DOCSLIB.ORG

PURIFICATION of Ticl4 TROUGH the PRODUCTION of NEW CO

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
PURIFICATION of Ticl4 TROUGH the PRODUCTION of NEW CO (19) TZZ _T (11) EP 2 678 276 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C01G 23/02 (2006.01) 26.11.2014 Bulletin 2014/48 (86) International application number: (21) Application number: 12716742.7 PCT/US2012/026196 (22) Date of filing: 22.02.2012 (87) International publication number: WO 2012/116120 (30.08.2012 Gazette 2012/35) (54) PURIFICATION OF TiCL4 TROUGH THE PRODUCTION OF NEW CO-PRODUCTS REINIGUNG VON TICL4 DURCH HERSTELLUNG NEUER NEBENPRODUKTE PURIFICATION DE TiCL4 PAR LA PRODUCTION DE NOUVEAUX CO-PRODUITS (84) Designated Contracting States: (72) Inventor: HELBERG, Lisa Edith AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Middletown, Delaware 19709 (US) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR (74) Representative: Towler, Philip Dean Dehns (30) Priority: 23.02.2011 US 201161445792 P St Bride’s House 23.02.2011 US 201161445801 P 10 Salisbury Square London (43) Date of publication of application: EC4Y 8JD (GB) 01.01.2014 Bulletin 2014/01 (56) References cited: (73) Proprietor: E.I. Du Pont De Nemours and Company US-A- 2 416 191 US-A- 4 783 324 Wilmington, Delaware 19898 (US) US-A1- 2002 179 427 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 678 276 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 678 276 B1 2 Description requires a high purity level, such as gallium arsenide pro- duction. As a result, using distillation to produce a highly FIELD OF THE INVENTION concentrated AsCl3 product would reduce the yield loss of TiCl4 but would not yield a useful product. The 5 [0001] This invention relates to a process for purifying AsCl3/TiCl4 stream would need disposal in a proper man- TiCl4 produced via a chloride process. ner. Since the boiling points of AsCl3 and TiCl4 are so close, only 6 °C apart, a large amount of energy would BACKGROUND OF THE INVENTION be required to produce this waste stream. [0005] Another potential method for removing AsCl3 10 [0002] Pigmentary TiO2 is commercially produced from purified TiCl 4 isto use carbonadsorption. Thismeth- through the sulfate or the chloride process. The chloride od does not work on crude TiCl 4. Carbon adsorption can process is also used to produce TiCl4 for titanium metal remove the AsCl 3 to very low levels that would be suitable production. In the chloride process, titanoferrous ore is for allapplications including cosmetics. However,the car- carbochlorinated to produce TiCl4 and a range of other bon adsorption is not selective for only AsCl 3. Many other 15 metal chlorides from the ore impurities. The crude TiCl 4 species are present in the pure TiCl4 such as the sulfur produced in the carbochlorination is processed with a gases produced from the carbochlorination, like SO2, series of physical separation steps to produce a usable COS, and CS2. These species will adsorb competitively TiCl4 product. One contaminating element found in ti- on to the carbon, limiting the capacity. As a result, this tanoferrous ore is arsenic. The chlorination of the arsenic method is not commercially viable for large scale produc- 20 species present in the ore produces AsCl 3. AsCl3 has a tion such as pigmentary TiO 2 for large markets like plas- boiling point very similar to that of TiCl 4, making removal tics and coatings. more problematic. [0006] Thus, the problem to be solved is removal of [0003] Different ores can contain significantly different AsCl3 from TiCl 4 produced via the chloride process in an levels of arsenic ranging from non-detectible to greater economical, efficient, and safe manner. than 100 ppm. Standard purification methods for the chlo- 25 ride process involve first removing solids chlorides and SUMMARY OF THE INVENTION then removing vanadium in a separate step. AsCl3 is a liquid, so it is not removed by the solids removal steps. [0007] Applicants have solved the aforementioned Known vanadium removal steps such as organic treating problems by using tin metal to remove arsenic from crude 30 agents, like plant and animal oils, soaps, fats and waxes, TiCl4 produced via the chloride process. A separate proc- do not react with AsCl 3. Another known commercial proc- ess can also be applied to partially purified TiCl4 where ess is using elemental copper to remove vanadium from some of the impurities such as vanadium are first re- crude TiCl4. Copper also shows no reactivity to AsCl3. moved using known techniques which do not remove the As