WO2008053460A1 - Production de magnésium élémentaire par réduction carbothermique, utilisé dans la régénération de composés stockant l'hydrogène - Google Patents

Production de magnésium élémentaire par réduction carbothermique, utilisé dans la régénération de composés stockant l'hydrogène Download PDF

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Publication number
WO2008053460A1
WO2008053460A1 PCT/IL2007/001248 IL2007001248W WO2008053460A1 WO 2008053460 A1 WO2008053460 A1 WO 2008053460A1 IL 2007001248 W IL2007001248 W IL 2007001248W WO 2008053460 A1 WO2008053460 A1 WO 2008053460A1
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WO
WIPO (PCT)
Prior art keywords
magnesium
carbon
catalyst
powder
magnesium oxide
Prior art date
Application number
PCT/IL2007/001248
Other languages
English (en)
Inventor
Jonathan Goldstein
Menachem Givon
Original Assignee
Hyogen Ltd.
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 Hyogen Ltd. filed Critical Hyogen Ltd.
Publication of WO2008053460A1 publication Critical patent/WO2008053460A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
    • C01B6/15—Metal borohydrides; Addition complexes thereof
    • C01B6/19—Preparation from other compounds of boron
    • C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2

Definitions

  • the present invention relates to a process for improving the regeneration of hydrogen storage compounds based on chemical hydrides such as sodium borohydride and related borohydrides.
  • Goldstein's US application (US 20060042162) describes preparing sodium borohydride in a slurry form having beneficially high borohydride content, and treating the metaborate product so it is free of waters of crystallization.
  • the magnesium oxide product from Reaction 2 is most cheaply and directly converted back to magnesium metal by carbothermic reduction at high temperatures (>1500 degrees C), providing magnesium and carbon monoxide vapors according to reaction 3:
  • the prior art e.g., US patents 5782952 and 4290804, describes strategies for quenching the gaseous magnesium product while letting the carbon monoxide pass on. For example, supersonic cooling, solvation of magnesium vapor, inert gas injection or latent heat cooling of the products using a spray of molten magnesium have been proposed. These methods all have an energy penalty.
  • Reaction 4 is catalyzed by many transition metals, their alloys and their refractory compounds (Co, Ni, Fe, platinum group metals, W in particular and their oxides, carbides, nitrides) but their usual effectiveness lies between 400 0 C and 600
  • Reaction 4 will be driven to the right and, effectively, magnesium and carbon dioxide will leave the reaction bed. Not only the kinetics and yield are improved and the bed operating temperature somewhat reduced, but the magnesium vapor may be condensed to powder with no further product losses or energy losses.
  • This process will be hereafter referred to as the improved carbothermic reduction of magnesium oxide.
  • a process for the production of elemental magnesium from feed materials containing magnesium oxide and carbon comprising: exposing excess magnesium oxide and carbon to a high temperature reaction zone, in the presence of a catalyst, which is optionally supported, for disproportionation of carbon monoxide back to carbon and carbon dioxide, wherein the magnesium oxide and carbon react at a temperature of at least 1100. 0 C in the reaction zone to produce gaseous magnesium and carbon monoxide, and removing the gaseous magnesium and carbon dioxide from the reaction zone.
  • the improved carbothermic reduction process of magnesium oxide is integrated with the metaborate reduction process (Reaction 2, of US patent applications 20040249215 and 20050207959, the relevant teachings of which are incorporated herein by reference) as shown in Figure 1.
  • the effluent stream of magnesium oxide powder from the metaborate reduction process (9, Figure 1) is cheaply and efficiently reduced back to magnesium powder, to be reused by the metaborate reduction process (15, Figure 1).
  • tetrahydroborates per Reaction 2 (Suda, US application 20040249215) can be greatly enhanced by the addition of hydride forming materials or supported materials selected from the transition metals and their alloys, such as Pt, Pd Al, Fe, Ni, Co, Mg, Zn, V, Zr, Ti, La, Y, Ce, Ca, Nb, Nd, Pr or any metal or alloys that can form oxides with oxygen.
  • transition metals and their alloys such as Pt, Pd Al, Fe, Ni, Co, Mg, Zn, V, Zr, Ti, La, Y, Ce, Ca, Nb, Nd, Pr or any metal or alloys that can form oxides with oxygen.
  • the catalysts mentioned in the first and third embodiment can be added to magnesium powder as it is formed from the gaseous phase in the Mg powder condensation ( Figure 1).
  • said catalyst or the supported catalyst is selected from the group consisting of transition metals, their alloys and their refractory compounds.
  • said catalyst is selected from the group consisting of compounds of Co, Ni, Fe, platinum group metals, and W.
  • said compounds are selected from the group consisting of oxides, carbides, nitrides.
  • gaseous magnesium is condensed directly to magnesium powder.
  • gaseous magnesium is condensed to liquid magnesium.
  • the source of the magnesium oxide powder is a second process, said second process requiring magnesium powder as a raw material.
  • said second process is a process for synthesizing metal borohydrides as described in US patent application 20050207959.
  • said second process is a method for producing tetrahydroborates as described in US patent application 20040249215.
