CN112646972B - Method for separating vanadium and chromium from vanadium and chromium-containing material through chlorination-selective oxidation - Google Patents

Method for separating vanadium and chromium from vanadium and chromium-containing material through chlorination-selective oxidation Download PDF

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CN112646972B
CN112646972B CN202011273171.3A CN202011273171A CN112646972B CN 112646972 B CN112646972 B CN 112646972B CN 202011273171 A CN202011273171 A CN 202011273171A CN 112646972 B CN112646972 B CN 112646972B
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vanadium
chromium
chlorination
crcl
alcl
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CN112646972A (en
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王丽君
刘仕元
薛未华
周国治
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/08—Chloridising roasting
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium

Abstract

A method for separating vanadium and chromium from a material containing vanadium and chromium by chlorination-selective oxidation belongs to the technical field of chemical industry for extracting vanadium and chromium. Which comprises the following steps: under inert atmosphere, chloridizing vanadium-containing material to obtain VCl3‑CrCl3‑FeCl3‑AlCl3Then the chlorination product is subjected to selective oxidation reaction under the conditions of certain oxygen partial pressure and chlorination partial pressure to obtain VOCl3Gas and gas containing AlCl3‑CrCl3Salts of the VOCl3Collecting gas as a raw material for preparing a vanadium product; will contain CrCl3‑AlCl3Salt, heating under inert atmosphere to obtain AlCl gas3And containing CrCl3A salt. Compared with the traditional extraction method, ion exchange method, crystallization separation method and other methods, the method has short vanadium and chromium separation process and does not generate wastewater. Aiming at the problem that chromium in the traditional oxidized high-chromium vanadium slag is high-toxicity hexavalent chromium, the method avoids the generation of the high-toxicity hexavalent chromium.

