Conversion of Carbohydrates Biomass Into Levulinate Esters Using Heterogeneous Catalysts
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Rigid Biobased Building Blocks: Current Developments and Outlook
Rigid Biobased Building Blocks: Current Developments and Outlook Daan S. van Es Wageningen UR Food &Biobased Research, Wageningen, The Netherlands Received October 15, 2012; Accepted November 12, 2012 ABSTRACT: In this perspectives paper we will look at the state-of-the-art in rigid renewable building blocks for biobased materials, with a focus on two types of carbohydrate-based difunctional monomers, i.e.,isohexides and furan- 2,5-dicarboxylic acid (FDCA). KEYWORDS: Biobased building blocks, FDCA, isohexides, polymers 1 INTRODUCTION (i.e. high purity) aromatic monomers from lignin is not likely in the short term [3]. Whereas in the case of lignin The continuously increasing interest in biomass and the challenges are mostly chemical and technological, biobased materials is fuelled by growing concerns the use of, e.g., terpenes as feedstock for the produc- about fossil feedstock depletion, as well as greenhouse tion of aromatics is severely hampered by the limited gas emissions and global warming. Whereas most of availability compared to the potential demand. Since the current focus is on using terrestrial vegetable bio- carbohydrates (C6 and C5 sugars) are abundantly mass as alternative feedstock for energy carriers (e.g. available they are the most likely candidates as feed- transportation fuels) and chemicals production, aquatic stock for the production of bulk (platform) chemicals biomass (e.g. micro- and macroalgae) is also being for materials production. Basically two approaches can explored as a renewable feedstock source. A success- be distinguished in the transition towards a biobased ful transition from a fossil-feedstock-based economy to (i.e. carbohydrate based) economy; transformation of a biobased economy can only be achieved sustainably biomass feedstocks to existing (fossil based) chemicals, if there is no competition with food and feed produc- also known as drop-in, or transformation of biomass to tion, and negative effects of (indirect) land use change “new” chemicals. -
PRODUCTION of ETHYL LEVULINATE VIA ESTERIFICATION REACTION of LEVULINIC ACID in the PRESENCE of Zro2 BASED CATALYST
Malaysian Journal of Analytical Sciences, Vol 23 No 1 (2019): 45 - 51 DOI: https://doi.org/10.17576/mjas-2019-2301-06 MALAYSIAN JOURNAL OF ANALYTICAL SCIENCES ISSN 1394 - 2506 Published by The Malaysian Analytical Sciences Society PRODUCTION OF ETHYL LEVULINATE VIA ESTERIFICATION REACTION OF LEVULINIC ACID IN THE PRESENCE OF ZrO2 BASED CATALYST (Penghasilan Etil Levulinat Melalui Pengesteran Asid Levulinik dengan Kehadiran Mangkin Berasaskan ZrO2) Dorairaaj Sivasubramaniam1, Nor Aishah Saidina Amin1*, Khairuddin Ahmad1, Nur Aainaa Syahirah Ramli2 1Chemical Reaction Engineering Group (CREG), Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81300 Skudai, Johor, Malaysia 2Advanced Oleochemical Technology Division, Malaysian Palm Oil Board (MPOB), 6, Persiaran Institusi, Bandar Baru Bangi, 43000 Kajang, Selangor, Malaysia *Corresponding author: [email protected] Received: 13 April 2017; Accepted: 17 April 2018 Abstract Ethyl levulinate is widely used as a fuel additive, flavor or fragrance and as a component of fuel blending. This study focused on the production of ethyl levulinate from levulinic acid via esterification reaction in the presence of HPW/ZrO2.The catalyst was prepared using the wet impregnation method, characterized by using FTIR, BET and NH3-TPD and screened based on 20%, 40% and 60% HPW/ZrO2. The 40% HPW/ZrO2 catalyst exhibited the highest catalytic performance during the parameter screening stage which included catalyst loading (0.25‒1.25g) and volume ratio of levulinic acid to ethanol (1:4 – 1:8). The highest ethyl levulinate yield of 99% corresponded to a catalyst loading of 0.5 g and volume ratio of levulinic acid to ethanol of 1:5 with reaction conditions at 150 °C for 3 hours. -
