锌粉对聚氯乙烯的机械化学还原脱氯

以锌粉为还原剂进行了聚氯乙烯（PVC）的机械化学还原脱氯（简称脱氯）探索研究，考察了球磨转速、球料比（磨球与试样的质量比）、锌粉与PVC质量比等对脱氯率的影响，并对脱氯产物进行了X射线衍射、红外光谱等分析。实验结果表明，最佳工艺条件为球料比33、球磨转速528r／min、锌粉与PVC质量比9；产物中未形成结晶性氯化锌，且锌粉被氧化成ZnO；行星球磨比搅拌球磨对PVC的脱氯效果好，球磨时间超过3h，PVC的脱氯率可接近100％。     

Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

Mechanical treatment of automobile shredder residue for its application as a fuel

Enforcement of the Automobile Recycling Law in Japan requires utilization of automobile shredder residue (ASR). However, the high contents of copper (∼5%) and chlorine (∼1%) in ASR stand in the way of practical application. We studied methods for the removal of copper and chlorine from ASR so that it could be utilized as a fuel. By compression of the ASR for solidification with an extruder, the polyvinylchloride (PVC) that covered electrical cables was softened and stripped from the copper wire. The solidified ASR was comminuted with cutter mills and classified by dry density separation. The copper content of the obtained light products was 0.2%–0.5%. Furthermore, we studied the possibility of dechlorination of the ASR by mechanochemical (MC) activation. The light product of the ASR was milled with CaO or CaCO₃. The chlorine content decreased to about one-tenth of the original value after MC activation over 8 h. Therefore, the combined processing of softening–stripping and comminution liberated the PVC-covered cables and decreased the copper content of the ASR. In addition, dechlorination of the ASR was also possible by MC activation with the addition of calcium compounds.     

Effect of additives on dechlorination of PVC by mechanochemical treatment

Polyvinyl chloride (–CH₂–CHCl–) _n (PVC) was ground with a powdered inorganic material (CaO, CaCO₃, SiO₂, Al₂O₃, or slag) in a planetary ball mill under atmospheric conditions to investigate the effect of additions on its dechlorination. The grinding causes a dehydrochlorinating reaction, forming a mixture of partially dechlorinated PVC and inorganic chloride, depending on the grinding time. The dechlorination increases as the grinding progresses, and is improved with increasing amounts of additives. The most effective additive is a mixture of CaO, SiO₂, and Al₂O₃, which has the same constituent components as blast furnace slag. CaO, a mixture of CaO, SiO₂, and blast furnace slag, are also effective, but CaCO₃ is the least effective additive tired. Received: August 3, 2000 / Accepted: September 21, 2000     

Simultaneous treatment of PVC and oyster-shell wastes by mechanochemical means

This work presents a new process for dechlorinating poly-vinyl chloride (PVC) by the use of oyster-shell waste. The process consists of milling of PVC waste with oyster-shell waste, followed by washing the milled sample with water. The milling of PVC and oyster-shell mixture results in size reduction and rupture in bonds, leading to mechanically induced reactions between the two to form CaCl2 and hydrocarbon with C=C bonds. Washing the milled mixtures with water at room temperature allows complete removal of chlorine from the milled sample. More than 95% of chlorine in PVC was removed when 2h grinding is conducted for the mixture. The present process could offer a potential route to the handling and disposal of oyster-shell and PVC wastes.     

Deplasticization and dechlorination of flexible polyvinyl chloride in NaOH solution by microwave heating

This study investigated the deplasticization and dechlorination of flexible polyvinyl chloride (PVC) containing 59.2% PVC, 29.7% dioctyl phthalate (DOP), and approximately 12% stabilizers. Flexible PVC was treated with NaOH solutions at concentrations in the range 2–16 mol/l and heated by microwaves to temperatures between 100° and 250°C for 0–120 min. DOP was extracted from flexible PVC into the NaOH solution as a phthalic acid salt; the remaining PVC was subsequently dechlorinated by increasing the temperature. On internal heating using microwaves, the plasticizer was 100% extracted during processing at 150°C for 30 min, whereas the chlorides were 100% removed during processing at 235°C for 30 min; the residue was converted into hydrocarbon compounds. The maximum weight loss ratio was 71% compared to the pretreatment state. It was also found that 100% deplasticization and dechlorination was possible using 8 mol/l NaOH solution, which is almost half the concentration employed when using conventional external heating systems.     