Description

Method for separating vanadium and chromium from vanadium and chromium-containing material through chlorination-selective oxidation
Technical Field
The invention relates to the technical field of vanadium and chromium extraction chemical industry, in particular to a method for separating vanadium and chromium by chlorination-selective oxidation of a vanadium and chromium-containing material.
Background
Vanadium is used as a strategic metal and has important application in the industries of steel, batteries, catalysts and the like. China produces a large amount of vanadium every year, and about 85 percent of vanadium is applied to alloy steel smelting. Chromium can improve the oxidation resistance and corrosion resistance of steel and is an important alloy element of heat-resistant steel.
The vanadium titano-magnetite is a complex symbiotic mineral rich in iron, vanadium, chromium, titanium and other valuable components, and is a significant characteristic strategic resource in China. 4 is generated in the vanadium titano-magnetite smelting process every year in ChinaAbout 0 ten thousand tons of vanadium slag, wherein the vanadium slag contains valuable metals of vanadium and chromium. V in vanadium slag2O3Content 13-19 wt.%, Cr2O3In an amount of 1-6 wt.%. The vanadium slag mainly comprises the following phases: spinel phases (ferrovanadium spinel, vanadochium manganese spinel and ferrotitanium spinel), silicate phases (fayalite) and metallic iron phases. Vanadium exists in ferrovanadium spinel (FeV) mainly in trivalent form2O4) In which chromium is also present mainly in trivalent form in the hercynite (FeCr)2O4) In (1). At present, the comprehensive utilization of vanadium slag in industry mainly adopts a roasting-leaching method to ensure that pentavalent vanadium and hexavalent chromium enter a solution simultaneously. Because vanadium and chromium have very similar chemical properties, how to economically and effectively separate and extract vanadium and chromium from vanadium and chromium-containing slag becomes a worldwide problem. In patent 200610089232 "a method for separating and recovering vanadium and chromium from a vanadium-chromium-containing solution", a vanadium-chromium separation method is disclosed, wherein vanadium and chromium are separated by extraction; in patent 201410204195.1 "a method for the electrolytic separation of vanadium and chromium from a vanadium-chromium containing solution" the separation of pentavalent vanadium and hexavalent chromium in the solution is carried out by an electrochemical process. But the valence state of chromium is changed from trivalent to hexavalent, and the toxicity of chromium is increased by one hundred times. The valence state of vanadium is changed from trivalent to pentavalent, and the toxicity of vanadium is greatly increased. In order to reduce the harm of high-valence vanadium and chromium to the environment, it is very meaningful to research a new process for effectively extracting trivalent vanadium and trivalent chromium. In the patent 201611174538.X "a method for extracting iron and manganese from solid" we propose a method for selectively extracting iron and manganese, and in the patent 201610211017.0 "a method for extracting titanium, iron, manganese, vanadium and chromium from vanadium slag of iron and steel plant" we propose a new process for extracting vanadium and chromium, so as to obtain trivalent vanadium and trivalent chromium. Thus, after two chlorination treatments, the product containing VCl3And CrCl3The molten salt system of (1). In patent 201810117370.1 "a method for electrolytic separation of vanadium and chromium in vanadium-chromium-containing molten salt" it is mentioned that the separation of vanadium and chromium is achieved by molten salt electrolysis, and the separation temperature is high.
Disclosure of Invention
The invention aims to effectively separate vanadium and chromium from a material containing vanadium and chromium, and specifically comprises the following steps:
1) under inert atmosphere, chloridizing vanadium-containing material to obtain VCl3-CrCl3-FeCl3-AlCl3Then the chlorination product is subjected to selective oxidation reaction under the conditions of certain oxygen partial pressure and chlorination partial pressure to obtain VOCl3Gas and gas containing AlCl3-CrCl3Salts of the VOCl3Collecting gas as a raw material for preparing a vanadium product;
2) the AlCl obtained in the step 1)3-CrCl3Salt, under inert atmosphere, heating to obtain AlCl gas3And containing CrCl3A salt.
Further, the vanadium-containing material in the step 1) comprises any one or combination of more of vanadium slag, vanadium titano-magnetite, vanadium mica and stone coal.
Further, the inert atmosphere in step 1) includes one or more of nitrogen, argon and helium.
Further, the vanadium-containing material in the step 1) is chloridized by a chlorinating agent which comprises anhydrous aluminum trichloride and KCl, wherein the KCl is used for forming a low-melting-point molten salt, and one or more chlorides can be selected from alkali metal chlorides or alkaline earth metal chlorides to form the molten salt.
Further, the oxygen partial pressure in the step 1) is controlled by selecting one or more of air, carbon monoxide, carbon dioxide and oxygen; oxygen partial pressure less than 10-1atm。
Further, chlorine is selected to control the chlorine partial pressure in the step 1); chlorine partial pressure greater than 10-10atm。
Further, the temperature of the selective oxidation reaction in the step 1) is 130-800 ℃; the selective oxidation time is generally from 0.5 to 8 h.
Further, the heating temperature in the step 2) is 200-500 ℃; the reaction time is 0.5-8 h. The invention has the following characteristics:
(1) the invention provides a novel method for separating vanadium and chromium in a vanadium-containing material through chlorination-selective oxidation. VOCl with low boiling point for vanadium3Volatile as (127 ℃), chromium as high-boiling CrCl3(953 ℃ C.) shapeFormula (iii) is present in solid salts. Aiming at the problem that chromium in the traditional oxidized high-chromium vanadium slag is high-toxicity hexavalent chromium, the method avoids the generation of the high-toxicity hexavalent chromium.
V2O3+2AlCl3＝Al2O3+2VCl3
Cr2O3+2AlCl3＝Al2O3+2CrCl3
2VCl3+O2＝2VOCl3
(2) The method does not relate to a water phase system in the vanadium-chromium separation process, and avoids the problem that a large amount of wastewater is generated in the existing method for separating vanadium and chromium from an aqueous solution.
Detailed Description
The specific examples described herein are for the purpose of illustrating the invention only and are not intended to limit the invention, and it will be understood by those skilled in the art that the method of the present invention is not limited to the separation of vanadium from vanadium slag, vanadium titano-magnetite, vanadium mica and stone coal.
Example 1
Mechanically mixing 40 g of dried vanadium slag powder, 65 g of potassium chloride powder and 100 g of aluminum chloride powder in a certain steel and iron plant in China, putting the mixture into a crucible, putting the crucible into a vertical furnace filled with high-purity argon, heating to 900 ℃, and preserving heat for 0.5 h; and cooling the chloridized vanadium slag to 150 ℃, starting to introduce carbon monoxide, carbon dioxide and high-purity argon, preserving heat for 2 hours, continuously heating to 250 ℃ after heat preservation is finished, and preserving heat for 2 hours. Finally obtaining VOCl3、AlCl3And containing CrCl3A salt.
Example 2
Mechanically and uniformly mixing 40 g of dry vanadium titano-magnetite, 65 g of potassium chloride powder and 100 g of aluminum chloride powder, putting the mixture into a crucible, putting the crucible into a vertical furnace filled with high-purity argon, heating to 900 ℃, and preserving heat for 0.5 h; and cooling the chloridized vanadium slag to 140 ℃, starting to introduce carbon monoxide, carbon dioxide and high-purity argon, preserving heat for 2 hours, continuously heating to 250 ℃ after heat preservation is finished, and preserving heat for 2 hours. Finally obtaining VOCl3、AlCl3And containing CrCl3A salt.
Example 3
Mechanically mixing 40 g of dry vanadium mica powder, 65 g of potassium chloride powder and 100 g of aluminum chloride powder in a certain steel and iron plant in China, putting the mixture into a crucible, putting the crucible into a vertical furnace filled with high-purity argon, heating to 900 ℃, and preserving heat for 0.5 h; and cooling the chloridized vanadium slag to 160 ℃, starting to introduce carbon monoxide, carbon dioxide and high-purity argon, preserving heat for 2 hours, continuously heating to 250 ℃ after heat preservation is finished, and preserving heat for 2 hours. Finally obtaining VOCl3、AlCl3And containing CrCl3A salt.
Example 4
Mechanically mixing 40 g of dried stone coal powder, 65 g of potassium chloride powder and 100 g of aluminum chloride powder in a certain steel and iron plant in China, putting the mixture into a crucible, putting the crucible into a vertical furnace filled with high-purity argon, heating to 900 ℃, and preserving heat for 0.5 h; and cooling the chloridized vanadium slag to 160 ℃, starting to introduce carbon monoxide, carbon dioxide and high-purity argon, preserving heat for 2 hours, continuously heating to 250 ℃ after heat preservation is finished, and preserving heat for 2 hours. Finally obtaining VOCl3、AlCl3And containing CrCl3A salt.

