CN113003606A - Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution - Google Patents

Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution Download PDF

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CN113003606A
CN113003606A CN202110175001.XA CN202110175001A CN113003606A CN 113003606 A CN113003606 A CN 113003606A CN 202110175001 A CN202110175001 A CN 202110175001A CN 113003606 A CN113003606 A CN 113003606A
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China
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sodium
vanadium
ammonium
solution
vanadium pentoxide
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张廷安
吕国志
张伟光
豆志河
刘燕
赵秋月
张子木
傅大学
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Abstract

The method for preparing vanadium pentoxide by utilizing the multi-element circulation process and the sodium vanadate solution comprises the steps of taking the sodium vanadate solution as a raw material, preparing vanadium pentoxide by processes of ammonium salt vanadium precipitation, bipolar membrane electrolysis and the like, and realizing multi-element circulation of sodium, ammonium, sulfur and the like. The method comprises the following steps: firstly, adding ammonium sulfate into a sodium vanadate solution to obtain an ammonium polyvanadate precipitate and a vanadium precipitation solution with sodium sulfate as a main component; calcining ammonium polyvanadate to obtain a vanadium pentoxide product; electrolyzing the solution after vanadium precipitation by a bipolar membrane method to obtain sulfuric acid and sodium hydroxide; the sulfuric acid absorbs ammonia gas generated in the roasting process of ammonium polyvanadate to obtain ammonium sulfate, and the ammonium sulfate is returned to the vanadium precipitation process for recycling; sodium hydroxide returns to the previous step of sodium roasting to be used as a sodium source, and then sodium vanadate solution is obtained by water immersion to be used as a raw material for extracting vanadium. The method realizes the recycling and zero discharge of sodium, ammonium, sulfur and water in the process of preparing vanadium pentoxide by using sodium vanadate, and is a clean vanadium pentoxide production method.

