CN114959296A - Process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination - Google Patents
Process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination Download PDFInfo
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- CN114959296A CN114959296A CN202210537613.3A CN202210537613A CN114959296A CN 114959296 A CN114959296 A CN 114959296A CN 202210537613 A CN202210537613 A CN 202210537613A CN 114959296 A CN114959296 A CN 114959296A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 32
- 239000011701 zinc Substances 0.000 title claims abstract description 32
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 19
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005342 ion exchange Methods 0.000 title claims abstract description 9
- 238000000605 extraction Methods 0.000 title claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 239000000460 chlorine Substances 0.000 claims abstract description 43
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 39
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 19
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 17
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 4
- 230000020477 pH reduction Effects 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000746 purification Methods 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229940073609 bismuth oxychloride Drugs 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a process method for producing hydrochloric acid by ion exchange dechlorination sulfuric acid extraction in zinc hydrometallurgy, which comprises the following steps: step one, neutral leaching, acid leaching and purifying zinc-containing materials to obtain zinc sulfate liquid, and then enabling the zinc sulfate liquid to enter a cooling tower for acidification treatment; step two, pumping the liquid treated in the step one into an ion exchange resin tower, and continuously feeding in and out; step three, stopping when the Cl content of the outlet liquid of the ion exchange resin tower is more than 14g/LFeeding liquid, and cleaning the resin with 50% clear water; step four, adding 5% -15% sulfuric acid solution into the resin treated in the step three, and adding SO 4 2‑ Replacing chloride ions in the resin; fifthly, carrying out one-effect pressure reduction evaporation on the chlorine-containing waste acid water produced in the fourth step; step six, transferring the perchloric acid liquid produced in the step five into double-effect evaporation at normal pressure; and step seven, feeding the liquid condensed by the tower top condenser in the step six into a storage tank, and further concentrating hydrochloric acid to produce 15% -25% concentrated hydrochloric acid.
Description
Technical Field
The invention relates to a dechlorination process method in the zinc hydrometallurgy industry, in particular to a process method for producing hydrochloric acid by sulfuric acid extraction through dechlorination and ion exchange in zinc hydrometallurgy.
Background
In the current world zinc raw material production situation, about 80% of zinc raw materials are refined by adopting a zinc hydrometallurgy process. The zinc smelting process by the whole wet method is the most advanced zinc smelting technology at present after continuous technical improvement and development.
Meanwhile, with the continuous exploitation of mineral resources, the grade of the zinc ore is continuously lowered, and particularly, the chlorine content in the ore is increased, so that a greater challenge is provided for a zinc smelting process. In the traditional zinc hydrometallurgy process, 70 percent of chlorine impurities can enter a flue gas acid making system in the boiling roasting process, but 30 percent of chlorine impurities can enter a wet system along with zinc oxide smoke dust. The fluorine and chlorine can affect the whole zinc hydrometallurgy process, cause the chlorine content of the system to exceed the standard, and affect the production.
The main influence of chloride ions in the zinc hydrometallurgy process is the leaching, purification and electrolysis processes. They can corrode and dissolve the blades and blender components of the pump that are operating at high speeds, causing leakage from the pump. Meanwhile, in the electrolytic production, the lead-silver plate as an anode plate is corroded by chloride ions, and a corrosion product is deposited on a cathode, so that the precipitation grade rate of zinc is directly influenced. Therefore, the chlorine content of the liquid in the electrolysis process needs to be controlled within 1000 mg/L.
The method for removing chloride ions in the zinc hydrometallurgy process mainly comprises the following steps:
1. the silver chloride precipitation method removes chloride ions by using silver chloride precipitates generated by the reaction of silver salts and chloride ions in liquid, but the method has high cost, is difficult to recycle silver and is difficult to use in large-scale production.
2. The cuprous chloride precipitation method is characterized in that the cuprous chloride precipitation is generated by utilizing the disproportionation reaction of copper and chloride ions in the copper slag removing process for dechlorination. However, the method requires high copper content in the raw materials, and the copper slag is not easy to recycle after dechlorination, so the operation cost is high.
3. Bismuth oxychloride precipitation method, which is characterized in that bismuth oxide is utilized to react with chloride ions in electrolyte, so that bismuth ions are in a free state and then react with the chloride ions to generate bismuth trioxide, and the bismuth trioxide is hydrolyzed into bismuth oxychloride for precipitation and dechlorination. However, the cost of the key raw material bismuth oxide used in the method is high, and the application of the bismuth oxychloride precipitation method in industrial production is limited.
4. An ion exchange method, which utilizes the characteristic of exchangeable ions of resin and dechlorination is carried out by adsorbing chloride ions by the resin. However, the method generates a large amount of chlorine-containing waste water, and the loss of zinc in the waste water reaches about 5 percent, thereby limiting the application of the method.
5. The electrochemical method has good effect on removing organic chlorine in water phase, and the working principle is that chlorine ions are utilized to form specific precipitate in solution by controlling electrochemical conditions for dechlorination. But the application of the method in the zinc hydrometallurgy process is in a research stage.
