仿酶催化木素降解研究进展

综述了近年来仿酶催化木素降解的研究进展,重点介绍了木素降解的机理和产物形成做了概述总结,并对仿酶催化剂进行了介绍归纳,包括Fenton催化剂、Salen配合物、金属卟啉配合物和GIF体系等。简要分析了木素降解的机理,并给出采用不同仿酶催化剂降解木素的代表性案例。鉴于传统的木素降解方法条件较为苛刻且不符合环保要求,为了使木素在温和环保的条件中降解,文中专门对仿酶催化剂的处理条件作了较详细的介绍。最后展望了仿酶催化木素降解的发展前景。对木素降解研究工作具有一定参考价值。     

响应面法优化Fe_3O_4/NiO催化聚对苯二甲酸乙二醇酯醇解

以Fe_3O_4为磁性基质,采用液相共沉淀法制备磁性固体碱催化剂Fe_3O_4/Ni O,并用于聚对苯二甲酸乙二醇酯(PET)的醇解反应。以催化醇解反应得到的对苯二甲酸二乙二醇酯(BHET)回收率为指标,通过响应面法优化得到催化剂合成的最佳条件,即前驱体n(Fe_3O_4)∶n[Ni(AC)_2]=1∶3.94,反应时间1.67 h,催化剂煅烧时间2.01 h,煅烧温度600℃。以最优条件制备的催化剂在乙二醇介质,反应温度195℃,降解反应时间4 h,催化剂用量为PET质量的2.0%的条件下进行醇解反应,BHET回收率达到81.47%。采用XRD、BET和SEM对催化剂进行表征,结果表明:催化剂具有片状结构,比表面积较大,降解产物是BHET。     

磁性催化剂的研究进展

磁性催化剂是一种新型的催化剂,它不仅具有催化特性,还具有独特的磁响应性。磁性催化剂在外加磁场的作用下能与反应物和产物分离,实现了催化剂的回收与重复利用,在工业生产得以连续化的同时,也降低了生产的成本。本文简单介绍了磁性催化剂性质与分类,综述了磁性催化剂在不同领域的应用,探讨了影响磁回收率的因素,和未来的磁性催化剂的发展方向。     

立方块型Fe_3O_4表面修饰TiO_2磁性复合光催化剂的制备及光降解性能研究

以氯化铁为起始原料,制备得到了高磁性的立方块型纳米四氧化三铁,然后对所得到的四氧化三铁表面用二氧化钛进行修饰,优化条件得到TiO_2/Fe_3O_4复合催化剂,并通过透射电镜、XRD、紫外-可见光分光光度计和物性测试系统等仪器对所得到的催化剂进行详细地表征。优化得到的复合物催化剂对罗丹明B紫外光下的降解效率达到85%,在太阳光下降解率可达68%,且催化剂可以方便地经磁性分离回收。     

中北大学磁载钛硅基催化剂制备成功

正中北大学在磁载钛硅基催化剂制备及磁分离反应方面的研究取得突破,开发出具有催化活性且可磁分离功能的复合催化剂,研制了磁分离反应一体化装置,解决了细小催化剂的固液分离难题,并减少了后序固液分离装置和相关配套设施。中北大学该项研究可用于磁性钛硅分子筛催化环己酮氨肟化制环己酮肟、磁性氧化钛光催化降解有机废水、磁性铜硅催化剂催化糠醛加氢制糠醇和磁性固体酸催化烯烃制     

磁性微胶囊负载铜配合物的制备及其对染料的催化降解性能

通过化学乳化交联法制备出球状的负载铜配合物C_(18)H_(16)N_2O_4CuCl_2·H_2O(CuL)的磁性微胶囊,采用光学显微镜、扫描电镜、透射电镜表征微胶囊的结构;采用电感耦合等离子发射光谱仪检测了微胶囊中铜配合物的负载量;通过紫外可见光谱扫描检测磁性微胶囊对过氧化氢降解活性染料KN-R的催化活性;通过缓释实验来检测铜配合物在微胶囊中的负载稳定性。研究表明,负载铜配合物的磁性微胶囊对活性染料KN-R具有较高的催化降解活性,且催化降解循环次数可以达到5次以上。     

MnFe2O4的合成及其非均相Fenton法降解工业废水的性能

采用水热合成法制备了尖晶石铁氧体MnFe₂O₄磁性纳米催化剂,通过XRD、SEM、TEM、BET、TG/DTA等对其物相结构进行表征,并通过降解亚甲基蓝、罗丹明B和苯酚作为探针反应行了活性测试。结果表明,在反应溶液体系pH=7、催化剂加入量0.5g/L、过氧化氢浓度1.25mmol/L、反应温度20℃时,亚甲基蓝、罗丹明B、苯酚的降解率在130min内分别达到了97.34%、94.48%、16.63%。反应体系引入超声辅助后50min内亚甲基蓝降解率为95.61%,高于单一非均相Fenton催化体系50min内对其80%的降解率,表明超声空化与非均相Fenton反应之间具有协同效应,有助于提高反应物降解率。活性中心鉴定表明高价铁氧体为染料降解的主要活性中心,而羟基自由基则是苯酚降解的主要活性中心。循环测试实验表明,催化剂活性高、稳定性高、可再生、不易溶出失活。     

