- Endocrine activities of phthalate alternatives; Assessing the safety profile of furan dicarboxylic acid esters using a panel of human cell based reporter gene assays
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FDCA esters are highly relevant biobased alternatives for currently used benzene dicarboxylic acid esters. Despite all the developments on 2,5-FDCA applications, to the best of our knowledge thus far no toxicological data were available for 2,5-FDCA esters. In the present study we aimed to fill this gap, by using an in vitro reporter gene assay approach to compare the activity profile of commonly used phthalates to that of their furan-based counterparts. The assay selection was aimed at the detection of endocrine activity, since several phthalates are heavily scrutinised for their endocrine disrupting properties. However, to avoid missing other relevant toxicological endpoints, several assays able to detect various forms of cellular stress were also included in the panel. The results showed that the (ortho)benzene dicarboxylic acid esters were predominantly active on several of the endocrine assays. In comparison, six of the seven furan dicarboxylic acid based diesters tested here showed no activity in any of the 13 assays used. Only the isobutyl derivative DIBF showed moderate estrogenic activity on one assay, compared to much more pronounced activities on four assays for the ortho-phthalate analogue. Overall, the results presented in this paper are a strong indication that 2,5-FDCA based diesters in general are not only technically viable alternatives to phthalates, but also offer significant toxicological benefits, which supports a non-regrettable substitution.
- Van Vugt-Lussenburg, Barbara M. A.,Van Es, Daan S.,Naderman, Matthijs,Le Notre, Jerome,Klis, Frits Van Der,Brouwer, Abraham,Van Der Burg, Bart
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- Municipal solid waste incineration bottom ash: Characterization and kinetic studies of organic matter
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Bottom ash is the main solid residue (in weight) which is produced by municipal solid waste incineration (MSWI) facilities. To be reused in public works, it has to be stored previously a few months. This material is composed primarily of a mineral matrix but also contains unburnt organic matter. The mineral content and its change in the course of aging are relatively well- known, in contrast with the organic content. So in order to detect the phenomena responsible for changes in organic matter and their effects during aging, the concentrations of the main organic compounds previously characterized, the number of microorganisms, and the release of carbon dioxide were followed kinetically (over 13 months) in model laboratory conditions (mass, particle size, humidity, temperature, aerobiosis). The results showed that the aging process led to the natural biodegradation of the organic matter available in bottom ash, composed essentially of carboxylic acids and n-alkanes (steroids and PAH's to a lesser extent), and consequently that it would improve the bottom ash quality. Furthermore these results were confirmed by the study of aging Conducted in conditions used in the industrial scale (over 12 months).
- Dugenest,Combrisson,Casabianca,Grenier-Loustalot
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- A novel hydrogen-bonded silica-supported acidic ionic liquid: An efficient, recyclable and selective heterogeneous catalyst for the synthesis of diesters
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Abstract: In this study, two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles (SNPs) via hydrogen bonding. The materials were characterized by FT-IR, NMR, SEM, nitrogen physisorption measurement, TGA and acid-base titration. The catalytic activity of the prepared catalysts was investigated in the synthesis of phthalate, maleate and succinate diesters under solvent-free conditions. It was found that nanosilica@[HFDAIL] with higher availability of acidic sites and higher hydrophilicity was more efficient compared to the nanosilica@[SFDAIL]. Notably, nanosilica@[HFDAIL] catalyst has also demonstrated excellent selectivity for the diester product while the monoester product was predominant in the case of nanosilica@[SFDAIL] even after prolonged reaction time or higher catalyst loading. In addition, the nanosilica@[HFDAIL] catalyst could be separated by simple filtration and reused several times without any significant loss of catalytic performance, but a remarkable decrease in activity was observed for nanosilica@[SFDAIL] in the next runs. GRAPHICAL ABSTRACT?: SYNOPSIS Two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles via hydrogen bonding. The catalytic activity of the catalysts was investigated in the synthesis of diesters under solvent-free conditions.
