CN117756138A - Method for recovering potassium, rubidium and cesium in mixed alum - Google Patents
Method for recovering potassium, rubidium and cesium in mixed alum Download PDFInfo
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- CN117756138A CN117756138A CN202311797923.XA CN202311797923A CN117756138A CN 117756138 A CN117756138 A CN 117756138A CN 202311797923 A CN202311797923 A CN 202311797923A CN 117756138 A CN117756138 A CN 117756138A
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 118
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 117
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229940037003 alum Drugs 0.000 title claims abstract description 115
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 100
- 239000011591 potassium Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 142
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 133
- 238000000605 extraction Methods 0.000 claims abstract description 112
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- 239000012074 organic phase Substances 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 34
- 238000009993 causticizing Methods 0.000 claims abstract description 29
- 230000008014 freezing Effects 0.000 claims abstract description 28
- 238000007710 freezing Methods 0.000 claims abstract description 28
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 27
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 229910052629 lepidolite Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 150000003297 rubidium Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 239000003350 kerosene Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003085 diluting agent Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- QJNBIFRUSFIANU-UHFFFAOYSA-N 4-butan-2-yl-2-(1-phenylethyl)phenol Chemical compound CCC(C)C1=CC=C(O)C(C(C)C=2C=CC=CC=2)=C1 QJNBIFRUSFIANU-UHFFFAOYSA-N 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- JVJMRLZNFIEHGR-UHFFFAOYSA-N 4-tert-butyl-2-(1-phenylethyl)phenol Chemical compound C=1C(C(C)(C)C)=CC=C(O)C=1C(C)C1=CC=CC=C1 JVJMRLZNFIEHGR-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 154
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000012535 impurity Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940102127 rubidium chloride Drugs 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 2
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 rubidium salt Chemical class 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Extraction Or Liquid Replacement (AREA)
Abstract
The application discloses a method for recovering potassium, rubidium and cesium in mixed alum, belonging to the technical field of mineral comprehensive utilization. The method comprises the following steps: obtaining mixed alum; mixing the mixed alum and a causticizing agent for solid phase reaction to obtain a mixed material, and adding a leaching agent into the mixed material for leaching to obtain sulfate leaching liquid; freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate; enriching rubidium and cesium in the mixed sulfate solution to obtain an enrichment solution; carrying out multistage extraction on the enrichment liquid, and collecting a first organic phase with a first preset stage number and a second organic phase with a second preset stage number, wherein the first preset stage number is smaller than the second preset stage number; back-extracting the first organic phase to obtain cesium salt; and carrying out back extraction on the second organic phase to obtain rubidium salt. The method realizes the efficient recovery of potassium, rubidium and cesium in the mixed alum after lithium extraction from lepidolite.
Description
Technical Field
The application relates to the technical field of mineral comprehensive utilization, in particular to a method for recovering potassium, rubidium and cesium in mixed alum.
Background
Lepidolite is an important mineral raw material for extracting lithium, and not only lithium but also valuable metals such as potassium, rubidium and cesium are included in the lepidolite, so that comprehensive utilization of the valuable metals in the lepidolite is realized, the resource value can be fully excavated, and the process technology economy is improved.
However, the conventional lepidolite is mainly focused on lithium extraction, and the mixed alum containing valuable metals such as potassium, rubidium, cesium and the like obtained after the lithium extraction is not further treated, so that the resources of the potassium, rubidium and cesium are difficult to effectively recover, and serious waste of key mineral resources is caused.
The foregoing is merely provided to facilitate an understanding of the principles of the present application and is not admitted to be prior art.
Disclosure of Invention
The main purpose of the application is to provide a method for recovering potassium, rubidium and cesium in mixed alum, which aims to realize efficient recovery of potassium, rubidium and cesium in mixed alum after lithium extraction from lepidolite.
