CN115676854A - Method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in soda ash industry - Google Patents
Method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in soda ash industry Download PDFInfo
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Abstract
The invention discloses a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda industry, which comprises the following steps: mixing low-salt soda ash with water to obtain NaCO 3 Adjusting the solution to be alkaline, and filtering to obtain clear liquid A; cooling, crystallizing, filtering and separating to obtain a filter cake and a mother liquor I; treating the filter cake to obtain a battery grade high-purity sodium carbonate product; acidifying the salt slurry to form mixed slurry B, flocculating, precipitating, filtering and separating to obtain coarse calcium filter cake and MgSO 4 Filtering the solution; mixing the mother liquor I with MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C, filtering and washing to obtain basic magnesium carbonate solid and mother liquor II. The invention can make the chlorine content in the finally prepared sodium carbonate be at an extremely low level to reach a battery grade product under the condition of not destroying the balance of the original alkali preparation system.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling, and particularly relates to a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda industry.
Background
The lithium ion battery has excellent comprehensive performance, but the lithium is only 0.0065 percent in the crust of the earth, the resource distribution is uneven, the contradiction of supply is increasingly prominent, and the lithium ion battery is listed as a strategic mineral resource in many countries. The sodium element has rich resource, wide distribution and low cost, and the sodium ion battery has the unique advantages of good high-low temperature performance, strong quick charging capability, high safety and the like, thereby being capable of being used as important supplement and replacement of the lithium battery and having great economic value and strategic significance. At present, the sodium ion battery has a primary scale in technical development and product production, and more than twenty enterprises have developed industrialized layouts.
The battery grade sodium carbonate is a key raw material for preparing the anode material of the sodium ion battery, and has strict requirements on quality indexes (key impurity indexes such as Cl) for ensuring the comprehensive performance of the battery — Less than or equal to 0.01 percent). The current industrial grade low-salt dense soda ash contains Cl — 0.2 percent, is limited by factors such as mother liquor balance in the alkali preparation process and the like, and can not directly obtain a high-purity product by increasing the amount of filtered washing water to control the salt content of the heavy alkali; the sodium carbonate is adopted for washing, so that a considerable amount of undigestable salt-containing mother liquor is generated, and the consumption of the sodium carbonate is increased; the energy consumption of the route of sodium carbonate carbonization, full washing of baking soda and calcination decomposition is high, and the volume expansion of the surplus mother liquor is further aggravated; the disclosed purification technologies such as precipitation crystallization, chemical complexation, ion adsorption and the like are complex in process and high in cost, and are not suitable for industrial production and large-scale requirements of future sodium ion battery industry.
Disclosure of Invention
The invention aims to provide a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry so as to solve one or more technical problems. The preparation method provided by the invention is coupled with the existing industrial alkali-making process, and can enable the chlorine content in the finally prepared sodium carbonate to be at an extremely low level to reach a battery-grade product under the condition of not destroying the balance of the original alkali-making system.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry, which comprises the following steps of:
mixing low-salt sodium carbonate produced in sodium carbonate industry with water to obtain NaCO with preset concentration 3 A solution; adjusting the NaCO by using NaOH solution with preset concentration 3 The pH value of the solution is changed to be alkaline, and mixed solution is obtained; filtering the mixture to remove insoluble matterImpurities to obtain Na-rich + And CO 3 2- The clear solution A of (1); cooling and crystallizing the clear liquid A, and performing suction filtration and separation after crystallizing for a preset time to obtain a filter cake and a mother liquid I; washing and drying the filter cake to obtain a battery grade high-purity sodium carbonate product;
acidifying salt mud generated in soda industry to form MgSO 4 Mixed slurry B of the solution and the calcium sulfate dihydrate precipitate; performing flocculation precipitation and suction filtration separation on the mixed slurry B to obtain a coarse calcium filter cake and MgSO 4 Filtering the solution;
mixing the mother liquor I with the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals;
filtering and washing the mixed slurry C to obtain basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride; and drying the basic magnesium carbonate solid to obtain a basic magnesium carbonate product.