WO 2017/003293 Al 5 January 2017 (05.01.2017) P O P C T
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization I International Bureau (10) International Publication Number (43) International Publication Date WO 2017/003293 Al 5 January 2017 (05.01.2017) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07D 307/50 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/NL20 16/050469 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 1 July 20 16 (01 .07.2016) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 2015065 1 July 2015 (01.07.2015) NL (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: FURANIX TECHNOLOGIES B.V. GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, [NL/NL]; 29, Zekeringstraat, 1014 BV Amsterdam (NL). -
Valerolactone Using Polymer-Based Metal-Containing Catalysts, Chemical Engineering Transactions, 61, 895-900 DOI:10.3303/CET1761147 896
895 A publication of CHEMICAL ENGINEERING TRANSACTIONS VOL. 61, 2017 The Italian Association of Chemical Engineering Online at www.aidic.it/cet Guest Editors: Petar S Varbanov, Rongxin Su, Hon Loong Lam, Xia Liu, Jiří J Klemeš Copyright © 2017, AIDIC Servizi S.r.l. ISBN 978-88-95608-51-8; ISSN 2283-9216 DOI: 10.3303/CET1761147 Hydrogenation of Biomass-Derived Levulinic Acid to Gamma- Valerolactone Using Polymer-Based Metal-Containing Catalysts Linda Zh. Nikoshvili*, Igor I. Protsenko, Dialia A. Abusuek, Anna O. Zaykovskaya, Alexey V. Bykov, Valentina G. Matveeva, Esther M. Sulman Tver Technical University, A.Nikitina str. 22, 170026, Tver, Russian Federation [email protected] Nowadays the development of effective catalytic systems of selective hydrogenation of levulinic acid (LA) to gamma -valerolactone (GVL) is of high importance. However, there is a lack of data concerning the use of polymer -based catalyst in this process. The possibility to use of Ru-containing catalysts on the basis of hypercrosslinked polystyrene (HPS) in hydrogenation of LA to GVL is discussed. Catalyst 5%-Ru/HPS is shown to be highly active and selective in hydrogenation of LA in aqueous medium (yield of GVL more than 99%) at mild reaction conditions (90 °C, 2 MPa of hydrogen partial pressure) and the absence of co-catalysts. 1. Introduction Global petro-chemical market faces increasing competition and a dependency on external sources, and is under considerable cost and ecological pressure. Biomass has received considerable attention as a sustainable feedstock that can replace diminishing fossil fuels for the production of energy, especially for the transportation sector. -
Safety Assessment of Levulinic Acid and Sodium Levulinate As Used in Cosmetics
Safety Assessment of Levulinic Acid and Sodium Levulinate as Used in Cosmetics Status: Draft Tentative Report for Panel Review Release Date: February 16, 2021 Panel Meeting Date: March 11-12, 2021 The Expert Panel for Cosmetic Ingredient Safety members are: Chair, Wilma F. Bergfeld, M.D., F.A.C.P.; Donald V. Belsito, M.D.; David E. Cohen, M.D.; Curtis D. Klaassen, Ph.D.; Daniel C. Liebler, Ph.D.; Lisa A. Peterson, Ph.D.; Ronald C. Shank, Ph.D.; Thomas J. Slaga, Ph.D.; and Paul W. Snyder, D.V.M., Ph.D. Previous Panel member involved in this assessment: James G. Marks, Jr., M.D. The Cosmetic Ingredient Review (CIR) Executive Director is Bart Heldreth, Ph.D. This safety assessment was prepared by Preethi S. Raj, M.Sc., Senior Scientific Analyst/Writer, CIR. © Cosmetic Ingredient Review 1620 L Street, NW, Suite 1200 ♢ Washington, DC 20036-4702 ♢ ph 202.331.0651 ♢ fax 202.331.0088 ♢ [email protected] Distributed for Comment Only -- Do Not Cite or Quote Commitment & Credibility since 1976 Memorandum To: Expert Panel for Cosmetic Ingredient Safety Members and Liaisons From: Preethi S. Raj, M.Sc. Senior Scientific Analyst/Writer, CIR Date: February 16, 2021 Subject: Safety Assessment of Levulinic Acid and Sodium Levulinate as Used in Cosmetics Enclosed is the Draft Tentative Report of the Safety Assessment of Levulinic Acid and Sodium Levulinate as Used in Cosmetics (identified as levaci032021rep in the pdf). This is the second time the Panel is seeing a safety assessment of these cosmetic ingredients. At the September 2020 Panel Meeting, the Panel issued an Insufficient Data Announcement (IDA), and the following data were requested. -
