CN103183366B - Method for extracting lithium salt from spodumene by soda ash pressure leach method - Google Patents
Method for extracting lithium salt from spodumene by soda ash pressure leach method Download PDFInfo
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Abstract
The invention discloses a method for extracting lithium salt from spodumene by a soda ash pressure leach method. The method comprises the following technological process: (1) roasting and transforming; (2) cooling and grinding; (3) size mixing; (4) pressure leaching; and (5) cooling and decompressing. The method is characterized by further comprising the following technological process: (6) pressure filtering and separating; (7) acidifying and transforming; (8) separating and washing; (9) condensing and separating out sodium; (10) evaporating and crystallizing; (11) centrifugal separation; and (12) drying. The method for extracting lithium salt from spodumene by the soda ash pressure leach method provided by the invention is simple in process, low in cost and high in resource utilization rate.
Description
Technical field
The present invention relates to extract the preparation method of lithium salts, particularly relate to soda ash pressing immersion method and from triphane, extract the method for lithium salts.
Background technology
The industrial method of producing lithium salts is mainly divided into two classes:
One class is from containing lithium bittern, by the mineral of other valuable metals in bittern are carried out to comprehensive extraction and application, makes the lithium in bittern obtain enrichment, finally can obtain Li
2cO
3or Li
2sO
4h
2the lithium salts products such as O, still, because domestic salt lake brine major part has low Mg/Li ratio, development difficulty is large, and bittern is put forward the industrializing implementation difficulty of lithium;
Another kind of method is by destroying its original gangue structure to main containing lithium ore---pyrogenic process or the wet processing of triphane and lithionite, making Li wherein
2o is dissolved out with the form of solvable lithium salts, can obtain such as Li
2sO
4lithium salts with other form.From triphane, extract lithium salts and have that streams flux is little, production efficiency is high, energy consumption is low, the rate of recovery advantages of higher of lithium, so take triphane at present, as raw material, to carry lithium be the method extensively adopting.
The method of utilizing at present triphane to carry lithium mainly contains sulfuric acid process and lime method, and lime method is because of less employings of shortcoming such as energy consumption are high, the rate of recovery is low, production cost is high.And sulfuric acid rule is because consuming a large amount of sulphur bronsted lowry acids and bases bronsted lowries, exist industrial flow long, to equipment requirements the shortcoming such as high and contaminate environment.
Chinese patent CN201010279730.1 discloses a kind of method of extracting lithium salts from lithium brightness, this patent employing sodium carbonate pressing immersion method is carried lithium from triphane and is prepared battery-level lithium carbonate, triphane presses the Quilonum Retard obtaining after soaking to insert together with slag through sodium carbonate in carbonization still, to carry out degree of depth carbonization, Quilonum Retard is converted into soluble lithium bicarbonate completely, be separated by filtration lithium bicarbonate and pressure is soaked slag, then lithia water thermal degradation is obtained to pure Lithium Carbonate.There are two shortcomings in this method, the one, together with Quilonum Retard is mixed in slag, by carbonization, be difficult to completely Quilonum Retard is converted into lithium bicarbonate, cause part Quilonum Retard to enter in slag and discard, having reduced the lithium rate of recovery, the 2nd,, adopt this method can only prepare battery-level lithium carbonate, preparing Lithium chloride (anhydrous), lithium nitrate needs acidified, evaporation concentration, drying and other steps, and the method for preparing Lithium chloride (anhydrous) and lithium nitrate with respect to this patent has increased operation, causes production cost to increase.
Summary of the invention
The present invention completes in order to solve deficiency of the prior art, the object of this invention is to provide the soda ash pressing immersion method that a kind of technique is simple, cost is low, resource utilization is high and from triphane, extracts the method for lithium salts.