Description

Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution
Technical Field
The invention belongs to the field of clean preparation of vanadium pentoxide, and particularly relates to a method for preparing vanadium pentoxide by utilizing a sodium, ammonium and sulfur multi-component circulation process and a sodium vanadate solution.
Background
The vanadium titano-magnetite in China is abundant in resources, the storage capacity can reach more than one billion tons at present, and vanadium slag generated in the smelting process by using the resources generally contains 10 to 15 percent of vanadium, so that the vanadium titano-magnetite is an important raw material for producing vanadium and vanadium products. Vanadium is 'modern industrial monosodium glutamate' and is an indispensable important material for developing modern industry, modern national defense and modern scientific technology. At present, vanadium and vanadium products are widely applied in the fields of batteries, special alloys, military industry, chemical industry, electronics, traffic and the like, and are continuously expanded in application in other fields, and have good development prospects. As a main raw material of vanadium and related products, the annual output of vanadium pentoxide in China currently reaches over 8 ten thousand tons. At present, relevant practitioners in China carry out a great deal of research on the preparation of vanadium pentoxide by using a sodium vanadate solution.
The patent of 'a clean production method of vanadium oxide' with the application number of 200810305601.8 discloses a production method of vanadium oxide, which comprises the steps of preparing a roasting raw material, calcifying roasting, leaching, solid-liquid separation, ammonium salt vanadium precipitation, calcining deamination or reduction and the like to prepare vanadium oxide, neutralizing vanadium extraction waste water with lime milk, and returning the neutralized waste water to a system for recycling, thereby realizing zero discharge of waste water;
the patent of 'concentration and cold separation method of sodium sulfate and ammonium sulfate in vanadium precipitation mother liquor high-salt wastewater' with the application number of 201110112096.7 discloses a treatment method of vanadium precipitation mother liquor, wherein after vanadium and chromium are removed from the wastewater mother liquor, the mother liquor is evaporated and concentrated at 75 ℃ and 65 ℃ to separate out anhydrous sodium sulfate by crystallization, the anhydrous sodium sulfate is separated out by centrifugation, the separated dense slurry is cooled and cooled to 0-5 ℃ to separate out ammonium sulfate and sodium sulfate double salt, and the residual liquid is an ammonium sulfate solution which enters a storage tank to be directly recycled; and drying the double salt, mixing with the separated anhydrous sodium sulfate, packaging and combining for use.
The patent of 'a method for recycling acid vanadium precipitation wastewater' with the application number of 201210334185.0 discloses a method for recycling acid vanadium precipitation wastewater, which comprises the following steps: adjusting the acidic vanadium precipitation wastewater to be alkaline by using lime milk, and then carrying out solid-liquid separation to obtain an alkaline solution and gypsum residues; adding a decalcifying agent into the alkaline solution for decalcification, and then carrying out solid-liquid separation to obtain supernatant and decalcification residues; and adjusting the pH value of the supernatant to 3-7 by using sulfuric acid, and then returning the supernatant to the leaching process for recycling.
At present, vanadium pentoxide is mainly produced by treating a sodium vanadate solution obtained by sodium salt roasting, water leaching, calcification roasting, sodium carbonate leaching, sub-molten salt leaching, calcification roasting, sulfuric acid leaching, ion exchange/solvent extraction and other processes of vanadium slag, wherein the sodium vanadate solution is precipitated to obtain ammonium metavanadate or ammonium polyvanadate, and then is calcined to obtain vanadium pentoxide, and ammonium chloride and an ammonium sulfate solution are generally adopted as ammonium salt precipitators at present. Problems currently existing in this process: 1. sodium salt in the vanadium precipitation mother liquor can be gradually enriched after being circulated for many times and is difficult to utilize; 2. the ammonium in the ammonium salt is finally discharged in the form of ammonia gas in the calcining process, so that the ammonium is difficult to recycle, the cost is increased, and the environment is polluted.
Disclosure of Invention
Aiming at the technical defects existing in the process of producing vanadium pentoxide by using the existing sodium vanadate solution, the invention provides a sodium, ammonium and sulfur multi-component circulation treatment process and a method for cleanly preparing vanadium pentoxide by using the sodium vanadate solution, and the method is carried out according to the following steps:
(1) adjusting the acid of sodium vanadate solution and then performing VO (vanadium oxide) regulation3 -And NH4 +Adding an ammonium sulfate solution with the concentration of 50-300 g/L in the proportion of 1-2.5, mixing, heating to 70-95 ℃, stirring at the rotation speed of 200-500r/min, keeping the temperature for precipitating vanadium for 1-2 hours, precipitating and filtering after the reaction is finished to obtain ammonium polyvanadate, wherein the solution after the precipitation is a sodium sulfate solution, and the obtained ammonium polyvanadate is calcined to obtain vanadium pentoxide with the content of not less than 98.7 percent and simultaneously generate ammonia gas; the calcination temperature of the ammonium polyvanadate is 400-800 ℃, and the calcination time is 2-4 hours;
(2) obtaining sulfuric acid and sodium hydroxide from the obtained sodium sulfate solution by a bipolar membrane method electrolysis method; wherein the obtained sodium hydroxide is returned to the sodium salt roasting link to be used as a sodium source, and then is soaked in water to obtain a sodium vanadate solution;
(3) and (3) sulfuric acid obtained by the bipolar membrane method electrolysis method is used for absorbing ammonia gas generated in the calcining process of ammonium polyvanadate, and ammonium sulfate is returned to the vanadium precipitation process in the step (1) for recycling after being obtained through reaction.
