Effect of polyethylene terephthalate (PET) on the pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br)

Pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br) was performed at 430°C in the presence of 0.1 wt% of polyethylene terephthalate (PET) in a Pyrex glass reactor. Two different types of brominated flame retardants (decabromodiphenyl ether and decabromodiphenyl ethane) with or without antimony trioxide (as synergist) 5 wt% were used. The presence of PET had a significant effect on the material balance, decreasing the gaseous product and increasing the residue. The type of flame retardant had no effect on the yield of liquid product; however, the presence of Sb resulted in a marked difference in the distribution of decomposition products. Analysis by a gas chromatograph equipped with a flame ionization detector showed that the hydrocarbons were distributed in the range n-C₇ to n-C₂₅ with major peaks at n-C₉ and n-C₁₇. The presence of PET increased the formation of brominated compounds by several times and affected both the type and quantity of polybrominated compounds. The liquid products obtained from the pyrolysis of HIPS-Br/PET have to be treated before they can be used     

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.     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.     

氯系阻燃剂四氯双酚A的毒性及降解技术研究进展

作为目前广泛使用的氯系阻燃剂,四氯双酚A(TCBPA)在运输、使用和处理的过程中会不可避免地释放到环境中,并通过各种途径进入人体,产生危害。简介了TCBPA的基本性质和制备,阐述了其环境分布及毒性,并总结了其降解技术的研究进展,最后对该领域未来的研究方向进行了展望。指出:应当进一步研究TCBPA微生物降解的机理和分子基础,并引入光催化、高级氧化等其他降解技术;同时,开发新型环境友好的阻燃剂不失为一种根源上的解决方式。     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

D401与N-117负载 Fe（Ⅱ）非均相Fenton法催化降解苯酚

分别采用D401和N-117负载Fe（Ⅱ）制备非均相Fenton催化剂,探讨两种催化剂在不同初始溶液pH、初始H₂O₂质量浓度和保存条件下,催化降解苯酚的效果和铁溶出情况。结果表明：两种催化剂均能拓展Fenton反应pH范围;D401负载Fe（Ⅱ）催化苯酚降解速率较快,苯酚降解率随初始溶液pH升高而下降,溶出铁催化的均相Fenton反应是苯酚降解的主要原因;N-117负载Fe（Ⅱ）催化剂苯酚降解速率随初始溶液pH升高而下降,非均相Fenton反应是主要反应过程;初始H₂O₂质量浓度升高能使D401负载Fe（Ⅱ）的溶出总铁质量浓度显著升高,但对N-117负载Fe（Ⅱ）影响很小;水中较高的DO能显著降低两种催化剂的苯酚降解效果。     

Effect of metal chlorides on thermal degradation of (waste) polycarbonate

In this study, we investigated how to treat (waste) polycarbonate efficiently to reduce its degraded residue. The study was carried out in an isothermal reactor under continuous nitrogen flow at atmospheric pressure to pyrolyze polycarbonate (PC) alone and in the presence of metal chloride. Some metal chlorides were shown to be catalytic active for the degradation of PC at 400 degrees C, which increased degradation conversion from 8.5% to more than 58.3%. Among those active metal chlorides, ZnCl2 and SnCl2 can produce higher liquid product yields. Effects such as particle size of PC, temperature, the weight ratio of metal chloride/PC, and degradation time on the degradation conversion of PC without and with these two most active metal chlorides were studied. Results of the liquid product analysis by GC/MS demonstrated the product composition of PC degradation over the metal chlorides is much simpler than that of degradation alone. The main liquid product is phenol, p-isopropylphenol, diphenyl carbonate, and bisphenol A for all cases.     

