CN103215449A - Method for separating chlorine from zinc sulfate solution with high chlorine concentration - Google Patents
Method for separating chlorine from zinc sulfate solution with high chlorine concentration Download PDFInfo
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- CN103215449A CN103215449A CN2013101433636A CN201310143363A CN103215449A CN 103215449 A CN103215449 A CN 103215449A CN 2013101433636 A CN2013101433636 A CN 2013101433636A CN 201310143363 A CN201310143363 A CN 201310143363A CN 103215449 A CN103215449 A CN 103215449A
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- chlorine
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 112
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 112
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 112
- 239000000460 chlorine Substances 0.000 title claims abstract description 87
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 81
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000000605 extraction Methods 0.000 claims abstract description 137
- 239000012074 organic phase Substances 0.000 claims abstract description 112
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 238000006298 dechlorination reaction Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000003350 kerosene Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 9
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 7
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000003921 oil Substances 0.000 abstract description 5
- 239000000284 extract Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 7
- 238000010790 dilution Methods 0.000 abstract 3
- 239000012895 dilution Substances 0.000 abstract 3
- 239000012071 phase Substances 0.000 abstract 2
- -1 chlorine ions Chemical class 0.000 abstract 1
- 239000010742 number 1 fuel oil Substances 0.000 abstract 1
- 241000370738 Chlorion Species 0.000 description 26
- 239000011701 zinc Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 230000000382 dechlorinating effect Effects 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 238000000926 separation method Methods 0.000 description 8
- 238000000638 solvent extraction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 125000003010 ionic group Chemical group 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XSNQEMWVLMRPFR-UHFFFAOYSA-N silver nitride Chemical compound [N-3].[Ag+].[Ag+].[Ag+] XSNQEMWVLMRPFR-UHFFFAOYSA-N 0.000 description 1
- XDNDXYZWMMAEPS-UHFFFAOYSA-N silver sulfuric acid Chemical compound [Ag].OS(O)(=O)=O XDNDXYZWMMAEPS-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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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Abstract
The invention discloses a method for separating chlorine from a zinc sulfate solution with high chlorine concentration. The method comprises the following steps of: mixing an extraction agent and a dilution agent to obtain an extraction organic phase; performing acidification treatment on the extraction organic phase by using sulfuric acid; adjusting the pH value of the zinc sulfate solution to be 0.2-1.5 by using the sulfuric acid; extracting the zinc sulfate solution subjected to pH value adjustment by the acidified extraction organic phase to obtain a chlorine-enrichment organic phase and raffinate; and removing an oil phase and a water phase from the raffinate to obtain the zinc sulfate solution. Organic amine serves as the extraction agent; coal oil or octanol serves as the dilution agent; the extraction organic phase is obtained by mixing the extraction agent and the dilution agent according to a certain volume percentage; the acidified extraction organic phase extracts the treated chlorine-enrichment zinc sulfate solution by multiple stages, so that the chlorine-enrichment organic phase and the zinc sulfate solution are obtained; and therefore, chlorine ions can be separated from the zinc sulfate solution, and the chlorine removal rate is high.
Description
[technical field]
The present invention relates to a kind of method of separating chlorine in the solution of zinc sulfate, relate in particular to a kind of method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine.
[background technology]
Reclaiming zinc from solution of zinc sulfate takes place with electrolysis usually.In electrolysis zinc sulfate process, chlorion is quite deleterious material, and electrolysis must be lower than 300mg/L with the chloride ion content in the solution of zinc sulfate, because excessive chlorion can corrode negative electrode and anode surface, increase power consumption, reduced the quality of electrolytic zinc simultaneously.Therefore, solution of zinc sulfate must be removed most chlorion before sending electrolysis.