3 in Methyl Levulinate Production from Biomass Carbohydrates
ARTICLE IN PRESS JID: JECHEM [m5G; November 9, 2017;20:14 ] Journal of Energy Chemistry xxx (2017) xxx–xxx Contents lists available at ScienceDirect Journal of Energy Chemistry http://www.journals.elsevier.com/ journal-of-energy-chemistry/ journal homepage: www.elsevier.com/locate/jechem Catalysis performance comparison of a Brønsted acid H 2 SO 4 and a Lewis acid Al 2 (SO 4 ) 3 in methyl levulinate production from biomass carbohydrates ∗ Q1 Xueli Chen, Yuxuan Zhang, Tao Hou, Lujia Han, Weihua Xiao College of Engineering, China Agricultural University, Beijing 10 0 083, China a r t i c l e i n f o a b s t r a c t Article history: An experimental investigation was conducted to understand the roles of the Brønsted acid H 2 SO 4 and Received 5 July 2017 Lewis acid Al (SO ) in methyl levulinate (ML) production from biomass carbohydrates, including glucose, 2 4 3 Revised 5 November 2017 fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was Accepted 6 November 2017 responsible for the isomerization of methyl glucoside (MG), producing a significant amount of the subse- Available online xxx quent product 5-methoxymethylfurfural (MMF), while the Brønsted acid facilitated the production of ML Keywords: from MMF. Al 2 (SO 4 ) 3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled Carbohydrates cellulose with Al 2 (SO 4 ) 3 resulted in a desired ML yield within a reasonable reaction time. The significant Brønsted acid catalysis performances of two types of acids will guide the design of efficient catalytic processes for the Lewis acid selective conversion of biomass into levulinate esters. -
Supplementary Information Experimental Products (Furfurals) Were Calculated by Comparison with an Internal Standard Solvent As the Reference Sample (N-Octanol)
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2019 Supplementary Information Experimental products (furfurals) were calculated by comparison with an internal standard solvent as the reference sample (n-octanol). Chemicals The MLA and n-octanol relevant line equation is For this study, bamboo particles was collected from a local y=2.06543x–0.02107 (coefficient of correlation R2 =0.9998), farm in Jiangsu Province, China. All materials were passed the intermediate products (such as MMF) and n-octanol through a 250–425 μm sieve and dried to a constant weight for relevant line equation is y=1.9657x+0.0612 (coefficient of 24 h at 105 °C. The absolute-dried particles were kept in a correlation R2 = 0.9996). desiccator until used. The High Performance Liquid Chromatography HPLC instrument (Shimadzu LC–10ATVP, Aminex HPX–87H column) Analytic methods with a RID-20A detector was used to quantitative analyzed the Gas chromatography (GC) mass spectrometry (MS) (Agilent methyl pentose glycosides (C5-Gly) and methyl hexose 5975C VL MSD) analysis was used a HP-5 fused capillary glucosides (C6-Gly). Used 0.005 mmol sulfuric acid (sonication, column (l= 30 m, i d= 0.32 mm, t= 0.25 μm) with poly dimethyl deaeration) in water as the mobile phase and the flow rate siloxane with 5% phenyl methyl substitution as the stationary was of 0.5 mL/min, and the column temperature was kept at phase. The injection mode was split at a rate of 35. The carrier 45 °C for 30 min. The standard curve of concentration of −1 gas was He at a flow rate of 1.5 mL min . -
Microwave Assisted Synthesis of Dehydrated Sugar Derivatives Hydroxymethylfurfural, Levulinic Acid, Anhydrosugar Alcohols, and E
