CN116081646A - Method for efficiently treating ammonia desulfurization mother liquor through multistage oxidation - Google Patents
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- 230000003647 oxidation Effects 0.000 title claims abstract description 100
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 100
- 239000012452 mother liquor Substances 0.000 title claims abstract description 89
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 56
- 230000023556 desulfurization Effects 0.000 title claims abstract description 56
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 46
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 38
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000010413 mother solution Substances 0.000 claims description 7
- -1 sulfur ions Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 21
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 abstract description 13
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 238000003723 Smelting Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 23
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Abstract
The invention relates to a method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation, belonging to the technical field of ammonium sulfate production. Adding a manganese dioxide catalyst into ammonia desulfurization mother liquor, then introducing oxygen, performing primary oxidation, oxidizing most of ammonium sulfite in the ammonia desulfurization mother liquor, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain absorption mother liquor after the oxygen oxidation; adding ammonium persulfate into the absorption mother liquor subjected to oxygen oxidation for secondary oxidation, and oxidizing ammonium thiosulfate to obtain qualified mother liquor; and sending the qualified mother liquor to a subsequent step to produce ammonium sulfate solid. The invention utilizes oxygen to oxidize most of ammonium sulfite in the desulfurization mother liquor into ammonium sulfate, then oxidizes ammonium thiosulfate into ammonium sulfate through ammonium persulfate, and realizes S in the ammonia desulfurization mother liquor through multistage oxidation 2 O 3 2‑ 、SO 3 2‑ The high-efficiency purification of the catalyst can greatly reduce the treatment cost, and provides a foundation for the industrial application of improving the quality and enhancing the efficiency of the ammonium sulfate which is a smelting flue gas desulfurization product.
Description
Technical Field
The invention discloses a method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation, belonging to the technical field of ammonium sulfate production.
Background
The nonferrous metal is produced by taking sulphide ore as a main raw material, and the produced smelting flue gas contains a large amount of SO 2 . The industrial byproducts produced by utilizing the smelting flue gas desulfurization have the significance of irreplaceable environmental protection and sulfur recycling. The ammonia desulfurization process for producing ammonium sulfate is widely used because of the advantages of high desulfurization efficiency, wide byproduct ammonium sulfate sales channel, etc. The process flow is generally as follows: the low-concentration sulfur dioxide flue gas is cooled and washed and then enters a desulfurization absorption tower to generate desulfurization reaction to generate the sulfur-containing salt ((NH) 4 ) 2 SO 3 And NH 4 HSO 3 ) Is used for absorbing mother liquor. When the absorption mother liquor reaches a certain density, the absorption mother liquor is sent to a mixing tank, and then an oxidant is added to oxidize the sub-salt into ammonium sulfate and release high-concentration sulfur dioxide gas (the gas can be sent to an acid making system to produce concentrated sulfuric acid). And neutralizing, evaporating and crystallizing the solution to obtain qualified white fertilizer ammonium sulfate. The common oxidants in industry are air, oxygen, concentrated sulfuric acid, etc., wherein concentrated sulfuric acid is often used for treating mother liquor with high concentration of salt because of high oxidation speed and high efficiency.
However, the ammonium thiosulfate impurity content in the desulfurization mother liquor can gradually rise after long-time production of ammonium sulfate by smelting flue gas desulfurization, and at this time, the mother liquor becomes very turbid. When the concentrated sulfuric acid oxidant is added, a large amount of yellow sulfur foam is generated in the mixing tank, the liquid level exceeds the standard, acid addition cannot be performed, and a large amount of suspended sulfur can appear in the crystallizer, as shown in reaction formulas (1-3). The finally obtained ammonium sulfate product is abnormal in chromaticity and is generally yellow.
