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WO2016192648A1 - Procédé pour la préparation de magnésium métallique - Google Patents

Procédé pour la préparation de magnésium métallique Download PDF

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Publication number
WO2016192648A1
WO2016192648A1 PCT/CN2016/084478 CN2016084478W WO2016192648A1 WO 2016192648 A1 WO2016192648 A1 WO 2016192648A1 CN 2016084478 W CN2016084478 W CN 2016084478W WO 2016192648 A1 WO2016192648 A1 WO 2016192648A1
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WO
WIPO (PCT)
Prior art keywords
magnesium
chamber
cathode
anode
exchange membrane
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2016/084478
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English (en)
Chinese (zh)
Inventor
张无量
张特瑞莎
张君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Magnesium Co Ltd
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General Magnesium Co 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 General Magnesium Co Ltd filed Critical General Magnesium Co Ltd
Publication of WO2016192648A1 publication Critical patent/WO2016192648A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • 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
    • Y02P10/20—Recycling

Definitions

  • This invention relates to a wet metallurgy process, and more particularly to a process for the preparation of magnesium metal.
  • Silver-white metallic magnesium is a lightweight structural material. It is often alloyed with aluminum, manganese, zinc, rare earth metals, etc., based on its light weight, high specific strength and easy recovery. Therefore, magnesium alloy can be widely used in automotive parts and housings of portable electronic products.
  • the prior art methods for preparing magnesium metal include molten salt electrolysis and ferrosilicon thermal reduction.
  • the molten salt electrolysis method is to obtain molten magnesium and chlorine by electrolyzing molten anhydrous magnesium chloride at a reduction temperature of about 700 °C.
  • the ferrosilicon thermal reduction method uses dolomite as a raw material in a vacuum reduction tank, and uses ferrosilicon as a reducing agent to reduce magnesium oxide in the dolomite to magnesium vapor at a reduction temperature of about 1200 ° C, and then passes through a condenser. Magnesium vapor is condensed to produce metallic magnesium.
  • the molten salt electrolysis method consumes about equivalent to 20 kilowatts (kW) of energy for preparing 1 kilogram of metallic magnesium
  • the ferrosilicon thermal reduction method requires about 1 kilogram (kg) of magnesium metal to be consumed. It is effective for 24 kW, and the molten salt electrolysis method and the ferrosilicon thermal reduction method require a relatively high reduction temperature to produce magnesium metal. Therefore, the production of magnesium metal by molten salt electrolysis and ferrosilicon thermal reduction requires a large amount of consumption. Energy and cost.
  • the technical means adopted by the present invention is that the method for preparing magnesium metal comprises the following steps:
  • an ion membrane electrolysis system comprising a raw material chamber, an anode chamber, a cathode chamber, a cation exchange membrane, an anion exchange membrane, an iron anode and a cathode, the anion exchange membrane being located between the raw material chamber and the anode chamber
  • the cation exchange membrane is located between the raw material chamber and the cathode chamber, and the iron anode and the cathode are respectively provided In the anode chamber and the cathode chamber;
  • An electrolytic voltage is applied between the iron anode and the cathode to obtain metallic magnesium and a concentrated aqueous solution of ferric chloride.
  • the amount of ferric chloride contained in the concentrated aqueous solution of ferric chloride is more than the amount of ferric chloride contained in the aqueous solution of ferric chloride.
  • the iron anode refers to an iron anode containing at least 99.95 weight percent (wt%) of iron.
  • the iron anode has an iron content of at least 99.98% by weight.
  • the iron anode contains carbon and iron, and the iron anode has a carbon content of 0.02 wt% to 0.05 based on the total weight of the iron anode. Between wt%.
  • the cathode of the ion-exchange membrane electrolysis system is made of stainless steel, glassy carbon or carbon aerogel.
  • the anhydrous organic electrolyte solution comprises a solvent, an organomagnesium electrolyte, and a supporting electrolyte
  • the solvent comprising selected from the group consisting of ethyl ether, tetrahydrofuran, and 2- An ether compound in the group consisting of 2-methyltetrahydrofuran and cyclopentyl methyl ether
  • the organomagnesium electrolyte comprising selected from the group consisting of methyl magnesium chloride
  • the supporting electrolyte comprises aluminum chloride or lithium perchlorate.
  • the organomagnesium electrolyte is 0.8 mol/L (mol/L) to 2.0 mole/L based on the total amount of the anhydrous organic electrolyte, and the supporting electrolyte is 0.10 mol/L to 0.20 mol/ L. Still preferably, the organomagnesium electrolyte is from 1.0 mol/L to 1.5 mol/L, and the supporting electrolyte is from 0.12 mol/L to 0.15 mol/L, based on the total amount of the anhydrous organic electrolyte.
