DOCSLIB.ORG

Adipic Acid Route: Oxidation of Cyclohexene Vs. Cyclohexane

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Adipic Acid Route: Oxidation of Cyclohexene Vs. Cyclohexane catalysts Article Adipic Acid Route: Oxidation of Cyclohexene vs. Cyclohexane Ana P. C. Ribeiro 1 , Elisa Spada 2, Roberta Bertani 2 and Luísa M. D. R. S. Martins 1,* 1 Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; [email protected] 2 Department of Industrial Engineering, University of Padova, 35122 Padova, Italy; [email protected] (E.S.); [email protected] (R.B.) * Correspondence: [email protected]; Tel.: +351-218-419-389 Received: 20 November 2020; Accepted: 8 December 2020; Published: 10 December 2020 Abstract: A cleaner alternative to the current inefficient oxidation of cyclohexane to adipic acid is presented. Direct oxidation of neat cyclohexene by aq. hydrogen peroxide to adipic acid is selectively achieved in good yield (46%), in the presence of the recyclable C-homoscorpionate iron(II) complex 3 [FeCl2{κ -HC(pz)3}] (pz = pyrazol-1-yl) and microwave irradiation, by a nitrous oxide-free protocol. Keywords: cyclohexene; adipic acid; oxidation; nitrous oxide; C-scorpionate; iron; microwave; ionic liquid; recyclable 1. Introduction Adipic acid (AA) is a highly relevant commodity produced at a large scale (over 3.5 mio metric tons/year and growing by ca. 5%/year) [1,2] worldwide, as it constitutes a building block for several industrial processes. It is mostly used for the synthesis of Nylon-6,6 polyamide; therefore, the rising demand for engineered plastics requires increased production of AA. Currently, adipic acid is mainly obtained by an inefficient and environmentally harmful two-step process [1,3] involving catalytic cyclohexane oxidation to cyclohexanol and cyclohexanone mixture followed by its oxidation with nitric acid. Thus, AA production is the largest source of industrial greenhouse gas N2O emissions (300 kg of N2O per ton of produced adipic acid) [2], which corresponds to 8% of the worldwide anthropogenic N2O emissions. In addition, cyclohexane oxidation is a low-efficiency industrial process, with conversions usually lower than 10% to ensure a selectivity of 80% for the cyclohexanol/cyclohexanone mixture [1,4]. Therefore, the development of a sustainable catalytic system for such a large-scale process is a task of high significance. In this work, we present a nitrous oxide-free alternative oxidative process (Scheme1a), using cyclohexene (instead of cyclohexane) as substrate, the environmentally acceptable aqueous H2O2 as oxidant, and employing a known [5–7] efficient homogeneous catalyst for the oxidation of cyclohexane, 3 the hydrotris(pyrazol-1-yl)methane Fe(II) complex [FeCl2{κ -HC(pz)3}] (pz = pyrazolyl) (Scheme1b) [ 8], not yet applied for alkene oxidations. The iron compound exhibits a tetragonal pyramid coordination polyhedron bearing one of the donor nitrogen pyrazolyl atoms at the axial position and where the iron atom has a vacant coordination site that could be easily occupied by a substrate [9]. In addition, this complex is easy (one step) to synthesize [8] at r.t. and requires the simplest ligand of the tris(pyrazol-1-yl)methane carbon scorpionate class. C-scorpionate tripodal ligands, with their three N atoms of the pyrazolyl moieties, are recognized to be involved in key catalytic oxidative processes with aq. hydrogen peroxide [8]. 3 Moreover, [FeCl2{κ -HC(pz)3}] displays high solubility in aqueous solvents [7], favoring the use of this oxidant. Furthermore, the alternative energy source of microwaves (MW) was chosen, aiming at Catalysts 2020, 10, 1443; doi:10.3390/catal10121443 www.mdpi.com/journal/catalysts Catalysts 2020, 10, 1443 2 of 7 enhancing product yield and selectivity while being more energy-efficient and economic relative to Catalystsconventional 2020, 10 thermal, x FOR PEER heating REVIEW methods (e.g., oil bath) [10–12]. 