Claims (5)

1. A method for separating vanadium and chromium from a material containing vanadium and chromium by chlorination-selective oxidation is characterized by comprising the following steps:
1) under the nitrogen or inert atmosphere, the vanadium-containing material is chloridized to obtain VCl3-CrCl3-FeCl3-AlCl3Then the chlorination product is subjected to selective oxidation reaction under the conditions of certain oxygen partial pressure and chlorination partial pressure to obtain VOCl3Gas and gas containing AlCl3-CrCl3Salts of the VOCl3Collecting gas as a raw material for preparing a vanadium product; the oxygen partial pressure is controlled by selecting one or more of air, carbon monoxide, carbon dioxide and oxygen; oxygen partial pressure less than 10-1atm; chlorine partial pressure is controlled by selecting chlorine; chlorine partial pressure greater than 10-10atm; the reaction temperature is 130-800 ℃; the selective oxidation time is 0.5-8 h;
2) the AlCl obtained in the step 1)3-CrCl3Heating salt under inert atmosphere to obtain AlCl gas3And containing CrCl3Salt to achieve AlCl3With CrCl3Separation of (4).
2. The method for separating vanadium and chromium from a vanadium and chromium-containing material by chlorination-selective oxidation according to claim 1, wherein the vanadium-containing material in the step 1) comprises any one or more of vanadium slag, vanadium titanomagnetite, vanadium mica and stone coal.
3. The method for separating vanadium and chromium from a vanadium and chromium containing material by chlorination-selective oxidation as claimed in claim 1, wherein the inert atmosphere in step 1) comprises one or more of argon and helium.
4. The chlorination-selective oxidation method for separating vanadium and chromium from vanadium and chromium-containing material according to claim 1, wherein the vanadium-containing material in the step 1) is chlorinated by using a chlorinating agent comprising anhydrous aluminum trichloride and KCl, wherein the KCl is used for forming a low-melting-point molten salt.
5. The method for separation of vanadium and chromium from a vanadium and chromium containing material by chlorination-selective oxidation as claimed in claim 1, wherein the heating temperature in step 2) is 200-500 ℃; the reaction time is 0.5-8 h.
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CN113234935B (en) * 2021-05-10 2022-04-01 北京科技大学 Method for co-extracting vanadium, titanium and chromium from vanadium slag
CN115650290B (en) * 2022-12-22 2023-04-11 北京科技大学 Method for preparing high-purity vanadium oxychloride from vanadium-chromium slag through carbon-free low-temperature chlorination