  • the ferric chloride contained in the aqueous solution of ferric chloride is from 0.3 mol/L to 0.5 mol/L based on the total amount of the aqueous solution of ferric chloride. . More preferably, the ferric chloride contained in the aqueous solution of ferric chloride is from 0.4 mol/L to 0.5 mol/L based on the total amount of the aqueous solution of ferric chloride.
  • the magnesium chloride hexahydrate contained in the aqueous solution of magnesium chloride hexahydrate is from 0.3 mol/L to 0.5 mol/L, based on the total amount of the aqueous solution of magnesium chloride hexahydrate.
  • the cation exchange membrane may be a perfluorosulfonic acid cation exchange membrane, but is not limited thereto.
  • At least one side of the cation exchange membrane is coated with a magnesium ion conductive solid polymer electrolyte.
  • the anion exchange membrane is a homogeneous anion exchange membrane.
  • the step of applying the electrolysis voltage between the anode and the cathode of the iron to obtain the metal magnesium and the concentrated aqueous solution of ferric chloride comprises:
  • the atmospheric pressure is 1 atm.
  • the method for preparing magnesium metal can obtain 1 kilogram of metal magnesium by using only 5.2 kilowatts or less of energy, thereby achieving the advantages of saving production energy and cost of metal magnesium.
  • the method for preparing magnesium metal is the same as producing the concentrated aqueous solution of ferric chloride while producing the magnesium metal, instead of producing a large amount of unfavorable environment such as chlorine gas or carbon dioxide, in addition to reducing the harm to the environment,
  • the ferric chloride in the concentrated aqueous solution of ferric chloride can be further used as a flocculant for the treatment of sewage. Therefore, the method for preparing magnesium metal has the advantages of low energy and cost consumption and environmental friendliness.
  • Figure 1 is a flow chart of a method for preparing magnesium metal according to the present invention
  • FIG. 2 is a schematic view of an ion-exchange membrane electrolysis system used in the method for producing magnesium metal of the present invention.
  • the method for preparing magnesium metal of the present embodiment is completed by the steps described below.
  • an ion-exchange membrane electrolysis system 10 is provided as described in step S1.
  • the ionic membrane electrolysis system 10 comprises a chamber 11, a cation exchange membrane 12, an anion exchange membrane 13, an iron anode 14 and a cathode 15, the cation exchange membrane 12 being coated with at least one side of a solid polymer electrolyte capable of conducting magnesium ions.
  • the cation exchange membrane 12 is a perfluorosulfonic acid cation exchange membrane 12 of DuPont Chemical Company.
  • the cation exchange membrane 12 and the anion exchange membrane 13 partition the interior of the chamber 11 into a raw material chamber 111, an anode chamber 112, and a cathode chamber 113.
  • the anion exchange membrane 13 is located between the raw material chamber 111 and the anode chamber 112.
  • the exchange membrane 12 is located between the raw material chamber 111 and the cathode chamber 113, and the anion exchange membrane 13 is a homogeneous anion exchange membrane of DuPont Chemical Co., Ltd., and the iron anode 14 and the cathode 15 are respectively disposed in the anode chamber 112 and the cathode chamber. 113.
  • the iron anode 14 contains iron and carbon, and the iron anode 14 has a carbon content of 0.02% by weight based on the total weight of the iron anode 14, and the cathode 15 is made of stainless steel.
  • a non-aqueous organic electrolytic solution is injected into the cathode chamber 113, an aqueous solution of magnesium chloride hexahydrate is injected into the raw material chamber 111, and the aqueous solution of ferric chloride is injected into the anode chamber 112.
  • the anhydrous organic electrolyte is composed of a solvent, an organomagnesium electrolyte and a supporting electrolyte, the solvent is tetrahydrofuran, the organomagnesium electrolyte is ethyl magnesium chloride, the supporting electrolyte is aluminum chloride, and the ethyl magnesium chloride is used in an amount of 1.5.
  • the mole, the amount of aluminum chloride used is 0.15 mol, and the amount of the tetrahydrofuran is 1.0 liter (liter, L).
  • the aqueous solution of ferric chloride contains ferric chloride and water, and the molar concentration of the aqueous solution of ferric chloride is 0.4 mol/L.
  • the aqueous solution of magnesium chloride hexahydrate contains magnesium chloride hexahydrate and water, and the molar concentration of the aqueous solution of magnesium chloride hexahydrate is 0.5 mol/L.
