Chuan Ma

Thermal degradation of PVC: A review.

This review summarized various chemical recycling methods for PVC, such as pyrolysis, catalytic dechlorination and hydrothermal treatment, with a view to solving the problem of energy crisis and the impact of environmental degradation of PVC. Emphasis was paid on the recent progress on the pyrolysis of PVC, including co-pyrolysis of PVC with biomass/coal and other plastics, catalytic dechlorination of raw PVC or Cl-containing oil and hydrothermal treatment using subcritical and supercritical water. Understanding the advantage and disadvantage of these treatment methods can be beneficial for treating PVC properly. The dehydrochlorination of PVC mainly happed at low temperature of 250-320°C. The process of PVC dehydrochlorination can catalyze and accelerate the biomass pyrolysis. The intermediates from dehydrochlorination stage of PVC can increase char yield of co-pyrolysis of PVC with PP/PE/PS. For the catalytic degradation and dechlorination of PVC, metal oxides catalysts mainly acted as adsorbents for the evolved HCl or as inhibitors of HCl formation depending on their basicity, while zeolites and noble metal catalysts can produce lighter oil, depending the total number of acid sites and the number of accessible acidic sites. For hydrothermal treatment, PVC decomposed through three stages. In the first region (T<250°C), PVC went through dehydrochlorination to form polyene; in the second region (250°C<T<350°C), polyene decomposed to low-molecular weight compounds; in the third region (350°C<T), polyene further decomposed into a large amount of low-molecular weight compounds.

Fe3 xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal

A series of novel spinel Fe3-xCuxO4 (0<x<0.71) composites, synthesized by chemical co-precipitation method, are proposed synthesized to use as highly active heterogeneous Fenton-like catalysts to remove elemental mercury (Hg0) from the simulated flue gases. Inductively coupled plasma-Atomic emission spectrometry (ICP-AES), X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectrometer (XPS) were used to characterize the catalysts. The catalysts were confirmed the presence of the redox pairs Fesurf2+/Fesurf3+ and Cusurf+/Cusurf2+ on the surface of the cubic structure. The performance of heterogeneous Fenton-like reactions for Hg0 removal was evaluated in a lab-scale bubbling reactor at the solution temperature of 50°C. The systematic studies on the effects of different catalysts, H2O2 concentration and solution pH values on Hg0 removal efficiencies were performed. The recycling of the Fe3-xCuxO4 catalysts in Fenton-like solution is stable and Hg0 removal efficiency remain above 90% after 3 cycles. The active hydroxyl radical (OH) generated during heterogeneous Fenton-like reactions was confirmed through electron spin resonance (ESR) spin-trapping technique. The Hg0 removal mechanism has been discussed based on the experimental and analytical results.

Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China.

This study aims to vaporize heavy metals and alkali/alkaline earth metals from two different types of fly ashes by thermal treatment method. Fly ash from a fluidized bed incinerator (HK fly ash) was mixed with one from a grate incinerator (HS fly ash) in various proportions and thermally treated under different temperatures. The melting of HS fly ash was avoided when treated with HK fly ash. Alkali/alkaline earth metals in HS fly ash served as Cl-donors to promote the vaporization of heavy metals during thermal treatment. With temperature increasing from 800 to 900°C, significant amounts of Cl, Na and K were vaporized. Up to 1000°C in air, less than 3% of Cl and Na and less than 5% of K were retained in ash. Under all conditions, Cd can be vaporized effectively. The vaporization of Pb was mildly improved when treated with HS fly ash, while the effect became less pronounced above 900°C. Alkali/alkaline earth metals can promote Cu vaporization by forming copper chlorides. Comparatively, Zn vaporization was low and only slightly improved by HS fly ash. The low vaporization of Zn could be caused by the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4. Under all conditions, less than 20% of Cr was vaporized. In a reductive atmosphere, the vaporization of Cd and Pb were as high as that in oxidative atmosphere. However, the vaporization of Zn was accelerated and that of Cu was hindered because the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4 and copper chloride was depressed in reductive atmosphere.

Mechanism on heavy metals vaporization from municipal solid waste fly ash by MgCl2⋅6H2O

This work aims to study the mechanism of heavy metals vaporization by MgCl2⋅6H2O. Firstly, the decomposition mechanism of MgCl2⋅6H2O was investigated by thermodynamic equilibrium calculations, XRD and TG. Upon heating, MgCl2⋅6H2O went through the processes of dehydration and hydrolysis simultaneously accompanied by the release of HCl between 150 and 500°C. At temperature higher than 500°C, Mg(OH)Cl gradually release part of HCl. MgCl2⋅6H2O followed the similar processes of decomposition at both oxidative and reductive atmospheres. In oxidative atmosphere, vaporization of Zn and Cu was significantly accelerated by MgCl2⋅6H2O. However, in inert atmosphere, vaporization of Cu was not promoted since copper chloride was only stable in oxidative atmosphere. Under slow heating condition, vaporization of heavy metals were close to that under fast heating condition. This may be partially attributed to that most heavy metals already reacted with HCl forming metal chlorides below 500°C, which can be vaporized at higher temperature. Moreover, the Mg(OH)Cl contributed to release HCl up to 800°C. At such high temperature, the metal chlorides continue to be formed and then vaporized. After treatment, the leaching concentration of heavy metals from treated fly ashes were much lower than that from raw fly ash and met the regulatory limit of leachate. Since a large amount of MgSiO3 were formed during thermal treatment, the fly ash treated with MgCl2⋅6H2O can be used as raw materials for glass-ceramics production.

Detoxification of ashes from a fluidized bed waste incinerator

This paper was to test and control the toxicity of bottom and fly ashes from a circulated fluidized bed (CFB) incinerator. Bottom and fly ashes were firstly subject to TCLP test. Even though leachates of most particle size of bottom ash were below regulatory limit, the leachates of finer bottom ash may exceed the regulatory limit. Therefore, finer bottom ash should be separated and treated before landfilled directly or used as cement replacement. Due to high amounts of leached heavy metals, thermal treatment of fly ash was carried out to remove heavy metals. The influence of temperature, residence time, metal chloride and gas velocity were studied. In all conditions, Cd can be well removed. Pb can be almost completely removed with MgCl2 addition at 1000°C in 1h. The removal of Zn and Cu was accelerated significantly by MgCl2 and higher temperature separately. At optimum conditions, more than 90% of Cu and 95% of Zn could be removed, while a maximum 20% of Cr was removed due to the existence or formation of CaCr2O4, MgCr2O4 and K2Cr2O4 in raw or treated fly ashes.