Decomposition reactions of epoxy resin and polyetheretherketone resin in sub- and supercritical water

Epoxy resin and polyetheretherketone (PEEK) resin were decomposed into their monomers such as phenol, cresols, and their analogues by thermal treatment in sub- and supercritical water in a 10-ml tubing bomb reactor. The addition of basic compounds such as Na₂CO₃ was effective in promoting the decomposition reaction of the resins. In the reaction of epoxy resin, the yield of identified products reached 10% for the reaction at 703K over 1h. In the reaction of PEEK resin, the total yield of phenol and dibenzofuran reached 88% for the reaction at 703K over 3h. Chemical participation of water in the decomposition reaction was confirmed by the reaction of dinaphthylether.     

Rapid hydropyrolysis of model compounds for epoxy resin oligomers and biomass tar

The rapid hydropyrolysis of model compounds for epoxy resin oligomers and biomass tar was carried out in a hydrogen atmosphere at 1073 K and 973 K. The assumed oligomers were partially pyrolyzed epoxy resin with biomass tar as solvent for the resin. The product distributions obtained from rapid hydropyrolysis of phenol and bisphenol-A are shown. We also discuss the effects of reaction temperature and hydrogen partial pressure on the product yield. In particular, more phenol was produced from bisphenol-A at 973 K than at 1073 K. The yield of methane, which was the final hydropyrolysis product, increased with increasing hydrogen partial pressure, whereas benzene and phenol were believed to behave as intermediate products in the hydropyrolysis reaction. The results suggest that phenol could be obtained with high selectivity from tar by optimizing the reaction conditions.     

Degradation Mechanism of CF/EP Composites in Supercritical <Emphasis Type="Italic">n</Emphasis>-Butanol with Alkali Additives

CF/EP (carbon fibre/epoxy resin) composites were degraded by supercritical n-butanol with alkali additive KOH in a batch reactor. The catalytic degradation mechanism of the composites was investigated based on the analysis of liquid phase products by GC–MS and solid phase products by FTIR. The results indicate that alkali additive (KOH) can promote Guerbet reaction and increase hydrogen donor capability of supercritical n-butanol. The H^· can combine promptly with the free radical formed by the scission of linear and crosslinked chains in epoxy resin to generate the liquid products, including phenol, 4-isopropylphenol, 4-(2-methylallyl)phenol and other derivatives of benzene and phenol. The combination of supercritical n-butanol with alkali additive is an effective way to degrade and recycle CF/EP composites.     

Feasibility investigation on a dual waste-plastics recycling system concept

Fiber-reinforced plastics (FRP) were first used as a material for boats and bath tubs about 40 years ago. Because of their great durability, wastes including FRP products are increasing. In addition, since the FRP resin is synthesized from expensive reactants, material recycling is highly desirable. Recycling using supercritical water is one solution; however, the cost of producing the high pressure and temperature needed to produce supercritical water prevents the concept from being realized. Therefore, we proposed a system concept based on dual waste-plastics recycling. A numerical survey of the results confirmed that our concept was feasible and would contribute to resource recycling as we expected. Received: January 6, 1998 / Accepted: July 23, 1999     

用废旧电路板热解油制备酚醛树脂

在碳酸钙存在下,采用热解技术将废旧电路板中的树脂转化为富含酚的热解油,然后直接加入甲醛溶液反应制备热解油型酚醛树脂,实现了废旧电路板中树脂的再生,酚醛树脂的性能结构类似于氨催化的酚醛树脂。实验结果表明：在n（甲醛）：n（热解油）为1．8～2．1的条件下,无需外加催化剂,在60,80,90℃下分别反应30min制备的热解油型酚醛树脂的性能最佳,且可满足GB／T14732—93《木材工业胶黏剂用脲醛、酚醛、三氧氰胺甲醛树脂》中层压材料用酚醛树脂产品的相关标准。     

Recycling of carbon fiber-reinforced plastic using supercritical and subcritical fluids

The recycling of waste plastics is important for the prevention of the exhaustion of fossil resources. In this paper, recycling techniques of carbon fiber-reinforced plastic (CFRP) using supercritical and subcritical fluids were reviewed. The matrix resin of CFRP such as epoxy resin or resol resin was decomposed by supercritical and subcritical fluids, and the carbon fiber without thermal damage was recovered from CFRP. Mainly, water or alcohol was used as decomposition medium.     