- Fareghi-Alamdari, Reza,Niri, Mehri Nadiri,Hazarkhani, Hassan
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- Catalytic upcycling of PVC waste-derived phthalate esters into safe, hydrogenated plasticizers
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Recycling of end-of-life polyvinyl chloride (PVC) calls for solutions to deal with the vast amounts of harmful phthalate plasticizers that have historically been incorporated in PVC. Here, we report on the upcycling of such waste-extracted phthalate esters into analogues of the much safer diisononyl 1,2-cyclohexanedicarboxylate plasticizer (DINCH), via a catalytic one-pot (trans)esterification-hydrogenation process. For most of the virgin phthalates, Ru/Al2O3 is a highly effective hydrogenation catalyst, yielding >99% ring-hydrogenated products under mild reaction conditions (0.1 mol% Ru, 80 °C, 50 bar H2). However, applying this reaction to PVC-extracted phthalates proved problematic, (1) as benzyl phthalates are hydrogenolyzed to benzoic acids that inhibit the Ru-catalyst, and (2) because impurities in the plasticizer extract (PVC, sulfur) further retard the hydrogenation. These complications were solved by coupling the hydrogenation to an in situ (trans)esterification with a higher alcohol, and by pretreating the extract with an activated carbon adsorbent. In this way, a real phthalate extract obtained from post-consumer PVC waste was eventually completely (>99%) hydrogenated to phthalate-free, cycloaliphatic plasticizers. This journal is
- Bals, Sara,De Vos, Dirk E.,Diefenhardt, Thomas,Jain, Noopur,Marquez, Carlos,Schlummer, Martin,Windels, Simon
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supporting information
p. 754 - 766
(2022/02/02)
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- Micro-flow nanocatalysis: synergic effect of TfOH@SPIONs and micro-flow technology as an efficient and robust catalytic system for the synthesis of plasticizers
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The combination of continuous flow technology with immobilizing of only 0.13?mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h?1 compared to 403.8 to 3099 h?1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.
- Tashi, Maryam,Shafiee, Behnaz,Sakamaki, Yoshie,Hu, Ji-Yun,Heidrick, Zachary,Khosropour, Ahmad R.,Beyzavi, M. Hassan
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p. 37835 - 37840
(2018/11/26)
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- Diacidic ionic liquid supported on magnetic-silica nanocomposite: a novel, stable, and reusable catalyst for selective diester production
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Abstract: Supported diacidic ionic liquid on magnetic silica nanoparticles (SDAIL@magnetic nanoSiO2) was successfully prepared through a multi-step approach. 2,2- bis ((3- methylimidazolidin-1-yl) methyl) propane- 1,3- diol bromide salt was immobilized onto the surface of magnetic silica nanoparticles via covalent bonding to prepare a novel powerful acidic catalyst. The synthesized catalyst was characterized by FT-IR, SEM, TGA, VSM, N2 adsorption–desorption measurements and acid-base titration. The catalytic activity of the prepared SDAIL@magnetic nanoSiO2 was investigated for the selective diesterification of alcohols by phthalic anhydride to afford corresponding dialkyl plasticizers under solvent-free conditions. The nature of two acidic counter anions as well as the presence of Lewis acidic species (Fe3O4) on the magnetic nanosilica and high surface area of the nanosilica influenced the behavior of the catalyst. Surperisingly, the high acidic character of the catalyst facilitates the reaction with a short reaction time. Furthermore, TG analysis strongly demonstrates that major content of IL is still stable on the support up to 290?°C, so catalyst has a good thermal stability. Under the optimized conditions, the conversion of phthalic anhydride was 100% and diester plasticizers were obtained with excellent yields (80–100%). The SDAIL@magnetic nanoSiO2 catalyst showed a good reusability and could be easily separated from the reaction mixture using an external magnet thanks to its superparamagnetic behavior and reused for several runs without significant activity loss. An important advantage of the SDAIL@magnetic nanoSiO2 was its high-hydrophilicity resulted in excellent selectivity towards the formation of only diesters which are commonly used plasticizers in different industries. Graphical abstract [Figure not available: see fulltext.].
- Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan,Zekri, Negar
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p. 2615 - 2629
(2018/09/13)
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- Synthesis and characterization of a new hydroxyl functionalized diacidic ionic liquid as catalyst for the preparation of diester plasticizers
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Two new functionalized diacidic ionic liquids (FDAILs) including hydroxyl functionalized diacidic ionic liquid (HFDAIL) and sulfonated diacidic ionic liquid (SFDAIL) were synthesized and characterized by 1HNMR, 13CNMR and FT-IR. The catalytic activities of these FDAILs were examined in esterification reaction of anhydrides with some alcohols to give corresponding dialkyl plasticizers under solvent-free conditions. The results indicate that HFDAIL, as hydroxyl-bearing catalyst, show better catalytic performance. Under the optimum conditions, using HFDAIL, the conversion of phthalic anhydride was high and diester plasticizers were obtained with good to excellent yields in the presence of only 10?mol% of ionic liquid. All the produced diesters could be easily recovered due to their immiscibility with the ionic liquid. Recycling experiments suggests that these ionic liquids can be reused several times without remarkable loss in their catalytic activity.
- Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan
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p. 153 - 160
(2016/12/30)
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- A liquid phase oxidation of O-xylene with esterification coupling preparation of phthalic acid diester method
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The invention relates to a method for preparation of diester phthalate by o-xylene liquid-phase oxidation and esterification coupling. In the presence of a catalyst, air or oxygen is used as an oxygen source for preparation of the diester phthalate by o-xylene liquid-phase oxidation and esterification coupling. The method has the advantages of mild reaction conditions, safe operation, low raw material and energy consumption, high conversion rate and high selectivity and the like.
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Paragraph 0020-0023; 0026
(2017/02/24)
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- Nano-SO42-/TiO2catalyzed eco-friendly esterification of dicarboxylic acids
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Nano-SO42-/TiO2 was prepared by wet impregnation method. The structure and properties of the prepared nano-SO42-/TiO2catalyst was characterized by XRD, SEM, TEM and BET analysis. The catalytic activities of the catalysts were tested by the esterification of sebacic acid with 2-ethyl hexanol and a series of other dicarboxylic acid. The influence factors on the reaction, such as the catalyst calcination temperature, reaction temperature/time and the molar ratio of acid to alcohol were extensively explored. Nano-SO42-/TiO2prepared exhibited much higher catalytic activity in esterification reactions. By applying the optimized reaction condition, i.e. 160 C, 2 h, 5 wt % nano-SO42-/TiO2with a 1:3 molar ratio of sebacic acid to 2-ethyl hexanol, higher than 99 % isolated of the desired ester could be obtained.
- Ji, Xianbing,Chen, Yinxia,Shen, Zuoyuan
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p. 5769 - 5772
(2014/12/11)
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- Sulfonated graphene as highly efficient and reusable acid carbocatalyst for the synthesis of ester plasticizers
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Plasticizers are well known for their effectiveness in producing flexible plastics. The automotive, plastic and pharmaceutical industries, essential to a healthy economy, rely heavily on plasticizers to produce everything from construction materials to medical devices, cosmetics, children toys, food wraps, adhesives, paints, and 'wonder drugs'. Although H2SO4 is commonly used as commodity catalyst for plasticizer synthesis it is energy-inefficient, non-recyclable, and requires tedious separation from the homogeneous reaction mixture resulting in abundant non-recyclable acid waste. In this study, for the first time, we report an efficient synthesis of ester plasticizers (>90% yields) using sulfonated graphene (GSO3H) as an energy-efficient, water tolerant, reusable and highly active solid acid carbocatalyst. The hydrothermal sulfonation of reduced graphene oxide with fuming H2SO4 at 120°C for 3 days afforded GSO3H with remarkable acid activity as demonstrated by 31P magic-angle spinning (MAS) NMR spectroscopy. The superior catalytic performance of GSO3H over traditional homogeneous acids, Amberlyst-15, and acidic ionic liquids has been attributed to the presence of highly acidic and stable sulfonic acid groups within the two dimensional graphene domain, which synergistically work for high mass transfer in the reaction. Furthermore, the preliminary experimental results indicate that GSO3H is quite effective as a catalyst in the esterification of oleic and salicylic acid and thus may pave the way for its broad industrial applications in the near future.
