CN109987617A - A method of shraff containing lithium prepares lithium hydroxide - Google Patents
A method of shraff containing lithium prepares lithium hydroxide Download PDFInfo
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- CN109987617A CN109987617A CN201910395466.9A CN201910395466A CN109987617A CN 109987617 A CN109987617 A CN 109987617A CN 201910395466 A CN201910395466 A CN 201910395466A CN 109987617 A CN109987617 A CN 109987617A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/16—Waste materials; Refuse from building or ceramic industry
- C04B18/165—Ceramic waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention belongs to environmental technology fields, are related to a kind of method that shraff containing lithium prepares lithium hydroxide, described method includes following steps: mixing shraff containing lithium and water obtain mixed slurry after water logging；Filtering gained mixed slurry, obtains water logging slag and infusion；Washing gained water logging slag obtains pre- except lithium material and washing lotion；Mixing gained infusion and washing lotion, obtain mixed liquor, and mixing caustic and mixed liquor carry out causticizing reaction, obtain causticized slurry；Filtering gained causticized slurry, obtains causticization slag and causticization liquid；Causticization liquid obtained by evaporative crystallization is dried solid after separation of solid and liquid, obtains lithium hydroxide product.The method is easy to operate, mild condition, the requirement to Preparation equipment are low, low in cost, can recycle from shraff containing lithium and obtain lithium hydroxide product, have good prospects for commercial application.
Description
Technical field
The invention belongs to environmental technology field, it is related to a kind of method for mentioning lithium from solid waste containing lithium more particularly to one kind contains
The method that lithium shraff prepares lithium hydroxide.
Background technique
Lithium is a kind of important metallic element, is widely used in the energy, metallurgy, glass, ceramics, rubber and lubricating grease
In.There are mainly two types of the sources of current lithium: one is the lithium ion in salt lake bittern by extraction, absorption method, salting out method or
The lithium salt compound that person's coprecipitation obtains after extracting；Another kind is led to from containing lithium ore such as lepidolite or spodumene
It crosses roasting or acid system produces to obtain lithium salt compound.With the fast development of the development of new energy industry, especially lithium battery,
The demand of lithium continues rapidly to increase, and lithium salts is caused the situation of demand anxiety occur.
With the fast development of new energy industry, the output and demand of anode material of lithium battery continue to increase.Lithium electricity
Pond positive electrode is using LiMn2O4, cobalt acid lithium, lithium nickelate, nickle cobalt lithium manganate and nickel cobalt lithium aluminate as representative.Lithium is recycled
Research be concentrated mainly in the recycling to positive electrode.
The one kind that 104538695 A of CN discloses recycles metal from useless nickle cobalt lithium manganate battery and prepares nickle cobalt lithium manganate
Used Li ion cell is discharged, disassembled or is collected positive leftover pieces, positive relic, obtained by the method for positive electrode, this method
Must give up positive plate, and useless positive plate is fired, water dissolution, filters the useless nickle cobalt lithium manganate powder of acquisition；By useless nickle cobalt lithium manganate powder
It is roasted after being mixed in a certain ratio with potassium pyrosulfate, product of roasting is gone out with water logging, after solution of potassium carbonate then is added into solution
Filtering, obtains nickel-cobalt lithium manganate cathode material after ball milling, compression, roasting.
103045870 A of CN discloses a kind of side of the recycling of the comprehensive resource from waste lithium ion valuable metal
Method, this method by being discharged waste lithium ion, being air-dried, disassembled, it is broken after using screening, gravity treatment, vortex, divide
Numerous tedious steps such as choosing, Chemical Leaching, ion sieve separating Li and nickel cobalt manganese in waste lithium ion valuable metal, every
The materials comprehensive reutilization such as film, graphite.
But current anode material of lithium battery, using high temperature sintering reaction preparation, sintering process generallys use ceramics
Firing container of the crucible as lithium raw material and nickel cobalt manganese raw material, high temperature firing process ceramic crucible body easily with lithium raw material and nickel cobalt
Manganese forerunner's precursor reactant, cause saggar crucible occur peeling, be chapped from the cold, be crushed and scrap, the discarded saggar scrapped contain a large amount of lithium,
The valuable metals such as nickel cobalt manganese be easy to cause environmental pollution, at present still without good Land use systems.Although 108500740 A of CN
A kind of old saggar Retreatment method is disclosed, but this method also only coats nickle cobalt lithium manganate solution on the old saggar bottom surface of abrasion
Or cobalt acid lithium solution is to prolong the service life.With the fast development of lithium electricity New Energy Industry, lithium electricity gives up saggar bring ring
Border problem and the wasting of resources will become more and more important, and the research work of current useless saggar concentrates on invading for saggar ceramic body
Mechanism is lost and scraps, the recycling and higher value application about useless saggar still lack research.