Upgrading of poly(vinyl chloride) by chemical modifications using sodium sulfide

The recycling of poly(vinyl chloride) (PVC) is one of the most important issues in the treatment of waste plastics. To improve PVC recycling, it is necessary to develop new recycling techniques, including new techniques for the dechlorination of chlorine-containing polymers. It has been established that wet dechlorination of PVC in NaOH/ethylene glycol solution is more effective than dry dechlorination. In this study, the wet process was used, and the chemical modification of PVC by nucleophilic substitution was considered for upgrading waste PVC. Chlorine was substituted in solution by several nucleophilic reagents, thus changing the properties of PVC. The reaction of PVC in Na2S/ethylene glycol solution at 170°C resulted in the formation of a mixture comprising 32% elimination and 26% substitution products. The scanning electron microscopy/energy dispersive X-ray spectroscopy mappings and elementary analysis of PVC indicated that this chlorine-substitution process led to cross-linking by sulfur.     

Dechlorination of polyvinyl chloride in NaOH/ethylene glycol solution by microwave heating

This study investigated the dehydrochlorination of flexible polyvinyl chloride (PVC) containing 59.2% PVC, 29.7% dioctyl phthalate (DOP), and approximately 12% stabilizers. Flexible PVC was treated with NaOH/ethylene glycol (NaOH/EG) solutions at NaOH concentrations in the range 0.5–4 mol/l and was heated in a microwave heater at a temperature between 100° and 160°C for 0–30 min. All chlorides were completely eliminated by internal heating at 160°C using microwaves for 10 min in a 1 mol/l NaOH/EG solution, and the residue was made up of hydrocarbons. The weight loss rate reached a maximum of 74.7% at a temperature of 160°C. It was discovered that the use of microwaves significantly shortened the reaction time compared to using conventional electric heaters or other external heating systems and also allowed the use of lower concentrations of NaOH. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

锌粉对1,2,4-三氯苯的脱氯性能

采用锌粉对1,2,4-三氯苯（1,2,4-TCB）进行了脱氯的研究。实验结果表明,在40mL质量浓度为22.94m g/L的1,2,4-TCB水溶液中加入1.0g锌粉,反应24h时,1,2,4-TCB的还原率可达94.6%;反应16h时,试样中的Cl-浓度约为1,2,4-TCB完全脱氯所得Cl-理论浓度的30%;锌粉还原1,2,4-TCB的反应能在较宽的pH范围内进行,弱碱性条件下的脱氯效果最好,1,2,4-TCB的还原率达70%。     

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     

Carbonization of waste PVC to develop porous carbon material without further activation

Efficient removal of chlorine from PVC achieved by two-stage heat-treatment (280 and 410 degrees C) provided chlorine-free isotropic pitch containing additive. The pitch was stabilized and carbonized into porous carbons with surface areas of approximately 300 m2/g. Resultant porous carbons showed three pore structures of supermicropore, micropore and mesopore. The generation of CO2 from the decomposition of the CaCO3 additive in waste PVC is responsible for the development of porous structures. The surface area of the carbonized product increased after the removal of CaO.     

零价铁、镍-铁和铜-铁双金属对四氯乙烯的脱氯性能研究

研究了零价铁、镍-铁和铜-铁双金属对四氯乙烯（PCE）的还原性脱氯性能。实验结果表明，零价铁、镍-铁和铜-铁双金属对PCE的脱氯反应符合准一级反应动力学方程；双金属对P（=E的脱氯反应速率高于零价铁，镍-铁双金属对PCE的脱氯反应速率常数是零价铁的2．486倍；镍-铁和铜-铁双金属可使PCE完全脱氯，零价铁在对PCE脱氯的过程中产生一定量的三氯乙烯；增加金属质量，可提高PCE的脱氯反应速率；金属颗粒越小，越有利于PCE脱氯反应。     

Dehydrochlorination behavior of polyvinyl chloride and utilization of carbon residue: effect of plasticizer and inorganic filler

The dehydrochlorination behavior of plasticizer (DOP) and inorganic filler (CaCO₃) contained in PVC samples and the properties of the activated carbons produced from those carbon residues have been investigated. In the dehydrochlorination process, both additives contributed not only to a decrease in HCl yield but also to the prolonged evolution of HCl. Part of the Cl species were observed to be stabilized as CaCl₂ by reaction with calcium ions when CaCO₃ was added. More than 80% of chlorine removal was achieved in all samples at 533 K. The use of potassium as an activation agent led to the production of activated carbon with a specific surface area greater than 1000 m²/g at the low temperature of 1023 K and assisted also in the elimination of residual Cl species by the formation of KCl during activation. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

The effect of chlorine position of chlorinated phenols on their dechlorination kinetics by Fenton's reagent

