Novel polyol initiator from polyurethane recycling residue

Flexible polyurethane foams can be advantageously treated by two-phase glycolysis in order to recover polyols with improved quality. The bottom phase obtained, which contains highly toxic reaction by-products and the excess glycol, presents an environmental and economic problem which should be solved. The main purpose of this work is the development of process for the valorization of these by-products, converting them in non-dangerous and profitable substances. For this process, most of the glycol can be recovered by means of vacuum distillation in order to reuse it in the glycolysis. On the other hand, the vacuum residue, containing the isocyanate part of the glycolysis by-products, was assayed as initiator in the synthesis of new polyols. Propoxylation of the initiator was carried out in different experimental conditions to obtain several polyether-polyols. Rigid polyurethane foams with suitable technical properties were synthesized with those polyols synthesized with the dangerous glycolysis by-products.     

Thermo-Chemical Decomposition Study of Polyurethane Elastomer Through Glycerolysis Route with Using Crude and Refined Glycerine as a Transesterification Agent

Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemical recycling. The main effort of this paper focuses on the employment of commercial glycerine of analytical grade and waste glycerine without purification derived from the biodiesel production, as a decomposing agent for polyurethane recycling. In this study, the influence of polyurethane to glycerine mass ratio (PU/GL) and the type of decomposing agent on the chemical structure by FTIR, ¹H NMR and GPC was examined. FTIR analysis of the glycerolysates showed absorption peaks similar to the virgin polyol. Those results are in compliance with GPC chromatograms, which showed for all samples, well-defined peak at ca. 13 min of retention time. The molecular weight of glycerolysates was ranging from 800 to 1300 g mol^?1 depending on PU/GL mass ratio. The novel decomposition agent, namely waste glycerine derived from biodiesel production was successfully used in glycerolysis process.     

Synthesis of unsaturated polyester resin from glycolysed postconsumer PET wastes

The purpose of this study was to explore ways to extend the chemical recycling of poly(ethylene terephthalate) (PET) as a valuable feedstock for chemical processes. First, PET wastes were depolymerised using a glycolysis method in the presence of sodium carbonate, which is considered to be a less environmentally damaging option for a catalyst. Good yields of the monomer bis(2-hydroxyethyl) terephthalate (BHET) were obtained (80 %). Second, to develop an economically viable recycling programme for the reclaimed BHET, the conversion of purified BHET into unsaturated polyester resins (UPR) was studied. The recovered monomer was thus polyesterified with maleic anhydride and subsequently mixed with styrene monomer to prepare UPRs. The resins were casted by a crosslinking reaction using methyl ethyl ketone peroxide and cobalt 2-ethylhexanoate as the initiator and catalyst, respectively. The polyesterification reaction was followed by gel permeation chromatography. The curing process was studied by differential scanning calorimetry and infrared spectroscopy. The cured resin was subjected to various characterisation methods in order to determine its chemical, physical and mechanical properties. Resins with suitable properties for commercial application were obtained.     

Glycolysis of flexible polyurethane wastes using stannous octoate as the catalyst

Flexible polyurethane foam wastes can be advantageously treated by two-phase glycolysis to recover the polyols with an improved quality compared to single-phase processes. This reaction has been traditionally catalyzed by alkanolamines, titanium compounds, or acetates. Recently, the employment of new catalysts based on potassium and calcium octoates has opened up a new way to catalyze the glycolysis of polyurethanes. In this work, the use of stannous octoate, which has never before been applied in the glycolysis reactions of polyurethanes, is proposed. The catalytic activity of stannous octoate in such a process was studied. The decomposition rate and the purity of polyol obtained were greater than those obtained using other catalysts previously employed for this application.     

