CN109911946A

CN109911946A - A method for recycling waste saggars in the preparation process of lithium cobalt oxide battery materials

Info

Publication number: CN109911946A
Application number: CN201711330025.8A
Authority: CN
Inventors: 孙振华; 李少鹏; 李会泉
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2017-12-13
Filing date: 2017-12-13
Publication date: 2019-06-21
Anticipated expiration: 2037-12-13
Also published as: CN109911946B

Abstract

The invention provides a method for recycling and processing waste saggars in the preparation process of lithium cobalt oxide battery materials. The discarded saggar contains silicon, aluminum and magnesium impurities, and the method includes the following steps: 1) mixing the discarded saggar, acid solution and additives, carrying out a leaching reaction, and separating after the reaction to obtain a purification saggar and leachate; 2) adjusting The pH of the leachate is adjusted to 2-5, and the solid slag and the separation solution are obtained by separation; 3) Add an aluminum remover to the separation solution, crystallize, and then separate to obtain the solid slag and the aluminum removal solution; 4) Adjust the pH of the aluminum removal solution to ≥8.5, Separating to obtain cobalt-containing material and cobalt-precipitating liquid; 5) adding a magnesium removing agent to the cobalt-precipitating liquid, adjusting pH≥11, and separating to obtain solid slag and a magnesium-removing liquid; 6) adding a precipitating agent to the magnesium-removing liquid for reaction , the lithium-containing material and the lithium-precipitating liquid are obtained by separation. The method of the invention realizes the recovery and utilization of cobalt and lithium in the discarded saggar, and the discarded saggar is purified, which is easy for industrialized production.

Description

The method of saggar recovery processing is discarded in a kind of cobalt acid lithium battery material preparation process

Technical field

The present invention relates to the method for new energy industry solid waste recovery processing more particularly to a kind of cobalt acid lithium batteries just The method of saggar recovery processing is discarded in the material preparation process of pole.

Background technique

In recent years, with vigorously supporting for national policy and quickly propelling for the current energy and information industry, with electronic Automobile is that the New Energy Industry of representative is grown rapidly, and lithium battery industry is developed rapidly therewith, and will greatly be driven up and down The rapid development of trip industry.

Lithium cobaltate cathode material is widely used as a kind of important cell positive material in new energy field, and due to just The upgrading of pole material development.It is usually carried out using mullite Cordierite Basic Sagger as container in the sintering procedure of cobalt acid lithium powder Pyroreaction.Cobalt acid lithium raw material reacts with saggar after roasting, cause saggar ontology physical property reduction, it is difficult to further into Row roasting positive electrode, while discarded saggar remained on surface part lithium cobalt powder body, directly return can not prepare saggar process, if energy It realizes valuable metal recovery and saggar is used to prepare new saggar raw material, then can have good economic and social profit.

The current method of comprehensive utilization for discarded saggar is less, and application mode focuses primarily upon refractory material or ceramics The production process of material.CN101284723A discloses " a method of utilize the empty clay brick of useless sagger preparation the 7th ", is The useless saggar of ceramsite propping agent sintering procedure progress water is further crushed classification thickness material as a kind of original after bored, cleaning Material be added to the sintering procedure of low stomata clay brick, it can be achieved that useless saggar utilization, reduce environmental pollution and save natural resources, However lithium cobaltate cathode material discards saggar since there are also alkali metal for itself, it is difficult to direct Returning utilization.CN103383192A is public Opened " using the method for discarded saggar production saggar product ", the saggar discarded using household porcelain production process by smashing, After ball milling, screening be used as a kind of clinker, after through mix with raw material, practice, molding, roast etc. can be made into aluminium silicon magnesium saggar, The additional amount of useless saggar up to the 50% of raw material, stablize by saggar quality of item, meets relevant criterion.However, lithium cobaltate cathode material Expect that production process discards saggar since the alkali metal on surface reacts, causes to be difficult to direct Returning utilization, and there is no related at present New energy industry discards the pertinent literature report of saggar comprehensive utilization.And with the fast development of new energy industry, new energy row The demand of the useless saggar comprehensive utilization of industry will be more more and more urgent.

Therefore, it develops in a kind of cobalt acid lithium battery material preparation process and discards the method pair of saggar recovery processing comprehensive utilization It has great significance in this field.

Summary of the invention

Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of cobalt acid lithium battery material systems The method of discarded saggar recovery processing during standby.Method provided by the invention can carry out integrated treatment recycling to discarded saggar It utilizes, and simple process, reaction condition are mild, processing cost is low, product can comprehensively utilize, no waste water generates, and has good Social benefit and economic benefit.

In order to achieve the above object, the invention adopts the following technical scheme:

The present invention provides a kind of method that saggar recovery processing is discarded in cobalt acid lithium battery material preparation process, described discarded Saggar includes silicon, aluminium and magnesium addition, be the described method comprises the following steps:

(1) acid-leaching reaction: discarded saggar, acid solution and additive are mixed, and are carried out Leach reaction, are divided after reaction From being purified saggar and leachate；

(2) remove silicon: regulating step (1) the leachate pH to 2~5 is reacted, and is separated by solid-liquid separation to obtain after reaction Solid slag and separating liquid；

(3) it removes aluminium: aluminium removal is added into step (2) described separating liquid, is crystallized, solid-liquid point is carried out after the completion of crystallization From obtaining solid slag and except molten aluminum；

(4) heavy cobalt: pH >=8.5 except molten aluminum that regulating step (3) obtains are reacted, and solid-liquid point is carried out after reaction From obtaining substance containing cobalt and heavy cobalt liquid；

(5) demagging: demagging agent being added into step (4) the heavy cobalt liquid, adjusts pH >=11 and is reacted, solid-liquid after reaction Isolated solid slag and remove magnesium liquid；

(6) it sinker: is reacted to addition precipitating reagent in magnesium liquid is removed described in step (5), is separated by solid-liquid separation and is contained after reaction Lithium substance and sinker liquid.

In the present invention, step (2) regulating step (1) the leachate pH to 2~5, such as 2,3,4 or 5 etc., but simultaneously not only It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.

In the present invention, pH >=8.5 except molten aluminum that step (4) regulating step (3) obtains, such as 8.5,9,9.5 or 10 etc..

In the present invention, step (5) adjusts pH >=11, such as 11,12,13 or 14 etc..

In the present invention, using acidleach, removes silicon, except aluminium, heavy cobalt, demagging and sinker technique, it is discarded effectively to realize cobalt acid lithium The comprehensive reutilization of saggar, lithium, cobalt valuable element recovery utilization rate are high, while in turn ensuring and can use after discarded saggar is purified In production saggar or the raw material of refractory material, entire technical conditions are mild, and easy to operate, raw material cost is low, equipment Simply, there is preferable prospects for commercial application.

In step (1) of the present invention, the effect of additive is to promote the dissolution of cobalt, lithium etc. in acid system.Step (2) is adjusted Step (1) the leachate pH to 2~5, can be realized the precipitating of silicon, so that silicon is removed with the method being separated by solid-liquid separation, without independent Precipitating reagent is added.In step (4), continues to improve pH value to pH >=8.5, the substance containing cobalt to precipitate can be obtained, without single Precipitating reagent is solely added.The substance containing cobalt that step (4) obtains is thick cobalt mixture, wherein contain some impurity, it can be further smart System is to improve its quality.

In the present invention, cobalt acid lithium battery material system is carried out according to acidleach, except silicon, except the sequence of aluminium, heavy cobalt, demagging and sinker Discarded saggar recovery processing, steps up pH value during standby, it is ensured that dust removal rate improves lithium, the recycling of cobalt valuable element Utilization rate, while reducing the consumption of raw materials during recovery processing, save the cost.