固态反应法制备FeHY催化剂及其催化降解活性艳蓝的性能研究

分别以NaY、NH4Y和HY沸石为载体,以乙酰丙酮铁为铁源,采用固态反应法制备了铁负载量均为10%（w）的FeNaY-10、FeNH4Y-10和FeHY-10催化剂。考察了各催化剂对活性艳蓝（KN-R）的降解效果,其中FeHY-10的催化降解效果最佳。采用XRD和FTIR技术对FeHY-10催化剂进行表征。表征结果显示,FeHY催化剂晶体结构仍然保持了Y分子筛特有的孔道结构,铁物种在Y 分子筛表面高度分散。催化降解实验表明,催化降解KN-R的最佳工艺条件为KN-R溶液（质量浓度为300 mg/L）加入量为50 mL、溶液pH为2、催化剂FeHY-25（铁负载量为25%（w））加入量为0.281 3 g、H2O2质量浓度为6.356 g/L、降解温度为35 ℃、降解时间为140 min,在此工艺条件下FeHY催化剂对KN-R的降解率为97.4%。     

Recovery of benzene-rich oil from the degradation of metal- and metal oxide-containing poly(ethylene terephthalate) composites

Pure poly(ethylene terephthalate) (PET) resin and metal-/metal oxide-containing PET composites were thermally decomposed in the presence of Ca(OH)₂ using a tube reactor. The effects of batch and continuous processing, the presence of Ca(OH)₂, and PET size on benzene production were investigated. A maximum benzene yield and purity of 82.9 % and 78.8 wt%, respectively, were obtained at 700 °C in the presence of Ca(OH)₂ when using small PET particles; further, a continuous feed reactor was favored over a batch reactor. Effective contact between PET and Ca(OH)₂ was important in the PET degradation, which promoted hydrolysis of PET and decarboxylation of terephthalic acid, whereas pyrolysis was suppressed. Furthermore, the results of thermal decomposition of PET-based waste—PET-based X-ray films, magnetic tape, and prepaid cards—indicated that the metal and metal oxides contained in the waste had no significant catalytic effect on PET degradation or on the recovery of benzene-rich oil in the presence of Ca(OH)₂.     

Flame Propagation Across Gelled Alkane-In-Water Emulsions

Flame propagation rates were measured for flames spreading across surfaces of gel-like alkane-in-water emulsions. A long, slender, water-cooled trough was used to contain the mixtures. Abrupt changes in the flame propagation velocities - of nearly two orders of magnitude - were observed to occur near ‘critical’ concentrations of certain alkane/water mixtures. Four alkanes were used - pentane, hexane, heptane, and octane - and fuel rich emulsions (in which water was the continuous phase) were employed. The ability of the aqueous phase of the emulsion to inhibit the release of fuel into the vapor phase plays an important role in the observed behavior. That is, the rate at which fuel can diffuse through both the emulsion and the thin liquid layers that reside on it, is an essential kinetic aspect of the phenomena which determine the flame propagation rate across gelled alkane-in-water emulsions.     

Carbon materials-catalyzed hydroliquefaction of flame-retardant plastics in organic solvents

Flame-retardant plastics, such as desktop and laptop personal computer bodies, could be completely liquefied by carbon materials-catalyzed hydroliquefaction in tetralin without using H₂ as a hydrogen source. Active carbons with larger surface areas (1450–3450 m²/g) acted as superior catalysts in transferring tetralin hydrogens to plastics. On the other hand, carbon blacks and fullerene-rich soot were less active catalysts. Graphite and mesocarbon microbeads did not show any catalytic effects. Benzene, toluene, and ethylbenzene were obtained as recyclable hydrocarbons; their total amounts varied from 4 wt% to 12 wt% depending on the types of plastics and the carbon materials used. Organic bromides such as polybromodioxins were not contained in the gases and oils of the product. Received: July 19, 2000 / Accepted: September 17, 2000     

铜基多相催化剂催化氧气氧化降解水中水合肼

制备了3种铜基多相催化剂,用于催化氧气氧化降解水中水合肼。实验结果表明:三组分催化剂c-CuZnCr比单组分催化剂CuO(c-Cu)和双组分催化剂c-CuZn具有更好的催化性能;在200 mL浓度0.04 mol/L的水合肼水溶液中投加23 mg c-CuZnCr,常温常压下反应360 min,水合肼的降解率达99.96%;c-CuZnCr在使用中稳定性好,循环使用5次未见活性降低。表征结果显示,三组分催化剂具有最大的比表面积,因而表现出最高的催化活性。动力学研究结果表明,c-CuZnCr催化的反应活化能为32.73 kJ/mol,与水合肼浓度和氧气压力相关的反应级数分别为0.97和0.78。     

