CN109721081A - A method of extracting lithium from rich lithium flyash alkaline process mother liquor - Google Patents
A method of extracting lithium from rich lithium flyash alkaline process mother liquor Download PDFInfo
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Abstract
The method that the invention discloses a kind of to extract lithium from rich lithium flyash alkaline process mother liquor, belong to solid waste resource recovery and utilizes field, using rich lithium flyash as raw material, by rich lithium coal ash for manufacturing at alkaline process mother liquor, lithium is mentioned again, the following steps are included: 1) desiliconization: according to alkaline process mother liquor siliceous modulus, carrying out desiliconization processing, slurries, which are separated by solid-liquid separation, collects filtrate I；2) pH regulates and controls: the pH of filtrate I being adjusted to 7~9, is separated by solid-liquid separation to obtain sediment A and filtrate II；3) aluminium lithium co-deposited synthesis: add carbon dioxide or diluted acid into filtrate II, it is separated by solid-liquid separation to obtain sediment B, will sediment A and B mix after roast, wash, filter to get filtrate III and filter residue I, carbonating recycling lithium carbonate after filtrate III is concentrated, filter residue I is as the raw material for mentioning aluminium.The present invention has simple process, the features such as being easily isolated and recycled, is total to associated metal resource higher value application for lithium, aluminium in bulk solid waste flyash etc. and provides new method, economic benefit and environmental benefit are obvious.
Description
Technical field
The present invention relates to rich lithium flyash, especially a kind of method for extracting lithium belongs to solid waste resource recovery utilization
Field.
Background technique
Lithium is that nature is most light, the smallest silvery white alkali metal of radius.Common lithium salts has lithium carbonate, lithium sulfate, chlorination
Lithium etc., lithium and its compound have many distinctive excellent performances, have important strategic position in Chinese national economy construction, extensively
General to be applied to the fields such as electronics, ceramics, glass, medicine, aerospace, as clean energy technology continues to develop, lithium demand is got over
Come bigger.
Flyash belongs to bulk solid waste, and 2016 annual emissions are more than 600,000,000 tons, wherein rich lithium flyash year discharge
Amount is up to 30,000,000 tons or more, and lithium content is up to 0.8%(in terms of lithia in ash), have reached comprehensive utilization standard.Flyash
Consumption approach utilized for a long time for low value always, be mainly used for filling, build the road, construction material etc., still, such richness lithium powder
For coal ash often containing the aluminium oxide of high-content, the aluminium oxide that part is even up to bauxite utilizes grade, therefore, this kind of flyash
High-valued utilization ways must be walked.
From high alumina richness lithium flyash recycle useful metal general thought be with the essential elements such as aluminium, silicon recycling based on,
It walks comprehensive extract and recycles other metals such as lithium, gallium, germanium, rare earth metal etc., can be only achieved processing technology routine value maximization, ring
Border maximizing the benefits.Currently, aluminous fly-ash recycling alloying technology mainly has acidleach, alkali leaching or acid and alkali combination method etc., acid system energy
Realize that fly ash highly leaches, but the high requirements on the equipment, leachate impurity composition and type are complicated, are unfavorable for subsequent processing.
Alkaline reaction condition is relatively mild, and the impurity such as iron oxide will not dissolve out, and mature technology such as Bayer process recycling aluminium, benefit can be used
In commercial introduction.
Flyash alkaline process is handled to obtain with sodium aluminate solution as main component, also containing the impurity such as a large amount of silicates, silicon
There are the separation and recovery of extreme influence aluminium, lithium, unfavorable to product quality, therefore, no matter the alkaline process mother liquor is selected from fine coal
Sodium aluminate solution or alkali soluble solution that the process such as grey sintering process, Bayer process obtain are formed by one in sodium aluminate solution
Kind is a variety of, requires by desiliconization, then separates and recovers useful metal ingredient by separating technology and main body complicated solution system.
In order to reduce the silicon in alkaline process sodium aluminate solution and recycling lithium, researchers at home and abroad propose many methods.