Chlorine position of chlorophenol isomers has a significant effect on the dechlorination kinetics of monochlorophenols, dichlorophenols, and trichlorophenols during Fenton oxidation. The effects have been evaluated by the rate constants of the dechlorination kinetic model developed in this study. It is found that the dechlorination rate of 3-CP is faster than that of 4-CP, which is faster than that of 2-CP. Since OH and Cl groups on the aromatic ring are ortho and para directors, the directory effect of OH and Cl groups enhances the dechlorination kinetics of 2-CP due to acceleration of the hydroxylation of 2-CP. Therefore, the dechlorination kinetics increases accordingly. For trichlorophenols (TCP), steric hindrance plays an important role during their dechlorination process. Specifically, the closer the chlorine atoms locate with each other on the aromatic ring, the more difficult the dechlorination processes will be. The dechlorination kinetics of dichlorophenols seems to be affected by both directory effect of OH and Cl groups and the effect of steric hindrance of chlorine atoms. The directory effect of OH and Cl groups on trichlorophenols decreases since the chlorine atom occupied the positions which are the most favorable for hydroxyl radical attack.     

Feedstock recycling of waste polymeric material

The first International Symposium on Feedstock Recycling of Polymeric Materials (ISFR) was hosted in 1999 in Sendai, Japan. Since then, the ISFR has been held five times in different places in Asia and Europe. Each of these conferences focused on special issues covered by the Journal of Material Cycles and Waste Management. The topics included thermal processes with and without catalysts, wet processes in various solvents, the dehydrochlorination of PVC, mechanical recycling and separation techniques, as well as the treatment of biomaterials. This review is a compilation of the most interesting and important developments discussed at the ISFR during the last decade.     

Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate) on poly(vinyl chloride) dehydrochlorination

Recycling of poly(vinyl chloride) (PVC) waste is a serious problem because of its high chlorine content. Dehydrochlorination of PVC-containing polymer waste produces solid residue char, for which conversion to pyrolysis oil in a petrochemical plant seems to be an attractive way of recycling PVC waste. Unfortunately, some polymer admixtures react with HCl and cause formation of chloroorganic compounds in a char. This article describes the influence of polycarbonates and poly(ethylene terephthalate) on thermal feedstock recycling of PVC wastes using a two-stage method. It was found that the presence of polycarbonate causes the formation of small amounts of benzyl chloride and other chloroaryl or chloroalkylaryl compounds. Poly(ethylene terephthalate) interacts with HCl forming significant amounts of various chlorocompounds – mainly chloroethyl esters of terephthalic and benzoic acids, but derivatives possessing chlorine directly connected to the aromatic ring are also formed.     

Study on dechlorination technology for municipal waste plastics containing polyvinyl chloride and polyethylene terephthalate

It is necessary to remove chlorine efficiently 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 efficient 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.     

Oyster shell as substitute for aggregate in mortar.

Enormous amounts of oyster shell waste have been illegally disposed of at oyster farm sites along the southern coast of Korea. In this study to evaluate the possibility of recycling this waste for use as a construction material, the mechanical characteristics of pulverized oyster shell were investigated in terms of its potential utilization as a substitute for the aggregates used in mortar. The unconfined compressive strengths of various soil mortar specimens, with varying blending ratios of cement, water and oyster shell, were evaluated by performing unconfined compression tests, and the results were compared with the strengths of normal cement mortar made with sand. In addition, the effect of organic chemicals on the hardening of concrete was evaluated by preparing ethyl-benzene-mixed mortar specimens. The long-term strength improvement resulting from the addition of fly ash was also examined by performing unconfined compression tests on specimens with fly-ash content. There was no significant reduction in the compressive strength of the mortars containing small oyster shell particles instead of sand. From these test data, the possible application of oyster shells in construction materials could be verified, and the change in the strength parameters according to the presence of organic compounds was also evaluated.     

Characterization of alkali-activated thermally treated incinerator bottom ash

The fine fraction (<14mm) of incinerator bottom ash (IBA) obtained from a UK energy from waste plant has been milled and thermally treated at 600, 700, 800 and 880 degrees C. Treated materials have been activated with Ca(OH)(2) (10wt%) and the setting times and compressive strengths at different curing times measured. In addition to decomposition of CaCO(3) to CaO, thermal treatment increases the content of gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)). Thermally treated samples were significantly more reactive than milled IBA and heating to 700 degrees C produced a material which rapidly set. Silica, gehlenite and wollastonite were the main crystalline phases present in hydrated samples and a mixed sulphate-carbonate AFm-type phase (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33).11H(2)O) formed. Significant volumes of gas were generated during curing and this produced a macro-porous microstructure that limited strength to 2.8MPa. The new materials may have potential for use as controlled low-strength materials.