DOCSLIB.ORG

Catalytic Conversion of Starch to 5-Hydroxymethylfurfural by Tin Phosphotungstate

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Catalytic Conversion of Starch to 5-Hydroxymethylfurfural by Tin Phosphotungstate ORIGINAL RESEARCH published: 28 May 2021 doi: 10.3389/fenrg.2021.679709 Catalytic Conversion of Starch to 5-Hydroxymethylfurfural by Tin Phosphotungstate Jiawen Hao 1, Xueping Song 1,2, Shaowu Jia 1, Wei Mao 1, Yuxiao Yan 3* and Jinghong Zhou 1,2* 1College of Light Industry and Food Engineering, Guangxi University, Nanning, China, 2Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, Guangxi University, Nanning, China, 3College of Life Science and Technology, Guangxi University, Nanning, China Heteropoly acids containing Brønsted and Lewis acids show excellent catalytic activity. Brønsted acids promote the depolymerization of polysaccharides (such as starch and cellulose) into glucose, while Lewis acids catalyze the conversion of glucose to 5- hydroxymethylfurfural (HMF). Designing stable Brønsted-Lewis acid-containing bifunctional heterogeneous catalysts is crucial for the efficient catalytic conversion of polysaccharides to HMF. In this study, a series of Brønsted -Lewis acid bifunctional catalysts (SnxPW, X 0.10–0.75) were investigated for the conversion of cassava starch to Edited by: HMF. The structure of the catalysts was characterized by X-ray diffraction, Fourier Cameron M. Moore, transform infrared spectroscopy, Pyridine Fourier transform infrared spectroscopy, and Los Alamos National Laboratory (DOE), United States X-ray photoelectron spectroscopy. The acid strength and acid capacity were also Reviewed by: investigated. The effects of reaction time, temperature, catalyst concentration, and Jacob Kruger, cassava starch concentration on the selectivity, conversion rate, and yield were National Renewable Energy Laboratory (DOE), United States examined. The results showed that, among the analyzed catalysts, Sn0.1PW presented Pedro Maireles-Torres, the best ability under the test conditions for catalyzing the conversion of starch to HMF. At University of Malaga, Spain the optimized conditions of a reaction temperature of 160°C, a catalyst dosage of *Correspondence: 0.50 mmol/gstarch, and a 1 h reaction time, the starch conversion rate was 90.61%, Yuxiao Yan [email protected] and the selectivity and yield of HMF were 59.77 and 54.12%, respectively. Our Jinghong Zhou findings contribute to the development of HMF production by the dehydration of [email protected] carbohydrates. Specialty section: Keywords: starch, heteropoly, phosphotungstate, catalytic reaction, 5-hydroxymethylfurfural This article was submitted to Bioenergy and Biofuels, a section of the journal INTRODUCTION Frontiers in Energy Research Received: 12 March 2021 Abundant renewable biomass is an ideal and promising alternative for the production of valuable Accepted: 12 May 2021 chemicals (Perea-Moreno et al., 2019). Among various compounds derived from biomass, 5- Published: 28 May 2021 hydroxymethylfurfural (HMF) is an important and versatile platform intermediate for the Citation: production of fuels and chemicals such as 2,5-furandicarboxilic acid (FDCA), 2,5- Hao J, Song X, Jia S, Mao W, Yan Y dhydroxymethylfuran (2,5-DMF), 5-ethoxymethylfurfural (5-EMF), and levulinic acid (LA). and Zhou J (2021) Catalytic Among these chemicals, 2,5-DMF and 5-EMF have attracted much attention because of their Conversion of Starch to 5- excellent biofuel characteristics. 5-EMF can be prepared without a cumbersome hydrogenation step, Hydroxymethylfurfural by fi Tin Phosphotungstate. requiring only HMF and ethanol etheri cation (Mascal and Nikitin, 2008). At present, multiple Front. Energy Res. 9:679709. catalysts have been reported for the catalytic conversion of HMF to 2.5-DMF (Huang et al., 2014; doi: 10.3389/fenrg.2021.679709 Wang et al., 2014). 