DOCSLIB.ORG

Evaluation of Maleate, Fumarate, and Succinate Diesters As Potential Green Plasticizers

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Evaluation of Maleate, Fumarate, and Succinate Diesters As Potential Green Plasticizers Evaluation of maleate, fumarate, and succinate diesters as potential green plasticizers by Hanno Christian Erythropel A thesis submitted to McGill University in partial fulfillment of the requirements of the degree of Doctor of Philosophy Department of Chemical Engineering McGill University Montréal, Canada December 2015 ©Hanno C. Erythropel, 2015 Être homme, c’est précisément être responsable. C’est connaître la honte en face d’une misère qui ne semblait pas dépendre de soi. C’est être fier d’une victoire que les camarades ont remportée. C’est sentir, en posant sa pierre, que l’on contribue à bâtir le monde. -Antoine de Saint-Exupéry Gewidmet meinen lieben Eltern Eda & Karl-Heinz, sowie Thilo mit Marla. Abstract The industrial success of poly(vinyl chloride) (PVC) would not have been possible without compounds known as plasticizers, the most important class of additives to brittle polymers such as PVC. Plasticizers facilitate the processing of PVC and render the final product soft and flexible, and plasticizer content can reach up to 50 weight-percent. Due to the ever-increasing use of flexible PVC, plasticizers are produced in the range of several million metric tonnes per year. The most important class of plasticizers are phthalate diesters and di (2-ethylhexyl) phthalate (DEHP) is the most frequently used compound. The vast majority of plasticizers is simply blended with a polymer at elevated temperatures and thus is not bound to the polymer matrix, which results in their tendency to leach from the material over time, ultimately ending up in the environment. Once in the environment, the microbial biodegradation rates of phthalates are low, leading to their omnipresence in environmental samples. Moreover, the metabolites produced during the microbial breakdown are also stable compounds, as for example the corresponding monoester to DEHP, mono (2-ethylhexyl) phthalate (MEHP). Many studies have been carried out to investigate the toxicological effects of phthalates and their metabolites, and a variety of negative effects have been reported including endocrine disrupting and anti-androgenic effects. As a result, six phthalates have been banned in toys and childcare articles in Canada and other major markets. This ban has led to increased efforts to develop efficient plasticizers that are less environmentally persistent and show a lower toxicity profile. The research reported in this thesis aimed at evaluating plasticizer effectiveness and biodegradation rates of diesters synthesised from four-carbon diacids esterified with a linear alcohols ranging from ethanol (C2) to octanol (C8), and one branched alcohol, 2-ethylhexanol. The diacids were chosen due to their structural resemblance to the phthalate molecule, of which two were unsaturated (i.e., maleate: cis; fumarate: trans) and one saturated (i.e., succinate). The goal of this thesis was to gain insight on the influence of the geometry of the central structure and the length and branching of the side chains on plasticizer efficiency and biodegradability. The plasticizer candidates were blended with PVC at varying concentrations and the plasticizer effectiveness was evaluated by the measurement of the glass transition temperature Tg, tensile testing, dynamic mechanical thermal analysis (DMTA), and surface I hardness. The obtained results were then compared to similar blends containing the commercial plasticizers DEHP and DINCH®. Biodegradation properties were assessed by exposing the common soil bacterium Rhodococcus rhodocrous (ATCC 13808) to candidate plasticizers with hexadecane as carbon source. The results revealed important differences arising from central structures and indicated that the saturated (succinate) and the cis-structure (maleate) made for the most efficient plasticizers. Further studies of the succinate revealed that any groups hindering free rotation around the central chain of the molecule reduced its plasticizing efficiency. Side chain length was important and maximum efficiency occurred for a side chain length around six carbons. The added ethyl branch in those diesters with 