a result, all of the AsCl3 that forms from chlorination arsenic. Tin metal is then reacted with the arsenic in a 35 is present in the pure TiCl 4 sent to oxidation and can end separate treatment step. up in the TiO2 product. High levels of arsenic are unde- [0008] One aspect is for a process for the purification sirable in TiO2 pigment. Pigmentary TiO2 used in FDA of crude TiCl4 comprising contacting arsenic-containing products such as cosmetics require < 1 ppm arsenic by crude TiCl4 with tin to produce purified TiCl 4, SnCl4, and the FDA method. Low levels are also desired in other solid arsenic and separating the solid arsenic from the 40 pigmentary application such as some plastics and coat- purified TiCl 4 and SnCl 4. In some aspects, the contacting ings products. Arsenic levels in TiCl4 used to produce and separating steps are performed by a two stage proc- titanium metal must also be kept low to avoid deforma- ess comprising reducing the arsenic content in the ar- tions in the final metal pieces. Typical levels for TiCl 4 for senic-containing crude TiCl4 by contacting the arsenic- titanium metal are <10 ppm arsenic. containing crude TiCl4 with a less than excess amount 45 [0004] Since AsCl3 passes through all the known va- of tin to produce partially purified TiCl 4, SnCl4, and solid nadium removal processes, such as organic treatment arsenic; separating the solid arsenic from the partially or copper metal, all the AsCl3 will end up in the purified purified TiCl 4 and SnCl 4;further reducing the arsenic con- TiCl4. If high concentrations of arsenic were present in tent in the partially purified TiCl4 by contacting the par- the ore, elevated levels of AsCl 3 will also be present. Two tially purified TiCl4 with an excess of tin to produce puri- 50 technologies are known to remove AsCl 3 from pure TiCl 4. fied TiCl4, SnCl4, solid arsenic, and excess tin; and sep- If a partial reduction of the concentration from, for exam- arating the solid arsenic and excess tin from the purified ple, 100 ppm to 10 ppm is all that is required, distillation TiCl4 and SnCl4. can be used with effective production of the desired prod- [0009] Another aspect is for a process for the purifica- uct, but a significant yield loss of TiCl4 is also required. tion of crude TiCl4 comprising contacting arsenic- and 55 Lower concentrations can also be achieved at greater vanadium-containing crude TiCl4 with tin to produce pu- penalties for energy consumption and equipment sizing. rified TiCl4, SnCl4, solid arsenic, and solid vanadium and AsCl3 has little commercial value. Arsenic is currently separating the solid arsenic and solid vanadium from the only used in a few specific applications, and each of these purified TiCl 4 and SnCl 4. In some aspects, the contacting 2 3 EP 2 678 276 B1 4 and separating steps are performed by a two stage proc- or preferred value, regardless of whether ranges are sep- ess comprising reducing the arsenic and vanadium con- arately disclosed. Where a range of numerical values is tent in the arsenic- and vanadium-containing crude TiCl 4 recited herein, unless otherwise stated, the range is in- by contacting the arsenic- and vanadium-containing tended to include the endpoints thereof, and all integers 5 crude TiCl4 with a less than excess amount of tin to pro- and fractions within the range. It is not intended that the duce partially purified TiCl 4, SnCl 4, solid arsenic, and sol- scope of the invention be limited to the specific values id vanadium; separating the solid arsenic and the solid recited when defining a range. vanadium from the partially purified TiCl 4 and SnCl 4; fur- [0014] In the production of TiCl 4 for a commercial proc- ther reducing the arsenic and vanadium content in the ess, several stages of purification may be required de- 10 partially purified TiCl4 by contacting the partially purified pending on the specifics of the process, the starting ma- TiCl4 with an excess of tin to produce purified TiCl4, terials, and the final product TiCl4 requirements. First, SnCl4, solid arsenic, solid vanadium, and excess tin; and the TiO2-bearing ore is carbochlorinated by mixing with separating the solid arsenic and the solid vanadium and a carbon source and chlorine at high temperature. Car- excess tin from the purified TiCl 4 and SnCl4. bochlorination produces a vapor stream containing most [0010] In another embodiment of this invention, crude 15 of the impurities present in the ores now converted into TiCl4 from the chloride process, containing vanadium, metal chlorides along with the TiCl4 vapor.
