WO1997006910A1 - Dispersions de metaux alcalins - Google Patents

Dispersions de metaux alcalins Download PDF

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Publication number
WO1997006910A1
WO1997006910A1 PCT/US1996/013137 US9613137W WO9706910A1 WO 1997006910 A1 WO1997006910 A1 WO 1997006910A1 US 9613137 W US9613137 W US 9613137W WO 9706910 A1 WO9706910 A1 WO 9706910A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
particles
metal
oil
lithium
Prior art date
Application number
PCT/US1996/013137
Other languages
English (en)
Inventor
B. Troy Dover
Conrad W. Kamienski
Robert C. Morrison
R. Thomas Currin, Jr.
James A. Schwindeman
Original Assignee
Fmc Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to DE19681528T priority Critical patent/DE19681528B4/de
Priority to AU67238/96A priority patent/AU6723896A/en
Priority to GB9803042A priority patent/GB2319024B/en
Publication of WO1997006910A1 publication Critical patent/WO1997006910A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D13/00—Compounds of sodium or potassium not provided for elsewhere

Definitions

  • This invention concerns a process for preparing novel alkali metal dispersions and metal powders derived therefrom by melting an alkali metal in an inert liquid hydrocarbon oil medium, agitating the molten metal under dispersion conditions to produce a dispersion, contacting the molten dispersion with carbon dioxide.
  • the dispersion can be recovered by traditional means.
  • the present invention provides a process for producing atmospherically stable alkali metal particles comprising heating, in an inert atmosphere, an alkali metal selected from the group consisting of sodium and lithium in a hydrocarbon oil to a temperature above the melting point of the alkali metal, agitating the metal in hydrocarbon oil mixture, under dispersion conditions, which mixture optionally contains a dispersing agent, contacting the molten metal-hydrocarbon oil dispersion mixture, above or below its surface, for at least one minute while the mixture is being agitated under dispersion conditions, with at least 0.3 weight percent of anhydrous carbon dioxide, based on the weight of the alkali metal and cooling the alkali metal dispersion to below the melting point of the alkali metal to produce coated alkali metal particles dispersed in oil.
  • lithium and sodium metal dispersions in hydrocarbon oil are readily prepared by heating, in an inert atmosphere, to above the melting point of the metals, a temperature range of 100 to 240 °C, about 100 to 150 °C for sodium and 180 to 240 °C for lithium vigorously agitating the molten metal-hydrocarbon oil mixture under high tangential shear (dynamic conditions) for sufficient time to produce a dispersion or emulsion of the metal into uniform particles or globules in the hydrocarbon oil.
  • the dispersion can be prepared by vigorous stirring at dispersion speeds in the presence of a dispersing agent, then contacting the dispersed metal with anhydrous carbon dioxide gas while maintaining the high tangential shear stirring at dispersion speeds for a certain period of time, at least about a minute, to provide a predetermined amount of the gas for contact and reaction with the metal. Varying the amount of dispersing agent makes it possible to produce particles having different particle size ranges.
  • Typical alkali metal dispersing or "emulsifying" devices in use commercially, employ high tangential shear during agitation according to Fatt and Tashima (p 49).
  • the anhydrous carbon dioxide of this invention is added to the molten metal dispersion mixtures of this invention, while the mixtures are under high tangential shear agitation, until 0.3-5 weight percent carbon dioxide based on alkali metal has been introduced into the mixture.
  • carbon dioxide is preferably introduced below the surface of the mixture, the vigorous agitation conditions necessary to produce dispersions generally gives adequate contact with carbon dioxide introduced in the gas space above the dispersion mixture.
  • the amount of carbon dioxide introduced should be between 0.3 - 5 weight percent based on the metal.
  • anhydrous carbon dioxide can be employed but do not appear to provide additional advantages. Some minimum contact time between the anhydrous carbon dioxide and metal is necessary, one minute being adequate, and 1 to 5 minutes a practical reaction period. Although, according to US Serial number 08/210,840, one may prepare these dispersions using anhydrous carbon dioxide alone (no dispersing agent present), better control of the metal particle sizes and their size distribution is obtained if one first disperses the metal in the presence of a suitable dispersing agent, and then afterwards adds the anhydrous carbon dioxide under high tangential shear conditions.