  • step S3 the electrolysis voltage of the direct current power supply is adjusted at a normal pressure and an operating temperature of 25 ° C to achieve a current density of 10 mA/cm 2 between the iron anode 14 and the cathode 15 for 1 hour, thereby Obtaining a non-aqueous organic electrolyte containing magnesium metal in the cathode chamber 113 and obtaining a concentrated aqueous solution of ferric chloride in the anode chamber 112; thereafter, separating the anhydrous organic electrolyte containing magnesium metal to obtain magnesium metal And the separated anhydrous organic electrolyte; wherein, under the condition of a membrane square (m 2 ) membrane area, the yield of metallic magnesium is 38.54 g (gram, g), and the concentrated ferric chloride The difference between the content of ferric chloride in the aqueous solution and the ferric chloride in the aqueous solution of ferric chloride is 200.06 g, that is, the method for producing magnesium metal of the present embodiment can
  • Iron anode Fe (s) -2e - ⁇ Fe 2+ (aq)
  • the actual amount of magnesium metal obtained by the method for producing magnesium metal was 38.54 g, and the method for producing magnesium metal produced iron dichloride (FeCl 2 ) of 200.06 g.
  • FeCl 2 iron dichloride
  • the theoretical amount of magnesium metal prepared by the above method is 24.5 volts, the current density of 10 mA/cm 2 , the working time of 1 hour, and the membrane area of 1 square meter.
  • the output of ferric chloride was 236 grams. From this, it can be inferred that the current efficiency of the method for preparing metallic magnesium is 85%.
  • the actual amount of metallic magnesium obtained by the method for preparing magnesium metal is 38.54 g and the electrolytic voltage is 2 volts, and it can be known that the method for preparing metallic magnesium produces 1 kg of magnesium metal per method.
  • the power consumption is 5.19 kilowatts, and at the same time, 5.2 kilograms of ferric chloride is produced.
  • the method for preparing magnesium metal can further make the concentrated aqueous solution of ferric chloride contain more than 5.2 kg of the aqueous solution of ferric chloride, each time 1 kg of metallic magnesium is obtained. Ferric chloride content.
  • the use of the ion-exchange membrane electrolysis system 10 containing the iron anode 14 is carried out by applying the electrolysis voltage to the iron anode in combination with the use of the anhydrous organic electrolyte solution, the aqueous solution of magnesium chloride hexahydrate and the aqueous solution of ferric chloride.
  • the method for preparing magnesium metal in the foregoing embodiment can obtain energy and cost by using only 1.19 kilowatts of energy to obtain 1 kilogram of metallic magnesium and the concentrated aqueous solution of ferric chloride.
  • the method for preparing magnesium metal produces the concentrated aqueous solution of ferric chloride while producing magnesium metal, and does not generate a large amount of gas such as chlorine gas or carbon dioxide, in addition to reducing environmental damage, the concentration
  • the ferric chloride in the aqueous solution of ferric chloride can be further processed into ferric chloride for use as a flocculant for sewage treatment.
  • the method for preparing magnesium metal can be applied to a working pressure of normal pressure, an operating temperature of 20 ° C to 25 ° C, a current density of 10 mA / cm 2 to 25 mA / cm 2 and an electrolytic voltage of 2 volts to 5 volts. There is no need to additionally regulate the working pressure and the operating temperature, and therefore, the method of preparing magnesium metal has the advantage of saving energy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé pour la préparation de magnésium métallique, comprenant les étapes suivantes : l'utilisation d'un système d'électrolyse à membranes échangeuses d'ions (10) comprenant une chambre de matière première (111), une chambre anodique (112), une chambre cathodique (113), une membrane échangeuse de cations (12), une membrane échangeuse d'anions (13), une cathode (15) et une anode constituée de fer (14), la membrane échangeuse d'anions (13) étant située entre la chambre de matière première (111) et la chambre anodique (112), la membrane échangeuse de cations (12) étant située entre la chambre de matière première (111) et la chambre cathodique (113) et l'anode constituée de fer (14) et la cathode (15) étant respectivement disposées dans la chambre anodique (112) et la chambre cathodique (113) ; le remplissage de la chambre cathodique (113), de la chambre de matière première (111) et de la chambre anodique (112) du système d'électrolyse à membranes échangeuse d'ions avec un électrolyte organique anhydre, une solution aqueuse de chlorure de magnésium hexahydraté et une solution aqueuse de chlorure ferreux, respectivement ; et l'application d'une tension électrolytique entre l'anode constituée de fer (14) et la cathode (15), pour obtenir du magnésium métallique et une solution aqueuse concentrée de chlorure ferreux. Par conséquent, le procédé précédent pour la préparation de magnésium métallique présente les avantages d'une faible consommation d'énergie et d'un faible coût et de respect de l'environnement.
PCT/CN2016/084478 2015-06-05 2016-06-02 Procédé pour la préparation de magnésium métallique Ceased WO2016192648A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510305030.8 2015-06-05
CN201510305030.8A CN106283113B (zh) 2015-06-05 2015-06-05 制备金属镁的方法