Recycling of waste PET into useful textile auxiliaries

Polyethylene terephthalate (PET) waste fibers were initially depolymerized using a glycolysis route in the presence of sodium sulfate as a catalyst, which is a commonly used chemical and ecofriendly as compared to heavy metal catalysts. Good yield of the pure monomer bis(2-hydroxyethylene terephthalate) (BHET) was obtained. Further, to attempt its reuse, the purified BHET was converted to different fatty amide derivatives to obtain quaternary ammonium compounds that have a potential for use as softener in the textile finishing process. The products were characterized by infrared spectroscopy. Application of these synthesized compounds was carried out on cotton fabric; they were evaluated for performance and were found to give good results. The chemicals used during depolymerization and reuse of PET are inexpensive and comparatively less harmful to the environment, and thus offer advantages in the chemical recycling of polyester waste fibers.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Studies on the Glycolysis Behavior of Polyurethane Fiber Waste with Diethylene Glycol

Glycolysis behavior of polyurethane fiber waste with diethylene glycol (DEG) was studied. The glycolysis products were separated into two phases, white waxy material and brown liquid via freezing process. The white waxy material was characterized by Flourier Transform Infrared spectrometer. It has been proved that the glycolysis process of the fiber waste is affected by the reaction temperature and time. The glycolysis kinetics was investigated by reacting the waste in a twin-screw-Micro Compounder. A second-order kinetic model for the glycolysis was adopted, and the experiment data fit it quite well. The rate constants and the activation energy of glycolysis process were calculated.     

脉冲电晕放电低温等离子体分解NH_3的动力学及机理研究

探讨了脉冲电晕放电低温等离子体分解NH_3的反应动力学及机理。采用比色法和离子色谱法分析了反应产物。考察了低温等离子体分解—水吸收联合工艺对含NH_3气体的处理效果。实验结果表明:低温等离子体分解NH_3符合准一级动力学经验模型kt=ln(ρ0/ρt)=-ln(1-D),其中k=0.007 9P-0.190 3(P≥24.08);NH_3的去除主要通过高能电子作用直接分解或与中间产物反应生成NH_4NO_3和NH_4NO_2两种方式;该联合工艺不仅可去除NH_4NO_3、NH_4NO_2等水溶性降解产物,同时臭氧遇水生成的·OH还可进一步分解水溶液中溶解性NH_3。     

高分子除氯剂对水中氯离子的吸附机理

采用高分子除氯剂吸附水中的氯离子,考察了除氯剂投加量、反应时间、反应温度、竞争离子等对氯离子去除率的影响。实验结果表明:随着除氯剂投加量增加,氯离子去除率不断提高;吸附动力学符合拟二级动力学模型,表明化学吸附可能是氯离子吸附过程的速率控制步骤;Elovich模型表明除氯剂表面吸附的氯离子存在非均相扩散的吸附-脱附过程;Freundlich等温吸附模型能更好地描述吸附过程,结合热力学计算表明该过程是一个自发进行的吸热熵增的化学吸附过程,温度越高自发程度越大。     

Effects of Saturated Acids on Physical Properties of UPE Resins Prepared from Recycled PET Products

In this study, effects of saturated acids on physical properties, including hardness, impact strength, flexural properties and thermal properties, of unsaturated polyester or UPE resins prepared from recycled PET bottles and fabrics were investigated. PET was depolymerized by glycolysis reaction with the excess propylene glycol in the presence of zinc acetate as a catalyst. UPE resins were then synthesized by polyesterification of these glycolyzed products with maleic anhydride as an unsaturated diacid as well as succinic acid and adipic acid as a saturated diacid. With the addition of styrene monomer, UPEs were subsequently casted into specimens by crosslinking reaction using methyl ethyl ketone peroxide and cobalt octoate as an initiator and a catalyst, respectively. Physical properties of the cured specimens were then studied. The results showed that, when a saturated acid was incorporated, the hardness of the cured UPE resins decreased due to the decreasing amount of crosslinks. The extended distance between crosslinking sites on molecular chains facilitated load distribution, resulting in the significant improvement of impact strength. The flexural strength was also improved when the small amount of saturated acid was used. The onset thermal degradation temperatures and the glass transition temperatures of the prepared UPE resins were almost unchanged.     