Soda ash pressing immersion method of the present invention extracts the method for lithium salts from triphane, comprise following technical process:
(1) roasting makes the transition: by triphane concentrate (Li
2oAl
2o
34SiO
2) be placed in internal-heated rotary furnace, temperature is controlled at carries out roasting transition under the high temperature of 1150-1250 ℃, makes triphane concentrate transfer β type to by α type;
(2) cooling levigate: the raw material after step (1) roasting to be cooled to normal temperature, then to be milled down to 50-325 object triphane;
(3) size mixing: soda ash and step (2) are obtained levigate after triphane add the water of metering to be deployed into slip, and to control sodium lithium mol ratio be 2-7, liquid-solid ratio is 3-5, the weight of described basic salt counts in liquid phase;
(4) press and to soak: the slip heating that utilizes high pressure steam to obtain to step (3), make described slurry temperature be raised to 180-270 ℃, and to keep the constant temperature and pressure time be 0.5-3.5h, the pressure of described high pressure steam is 0.8～6Mpa, presses and leaches Quilonum Retard;
(5) cooling decompression: the slip that cooling step (4) obtains is decompressed to atmospheric pressure state, and be cooled to 60～90 ℃;
It is characterized in that: also comprise the following steps in turn:
(6) press filtration is separated: the cooled pressure of step (5) is soaked to slip and carry out press filtration separation, obtain triphane pressure and soak slag and mother liquor, mother liquor is back to step (3) and sizes mixing;
(7) acidifying makes the transition: the triphane pressure that step (6) is obtained is soaked slag and inserted in still transition, add wash water or the pure water that step (8) is returned to be deployed into triphane slip, the solvent and solute weight ratio of described triphane slip is 2～3, and to transition, add the acid of metering in still, stirring reaction 0.5-1.5h, is converted into solubility lithium salts completely by Quilonum Retard, and then in still, adds NaOH toward transition, in stirring and 0.5-1.5h, until the pH of regulator solution is to 7-10;
(8) separated, washing: the slip by step (7) after transition obtains filtrate and filter residue through press filtration, filter residue abandons after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) the concentrated sodium of analysing: the filtrate evaporation concentration that will obtain through step (8) to the density of solution is 1.29-1.31g/cm
3, be then cooled to 60 ℃ of following stirring reaction 0.5-1.5h and analyse sodium, after press filtration, obtain lithium salts scavenging solution;
(10) evaporative crystallization: it is 30-60% that the lithium salts scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration of volume percent;
(11) centrifugation: the magma that step (10) is obtained is put into whizzer and dewatered, obtains water content and is 2～5% lithium salts wet feed, and described water content is mass percent;
(12) dry: the lithium salts wet feed that step (11) is obtained is dry 1-2.5h at 150-250 ℃, obtains anhydrous lithium salts product.
The method that soda ash pressing immersion method of the present invention extracts lithium salts from triphane can also be:
In described (7) step, add the calculation formula of sour amount to be:
V
acid=(m
triphane* Li
2o% * 95% * M
acid* 2 * 1.1)/(30 * ω
acid% * ρ
acid), wherein, V
acidfor adding sour volume, unit is for rising; m
triphanefor the triphane weight dropping into, unit is Kg; Li
2o% is the mass percent wt% of Lithium Oxide 98min in triphane; 95% soaks leaching yield for pressing; M
acidfor adding sour molecular weight; 1.1 represent to add excessive acid 10%; 30 is the molecular weight of Lithium Oxide 98min; ω
acidfor adding sour mass percent wt%; ρ
acidfor adding sour density, unit is Kg/l.
Acid in described step (7) is HCl or HNO
3.
Soda ash pressing immersion method of the present invention extracts the method for lithium salts from triphane, it is by after above-mentioned steps, in terms of existing technologies, mother liquor after soaking is made the transition and is prepared lithium chloride or the lithium nitrate that purity is higher by direct acidifying, and prior art is converted into lithium bicarbonate by the carbonization of the mother liquor degree of depth, Quilonum Retard is prepared in thermolysis, and then makes the transition and prepare lithium chloride or lithium nitrate product through acidifying.Therefore, this technique has advantages of features simple and practical process, production cost is low, the utilization of resources is high, has good economic and social benefit, is suitable for the advantage that lithium is carried in industrialization.
Accompanying drawing explanation
Fig. 1 soda ash pressing immersion method of the present invention extracts the process flow sheet of the method for lithium salts from triphane.
Embodiment
Fig. 1 below in conjunction with accompanying drawing is described in further detail from the method for triphane extraction lithium salts soda ash pressing immersion method of the present invention.