磁性碳纳米管基催化剂TiO2/CNTs光降解氨比西林抗生素水溶液的研究

以磁性多壁碳纳米管(MWCNTs)为载体,钛酸四丁酯为钛源,采用表面溶胶包覆-醇热联用法制备TiO2/CNTs复合管光催化剂。以氨比西林溶液的降解为目标反应,考察了催化剂在紫外灯下的催化活性。结果表明,二氧化钛在MWCNTs表面分布均匀,提高了对光的吸收和利用,因此TiO2/MWCNTs复合光催化剂表现出较高的光催化活性,催化剂的活性随着pH值的增大而增大,并且磁性催化剂易从降解后的溶液中分离。     

纳米二氧化钛光催化应用条件

采用自制的纳米TiO2粉体作光催化剂,以甲基橙模拟有机污染物,研究了光照时间、催化剂用量、被降解物浓度、系统酸度等对其光催化性能的影响。结果表明：降解某一物质时,不同光催化剂,有一个降解速率最大的时间;在每一个降解的过程中催化剂有一个合适的用量;在弱酸性条件（pH=3）,甲基橙降解效果比较好;被降解物的浓度选取合适,降解率最高。     

纳米二氧化钛光催化降解的影响因素

采用自制的纳米TiO_2粉体作光催化剂,以甲基橙模拟有机污染物,研究了光照时间、催化剂用量、被降解物浓度、系统酸度等对其光催化性能的影响。结果表明:降解某一物质时,不同光催化剂,有一个降解速率最大的时间;在每一个降解的过程中催化剂有一个合适的用量;在弱酸性条件(pH=3),甲基橙降解效果比较好;被降解物的浓度选取合适,降解率最高。     

过渡金属Mn取代多金属氧簇催化醇解废旧PET

合成了一种具有三明治结构的过渡金属Mn取代的多金属氧簇(POMs)催化剂Na12[WZnMn2(H2O)2(ZnW9O34)2],用于催化聚对苯二甲酸乙二醇酯(PET)的醇解过程,对反应温度、反应时间和催化剂量等实验条件进行了优化。结果表明,在催化剂量为PET质量的1.0%、质量比PET/EG(乙二醇)为1:4及190℃的条件下反应80 min,PET降解率可达100%,对苯二甲酸乙二醇酯(BHET)的收率达84.42%。     

Solubility determination and thermodynamic modeling of bis-2-hydroxyethyl terephthalate (BHET) in different solvents

Studies on the degradation process of waste polyethylene terephthalate (PET) have become increasingly mature, but there are relatively few studies on the separation of degradation products. The products contain many components and the separation of which is difficult. Therefore, the study on phase equilibrium thermodynamics of bis-2-hydroxyethyl terephthalate (BHET) is of great theoretical significance and practical value to provide basic data for the BHET crystallization separation. In this work, the degraded products were purified and characterized. The solubility of BHET in methanol, ethanol, ethylene glycol, water and the mixture of ethylene glycol + water were determined by static method. The experimental results were correlated with different models, such as ideal solution (IS) model, λh equation, Apelblat equation and NRTL model. Based on the van't Hoff equation, the mixing Gibbs energy, enthalpy and entropy were calculated. From this work, the basic data which can be used to guide the crystallization process of BHET were obtained, including solubility data, correlation model and thermodynamic properties.     

聚酯废丝的化学回收研究

使用乙二醇(EG)对有色聚酯(PET)废料解聚,经分离提纯,得到对苯二甲酸二乙二醇酯(BHET)。研究了物料比、反应温度、反应时间、催化剂对醇解率的影响。结果表明,在m(乙二醇)∶m(PET)=2∶1,反应温度196℃,反应时间3 h,催化剂用量为PET质量的0.5%条件下,聚酯解聚很彻底,产物羟值可达434 mg/g以上,主要成分是BHET单体及其低聚物。并通过IR,DSC,HPLC验证了产物的组成,BHET单体纯度可达96.457%。     

Studies of glycolysis of poly(ethylene terephthalate) recycled from postconsumer soft‐drink bottles. I. Influences of glycolysis conditions

The glycolysis of recycled poly(ethylene terephthalate) flakes by ethylene glycol (EG) is investigated. Bis‐2‐hydroxyethyl terephthalate (BHET) and oligomers are predominately glycolysis products. The influences of glycolysis temperature, glycolysis time, and the amount of catalyst (cobalt acetate) are illustrated. The BHET, dimer, and oligomers are predominately glycolysis products. The optimum glycolysis temperature is found to be 190°C. If a 190°C glycolysis temperature, 1.5‐h glycolysis time, and 0.002 mol glycolysis catalyst (cobalt acetate) are used, the glycolysis conversion is almost 100%. The glycolysis conversion rate increases significantly with the glycolysis temperature, glycolysis time, and the amount of cobalt acetate. Thermal analyses of glycolysis products are examined by differential scanning calorimetry. In addition, the chemical structures of glycolysis products are also determined by a Fourier transform IR spectrophotometer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 943–948, 2001     

