Peroxide-Forming Chemicals
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Energy-Saving Reduced-Pressure Extractive Distillation with Heat
Energy-Saving Reduced-Pressure Extractive Distillation with Heat Integration for Separating the Biazeotropic Ternary Mixture Tetrahydrofuran–Methanol–Water Jinglian Gu, Xinqiang You, Changyuan Tao, Jun Li, Vincent Gerbaud To cite this version: Jinglian Gu, Xinqiang You, Changyuan Tao, Jun Li, Vincent Gerbaud. Energy-Saving Reduced- Pressure Extractive Distillation with Heat Integration for Separating the Biazeotropic Ternary Mixture Tetrahydrofuran–Methanol–Water. Industrial and engineering chemistry research, American Chemical Society, 2018, 57 (40), pp.13498-13510. 10.1021/acs.iecr.8b03123. hal-01957130 HAL Id: hal-01957130 https://hal.archives-ouvertes.fr/hal-01957130 Submitted on 17 Dec 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible This is an author’s version published in: http://oatao.univ-toulouse.fr/21066 Official URL: https://doi.org/10.1021/acs.iecr.8b03123 To cite this version: Gu, Jinglian and You, Xinqiang and Tao, Changyuan and Li, Jun and Gerbaud, Vincent Energy-Saving Reduced-Pressure Extractive Distillation with Heat Integration for Separating the Biazeotropic Ternary Mixture Tetrahydrofuran–Methanol–Water. -
Poly(Ethylene Oxide-Co-Tetrahydrofuran) and Poly(Propylene Oxide-Co-Tetrahydrofuran): Synthesis and Thermal Degradation
Revue Roumaine de Chimie, 2006, 51(7-8), 781–793 Dedicated to the memory of Professor Mircea D. Banciu (1941–2005) POLY(ETHYLENE OXIDE-CO-TETRAHYDROFURAN) AND POLY(PROPYLENE OXIDE-CO-TETRAHYDROFURAN): SYNTHESIS AND THERMAL DEGRADATION Thomas HÖVETBORN, Markus HÖLSCHER, Helmut KEUL∗ and Hartwig HÖCKER Lehrstuhl für Textilchemie und Makromolekulare Chemie der Rheinisch-Westfälischen Technischen Hochschule Aachen, Pauwelsstr. 8, 52056 Aachen, Germany Received January 12, 2006 Copolymers of tetrahydrofuran (THF) and ethylene oxide (EO) (poly(THF-co-EO) and THF and propylene oxide (PO) (poly(THF-co-PO) were obtained by cationic ring opening polymerization of the monomer mixture at 0°C using boron trifluoride etherate (BF3.OEt2) as the initiator. From time conversion plots it was concluded that both monomers are consumed from the very beginning of the reaction and random copolymers are obtained. For poly(THF-co-PO) the molar ratio of repeating units was varied from [THF]/[PO] = 1 to 10; the molar ratio of monomers in the feed corresponds to the molar ratio of repeating units in the copolymer. Thermogravimetric analysis of the copolymers revealed that both poly(THF-co-EO) and poly(THF-co-PO) decompose by ca. 50°C lower than poly(THF) and by ca. 100°C lower than poly(EO); 50% mass loss is obtained at T50 = 375°C for poly(EO), T50 = 330°C for poly(THF) and at T50 = 280°C for both copolymers. The [THF]/[PO] ratio does not influence the decomposition temperature significantly as well. For the copolymers the activation energies of the thermal decomposition (Ea) were determined experimentally from TGA measurements and by density functional calculations on model compounds on the B3LYP/6-31+G* level of theory. -
Indiana State University ISU Laboratory Safety Guideline
ISU Laboratory Safety Guideline Working with Organic Peroxides and Storage Guidelines Date: December 2012 Indiana State University Organic peroxide is a compound containing the -O-O- structure and is considered a structural derivative of hydrogen peroxide. Organic peroxides are one of the most hazardous materials handled in the laboratory. These peroxides are low powered explosives that are sensitive to shock, sparks or other accidental ignition due to the weak –O-O bond. Organic compounds such as ethers can react with oxygen to form unstable peroxides. Peroxide formation can also occur under normal storage conditions when compounds become concentrated by evaporation or when mixed with other compounds. Types of Compounds known to form peroxides : Ethers containing primary and secondary alkyl groups (never distill an ether before it has been shown to be free of peroxide) Compounds containing benzylic hydrogens Compounds