改性Y沸石催化降解聚苯乙烯的研究

用热重分析方法研究了HY沸石与改性Y沸石(UHY)作为催化降解聚苯乙烯的催化剂对聚苯乙烯催化降解的作用及影响,对聚苯乙烯的催化降解与热降解反应产物进行了比较。结果表明,催化剂的存在能显著地降低聚苯乙烯的降解温度,催化剂的酸量和孔结构对聚苯乙烯的降解温度、活化能、积炭的生成量及裂解产物有很大的影响。     

电解法降解有机污染物机理及动力学的研究

对阳极电解催化降解有机污染物的机理进行了研究。结果表明 ,在电解过程中能够产生氧化能力极强的羟基自由基 (HO· ) ,使有机污染物以间接氧化的方式降解。用非线性最小二乘法对试验数据的分析表明 ,降解过程基本符合两步一级模型 ,并得到了水杨酸降解过程中的两步速率常数和 2 ,3-二羟基苯甲酸在 5 10 nm处的摩尔吸光系数     

A study of the oxidative degradation of polyolefins

The oxidative degradation of polyolefins in the presence of transition metal catalysts is well known in the patent and technical literature. It has been suggested that a properly designed oxidatively degradable polymer could be used in limited lifetime articles and also on those whose primary method of disposal is composting, wherein the thermal activity is used to accelerate the oxidation process. The results of a detailed study of transition metal reactivity in the presence of numerous oxidation promoting species in polyolefins are presented. The oxidative degradation of these polyolefins was demonstrated at moderate temperatures under air and in a simulated compost environment. Approaches to determining the ultimate fate of these materials are discussed.     

Cracking styrene derivative polymers in decalin solvent with metal-supported carbon catalysts

The cracking of styrene derivative polymers dissolved in decalin was conducted with metal-supported carbon catalysts under an inert gas atmosphere to recover monosubstituted styrene or monosubstituted ethylbenzene in higher yields than is obtained by pyrolysis, and to elucidate the detailed reaction mechanisms in the solvent. Poly-(4-methylstyrene), poly-(4-t-butylstyrene), poly-(α-methylstyrene), and polystyrene were used. In decalin without a catalyst, each polymer was decomposed into the monomer, dimer, and trimer derived from the corresponding polymer except for poly-(α-methylstyrene), which was decomposed into the monomer and styrene. By using metal-supported carbon, the olefinic compounds derived from the corresponding polymer were thoroughly hydrogenated to the saturated form in a nitrogen atmosphere by a hydrogen transfer reaction from decalin, which was simultaneously dehydrogenated to tetralin and naphthalene with the evolution of hydrogen gas. In comparison with metal species, Pd- and Ru-supported carbon catalysts maintained the hydrogenation activity for a longer time and with a lower evolution of hydrogen than Pt or Rh. The dehydrogenation of decalin was mainly observed not on the metal surfaces, but on the carbon surfaces over Pd-supported carbon. Stabilization of the monomers will be able to suppress the coking which occurs with repolymerization in long running process. Received: July 19, 2000 / Accepted: March 16, 2001     

TiO2载体对Mn-Ce/TiO2催化剂脱硝活性的影响

以TiO₂为载体,选取过渡金属元素Mn为活性组分,稀土金属元素Ce为活性助剂,采用分步共混法制备了Mn-Ce/TiO₂催化剂（活性组分负载量16%）,系统研究了TiO₂载体的晶型和晶粒尺寸对催化剂脱硝活性的影响。实验结果表明：分别以锐钛矿型和金红石型TiO₂为载体制备的催化剂,其低温脱硝活性相差不大,活性组分均以无定型态高度分散于载体中,以金红石型TiO₂为载体制备的催化剂中部分TiO₂转变为锐钛矿型;以不同晶粒尺寸TiO₂载体制备的催化剂的低温脱硝活性相差较大,比表面积较大、晶粒尺寸较小的TiO₂载体制备的催化剂,其脱硝活性低于晶粒尺寸较大的TiO₂载体制备的催化剂。     