In order to achieve the above purpose, the present application provides a method for recovering potassium, rubidium and cesium from mixed alum, wherein the mixed alum is a byproduct of lithium extraction from lepidolite, and the method comprises the following steps:
obtaining mixed alum;
mixing the mixed alum and a causticizing agent for solid phase reaction to obtain a mixed material, and adding a leaching agent into the mixed material for leaching to obtain sulfate leaching liquid;
freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate;
enriching rubidium and cesium in the mixed sulfate solution to obtain an enrichment solution;
carrying out multistage extraction on the enrichment liquid, and collecting a first organic phase with a first preset stage number and a second organic phase with a second preset stage number, wherein the first preset stage number is smaller than the second preset stage number;
back-extracting the first organic phase to obtain cesium salt;
and carrying out back extraction on the second organic phase to obtain rubidium salt.
Optionally, the step of enriching rubidium and cesium in the mixed sulfate solution comprises:
and under the condition that the concentration of the mixed sulfate solution does not reach a preset concentration threshold, taking the mixed sulfate solution as a leaching agent, and returning to execute the step of acquiring the mixed alum until the concentration of the mixed sulfate solution reaches the preset concentration threshold, executing the step of carrying out multistage extraction on the enriched liquid, and collecting a first organic phase with a first preset level and a second organic phase with a second preset level.
Optionally, the reaction temperature of the solid phase reaction is 60-90 ℃, and the solid phase reaction time is 0.5-5 h;
and/or, the causticizing agent comprises: at least one of calcium oxide and calcium hydroxide.
Optionally, the leaching reaction temperature is 60-90 ℃, and the leaching reaction time is 0.5-2 h;
and/or the reaction temperature of the freezing crystallization is-5-25 ℃.
Optionally, after the step of subjecting the enriched liquid to multi-stage extraction, the method further comprises:
collecting raffinate after the second predetermined number of extractions;
the raffinate is used as the leaching agent.
Optionally, the extractant used for the multistage extraction comprises: at least one of 4-sec-butyl-2 (α -methylbenzyl) phenol and 4-tert-butyl-2 (α -methylbenzyl) phenol;
and/or the diluents used for the multistage extraction include: sulfonated kerosene;
and/or, the stripping agent used for the stripping comprises: at least one of sulfuric acid, hydrochloric acid and nitric acid.
Optionally, the extraction stage number of the multistage extraction is 4-10 stages.
Optionally, the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent is 1 (1.5-1.7).
Optionally, the concentration of potassium in the sulphate leaching solution is greater than 40g/L.
Optionally, the concentration of potassium in the enriched liquid is less than or equal to 40g/L, the concentration of rubidium is greater than 100g/L, and the concentration of cesium is greater than 40g/L.
The application discloses a recovery method of potassium, rubidium and cesium in mixed alum, which comprises the steps of obtaining mixed alum, mixing the mixed alum with a causticizing agent for solid-phase reaction to obtain a mixed material, adding a leaching agent into the mixed material for leaching, and obtaining sulfate leaching liquid after impurity removal; the crystallization water carried by the mixed alum is utilized to promote the solid phase reaction, so that the utilization rate of the causticizing agent is improved, the impurity removal efficiency is improved, and the separation of aluminum element in the mixed alum is realized; freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate; the method comprises the steps of separating potassium sulfate by utilizing the solubility difference between potassium sulfate, rubidium salt and cesium salt in a freezing crystallization mode, re-mixing a freezing solution (mixed sulfate solution) with a mixed material for multiple leaching, concentrating rubidium and cesium in the mixed sulfate solution without evaporation, and carrying out multistage extraction on the obtained concentrated solution to collect a first organic phase with a first preset level and a second organic phase with a second preset level, wherein the first preset level is smaller than the second preset level; and then back-extracting the first organic phase to obtain cesium salt; performing back extraction on the second organic phase to obtain rubidium salt; the enriched rubidium and cesium solutions are separated by utilizing a solvent extraction mode, so that the extraction efficiency is improved, the investment of an extraction system is reduced, and the efficient recovery of potassium, rubidium and cesium in the mixed alum after lithium extraction from lepidolite is realized.
Drawings
FIG. 1 is a schematic flow chart of a method for recovering potassium, rubidium and cesium from mixed alum according to an embodiment of the present application;
fig. 2 is a process flow diagram of a method for recovering potassium, rubidium and cesium from mixed alum according to an embodiment of the present application.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
The lepidolite is an important mineral raw material for extracting lithium, and not only does the lepidolite comprise lithium, but also valuable metals such as potassium, rubidium and cesium, so that the comprehensive utilization of the valuable metals in the lepidolite is realized, the resource value is fully excavated, the production cost of lithium carbonate can be reduced, and the process technology economy is improved.
