CN111170284A - Renewable method for dechlorinating chlorine-containing waste sulfuric acid - Google Patents
Renewable method for dechlorinating chlorine-containing waste sulfuric acid Download PDFInfo
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- CN111170284A CN111170284A CN201911286097.6A CN201911286097A CN111170284A CN 111170284 A CN111170284 A CN 111170284A CN 201911286097 A CN201911286097 A CN 201911286097A CN 111170284 A CN111170284 A CN 111170284A
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- silver
- sulfuric acid
- chlorine
- waste sulfuric
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 239000000460 chlorine Substances 0.000 title claims abstract description 34
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 48
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000012071 phase Substances 0.000 claims abstract description 36
- 229910000367 silver sulfate Inorganic materials 0.000 claims abstract description 36
- 239000002244 precipitate Substances 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims abstract description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/04—Halides
Abstract
The invention relates to the technical field of dechlorination of chlorine-containing waste sulfuric acid, in particular to a renewable method for dechlorinating the chlorine-containing waste sulfuric acid, which is carried out according to the following steps: adding silver sulfate and an oil phase solvent into the chlorine-containing waste sulfuric acid to obtain a mixed solution; adding a phase transfer agent into the mixed solution, performing reflux reaction, and performing liquid separation to obtain an organic phase and a waste sulfuric acid water phase; filtering, washing and drying the organic phase, firstly burying excessive iron sheets in the silver chloride precipitate, then adding concentrated hydrochloric acid solution, and carrying out reduction reaction to obtain silver powder; adding a nitric acid solution into the silver powder, and stirring to react to obtain a silver nitrate solution; and adding ammonium sulfate into the silver nitrate solution to obtain silver sulfate. The method utilizes the reaction of silver sulfate and trace chloride ions in the solution to dechlorinate the chlorine-containing waste sulfuric acid, and utilizes the phase transfer method to recover silver chloride, thereby realizing the maximum resource utilization.
Description
Technical Field
The invention relates to the technical field of dechlorination of chlorine-containing waste sulfuric acid, and discloses a renewable method for dechlorinating the chlorine-containing waste sulfuric acid.
Background
In the chlor-alkali industry, large amounts of spent sulfuric acid containing chlorine at a concentration of about 70% are generated during the drying of chlorine. In the traditional process for treating the waste sulfuric acid, the waste sulfuric acid with the concentration of 70 percent needs to be recycled and returned to a factory for reabsorption to improve the concentration of the waste sulfuric acid. It has certain drawbacks: (1) the sulfuric acid contains chloride ions, and can cause serious corrosion to equipment for absorbing the sulfuric acid in the sulfuric acid recovery process; (2) the treatment cost of the waste sulfuric acid after being returned to the factory is about 350 yuan/ton, the treatment cost of the factory is very expensive in one year, and the high recovery cost is a serious burden for enterprises. In addition, the method of vacuum dechlorination of the waste sulfuric acid can be used for evaporating the moisture and the hydrogen chloride in the waste sulfuric acid, but the large-scale application of the waste sulfuric acid in enterprises is limited based on the high equipment purchasing cost. As a method for purifying chlorine ions, there are a copper slag dechlorination method, an ion exchange method and the like. Some researches show that the dechlorination of the copper slag needs to add an oxidant additionally, and high cost is needed; the efficiency of the ion exchange method for removing chlorine is too low, and the subsequent treatment is very difficult.
Disclosure of Invention
The invention provides a renewable method for dechlorination of chlorine-containing waste sulfuric acid, overcomes the defects of the prior art, and can effectively solve the problems of poor dechlorination effect and high dechlorination cost of the chlorine-containing waste sulfuric acid dechlorination in the prior art.
