CN112551555A - Preparation method of anhydrous sodium sulphate based on salt lake ore and lithium polymer - Google Patents
Preparation method of anhydrous sodium sulphate based on salt lake ore and lithium polymer Download PDFInfo
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- anhydrous sodium
- sodium sulphate
- salt lake
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- sodium sulfate
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 97
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 40
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 15
- 238000007710 freezing Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000009993 causticizing Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000010446 mirabilite Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010902 jet-milling Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000008237 rinsing water Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 boride Chemical compound 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical compound OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/18—Dehydration
Abstract
The invention discloses a preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers, belonging to the technical field of anhydrous sodium sulphate preparation and comprising the following steps: the preparation method comprises the following steps of sequentially calcining, cooling, finely grinding, adding acid for reaction, cooling, mixing slurry, leaching, filtering and washing, adding salt lake ore, purifying, causticizing, freezing and crystallizing, dissolving mirabilite, evaporating and concentrating, centrifugally separating, drying and carrying out jet milling on the lithium polymer to obtain anhydrous sodium sulphate. The preparation method adopts the continuous freezing crystallization technology to separate the sodium sulfate, ensures the stable growth of crystal nucleus and the continuity of production, can produce high-quality products, shortens the production period and saves the cost.
Description
Technical Field
The invention belongs to the technical field of anhydrous sodium sulphate preparation, and particularly relates to a preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers.
Background
Glauber salt refers to sodium sulfate, also called mirabilite. Sodium sulfate, an inorganic compound, sodium sulfate decahydrate, also known as mirabilite, and a high-purity, finely-grained anhydrate called glauber salt. The anhydrous sodium sulphate is mainly used for manufacturing water glass, porcelain glaze, paper pulp, refrigerating mixing agent, detergent, drying agent, dye diluent, analytical chemical reagent, medicinal products, feed and the like. The main methods for producing anhydrous sodium sulphate at present are a beach field method, a mechanical freezing method, a salt lake comprehensive utilization method and the like.
The beach field method is to evaporate water from the material liquid by means of the temperature change in different seasons to crystallize out coarse mirabilite. In summer, the salt water containing sodium chloride, sodium sulfate, magnesium chloride, etc. is poured into beach field, and after sun-drying and evaporation, crude mirabilite is separated out in winter. The method is a main method for extracting mirabilite from natural resources, and has the advantages of simple process, low energy consumption, poor operation conditions and easy mixing of impurities such as sand and the like in the product.
The mechanical freezing method is to utilize mechanical equipment to heat and evaporate the raw material liquid and then freeze the raw material liquid to-5 to-10 ℃ to separate out mirabilite. Compared with the beach field method, the method is not affected by seasons and natural conditions. The product quality is good, but the energy consumption is high.
The comprehensive utilization method of the salt lake is mainly used for sulfate-carbonate type salt water containing various components. The crude mirabilite is separated while extracting various useful components. For example, salt lake water containing sodium carbonate, sodium sulfate, sodium chloride, boride, potassium, bromine and lithium can be processed by firstly carbonizing salt lake brine to convert sodium carbonate into sodium bicarbonate to be crystallized; cooling the mother liquor to 5-15 ℃ to crystallize borax; and (4) freezing the secondary mother liquor after borax separation to 0-5 ℃, and separating out mirabilite.
Therefore, how to prepare anhydrous sodium sulphate with less impurities, high quality and low cost is a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers, and aims to solve the problem that the existing preparation method is difficult to produce anhydrous sodium sulphate with less impurities, high quality and low cost.