CN107758714A discloses a kind of method that the collaboration of aluminium silicon lithium gallium combination method is extracted in flyash, and the method includes pre-desiliconizings
The alumina extraction and pre-desiliconizing liquid essence that filter residue, Bayer Process digestion, sub-molten salt dissolution, Crystallization Separation, desiliconization, kind point are decomposed
Filter, purification, Adsorption and desorption, concentration and carbonating sinker extract, and still, this method is merely with the lithium in pre-desiliconizing liquid, and desiliconization
Liquid is separated only with refined filtration, also will cause the loss of lithium, and the recovery technology similar industrial Bayer digestion of bauxite of aluminium extracts aluminium oxide
Process, it is easy to accomplish, but dissolved out using multistep, long flow path, aluminium loss is obvious.Flyash alkaline process recycle aluminium, lithium correlative study compared with
Few, portion of techniques method only considers the separation and recovery of a certain metallic element, and in richness lithium flyash silicone content be up to 30~
60%, great amount of soluble silicon enters sodium aluminate solution after alkali soluble, it is necessary to carry out desiliconization processing.
In short, only angle is concentrated to realize concentration and separation from single ionic separation and leachate in existing method, do not consider molten
The removal of advantage ion such as silicate, lithium concentration are much lower with respect to silicate, aluminium ion concentration in liquid, and common separation method is difficult
Separate, therefore, find it is a kind of can accomplish simple process from the method for complicated lye system separating Li, entrainment impurity is few, and separation is held
Easy recovery method is the key that the high-valued recycling lithium of flyash.
Summary of the invention
The method that the technical problem to be solved by the invention is to provide a kind of to extract lithium from rich lithium flyash alkaline process mother liquor,
The high silicon of content in alkaline process mother liquor is effectively removed, process flow complexity is reduced, improves the recovery rate of lithium, realizes rich lithium powder
Coal ash alkaline process recycles the purpose of useful metal, is total to associated resources for lithium, aluminium in bulk solid waste flyash and efficiently separates and mentions
It takes and provides new approaches, new method with higher value application.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A method of lithium is extracted from rich lithium flyash alkaline process mother liquor, using rich lithium flyash as raw material, first by rich lithium flyash
It is prepared into sodium aluminate liquor and extracts lithium as alkaline process mother liquor, then from alkaline process mother liquor, comprising the following steps:
1) desiliconization: according to the siliceous modulus in alkaline process mother liquor, desiliconization processing is carried out, obtained reacting slurry is separated by solid-liquid separation simultaneously
Collect filtrate I；
2) pH regulates and controls: the pH value of filtrate I being adjusted to 7~9, separation of solid and liquid obtains sediment A and filtrate II；
3) aluminium lithium co-deposited synthesis: being passed through carbon dioxide into filtrate II or diluted acid is added, and separation of solid and liquid obtains sediment B, will
It is roasted after sediment A and B mixing, then washes, filtrate III and filter residue I is obtained by filtration, carbonating recycling carbon after filtrate III is concentrated
Sour lithium, filter residue I is as the raw material for extracting aluminium.
Technical solution of the present invention further improvement lies in that: alkaline process mother liquor is selected from rich lithium flyash sintering process or Bayer process work
The sodium aluminate liquor or alkali soluble solution that skill is handled are formed by one of sodium aluminate solution or a variety of mixing.
Technical solution of the present invention further improvement lies in that: it is de- to be divided into one section of desiliconization and two sections for desiliconization processing in step 1)
Silicon, the process of one section of desiliconization is to mix desiliconization agent I by 40~100g/L of solid-to-liquid ratio with alkaline process mother liquor, at 90~190 DEG C
Under the conditions of be stirred to react 1~6h；The process of two-stage desilication is to carry out desiliconization agent II and alkaline process mother liquor by 30~70g/L of solid-to-liquid ratio
Mixing, is stirred to react 1~4h under the conditions of 80~140 DEG C.
Technical solution of the present invention further improvement lies in that: the preparation process of desiliconization agent I be 20 by mass concentration~
40% sodium hydroxide solution and rich lithium flyash are mixed with liquid-solid ratio for 5~15mL/g, are 90~150 DEG C of items in temperature
0.5~2h is reacted under part, is then separated by filtration slurries, is desiliconization agent I, obtained filtrate and alkali after obtained filter residue and drying
Subsequent reactions are carried out after the mixing of method mother liquor；Desiliconization agent II be calcium oxide, calcium chloride and calcium sulfate with molar ratio 6:3:1 mixing and
At.