5-EMF is considered a very good fuel additive. Its energy density is close to that of Frontiers in Energy Research | www.frontiersin.org 1 May 2021 | Volume 9 | Article 679709 Hao et al. Catalytic Synthesis of HMF gasoline (8.8 kwh/L) and diesel (8.7 kwh/L), and higher than that linked through α-1,4 and α-1,6-glycosidic bonds. The glycosidic of fuel ethanol (6.1 kwh/L; Mascal and Nikitin, 2008). FDCA may bonds are unstable in acid solution and can be easily hydrolyzed replace terephthalic acid, the main component of polyethylene to glucose. Chheda et al. (2007) used hydrochloric acid as catalyst terephthalate. Based on the wide application of FDCA as a to prepare HMF from starch in a water-MIBK-sec-butyl alcohol platform chemical, FDCA is listed as one of the 12 important solvent mixture, with a yield of 43%. Wu et al. (2018) reported glycosyl platform chemicals for the production of bio-based that homogeneous Fenton reagent was able to promote starch chemicals and materials. dehydration, and a 46.5% yield of HMF was achieved. Nikolla Various carbohydrates can be used to synthesize HMF, e.g., et al. (2011) obtained a 51.75% yield of HMF using β-zeolite fructose (Akien et al., 2012), glucose (Chheda et al., 2007), sucrose containing tin (Sn) and hydrochloric acid in a water/ (Yu et al., 2017), starch (Chun et al., 2010), and cellulose (Fang tetrahydrofuran two-phase system. However, because the yield et al., 2020). Generally, there are two pathways for the conversion of HMF prepared from starch is generally low, it is important to of glucose to HMF. One is the direct dehydration of glucose to develop an efficient catalyst for the effective utilization of starch. HMF, and the other includes two steps: glucose isomerization to In this paper, we report a catalytic SnxP system with a fructose, followed by the dehydration of fructose to HMF controllable amount of Brønsted and Lewis acids. Different fi (Choudhary et al., 2013; Zhao et al., 2018). The rst pathway amounts of SnCl4 were introduced into phosphotungstic acid is usually more difficult than the second one because of the to prepare catalysts with different amounts of Brønsted and Lewis different homomorphic conformation distributions of glucose acids for the production of HMF from starch. Here, Sn provides and fructose in solution. While the isomerization of glucose into Lewis acid sites that promote the isomerization of glucose to fructose is usually completed in an alkaline reaction system fructose, while phosphotungstic acid (HPW) provides Brønsted (Binder and Raines, 2009; Su et al., 2009), the dehydration of acid sites that promote starch hydrolysis to glucose and fructose fructose to HMF requires an acidic environment (Nie et al., 2020). and then dehydration to HMF. We found a significant increase in The introduction of metal ions through Brønsted acidification of HMF yield when moving from HPW to Sn-doped HPW, without heteropoly acids (HPAs) can form a range of insoluble solid any significant structural changes to the catalyst, which we Lewis-Brønsted acidic catalysts that are effective in the attribute to the introduction of Lewis acid sites to the catalyst. conversion of glucose and sucrose to HMF (Carniti et al., The effects of reaction temperature, reaction time, catalyst, and 2011; Deng et al., 2012). These heterogeneous acid catalysts substrate concentration on the conversion of cassava starch, HMF possess Lewis (metal sites) and Brønsted acidic sites. Zhao yield, and selectivity were studied. et al. (2011) reported that the catalytic conversion of fructose to HMF, with solid HPA and Cs2.5H0.5PW12O40 as catalysts, presented excellent selectivity (94.7%) and a relatively high yield MATERIALS AND METHODS (74.0%) after 60 min at 388 K. This new catalyst is tolerant to high feedstock concentrations, and it can be recycled. Hu et al. (2009) Materials revealed that Sn4+ can efficiently catalyze the conversion of Cassava starch was obtained from Hongfeng Starch Co., Ltd. sucrose to HMF in an ionic liquid, with a maximum yield of (Guangxi, China). Methanol and glacial acetic acid were of 65%. The Sn atoms act as isolated Lewis acid centers and are chromatographic grades, and all other reagents were of responsible for the isomerization of glucose to fructose. The analytical grade and used without further purification. bifunctional PTSA-POM/AlCl3.6H2O (60.7%HMF