  • An advantage of the process is that the anhydrous carbon dioxide unexpectedly reacts sufficiently with molten alkali metals, in particulate or very small molten globule form, suspended in a hydrocarbon oil to form a protective, dispersive coating around the metal particles.
  • This is an unexpected result since Markowitz, discussed below, reports that anhydrous CO 2 does not react with dry 100-125 sieve lithium metal particles (125-150 microns) up to 250 °C under static conditions and only slightly with wet CO 2 under these conditions.
  • Wet CO 2 is not desirable since it generates hydrogen which may react with lithium metal to produce lithium hydride or may be liberated from the vessel as a dangerous gas.
  • organoalkali compounds such as organolithium compounds
  • organolithium compounds may be alkyllithiums and aryllithiums, lithium dialkylamides, lithium cycloalkylamides, and lithium alkoxides .
  • Another unexpected advantage of the process is that the large (1-3%) amount of dispersing agent, e.g., oleic acid, ordinarily required to maintain the metal particles at a desired particle size of 10-50 microns, is not required when anhydrous carbon dioxide is added in the process afterwards. Generally, amounts of oleic acid required to achieve this particle size range when CO 2 is employed are less than one percent.
  • a lithium (or sodium) metal powder is produced on cooling the dispersions produced by this invention to ambient temperature and removing the hydrocarbon oil medium by washing the metal particles with a low boiling hydrocarbon of choice and evaporating said low boiling hydrocarbon under a stream of dry argon.
  • alkali metal powders of this invention are unexpectedly reactive to a number of organic compounds. Conventionally produced alkali metal powders exposed to the ambient atmosphere are well known to react quickly with the components of the atmosphere, rapidly losing activity and occasionally igniting.
  • XPS X-ray photoelectron spectroscopy
  • the process of this invention produces alkali metal dispersions having metal particle sizes in the range of 10 to 300 microns, and even larger sized metal particle powders (to 1000 microns) can easily be produced.
  • the resulting alkali metal dispersions of this invention are readily filtered to remove the bulk of the dispersant hydrocarbon oil and the metal is then washed with hexane to remove residual oil, after which the metal powder is dried.
  • the process can be controlled to produce various particle size ranges, such as 10 to 50 microns, 10 to 300 microns, 50 to 400 microns, 10 to 1000 microns, and so forth.
  • the resulting dried metal powders (“Dry Pack”) are unexpectedly stable to ambient atmosphere for periods up to about an hour allowing their safe transfer in such atmospheres from one container to another.
  • the lithium and sodium powders of this invention have been found to be non-pyrophoric by standard pyrophoricity tests.
  • Lithium metal particle sizes in the inventive dispersions, prepared in the hydrocarbon oil of choice, can be varied by adjusting the amount of dispersing agent (oleic acid) employed, as shown in the tables below .
  • Sodium metal, incorporated in the lithium must be kept below the alloy composition, i.e., below 0.88 wt %, in order to prevent thickening or gellation of the dispersion mass during the preparation of conventional lithium dispersions e.g., using oleic acid alone.
  • the substitution of carbon dioxide for part or all of the oleic acid there is no practical upper limit for sodium incorporation.
  • Table 2 shows a 5 weight sodium incorporation, based on lithium, which has no tendency to thicken.
  • hydrocarbon oils may be used successfully in the present invention.
  • hydrocarbon oil includes various oily liquids consisting chiefly or wholly of mixtures of hydrocarbons and includes mineral oils, i.e., liquid products of mineral origin having viscosity limits recognized for oils and hence includes but is not limited to petroleum, shale oils, paraffin oils and the like.
  • mineral oils i.e., liquid products of mineral origin having viscosity limits recognized for oils and hence includes but is not limited to petroleum, shale oils, paraffin oils and the like.
  • white oils highly refined
  • Even certain purified hydrocarbon solvents which boil in a range encompassing the melting point of lithium or sodium metal may be used, such as UNOCAL's 140 Solvent (b.p.