At present, the method for removing chlorion from solution of zinc sulfate is a lot, mainly comprises resin dechlorinating process, alkali cleaning dechlorinating process, mantoquita precipitation dechlorinating process, silver salt precipitation dechlorinating process etc.Wherein, the resin dechlorinating process, though in theory very perfect, in industrial actual application, because the dopant species and the content difference of various solution of zinc sulfate, caused side reaction more, simultaneously, hinder the carrying out that reacts in the easy fouling of resin surface, so in the application of reality, the effect of dechlorination is also bad, and dechlorination efficient all has only about 50%; The alkali cleaning dechlorinating process, because the content height of the zine ion in the solution of zinc sulfate, directly a large amount of zinc of alkali cleaning meeting loss is bad to the removal effect of chlorine simultaneously, is difficult to reach the concentration range of electrolysis requirement chlorine; Mantoquita precipitation dechlorinating process, this method adds Cu in solution of zinc sulfate
2+The control reducing atmosphere, make copper be precipitated out with the form of cuprous chloride, thereby reach the purpose of chlorion, though this method principle is simple, but in the operating process of reality, be difficult to control, because this method is strict to the pH value of solution, the general requirement pH value is not more than 3, when bigger change takes place in pH value, its dechlorination efficiency can descend significantly, the protochloride copper ashes that generates is along with Red copper oxide is resolved in the rising of the pH value of solution again, and chlorine can be transferred to again in the solution of zinc sulfate, and the dechlorination efficiency of this method generally also can only reach 70%; Silver salt precipitation dechlorinating process, this method adopts sulfuric acid silver powder or silver powder, joins in the solution of zinc sulfate, forms more stable silver nitride precipitation thing with chlorion, thereby reaches the purpose of effectively deviating from chlorion, and still, the shortcoming of present method maximum is exactly that cost is too high.
To sum up, adopt the resin dechlorinating process to remove chlorion in the solution of zinc sulfate, theory improves but dechlorination efficiency is low; Adopt the alkali cleaning dechlorinating process to remove chlorion in the solution of zinc sulfate, a large amount of zinc in the loss solution, dechlorination efficiency is low simultaneously; Adopt mantoquita precipitation dechlorinating process to remove chlorion in the solution of zinc sulfate, technology be difficult to control and also dechlorination efficiency low; Adopt silver salt precipitation dechlorinating process to remove chlorion in the solution of zinc sulfate, though can effectively deviate from the solution chlorion, its cost height.
[summary of the invention]
The technical problem to be solved in the present invention is to overcome prior art and removes that chlorine efficient is low in the solution of zinc sulfate, cost is high, the defective of complex process, and a kind of dechlorination efficiency height, with low cost, technology is simply separated chlorine from the solution of zinc sulfate that contains high concentration cl method are provided.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
A kind of method of separating chlorine from the solution of zinc sulfate that contains high concentration cl comprises the steps:
Step S1: extraction agent and mixing diluents are obtained extracted organic phase, and wherein, described extraction agent is an organic amine, and described thinner is at least a in kerosene or the secondary octanol;
Step S2: described extracted organic phase is handled with sulfuric acid acidation;
Step S3: be adjusted between 0.2～1.5 with the pH value of sulfuric acid with described solution of zinc sulfate;
Step S4: will obtain rich chlorine organic phase and raffinate through the solution of zinc sulfate of the extraction of the extracted organic phase after the acidification after pH value is regulated; And
Step S5: with the solution of zinc sulfate of described raffinate after obtaining dechlorination behind de-oiling, the water.
In the present embodiment, described method of separating chlorine from the solution of zinc sulfate that contains high concentration cl also comprises the steps:
Step S6: with reverse-extraction agent back extraction described rich chlorine organic phase, wherein, described reverse-extraction agent is at least a in sodium carbonate solution or the sodium hydroxide solution.
In the present embodiment, among the step S1, described organic amine is any one in three hot decyl amine, three positive heptyl amices or the tri-n-octyl amine.
In the present embodiment, among the step S1, described extraction agent and thinner by volume percentage concentration are 30%～50%: 70%～50% mixes.
In the present embodiment, among the step S2, described sulfuric acid concentration is 0.5mol/L～2.5mol/L, and acidificatoin time is 3min～10min, and described extracted organic phase and described sulfuric acid volume ratio are 2:1～1:2.
In the present embodiment, among the step S3, described vitriolic concentration is 1mol/L～18mol/L.
In the present embodiment, among the step S4, the condition of described extraction is: the extraction time is 3min～10min, and temperature is 15 ℃～30 ℃, settling time 4min～10min, and described extracted organic phase and water volume ratio are 1:1～2:1 during extraction.
In the present embodiment, among the step S5, described raffinate adopts the activated carbon de-oiling, and the content of described activated carbon is 3g/L～10g/L, and the de-oiling temperature is 15 ℃～40 ℃.
In the present embodiment, among the step S6, the mass percentage concentration of described sodium carbonate solution is 2%～8%, and the mass percentage concentration of described sodium hydroxide is 3%～10%.