Technical solution of the present invention further improvement lies in that: in step 1) when the siliceous modulus of alkaline process mother liquor is less than 600,
Desiliconization treatment process is first to carry out one section of desiliconization, then carry out two-stage desilication；When the siliceous modulus of alkaline process mother liquor is greater than 600, take off
Silicon treatment process is only to carry out two-stage desilication.
Technical solution of the present invention further improvement lies in that: step 2 regulate and control pH Shi Jiashui or be added diluted acid.
Technical solution of the present invention further improvement lies in that: be passed through in step 3) excess carbon dioxide or concentration be 1~
The dilute acid soln of 4mol/L controls the pH of filtrate II 5~8, after being then stirred to react 0.5~2h under the conditions of 60~95 DEG C
It is separated by solid-liquid separation；The temperature of roasting is 300~500 DEG C, and calcining time is 30~120min.
Technical solution of the present invention further improvement lies in that: in step 3) will sediment A and B mix after soaked with hydro-thermal method
Out, it is separated by solid-liquid separation and obtains filter residue II and leachate containing lithium, carbonating obtains lithium carbonate product, filter residue II after the concentration of leachate containing lithium
As the raw material for extracting aluminium.
Technical solution of the present invention further improvement lies in that: hydro-thermal method leaching process be stirred under the conditions of 150~280 DEG C
Carry out 1~4h of hydro-thermal reaction.
Technical solution of the present invention further improvement lies in that: the concentration of the solution to be carbonated after concentration be 1~50g/L.
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
The present invention has simple process, is the total companion such as lithium, aluminium in bulk solid waste flyash the features such as being easily isolated and recycled
Raw metal resource higher value application provides new method, and economic benefit and environmental benefit are obvious.
The present invention effectively gets rid of the high silicon of content in alkaline process mother liquor, reduces process flow complexity, improves
The recovery rate of lithium realizes the purpose of rich lithium flyash alkaline process recycling useful metal, is in bulk solid waste flyash
Lithium, aluminium are total to associated resources and efficiently separate extraction and higher value application offer new approaches, new method.
The present invention extracts aluminium, lithium in flyash using desiliconization-original position coprecipitation, realizes two by simply synthesizing or matching
The preparation of section desiliconization agent can realize that aluminium lithium is co-precipitated in situ by cleaning and orienting regulation or else under conditions of additional silicon source, from
And separate aluminium, lithium and complicated leachate system, complicated more separation of metal ions processes are avoided, process flow is shortened,
With advantages, energy while industrialized production lithium carbonate and the aluminium products such as at low cost, simple, the utilization rate height of extraction separation, maximum limit
Degree really realizes the higher value application of flyash using useful component in flyash.
Detailed description of the invention
Fig. 1 is the process flow diagram for the method that the present invention extracts lithium from rich lithium flyash alkaline process mother liquor.
Specific embodiment
A method of lithium is extracted from rich lithium flyash alkaline process mother liquor, using rich lithium flyash as raw material, first by rich lithium powder
Coal ash is prepared into sodium aluminate liquor as alkaline process mother liquor, then lithium is extracted from alkaline process mother liquor, and wherein alkaline process mother liquor is selected from rich lithium powder
The sodium aluminate liquor or alkali soluble solution that coal ash sintering process or bayer process are handled are formed by one of sodium aluminate solution
Or a variety of mixing.The step of lithium is extracted from alkaline process mother liquor is as follows:
1) it desiliconization: according to the siliceous modulus (mass ratio for referring to aluminium and silicon in alkaline process mother liquor) in alkaline process mother liquor, carries out at desiliconization
Reason, obtained reacting slurry are separated by solid-liquid separation and are collected filtrate I, and filtrate carries out subsequent step and extracts lithium, and filter residue is silicon
Calcium slag can be comprehensively utilized further.Wherein desiliconization processing is divided into one section of desiliconization and two-stage desilication, and the process of one section of desiliconization is that will take off
(preparation process of desiliconization agent I is that the sodium hydroxide solution for being 20~40% by rich lithium flyash and mass concentration is consolidated with liquid to silicea I
Than the ratio between (volume of sodium hydroxide solution with rich lithium flyash quality), 5~15mL/g is mixed, and is 90~150 DEG C in temperature
Under the conditions of react 0.5~2h, then slurries are separated by filtration, after obtained filter residue and drying be desiliconization agent I, obtained filtrate with
Carry out subsequent reactions after the mixing of alkaline process mother liquor) with alkaline process mother liquor by solid-to-liquid ratio (quality of the desiliconization agent of addition and alkaline process mother liquor
The ratio between volume) 40~100g/L mixed, 1~6h is stirred to react under the conditions of 90~190 DEG C；The process of two-stage desilication is will
Desiliconization agent II (desiliconization agent II is that calcium oxide, calcium chloride and calcium sulfate are mixed with molar ratio 6:3:1) is with alkaline process mother liquor by solid
Liquor ratio the ratio between (quality of the desiliconization agent of addition with the volume of alkaline process mother liquor) 30~70g/L is mixed, in 80~140 DEG C of conditions
Under be stirred to react 1~4h.When the siliceous modulus of alkaline process mother liquor is less than 600, desiliconization treatment process is first one section of desiliconization of progress, then
Two-stage desilication is carried out, silicon amount in mother liquor of making every effort to is down at least；When the siliceous modulus of alkaline process mother liquor is greater than 600, desiliconization is processed
Journey is only to carry out two-stage desilication to meet post precipitation requirement.
