CN114195174A - Method for preparing sodium sulfate from sodium bicarbonate desulfurized fly ash by wet method - Google Patents
Method for preparing sodium sulfate from sodium bicarbonate desulfurized fly ash by wet method Download PDFInfo
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- CN114195174A CN114195174A CN202111366464.0A CN202111366464A CN114195174A CN 114195174 A CN114195174 A CN 114195174A CN 202111366464 A CN202111366464 A CN 202111366464A CN 114195174 A CN114195174 A CN 114195174A
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- sodium bicarbonate
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 title claims abstract description 122
- 229910000030 sodium bicarbonate Inorganic materials 0.000 title claims abstract description 65
- 235000017557 sodium bicarbonate Nutrition 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 50
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 40
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 29
- 239000010881 fly ash Substances 0.000 title claims abstract description 16
- 239000002956 ash Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 29
- 230000023556 desulfurization Effects 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000012445 acidic reagent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 39
- 239000011734 sodium Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 9
- 239000010959 steel Substances 0.000 abstract description 9
- 239000002910 solid waste Substances 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 13
- 239000007789 gas Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000537371 Fraxinus caroliniana Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000010891 Ptelea trifoliata Nutrition 0.000 description 1
- 238000003723 Smelting Methods 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
- 239000003513 alkali Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for preparing sodium sulfate from sodium bicarbonate desulfurized fly ash by a wet method, which comprises the steps of firstly detecting the content of each component in the sodium bicarbonate desulfurized fly ash, mixing the qualified sodium bicarbonate desulfurized fly ash with water to prepare suspension, then sequentially adding an oxidant and an acid reagent for reaction, and finally evaporating, crystallizing and separating to obtain a target product Na2SO4·10H2And O. The method can thoroughly convert the desulfurization ash of the solid waste baking soda in the steel mill into the hydrated sodium sulfate product with high purity and higher economic value, and the product is widely applied in various industries such as chemical industry, food, pharmacy and the like and can generate better economic benefit. Compared with other existing methods for recycling and reusing the desulfurized fly ash solid waste resources, the method provided by the invention has the advantages of large treatment capacity, thorough conversion, high product purity, less wastewater, no limitation of other conditions and the like, and is beneficial to promoting the construction of green steel plants.
Description
Technical Field
The invention relates to the technical field of resource recycling of desulfurization ash solid waste, in particular to a method for preparing sodium sulfate from baking soda desulfurization ash by a wet method.
Background
In long-flow steel enterprises, the excess blast furnace/converter/coke oven gas is often recovered and utilized by gas power generation. In recent years, with the popularization of national ultra-low emission requirements in the steel industry, a gas boiler generally adopts a baking soda dry desulphurization process to purify flue gas. Although the baking soda dry desulphurization process meets the requirement of ultralow emission of flue gas, the process also brings the problem of secondary pollution of byproduct desulfurized ash. Practice shows that the components of the baking soda desulfurization ash are complex and changeable, and the corresponding utilization means is relatively lack, so the baking soda desulfurization ash becomes a new solid waste resource utilization problem which needs to be faced by iron and steel enterprises.
The metallurgical gas boiler uses the deeply purified blast furnace and converter gas as the power generation medium, the flue gas is relatively clean, and the obtained sodium bicarbonate desulfurized ash mainly contains Na2SO4、Na2SO3、NaHCO3And the like, and insoluble impurities are less. The search shows that only a few technical reports on the utilization of the sodium bicarbonate desulfurized ash and similar solid wastes in the prior literature. For example, chinese patents CN 110451532A and CN110697738A report a resource treatment method for sodium-based desulfurized ash, which adopts a technical route that after desulfurized ash is completely dissolved, impurities such as suspended matters and the like are precipitated and filtered by using a flocculant, sulfuric acid is added to adjust the pH value, sodium sulfate in the desulfurized ash is recovered through steps of evaporation crystallization, centrifugation and the like, and the centrifuged liquid is recovered for dissolving desulfurized ash, however, the scheme is hardly suitable for sodium bicarbonate desulfurized ash generated by a gas boiler in a metallurgical process. Furthermore, the technical solutions do not disclose the specific components of the treated sodium-based desulfurized fly ash, which are usedThe mechanical stirring or the stirring by blowing air cannot ensure the complete oxidation of the sodium sulfite in the desulfurized fly ash to sodium sulfate. More importantly, in the technical schemes, no clear control means is provided for the water quantity and the purification process, and the purity and the recovery rate of the sodium sulfate product are not effectively controlled. Generally, these methods are only suitable for the occasions (such as washing, glass, etc.) with high impurity content of the raw material desulfurized fly ash and low requirement on the purity of sodium sulfate, but are not suitable for the occasions (such as food, medicine, etc.) with low content of insoluble impurities of the raw material desulfurized fly ash and high requirement on the purity of sodium sulfate.