It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.

As currently preferred technical solution, the gross mass to discard saggar is the quality of the element silicon in terms of 100% Score is 15wt%~20wt%, such as 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt% etc., but not It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 17.37wt%.

Preferably, be in terms of 100% by the gross mass for discarding saggar, the mass fraction of the aluminium element be 18wt%~ 23wt%, such as 18wt%, 19wt%, 20wt%, 21wt%, 22wt% or 23wt% etc., it is not limited to cited Numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 21.29wt%.

Preferably, be in terms of 100% by the gross mass for discarding saggar, the mass fractions of the magnesium elements be 3wt%~ 5wt%, such as 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt% etc., it is not limited to cited numerical value, the number It is equally applicable to be worth other unlisted numerical value in range, preferably 4.143wt%.

As the present invention preferably technical solution, in step (1), the acid solution is sulfuric acid solution.

Preferably, the concentration of the sulfuric acid solution is 0.5mol/L~5mol/L, such as 0.5mol/L, 1mol/L, 2mol/ L, 3mol/L, 4mol/L or 5mol/L etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range It is worth equally applicable, preferably 2mol/L~3mol/L.

Preferably, in step (1), the additive includes any one in hydrogen peroxide, sodium sulfite or sodium thiosulfate Kind or at least two combination, it is typical but be non-limiting combination and have: the combination of hydrogen peroxide and sodium sulfite, hydrogen peroxide and sulphur The combination etc. of the combination of sodium thiosulfate, sodium sulfite and sodium thiosulfate.In the present invention, the preferred additive of mentioned kind is Because the additive of mentioned kind is preferable to the reducing property of cobalt in sulfuric acid solution, preferably cobalt can be restored.

Preferably, in step (1), leaching is leached or is crushed using whole to discarded saggar in the Leach reaction.

Preferably, in step (1), the temperature of the Leach reaction is 10 DEG C~90 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C etc., it is not limited to cited numerical value, other are not arranged in the numberical range The numerical value of act is equally applicable, and preferably 30 DEG C~60 DEG C.

Preferably, in step (1), time of the Leach reaction is 6h~12h, for example, 6h, 7h, 8h, 9h, 10h, 11h or 12h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, in step (1), further include to the purification saggar washing after recycle, be used to prepare saggar or its Its refractory material.

Preferably, in step (1), discarded saggar is rejoined in Xiang Suoshu leachate and carries out Leach reaction, repeat to leach Process.

Preferably, in step (2), the pH for the leachate that neutralizer regulating step (1) obtains is used.

Preferably, the neutralizer includes any one in calcium oxide, calcium hydroxide or calcium carbonate or at least two Combination, it is typical but be non-limiting combination and have: the combination of the combination of calcium oxide and calcium hydroxide, calcium oxide and calcium carbonate, hydrogen Calcium oxide and the combination of calcium carbonate etc., but be not limited to the neutralizer enumerated, other are commonly used in the art to can reach identical effect The neutralizer of fruit can also be used for the present invention.Using the neutralizer of above-mentioned calcic, can not only play the role of adjusting pH, it can also be with Silicon forms calcium silicates, improves and removes silicon effect.Using above-mentioned calcic neutralizer when, solid slag obtained in step (2) is calcium slag.

Preferably, in step (2), adjusting pH value of solution is 2~3, such as 2,2.5 or 3 etc., it is not limited to cited Numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, in step (2), reaction time of the reaction is 0.5h~2h, such as 0.5h, 1h, 1.5h or 2h etc., It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, in step (2), the mode of the separation of solid and liquid is to be separated by filtration.

It preferably, further include that the solid slag is washed and filtered in step (2).

Preferably, the washing lotion of the washing is mixed into separating liquid described in step (2).In the present invention, use is this The cycling and reutilization of washing lotion may be implemented in mixing.

Preferably, step (2) further include: the leachate before neutralizer is added, first carry out being separated by filtration removing its In solid.

As currently preferred technical solution, in step (3), the aluminium removal is potassium sulfate.

Preferably, in step (3), the crystallization is crystallisation by cooling.

Preferably, in step (3), the temperature of the crystallization is -10 DEG C~30 DEG C, for example, -10 DEG C, -5 DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 20 DEG C or 30 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable With preferably -5 DEG C~10 DEG C.

Preferably, in step (3), time of the crystallization is 1h~2h, such as 1h, 1.5h or 2h etc., but is simultaneously not only limited It is equally applicable in other unlisted numerical value in cited numerical value, the numberical range.

Preferably, in step (3), the mode of the separation of solid and liquid is centrifugal filtration.

It preferably, further include being washed to the solid slag in step (3).

Preferably, in step (3), the solid slag is potassium alum.

As currently preferred technical solution, in step (4), described removed using what neutralizer regulating step (3) obtained The pH of molten aluminum.

Preferably, the neutralizer includes any one in calcium oxide, calcium hydroxide or potassium hydroxide or at least two Combination, it is typical but be non-limiting combination and have: the group of the combination of calcium oxide and calcium hydroxide, calcium oxide and potassium hydroxide It closes, calcium hydroxide and the combination of potassium hydroxide etc., but is not limited to the neutralizer enumerated, other are commonly used in the art to can reach The neutralizer of same effect can also be used for the present invention.It is described obtained in step (4) when using above-mentioned neutralizer in the present invention Substance containing cobalt is mainly cobalt hydroxide.

Preferably, in step (4), the pH except molten aluminum that regulating step (3) obtains is 8.5~10, such as 8.5,9, 9.5 or 10 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably It is 9.0~10.

Preferably, in step (4), reaction time of the reaction is 0.5h~5h, for example, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h or 5h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable With.

Preferably, in step (4), the mode of the separation of solid and liquid is to be separated by filtration.

It preferably, further include that the substance containing cobalt is washed and dried in step (4).

Preferably, the washing lotion of the washing is mixed into heavy cobalt liquid described in step (4).By the step for, Ke Yishi The recycling and reusing of existing washing lotion.

Preferably, in step (4), further include the purification of step (4 ') cobalt: the substance containing cobalt being added in acid solution and is carried out It re-dissolves to obtain lysate, aluminium removal and cleaner is added into lysate, first time separation of solid and liquid, Xiang Gu are carried out after reaction Precipitating reagent is added in the isolated liquid of liquid, mixes and carry out precipitation reaction, and second of solid-liquid point is carried out after precipitation reaction From solid is taken, the substance containing cobalt that is refined.

Preferably, in step (4 '), the acid solution is sulfuric acid solution.

Preferably, in step (4 '), the aluminium removal includes calcium oxide, calcium hydroxide, calcium carbonate, potassium hydroxide or carbonic acid In potassium any one or at least two combination.But it is not limited to the aluminium removal enumerated, other are commonly used in the art reachable Aluminium removal to same effect can also be used for the present invention.

Preferably, in step (4 '), the dosage of aluminium removal meets the pH 4~5 for making the lysate, such as 4,4.5 or 5 Deng, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 4.5~ 5。

Preferably, in step (4 '), the cleaner is fluorine-containing.It is because of fluorine-containing removal of impurities used here as fluorine-containing cleaner Agent can remove calcium and magnesium impurity by generating the sediments such as calcirm-fluoride, magnesium fluoride.

Preferably, in step (4 '), the cleaner is for any one in sodium fluoride, potassium fluoride or ammonium fluoride or at least Two kinds of combination.

Preferably, the dosage of the cleaner meets the total content of magnesium and calcium and fluorine ion in the lysate after aluminium removal is added Molar ratio is 1:2.