- Garg, Bhaskar,Bisht, Tanuja,Ling, Yong-Chien
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p. 57297 - 57307
(2015/02/02)
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- Synthesis of monoesters and diesters using eco-friendly solid acid catalysts - Cerium(IV) and thorium(IV) phosphates
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In the present endeavour, amorphous cerium phosphate (CP) and thorium phosphate (TP) have been synthesized by sol-gel method and also under microwave irradiation to yield CPM and TPM. CP, TP, CPM and TPM have been characterized for elemental analysis (ICP-AES), spectral analysis (FTIR), thermal analysis (TGA), X-ray diffraction studies, SEM, EDX, surface area (BET) and surface acidity (NH3-TPD). The potential use of these materials as solid acid catalysts has been explored by studying esterification as a model reaction. Monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA), benzyl acetate (BzAc) and diesters such as diethyl malonate (DEM), diethyl succinate (DES), dibutyl phthalate (DBP), dioctyl phthalate (DOP) have been synthesized. Esterification conditions have been optimized by varying several parameters such as reaction time, catalyst amount and mole ratio of reagents. The catalytic activity has been compared and correlated with reference to surface acidity of the catalysts. It is found that catalytic activity of CPM > CP > TP M > TP. The regenerated catalysts could be reused upto two catalytic runs without significant loss in % yields of esters formed. The highlighting feature of the present work is the catalysts CPM and TPM that are synthesized in a much shorter reaction time with higher surface acidity giving good % yield of esters.
- Parangi, Tarun,Wani, Bina,Chudasama, Uma
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p. 430 - 438
(2013/09/23)
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- HETEROGENEOUS ORGANOTIN CATALYSTS
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Supported heterogeneous organotin catalysts of the formula X1, X2, or X3: wherein Z is a spacer group; Y is an insoluble phenyl-group containing copolymer; R1, R2, R3, R5, and R6 are independently selected from halogen, alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, aralkyl, and Z; and R4 is alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, or aralkyl.
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Page/Page column 6-7
(2010/06/22)
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- DEGRADATION OF POLYCYCLIC AROMATIC HYDROCARBONS TO RENDER THEM AVAILABLE FOR BIODEGRADATION
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A method for the degradation of polycyclic aromatic compounds is disclosed that involves dissolving ozone in a bipolar solvent comprising a non-polar solvent in which is of sufficiently non-polar character to solubilized the polycyclic aromatic compounds, and a polar-water-compatible solvent which is fully miscible with the non-polar solvent to form a single phase with the non-polar solvent. The bipolar solvent with dissolved ozone is contacted with the polycyclic aromatic compounds to solubilize the polycyclic aromatic compounds and react the dissolved polycyclic aromatic compounds with the ozone to degrade the dissolved polycyclic aromatic compounds to oxygenated intermediates. The bipolar solvent is then mixed with sufficient water to form separate non-polar and polar phases, the non-polar phase comprising the non-polar solvent and the polar phase comprising the non-polar solvent and the oxygenated intermediates. The polar phase is then diluted and incubated with bacteria to biodegrade the oxygenated intermediates.
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Page/Page column 9-11; 17-18
(2008/12/07)
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- Dicarboxylic diester, process for producing the same, and refrigerating machine lubricating oil comprising the ester
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A diester represented by the formula wherein A represents a cyclohexane ring, cyclohexene ring or benzene ring, X is H or methyl group, RX and RY are the same or different and each is C3-C18 branched-chain alkyl group, C1-C18 straight-chain alkyl group, C2-C18 straight-chain alkenyl or C3-C18 cycloalkyl, provided that when A is a benzene ring, RX and RY are different from each other and —COORX and —COORY are attached to two adjacent carbon atoms of the benzene ring, and having the following properties: 1) a total acid number of 0.05 mgKOH/g or less, 2) a sulfated ash content of 10 ppm or less, 3) a sulfur content of 20 ppm or less, 4) a phosphorus content of 20 ppm or less, 5) a peroxide value of 1.0 meq/kg or less, 6) a carbonyl value of 10 or less; 7) a volume resistivity of 1×1011 Ω·cm or more, 8) a hydroxyl value of 3 mgKOH/g or less, and 9) a water content of 100 ppm or less, a process for preparing the same and a refrigerator lubricating oil comprising the diester.
