CN115784263B - Method for preparing sodium carbonate by sodium sulfate and application thereof - Google Patents
Method for preparing sodium carbonate by sodium sulfate and application thereof Download PDFInfo
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 73
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 57
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 36
- 239000007791 liquid phase Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000007790 solid phase Substances 0.000 claims abstract description 44
- 238000001704 evaporation Methods 0.000 claims abstract description 27
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 24
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 24
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 24
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- 235000017550 sodium carbonate Nutrition 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 8
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 239000012265 solid product Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 20
- 239000011734 sodium Substances 0.000 description 20
- 239000007787 solid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 238000005649 metathesis reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for preparing sodium carbonate by sodium sulfate and application thereof, wherein the method comprises the following steps: fully mixing and reacting ammonium bicarbonate and sodium sulfate, separating the reaction, and calcining a solid phase in the reaction to obtain sodium carbonate; introducing carbon dioxide into the liquid phase to carry out carbonation reaction to obtain a carbonation intermediate; and separating the carbonated intermediate after low-temperature evaporation, and then, putting the separated solid product into ammonium bicarbonate and sodium sulfate again for reaction. According to the method, after the double decomposition reaction of sodium sulfate and ammonium bicarbonate is completed, the remaining first liquid phase is filtered through carbonation and evaporated, and unreacted sodium sulfate and ammonium bicarbonate can be effectively separated, so that the sodium sulfate and ammonium bicarbonate can be put into the double decomposition reaction again, and the conversion rate and the utilization rate in the process of preparing sodium carbonate from ammonium sulfate and ammonium bicarbonate are greatly improved.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing sodium carbonate by sodium sulfate and application thereof.
Background
Sodium sulfate widely exists in salt lakes, mines and soil in the nature, and a large amount of byproduct sodium sulfate is discharged in the industries of chemical industry, medicine, new energy, environmental protection and the like.
The main method for industrial application of sodium sulfate is to prepare mirabilite or anhydrous sodium sulfate which is used in chemical industry, glass industry, papermaking industry, metallurgy industry and textile industry, but the problems of low product value, high energy processing cost and limited market demand exist, and few industrial application examples exist in converting sodium sulfate into other bulk chemical raw materials.
The technology for preparing sodium carbonate by adopting the sodium sulfate and ammonium bicarbonate double decomposition method has more advantages, such as mild reaction conditions, relatively low energy consumption, less generation of three wastes, less equipment investment and the like. However, after the calcined soda is obtained by one-time calcination, a large amount of byproducts still exist, and the byproducts have more useful substances and can be recycled.
In order to improve the utilization rate of sodium sulfate and ammonium bicarbonate for preparing sodium carbonate by a double decomposition method, in the prior art, a technical route of twice freezing and high-temperature ammonia distillation is adopted in the subsequent process of the double decomposition method, but the method has high energy consumption and large industrialization difficulty, and is stopped after expansion test. In general, the existing technology for preparing sodium carbonate by adopting a sodium sulfate and ammonium bicarbonate double-decomposition method is still not mature enough, the yield is unstable, and the technology for preparing sodium carbonate by adopting the sodium sulfate and ammonium bicarbonate double-decomposition method is still lack of economy and high efficiency. The above problems are technical problems to be solved in the art.
Disclosure of Invention
The invention mainly solves the technical problem of providing a method for preparing sodium carbonate by sodium sulfate, which can efficiently convert sodium sulfate.
According to a first aspect, the present application provides a method for preparing soda ash by sodium sulfate, comprising the steps of:
step S1: fully mixing and reacting ammonium bicarbonate with 20-40 wt% of sodium sulfate at 30-45 ℃ to obtain a first solid-liquid mixture; among them, the reaction process may be a batch type or a continuous type, but in industrial applications, a continuous type process advantageous on an industrial scale may be preferable.
Step S2: separating the first solid-liquid mixture to obtain a first solid phase and a first liquid phase;
step S3: calcining the first solid phase at 200-300 ℃ to obtain sodium carbonate.
Step S4: carrying out carbonation reaction on the first liquid phase and carbon dioxide to obtain a carbonation intermediate;
step S5: evaporating the carbonating intermediate at a low temperature of between 25 and 49 ℃ to obtain a second solid-liquid mixture;
step S6: separating the second solid-liquid mixture to obtain a second solid phase and a second liquid phase, and repeating the steps S1 to S6 by taking the second solid phase as a raw material.
