CN104445327A - Method for treating potassium element in aluminum electrolyte by using acid process - Google Patents

Method for treating potassium element in aluminum electrolyte by using acid process Download PDF

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Publication number
CN104445327A
CN104445327A CN201410636296.6A CN201410636296A CN104445327A CN 104445327 A CN104445327 A CN 104445327A CN 201410636296 A CN201410636296 A CN 201410636296A CN 104445327 A CN104445327 A CN 104445327A
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potassium
potassium element
aluminium electrolyte
filtrate
molecular sieve
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CN104445327B (en
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王兆文
侯剑峰
石忠宁
高炳亮
胡宪伟
于江玉
张鹏举
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00—Nitrates of sodium, potassium or alkali metals in general
    • C01D9/16—Purification

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention discloses a method for treating a potassium element in aluminum electrolyte by using an acid process. The method is characterized by comprising the following steps of (1) adding aluminum electrolyte containing the potassium element into a concentrated acid solution to react, filtering the material after reacting to obtain filtrate and a filtered solid, and drying to remove water in the filtered solid to obtain cryolite; (2) introducing the filtrate to a molecular sieve for adsorbing potassium ions to separate the potassium ions and sodium ions, desorbing the absorbed molecular sieve by using an ammonium nitrate solution, and carrying out evaporative crystallization on the desorbed solution to obtain potassium nitrate; and (3) carrying out evaporative crystallization on the adsorbed filtrate to obtain sodium nitrate. By using the method, a series of problems of superheat, carbon material damage, electrolytic tank service life loss and the like generated in the aluminum electrolysis production process because of the existence of the potassium element in the aluminum electrolysis industry are solved, the production benefit is increased, and a feasible method is provided for realizing electrolytic aluminum production under a complex electrolyte system.