2-ethylhexyl side chains was not found to have an enhancing effect on plasticizer effectiveness. The biodegradation experiments revealed a crucial influence of the central structure, as the saturated compound (succinate) was rapidly degraded and metabolite buildup was small and only transient. Between the two unsaturated compounds, those with the ester groups in trans position (fumarate) were more quickly degraded than those in cis-position (maleate); the latter showing almost no degradation over the course of the experiment. This could also explain the observed slow biodegradation of phthalate diesters, in which the ester groups are in a similar arrangement as in the maleate. Slower degradation rates were found with increasing side chain length as well as branching, but effects were not as important as that of the central structure. Nonetheless, when linear side chains were used, no or only small, transient buildup of the released alcohol was found, contrarily to 2-ethylhexanol which built up significantly during the according experiments. Taken together, dibutyl and dihexyl diesters of succinic- and maleic acid showed the most promising results in terms of plasticizer efficiency and biodegradability, yet further toxicological experiments are required to determine if these are truly “green” plasticizers. II Résumé Le succès industriel du polymère poly(chlorure de vinyle) (PVC) n’aurait pas été possible sans des molécules appelées plastifiants, qui représentent l’additif le plus important du PVC. Les plastifiants facilitent les étapes de production du PVC et rendent les produits finaux souples et flexibles. Plusieurs millions de tonnes de plastifiants sont produits chaque année. Les diesters de phthalate comme le di (2-éthylhexyle) phthalate (DEHP) représentent le type le plus important de plastifiant. Les plastifiants sont mélangés avec des polymères à des températures élevées, mais généralement, aucun lien chimique n’est établi entre le plastifiant et le polymère. C’est pour cette raison que les plastifiants ont tendance à se retirer du mélange au fil du temps, pour ensuite finir comme polluant dans l’environnement. Le taux de biodégradation des phthalates dans l’environnement est faible, ils sont donc omniprésents. Les métabolites qui sont produits pendant ce processus sont stables. Un exemple d’un tel métabolite est le monoester mono (2-éthylhexyle) phthalate (MEHP) pour DEHP. Plusieurs études ont démontré des mécanismes toxiques des phthalates et leurs métabolites. Les effets les plus lancinants affectent le système endocrinien, résultant dans des effets anti-androgènes. Basé sur ces résultats, six phthalates ont été bannis de jouets et d’articles de puériculture dans le Canada et d’autres marchés majeurs. Par conséquent, le développement de nouveaux plastifiants efficaces, moins persistants et toxiques dans l’environnement est nécessaire. Cette thèse vise à évaluer l’efficacité du plastifiant et les taux de biodégradations de plusieurs diesters synthétisés avec des alcools linéaires, qui variaient d’une longueur de deux (éthanol) à huit (octanol) charbons, et un alcool ramifié, soit 2-éthylhexanol. Les acides dicarboxyliques utilisés ont été choisis à cause de leur similitude à la structure du phthalate, et un total de trois structures centrales différentes ont été évaluées. Celles-ci comprenaient deux structures insaturées, le maléate (cis) et le fumarate (trans), et une structure saturée, le succinate. L’objectif de cette thèse était d’ailleurs de mieux comprendre l’influence de la géométrie de la partie centrale de la molécule et de la longueur de la chaîne latérale sur l’efficacité du plastifiant et le taux de biodégradation. Les molécules étudiées étaient mélangées à différentes concentration avec du PVC non-plastifié, et leur efficacité du plastifiant a été évaluée à l’aide de plusieurs essais, dont la détermination de la température de transition vitreuse (Tg), des essais de traction, l’analyse thermomécanique dynamique III (ATMD), et la dureté superficielle. Les résultats obtenus étaient ensuite comparés avec des résultats d’essais semblables avec des plastifiants commerciaux comme DEHP et DINCH®. Les taux de biodégradation ont été évalués à l’aide d’une bactérie courante dans le sol, Rhodococcus rhodocrous (ATCC 13808) et hexadécane comme source de carbone. Les résultats obtenus