Chinese patent CN 109881019A reports a method for recycling vanadium-containing desulfurized slag, and the method mixes the vanadium-containing desulfurized slag with water, adds a precipitator and heats the mixture, then carries out solid-liquid separation on the material to ensure that vanadium enters solid-phase slag, and crystallizes a liquid phase to obtain sodium sulfate. The method is only suitable for the desulfurized slag generated in the pretreatment process of molten iron for smelting specific steel grades, and the used raw materials of the method are completely different from the desulfurized ash.
Chinese patent CN 102530997A reports a desulfurization product recovery process, and the collected waste residue is subjected to processes of dissolution oxidation, flocculation clarification, evaporation crystallization, thickening, centrifugation, drying and the like to obtain an anhydrous mirabilite product. The method is only suitable for recycling by-products obtained by flue gas desulfurization of the sodium-alkali glass furnace. Because the glass furnace kiln is suitable for solid raw materials, the dust content is high, the impurity content of the desulphurization by-product is high, the method lacks effective control on the product purity, and the high-purity sodium sulfate product is difficult to obtain. In addition, the blast oxidation adopted by the method is a typical gas-liquid two-phase reaction, the reaction efficiency is low, the oxidation rate of sodium sulfite is not guaranteed, and no corresponding measures are taken in the technical scheme, so that the purity of the product is influenced.
Aiming at the problem of resource utilization of the desulfurization ash of the baking soda of a metallurgical gas boiler, the invention provides a novel method for treating the desulfurization ash of the baking soda by using a chemical method, and the desulfurization ash of the baking soda is converted into a hydrated sodium sulfate product with high purity and higher economic value by solution reaction.
Disclosure of Invention
The invention aims at providingA method for preparing sodium sulfate by baking soda desulfurization ash through a wet process comprises the following steps: firstly mixing sodium bicarbonate desulfurized ash with water to obtain suspension, then adding an oxidant into the suspension for reaction, then adding an acid reagent for continuous reaction, and finally concentrating, crystallizing and separating to obtain a hydrated sodium sulfate product (Na)2SO4·10H2O)。
Further, before preparation, a sample of the desulphurised sodium bicarbonate ash was first analysed to ensure that its composition (in mass%) was: na (Na)2SO4 30％-60％、Na2SO3 10％-20％、NaHCO320-60 percent, and the balance of a small amount of crystal water and trace other impurities.
Furthermore, the grain size of the sodium bicarbonate desulfurization ash is not less than 200 meshes (75 mu m) and is not less than 90 percent.
Further, Na in the sodium bicarbonate desulfurized fly ash2SO4With Na2SO3The content ratio of (B) is more than 2.
Further, mixing sodium bicarbonate desulfurized ash with water according to a water-ash ratio of 1-1.5:1, heating the obtained mixture to 30-50 ℃, and stirring for 5-15min to obtain a suspension. The heating and stirring can promote the sodium bicarbonate desulfurization ash to be quickly and completely dissolved, so that more raw materials are provided for the subsequent chemical reaction.
Further, the oxidant is about 30 wt% hydrogen peroxide solution, and the amount of the oxidant added is slightly excessive.
Preferably, H is added to the aqueous hydrogen peroxide solution2O2The molar weight of the sodium bicarbonate is equivalent to that of Na in sodium bicarbonate desulfurization ash2SO31.1-1.5 times of the molar weight.
Further, the acid reagent is a 20 wt% -50 wt% dilute sulfuric acid solution, and the addition amount of the acid reagent is slightly excessive.
Preferably, H is added to the dilute sulfuric acid solution2SO4The molar quantity of the sodium bicarbonate is equivalent to NaHCO in sodium bicarbonate desulfurization ash30.5-0.75 times of the molar weight.