In order to realize the purpose of the invention, the technical scheme is as follows: a preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers comprises the following steps:
s1, calcining, cooling, finely grinding, adding acid for reaction and cooling a lithium polymer in sequence, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then adding water to prepare slurry, wherein the solid content of the slurry is 10-70%; wherein the calcining temperature is 950-1200 ℃, and after calcining, water cooling is carried out in a roasting cooling kiln; after the acid addition reaction, cooling the mixture by an acidification cooling kiln;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃, adjusting the pH value to 5.5-6, adding calcium oxide to adjust the pH value to 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into a clear filtering liquid, purifying the mixed liquid by using a calcium oxide or lithium hydroxide solution, adjusting the pH value to 9-12, and removing impurities of iron, manganese, aluminum and calcium in the clear filtering liquid;
s3, filtering the mixed liquid obtained after purification in the step S2 again to obtain purified liquid and purified filter residues, adding water into the purified filter residues to prepare slurry with the solid content of 10% -70%, returning to the step S1, and causticizing by using an alkaline solution with the concentration of 10% -50%;
s4, filtering the solution causticized in the step S3 to obtain causticized liquid and causticized filter residues, and filtering the causticized liquid through a precision filter to remove part of calcium ions;
s5, pumping the causticized liquid which is filtered by the precision filter and part of calcium ions are removed in the step S4 into a freezing system, and cooling the causticized liquid by using the forced freezing action of an ice machine, wherein the freezing temperature is-5 to-20 ℃; crystallizing and separating out sodium sulfate in the form of sodium sulfate decahydrate at low temperature, and dissolving the sodium sulfate decahydrate separated from the solution in a crystal melting tank under the centrifugal separation effect;
s6, evaporating, concentrating and purifying sodium sulfate decahydrate, heating, taking out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, centrifugally separating the concentrated anhydrous sodium sulfate slurry, drying an anhydrous sodium sulfate wet product by a flash evaporation dryer to obtain anhydrous sodium sulfate, drying at the temperature of 50-150 ℃, and returning the centrifuged mother liquor to a crystal melting tank or a purification tank;
and S7, carrying out gas-solid separation on anhydrous sodium sulphate obtained after drying by the flash evaporation dryer in the step S6 through a two-stage cyclone separator, and packaging the solid anhydrous sodium sulphate by an automatic packaging machine and then warehousing.
As a further alternative, in step S1, the particle size of the fine powder is required to be 200 meshes, acid is added for reaction, sulfuric acid with a concentration of 98% is added, and the acid-to-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃.
As a further alternative, in step S1, the calcination is performed by a rotary kiln, and dust collected by a kiln tail cover, a bag-type dust collector, and a multi-tube ceramic dust collector of the rotary kiln is collected into a bin, and is then conveyed back to the bin of the lithium concentrate storage by a bin pump, and is then conveyed back to the plate-type feeder by a humidifier, and is conveyed back to the rotary kiln by a bucket elevator and a belt.
As a further alternative, in step S2, if the alkaline solution is a lithium hydroxide solution, the concentration of the lithium hydroxide solution is 10% to 50%; if calcium oxide is used, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10% -55%.
As a further alternative, in the step S3, the pH value of the causticized solution is 11-14, and the temperature is normal temperature.
As a further alternative, in step S4, after adding water into the causticized filter residue to prepare slurry with the solid content of 10-70%, returning to the step S2 for purification.
As a further alternative, the frozen clear solution separated from the solution during the centrifugal separation in the step S5 is transferred to a frozen post-liquid buffer tank, filtered by a precision filter, and then enters a crude product feeding buffer tank.
As a further alternative, in step S6, the hot air required by the flash evaporation dryer is provided by a matched hot blast stove, the fuel of the hot blast stove is natural gas, and the usage amount is 600m3/h。
Alternatively, in step S7, the water content of the solid anhydrous sodium sulfate obtained by gas-solid separation is 5%.
The invention has the beneficial effects that: the preparation method takes salt lake ore and lithium polymer as raw materials to produce anhydrous sodium sulphate, salt lake ore Li2SO4·H2The content of O is 80.1-92.1%, the average content is 85.1%, the grade of lithium polymer is 8.5-12% (Li2O), the content of Al is 25.05%, the content of Mg is 1.23%, the content of Si is 0.84%, the content of Mn is 0.69%, the grade is high and the content of impurities is low, the sodium sulfate can be produced by mixing the two, the preparation method applies the continuous freezing crystallization technology to separate the sodium sulfate, the stable growth of crystal nucleus and the continuity of production are ensured, the high-quality product can be produced, the production period is shortened, and the cost is saved.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it should be understood that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing anhydrous sodium sulphate based on salt lake ores and lithium polymers, which is provided by the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. It is to be understood that the drawings are provided solely for the purposes of reference and illustration and are not intended as a definition of the limits of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention is further described with reference to the following figures and specific embodiments.