2) pH regulates and controls: adding water into filtrate I or diluted acid is added, the pH value of filtrate I is adjusted to 7~9, separation of solid and liquid obtains
Sediment A and filtrate II；Wherein diluted acid includes one or more of hydrochloric acid, nitric acid etc..
3) it is the dilute of 1~4mol/L that aluminium lithium co-deposited synthesis:, which being passed through excess carbon dioxide into filtrate II, or concentration is added
Acid solution (including one or more of hydrochloric acid, nitric acid etc.) controls the pH of filtrate II 5~8, then in 60~95 DEG C of items
It is stirred to react 0.5~2h under part, aluminium lithium original position coprecipitation reaction occurs, separation of solid and liquid obtains sediment B, sediment A and B are mixed
It is roasted after conjunction, the temperature of roasting is 300~500 DEG C, and calcining time is 30~120min, washes again later, filtrate is obtained by filtration
III and filter residue I, will filtrate III be concentrated after carbonating recycling lithium carbonate, raw material of the filter residue I as extraction aluminium；After concentration to carbonic acid
The concentration for changing solution is 1~50g/L.Hydro-thermal method also can be used after wherein mixing sediment A and B to leach, separation of solid and liquid obtains
Filter residue II and leachate containing lithium, carbonating obtains lithium carbonate product after the concentration of leachate containing lithium, filter residue II (containing aluminum oxide,
Hydroxide) as the raw material for extracting aluminium；Hydro-thermal method leaching process is that stirring carries out hydro-thermal reaction 1 under the conditions of 150~280 DEG C
~4h, the time of preferred hydro-thermal reaction are 2h；The concentration of solution to be carbonated after concentration is 1~50g/L.
Embodiment 1
The present embodiment, which is directed to, to be obtained using after the rich agglutinants sintering process such as lithium flyash and sodium carbonate using the methods of alkali leaching, water logging
Alkaline process mother liquor extract lithium technology.More particularly to the mother liquor that diluted alkaline after flyash and sodium carbonate roasting embathes, siliceous modulus is
230, as shown in Figure 1, the step of extracting lithium from alkaline process mother liquor is as follows:
1) desiliconization: according to the siliceous modulus of alkaline process mother liquor, one section of desiliconization is first carried out, then carry out two-stage desilication, specific first segment
Desiliconization agent preparation condition is mixed the NaOH solution of flyash and 40% mass fraction concentration with liquid-solid ratio 5mL/g, in temperature 120
DEG C, under time 1h after the reaction was completed, slurries are separated by filtration, desiliconization agent I is used as after filter residue and drying, filtrate returns to mother liquor.It will take off
Silicea I is added in alkaline process mother liquor, makes solid-to-liquid ratio 50g/L, reacts 2h, silicon under 110 DEG C of temperature, 600rpm/min stirring condition
Volume index becomes 980.Carry out two-stage desilication again, in two-stage desilication desiliconization agent II be use ratio for calcium oxide, calcium chloride and
6:3:1 is mixed calcium sulfate in molar ratio, and desiliconization agent II is added in the solution after one section of desiliconization, solid-to-liquid ratio 30g/L is made,
140 DEG C of temperature, 2h is carried out under 800rpm/min stirring condition, siliceous modulus reaches 10000 or more.It is filtered, obtains later
Filtrate I.