Preferably, in step (4 '), the mode that the first time is separated by solid-liquid separation is to be separated by filtration.

Preferably, in step (4 '), described be mixed into is stirred.

Preferably, in step (4 '), the precipitating reagent includes in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate Any one or at least two combination, it is typical but be non-limiting combination and have: the combination of sodium hydroxide and potassium hydroxide, hydrogen The combination etc. of the combination of potassium oxide and sodium carbonate, sodium carbonate and potassium carbonate.But it is not limited to the precipitating reagent enumerated, other abilities The precipitating reagent that domain commonly can reach same effect can also be used for the present invention.

Preferably, in step (4 '), the anionic charge sum that the dosage of the precipitating reagent meets precipitating reagent is no less than The charge sum of the secondary cobalt ions being separated by solid-liquid separation in obtained liquid.

Preferably, in step (4 '), the temperature of the precipitation reaction is 50 DEG C~80 DEG C, for example, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, in step (4 '), time of the precipitation reaction is 1h~3h, such as 1h, 2h or 3h etc., but simultaneously not only It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.

Preferably, in step (4 '), described second mode being separated by solid-liquid separation is to be separated by filtration.

It preferably, further include that the substance containing cobalt of the purification is washed and is dried to obtain to produce containing cobalt in step (4 ') Product.

Preferably, in step (4 '), the substance containing cobalt of the purification is cobalt carbonate and/or cobalt hydroxide." the cobalt carbonate And/or cobalt hydroxide " referring to can be cobalt carbonate, or cobalt hydroxide can also be the mixed of cobalt carbonate or cobalt hydroxide Close object.

Preferably, in step (4 '), further includes: calcic neutralizer first is added simultaneously before aluminium removal is added in the lysate Isolate the solid of generation.

Preferably, the calcic neutralizer include calcium oxide, calcium hydroxide, in calcium carbonate any one or at least two Combination.But it is not limited to the calcic neutralizer enumerated, other calcics that can reach same effect commonly used in the art neutralize Agent can also be used for the present invention.

Preferably, the solid of the generation is gypsum.

As currently preferred technical solution, in step (5), the demagging agent includes calcium oxide, calcium hydroxide or hydrogen In potassium oxide any one or at least two combination.But be not limited to cited demagging agent, other it is commonly used in the art can The demagging agent for reaching same effect can also be used for the present invention.

Preferably, in step (5), adjusting pH value is 11~13, such as 11,12 or 13 etc., it is not limited to cited Numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 11.5~12.5.

Preferably, in step (5), time of the reaction is 0.5h~5h, for example, 0.5h, 1.5h, 2.5h, 3h, 3.5h, 4.5h or 5h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, described to be separated by solid-liquid separation to be separated by filtration in step (5).

As currently preferred technical solution, in step (5), further includes step (5 ') concentration: will be removed described in step (5) Magnesium liquid is concentrated to get concentrate.

Preferably, in step (5 '), the mode of the concentration is to be concentrated by evaporation.

Preferably, in step (5 '), make concentration 20g/L~30g/L of Li in finally obtained concentrate, such as 20g/ L, 24g/L, 26g/L, 28g/L or 30g/L etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value it is equally applicable.

Preferably, in step (5 '), the condensed water that concentration process obtains is sharp again back to progress during washing or complex acid With.

As currently preferred technical solution, in step (6), the precipitating reagent is soluble carbonate salt solution.

Preferably, the soluble carbonate salt solution is solution of potassium carbonate.

Preferably, the soluble carbonate salt solution is saturated solution.

Preferably, in step (6), the temperature of the reaction is 80 DEG C~100 DEG C, such as 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C Or 100 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably It is 85 DEG C~95 DEG C.

Preferably, in step (6), time of the reaction is 0.5h~5h, for example, 0.5h, 1.5h, 2.5h, 3h, 3.5h, 4.5h or 5h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, in step (6), the mode of the separation of solid and liquid is to be separated by filtration.

It preferably, further include the substance containing lithium being washed and being dried to obtain product containing lithium in step (6).

Preferably, in step (6), the substance containing lithium is lithium carbonate.

Preferably, step (6) further include: to before described in step (5) except precipitating reagent is added in magnesium liquid, first to step (5) institute It states except potassium fluoride is added by the total content of magnesium and calcium and fluorine ion molar ratio 1:2 in magnesium liquid, is stirred to react and is filtered to remove solid therein.

As currently preferred technical solution, the method also includes step (7) crystallizations: to obtained in step (6) Obtained separating liquid is separated by solid-liquid separation in sinker liquid and step (4 ') for the second time to be crystallized, is separated by solid-liquid separation later, obtain solid and Separating liquid.

Preferably, the crystallization is crystallisation by cooling.

Preferably, the temperature of the crystallization is -10 DEG C~10 DEG C, such as -10 DEG C, -5 DEG C, 0 DEG C, 5 DEG C or 10 DEG C etc., but It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.

Preferably, the crystallization carries out in a crystallizer.

Preferably, the mode of the separation of solid and liquid is centrifuge separation.

Preferably, the isolated solid of solid is potassium sulfate.

Preferably, the potassium sulfate, which returns to, is used as aluminium removal in step (3), the cycling and reutilization of raw material may be implemented.

Preferably, the separating liquid is back to the preparation of progress precipitating reagent in step (6), it can be achieved that cycling and reutilization.

As the further preferred technical solution of the method for the invention, the described method comprises the following steps:

(1) acid-leaching reaction: by the discarded saggar comprising silicon, aluminium and magnesium addition, the sulfuric acid that concentration is 2mol/L~3mol/L Solution and additive mixing carry out Leach reaction, and reaction temperature is 30 DEG C~60 DEG C, and the reaction time is 6h~12h, the leaching Leaching is leached or is crushed using whole to discarded saggar in reaction, is separated after reaction, is purified saggar and leachate, To being recycled after purification saggar washing, it is used to prepare saggar or other refractory materials, is added again in Xiang Suoshu leachate Enter discarded saggar and carry out Leach reaction, repeats leaching process；Gross mass to discard saggar is the mass fraction of silicon in terms of 100% For 15wt%~20wt%, the mass fraction of aluminium is 18wt%~23wt%, and the mass fraction of magnesium is 3wt%~5wt%.

(2) it removes silicon: step (1) described leachate first being carried out to be separated by filtration removing solid therein, adds neutralizer, PH value of solution is adjusted to 2~3,0.5h~2h is reacted, is separated by filtration to obtain solid slag and separating liquid after reaction, to the solid Slag is washed and is filtered, and the washing lotion of washing is mixed into separating liquid described in step (2)；

(3) it removes aluminium: being added potassium sulfate into step (2) described separating liquid, carry out crystallisation by cooling, crystallization temperature is -5 DEG C~ 10 DEG C, crystallization time is 1h~2h, carries out centrifugal filtration after the completion of crystallization, obtains potassium alum and removes molten aluminum, to the potassium alum It is washed；

(4) heavy cobalt: described except neutralizer is added in molten aluminum to what step (3) obtained, adjusting pH is 9.0~10, reaction 2.5h~3.5h is separated by filtration to obtain substance containing cobalt and heavy cobalt liquid after reaction, the substance containing cobalt is washed and done It is dry, the washing lotion of washing is mixed into the heavy cobalt liquid；