制备条件对Mn-Fe/TiO2催化剂低温脱硝性能的影响

通过浸渍法制备了一系列Mn-Fe/TiO2催化剂,并采用XRD技术对其进行了表征,考察了锰前体种类、负载量（活性组分质量占载体质量的百分比）、Fe含量（Fe物质的量占活性组分物质的量的百分比）、焙烧温度等因素对催化剂低温选择性催化还原NO性能的影响。实验结果表明：以乙酸锰为前体制备的催化剂的脱硝活性明显高于以硝酸锰为前体制备的催化剂;负载量的增加有利于脱硝活性的提高,而Fe的添加对提高催化剂的活性有重要作用,但Fe含量超过15%后,对催化剂脱硝性能的影响并不明显;焙烧温度超过650 ℃时会使活性组分的结晶度提高,导致脱硝活性的降低。在锰前体为乙酸锰、负载量为15%、Fe含量为15%、焙烧温度为500 ℃、焙烧时间为6 h、反应温度为200 ℃的条件下,Mn-Fe/TiO2催化剂的NO转化率约为95%。     

堇青石负载Pd和过渡金属氧化物催化剂的表征及其对CO的催化氧化活性

以堇青石蜂窝陶瓷(CC)为载体,采用浸渍法制备了堇青石负载Pd和过渡金属混合氧化物催化剂,记作Pd-M-Mn(M=Cu,Co,Fe,Ni)/CC。实验结果表明:Pd-Co-Mn/CC催化剂的催化活性最高;随着Pd负载量的增加,CO转化率提高;当Pd负载量为1.00%时,反应温度为150℃时CO转化率达到98%,200℃时CO转化率达到100%;在反应温度150℃条件下,Pd-Co-Mn/CC催化剂(Pd负载量1.00%)的CO转化率在前30h内小幅度下降,随后稳定在90%以上,反应100h后,催化剂表面颜色由黑色变为棕褐色。     

Individual and simultaneous degradation of brominated high impact polystyrene and brominated acrylonitrile-butadiene-styrene and removal of heteroelements (Br,N, and O) from degradation oil by multiphase catalytic systems

Brominated high-impact polystyrene (HIPS-Br), which contained decabromodiphenyl ether flame retardant, and brominated acrylonitrile butadiene styrene (ABS-Br), which contained bromine-containing epoxy-type flame retardant, were degraded at 450°C individually and in a 1/1 mixture by a thermal and catalytic procedure using folded sheet mesoporous (FSM) and ZSM-5 zeolite in liquid phase contact mode. The two polymers produced similar degradation oils but at a higher yield for HIPS-Br. However, the composition and distribution of Br-, N-, and O-containing compounds depended on the type of flame retardant in HIPS-Br and ABS-Br. Multiphase catalytic systems consisting of FSM in liquid phase contact mode and various CaH-, FeO-, CoMo-, and NiMo-based catalysts, or combinations of these catalysts, in vapor phase contact mode were used to decrease the amount of heteroatoms (Br, N, and O) in the degradation oils. Each system gave particular results in terms of mass balance and concentrations of heteroatoms. A FSM (liquid phase contact)/CaHC (vapor phase contact) combination was the best catalytic system to remove Br-, N-, and O-containing compounds from degradation oils.     

二氧化钛对活性艳红X-3B的光催化降解研究

以TiO2作为光催化剂,研究了TiO2对活性艳红X-3B的光催化氧化降解行为。结果表明,以锐钛矿为主的混晶型Ti02的催化活性最好;X-3B的光催化降解动力学符合Langmuir-Hinshelwood动力学模式,并求出其动力学参数女(表观反应速率常数)为0．5921,KA(吸附平衡常数)为0．1725;温度对X-3B的降解影响很小,其活化能仅为6．04kJ／mol;溶液中盐度的增加会不断降低TiO2对X-3B的光催化降解速率。     

钯负载泡沫镍电极电化学还原水中三氯乙酸

采用非电沉积法制备了钯负载泡沫镍电极,运用SEM技术对其进行了表征,并以其阴极、铂丝为阳极进行了电化学还原三氯乙酸的研究,考察了工艺条件对三氯乙酸降解效果的影响,并对反应动力学和反应机理和进行了探讨。结果表明:钯负载泡沫镍电极具有较高的比表面积和良好的储氢性能;以20 mmol/L硫酸钠为电解质,在电解温度为20℃、钯负载量为4.5 mg/cm~2的条件下恒流(10 mA)电解240 min,三氯乙酸降解率达99.76%,氯原子脱除率达73.86%;三氯乙酸的电化学还原反应过程以及三氯乙酸上未脱除氯原子浓度的变化均符合拟一级反应动力学方程;三氯乙酸在电化学还原过程中逐个脱除氯原子。     