containing allylic hydrogens (C=C-CH) Compounds containing a tertiary C-H group (e.g., decalin and 2,5-dimethlyhexane) Compounds containing conjugated, polyunsaturated alkenes and alkynes (e.g., 1,3-butadiene, vinyl acetylene) Compounds containing secondary or tertiary C-H groups adjacent to an amide (e.g., 1-methyl-2- pyrrolidinone Prudent Practices in the Laboratory: Handling and Management of Chemical Hazards, Updated Version General Procedures for working with Peroxide-forming chemicals: • Be aware of the use of peroxide-forming chemicals when designing or conducting a new experiment. • If possible, purchase material containing an inhibitor such as butylated hydroxytoluene (BHT). • Date the container when received, opened and tested. • Consult Prudent Practices or other resources for storage shelf-life and testing procedures. -
Peroxide-Forming Chemicals
Peroxide-Forming Chemicals 4 Ways to stop explosions, injuries, and added expenses: 1) Track shelf life A) label when tested and when to retest B) date when received 2) Handle with proper personal protective equipment A) gloves B) googles/safety glasses C) flame-resistant lab coat D) training E) Ask [the Dept. of Chemistry and Dept. of Environmental Health & Safety] for help 3) Store properly A) flammable storage cabinet if applicable B) avoid i) heat (keep in a cool place) ii) impact iii) friction iv) light (keep in a dark place) 4) Buy the right amount A) based on what will be used B) reduce the disposal of any un-used material (Dubiel). The Department of Chemistry wants you to learn from our experiences. Amides, Dioxane, Ethers, secondary alcohols, and Tetrahydrofuran (as well as other cyclic ethers) must be checked for peroxides. The University of Pittsburgh Department of Environmental Health and Safety (EH&S) recommends that all peroxide-forming chemicals should be tested every six months for peroxide content, and any chemicals that test positive should either be purified before use to remove the peroxide or discarded as chemical waste and replaced with fresh material. (http://www.ehs.pitt.edu/assets/docs/peroxide-forming.pdf). Ken Migliorese, a previous staff member, emailed the Department of Chemistry to remind us of the importance of doing peroxide testing on a regular basis. The need to test for peroxides was made clear to us by a series of unfortunate explosions which occurred in the undergraduate organic teaching labs in 2008. We had multiple defective layers of protection that caused failures of safety measures and three catastrophic errors (Reason). -
Peroxide Forming Chemicals
What are organic peroxides? Organic peroxides are a class of compounds that have unusual stability problems that make them among the most hazardous substances found in the laboratory. The lack of stability is due to the presence of an oxidation and reduction center within the same molecule. R-O-O-R R = organic side chains O-O = Peroxo bridge As a class, organic peroxides are considered to be powerful explosives and are sensitive to heat, friction, impact, light, as well as to strong oxidizing and reducing agents. Peroxide formers react with oxygen even at low concentrations to form peroxy compounds. Autoxidation of organic material proceeds by a free-radical chain mechanism and commonly affects organic solvents. R-H R- R-O-O R-O-O-R (In the presence of oxygen) The instability of the molecule (R-O-O-R) can cause auto-decomposition simply by bumping or jarring the container, addition of heat, light, or opening the cap. The risk associated with the peroxide increases if the peroxide crystallizes or becomes concentrated by evaporation or distillation. Peroxide crystals may form on the container plug or the threads of the cap and detonate as a result of twisting the lid. Classes of Peroxide Formers Aldehydes Ethers - especially cyclic ethers and those containing primary and secondary alcohol groups Compounds containing benzylic hydrogen atoms (particularly if the hydrogens are on tertiary carbon atoms) Compounds containing the allylic structure, including most alkenes. Vinyl and vinylidene compounds. Preventing Formation of Organic Peroxides No single method of inhibition of peroxide formation is suitable for all peroxide formers. -