The invention is further improved in that the low-salt soda ash produced in soda ash industry is mixed with water to obtain NaCO with preset concentration 3 The steps of the solution include:
at 35-70 deg.c, deionized water is used to dissolve low-salt sodium carbonate and through stirring to obtain NaCO 3 A solution; wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the deionized water is 1: (2-4).
The further improvement of the invention is that in the step of cooling and crystallizing the clear liquid A, filtering and separating after crystallizing for a preset time to obtain a filter cake and a mother liquid I,
the final temperature of cooling crystallization is set to be 15-30 ℃;
when the filtration separation is carried out, a separation membrane made of aromatic polyamide is selected.
The invention is further improved in that Cl is used — And (3) counting, the chlorine content of the prepared battery grade high-purity sodium carbonate product is less than 0.005%.
In a further development of the invention, the method comprisesMixing the mother liquor I with the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, raising the temperature to convert the magnesium carbonate into basic magnesium carbonate, and forming mixed slurry C containing the basic magnesium carbonate crystals,
mother liquor I and MgSO 4 The mixing volume ratio of the filtrate is 1: (8-10).
In a further improvement of the invention, the mother liquor I is mixed with MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, raising the temperature to convert the magnesium carbonate into basic magnesium carbonate, and forming mixed slurry C containing the basic magnesium carbonate crystals,
when heating to generate magnesium carbonate, the temperature is controlled at 50-80 ℃.
In a further improvement of the invention, the mother liquor I is mixed with MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, heating to convert the magnesium carbonate into basic magnesium carbonate, forming mixed slurry C containing basic magnesium carbonate crystals,
heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate, wherein the preset time is 20-60 min; the temperature after temperature rise is controlled to be 80-120 ℃.
The invention has the further improvement that the basic magnesium carbonate product obtained by preparation is basic magnesium carbonate tetrahydrate; with Cl — The chlorine content is 0.03-0.05%.
The invention is further improved in that the mother liquor II obtained by preparation is used for producing soda ash.
The invention is further improved in that the obtained crude calcium filter cake is used for preparing the semi-hydrated gypsum.
Compared with the prior art, the invention has the following beneficial effects:
in the preparation method provided by the invention, the existing industrial alkali-making process is coupled, the high-purity sodium carbonate is industrially prepared under the condition of not destroying the balance of the original alkali-making system, the advantages of sodium resources are promoted to be converted into the advantages of productivity, and the dilemma of lithium resources is broken; while removing impurities from sodium carbonate, the method promotes the synchronous dechlorination of the original soda ash product, so that the chlorine content in the finally prepared sodium carbonate is extremely low and reaches the battery grade product; the crystallized sodium carbonate mother liquor can directly react with the magnesium leaching liquor after acid leaching to prepare basic magnesium carbonate without additional operations such as concentration or dilution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow diagram of a process for the integrated production of battery grade sodium carbonate and basic magnesium carbonate in the soda ash industry according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an electronic grade sodium carbonate product produced in an embodiment of the present invention;
FIG. 3 is a schematic diagram of a basic magnesium carbonate product produced in an example of the present invention.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps recited in the present disclosure are not exclusive of other method steps that may also be present before or after the recited combination of steps or that other method steps may also be inserted between the explicitly recited steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is only a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or the scope of the invention, and changes or modifications in the relative relationship thereof may be regarded as the scope of the invention without substantial change in the technical content.