yield) Phosphotungstic acid hydrate, Sn chloride (99.998%), 5- catalyst showed a higher activity than the Lewis acid catalyst hydroxymethyl-2-furadehyde (99%), dimethyl sulfoxide AlCl3.6H2O (50.8% HMF yield) and the Brønsted acid catalyst (anhydrous solvent grade), and tetrahydrofuran (anhydrous PTSA-POM (9.4% HMF yield), and directly transformed glucose solvent grade) were obtained from Shanghai Aladdin to HMF owing to the balanced Lewis and Brønsted acid sites, with Industrial Inc. (China). a 60.7% HMF yield (Xin et al., 2017). These results indicated that a bifunctional acid catalyst with balanced Brønsted and Lewis Catalyst Preparation – acid sites can obtain a high yield of HMF from hexose. In general, Sn phosphotungstate catalysts SnxPW (x 0.10 0.75) were a high HMF yield can be obtained from monosaccharides, such as synthesized as reported in the literature (Okuhara et al., 2000). fructose and glucose (Nie et al., 2020). SnCl4 is a common Lewis A series of SnxPWs were prepared by titration, with the Sn acid, being cost-effective, highly active, and having a low toxicity, content ranging from 0.1 to 0.75 mmol. Six parts of which is often used in glucose conversion to HMF (Hu et al., phosphotungstic acid (1 mmol) were completely dissolved in 2009; Qiu et al., 2020). However, fructose and glucose are not 100 ml of distilled water, into which SnCl4 was slowly added, abundant, and thus, are expensive, thereby limiting the large- respectively. These mixtures were maintained under magnetic scale sustainable production of HMF. Therefore, an efficient stirring at 60°C for 6 h until the solution was clear and process must be developed to produce HMF using starch, transparent. Subsequently, the prepared solution was slowly cellulose, and other cheap polysaccharides as raw materials. dried at 60°C until the water completely evaporated and a Starch is one of the most abundant carbohydrates on earth white solid appeared. After drying, the white precipitate was and is widely explored in the chemical industry (Hornung calcined in a tubular furnace at 300°C for 2 h under a nitrogen et al., 2016).
Load more

Recommended publications
  • Synthesis of Terephthalic Acid Via Diels-Alder Reactions with Ethylene and Oxidized Variants of 5-Hydroxymethylfurfural
    Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural Joshua J. Pacheco and Mark E. Davis1 Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 Contributed by Mark E. Davis, May 7, 2014 (sent for review April 16, 2014) Terephthalic acid (PTA), a monomer in the synthesis of polyethylene can react to form PX in a one-pot Diels-Alder dehydration re- terephthalate (PET), is obtained by the oxidation of petroleum- action (7). This reaction has received much attention recently, derived p-xylene. There is significant interest in the synthesis of and it is catalyzed by homogeneous Lewis acids and a wide va- renewable, biomass-derived PTA. Here, routes to PTA starting riety of heterogeneous Brønsted acid-containing solids (7–12). from oxidized products of 5-hydroxymethylfurfural (HMF) that can Although nearly 100% PX yields from the Diels-Alder de- be produced from biomass are reported. These routes involve Diels- hydration reaction can be achieved, the reduction step to convert Alder reactions with ethylene and avoid the hydrogenation of HMF HMF to DMF requires expensive metal catalysts and a hydrogen to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with source, making this route challenging to commercially imple- ethylene over solid Lewis acid catalysts that do not contain strong ment (13). Therefore, the discovery of routes to PTA from HMF Brønsted acids to synthesize intermediates of PTA and its equally that avoid any hydrogenation steps could be useful. important diester, dimethyl terephthalate (DMT). The partially oxi- An oxidation route to PTA that has previously been consid- dized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with ered is the Diels-Alder dehydration reaction of ethylene with the high pressure ethylene over a pure-silica molecular sieve containing fully oxidized HMF, 2,5-furandicarboxylic acid (FDCA).