The technical scheme of the invention is realized by the following measures: a renewable method for dechlorinating chlorine-containing waste sulfuric acid is carried out according to the following method: according to the content of chloride ions, adding silver sulfate with the mole ratio of the silver sulfate to the chloride ions being 1:1, and then adding silver sulfate and waste sulfuric acid containing chlorine with the volume ratio of 0.5-1: 1, fully mixing and stirring the oil phase solvent, the silver sulfate and the oil phase solvent to obtain a mixed solution; secondly, adding a required amount of phase transfer agent into the mixed solution, carrying out reflux reaction for 0.5 to 2 hours under a closed condition, and carrying out liquid separation after the reaction is finished to obtain an organic phase containing silver chloride precipitate and a dechlorinated waste sulfuric acid water phase; thirdly, filtering an organic phase containing the silver chloride precipitate to obtain a silver chloride precipitate, washing and drying the silver chloride precipitate, burying excessive iron sheets in the silver chloride precipitate, adding a concentrated hydrochloric acid solution to completely submerge the silver chloride precipitate and the iron sheets, heating to boil, stirring to perform a reduction reaction to obtain silver powder, and drying the silver powder, wherein the molar ratio of the iron sheets to the silver chloride in the silver chloride precipitate is 1: 1-2; fourthly, adding a nitric acid solution into the dried silver powder, and stirring and reacting for 10 to 20 minutes under a closed condition at room temperature to obtain a silver nitrate solution; and fifthly, adding ammonium sulfate into the silver nitrate solution and heating to 60-100 ℃ to obtain the silver sulfate, wherein the molar ratio of the ammonium sulfate to the silver nitrate solution is 1: 1.
The following is further optimization or/and improvement of the technical scheme of the invention:
the oil phase solvent is more than one of petroleum ether, n-hexane and cyclohexane.
The phase transfer agent is one or more of sodium oleate, oleylamine and oleic acid.
In the second step, the molar ratio of the phase transfer agent to the chloride ion is 1:1 to 2.
The reflux reaction temperature is 70 ℃ to 100 ℃.
In the third step, the volume percentage of the concentrated hydrochloric acid solution is 37.5%.
The volume percentage of the nitric acid solution is 10-65%.
The method utilizes the reaction of silver sulfate and trace chloride ions in the solution to dechlorinate the chlorine-containing waste sulfuric acid, and utilizes the phase transfer method to recover silver chloride, thereby realizing the maximum resource utilization.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the regeneration method of the chlorine-containing waste sulfuric acid dechlorination is carried out according to the following steps: according to the content of chloride ions, adding silver sulfate with the mole ratio of the silver sulfate to the chloride ions being 1:1, and then adding silver sulfate and waste sulfuric acid containing chlorine with the volume ratio of 0.5-1: 1, fully mixing and stirring the oil phase solvent, the silver sulfate and the oil phase solvent to obtain a mixed solution; secondly, adding a required amount of phase transfer agent into the mixed solution, carrying out reflux reaction for 0.5 to 2 hours under a closed condition, and carrying out liquid separation after the reaction is finished to obtain an organic phase containing silver chloride precipitate and a dechlorinated waste sulfuric acid water phase; thirdly, filtering an organic phase containing the silver chloride precipitate to obtain a silver chloride precipitate, washing and drying the silver chloride precipitate, burying excessive iron sheets in the silver chloride precipitate, adding a concentrated hydrochloric acid solution to completely submerge the silver chloride precipitate and the iron sheets, heating to boil, stirring to perform a reduction reaction to obtain silver powder, and drying the silver powder, wherein the molar ratio of the iron sheets to the silver chloride in the silver chloride precipitate is 1: 1-2; fourthly, adding a nitric acid solution into the dried silver powder, and stirring and reacting for 10 to 20 minutes under a closed condition at room temperature to obtain a silver nitrate solution; and fifthly, adding ammonium sulfate into the silver nitrate solution and heating to 60-100 ℃ to obtain the silver sulfate, wherein the molar ratio of the ammonium sulfate to the silver nitrate solution is 1: 1.
The invention relates to a renewable method for dechlorinating chlorine-containing waste sulfuric acid, which utilizes the reaction of silver sulfate and trace chloride ions in a solution and utilizes a phase transfer method to recover silver chloride, thereby realizing the maximum resource utilization and finally achieving the purposes of saving energy, reducing cost and realizing high-value utilization of resources. The dechlorination process is simple, expensive vacuum dechlorination equipment is not needed, the energy consumption of vacuum dechlorination is avoided, and the dechlorination cost of the waste sulfuric acid is effectively reduced; meanwhile, the silver chloride in the oil phase can be made into silver sulfate again for dechlorination, so that the cyclic utilization is realized.
In the invention, the content of chloride ions in the waste sulfuric acid containing chlorine can be determined by adopting an X fluorescence analysis method.
In the invention, the silver sulfate can be liquid silver sulfate or solid silver sulfate.