Description

A kind of method of potassium element in acidic process aluminium electrolyte
Technical field
The present invention relates to the method for potassium sodium cryolite material in a kind of process aluminum electrolytic matter, be specifically related to the method for potassium element in a kind of acidic process aluminium electrolyte, belong to technical field of inorganic.
Background technology
In recent years, along with developing rapidly of China's Aluminium Industry, the demand of bauxite resource is sharply increased.Therefore a large amount of middle-low bauxite is opened Bian and for the preparation of metallurgical-grade aluminum oxide.In bauxite containing a large amount of alkali metal, particularly China's bauxite major production areas in this middle-low bauxite, potassium salts content is higher.The content of the metallurgical-grade aluminum oxide prepared with this kind of bauxite wherein potassium element can be more than 50 times of external metallurgical-grade aluminum oxide Determination of Potassium.A large amount of aluminum oxide containing sylvite is used for Aluminum Electrolysis Production as raw material.This aluminum oxide joins in ionogen, and sylvite also enters electrolyzer thereupon together, and constantly accumulates in the electrolyte.Along with continuing of producing, sylvite content in the electrolyte increases, thus makes ionogen component generation consecutive variations.Along with in ionogen, the content of potassium progressively raises, and electrolyte primary crystal temperature reduces gradually, and under such condition, superheating temperature can be elevated to more than 30 DEG C sometimes.Superheating temperature is too high, and stove side forms difficulty, and established stove side is thinning, affects the steady running of aluminium cell and reduces the life-span of aluminium cell.And the negative electrode of potassium element to electrolyzer has very large destruction, this is that the potassium metal generated at cathode surface due to the potassium ion in fused electrolyte infiltrates in cathode material, causes and damages carbon materials expansion.Therefore, potassium element creates very large impact for Aluminium Electrolysis, should be adopted the potassium element in suitable technique recovery ionogen afterwards, remove the impact of potassium element for Aluminium Electrolysis by harmless process.By retrieval analysis, the document not having potassium sodium cryolite material in process aluminum electrolytic matter at present is both at home and abroad disclosed report.
Summary of the invention
Object of the present invention is just the problems referred to above solving prior art existence, after research and lot of experiments screen repeatedly, provides the method for potassium element in a kind of acidic process aluminium electrolyte.The present invention is based on the object removing harmful element potassium in aluminium electrolyte, successfully work out the technique that this acidic process contains potassium element aluminium electrolyte, for electrolysis of aluminum industry solves, superheating temperature in the Aluminium Electrolysis that the existence due to potassium element causes is high, the series of problems such as carbon materials is damaged, electrolyzer reduction in work-ing life, both adding productivity effect, providing practicable method for carrying out Aluminum Electrolysis Production under complicated electrolyte system again.
The present invention provide technical scheme be.
A method for potassium element in acidic process aluminium electrolyte, is characterized in comprising the following steps.
(1) levigate to granularity 100um-150um after being pulverized by the aluminium electrolyte containing potassium element, mixed with technical grade Sodium Fluoride by aluminium electrolyte powder, join in concentrated acid solution, add-on is 75-125g/L according to mixture concentration in concentrated acid solution; Under the condition stirred and heat, react 60-180min, reacted material, at 100-300 r/min, filters by mixing speed, obtains reacting rear filtrate and filtering solid phase.
(2) filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), dry removal moisture, (molecular formula is Na to obtain sodium aluminum fluoride 3alF 6).
(3) filtrate is imported the fractionation by adsorption of carrying out potassium ion in the aqueous solution in potassium ion type molecular sieve, desorption is carried out to molecular sieve after absorption, solution after desorption is carried out evaporative crystallization and obtain saltpetre (molecular formula is KNO 3).
(4) filtrate after absorption is carried out evaporative crystallization to obtain SODIUMNITRATE (molecular formula is NaNO 3).
Concentrated acid solution in described step (1) is HNO 3the aqueous solution, concentration 13-65wt%.
Sodium aluminum fluoride purity in described step (2) is more than 95%.
Molecular sieve in described step (3) is potassium ion type binding molecule sieve, and desorbing agent is 30wt% aqueous ammonium nitrate solution, and saltpetre purity is more than 95%.
SODIUMNITRATE purity in described step (4) is more than 95%.
In described step (1), the aluminium electrolyte powder containing potassium element and sodium fluoride powder are mixed to join in concentrated acid solution, when stirring and react at 20 DEG C-100 DEG C, should to make up water in reaction soln to keep cumulative volume constant.
In the present invention, dry moisture method of removing for dry more than 1h under 120 ± 5 DEG C of conditions.
Compared with prior art, the invention has the beneficial effects as follows; By the enforcement of technical solution of the present invention, effectively can remove potassium element harmful in ionogen, the higher industrial electrolysis matter being applicable to Aluminum Electrolysis Production of purity can be obtained simultaneously, the energy consumption of Aluminum Electrolysis Production can be reduced; But also the industrial chemicals such as saltpetre and SODIUMNITRATE can be reclaimed, comprehensive average treatment expense is lower, is applicable to carrying out application in the industrial production.
The present invention has the following advantages: use and be the common raw material of chemical field, low price, and this scheme of the invention is lower to equipment requirements, common molding device; Flow process is single, and separable go out many kinds of substance, gained material purity is higher.
