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.     

Effect of pressure on the hydropyrolysis of Jatropha seed deoiled cake

The necessity to move towards a sustainable economy is increasing day by day owing to various problems like climate change, increasing crude oil prices, etc. In this line, hydropyrolysis of Jatropha seed deoiled cake has been carried out at various pressures of hydrogen (1, 20, 40 and 52 bar) at 450 °C. With an increase in pressure under the experimental conditions of present study from 1 to 40 bar, the yield of bio-oil is found to have increased and beyond 40 bar the bio-oil yields have decreased. It has been observed that the liquid bio-oil yield is highest at 17 wt% at 40 bar. The FTIR spectrum of the bio-oil and char at 40 bar shows maximum functionality, indicating the clear opening of the macromolecular structure. The EDAX analysis of the hydropyrolysis char obtained at 40 bar pressure show a maximum of 85 wt% carbon and minimum of oxygen 13 wt%.     

Valorisation of forestry waste by pyrolysis in an auger reactor

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.     

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.     

Effect of polyethylene addition to coal on hydrogasification enhancement

Hydrogasification of a coal/polyethylene mixture was carried out using a low concentration of polyethylene in the samples with the aim of industrial application. Coal/polyethylene mixtures in the ratio of 90:10 and 75:25 were used in this study. A hydrogasification experiment was conducted using a unique batch reactor at 1073 K under a 7.1 MPa hydrogen atmosphere. The reaction time varied from 1 to 80 s. The results revealed a methane yield from the mixtures that was noticeably greater than the values calculated from experimental results obtained from coal and polyethylene respectively, assuming no mutual influences. A significant synergistic effect was observed even when the polyethylene content was as low as 10 %. It is suggested that there might be an advantage in hydrogasification processes if waste plastics are mixed with coal, such content being practically assumed.     

酚焦油资源化技术研究(Ⅱ)--裂解产物的分离

开发出一种精馏与钠盐法相结合的分离酚焦油裂解产物的新工艺，裂解产物经精馏，蒸出异丙苯等轻组分、苯酚馏分和共沸物。共沸物中加入氢氧化钠，分离出酚钠盐和苯乙酮。轻组分和酚钠盐均返回苯酚、丙酮生产装置。裂解产物中有用物质的收率为92．91％，苯乙酮的收率为82．38％，其纯度大于98％。     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Leaching studies for tin recovery from waste e-scrap

Printed circuit boards (PCBs) are the most essential components of all electrical and electronic equipments, which contain noteworthy quantity of metals, some of which are toxic to life and all of which are valuable resources. Therefore, recycling of PCBs is necessary for the safe disposal/utilization of these metals. Present paper is a part of developing Indo-Korean recycling technique consists of organic swelling pre-treatment technique for the liberation of thin layer of metallic sheet and the treatment of epoxy resin to remove/recover toxic soldering material. To optimize the parameters required for recovery of tin from waste PCBs, initially the bench scale studies were carried out using fresh solder (containing 52.6% Sn and 47.3% Pb) varying the acid concentration, temperature, mixing time and pulp density. The experimental data indicate that 95.79% of tin was leached out from solder material using 5.5M HCl at fixed pulp density 50g/L and temperature 90°C in mixing time 165min. Kinetic studies followed the chemical reaction controlled dense constant size cylindrical particles with activation energy of 117.68kJ/mol. However, 97.79% of tin was found to be leached out from solder materials of liberated swelled epoxy resin using 4.5M HCl at 90°C, mixing time 60min and pulp density 50g/L. From the leach liquor of solder materials of epoxy resin, the precipitate of sodium stannate as value added product was obtained at pH 1.9. The Pb from the leach residue was removed by using 0.1M nitric acid at 90°C in mixing time 45min and pulp density 10g/L. The metal free epoxy resin could be disposed-of safely/used as filling material without affecting the environment.     