  • Preferably said method for producing tetrahydroborates is enhanced by the addition of hydride forming materials.
  • said method for producing tetrahydroborates is enhanced by the addition of supported materials.
  • said hydride forming materials or supported materials are selected from the group consisting of transition metals and their alloys.
  • said hydride forming materials or supported materials are selected from the group consisting of Pt, Pd, Al, Fe, Ni, Co, Mg, Zn, V, Zr, Ti, La, Y, Ce, Ca, Nb, Nd, Pr.
  • said hydride forming materials or supported materials are selected from any metal or alloy that can form oxides with oxygen.
  • heat produced in the reaction zone is used to preheat the feed material for said second process.
  • the catalysts are embedded in the magnesium oxide powder produced in said second process.
  • said hydride forming materials are embedded in the magnesium powder fed from the process defined herein.
  • Figure 1 is a block diagram showing the integration of a metaborate reduction process (A) with improved carbothermic reduction of magnesium oxide (B).
  • Figure 2 is a schematic presentation of components for carrying out the improved process of the present invention as described in the example below.
  • magnesium oxide is reacted at temperature with carbon in the presence of a tungsten catalyst for disproportionation of carbon monoxide, in order to generate magnesium powder and carbon dioxide with high yield.
  • Magnesium oxide powder (40 gm) was intimately mixed with carbon powder (5 gm) and tungsten powder (1 gm) as catalyst, using powders of below 300 mesh particle size, and the mixture was placed in a stainless steel crucible (1) that was fitted with a stainless steel tube section (2).
  • the magnesium oxide reactant is in stoichiometric excess to the carbon.
  • the crucible was placed in a furnace (3) with arc heating capability so that the tube section projected from the furnace hot zone out of the furnace directly into an oil cooled stainless steel condenser (4).
  • a further length of tubing (5) exiting from the condenser proceeded into a bath of aqueous 10% sodium hydroxide solution (6) where gas, emerging from the tube (5), could displace alkali from an inverted cylinder (7).
  • the system was fitted with argon purge line (8).
  • the system was first flushed with argon, the furnace was heated to a temperature close to the magnesium melting point (900 0 C) and when argon traces stopped bubbling from the tube the alkali filled inverted cylinder (7) was placed over the tube (5). To initiate the reaction the furnace temperature was gradually raised above 1100 0 C, which was the boiling point of magnesium. Gas was seen to evolve again and initially displace alkali from the cylinder. When no further gas was observed, the condenser (4) was disconnected from the furnace (3) area and the furnace was shut off. The condenser when opened was found to contain 17 gm of magnesium powder, together with small amounts of magnesium oxide and carbon.
  • the alkali in the inverted cylinder (7) absorbed nearly all the gas generated, confirming it was mainly carbon dioxide (and not carbon monoxide which is not dissolved by alkali).
  • the crucible (1) when opened was found to contain unreacted excess of magnesium oxide together with the tungsten powder catalyst which was unchanged. The yield of magnesium in this experiment was in excess of 70%.
  • magnesium powder from the first part of the example is reacted at temperature with sodium metaborate and hydrogen in the presence of a nickel-lanthanum alloy hydriding catalyst to generate sodium borohydride with high yield.
  • magnesium powder (12 gm) from the process above was mixed with anhydrous sodium metaborate (8.7 gm) and nickel-lanthanum alloy (LaNi 5 ) powder hydriding catalyst (1 gm).
  • This mixture was preheated in a tube furnace in a hydrogen atmosphere at over 5 bar at 400 degrees C, and then heated at an heating rate exceeding 10 degrees C per minute to 600 degrees C, maintaining this temperature for an hour and allowed to cool in hydrogen.
  • the resulting powder was treated with 10% aqueous sodium hydroxide to extract the sodium borohydride, and analysis showed that 8 gm of sodium borohydride had been produced, corresponding to a yield exceeding 80%.
  • the remaining powder comprised unreacted magnesium oxide, sodium metaborate and unchanged catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de magnésium élémentaire à partir de matériaux de charge contenant de l'oxyde de magnésium et du carbone, ledit procédé comprenant : l'exposition de l'oxyde de magnésium et du carbone en excès à une zone de réaction à température élevée, en présence d'un catalyseur, qui est éventuellement supporté, pour une dismutation du monoxyde de carbone de nouveau en carbone et en dioxyde de carbone, lesdits oxyde de magnésium et carbone réagissant à une température d'au moins 1 100°C dans ladite zone de réaction afin de produire du magnésium gazeux et du monoxyde de carbone, et le retrait desdits magnésium gazeux et dioxyde de carbone de ladite zone de réaction. La poudre de magnésium obtenue est utilisée dans un processus de synthèse ou de régénération de composés stockant l'hydrogène, tels que les borohydrures métalliques.
PCT/IL2007/001248 2006-11-02 2007-10-18 Production de magnésium élémentaire par réduction carbothermique, utilisé dans la régénération de composés stockant l'hydrogène WO2008053460A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL179,005 2006-11-02
IL179005A IL179005A0 (en) 2006-11-02 2006-11-02 A process for improving the regeneration of hydrogen storage compounds