The purification of (4 ') cobalt: the substance containing cobalt is added in sulfuric acid solution and is re-dissolved to obtain lysate, to dissolution Calcic neutralizer is added in liquid and isolates gypsum, aluminium removal, the dosage of aluminium removal is added into the lysate after separation gypsum Meet the pH 4.5~5 for making to separate the lysate after gypsum, add fluorine-containing cleaner, the dosage of cleaner, which meets, to be added The molar ratio of the total content of magnesium and calcium and fluorine ion in lysate after aluminium removal is 1:2, carries out being separated by filtration for the first time after reaction, to It is separated by solid-liquid separation obtained liquid and precipitating reagent is added, stir and carry out precipitation reaction, the temperature of precipitation reaction is 50 DEG C~80 DEG C, is sunk The time of shallow lake reaction is 1h~3h, is separated by filtration for the second time after precipitation reaction and takes solid, the object containing cobalt refined Matter is washed and is dried to the substance containing cobalt of the purification, and cobalt carbonate and/or cobalt hydroxide product are obtained；The precipitating reagent Including in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate any one or at least two combination；

(5) demagging: demagging agent being added into step (4) the heavy cobalt liquid, and adjusting pH is 11.5~12.5, and reaction 2.5h~ 3.5h is separated by filtration to obtain solid slag and except magnesium liquid after reaction；

(5 ') it is concentrated: being the concentration of 20g/L~30g/L by the concentration that magnesium liquid is concentrated by evaporation to obtain Li is removed described in step (5) Liquid, the condensed water that concentration process obtains are recycled in the process back to washing or complex acid；

(6) sinker: potassium fluoride is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium into step (the 5 ') concentrate and stirs It mixes and reacts and be filtered to remove solid therein, take filtrate, unsaturated carbonate potassium solution is added into filtrate and is reacted, reaction temperature It is 85 DEG C~95 DEG C, the time of reaction is 1.5h~2.5h, is separated by filtration to obtain lithium carbonate and sinker liquid after reaction, to the carbon Sour lithium is washed and is dried to obtain lithium carbonate product；

(7) it crystallizes: to the separating liquid being separated by filtration for the second time in sinker liquid obtained in step (6) and step (4 ') Crystallisation by cooling is carried out in a crystallizer, and crystallization temperature is -10 DEG C~10 DEG C, is centrifugated later, obtains potassium sulfate solid and divides Chaotropic, the potassium sulfate return to and are used as aluminium removal in step (3), and the separating liquid carries out saturated carbon back to step (6) are middle The preparation of sour potassium solution.

Compared with the prior art, the invention has the following beneficial effects:

(1) the present invention provides for a whole set of side for discarding saggar comprehensive utilization in cobalt acid lithium battery material preparation process Method efficiently realizes the recycling for discarding the valuable cobalt and lithium of saggar in lithium cobaltate cathode material production process, removes aluminium rate Up to 76%, the recovery rate of cobalt element is up to 74%, and the recovery rate of elemental lithium is up to 83%, while discarded saggar is purified, Reaction condition is mild, and technical process is simple, and equipment requirement is low, and raw material sources are extensive, cheap, it is easy to accomplish industrial metaplasia It produces.

(2) it in method provided by the invention, is refined, can significantly be mentioned by the substance containing cobalt obtained to step (4) The purity of high finally obtained cobalt product, reduces impurity content.

(3) in method provided by the invention, the waste that multiple steps generate is all recyclable to be recycled, not only saved cost but also Reduce waste discharge.

Detailed description of the invention

Saggar recovery processing is discarded in a kind of lithium cobaltate cathode material preparation process that Fig. 1 provides for the embodiment of the present invention 1 Method flow diagram, arrow direction is the process flow direction for the method that the embodiment of the present invention 1 provides in figure.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.But following embodiments are only Simple example of the invention does not represent or limits the scope of the present invention, and the scope of the present invention is with claim Subject to book.

Embodiment 1

The present embodiment provides a kind of methods that saggar recovery processing is discarded in cobalt acid lithium battery material preparation process.It is specific Method are as follows:

(1) discarded saggar described in table 1 is immersed in the leaching tanks for the 10L sulfuric acid that molar concentration is 2mol/L and is carried out instead It answers, the hydrogen peroxide that 100mL is added carries out room temperature Leach reaction as additive, takes out saggar, purified saggar after leaching 10h It is put into clear water and is impregnated, impregnating after being rinsed after 4h using clear water saggar, to prepare mullite cordierite compound for crushing and screening Ceramic raw material (refractory powder).

(2) it repeats after leaching 10 discarded saggars, for leachate first using being separated by filtration, filter residue, which returns, leaches groove depth leaching Out, solid waste outlet is used as after the completion of washing, filtered filtrate is added calcium hydroxide (neutralizer) and is neutralized, and controls pH terminal It is 2.0, is separated by filtration after reacting 30min, the solid after separation is used as calcium sulfate and calcium silicate products (i.e. after the washing of 1:1 Calcium slag).

(3) potassium sulfate solid (aluminium removal) is added in the filtrate finally obtained one step up, and control conversion temperature is 5 DEG C, knot It is centrifugated after brilliant 2h, obtained solid is potassium alum.

(4) separating liquid that previous step finally obtains is added calcium hydroxide (neutralizer) with continuous stirring, controls pH terminal It is 9, is separated by filtration after reacting 3h, is used as thick cobalt mixture after Washing of Filter Cake filtering.

(4 ') re-dissolve thick cobalt mixture using 30% sulfuric acid, be added into dissolved solution calcium oxide (in And agent), and the gypsum of generation is isolated, slowly that calcium hydroxide is added is (heavy to the separating liquid after gypsum is isolated under stirring Aluminium agent), pH is adjusted 4.5, and potassium fluoride (cleaner) is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium later and is stirred to react, It is separated by filtration after reaction, solution of potassium carbonate is added for 1:1 by cobalt and carbonate molar ratio in refined liquid and carries out precipitation reaction, 70 DEG C of reaction temperature, react 2h after after be separated by filtration, filtrate can return to Crystallization Procedure, be dried to obtain carbonic acid after Washing of Filter Cake Cobalt solid.

(5) 40% potassium hydroxide (demagging agent) solution is slowly added to after the filtrate mixing washing lotion that step (4) finally obtains It is stirred neutralization reaction, control pH value of solution is 12.5, is separated by filtration after reacting 3h, is used as magnesium hydroxide after Washing of Filter Cake filtering Product.

(5 ') magnesium hydroxide filter liquor mixing washing lotion enters evaporization process, evaporates the water in solution, is concentrated into solution Lithium concentration be 25g/L, complex acid or washing procedure are returned after the water condensation after evaporation.

(6) evaporation mother liquor is added 2.3g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 95 DEG C of reaction temperature, take advantage of after reaction time 2h Heat filtering separation, filtered filter cake are used as lithium carbonate product after washing separation.

(7) the mother liquor mixed carbonic acid cobalt mother liquor of precipitation of ammonium after separating passes through decrease temperature crystalline, and crystallization temperature is 0 DEG C, is added a small amount of It is centrifugated after potassium sulfate seeded crystallization, filtrate can return to alkali process, and potassium sulfate is back to except aluminium process.

Binary useless saggar of the discarded saggar raw material that the present embodiment uses using certain positive electrode factory output, chemistry Ingredient is as shown in table 1.

Table 1 discards saggar element composition table (wt%)

Except aluminium rate is 70% in the present embodiment, the recovery rate of cobalt element is 68%, and the recovery rate of elemental lithium is 75%, respectively Cobalt carbonate and lithium carbonate product are obtained, discarded saggar has obtained effective purification.

The flow diagram of the present embodiment is as shown in Figure 1, arrow direction is the method that the embodiment of the present invention 1 provides in figure Process flow direction.