Soda ash pressing immersion method of the present invention extracts the method for lithium salts from triphane, please refer to Fig. 1, comprises following technical process:
(1) roasting makes the transition: by triphane concentrate (Li
2oAl
2o
34SiO
2) be placed in internal-heated rotary furnace, temperature is controlled at carries out roasting transition under the high temperature of 1150-1250 ℃, makes triphane concentrate transfer β type to by α type;
(2) cooling levigate: the raw material after step (1) roasting to be cooled to normal temperature, then to be milled down to 50-325 object triphane;
(3) size mixing: soda ash and step (2) are obtained levigate after triphane add the water of metering to be deployed into slip, and to control sodium lithium mol ratio be 2-7, liquid-solid ratio is 3-5, the weight of described basic salt counts in liquid phase;
(4) press and to soak: the slip heating that utilizes high pressure steam to obtain to step (3), make described slurry temperature be raised to 180-270 ℃, and to keep the constant temperature and pressure time be 0.5-3.5h, the pressure of described high pressure steam is 0.8～6Mpa, presses and leaches Quilonum Retard;
(5) cooling decompression: the slip that cooling step (4) obtains is decompressed to atmospheric pressure state, and be cooled to 60～90 ℃;
It is characterized in that: also comprise the following steps in turn:
(6) press filtration is separated: the cooled pressure of step (5) is soaked to slip and carry out press filtration separation, obtain triphane pressure and soak slag and mother liquor, mother liquor is back to step (3) and sizes mixing;
(7) acidifying makes the transition: the triphane pressure that step (6) is obtained is soaked slag and inserted in still transition, add wash water or the pure water that step (8) is returned to be deployed into triphane slip, the solvent and solute weight ratio of described triphane slip is 2～3, and to transition, add the acid of metering in still, stirring reaction 0.5-1.5h, is converted into solubility lithium salts completely by Quilonum Retard, and then in still, adds NaOH toward transition, in stirring and 0.5-1.5h, until the pH of regulator solution is to 7-10;
(8) separated, washing: the slip by step (7) after transition obtains filtrate and filter residue through press filtration, filter residue abandons after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) the concentrated sodium of analysing: the filtrate evaporation concentration that will obtain through step (8) to the density of solution is 1.29-1.31g/cm
3, be then cooled to 60 ℃ of following stirring reaction 0.5-1.5h and analyse sodium, after press filtration, obtain lithium salts scavenging solution;
(10) evaporative crystallization: it is 30-60% that the lithium salts scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration of volume percent;
(11) centrifugation: the magma that step (10) is obtained is put into whizzer and dewatered, obtains water content and is 2～5% lithium salts wet feed, and described water content is mass percent;
(12) dry: the lithium salts wet feed that step (11) is obtained is dry 1-2.5h at 150-250 ℃, obtains anhydrous lithium salts product.
Concrete analysis: described step (2) cooling levigate in, levigate order number is the bigger the better, and order number is more beneficial to more greatly the leaching of lithium, but the larger energy consumption of order number is higher, therefore the preferred span of order number is 50～325 orders, when order number within the scope of this energy consumption and leaching yield more reasonable.
The principle that described step (6) acid adding makes the transition is:
Li
2CO
3+2HCl=2LiCl+H
2O+CO
2
Li
2CO
3+2HNO
3=2LiNO
3+H
2O+CO
2
Soda ash pressing immersion method of the present invention extracts the method for lithium salts from triphane, it is by after above-mentioned steps, and in terms of existing technologies, it has features simple and practical process, production cost is low, the utilization of resources is high, there is good economic and social benefit, be suitable for the advantage that lithium is carried in industrialization.
Soda ash pressing immersion method of the present invention extracts the method for lithium salts from triphane, on the basis of previous technique scheme, can also be:
In described (7) step, add the calculation formula of sour amount to be:
V
acid=(m
triphane* Li
2o% * 95% * M
acid* 2 * 1.1)/(30 * ω
acid% * ρ
acid), wherein, V
acidfor adding sour volume, unit is for rising; m
triphanefor the triphane weight dropping into, unit is Kg; Li
2o% is the mass percent wt% of Lithium Oxide 98min in triphane; 95% soaks leaching yield for pressing; M
acidfor adding sour molecular weight; 1.1 represent to add excessive acid 10%; 30 is the molecular weight of Lithium Oxide 98min; ω
acidfor adding sour mass percent wt%; ρ
acidfor adding sour density, unit is Kg/l.Can also be that acid in described step (7) is HCl or HNO
3.