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299016A (en) * 1963-09-03 1967-01-17 Phillips Petroleum Co Polymers of 1-monoolefins and an alkenyl acetylene and process for preparing same
CN101121962A (en) * 2006-08-10 2008-02-13 中国科学院过程工程研究所 Method for separating and reclaiming vanadium and chromium from solution containing vanadium and chromium
CN101845552A (en) * 2010-04-23 2010-09-29 河北钢铁股份有限公司承德分公司 Method for reclaiming valuable element through gradient chlorination of vanadium slag
CN103130279A (en) * 2011-11-29 2013-06-05 刘艳梅 Method for producing high-purity vanadium pentoxide by chlorination
CN103966438A (en) * 2014-05-14 2014-08-06 攀钢集团攀枝花钢铁研究院有限公司 Method for electrolytic separation of vanadium and chromium in vanadium-chromium containing solution
CN105087932A (en) * 2015-09-01 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 Method for removing silicon in acid vanadium-enriched liquid and preparation method of vanadium oxide
CN105567964A (en) * 2015-12-28 2016-05-11 中南大学 Method for selectively reducing, separating and recycling vanadium and chrome from solution containing vanadium and chrome
CN105984897A (en) * 2015-01-30 2016-10-05 中国科学院过程工程研究所 System and method for producing high-purity vanadium pentoxide powder
CN109835951A (en) * 2017-11-24 2019-06-04 中国科学院过程工程研究所 A kind of system and method for chloridising production powder vanadium

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL291029A (en) * 1962-04-07
CN102127654B (en) * 2010-01-13 2013-01-23 中国科学院过程工程研究所 Method for decomposing chromium-containing vanadium slag by using sodium hydroxide molten salt
CN104313361B (en) * 2014-10-16 2016-11-23 中国科学院过程工程研究所 A kind of Leaching of Vanadium from Vanadium slag containing chromium and the process of coproduction chromium-base alloy
CN105984898B (en) * 2015-01-30 2017-06-13 中国科学院过程工程研究所 A kind of system and method for producing high-purity vanadium tetraoxide powder
CN109868370B (en) * 2019-04-19 2020-09-29 重庆科技学院 Method for recovering valuable metals in vanadium-chromium slag

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299016A (en) * 1963-09-03 1967-01-17 Phillips Petroleum Co Polymers of 1-monoolefins and an alkenyl acetylene and process for preparing same
CN101121962A (en) * 2006-08-10 2008-02-13 中国科学院过程工程研究所 Method for separating and reclaiming vanadium and chromium from solution containing vanadium and chromium
CN101845552A (en) * 2010-04-23 2010-09-29 河北钢铁股份有限公司承德分公司 Method for reclaiming valuable element through gradient chlorination of vanadium slag
CN103130279A (en) * 2011-11-29 2013-06-05 刘艳梅 Method for producing high-purity vanadium pentoxide by chlorination
CN103966438A (en) * 2014-05-14 2014-08-06 攀钢集团攀枝花钢铁研究院有限公司 Method for electrolytic separation of vanadium and chromium in vanadium-chromium containing solution
CN105984897A (en) * 2015-01-30 2016-10-05 中国科学院过程工程研究所 System and method for producing high-purity vanadium pentoxide powder
CN105087932A (en) * 2015-09-01 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 Method for removing silicon in acid vanadium-enriched liquid and preparation method of vanadium oxide
CN105567964A (en) * 2015-12-28 2016-05-11 中南大学 Method for selectively reducing, separating and recycling vanadium and chrome from solution containing vanadium and chrome
CN109835951A (en) * 2017-11-24 2019-06-04 中国科学院过程工程研究所 A kind of system and method for chloridising production powder vanadium

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Reaction process of vanadium dichloride oxide and vanadium trichloride with oxygen;Akimasa YAJIMA等;《Bulletin of the chemical society of japan》;19791231;第52卷(第12期);第3549-3552页 *
矾渣中有价元素Fe、Mn、V、Cr和Ti选择性氯化及高价值化基础研究;刘仕元;《中国博士学位论文全文数据库（电子期刊） 工程科技I辑》;20191215;B023-24 *

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