According to the method, after the double decomposition reaction of sodium sulfate and ammonium bicarbonate is completed, the remaining first liquid phase is filtered through carbonation and evaporated, and unreacted sodium sulfate and ammonium bicarbonate can be effectively separated, so that the sodium sulfate and ammonium bicarbonate can be put into the double decomposition reaction again, and the conversion rate and the utilization rate in the process of preparing sodium carbonate from ammonium sulfate and ammonium bicarbonate are greatly improved.
In an alternative embodiment, in step S3, the carbonation reaction temperature is between 25 ℃ and 49 ℃ and the reaction pressure is between 1 bar and 3bar.
In step S3, carbon dioxide may be provided by carbon dioxide produced after calcination in step S3, wherein the carbon dioxide is added in an amount corresponding to Na in the solution 2 CO 3 The molar ratio of (2) is 1:2.3.
In an alternative embodiment, the step S6 further includes the step of:
step S7: fully mixing and reacting the second liquid phase with dilute sulfuric acid to obtain a reaction solution;
step S8: adding sodium hydroxide to neutralize the reaction solution, and evaporating the neutralized reaction solution for one time to obtain a third solid-liquid mixture;
step S9: separating the third solid-liquid mixture to obtain a third liquid phase and a third solid phase, diluting the third solid phase to 20-40 wt% and replacing sodium sulfate, and repeating the steps S1-S9.
In step S7, the amount of dilute sulfuric acid added is related to the amount of carbonate in the solution, wherein the molar ratio of carbonate to sulfate is 1.95:1, and in the actual production process, an excess of dilute sulfuric acid may be added to make the reaction sufficient.
In an alternative embodiment, in the step S8, the pH value of the reaction solution after the neutralization is 7 to 8, and the temperature of the primary evaporation is 30 to 90 ℃.
The primary evaporation in step S8 may be low temperature evaporation, multiple effect evaporation, or mechanical recompression evaporation of steam.
In an alternative embodiment, the step S9 further includes the step of:
step S10: performing secondary evaporation on the third liquid phase until the third liquid phase is crystallized, and recovering the crystallized phase to obtain (NH) 4 ) 2 SO 4 ；
Step S11: recovering the third liquid phase which is not crystallized, mixing the third liquid phase which is not crystallized with the carbonated intermediate, and repeating steps S5 to S10.
In step S9, the secondary evaporation may be low temperature evaporation, multiple effect evaporation, or vapor mechanical recompression evaporation.
In an alternative embodiment, in step S10, the temperature of the secondary evaporation is 30-120 ℃.
In an alternative embodiment, in step S1, the molar ratio of the ammonium bicarbonate to the sodium sulfate is 2.01-2.5, the reaction temperature is 25-45 ℃, and the reaction pressure is 1.01-1.5bar.
In an alternative embodiment, the step S3 further includes the steps of: washing the first solid phase with water at 20-40 ℃.
In step S3, to eliminate non-NaHCO in the first powder 3 In this step, the first solid phase may be washed with 2 to 5 parts by mass of water of the first solid phase, and then washed at 20 to 40℃to concentrate the washed water, and then put into step 1 again to carry out the metathesis reaction.
According to a second aspect, the present application provides a method for producing soda ash based on a byproduct of a new energy lithium product, including the above method, wherein sodium sulfate in the step S1 is separated from the byproduct of the new energy lithium product.
According to a third aspect, the present application provides the use of the method described above in the production of new energy lithium products.
The method can greatly improve the conversion rate of sodium sulfate and ammonium bicarbonate for preparing sodium carbonate, so that stable yield can be obtained.
The method can be applied to the production process of new energy management products, and sodium sulfate in the new energy management products can be effectively recovered and reused after a plurality of byproducts are separated.
Drawings
Fig. 1 is an overall process flow diagram of the present application.
Detailed Description
The invention will be described in further detail below with reference to the drawings by means of specific embodiments. Wherein like elements in different embodiments are numbered alike in association. In the following embodiments, numerous specific details are set forth in order to provide a better understanding of the present application. However, one skilled in the art will readily recognize that some of the features may be omitted, or replaced by other elements, materials, or methods in different situations. In some instances, some operations associated with the present application have not been shown or described in the specification to avoid obscuring the core portions of the present application, and may not be necessary for a person skilled in the art to describe in detail the relevant operations based on the description herein and the general knowledge of one skilled in the art.