  • unrefined oils such as Unocal's 460 Solvent (b.p. range 189-262°C) , Hydrocarbon Seal oil (b.p. 270-321 °C) and Exxon's Telura 401 (b.p. 174-322°C) and Telura 407 (b.p. 245-450°C) may also be used.
  • Solvents useful in the practice of this invention include aliphatics, especially lower alkanes containing 5 to 10 carbon atoms, aromatics containing 6 to 10 carbon atoms and mixtures thereof including petroleum ether and other commercially available mixtures of hydrocarbons having rather narrow boiling ranges.
  • Coated lithium particles of this invention can also be prepared by spraying (using a high shear nozzle) molten alkali metal into a carbon dioxide atmosphere, as into a container having a carbon dioxide atmosphere, and collecting the particles in a solvent such as hexane.
  • the metal powders of this invention can be dried and packaged in suitable containers under an inert atmosphere, such as argon ("Dry PAck").
  • the powders can easily be introduced into commercial or laboratory reactions as dry powders or slurried in an inert solvent and introduced into the reaction as a slurry.
  • the dispersions are of course useful in chemical reactions as dispersions in oil, as oil wet particles after filtering to remove the bulk of the oil, or solvent wet particles obtained by washing the oil wet particles with a suitable hydrocarbon solvent to produce solvent wet particles.
  • the coating on the alkali metal particles produced by the process of this invention did not retard the reactivity of the metal with alkyl halides, but did protect the alkali metal from reaction with the ambient atmosphere. It was found that n-butyllithium could be prepared in an 82% yield from such a lithium powder that had been exposed to an ambient atmosphere for a 1 hour period One might conjecture that a such a protective coating would prevent reactions with such organic substrates from occurring since much smaller molecules, such as oxygen and nitrogen, do not react readily with the coated powders.
  • the lithium dispersions and dried lithium powders of this invention unexpectedly have been found to be capable of forming a variety of organolithium products in good yields from corresponding organic chlorides and organoamines.
  • organolithiums are n-, sec-, iso- and tert-butyllithiums, phenyllithium, n-hexyllithium, and 2-ethylhexyllithium.
  • lithium dialkylamides such as lithium diisopropylamide could be prepared by metalation of the corresponding dialkylamines (see Table 1).
  • Other organic compounds are also capable of reacting with the metal powders of this invention, such as e.g., alcohols, esters, aldehydes and ketones.
  • Lithium powder, generated by the process of this invention protected from ambient conditions and stored under argon for 30 days, produced high (90-95%) yields of n- and sec-butyllithium in hydrocarbon solutions and such n- and sec- butyllithium possessed remarkably low color, platinum-cobalt colors (APHA) of ⁇ 25 to ⁇ 100.
  • Tables 1 and 2 list a number of organolithium compounds prepared from the lithium dispersions and powders of this invention and their yields, chloride content, and color.
  • the Pt/Co colors of ⁇ 25 to ⁇ 100 are to be compared to typical values of Pt/ Co values of 150-250 for typical production run n-butyllithium.
  • An additional advantage in the use of carbon dioxide coated lithium metal powders is the striking effect on the chloride content of the organolithium solutions in hydrocarbon solvent media (prepared from organic chlorides) when using the lithium metal dispersions prepared by the process of the invention.
  • the values for the soluble inorganic chloride in these solutions are substantially lower then produced by a conventional lithium dispersion.
  • the soluble inorganic chloride from the present invention varies from ⁇ 100 to ⁇ 1000 ppm, depending on whether n- butyllithium or s-butyllithium is being made and the concentration of the alkyllithium solution.
  • the same products produced from lithium metal dispersions that do not contain a coating composition of this invention are higher, in the range of 300 ppm and higher. Lower chloride levels are associated with clearer product alkyllithium solutions which have enhanced marketability (see Table 2).
  • Lithium metal 300 g of low sodium grade was charged to a 3 liter stainless steel resin flask reactor with a 4" (10.16 cm) top fitted with a stirring shaft connected to a fixed high speed stirrer motor with a flexible shaft and top and bottom heating mantles in a dry atmosphere room under argon.