Embodiment 1
(1) 1000Kg triphane concentrate is placed in internal-heated rotary furnace, under 1250 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to;
(2) cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process and have enough contact surfaces for making to roast material with feed liquid, then roasting is milled down to 325 orders, the content of analyzing Lithium Oxide 98min is 5.63%.
(3) size mixing: 800Kg soda ash and the levigate triphane of 1000Kg are added to 3200Kg water allotment pulping, and controlling sodium lithium mol ratio is 4, and liquid-solid ratio is 4, and soda ash weight counts liquid phase.
(4) press and soak: utilize high pressure steam that slip is warmed up to 270 ℃, the relevant pressure of high pressure steam is 2.4Mpa, and the constant temperature and pressure time is 3.5h.
(5) cooling decompression: the pressure of step (4) is soaked slip and is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 90 ℃.
(6) press filtration is separated: the pressure that step 5 is obtained is soaked slip and carried out press filtration separation, obtains filtrate 3.9m
3, to press triphane to press and soak slag 1300Kg, filtrate is back to step (3) for sizing mixing;
(7) acidifying transition: the 1300Kg triphane that step (6) is obtained is pressed and soaked slag (being 1000kg containing triphane butt) and insert in still transition, adds pure water 2m
3be made into triphane slip (solvent and solute weight ratio is 2.30), and in still, add 400L30%(wt% to turning) hydrochloric acid, stirring reaction 1.5h, Quilonum Retard is converted into lithium chloride completely, and then add 100L35%(wt% toward transition in still) NaOH, in stirring and 1.5h, the pH of regulator solution is 10;
(8) separated, washing: the slip by step (7) after transition obtains 2.5m through press filtration
3filtrate and 1300Kg filter residue, filter residue discards after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) concentrate and analyse sodium: by the filtrate evaporation concentration obtaining through step (8) to density, be 1.31g/cm
3, being then cooled to 50 ℃, stirring reaction 1.5h analyses sodium, obtains 0.3m after press filtration
3lithium chloride scavenging solution;
(10) evaporative crystallization: it is 60%(volume percent that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 3.8%(wt%);
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 2.5h at 250 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A1.
Embodiment 2:
(1) 1500Kg triphane concentrate is placed in internal-heated rotary furnace, under 1150 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to;
(2) cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process for to make material and feed liquid after roasting have enough contact surfaces, then the material after roasting is milled down to 50 orders, the quality percentage composition of analyzing Lithium Oxide 98min is 5.15%;
(3) size mixing: the levigate triphane of 1500Kg that 600Kg soda ash and step (2) are obtained adds 5400Kg water allotment pulping, and controlling sodium lithium mol ratio is 2.2, and liquid-solid ratio is 4, and soda ash weight counts liquid phase;
(4) press and soak: the slip that utilizes high pressure steam that step (3) is obtained is warmed up to 180 ℃, and the relevant pressure of high pressure steam is 1.0Mpa, keeping the constant temperature and pressure time is 0.5h;
(5) cooling decompression: the pressure of step (4) is soaked slip and is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 60 ℃;
(6) press filtration is separated: the pressure that step (5) is obtained is soaked slip and carried out press filtration separation, obtains filtrate 6m
3, triphane is pressed and is soaked slag 2000Kg, and filtrate is that mother liquor is back to step (3) for sizing mixing;
(7) acidifying makes the transition: the 2000Kg triphane pressure that step (6) is obtained is soaked slag (being 1500kg containing triphane butt) and inserted in still transition the wash water 3m that adds step (8) to return
3be made into triphane slip (solvent and solute weight ratio is 2.33), and in still, add 720L25%(wt% to turning) hydrochloric acid, stirring reaction 0.5h, Quilonum Retard is converted into solubility chlorination lithium completely, and then in still, add 175L30%(wt% toward transition) NaOH, in stirring and 0.5h, the pH of regulator solution is 10;
(8) separated, washing: the slip by step (7) after transition obtains 3.8m through press filtration
3filtrate and 1900Kg filter residue, filter residue discards after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) the concentrated sodium of analysing: be 1.29g/cm by the filtrate evaporation concentration obtaining through step (8) to the density of solution
3, being then cooled to 30 ℃, stirring reaction 0.5h analyses sodium, obtains 0.45m after press filtration
3lithium chloride scavenging solution;
(10) evaporative crystallization: it is 30%(volume percent that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 4.2%(wt%);
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 1h at 150 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A2.