Referring to fig. 1, a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry according to an embodiment of the present invention includes the following specific steps:
step 1, mixing low-salt soda ash produced in soda ash industry with water to obtain high-concentration NaCO 3 A solution;
step 2, adding NaCO 3 Adding a certain amount of NaOH into the solution to adjust the pH value to be alkaline and promote Ca in the solution 2+ 、Mg 2+ Converting into a precipitate;
step 3, filtering the mixed liquid obtained in the step 2 to remove CaCO 3 、Mg(OH) 2 And other insoluble impurities to obtain Na-rich product + And CO 3 2- The clear solution A of (1);
step 4, cooling and crystallizing the clear liquid A, performing suction filtration after crystallizing for a period of time, and separating to obtain a clear liquid I which is a mother liquid containing sodium chloride and sodium carbonate; washing the filter cake, and drying the filter cake at 105-125 ℃ to obtain a battery grade high-purity sodium carbonate product;
step 5, acidifying the salt mud generated in the soda ash industry to remove Ca in the slurry 2+ Precipitate out to form MgSO 4 Mixed slurry B of the solution and the calcium sulfate dihydrate precipitate; then, flocculation precipitation and suction filtration separation are carried out, the coarse calcium filter cake is sent to the calcium preparation procedure to prepare semi-hydrated gypsum, mgSO 4 The filtrate is sent to a magnesium preparation link;
step 6, the mother liquor I obtained in the step 4 and MgSO obtained in the step 5 4 Mixing and heating the filtrate to generate magnesium carbonate, raising the heating temperature after a period of time to promote the magnesium carbonate to be converted into basic magnesium carbonate, and forming mixed slurry C containing basic magnesium carbonate crystals;
step 7, filtering and washing the slurry C to obtain basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride, and sending the mother liquor II into a brine refining unit for producing soda ash; drying to obtain basic magnesium carbonate product.
In the embodiment of the invention, the step 1 is to specifically select deionized water to dissolve the low-salt sodium carbonate at the temperature of 35-70 ℃, and stir the low-salt sodium carbonate and the water, wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the water is 1: (2-4).
The embodiment of the invention is exemplarily and optionally, the concentration of the NaOH solution adopted in the step 2 is 0.2-5 g/L, and the temperature and the stirring condition are kept unchanged in the step 1.
Specifically, in the embodiment of the invention, the filtration in the step 3 adopts a centrifugal separation technology, the centrifugal time is 4-5 min under the condition of a rotating speed of 2000 r/min-5000 r/min, the residue and the clear liquid in the sodium carbonate mixed solution are effectively separated, and the turbidity of the clear liquid is 0.2 NTU.
The embodiment of the invention is further preferable, the temperature of the final temperature of the temperature reduction and crystallization of the clear liquid A in the step 4 is set to be 15-30 ℃, so that the crystallization yield of the sodium carbonate can be ensured, and the chlorine content of a sodium carbonate crystallization product can be controlled to be maintained at a lower level.
In the embodiment of the invention, the suction filtration unit adopted in the suction filtration separation in the step 4 is a separation membrane made of aromatic polyamide, the membrane aperture is 1nm, a one-stage two-stage design (6-core membrane shell) is adopted, and the number ratio of the one-stage membrane shell to the two-stage membrane shell is 2; the molecular weight cut-off range of the scheme is 200-1000 daltons, the surface of the molecular weight cut-off range is provided with negative charges, divalent or high-valent ions, particularly anions, can be efficiently intercepted, and the cut-off rate of sodium chloride reaches 95%.
In the embodiment of the invention, the sodium carbonate product obtained in the step 4 is washed by absolute ethyl alcohol which is used for removing residual chlorination in the sodium carbonate nano-rodsSodium and other impurities, the purity of the finally obtained sodium carbonate product is more than 99 percent, and the chlorine content (as Cl) — Calculated) is less than 0.005%.
In step 5 of the embodiment of the invention, salt slurry is prepared by mixing salt slurry and tap water; the coagulating link can adopt anionic Polyacrylamide (PAM) or polyaluminium chloride (PAC) as a coagulant.
In step 6 of the inventive example, mother liquor I was mixed with MgSO 4 The mixing volume ratio of the filtrate is 1: (8-10), controlling the hydrothermal temperature after mixing at 50-80 ℃, and adopting a propeller stirring with the stirring speed of 50-300 r/min to promote the hydrothermal reaction. After the hydrothermal reaction stage lasts for 20-60 min, the temperature is raised to 80-120 ℃ for magnesium carbonate pyrolysis reaction, and simultaneously, the propeller stirring with the stirring speed of 50-300 r/min is continuously maintained to promote the pyrolysis reaction.