Publications (1)

Publication Number Publication Date
WO2008053460A1 true WO2008053460A1 (fr) 2008-05-08

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Country Status (2)

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IL (1) IL179005A0 (fr)
WO (1) WO2008053460A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102828053A (zh) * 2012-09-05 2012-12-19 北方民族大学 一种用稀土废料作为矿化剂冶炼金属镁的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139181A (en) * 1976-09-24 1979-02-13 Toyo Soda Manufacturing Co., Ltd. Apparatus for preparing metallic magnesium
US4762528A (en) * 1986-09-05 1988-08-09 Reichl Eric H Fluid fuel from coal and method of making same
JP2001354406A (ja) * 2000-06-12 2001-12-25 Hirobe:Kk 高表面積物質の製造方法
WO2002062701A1 (fr) * 2001-02-08 2002-08-15 Yu Zhou Procede de synthese de borohydrures metalliques
US20040249215A1 (en) * 2000-04-26 2004-12-09 Seijirau Suda Method for producing tetrahydroborates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139181A (en) * 1976-09-24 1979-02-13 Toyo Soda Manufacturing Co., Ltd. Apparatus for preparing metallic magnesium
US4762528A (en) * 1986-09-05 1988-08-09 Reichl Eric H Fluid fuel from coal and method of making same
US20040249215A1 (en) * 2000-04-26 2004-12-09 Seijirau Suda Method for producing tetrahydroborates
JP2001354406A (ja) * 2000-06-12 2001-12-25 Hirobe:Kk 高表面積物質の製造方法
WO2002062701A1 (fr) * 2001-02-08 2002-08-15 Yu Zhou Procede de synthese de borohydrures metalliques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102828053A (zh) * 2012-09-05 2012-12-19 北方民族大学 一种用稀土废料作为矿化剂冶炼金属镁的方法

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