2) pH regulates and controls: it is 9 that filtrate I, which is diluted with water to pH, has sediment A generation, filtrate II and precipitating are obtained after filtering
Object A.
3) excessive CO aluminium lithium co-deposited synthesis: is passed through into filtrate II2, the co-precipitation of aluminium lithium is obtained in temperature 60 C reaction 1h
Sediment B is obtained by filtration 7 or so in object B, final pH, and sediment A, B are mixed in 300 DEG C of roasting 1h, filtering point after washing
From obtaining filtrate III and filter residue I, filtrate III makes 1~50g/L of concentration, recarbonation recycling lithium carbonate after being concentrated；Filter residue I is made
For the raw material for mentioning aluminium.The yield of lithium carbonate is up to 63%.
Embodiment 2
The present embodiment proposes aluminium process more particularly to rich lithium flyash Bayer process and obtains sodium aluminate liquor, and as alkaline process mother liquor, silicon amount refers to
Number is 310, as shown in Figure 1, the step of extracting lithium from alkaline process mother liquor is as follows:
1) desiliconization: according to the siliceous modulus of alkaline process mother liquor, one section of desiliconization is first carried out, then carry out two-stage desilication, specific first segment
Desiliconization agent preparation condition is mixed the NaOH solution of flyash and 20% mass fraction concentration with liquid-solid ratio 10mL/g, in temperature 95
DEG C, under time 5h after the reaction was completed, slurries are separated by filtration, desiliconization agent I is used as after filter residue and drying, filtrate returns to mother liquor.It will take off
Silicea I is added in alkaline process mother liquor, makes solid-to-liquid ratio 35g/L, 1h, silicon amount are reacted under 180 DEG C of temperature, 600rpm/min stirring condition
Index becomes 2100.Carry out two-stage desilication again, in two-stage desilication desiliconization agent II be use ratio for calcium oxide, calcium chloride and sulphur
6:3:1 is mixed sour calcium in molar ratio, and desiliconization agent II is added in the solution after one section of desiliconization, solid-to-liquid ratio 65g/L, desiliconization are made
It 90 DEG C of temperature, carries out under 800rpm/min stirring condition, siliceous modulus reaches 10000 or more.It is filtered later, obtains filtrate
Ⅰ。
2) pH regulates and controls: filtrate I being reacted to pH with 1mol/L dilute hydrochloric acid in 8 or so, has precipitate A generation, obtains after filtering
Filtrate II and sediment A.
3) aluminium lithium co-deposited synthesis: 2mol/L dilute hydrochloric acid is added into filtrate II, obtains aluminium in 85 DEG C of reaction 0.5h of temperature
Sediment B is obtained by filtration 6 or so in lithium co-precipitate B, final pH, and sediment A, B are mixed and are placed in reaction kettle 260 DEG C
Hydro-thermal reaction 1h occurs, is separated by filtration, obtains filtrate III and filter residue II, filtrate III makes 1~50g/L of concentration, then carbon after being concentrated
Acidification recycling lithium carbonate, filter residue II are used as and mention aluminum feedstock.Lithium carbonate yield is up to 72%.
Embodiment 3
The present embodiment is specifically related to the direct alkali extraction lithium process of rich lithium flyash NaOH and obtains sodium aluminate liquor, as alkaline process mother liquor,
Siliceous modulus is 125, as shown in Figure 1, the step of extracting lithium from alkaline process mother liquor is as follows:
1) desiliconization: according to the siliceous modulus of alkaline process mother liquor, one section of desiliconization is first carried out, then carry out two-stage desilication, specific first segment
Desiliconization agent preparation condition is mixed the NaOH solution of flyash and 30% mass fraction concentration with liquid-solid ratio 15mL/g, in temperature
145 DEG C, under time 3h after the reaction was completed, slurries are separated by filtration, desiliconization agent I is used as after filter residue and drying, filtrate returns to mother liquor.It will
Desiliconization agent I is added in alkaline process mother liquor, makes solid-to-liquid ratio 90g/L, reacts 2h, silicon under 150 DEG C of temperature, 600rpm/min stirring condition
Volume index becomes 1700.Carry out two-stage desilication again, in two-stage desilication desiliconization agent II be use ratio for calcium oxide, calcium chloride and
6:3:1 is mixed calcium sulfate in molar ratio, and desiliconization agent II is added in the solution after one section of desiliconization, solid-to-liquid ratio 55g/L is made, is taken off
120 DEG C of silicon temperature, 4h is carried out under 800rpm/min stirring condition, siliceous modulus reaches 10000 or more.It is filtered, obtains later
To filtrate I.