montraient que les plastifiants les plus efficaces contenaient des structures centrales insaturées en configuration cis (maléate) ou saturées (succinate). La capacité de rotation autour de la chaîne centrale du succinate était un facteur important dans l’efficacité du plastifiant, et l’attachement de groupes chimiques qui empêchaient cette capacité de rotation menait à des plastifiants moins efficaces. La longueur de la chaîne latérale jouait aussi un rôle important : l’efficacité maximale des plastifiants était atteinte quand cette chaîne latérale était formée d’environ six charbons. Quant à la chaîne ramifiée, l’addition d’une branche éthylique au diester n’améliorait pas l’efficacité du plastifiant, mais l’efficacité trouvée était semblable à celle de la molécule avec la même longueur. Les expériences de biodégradation révélaient l’importance de la géométrie de la structure centrale : les molécules saturées (succinates) étaient biodégradées rapidement, et l’accumulation de métabolites était faible et seulement transitoire. Entre les structures centrales contentant des liens non-saturés,
Load more

Recommended publications
  • Thèse Docteur De L'université De Haute-Alsace
    UNIVERSITE DE HAUTE-ALSACE UNIVERSITE DE STRASBOURG Thèse Présentée pour l’obtention du grade de Docteur de l’Université de Haute-Alsace Ecole Doctorale : ED 222 - Sciences Chimiques Discipline : Chimie, Physique et Matériaux Présentée et soutenue publiquement par Franklin BAUER Le 30 novembre 2017 Une meilleure caractérisation des mécanismes d’action toxique à partir de la structure moléculaire. Thèse CIFRE Sous la Direction de : Directeur de thèse : Prof. Serge NEUNLIST Co-directeur de thèse : Dr. Samuel FOUCHARD Encadrée en entreprise par : Dr. Paul THOMAS Jury : Dr. Karine AUDOUZE, université Paris Diderot (Rapporteur) Dr. Patrice GONZALEZ, université de Bordeaux (Rapporteur) Prof. Jean-Philippe GODDARD, université de Haute-Alsace (Président) Prof. Eric PINELLI, université de Toulouse III Prof. Serge NEUNLIST, université de Haute-Alsace Dr. Samuel FOUCHARD, université de Haute-Alsace Dr. Paul THOMAS, KREATiS 3 Table des matières Table des figures .................................................................................................................. 6 Table des tableaux ............................................................................................................... 7 Liste des abréviations .......................................................................................................... 8 Remerciements ................................................................................................................. 10 Résumé de la thèse en anglais – Abstract ........................................................................
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,620,949 B1 Sutton Et Al
    USOO6620949B1 (12) United States Patent (10) Patent No.: US 6,620,949 B1 Sutton et al. (45) Date of Patent: Sep. 16, 2003 (54) PROCESS FOR THE SIMULTANEOUS 6,191,322 B1 2/2001 Bertola ....................... 568/864 PRODUCTION OF MALEC ANHYDRIDE 6.274,743 B1 * 8/2001 Tucket al. ................. 549/295 AND ITS HYDROGENATED DERVATIVES 6,380,402 B2 4/2002 Cho et al. ................... 549/325 6,433,193 B1 * 8/2002 Bertola et al. .............. 549/295 (75) Inventors: David Mark Sutton, 6,492,535 B1 * 12/2002 Castiglioni et al. ......... 549/325 Kingston-upon-Thames (GB); Andrew 6,515,148 B2 2/2003 Schiodt ...................... 549/326 George Hiles, Amersham (GB); Adrian FOREIGN PATENT DOCUMENTS Francis Backes, London (GB) GB 22O7914 2/1989 (73) Assignee: Davy Process Technology Limited, WO 9743234 11/1997 WO 9743242 11/1997 London (GB) WO 9948852 9/1999 (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 * cited by examiner U.S.C. 154(b) by 0 days. Primary Examiner Deborah C. Lambkin (21) Appl. No.: 10/110,444 (74) Attorney, Agent, or Firm-Davidson, Davidson & Kappel, LLC (22) PCT Filed: Oct. 4, 2000 (57) ABSTRACT (86) PCT No.: PCT/GB00/03805 A proceSS is described for the co-production of maleic S371 (c)(1), anhydride and at least one C compound Selected from (2), (4) Date: Jul. 22, 2002 butane-1,4-diol, Y-butyrolactone, and tetrahydrofuran in (87) PCT Pub. No.: WO01/27058 which maleic anhydride is produced by partial oxidation of a hydrocarbon feedstock Selected from C.