Treatment of waste containing EDTA by chemical oxidation

Ethylenediaminetetraacetic acid (EDTA) is a chelating agent that has been extensively used to enhance the solubilization of heavy metal cations and release of EDTA contributes to environmental problems. EDTA is recalcitrant to microbial metabolism and chemical oxidation is considered a possible method of remedial treatment. The use of the commercially available process of MIOX Corporation generates mixed oxidants on site and this solution is markedly effective in the destruction of the chelating characteristic and the decarboxylation of EDTA. When measuring the release of C-14 from carboxyl labeled EDTA, the mixed oxidant solution was comparable to the Fenton's reaction over a broad pH range. The presence of Mn²⁺, Cr³⁺, or Fe³⁺ at levels equal to that of EDTA stimulated the rate of EDTA decomposition; however, the rate of EDTA breakdown was inhibited when the concentration of Cr³⁺ or Mn²⁺ exceeded the concentration of EDTA. The treatment of Co²⁺–EDTA or Cu²⁺–EDTA with mixed oxidants in the presence of ultra violet light resulted in the loss of chelation ability of EDTA. In the absence of chelated metals, over 75% of the chelation property of a 70 mM EDTA solution was destroyed in 45 min. The reaction products resulting from the use of mixed oxidants added to EDTA were non-toxic to bacteria and should not contribute to additional environmental problems.     

Valorization of titanium metal wastes as tanning agent used in leather industry

The development of new tanning agents and new technologies in the leather sector is required to cope with the increasingly higher environmental pressure on the current tanning materials and processes such as tanning with chromium salts. In this paper, the use of titanium wastes (cuttings) resulting from the process of obtaining highly pure titanium (ingots), for the synthesis of new tanning agent and tanning bovine hides with new tanning agent, as alternative to tanning with chromium salts are investigated. For this purpose, Ti waste and Ti-based tanning agent were characterized for metal content by inductively coupled plasma mass spectrometry (ICP-MS) and chemical analysis; the tanned leather (wet white leather) was characterized by Scanning Electron Microscope/Energy Dispersive Using X-ray (Analysis). SEM/EDX analysis for metal content; Differential scanning calorimetric (DSC), Micro-Hot-Table and standard shrinkage temperature showing a hydrothermal stability (ranged from 75.3 to 77 °C) and chemical analysis showing the leather is tanned and can be processed through the subsequent mechanical operations (splitting, shaving). On the other hand, an analysis of major minor trace substances from Ti-end waste (especially vanadium content) in new tanning agent and wet white leather (not detected) and residue stream was performed and showed that leachability of vanadium is acceptable. The results obtained show that new tanning agent obtained from Ti end waste can be used for tanning bovine hides, as eco-friendly alternative for chrome tanning.     

Influence of zinc chloride addition on the chemical structure of bio-oil obtained during co-pyrolysis of wood/synthetic polymer blends

The chemical structure of liquid products of the pinewood sawdust (W) co-pyrolysis with polystyrene (PS) and polypropylene (PP) with and without the zinc chloride as an additive was investigated. The pyrolysis process was carried out at 450 °C with the heating rate of 5 °C/min. The yield of liquid products of pyrolysis was in the range of 37–91 wt% and their form was liquid or semi-solid depending on the composition of the wood/polymer blend. The zinc chloride addition to wood/polymer blends has influenced the range of samples decomposition as well as the chemical structure of resulted bio-oils. All bio-oils from wood/polypropylene blends were two-phase (liquid and solid). Contrarily, all bio-oils obtained from biopolymer/polypropylene blends with zinc chloride added were yellow liquids. All analyses proved that the structure and the quality of bio-oil strongly depend on both the composition of the blend and the presence of ZnCl₂ as an additive. The FT-IR analyses of oils showed that oxygen-containing groups and hydrocarbons content highly depend on the composition of biomass/synthetic polymer mixture. The fractionation of bio-oils by column chromatography with four different solvents was followed by GC–MS analysis. Results confirmed the significant removal and/or transformation of oxygen-containing organic compounds due to the zinc chloride presence during pyrolysis process.     