废弃线路板热解油合成改性酚醛树脂

以废弃线路板热解油为原料,采用碱溶—中和—萃取工艺提取其中以苯酚为主的粗酚,并合成改性酚醛树脂。合成硼酸改性酚醛树脂的优化工艺条件为n(粗酚)∶n(外加苯酚)=2∶3,n(粗酚+外加苯酚)∶n(甲醛)∶n(NaOH)∶n(硼酸)=1∶1.5∶0.15∶0.17;合成有机硅改性酚醛树脂的优化工艺条件为n(粗酚)∶n(外加苯酚)=2∶3,n(粗酚+外加苯酚)∶n(甲醛)∶n(NaOH)∶n(正硅酸乙酯)=1∶1.3∶0.1∶0.1。所合成的硼酸改性和有机硅改性酚醛树脂的主要性能指标均满足YB/T4131—2005《耐火材料用酚醛树脂》中牌号为PFn-5301的热固性液体树脂性能的要求。     

Destruction of PAHS from soil by using pressurized hot water extraction coupled with supercritical water oxidation

Chemical processes utilizing water both as extraction solvent and reaction medium are promising "Green Chemistry" alternatives to conventional techniques. Equipment for on-line coupled hot water extraction and supercritical water oxidation was constructed to extract polyaromatic hydrocarbons and toluene from sea sand followed by oxidation using hydrogen peroxide. The effectiveness of the technique is based on the physico-chemical properties of heated and pressurized water. Extraction efficiency increased with temperature and time; the best results were obtained at 300 degrees C with 40 min extraction time. In the oxidation stage, conversion of the PAHs increased with reaction time and oxidant concentration and the best conversion (97.0-99.9%, depending on the compound) was obtained at 425 degrees C with 43 s reaction time. Benzaldehyde and benzoic acid were the most abundant reaction intermediates in the oxidation process. In addition, phenol, p-cresol, and benzyl alcohol were found as intermediates. The intermediates originated mainly from toluene, which was present in much greater concentration than PAHs in the reaction medium.     

Polyethylene conversion by partial oxidation in supercritical water

This paper gives the results of partial oxidation experiments of polyethylene (PE) in supercritical water (SCW). The experiments were carried out at a reaction temperature of 693K and a reaction time of 30 min using 6 cm³ of a batch-type reactor. The loaded sample weight was 0.3 g and there was 2.52 g water (0.42 g/cm³). The ratio of oxygen atoms to carbon atoms was 0.3. The results show a significant CO formation in O₂–SCW, and the 1-alkene/n-alkane ratio in partial oxidation was higher than that in SCW pyrolysis. These results suggest the possibility of the hydrogenation of hydrocarbon through partial oxidation followed by a water–gas shift reaction. Received: July 19, 2000 / Accepted: September 28, 2000     

高浓度酚醛树脂生产废水的预处理

采用二次缩合反应预处理高浓度酚醛树脂生产废水。一次反应的最佳工艺条件为：甲醛加入量0.010 0 mL/mL,Ba（OH）2加入量0.005 g/mL,反应时间3 h,反应温度85 ℃。最佳工艺条件下的一次反应COD去除率为 52.9%。二次反应中,当反应温度为80 ℃、反应时间为3 h、尿素加入量为3 g/L时,二次反应COD去除率最高,为31.5%。COD=85 000 mg/L、ρ（挥发酚）= 12 000 mg/L、ρ（甲醛）=6 740 mg/L的废水经两次缩合反应处理后,出水中COD=27 400 mg/L,COD的总去除率为67.8%;ρ（挥发酚）=2 400 mg/L,挥发酚的总去除率达80.0%;ρ（甲醛）= 980 mg/L,甲醛的总去除率达84.9%。处理1 t废水还可回收酚醛树脂6.75 kg。     

HZ-16型大孔树脂吸附处理含RDT-8废水

采用HZ-16型大孔树脂对含三（三溴苯氧基）三嗪（RDT-8）废水进行吸附及脱附处理。实验结果表明：在废水流量为4.0 BV/h的条件下,树脂最佳吸附工艺条件为出水体积88.0 BV,此条件下出水COD小于291 mg/L,挥发酚质量浓度小于0.08 mg/L;在脱附液流量为0.5 BV/h的条件下,树脂最佳脱附工艺条件为脱附液体积3.0 BV,此条件下脱附液中挥发酚质量浓度为30.6 mg/L,挥发酚脱附率高达76.4%。在最佳吸附-脱附工艺条件下,连续进行10次动态吸附-脱附实验,吸附出水中COD为137~294 mg/L,COD去除率为72.5%~89.1%,挥发酚质量浓度稳定在0.05 mg/L以下,挥发酚去除率为99.8%~100%,说明HZ-16型大孔树脂的吸附-脱附性能稳定。     

Experimental study of the bio-oil production from sewage sludge by supercritical conversion process

Environment-friendly treatment of sewage sludge has become tremendously important. Conversion of sewage sludge into energy products by environment-friendly conversion process, with its energy recovery and environmental benefits, is being paid significant attention. Direct liquefaction of sewage sludge into bio-oils with supercritical water (SCW) was therefore put forward in this study, as de-water usually requiring intensive energy input is not necessary in this direct liquefaction. Supercritical water may act as a strong solvent and also a reactant, as well as catalyst promoting reaction process. Experiments were carried out in a self designed high-pressure reaction system with varying operating conditions. Through orthogonal experiments, it was found that temperature and residence time dominated on bio-oil yield compared with other operating parameters. Temperature from 350 to 500 °C and reaction residence time of 0, 30, 60 min were accordingly investigated in details, respectively. Under supercritical conversion, the maximum bio-oil yield could achieve 39.73%, which was performed at 375 °C and 0 min reaction residence time. Meanwhile, function of supercritical water was concluded. Fuel property analysis showed the potential of bio-oil application as crude fuel.     