Load more

Recommended publications
  • Transport of Dangerous Goods
    ST/SG/AC.10/1/Rev.16 (Vol.I) Recommendations on the TRANSPORT OF DANGEROUS GOODS Model Regulations Volume I Sixteenth revised edition UNITED NATIONS New York and Geneva, 2009 NOTE The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. ST/SG/AC.10/1/Rev.16 (Vol.I) Copyright © United Nations, 2009 All rights reserved. No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical, photocopying or otherwise, without prior permission in writing from the United Nations. UNITED NATIONS Sales No. E.09.VIII.2 ISBN 978-92-1-139136-7 (complete set of two volumes) ISSN 1014-5753 Volumes I and II not to be sold separately FOREWORD The Recommendations on the Transport of Dangerous Goods are addressed to governments and to the international organizations concerned with safety in the transport of dangerous goods. The first version, prepared by the United Nations Economic and Social Council's Committee of Experts on the Transport of Dangerous Goods, was published in 1956 (ST/ECA/43-E/CN.2/170). In response to developments in technology and the changing needs of users, they have been regularly amended and updated at succeeding sessions of the Committee of Experts pursuant to Resolution 645 G (XXIII) of 26 April 1957 of the Economic and Social Council and subsequent resolutions.
    [Show full text]
  • PROVISIONAL PEER-REVIEWED TOXICITY VALUES for VANADIUM and ITS SOLUBLE INORGANIC COMPOUNDS OTHER THAN VANADIUM PENTOXIDE (CASRN 7440-62-2 and Others)
    EPA/690/R-09/070F l Final 9-30-2009 Provisional Peer-Reviewed Toxicity Values for Vanadium and Its Soluble Inorganic Compounds Other Than Vanadium Pentoxide (CASRN 7440-62-2 and Others) Derivation of Subchronic and Chronic Oral RfDs Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 Commonly Used Abbreviations BMD Benchmark Dose IRIS Integrated Risk Information System IUR inhalation unit risk LOAEL lowest-observed-adverse-effect level LOAELADJ LOAEL adjusted to continuous exposure duration LOAELHEC LOAEL adjusted for dosimetric differences across species to a human NOAEL no-observed-adverse-effect level NOAELADJ NOAEL adjusted to continuous exposure duration NOAELHEC NOAEL adjusted for dosimetric differences across species to a human NOEL no-observed-effect level OSF oral slope factor p-IUR provisional inhalation unit risk p-OSF provisional oral slope factor p-RfC provisional inhalation reference concentration p-RfD provisional oral reference dose RfC inhalation reference concentration RfD oral reference dose UF uncertainty factor UFA animal to human uncertainty factor UFC composite uncertainty factor UFD incomplete to complete database uncertainty factor UFH interhuman uncertainty factor UFL LOAEL to NOAEL uncertainty factor UFS subchronic to chronic uncertainty factor i FINAL 9-30-2009 PROVISIONAL PEER-REVIEWED TOXICITY VALUES FOR VANADIUM AND ITS SOLUBLE INORGANIC COMPOUNDS OTHER THAN VANADIUM PENTOXIDE (CASRN 7440-62-2 and others) Background On December 5, 2003, the U.S. Environmental Protection Agency's (U.S. EPA) Office of Superfund Remediation and Technology Innovation (OSRTI) revised its hierarchy of human health toxicity values for Superfund risk assessments, establishing the following three tiers as the new hierarchy: 1) U.S.