Embodiment 2

(1) the discarded saggar for using embodiment 1 immerses the leaching tanks for the 20L sulfuric acid that molar concentration is 3mol/L In reacted, be added 800mL hydrogen peroxide carry out room temperature Leach reaction, leach 8h after take out saggar, purified saggar is put Enter in clear water and impregnated, saggar prepares mullite cordierite composite ceramic for crushing and screening after being rinsed after immersion 4h using clear water Porcelain raw material.

(2) it repeats after leaching discarded 22, saggar, for leachate first using being separated by filtration, filter residue, which returns, leaches groove depth leaching Solid waste outlet is used as after out after the completion of washing, filtered filtrate is added calcium hydroxide and is neutralized, and control pH terminal is 3.0, It is separated by filtration after reaction 30min, the solid after separation is used as calcium sulfate and calcium silicate products after the washing of 1:1.

(3) potassium sulfate solid is added in the filtrate finally obtained one step up, and control conversion temperature is 0 DEG C, crystallizes mistake after 1h Filter separation.

(4) calcium oxide is added in the filtrate that previous step finally obtains with continuous stirring, and control pH terminal is 9.5, reacts 3h After be separated by filtration, Washing of Filter Cake filtering after be used as thick cobalt product.

(4 ') re-dissolve thick cobalt product using 30% sulfuric acid, are slowly added to oxygen under stirring in solution after dissolution Change calcium, adjusts pH 5, sodium fluoride is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium later and is stirred to react, after reaction mistake Filter separates, and solution of potassium carbonate progress precipitation reaction, reaction temperature 50 is added for 1:1 by cobalt and carbonate molar ratio in refined liquid DEG C, react 3h after after be separated by filtration, filtrate can return to Crystallization Procedure, and cobalt carbonate solid is dried to obtain after Washing of Filter Cake.

(5) calcium oxide is added after the filtrate mixing washing lotion that step (4) finally obtains and is stirred neutralization reaction, controls solution PH is 13, is separated by filtration after reacting 3h, and filter cake is calcium and magnesium slag.

(5 ') calcium and magnesium slag filter liquor mixing washing lotion enters evaporization process, evaporates the water in solution, until the lithium in solution Concentration is 29g/L, and complex acid or washing procedure are returned after the water condensation after evaporation.

(6) evaporation mother liquor is added 1.7g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 95 DEG C of reaction temperature, take advantage of after reaction time 2h Heat filtering separation, filtered filter cake are used as lithium carbonate product after washing separation.

(7) the mother liquor mixed carbonic acid cobalt mother liquor of precipitation of ammonium after separating passes through decrease temperature crystalline, and crystallization temperature is 10 DEG C, is added a small amount of It is separated by filtration after potassium sulfate seeded crystallization, filtrate can return to alkali process, and potassium sulfate is back to except aluminium process.

Except aluminium rate is 76% in the present embodiment, the recovery rate of cobalt element is 74%, and the recovery rate of elemental lithium is 83%, respectively Cobalt carbonate and lithium carbonate product are obtained, discarded saggar has obtained effective purification.

Embodiment 3

(1) the discarded saggar for using embodiment 1 immerses the leaching for the 10L sulfuric acid that molar concentration is 2.5mol/L It is reacted in slot, the hydrogen peroxide that 600mL is added carries out room temperature Leach reaction, takes out saggar, purified saggar after leaching 6h It is put into clear water and is impregnated, impregnating after being rinsed after 4h using clear water saggar, to prepare mullite cordierite compound for crushing and screening Ceramic raw material.

(2) it repeats after leaching discarded 10, saggar, for leachate first using being separated by filtration, filter residue, which returns, leaches groove depth leaching Solid waste outlet is used as after out after the completion of washing, filtered filtrate is added calcium carbonate and is neutralized, and control pH terminal is 2.5, instead It is separated by filtration after answering 30min, the solid after separation is used as calcium sulfate and calcium silicate products after the washing of 1:1.

(3) potassium sulfate solid is added in the filtrate finally obtained one step up, and control conversion temperature is 5 DEG C, crystallizes mistake after 2h Filter separation.

(4) 40% potassium hydroxide solution is added in the filtrate that previous step finally obtains with continuous stirring, controls pH terminal It is 9.5, is separated by filtration after reacting 3h, is used as thick cobalt product after Washing of Filter Cake filtering.

(4 ') re-dissolve thick cobalt product using 30% sulfuric acid, are slowly added to carbon under stirring in solution after dissolution Sour calcium adjusts pH 4.5, ammonium fluoride is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium later and is stirred to react, after reaction It is separated by filtration, carries out precipitation reaction by the potassium hydroxide solution that cobalt and potassium hydroxide molar ratio are 1:2 addition 40% in refined liquid, 70 DEG C of reaction temperature, react 3h after after be separated by filtration, filtrate can return to Crystallization Procedure, be dried to obtain carbonic acid after Washing of Filter Cake Cobalt solid.

(5 ') calcium and magnesium slag filter liquor mixing washing lotion enters evaporization process, evaporates the water in solution, until the lithium in solution Concentration is 20g/L, and complex acid or washing procedure are returned after the water condensation after evaporation.

(6) evaporation mother liquor is added 2.7g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 90 DEG C of reaction temperature, take advantage of after reaction time 2h Heat filtering separation, filtered filter cake are used as lithium carbonate product after washing separation.

(7) the mother liquor mixed carbonic acid cobalt mother liquor of precipitation of ammonium after separating passes through decrease temperature crystalline, and crystallization temperature is 5 DEG C, is added a small amount of It is separated by filtration after potassium sulfate seeded crystallization, filtrate can return to alkali process, and potassium sulfate is back to except aluminium process.

Except aluminium rate is 70% in the present embodiment, the recovery rate of cobalt element is 72%, and the recovery rate of elemental lithium is 66%, respectively Cobalt hydroxide and lithium carbonate product are obtained, discarded saggar has obtained effective purification.

Embodiment 4

(1) the discarded saggar for using embodiment 1 immerses the leaching for the 10L sulfuric acid that molar concentration is 2.5mol/L It is reacted in slot, the hydrogen peroxide that 1000mL is added carries out room temperature Leach reaction, takes out saggar, purified casket after leaching 12h Alms bowl, which is put into clear water, to be impregnated, and saggar prepares mullite cordierite for crushing and screening and answers after being rinsed after immersion 5h using clear water Close ceramic raw material.

(2) it repeats after leaching discarded 12, saggar, for leachate first using being separated by filtration, filter residue, which returns, leaches groove depth leaching Solid waste outlet is used as after out after the completion of washing, filtered filtrate is added calcium carbonate and is neutralized, and control pH terminal is 3.0, instead It is separated by filtration after answering 2h, the solid after separation is used as calcium sulfate and calcium silicate products after the washing of 1:1.

(3) potassium sulfate solid is added in the filtrate finally obtained one step up, and control conversion temperature is 0 DEG C, crystallizes mistake after 2h Filter separation.

(4) 40% potassium hydroxide solution is added in the filtrate that previous step finally obtains with continuous stirring, controls pH terminal It is 9, is separated by filtration after reacting 3h, is used as thick cobalt product after Washing of Filter Cake filtering.

(4 ') re-dissolve thick cobalt product using 30% sulfuric acid, are slowly added to carbon under stirring in solution after dissolution Sour calcium adjusts pH 5, potassium fluoride is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium later and is stirred to react, after reaction mistake Filter separates, and solution of potassium carbonate progress precipitation reaction, reaction temperature is added for 1:1.05 by cobalt and carbonate molar ratio in refined liquid 80 DEG C, react 1h after after be separated by filtration, filtrate can return to Crystallization Procedure, and cobalt carbonate solid is dried to obtain after Washing of Filter Cake.