The method for preparing vanadium pentoxide by utilizing the multi-component circulation process and the sodium vanadate solution comprises the following steps:
in the step (1), sodium vanadate solution is obtained through the sodium salt roasting-water leaching process of vanadium slag; adjusting the pH value range of the sodium vanadate solution to 1.8-2.5 by sulfuric acid. The reaction of the intermediate precipitation vanadium and the calcination process is as follows:
and (3) vanadium precipitation process:
6NaVO3+2H2SO4+(NH4)2SO4＝(NH4)2V6O16+3Na2SO4+2H2O
and (3) calcining:
(NH4)2V6O16＝2NH3+3V2O5+H2O
in the step (2), the reaction of sulfuric acid and sodium hydroxide obtained by electrolyzing the sodium sulfate solution obtained after the vanadium precipitation of the ammonium salt by using a bipolar membrane method is as follows:
Na2SO4+2H2O＝2NaOH+H2SO4
the invention has the beneficial effects that:
(1) sodium, ammonium and sulfur related in the reaction system can be recycled, ammonia emission is avoided, and the environment-friendly effect is obvious;
(2) the sodium salt is converted into a form of sodium hydroxide and directly returned to the sodium salt roasting process as a raw material, so that the operation cost of vanadium extraction is reduced.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention.
Detailed Description
The process flow of the embodiments 1-3 of the invention is shown in FIG. 1.
The sodium vanadate solution adopted by the embodiment of the invention is from a sodium roasting-sodium carbonate leaching process, and the concentration is 8.45 g/L;
the production content of the invention is not limited to the adoption of the raw materials, and any solution containing sodium vanadate can be treated by adopting the method.
Example 1
A method for preparing vanadium pentoxide by utilizing a multi-component circulation process and a sodium vanadate solution comprises the following specific operation steps:
(1) adjusting the pH value of the sodium vanadate solution to 2.5 by sulfuric acid, and then according to VO3 -And NH4 +Adding ammonium sulfate with the concentration of 50g/L according to the molar ratio of 1:1, heating to 70 ℃, keeping the temperature for 2 hours at the stirring speed of 200r/min, completing vanadium precipitation reaction, precipitating and filtering to obtain ammonium polyvanadate, wherein the solution after precipitation is a sodium sulfate solution; the obtained sodium polyvanadate solid is calcined for 4 hours at 400 ℃ after being washed; obtained V2O5Content greater than 99.2%, K2O+Na2A vanadium pentoxide product with O content of 0.19% and S content less than 0.01%;
(2) obtaining sulfuric acid and sodium hydroxide from the obtained sodium sulfate solution by a bipolar membrane method electrolysis method; wherein the obtained sodium hydroxide is returned to the sodium salt roasting link to be used as a sodium source, and then is soaked in water to obtain a sodium vanadate solution;
(3) and (3) sulfuric acid obtained by the bipolar membrane method electrolysis method is used for absorbing ammonia gas generated in the calcining process of ammonium polyvanadate, and ammonium sulfate is returned to the vanadium precipitation process in the step (1) for recycling after being obtained through reaction.
Example 2
A method for preparing vanadium pentoxide by utilizing a multi-component circulation process and a sodium vanadate solution comprises the following specific operation steps:
(1) adjusting the pH value of the sodium vanadate solution to 1.8 by sulfuric acid, and then according to VO3 -And NH4 +Adding ammonium sulfate with the concentration of 250g/L according to the molar ratio of 1:2, heating to 95 ℃, keeping the temperature for 2 hours at the stirring speed of 500r/min, completing vanadium precipitation reaction, precipitating and filtering to obtain ammonium polyvanadate, wherein the solution after precipitation is a sodium sulfate solution; the obtained sodium polyvanadate solid is calcined for 3 hours at 800 ℃ after being washed; obtained V2O5Content greater than 99.3%, K2O+Na2A vanadium pentoxide product with O content of 0.31% and S content less than 0.01%;
(2) obtaining sulfuric acid and sodium hydroxide from the obtained sodium sulfate solution by a bipolar membrane method electrolysis method; wherein the obtained sodium hydroxide is returned to the sodium salt roasting link to be used as a sodium source, and then is soaked in water to obtain a sodium vanadate solution;
(3) and (3) sulfuric acid obtained by the bipolar membrane method electrolysis method is used for absorbing ammonia gas generated in the calcining process of ammonium polyvanadate, and ammonium sulfate is returned to the vanadium precipitation process in the step (1) for recycling after being obtained through reaction.
Example 3
A method for preparing vanadium pentoxide by utilizing a multi-component circulation process and a sodium vanadate solution comprises the following specific operation steps:
(1) adjusting the pH value of the sodium vanadate solution to 2.5 by sulfuric acid, and then according to VO3 -And NH4 +Adding 200g/L ammonium sulfate according to the molar ratio of 1:2.5, heating to 90 ℃, stirring at the rotating speed of 350r/min, preserving the heat for 1 hour to complete vanadium precipitation reaction, precipitating and filtering to obtain ammonium polyvanadate, wherein the solution after precipitation is a sodium sulfate solution; the obtained sodium polyvanadate solid is calcined for 4 hours at 800 ℃ after being washed; obtained V2O5Content greater than 99.24%, K2O+Na2A vanadium pentoxide product with O content of 0.24% and S content less than 0.01%;
(2) obtaining sulfuric acid and sodium hydroxide from the obtained sodium sulfate solution by a bipolar membrane method electrolysis method; wherein the obtained sodium hydroxide is returned to the sodium salt roasting link to be used as a sodium source, and then is soaked in water to obtain a sodium vanadate solution;
(3) and (3) sulfuric acid obtained by the bipolar membrane method electrolysis method is used for absorbing ammonia gas generated in the calcining process of ammonium polyvanadate, and ammonium sulfate is returned to the vanadium precipitation process in the step (1) for recycling after being obtained through reaction.

