CN110563007A - Method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide - Google Patents
Method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide Download PDFInfo
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- CN110563007A CN110563007A CN201910933767.2A CN201910933767A CN110563007A CN 110563007 A CN110563007 A CN 110563007A CN 201910933767 A CN201910933767 A CN 201910933767A CN 110563007 A CN110563007 A CN 110563007A
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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 65
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 61
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 53
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 43
- 229910000030 sodium bicarbonate Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 33
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 31
- 235000017557 sodium bicarbonate Nutrition 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000011268 mixed slurry Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000013589 supplement Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000009775 high-speed stirring Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 12
- 239000007832 Na2SO4 Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
the invention relates to a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide, which comprises the following steps: firstly, mixing sodium sulfate and calcium oxide, uniformly spraying and adding water to obtain a granular or powdery mixed material; putting the mixed material into a ball mill with a sealing function for full grinding, and simultaneously introducing CO into the ball mill2A gas; after the mixed materials are fully ground and reacted, the powdery mixed materials are moved out of the ball mill to a reactor, water is added to be fully mixed with the powdery mixed materials to obtain slurry, and CO is introduced into the reactor2gas, stirring at high speed to make the above reaction fully and thoroughly proceed in liquid phase; stopping stirring after the reaction is completed, separating the mixed slurry by a solid-liquid separation device to obtain clear liquid, namely NaHCO3Solution, solid mainly CaSO4And CaCO3. Compared with the prior art, the method has the advantages of easy operation, low cost, easy realization of industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of sodium sulfate wastewater recovery, and particularly relates to a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide.
Background
In many chemical and smelting production processes, a large amount of industrial wastewater containing sodium sulfate is generated, and if the high-salt wastewater is directly discharged without being treated, serious pollution is caused to the environment, and resources are wasted. Therefore, an economical and effective sodium sulfate treatment technology is developed, the resource utilization of the sodium sulfate is promoted, and the key problem of water resource recycling is solved.
Currently, there are three general treatment methods for sodium sulfate: the first method is to directly concentrate and crystallize sodium sulfate wastewater to obtain sodium sulfate solid containing crystal water, but the method needs to consume a large amount of steam, has high energy consumption and has high requirements on equipment; secondly, the coke (C) is used for reducing the sodium sulfate at high temperature to prepare the sodium sulfide, and the method has high investment cost, high requirement on equipment and high energy consumption; thirdly, the sodium sulfate is converted into sodium hydroxide with more economic value by adding lime water, and Chinese patent CN10789231A discloses a method for preparing sodium hydroxide by using waste water containing sodium sulfate, wherein calcium carbide slurry (rich in Ca (OH)) is added into the waste water containing sodium sulfate2) In order to promote the reaction, a certain amount of sucrose is added to increase the solubility of calcium hydroxide, but the method still only has about 50% of sodium sulfate conversion rate.
The reaction of calcium oxide or calcium hydroxide with sodium sulfate to produce sodium hydroxide is feasible, the reaction is difficult to complete because the product contains sodium hydroxide as strong base, and the produced calcium sulfate is easy to coat the surface of lime/slaked lime particles to block the contact with sodium sulfate, so that the utilization rate is low2the sodium hydroxide is further converted into the sodium bicarbonate to promote the reaction, and the calcium sulfate coated on the surface of the slaked lime can be stripped off by adopting the ball milling reaction under the action of mechanical force, so that the particle size of the particulate matter is reduced, the reaction contact area is increased, and the reaction efficiency is improved.
disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide.
The purpose of the invention can be realized by the following technical scheme: a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide is characterized by comprising the following steps:
Firstly, mixing sodium sulfate and calcium oxide, uniformly spraying and adding water to obtain a granular or powdery mixed material with good fluidity;
Secondly, putting the mixed material into a ball mill with a sealing function for full grinding, and simultaneously introducing CO into the ball mill2a gas; by continuously grinding, Na is made2SO4with CaO and CO2Are in full contact with each other to react, and can make Na react2SO4 is mostly converted into NaHCO3The reaction that takes place is as follows:
CaO+Na2SO4+2CO2+H2O→CaSO4+2NaHCO3
Ca(OH)2+Na2SO4+2CO2→CaSO4+2NaHCO3
Thirdly, after the mixed materials are fully ground and reacted, the powdery mixed materials are moved out of the ball mill to a reactor, water is added to be fully mixed with the powdery mixed materials to obtain slurry, and CO is introduced into the reactor2gas, stirring at high speed to make the above reaction fully and thoroughly proceed in liquid phase;
Fourthly, stopping stirring after the reaction is completed, separating the mixed slurry by a solid-liquid separation device, and separating to obtain clear liquid, namely NaHCO3Solution, solid mainly CaSO4And CaCO3。
Further, the molar ratio of the sodium sulfate to the calcium oxide in the first step is 1-1.5: 1;
The water is added in a spraying mode, and the addition amount is that the water content of the free water of the mixed material is controlled to be 4-8%.
further, the calcium oxide described in the first step is quicklime (CaO) or slaked lime (Ca (OH)2) One or a mixture of them, or rich in Ca (OH)2The carbide slag;
The sodium sulfate is anhydrous sodium sulfate, sodium sulfate containing crystal water, or aqueous solution of sodium sulfate.