(5) potassium hydroxide solution that 40% is added after the filtrate mixing washing lotion that step (4) finally obtains is stirred neutralization Reaction, control pH value of solution are 13, are separated by filtration after reacting 3h, are magnesium hydroxide after Washing of Filter Cake is dry.

(5 ') calcium and magnesium slag filter liquor mixing washing lotion enters evaporization process, evaporates the water in solution, until the lithium in solution Concentration is 28g/L, and complex acid or washing procedure are returned after the water condensation after evaporation.

(6) evaporation mother liquor is added 1.8g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 90 DEG C of reaction temperature, after reaction time 1.5h It is separated by filtration while hot, filtered filter cake is used as lithium carbonate product after washing separation.

(7) the mother liquor mixed carbonic acid cobalt mother liquor of precipitation of ammonium after separating passes through decrease temperature crystalline, and crystallization temperature is 0 DEG C, is added a small amount of It is separated by filtration after potassium sulfate seeded crystallization, filtrate can return to alkali process, and potassium sulfate is back to except aluminium process.

Except aluminium rate is 73% in the present embodiment, the recovery rate of cobalt element is 66%, and the recovery rate of elemental lithium is 74%, respectively Cobalt carbonate and lithium carbonate product are obtained, discarded saggar has obtained effective purification.

Embodiment 5

(1) the discarded saggar for using embodiment 1 immerses the leaching for the 20L sulfuric acid that molar concentration is 0.5mol/L It is reacted in slot, the hydrogen peroxide that 800mL is added carries out 10 DEG C of Leach reactions, takes out saggar, purified saggar after leaching 8h It is put into clear water and is impregnated, impregnating after being rinsed after 4h using clear water saggar, to prepare mullite cordierite compound for crushing and screening Ceramic raw material.

(2) it repeats after leaching discarded 22, saggar, for leachate first using being separated by filtration, filter residue, which returns, leaches groove depth leaching Solid waste outlet is used as after out after the completion of washing, filtered filtrate is added calcium hydroxide and is neutralized, and control pH terminal is 5.0, It is separated by filtration after reaction 1h, the solid after separation is used as calcium sulfate and calcium silicate products after the washing of 1:1.

(3) potassium sulfate solid is added in the filtrate finally obtained one step up, and control conversion temperature is 10 DEG C, after crystallizing 1.5h It is separated by filtration.

(4) calcium oxide is added in the filtrate that previous step finally obtains with continuous stirring, and control pH terminal is 8.5, reaction It is separated by filtration after 0.5h, is used as thick cobalt product after Washing of Filter Cake filtering.

(4 ') re-dissolve thick cobalt product using 30% sulfuric acid, are slowly added to oxygen under stirring in solution after dissolution Change calcium, adjusts pH 4, sodium fluoride is added with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium later and is stirred to react, after reaction mistake Filter separates, and solution of potassium carbonate progress precipitation reaction, reaction temperature 50 is added for 1:1 by cobalt and carbonate molar ratio in refined liquid DEG C, react 3h after after be separated by filtration, filtrate can return to Crystallization Procedure, and cobalt carbonate solid is dried to obtain after Washing of Filter Cake.

(5) calcium oxide is added after the filtrate mixing washing lotion that step (4) finally obtains and is stirred neutralization reaction, controls solution PH is 11, is separated by filtration after reacting 5h, and filter cake is calcium and magnesium slag.

(5 ') calcium and magnesium slag filter liquor mixing washing lotion enters evaporization process, evaporates the water in solution, until the lithium in solution Concentration is 30g/L, and complex acid or washing procedure are returned after the water condensation after evaporation.

(6) evaporation mother liquor is added 1.7g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 80 DEG C of reaction temperature, after reaction time 0.5h It is separated by filtration while hot, filtered filter cake is used as lithium carbonate product after washing separation.

(7) the mother liquor mixed carbonic acid cobalt mother liquor of precipitation of ammonium after separating passes through decrease temperature crystalline, and crystallization temperature is -10 DEG C, is added few It is separated by filtration after amount potassium sulfate seeded crystallization, filtrate can return to alkali process, and potassium sulfate is back to except aluminium process.

Except aluminium rate is 72% in the present embodiment, the recovery rate of cobalt element is 48%, and the recovery rate of lithium is 55%, is respectively obtained Cobalt carbonate and lithium carbonate product, discarded saggar have obtained effective purification.

Embodiment 6

(1) the discarded saggar for using embodiment 1 immerses the leaching tanks for the 20L sulfuric acid that molar concentration is 5mol/L In reacted, be added 800mL hydrogen peroxide carry out 30 DEG C of Leach reactions, leach 8h after take out saggar, purified saggar is put Enter in clear water and impregnated, saggar prepares mullite cordierite composite ceramic for crushing and screening after being rinsed after immersion 4h using clear water Porcelain raw material.

(3) potassium sulfate solid is added in the filtrate finally obtained one step up, and control conversion temperature is -5 DEG C, crystallizes mistake after 1h Filter separation.

(4) calcium oxide is added in the filtrate that previous step finally obtains with continuous stirring, and control pH terminal is 10, after reacting 5h It is separated by filtration, is used as thick cobalt product after Washing of Filter Cake filtering.

(5) calcium oxide is added after the filtrate mixing washing lotion that step (4) finally obtains and is stirred neutralization reaction, controls solution PH is 11.5, is separated by filtration after reacting 0.5h, and filter cake is calcium and magnesium slag.

(6) evaporation mother liquor is added 1.7g potassium fluoride with fluorine ion molar ratio 1:2 by the total content of magnesium and calcium and is stirred to react, and reaction terminates After be separated by filtration, be added saturated solution of potassium carbonate in filtrate, carry out precipitation reaction, 95 DEG C of reaction temperature, take advantage of after reaction time 5h Heat filtering separation, filtered filter cake are used as lithium carbonate product after washing separation.

Except aluminium rate is 88% in the present embodiment, the recovery rate of cobalt element is 53%, and the recovery rate of lithium is 57%, is respectively obtained Cobalt carbonate and lithium carbonate product, discarded saggar have obtained effective purification.

Embodiment 7

It is specific the present embodiment provides a kind of method for discarding saggar recovery processing in cobalt acid lithium battery material preparation process Referring to embodiment 2, difference is method:

The chemical component of the discarded saggar used is as shown in table 2.

Table 2 discards saggar element composition table (wt%)

In step (1), extraction temperature is 90 DEG C.

In step (3), control conversion temperature is -10 DEG C.

In step (6), reaction temperature is 100 DEG C.

Other conditions are same as Example 2.

Except aluminium rate is 83% in the present embodiment, the recovery rate of cobalt element is 95%, and the recovery rate of lithium is 97%, is respectively obtained Cobalt carbonate and lithium carbonate product, discarded saggar have obtained effective purification.

Embodiment 8

The chemical component of the discarded saggar used is as shown in table 3.

Table 3 discards saggar element composition table (wt%)

In step (1), extraction temperature is 60 DEG C.

In step (3), control conversion temperature is 30 DEG C.

In step (6), reaction temperature is 85 DEG C.

Other conditions are same as Example 2.

Except aluminium rate is 69% in the present embodiment, the recovery rate of cobalt element is 75%, and the recovery rate of lithium is 81%, is respectively obtained Cobalt carbonate and lithium carbonate product, discarded saggar have obtained effective purification.

Comparative example 1

This comparative example will be in addition to that will remove aluminium step (step (3)) and heavy cobalt and its purification step (step (4) and step (4 ')) Outside reversed order, other methods and condition are same as Example 1.