Furthermore, the described features, operations, or characteristics of the description may be combined in any suitable manner in various embodiments. Also, various steps or acts in the method descriptions may be interchanged or modified in a manner apparent to those of ordinary skill in the art. Thus, the various orders in the description and drawings are for clarity of description of only certain embodiments, and are not meant to be required orders unless otherwise indicated.
The numbering of the components itself, e.g. "first", "second", etc., is used herein merely to distinguish between the described objects and does not have any sequential or technical meaning. The terms "coupled" and "connected," as used herein, are intended to encompass both direct and indirect coupling (coupling), unless otherwise indicated.
Example 1
As shown in FIG. 1, step S1, a certain amount of sodium sulfate powder is weighed, distilled water is added into the sulfuric acid powder until the concentration of sodium sulfate reaches 12wt%, and Na with the concentration of 12wt% 2 SO 4 Concentrating the solution by ED, and concentrating Na in the solution 2 SO 4 The concentration was raised to 28wt%, the solution temperature was again adjusted to 38℃and poured into a stirred metathesis reactor at a flow rate of 14.9t/h, while ammonium bicarbonate solids were added to the reactor at a rate of 5.1t/h,the temperature of the reactor is controlled at 38 ℃ and the pressure is controlled at 1.02bar, and after the reactor and the reactor are fully mixed, a first solid-liquid mixture is obtained.
In this step, na 2 SO 4 With NH 4 HCO 3 The double decomposition reaction occurs, and the first solid-liquid mixture contains NaHCO as the reaction product 3 、(NH 4 ) 2 SO 4 NH that has not fully reacted 4 HCO 3 、Na 2 SO 4 And a small amount of Na 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the The specific reaction formula of the step is shown as a formula (1):
2NH 4 HCO 3 +Na 2 SO 4 →2NaHCO 3 +(NH 4 ) 2 SO 4 (1)
in this reaction, about 80-90% of NaHCO3 is present in the solid phase.
And S2, discharging the first solid-liquid mixture generated by the reaction, and filtering the mixture, wherein the obtained solid material is a first solid phase, and the obtained liquid is a first liquid phase.
Step S3, weighing pure water of 30 ℃ which is 3 times the mass of the first solid phase, washing the first solid phase, then filtering again, sending the filtered first solid phase to a calciner, and calcining at 270 ℃ to obtain Na 2 CO 3 White powder product.
In this step, since the first solid phase left after filtration and washing is mainly NaHCO 3 ，NaHCO 3 Calcining at 200-300 ℃ to generate sodium carbonate, wherein the specific reaction formula is shown as formula (2):
2NaHCO 3 →Na 2 CO 3 +CO 2 +H 2 O (2)
step S4, adding the second liquid phase into the carbonization device, and then adding the second liquid phase into the carbonization device at a speed of 1.2m 3 Carbon dioxide is introduced into the carbonization device at the rate of/h, the carbonation reaction is carried out under the conditions that the pressure is 2bar and the temperature is 48 ℃, and the liquid after the carbonation reaction is recorded as a carbonation intermediate.
In this step, since the second liquid phase contains unreacted complete reactant and part of the product, it contains (NH) 4 ) 2 SO 4 、NH 4 HCO 3 、Na 2 SO 4 、Na 2 CO 3 And a small amount of NaHCO 3 Equal components; at this time add CO 2 When carbonation reaction is carried out, sodium carbonate mixed in the second liquid phase can be reacted into sodium bicarbonate, and the specific reaction formula is shown as a formula (3):
Na 2 CO 3 +CO 2 +H 2 O→2NaHCO 3 (3)
and S5, evaporating the carbonated intermediate at a low temperature of 45 ℃, and marking the obtained solid-liquid mixture as a second solid-liquid mixture.
In this step, NH in a dissolved state of 90% or more is evaporated at low temperature 4 HCO 3 、Na 2 SO 4 Transition to solid state, and 95% or more of NaHCO in dissolved state 3 Will turn into a solid state and separate from the solution.
And S6, filtering the second solid-liquid mixture, wherein the obtained solid is a second solid phase, and the obtained liquid is a second liquid phase.
Through the reactions of the above formulas (1) to (3), the second solid phase contains NH 4 HCO 3 、NaHCO 3 Part of Na 2 SO 4 These components may be newly charged into the metathesis reaction vessel of step S1 to undergo the metathesis reaction again.
Step S7, adding 15kg of dilute sulfuric acid into the filtered second liquid phase under stirring, wherein the addition amount of the dilute sulfuric acid can be adaptively adjusted according to the amount of carbonate in the solution, specifically, the carbonate and H 2 SO 4 The molar ratio of (2) was 1.95:1.