2 of 7 Cl N N Fe C H N N Cl N N (a) (b) 3 3 3 Scheme 1. ((aa)) Oxidation Oxidation of of cyclohexene cyclohexene to to adipic adipic acid acid catalyzed catalyzed by by [FeCl [FeCl2{κ2{-HC(pz)κ -HC(pz)3}];3 (}];b) ([FeClb) [FeCl2{κ 2- 3 {HC(pz)κ -HC(pz)3}] structure.3}] structure. 3 The[FeCl iron2{κ compound-HC(pz)3}] exhibits has proven a te itstragonal catalytic pyramid activity coordination for the selective polyhedron peroxidative bearing oxidation one of the of donorcyclohexane nitrogen to the pyrazolyl cyclohexanone atoms and at cyclohexanol the axial position mixture (upand to where ca. 35 %the max iron overall atom yield) has [ 6–a9 ,vacant13–17] coordinationbut neither further site that oxidized could be species easily were occupied formed by undera substrate the used [9]. In conditions, addition, northis was complex the complex is easy (oneassayed step) with to synthesize alkene substrates. [8] at r.t. and requires the simplest ligand of the tris(pyrazol-1-yl)methane carbonCyclohexene scorpionate oxidative class. C-scorpionate cleavage with tripodal H2O2 hasligands, been with used their by Noyori three N et atoms al. [18 ,19of ]the as onepyrazolyl of the moieties,most promising are recognized and environmentally to be involved tolerable in key routes catalytic to adipic oxidative acid, althoughprocesses the with price aq. of hydrogen peroxide impaired[8]. Moreover, its industrial [FeCl2{κ implementation.3-HC(pz)3}] displays Thus, high finding solubility a suitable in aqueous catalyst solvents would be[7], crucial favoring for the use sustainability of this oxidant. of this Furthermore, process. the alternative energy source of microwaves (MW) was chosen, aiming at enhancing product yield and selectivity while being more energy-efficient and economic 2. Results and Discussion relative to conventional thermal heating methods (e.g., oil bath) [10–12]. 3 3 [FeClThe present2{κ -HC(pz) [FeCl3}]2{ κhas-HC(pz) proven3}]-based its catalytic new activity catalytic for system the selective afforded peroxidative adipic acid directlyoxidation from of cyclohexanethe selective oxidationto the cyclohexanone (by H2O2, 4.2 and equiv.) cyclohexanol of cyclohexene mixture in a (up good to yieldca. 35 (46%, % max Figure overall1) after yield) 24 h [6– of 9,13–17]MW irradiation but neither at 60 further◦C, without oxidized the needspecies of nitricwere acid,formed another under strong the used oxidant, conditions, additive nor or was solvent the complex(see experimental, assayed with ESI). alkene Moreover, substrates. AA precipitates from the reaction mixture, allowing its separation by filtrationCyclohexene and prompt oxidative isolation cleavage in a with pure H form2O2 has (see been Figure used S1, by ESI). Noyori et al. [18,19] as one of the mostcis promising-cyclohexane-1,2-diol, and environmentally its α-hydroxy-ketone tolerable routes derivative to adipic and acid, the although lactone 7-hydroxyoxepan-2-one the price of hydrogen wereperoxide also impaired detected its by industrial GC-MS and implementation.1H and 13C NMR Thus, techniques. finding a Thesuitable time catalyst evolution would of the be reaction crucial formixture the sustainability composition of is depictedthis process. in Figure 1. The unprecedented use of low-power MW irradiation in the present route to AA proved the ability 2.of Results this method and toDiscussion reduce the reaction time and energy consumption, thus being advantageous over the conventional heating method. For example, 24 h of water bath heating at 60 C of the above-mentioned The present [FeCl2{κ3-HC(pz)3}]-based new catalytic system afforded◦ adipic acid directly from reaction mixture led exclusively to cis-cyclohexane-1,2-diol. the selective oxidation (by H2O2, 4.2 equiv.) of cyclohexene in a good yield (46%, Figure 1) after 24 h of MWThe irradiation effect of theat 60 addition °C, without of a the free need radical of nitr scavengeric acid, another (CBrCl strong3 or Ph oxidant,2NH) in