The heavy cobalt operating process of this comparative example will lead to aluminium while be precipitated out, and further increase the consumption of raw material, simultaneously meeting Lead to cobalt aluminium mixture while being precipitated out, further increase the increase of the acid and aluminium removal when cobalt weighs molten, and has aluminium ion It is mixed into subsequent magnesium sinking sinker process, increases processing difficulty, influences its commercial viability.

It can be seen that cobalt acid lithium battery material provided by the invention with the result of comparative example based on the above embodiments to prepare The method that saggar recovery processing is discarded in journey, which efficiently realizes, discards the valuable of saggar in lithium cobaltate cathode material production process The recycling of cobalt and lithium, while discarded saggar is purified, reaction condition is mild, and technical process is simple, and equipment requirement is low, former Expect it is from a wealth of sources, it is cheap, it is easy to accomplish industrialized production.Comparative example does not use the solution of the present invention, thus can not take Obtain excellent results of the invention.

The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims

1. in a kind of cobalt acid lithium battery material preparation process discard saggar recovery processing method, the discarded saggar include silicon, Aluminium and magnesium addition, which is characterized in that the described method comprises the following steps:

(1) acid-leaching reaction: discarded saggar, acid solution and additive are mixed, and are carried out Leach reaction, are separated after reaction, It is purified saggar and leachate；

(2) remove silicon: regulating step (1) the leachate pH to 2~5 is reacted, and is separated by solid-liquid separation to obtain solid after reaction Slag and separating liquid；

(3) it removes aluminium: aluminium removal is added into step (2) described separating liquid, is crystallized, be separated by solid-liquid separation after the completion of crystallization, Obtain solid slag and except molten aluminum；

(4) heavy cobalt: pH >=8.5 except molten aluminum that regulating step (3) obtains are reacted, and carry out being separated by solid-liquid separation after reaction To substance containing cobalt and heavy cobalt liquid；

(5) demagging: demagging agent being added into step (4) the heavy cobalt liquid, adjusts pH >=11 and is reacted, is separated by solid-liquid separation after reaction Obtain solid slag and except magnesium liquid；

(6) it sinker: is reacted to addition precipitating reagent in magnesium liquid is removed described in step (5), is separated by solid-liquid separation after reaction and obtains object containing lithium Matter and sinker liquid.

2. the method according to claim 1, wherein being the silicon member in terms of 100% by the gross mass for discarding saggar The mass fraction of element is 15wt%~20wt%, preferably 17.37wt%；

It preferably, is in terms of 100% by the gross mass for discarding saggar, the mass fraction of the aluminium element is 18wt%~23wt%, Preferably 21.29wt%；

It preferably, is in terms of 100% by the gross mass for discarding saggar, the mass fraction of the magnesium elements is 3wt%~5wt%, excellent It is selected as 4.143wt%.

3. method according to claim 1 or 2, which is characterized in that in step (1), the acid solution is sulfuric acid solution；

Preferably, the concentration of the sulfuric acid solution is 0.5mol/L~5mol/L, preferably 2mol/L~3mol/L；

Preferably, in step (1), the additive include in hydrogen peroxide, sodium sulfite or sodium thiosulfate any one or At least two combination；

Preferably, in step (1), leaching is leached or is crushed using whole to discarded saggar in the Leach reaction；

Preferably, in step (1), the temperature of the Leach reaction is 10 DEG C~90 DEG C, preferably 30 DEG C~60 DEG C；

Preferably, in step (1), the time of the Leach reaction is 6h~12h；

Preferably, in step (1), further include being recycled to after purification saggar washing, be used to prepare saggar or other resistance to Fiery material；

Preferably, in step (1), discarded saggar is rejoined in Xiang Suoshu leachate and carries out Leach reaction, repeats leaching process；

Preferably, in step (2), the pH for the leachate that neutralizer regulating step (1) obtains is used；

Preferably, the neutralizer include in calcium oxide, calcium hydroxide or calcium carbonate any one or at least two combination；

Preferably, in step (2), adjusting pH value of solution is 2~3；

Preferably, in step (2), the reaction time of the reaction is 0.5h~2h；

Preferably, in step (2), the mode of the separation of solid and liquid is to be separated by filtration；

It preferably, further include that the solid slag is washed and filtered in step (2)；

Preferably, the washing lotion of the washing is mixed into separating liquid described in step (2)；

Preferably, step (2) further include: the leachate before neutralizer is added, first carry out being separated by filtration remove it is therein Solid.

4. method according to claim 1-3, which is characterized in that in step (3), the aluminium removal is sulfuric acid Potassium；

Preferably, in step (3), the crystallization is crystallisation by cooling；

Preferably, in step (3), the temperature of the crystallization is -10 DEG C~30 DEG C, preferably -5 DEG C~10 DEG C；

Preferably, in step (3), the time of the crystallization is 1h~2h；

Preferably, in step (3), the mode of the separation of solid and liquid is centrifugal filtration；

It preferably, further include being washed to the solid slag in step (3)；

Preferably, in step (3), the solid slag is potassium alum.

5. method according to claim 1-4, which is characterized in that in step (4), use neutralizer regulating step (3) pH except molten aluminum obtained；

Preferably, the neutralizer include in calcium oxide, calcium hydroxide or potassium hydroxide any one or at least two group It closes；

Preferably, in step (4), the pH except molten aluminum that regulating step (3) obtains is 8.5~10, preferably 9.0~10；

Preferably, in step (4), the reaction time of the reaction is 0.5h~5h；

Preferably, in step (4), the mode of the separation of solid and liquid is to be separated by filtration；

It preferably, further include that the substance containing cobalt is washed and dried in step (4)；

Preferably, the washing lotion of the washing is mixed into heavy cobalt liquid described in step (4)；

Preferably, in step (4), further include the purification of step (4 ') cobalt: the substance containing cobalt being added in acid solution and is carried out again Dissolution obtains lysate, and aluminium removal and cleaner are added into lysate, and first time separation of solid and liquid is carried out after reaction, to solid-liquid point Precipitating reagent is added from obtained liquid, mixes and carries out precipitation reaction, second of separation of solid and liquid is carried out after precipitation reaction and is taken Solid, the substance containing cobalt refined；

Preferably, in step (4 '), the acid solution is sulfuric acid solution；

Preferably, in step (4 '), the aluminium removal includes in calcium oxide, calcium hydroxide, calcium carbonate, potassium hydroxide or potassium carbonate Any one or at least two combination；

Preferably, in step (4 '), the dosage of aluminium removal meets the pH 4~5 for making the lysate, and preferably 4.5~5；

Preferably, in step (4 '), the cleaner is fluorine-containing；

Preferably, in step (4 '), the cleaner is any one or at least two in sodium fluoride, potassium fluoride or ammonium fluoride Combination；

Preferably, the dosage of the cleaner meets mole of the total content of magnesium and calcium and fluorine ion in the lysate after aluminium removal is added Than for 1:2；

Preferably, in step (4 '), the mode that the first time is separated by solid-liquid separation is to be separated by filtration；

Preferably, in step (4 '), described be mixed into is stirred；

Preferably, in step (4 '), the precipitating reagent includes any in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate It is a kind of or at least two combination；

Preferably, in step (4 '), the dosage of the precipitating reagent meets no less than second of anionic charge sum of precipitating reagent It is separated by solid-liquid separation the charge sum of the cobalt ions in obtained liquid；

Preferably, in step (4 '), the temperature of the precipitation reaction is 50 DEG C~80 DEG C；

Preferably, in step (4 '), the time of the precipitation reaction is 1h~3h；

Preferably, in step (4 '), described second mode being separated by solid-liquid separation is to be separated by filtration；

It preferably, further include being washed and being dried to obtain product containing cobalt to the substance containing cobalt of the purification in step (4 ')；

Preferably, in step (4 '), the substance containing cobalt of the purification is cobalt carbonate and/or cobalt hydroxide；

Preferably, in step (4 '), further includes: the lysate is first added calcic neutralizer and separates before aluminium removal is added The solid generated out；

Preferably, the calcic neutralizer include calcium oxide, calcium hydroxide, in calcium carbonate any one or at least two group It closes；

Preferably, the solid of the generation is gypsum.