Two methods for recycling potassium, rubidium and cesium are commonly used in the conventional lithium extraction process of lepidolite; one is to recover an intermediate product form such as a mixed alum salt or a single alum salt, for example, by repeatedly dissolving the mixed alum salt or the single alum salt in a frozen state, the mixed alum salt or the single alum salt of potassium, rubidium and cesium is not further purified, and the mixed alum salt is difficult to directly use as a large-scale chemical product, so that high value-added utilization of valuable metals such as potassium, rubidium and cesium is difficult to realize; the other method is to recover by extraction, but the extraction system is huge due to the low concentration of rubidium and cesium and high concentration of potassium in the stock solution.
In view of this, the application provides a recovery method of potassium, rubidium and cesium in mixed alum, which comprises mixing mixed alum with causticizing agent for solid phase reaction to obtain mixed material, adding water into the mixed material for leaching, and removing impurities to obtain sulfate leaching solution; the crystallization water carried by the mixed alum is utilized to promote the solid phase reaction, so that the utilization rate of the causticizing agent is improved, the impurity removal efficiency is improved, and the separation of aluminum element in the mixed alum is realized; freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate; the method comprises the steps of separating potassium sulfate by utilizing the solubility difference between potassium sulfate, rubidium salt and cesium salt in a freezing crystallization mode, re-mixing a freezing solution (mixed sulfate solution) with a mixed material for multiple leaching, concentrating rubidium and cesium in the mixed sulfate solution without evaporation, and carrying out multistage extraction on the obtained concentrated solution to collect a first organic phase with a first preset level and a second organic phase with a second preset level, wherein the first preset level is smaller than the second preset level; and then back-extracting the first organic phase to obtain cesium salt; performing back extraction on the second organic phase to obtain rubidium salt; the enriched rubidium and cesium solutions are separated by utilizing a solvent extraction mode, so that the extraction efficiency is improved, the investment of an extraction system is reduced, and the efficient recovery of potassium, rubidium and cesium in the mixed alum after lithium extraction from lepidolite is realized.
An embodiment of the present invention provides a method for recovering potassium, rubidium and cesium from mixed alum, referring to fig. 1, the method for recovering potassium, rubidium and cesium from mixed alum includes:
s10, obtaining mixed alum;
in the embodiment, the byproduct mixed alum obtained after lithium extraction of lepidolite contains valuable metals such as potassium, rubidium, cesium and the like, so that the recovery application value is high; therefore, the by-product mixed alum obtained after lepidolite lithium extraction is used as a reaction raw material to obtain the mixed alum.
Optionally, the mixed alum can be mixed alum generated by freezing and crystallizing in the lithium extraction process, and then the mixed alum is frozen and crystallized into alum, so that the alum is separated from sodium elements in the solution before crystallization, and further the influence of high sodium content in the mixed alum on subsequent rubidium and cesium recovery is avoided.
Optionally, the step of obtaining the mixed alum may be obtaining the mixed alum generated by freezing and crystallizing in the lithium extraction process, and putting the mixed alum into a corresponding reaction kettle to perform the subsequent steps of solid phase reaction, leaching reaction and the like.
Step S20, mixing the mixed alum and a causticizing agent for solid phase reaction to obtain a mixed material, and adding a leaching agent into the mixed material for leaching to obtain sulfate leaching liquid;
mixing a byproduct mixed alum obtained after lithium extraction of lepidolite with a causticizing agent as a reaction raw material to perform solid phase reaction to obtain a mixed material; the crystallization water carried by the mixed alum is utilized to promote the solid phase reaction, so that the utilization rate of the causticizing agent is improved, the impurity removal efficiency is improved, and the separation of aluminum element in the mixed alum is realized; and adding a leaching agent into the mixed material for leaching, and performing solid-liquid separation after leaching to remove aluminum element in the mixed alum so as to obtain the sulfate leaching solution after impurity removal.