In step 7 of the embodiment of the invention, the solid-liquid rapid separation can be realized by adopting suction filtration equipment through a filter membrane with the aperture of 0.45 mu m, the obtained basic magnesium carbonate product is tetrahydrate basic magnesium carbonate, the purity is more than 99 percent, and the chlorine content (in terms of Cl) is higher than that of the tetrahydrate basic magnesium carbonate — Calculated) is 0.03 to 0.05 percent.
The method of the embodiment of the invention is coupled with the existing industrial alkali-making process, and the high-purity sodium carbonate is industrially prepared under the condition of not damaging the balance of the original alkali-making system, so that the advantages of sodium resources are promoted to be converted into the advantages of productivity, and the dilemma of lithium resources is broken. While removing impurities from the sodium carbonate, calcium and magnesium carbonate promote the synchronous dechlorination of the original soda ash product, so that the chlorine content in the finally prepared sodium carbonate is extremely low and reaches the battery grade product. The crystallized sodium carbonate mother liquor can directly react with the magnesium leaching liquor after acid leaching to prepare basic magnesium carbonate without additional operations such as concentration or dilution. The battery grade high-purity sodium carbonate is subjected to secondary carbonization, dehydration and drying to obtain an injection grade sodium bicarbonate product, and the mother liquor is reused in an alkali making system.
The technical route provided by the embodiment of the invention avoids the technical problem of mother liquor expansion caused by direct washing and salt reduction of raw materials or product ends, makes up for the technical defects of complicated process flow, high cost and difficult industrialization of the existing purification process, and refines salt mud, mother liquor and other coupling brine discharged in the alkali making-purification process to form series products of basic magnesium carbonate, semi-hydrated gypsum and the like with high added values, thereby realizing the recycling of all by-products, realizing zero waste discharge of the process flow and improving the product profit space of the soda industry. And (4) carrying out preliminary accounting, wherein the net income of each 1 ton of the salty mud is about 270 yuan. According to the output of the salty mud, the net profit per day is about 27 ten thousand yuan, the annual profit exceeds 9000 ten thousand yuan, and the method has outstanding economic benefit, environmental benefit and social benefit.
Example 1
Referring to fig. 1 to 3, in a new method for jointly preparing battery grade sodium carbonate and basic magnesium carbonate in soda ash industry according to an embodiment of the present invention, low-salt soda ash produced in soda ash industry is first mixed with water to obtain high-concentration NaCO 3 Adding NaOH solution to adjust pH to promote Ca in the solution 2+ 、Mg 2+ Converting into precipitate; after filtration, the NaCO is rich 3 Cooling and crystallizing the clear liquid A, performing suction filtration and separation to obtain a mother solution I, conveying the mother solution I to a subsequent magnesium preparation link, and washing and drying a filter cake to obtain a battery grade high-purity sodium carbonate product; mixing the industrial salt slurry of soda ash with sulfuric acid, and carrying out acidification treatment; then carrying out flocculation precipitation and suction filtration separation, sending the coarse calcium filter cake to a calcium preparation process to prepare semi-hydrated gypsum, mgSO 4 The filtrate is sent to a magnesium preparation link; then, the mother liquor I is mixed with MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, and raising the temperature after a period of time to promote the conversion of the magnesium carbonate into basic magnesium carbonate so as to form mixed slurry C containing the crystals of the basic magnesium carbonate; finally, filtering and washing the slurry C to obtain a basic magnesium carbonate filter cake and a mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride, and sending the mother liquor II into a brine refining unit for producing soda ash; the filter cake is dried to obtain basic magnesium carbonate product, and the basic magnesium carbonate is processed to prepare other magnesium products.
In one embodiment of the invention, the salt mud selected in the experiment is salt mud produced by a chemical industry enterprise in Tangshan mountain in Hebei, the water content of the salt mud is known to be 40% -48%, the main elements of the salt mud are shown in Table 1, and the treatment steps are as follows.