| 3S 2 O 3 2- + 2H + → 4S + 2SO 4 2- + H 2 O （1） |
| 2S 2 O 3 2- + H + → 2S + SO 3 2- + HSO 3 - （2） |
| S 2 O 3 2- + 2H + → S + SO 2 + H 2 O （3） |
Thiosulfate and sulfite coexist in the absorption mother liquor. Thiosulfate is the root cause of yellowing of ammonium sulfate products, while sulfite affects the crystallization effect of the product. Therefore, thiosulfate and sulfite in the mother liquor need to be purified efficiently, so that the quality problem of the ammonium sulfate product can be fundamentally solved. Patent CN114410552A adopts Pseudomonas stutzeriPseudomonas gessardiiP4) sodium thiosulfate with the oxidation concentration of 50mmol/L can reach more than 95% in 16h, and the process can avoid adding acid, but the oxidation is completed for a long time. The patent CN111017884A selects to separate and burn the sulfur generated by the desulfurization mother liquor, so that the sulfur is reconverted into sulfur dioxide and returned to the desulfurization step. The patent CN114655933a reduces the incineration cost by separating and directly drying the generated sulfur into sulfur, but the purity of the generated sulfur is only 85%, and pure sulfur can be obtained through subsequent treatment. Patent CN114907149A discloses a method for directly oxidizing desulfurization mother liquor by using ammonium persulfate instead of concentrated sulfuric acid, wherein the removal rates of thiosulfate and sulfite after treatment are respectively up to 94% to 96%, ammonium sulfate products with normal chromaticity can be obtained, but the addition amount of ammonium persulfate is large (80-280 g of ammonium persulfate per liter of mother liquor), and the treatment cost is high.
Disclosure of Invention
Against the prior artThe invention provides a method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation. The invention utilizes oxygen to oxidize most of ammonium sulfite in the desulfurization mother liquor into ammonium sulfate, then oxidizes ammonium thiosulfate into ammonium sulfate through ammonium persulfate, and realizes S in the ammonia desulfurization mother liquor through multistage oxidation 2 O 3 2- 、SO 3 2- The high-efficiency purification of the catalyst can greatly reduce the treatment cost, and provides a foundation for the industrial application of improving the quality and enhancing the efficiency of the ammonium sulfate which is a smelting flue gas desulfurization product.
The invention is realized by the following technical scheme:
a method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation comprises the following specific steps:
1) Primary oxidation: adding a manganese dioxide catalyst into ammonia desulfurization mother liquor, then introducing oxygen, performing primary oxidation, oxidizing most of ammonium sulfite in the ammonia desulfurization mother liquor, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain absorption mother liquor after the oxygen oxidation;
2) Secondary oxidation: adding ammonium persulfate into the absorption mother liquor obtained in the step 1) after oxygen oxidation for secondary oxidation, and oxidizing ammonium thiosulfate to obtain qualified mother liquor;
3) And 2) sending the qualified mother liquor obtained in the step 2) to a subsequent step to produce ammonium sulfate solid.
The content of relevant sulfur ions in the ammonia desulfurization mother liquor in the step 1) is as follows: s is S 2 O 3 2- The content is 8-40 g/L; HSO (high speed oxygen) 3 2- +SO 3 2- The content of the salt is 20-80 g/L, S 2- The content is 0.004-1.2 g/L, SO 4 2- The content is 260-400 g/L.
The manganese dioxide content in the manganese dioxide catalyst in the step 1) is more than 98wt%, and the addition amount of the manganese dioxide catalyst is 0.1-0.5 g/L ammonia desulfurization mother liquor.
The oxygen content of the gas introduced in the step 1) is more than 99%, the introduced amount is 0.1-2L/min, the reaction time is 0.5-6h, the reaction temperature is room temperature-60 ℃, the gas needs to be uniformly distributed in the mother liquor through an aeration device, and the reaction process needs to be mechanically stirred to promote the dispersion of oxygen bubbles.
The ammonium persulfate purity in the step 2) is more than 98%, the adding amount is 10-70 g of ammonium sulfate added into each 1L of mother solution, the reaction time is from the adding of the ammonium sulfate to the complete dissolution, and mechanical stirring can be added in the reaction process to promote the dissolution of the ammonium sulfate.