In this step, the main component in the second liquid phase is (NH 4 ) 2 SO 4 And a small amount of NH 4 HCO 3 、Na 2 SO 4 The components, at this time, dilute sulfuric acid is added and stirred, so that the residual ammonium bicarbonate can be completely decomposed into (NH) 4 ) 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The specific reaction formula is shown as formula (4):
2NH 4 HCO 3 +H 2 SO 4 →(NH 4 ) 2 SO 4 +2CO 2 +2H 2 O (3)
and S8, after the second liquid phase is fully reacted with the dilute sulfuric acid, adding NaOH into the reacted second liquid phase, adjusting the pH of the second liquid phase to 8, and then performing primary evaporation at 60 ℃, thereby obtaining a solid-liquid mixture containing a small amount of solid phase.
Step S9, filtering the third solid-liquid mixture, and marking the filtered solid as a third solid phase, and the filtered liquid as a third liquid phase, wherein the main component of the third solid phase is Na 2 SO 4 It may be newly put into step S1 as a raw material and the above steps are repeated.
In step S8, naOH is added to the third liquid phase, and the NaOH is mixed with (NH) 4 ) 2 SO 4 The reaction is carried out, so that fixed sodium sulfate is obtained, and the sodium sulfate can be separated out through filtration.
Step S10, filtering, further evaporating the third liquid phase at 90deg.C until the second liquid phase is crystallized, filtering the second liquid phase, and collecting the obtained crystal phase, which is (NH) 4 ) 2 SO 4 And (5) a product.
After the steps S1 to S9, the remaining third liquid phase is mainly composed of (NH) 4 ) 2 SO 4 At this time, (NH) can be obtained by the secondary evaporation 4 ) 2 SO 4 And precipitated as crystals.
Step S11, the precipitated second liquid phase contains a small amount of useful substances, and in this case, the crystallized second liquid phase may be mixed with the carbonated intermediate, and the steps S5 to S10 may be repeated.
Soda Na finally obtained by the above example 1 2 CO 3 The main content is 98.85%, the quality of the product reaches the quality standard (GB 210-2004) class II first-class product of sodium carbonate products, and the quality of the ammonium sulfate reaches the quality standard (GB 535-1995) first-class product of ammonium sulfate products. For sodium sulfate before and after reactionThe conversion was determined to be 94% by weight.
Example 2
Step S1, preparing a sodium sulfate solution with the concentration of 31wt%, regulating the temperature of the sodium sulfate solution to 35 ℃, feeding the sodium sulfate solution into a double decomposition gap reactor with stirring at the flow rate of 13t/h, simultaneously adding 4.5t of ammonium bicarbonate solid into the reactor at 45min, controlling the temperature of the reactor to 49 ℃, controlling the pressure to 1.02bar, and reacting for about 1h to obtain a first solid-liquid mixture.
And S2, filtering the first solid-liquid mixture obtained in the step S1 to obtain a first solid phase and a first liquid phase.
Step S3, washing the obtained first solid phase with 4 times of pure water at 30 ℃, filtering, sending the filtered first solid phase to a calciner, and calcining at 280 ℃ to obtain sodium carbonate Na 2 CO 3 And (5) a product.
Step S4, 1.25m 3 And adding carbon dioxide into the first liquid phase obtained after filtration at the flow rate of/h, and performing carbonation reaction at the temperature of 2.5bar and 45 ℃ to obtain a carbonation intermediate.
And S5, performing low-temperature evaporation on the carbonating intermediate at 40 ℃ to obtain a second solid-liquid mixture.
And S6, filtering the second solid-liquid mixture to obtain a second solid phase and a second liquid phase, wherein the second solid phase is used as a raw material, and the steps S1 to S6 are repeated.
And step S7, adding 13kg of dilute sulfuric acid into the obtained second liquid phase under stirring to react.
And S8, after the reaction is finished, naOH is added to adjust the pH to 8, and the mixture is evaporated at 60 ℃ to obtain a third solid-liquid mixture containing a small amount of solid phase.
And S9, filtering the third solid-liquid mixture, separating to obtain a third solid phase and a third liquid phase, and returning the third solid phase to the step S1 for repeated use.
Step S10, filtering, further evaporating the second liquid phase at 90 ℃ for a second time, crystallizing to obtain solid (NH) 4 ) 2 SO 4 And (5) a product.