    [Show full text]
  • Environmental Protection Agency § 712.30
    Environmental Protection Agency § 712.30 (2) A confidentiality statement § 712.30 Chemical lists and reporting signed and dated by an authorized per- periods. son located at the plant site or cor- (a)(1) Persons subject to this subpart porate headquarters of the respondent B must submit a Preliminary Assess- company. ment Information Manufacturer’s Re- (3) The specific chemical name and port for each chemical substance or Chemical Abstracts Service (CAS) Reg- mixture that is listed or designated in istry Number listed in 40 CFR 712.30. this section. (4) The name, company, address, city, State, ZIP code, and telephone number (2) Unless a respondent has already of a person who is submitting the form, prepared a Manufacturer’s Report in which may be a person located at a conformity with conditions set forth in plant site or corporate headquarters paragraph (a)(3) of this section, the in- that will serve as the respondent, and formation in each Manufacturer’s Re- will be able to answer questions about port must cover the respondent’s latest the information submitted by the com- complete corporate fiscal year as of the pany to EPA. A respondent to this sub- effective date. The effective date will part must include the appropriate Dun be 30 days after the FEDERAL REGISTER and Bradstreet Number for each plant publishes a rule amendment making site reported. the substance or mixture subject to (5) The plant site activities, such as this subpart B. the manufacturing of a chemical sub- (3) Persons subject to this subpart B stance, including the total quantity of need not comply with the requirements the chemical substance (in kilograms) of paragraph (a)(2) of this section if imported in bulk during the reporting they meet either one of the following period.
    [Show full text]
  • Crude Ticl4 Purification: a Review of the Current State of the Art and Future Opportunities
    Crude TiCl4 purification: a review of the current state of the art and future opportunities L. Hockaday and A. Kale Mintek, Randburg, South Africa Raw titanium tetrachloride (TiCl4) is produced by chlorination of titania feedstock. Prior to its utilization in the manufacture of titanium dioxide pigment or titanium metal, the TiCl4 is purified by adding reagents that react with the impurities in the crude TiCl4, followed by distillation of the mixture. The current state of the art in purification of crude TiCl4 was surveyed. Tests were conducted at the laboratory scale to assess the efficiency of various additives used in the purification process to minimize the vanadium content in the distillate. The effects of various reagents, namely oleic acid, sodium oleate, potassium oleate, and copper on the purification of crude TiCl4 were compared. The purified TiCl4 was water-clear in aspect and analysed < 2 ppm vanadium for all reagents tested. Possible reactions between the impurities in the crude TiCl4 and the reagents are investigated thermodynamically with the FactSage program. INTRODUCTION Titanium tetrachloride (TiCl4) is obtained by the chlorination of a titanium-bearing mineral such as ilmenite and rutile, as well as from titanium slag. The chlorination process usually takes place in a fluidized bed in the presence of chlorine gas and a reducing agent such as petroleum coke, resulting in crude titanium tetrachloride. TiCl4 is an intermediate product in the production of titanium dioxide (TiO2) pigment and titanium metal. The pure form of titanium dioxide is used in the pigment industry for paints, food colouring etc., and titanium metal is widely used in the aerospace, medicine, sport, and semiconductor production industries.