2) pH regulates and controls: using 1mol/L dilute nitric acid reaction, in 8 or so, to have precipitate A generation to pH, obtain after filtering filtrate I
Filtrate II and sediment A.
3) aluminium lithium co-deposited synthesis: 2mol/L dust technology is added into filtrate II, obtains aluminium lithium in 65 DEG C of reaction 1h of temperature
Sediment B is obtained by filtration 6 or so in co-precipitate B, final pH, and precipitate A, B are mixed and are placed on 200 DEG C of generations in reaction kettle
Hydro-thermal reaction 2h, is separated by filtration, and obtains filtrate III and filter residue II, and filtrate III makes 1~50g/L of concentration, recarbonation after being concentrated
Lithium carbonate is recycled, filter residue II is used as and mentions aluminum feedstock.Lithium carbonate yield is up to 67%.
Embodiment 4
The present embodiment, which is directed to, to be obtained using after the rich agglutinants sintering process such as lithium flyash and sodium carbonate using the methods of alkali leaching, water logging
Alkaline process mother liquor extract lithium technology.More particularly to the mother liquor that diluted alkaline after flyash and sodium carbonate roasting embathes, siliceous modulus is
630, as shown in Figure 1, the step of extracting lithium from alkaline process mother liquor is as follows:
1) desiliconization: according to the siliceous modulus of alkaline process mother liquor, only carrying out two-stage desilication, and desiliconization agent II is to adopt in specific two-stage desilication
6:3:1 is mixed calcium oxide, calcium chloride and the calcium sulfate for being with ratio in molar ratio, after one section of desiliconization is added in desiliconization agent II
Solution in, make solid-to-liquid ratio 30g/L, carry out 1h under 120 DEG C of temperature, 800rpm/min stirring condition, siliceous modulus reaches
10000 or more.It is filtered later, obtains filtrate I.
2) pH regulates and controls: it is 7 that filtrate I, which is diluted with water to pH, has sediment A generation, filtrate II and precipitating are obtained after filtering
Object A.
3) excessive CO aluminium lithium co-deposited synthesis: is passed through into filtrate II2, it is coprecipitated that aluminium lithium is obtained in temperature 70 C reaction 0.5h
Sediment B is obtained by filtration 6 or so in starch B, final pH, and sediment A, B are mixed in 500 DEG C of roasting 2h, filtering point after washing
From obtaining filtrate III and filter residue I, filtrate III makes 1~50g/L of concentration, recarbonation recycling lithium carbonate after being concentrated；Filter residue I is made
For the raw material for mentioning aluminium.The yield of lithium carbonate is up to 70%.
Embodiment 5
The present embodiment is specifically related to the direct alkali extraction lithium process of rich lithium flyash NaOH and obtains sodium aluminate liquor, as alkaline process mother liquor,
Siliceous modulus is 720, as shown in Figure 1, the step of extracting lithium from alkaline process mother liquor is as follows:
1) desiliconization: according to the siliceous modulus of alkaline process mother liquor, only carrying out two-stage desilication, and desiliconization agent II is to adopt in specific two-stage desilication
6:3:1 is mixed calcium oxide, calcium chloride and the calcium sulfate for being with ratio in molar ratio, after one section of desiliconization is added in desiliconization agent II
Solution in, make solid-to-liquid ratio 45g/L, 130 DEG C of desiliconization temperature, carry out 2h under 800rpm/min stirring condition, siliceous modulus reaches
10000 or more.It is filtered later, obtains filtrate I.
2) pH regulates and controls: using 1mol/L dilute nitric acid reaction, in 8 or so, to have precipitate A generation to pH, obtain after filtering filtrate I
Filtrate II and sediment A.