    [Show full text]
  • Report of the Advisory Group to Recommend Priorities for the IARC Monographs During 2020–2024
    IARC Monographs on the Identification of Carcinogenic Hazards to Humans Report of the Advisory Group to Recommend Priorities for the IARC Monographs during 2020–2024 Report of the Advisory Group to Recommend Priorities for the IARC Monographs during 2020–2024 CONTENTS Introduction ................................................................................................................................... 1 Acetaldehyde (CAS No. 75-07-0) ................................................................................................. 3 Acrolein (CAS No. 107-02-8) ....................................................................................................... 4 Acrylamide (CAS No. 79-06-1) .................................................................................................... 5 Acrylonitrile (CAS No. 107-13-1) ................................................................................................ 6 Aflatoxins (CAS No. 1402-68-2) .................................................................................................. 8 Air pollutants and underlying mechanisms for breast cancer ....................................................... 9 Airborne gram-negative bacterial endotoxins ............................................................................. 10 Alachlor (chloroacetanilide herbicide) (CAS No. 15972-60-8) .................................................. 10 Aluminium (CAS No. 7429-90-5) .............................................................................................. 11
    [Show full text]
  • Broda 1 Potential Synthesis Pathway for Redox-Active DNA Nucleoside
    Broda 1 Potential Synthesis Pathway for Redox-Active DNA Nucleoside Nicole M. Broda Thesis Advisor: Robert Kuchta, Ph.D.: Department of Chemistry and Biochemistry Committee Members: Liu Xuedong, Ph.D.: Department of Chemistry and Biochemistry Levente Szentkirályi, Ph.D.: Program For Writing and Rhetoric Undergraduate Thesis March 23rd, 2018 University of Colorado at Boulder Department of Chemistry and Biochemistry Broda 2 Acknowledgements I am incredibly thankful for the mentorship and experience I have received from Robert Kuchta, who gave me the opportunity to be an undergraduate research assistant and supported me during numerous independent projects. Likewise, I want to extend my thanks to the other members of the Kuchta lab that have been crucial in my development as a researcher and in the intricacies of this thesis: Sarah Dickerson, for her guidance through the research process and creation of a friendly working environment; Ayman Alawneh, for his mentorship in the art of organic synthesis from the bottom-up and for answering my numerous questions about the theory behind it all; and Michelle Ledru, for sharing the long synthesis days and learning the process with me. Additionally, thank you to my honors committee members Liu Xuedong and Levente Szentkirályi for volunteering their time to participate in this undergraduate thesis defense. A special thanks to Levente Szentkirályi, for helping me through the thesis writing process from the draft to the final and for instilling in me the responsibility we as a scienctific community have to make science accessible to interdisciplinary readers and the general public. I extend my appreciation to Michael J.
    [Show full text]
  • Catalyst in Basic Oleochemicals
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Diponegoro University Institutional Repository Bulletin of Chemical Reaction Engineering & Catalysis, 2(2-3), 2007, 22-31 Catalyst in Basic Oleochemicals Eva Suyenty, Herlina Sentosa, Mariani Agustine, Sandy Anwar, Abun Lie, and Erwin Sutanto * Research and Development Department, PT. Ecogreen Oleochemicals Jln. Pelabuhan Kav 1, Kabil, Batam 29435, Telp/Fax: (0778)711374 Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia Abstract Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty ac- ids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydro- genation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methy- late is derived from direct reaction of sodium metal and methanol under inert gas.