Tetrahydrofuran
SOME CHEMICALS THAT CAUSE TUMOURS OF THE URINARY TRACT IN RODENTS VOLUME 119 This publication represents the views and expert opinions of an IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, which met in Lyon, 6–13 June 2017 LYON, FRANCE - 2019 IARC MONOGRAPHS ON THE EVALUATION OF CARCINOGENIC RISKS TO HUMANS TETRAHYDROFURAN 1. Exposure Data Boiling point: 65–66 °C (EPA, 2012) Melting point: −108.44 °C (ECHA, 2018) 1.1 Identification of the agent Relative density: 0.883 at 25 °C (water, 1) (ECHA, 2018) 1.1.1 Nomenclature Solubility: Miscible in water (ECHA, 2018) Chem. Abstr. Serv. Reg. No.: 109-99-9 Volatility: Vapour pressure, 19.3 kPa at 20 °C (IPCS, 1997) EC/List No.: 203-726-8 Relative vapour density: 2.5 (air = 1); relative Chem. Abstr. Serv. name: Tetrahydrofuran density of the vapour/air mixture at 20 °C IUPAC systematic name: Oxolane (air = 1): 1.28 (IPCS, 1997) Synonyms: Butane alpha,delta-oxide; butane, Stability: Tetrahydrofuran is prone to oxida- 1,4-epoxy-; cyclotetramethylene oxide; dieth- tion to peroxides, butyric acid, butyralde- ylene oxide; 1,4-epoxybutane; furan, tetra- hyde, and related compounds, mainly on hydro-; furanidine; hydrofuran; oxacyclo- ageing and in the presence of light, heat, pentane; tetramethylene oxide; THF and moisture. The formation of peroxides can be retarded by adding stabilizers such as 1.1.2 Structural and molecular formulae, and hydroquinone or 2,6-di-tert-butyl-p-cresol at relative molecular mass 250 mg/kg (Coetzee & Chang, 1985; Müller, 2012). O Flash point: −14.5 °C -
United States Patent 0 Ice Patented Jan
3,489,528 United States Patent 0 ice Patented Jan. 13, 1970 1 2 number of (BHZNHZ) groups, but the product is con 3,489,528 PREPARATION OF POLYAMINOBORANES sistent in composition, as shown by infra-red and ele William E. Zanieski, Pittsburgh, Pa., assignor to Mine mental analyses, and the average value of n is about 4. Safety Appliances Company, a corporation of In another example a solution of THF-EH3 contain— Pennsylvania ing 2.99 g. of B2H6 in 150 ml. of THF was prepared N0 Drawing. Filed Apr. 5, 1965, Ser. No. 445,707 in the same manner as the previous example and the Int. Cl. C01b 21/00 solution was warmed to -30° C. 3.12 g. of gaseous US. Cl. 23—358 6 Claims ammonia was bubbled into and dissolved in the solution at —30° C. and the resultant clear solution was warmed to 0° C, at which temperature hydrogen was evolved and polyaminoborane, identical to that obtained in the ABSTRACT OF THE DISCLOSURE previous example, precipitated from the reaction mix Ammonia and diborane are reacted in tetrahydrofuran ture. at a temperature below about —30° C.; polyaminoboranes ‘Although the invention is not limited to any particular are precipitated when the reaction mixture is warmed. 15 reaction mechanism, it appears that the reaction of NH3 Aging of an ammonia solution of the polyaminoboranes and BZHS in THF forms an intermediate that is formed so produced yields an ammonia insoluble, more highly and is stable only at temperatures below about —30° C. polymerized polyaminoborane. and that this intermediate decomposes at temperatures above about —30° C. -
Tetrahydrofuran (THF)
Tetrahydrofuran (THF) Typical Physical Properties of THF Molecular Weight 72.11 g/mol Empirical Formula C4H8O Appearance Colorless Freezing Point ‐108°C (‐ 164.4°F) Flash Point – Closed Cup ‐20°C (‐4°F) Boiling Point @ 760mmHg 66°C (150.8°F) Autoignition Temperature 230°C (446°F) Density @ 20°C 0.89 kg/l Tetrahydrofuran (THF) is a clear, colorless liquid with 7.43 lb/gal an ether‐like odor. The principal end uses of THF Vapor Pressure @ 20°C 193 hPa include PTMEG, pharmaceutical solvent, adhesives, PVC cement and magnetic tape. Due to its' tendency Evaporation Rate (nBuAc = 1) 8 to form peroxides during storage, THF is inhibited with Solubility @ 20°C (in Water) Complete BHT. Refractive Index @ 20°C 1.407 CAS number Viscosity @ 20°C 0.516 cP Lower Flammability in Air 1.5% v/v 109‐99‐9 Upper Flammability in Air 12.4% v/v Synonyms Note: The properties reported above are typical physical properties. Monument Chemical in no way guarantees that the 1,4‐epoxybutane; Cyclotetramethylene oxide; Butane product from any particular lot will conform exactly to the given .alpha.,.delta.