Evaluation of a recycling process for printed circuit board by physical separation and heat treatment

Printed circuit boards (PCBs) from discarded personal computer (PC) and hard disk drive were crushed by explosion in water or mechanical comminution in order to disintegrate the attached parts. More parts were stripped from PCB of PC, composed of epoxy resin; than from PCB of household appliance, composed of phenol resin.In an attempt to raise the copper grade of PCB by removing other components, a carbonization treatment was investigated. The crushed PCB without surface-mounted parts was carbonized under a nitrogen atmosphere at 873–1073 K. After screening, the char was classified by size into oversized pieces, undersized pieces and powder. The copper foil and glass fiber pieces were liberated and collected in undersized fraction. The copper foil was liberated easily from glass fiber by stamping treatment.As one of the mounted parts, the multi-layered ceramic capacitors (MLCCs), which contain nickel, were carbonized at 873 K. The magnetic separation is carried out at a lower magnetic field strength of 0.1 T and then at 0.8 T. In the +0.5 mm size fraction the nickel grade in magnetic product was increased from 0.16% to 6.7% and the nickel recovery is 74%.The other useful mounted parts are tantalum capacitors. The tantalum capacitors were collected from mounted parts. The tantalum-sintered bodies were separated from molded resins by heat treatment at 723–773 K in air atmosphere and screening of 0.5 mm. Silica was removed and 70% of tantalum grade was obtained after more than 823 K heating and separation.Next, the evaluation of Cu recycling in PCB is estimated. Energy consumption of new process increased and the treatment cost becomes 3 times higher comparing the conventional process, while the environmental burden of new process decreased comparing conventional process.The nickel recovery process in fine ground particles increased energy and energy cost comparing those of the conventional process. However, the environmental burden decreased than the conventional one.The process for recovering tantalum used more heat for the treatment and therefore the energy consumption increased by 50%, when comparing with conventional process. However, the market price for tantalum is very large; the profit for tantalum recovery is added. Also the environmental burden decreased by the recycling of tantalum recovery. Therefore, the tantalum recovery is very important step in the PCB recycling. If there is no tantalum, the consumed energy and treatment cost increase in the new process, though the environmental burden decreases.     

Catalytic hydrothermal depolymerization of nylon 6

Depolymerization of nylon 6 to produce ε-caprolactam using an environmentally friendly heteropoly acid catalyst was studied at temperatures between 553 and 603 K in water. The products of depolymerization were analyzed qualitatively and quantitatively by means of mass spectrometry and high-performance liquid chromatography. The results showed that the depolymerized product was mainly ε-caprolactam with a little 6-aminocaproic acid and oligomers. The phosphotungstic heteropoly acid used as a catalyst can improve the hydrolysis rate and yield of ε-caprolactam. The optimum hydrolysis conditions for ε-caprolactam yield were as follows: phosphotungstic heteropoly acid content, 3%; reaction temperature, 573 K; and reaction time, 85 min. Under these conditions, the yield of ε-caprolactam was 77.96%. In the temperature range 553–603 K, the activation energy of 3% phosphotungstic heteropoly acid-catalyzed depolymerization was evaluated as 77.38 kJ/mol, which is lower than the 86.64 kJ/mol value for no catalyst.     

Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition

Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H₂, CO, CH₄, CO₂ and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.     

Renewable hydrocarbons through biomass hydropyrolysis process: challenges and opportunities

Considering the current issues of carbon control and the desire to become less dependent on imported oil, the utilization of renewable hydrocarbons for the reduction of CO₂ emission and production of liquid synthetic fuels/chemicals has been proposed by researchers worldwide. Efforts to make chemicals/fuels from renewable resources have escalated over the past few years. Biomass-based renewable hydrocarbons are considered to be one of the sources with the highest potential to contribute to the energy needs of modern society for both developed and developing economies worldwide. Fast pyrolysis is becoming an important thermal route to convert biomass to liquid fuels; however, the raw bio-oils obtained have a number of negative properties such as high acidity, high water content, and variable viscosity over time. To overcome this problem and produce bio-oil of good quality, process of ‘hyropyrolysis’ has been developed. The scope for using pyrolysis under hydrogen pressure and also by process of hydropyrolysis followed by in situ hydroconversion of vapors to give oils with much lower oxygen contents has been reviewed.     