FIG. 1 shows a preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers, which comprises the following steps:
s1, calcining, cooling, finely grinding, adding acid for reaction and cooling a lithium polymer in sequence, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then adding water to prepare slurry, wherein the solid content of the slurry is 10-70%; wherein the calcining temperature is 950-1200 ℃, and after calcining, water cooling is carried out in a roasting cooling kiln; after the acid addition reaction, cooling the mixture by an acidification cooling kiln;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃, adjusting the pH value to 5.5-6, adding calcium oxide to adjust the pH value to 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into a clear filtering liquid, purifying the mixed liquid by using a calcium oxide or lithium hydroxide solution, adjusting the pH value to 9-12, and removing impurities of iron, manganese, aluminum and calcium in the clear filtering liquid;
s3, filtering the mixed liquid obtained after purification in the step S2 again to obtain purified liquid and purified filter residues, adding water into the purified filter residues to prepare slurry with the solid content of 10% -70%, returning to the step S1, and causticizing by using an alkaline solution with the concentration of 10% -50%;
s4, filtering the solution causticized in the step S3 to obtain causticized liquid and causticized filter residues, and filtering the causticized liquid through a precision filter to remove part of calcium ions;
s5, pumping the causticized liquid which is filtered by the precision filter and part of calcium ions are removed in the step S4 into a freezing system, and cooling the causticized liquid by using the forced freezing action of an ice machine, wherein the freezing temperature is-5 to-20 ℃; crystallizing and separating out sodium sulfate in the form of sodium sulfate decahydrate at low temperature, and dissolving the sodium sulfate decahydrate separated from the solution in a crystal melting tank under the centrifugal separation effect;
s6, evaporating, concentrating and purifying sodium sulfate decahydrate, heating, taking out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, centrifugally separating the concentrated anhydrous sodium sulfate slurry, drying an anhydrous sodium sulfate wet product by a flash evaporation dryer to obtain anhydrous sodium sulfate, drying at the temperature of 50-150 ℃, and returning the centrifuged mother liquor to a crystal melting tank or a purification tank;
and S7, carrying out gas-solid separation on anhydrous sodium sulphate obtained after drying by the flash evaporation dryer in the step S6 through a two-stage cyclone separator, and packaging the solid anhydrous sodium sulphate by an automatic packaging machine and then warehousing.
In step S1, the particle size of the fine grinding is required to be 200 mesh, acid is added for reaction, sulfuric acid with a concentration of 98% is added, and the acid-to-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃.
In step S1, the calcination is performed by a rotary kiln, and dust collected by a kiln hood of the rotary kiln, a bag-type dust collector, and a multi-tube ceramic dust collector is collected in a bin, and is then conveyed back to the bin of the lithium concentrate storage by a bin pump, and is then conveyed back to a plate-type feeder by a humidifier, and is conveyed back to the rotary kiln by a bucket elevator and a belt.
In step S2, if the alkaline solution is a lithium hydroxide solution, the concentration of the lithium hydroxide solution is 10% to 50%; if calcium oxide is used, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10% -55%.
The calcium carbonate slurry is prepared into slurry by using calcium carbonate and water, and the solid content is 10-55 percent. After filtering by the filter press, the filter cake can be rinsed by tap water or process water, the filter cake is purged by compressed air, the water content of the filter cake is less than or equal to 20%, and the rinsing water is returned for slurry mixing in the step S1.
In step S3, the pH of the causticized solution is 11-14 and the temperature is normal temperature. The alkaline solution may be a sodium hydroxide solution, a lithium hydroxide solution, or a mixture thereof.
In step S4, adding water into the causticized filter residue to prepare slurry with the solid content of 10-70%, and then returning to the step S2 for purification.
And S5, transferring the frozen clear liquid separated from the solution during centrifugal separation into a frozen liquid buffer barrel, filtering the frozen clear liquid by a precision filter, and feeding the filtered clear liquid into a crude product feeding buffer barrel.
In step S6, hot air required by the flash evaporation dryer is provided by a matched hot blast stove, the fuel of the hot blast stove is natural gas, and the usage amount is 600m3H is used as the reference value. In step S7, the water content of the solid anhydrous sodium sulfate obtained by gas-solid separation is 5%.
In step S1, the lithium polymer is sequentially calcined in a rotary kiln at a high temperature, cooled in a roasting cooling kiln, finely ground in a ball mill, subjected to an acid addition reaction in an acidification kiln, and cooled in an acidification cooling kiln. And S2, conveying the calcium carbonate into a stirring tank by using a screw conveyor, mixing the calcium carbonate with water to form slurry, mixing the slurry with the slurry obtained in the step S1, stirring and leaching, wherein the solid content is 10% -55%, the temperature in the leaching tank is less than or equal to 60 ℃, the pH value is more than or equal to 5, conveying the leachate to a filter press by using a pump, rinsing a filter cake by using tap water or process water, blowing the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, returning rinsing water for slurry mixing in the step S1, enabling the filtered filtrate to reach a leaching filtrate buffer tank, adding salt lake ore into the filtered clear liquid, purifying the mixed liquid in a purifying tank by using a calcium oxide or lithium hydroxide solution, adjusting the pH value to 9-12, and removing impurities such as iron, manganese, aluminum and calcium from the.
The invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention, but any changes in shape or structure thereof, which fall within the scope of the present invention as defined in the claims, fall within the scope of the present invention.
Claims (9)
1. A preparation method of anhydrous sodium sulphate based on salt lake ores and lithium polymers is characterized by comprising the following steps:
s1, calcining, cooling, finely grinding, adding acid for reaction and cooling a lithium polymer in sequence, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then adding water to prepare slurry, wherein the solid content of the slurry is 10-70%; wherein the calcining temperature is 950-1200 ℃, and after calcining, water cooling is carried out in a roasting cooling kiln; after the acid addition reaction, cooling the mixture by an acidification cooling kiln;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃, adjusting the pH value to 5.5-6, adding calcium oxide to adjust the pH value to 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into a clear filtering liquid, purifying the mixed liquid by using a calcium oxide or lithium hydroxide solution, adjusting the pH value to 9-12, and removing impurities of iron, manganese, aluminum and calcium in the clear filtering liquid;
s3, filtering the mixed liquid obtained after purification in the step S2 again to obtain purified liquid and purified filter residues, adding water into the purified filter residues to prepare slurry with the solid content of 10% -70%, returning to the step S1, and causticizing by using an alkaline solution with the concentration of 10% -50%;
s4, filtering the solution causticized in the step S3 to obtain causticized liquid and causticized filter residues, and filtering the causticized liquid through a precision filter to remove part of calcium ions;
s5, pumping the causticized liquid which is filtered by the precision filter and part of calcium ions are removed in the step S4 into a freezing system, and cooling the causticized liquid by using the forced freezing action of an ice machine, wherein the freezing temperature is-5 to-20 ℃; crystallizing and separating out sodium sulfate in the form of sodium sulfate decahydrate at low temperature, and dissolving the sodium sulfate decahydrate separated from the solution in a crystal melting tank under the centrifugal separation effect;
s6, evaporating, concentrating and purifying sodium sulfate decahydrate, heating, taking out crystal water to obtain anhydrous sodium sulfate, heating at the temperature of 200-800 ℃, centrifugally separating the concentrated anhydrous sodium sulfate slurry, drying an anhydrous sodium sulfate wet product by a flash evaporation dryer to obtain anhydrous sodium sulfate, drying at the temperature of 50-150 ℃, and returning the centrifuged mother liquor to a crystal melting tank or a purification tank;
and S7, carrying out gas-solid separation on anhydrous sodium sulphate obtained after drying by the flash evaporation dryer in the step S6 through a two-stage cyclone separator, and packaging the solid anhydrous sodium sulphate by an automatic packaging machine and then warehousing.
2. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer according to claim 1, wherein in step S1, the particle size of the fine ground is required to be 200 meshes, acid is added for reaction, sulfuric acid with the concentration of 98% is added, and the acid-to-material ratio is 2-5: 1, adding acid for reaction, and cooling to below 60 ℃.
3. The method for preparing anhydrous sodium sulphate based on salt lake ores and lithium polymers as claimed in claim 1, wherein in step S1, the calcination is performed by a rotary kiln, and the dust collected by a kiln tail cover, a bag-type dust remover and a multi-tube ceramic dust remover of the rotary kiln is collected in a bin, then is conveyed back to the bin of the lithium concentrate storage by a bin pump, then is conveyed back to a plate-type feeder by a humidifier, and is conveyed back to the rotary kiln by a bucket elevator and a belt.
4. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer according to claim 1, wherein in step S2, when the alkaline solution is lithium hydroxide solution, the concentration of the lithium hydroxide solution is 10-50%; if calcium oxide is used, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10% -55%.
5. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer according to claim 1, wherein in step S3, the pH of the causticized solution is 11-14, and the temperature is normal temperature.
6. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer as claimed in claim 1, wherein in step S4, the causticized filter residue is added with water to be made into slurry with solid content of 10% -70%, and then the process returns to step S2 for purification.
7. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer according to claim 1, wherein the clear frozen solution separated from the solution during the centrifugal separation in step S5 is transferred to a buffer tank of the frozen solution, filtered by a fine filter and then fed into a crude product feeding buffer tank.
8. The method for preparing anhydrous sodium sulphate based on salt lake ore and lithium polymer according to claim 1, wherein in step S6, the hot air required by the flash dryer is provided by a matched hot blast stove, the fuel of the hot blast stove is natural gas, and the usage amount is 600m3/h。
9. The method for preparing anhydrous sodium sulfate based on salt lake ore and lithium polymer according to claim 1, wherein the water content of the solid anhydrous sodium sulfate obtained by gas-solid separation in step S7 is 5%.
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