In the present embodiment, among the step S6, the condition of described back extraction is: the back extraction time is 3min～8min, and temperature is 15 ℃～30 ℃, settling time 3min～10min, and described rich chlorine organic phase and water volume ratio are 1:1～1:3 during back extraction.
Adopt technique scheme, beneficial effect of the present invention is:
The method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine that the above embodiment of the present invention provides, with the organic amine is extraction agent, kerosene or secondary octanol are thinner, extraction agent mixed by certain concentration of volume percent with thinner obtain extracted organic phase, and will be through the solution of zinc sulfate that is rich in chlorine after the extracted organic phase multi-stage solvent extraction after the acidification is handled, thereby obtain rich chlorine organic phase and solution of zinc sulfate, that has realized chlorion and solution of zinc sulfate separates the dechlorination efficiency height.
In addition, the above embodiment of the present invention also provides with sodium carbonate solution or sodium hydroxide solution as reverse-extraction agent, the rich chlorine organic phase of back extraction, thereby realized separating of chlorion and organic phase, obtain organic phase and can be used to extract the solution of zinc sulfate that is rich in chlorine once more, realize recycling of extracted organic phase, reduced cost.
In addition, the method technology of separating chlorine from the solution of zinc sulfate that contains high concentration cl that the above embodiment of the present invention provides is simple, and easy handling is low for equipment requirements, can be in large-scale application.
[description of drawings]
The flow chart of steps of from the solution of zinc sulfate that contains high concentration cl, separating the method for chlorine that Fig. 1 provides for the embodiment of the invention.
[embodiment]
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and the specific embodiments.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, steps flow chart Figure 100 that from the solution of zinc sulfate that contains high concentration cl, separates the method for chlorine that Fig. 1 provides for the embodiment of the invention, as can be seen from Fig. 1, the method for separating chlorine from the solution of zinc sulfate that contains high concentration cl comprises the steps:
Step S1: extraction agent and mixing diluents are obtained extracted organic phase, and wherein, extraction agent is an organic amine, and thinner is at least a in kerosene or the secondary octanol.
In the present embodiment, organic amine is preferably any one in three hot decyl amine, three positive heptyl amices or the tri-n-octyl amine.
In the present embodiment, extraction agent and thinner by volume percentage concentration be 30%～50%: 70%～50% mixes.
Be appreciated that, choose the particularly important of suitable extraction agent and thinner, technical scheme provided by the invention is extraction agent with the organic amine, with at least a in kerosene or the secondary octanol is thinner, the two is mixed according to a certain percentage obtain extracted organic phase, extract rich sulfuric chlorohydrin zinc solution by this extracted organic phase, thus realize chlorion and solution of zinc sulfate separate the dechlorination efficiency height.
Step S2: above-mentioned extracted organic phase is handled with sulfuric acid acidation.
In the present embodiment, the extracted organic phase that obtains among the step S1 is added an amount of sulfuric acid carry out acidifying, static phase-splitting, and collect extracted organic phase after organic phase promptly obtains acidifying, wherein, vitriolic concentration is 0.5mol/L～2.5mol/L, and acidificatoin time is 3min～10min, and extracted organic phase and sulfuric acid volume ratio are 2:1～1:2.
Be appreciated that present embodiment chooses sulfuric acid extracted organic phase is carried out acidifying, effectively avoided adopting other acidic substance and introduced new impurity, make that the solution of zinc sulfate after the dechlorination is impure, thereby improved the purity of solution of zinc sulfate to solution of zinc sulfate.
Step S3: be adjusted between 0.2～1.5 with the pH value of sulfuric acid with solution of zinc sulfate.
In the present embodiment, the chlorine ion concentration scope that contains the solution of zinc sulfate of high concentration cl is 5g/L～30g/L.Also added sulfuric acid and carry out the pH value adjusting before dechlorination, wherein, vitriolic concentration is 1mol/L～18mol/L, and the pH value of solution of zinc sulfate is between 0.2～1.5 after above-mentioned sulfuric acid is regulated.
Being appreciated that present embodiment is chosen regulates the pH value of solution of zinc sulfate, has effectively avoided adopting other acidic substance and has introduced new impurity to solution of zinc sulfate, makes that the solution of zinc sulfate after the dechlorination is impure, thereby has improved the purity of solution of zinc sulfate.
Step S4: will obtain rich chlorine organic phase and raffinate through the solution of zinc sulfate of the extraction of the extracted organic phase after the acidification after pH value is regulated.