    [Show full text]
  • Toxicological Profile for Vanadium
    VANADIUM 107 4. CHEMICAL AND PHYSICAL INFORMATION 4.1 CHEMICAL IDENTITY Vanadium is a naturally occurring element that appears in group 5(B5) of the periodic table (Lide 2008). Vanadium is widely distributed in the earth’s crust at an average concentration of 100 ppm nd (approximately 100 mg/kg), similar to that of zinc and nickel (Byerrum 1991). Vanadium is the 22 most abundant element in the earth’s crust (Baroch 2006). Vanadium is found in about 65 different minerals; carnotite, roscoelite, vanadinite, and patronite are important sources of this metal along with bravoite and davidite (Baroch 2006, Lide 2008). It is also found in phosphate rock and certain ores and is present in some crude oils as organic complexes (Lide 2008). Table 4-1 lists common synonyms and other pertinent identification information for vanadium and representative vanadium compounds. 4.2 PHYSICAL AND CHEMICAL PROPERTIES Vanadium is a gray metal with a body-centered cubic crystal system. It is a member of the first transition series. Because of its high melting point, it is referred to as a refractory metal (Baroch 2006). When highly pure, it is a bright white metal that is soft and ductile. It has good structural strength and a low- fission neutron cross section. Vanadium has good corrosion resistance to alkalis, sulfuric and hydrochloric acid, and salt water; however, the metal oxidizes readily above 660 °C (Lide 2008). The chemistry of vanadium compounds is related to the oxidation state of the vanadium (Woolery 2005). Vanadium has oxidation states of +2, +3, +4, and +5. When heated in air at different temperatures, it oxidizes to a brownish black trioxide, a blue black tetraoxide, or a reddish orange pentoxide.
    [Show full text]
  • 2020 Emergency Response Guidebook
    2020 A guidebook intended for use by first responders A guidebook intended for use by first responders during the initial phase of a transportation incident during the initial phase of a transportation incident involving hazardous materials/dangerous goods involving hazardous materials/dangerous goods EMERGENCY RESPONSE GUIDEBOOK THIS DOCUMENT SHOULD NOT BE USED TO DETERMINE COMPLIANCE WITH THE HAZARDOUS MATERIALS/ DANGEROUS GOODS REGULATIONS OR 2020 TO CREATE WORKER SAFETY DOCUMENTS EMERGENCY RESPONSE FOR SPECIFIC CHEMICALS GUIDEBOOK NOT FOR SALE This document is intended for distribution free of charge to Public Safety Organizations by the US Department of Transportation and Transport Canada. This copy may not be resold by commercial distributors. https://www.phmsa.dot.gov/hazmat https://www.tc.gc.ca/TDG http://www.sct.gob.mx SHIPPING PAPERS (DOCUMENTS) 24-HOUR EMERGENCY RESPONSE TELEPHONE NUMBERS For the purpose of this guidebook, shipping documents and shipping papers are synonymous. CANADA Shipping papers provide vital information regarding the hazardous materials/dangerous goods to 1. CANUTEC initiate protective actions. A consolidated version of the information found on shipping papers may 1-888-CANUTEC (226-8832) or 613-996-6666 * be found as follows: *666 (STAR 666) cellular (in Canada only) • Road – kept in the cab of a motor vehicle • Rail – kept in possession of a crew member UNITED STATES • Aviation – kept in possession of the pilot or aircraft employees • Marine – kept in a holder on the bridge of a vessel 1. CHEMTREC 1-800-424-9300 Information provided: (in the U.S., Canada and the U.S. Virgin Islands) • 4-digit identification number, UN or NA (go to yellow pages) For calls originating elsewhere: 703-527-3887 * • Proper shipping name (go to blue pages) • Hazard class or division number of material 2.