  • the reactor was then assembled and 2.25 g of sodium metal and 90% g of Peneteck * hydrocarbon oil were added.
  • Peneteck hydrocarbon oil is a product of Penreco Division of Pennzoil Products Co.
  • the reactor was then heated to 200°C until the lithium and sodium metals became molten. Stirring was maintained gently and intermittently until all the metal was completely molten. Then the mixture was stirred at high speed (10,000 ⁇ m) for 5 minutes.
  • the high speed stirring incorporated the carbon dioxide into the metal-hydrocarbon mixture.
  • the stirring was stopped, heating mantles removed and the reactor cooled to about 65°C before bottling the product dispersion.
  • the metal particle size range was found to be 10-200 microns.
  • a weight of 12.7 pounds of lithium metal, 0.033 pounds of sodium metal and 34 pounds of Peneteck oil were charged to a 15 gallon stainless steel reactor. The mixture was heated to about 190°C and held there until all of the metal became molten. Intermittent stirring was employed to speed the melting process. High speed shear stirring was begun when the metal became completely molten and sustained for two minutes. The stirring rate was then slowed, 20 grams of oleic acid added, and high speed stirring continued for an additional 2 minutes before starting CO 2 addition . A total of 85 grams of CO 2 was added over a 5 minute period, the temperature rising about 30 degrees. When CO 2 addition was complete, stirring was discontinued, the heating source removed, and cooling applied.
  • Lithium dispersion (lot 7218) prepared as in Example 1 above was filtered and washed in an enclosed, sintered glass filter funnel (fine porosity) to remove the hydrocarbon oil medium. Filtration to remove the bulk of the oil occurred rapidly, as did the subsequent hexane washings (3). Finally, the lithium metal residue in the funnel was washed once with n-pentane, filtered, and the funnel heated with a heat gun to remove traces of solvents. The resulting free-flowing powder was transferred from the funnel to a tightly capped storage bottle.
  • a pyrophoricity test [Code of Federal Regulations 49- Transportation Section 173.125 and Appendix E (CFR 49)] carried out on this material showed it to be non-pyrophoric.
  • An exposure test (Experiment #7231) carried out on a sample of this dry powder placed on a watch glass and exposed to ambient air conditions; no heat was generated on exposure to the air nor did any color change occur within 8 hours as occurs with normally prepared lithium dispersion powders. There was no odor of ammonia, either, as normally occurs due to nitridation of the metal.
  • Example 1 with carbon dioxide (#7218) was filtered and the metal washed 3 times with hexane, once with n-pentane, and blown dry. A 9.0 gram (1 .30 moles) portion of this metal powder was placed in an open Petri dish and exposed to ambient air (80% relative humidity) for approximately one hour. It was then transferred to a reaction flask along with 164 mis of hexane and 5 ml. of a 15 wt % n-butyllithium in hexane conditioner and stirred for about 20 min. before starting a feed of 54.6 g (0.584 moles) of n-butyl chloride.
  • the reactor and apparatus consisted of a 3 liter stainless steel round bottom flask with 4" (10.16 cm) opening, a 4" (10.16 cm) head with stirring shaft fixed therein, and connected to a high speed stirrer motor via a flexible shaft and a fixed argon inlet and a stainless steel sintered sparger disc and top and bottom heating mantles.
  • the sparger disc (2 1/2" [6.35 cm] biscuit type) was fixed directly below the cutting blade of the stirring shaft and was approximately 3/4" (1.8 cm) off the bottom of reactor.
  • Lithium metal 350.0 grams was charged to the reactor in the dry atmosphere room.
  • the reactor was assembled and 2.625 g of sodium and Peneteck hydrocarbon oil were added.
  • the reactor was then heated to about 200°C and the contents stirred gently until all metal was molten (approx. 30 minutes).
  • Metal and oil were then stirred at high speed (10,000 rpm) for 4 minutes, then carbon dioxide was fed in through the sparger for a period of 2 minutes.
  • Temperature of the reaction rose 11°C (from 191 - 202°C) when the carbon dioxide was charged.
  • stirring was stopped, the heating mantle was removed and the dispersion cooled to about 65°C before transferring to tightly capped storage bottles.
  • Claisen adapter 125 ml dropping funnel, a stirring shaft with teflon blade, stirring motor, and a thermometer probe with an electronic read out.