The working principle of the invention is as follows: through thermodynamic calculation and experimental research, when oxygen or ammonium persulfate is used as an oxidant, SO is obtained when the addition amount of the oxidant is insufficient 3 2- Ratio S 2 O 3 2- More readily oxidized to SO 4 2- And S in the case of complete sufficiency of oxidizing agent 2 O 3 2-- Specific SO 3 2 More readily oxidized to SO 4 2- . Therefore, the absorption mother liquor is purified by using an oxygen-ammonium persulfate multistage oxidation method, and the principle is that most of ammonium sulfite in the desulfurization mother liquor is oxidized into ammonium sulfate by using oxygen, then ammonium thiosulfate is oxidized into ammonium sulfate by using ammonium persulfate, and the treated mother liquor is sent to a subsequent step to continuously produce an ammonium sulfate product. The oxygen is a high-quality ammonium sulfite oxidant because of low price, but the oxidizing property of the oxygen to the ammonium thiosulfate is poor and the time is long; ammonium persulfate has stronger oxidizing property than concentrated sulfuric acid and stronger oxidizing property to ammonium thiosulfate. The stepwise oxidation method combining oxygen and ammonium persulfate not only solves the problem of poor oxidation effect of single oxygen on thiosulfate, but also can effectively reduce the dosage of ammonium persulfate during the oxidation of single ammonium persulfate, thereby greatly reducing the treatment cost. The oxidation rate of thiosulfate in the mother liquor treated by the method reaches more than 80%, and the oxidation rate of sulfite reaches more than 90%, so that the production requirement is completely met.
The beneficial effects of the invention are as follows:
(1) The invention discloses a method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation, which adopts oxygen to oxidize most of ammonium sulfite in the desulfurization mother liquor into ammonium sulfate first, and then oxidizes ammonium thiosulfate into ammonium sulfate by ammonium persulfate, so that the problems of poor oxidation effect and long time of independent oxygen on thiosulfate can be solved, and the consumption of ammonium persulfate during independent ammonium persulfate oxidation can be effectively reduced, thereby greatly reducing the treatment cost.
(2) The oxidation rate of thiosulfate in the mother liquor after treatment reaches more than 80%, and the oxidation rate of sulfite reaches more than 90%, so that the production requirement is completely met.
(3) The method can efficiently remove the thiosulfate and sulfite impurities in the desulfurization mother liquor, solves the problems that the ammonium sulfate product turns yellow due to the thiosulfate, the crystallization effect of the product is affected by the sulfite, and the like, and breaks through the bottleneck of improving quality and enhancing efficiency of the ammonium sulfate produced by smelting flue gas.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a comparative graph of the white ammonium sulfate product obtained in example 1 of the present invention and the ammonium sulfate product obtained in comparative example 1', comparative example 1", wherein FIG. (a) is the white ammonium sulfate product obtained in example 1 of the present invention, FIG. (b) is the yellow ammonium sulfate solid product obtained by oxidizing comparative example 1' with concentrated sulfuric acid, and FIG. (c) is the white ammonium sulfate product obtained in comparative example 1" by the ammonium persulfate oxidation alone.
Detailed Description
The invention will be further described with reference to the drawings and detailed description.
Example 1
As shown in FIG. 1, the method for efficiently treating the ammonia desulfurization mother liquor by multistage oxidation comprises the following specific steps:
1) Primary oxidation: 500mL of ammonia desulfurization mother liquor (the content of related sulfur ions is S) 2 O 3 2- 32.51g/L、SO 3 2- 53.25g/L, pH=7) adding 0.25g of manganese dioxide catalyst at room temperature, then introducing oxygen (with purity of 99%) with flow of 0.8L/min, uniformly distributing the oxygen in the solution through stirring of aerated stone and 400r/min, performing primary oxidation for 5h, oxidizing most of ammonium sulfite in the ammonia desulfurization mother liquor, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain an absorption mother liquor after the oxygen oxidation;
2) Secondary oxidation: adding 7g of ammonium persulfate (AR) into 100mL of the absorption mother solution obtained in the step 1) after oxygen oxidation for secondary oxidation, oxidizing ammonium thiosulfate, stirring uniformly, and then using ammonia water (NH) 3 The concentration is 25 percent) and the pH value of the solution is adjusted to 8, so that qualified mother liquor is obtained;
3) And 2) sending the qualified mother liquor obtained in the step 2) to a subsequent step to produce ammonium sulfate solid.
