HRTEM、N2吸附、XRD和TPR等对样品进行了表征。结果表明,铈前驱体对载体的性能有较大的影响,以硝酸铈铵为前驱体所制H4载体具有较小的粒径(约5 nm)和平均孔径(5.3 nm)、较大的比表面积(243 m2/g),而硝酸亚铈所制H3载体具有较大的平均孔径(7.9 nm)。POM结果表明,纳米CeO2负载的Au-Pd催化剂具有较好的催化性能,300℃时,Au-Pd/H3的活性和H2选择性分别达100%和59.7%。低温时催化剂的活性和H2选择性为:Au-Pd/H3>Au-Pd/H4,而高温时顺序相反,这是由于低温时催化剂的孔径对反应物和产物的扩散影响较大,高温时催化剂的比表面积和活性组分分散度起主要作用。     

复合氧化物催化剂上异丁烯选择氧化的研究进展

异丁烯选择氧化制备甲基丙烯醛是异丁烯法制备甲基丙烯酸甲酯的关键步骤. 本工作系统地综述了异丁烯选择氧化制备甲基丙烯醛复合氧化物催化剂的组成、微观结构、助剂作用以及催化机理的研究进展,认为具有实际应用意义的催化剂组成元素众多,各组分在立体结构和基元反应上高度协调,共同促进了催化剂的高效和稳定. 因此,多组分间的协同作用、活性位的形成机制及各种添加剂实际作用的进一步深入研究对改进催化反应性能具有重要意义.     

甲基丙烯醛一步氧化酯化制备甲基丙烯酸甲酯

制备了用于甲基丙烯醛(MAL)一步氧化酯化为甲基丙烯酸甲酯(MMA)的新型催化剂. 在常压和连续搅拌的条件下,考察了反应条件对MAL转化率和MMA选择性的影响,并对反应动力学进行了初步研究. 实验结果表明：当反应温度50℃、氧气流速6 mL/min、甲醇与甲基丙烯醛的摩尔比75、催化剂在反应物中含量2.4%、反应时间60 min时,MAL的转化率可达99.4%, MMA的选择性为95.7%.     

Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods

Porous ceramics of Y₂O₃-stabilized ZrO₂ (YSZ) were prepared by tape-casting methods using both pyrolyzable pore formers and NiO followed by acid leaching. The porosity of YSZ wafers increased in a regular manner with the mass of graphite or polymethyl methacrylate (PMMA) to between 60% and 75% porosity. SEM indicated that the shape of the pores in the final ceramic was related to the shape of the pore formers, so that the pore size and microstructure of YSZ wafers could be controlled by the choice of pore former. Dilatometry measurements showed that measurable shrinkage started at 1300 K, and a total shrinkage of 26% was observed, independent of the amount or type of pore former used. Temperature-programmed oxidation (TPO) measurements on the green tapes demonstrated that the binders and dispersants were combusted between 550 and 750 K, that PMMA decomposed to methyl methacrylate between 500 and 700 K, and that graphite combusted above 900 K. The porosity of YSZ ceramics prepared by acid leaching of nickel from NiO–YSZ, with 50 wt% NiO, was studied as a function of NiO and YSZ particle size. Significant changes in pore dimension were found when NiO particle size was changed.     

Co-Mo-Ni-W/γ-Al2O3柴油加氢精制催化剂的研制

采用浸渍法制备Co-Mo-Ni-W/γ-Al₂O₃柴油加氢精制催化剂,考察了扩孔剂及焙烧温度对载体物化性能的影响和浸渍液的配制方法对其稳定性的影响。并考察了催化剂第1次浸渍后的焙烧温度以及3种催化剂的加氢精制活性。实验结果表明,在载体制备过程中适量加入扩孔剂,可得到孔分布集中、比表面积和孔容适中的载体;载体于550 ℃焙烧时,可制备出具有良好的孔分布和较高机械强度及较大的比表面积的催化剂;在低温条件下配制的浸渍液具有良好的稳定性和可溶性;催化剂第1次浸渍后于450 ℃条件下焙烧,可使催化剂中的各活性组分均匀分布于载体上; 通过催化剂的加氢活性评价,3种催化剂均具有良好的柴油加氢精制活性和工业应用前景。     

Dependence of morphological changes of polymer particles on hydrophobic/hydrophilic additives