植物法改性类Fenton反应催化剂降解甲基橙

采用银杏叶和桑叶提取液制备了改性类Fenton反应催化剂并进行了表征分析,研究了溶液初始p H、反应温度、催化剂加入量、甲基橙初始质量浓度等因素对甲基橙降解率的影响,同时考察了催化剂的重复使用效果。表征结果表明:制备出的催化剂为Fe_2O_3和Fe OOH的混合物;桑叶改性催化剂的粒径分布较银杏叶改性催化剂均匀,粒径较小,比表面积较大。实验结果表明:在初始p H为6.23、反应温度60℃、催化剂用量1 g/L、甲基橙初始质量浓度100 mg/L的条件下,银杏叶改性催化剂的甲基橙降解率为99.40%,桑叶改性催化剂的甲基橙降解率为99.96%;碱性条件下,甲基橙降解率仍接近100%,扩宽了反应的p H适用范围,为碱性条件下处理偶氮染料提供了新思路;催化剂重复使用6次之后,甲基橙降解率仍可达到99%。根据反应前后溶液的紫外-可见吸收光谱,初步探讨了降解机理。     

Geotechnical properties of municipal solid waste at different phases of biodegradation

This paper presents the results of laboratory investigation conducted to determine the variation of geotechnical properties of synthetic municipal solid waste (MSW) at different phases of degradation. Synthetic MSW samples were prepared based on the composition of MSW generated in the United States and were degraded in bioreactors with leachate recirculation. Degradation of the synthetic MSW was quantified based on the gas composition and organic content, and the samples exhumed from the bioreactor cells at different phases of degradation were tested for the geotechnical properties. Hydraulic conductivity, compressibility and shear strength of initial and degraded synthetic MSW were all determined at constant initial moisture content of 50% on wet weight basis. Hydraulic conductivity of synthetic MSW was reduced by two orders of magnitude due to degradation. Compression ratio was reduced from 0.34 for initial fresh waste to 0.15 for the mostly degraded waste. Direct shear tests showed that the fresh and degraded synthetic MSW exhibited continuous strength gain with increase in horizontal deformation, with the cohesion increased from 1 kPa for fresh MSW to 16–40 kPa for degraded MSW and the friction angle decreased from 35° for fresh MSW to 28° for degraded MSW. During the triaxial tests under CU condition, the total strength parameters, cohesion and friction angle, were found to vary from 21 to 57 kPa and 1° to 9°, respectively, while the effective strength parameters, cohesion and friction angle varied from 18 to 56 kPa and from 1° to 11°, respectively. Similar to direct shear test results, as the waste degrades an increase in cohesion and slight decrease in friction angle was observed. Decreased friction angle and increased cohesion with increased degradation is believed to be due to the highly cohesive nature of the synthetic MSW. Variation of synthetic MSW properties from this study also suggests that significant changes in geotechnical properties of MSW can occur due to enhanced degradation induced by leachate recirculation.     

A comparison study on high-temperature water–gas shift reaction over Fe/Al/Cu and Fe/Al/Ni catalysts using simulated waste-derived synthesis gas

A comparative study on Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts in high-temperature water–gas shift reaction (HT–WGS) using simulated waste-derived synthesis gas has been carried out. The metal oxide (Cu and Ni) and aluminum incorporated Fe catalysts were designed to get highly active HT–WGS catalysts. Despite the high CO concentration in the simulated waste-derived synthesis gas, Fe/Al/Cu catalyst exhibited the highest CO conversion (84 %) and 100 % selectivity to CO₂ at a very high gas hourly space velocity (GHSV) of 40,057 h^?1. The outstanding catalytic performance is mainly due to easier reducibility, the synergy effect of Cu and Al, and the stability of the magnetite.     

TiO2光催化法降解空气中的苯

以紫外灯为光源,采用P25型TiO₂光催化降解空气中的苯。为保证TiO₂的高分散性、增加其在铝板上的附着牢固性,加入了聚乙烯醇和硅溶胶,这在一定程度上增加了催化剂对光能的利用率,但也造成了催化剂活性的降低。实验结果表明：苯的光催化降解反应属一级动力学反应;苯降解率随初始苯质量浓度的增加而减小,随反应面积的增大而增大,在253.7 nm波长光源下的降解效果优于365.0 nm;苯降解所得的气相产物主要为CO₂和CO;随使用次数的增加,催化剂失活现象逐步显现;双氧水对催化剂的再生效果优于去离子水。     

Development of a catalytic dehalogenation (Cl,Br) process for municipal waste plastic-derived oil