The thiosulfate and sulfite content in steps 1) and 2) was determined by iodometry. The oxidation rate of thiosulfate after the first stage of oxygen oxidation by step oxidation is 45.73%, the oxidation rate of sulfite is 96.99%, the oxidation rate of thiosulfate after the second stage of ammonium persulfate oxidation is 85.32%, and the oxidation rate of sulfite is 98.12%. The color of the ammonium sulfate produced by the novel method through the steps is white solid as shown in the figure 2 (a), and accords with the color index specified for fertilizer grade ammonium sulfate in GB/T535-2020 fertilizer grade ammonium sulfate.
Comparative example 1'
100mL ammonia process is used for simulating and absorbing mother liquor (the content of related sulfur ions is S) 2 O 3 2- 32.51g/L、SO 3 2- 53.25g/L, ph=7) into a 300mL beaker, adding 98% concentrated sulfuric acid quickly into the mother liquor to adjust the pH of the mother liquor to 2; then adding ammonia water into the mother solution to adjust the pH value to 8, and measuring the content of thiosulfate and sulfite in the mother solution by using an iodometry.
The oxidation rate of thiosulfate after the steps are oxidized by adopting concentrated sulfuric acid is 67.74%, the oxidation rate of sulfite is 82.70%, and the yellow solid obtained after evaporation and crystallization is shown in the figure 2 (b) and does not accord with the color index specified for fertilizer grade ammonium sulfate in GB/T535-2020 fertilizer grade ammonium sulfate.
Comparative example 1'
100mL of ammonia absorption simulation mother liquor (the content of related sulfur ions is S) 2 O 3 2- 32.51g/L、SO 3 2- 53.25g/L, pH=7) was added to a 300mL beaker, 16g ammonium persulfate (AR) was added to the mother liquor, the pH of the solution was adjusted to 8 with ammonia after stirring uniformly, and the content was measured by iodometryThiosulfate and sulfite content.
The mother liquor oxidized by the ammonium persulfate method is colorless liquid. Through tests, the oxidation rate of thiosulfate in the mother liquor oxidized by the ammonium persulfate method reaches 84.30%, and the oxidation rate of sulfite reaches 96.22%. Therefore, under the condition of obtaining the same oxidation effect of thiosulfate and sulfite, the multistage oxidation can save 56.25% of the use amount of the ammonium persulfate oxidant compared with the single ammonium persulfate oxidation method, and the cost is greatly reduced.
The above examples illustrate that the process of multistage oxidation of peroxo-ammonium persulfate can avoid the production of sulfur from ammonium thiosulfate under the condition of reducing the use amount of ammonium persulfate, thereby achieving the purpose of purifying the desulfurization mother liquor.
Example 2
As shown in FIG. 1, the method for efficiently treating the ammonia desulfurization mother liquor by multistage oxidation comprises the following specific steps:
1) Primary oxidation: 500mL of ammonia desulfurization mother liquor (the content of related sulfur ions is S) 2 O 3 2- 12.35g/L、SO 3 2- 40.86g/L, pH=7) adding 0.2g of manganese dioxide catalyst at room temperature, then introducing oxygen with the flow rate of 1.0L/min (the purity is 99%), uniformly distributing the oxygen in the solution through the stirring of aerated stone and 300r/min, performing primary oxidation for 4 hours, oxidizing most of ammonium sulfite in the ammonia desulfurization mother liquor, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain an absorption mother liquor after the oxygen oxidation;
2) Secondary oxidation: adding 4g of ammonium persulfate (AR) into 100mL of the absorption mother solution obtained in the step 1) after oxygen oxidation for secondary oxidation, oxidizing ammonium thiosulfate, stirring uniformly, and then using ammonia water (NH) 3 The concentration is 25 percent) and the pH value of the solution is adjusted to 8, so that qualified mother liquor is obtained;
3) And 2) sending the qualified mother liquor obtained in the step 2) to a subsequent step to produce ammonium sulfate solid.
The thiosulfate and sulfite content in steps 1) and 2) was determined by iodometry. The oxidation rate of thiosulfate after the first stage of oxygen oxidation by step oxidation is 38.22%, the oxidation rate of sulfite is 90.56%, the oxidation rate of thiosulfate after the second stage of ammonium persulfate oxidation is 89.35%, and the oxidation rate of sulfite is 98.33% (the residual concentration of sulfite is 0.68 g/L).