additive the peroxidative or solvent (seeoxidation experimental, medium ESI). was Moreover, evaluated, AA leading precipitates to a drastic from decrease the reaction in all mixture, product allowing yields, thus its separation indicating bythe filtration radical involvement and prompt inisolation the first in step a pure of the form oxidation (see Figure process. S1, ESI). Then, for Baeyer–Villiger oxidation and hydrolyses,cis-cyclohexane-1,2-diol, follow [18,19 ]its (Scheme α-hydroxy-ketone1). derivative and the lactone 7-hydroxyoxepan-2- 3 one wereThe stabilityalso detected of the by homogeneous GC-MS and 1H catalyst and 13C [FeClNMR2 {techniques.κ -HC(pz)3 The}] was time assessed evolution at theof the end reaction of the 3 mixtureMW-assisted composition oxidation is reaction.depicted Thein Figure far-infrared 1. spectrum of the used [FeCl2{κ -HC(pz)3}] (Figure S2, ESI) shows that the genuine ν(Fe-Cl) bands [7] are maintained after the catalytic oxidation reaction. However, its activity in a further catalytic cycle was minimal. The catalyst observed deactivation may be due to the coordination of a water molecule (e.g., from the oxidant solution) to the free site of the iron coordination sphere, thus blocking the previously vacant position and impairing the access of the substrate to it. Catalysts 2020, 10, 1443 3 of 7 The potential recyclability of the iron catalyst was explored by using room-temperature ionic liquids, ILs, as reaction media. Tetradecyltrihexylphosphonium dicyanamide ([P6,6,6,14][N(CN)2], ® CYPHOS 105), hexylmethylimidazolium bis(trifluoromethanesulfonyl)imide, [C6mim][NTf2] [NTf2 = ® N(SO2CF3)2] and methyltrioctylammonium chloride ({[CH3(CH2)7]3NCH3}Cl, Aliquat 336), the last one known as an efficient phase transfer catalyst for the oxidation of cyclohexene [18], were chosen in 3 view of their ability to act as suitable solvents for [FeCl2{κ -HC(pz)3}]. The conversion of cyclohexene Catalysts 2020, 10, x FOR PEER REVIEW 3 of 7 exhibited a marked dependency on the IL used, as depicted in Figure2. 100 80 60 40 20 0 Relative amount (%) of substrate and products and substrate of (%) amount Relative 0 4 8 12162024 Time / h Figure 1.
Load more

Recommended publications
  • Chapter 21 the Chemistry of Carboxylic Acid Derivatives
    Instructor Supplemental Solutions to Problems © 2010 Roberts and Company Publishers Chapter 21 The Chemistry of Carboxylic Acid Derivatives Solutions to In-Text Problems 21.1 (b) (d) (e) (h) 21.2 (a) butanenitrile (common: butyronitrile) (c) isopentyl 3-methylbutanoate (common: isoamyl isovalerate) The isoamyl group is the same as an isopentyl or 3-methylbutyl group: (d) N,N-dimethylbenzamide 21.3 The E and Z conformations of N-acetylproline: 21.5 As shown by the data above the problem, a carboxylic acid has a higher boiling point than an ester because it can both donate and accept hydrogen bonds within its liquid state; hydrogen bonding does not occur in the ester. Consequently, pentanoic acid (valeric acid) has a higher boiling point than methyl butanoate. Here are the actual data: INSTRUCTOR SUPPLEMENTAL SOLUTIONS TO PROBLEMS • CHAPTER 21 2 21.7 (a) The carbonyl absorption of the ester occurs at higher frequency, and only the carboxylic acid has the characteristic strong, broad O—H stretching absorption in 2400–3600 cm–1 region. (d) In N-methylpropanamide, the N-methyl group is a doublet at about d 3. N-Ethylacetamide has no doublet resonances. In N-methylpropanamide, the a-protons are a quartet near d 2.5. In N-ethylacetamide, the a- protons are a singlet at d 2. The NMR spectrum of N-methylpropanamide has no singlets. 21.9 (a) The first ester is more basic because its conjugate acid is stabilized not only by resonance interaction with the ester oxygen, but also by resonance interaction with the double bond; that is, the conjugate acid of the first ester has one more important resonance structure than the conjugate acid of the second.