Furthermore, the ball mill adopted in the second step has the sealing function, and CO is introduced in the ball milling process2Keeping the internal pressure at 0.2-0.5 MPa;
The carbon dioxide used is industrial grade or industrial tail gas with a volume concentration higher than 50%.
Further, the mixed material in the second step is ground in a ball mill for 0.5 to 3 hours with a grinding average particle size in the range of 0.5 to 5 μm.
Furthermore, the water is added into the reactor in the third step to dilute the mixed material into slurry with the solid content of 10-30%.
further, introducing CO into the reactor in the third step2Gas, to maintain the internal pressure of the reactor at 0.2-0.5 MPa.
further, the high-speed stirring speed in the reactor in the third step is 100-200rpm, and the time is 0.5-2 hours.
further, in the third step, in the latter stage of the reaction, the stirring rate is reduced, thereby allowing CaSO to be generated by the reaction4Large particles are formed by crystallization, which facilitates filtration and separation.
Further, the fourth step is by crystallization of NaHCO3Recovering the solid from the solution, or directly returning the solution to a desulfurization system to supplement sodium alkali;
CaSO4The solid can be used as mineral smelting auxiliary material for cyclic utilization, wherein a small amount of CaCO3the use quality of the product is not affected.
Compared with the prior art, the invention has the following advantages:
1. by using CO2The sodium hydroxide generated in the reaction is converted into sodium bicarbonate and simultaneouslyThe reaction efficiency is improved by full grinding, and the conversion rate of sodium sulfate can reach 50-65%;
2. the method can effectively recover sodium sulfate generated in the smelting industry, obtain sodium bicarbonate with higher economic value, can crystallize and recover solid or directly return to a desulfurization system to be used as a sodium-alkali supplement, realize waste recycling and generate no secondary pollution.
3. The raw materials of lime, calcium hydroxide and carbon dioxide used in the method are all easily available materials, and the raw materials are low in cost and are non-toxic and harmless;
The technical principle of the method is as follows:
Na2SO4+Ca(OH)2＝→2NaOH+CaSO4
NaOH+CO2＝NaHCO3
Ca(OH)2+2CO2＝Ca(HCO3)2
Ca(HCO3)2+Na2SO4＝CaSO4+2NaHCO3。
Drawings
FIG. 1 is a schematic diagram of the process employed in the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
example 1:
As shown in fig. 1, a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide comprises the following steps:
1. 56g of calcium oxide and 142g of sodium sulfate are weighed, mixed and added with 10mL of deionized water to be stirred, and mixed material with certain moisture content is prepared.
2. Transferring the mixed material to a ball mill, and introducing CO2and (3) keeping the air pressure in the ball milling tank at 0.2MPa for 2 h.
3. The reacted materials are removed out for ball millingThe mixture is canned into a stainless steel reactor, 500mL of deionized water is added for dissolution, and CO is introduced at the same time2Gas, the pressure in the reactor was maintained at 0.2MPa, and the mixture was stirred at 200rpm for 2 hours.
4. The stirring was stopped and the slurry in the reactor was filtered to give a sodium bicarbonate solution, the sodium bicarbonate concentration analyzed as: 235.5g/L, the conversion rate of sodium sulfate is 60.1 percent.
Example 2:
1. 56g of calcium oxide and 142g of sodium sulfate are weighed, mixed and added with 10mL of deionized water to be stirred, and mixed material with certain moisture content is prepared.
2. Transferring the mixed material to a ball mill, and introducing CO2And (3) keeping the air pressure in the ball milling tank at 0.5MPa for 2 h.
3. And (3) moving the reacted materials out of the ball milling tank to a stainless steel reactor, adding 500mL of deionized water for dissolving, introducing CO2 gas, keeping the air pressure in the reactor at 0.5MPa, and stirring at the rotating speed of 200rpm for 2 hours.
4. The stirring was stopped and the slurry in the reactor was filtered to give a sodium bicarbonate solution, the sodium bicarbonate concentration analyzed as: 286.6g/L, sodium sulfate conversion was 55.3%.
Example 3:
1. 56g of calcium oxide and 142g of sodium sulfate are weighed, mixed and added with 10mL of deionized water to be stirred, and mixed material with certain moisture content is prepared.
2. Transferring the mixed material into a ball mill, introducing CO2 gas, and keeping the air pressure in a ball milling tank at 0.5MPa for 3 h.