Alternatively, the leaching agent may be water and/or a recovery solvent in a recovery process of potassium, rubidium, cesium in mixed alum, e.g., sulfate leaching solution, mixed sulfate solution, raffinate, etc.
Optionally, performing solid-liquid separation after leaching to obtain a leaching solution and solid slag, wherein the leaching solution is sulfate leaching solution, namely mixed sulfate solution containing potassium, rubidium and cesium; the solid slag is aluminum-calcium slag, comprising: aluminum hydroxide and calcium sulfate, wherein the content of the aluminum hydroxide is 25.0-35.0%, and the content of the calcium sulfate is 60.0-75.0%.
Optionally, the main components in the mixed alum include: aluminum: 4.0 to 7.0 percent of potassium: 5.0 to 9.0 percent of rubidium: 0.2 to 1.0 percent of cesium: 0.1 to 0.5 percent.
In one possible embodiment, the reaction temperature of the solid phase reaction is 60 to 90 ℃.
In this example, if the temperature of the solid phase reaction is low, the solid phase reaction is difficult to occur, or the reaction rate is low; if the temperature of the solid phase reaction is higher, the mixed alum can be dissolved, and the energy consumption required by the high temperature is higher, so that the production cost is increased; thus, the reaction temperature of the solid phase reaction was determined to be 60 to 90 ℃.
Alternatively, the reaction temperature of the solid phase reaction may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or the like.
In one possible embodiment, the solid phase reaction time is from 0.5 to 5 hours.
In this embodiment, if the solid phase reaction time is short, it is difficult to fully react the mixed alum with the causticizing agent, so as to reduce the impurity removal rate; if the solid phase reaction time is longer, the impurity removal efficiency is not promoted, and the production time is increased; thus, the solid phase reaction time was determined to be 0.5 to 5 hours.
Alternatively, the solid phase reaction time may be 0.5h, 1h, 2h, 3h, 4h, 5h, etc.
In a possible embodiment, the causticizing agent comprises: at least one of calcium oxide and calcium hydroxide.
In a possible embodiment, the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of causticizing agent is 1 (1.5-1.7).
In this embodiment, if the amount of causticizing agent is low, it is difficult to react with impurities in the mixed alum sufficiently, which affects the impurity removal efficiency; if the content of the causticizing agent is higher, the alkali in the mixed solution is excessive in the subsequent leaching, the main impurity in the mixed alum is aluminum, and aluminum hydroxide precipitate generated by the reaction of the aluminum and the causticizing agent can further react to generate metaaluminate and then dissolve, so that the impurity removal rate is reduced; thus, the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent is determined to be 1 (1.5-1.7).
Alternatively, the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent may be 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, etc.
Alternatively, the amount of potassium species in the mixed alum can be measured by inductively coupled plasma emission spectroscopy; the amounts of rubidium and cesium species in the mixed alum can be measured by atomic absorption photometry.
In a possible embodiment, the leaching agent may be any one or more of water, a sulphate leach solution, a mixed sulphate solvent and a second raffinate.
In a possible embodiment, the concentration of potassium in the sulphate leaching solution is greater than 40g/L.
In this example, after the sulfate leaching solution is obtained, potassium sulfate in the sulfate solution can be separated by freeze crystallization; if the concentration of potassium in the sulfate leaching solution is low, the crystallization efficiency is low, and the production cost of the process is increased; thus, it was determined that the concentration of potassium in the sulfate leach was greater than 40g/L.
Optionally, after the sulfate leaching solution is obtained, whether the concentration of potassium in the sulfate leaching solution is greater than 40g/L can be judged; if yes, performing freezing crystallization on the sulfate leaching solution, and performing subsequent steps; if not, taking the sulfate leaching solution as a leaching agent, and returning to the step of executing the step of obtaining the mixed alum; for example, new mixed alum is obtained, and the new mixed alum is put into a corresponding reaction kettle again to carry out solid-phase reaction with newly added causticizing agent, so as to obtain a mixed material; adding the sulfate leaching solution obtained in the last time into the mixed material as a leaching agent for leaching to obtain new sulfate leaching solution, and judging whether the concentration of potassium in the new sulfate leaching solution is more than 40g/L; until the concentration of potassium in the sulfate leaching solution is greater than 40g/L, performing the freezing crystallization on the sulfate leaching solution, and performing the subsequent steps; realizing the enrichment of potassium in the sulfate leaching solution.