    [Show full text]
  • New Synthesis Routes for Production of Ε-Caprolactam by Beckmann
    New synthesis routes for production of ε-caprolactam by Beckmann rearrangement of cyclohexanone oxime and ammoximation of cyclohexanone over different metal incorporated molecular sieves and oxide catalysts Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation vorgelegt von Anilkumar Mettu aus Guntur/Indien Berichter: Universitätprofessor Dr. Wolfgang F. Hölderich Universitätprofessor Dr. Carsten Bolm Tag der mündlichen Prüfung: 29.01.2009 Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar. Dedicated to my Parents This work reported here has been carried out at the Institute for Chemical Technolgy and Heterogeneous Catalysis der Fakultät für Mathematik, Informatik und Naturwissenschaften in the University of Technology, RWTH Aachen under supervision of Prof. Dr. Wolfgang F. Hölderich between June 2005 and August 2008. ACKNOWLEDGEMENTS I would like to express my deepest sence of gratitude to my supervisor Prof. Dr. rer. nat. W. F. Hölderich for giving me the opportunity to do my doctoral study in his group. His guidance and teaching classes have allowed me to grow and learn my subject during my Ph.d. He has provided many opportunities for me to increase my abilities as a researcher and responsibilities as a team member. I am grateful for the financial support of this work from Sumitomo Chemicals Co., Ltd, Niihama, Japan (Part One) and Uhde Inventa-Fischer GmBH, Berlin (Part Two). Our collaborators at Sumitomo Chemicals Co., Ltd (Dr. C. Stoecker) and Uhde Inventa- Fischer GmBH (Dr. R. Schaller and Dr. A. Pawelski) provided thoughtful guidance and suggestions for each project.
    [Show full text]
  • Selective Hydrogenation of Phenol to Cyclohexanol Over Ni/CNT in the Absence of External Hydrogen
    energies Article Selective Hydrogenation of Phenol to Cyclohexanol over Ni/CNT in the Absence of External Hydrogen Changzhou Chen 1,2, Peng Liu 1,2, Minghao Zhou 1,2,3,*, Brajendra K. Sharma 3,* and Jianchun Jiang 1,2,* 1 Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, Jiangsu Province, National Engineering Laboratory for Biomass Chemical Utilization, Key and Open Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, China; [email protected] (C.C.); [email protected] (P.L.) 2 Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China 3 Illinois Sustainable Technology Center, Prairie Research Institute, one Hazelwood Dr., Champaign, University of Illinois at Urbana-Champaign, Champaign, IL 61820, USA * Correspondence: [email protected] (M.Z.); [email protected] (B.K.S.); [email protected] (J.J.) Received: 7 January 2020; Accepted: 11 February 2020; Published: 14 February 2020 Abstract: Transfer hydrogenation is a novel and efficient method to realize the hydrogenation in different chemical reactions and exploring a simple heterogeneous catalyst with high activity is crucial. Ni/CNT was synthesized through a traditional impregnation method, and the detailed physicochemical properties were performed by means of XRD, TEM, XPS, BET, and ICP analysis. Through the screening of loading amounts, solvents, reaction temperature, and reaction time, 20% Ni/CNT achieves an almost complete conversion of phenol after 60 min at 220 ◦C in the absence of external hydrogen. Furthermore, the catalytic system is carried out on a variety of phenol derivatives for the generation of corresponding cyclohexanols with good to excellent results.
    [Show full text]
  • Oxalic Acid As a Heterogeneous Ice Nucleus in the Upper Troposphere and Its Indirect Aerosol Effect” by B
    Atmos. Chem. Phys. Discuss., 6, S1765–S1768, 2006 Atmospheric www.atmos-chem-phys-discuss.net/6/S1765/2006/ Chemistry ACPD c Author(s) 2006. This work is licensed and Physics 6, S1765–S1768, 2006 under a Creative Commons License. Discussions Interactive Comment Interactive comment on “Oxalic acid as a heterogeneous ice nucleus in the upper troposphere and its indirect aerosol effect” by B. Zobrist et al. B. Zobrist et al. Received and published: 13 July 2006 The authors would like to thank anonymous referee #1 for his/her constructive comments. We have addressed the referee’s concerns point-by-point below. Full Screen / Esc Succinic and Adipic acid as immersion IN: The solubility of these dicarboxylic acids is very low at temperatures of about 235 K, Printer-friendly Version as supported by the deliquescence measurements of Parsons et al. (JGR 109, D06212, 2004) which are close to 100 % RH. In our experiments, the droplets of Interactive Discussion these acids are completely liquid in the first cooling cycle with concentrations of Discussion Paper 7.3 wt% for succinic acid and 1.6 wt% for adipic acid, which is why they nucleate ice S1765 EGU homogeneously at temperatures below that of pure water. When the acids precipitate, the concentration of the remaining liquid corresponds to the equilibrium solubility at ACPD each temperature when the samples are cooled in the second cycle. Because of the 6, S1765–S1768, 2006 low solubility at lower temperatures we expect the observed rise in the homogeneous ice nucleation temperature when compared to the first cooling run. In fact, if we use the measured freezing temperatures and assume they are due to homogeneous ice Interactive nucleation, we can use water-activity-based ice nucleation theory to deduce the water Comment activity of the liquid part of the samples.