‐oxide values. Health and safety information Under current U.S. OSHA's Hazardous Communication program THF is classified as a flammable liquid, can cause eye and respiratory irritation. Keep the material away from heat sources, hot surfaces, open flames, and sparks. Use only in a well‐ventilated area. Observe good industrial hygiene practices and use appropriate Personal Protective Equipment. For full safety information please refer to the Safety Data Sheet. Storage and Handling specific product Technical Data Sheet (TDS) is accurate, but makes no representations as to the sufficiency or THF should be stored only in tightly closed, properly completeness of the product or information in this TDS vented containers away from heat, sparks, open flame and makes no commitment to correct or bring up‐to‐date or strong oxidizing agents. -
Hazardous Material Inventory Statement
City of Brooklyn Park FIRE DEPARTMENT 5200 - 85th Avenue North Brooklyn Park MN 55443 Phone: (763)493-8020 Fax: (763) 493-8391 Hazardous Materials Inventory Statement Users Guide A separate inventory statement shall be provided for each building. An amended inventory statement shall be provided within 30 days of the storage of any hazardous materials or plastics that changes or adds a hazard class or which is sufficient in quantity to cause an increase in the quantity which exceeds 5 percent for any hazard class. The hazardous materials inventory statement shall list by hazard class categories. Each grouping shall provide the following information for each hazardous material listed for that group including a total quantity for each group of hazard class. 1. Hazard class. (See attached Hazardous Materials Categories Listing) 2. Common or trade name. 3. Chemical Abstract Service Number (CAS number) found in 29 Code of Federal Regulations (C.F.R.). 4. Whether the material is pure or a mixture, and whether the material is a solid, liquid or gas 5. Maximum aggregate quantity stored at any one time. 6. Maximum aggregate quantity In-Use (Open to atmosphere) at any one time. 7. Maximum aggregate quantity In-Use (Closed to atmosphere) at any one time. 8. Storage conditions related to the storage type, high-pile, encapsulated, non-encapsulated. Attached is a listing of categories that all materials need to be organized to. Definitions of these categories are also attached for your use. At the end of this packet are blank forms for completing this project. For questions regarding Hazardous Materials Inventory Statement contact the Fire Department at 763-493-8020. -
Contribution of Cyclopentyl Methyl Ether (CPME) to Green Chemistry
sustainability / green chemistry Industry perspective Shunji Sakamoto Contribution of Cyclopentyl Methyl Ether (CPME) to Green Chemistry Shunji sakamoto Specialty Chemicals Division, ZEON CORPORATION, 1-6-2 Marunouchi, Chiyoda-ku, Tokyo, 1008246, Japan easy peroxide formation and water miscibility, the demand KEyWORDS for CPME has steadily been growing in the pharmaceutical Cyclopentyl methyl ether, CPME, Green Chemistry, industry as well as in the electronic and fragrance solvent, process, ICH. industries. Also, CPME has been registered or listed in the corresponding legislations for new chemical substances of United States of America, Canada, European Union, ABSTRACT Japan, South Korea, China and Chinese Taipei, and is commercially available in these countries and regions as Cyclopentyl methyl ether (CPME) is an alternative well as others including India. solvent and has preferable properties including higher In this article, I answer the question why CPME is “Green” hydrophobicity, lower formation of peroxides and better even though it is derived from petroleum. stability under acidic and basic conditions compared to other traditional ether solvents such as tetrahydrofuran. Due to the above unique properties, CPME has particular UNIQUE