Fairly uniform microspheres of poly(styrene‐co‐methyl methacrylate) were prepared by employing a microporous glass membrane [Shirasu porous glass (SPG)]. The single‐step SPG emulsification, the emulsion composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor, was then transferred to a reactor, and subsequent suspension polymerization followed. The droplets obtained were polymerized at 75°C under a nitrogen atmosphere for 24 h. The uniform poly(styrene‐co‐methyl methacrylate) microspheres with diameters ranging from 7 to 14 μm and a narrow particle‐size distribution with a coefficient of variation close to 10% were prepared by using SPG membrane with a pore size of 1.42 μm. The effects of the crosslinking agent and hydrophobic additives on the particle size, particle‐size distribution, and morphologies were investigated. It was found that the particle size decreased with a narrower size distribution when the additives were changed from long‐chain alkanes to long‐chain alcohols and long‐chain esters, respectively. Various microspheres with different morphologies were obtained, depending on the composition of the oil phase. The spherical poly(styrene‐co‐methyl methacrylate) particles without phase separation were obtained when using an adequate amount of the crosslinking agent and methyl palmitate as an additive. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1013–1028, 2000     

Effect of polymer structure on the morphologies and dielectric properties of nanoporous polyimide films

Low dielectric constant polyimide (PI) films have potential applications in integrated circuit. In this study, poly(methyl methacrylate), poly(ethylene oxide), and polystyrene as thermally labile materials were used as templates to generate PI films with nanopores by first mixing the polymer templates with the precursor of PI, poly(amic acid), followed by imidization of poly(amic acid) together with degradation of the polymer templates. The sizes of the formed pores, the thermal and dielectric constant of the nanofoamed PI films were studied and compared in detail. It is concluded that the dielectric constant of PI films using poly(ethylene oxide) as pore template is more stable because of the formation of uniform pores which is from the great accordance of imidization temperature of poly(amic acid) with the degradation temperature of poly(ethylene oxide). But that using poly(methyl methacrylate) as pore template is frequency dependent as the influence of inhomogeneous pores and PMMA residue from incompletely degradation of poly(methyl methacrylate). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41480.     

Effect of pore size on the performance of mesoporous material supported chiral Mn(III) salen complex for the epoxidation of unfunctionalized olefins

A series of mesoporous MCM-41 and MCM-48 materials with different pore sizes were synthesized and used as supports to immobilize chiral Mn(III) salen complex. The heterogeneous catalysts were characterized by XRD, FT-IR, DR UV–vis, and N₂ sorption, and the results indicated the successful immobilization of chiral Mn(III) salen complex. The confinement effect of pore size on the catalytic performance of the heterogeneous catalysts was studied for the asymmetric epoxidation of unfunctionalized olefins with m-chloroperoxybenzoic acid as an oxidant. It was found that the conversions and enantiomeric excess (ee) values were closely correlated with the pore sizes of parent supports. The catalysts immobilized on the large-pore mesoporous supports exhibited higher conversions, and for the catalysts immobilized on MCM-41 materials, the ee values improved with increasing pore size. However, for the MCM-48 material-supported catalysts, the compatible pore size of the support with the substrate was beneficial for obtaining higher enantioselectivity in olefin epoxidation.     

选择性氧化制备甲基丙烯醛催化剂及工艺条件优化

采用共沉淀法制备Mo-V-Bi系复合氧化物催化剂,并将其应用于叔丁醇选择性氧化制甲基丙烯醛反应。采用XRD及BET考察焙烧温度对催化剂性能的影响。结果表明,焙烧温度会影响催化剂的比表面积和孔结构,进而影响催化剂性能。低温焙烧的催化剂会形成一种Mo O3的物相,这种物相会抑制产物甲基丙烯醛选择性,而高温有利于催化剂Fe Mo O4、Bi Mo O6物相的生成,两物相的增加有利于提高甲基丙烯醛选择性。对筛选的最优催化剂进行长周期评价,叔丁醇转化率接近100%,甲基丙烯醛选择性为87.1%,达到了良好的工业效果。     

氧化铝煅烧温度对丙烷脱氢催化剂性能的影响

针对丙烷脱氢催化剂用氧化铝作为载体时存在的孔结构与表面酸性调节的问题,开发了以海藻酸盐为黏合剂,采用挤出滚圆方法,制备了大孔球形氧化铝颗粒,并以此作为载体负载Pt、Sn活性组分制备了丙烷脱氢催化剂,研究了氧化铝载体煅烧温度对催化剂晶型、孔道结构、表面酸性、H2还原性能与丙烷脱氢性能的影响.实验结果表明:随氧化铝载体煅烧...