有机磷阻燃剂生产废水预处理工艺研究

采用液膜萃取—酸析沉降—络合萃取组合工艺对有机磷阻燃剂生产废水进行预处理.最佳工艺条件为:液膜萃取时,液膜油相(表面活性剂与煤油的混合液)与内水相(H2SO4溶液)的体积比2∶1、乳化液膜与废水的体积比1∶8、废水pH 13.0,硫酸体积分数10％、煤油中表面活性剂质量浓度30 g/L、液膜萃取时间 15 min;酸析沉降时,废水pH l.0,酸析沉降时间30 min;络合萃取时,络合萃取剂(烷基叔胺N235与煤油的混合液)中烷基叔胺N235体积分数30％,络合萃取剂与废水的体积比1∶4,废水pH l.0,络合萃取时间30 min.在此最佳处理条件下,废水COD总去除率可达93％,吡啶去除率达99.9％以上,总磷去除率可达97％,BOD5/COD提高至0.32,有利于后续生化处理.     

Pyrolysis of municipal plastic wastes II: Influence of raw material composition under catalytic conditions

In this work, the results obtained in catalytic pyrolysis of three plastic waste streams which are the rejects of an industrial packing wastes sorting plant are presented. The samples have been pyrolysed in a 3.5 dm(3) reactor under semi-batch conditions at 440 °C for 30 min in nitrogen atmosphere. Commercial ZSM-5 zeolite has been used as catalyst in liquid phase contact. In every case, high HHV gases and liquids which can be useful as fuels or source of chemicals are obtained. A solid fraction composed of the inorganic material contained in the raw materials and some char formed in the pyrolysis process is also obtained. The zeolite has shown to be very effective to produce liquids with great aromatics content and C3-C4 fraction rich gases, even though the raw material was mainly composed of polyolefins. The characteristics of the pyrolysis products as well as the effect of the catalyst vary depending on the composition of the raw material. When paper rich samples are pyrolysed, ZSM-5 zeolite increases water production and reduces CO and CO(2) generation. If stepwise pyrolysis is applied to such sample, the aqueous liquid phase can be separated from the organic liquid fraction in a first low temperature step.     

Pyrolysis of low-density polyethylene using synthetic catalysts produced from fly ash

Catalytic pyrolysis of low-density polyethylene (LDPE) was investigated using various fly ash-derived silica–alumina catalysts (FSAs). FSAs were prepared by a simple activation method that basically includes NaOH treatment of fly ash by a fusion method, followed by an aging process. A series of LDPE pyrolysis experiments was conducted and the catalytic performance of FSAs was assessed in terms of the degradation temperature and the simulated boiling point distribution of the liquid products. The effects of synthesis conditions such as NaOH/fly ash weight ratio and aging time were examined by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET) surface area analyzer, and scanning electron microscope to clarify the controlling factors affecting the catalytic activity. To obtain catalyst with high activity, it is necessary to produce sufficient silica and alumina species that can be easily co-precipitated into solid acid catalyst by destruction of the fly ash structure and to optimize the activation time for catalyst synthesis to prevent the transformation into inactive phases. The catalytic performance of FSA obtained from optimal conditions was equivalent to that of commercial catalysts, demonstrating the effectiveness of the catalyst.     

十溴联苯醚环境修复技术的研究进展

介绍了溴代阻燃剂十溴联苯醚（BDE-209）环境修复技术的研究进展。从光降解、零价铁降解、生物降解3个方面对BDE-209的降解机理和降解后的产物进行了介绍。BDE-209经光照、厌氧微生物、零价铁的脱溴作用后,降解成低溴代联苯醚产物;好氧微生物利用低溴代联苯醚作为生长碳源,将其在酶的作用下开环降解,进入三羧酸循环或彻底分解成CO₂和H₂O。提出应采用多种方法协同作用,更有效地降解多溴联苯醚化合物。     