Embodiment 3:
(1) 800Kg triphane concentrate is placed in internal-heated rotary furnace, under 1200 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to;
(2) cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process for making and have enough contact surfaces with feed liquid after roasting, then by 260 orders that are milled down to after roasting, the quality percentage composition of analyzing Lithium Oxide 98min is 5.58%.
(3) size mixing: add 2560Kg water to be deployed into slip 640Kg soda ash and the levigate triphane of 800Kg, controlling sodium lithium mol ratio is 4, and liquid-solid ratio is 4, and soda ash weight counts liquid phase.
(4) press and soak: utilize high pressure steam that step (3) is obtained to slip and be warmed up to 200 ℃, the relevant pressure of high pressure steam is 1.6Mpa, keeping the constant temperature and pressure time is 2h.
(5) cooling decompression: the slip of step (4) is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 70 ℃.
(6) press filtration is separated: the pressure that step (5) is obtained is soaked slip and carried out press filtration separation, obtains triphane pressure and soaks slag and mother liquor, wherein mother liquor 3m
3, triphane is pressed and is soaked slag 1000Kg, and filtrate is that mother liquor is back to step 3 for sizing mixing;
(7) acidifying transition: the 1000Kg triphane that step (6) is obtained is pressed and soaked slag (containing triphane butt 800kg) and insert in still transition, the wash water 1.6m that adds step (8) to return
3wash water furnishing triphane slip (solvent and solute weight ratio is 2.25), and add 225L40%(wt% in still to turning) hydrochloric acid, stirring reaction 1h, Quilonum Retard is converted into lithium chloride completely, and then add 70L40%(wt% toward transition in still) NaOH, in stirring and 1h, the pH of regulator solution is 7.
(8) separated, washing: the slip by step (7) after transition obtains 2m through press filtration
3filtrate and 980Kg filter residue, filter residue is that mother liquor discards after three washings, the wash water cleaning after filter residue returns to step (7).
(9) the concentrated sodium of analysing: be 1.30g/cm by the filtrate evaporation concentration obtaining through step (8) to the density of solution
3, being then cooled to 40 ℃, stirring reaction 1h analyses sodium, obtains 0.2m after press filtration
3lithium chloride scavenging solution;
(10) evaporative crystallization: it is 50%(volume percent that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 4.8%(wt%).
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 2.3h at 200 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A3.
Embodiment 4:
(1) 2000Kg triphane concentrate is placed in internal-heated rotary furnace, under 1200 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to; Cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process for to make material and feed liquid after roasting have enough contact surfaces.
(2) again the material after roasting is milled down to 250 orders, the quality percentage composition of analyzing Lithium Oxide 98min is 5.36%.
(3) size mixing: 1200Kg soda ash and the levigate triphane of 2000Kg are added to 6800Kg water allotment pulping, and controlling sodium lithium mol ratio is 3.2, and liquid-solid ratio is 4, and soda ash weight counts liquid phase.
(4) press and soak: utilize high pressure steam that slip is warmed up to 250 ℃, the relevant pressure of high pressure steam is 2.2Mpa, and the constant temperature and pressure time is 3h.
(5) cooling decompression: the pressure of step (4) is soaked slip and is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 40 ℃.
(6) press filtration is separated: the pressure that step (5) is obtained is soaked slip and carried out press filtration separation, obtains filtrate 8m
3, to press and soak slag 2600Kg, filtrate is that mother liquor is back to step 3 for sizing mixing;
(7) acidifying makes the transition: the 2600Kg triphane pressure that step (6) is obtained is soaked slag (being 2000kg containing triphane butt) and inserted in still transition the wash water 4m that adds step (8) to return
3be made into triphane slip (solvent and solute weight ratio is 2.3), and in still, add 728.57L35%(wt% to turning) hydrochloric acid, stirring reaction 1h, Quilonum Retard is converted into lithium chloride completely, and then in still, add 291.17L30%(wt% toward transition) NaOH solution, in stirring and 1h, the pH of regulator solution is 9;
(8) separated, washing: the slip by step (7) after transition obtains 5.1m through press filtration
3filtrate and 2500kg filter residue, filter residue discards after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) the concentrated sodium of analysing: be 1.31g/cm by the filtrate evaporation concentration obtaining through step (8) to the density of solution
3, being then cooled to 50 ℃, stirring reaction 1h analyses sodium, obtains 0.7m after press filtration
3lithium chloride scavenging solution;
(10) evaporative crystallization: it is 45%(volume ratio that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 4.33%(wt%).