(19) TZZ _T (11) EP 2 598 466 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 51/00 (2006.01) C07D 307/02 (2006.01) 28.09.2016 Bulletin 2016/39 C07C 67/00 (2006.01) C07D 307/93 (2006.01) C07D 493/04 (2006.01) C07D 307/46 (2006.01) (2006.01) (2006.01) (21) Application number: 11812946.9 C07D 307/48 C07D 307/50 C07C 59/185 (2006.01) (22) Date of filing: 18.07.2011 (86) International application number: PCT/US2011/044324 (87) International publication number: WO 2012/015616 (02.02.2012 Gazette 2012/05) (54) MICROWAVE ASSISTED SYNTHESIS OF DEHYDRATED SUGAR DERIVATIVES HYDROXYMETHYLFURFURAL, LEVULINICACID, ANHYDROSUGAR ALCOHOLS, AND ETHERS THEREOF MIKROWELLENUNTERSTÜTZTE SYNTHESE VON DEHYDRIERTEN ZUCKERDERIVATEN, HYDROXYMETHYLFURFURAL, LÄVULINSÄURE, ANHYDROZUCKERALKOHOLEN SOWIE DEREN ETHERN SYNTHÈSE ASSISTÉE PAR RAYONNEMENT MICROONDES DES DÉRIVÉS DE SUCRES DÉSHYDRATÉS HYDROXYMÉTHYLFURFURAL, ACIDE LÉVULINIQUE, ALCOOLS DE SUCRE ANHYDRES ET LEURS ÉTHERS (84) Designated Contracting States: (74) Representative: dompatent von Kreisler Selting AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Werner - GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Partnerschaft von Patent- und Rechtsanwälten PL PT RO RS SE SI SK SM TR mbB Deichmannhaus am Dom (30) Priority: 30.07.2010 US 369350 P Bahnhofsvorplatz 1 50667 Köln (DE) (43) Date of publication of application: 05.06.2013 Bulletin 2013/23 (56) References cited: WO-A2-2009/155020 US-A- 5 558 899 (73) Proprietor: Archer-Daniels-Midland Company US-A1- 2007 213 544 US-A1- 2007 213 544 Decatur, IL 62526 (US) US-A1- 2009 156 841 US-A1- 2009 156 841 US-A1- 2009 253 920 US-A1- 2009 281 338 (72) Inventors: • HOWARD, Stephen J. -
Hydrogenation of 2-Methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts
The University of Maine DigitalCommons@UMaine Electronic Theses and Dissertations Fogler Library Fall 12-2020 Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts Matthew J. Kline University of Maine, [email protected] Follow this and additional works at: https://digitalcommons.library.umaine.edu/etd Part of the Catalysis and Reaction Engineering Commons, and the Petroleum Engineering Commons Recommended Citation Kline, Matthew J., "Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts" (2020). Electronic Theses and Dissertations. 3284. https://digitalcommons.library.umaine.edu/etd/3284 This Open-Access Thesis is brought to you for free and open access by DigitalCommons@UMaine. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of DigitalCommons@UMaine. For more information, please contact [email protected]. HYDROGENATION OF 2-METHYLNAPHTHALENE IN A TRICKLE BED REACTOR OVER BIFUNCTIONAL NICKEL CATALYSTS By Matthew J. Kline B.S. Seton Hill University, 2018 A THESIS Submitted in Partial Fulfillment of the Requirements For the Degree of Master oF Science (in Chemical Engineering) The Graduate School The University of Maine December 2020 Advisory Committee: M. Clayton Wheeler, Professor of Chemical Engineering, Advisor Thomas J. Schwartz, Assistant ProFessor oF Chemical Engineering William J. DeSisto, ProFessor oF Chemical Engineering Brian G. Frederick, ProFessor oF Chemistry -
(12) United States Patent (10) Patent No.: US 8,350,056 B2 FOO Et Al
USOO835.0056B2 (12) United States Patent (10) Patent No.: US 8,350,056 B2 FOO et al. (45) Date of Patent: *Jan. 8, 2013 (54) FUNCTIONALIZED N-SUBSTITUTED 2010, 0140166 A1* 6, 2010 Erdner-Tindall et al. ..... 210,603 2010.0143992 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 PYRROLIDONIUM IONIC LIOUIDS 2010.0143993 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 2010.0143994 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 (75) Inventors: Thomas Foo, Wilmington, DE (US); 2010.0143995 A1 6, 2010 Erdner-Tindall et al. ..... 435,160 Mark Andrew Harmer, Landenberg, 2010.0143999 A1* 6, 2010 Erdner-Tindall et al. ..... 435,161 2010/0.144000 A1* 6, 2010 Erdner-Tindall et al. ..... 435,161 PA (US); Keith W. Hutchenson, Lincoln 2010, 0145073 A1 6, 2010 Foo University, PA (US); Christopher P. 2010, O152465 A1 6, 2010 Davis Junk, Wilmington, DE (US); Berlyn R. Mellein, Wilmington, DE (US); Aaron FOREIGN PATENT DOCUMENTS Minter, Wilmington, DE (US) WO O3O48078 A2 6, 2003 WO 201OO65816 6, 2010 WO 201OO65841 6, 2010 (73) Assignee: E I du Pont de Nemours and WO 2010.065873 6, 2010 Company, Wilmington, DE (US) WO WO 2010.065606 A2 * 6, 2010 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 Cardoso et al., Synthesis, Characterization, and Thermal and Dielec U.S.C. 154(b) by 136 days. tric Properties of Three Different Methacrylate Polymers With Zwit terionic Pendant Groups, J. Polymer Sci., Part B: Polymer Physics, This patent is Subject to a terminal dis 1997, vol. -