FEATURES OF CPME 24 advantages and renders some conventional reaction sequences in one pot or easier process as a result of CPME is an asymmetric aliphatic ether having a cyclopentyl solvent unification and facile isolation of the products, group. It has seven unique features attributed to its structure which contribute to Green Chemistry as well as to (Table 1). process innovation. CPME meets eight definitions out of the 12 Principles of Green Chemistry (1) because of Extremely lower miscibility with water the above characteristics as well as its manufacturing The solubility of CPME in water is only 1.1% and that of water process and its applications. -
Q3C (R8): Impurities: Guideline for Residual Solvents Step 2B
04 May 2020 EMA/CHMP/ICH/213867/2020 Committee for Medicinal Products for Human Use Q3C (R8): Impurities: guideline for residual solvents Step 2b Transmission to CHMP 30 April 2020 Adoption by CHMP 30 April 2020 Release for public consultation 4 May 2020 Deadline for comments 30 July 2020 Comments should be provided using this template. The completed comments form should be sent to [email protected] Official address Domenico Scarlattilaan 6 ● 1083 HS Amsterdam ● The Netherlands Address for visits and deliveries Refer to www.ema.europa.eu/how-to-find-us Send us a question Go to www.ema.europa.eu/contact Telephone +31 (0)88 781 6000An agency of the European Union © European Medicines Agency, 2020. Reproduction is authorised provided the source is acknowledged. PDE for 2-Methyltetrahydrofuran, Cyclopentyl Methyl Ether, and Tertiary-Butyl Alcohol INTERNATIONAL COUNCIL FOR HARMONISATION OF TECHNICAL REQUIREMENTS FOR PHARMACEUTICALS FOR HUMAN USE ICH HARMONISED GUIDELINE IMPURITIES: GUIDELINE FOR RESIDUAL SOLVENTS Q3C(R8) PDE FOR 2-METHYLTETRAHYDROFURAN, CYCLOPENTYL METHYL ETHER, AND TERTIARY-BUTYL ALCOHOL Draft version Endorsed on 25 March 2020 Currently under public consultation Note : This document contains only the PDE levels for three solvents: 2- methyltetrahydrofuran, cyclopentylmethylether and tert-butanol that were agreed to be included in the ICH Q3C(R8) revision. Further to reaching Step 4, these PDEs would be integrated into a complete Q3C(R8) Guideline document. At Step 2 of the ICH Process, a consensus draft text or guideline, agreed by the appropriate ICH Expert Working Group, is transmitted by the ICH Assembly to the regulatory authorities PDE for 2-Methyltetrahydrofuran, Cyclopentyl Methyl Ether, and Tertiary-Butyl Alcohol of the ICH regions for internal and external consultation, according to national or regional procedures. -
1- MANUFACTURING of MATERIAL BASED HYDROGEN FUEL for LIGHTWEIGHT VEHICLES by ALI KHAGHANI a Thesis
MANUFACTURING OF MATERIAL BASED HYDROGEN FUEL FOR LIGHTWEIGHT VEHICLES Item Type text; Electronic Thesis Authors KHAGHANI, ALI Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 23/09/2021 12:36:34 Link to Item http://hdl.handle.net/10150/613155 MANUFACTURING OF MATERIAL BASED HYDROGEN FUEL FOR LIGHTWEIGHT VEHICLES By ALI KHAGHANI ____________________ A Thesis Submitted to The Honors College In Partial Fulfillment of the Bachelors degree With Honors in Chemical Engineering THE UNIVERSITY OF ARIZONA M A Y 2016 Approved by: ____________________________ Dr. Kimberly Ogden Chemical and Environmental Engineering -1- Abstract Vehicles powered by hydrogen fuel cells store hydrogen as a cooled liquid at 20 degrees kelvin or a compressed gas at 10,000 pounds per square inch. An alternative that eliminates the need for these extremes of temperature and pressure is to heat a compound containing covalently bonded hydrogen, causing it to release the hydrogen to the fuel cell. Ammonia borane, which is stable at ambient conditions, requires minimal energy for dehydrogenation, and is rich in hydrogen, is a possible storage medium for hydrogen. If a viable storage system could be engineered, demand for ammonia borane as a source of hydrogen would increase. The goal of this project is to develop a processing plant and to optimize design specifications for scaling up processing of ammonia borane through the metathesis reaction pathway.