    [Show full text]
  • Step-Growth Polymerisation of Alkyl Acrylates Via Concomitant Oxa-Michael and Transesterification Reactions
    Step-growth polymerisation of alkyl acrylates via concomitant oxa-Michael and transesterification reactions Karin Ratzenböck,a David Pahovnikb and Christian Slugovc *a,c a Christian Doppler Laboratory for Organocatalysis in Polymerization, Stremayrgasse 9, A 8010 Graz, Austria b National Institute of Chemistry, Department of Polymer Chemistry and Technology, Hajdrihova 19, 1000 Ljubljana, Slovenia c Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A 8010 Graz, Austria Herein we propose an auto-tandem catalytic approach towards the preparation of poly(ester- ether)s from simple alkyl acrylates and diols. By combining oxa-Michael addition with transesterification the preparation of hydroxy functionalized acrylate monomers can be avoided. Introduction. Polymerisation of acrylates is typically performed by free radical polymerisation. Formed poly(acrylates) based on C-C main chains are widely used as paintings, surface coatings, adhesives, or fibres.1 However, the oxa-Michael addition reaction2 presents an alternative method for the polymerisation of acrylates leading to potentially more easily degradable poly(ester-ether)s in which functional groups are incorporated in the polymer main chain. Oxa-Michael addition polymerisation of hydroxyalkyl acrylates, also referred to as hydrogen-transfer polymerisation, was first reported in 1975.3 The polymerisation of 2- hydroxyethyl acrylate (HEA) could be initiated with LiH or PPh3. Since then few studies on the polymerisation of hydroxy functionalized
    [Show full text]
  • 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.
    [Show full text]
  • 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.
    [Show full text]
  • A Possible Emergent Cause of Honey Bee Mortality? Lara Zirbes, Bach Kim Nguyen, Dirk C
    Subscriber access provided by Université de Liège Review Hydroxymethylfurfural: a possible emergent cause of honey bee mortality? Lara Zirbes, Bach Kim Nguyen, Dirk C. de Graaf, Bruno De Meulenaer, Wim Paul Reybroeck, Eric Haubruge, and Claude Saegerman J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/jf403280n • Publication Date (Web): 15 Oct 2013 Downloaded from http://pubs.acs.org on October 21, 2013 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
    [Show full text]
  • 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.
    [Show full text]
  • Application of Simultaneous Oil Extraction and Transesterification in Biodiesel Fuel Synthesis: a Review
    energies Review Application of Simultaneous Oil Extraction and Transesterification in Biodiesel Fuel Synthesis: A Review Violeta Makareviciene * , Egle Sendzikiene and Milda Gumbyte Faculty of Forest Sciences and Ecology, Agriculture Academy, Vytautas Magnus University, LT-44248 Kaunas, Lithuania; [email protected] (E.S.); [email protected] (M.G.) * Correspondence: [email protected] Received: 7 April 2020; Accepted: 28 April 2020; Published: 2 May 2020 Abstract: Increasing concentrations of greenhouse gases in the atmosphere are leading to increased production and use of biofuels. The industrial development of biodiesel production and the use of biodiesel in the EU transport sector have been ongoing for almost two decades. Compared to mineral diesel production, the process of producing biodiesel is quite complex and expensive, and the search for new raw materials and advanced technologies is needed to maintain production value and expand the industrial production of biodiesel. The purpose of this article is to review the application possibilities of one of the new technologies—simultaneous extraction of oil from oily feedstock and transesterification (in situ)—and to evaluate the effectiveness of the abovementioned process under various conditions. Keywords: biodiesel; in situ; simultaneous oil extraction and transesterification 1. Introduction With the increase in atmospheric pollution in the form of greenhouse gases, the development of the use of biofuels in the transport sector is receiving increasing attention. Biodiesel is a well-known type of biofuel that has been used for a relatively long time. It is produced from various oily raw materials. Recently, the possibilities of utilizing non-food raw materials and residual waste in the synthesis of biodiesel have been intensively studied.