Further, adding an oxidant into the suspension, then keeping the temperature and stirring for 20-45min at 30-50 ℃, adding an acid reagent into the suspension, and then keeping the temperature and stirring for 5-15min at 30-50 ℃.
Further, the specific processes of concentration, crystallization and separation are as follows: firstly, heating the mixed solution obtained by the reaction to evaporate partial water, and ensuring that the total mass of the residual mixed solution is equivalent to Na contained in the mixed solution2SO42.5-3 times of the mass, cooling the mixed solution to 0-10 ℃, filtering, and collecting filter residue which is the target product Na2SO4·10H2O。
Aiming at the difficult problem of resource utilization of the sodium bicarbonate desulfurization ash, the invention combines the components or the composition characteristics of the sodium bicarbonate desulfurization ash, and converts and purifies the sodium bicarbonate desulfurization ash into a hydrated sodium sulfate product by an oxidant and an acid reagent in sequence, wherein the process involves the following chemical reactions:
Na2SO3+H2O2＝Na2SO4+H2O (1)
2NaHCO3+H2SO4＝Na2SO4+2H2O+2CO2↑ (2)
the detection result shows that the sodium bicarbonate desulfurized ash produced by me contains Na mainly2SO4、Na2SO3And NaHCO3And the like, and the collected desulfurized ash contains no crystal water or a small amount of crystal water in consideration of the fact that the desulfurization temperature of the flue gas is usually over 120 ℃. H selected by the invention2O2Is an excellent green oxidant, and can easily react with Na2SO3The sodium sulfate is oxidized into the sodium sulfate and is converted into water, so that impurities cannot be introduced into a mixture system, and the subsequent reaction and purification process cannot be influenced by excessive hydrogen peroxide. NaHCO 23And H2SO4Reaction to form Na2SO4、H2O and CO2The step can completely convert the bicarbonate in the desulfurized fly ash into sulfate, also does not introduce impurities into the mixture system, and the small excess of sulfuric acid does not influence the crystallization and purification of the sodium sulfate. Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects:
(1) the method not only recycles the solid waste resources of the baking soda ash desulfurization ash of the steel mill, but also thoroughly converts the solid waste resources into the hydrated sodium sulfate product with high purity and good quality, the product can be used in various industries such as chemical industry, food, pharmacy and the like, the value of each ton is thousands of yuan, and the economic benefit is obvious;
(2) the whole process flow is simple, the required raw materials and equipment are cheap and easy to obtain, no typical pollutant is generated except a small amount of dischargeable wastewater, and the requirement of environmental protection is met;
(3) compared with the existing method for treating wastewater by taking the desulfurized fly ash as a reducing agent or an alkaline substance, the invention provides a novel high-value-added utilization way of the desulfurized fly ash of sodium bicarbonate, and the treatment capacity is relatively larger and is not limited by other conditions;
(4) the invention thoroughly solves the problems of difficult solid waste treatment and difficult resource recycling of iron and steel enterprises, effectively reduces the solid waste discharge of the enterprises, and makes important contribution to promoting the construction of green steel mills and protecting the natural environment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the specific embodiments and the accompanying drawings.
The technological process of the invention is shown in figure 1, firstly sodium bicarbonate is desulfurized ash (Na)2SO4 30％～60％、Na2SO310％～20％、NaHCO320-60 percent of the rest of the crystal water and trace other impurities) is placed in a stirring tank, a proper amount of pure water is added into the tank according to the water-cement ratio of 1-1.5:1, then the mixture is heated to 30-50 ℃ and is stirred for 5-15min under heat preservation. Adding 30 wt% hydrogen peroxide solution into the stirring tank to ensure the added H2O2The molar weight of the sodium bicarbonate is Na in the sodium bicarbonate desulfurization ash2SO3The molar weight is 1.1-1.5 times, and the obtained mixture is subjected to heat preservation and stirring reaction at the temperature of 30-50 ℃ for 20-45 min. Adding 20-40 wt% dilute sulfuric acid solution into the stirring tank to ensure the added H2SO4The molar weight is smallNaHCO in soda ash3The molar weight is 0.5-0.75 time, and the obtained mixture is subjected to heat preservation and stirring reaction at the temperature of 30-50 ℃ for 5-15 min. After the reaction, the mixture was transferred to a crystallizer, and Na in the reaction mixture was calculated from the initial composition2SO4Heating the mixture to evaporate a part of the water content, thereby ensuring that the remaining mixture contains Na contained in the reaction solution2SO42.5-3 times of the mass. Cooling the concentrated mixture to 0-10 deg.C, and filtering while it is cold, wherein the residue is Na2SO4·10H2And O, and discarding the rest small amount of filtrate.