In the present embodiment, the extracted organic phase extraction solution of zinc sulfate after above-mentioned steps is handled is obtained rich chlorine organic phase and raffinate.Wherein, the condition of extraction is: the extraction time is 3min～10min, and temperature is 15 ℃～30 ℃, settling time 4min～10min, and extracted organic phase and water volume ratio are 1:1～2:1 during extraction, the least number of times of extraction is 1 time.
Be appreciated that behind step S4, to obtain rich chlorine organic phase and raffinate, wherein, be mainly solution of zinc sulfate in the raffinate, thereby realized separating of chlorion and solution of zinc sulfate that along with the increase of extraction times, the solution of zinc sulfate purity that obtains is high more.
Step S5: raffinate is obtained solution of zinc sulfate behind de-oiling, water.
In the present embodiment, adopt activated carbon to carry out de-oiling raffinate, wherein, the content of activated carbon is 3g/L～10g/L, and the de-oiling temperature is 15 ℃～40 ℃.
Be appreciated that in the raffinate extraction agent of trace and thinner through by charcoal absorption, thereby further improved the purity of solution of zinc sulfate.
Behind above-mentioned steps S1～S5, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
In addition, the method for separation chlorine also comprises the steps: from the solution of zinc sulfate that contains high concentration cl
Step S6: with the rich chlorine organic phase of reverse-extraction agent back extraction, wherein, reverse-extraction agent is at least a in sodium carbonate solution or the sodium hydroxide solution.
In the present embodiment, the mass percentage concentration of sodium carbonate solution is 2%～8%, and the mass percentage concentration of sodium hydroxide is 3%～10%.
In the present embodiment, the condition of back extraction is: the back extraction time is 3min～8min, and temperature is 15 ℃～30 ℃, settling time 3min～10min, and rich chlorine organic phase and water volume ratio are 1:1～1:3 during back extraction.
Be appreciated that with reverse-extraction agent back extraction rich chlorine organic phase and realized separating of chlorion and organic phase, obtain organic phase and can be used to extract the solution of zinc sulfate that contains high concentration cl once more, realized recycling of extracted organic phase, reduced cost.
The method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine that the above embodiment of the present invention provides, with the organic amine is extraction agent, kerosene or secondary octanol are thinner, extraction agent mixed by certain concentration of volume percent with thinner obtain extracted organic phase, and will be through the solution of zinc sulfate that is rich in chlorine after the extracted organic phase multi-stage solvent extraction after the acidification is handled, thereby obtain rich chlorine organic phase and solution of zinc sulfate, that has realized chlorion and solution of zinc sulfate separates the dechlorination efficiency height.
In addition, the above embodiment of the present invention also provides with sodium carbonate solution or sodium hydroxide solution as reverse-extraction agent, the rich chlorine organic phase of back extraction, thereby realized separating of chlorion and organic phase, obtain organic phase and can be used to extract the solution of zinc sulfate that is rich in chlorine once more, realize recycling of extracted organic phase, reduced cost.
In addition, the method technology of separating chlorine from the solution of zinc sulfate that contains high concentration cl that the above embodiment of the present invention provides is simple, and easy handling is low for equipment requirements, can be in large-scale application.
Further set forth the present invention by the following examples, these embodiment are only presented for purposes of illustration, do not limit the scope of the invention.Except that the actual conditions that indicates, the test method among the embodiment is all carried out according to normal condition.
Embodiment 1
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+127g/L, SO
4 2-180g/L, Cl
-25g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: three hot decyl amine (N235) are as extraction agent, and select for use sulfonated kerosene and secondary octanol as thinner, three's volume ratio is three hot decyl amine: secondary octanol: sulfonated kerosene=30%: 10%: 60%, sulfuric acid with 1mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 10mol/L sulfuric acid is adjusted to 0.5, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 1.5:1,25 ℃ of extraction temperature, and mixing time 5min, settling time 5min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99.66%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 1mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 1:1, and acidificatoin time 5min leaves standstill phase-splitting, can obtain the acidizing extraction organic phase.
The chloride 0.085g/L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 3g/L again, and the de-oiling temperature is 25 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 24.935g/L in the rich chlorine organic phase, the sodium carbonate solution with 3.8% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 1:1, and the back extraction temperature is 25 ℃, back extraction time 5min, back extraction chlorine extrusion rate reaches more than 99%.