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 2h at 200 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A4.
Embodiment 5:
(1) 1000Kg triphane concentrate is placed in internal-heated rotary furnace, under 1180 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to;
(2) cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process for to make material and feed liquid after roasting have enough contact surfaces, then the material after roasting is milled down to 150 orders, the quality percentage composition of analyzing Lithium Oxide 98min is 5.52%.
(3) size mixing: 600Kg soda ash and the levigate triphane of 1000Kg are added to 3400Kg water allotment pulping, and controlling sodium lithium mol ratio is 3.1, and liquid-solid ratio is 4, and soda ash weight counts liquid phase.
(4) press and soak: utilize high pressure steam that slip is warmed up to 220 ℃, the relevant pressure of high pressure steam is 1.9Mpa, and the constant temperature and pressure time is 2.5h.
(5) cooling decompression: the pressure of step (4) is soaked slip and is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 85 ℃.
(6) press filtration is separated: the pressure that step (5) is obtained is soaked slip and carried out press filtration separation, obtains filtrate 3.4m
3, triphane is pressed and is soaked slag 1300Kg, and filtrate is that mother liquor is back to step (3) for sizing mixing;
(7) acidifying makes the transition: the 1300Kg triphane that step (6) is obtained soaks slag (being 1000kg containing triphane butt) and inserts in still transition the wash water 2m that adds step (8) to return
3be made into triphane slip (liquid-solid ratio is 2.3), and in still, add 450L20%(wt% to turning) hydrochloric acid, stirring reaction 1h, Quilonum Retard is converted into lithium chloride completely, and then add 80L35%(wt% toward transition in still) NaOH, in stirring and 1h, the pH of regulator solution is 7.
(8) separated, washing: the slip by step (7) after transition obtains 2.4m through press filtration
3filtrate and 1300kg filter residue, filter residue discards after three washings, and the wash water cleaning after filter residue returns to step (7).
(9) the concentrated sodium of analysing: be 1.31g/cm3 by the filtrate evaporation concentration obtaining through step (8) to the density of solution, be then cooled to 50 ℃, stirring reaction 1.5h analyses sodium, obtains 0.2m after press filtration
3lithium chloride scavenging solution;
(10) evaporative crystallization: it is 40%(volume ratio that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 4.1%(wt%).
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 1.5h at 220 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A5.
Embodiment 6
(1) 1000Kg triphane concentrate is placed in internal-heated rotary furnace, under 1250 ℃ of high temperature, carries out conversion roasting, make it by α type, transfer β type to;
(2) cooling levigate: the material after roasting still has higher waste heat, therefore its heat exchange is cooled to normal temperature; In pressure, soak in process for to make material and feed liquid after roasting have enough contact surfaces, then the material after roasting is milled down to 250 orders, the quality percentage composition of analyzing Lithium Oxide 98min is 5.28%.
(3) size mixing: 700Kg soda ash and the levigate triphane of 1000Kg are added to 2300Kg water allotment pulping, and controlling sodium lithium mol ratio is 3.75, and liquid-solid ratio is 3, and soda ash weight counts liquid phase.
(4) press and soak: utilize high pressure steam that slip is warmed up to 220 ℃, the relevant pressure of high pressure steam is 1.9Mpa, and the constant temperature and pressure time is 2.5h.
(5) cooling decompression: the pressure of step (4) is soaked slip and is decompressed to atmospheric pressure state, and the slip after pressure is soaked cools to 85 ℃.
(6) press filtration is separated: the pressure that step (5) is obtained is soaked slip and carried out press filtration separation, obtains filtrate 2.7m
3, triphane is pressed and is soaked slag 1300Kg, and filtrate is that mother liquor is back to step (3) for sizing mixing;
(7) acidifying makes the transition: the 1300Kg triphane that step (6) is obtained soaks slag (being 1000kg containing triphane butt) inserts in still transition, adds pure water 2.5m
3be made into triphane slip (liquid-solid ratio is 2.8), and in still, add 340L45%(wt% to turning) nitric acid, stirring reaction 1h, Quilonum Retard is converted into lithium nitrate completely, and then add 93L35%(wt% toward transition in still) NaOH, in stirring and 1h, the pH of regulator solution is 7.