    [Show full text]
  • Transesterification of Vegetable Oils with Ethanol and Characterization of the Key Fuel Properties of Ethyl Esters
    Energies 2009, 2, 362-376; doi:10.3390/en20200362 OPEN ACCESS energies ISSN 1996-1073 www.mdpi.com/journal/energies Article Transesterification of Vegetable Oils with Ethanol and Characterization of the Key Fuel Properties of Ethyl Esters George Anastopoulos 1, Ypatia Zannikou 1, Stamoulis Stournas 1 and Stamatis Kalligeros 2,* 1 National Technical University of Athens, School of Chemical Engineering, Laboratory of Fuels Technology and Lubricants, Iroon Polytechniou 9, Athens 15780, Greece E-Mails: [email protected] (G.A.); [email protected] (Y.Z.); [email protected] (S.S.) 2 Hellenic Organization for Standardization, Technical Committee 66, 67 Prevezis Street, Athens, 10444, Greece * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +30-210- 5154695; Fax: +30-210-5154695 Received: 28 April 2009; in revised form: 24 May 2009 / Accepted: 3 June 2009/ Published: 5 June 2009 Abstract: The transesterification reactions of four different vegetable oils (sunflower, rapeseed, olive oil and used frying oil) with ethanol, using sodium hydroxide as catalyst, were studied. The ester preparation involved a two-step transesterification reaction, followed by purification. The effects of the mass ratio of catalyst to oil (0.25 – 1.5%), the molar ratio of ethanol to oil (6:1 – 12:1), and the reaction temperature (35 – 90 °C ) were studied for the conversion of sunflower oil to optimize the reaction conditions in both stages. The rest of the vegetable oils were converted to ethyl esters under optimum reaction parameters. The optimal conditions for first stage transesterification were an ethanol/oil molar ratio of 12:1, NaOH amount (1% wt/wt), and 80 °C temperature, whereas the maximum yield of ethyl esters reached 81.4% wt/wt.
    [Show full text]
  • Dehydration of D-Fructose to 5-Hydroxymethyl-2-Furfural in DMSO
    www.nature.com/scientificreports OPEN Dehydration of d‑fructose to 5‑hydroxymethyl‑2‑furfural in DMSO using a hydrophilic sulfonated silica catalyst in a process promoted by microwave irradiation Sandro L. Barbosa1*, Milton de S. Freitas1, Wallans T. P. dos Santos1, David Lee Nelson1, Stanlei I. Klein2, Giuliano Cesar Clososki3, Franco J. Caires3, Adriano C. M. Baroni4 & Alexandre P. Wentz5 2 3 −1 + SiO2‑SO3H, with a surface area of 115 m /g, pore volumes of 0.38 cm g and 1.32 mmol H /g, was used as a 10% w/w catalyst for the preparation of 5‑hydroxymethyl‑2‑furfural (HMF) from fructose. A conversion of 100% was achieved in a microwave reactor during 10 min at 150 °C in DMSO, with 100% selectivity for HMF, at a molar ratio of fructose: DMSO equal to 1:56. The catalyst could be re‑used three times. 5-Hydroxymethyl-2-furfural (HMF), which can be obtained from the dehydration of sugars, has a high potential as renewable raw material for the production of a variety of important molecules containing or derived of the furan ring, including biofuels, solvents, drugs, and biopolymer monomers 1–3. Tus, several studies have described the synthesis of HMF by catalytic dehydration of fructose4–18, Fig. 1. Glucose is less efcient than fructose for the synthesis of HMF19–21; according to Kuster22,23 and Zakrzewska et al.24, this results from the diference in stability of the two cyclical sugar structures, which are composed of six atoms in glucose (pyranose form) and fve atoms in fructose (furanose form).
    [Show full text]