Through the embodiment, the main content of the finally obtained sodium carbonate Na2CO3 is 99.05 percent, the quality of the sodium carbonate reaches the quality standard (GB 210-2004) class II first-class product of sodium carbonate products, and the quality of the ammonium sulfate reaches the quality standard (GB 535-1995) first-class product of ammonium sulfate products. Sodium sulfate (Na 2SO 4) conversion was 95%.
Example 3
The method for purifying the sodium sulfate can adopt the existing method, and the application is not particularly limited. For example, when the by-product contains lithium ions and potassium ions in addition to sodium sulfate, the concentration of lithium and potassium ions in the by-product solution can be reduced to 42ppm or less and 12ppm or less by adsorption.
Step S1, dissolving the sodium sulfate in water, concentrating ED to make the concentration reach 30wt%, obtaining 30wt% sodium sulfate solution, regulating the temperature of the sodium sulfate solution to 35 ℃, feeding the sodium sulfate solution into a double decomposition reactor with stirring at a flow rate of 12t/h, simultaneously adding ammonium bicarbonate solid into the reactor at a speed of 4.6t/h, controlling the temperature of the reactor to 40 ℃ and the pressure to 1.02bar, and reacting to obtain a first solid-liquid mixture.
And S2, filtering the first solid-liquid mixture obtained in the step S1 to obtain a first solid phase and a first liquid phase.
Step S3, washing the obtained first solid phase with 3 times of pure water at 30 ℃, filtering, sending the filtered first solid phase to a calciner, and calcining at 270 ℃ to obtain sodium carbonate Na 2 CO 3 And (5) a product.
Step S4, 1.3m 3 And adding carbon dioxide into the first liquid phase obtained after filtration at the flow rate of/h, and performing carbonation reaction at the temperature of 2bar and 48 ℃ to obtain a carbonation intermediate.
And S5, performing low-temperature evaporation on the carbonated intermediate liquid at 40 ℃ to obtain a second solid-liquid mixture.
And S6, filtering the second solid-liquid mixture to obtain a second solid phase and a second liquid phase, wherein the second solid phase is used as a raw material, and the steps S1 to S6 are repeated.
And step S7, adding 16kg of dilute sulfuric acid into the obtained second liquid phase under stirring to react.
And S8, after the reaction is finished, naOH is added to adjust the pH to 8, and the mixture is evaporated at 60 ℃ to obtain a third solid-liquid mixture containing a small amount of solid phase.
And S9, filtering the third solid-liquid mixture, separating to obtain a third solid phase and a third liquid phase, and returning the third solid phase to the step S1 for repeated use.
Step S10, filtering, further evaporating the second liquid phase at 90 ℃ for a second time, crystallizing to obtain solid (NH) 4 ) 2 SO 4 And (5) a product.
Through the above examples, the sodium carbonate Na is finally obtained 2 CO 3 The main content is 98.8 percent, the quality of the product reaches the quality standard (GB 210-2004) class II first-class product of sodium carbonate products, and the quality of the ammonium sulfate reaches the quality standard (GB 535-1995) first-class product of ammonium sulfate products. Sodium sulfate (Na) 2 SO 4 ) The conversion was 93%. The lithium ion yield was 96%.
The foregoing description of the invention has been presented for purposes of illustration and description, and is not intended to be limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.
Claims (8)
1. A method for preparing sodium carbonate by sodium sulfate, which is characterized by comprising the following steps:
step S1: fully mixing and reacting ammonium bicarbonate with 20-40 wt% of sodium sulfate at 30-45 ℃ to obtain a first solid-liquid mixture;
step S2: separating the first solid-liquid mixture to obtain a first solid phase and a first liquid phase;
step S3: calcining the first solid phase at 200-300 ℃ to obtain sodium carbonate;
step S4: carrying out carbonation reaction on the first liquid phase and carbon dioxide to obtain a carbonation intermediate;
step S5: evaporating the carbonating intermediate at a low temperature of between 25 and 49 ℃ to obtain a second solid-liquid mixture;
step S6: separating the second solid-liquid mixture to obtain a second solid phase and a second liquid phase, and repeating the steps S1 to S6 based on ammonium bicarbonate and sodium sulfate in the second solid phase;
step S7: fully mixing and reacting the second liquid phase with dilute sulfuric acid to obtain a reaction solution;
step S8: adding sodium hydroxide to neutralize the reaction solution, and evaporating the neutralized reaction solution for one time to obtain a third solid-liquid mixture;
step S9: separating the third solid-liquid mixture to obtain a third liquid phase and a third solid phase, diluting the third solid phase to 20-40 wt% and replacing sodium sulfate, and repeating the steps S1-S9.