    [Show full text]
  • Dielectric Constant Chart
    Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG. F CONSTANT ABS RESIN, LUMP 2.4-4.1 ABS RESIN, PELLET 1.5-2.5 ACENAPHTHENE 70 3 ACETAL 70 3.6 ACETAL BROMIDE 16.5 ACETAL DOXIME 68 3.4 ACETALDEHYDE 41 21.8 ACETAMIDE 68 4 ACETAMIDE 180 59 ACETAMIDE 41 ACETANILIDE 71 2.9 ACETIC ACID 68 6.2 ACETIC ACID (36 DEGREES F) 36 4.1 ACETIC ANHYDRIDE 66 21 ACETONE 77 20.7 ACETONE 127 17.7 ACETONE 32 1.0159 ACETONITRILE 70 37.5 ACETOPHENONE 75 17.3 ACETOXIME 24 3 ACETYL ACETONE 68 23.1 ACETYL BROMIDE 68 16.5 ACETYL CHLORIDE 68 15.8 ACETYLE ACETONE 68 25 ACETYLENE 32 1.0217 ACETYLMETHYL HEXYL KETONE 66 27.9 ACRYLIC RESIN 2.7 - 4.5 ACTEAL 21 3.6 ACTETAMIDE 4 AIR 1 AIR (DRY) 68 1.000536 ALCOHOL, INDUSTRIAL 16-31 ALKYD RESIN 3.5-5 ALLYL ALCOHOL 58 22 ALLYL BROMIDE 66 7 ALLYL CHLORIDE 68 8.2 ALLYL IODIDE 66 6.1 ALLYL ISOTHIOCYANATE 64 17.2 ALLYL RESIN (CAST) 3.6 - 4.5 ALUMINA 9.3-11.5 ALUMINA 4.5 ALUMINA CHINA 3.1-3.9 ALUMINUM BROMIDE 212 3.4 ALUMINUM FLUORIDE 2.2 ALUMINUM HYDROXIDE 2.2 ALUMINUM OLEATE 68 2.4 1 Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG. F CONSTANT ALUMINUM PHOSPHATE 6 ALUMINUM POWDER 1.6-1.8 AMBER 2.8-2.9 AMINOALKYD RESIN 3.9-4.2 AMMONIA -74 25 AMMONIA -30 22 AMMONIA 40 18.9 AMMONIA 69 16.5 AMMONIA (GAS?) 32 1.0072 AMMONIUM BROMIDE 7.2 AMMONIUM CHLORIDE 7 AMYL ACETATE 68 5 AMYL ALCOHOL -180 35.5 AMYL ALCOHOL 68 15.8 AMYL ALCOHOL 140 11.2 AMYL BENZOATE 68 5.1 AMYL BROMIDE 50 6.3 AMYL CHLORIDE 52 6.6 AMYL ETHER 60 3.1 AMYL FORMATE 66 5.7 AMYL IODIDE 62 6.9 AMYL NITRATE 62 9.1 AMYL THIOCYANATE 68 17.4 AMYLAMINE 72 4.6 AMYLENE 70 2 AMYLENE BROMIDE 58 5.6 AMYLENETETRARARBOXYLATE 66 4.4 AMYLMERCAPTAN 68 4.7 ANILINE 32 7.8 ANILINE 68 7.3 ANILINE 212 5.5 ANILINE FORMALDEHYDE RESIN 3.5 - 3.6 ANILINE RESIN 3.4-3.8 ANISALDEHYDE 68 15.8 ANISALDOXINE 145 9.2 ANISOLE 68 4.3 ANITMONY TRICHLORIDE 5.3 ANTIMONY PENTACHLORIDE 68 3.2 ANTIMONY TRIBROMIDE 212 20.9 ANTIMONY TRICHLORIDE 166 33 ANTIMONY TRICHLORIDE 5.3 ANTIMONY TRICODIDE 347 13.9 APATITE 7.4 2 Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG.