6. method according to claim 1-5, which is characterized in that in step (5), the demagging agent includes oxidation In calcium, calcium hydroxide or potassium hydroxide any one or at least two combination；

Preferably, in step (5), adjusting pH value is 11~13, preferably 11.5~12.5；

Preferably, in step (5), the time of the reaction is 0.5h~5h；

7. method according to claim 1-6, which is characterized in that further include that step (5 ') is dense in step (5) Contracting: concentrate is concentrated to get by magnesium liquid is removed described in step (5)；

Preferably, in step (5 '), the mode of the concentration is to be concentrated by evaporation；

Preferably, in step (5 '), make concentration 20g/L~30g/L of Li in finally obtained concentrate；

Preferably, in step (5 '), the condensed water that concentration process obtains is recycled in the process back to washing or complex acid.

8. method according to claim 1-7, which is characterized in that in step (6), the precipitating reagent is solubility Carbonate solution；

Preferably, the soluble carbonate salt solution is solution of potassium carbonate；

Preferably, the soluble carbonate salt solution is saturated solution；

Preferably, in step (6), the temperature of the reaction is 80 DEG C~100 DEG C, preferably 85 DEG C~95 DEG C；

Preferably, in step (6), the time of the reaction is 0.5h~5h；

Preferably, in step (6), the mode of the separation of solid and liquid is to be separated by filtration；

It preferably, further include the substance containing lithium being washed and being dried to obtain product containing lithium in step (6)；

Preferably, in step (6), the substance containing lithium is lithium carbonate；

Preferably, step (6) further include: to before being removed described in step (5) precipitating reagent is added in magnesium liquid, first to being removed described in step (5) Potassium fluoride is added by the total content of magnesium and calcium and fluorine ion molar ratio 1:2 in magnesium liquid, is stirred to react and is filtered to remove solid therein.

9. according to the method described in claim 5, it is characterized in that, the method also includes step (7) crystallizations: to step (6) Obtained in be separated by solid-liquid separation obtained separating liquid for the second time in sinker liquid and step (4 ') and crystallized, be separated by solid-liquid separation, obtain later To solid and separating liquid；

Preferably, the crystallization is crystallisation by cooling；

Preferably, the temperature of the crystallization is -10 DEG C~10 DEG C；

Preferably, the crystallization carries out in a crystallizer；

Preferably, the mode of the separation of solid and liquid is centrifuge separation；

Preferably, the isolated solid of solid is potassium sulfate；

Preferably, the potassium sulfate, which returns to, is used as aluminium removal in step (3)；

Preferably, preparation of the separating liquid back to progress precipitating reagent in step (6).

10. -9 described in any item methods according to claim 1, which is characterized in that the described method comprises the following steps:

(1) acid-leaching reaction: by the discarded saggar comprising silicon, aluminium and magnesium addition, the sulfuric acid solution that concentration is 2mol/L~3mol/L It is mixed with additive, carries out Leach reaction, reaction temperature is 30 DEG C~60 DEG C, and the reaction time is 6h~12h, the Leach reaction In to discarded saggar using it is whole leach or it is broken leach, separated after reaction, saggar and leachate be purified, to institute It is recycled after stating purification saggar washing, is used to prepare saggar or other refractory materials, is rejoined in Xiang Suoshu leachate useless It abandons saggar and carries out Leach reaction, repeat leaching process；Gross mass to discard saggar is in terms of 100%, and the mass fraction of silicon is 15wt%~20wt%, the mass fraction of aluminium are 18wt%~23wt%, and the mass fraction of magnesium is 3wt%~5wt%；

(2) it removes silicon: step (1) described leachate first being carried out to be separated by filtration removing solid therein, neutralizer is added, adjusts PH value of solution reacts 0.5h~2h, is separated by filtration to obtain solid slag and separating liquid after reaction to 2~3, to the solid slag into Row washing and filtering, the washing lotion of washing is mixed into separating liquid described in step (2)；

(3) it removes aluminium: potassium sulfate being added into step (2) described separating liquid, carry out crystallisation by cooling, crystallization temperature is -5 DEG C~10 DEG C, crystallization time is 1h~2h, carries out centrifugal filtration after the completion of crystallization, obtain potassium alum and except molten aluminum, to the potassium alum into Row washing；

(4) heavy cobalt: described except neutralizer is added in molten aluminum to what step (3) obtained, adjusting pH is 9.0~10, reaction 2.5h~ 3.5h is separated by filtration to obtain substance containing cobalt and heavy cobalt liquid after reaction, the substance containing cobalt is washed and dried, will be washed The washing lotion washed is mixed into the heavy cobalt liquid；

The purification of (4 ') cobalt: the substance containing cobalt is added in sulfuric acid solution and is re-dissolved to obtain lysate, into lysate Calcic neutralizer is added and isolates gypsum, aluminium removal is added into the lysate after separation gypsum, the dosage of aluminium removal meets Make the pH 4.5~5 for separating the lysate after gypsum, add fluorine-containing cleaner, the dosage of cleaner, which meets to be added, removes aluminium The molar ratio of the total content of magnesium and calcium and fluorine ion in lysate after agent is 1:2, carries out being separated by filtration for the first time after reaction, to solid-liquid Precipitating reagent is added in isolated liquid, stirs and carry out precipitation reaction, and the temperature of precipitation reaction is 50 DEG C~80 DEG C, and precipitating is anti- The time answered is 1h~3h, is separated by filtration for the second time after precipitation reaction and takes solid, the substance containing cobalt refined is right The substance containing cobalt of the purification is washed and is dried, and cobalt carbonate and/or cobalt hydroxide product are obtained；The precipitating reagent includes hydrogen In sodium oxide molybdena, potassium hydroxide, sodium carbonate or potassium carbonate any one or at least two combination；

(5 ') it is concentrated: being the concentrate of 20g/L~30g/L by the concentration that magnesium liquid is concentrated by evaporation to obtain Li is removed described in step (5), it is dense The condensed water that compression process obtains is recycled in the process back to washing or complex acid；

(6) potassium fluoride stirring sinker: is added instead by the total content of magnesium and calcium and fluorine ion molar ratio 1:2 into step (the 5 ') concentrate It should and be filtered to remove solid therein, take filtrate, unsaturated carbonate potassium solution is added into filtrate and is reacted, reaction temperature 85 DEG C~95 DEG C, the time of reaction is 1.5h~2.5h, is separated by filtration to obtain lithium carbonate and sinker liquid after reaction, to the lithium carbonate Washed and be dried to obtain lithium carbonate product；

(7) it crystallizes: the separating liquid being separated by filtration for the second time in sinker liquid obtained in step (6) and step (4 ') is being tied Crystallisation by cooling is carried out in brilliant device, crystallization temperature is -10 DEG C~10 DEG C, it is centrifugated later, obtains potassium sulfate solid and separating liquid, The potassium sulfate returns to and is used as aluminium removal in step (3), and the separating liquid is molten back to progress saturated potassium carbonate in step (6) The preparation of liquid.