3. and (3) moving the reacted materials out of the ball milling tank to a stainless steel reactor, adding 500mL of deionized water for dissolving, introducing CO2 gas, keeping the air pressure in the reactor at 0.5MPa, and stirring at the rotating speed of 200rpm for 2 hours.
4. The stirring was stopped and the slurry in the reactor was filtered to give a sodium bicarbonate solution, the sodium bicarbonate concentration analyzed as: 297g/L, the sodium sulfate conversion was 58.4%.
Example 4
a method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide comprises the following steps:
Firstly, mixing sodium sulfate and calcium oxide according to a molar ratio of 1:1, uniformly spraying and adding water in a spraying manner to control the water content of free water of a mixed material to be 4%, and obtaining a granular or powdery mixed material with good fluidity;
The calcium oxide is quicklime (CaO), and the sodium sulfate is anhydrous sodium sulfate.
secondly, putting the mixed material into a ball mill with a sealing function for full grinding, and simultaneously introducing CO into the ball mill2Gas, keeping the internal pressure at 0.2 MPa; the carbon dioxide used is industrial grade or industrial tail gas with a volume concentration higher than 50%. Continuously grinding for 0.5 hr to obtain Na powder with average particle size of 0.5-5 μm2SO4With CaO and CO2Are in full contact with each other to react, and can make Na react2SO4 is mostly converted into NaHCO3The reaction that takes place is as follows:
CaO+Na2SO4+2CO2+H2O→CaSO4+2NaHCO3
Ca(OH)2+Na2SO4+2CO2→CaSO4+2NaHCO3
Thirdly, after the mixed materials are fully ground and reacted, the powdery mixed materials are moved out of the ball mill to a reactor, water is added to be fully mixed with the powdery mixed materials to obtain slurry with the solid content of 10%, and then CO is introduced into the reactor2Gas, keeping the internal pressure of the reactor at 0.2MPa, and stirring at a high speed of 100rpm for 2 hours to fully and thoroughly carry out the reaction in a liquid phase;
in the later stage of the reaction, the stirring rate is reduced, so that CaSO generated by the reaction4Large particles are formed by crystallization, which facilitates filtration and separation.
Fourthly, stopping stirring after the reaction is completed, and feeding the mixed slurry into a solid-liquid separation deviceseparating to obtain clear liquid, namely NaHCO3Solution, solid mainly CaSO4And CaCO3。
By crystallization of NaHCO3recovering the solid from the solution, or directly returning the solution to a desulfurization system to supplement sodium alkali; CaSO4The solid can be used as mineral smelting auxiliary material for cyclic utilization, wherein a small amount of CaCO3The use quality of the product is not affected.
Example 5
A method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide comprises the following steps:
Firstly, mixing sodium sulfate and calcium oxide according to a molar ratio of 1.5:1, and uniformly spraying and adding water in a spraying manner to control the water content of free water of the mixed material to be 8% so as to obtain a granular or powdery mixed material with good fluidity;
The calcium oxide is rich in Ca (OH)2the carbide slag; the sodium sulfate is sodium sulfate containing crystal water.
Secondly, putting the mixed material into a ball mill with a sealing function for full grinding, and simultaneously introducing CO into the ball mill2Gas, keeping the internal pressure at 0.5 MPa; the carbon dioxide used is industrial grade or industrial tail gas with a volume concentration higher than 50%. Continuously grinding for 3 hours to obtain Na with average particle size of 0.5-5 μm2SO4With CaO and CO2are in full contact with each other to react, and can make Na react2SO4 is mostly converted into NaHCO3the reaction that takes place is as follows:
CaO+Na2SO4+2CO2+H2O→CaSO4+2NaHCO3
Ca(OH)2+Na2SO4+2CO2→CaSO4+2NaHCO3
Thirdly, after the mixed materials are fully ground and reacted, the powdery mixed materials are moved out of the ball mill to a reactor, and water is added to be fully mixed with the powdery mixed materials to obtain the mixture with the solid content of 30 percentIntroducing CO into the reactor2Gas, keeping the internal pressure of the reactor at 0.5MPa, and stirring at a high speed of 200rpm for 0.5 hour to fully and thoroughly carry out the reaction in a liquid phase;
in the later stage of the reaction, the stirring rate is reduced, so that CaSO generated by the reaction4Large particles are formed by crystallization, which facilitates filtration and separation.
Fourthly, stopping stirring after the reaction is completed, separating the mixed slurry by a solid-liquid separation device, and separating to obtain clear liquid, namely NaHCO3Solution, solid mainly CaSO4And CaCO3。
By crystallization of NaHCO3Recovering the solid from the solution, or directly returning the solution to a desulfurization system to supplement sodium alkali; CaSO4The solid can be used as mineral smelting auxiliary material for cyclic utilization, wherein a small amount of CaCO3The use quality of the product is not affected.