Pyrolysis of latex gloves in the presence of Y-zeolite

In this study we have investigated the possibility of processing waste rubber gloves using pyrolysis. Y-zeolite catalyst was employed to upgrade the pyrolysis products to give higher yields of valuable aromatic compounds such as toluene and xylenes. The composition of the pyrolysis products was determined using gas chromatography with linked mass spectrometry (GC-MS), gas chromatograph equipped with a flame ionization detector (GC-FID), gas chromatograph fitted with dual thermal conductivity detectors (GC-TCD), and Fourier Transform Infra-Red Spectrometry (FT-IR). It was found that when rubber gloves were pyrolysed in the absence of a catalyst, the pyrolysis oil consisted mainly of limonene and oligomers of polyisoprene. When Y-zeolite was added to the reaction system, the yields of toluene, xylene, methylbenzenes, ethylbenzenes, and naphthalenes increased dramatically. The Y-zeolite also catalysed the decomposition of limonene, which was absent from the catalytic pyrolysis products. The presence of the Y-zeolite catalyst also increased the yield of hydrocarbon gases. The tests were carried out at both 380 degrees C and 480 degrees C and it was found that the higher reaction temperature led to increased yields of all the major compounds, both in the presence and absence of the Y-zeolite catalyst.     

采用两级物化法去除黄磷废水中的氟化物

采用向含氟废水中加入适量石灰和聚合氯化铝，然后投加适量钙盐、磷酸和聚丙烯酰胺的二级处理工艺除氟，通过控制合适的pH、钙盐和磷酸的投加量、反应时间、反应温度、搅拌强度和絮凝剂的投加量，可使黄磷废水中氟的质量浓度降至5mg/L，氟的去除率达到99％以上，出水中氟的质量浓度达到GB8978－1996一级排放标准。     

Pyrolysis kinetics of waste PVC pipe.

The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction.     

Investigation of the ozonolysis of ethylenebisdithiocarbamate-fungicides in model solutions

A study of the effectiveness of ozonation for the removal of nabam (disodium ethylenebisdithiocarbamate) from aqueous solutions was carried out. Nabam is the parent compound of a commonly used group of fungicides. The process of nabam degradation was followed in terms of several parameters such as nabam concentration, chemical oxygen demand (COD), sulphate ion concentration as a measure of the relative degree of mineralization of nabam, and the pH value of the solution. Ozonation accelerates the decomposition of nabam with the formation of sulphates and nitrates as final products. The intermediate decomposition products of nabam are more resistant to degradation by ozone than the parent compound. The amounts of ozone which are used in wastewater treatment plants for disinfection may be sufficient to remove both nabam and its decomposition products, at a low level of contamination, but if the concentration of nabam is too high the intermediate decomposition products can still be present. Lowering the pH of the medium favours the oxidation of nabam.     

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.     

从废甲醇合成催化剂中回收铜锌

将废RK-05甲醇合成催化剂经过煅烧、浸取、精制等工序回收其中的铜和锌。经正交实验得到煅烧废催化剂的最优工艺参数为:废催化剂筛目100目,煅烧温度950℃,煅烧时间60 min。最佳浸取工艺条件为:废催化剂加入量约4 g/L,浸取温度75℃,浸取剂用量与理论用量体积比2.0~3.0,浸取剂浓度4.0 mol/L,浸取时间10min。精制工序制备CuO的最佳工艺条件为:锌粒与滤渣质量比为1.00,反应时间3 h,煅烧温度450℃,煅烧时间4 h。制备ZnO的最佳工艺条件为:煅烧温度800℃,煅烧时间60 min。回收的产品CuO纯度为99.1%,满足GB/T674—2003《化学试剂粉状氧化铜》中优级品的标准。回收的产品ZnO纯度为99.6%,满足GB/T3185—1992《氧化锌(间接法)》中一级品的标准。     

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.