    [Show full text]
  • Poly(Lactic Acid) Science and Technology: Processing, Properties, Additives and Applications
    Poly(lactic acid) Science and Technology Processing, Properties, Additives and Applications RSC Polymer Chemistry Series Editor-in-Chief: Ben Zhong Tang, The Hong Kong University of Science and Technology, Hong Kong, China Series Editors: Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada Stephen Craig, Duke University, USA Jianhua Dong, National Natural Science Foundation of China, China Toshio Masuda, Fukui University of Technology, Japan Christoph Weder, University of Fribourg, Switzerland Titles in the Series: 1: Renewable Resources for Functional Polymers and Biomaterials 2: Molecular Design and Applications of Photofunctional Polymers and Materials 3: Functional Polymers for Nanomedicine 4: Fundamentals of Controlled/Living Radical Polymerization 5: Healable Polymer Systems 6: Thiol-X Chemistries in Polymer and Materials Science 7: Natural Rubber Materials: Volume 1: Blends and IPNs 8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites 9: Conjugated Polymers: A Practical Guide to Synthesis 10: Polymeric Materials with Antimicrobial Activity: From Synthesis to Applications 11: Phosphorus-Based Polymers: From Synthesis to Applications 12: Poly(lactic acid) Science and Technology: Processing, Properties, Additives and Applications How to obtain future titles on publication: A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication. For further information please contact: Book Sales Department, Royal Society of Chemistry, Thomas Graham
    [Show full text]
  • 156 Part 175—Indirect Food Addi
    Pt. 175 21 CFR Ch. I (4–1–11 Edition) The Food and Drug Administration food in accordance with the following will exempt substances whose uses it prescribed conditions: determines meet the criteria in § 170.39 (1) The adhesive is prepared from one of this chapter from regulation as food or more of the optional substances additives and, therefore, a food addi- named in paragraph (c) of this section, tive petition will not be required for subject to any prescribed limitations. the exempted use. (2) The adhesive is either separated from the food by a functional barrier or [60 FR 36596, July 17, 1995] used subject to the following additional limitations: PART 175—INDIRECT FOOD ADDI- (i) In dry foods. The quantity of adhe- TIVES: ADHESIVES AND COMPO- sive that contacts packaged dry food NENTS OF COATINGS shall not exceed the limits of good manufacturing practice. Subpart A [Reserved] (ii) In fatty and aqueous foods. (a) The quantity of adhesive that contacts Subpart B—Substances for Use Only as packaged fatty and aqueous foods shall Components of Adhesives not exceed the trace amount at seams Sec. and at the edge exposure between pack- 175.105 Adhesives. aging laminates that may occur within 175.125 Pressure-sensitive adhesives. the limits of good manufacturing prac- tice. Subpart C—Substances for Use as (b) Under normal conditions of use Components of Coatings the packaging seams or laminates will 175.210 Acrylate ester copolymer coating. remain firmly bonded without visible 175.230 Hot-melt strippable food coatings. separation. 175.250 Paraffin (synthetic). (b) To assure safe usage of adhesives, 175.260 Partial phosphoric acid esters of pol- the label of the finished adhesive con- yester resins.
    [Show full text]
  • Dr. Dennis Keefe Director of the Office of Food Additive Safety
    NATURAL RESOURCES DEFENSE COUNCIL BREAST CANCER FUND CENTER FOR ENVIRONMENTAL HEALTH CENTER FOR FOOD SAFETY CENTER FOR SCIENCE IN THE PUBLIC INTEREST CHILDREN’S ENVIRONMENTAL HEALTH NETWORK CLEAN WATER ACTION ENVIRONMENTAL WORKING GROUP IMPROVING KIDS’ ENVIRONMENT October 17, 2014 (REVISED FROM VERSION FILED October 16, 2014) Dr. Dennis Keefe Director of the Office of Food Additive Safety (HFS-200) Center for Food Safety and Applied Nutrition 5100 Paint Branch Parkway College Park, MD 20740 Re: Petition seeking amended food additive regulation to remove FDA’s approval at 21 C.F.R. § 176.170 of the use of long-chain perfluorocarboxylate oil and grease repellents in paper and paperboard - Pre-Notification Consultation 1417 (PNC 1417) Dear Dr. Keefe: In 2010, the U.S. Food and Drug Administration’s (FDA) food additives toxicologists concluded that, in animal studies, long-chain perfluorinated compounds adversely affect fetal and newborn development and that one group of these compounds, long-chain perfluorocarboxylates1, adversely affect the male, and, possibly the female, reproductive systems.2 A ‘long-chain’ means the compound has eight or more carbons (“≥ C8”) connected together and the carbons are saturated with fluorine atoms. As the chain lengthens, FDA’s toxicologists noted that the chemical’s biopersistence, and hence potency, in the human body increases.3 These findings on long-chain perfluorocarboxylates expand on the toxicologist’s 2007 conclusion that carcinogenicity was a concern for chemicals that were structurally similar to the perfluorooctanoic acid (PFOA).4 The agency’s food additive toxicologists stated that “[d]ue to the considerable uncertainties remaining regarding the toxic effects of perfluorinated compounds as a class in humans, significant questions remain regarding the safe levels of dietary exposure to ≥ C8 perfluorinated 1 Including chemicals that may be converted to perfluorocarboxylates.