Summary of the invention
The purpose of the present invention is to provide a kind of method that shraff containing lithium prepares lithium hydroxide, the method will contain lithium
Lithium present in shraff is recycled, and shraff containing lithium is made to have obtained resource utilization, and easy to operate, condition temperature
It is low with the requirement to Preparation equipment, low in cost, lithium can be recycled from shraff containing lithium to obtain lithium hydroxide product, also
It solves problem of environmental pollution caused by the stacking of shraff containing lithium, there is good prospects for commercial application.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention provides a kind of methods that shraff containing lithium prepares lithium hydroxide, and described method includes following steps:
(1) water logging is reacted: mixing shraff containing lithium and water obtain mixed slurry after water logging；
(2) filter: mixed slurry obtained by filtration step (1) obtains water logging slag and infusion；
(3) washing separation: water logging slag obtained by washing step (2) obtains pre- except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixes caustic
Causticizing reaction is carried out with mixed liquor, obtains causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (4) is dried solid after separation of solid and liquid, obtains
To lithium hydroxide product.
Shraff containing lithium of the present invention includes but is not limited to that anode material for lithium-ion batteries is produced during the preparation process
Saggar is scrapped, any shraff containing lithium is shraff containing lithium of the present invention, such as can be production cobalt acid lithium just
Production when the useless saggar that is generated when the useless saggar that is generated when the material of pole, production manganate cathode material for lithium, production lithium nickelate positive electrode
Generation when the useless saggar that is generated when raw useless saggar, production nickel-cobalt lithium manganate cathode material, production nickel cobalt lithium aluminate cathode material
Useless saggar or production lithium iron phosphate positive material when the useless saggar that generates.
The present invention, as raw material is leached, passes through water logging, washing, causticization and steaming using the water of low in cost and easy acquisition
The techniques such as hair crystallization effectively realize the recycling of lithium in shraff containing lithium, the method for the invention mild condition, operation
Simply, low to the requirement of Preparation equipment, lithium hydroxide product can be obtained at lower cost, before there is preferable industrial application
Scape.
Preferably, the shraff containing lithium is the shraff containing lithium by physical separation, and the physical separation makes to contain
The phase layer of object containing lithium of lithium shraff is separated with ceramic body, and the method for the physical separation includes but is not limited to broken, removing
One of ball milling or at least two combination.
The lithium in shraff containing lithium obtained by physical separation is easier to be flooded out, reduces the subsequent difficulty for mentioning lithium
Degree.
Preferably, the liquid-solid ratio of step (1) water and the shraff containing lithium is (1-20): 1, such as can be 1:1,2:
1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:1、
19:1 or 20:1, preferably (2-15): 1.
Preferably, the temperature of step (1) described water logging be 10-90 DEG C, such as can be 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, preferably 20-80 DEG C.
Preferably, the time of step (1) described water logging be 20-300min, such as can be 20min, 40min, 50min,
60min, 80min, 100min, 120min, 140min, 150min, 170min, 200min, 230min, 250min, 270min or
300min, preferably 30-60min.
Preferably, the method for step (3) described washing includes agitator treating and/or elution.
Preferably, the number of step (3) described washing is 1-10 times, such as can be 1 time, 2 times, 3 times, 4 times, 5 times, 6
Secondary, 7 times, 8 times, 9 times or 10 times, preferably 3-8 times.
Preferably, step (3) washing is to be washed with water.
Preferably, the liquid-solid ratio of step (3) the washing Shi Shuiyu water logging slag is (1-20): 1, such as can be 1:1,2:
1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:1、
19:1 or 20:1, preferably (5-15): 1.
Preferably, the temperature of step (3) described washing be 10-90 DEG C, such as can be 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C,
30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C, preferably 25-40 DEG C.
The present invention uses the method for washing by the lithium ion transfer in water logging slag to washing lotion, washing Shi Shuiyu of the present invention
The liquid-solid ratio of water logging slag is (1-20): 1 be the liquid-solid ratio of single wash Shi Shuiyu water logging slag is (1-20): 1, after single wash
Washing lotion can be used for next washing, can also mix with the washing lotion that next time, washing generated, but very few slurry is unfavorable for lithium ion
Precipitation, excessive slurry then will increase the energy consumption of subsequent evaporation crystallization, therefore the liquid of single wash Shi Shuiyu water logging slag
Gu ratio can reasonably be selected according to washing times.