The present invention is based on and solve the object of potassium element for the impact of electrolysis of aluminum, successfully work out the method for potassium element in acidic process aluminium electrolyte, affect problem for electrolysis of aluminum industry solves potassium element, too increase benefit, improve the level of aggregation of China's aluminium electrolytic industry.
Specific embodiments
The aluminium electrolyte sample of process of the present invention is from certain electrolytic aluminium factory 300kA electrolyzer, and the direct fragmentation of sample, levigate analysis, this ionogen contains Na 3alF 6, Al 2o 3, K 2naAlF 6; Electrolytical elementary composition and content Na 30.31%, F 52.55%, K 2.54%, Al 13.59%, O 1.01%.
The Sodium Fluoride that wherein the present invention adopts is technical grade Sodium Fluoride, and composition is containing sodium fluoride >=98% by mass percentage, silicon-dioxide≤0.5, vitriol≤0.3, sodium carbonate≤0.5, water (H2O)≤0.5, other impurity≤0.2%.
In the present invention, dry moisture method of removing for dry more than 1h under 120 ± 5 DEG C of conditions.
Embodiment 1.
Get 10g aluminium electrolyte, levigate to granularity 100um-150um after pulverizing, obtain aluminium electrolyte powder; Aluminium electrolyte powder is mixed with 2g sodium fluoride powder, and joins the HNO of 100ml 3in the aqueous solution, HNO 3concentration of aqueous solution is 65wt%; Stirring and reacting 60min under the condition of 40 DEG C, mixing speed at 150 r/min, in reaction process to make up water in reaction soln to keep cumulative volume constant.
Filtered by reacted material, obtain reacting rear filtrate and filtering solid phase, filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), moisture is removed in drying, obtains the sodium aluminum fluoride that 10.2g purity is more than 95%.
Filtrate is imported in molecular sieve and carry out being separated of potassium ion and sodium ion; Carry out desorption to molecular sieve after absorption, solution after desorption being carried out evaporative crystallization, to obtain 0.69g purity be more than 95% saltpetre.
Filtrate after absorption being carried out evaporative crystallization, to obtain 3.7g purity be more than 95% SODIUMNITRATE.
Embodiment 2.
Get 5g aluminium electrolyte, levigate to granularity 100um-150um after pulverizing, obtain aluminium electrolyte powder; Aluminium electrolyte powder is mixed with 1g sodium fluoride powder, and joins the HNO of 50ml 3in the aqueous solution, HNO 3concentration of aqueous solution is 65wt%; Stirring and reacting 90min under the condition of 60 DEG C, mixing speed at 200 r/min, in reaction process to make up water in reaction soln to keep cumulative volume constant.
Filtered by reacted material, obtain reacting rear filtrate and filtering solid phase, filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), moisture is removed in drying, obtains the sodium aluminum fluoride that 5.11g purity is more than 95%.
Filtrate is imported in molecular sieve and carry out being separated of potassium ion and sodium ion; Carry out desorption to molecular sieve after absorption, solution after desorption being carried out evaporative crystallization, to obtain 0.33g purity be more than 95% saltpetre.
Filtrate after absorption being carried out evaporative crystallization, to obtain 1.75g purity be more than 95% SODIUMNITRATE.
Embodiment 3.
Get 150g aluminium electrolyte, levigate to granularity 100um-150um after pulverizing, obtain aluminium electrolyte powder; Aluminium electrolyte powder is mixed with 10g sodium fluoride powder, and joins the HNO of 1500ml 3in the aqueous solution, HNO 3concentration of aqueous solution is 35wt%; Stirring and reacting 120min under the condition of 20 DEG C, mixing speed at 250 r/min, in reaction process to make up water in reaction soln to keep cumulative volume constant.
Filtered by reacted material, obtain reacting rear filtrate and filtering solid phase, filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), moisture is removed in drying, obtains the sodium aluminum fluoride that 152.82g purity is more than 95%.
Filtrate is imported in molecular sieve and carry out being separated of potassium ion and sodium ion; Carry out desorption to molecular sieve after absorption, solution after desorption being carried out evaporative crystallization, to obtain 9.81g purity be more than 95% saltpetre.
Filtrate after absorption being carried out evaporative crystallization, to obtain 12.04g purity be more than 95% SODIUMNITRATE.
Embodiment 4.
Get 60g aluminium electrolyte, levigate to granularity 100um-150um after pulverizing, obtain aluminium electrolyte powder; Aluminium electrolyte powder is mixed with 6g sodium fluoride powder, and joins the HNO of 800ml 3in the aqueous solution, HNO 3concentration of aqueous solution is 22wt%; Stirring and reacting 180min under the condition of 85 DEG C, mixing speed at 150 r/min, in reaction process to make up water in reaction soln to keep cumulative volume constant.
Filtered by reacted material, obtain reacting rear filtrate and filtering solid phase, filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), moisture is removed in drying, obtains the sodium aluminum fluoride that 61.14g purity is more than 95%.
Filtrate is imported in molecular sieve and carry out being separated of potassium ion and sodium ion; Carry out desorption to molecular sieve after absorption, solution after desorption being carried out evaporative crystallization, to obtain 3.92g purity be more than 95% saltpetre.
Filtrate after absorption being carried out evaporative crystallization, to obtain 9.35g purity be more than 95% SODIUMNITRATE.
Embodiment 5.
Get 500g aluminium electrolyte, levigate to granularity 100um-150um after pulverizing, obtain aluminium electrolyte powder; Aluminium electrolyte powder is mixed with 25g sodium fluoride powder, and joins the HNO of 5000ml 3in the aqueous solution, HNO 3concentration of aqueous solution is 65wt%; Stirring and reacting 60min under the condition of 95 DEG C, mixing speed at 300 r/min, in reaction process to make up water in reaction soln to keep cumulative volume constant.
Filtered by reacted material, obtain reacting rear filtrate and filtering solid phase, filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), moisture is removed in drying, obtains the sodium aluminum fluoride that 509.33g purity is more than 95%.
Filtrate is imported in molecular sieve and carry out being separated of potassium ion and sodium ion; Carry out desorption to molecular sieve after absorption, solution after desorption being carried out evaporative crystallization, to obtain 32.52g purity be more than 95% saltpetre.
Filtrate after absorption being carried out evaporative crystallization, to obtain 23.31g purity be more than 95% SODIUMNITRATE.