Hydrochloric acid is a common chemical product and is widely applied to the processes of chemical industry, metallurgy, metal surface treatment, rare earth production and the like. The treatment and recycling of the high-chlorine wastewater produced in the zinc hydrometallurgy industry are a great problem of wastewater treatment, and along with the increase of the national environmental pollution control and the requirement of comprehensive utilization of resources, the comprehensive recycling of the high-chlorine wastewater becomes a problem to be solved urgently in the industry. The existing methods for recycling dilute waste hydrochloric acid mainly comprise an electrodialysis method, a concentration distillation method and a chlorine and hydrogen reaction preparation method. However, since the high-chlorine wastewater produced by the zinc hydrometallurgy contains sulfate radicals and various heavy metal ions, the traditional dilute waste hydrochloric acid treatment method cannot carry out resource utilization on the high-chlorine wastewater produced by the zinc hydrometallurgy.
Disclosure of Invention
The invention aims to provide a process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination, which can realize the removal of chlorine and resource utilization.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination comprises the following steps:
step one, performing neutral leaching, acidic leaching and purification on a zinc-containing material to obtain zinc sulfate liquid, then allowing the zinc sulfate liquid to enter a cooling tower for acidification treatment, controlling the temperature of outlet liquid to be 40-50 ℃, and controlling the pH value to be: 3.5-4.5;
step two, pumping the zinc sulfate liquid treated in the step one into an ion exchange resin tower, continuously feeding the zinc sulfate liquid in and out, and pouring the outlet liquid containing less than 1g/L of chlorine into an electrolytic liquid tank;
step three, when the Cl content of the outlet liquid of the ion exchange resin tower is more than 14g/L, stopping feeding liquid, and cleaning the resin by using 50% of clear water;
step four, adding 5% -15% sulfuric acid solution into the resin treated in the step three, controlling the temperature to be 35-80 ℃, and using SO 4 2- Displacing chloride ions in the resin until the liquid chlorine is less than 1g/L after cleaning to generate waste acid water containing chlorine;
fifthly, carrying out one-effect pressure reduction evaporation on the chlorine-containing waste acid water produced in the fourth step at 40-80 kpa and 70 ℃ to produce evaporation water and chlorine-containing high acid liquid, wherein the acid concentration of the high acid liquid is 11% -16%, and the evaporation water is recycled to the neutral leaching, acid leaching or purification process in the first step;
step six, transferring the high-chlorine high-acid solution produced in the step five into double-effect evaporation at normal pressure, adding concentrated sulfuric acid, and keeping the mass fraction of the sulfuric acid in the solution: 25% -50%; the temperature is 115-120 ℃, steam generated in the tower kettle enters a rectifying tower, and mass transfer separation is carried out in the rectifying tower;
and step seven, feeding the liquid condensed by the condenser at the top of the tower in the step six into a storage tank, adjusting the reflux ratio to be 0.2-1.0, generating 8-15% of dilute hydrochloric acid at the bottom of the rectifying tower, installing a reboiler at the bottom of the rectifying tower, controlling the temperature to be 105-108 ℃, further concentrating the hydrochloric acid, and generating 15-25% of concentrated hydrochloric acid.
After the technical scheme is adopted, the temperature and the solution acidity are controlled after purified liquid passes through a cooling tower, so that chloride ions in new liquid can be adsorbed to chloride ion exchange resin, after chlorine is adsorbed to be nearly saturated, dilute sulfuric acid is used for resolving the resin, the chloride ions adsorbed to the resin are replaced, waste acid water containing chlorine is generated, the zinc liquid is filtered again for the resolved resin, and the purpose of extracting industrial hydrochloric acid from the sulfuric acid is achieved by controlling the concentration and the node of the added sulfuric acid and the temperatures of different evaporation sections aiming at the treatment of the waste acid water containing the chlorine.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
The invention discloses a process method for producing hydrochloric acid by ion exchange dechlorination sulfuric acid extraction in zinc hydrometallurgy, which comprises the following steps:
step one, performing neutral leaching, acidic leaching and purification on a zinc-containing material to obtain zinc sulfate liquid, then allowing the zinc sulfate liquid to enter a cooling tower for acidification treatment, controlling the temperature of outlet liquid to be 40-50 ℃, and controlling the pH value to be: 3.5-4.5.