Preferably, the amount and liquid-solid ratio (1-20) for the water logging slag that the present invention is generated according to step (2): when 1 selection washing
Water consumption, and recycled washing water phase analysis 1-10 times using the washing water of selected amount.
Preferably, step (4) described caustic includes calcium oxide and/or calcium hydroxide.
Preferably, the calcium silicon ratio (1-2) when step (4) described causticizing reaction: 1, such as can be 1:1,1.1:1,1.2:
1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1 or 2:1.
Preferably, the temperature of step (4) described causticizing reaction be 50-120 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C,
80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C, preferably 60-100 DEG C.
Preferably, the time of step (4) described causticizing reaction be 20-300min, such as can be 20min, 40min,
50min、60min、80min、100min、120min、140min、150min、170min、200min、230min、250min、
270min or 300min, preferably 60-180min.
Preferably, the temperature of step (6) described evaporative crystallization be 60-100 DEG C, such as can be 60 DEG C, 65 DEG C, 70 DEG C,
75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C, preferably 80-90 DEG C.
Preferably, the time of step (6) described evaporative crystallization be 2-5h, such as can be 2h, 2.5h, 3h, 3.5h, 4h,
4.5h or 5h, preferably 3-4h.
Preferably, the method for step (6) described drying process includes microwave drying and/or tray drying.
Preferably, the recycling condensing water that step (6) evaporative crystallization generates in step (1) the water logging reaction and/or
Step (3) the washing separation.
As the optimal technical scheme of first aspect present invention the method, described method includes following steps:
(1) water logging is reacted: according to liquid-solid ratio (1-20): 1 mixing water and shraff containing lithium, 10-90 DEG C of water logging 20-
Mixed slurry is obtained after 300min；
(2) filter: mixed slurry obtained by filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 10-90 DEG C, with liquid-solid ratio (1-20): water logging slag 1-10 times obtained by 1 water-washing step (2), obtaining
To in advance except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixes caustic
Causticizing reaction is carried out with mixed liquor, calcium silicon ratio when causticizing reaction is (1-2): 1, the temperature of causticizing reaction is 50-120 DEG C, severe
The time for changing reaction is 20-300min, obtains causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid 2-5h obtained by evaporative crystallization steps (4) at 60-100 DEG C, to solid after separation of solid and liquid
It is dried, obtains lithium hydroxide product, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction
And/or step (3) the washing separation.
Compared with the existing technology, the invention has the following advantages:
The present invention, as raw material is leached, passes through water logging, washing, causticization and steaming using the water of low in cost and easy acquisition
The techniques such as hair crystallization effectively realize the recycling of lithium in shraff containing lithium, and the recovery rate of elemental lithium is up to 42%, and grasps
It is low, low in cost to make simple, mild condition, the requirement to Preparation equipment, not only recycling lithium obtains from shraff containing lithium
Lithium hydroxide product also solves problem of environmental pollution caused by shraff containing lithium is stacked.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that the shraff containing lithium that embodiment 1 provides prepares lithium hydroxide.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, the process flow chart of the method as shown in Figure 1,
Include the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 500g water and 500g after ball-milling treatment, 40 DEG C of water logging 50min
After obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 40 DEG C, to obtain pre- water logging slag 5 times obtained by the water cycling elution step (2) of liquid-solid ratio 3:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixed oxidization calcium
Causticizing reaction is carried out with mixed liquor, calcium silicon ratio when causticizing reaction is 2:1, and the temperature of causticizing reaction is 90 DEG C, causticizing reaction
Time is 300min, obtains causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 100 DEG C carries out microwave to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 32% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 1 provides realizes the shraff containing lithium produces lithium hydroxide.
Embodiment 2
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the mixing shraff containing lithium of 2000g water and 100g through break process, after 25 DEG C of water logging 50min
Obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 25 DEG C, to obtain pre- water logging slag 4 times obtained by the water cycling elution step (2) of liquid-solid ratio 1:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixed oxidization calcium
Causticizing reaction is carried out with mixed liquor, calcium silicon ratio when causticizing reaction is 1.1:1, and the temperature of causticizing reaction is 90 DEG C, causticizing reaction
Time be 120min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 90 DEG C carries out disc type to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 39% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 2 provides realizes the shraff containing lithium produces lithium hydroxide.