Claims (2)

1. A method for preparing vanadium pentoxide by utilizing a multi-component circulation process and a sodium vanadate solution is characterized by comprising the following steps:
(1) adjusting the acid of sodium vanadate solution and then performing VO (vanadium oxide) regulation3 -And NH4 +Adding an ammonium sulfate solution with the concentration of 50-300 g/L in the proportion of 1-2.5, mixing, heating to 70-95 ℃, stirring at the rotation speed of 200-500r/min, keeping the temperature for precipitating vanadium for 1-2 hours, precipitating and filtering after the reaction is finished to obtain ammonium polyvanadate, wherein the solution after the precipitation is a sodium sulfate solution, and the obtained ammonium polyvanadate is calcined to obtain vanadium pentoxide with the content of not less than 98.7 percent and simultaneously generate ammonia gas; the calcination temperature of the ammonium polyvanadate is 400-800 ℃, and the calcination time is 2-4 hours;
(2) obtaining sulfuric acid and sodium hydroxide from the obtained sodium sulfate solution by a bipolar membrane method electrolysis method;
(3) and (3) sulfuric acid obtained by the bipolar membrane method electrolysis method is used for absorbing ammonia gas generated in the calcining process of ammonium polyvanadate, and ammonium sulfate is obtained through reaction and then returns to the vanadium precipitation process in the step (1).
2. The method for preparing vanadium pentoxide according to claim 1, wherein in the step (1), the pH value of the sodium vanadate solution is adjusted to 1.8-2.5 by sulfuric acid.
CN202110175001.XA 2021-02-09 2021-02-09 Method for preparing vanadium pentoxide by utilizing multi-component circulation process and sodium vanadate solution Pending CN113003606A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115072778A (en) * 2022-07-27 2022-09-20 西安航天华威化工生物工程有限公司 Ammonium polyvanadate continuous reaction crystallization process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102219257A (en) * 2011-04-01 2011-10-19 中国恩菲工程技术有限公司 Method for preparing vanadium pentoxide
CN102476880A (en) * 2010-11-26 2012-05-30 攀钢集团钢铁钒钛股份有限公司 Treatment method of wastewater with sedimentated vanadium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102476880A (en) * 2010-11-26 2012-05-30 攀钢集团钢铁钒钛股份有限公司 Treatment method of wastewater with sedimentated vanadium
CN102219257A (en) * 2011-04-01 2011-10-19 中国恩菲工程技术有限公司 Method for preparing vanadium pentoxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115072778A (en) * 2022-07-27 2022-09-20 西安航天华威化工生物工程有限公司 Ammonium polyvanadate continuous reaction crystallization process

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