In a possible embodiment, the reaction temperature of the leaching is 60-90 ℃.
In this embodiment, if the temperature of the leaching reaction is low, the leaching reaction is difficult to occur, or the reaction rate is low; if the temperature of the leaching reaction is higher, the leaching of sulfate is not promoted, the required energy consumption is higher, and the production cost is increased; the reaction temperature of the leaching reaction was thus determined to be 60-90 ℃.
Alternatively, the reaction temperature of the leaching may be 60 ℃, 70 ℃, 80 ℃, 90 ℃, etc.
In one possible embodiment, the leaching reaction time is between 0.5 and 2 hours.
In this embodiment, if the leaching reaction time is short, the sulfate in the mixed material is difficult to fully leach, so that the leaching rate of the sulfate is reduced; if the leaching reaction time is longer, the leaching rate of sulfate is not promoted, and the production time is increased; thus, the leaching reaction time is determined to be 0.5-5 h.
Alternatively, the leaching reaction time may be 0.5h, 1h, 1.5h, 2h, etc.
Step S30, freezing and crystallizing the sulfate leaching solution, and obtaining mixed sulfate solution and potassium sulfate after solid-liquid separation;
freezing and crystallizing the sulfuric acid leaching solution, and performing solid-liquid separation to obtain potassium sulfate and potassium sulfate mother liquor, wherein the potassium sulfate mother liquor is mixed sulfate solution.
In a possible embodiment, the reaction temperature of the freeze crystallization is-5 to 25 ℃.
In this example, the reaction temperature of the freeze crystallization was determined according to the solubility of potassium sulfate at different temperatures; if the reaction temperature of the freezing crystallization is too high, the crystallization effect of potassium sulfate is poor; if the reaction temperature of the freeze crystallization is too low, rubidium and cesium in the sulfate solution may be precipitated, resulting in a decrease in the purity of potassium sulfate; thus, the reaction temperature of the freeze crystallization was determined to be-5 to 25 ℃.
Alternatively, the reaction temperature of the freeze crystallization may be-5 ℃,0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, or the like.
Step S40, enriching rubidium and cesium in the mixed sulfate solution to obtain an enriched solution;
and enriching rubidium and cesium in the mixed sulfate solution to obtain an enrichment solution.
In a possible embodiment, step S40, the step of enriching rubidium and cesium in the mixed sulfate solution includes:
and step S41, taking the mixed sulfate solution as a leaching agent when the concentration of the mixed sulfate solution does not reach a preset concentration threshold, and returning to execute the step of acquiring mixed alum until the concentration of the mixed sulfate solution reaches the preset concentration threshold, executing the step of carrying out multistage extraction on the enriched liquid, and collecting a first organic phase with a first preset level and a second organic phase with a second preset level.
And under the condition that the concentration of the mixed sulfate solution does not reach the preset concentration threshold, the mixed sulfate solution is used as a leaching agent if the concentration of rubidium and cesium in the mixed sulfate solution is lower, the step of obtaining the mixed alum is carried out in a returning mode, the mixed sulfate solution is mixed with the newly obtained mixed material for leaching until the concentration of the mixed sulfate solution reaches the preset concentration threshold, and the step of carrying out multistage extraction on the enriched solution and collecting a first organic phase with a first preset level and a second organic phase with a second preset level is carried out.
Alternatively, if the concentration of potassium in the mixed sulfate solution is less than or equal to 40g/L, the concentration of rubidium is less than or equal to 100g/L, and the concentration of cesium is less than or equal to 40g/L, indicating that the concentrations of rubidium and cesium in the mixed sulfate solution are low, the mixed sulfate solution is used as a leaching agent, and the step of obtaining mixed alum is performed back.