Embodiment 3
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 600g water and 200g after ball-milling treatment, 20 DEG C of water logging 60min
After obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 25 DEG C, to obtain pre- water logging slag 8 times obtained by the water cycling elution step (2) of liquid-solid ratio 1:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixed oxidization calcium
Causticizing reaction is carried out with mixed liquor, calcium silicon ratio when causticizing reaction is 1.2:1, and the temperature of causticizing reaction is 50 DEG C, causticizing reaction
Time be 300min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 80 DEG C carries out disc type to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 35% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 3 provides realizes the shraff containing lithium produces lithium hydroxide.
Embodiment 4
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 1000g water and 1000g after ball-milling treatment, 60 DEG C of water loggings
Mixed slurry is obtained after 60min；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 25 DEG C, to obtain pre- water logging slag 1 time obtained by the water cycling elution step (2) of liquid-solid ratio 1:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixed oxidization calcium
Causticizing reaction is carried out with mixed liquor, calcium silicon ratio when causticizing reaction is 1.5:1, and the temperature of causticizing reaction is 60 DEG C, causticizing reaction
Time be 300min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 90 DEG C carries out disc type to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 28% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 4 provides realizes the shraff containing lithium produces lithium hydroxide.
Embodiment 5
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 600g water and 300g after ball-milling treatment, 80 DEG C of water logging 30min
After obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 25 DEG C, to obtain water logging slag 10 times obtained by the water cycling elution step (2) of liquid-solid ratio 1:1
Lithium material and washing lotion are removed in advance；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixes hydroxide
Calcium and mixed liquor carry out causticizing reaction, and calcium silicon ratio when causticizing reaction is 1:1, and the temperature of causticizing reaction is 80 DEG C, causticizing reaction
Time be 120min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 90 DEG C carries out disc type to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 42% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 5 provides realizes the shraff containing lithium produces lithium hydroxide.
Embodiment 6
Present embodiments provide a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 1000g water and 1000g after ball-milling treatment, 80 DEG C of water loggings
Mixed slurry is obtained after 30min；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 25 DEG C, to obtain pre- water logging slag 5 times obtained by the water cycling elution step (2) of liquid-solid ratio 1:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by infusion obtained by mixing step (2) and step (3) obtains mixed liquor, mixes hydroxide
Calcium and mixed liquor carry out causticizing reaction, and calcium silicon ratio when causticizing reaction is 1:1, and the temperature of causticizing reaction is 100 DEG C, causticizing reaction
Time be 60min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 80 DEG C carries out disc type to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 37% in the present embodiment, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product, and the low cost that the method that embodiment 6 provides realizes the shraff containing lithium produces lithium hydroxide.
Comparative example 1
This comparative example provides a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 500g water and 500g after ball-milling treatment, 40 DEG C of water logging 50min
After obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) causticization: infusion obtained by mixed oxidization calcium and step (2) carries out causticizing reaction, calcium silicon ratio when causticizing reaction
For 2:1, the temperature of causticizing reaction is 90 DEG C, and the time of causticizing reaction is 300min, obtains causticized slurry；
(4) filter: causticized slurry obtained by filtration step (3) obtains causticization slag and causticization liquid；
(5) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 100 DEG C carries out microwave to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 12% in this comparative example, and being prepared is monohydrate lithium hydroxide product, step (4)
To causticization slag can be used for preparing building material product.
Comparative example 2
This comparative example provides a kind of method that shraff containing lithium prepares lithium hydroxide, the source of shraff containing lithium
The lithium electricity used in anode material for lithium-ion batteries preparation process gives up saggar, includes the following steps:
(1) water logging is reacted: the shraff containing lithium of mixing 500g water and 500g after ball-milling treatment, 40 DEG C of water logging 50min
After obtain mixed slurry；
(2) filter: mixed slurry obtained by vacuum filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 40 DEG C, to obtain pre- water logging slag 5 times obtained by the water cycling elution step (2) of liquid-solid ratio 3:1
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by mixed oxidization calcium and step (3) carries out causticizing reaction, and calcium silicon ratio when causticizing reaction is
2:1, the temperature of causticizing reaction are 90 DEG C, and the time of causticizing reaction is 300min, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (5) at 100 DEG C carries out microwave to solid after separation of solid and liquid
It is dry, lithium hydroxide product is obtained, the recycling condensing water that evaporative crystallization generates is in step (1) the water logging reaction and/or step
(3) the washing separation.
The recovery rate of elemental lithium is 25% in this comparative example, and the product being prepared is monohydrate lithium hydroxide product；Step
(3) obtaining in is pre- except lithium material can be used for extracting aluminium, magnesium, lithium, nickel, cobalt or the valuable metals such as violent；The causticization that step (5) obtains
Slag can be used for preparing building material product.