Embodiment 2
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+130g/L, SO
4 2-185g/L, Cl
-230g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: three hot decyl amine (N235) are as extraction agent, and select for use No. 200 kerosene and secondary octanol as thinner, three's volume ratio is three hot decyl amine: secondary octanol: No. 200 kerosene=40%: 10%: 50%, sulfuric acid with 2.5mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 18mol/L sulfuric acid is adjusted to 0.2, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 1:1,30 ℃ of extraction temperature, and mixing time 10min, settling time 10min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99.49%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 2.5mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 2:1, and acidificatoin time 10min leaves standstill phase-splitting, can obtain the acidizing extraction organic phase.
The chloride 0.153g/L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 10g/L again, and the de-oiling temperature is 40 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 29.84g/L in the rich chlorine organic phase, the sodium carbonate solution with 25% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 1:3, and the back extraction temperature is 30 ℃, back extraction time 10min, back extraction chlorine extrusion rate reaches more than 99%.
Embodiment 3
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+20g/L, SO
4 2-36g/L, Cl
2-5g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: three positive heptyl amices (N208) are as extraction agent, and select for use No. 260 solvent oils as thinner, the volume ratio of the two is three positive heptyl amices: No. 260 solvent oils=30%: 70%, sulfuric acid with 0.5mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 1mol/L sulfuric acid is adjusted to 1.5, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 2:1,15 ℃ of extraction temperature, and mixing time 3min, settling time 4min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 0.5mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 1:2, and acidificatoin time 3min leaves standstill phase-splitting, can obtain the acidifying extracted organic phase.
The chloride 0.050g/L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 6g/L again, and the de-oiling temperature is 35 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 4.95g/L in the rich chlorine organic phase, the sodium carbonate solution with 2% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 2:1, and the back extraction temperature is 30 ℃, back extraction time 3min, back extraction chlorine extrusion rate reaches more than 99%.
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+127g/L, SO
4 2-175g/L, Cl
2-25g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: tri-n-octyl amine (N235) is as extraction agent, and select for use secondary octanol as thinner, the volume ratio of the two is a tri-n-octyl amine: secondary octanol=50%: 50%, sulfuric acid with 1mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 10mol/L sulfuric acid is adjusted to 0.5, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 1.5:1,25 ℃ of extraction temperature, and mixing time 5min, settling time 5min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99.66%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 1mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 1:1, and acidificatoin time 5min leaves standstill phase-splitting, can obtain the acidifying extracted organic phase.
The chloride 0.085g/L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 6g/L again, and the de-oiling temperature is 25 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 24.935g/L in the rich chlorine organic phase, the sodium hydroxide solution with 4% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 1:1, and the back extraction temperature is 25 ℃, back extraction time 5min, back extraction chlorine extrusion rate reaches more than 99%.
Embodiment 5
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+130g/L, SO
4 2-185g/L, Cl
2-30g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: three positive heptyl amices (N208) are as extraction agent, and select for use No. 260 solvent oils as thinner, the volume ratio of the two is three positive heptyl amices: No. 260 solvent oils=40%: 60%, sulfuric acid with 2.5mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 18mol/L sulfuric acid is adjusted to 0.2, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 1:1,30 ℃ of extraction temperature, and mixing time 10min, settling time 10min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99.49%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 2.5mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 2:1, and acidificatoin time 10min leaves standstill phase-splitting, can obtain the acidifying extracted organic phase.
The chloride 0.153L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 10g/L again, and the de-oiling temperature is 40 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 29.84g/L in the rich chlorine organic phase, the sodium hydroxide solution with 20% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 1:3, and the back extraction temperature is 30 ℃, back extraction time 8min, back extraction chlorine extrusion rate reaches more than 99%.
Embodiment 6
Adopt method provided by the present invention to handle the solution of zinc sulfate that contains high concentration cl, wherein, the ionic group of solution of zinc sulfate becomes: Zn
2+20g/L, SO
4 2-36g/L, Cl
2-5g/L, PH=5.0 obtain extracted organic phase with extraction agent and mixing diluents.Concrete extraction conditions is: tri-n-octyl amine (N204) is as extraction agent, and select for use No. 200 kerosene as thinner, the volume ratio of the two is a tri-n-octyl amine: No. 200 kerosene=30%: 70%, sulfuric acid with 0.5mol/L carries out acidifying to extracted organic phase again, the PH that will contain the solution of zinc sulfate of high concentration cl with 1mol/L sulfuric acid is adjusted to 1.5, carry out the multi-stage solvent extraction dechlorination then, obtain rich chlorine organic phase and raffinate.Extracted organic phase and water during extraction after the acidifying are in a ratio of 2:1,15 ℃ of extraction temperature, and mixing time 3min, settling time 4min, 4 grades of extraction progression, the extraction dechlorination efficiency is 99%.