Recycling of waste poly(ethylene terephthalate) into flame‐retardant rigid polyurethane foams

Waste poly(ethylene terephthalate) (PET) textiles were effectively chemical recycling into flame‐retardant rigid polyurethane foams (PUFs). The PET textile wastes were glycolytically depolymerized to bis(2‐hydroxyethyl) terephthalate (BHET) by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst. The PUFs were produced from BHET and polymeric methane diphenyl diisocyanate. The structures of BHET and PUFs were identified by FTIR spectra. The limiting oxygen index (LOI) of the PUFs (≥23.27%) was higher than that of common PUFs (16–18%), because the aromatic substituent in the depolymerized products improved the flame retardance. To improve the LOI of the PUFs, dimethyl methylphosphonate doped PUFs (DMMP‐PUFs) were produced. The LOI of DMMP‐PUFs was approached to 27.69% with the increasing of the doped DMMP. The influences of the flame retardant on the foams density, porosity, and compression properties were studied. Furthermore, the influences of foaming agent, catalyst, and flame retardant on the flame retardation were also investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40857.     

α-MnO2纳米管的合成及催化降解性能的研究

在水热条件下制备出α型二氧化锰（α-MnO2）纳米管,所得产物经X射线衍射（XRD）和场发射扫描电子显微镜（FE-SEM）表征,并考察了所制备的二氧化锰纳米管在微波加热条件下催化降解塑料PET（聚对苯二甲酸乙二醇酯）的性能,当MnO2的用量是PET用量的2%时其降解率达到100%1,H NMR和FT-IR分析证明降解产物为纯BHET（对苯二甲酸乙二醇酯）单体。     

Kinetics of diethylene glycol formation from bishydroxyethyl terephthalate with proton catalyst in the preparation of poly(ethylene terephthalate)

This research focused on the kinetics of diethylene glycol (DEG) formation from the bishydroxyethyl terephthalate (BHET) monomer with a proton catalyst. In this study, the effect of proton concentration and of reaction temperature on DEG formation are discussed. Also, the rate equation of DEG formation from the BHET monomer with a proton catalyst is described. It was found that, as far as kinetics is concerned, the reactivity of the hydroxyl end groups of BHET with protons is greater than that of ethylene glycol (EG) with protons in DEG formation. In addition, the activation energy of BHET with protons is much lower than that of BHET with itself, that is, as protons emerge during the process of PET synthesis from BHET, they catalyze DEG formation. This study provides additional kinetics data to that described in our studies previously published (J Polym Sci Polym Chem Ed 1998, 36, 3073; 1998, 36, 3081). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1221–1228, 2000     

Attapulgite‐supported aluminum oxide hydroxide catalyst for synthesis of poly(ethylene terephthalate)

A novel nanocomposite catalyst was prepared from immobilization of aluminum oxide hydroxide onto the attapulgite. Characterizations with scanning electron microscopy (SEM) and wide angle X‐ray diffraction (XRD) of the as‐prepared catalyst revealed that AlO(OH) nanoparticles were distributed on the attapulgite. Thermogravimetric analysis‐infrared spectrometry (TGA‐IR) of the mixture prepared by mixing of bishydroxy ethylene terephthalate (BHET) and the catalyst indicated that attapulgite‐supported aluminum oxide hydroxide catalyst can catalyze BHET polycondensation under the applied conditions. A kinetic model for determining the activation energy has been applied to evaluate the catalyst activity. The catalyst activity was examined through comparative experiments, and the results showed that the new catalyst exhibited higher activity for BHET polycondensation under identical reaction conditions, and the viscosity‐average molecular weight of poly(ethylene terephthalate) (PET) product obtained was increased about 2000 g/mol. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pretreatment of low-grade poly(ethylene terephthalate) waste for effective depolymerization to monomers

Pretreatment process of silica-coated PET fabrics, a major low-grade PET waste, was developed using the reaction with NaOH solution. By destroying the structure of silica coating layer, impurities such as silica and pigment dyes could be removed. The removal of impurity was confirmed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). The pretreated PET fabric samples were used for depolymerization into its monomer, bis(2-hydroxylethyl) terephthalate (BHET), by glycolysis with ethylene glycol (EG), and zinc acetate (ZnAc) catalyst. The quality of BHET was confirmed by DSC, TGA, HPLC and NMR analyses. The highest BHET yield of 89.23% was obtained from pretreated PET fabrics, while glycolysis with raw PET fabric yielded 85.43%. The BHET yield from untreated silica-coated PET fabrics was 60.39%. The pretreatment process enhances the monomer yield by the removal of impurity and also improves the quality of the monomer.     

酯化法合成对苯二甲酸二(β-羟乙基酯)的研究

以对苯二甲酸和乙二醇为原料,采用自制催化剂合成出了对苯二甲酸二(β-羟乙基酯)(BHET).最佳反应条件:1 mol对苯二甲酸使用0.2 g催化剂,醇酸摩尔比为12∶1,反应时间为10h,反应温度为185℃.粗品经结晶、重结晶可得质量分数＞99％的BHET产品.