Conversion of Furfuryl Alcohol Into Ethyl Levulinate Over Glucose-Derived Carbon-Based Solid Acid in Ethanol
molecules Article Conversion of Furfuryl Alcohol into Ethyl Levulinate over Glucose-Derived Carbon-Based Solid Acid in Ethanol Geng Zhao 1,*, Ming Liu 1, Xinkui Xia 2, Li Li 1 and Bayin Xu 1 1 Analysis and Testing Center, College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, Henan, China; [email protected] (M.L.); [email protected] (L.L.); [email protected] (B.X.) 2 College of Food Science, Xinyang Agriculture and Forestry University, Xinyang 464000, Henan, China; [email protected] * Correspondence: [email protected]; Tel.: +86-376-639-3155 Received: 27 March 2019; Accepted: 15 May 2019; Published: 16 May 2019 Abstract: In this study, a carbon-based solid acid was created through the sulfonation of carbon obtained from the hydrothermal pretreatment of glucose. Additionally, ethyl levulinate, a viable liquid biofuel, was produced from furfuryl alcohol using the environmentally benign and low-cost catalyst in ethanol. Studies for optimizing the reaction conditions, such as reaction time, temperature, and catalyst loading, were performed. Under the optimal conditions, a maximum ethyl levulinate yield of 67.1% was obtained. The recovered catalyst activity (Ethyl levulinate yield 57.3%) remained high after being used four times, and it was easily regenerated with a simple sulfonation process. Moreover, the catalyst was characterized using FT-IR, XRD, SEM, elemental analysis, and acid-base titration techniques. Keywords: furfuryl alcohol; ethanol; ethyl levulinate; carbon-based solid acid 1. Introduction Because of the recent diminishment of fossil fuel resources, as well as environmental degradation resulting from greenhouse gas emissions, significant effort has been devoted to converting renewable biomass into liquid fuels, fuel additives, and organic bulk chemicals [1–3]. -
Valerolactone from Biomass-Derived Levulinic Acid Over Zr–Al-Beta Zeolite Catalyst
catalysts Article Stable Continuous Production of γ-Valerolactone from Biomass-Derived Levulinic Acid over Zr–Al-Beta Zeolite Catalyst Clara López-Aguado 1, Marta Paniagua 1 , Juan A. Melero 1 , Jose Iglesias 1 , Pablo Juárez 1, Manuel López Granados 2 and Gabriel Morales 1,* 1 Chemical and Environmental Engineering Group, Escuela Superior de Ciencias Experimentales y Tecnología (ESCET), Universidad Rey Juan Carlos, C/Tulipán s/n, Móstoles, E28933 Madrid, Spain; [email protected] (C.L.-A.); [email protected] (M.P.); [email protected] (J.A.M.); [email protected] (J.I.); [email protected] (P.J.) 2 Energy and Sustainable Chemistry (EQS) Group, Institute of Catalysis and Petrochemistry, CSIC, Marie Curie 2, Campus de Cantoblanco, 28049 Madrid, Spain; [email protected] * Correspondence: [email protected]; Tel.: +34-91-488-80-91 Received: 20 May 2020; Accepted: 15 June 2020; Published: 17 June 2020 Abstract: The one-pot conversion of biomass-derived platform molecules such as levulinic acid (LA) and furfural (FAL) into γ-valerolactone (GVL) is challenging because of the need for adequate multi-functional catalysts and high-pressure gaseous hydrogen. As a more sustainable alternative, here we describe the transfer hydrogenation of LA to GVL using isopropanol as a hydrogen donor over a Zr-modified beta zeolite catalyst in a continuous fixed-bed reactor. A stable sustained production of GVL was achieved from the levulinic acid, with both high LA conversion (ca. 95%) and GVL yield (ca. 90%), for over at least 20 days in continuous operation at 170 ◦C. Importantly, the small decay in activity can be advantageously overcome by the means of a simple in situ thermal regeneration in the air atmosphere, leading to a complete recovery of the catalyst activity.