Example 3
As shown in FIG. 1, the method for efficiently treating the ammonia desulfurization mother liquor by multistage oxidation comprises the following specific steps:
1) Primary oxidation: 500mL of ammonia desulfurization mother liquor (the content of related sulfur ions is S) 2 O 3 2- 32.51g/L、SO 3 2- 53.25g/L, pH=7) adding 0.4g of manganese dioxide catalyst at room temperature, then introducing oxygen (with purity of 99%) with flow of 0.7L/min, uniformly distributing the oxygen in the solution through the stirring of aerated stone and 300r/min, performing primary oxidation for 3h, oxidizing most of ammonium sulfite in the ammonia desulfurization mother liquor, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain an absorption mother liquor after the oxygen oxidation;
2) Secondary oxidation: adding 5g of ammonium persulfate (AR) into 100mL of the absorption mother solution obtained in the step 1) after oxygen oxidation for secondary oxidation, oxidizing ammonium thiosulfate, stirring uniformly, and then using ammonia water (NH) 3 The concentration is 25 percent) and the pH value of the solution is adjusted to 8, so that qualified mother liquor is obtained;
3) And 2) sending the qualified mother liquor obtained in the step 2) to a subsequent step to produce ammonium sulfate solid.
The thiosulfate and sulfite content in steps 1) and 2) was determined by iodometry. The oxidation rate of thiosulfate after the first-stage oxygen oxidation by step oxidation is 29.82%, the oxidation rate of sulfite is 99.8%, the oxidation rate of thiosulfate after the second-stage ammonium persulfate oxidation is 83.31%, and the oxidation rate of sulfite is 100%.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation is characterized by comprising the following specific steps:
1) Primary oxidation: adding a manganese dioxide catalyst into ammonia desulfurization mother liquor, then introducing oxygen, performing primary oxidation, and filtering and separating the manganese dioxide catalyst and the ammonia desulfurization mother liquor after the oxidation is completed to obtain absorption mother liquor after the oxygen oxidation;
2) Secondary oxidation: adding ammonium persulfate into the absorption mother liquor obtained in the step 1) after oxygen oxidation for secondary oxidation to obtain qualified mother liquor;
3) And 2) sending the qualified mother liquor obtained in the step 2) to a subsequent step to produce ammonium sulfate solid.
2. The method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation according to claim 1, which is characterized in that: the content of relevant sulfur ions in the ammonia desulfurization mother liquor in the step 1) is as follows: s is S 2 O 3 2- The content is 8-40 g/L; HSO (high speed oxygen) 3 2- +SO 3 2- The content of the salt is 20-80 g/L, S 2- The content is 0.004-1.2 g/L, SO 4 2- The content is 260-400 g/L.
3. The method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation according to claim 1, which is characterized in that: the manganese dioxide content in the manganese dioxide catalyst in the step 1) is more than 98wt%, and the addition amount of the manganese dioxide catalyst is 0.1-0.5 g/L ammonia desulfurization mother liquor.
4. The method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation according to claim 1, which is characterized in that: the oxygen content of the gas introduced in the step 1) is more than 99%, the introduced amount is 0.1-2L/min, the reaction time is 0.5-6h, the reaction temperature is room temperature-60 ℃, the gas needs to be uniformly distributed in the mother liquor through an aeration device, and the reaction process needs to be mechanically stirred to promote the dispersion of oxygen bubbles.