(8) separated, washing: the slip by step (7) after transition obtains 2.5m through press filtration
3filtrate and 1300kg filter residue, filter residue discards after three washings, and the wash water cleaning after filter residue returns to step (7).
(9) the concentrated sodium of analysing: be 1.31g/cm3 by the filtrate evaporation concentration obtaining through step (8) to the density of solution, be then cooled to 50 ℃, stirring reaction 1.5h analyses sodium, obtains 0.3m after press filtration
3lithium nitrate scavenging solution;
(10) evaporative crystallization: it is 40%(volume ratio that the lithium chloride scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration);
(11) lithium chloride wet feed centrifugation: the magma that step (10) is obtained is put into whizzer dehydration, and obtaining water content is 3.7%(wt%).
(12) dry: the lithium chloride wet feed that step (11) is obtained is dry 1.5h at 230 ℃, obtains Lithium chloride (anhydrous) product, and production code member is A6.
Lithium chloride and lithium nitrate product that above-described embodiment 1～6 is obtained detect, and obtain technical indicator
As follows:
The conclusion that can be drawn by above-mentioned technical indicator is: the Lithium chloride (anhydrous) of preparation and the product purity of lithium nitrate are high, Lithium chloride (anhydrous) quality product meets national standard (GB/T10575-2007) LiCl～1 requirement, and anhydrous nitric acid lithium quality product meets customer need.
Above-mentionedly only several specific embodiments in the present invention are illustrated; but can not be as protection scope of the present invention; every equivalence variation of having done according to the design spirit in the present invention or modification or equal proportion zoom in or out etc., all should think and fall into protection scope of the present invention.
Claims (3)
1. soda ash pressing immersion method extracts the method for lithium salts from triphane, comprises following technical process:
(1) roasting makes the transition: by triphane concentrate (Li
2oAl
2o
34SiO
2) be placed in internal-heated rotary furnace, temperature is controlled at carries out roasting transition under the high temperature of 1150-1250 ℃, makes triphane concentrate transfer β type to by α type;
(2) cooling levigate: the raw material after step (1) roasting to be cooled to normal temperature, then to be milled down to 50-325 object triphane;
(3) size mixing: soda ash and step (2) are obtained levigate after triphane add the water of metering to be deployed into slip, and to control sodium lithium mol ratio be 2-7, liquid-solid ratio is 3-5, the weight of described basic salt counts in liquid phase;
(4) press and to soak: the slip heating that utilizes high pressure steam to obtain to step (3), make described slurry temperature be raised to 180-270 ℃, and to keep the constant temperature and pressure time be 0.5-3.5h, the pressure of described high pressure steam is 0.8～6Mpa, presses and leaches Quilonum Retard;
(5) cooling decompression: the slip that cooling step (4) obtains is decompressed to atmospheric pressure state, and be cooled to 60～90 ℃;
It is characterized in that: also comprise the following steps in turn:
(6) press filtration is separated: the cooled pressure of step (5) is soaked to slip and carry out press filtration separation, obtain triphane pressure and soak slag and mother liquor, mother liquor is back to step (3) and sizes mixing;
(7) acidifying makes the transition: the triphane pressure that step (6) is obtained is soaked slag and inserted in still transition, add wash water or the pure water that step (8) is returned to be deployed into triphane slip, the solvent and solute weight ratio of described triphane slip is 2～3, and to transition, add the acid of metering in still, stirring reaction 0.5-1.5h, is converted into solubility lithium salts completely by Quilonum Retard, and then in still, adds NaOH toward transition, in stirring and 0.5-1.5h, until the PH of regulator solution is to 7-10;
(8) separated, washing: the slip by step (7) after transition obtains filtrate and filter residue through press filtration, filter residue abandons after three washings, and the wash water cleaning after filter residue returns to step (7);
(9) the concentrated sodium of analysing: the filtrate evaporation concentration that will obtain through step (8) to the density of solution is 1.29-1.31g/cm
3, be then cooled to 60 ℃ of following stirring reaction 0.5-1.5h and analyse sodium, after press filtration, obtain lithium salts scavenging solution;
(10) evaporative crystallization: it is 30-60% that the lithium salts scavenging solution that step (9) is obtained carries out evaporating, concentrating and crystallizing to magma concentration of volume percent;
(11) centrifugation: the magma that step (10) is obtained is put into whizzer and dewatered, obtains water content and is 2～5 lithium salts wet feed, and described water content is mass percent WT%;
(12) dry: the lithium salts wet feed that step (11) is obtained is dry 1-2.5h at 150-250 ℃, obtains anhydrous lithium salts product.