Claims (6)

1. the method for potassium element in acidic process aluminium electrolyte, is characterized in that comprising the following steps:
(1) levigate to granularity 100um-150um after being pulverized by the aluminium electrolyte containing potassium element, mixed with technical grade Sodium Fluoride by aluminium electrolyte powder, join in concentrated acid solution, add-on is 75-125g/L according to mixture concentration in concentrated acid solution; Under the condition stirred and heat, react 60-180min, reacted material, at 100-300 r/min, filters by mixing speed, obtains reacting rear filtrate and filtering solid phase;
(2) filtration solid phase is washed with water to washing lotion aobvious neutral (pH=7.0), dry removal moisture, obtains sodium aluminum fluoride;
(3) filtrate is imported in potassium ion type molecular sieve and carry out being separated of potassium ion and sodium ion; Desorption is carried out to molecular sieve after absorption, solution after desorption is carried out evaporative crystallization and obtains saltpetre;
(4) filtrate after absorption is carried out evaporative crystallization and obtain SODIUMNITRATE.
2. the method for potassium element in a kind of acidic process aluminium electrolyte according to claims, is characterized in that the concentrated acid solution described in step (1) is HNO 3the aqueous solution, concentration 13-65wt%.
3. the method for potassium element in a kind of acidic process aluminium electrolyte according to claims, is characterized in that the sodium aluminum fluoride purity described in step (2) is more than 95%.
4. the method for potassium element in a kind of acidic process aluminium electrolyte according to claims, it is characterized in that the molecular sieve described in step (3) is potassium ion type binding molecule sieve, desorbing agent is 30wt% aqueous ammonium nitrate solution, and saltpetre purity is more than 95%.
5. the method for potassium element in a kind of acidic process aluminium electrolyte according to claims, is characterized in that the SODIUMNITRATE purity told in step (4) is more than 95%.
6. the method for potassium element in a kind of acidic process aluminium electrolyte according to claims, the aluminium electrolyte containing potassium element and Sodium Fluoride is it is characterized in that to be mixed to join in concentrated acid solution, when stirring and react at 20 DEG C-100 DEG C, should to make up water in reaction soln to keep cumulative volume constant.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108677020A (en) * 2018-06-19 2018-10-19 东北大学 It is a kind of by aluminium scrap electrolyte is innoxious and recycling processing method
CN112342386A (en) * 2020-10-19 2021-02-09 东北大学 Resource treatment method for complex aluminum electrolyte

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CN101318679A (en) * 2007-06-07 2008-12-10 多氟多化工股份有限公司 Method for preparing kryocide
CN101804996A (en) * 2010-04-02 2010-08-18 北京矿冶研究总院 Method for recovering sodium fluoride from electrolytic aluminum waste cathode carbon block
CN101823741A (en) * 2010-02-03 2010-09-08 中南大学 Method for continuously producing aluminium electrolysis raw materials high-fluorine alumina, cryolite and sodium silicate with aluminum dust
CN102732914A (en) * 2012-07-25 2012-10-17 深圳市新星轻合金材料股份有限公司 Method for preparing electrolyte and supplementing system thereof in aluminum electrolysis process
US8679318B2 (en) * 2012-05-23 2014-03-25 Shenzhen Sunxing Light Alloys Materials Co., Ltd. Electrolyte supplement system in aluminium electrolysis process and method for preparing the same

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101318679A (en) * 2007-06-07 2008-12-10 多氟多化工股份有限公司 Method for preparing kryocide
CN101823741A (en) * 2010-02-03 2010-09-08 中南大学 Method for continuously producing aluminium electrolysis raw materials high-fluorine alumina, cryolite and sodium silicate with aluminum dust
CN101804996A (en) * 2010-04-02 2010-08-18 北京矿冶研究总院 Method for recovering sodium fluoride from electrolytic aluminum waste cathode carbon block
US8679318B2 (en) * 2012-05-23 2014-03-25 Shenzhen Sunxing Light Alloys Materials Co., Ltd. Electrolyte supplement system in aluminium electrolysis process and method for preparing the same
CN102732914A (en) * 2012-07-25 2012-10-17 深圳市新星轻合金材料股份有限公司 Method for preparing electrolyte and supplementing system thereof in aluminum electrolysis process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108677020A (en) * 2018-06-19 2018-10-19 东北大学 It is a kind of by aluminium scrap electrolyte is innoxious and recycling processing method
CN108677020B (en) * 2018-06-19 2019-09-24 东北大学 It is a kind of by aluminium scrap electrolyte is innoxious and recycling processing method
CN112342386A (en) * 2020-10-19 2021-02-09 东北大学 Resource treatment method for complex aluminum electrolyte
CN112342386B (en) * 2020-10-19 2021-07-20 东北大学 Resource treatment method for complex aluminum electrolyte

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