Step S50, carrying out multistage extraction on the enrichment liquid, and collecting a first organic phase with a first preset stage number and a second organic phase with a second preset stage number, wherein the first preset stage number is smaller than the second preset stage number;
carrying out multistage extraction on the enrichment liquid; according to the difference of binding capacities between cesium and rubidium and an extracting agent, the extracting agent extracts cesium and rubidium in sequence; and sequentially collecting a first organic phase with a first preset level and a second organic phase with a second preset level.
In a possible embodiment, the concentration of potassium in the enriched solution is less than or equal to 40g/L, the concentration of rubidium is greater than 100g/L, and the concentration of cesium is greater than 40g/L.
In this embodiment, the enrichment solution is mainly used for extracting rubidium and cesium, and although the extraction sequence of cesium and rubidium is earlier than that of potassium, potassium and the extractant also have certain affinity, so if the concentration of potassium in the enrichment solution is higher, the purity of the obtained cesium and rubidium can be reduced; if the concentration of rubidium and cesium in the enrichment solution is low, the extraction efficiency of rubidium and cesium is low; thus, it was determined that the concentration of potassium in the enriched solution was less than or equal to 40g/L, the concentration of rubidium was greater than 100g/L, and the concentration of cesium was greater than 40g/L.
In a possible embodiment, the extractant used for the multistage extraction comprises: at least one of 4-sec-butyl-2 (α -methylbenzyl) phenol and 4-tert-butyl-2 (α -methylbenzyl) phenol.
In a possible embodiment, the diluents used for the multistage extraction include: sulfonated kerosene;
in a possible embodiment, the extraction stages of the multistage extraction are 4 to 10 stages.
In this embodiment, the purpose of the multistage extraction is to increase the concentration of target substances, i.e., rubidium and cesium, as much as possible; if the extraction level is too low, the extraction efficiency is low; if the extraction level is too high, the dosage of the extractant is increased, and the process cost is increased; therefore, the extraction stage number of the multistage extraction is determined to be 4-10 stages.
Alternatively, the extraction stages of the multi-stage extraction may be 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages, 10 stages, etc.
The extraction level of the multi-stage extraction is 6 stages, and the first preset level is 3, namely 3 times of extraction are carried out; the second preset stage number is 6, namely 3 times of extraction are carried out after 3 times of extraction are carried out, and then organic phase after the 6 th extraction is collected.
Optionally, adding an extractant and a diluent into the enriched liquid to perform multistage extraction of a first preset stage number, and separating to obtain a first organic phase and a first raffinate; and then continuously adding an extractant and a diluent into the first raffinate to continuously perform multistage extraction until the extraction stage number is a second preset stage number, and separating to obtain a second organic phase and a second raffinate.
Optionally, adding alkali into the enrichment solution to adjust the pH value, and performing multistage extraction on the enrichment solution after adjusting the pH value; the extraction effect of the extractant used in the multistage extraction under the alkaline condition is better, so that the pH value is adjusted to be 10-13 by adding alkali into the enrichment solution.
Optionally, adding alkali into the first raffinate to adjust the pH value, and performing multistage extraction on the first raffinate after adjusting the pH value; since the extractant used in the multistage extraction has better extraction effect under alkaline condition, alkali is added into the first raffinate to adjust the pH value to 10-13.
Optionally, after the step of performing multistage extraction on the enriched liquid in step S50, the method further includes:
step S51, collecting raffinate after the extraction of the second preset level;
and step S52, taking the raffinate as the leaching agent.
Extracting the enriched liquid in a second preset stage number, separating to obtain a second organic phase and raffinate (second raffinate), and further mixing the raffinate (second raffinate) serving as the leaching agent with the mixed material again to perform leaching and subsequent treatment; the recycling of the reaction products is realized.
Step S60, carrying out back extraction on the first organic phase to obtain cesium salt;
the first organic phase and the stripping agent are mixed for stripping, and after separation, an aqueous phase is obtained, and the aqueous phase is evaporated and crystallized to obtain cesium salt.
In a possible embodiment, the stripping agent comprises: at least one of sulfuric acid, hydrochloric acid and nitric acid. The metal salt (cesium salt or rubidium salt) obtained after back extraction is the corresponding metal salt of the acid radical of the used back extractant; for example, the stripping agent is sulfuric acid, and the metal salt is sulfate; the back extractant is nitric acid, and the obtained metal salt is nitrate; the back extractant is hydrochloric acid, and the obtained metal salt is chloride.