    [Show full text]
  • High Performance Pressure Sensitive Adhesive Emulsion
    ~" ' INI II II II INI II II II Nil Ml Ml J European Patent Office ^ © Publication number: 0 339 473 B1 Office_„. europeen des brevets © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 06.04.94 © Int. CI.5: C08F 220/12, C08F 222/14, C09J 123/08, C09J 131/00, © Application number: 89107066.6 C09J 131/02, C09J 131/04, nn, C09J 131/06, ' //(C08F220/1 2,' w© Date of fi ing:a 19.04.89„on/100 222:14,218:08,210:02,220:18,_ _ _ „ „ ^„ „ ^ ^ „rt . The file contains technical information submitted 220:56,220:04), (C08F222/1 4, after the application was filed and not included in 220:1 2,21 8:08) this specification High performance pressure sensitive adhesive emulsion. © Priority: 27.04.88 US 186524 © Proprietor: AIR PRODUCTS AND CHEMICALS, INC. @ Date of publication of application: P.O. Box 538 02.11.89 Bulletin 89/44 Allentown, Pennsylvania 18105(US) © Publication of the grant of the patent: @ Inventor: Cheng, John Tze-Chiang 06.04.94 Bulletin 94/14 3360 Byrd Avenue Allentown, PA 18103(US) © Designated Contracting States: Inventor: Mao, Chung-Ling BE DE FR GB IT 4969 Sweetbriar Circle Emmaus, PA 18049(US) © References cited: EP-A- 0 017 986 EP-A- 0 110 209 © Representative: Kador & Partner US-A- 4 692 366 Corneliusstrasse 15 D-80469 Munchen (DE) 00 00 00 oo Note: Within nine months from the publication of the mention of the grant of the European patent, any person ® may give notice to the European Patent Office of opposition to the European patent granted.
    [Show full text]
  • Guide to Chemical Hazard Information
    GUIDE TO CHEMICAL HAZARD INFORMATION 3 1 0 EHS Ratings 2001 [v1] This Guide is intended to provide chemical hazard ratings for use with the EHS HMIS Labeling System. If a chemical is not listed, then please refer to the procedures for rating chemical hazards detailed in the EHS Chemical Hazard Reference Information Sheet and EHS HMIS Instruction Sheet. For more information contact Environmental Health and Safety at 882-7018 or visit our web site at http://web.missouri.edu/~muehs/. The information contained in this document was based on information from the Office of Radiation, Chemical & Biological Safety, Michigan State University. EHS Ratings 2001 [v1] Index Click within the blue outline to jump to the first page of chemical names that begin with the letter indicated. A M B N-O C P-R D S-T E-G U-Z H-L EHS Ratings 2001 [v1] CHEMICAL HAZARD RATINGS -- (A) Compound H F R SP HAZ Acetal 2 3 0 Acetaldehyde 3 4 2 Acetanilide 3 1 0 Acetic Acid (glacial) 3 2 0 Acetic Anhydride 3 2 1 W Acetoacetanilide 2 1 0 Acetoacet-ortho-toluidide 2 1 1 Acetoacet-para-phenetide 2 1 1 Acetone 1 3 0 Acetone cyanohydrin 4 2 2 Acetonitrile 2 3 0 Acetonyl acetone 1 1 0 Acetophenone 1 2 0 Acetyl Chloride 3 3 2 W Acetylene 0 4 3 Acetyl Peroxide. 1 2 4 Acrolein 4 3 3 Acrolein Dimer 1 2 1 Acrylamide 2 2 2 Acrylic Acid (glacial) 3 2 2 Acrylonitrile 4 3 2 Adipic Acid - 1 0 Adiponitrile 2 2 1 Adipoyl chloride 2 2 0 Adipyldinitrile 4 2 - Aldol 3 2 2 Allyl Acetate 1 3 0 Allyl Alcohol 4 3 1 Allylamine 4 3 1 Allyl Bromide 3 3 1 Allyl caproate 1 2 0 Allyl Chloride 3 3 1 Allyl
    [Show full text]
  • Identification of Carboxylesterase Metabolites of Residual Malathion