Step two, pumping the zinc sulfate liquid treated in the step one into an ion exchange resin tower, continuously feeding the zinc sulfate liquid in and out, and pouring the outlet liquid into a liquid tank for electrolysis when the chlorine content of the outlet liquid is less than 1 g/L;
step three, when the Cl content of the outlet liquid of the ion exchange resin tower is more than 14g/L, stopping feeding liquid, and cleaning the resin by using 50% of clear water;
step four, adding 5-15% sulfuric acid solution into the resin treated in the step three, controlling the temperature to be 35-80 ℃, and using SO 4 2- Displacing chloride ions in the resin until the liquid chlorine is less than 1g/L after cleaning to generate waste acid water containing chlorine;
fifthly, carrying out first-effect reduced pressure evaporation on the chlorine-containing waste acid water produced in the fourth step at the temperature of 70 ℃ at 40-80 kpa to produce evaporated water and chlorine-containing high acid liquid, wherein the concentration of the chlorine-containing high acid liquid is 11% -16%, and the evaporated water is recycled to the neutral leaching, acidic leaching or purifying process in the first step;
step six, transferring the high-chlorine high-acid solution produced in the step five into double-effect evaporation at normal pressure, adding concentrated sulfuric acid, and keeping the mass fraction of the sulfuric acid in the solution: 25% -50%; the temperature is 115-120 ℃, steam generated in the tower kettle enters a rectifying tower, and mass transfer separation is carried out in the rectifying tower;
and step seven, feeding the liquid condensed by the condenser at the top of the tower in the step six into a storage tank, adjusting the reflux ratio to be 0.2-1.0, generating 8-15% of dilute hydrochloric acid at the bottom of the rectifying tower, installing a reboiler at the bottom of the rectifying tower, controlling the temperature to be 105-108 ℃, further concentrating the hydrochloric acid, and generating 15-25% of concentrated hydrochloric acid.
Therefore, after purified zinc sulfate liquid passes through a cooling tower, the temperature and the acidity of the solution are controlled, so that chloride ions in the zinc sulfate liquid can be adsorbed to chloride ion exchange resin, after chlorine is adsorbed to be nearly saturated, the resin is analyzed by using dilute sulfuric acid with certain concentration, the chloride ions adsorbed to the resin are replaced, waste acid water containing chlorine is generated, and the zinc sulfate liquid can be filtered again by the analyzed resin, so that the effect of recycling the resin is achieved. Aiming at the treatment of the waste acid water containing chlorine, the aim of extracting the industrial hydrochloric acid from the sulfuric acid is achieved by controlling the concentration and the node of the added sulfuric acid and the temperature of different evaporation sections, so that the harmful element chlorine in the zinc hydrometallurgy is removed, the industrial hydrochloric acid is produced, and the aim of comprehensive utilization of resources is achieved.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.
Claims (1)
1. A process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination is characterized by comprising the following steps:
step one, performing neutral leaching, acid leaching and purification on a zinc-containing material to obtain zinc sulfate liquid, then putting the zinc sulfate liquid into a cooling tower for acidification treatment, controlling the temperature of outlet liquid to be 40-50 ℃, and controlling the pH value to be: 3.5-4.5;
step two, pumping the zinc sulfate liquid treated in the step one into an ion exchange resin tower, continuously feeding the zinc sulfate liquid in and out, and pouring the outlet liquid containing less than 1g/L of chlorine into an electrolytic liquid tank;
step three, when the Cl content of the outlet liquid of the ion exchange resin tower is more than 14g/L, stopping feeding liquid, and cleaning the resin by using 50% of clear water;
step four, adding 5-15% sulfuric acid solution into the resin treated in the step three, controlling the temperature to be 35-80 ℃, and using SO 4 2- Displacing chloride ions in the resin until the liquid chlorine is less than 1g/L after cleaning to generate waste acid water containing chlorine;
fifthly, carrying out one-step reduced pressure evaporation on the chlorine-containing waste acid water produced in the fourth step at the temperature of 70 ℃ at 40-80 kpa to produce evaporated water and chlorine-containing high acid liquid, wherein the acid concentration of the high chlorine high acid liquid is 11% -16%, and the evaporated water is recycled to the neutral leaching, acid leaching or purification process in the first step;
step six, under normal pressure, transferring the perchloric acid liquid produced in the step five into double-effect evaporation, adding concentrated sulfuric acid, and keeping the mass fraction of the sulfuric acid in the solution: 25% -50%; the temperature is 115-120 ℃, steam generated in the tower kettle enters a rectifying tower, and mass transfer separation is carried out in the rectifying tower;
and step seven, feeding the liquid condensed by the condenser at the top of the tower in the step six into a storage tank, adjusting the reflux ratio to be 0.2-1.0, generating 8-15% of dilute hydrochloric acid at the bottom of the rectifying tower, installing a reboiler at the bottom of the rectifying tower, controlling the temperature to be 105-108 ℃, further concentrating the hydrochloric acid, and generating 15-25% of concentrated hydrochloric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537613.3A CN114959296A (en) | 2022-05-18 | 2022-05-18 | Process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537613.3A CN114959296A (en) | 2022-05-18 | 2022-05-18 | Process method for producing hydrochloric acid by sulfuric acid extraction through zinc hydrometallurgy ion exchange dechlorination |
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| CA3008880A1 (en) * | 2017-06-22 | 2018-12-22 | Lifezone Limited | Hydrometallurgical treatment process for extraction of precious, base and rare elements |
| CN110055416A (en) * | 2019-05-24 | 2019-07-26 | 吉首大学 | A kind of method of zinc hydrometallurgy industrial sulphuric acid hydrochloric acid separating and recovering |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA3008880A1 (en) * | 2017-06-22 | 2018-12-22 | Lifezone Limited | Hydrometallurgical treatment process for extraction of precious, base and rare elements |
| CN110055416A (en) * | 2019-05-24 | 2019-07-26 | 吉首大学 | A kind of method of zinc hydrometallurgy industrial sulphuric acid hydrochloric acid separating and recovering |
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