Wherein, the acidulated condition of extracted organic phase is: adopt the sulfuric acid of 1mol/L that acidity is provided, during acidifying, extracted organic phase and vitriolic volume ratio are 1:2, and acidificatoin time 3min leaves standstill phase-splitting, can obtain the acidifying extracted organic phase.
The chloride 0.050L of raffinate adopts raffinate the activated carbon adsorption de-oiling of 3g/L again, and the de-oiling temperature is 30 ℃, the organic concentration of aqueous phase is less than 10ppm after the de-oiling, behind aforesaid operations, the chlorion more than 99% that contains in the solution of zinc sulfate of high concentration cl is separated, the separation efficiency height.Solution of zinc sulfate after dechlorination generates zinc by electrolysis.
Chloride 4.95g/L in the rich chlorine organic phase, the sodium hydroxide solution with 3% is a reverse-extraction agent, and the back extraction condition is: rich chlorine organic phase and water are in a ratio of 2:1, and the back extraction temperature is 30 ℃, back extraction time 3min, back extraction chlorine extrusion rate reaches more than 99%.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a method of separating chlorine from the solution of zinc sulfate that contains high concentration cl is characterized in that, comprises the steps:
Step S1: extraction agent and mixing diluents are obtained extracted organic phase, and wherein, described extraction agent is an organic amine, and described thinner is at least a in kerosene or the secondary octanol;
Step S2: described extracted organic phase is handled with sulfuric acid acidation;
Step S3: be adjusted between 0.2～1.5 with the pH value of sulfuric acid with described solution of zinc sulfate;
Step S4: will obtain rich chlorine organic phase and raffinate through the solution of zinc sulfate of the extraction of the extracted organic phase after the acidification after pH value is regulated; And
Step S5: with the solution of zinc sulfate of described raffinate after obtaining dechlorination behind de-oiling, the water.
2. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 1 is characterized in that, also comprises the steps:
Step S6: with reverse-extraction agent back extraction described rich chlorine organic phase, wherein, described reverse-extraction agent is at least a in sodium carbonate solution or the sodium hydroxide solution.
3. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 1 is characterized in that among the step S1, described organic amine is any one in three hot decyl amine, three positive heptyl amices or the tri-n-octyl amine.
4. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 1 is characterized in that, among the step S1, described extraction agent and thinner by volume percentage concentration are 30%～50%: 70%～50% mixes.
5. method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine according to claim 1, it is characterized in that among the step S2, described sulfuric acid concentration is 0.5mol/L～2.5mol/L, acidificatoin time is 3min～10min, and described extracted organic phase and described sulfuric acid volume ratio are 2:1～1:2.
6. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 1 is characterized in that among the step S3, described vitriolic concentration is 1mol/L～18mol/L.
7. method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine according to claim 1, it is characterized in that, among the step S4, the condition of described extraction is: the extraction time is 3min～10min, temperature is 15 ℃～30 ℃, settling time 4min～10min, described extracted organic phase and water volume ratio are 1:1～2:1 during extraction.
8. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 1 is characterized in that, among the step S5, described raffinate adopts the activated carbon de-oiling, and the content of described activated carbon is 3g/L～10g/L, and the de-oiling temperature is 15 ℃～40 ℃.
9. method of separating chlorine from the solution of zinc sulfate that contains high concentration cl according to claim 2 is characterized in that among the step S6, the mass percentage concentration of described sodium carbonate solution is 2%～8%, and the mass percentage concentration of described sodium hydroxide is 3%～10%.
10. method of from the solution of zinc sulfate that contains high concentration cl, separating chlorine according to claim 2, it is characterized in that, among the step S6, the condition of described back extraction is: the back extraction time is 3min～8min, temperature is 15 ℃～30 ℃, settling time 3min～10min, described rich chlorine organic phase and water volume ratio are 1:1～1:3 during back extraction.
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| CN112299591A (en) * | 2020-09-24 | 2021-02-02 | 昆明理工大学 | Method for recovering chlorine and preparing chlorine salt based on solvent extraction and salting-out effect integrated technology |
| CN114804410A (en) * | 2022-04-13 | 2022-07-29 | 南京工业大学 | Method for extracting chloride ions from wet flue gas desulfurization wastewater |
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