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WO2016192648A1 true WO2016192648A1 (fr) 2016-12-08

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107675202A (zh) * 2017-09-27 2018-02-09 广西七色珠光材料股份有限公司 颜料水解包膜反应器
CN117230459B (zh) * 2023-11-13 2024-02-13 中国科学院广州地球化学研究所 一种硅基纳微米材料的原位制备方法和装置

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1676670A (zh) * 2005-01-04 2005-10-05 华南理工大学 一种有机介质电解／超声波连续制备纳米金属粉末的方法
JP2010106356A (ja) * 2008-10-03 2010-05-13 Toyota Central R&D Labs Inc 第２族元素の酸化物の電解方法及びその装置
CN102586810A (zh) * 2012-03-17 2012-07-18 张无量 一种制备金属镁粉的方法
WO2014029031A1 (fr) * 2012-08-24 2014-02-27 Alliance Magnésium Processus de traitement de minerais contenant du magnésium

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US4216066A (en) * 1979-02-26 1980-08-05 Nalco Chemical Co. Preparation of tetramethyltin from a magnesium-tin alloy
US4401543A (en) * 1980-12-11 1983-08-30 Hiroshi Ishizuka Electrolytic cell for magnesium chloride
JPS6039189A (ja) * 1983-08-11 1985-02-28 Japan Storage Battery Co Ltd 亜鉛を電解採取するための電解槽
US4801363A (en) * 1987-01-05 1989-01-31 The Dow Chemical Company High purity alkaline earths via electrodeposition
US5593566A (en) * 1995-06-09 1997-01-14 General Motors Corporation Electrolytic production process for magnesium and its alloys
CN1664171A (zh) * 2004-12-14 2005-09-07 北京科技大学 一种直接电解氧化镁生产金属镁的方法
CN103031568B (zh) * 2011-10-08 2016-04-20 中国科学院青岛生物能源与过程研究所 一种电解制备金属锂的方法
CN103334132B (zh) * 2013-07-17 2016-05-25 沈阳大学 室温电沉积制备铝镁合金膜的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1676670A (zh) * 2005-01-04 2005-10-05 华南理工大学 一种有机介质电解／超声波连续制备纳米金属粉末的方法
JP2010106356A (ja) * 2008-10-03 2010-05-13 Toyota Central R&D Labs Inc 第２族元素の酸化物の電解方法及びその装置
CN102586810A (zh) * 2012-03-17 2012-07-18 张无量 一种制备金属镁粉的方法
WO2014029031A1 (fr) * 2012-08-24 2014-02-27 Alliance Magnésium Processus de traitement de minerais contenant du magnésium

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CN106283113B (zh) 2018-03-27
CN106283113A (zh) 2017-01-04

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