Example 2: the regeneration method of the chlorine-containing waste sulfuric acid dechlorination is carried out according to the following steps: according to the content of chloride ions, adding silver sulfate with the mole ratio of the silver sulfate to the chloride ions being 1:1, and then adding silver sulfate and waste sulfuric acid containing chlorine with the volume ratio of 0.5 or 1:1, fully mixing and stirring the oil phase solvent, the silver sulfate and the oil phase solvent to obtain a mixed solution; secondly, adding a required amount of phase transfer agent into the mixed solution, carrying out reflux reaction for 0.5h or 2h under a closed condition, and carrying out liquid separation after the reaction is finished to obtain an organic phase containing silver chloride precipitate and a dechlorinated waste sulfuric acid water phase; thirdly, filtering an organic phase containing the silver chloride precipitate to obtain a silver chloride precipitate, washing and drying the silver chloride precipitate, burying excessive iron sheets in the silver chloride precipitate, adding a concentrated hydrochloric acid solution to completely submerge the silver chloride precipitate and the iron sheets, heating to boil, stirring to perform a reduction reaction to obtain silver powder, and drying the silver powder, wherein the molar ratio of the iron sheets to the silver chloride in the silver chloride precipitate is 1: 1-2; fourthly, adding a nitric acid solution into the dried silver powder, and stirring and reacting for 10min or 20min under a closed condition at room temperature to obtain a silver nitrate solution; and fifthly, adding ammonium sulfate into the silver nitrate solution and heating to 60 ℃ or 100 ℃ to obtain the silver sulfate, wherein the molar ratio of the ammonium sulfate to the silver nitrate solution is 1: 1.
Example 3: in the optimization of the embodiment, the oil phase solvent is more than one of petroleum ether, normal hexane and cyclohexane.
Example 4: as an optimization of the above embodiment, the phase transfer agent is one or more of sodium oleate, oleylamine and oleic acid.
Example 5: as an optimization of the above example, in the second step, the molar ratio of the phase transfer agent to the chloride ion was 1:1 to 2.
Example 6: as an optimization of the above examples, the reflux reaction temperature was 70 ℃ to 100 ℃.
Example 7: as an optimization of the above example, the third step was carried out with a concentrated hydrochloric acid solution having a volume percentage of 37.5%.
Example 8: as an optimization of the above embodiment, the volume percentage of the nitric acid solution is 10% to 65%.
Example 9: firstly, 500ml of high-concentration industrial waste sulfuric acid is taken, wherein the industrial waste sulfuric acid contains 40g/L H2SO4(ii) a Adding 50ml of liquid silver sulfate into industrial waste sulfuric acid, adding 200ml of n-hexane and 20mmol of sodium oleate, stirring, transferring the generated silver chloride precipitate phase to an organic phase, separating the silver chloride of the organic phase, and filtering, washing and draining the silver chloride. Burying 2g of iron sheets in the silver chloride precipitate, adding 50ml of concentrated hydrochloric acid to submerge the iron sheets, heating the iron sheets to boil, stirring the mixture for 1 hour till the white silver chloride precipitate is completely changed into grey-white silver powder, drying the silver powder, adding a nitric acid solution to obtain a silver nitrate solution, adding ammonium sulfate under a heating condition to obtain silver sulfate, and recycling the silver sulfate for dechlorinating industrial waste sulfuric acid; the dechlorinated sulfuric acid can be directly used in various industrial applications.
Example 10: firstly, 500ml of high-concentration industrial waste sulfuric acid is taken, wherein the industrial waste sulfuric acid contains 50g/L H2SO4(ii) a Adding 80ml of liquid silver sulfate into industrial waste sulfuric acid, adding 250ml of n-hexane and 25mmol of sodium oleate, stirring, transferring the generated silver chloride precipitate phase to an organic phase, separating out the silver chloride of the organic phase, and filtering, washing and pumping to dry the silver chloride. Burying 4g iron pieces in silver chloride precipitate, adding 80ml concentrated hydrochloric acid to cover, heating to boil, stirring for 1 hr until white silver chloride precipitate is completely changed into grey white silver powder, oven drying the silver powder, adding nitric acid solution to obtain silver nitrate solution, adding ammonium sulfate under heating condition to obtain silver sulfate, and recycling silver sulfate for industrial useDechlorinating the waste sulfuric acid; the dechlorinated sulfuric acid can be directly used in various industrial applications.