5. The method for efficiently treating ammonia desulfurization mother liquor by multistage oxidation according to claim 1, which is characterized in that: the ammonium persulfate purity in the step 2) is more than 98%, the adding amount is 10-70 g of ammonium sulfate added into each 1L of mother solution, the reaction time is from the adding of the ammonium sulfate to the complete dissolution, and mechanical stirring can be added in the reaction process to promote the dissolution of the ammonium sulfate.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1309142A (en) * | 1969-08-22 | 1973-03-07 | Ambrossi C M | Process for obtaining ammonium sulphate |
| JPH0691132A (en) * | 1992-09-17 | 1994-04-05 | Chiyoda Corp | Exhaust gas treatment |
| CN1377721A (en) * | 2002-01-25 | 2002-11-06 | 华东理工大学 | Method for removing SO2 in flue gas with ammonia |
| CN203123776U (en) * | 2012-12-28 | 2013-08-14 | 云南亚太环境工程设计研究有限公司 | Novel cascade type ammonia process desulfurization and denitrification tower |
| CN103288286A (en) * | 2013-06-28 | 2013-09-11 | 陕西煤业化工技术研究院有限责任公司 | Catalytic oxidation treatment method for desulfurized waste liquid |
| CN105233647A (en) * | 2015-09-17 | 2016-01-13 | 昆明理工大学 | Desulphurization denitration method for ammonium sulfide solution |
| CN106422693A (en) * | 2016-11-10 | 2017-02-22 | 昆明新光能源环保科技有限公司 | Method and device of removing SO2 in flue gas by acid-ammonia method |
| US20170173557A1 (en) * | 2013-03-06 | 2017-06-22 | Energy & Environmental Research Foundation | Sorbent comprising carbon and nitrogen and methods of using the same |
| CN112320818A (en) * | 2020-10-20 | 2021-02-05 | 昆明理工大学 | Method for oxidizing sulfite in flue gas desulfurization slurry |
| CN114907149A (en) * | 2022-04-18 | 2022-08-16 | 昆明理工大学 | Method for improving quality of ammonium sulfate fertilizer by using ammonium persulfate |
| CN217247939U (en) * | 2022-05-12 | 2022-08-23 | 河南心连心化学工业集团股份有限公司 | Production device of flue gas desulfurization coupling ammonium persulfate product |
-
2022
- 2022-11-21 CN CN202211456836.3A patent/CN116081646B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1309142A (en) * | 1969-08-22 | 1973-03-07 | Ambrossi C M | Process for obtaining ammonium sulphate |
| JPH0691132A (en) * | 1992-09-17 | 1994-04-05 | Chiyoda Corp | Exhaust gas treatment |
| CN1377721A (en) * | 2002-01-25 | 2002-11-06 | 华东理工大学 | Method for removing SO2 in flue gas with ammonia |
| CN203123776U (en) * | 2012-12-28 | 2013-08-14 | 云南亚太环境工程设计研究有限公司 | Novel cascade type ammonia process desulfurization and denitrification tower |
| US20170173557A1 (en) * | 2013-03-06 | 2017-06-22 | Energy & Environmental Research Foundation | Sorbent comprising carbon and nitrogen and methods of using the same |
| CN103288286A (en) * | 2013-06-28 | 2013-09-11 | 陕西煤业化工技术研究院有限责任公司 | Catalytic oxidation treatment method for desulfurized waste liquid |
| CN105233647A (en) * | 2015-09-17 | 2016-01-13 | 昆明理工大学 | Desulphurization denitration method for ammonium sulfide solution |
| CN106422693A (en) * | 2016-11-10 | 2017-02-22 | 昆明新光能源环保科技有限公司 | Method and device of removing SO2 in flue gas by acid-ammonia method |
| CN112320818A (en) * | 2020-10-20 | 2021-02-05 | 昆明理工大学 | Method for oxidizing sulfite in flue gas desulfurization slurry |
| CN114907149A (en) * | 2022-04-18 | 2022-08-16 | 昆明理工大学 | Method for improving quality of ammonium sulfate fertilizer by using ammonium persulfate |
| CN217247939U (en) * | 2022-05-12 | 2022-08-23 | 河南心连心化学工业集团股份有限公司 | Production device of flue gas desulfurization coupling ammonium persulfate product |
Non-Patent Citations (3)
| Title |
|---|
| YANG, YB ET AL.: "Study on oxygen pressure thiosulfate leaching of gold without the catalysis of copper and ammonia", 《HYDROMETALLURGY》, 31 August 2019 (2019-08-31) * |
| 朱洪法: "《催化剂手册》", 31 August 2008, pages: 332 - 333 * |
| 王颖: "湿法同时脱硫脱硝特性及吸收液制过硫酸铵的实验研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 February 2017 (2017-02-15) * |
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