Table 1: full-rock index element analysis of salt mud
(1) Dissolving 40.00g of sodium carbonate solid (food grade) in 100mL of deionized water, and fully dissolving in a water bath at 35 ℃ under the stirring condition of 100 r/min;
(2) Adding 1mL of NaOH solution (0.25 g/L), and stirring at 100r/min under the condition of 35 ℃ water bath for fully reacting for 30min; centrifuging at 3000r/min for 4min to effectively separate residue and clear liquid in the mixed solution of sodium carbonate, wherein the turbidity of the clear liquid is 0.2NTU;
(3) Cooling and crystallizing the filtered clear liquid A at 25 ℃, filtering after 60min, washing by absolute ethyl alcohol, and drying in a 120 ℃ blast drying oven to obtain a sodium carbonate product with the purity of 99.5 percent and the chlorine content (by Cl) — Calculated) is 0.0043 percent, and the mother solution I is used for the subsequent magnesium preparation link;
(4) Taking 100.0g of wet soda ash salt slurry, adding 820mL of deionized water for pulping, adding 20mL of concentrated sulfuric acid for acidification, and controlling the reaction temperature at 50 ℃ after acidification is finished after full reaction and no bubbles are generated (60 min);
(5) And (4) adding a PAM solution into the mixed slurry B obtained in the step (4), wherein the content of PAM in the clear liquid A reaches 3mg/L, and the whole flocculation and precipitation process is carried out under the conditions of normal temperature and normal pressure. Controlling the stirring speed at 200r/min for 1min in the rapid stirring stage; and in the slow stirring stage, the stirring speed is controlled within the range of 60r/min, and the time is 3min. Standing for 10min after stirring to complete flocculation precipitation, and separating by sand filtration to obtain Mg-rich product 2+ 、SO4 2- 、Na + And Cl - The clear solution B of (1);
(6) Mixing 100mL of mother liquor I with 1000mL of clear liquid B, controlling the hydrothermal temperature to be 50 ℃, reacting for 30min under the stirring condition of 120r/min, then increasing the temperature to 85 ℃, reacting for 60min under the stirring condition of 120r/min, continuing aging for a period of time, washing, filtering and drying to obtain a final product, namely basic magnesium carbonate, wherein the purity of the final product is up to 99.3%, and the chlorine content (in terms of Cl is used as a chlorine content) — Calculated) is 0.03 to 0.05 percent. The rest filtered clear liquid is the by-product—Na 2 SO 4 And NaCl mixed liquid can be sent to a brine refining module for soda production.
Example 2
The embodiment of the invention provides a method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry, which comprises the following steps:
mixing low-salt sodium carbonate produced in sodium carbonate industry with water to obtain NaCO with preset concentration 3 A solution; adjusting the NaCO by using NaOH solution with preset concentration 3 The pH value of the solution is changed to be alkaline, and mixed solution is obtained; filtering the mixture to remove insoluble impurities to obtain Na-rich liquid + And CO 3 2- The clear solution A of (1); cooling and crystallizing the clear liquid A, and performing suction filtration and separation after crystallization for a preset time to obtain a filter cake and a mother liquid I; washing and drying the filter cake to obtain a battery grade high-purity sodium carbonate product;
acidifying the salt mud produced in soda industry to form MgSO 4 Mixed slurry B of the solution and the precipitate of calcium sulfate dihydrate; performing flocculation precipitation and suction filtration separation on the mixed slurry B to obtain a coarse calcium filter cake and MgSO 4 Filtering the solution;
mixing the mother liquor I with the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals;
filtering and washing the mixed slurry C to obtain basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride; drying the basic magnesium carbonate solid to obtain a basic magnesium carbonate product;
wherein, the low-salt sodium carbonate produced by the sodium carbonate industry is mixed with water to obtain NaCO with preset concentration 3 The steps of the solution include: at 35 deg.C, deionized water is selected for dissolving low-salt soda ash and stirring is carried out to obtain NaCO 3 A solution; wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the deionized water is 1:2;
cooling, cooling and crystallizing the clear liquid A, performing suction filtration and separation after crystallizing for a preset time, and setting the end temperature of cooling and crystallizing to be 15 ℃ in the step of obtaining a filter cake and a mother liquid I; when the extraction filtration separation is carried out, a separation membrane made of aromatic polyamide is selected;
wherein the mother liquor I and the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals, wherein the mother liquor I and MgSO 4 The mixing volume ratio of the filtrate is 1:8; when magnesium carbonate is generated by heating, the temperature is controlled at 50 ℃; heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate, wherein the preset time is 20min; the temperature after the temperature rise was controlled at 80 ℃.