2. soda ash pressing immersion method according to claim 1 extracts the method for lithium salts from triphane, it is characterized in that: in described (7) step, add the calculation formula of sour amount to be:
V
acid=(m
triphane* Li
2o% * 95% * M
acid* 2 * 1.1)/(30 * ω
acid% * ρ
acid), wherein, V
acidfor adding sour volume, unit is for rising; m
triphanefor the triphane weight dropping into, unit is Kg; Li
2o% is the mass percent wt% of Lithium Oxide 98min in triphane; 95% soaks leaching yield for pressing; M
acidfor adding sour molecular weight; 1.1 represent to add excessive acid 10%; 30 is the molecular weight of Lithium Oxide 98min; ω
acidfor adding sour mass percent wt%; ρ
acidfor adding sour density, unit is Kg/l.
3. soda ash pressing immersion method according to claim 1 and 2 extracts the method for lithium salts from triphane, it is characterized in that: the acid in described step (7) is HCl or HNO
3.
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| CN104003428B (en) * | 2014-06-11 | 2015-11-18 | 福州大学 | The method of lithium hydroxide is produced in a kind of triphane pipeline reactor stripping |
| CN107815557A (en) * | 2017-10-16 | 2018-03-20 | 福州大学 | A kind of spodumene pipe reaction puies forward lithium technique |
| US20210032724A1 (en) * | 2018-02-02 | 2021-02-04 | Tianqi Lithium Kwinana Pty Ltd | Process For Extracting Values from Lithium Slag |
| CN109133118A (en) * | 2018-09-18 | 2019-01-04 | 萍乡市拓源实业有限公司 | A kind of technique that spodumene soda ash autoclaving method prepares lithium carbonate |
| CN109455744B (en) * | 2018-12-28 | 2021-02-12 | 江西赣锋锂业股份有限公司 | Method for preparing industrial-grade lithium carbonate by recovering lithium from spodumene calcium magnesium slag |
| CN109485077A (en) * | 2019-01-15 | 2019-03-19 | 宁德叁源技术有限公司 | A kind of technique for extracting lithium from lithium ore |
| CN110510642A (en) * | 2019-09-27 | 2019-11-29 | 福州大学 | A kind of method that low-grade α spodumene economy mentions lithium |
| CN111017966B (en) * | 2019-12-06 | 2022-07-26 | 江西赣锋锂业股份有限公司 | Preparation method for preparing high-purity anhydrous lithium chloride by using butyl lithium residues |
| CN115323195A (en) * | 2022-07-13 | 2022-11-11 | 江西赣锋锂业股份有限公司 | Method for extracting lithium from brine by adsorption of lithium smelting slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060171869A1 (en) * | 2003-11-12 | 2006-08-03 | Anovitz Lawrence M | Method of extracting lithium |
| CN101224900A (en) * | 2007-10-11 | 2008-07-23 | 钟辉 | Novel method for spodumene calcining transformation |
| CN102115101A (en) * | 2011-01-05 | 2011-07-06 | 屈俊鸿 | Novel method for producing lithium carbonate and lithium hydroxide |
-
2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060171869A1 (en) * | 2003-11-12 | 2006-08-03 | Anovitz Lawrence M | Method of extracting lithium |
| CN101224900A (en) * | 2007-10-11 | 2008-07-23 | 钟辉 | Novel method for spodumene calcining transformation |
| CN102115101A (en) * | 2011-01-05 | 2011-07-06 | 屈俊鸿 | Novel method for producing lithium carbonate and lithium hydroxide |
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Address after: 338015 Longteng Road, Xinyu Economic Development Zone, Jiangxi, Xinyu Patentee after: Jiangxi Ganfeng Lithium Industry Group Co.,Ltd. Patentee after: YICHUN GANFENG LITHIUM INDUSTRY CO.,LTD. Address before: 338015 Longteng Road, Xinyu Economic Development Zone, Jiangxi, Xinyu Patentee before: JIANGXI GANFENG LITHIUM Co.,Ltd. Patentee before: YICHUN GANFENG LITHIUM INDUSTRY CO.,LTD. |