In this work, a sensitive and robust vacuum ultra-violet (VUV) single-photon ionization (SPI) ion trap time-of-flight mass spectrometer (VUV-SPI-IT-TOFMS) for on-line, realtime monitoring of chlorinated organic compounds in waste incineration flue gas has been newly developed. The fragment-free SPI technique with 121.6-nm VUV lamp irradiated by a microwave generator and the quadrupole ion trap to accumulate and select analyte ions were combined with a reflectron time-of-flight mass spectrometer to detect chlorinated organic compounds at trace level. This measuring system was tuned up to detect dioxins precursors with the aim at an application to monitoring trace level toxic substances in flue gases from incinerator furnaces. As a result, this technology has made it possible to analyze trichlorobenzene (T3CB), a dioxin precursor, in 18 s with a sensitivity of 80 ng/m3-N (10 pptv) using the selective accumulation of analyte substances and separation of interfering substances in the ion trap. Moreover, the first field test of the continuous monitoring T3CB in an actual waste incineration flue gas had been done for 7 months. The results show that this system has an exceeding robust performance and is able to maintain the high sensitivity in analyzing T3CB for long months of operation.

It is necessary to remove chlorine effi ciently from municipal waste plastics (MWP) that contain polyvinyl chloride (PVC) and other plastics containing chlorine. In this article we consider thermal degradation liquefaction technology. In Japan, the chlorine content of reclamation oil products must be kept below 100 ppm owing to the quality standard for pyrolysis oil. Liquefaction dechlorination technology for MWP is still an important issue to study. The twin-screw extruder that has been developed as dechlorination technology for blast furnaces and coke ovens has a shorter residence time for dechlorination than other dechlorination technologies. In this article, we used a single-screw extruder for the dechlorination process because it also has a short residence time. Experiments on the dechlorination process were carried out by using a single-screw extruder to assess its dechlorination performance. Practical use of the single-screw was demonstrated by the operation of a commercial oil reclamation plant operated by Sapporo Plastic Recycle Co., Ltd. (SPR). Moreover, an investigation of cascade recycling was carried out in 2008 in which material recycle wastes were mixed with MWP and processed by chemical recycling (liquefaction). It was demonstrated that cascade recycling is an effi cient recycling combination and contributes to local feedstock recycling. However, it was shown that MR wastes affect the quality of the reclamation oil when they make up more than 40% of the feed mix. If the quantity of MR wastes is kept below 40%, the reclamation oil is able to meet the quality standard. The SPR plant can be operated safely and in a stable manner.

It usuallytakes a few weeks to analyze dioxin concentrations and dioxin-TEQ (toxicity equivalency quantity) in fluegases from municipal solid waste (MSW) incinerators by a standard method provided by Japanese industrial standard (JIS 0311). To reduce the required time for analysis, we have developed a new on-line measuring system for furans homologues. This system is composed of a sensitive and robust vacuum ultraviolet (VUV) single-photon ionization (SPI) ion trap (IT) time-of-flight mass spectrometer (VUV-SPI-IT-TOFMS) and automatic sampling/concentrating process. In this work, pentachloro-dibenzofuran (P5CDF) was selected as an index homologue in chlorinated dibenzo-p-dioxin/ furan homologues (DXNs) because its concentration and I-TEF (international toxicity equivalency factor), which are 2,3,4,7,8-P5CDF is 0.5 and 1,2,3,7,8-P5CDF is 0.05, are high and the concentration correlates closely with the total amount of dioxin-TEQ. The lowest detectable limit, 1 pg (0.001 ng-TEQ/m3 N) was demonstrated by laboratory tests. This system underwent a field test at several actual MSW plants and the tests revealed the following: (a) This system is applicable for dioxin-TEQ evaluation from actual MSW incinerators. (b) It can continuously monitor P5CDF in a fluegas for 7 months. (c) The frequency of the measurements is once every 2-6 h, depending on the concentration of P5-CDF.

We measured sensitive real-time change of low-chlorinated (Cl(1)-Cl(3)) benzenes in gas phase from heated model and real solid samples using the recently developed vacuum ultraviolet (VUV) single-photon ionization (SPI) ion trap time-of-flight mass spectrometer (VUV-SPI-IT-TOFMS). Model solid samples that contained activated carbon, potassium chloride, silicon dioxide, and trace metallic compounds (copper, iron, lead, and zinc) were used to simulate fly ash at a municipal solid waste incinerator (MSWI). The concentrations of chlorobenzenes determined by integrating the area for 30 min using VUV-SPI-IT-TOFMS were correlated with gas-phase concentrations analyzed by GC/MS. Real-time changes had characteristic patterns dependent on metal species and compounds. Comparing gas-phase real-time patterns of low-chlorinated benzenes between real and model fly ashes, copper chloride- and oxide-like compounds in real fly ash at the postcombustion zone in a MSWI may play key factors in the formation of low-chlorinated benzenes. Lead and zinc compounds and iron oxide in solid phase did not affect the formation of low-chlorinated benzenes in gas phase. VUV-SPI-IT-TOFMS can be applied to the time-dependent characterization of volatile low-chlorinated benzenes in gas phase in various artificial and environmental processes.