In the embodiment of the invention, the prepared basic magnesium carbonate product is basic magnesium carbonate tetrahydrate; with Cl — The chlorine content is in the range of 0.03-0.05%; with Cl — And (3) counting, the chlorine content of the prepared battery grade high-purity sodium carbonate product is less than 0.005%.
Example 3
The method for jointly preparing the battery-grade sodium carbonate and the basic magnesium carbonate in the soda ash industry, which is provided by the embodiment of the invention, is different from the method in the embodiment 2 only in that low-salt soda ash produced in the soda ash industry is mixed with water to obtain NaCO with preset concentration 3 The steps of the solution include: at 50 deg.C, deionized water is selected to dissolve low-salt soda ash and stirred to obtain NaCO 3 A solution; wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the deionized water is 1:3; in the step of cooling, cooling and crystallizing the clear liquid A, and performing suction filtration and separation after crystallization for a preset time to obtain a filter cake and a mother liquid I, setting the end temperature of cooling and crystallization to be 20 ℃; the mother liquor I and the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals, wherein the mother liquor I and MgSO 4 The mixing volume ratio of the filtrate is 1:9; when magnesium carbonate is generated by heating, the temperature is controlled at 60 ℃; heating for a preset time and then heating to convert magnesium carbonate into basic magnesium carbonate, wherein the preset time is 40min(ii) a The temperature after the temperature rise was controlled at 100 ℃.
In the embodiment of the invention, the prepared basic magnesium carbonate product is basic magnesium carbonate tetrahydrate; with Cl — The chlorine content is in the range of 0.03-0.05%; with Cl — In terms of the content of chlorine in the prepared battery grade high-purity sodium carbonate product is less than 0.005%.
Example 4
The method for jointly preparing the battery-grade sodium carbonate and the basic magnesium carbonate in the soda ash industry, which is provided by the embodiment of the invention, is different from the method in the embodiment 2 only in that low-salt soda ash produced in the soda ash industry is mixed with water to obtain NaCO with preset concentration 3 The steps of the solution include: at 70 ℃, deionized water is selected for dissolving low-salt soda ash and stirring is carried out to obtain NaCO 3 A solution; wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the deionized water is 1:4; in the step of cooling, cooling and crystallizing the clear liquid A, and performing suction filtration and separation after crystallization for a preset time to obtain a filter cake and a mother liquid I, the final temperature of cooling and crystallization is set to be 30 ℃; the mother liquor I and the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals, wherein the mother liquor I and MgSO 4 The mixing volume ratio of the filtrate is 1:10; when magnesium carbonate is generated by heating, the temperature is controlled at 80 ℃; heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate, wherein the preset time is 60min; the temperature after the temperature rise was controlled at 120 ℃.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda industry is characterized by comprising the following steps:
mixing low-salt sodium carbonate produced in sodium carbonate industry with water to obtain NaCO with preset concentration 3 A solution; adjusting the NaCO by using NaOH solution with preset concentration 3 The pH value of the solution is changed to be alkaline, and mixed solution is obtained; filtering the mixture to remove insoluble impurities to obtain Na-rich mixture + And CO 3 2- The clear solution A of (1); cooling and crystallizing the clear liquid A, and performing suction filtration and separation after crystallization for a preset time to obtain a filter cake and a mother liquid I; washing and drying the filter cake to obtain a battery grade high-purity sodium carbonate product;
acidifying salt mud generated in soda industry to form MgSO 4 Mixed slurry B of the solution and the calcium sulfate dihydrate precipitate; performing flocculation precipitation and suction filtration separation on the mixed slurry B to obtain a coarse calcium filter cake and MgSO 4 Filtering the solution;
mixing the mother liquor I with the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals;
filtering and washing the mixed slurry C to obtain basic magnesium carbonate solid and mother liquor II containing sodium sulfate, magnesium sulfate, sodium carbonate and sodium chloride; and drying the basic magnesium carbonate solid to obtain a basic magnesium carbonate product.
2. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in soda ash industry according to claim 1, characterized in that low-salt soda ash produced in soda ash industry is mixed with water to obtain NaCO with preset concentration 3 The steps of the solution include:
at the temperature of 35-70 ℃, deionized water is selected for dissolving low-salt soda ash and stirring is carried out to obtain NaCO 3 A solution; wherein the solid-liquid mass ratio of the low-salt sodium carbonate to the deionized water is 1: (2-4).
3. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda ash industry according to claim 1, wherein in the step of cooling and crystallizing the clear liquid A, performing suction filtration and separation after crystallizing for a preset time to obtain a filter cake and a mother liquid I,
the final temperature of cooling crystallization is set to be 15-30 ℃;
when the filtration separation is carried out, a separation membrane made of aromatic polyamide is selected.
4. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in soda industry according to claim 1, wherein Cl is used — In terms of the content of chlorine in the prepared battery grade high-purity sodium carbonate product is less than 0.005%.
5. The method for industrially combined preparation of battery-grade sodium carbonate and basic magnesium carbonate from soda ash according to claim 1, wherein the mother liquor I and the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, raising the temperature to convert the magnesium carbonate into basic magnesium carbonate, and forming mixed slurry C containing the basic magnesium carbonate crystals,
mother liquor I and MgSO 4 The mixing volume ratio of the filtrate is 1: (8-10).
6. The method for industrially combined preparation of battery-grade sodium carbonate and basic magnesium carbonate from soda ash according to claim 1, wherein the mother liquor I and the MgSO 4 Mixing and heating the filtrate to generate magnesium carbonate, heating for a preset time, raising the temperature to convert the magnesium carbonate into basic magnesium carbonate, and forming mixed slurry C containing the basic magnesium carbonate crystals,
when heating to generate magnesium carbonate, the temperature is controlled at 50-80 ℃.
7. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in soda ash industry according to claim 6, wherein the mother liquor I and the MgSO (MgSO) are adopted 4 Mixing the filtrates, heating to obtainHeating magnesium carbonate for a preset time, heating to convert the magnesium carbonate into basic magnesium carbonate to form mixed slurry C containing basic magnesium carbonate crystals,
heating for a preset time, and then heating to convert the magnesium carbonate into basic magnesium carbonate, wherein the preset time is 20-60 min; the temperature after temperature rise is controlled to be 80-120 ℃.
8. The method for jointly preparing the battery-grade sodium carbonate and the basic magnesium carbonate in the soda industry according to claim 1, wherein the basic magnesium carbonate product is tetrahydrate; with Cl — The chlorine content is 0.03-0.05%.
9. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda industry according to claim 1, characterized in that mother liquor II obtained by preparation is used for soda production.
10. The method for jointly preparing battery-grade sodium carbonate and basic magnesium carbonate in the soda industry according to claim 1, characterized in that the obtained crude calcium filter cake is prepared for preparing hemihydrate gypsum.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117105246A (en) * | 2023-09-26 | 2023-11-24 | 福建省龙德新能源有限公司 | Synthesis process of electronic grade sodium carbonate |
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| CN117105246A (en) * | 2023-09-26 | 2023-11-24 | 福建省龙德新能源有限公司 | Synthesis process of electronic grade sodium carbonate |
| CN117105246B (en) * | 2023-09-26 | 2024-03-29 | 福建省龙德新能源有限公司 | Synthesis process of electronic grade sodium carbonate |
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