Claims (10)
1. A method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide is characterized by comprising the following steps:
Firstly, mixing sodium sulfate and calcium oxide, uniformly spraying and adding water to obtain a granular or powdery mixed material;
Secondly, putting the mixed material into a ball mill with a sealing function for full grinding, and simultaneously introducing CO into the ball mill2A gas;
Thirdly, after the mixed materials are fully ground and reacted, the powdery mixed materials are moved out of the ball mill to a reactor, water is added to be fully mixed with the powdery mixed materials to obtain slurry, and CO is introduced into the reactor2Gas, stirring at high speed to make the above reaction fully and thoroughly proceed in liquid phase;
fourthly, stopping stirring after the reaction is completed, separating the mixed slurry by a solid-liquid separation device, and separating to obtain clear liquid, namely NaHCO3solution, solid mainly CaSO4And CaCO3。
2. the method for converting sodium sulfate into sodium bicarbonate by using calcium oxide and carbon dioxide as claimed in claim 1, wherein the molar ratio of the sodium sulfate to the calcium oxide in the first step is 1-1.5: 1;
The water is added in a spraying mode, and the addition amount is that the water content of the free water of the mixed material is controlled to be 4-8%.
3. The method of claim 1, wherein the calcium oxide is quicklime (CaO) or slaked lime (Ca (OH) in the first step2) One or a mixture of them, or rich in Ca (OH)2The carbide slag;
The sodium sulfate is anhydrous sodium sulfate, sodium sulfate containing crystal water, or aqueous solution of sodium sulfate.
4. The method for converting sodium sulfate into sodium bicarbonate with calcium oxide and carbon dioxide as claimed in claim 1, wherein the ball mill used in the second step has sealing effect, and CO is introduced during the ball milling process2Keeping the internal pressure at 0.2-0.5 MPa;
The carbon dioxide used is industrial grade or industrial tail gas with a volume concentration higher than 50%.
5. The method for converting sodium sulfate into sodium bicarbonate with calcium oxide and carbon dioxide as claimed in claim 1, wherein the milling time of the mixed materials in the second step in the ball mill is 0.5-3 hours, and the average milling particle size is 0.5-5 μm.
6. The method for converting sodium sulfate into sodium bicarbonate with calcium oxide and carbon dioxide as claimed in claim 1, wherein the third step is to add water into the reactor to dilute the mixture into slurry with solid content of 10-30%.
7. The method for converting sodium sulfate into sodium bicarbonate with calcium oxide and carbon dioxide as claimed in claim 1, wherein the CO is introduced into the reactor in the third step2Gas, to maintain the internal pressure of the reactor at 0.2-0.5 MPa.
8. The method for converting sodium sulfate into sodium bicarbonate using calcium oxide and carbon dioxide as claimed in claim 1, wherein the third step is that the high speed stirring speed in the reactor is 100-200rpm for 0.5-2 hours.
9. The method of claim 1, wherein the third step is carried out by reducing the stirring rate at the end of the reaction to reduce the CaSO produced during the reaction4large particles are formed by crystallization, which facilitates filtration and separation.
10. The process of claim 1, wherein the fourth step is performed by crystallizing NaHCO3Recovering the solid from the solution, or directly returning the solution to a desulfurization system to supplement sodium alkali; CaSO4The solid can be used as mineral smelting auxiliary material for cyclic utilization, wherein a small amount of CaCO3The use quality of the product is not affected.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551552A (en) * | 2020-09-24 | 2021-03-26 | 宣城市楷昂化工有限公司 | Method for preparing sodium hydroxide by using carbon dioxide |
| CN115212713A (en) * | 2022-05-30 | 2022-10-21 | 湖北工业大学 | Carbon sequestration and emission reduction method for wet grinding kiln ash of cement plant |
| CN115893465A (en) * | 2022-11-28 | 2023-04-04 | 华南理工大学 | Waste salt recycling process |
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| CN105621457A (en) * | 2014-10-30 | 2016-06-01 | 赵建英 | Regeneration recycling method of sodium hydroxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112551552A (en) * | 2020-09-24 | 2021-03-26 | 宣城市楷昂化工有限公司 | Method for preparing sodium hydroxide by using carbon dioxide |
| CN115212713A (en) * | 2022-05-30 | 2022-10-21 | 湖北工业大学 | Carbon sequestration and emission reduction method for wet grinding kiln ash of cement plant |
| CN115212713B (en) * | 2022-05-30 | 2024-03-26 | 湖北工业大学 | Method for carbon fixation and emission reduction of wet mill kiln ash of cement plant |
| CN115893465A (en) * | 2022-11-28 | 2023-04-04 | 华南理工大学 | Waste salt recycling process |
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| CN110563007B (en) | 2021-11-26 |
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