选择性吸附-高效生物降解法处理含硝基苯与苯酚混合废水

结合NDA-150型树脂（简称树脂）选择性吸附和生物降解的优点，对含硝基苯和苯酚的模拟混合废水（简称混合废水）进行处理。通过树脂的选择性吸附，使混合废水中的硝基苯和苯酚分离，随后用高效菌对树脂所吸附的硝基苯进行生物降解，同时实现树脂的再生。实验结果表明：通过调节混合废水的pH，树脂可有效地将混合废水中的硝基苯和苯酚进行选择性吸附分离；树脂对硝基苯的吸附是可逆的；树脂的再生程度受微生物对可利用硝基苯质量浓度的下限（1．2mg／L）限制；吸附-生物再生循环实验结果表明，该树脂可有效抵抗微生物的生物降解与破坏。     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Aminolysis and aminoglycolysis of waste poly(ethylene terephthalate)

This paper describes the chemical degradation of waste poly(ethylene terephthalate) (PET) with polyamines or triethanolamine, the characteristics of the products, and a search for ways to use these products. Solvolysis of the polymer ester bonds was caused by diethylenetriamine, triethylenetetramine, and their mixtures, as well as mixtures of triethylenetetramine and p-phenylenediamine or triethanolamine. Products of aminolysis or aminoglycolysis of PET obtained in reactions performed at 200–210°C (with a molar ratio of the recurrent polymer unit to amine of 1 : 2) have been characterized using nuclear magnetic resonance (NMR). Viscosity and hydroxyl number measurements have been done for PET/triethanolamine products. Substances from aminolytical reactions with polyamines were tested as hardeners for liquid epoxy resins, and the product of polymer aminoglycolysis with triethanolamine was tested as an epoxy resin hardener, e.g., for water-borne paints, and a polyol component for rigid polyurethane foams. The compositions of epoxy resin hardeners have been characterized using DSC and rheometry. Comparative analyses of the hardened epoxy materials have been done on the basis of glass temperature and mechanical properties data, as well as some specific properties of the coating materials and rigid polyurethane foams. Received: September 15, 2000 / Accepted: September 21, 2000     

Supercritical water gasification of sewage sludge using bench-scale batch reactor: advantages and drawbacks

Sewage sludge, a byproduct of municipal wastewater treatment, was gasified by supercritical water using a bench-scale batch reactor. Configuration of bench-scale batch reactor and operation procedures are discussed in detail. Experience and challenges that arose during the experiment are also shared. Using the bench-scale reactor under the condition of 600 °C, 23 MPa, and a reaction time of 60 min without catalyst presence, a total gas yield of 9.8 mol/(kg-sewage sludge) was obtained. Furthermore, investigations on operational parameters were conducted. Extension of reaction time up to 60 min increased the gasification, reaching a plateau thereafter. Investigation on pressure indicated the superiority of supercritical pressure. The addition of Ni as a catalyst also promoted gasification, although inorganic salts and char seemed to cover the catalyst surface. With regard to the prospect of future operation at a municipal waste water treatment plant, the effect of operational parameters on heavy metal concentration in the liquid phase is also discussed.     

Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(6)kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.     

废印制线路板真空热解产物分析

在自行设计的间歇式固定床真空热解装置中热解废印制线路板(PCB),对热解产物进行了分析.在热解温度为550 ℃、热解压力为20 kPa、恒温时间为60 min的条件下,得到的热解产物质量分数为:热解渣70%;热解油3%～4%;不可冷凝热解气26%～27%.经气相色谱-质谱联用(GC-MS)分析,热解油经常压蒸馏后得到的低沸点液态油中含有29种化合物,主要有苯酚、对异丙基酚、3-乙基酚、4-甲酚及2-溴苯酚,还含有少量含溴化合物和含氯化合物.热解油经简单的蒸馏就可达到回收酚类化合物的目的.热解渣经风选可实现铜与黏附有碳黑的玻璃纤维的分离,其中铜质量分数约30%,黏附有碳黑的玻璃纤维质量分数约70%.     

废水中氨氮湿式空气氧化和超临界水氧化研究进展

湿式空气氧化法(WAO)和超临界水氧化法（SCWO)废水处理技术近年已有广泛研究。当催化剂存在于氧化体系时,不仅能降低反应温度、压力,而且可提高废水中有害物质的降解效率。介绍了氨的湿式空气氧化和超临界水氧化催化剂应用的研究进展、各种催化剂在超临界水中的稳定性能及氨的催化超临界水氧化情况。