    [Show full text]
  • Probing Nuclear Spin Effects on Electronic Spin Coherence Via EPR Measurements of Vanadium (IV) Complexes
    Supporting Information for: Probing Nuclear Spin Effects on Electronic Spin Coherence via EPR Measurements of Vanadium (IV) Complexes Michael J. Graham,† Matthew D. Krzyaniak,†,§ Michael R. Wasielewski,†,§ and Danna E. Freedman*,† †Department of Chemistry and §Argonne-Northwestern Solar Energy Research Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208- 3113, United States Inorg. Chem. S1 Table of Contents Experimental details S3 Table S1 Crystallographic information for 1 S12 Table S2 Crystallographic information for 2 S13 Table S3 Crystallographic information for 3 S14 Table S4 Cw-EPR fit parameters S15 Table S5 Proton grouping scheme used to calculate dipolar coupling in 1 S16 Table S6 Proton grouping scheme used to calculate dipolar coupling in 2 S17 Table S7 Proton grouping scheme used to calculate dipolar coupling in 3 S18 Table S8 ENDOR fit parameters S19 Table S9 T1 fit parameters S20 Table S10 Fit parameters for T1 temperature dependence S21 Table S11 T2 fit parameters in DMF-d7/toluene-d8 S22 Table S12 T2 fit parameters in MeCN-d3/toluene-d8 S23 Table S13 Variable-power nutation frequencies S24 Figure S1 Cw-EPR and echo-detected EPR spectra and fits S25 Figure S2 ENDOR spectra and fits S26 Figure S3 Saturation/inversion recovery data and fits S27 Figure S4 Selected Hahn echo decay data and fits S28 Figure S5 Nutation data S29 Figure S6 Fourier transforms of nutation data S30 Figure S7 Nutation frequency vs. pulsed field strength S31 References S32 S2 Experimental Details General Considerations. 2,6,8,10-Tetrathiobicyclo[5,3,0]dec-1(7)en-9-one (TTDEO) and the 1,2 ligands K2(C7H6S7) and K2(C9H6S8) were synthesized as previously reported.
    [Show full text]
  • United States Patent (19) 11) 4,182,747 Gravey Et Al
    United States Patent (19) 11) 4,182,747 Gravey et al. 45 - Jan. 8, 1980 54 PROCESS FOR PREPARATION OF 3,565,820 2/1971 Coons et al. ......................... 252/419 ANHYDROUS METALLC CHLORIDES 3,985,639 10/1976 Suggitt et al. ....................... 252/415 FROM WASTE CATALYSTS FOREIGN PATENT DOCUMENTS 75) Inventors: Guy Gravey; Jean Le Goff; Christian Gonin, all of Moutiers, France 65929 11/1972 Poland ....................................... 423/60 Primary Examiner-Earl C. Thomas 73) Assignee: Metaux Speciaux S.A., Paris, France Attorney, Agent, or Firm-Dennison, Dennison, (21) Appl. No.: 862,594 Meserole & Pollack (22 Filed: Dec. 20, 1977 57 ABSTRACT 30 Foreign Application Priority Data A process is disclosed for recovering metallic constitu Dec. 30, 1976 FR France ................................ 7639842 ents of spent or waste catalysts containing metallic com pounds fixed on an aluminous support. The process is 51) Int. C.’................................................ C01B 9/02 particularly applicable for the recovery of metals such 52 U.S. Cl. ...................................... 423/491; 423/60; as Al, Mo, V, Ni and Co, contained in spent catalyst. 423/62; 423/116; 423/137; 423/150; 423/492; The process comprises transforming the metals to be 423/493; 423/496; 252/411 R recovered into volatile chlorides by carbochlorination 58) Field of Search ............... 252/415, 416, 419, 411, and then separating the chlorides obtained by dry means 252/414; 423/60, 62, 65, 116, 136, 137, 150, and fixing them successively in a selective manner. The 492, 493, 495, 496 separation of AlCl3 is accomplished by passage through 56) References Cited granules of anhydrous NaCl, and the separation of U.S.