TABLE 1 Standard solubility Table for each of the principal substances in sodium bicarbonate desulfurized Ash
Table 1 lists the solubilities of the main species in the baking soda ash. As can be seen from Table 1, sodium sulfate, sodium sulfite and sodium bicarbonate have good solubility at about 40 deg.C, so that maintaining the reaction temperature of the mixture at about 40 deg.C is not only favorable for dissolving sodium salt in water, but also can promote the reaction to proceed smoothly and thoroughly.
In order to ensure the purity and yield of the target product, the sodium sulfate obtained by the purification reaction is recovered by adopting an evaporative cooling crystallization method. Since the hydrogen peroxide and the dilute sulfuric acid contain certain moisture, corresponding measures are taken to control the total water content in the mixture obtained by the reaction. Proper water amount is kept in the oxidation and acidification processes, so that the oxidation and acidification reactions are promoted to be smoothly carried out; sufficient water is kept before evaporation and crystallization to promote the sodium salt to be fully dissolved, and meanwhile, the water amount is not increased due to excessive water amount, and energy waste is caused. Further, when sodium sulfate is precipitated from water, hydrated sodium sulfate containing 10 crystal waters is formed, and a large amount of water in the system needs to be consumed. The sodium bicarbonate desulfurization ash may also contain trace amount of halogen or other water-soluble ions such as potassium and calcium, and a small amount of mother liquor is required to be left after cooling and crystallization to remove the impurities, so as to ensure the purity of the hydrated sodium sulfate. Therefore, in the whole process of chemical reaction and crystallization separation and purification, the reaction solution system needs to be effectively controlled, and the technical goals of fast and efficient reaction, ensuring the purity and recovery rate of target products, reducing energy consumption and the like are realized.
Example 1
1) The analysis of the sample of sodium bicarbonate desulfurization ash to be disposed shows that the composition is as follows: na (Na)2SO4 32％，Na2SO3 11％，NaHCO354% and the other components are small amount of crystal water and/or inevitable impurities.
2) 200g of sodium bicarbonate desulfurized ash is taken and placed in a stirring tank, 200g of pure water is added, the mixture is heated to 34 ℃ to prepare suspension, and the suspension is stirred for 12 min.
3) 24g (in terms of H) of 30 wt% hydrogen peroxide solution was added to the stirred tank2O2About 0.21mol) and stirring at 34 ℃ for 20 min.
4) To the stirring tank was added 25 wt% of a dilute sulfuric acid solution 327g (in terms of H)2SO4About 0.83mol), stirring at 34 ℃ for 7 min.
5) Transferring the mixture to a crystallizer, and calculating Na in the mixture after reaction2SO4Has a mass of about 180 g. To ensure product purity and yield, the mixture was heated to evaporate some of the water until about 470g of the mixture remained.
6) Cooling the concentrated mixture to 3 deg.C, filtering while it is cold, and collecting the residue as hydrated sodium sulfate product (Na)2SO4·10H2O), the filtrate was discarded. Final co-collection of Na2SO4·10H2And about 385g of O, the detection shows that the purity is about 99.3 percent, and the calculated yield is about 94.3 percent.
Example 2
1) The analysis of the sample of sodium bicarbonate desulfurization ash to be disposed shows that the composition is as follows: na (Na)2SO4 58％，Na2SO3 18％，NaHCO322% and the other components are small amounts of crystalline water and/or unavoidable impurities.
2) 250g of sodium bicarbonate desulfurized ash is taken and placed in a stirring tank, 300g of pure water is added, the mixture is heated to 46 ℃ to prepare suspension, and the suspension is stirred for 12 min.
3) 58g (in terms of H) of 30 wt% hydrogen peroxide solution was added to the stirring tank2O2About 0.51mol) and stirring at 46 ℃ for 40 min.
4) 83g (in terms of H) of a 50 wt% dilute sulfuric acid solution was added to the stirring tank2SO4About 0.42mol) and stirring at 46 ℃ for 12 min.
5) Transferring the mixture to a crystallizer, and calculating Na in the mixture after reaction2SO4Has a mass of about 242 g. To ensure product purity and yield, the mixture was heated to evaporate some of the water until about 630g of the mixture remained.