    92 Journal of Health Science, 53(1) pp 92–98 (2007) Identification of Carboxylesterase Metabolites of Residual Malathion in Wheat Kernels Using Semi-Micro Radio Liquid Chromatography Kimihiko Yoshii,∗,a Yasuhide Tonogai,b Jun’ichi Katakawa,c Hitoshi Ueno,c and Katsuhiko Nakamuroc aOsaka Prefectural Government, Pharmaceutical Affairs Division, Department of Public Health and Welfare, Otemae 2, Chuo-ku, Osaka 540–8570, Japan, bOsaka Pharmaceutical Association, 1–3–8 Izumi-cho, Chuo-ku, Osaka 540–0019, Japan, and cFaculty of Pharmaceutical Sciences, Setsunan University, 45–1 Nagaotoge-cho, Hirakata, Osaka 573–0101, Japan (Received September 16, 2006; Accepted September 30, 2006; Published oneline November 10, 2006) Since residual malathion in wheat kernels is shown to be enzymatically decomposed during sample preparation using the Japanese official method for pesticide analysis, the decomposition products were identified by semi-micro radio liquid chromatography (LC). The reaction mixture of the supernatant of wheat kernel homogenate incubated with [14C] malathion for 0–8 hr was fractionated, and the radioactive decomposition products in the fractions were identified by comparison with the retention time of fifteen reference standards. Twelve of these products occurring in the environment, diethyl fumarate, diethyl maleate, diethyl malate and diethyl succinate, and their hydrolysate and desmethyl malathion dicarboxylic acid were not detected in the reaction mixture, indicating no contribution of organophosphorus hydrolase or methyl transferase. A trace amount of desmethyl malathion was observed, however, this seemed to be non-enzymatically produced. Malathion monocarboxylic acid and malathion dicarboxylic acid were identified as the major products by the LC condition with and without an ion pair reagent, respectively.
    [Show full text]
  • Designing Green Plasticizers
    DESIGNING GREEN PLASTICIZERS Hanno Erythropel Department of Chemical Engineering McGill University Montréal, Québec, Canada February 2011 This thesis is submitted to McGill University in partial fulfillment of the requirements of the degree of Master of Engineering © Hanno C. Erythropel, 2011 i Abstract Plasticizers are additives in poly (vinyl chloride) (PVC) formulations that render the material flexible. This is important for many applications. Because these plasticizers are not bound to the polymer chemically, they will eventually leach out upon disposal. Considering also the widespread use of flexible PVC, it is not surprising that some plasticizers, such as di(2-ethylhexyl) phthalate (DEHP), are considered ubiquitous contaminants in the environment. Previous studies have shown that DEHP, upon degradation, forms stable, toxic metabolites. Because of this and other concerns, DEHP and other phthalates have already been banned in certain products in Canada and other countries. Hence, there is a strong incentive to develop new, green plasticizers. A series of diesters based on maleic acid, which resembles a part of the phthalate chemical structure, was tested, along with other series based on the structural isomer of maleic acid, fumaric acid, and the saturated analogue, succinic acid. The alcohols used to form the ester bonds varied in length from ethanol to octanol and, also, included the branched 2-ethyl hexanol. Each of these diesters was incorporated into unplasticized PVC at about 30 weight-percent and then evaluated for plasticizer properties such as glass transition temperature Tg and tensile strength. These data were compared to each other and to results with DEHP. Pure samples of the diesters were tested for their biodegradability by the common soil bacterium Rhodococcus rhodocrous (ATCC 13808) while it was growing on hexadecane as a primary carbon source.