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Page/Page column 43
(2010/02/10)
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- Complete study of the pyrolysis and gasification of scrap tires in a pilot plant reactor
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The pyrolysis and gasification of tires was investigated in a pilot plant reactor provided with a system for condensation of semivolatile matter. The study comprised experiments at 450°, 750°, and 1000°C both in nitrogen and 10% oxygen atmospheres. In the gas phase, only methane and benzene yields increased with temperature until 1000°C. In the liquids, the main components were styrene, limonene, and isoprene. The solid fraction (including soot) increased with temperature. Zinc content of the char decreased with increasing temperature. Analysis of the surface area of the solids showed that the area was similar in all cases to that of a commercial carbon black. The higher surface of the soot with respect to the chars was observed. The results coincided with published findings, i.e., kinetic severity function values would produce 0.2% of methane at 450°C and 4.5% at 750°-1000°C.
- Conesa, Juan A.,Martin-Gullon,Font,Jauhiainen
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p. 3189 - 3194
(2008/12/21)
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- Synthesis, characterization and catalytic properties of SAPO-11, -31 and -41 molecular sieves
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Medium pore molecular sieves, SAPO-11, SAPO-31 and SAPO-41, have been synthesized using di-n-propylamine and diethylamine as the organic template. They have been characterized by various methods such as elemental analysis, X-ray powder diffraction, solid state MAS NMR spectroscopy, and FT-IR spectroscopy in the framework and hydroxyl regions. Catalytic activities of these materials in the esterification of phthalic anhydride with different alcohols have been studied. The catalytic activity of these material is in the order: SAPO-41> SAPO-11> SAPO-31.
- Venkatathri,Srivastava
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p. 1039 - 1043
(2007/10/03)
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- Synthesis of di-, tri- and penta-nuclear titanium(IV) species from reactions of titanium(IV) alkoxides with 2,2′-biphenol (H 2L1) and 1,1′-binaphthol (H2L 2); crystal structures of [Ti3(μ2-OPr i)2(OPri)8L
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Reaction of titanium(IV) alkoxides [Ti(OR)4] (R = OPr i, OBun) with 2,2′-biphenol [C12H 8(OH)2, H2L1] affords two trinuclear species [Ti3(OPri)10L1] and [Ti3OPri)6L31] each possessing an open-chain V-shaped arrangement of three titanium atoms with the former having both bridging alkoxide and biphenylate groups and the latter having only biphenylate as bridging groups. Variations in reaction conditions yield the pentanuclear species [Ti5(μ3-O)2(OR) 8L41] (R = OPri, OBun) which have two central bridging oxygen atoms in the Ti5 framework and bridging alkoxide and biphenylate groups. In contrast 1,1′-binaphthol [C24H12(OH)2, H2L2] yields the dinuclear [Ti2(OPri)4L 22] where only the binaphthylate ligands act as bridging groups. Some of the compounds show catalytic activity in esterification reactions. The Royal Society of Chemistry 2004.
- Corden, Jonathan P.,Errington, William,Moore, Peter,Partridge, Martin G.,Wallbridge, Malcolm G. H.