    [Show full text]
  • Toxicological Profile for Vanadium
    TOXICOLOGICAL PROFILE FOR VANADIUM U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry September 2012 VANADIUM ii DISCLAIMER Use of trade names is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry, the Public Health Service, or the U.S. Department of Health and Human Services. VANADIUM iii UPDATE STATEMENT A Toxicological Profile for Vanadium, Draft for Public Comment was released in September 2009. This edition supersedes any previously released draft or final profile. Toxicological profiles are revised and republished as necessary. For information regarding the update status of previously released profiles, contact ATSDR at: Agency for Toxic Substances and Disease Registry Division of Toxicology and Human Health Sciences (proposed) Environmental Toxicology Branch (proposed) 1600 Clifton Road NE Mailstop F-62 Atlanta, Georgia 30333 VANADIUM iv This page is intentionally blank. VANADIUM v FOREWORD This toxicological profile is prepared in accordance with guidelines* developed by the Agency for Toxic Substances and Disease Registry (ATSDR) and the Environmental Protection Agency (EPA). The original guidelines were published in the Federal Register on April 17, 1987. Each profile will be revised and republished as necessary. The ATSDR toxicological profile succinctly characterizes the toxicologic and adverse health effects information for the toxic substances each profile describes. Each peer-reviewed profile identifies and reviews the key literature that describes a substance's toxicologic properties. Other pertinent literature is also presented but is described in less detail than the key studies. The profile is not intended to be an exhaustive document; however, more comprehensive sources of specialty information are referenced.
    [Show full text]
  • SAFETY DATA SHEET Revision Date 08/03/2021 Print Date 09/25/2021
    Version 6.3 SAFETY DATA SHEET Revision Date 08/03/2021 Print Date 09/25/2021 SECTION 1: Identification of the substance/mixture and of the company/undertaking 1.1 Product identifiers Product name : Vanadium(IV) chloride Product Number : 366617 Brand : Aldrich CAS-No. : 7632-51-1 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses : Laboratory chemicals, Synthesis of substances 1.3 Details of the supplier of the safety data sheet Company : Sigma-Aldrich Inc. 3050 SPRUCE ST ST. LOUIS MO 63103 UNITED STATES Telephone : +1 314 771-5765 Fax : +1 800 325-5052 1.4 Emergency telephone Emergency Phone # : 800-424-9300 CHEMTREC (USA) +1-703- 527-3887 CHEMTREC (International) 24 Hours/day; 7 Days/week SECTION 2: Hazards identification 2.1 Classification of the substance or mixture GHS Classification in accordance with 29 CFR 1910 (OSHA HCS) Acute toxicity, Oral (Category 3), H301 Acute toxicity, Inhalation (Category 3), H331 Acute toxicity, Dermal (Category 3), H311 Skin corrosion (Category 1B), H314 Serious eye damage (Category 1), H318 For the full text of the H-Statements mentioned in this Section, see Section 16. 2.2 GHS Label elements, including precautionary statements Pictogram Signal word Danger Aldrich - 366617 Page 1 of 10 The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the US and Canada Hazard statement(s) H301 + H311 + H331 Toxic if swallowed, in contact with skin or if inhaled. H314 Causes severe skin burns and eye damage. Precautionary statement(s) P261 Avoid breathing dust/ fume/ gas/ mist/ vapors/ spray.
    [Show full text]
  • IRIS Assessment Plan for Inhalation Exposure to Vanadium and Compounds (Scoping and Problem Formulation Materials)
    EPA/635/R-21/077 IRIS Assessment Plan www.epa.gov/iris IRIS Assessment Plan for Inhalation Exposure to Vanadium and Compounds (Scoping and Problem Formulation Materials) May 2021 Integrated Risk Information System Center for Public Health and Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency IRIS Assessment Plan for Vanadium (Inhalation) DISCLAIMER This document is a public comment draft for review purposes only. This information is distributed solely for the purpose of public comment. It has not been formally disseminated by EPA. It does not represent and should not be construed to represent any Agency determination or policy. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. This document is a draft for review purposes only and does not constitute Agency policy. ii DRAFT DO NOT CITE OR QUOTE ― IRIS Assessment Plan for Vanadium (Inhalation) CONTENTS AUTHORS | CONTRIBUTORS | REVIEWERS .................................................................................................. vi 1. INTRODUCTION ...................................................................................................................................... 1 2. SCOPING AND INITIAL PROBLEM FORMULATION .................................................................................. 3 2.1. BACKGROUND ............................................................................................................................... 3 2.2. SCOPING SUMMARY ....................................................................................................................
    [Show full text]