In conclusion, the method utilizes the reaction of silver sulfate and trace chloride ions in the solution to dechlorinate the waste sulfuric acid containing chlorine, and utilizes the phase transfer method to recover silver chloride, thereby realizing the maximum resource utilization.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (10)
1. A renewable method for dechlorinating chlorine-containing waste sulfuric acid is characterized by comprising the following steps: according to the content of chloride ions, adding silver sulfate with the mole ratio of the silver sulfate to the chloride ions being 1:1, and then adding silver sulfate and waste sulfuric acid containing chlorine with the volume ratio of 0.5-1: 1, fully mixing and stirring the oil phase solvent, the silver sulfate and the oil phase solvent to obtain a mixed solution; secondly, adding a required amount of phase transfer agent into the mixed solution, carrying out reflux reaction for 0.5 to 2 hours under a closed condition, and carrying out liquid separation after the reaction is finished to obtain an organic phase containing silver chloride precipitate and a dechlorinated waste sulfuric acid water phase; thirdly, filtering an organic phase containing the silver chloride precipitate to obtain a silver chloride precipitate, washing and drying the silver chloride precipitate, burying excessive iron sheets in the silver chloride precipitate, adding a concentrated hydrochloric acid solution to completely submerge the silver chloride precipitate and the iron sheets, heating to boil, stirring to perform a reduction reaction to obtain silver powder, and drying the silver powder, wherein the molar ratio of the iron sheets to the silver chloride in the silver chloride precipitate is 1: 1-2; fourthly, adding a nitric acid solution into the dried silver powder, and stirring and reacting for 10 to 20 minutes under a closed condition at room temperature to obtain a silver nitrate solution; and fifthly, adding ammonium sulfate into the silver nitrate solution and heating to 60-100 ℃ to obtain the silver sulfate, wherein the molar ratio of the ammonium sulfate to the silver nitrate solution is 1: 1.
2. The method of claim 1, wherein the solvent in the oil phase is one or more of petroleum ether, n-hexane and cyclohexane.
3. The regenerable process for dechlorination of chlorine-containing waste sulfuric acid as claimed in claim 1 or 2, wherein the phase transfer agent is one or more of sodium oleate, oleylamine and oleic acid.
4. A regenerable process for dechlorination of chlorine-containing waste sulfuric acid according to claim 1 or 2, characterized in that in the second step the molar ratio of phase transfer agent to chloride ion is 1:1 to 2.
5. A regenerable process for dechlorination of chlorine-containing waste sulfuric acid according to claim 3, characterized in that in the second step the molar ratio of phase transfer agent to chloride ion is 1:1 to 2.
6. The regenerable process for dechlorination of chlorine-containing spent sulfuric acid according to claim 1 or 2 or 5, characterized in that the reflux reaction temperature is 70 ℃ to 100 ℃.
7. The regenerable process for dechlorination of chlorine-containing spent sulfuric acid according to claim 3, characterized in that the reflux reaction temperature is 70 ℃ to 100 ℃.
8. The regenerable process for dechlorination of chlorine-containing waste sulfuric acid according to claim 4, wherein the reflux reaction temperature is 70 ℃ to 100 ℃.
9. The process for the regenerable dechlorination of chlorine-containing waste sulfuric acid according to any of claims 1 to 8, wherein in the third step the concentrated hydrochloric acid solution is 37.5% by volume.
10. The process for the regenerable dechlorination of chlorine-containing waste sulfuric acid according to any of claims 1 to 9, characterized in that the volume percentage of the nitric acid solution is 10% to 65%.
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| CN112279878A (en) * | 2020-12-08 | 2021-01-29 | 山东润德生物科技有限公司 | Method for preparing high-purity glucosamine potassium sulfate and application thereof |
| CN114477535A (en) * | 2022-01-22 | 2022-05-13 | 宿迁市兴立环保科技有限公司 | Cyclic dechlorination process for wastewater containing chlorine nitrate |
| CN115401060A (en) * | 2022-08-24 | 2022-11-29 | 浙江红狮环保股份有限公司 | Method for removing chlorine content in organic hazardous waste |
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| CN111573641A (en) * | 2020-05-20 | 2020-08-25 | 无锡中天固废处置有限公司 | Method for co-producing nitric acid and silver from electrode foil waste liquid |
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