  • Lithium metal dispersion (prepared as in Example 1 ) was hexane washed two times and pentane washed twice and dried with argon. The metal was then weighed and the experiment conducted using 10% excess lithium (14.42 g or 2.078 moles) and 395 milliliters of cydohexane solvent.
  • Cydohexane was used to transfer the lithium through a transfer tube to the reactor.
  • Conditioner 5 ml s-butyllithium in cydohexane, was added and the mixture stirred for 15-30 minutes.
  • One to three mis of sec-butyl chloride was added which raised the temperature from ambient to around 34 °C. When the temperature began to drop, a slow s- butyl chloride feed was started. The sec-butyl chloride was fed over one hour and forty-five minutes adding a total of 87.4g (0.944 moles) and the reaction temperature was maintained between 32-37 °C.
  • the reaction was stirred for 1.5 hours, then filtered through a 500 ml medium fritted filter using inert diatomaceous earth filter aid. The solution filtered very fast (less than 5 minutes).
  • the reactor and apparatus was as described in Example 5, plus heating mantle, and reflux condenser.
  • the lithium metal dispersion prepared as in Example 1 was hexane washed twice and pentane washed once and dried with argon. The metal was then weighed, 12.1 Og (1.743 moles).
  • Hexane 310 milliliters, was used to transfer the lithium through a transfer tube to the reactor.
  • the hexane-lithium mixture was heated to reflux (dry ice/hexane in condenser) and dropwise feed of n-butyl chloride begun.
  • the reaction proceeded instantaneously (refluxing) and the source of heat was removed.
  • 73.4g of n-butyl chloride (0.7924 moles) was fed in over a 40 minute period, the reaction heat controlled strictly by the rate of reflux.
  • the reaction mixture was allowed to cool to ambient (stirring) over a 2.5 hour period.
  • a stable alkali metal powder formed by heating an alkali metal in a hydrocarbon oil to a temperature above the melting point of the alkali metal, agitating the the molten alkali metal, maintaining agitation under conditions sufficient to disperse the alkali metal into small molten particles while contacting the alkali metal with at least 0.3 weight percent of anhydrous carbon dioxide for at least one minute to disperse the molten alkali metal and recovering a stable coated alkali metal powder having particle sizes in the range of 10 to 1000 microns in the form of a dry powder.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Lubricants (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Procédé de préparation de dispersions de particules de métaux alcalins revêtues et stables à l'atmosphère, ainsi que de poudres de métaux alcalins revêtues et stables à l'atmosphère, et qui consiste à agiter un mélange de métal alcalin en fusion dans une huile hydrocarbure à des vitesses de dispersions données, éventuellement en présence d'un agent dispersant, à mettre en contact la dispersion d'huile hydrocarbure et de métal alcalin en fusion, au-dessus ou au-dessous de la surface de la dispersion, avec 3 % en poids maximum de dioxyde de carbone anhydre, tout en agitant la dispersion pendant une minute au moins. On peut utiliser la dispersion dans l'huile directement dans des réactions chimiques. On peut retirer la masse d'huile des dispersions, afin d'obtenir des particules humides huileuses qu'on peut laver au moyen d'un hydrocarbure à point d'ébullition bas, de manière à obtenir des particules humides d'hydrocarbure qu'on peut sécher dans le but de préparer des poudres stables à l'atmosphère de particules de métal revêtues. On peut utiliser dans des réactions chimiques respectivement les particules dispersées dans l'huile, les particules humides huileuses, les particules humides d'hydrocarbure et les poudres stables à l'atmosphère. Après lavage et séchage, ce procédé permet d'obtenir des poudres de lithium, dont la composition de revêtement de surface contient 0,1-0,3 % atomique de lithium, 0,3-0,4 % atomique de carbone et 0,3-0,5 % atomique d'oxygène. On peut utiliser les produits obtenus afin d'effectuer la synthèse de composés organométalliques, dont les niveaux de chlorure inorganique sont peu colorés et peu solubles.
PCT/US1996/013137 1995-08-15 1996-08-13 Dispersions de metaux alcalins WO1997006910A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE19681528T DE19681528B4 (de) 1995-08-15 1996-08-13 Alkali-Metall-Dispersionen
AU67238/96A AU6723896A (en) 1995-08-15 1996-08-13 Alkali metal dispersions
GB9803042A GB2319024B (en) 1995-08-15 1996-08-13 Alkali metal dispersions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US233295P 1995-08-15 1995-08-15
US60/002,332 1995-08-15