    [Show full text]
  • Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate
    catalysts Article Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate Kira M. Fahy , Adam C. Liu, Kelsie R. Barnard, Valerie R. Bright, Robert J. Enright and Patrick E. Hoggard * Department of Chemistry and Biochemistry, Santa Clara University, Santa Clara, CA 95053, USA; [email protected] (K.M.F.); [email protected] (A.C.L.); [email protected] (K.R.B.); [email protected] (V.R.B.); [email protected] (R.J.E.) * Correspondence: [email protected]; Tel.: +1-408-554-7810 Received: 2 August 2018; Accepted: 18 September 2018; Published: 19 September 2018 Abstract: Tetraethylammonium tetrachloroferrate catalyzes the photooxidation of cyclohexane heterogeneously, exhibiting significant photocatalysis even in the visible portion of the spectrum. The photoproducts, cyclohexanol and cyclohexanone, initially develop at constant rates, implying that the ketone and the alcohol are both primary products. The yield is improved by the inclusion of 1% acetic acid in the cyclohexane. With small amounts of catalyst, the reaction rate increases with the amount of catalyst employed, but then passes through a maximum and decreases, due to increased reflection of the incident light. The reaction rate also passes through a maximum as the percentage of dioxygen above the sample is increased. This behavior is due to quenching by oxygen, which at the same time is a reactant. Under one set of reaction conditions, the photonic efficiency at 365 nm was 0.018 mol/Einstein. Compared to TiO2 as a catalyst, Et4N[FeCl4] generates lower yields at wavelengths below about 380 nm, but higher yields at longer wavelengths. Selectivity for cyclohexanol is considerably greater with Et4N[FeCl4], and oxidation does not proceed past cyclohexanone.
    [Show full text]
  • Phenol Hydrogenation Over Pd/Zro2 Using Ethanol As Hydrogen Source
    4th International Conference on Sensors, Measurement and Intelligent Materials (ICSMIM 2015) Phenol hydrogenation over Pd/ZrO2 using ethanol as hydrogen source Yunjie Shi1, a, Bin Wang1,b, Junjun Shen1,c and Rongrong Miao1,d* 1Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China [email protected], [email protected], [email protected], d*[email protected] Keywords: Ethanol, Phenol, Hydrogenation, Pd/ZrO2 Abstract. Phenol hydrogenation over the Pd/ZrO2 catalyst has been carried out using ethanol as hydrogen source. The reaction temperature, catalyst and ethanol quantity are found to be influencing factors for effective phenol conversion. In all cases, low quantity (5%~10%) of ethanol and high temperature is efficient for a high phenol conversion. The results show that low quantity (5%~10%) of ethanol is efficient for high cyclohexanone selectivity at low temperature (573K). However, the selectivity of cyclohexanone, cyclohexanol and cyclohexane are insensitive to the ethanol quantity at high temperature (653K). It seems that ethanol plays an important dual role: as hydrogen source and as additive to control the phenol conversion and products selectivity. Introduction Cyclohexanone is the key raw material for the preparation of nylon 6 and adipic acid for nylon 66 [1,2]. The industrial production of cyclohexanone commonly involves the selective catalytic hydrogenation of phenol. On the other hand, phenol is an established environmental toxin and phenol-based waste originates form a variety of industrial sources including oil refineries, petrochemical units, polymeric resin manufacturing and plastic units [7]. Therefore, catalytic hydrogenation of phenol for cyclohexanone is an important chemical process, and has been widely studied [3-10].