6) Cooling the concentrated mixture to 7 deg.C, filtering while it is cold, and collecting the residue as hydrated sodium sulfate product (Na)2SO4·10H2O), the filtrate was discarded. Final co-collection of Na2SO4·10H2About 523g of O, the purity of the product is 99.5 percent according to detection, and the calculated yield is 95.3 percent.
Example 3
1) The analysis of the sample of sodium bicarbonate desulfurization ash to be disposed shows that the composition is as follows: na (Na)2SO4 45％，Na2SO3 14％，NaHCO338% and the other components are small amounts of crystallized water and/or inevitable impurities.
2) 300g of sodium bicarbonate desulfurized fly ash is taken and placed in a stirring tank, 370g of pure water is added, the mixture is heated to 40 ℃ to prepare a suspension, and the stirring is carried out for 12 min.
3) 49g (in terms of H) of 30 wt% hydrogen peroxide solution is added into the stirring tank2O2About 0.43mol) was added, and stirred at 40 ℃ for 32 min.
4) 198g (in terms of H) of a 40 wt% dilute sulfuric acid solution was added to the stirring tank2SO4About 0.81mol) was added, and the mixture was stirred at 40 ℃ for 10 min.
5) Transferring the mixture to a crystallizer, and calculating Na in the mixture after reaction2SO4Has a mass of about 279 g. Heating the mixture to evaporate part of water until the product purity and yield are guaranteedThe remaining mixture was about 750 g.
6) Cooling the concentrated mixture to 5 deg.C, filtering while it is cold, and collecting the residue as hydrated sodium sulfate product (Na)2SO4·10H2O), the filtrate was discarded. Final co-collection of Na2SO4·10H2About 593g of O, the detection shows that the purity is 99.4 percent, and the calculated yield is 93.7 percent.
Claims (9)
1. A method for preparing sodium sulfate by baking soda desulfurization ash through a wet method is characterized by comprising the following steps: firstly mixing sodium bicarbonate desulfurized ash with water to obtain suspension, then adding an oxidant into the suspension for reaction, adding an acid reagent for continuous reaction, and finally concentrating, crystallizing and separating to obtain Na2SO4·10H2And (4) O products.
2. The method of claim 1, wherein: before preparation, sodium bicarbonate desulfurized ash is firstly sampled and analyzed to ensure that the sodium bicarbonate desulfurized ash comprises the following components in percentage by mass: na (Na)2SO4 30％-60％、Na2SO310％-20％、NaHCO320-60 percent, and the balance of a small amount of crystal water and trace impurities.
3. The method of claim 2, wherein: na in the sodium bicarbonate desulfurized fly ash2SO4With Na2SO3The content ratio of (B) is more than 2.
4. The method of claim 1 or 2, wherein: the particle size of the sodium bicarbonate desulfurization ash is less than 200 meshes and is not less than 90%.
5. The method of claim 1, wherein: mixing sodium bicarbonate desulfurized ash with water according to a water-to-ash ratio of 1-1.5:1, heating the obtained mixture to 30-50 ℃, and stirring for 5-15min to obtain a suspension.
6. The method of claim 1, wherein: the oxidant is specifically hydrogen peroxide solution, the acid reagent is specifically dilute sulfuric acid solution, and the adding amount of the acid reagent and the oxidant is slightly excessive.
7. The method of claim 6, wherein: addition of H2O2The molar weight of the sodium bicarbonate is equivalent to that of Na in sodium bicarbonate desulfurization ash2SO31.1-1.5 times of molar weight of H2SO4The molar quantity of the sodium bicarbonate is equivalent to NaHCO in sodium bicarbonate desulfurization ash30.5-0.75 times of the molar weight.
8. The method of claim 1, wherein: adding oxidant into the suspension, stirring at 30-50 deg.C for 20-45min, adding acid reagent into the suspension, stirring at 30-50 deg.C for 5-15 min.
9. The method of claim 1, wherein: the specific processes of concentration, crystallization and separation are as follows: heating the mixed solution obtained by the reaction to evaporate part of water, and ensuring that the total mass of the residual mixed solution is equivalent to Na contained in the mixed solution2SO42.5-3 times of the mass, then cooling to 0-10 ℃, filtering, and collecting filter residues.
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