Publications (1)

Publication Number Publication Date
WO1997006910A1 true WO1997006910A1 (fr) 1997-02-27

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PCT/US1996/013137 WO1997006910A1 (fr) 1995-08-15 1996-08-13 Dispersions de metaux alcalins

Country Status (4)

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AU (1) AU6723896A (fr)
DE (1) DE19681528B4 (fr)
GB (1) GB2319024B (fr)
WO (1) WO1997006910A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066640A1 (fr) * 2002-02-06 2003-08-14 Chemetall Gmbh Procede de production de composes d'alkyllithium par pulverisation de metal lithium
WO2006000833A2 (fr) * 2004-06-24 2006-01-05 Absl Power Solutions Ltd Accumulateur aux ions de lithium
WO2012052265A3 (fr) * 2010-09-28 2013-05-30 Chemetall Gmbh Poudre métallique de lithium stabilisée pure et son procédé de fabrication

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2058503A (en) * 1933-01-04 1936-10-27 Raffold Process Corp Colloidal calcium carbonate
US2394608A (en) * 1944-11-15 1946-02-12 Du Pont Dispersion
US2798831A (en) * 1952-07-30 1957-07-09 Du Pont Coating protected alkali metal product and process
US3293313A (en) * 1962-05-01 1966-12-20 Foote Mineral Co Method of making organic lithium compounds
US5332533A (en) * 1993-07-06 1994-07-26 Fmc Corporation Alkyllithium process
WO1994019100A1 (fr) * 1993-02-18 1994-09-01 Fmc Corporation Dispersions de metal alcalin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2058503A (en) * 1933-01-04 1936-10-27 Raffold Process Corp Colloidal calcium carbonate
US2394608A (en) * 1944-11-15 1946-02-12 Du Pont Dispersion
US2798831A (en) * 1952-07-30 1957-07-09 Du Pont Coating protected alkali metal product and process
US3293313A (en) * 1962-05-01 1966-12-20 Foote Mineral Co Method of making organic lithium compounds
WO1994019100A1 (fr) * 1993-02-18 1994-09-01 Fmc Corporation Dispersions de metal alcalin
US5332533A (en) * 1993-07-06 1994-07-26 Fmc Corporation Alkyllithium process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066640A1 (fr) * 2002-02-06 2003-08-14 Chemetall Gmbh Procede de production de composes d'alkyllithium par pulverisation de metal lithium
CN100341878C (zh) * 2002-02-06 2007-10-10 坎梅陶尔股份有限公司 锂金属喷雾法制备烷基锂化合物的方法
US7326372B2 (en) 2002-02-06 2008-02-05 Chemetall Gmbh Method for the production of alkyl lithium compounds by means of spraying of lithium metal
WO2006000833A2 (fr) * 2004-06-24 2006-01-05 Absl Power Solutions Ltd Accumulateur aux ions de lithium
WO2006000833A3 (fr) * 2004-06-24 2006-04-13 Absl Power Solutions Ltd Accumulateur aux ions de lithium
WO2012052265A3 (fr) * 2010-09-28 2013-05-30 Chemetall Gmbh Poudre métallique de lithium stabilisée pure et son procédé de fabrication
US10655229B2 (en) 2010-09-28 2020-05-19 Albemarle Germany Gmbh Stabilized, pure lithium metal powder and method for producing the same
US11021797B2 (en) 2010-09-28 2021-06-01 Albemarle Germany Gmbh Stabilized, pure lithium metal powder and method for producing the same

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Publication number Publication date
DE19681528T1 (de) 1999-07-15
AU6723896A (en) 1997-03-12
DE19681528B4 (de) 2006-10-05
GB2319024A (en) 1998-05-13
GB2319024B (en) 1999-09-29
GB9803042D0 (en) 1998-04-08

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