    [Show full text]
  • SAFETY DATA SHEET Cyclohexane BDH1111
    SAFETY DATA SHEET Cyclohexane BDH1111 Version 1.3 Revision Date 03/25/2015 Print Date 05/08/2015 SECTION 1. PRODUCT AND COMPANY IDENTIFICATION Product name : Cyclohexane MSDS Number : 000000011713 Product Use Description : Solvent Manufactured for : VWR International LLC Radnor Corporate Center Building One Suite 200 100 Matsonford Road Radnor PA 19087 For more information call : (Monday-Friday,8.00am-5:00pm) 1-800-932-5000 In case of emergency call : (24 hours/day, 7 days/week) 1-800-424-9300(USA Only) For Transportation Emergencies: 1-800-424-9300 (CHEMTREC - Domestic) 1-613-996-6666 (CANUTEC - Canada) SECTION 2. HAZARDS IDENTIFICATION Emergency Overview Form : liquid, clear Color : colourless Odor : mild sweet Page 1 / 15 SAFETY DATA SHEET Cyclohexane BDH1111 Version 1.3 Revision Date 03/25/2015 Print Date 05/08/2015 Classification of the substance or mixture Classification of the substance : Flammable liquids, Category 2 or mixture Skin irritation, Category 2 Specific target organ toxicity - single exposure, Category 3, Central nervous system Aspiration hazard, Category 1 GHS Label elements, including precautionary statements Symbol(s) : Signal word : Danger Hazard statements : Highly flammable liquid and vapour. May be fatal if swallowed and enters airways. Causes skin irritation. May cause drowsiness and dizziness. Precautionary statements : Prevention : Keep away from heat/sparks/open flames/hot surfaces. - No smoking. Keep container tightly closed. Ground/bond container and receiving equipment. Use explosion-proof electrical/ ventilating/ lighting/ equipment. Use only non-sparking tools. Take precautionary measures against static discharge. Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. Wash skin thoroughly after handling. Use only outdoors or in a well-ventilated area.
    [Show full text]
  • Safety Data Sheet: Cyclohexane
    Safety data sheet according to Regulation (EC) No. 1907/2006 (REACH), amended by 2015/830/EU Cyclohexane ROTISOLV® ≥99,9 %, UV/IR-Grade article number: CP81 date of compilation: 2018-05-03 Version: 2.0 en Revision: 2020-10-06 Replaces version of: 2018-05-03 Version: (1) SECTION 1: Identification of the substance/mixture and of the company/ undertaking 1.1 Product identifier Identification of the substance Cyclohexane ROTISOLV® ≥99,9 %, UV/IR-Grade Article number CP81 Registration number (REACH) 01-2119463273-41-xxxx Index No 601-017-00-1 EC number 203-806-2 CAS number 110-82-7 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses: laboratory chemical laboratory and analytical use 1.3 Details of the supplier of the safety data sheet Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D-76185 Karlsruhe Germany Telephone: +49 (0) 721 - 56 06 0 Telefax: +49 (0) 721 - 56 06 149 e-mail: [email protected] Website: www.carlroth.de Competent person responsible for the safety data : Department Health, Safety and Environment sheet: e-mail (competent person): [email protected] 1.4 Emergency telephone number Name Street Postal code/ Telephone Website city National Poisons Inform- Beaumont Road Dublin 9 01 809 2166 https://www.poisons.ie/ ation Centre Beaumont Hospital SECTION 2: Hazards identification 2.1 Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 (CLP) Classification acc. to GHS Section Hazard class Hazard class and cat- Hazard egory state- ment 2.6 flammable liquid (Flam.