In conclusion method provided by the invention recycles shraff containing lithium, especially anode material for lithium-ion batteries system
Lithium electricity used in the process of standby gives up saggar, and the recovery rate of elemental lithium can be made to be up to 42%, and the method is easy to operate, condition temperature
It is low with the requirement to Preparation equipment, low in cost, it can be recycled from shraff containing lithium and obtain lithium hydroxide product, had good
Good prospects for commercial application.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of method that shraff containing lithium prepares lithium hydroxide, which is characterized in that described method includes following steps:
(1) water logging is reacted: mixing shraff containing lithium and water obtain mixed slurry after water logging；
(2) filter: mixed slurry obtained by filtration step (1) obtains water logging slag and infusion；
(3) washing separation: water logging slag obtained by washing step (2) obtains pre- except lithium material and washing lotion；
(4) causticization: washing lotion obtained by mixing step (2) gained infusion and step (3) obtains mixed liquor, mixes caustic and mixes
It closes liquid and carries out causticizing reaction, obtain causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid obtained by evaporative crystallization steps (4) is dried solid after separation of solid and liquid, obtains hydrogen
Lithia product.
2. the method according to claim 1, wherein the liquid-solid ratio of step (1) water and the shraff containing lithium
For (1-20): 1, preferably (2-15): 1.
3. method according to claim 1 or 2, which is characterized in that the temperature of step (1) described water logging is 10-90 DEG C, excellent
It is selected as 20-80 DEG C.
4. method according to claim 1-3, which is characterized in that the time of step (1) described water logging is 20-
300min, preferably 30-60min.
5. method according to claim 1-4, which is characterized in that the method for step (3) described washing includes stirring
Mix washing and/or elution；
Preferably, the number of step (3) described washing is 1-10 times, preferably 3-8 times；
Preferably, step (3) washing is to be washed with water；
Preferably, the liquid-solid ratio of step (3) the washing Shi Shuiyu water logging slag is (1-20): 1, preferably (5-15): 1；
Preferably, the temperature of step (3) described washing is 10-90 DEG C, preferably 25-40 DEG C.
6. method according to claim 1-5, which is characterized in that step (4) described caustic includes calcium oxide
And/or calcium hydroxide；
Preferably, the calcium silicon ratio (1-2) when step (4) described causticizing reaction: 1；
Preferably, the temperature of step (4) described causticizing reaction is 50-120 DEG C, preferably 60-100 DEG C；
Preferably, the time of step (4) described causticizing reaction is 20-300min, preferably 60-180min.
7. method according to claim 1-6, which is characterized in that the temperature of step (6) described evaporative crystallization is
60-100 DEG C, preferably 80-90 DEG C；
Preferably, the time of step (6) described evaporative crystallization is 2-5h, preferably 3-4h.
8. method according to claim 1-7, which is characterized in that the method packet of step (6) described drying process
Include microwave drying and/or tray drying.
9. method according to claim 1-8, which is characterized in that step (6) evaporative crystallization generates cold
Condensate is back to step (1) the water logging reaction and/or step (3) the washing separation.
10. -9 described in any item methods according to claim 1, which is characterized in that described method includes following steps:
(1) water logging is reacted: according to liquid-solid ratio (1-20): 1 mixing water and shraff containing lithium, after 10-90 DEG C of water logging 20-300min
Obtain mixed slurry；
(2) filter: mixed slurry obtained by filtration step (1) obtains water logging slag and infusion；
(3) washing separation: at 10-90 DEG C, with liquid-solid ratio (1-20): water logging slag 1-10 times obtained by 1 water-washing step (2), obtaining pre-
Except lithium material and washing lotion；
(4) causticization: washing lotion obtained by mixing step (2) gained infusion and step (3) obtains mixed liquor, mixes caustic and mixes
It closes liquid and carries out causticizing reaction, calcium silicon ratio when causticizing reaction is (1-2): 1, the temperature of causticizing reaction is 50-120 DEG C, and causticization is anti-
The time answered is 20-300min, obtains causticized slurry；
(5) filter: causticized slurry obtained by filtration step (4) obtains causticization slag and causticization liquid；
(6) evaporative crystallization: causticization liquid 2-5h obtained by evaporative crystallization steps (4) at 60-100 DEG C carries out solid after separation of solid and liquid
Be dried, obtain lithium hydroxide product, the recycling condensing water that evaporative crystallization generates in step (1) the water logging reaction and/or
Step (3) the washing separation.
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