2. The method for preparing soda ash by sodium sulfate according to claim 1, wherein in the step S5, the carbonation reaction temperature is 30-49 ℃ and the reaction pressure is 1-3bar.
3. The method for preparing soda ash by sodium sulfate according to claim 1, wherein in the step S8, the pH value of the reaction solution after neutralization is 7-8, and the temperature of the primary evaporation is 30-90 ℃.
4. The method for preparing soda ash by sodium sulfate according to claim 1, wherein the step S9 further comprises the steps of:
step S10: performing secondary evaporation on the third liquid phase until the third liquid phase is crystallized, and recovering the crystallized phase to obtain (NH) 4 ) 2 SO 4 ；
Step S11: recovering the third liquid phase which is not crystallized, mixing the third liquid phase which is not crystallized with the carbonated intermediate, and repeating steps S5 to S10.
5. The method for preparing soda ash by sodium sulfate according to claim 4, wherein the temperature of the secondary evaporation in the step S10 is 30-120 ℃.
6. The method for preparing soda ash by sodium sulfate according to any of claims 1 to 5, wherein in the step S1, the molar ratio of the ammonium bicarbonate to the sodium sulfate is 2.01-2.5, the reaction temperature is 25-45 ℃ and the reaction pressure is 1.01-1.5bar.
7. The method for preparing soda ash by sodium sulfate according to any of claims 1 to 5, characterized in that the step S3 further comprises the steps of: washing the first solid phase with water at 20-40 ℃.
8. A method for producing soda ash based on a byproduct of a new energy lithium product, comprising the method according to any one of claims 1 to 7, wherein sodium sulfate in step S1 is separated from the byproduct of the new energy lithium product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654351A (en) * | 1990-12-18 | 1997-08-05 | Ormiston Mining And Smelting Co. Ltd. | Method for sodium carbonate compound recovery and formation of ammonium sulfate |
| US5830422A (en) * | 1995-06-23 | 1998-11-03 | Ormiston Mining And Smelting Co. Ltd. | Method for production of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate |
| CN104355326A (en) * | 2014-10-16 | 2015-02-18 | 中国中轻国际工程有限公司 | Thermal circulation technology of utilizing sodium sulfate solution or carrier to cogenerate sodium carbonate and ammonium sulfate |
| CN106865571A (en) * | 2017-03-20 | 2017-06-20 | 科莱环境工程（北京）有限公司 | A kind of method that chemical industry strong brine produces sodium bicarbonate and ammonium sulfate |
| CN109052434A (en) * | 2018-10-19 | 2018-12-21 | 四川金象赛瑞化工股份有限公司 | A method of using saltcake and ammonium hydrogen carbonate as raw material producing soda ash and composite nitrogen fertilizer |
| CN114132947A (en) * | 2021-10-30 | 2022-03-04 | 山西长林能源科技有限公司 | Using sodium sulfate and CO2Equipment and method for producing ammonium bicarbonate and sodium carbonate |
-
2022
- 2022-11-17 CN CN202211439192.7A patent/CN115784263B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654351A (en) * | 1990-12-18 | 1997-08-05 | Ormiston Mining And Smelting Co. Ltd. | Method for sodium carbonate compound recovery and formation of ammonium sulfate |
| US5830422A (en) * | 1995-06-23 | 1998-11-03 | Ormiston Mining And Smelting Co. Ltd. | Method for production of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate |
| CN104355326A (en) * | 2014-10-16 | 2015-02-18 | 中国中轻国际工程有限公司 | Thermal circulation technology of utilizing sodium sulfate solution or carrier to cogenerate sodium carbonate and ammonium sulfate |
| CN106865571A (en) * | 2017-03-20 | 2017-06-20 | 科莱环境工程（北京）有限公司 | A kind of method that chemical industry strong brine produces sodium bicarbonate and ammonium sulfate |
| CN109052434A (en) * | 2018-10-19 | 2018-12-21 | 四川金象赛瑞化工股份有限公司 | A method of using saltcake and ammonium hydrogen carbonate as raw material producing soda ash and composite nitrogen fertilizer |
| CN114132947A (en) * | 2021-10-30 | 2022-03-04 | 山西长林能源科技有限公司 | Using sodium sulfate and CO2Equipment and method for producing ammonium bicarbonate and sodium carbonate |
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