    [Show full text]
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • Cyclohexane Oxidation Continues to Be a Challenge Ulf Schuchardt A,∗, Dilson Cardoso B, Ricardo Sercheli C, Ricardo Pereira A, Rosenira S
    Applied Catalysis A: General 211 (2001) 1–17 Review Cyclohexane oxidation continues to be a challenge Ulf Schuchardt a,∗, Dilson Cardoso b, Ricardo Sercheli c, Ricardo Pereira a, Rosenira S. da Cruz d, Mário C. Guerreiro e, Dalmo Mandelli f , Estevam V. Spinacé g, Emerson L. Pires a a Instituto de Qu´ımica, Universidade Estadual de Campinas, P.O. Box 6154, 13083-970 Campinas, SP, Brazil b Depto de Eng. Qu´ımica, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil c College of Chemistry, University of California, Berkeley, CA 94720, USA d Depto Ciências Exatas e Tecnológicas, Universidade Estadual de Santa Cruz, 45650-000 Ilhéus, BA, Brazil e Universidade Federal de Lavras, Lavras, MG, Brazil f Instituto de Ciências Biológicas e Qu´ımicas, PUC-Campinas, 13020-904 Campinas, SP, Brazil g Sup. Caracterização Qu´ımica, IPEN, 05508-900 São Paulo, SP, Brazil Received 3 October 2000; received in revised form 21 December 2000; accepted 28 December 2000 Abstract Many efforts have been made to develop new catalysts to oxidize cyclohexane under mild conditions. Herein, we review the most interesting systems for this process with different oxidants such as hydrogen peroxide, tert-butyl hydroperoxide and molecular oxygen. Using H2O2, Na-GeX has been shown to be a most stable and active catalyst. Mesoporous TS-1 and Ti-MCM-41 are also stable, but the use of other metals such as Cr, V, Fe and Mo leads to leaching of the metal. Homogeneous systems based on binuclear manganese(IV) complexes have also been shown to be interesting. When t-BuOOH is used, the active systems are those phthalocyanines based on Ru, Co and Cu and polyoxometalates of dinuclear ruthenium and palladium.
    [Show full text]
  • Green Chemistry Accepted Manuscript
    Green Chemistry Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/greenchem Page 1 of 21 Green Chemistry Green Chemistry RSCPublishing CRITICAL REVIEW Catalytic Routes towards Acrylic Acid, Adipic Acid and ε-Caprolactam starting from Biorenewables Cite this: DOI: 10.1039/x0xx00000x Rolf Beerthuis, Gadi Rothenberg and N. Raveendran Shiju* Received 00th January 2012, The majority of bulk chemicals are derived from crude oil, but the move to biorenewable resources is Accepted 00th January 2012 gaining both societal and commercial interest. Reviewing this transition, we first summarise the types of today’s biomass sources and their economical relevance. Then, we assess the biobased productions DOI: 10.1039/x0xx00000x of three important bulk chemicals: acrylic acid, adipic acid and ε-caprolactam.
    [Show full text]
  • SAFETY DATA SHEET Cyclohexane
    SAFETY DATA SHEET Cyclohexane Section 1. Identification GHS product identifier : Cyclohexane Chemical name : Cyclohexane Synonyms : Benzene hexahydride; Hexahydrobenzene; Hexamethylene; CITGO® Material Code: 07504 Code : 07504 MSDS # : 07504 Supplier's details : CITGO Petroleum Corporation P.O. Box 4689 Houston, TX 77210 [email protected] Emergency telephone : Technical Contact: (832) 486-4000 (M-F - 8 AM to 4 PM CT) number (with hours of Medical Emergency: (832) 486-4700 (24 Hr) operation) CHEMTREC Emergency: (800) 424-9300 (24 Hr) (United States Only) Section 2. Hazards identification OSHA/HCS status : This material is considered hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200). Classification of the : FLAMMABLE LIQUIDS - Category 2 substance or mixture SKIN IRRITATION - Category 2 SPECIFIC TARGET ORGAN TOXICITY (SINGLE EXPOSURE) (Narcotic effects) - Category 3 ASPIRATION HAZARD - Category 1 AQUATIC HAZARD (ACUTE) - Category 1 AQUATIC HAZARD (LONG-TERM) - Category 1 GHS label elements Hazard pictograms : Signal word : Danger Hazard statements : Highly flammable liquid and vapor. Causes skin irritation. May be fatal if swallowed and enters airways. May cause drowsiness or dizziness. Very toxic to aquatic life with long lasting effects. Precautionary statements Prevention : Wear protective gloves. Wear eye or face protection. Keep away from heat, hot surfaces, sparks, open flames and other ignition sources. No smoking. Use explosion- proof electrical, ventilating, lighting and all material-handling equipment. Use only non- sparking tools. Take precautionary measures against static discharge. Keep container tightly closed. Use only outdoors or in a well-ventilated area. Avoid release to the environment. Avoid breathing vapor. Wash hands thoroughly after handling. Response : Collect spillage. IF INHALED: Remove person to fresh air and keep comfortable for breathing.
    [Show full text]