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。     

Studies on the dechlorination and oil-production technology of waste plastics

 Recycle technology for waste plastics containing polyvinyl chloride (PVC) has been developed in the Hokkaido National Industrial Research Institute for the production of solid and liquid fuel, and has established a recycling process which includes a dechlorination process for PVC plastics, and a two-stage catalytic pyrolysis process for plastics using zeolite catalysts. The dechlorination equipment consists of a two-axis screw extruder with a heating element, which can remove chlorine up to 99.9 wt. % from PVC containing plastics as hydrogen chloride. The product had about 44 000 kJ/kg calorific value and was fed into the next oil production process, although it could also be used as a solid fuel. Natural and synthetic zeolite were used as catalysts for the two-stage catalytic process, which produced a light oil with a boiling point which was between those of kerosene and gasoline. The yield of this oil reached 82 wt. %. The chemical type was analyzed using liquid chromatography, and was found to have many aromatic compounds. These technologies make it possible to produce a nonpolluting, high-calorie solid fuel and a liquid fuel very efficiently. Received: July 19, 2000 / Accepted: September 21, 2000     

Hydroreforming over Ni/H-beta of the thermal cracking products of LDPE, HDPE and PP for fuel production

The thermal cracking at 400?°C of pure polyolefins—low density polyethylene (LDPE), high density polyethylene (HDPE) and polypropylene (PP) and a standard polyolefin mixture (46?% LDPE?+?27?% HDPE?+?28?% PP)—was studied together with the catalytic hydroreforming of the obtained oils over Ni/h-beta at 310?°C under 20?bar of hydrogen. The oils obtained after the thermal cracking of PP contain the highest amount of gasoline (58?%), while those coming from HDPE the lowest (39?%). The bromine index of the oils was very high, ranging from 54.1 (LDPE) to 83.8 (PP), indicating a high olefinic content of the oils. Additionally, the thermal cracking of the mixture indicates the occurrence of a synergestic effect among plastics, with transfer of methyl groups from PP to polyethylenes. Ni/h-beta (Si/Al?=?25; Ni content?=?6.2?wt%) catalyst was used in the hydroreforming since it contains a bimodal pore size distribution (0.6/3.1?nm), which improves accessibility of the oil molecules to the catalytic sites. After the hydroreforming and regardless of the plastics used, the share of lighter products (gasoline and gases) increases, reaching a remarkable 68?% of gasolines with the oils coming from PP. Regardless of the starting feed, the amount of useful fuels (gasoline?+?light diesel) was within 80–85?%. Additionally, the oils were successfully hydrogenated since the bromine indexes dropped below 7, indicating that more than 90?% of the starting olefins were saturated. The usage of catalysts increased the amount of aromatics in the obtained oils within 13–20?%, depending on the starting plastic. Likewise, the isoparaffin content of the gasolines was within 35–40?%, except for PP, where it was enhanced to 62?%. However, the research octane number (RON) of the gasolines from LDPE and PP and the cetane indexes of the diesel from all the plastics were promising for their application as fuels.     

Thermal and Flame Retardancy Behavior of Oil Palm Based Epoxy Nanocomposites

The aim of present study was to investigate the thermal properties and flame retardancy behavior of flame retardant (FR) epoxy nanocomposites from chemically treated (bromine water and tin chloride) oil palm empty fruit bunch (OPEFB) nano filler at different filler loading (1, 3, 5%). Thermal properties were evaluated through thermogravimetry analyzer, derivative thermogravimetry and differential scanning calorimetry. FR properties of nanocomposites are evaluated through UL-94 vertical burning test and limiting oxygen index (LOI). The functional group analysis of all composites was made by FTIR spectroscopy. Thermal analysis shows that degradation temperature of epoxy composites shifts from 370 to 410 °C and char yield also increases for 3% loading. Furthermore LOI value of 29% and UL-94 rating of V-0 with no flame dripping and cotton ignition, revealed that 3% oil palm nano filler filled epoxy nanocomposites display satisfactory flame retardancy. The superior flame retardancy of epoxy nanocomposites are attributed to the chemical reactions occurred in the gaseous phases and the profound synergistic flame retardation effect of tin with bromine in the treated nano OPEFB filler. All the epoxy nanocomposites displayed almost similar FTIR spectra with the characteristics metal-halogen bond supporting the synergism. Homogeneous dispersion of 3% oil palm nano filler act as highly effective combustion chain terminating agent compared with 1 and 5% nano OPEFB/epoxy nanocomposites.