Dehalogenation is a key technology in the feedstock recycling of mixed halogenated waste plastics. In this study, two different methods were used to clarify the effectiveness of our proposed catalytic dehalogenation process using various carbon composites of iron oxides and calcium carbonate as the catalyst/sorbent. The first approach (a two-step process) was to develop a process for the thermal degradation of mixed halogenated waste plastics, and also develop dehalogenation catalysts for the catalytic dehydrochlorination of organic chlorine compounds from mixed plastic-derived oil containing polyvinyl chloride (PVC) using a fixed-bed flow-type reactor. The second approach (a single-step process) was the simultaneous degradation and dehalogenation of chlorinated (PVC) and brominated (plastic containing brominated flame retardant, HIPS–Br) mixed plastics into halogen-free liquid products. We report on a catalytic dehalogenation process for the chlorinated and brominated organic compounds formed by the pyrolysis of PVC and brominated flame retardant (HIPS–Br) mixed waste plastics [(polyethylene (PE), polypropylene (PP), and polystyrene (PS)], and also other plastics. During dehydrohalogenation, the iron- and calcium-based catalysts were transformed into their corresponding halides, which are also very active in the dehydrohalogenation of organic halogenated compounds. The halogen-free plastic-derived oil (PDO) can be used as a fuel oil or feedstock in refineries.     

Biodegradation of hydrocarbon residuals by biological activators in the presence of INIPOL EAP 22

This paper reports on a study the degradation of a highly aged hydrocarbon mixture originating from an accidental spill in an oil refinery. The biological activator BIOLEN IG 30 has been used as degradation agent microorganism and INIPOL EAP 22 as biodegradation process accelerator. The kinetic coefficients have been deduced by adjusting the two straight lines from a plot of the degradation process using zero-order kinetics. An aged hydrocarbon mixture dispersion was studied and efficiency ratios calculated. Degradation of the FINASOL OSR 51 dispersant used to disperse the hydrocarbon mixture has been also studied yielding the degradation process constant, biological oxygen demand (BOD), biological final demand (BOD_f), stabilization constant for the degradation process (k₁) and the biological stabilization constant (k).     

Degradation of Post-consumer PLA: Hydrolysis of Polymeric Matrix and Oligomers Stabilization in Aqueous Phase

Degradation of post-consumer PLA to lactic acid was analysed in order to assess the economic feasibility of the PLA chemical recycling process. Hydrolysis of PLA, in batch reactor, was analysed in the temperature range of 443–473 K, under autogenous pressure and a constant PLA to water ratio (equal to approximately 0.11 by weight), without the use of a catalyst. The experimental results suggest that the complete degradation of PLA can be obtained using relatively low reaction-times with the production of a mixture containing the monomer and traces of the dimer of lactic acid. The overall process was modelled using a two-step process: bulk degradation of PLA (in the solid or molten phase) with the solubilisation of low molecular weight oligomers, and their subsequent hydrolysis in water (stabilization). The model describes the trend of oligomer concentrations in the aqueous phase and PLA conversion as a function of time with both high accuracy and agreement with experimental results.     

用于有机污染物湿式氧化的铜系催化剂活性研究

对用铜系多相催化剂催化湿式氧化处理染料中间体Ｈ酸配水作了较为全面的研究。结果表明,铜氧化物催化剂在催化湿式氧化中的活性明显优于其他过渡金属氧化物,若能控制其溶出,则具有广阔的应用前景。     

锐钛矿-金红石混合晶型TiO2降解气相苯

用溶胶-凝胶法并通过控制煅烧温度合成不同晶相比的混合晶型纳米TiO_2,在紫外光光照下降解气相苯。考察了苯初始质量浓度、紫外灯光照强度和催化剂加入量对苯去除率的影响;探究了光催化降解气相苯的动力学特征。结果表明:450℃煅烧制备的催化剂降解苯效率最高,此催化剂金红石相质量分数为6.30%;在苯初始质量浓度为74.39 mg/m~3、催化剂加入量为7 g、光照强度为2.18 klux的最佳条件下反应84 min,苯去除率达99.73%;光催化降解率与光照强度之间符合0.5级动力学特征;当催化剂加入量为3 g时,单位时间单位质量催化剂降解苯的质量最多;苯的光催化降解反应均符合一级动力学方程。     

不同光照度下活性艳红X-3B的光催化降解动力学研究

以活性艳红X-3B为模型化合物，以TiO2为光催化剂，研究了不同光照度下污染物的多相光催化降解动力学。结果表明，活性艳红X-3B的光催化降解动力学符合Langmiur—Hinshelwood动力学模型，其中的表观反应速率常数(k)随入射光照度的增加而增大，吸附平衡常数(KA)却随入射光照度的增加而减小，在实验的光照度范围内，k和KA^-1与光照度的平方根成比。