3) aluminium lithium co-deposited synthesis: 2mol/L dust technology is added into filtrate II, obtains aluminium in 95 DEG C of reaction 0.5h of temperature
Sediment B is obtained by filtration 6 or so in lithium co-precipitate B, final pH, and precipitate A, B are mixed and are placed on 160 DEG C of hairs in reaction kettle
Unboiled water thermal response 3h, is separated by filtration, and obtains filtrate III and filter residue II, and filtrate III makes 1~50g/L of concentration, then carbonic acid after being concentrated
Change recycling lithium carbonate, filter residue II is used as and mentions aluminum feedstock.Lithium carbonate yield is up to 78%.
Claims (10)
1. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor, using rich lithium flyash as raw material, first by rich lithium fine coal
Ash is prepared into sodium aluminate liquor and extracts lithium as alkaline process mother liquor, then from alkaline process mother liquor, it is characterised in that the following steps are included:
1) desiliconization: according to the siliceous modulus in alkaline process mother liquor, desiliconization processing is carried out, obtained reacting slurry is separated by solid-liquid separation simultaneously
Collect filtrate I；
2) pH regulates and controls: the pH value of filtrate I being adjusted to 7~9, separation of solid and liquid obtains sediment A and filtrate II；
3) aluminium lithium co-deposited synthesis: being passed through carbon dioxide into filtrate II or diluted acid is added, and separation of solid and liquid obtains sediment B, will
It is roasted after sediment A and B mixing, then washes, filtrate III and filter residue I is obtained by filtration, carbonating recycling carbon after filtrate III is concentrated
Sour lithium, filter residue I is as the raw material for extracting aluminium.
2. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1, it is characterised in that: alkali
The sodium aluminate liquor or alkali soluble solution that method mother liquor is selected from rich lithium flyash sintering process or bayer process is handled are formed by aluminium
One of acid sodium solution or a variety of mixing.
3. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1, it is characterised in that: step
It is rapid 1) in desiliconization processing be divided into one section of desiliconization and two-stage desilication, the process of one section of desiliconization is by desiliconization agent I and alkaline process mother liquor by solid
40~100g/L of liquor ratio is mixed, and is stirred to react 1~6h under the conditions of 90~190 DEG C；The process of two-stage desilication is by desiliconization
Agent II is mixed with alkaline process mother liquor by 30~70g/L of solid-to-liquid ratio, is stirred to react 1~4h under the conditions of 80~140 DEG C.
4. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 3, it is characterised in that: de-
The preparation process of silicea I be 20~40% by mass concentration sodium hydroxide solution and rich lithium flyash with liquid-solid ratio be 5~
15mL/g is mixed, and 0.5~2h is reacted under the conditions of temperature is 90~150 DEG C, is then separated by filtration slurries, obtained filter
It is desiliconization agent I after slag is dry, obtained filtrate carries out subsequent reactions after mixing with alkaline process mother liquor；Desiliconization agent II be calcium oxide,
Calcium chloride and calcium sulfate are mixed with molar ratio 6:3:1.
5. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 3 or 4, feature exist
In: in step 1) when the siliceous modulus of alkaline process mother liquor is less than 600, desiliconization treatment process is first to carry out one section of desiliconization, then carry out
Two-stage desilication；When the siliceous modulus of alkaline process mother liquor is greater than 600, desiliconization treatment process is only to carry out two-stage desilication.
6. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1, it is characterised in that: step
It is rapid 2) to regulate and control pH Shi Jiashui or diluted acid is added.
7. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1, it is characterised in that: step
It is rapid 3) in be passed through the dilute acid soln that excess carbon dioxide or concentration are 1~4mol/L and control the pH of filtrate II 5~8, then
It is separated by solid-liquid separation after being stirred to react 0.5~2h under the conditions of 60~95 DEG C；The temperature of roasting is 300~500 DEG C, calcining time
For 30~120min.
8. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1, it is characterised in that: step
It is rapid 3) in will sediment A and B mix after be leached with hydro-thermal method, separation of solid and liquid obtains filter residue II and leachate containing lithium, containing lithium leaching
Carbonating obtains lithium carbonate product after liquid concentration, and filter residue II is as the raw material for extracting aluminium.
9. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 8, it is characterised in that: water
Thermal method leaching process is that stirring carries out 1~4h of hydro-thermal reaction under the conditions of 150~280 DEG C.
10. a kind of method for extracting lithium from rich lithium flyash alkaline process mother liquor according to claim 1 or 8, feature exist
In: the concentration of the solution to be carbonated after concentration is 1~50g/L.
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