    [Show full text]
  • Rossi Lars.Pdf
    Submitted in partial fulfillment of the requirements for the degree of Master of Science Thermal treatment of drill cuttings Lars Martin Rossi Department of mathematics and natural science University of Stavanger June, 2016 Abstract Increased environmental stringency, and focus on cost efficiency, drives the oil & gas industry towards new and better solutions. Members of OSPAR have to follow strict discharge requirements for oil contaminated drill cuttings, based on the BAT, and BEP principles. The most successful technologies rely on thermal desorption. Only the TCC have received acceptance to treat and discharge OBM cuttings on the NCS, at a require- ment of 0:05 % oil by weight. Norwegian-Group AS is currently developing an integrated treatment solution for drilling fluids, waste water, and cuttings. In this thesis, thermal treatment of cuttings is investigated. The treatment concept rely on dielectric heating with microwaves, in combination with environmentally friendly, polar organic compounds. The initial study shows that glycols can be distilled without significant degradation, especially MEG. In addition to the benefits of increased process temperature, a significant reduction in energy requirement is possible. The energy required to vaporize MEG is in the order of magnitudes lower, than what is required to vaporize water. Due to a higher process temperature , the vapor pressure contribution from the oil was significantly increased. Drill cuttings was successfully treated to well below the OSPAR limit of 1 % oil by weight, by the use of susceptors. The presence of susceptors significantly increased the oil separation from cuttings, especially when the cuttings did not contain water. It is believed that the use of susceptors in combination with microwaves can challenge the TCC technology as BAT.
    [Show full text]
  • Related Properties from Molecular Structures
    Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2021 1 SUPPORTING INFORMATION 2 A multi-task deep learning neural network for predicting flammability- 3 related properties from molecular structures 4 Ao Yang‡a,b, Yang Su‡c,a, Zihao Wanga, Saimeng Jina, Jingzheng Renb, Xiangping Zhangd, 5 Weifeng Shen*a and James H. Clarke 6 aSchool of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China 7 bDepartment of Industrial and Systems Engineering, The Hong Kong Polytechnic University, Hong 8 Kong SAR, China 9 cSchool of Intelligent Technology and Engineering, Chongqing University of Science and Technology, 10 Chongqing 401331, China 11 dBeijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and 12 Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China 13 eGreen Chemistry Centre of Excellence, University of York, York YO105D, UK 14 *Correspondence should be addressed to: Weifeng Shen ([email protected]) 15 ‡These authors contributed equally to this work. 16 S1. Signature descriptors 17 The signature descriptor1 is an effective tool for encoding molecular structures with all 18 atomic neighborhood into strings. This descriptor involving two forms: the first one is the 19 atomic signatures generated at a specified root atom in a molecule, the other one is the molecular 20 signatures combined from all atom signatures linearly. The size of each atomic signature is 21 determined by a parameter named “height”, h. An atomic Signature is a tree subgraph including 22 all atoms/bonds extending out to the predefined distance h without backtracking.
    [Show full text]
  • United States Patent (19) (11 Patent Number: 4,795,824 Kippax Et Al
    United States Patent (19) (11 Patent Number: 4,795,824 Kippax et al. (45) Date of Patent: Jan. 3, 1989 54 PROCESS FOR THE PRODUCTION OF Primary Examiner-Werren B. Lone DALKYL MALEATES Assistant Examiner-Vera C. Clarke 75 Inventors: John W. Kippax, Bedale; Colin Attorney, Agent, or Firm-Bernard, Rothwell & Brown Rathmell, Yarm, both of England 57 ABSTRACT 73) Assignee: Davy McKee (London) Limited, A process is described for the production of a dialkyl London, England maleate by reaction of maleic anhydride with an alkyl alcohol in a monoesterification zone to form the corre (21) Appl. No.: 80,060 sponding monoalkyl maleate, followed by reaction of (22 Filed: Jul. 31, 1987 resulting monoalkyl maleate with further alkyl alcohol 30 Foreign Application Priority Data to form the corresponding dialkyl maleate, which in cludes the steps of supplying a first liquid feed compris Aug. 1, 1986 GB United Kingdom ................. 86.18888 ing said monoalkyl maleate to a secondary esterification 51 Int. Cl'.............................................. CO7C 67/03 zone containing a charge of a solid esterification cata 52 U.S. C. ...................................... 560/204; 203/14; lyst, supplying a second feed stream comprising said 203/DIG. 2; 203/DIG. 11; 502/11; 560/191; alkyl alcohol to said secondary esterification zone, 562/595 maintaining said secondary esterification zone at an 58 Field of Search ................ 560/204, 191; 562/595; elevated temperature sufficient to form or to maintain 502/11; 203/14, 2, 11 therein a vaporous stream containing said alkyl alcohol, 56 References Cited intimately contacting said first liquid feed in said sec ondary esterification Zone in the presence of said cata U.S.
    [Show full text]