Thermal decomposition of guaiacol in sub- and supercritical water and its kinetic analysis

The conversion of biomass waste into resources as a recycling process is receiving increased interest due to the perceived need for a sustainable global carbon cycle and environmental considerations. Several treatment processes are being developed. Hydrothermal treatment is one of the most effective approaches, because water at high temperatures and high pressures behaves as a reaction medium with remarkable properties. In this work, the reaction behavior of guaiacol as a biomass model compound was studied in subcritical water at 483–563 K and in supercritical water at 653–673 K using a batch reactor. Guaiacol can be considered representative of the aromatic ring structures present in lignin, a major component of woody biomass. The chemical species formed in aqueous products were identified by gas chromatography/mass spectrometry and quantified using high-performance liquid chromatography. The effect of pressure and reaction time on the conversion process of guaiacol is discussed. The results obtained indicate that this method has potential for efficient organic waste conversion.     

An innovative example of herb residues recycling by gasification in a fluidized bed

A utilization way of herb residues is designed to convert herb residues to gas fuel in industrial-scale by a circulating fluidized bed gasifier in this paper. The product gas is used in the production of Chinese medicine, and the heat of the flue gas from the boiler can be used in herb residues drying to realize the energy recycling and no herb residues discharge. The gasification characteristics of herb residues in the circulating fluidized bed of 300 kg/h were investigated for about 200 h. The results indicated that the gas composition and tar yield were affected by biomass flow rate, equivalence ratio (ER), moisture content and char circulating. The lower heating value of product gas was 4–5 MJ/m³ using herb residues as feedstock. When mean biomass flow rate was at 5.5 kg m^?2 s^?1 and ER at 0.35, the product gas reached a good condition with lower heating value of 4.89 MJ/m³ and cold gas efficiency of 62.36%. When the moisture content changed from 12.5% to 18.7%, the concentrations of H₂, CO and CO₂ changed from 4.66% to 6.92%, 11.23% to 10.15%, and 16.55% to 17.82% respectively, and the tar content in gas decreased from 15.1 g/m³ to 14.4 g/m³ when the moisture content increased from 12.5% to 15.4%. There are metal oxides in the ash of herb residues, especially CaO, MgO, K₂O, Al₂O₃, and Fe₂O₃ which have obvious function on tar catalytic decomposition. The ash that attaches to the char particles can decrease the tar yield and improve the quality of gas after returning to the gasifier.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Tar removal during the fluidized bed gasification of plastic waste

A recycled polyethylene was fed in a pilot plant bubbling fluidized bed gasifier, having an internal diameter of 0.381 m and a maximum feeding capacity of 90 kg/h. The experimental runs were carried out under various operating conditions: the bed temperature was kept at about 850 degrees C, the equivalence ratio varied between 0.2 and 0.35, the amount of bed material was between 131 and 215 kg, the fluidizing velocity was between 0.5 and 0.7 m/s, quartz sand and olivine were used as bed material, and air and steam were used as fluidizing reactants. The results confirm that the tar removal treatments applied inside the gasifier (primary methods) can eliminate or strongly reduce the need for a further downstream cleanup of the syngas. In particular, the utilization of a natural olivine as an in situ tar reduction agent remarkably improves the quality of the product gas, in terms of both high hydrogen volumetric fraction and larger syngas yield.     

Evaluation of waste pyrolysis characteristics in a pressurized fluidized bed reactor

To obtain the distribution of fuel components to gas, tar and char in a pressurized fluidized bed waste pyrolyzer, experiments were conducted with a laboratory scale fluidized bed reactor. Waste samples were fed batchwise from the top of the reactor into the fluidized bed of silica sand and pyrolyzed by nitrogen/nitrogen-O2 gas and the effects of pressure, particle size, heating rate and oxygen addition were investigated. In the case of rubber, the char yield tended to increase a little and the tar yield decrease over the pressure of 304-709 kPa. In comparison with the thermogravimetry data it was clearly demonstrated that the char yield from fluidized bed pyrolysis is much lower. A small amount of oxygen addition decreased both tar and char yields but its further increase did not affect them very much.     

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     

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。     

Noncatalytic liquefaction of tar with low-temperature hydrothermal treatment

Water at hydrothermal and supercritical conditions is considered a promising solvent for the degradation of hazardous waste into harmless compounds. Tar liquefaction experiments were conducted using a batch-type reactor at temperatures between 623 K and 673 K and at pressures between 25 and 40 MPa. A reaction mechanism for tar liquefaction is proposed. Moreover, on the basis of the experimental results, this method could become an efficient method for tar liquefaction, producing high yields of valuable chemical intermediates.