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p. 1846 - 1851
(2007/10/03)
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- Semivolatile and volatile compounds in combustion of polyethylene
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The evolution of semivolatile and volatile compounds in the combustion of polyethylene (PE) was studied at different operating conditions in a horizontal quartz reactor. Four combustion runs at 500 and 850°C with two different sample mass/air flow ratios and two pyrolytic runs at the same temperatures were carried out. Thermal behavior of different compounds was analyzed and the data obtained were compared with those of literature. It was observed that α,ω-olefins, α-olefins and n-paraffins were formed from the pyrolytic decomposition at low temperatures. On the other hand, oxygenated compounds such as aldehydes were also formed in the presence of oxygen. High yields were obtained of carbon oxides and light hydrocarbons, too. At high temperatures, the formation of polycyclic aromatic hydrocarbons (PAHs) took place. These compounds are harmful and their presence in the combustion processes is related with the evolution of pyrolytic puffs inside the combustion chamber with a poor mixture of semivolatile compounds evolved with oxygen. Altogether, the yields of more than 200 compounds were determined. The collection of the semivolatile compounds was carried out with XAD-2 adsorbent and were analyzed by GC-MS, whereas volatile compounds and gases were collected in a Tedlar bag and analyzed by GC with thermal conductivity and flame ionization detectors.
- Font, Rafael,Aracil, Ignacio,Fullana, Andrés,Conesa, Juan A.
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p. 615 - 627
(2007/10/03)
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- Process for the preparation of carboxylic esters
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Carboxylic esters are prepared by a process, which comprises reacting dicarboxylic or polycarboxylic acids or their anhydrides with alcohols in a liquid medium with the concomitant removal of water formed by the esterification reaction by azeotropic distillation together with the alcohol in the medium, wherein the amount of liquid removed from the reaction medium by azeotropic distillation is replaced in whole or in part with the alcohol.
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- Treatment of skin conditions by use of PPAR alpha activators
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Disorders of the skin and mucous membrane that have a disrupted or dysfunctional epidermal barrier are treated or prevented by topical application of compounds that are either activators of the farnesoid X receptor, activators of the peroxisome proliferator-activated receptor alpha , and oxysterol activators of the LXR alpha receptor. The same compounds are also effective in treating disorders of epidermal differentiation and proliferation.
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- Process for producing carboxylic acid esters and catalysts therefor
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A process for producing carboxylic acid esters by the following steps: a) preparation of a reaction mixture containing an alcohol and a carboxylic acid and/or a carboxylic anhydride and/or a carboxylic acid ester and or a partially esterified carboxylic acid, b) heating of this mixture to the suitable reaction temperature in the presence of a solid polysiloxane insoluble in the reaction medium and having sulphonic acid groups with intensive thorough mixing accompanied by continuous separation of the reaction water which forms, wherein the polysiloxane used as the catalyst in modified by treatment with a soluble aluminum, titanium or zirconium compound, and the spherical particles thereof have a diameter of 0.01 to 3 mm, a specific surface of 0.1 to 1200 m2 /g, a specific pore volume of 0.01 to 6.0 ml/g and a bulk density of 50 to 1000 g/l.
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- THE SIDE REACTIONS IN THE ESTERIFICATION OF PHTALIC ANHHYDRIDE WITH 2-ETHYLHEXANE-1-OL IN THE PRESENCE OF ORGANOTITANATES
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Using synthetic, chromatographic and spectral methods, we studied the side reactions accompanying the preparation of di-2-ethylhexyl phtalate from phtalic anhydride and 2-ethylhexane-1-ol in the presence of catalytic amounts of tetra-n-butyl titanate.The catalyst proper was titanium(IV) mono-2-ethylhexyl phtalate.The possibility of a simultaneous gas-chromatographic quantitative determination of mono-2-ethylhexyl phtalate, di-2-ethylhexyl phtalate, 2-ethylhexan-1-ol and tetra-n-butyl titanate, reported in literature, has been refuted.In the esterification catalysedby hydrated titanium dioxide homogeneous catalysis by the formed organotitanate was dominating.The dissolving of hydrated titanium dioxide in the esterification of phtalic anhydride with 2-ethylhexane-1-ol was studied polarographically.
- Novrocik, Jan,Novrocikova, Marta,Norek, Jiri,Koruna, Ivan,Ryska, Miroslav
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p. 253 - 266
(2007/10/02)
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