Optionally, the concentration of the first stripping agent is 0.1-2 mol/L; for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, etc.
In this embodiment, since the extraction efficiency of the extractant in the alkaline environment is higher, and the stripping efficiency of the stripper in the acidic environment is higher during stripping, the pH value in the first organic phase is adjusted by controlling the concentration of the stripper; thus, the concentration of the first stripping agent was determined to be 0.1 to 2mol/L.
Optionally, in performing the multistage extraction, the volume ratio between the enrichment liquid, the extractant and the diluent is (0.8-1.5): (0.1-0.6): (0.4-0.8).
Optionally, in performing the multistage extraction, the volume ratio between the first raffinate, the extractant and the diluent is (0.8-1): (0.5-1.2): (0.8-1.9).
In this embodiment, the more extractant is, the extraction effect can be improved, but the more extractant is used, the more power cost and energy consumption for recovering the subsequent extractant are increased, and the process cost is increased; the diluent has the functions of reducing the density and viscosity of the organic phase, improving the phase separation performance, reducing the loss of the extractant and regulating the concentration of the extractant in the organic phase so as to achieve ideal extraction rate and extraction selectivity; therefore, an excessive amount of diluent may result in a reduced content of extractant, reducing extraction efficiency; too little diluent can increase the density and viscosity of the organic phase and reduce the extraction efficiency; thus, the volume ratio between the enrichment liquid, the extractant and the diluent is determined to be (0.8-1.5): (0.1-0.6): (0.4 to 0.8); the volume ratio of the first raffinate to the extractant to the diluent is (0.8-1): (0.5-1.2): (0.8-1.9).
Alternatively, the volume ratio between the enrichment fluid, extractant and diluent may be (0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5): (0.1, 0.2, 0.3, 0.4, 0.5, 0.6): (0.4, 0.5, 0.6, 0.7, 0.8) or the like.
Alternatively, the volume ratio between the first raffinate, the extractant and the diluent may be (0.8, 0.9, 1): (0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2): (0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9) or the like.
Step S70, carrying out back extraction on the second organic phase to obtain rubidium salt;
and mixing the second organic phase with a stripping agent to carry out stripping, separating to obtain an aqueous phase, and carrying out evaporative crystallization on the aqueous phase to obtain rubidium salt.
In a possible embodiment, the second stripping agent comprises: at least one of sulfuric acid, hydrochloric acid and nitric acid.
Optionally, the concentration of the second stripping agent is 0.1-2 mol/L; for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.3mol/L, etc.
In this embodiment, since the extraction efficiency of the extractant in the alkaline environment is higher, and the stripping efficiency of the stripper in the acidic environment is higher during stripping, the pH value in the second organic phase is adjusted by controlling the concentration of the stripper; thus, the concentration of the first stripping agent was determined to be 0.1 to 2mol/L.
In the embodiment, mixed alum is obtained, mixed alum and causticizing agent are mixed for solid phase reaction to obtain a mixed material, leaching agent is added into the mixed material for leaching, and sulfate leaching liquid is obtained after impurity removal; the crystallization water carried by the mixed alum is utilized to promote the solid phase reaction, so that the utilization rate of the causticizing agent is improved, the impurity removal efficiency is improved, and the separation of aluminum element in the mixed alum is realized; freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate; the method comprises the steps of separating potassium sulfate by utilizing the solubility difference between potassium sulfate, rubidium salt and cesium salt in a freezing crystallization mode, re-mixing a freezing solution (mixed sulfate solution) with a mixed material for multiple leaching, concentrating rubidium and cesium in the mixed sulfate solution without evaporation, and carrying out multistage extraction on the obtained concentrated solution to collect a first organic phase with a first preset level and a second organic phase with a second preset level, wherein the first preset level is smaller than the second preset level; and then back-extracting the first organic phase to obtain cesium salt; performing back extraction on the second organic phase to obtain rubidium salt; the enriched rubidium and cesium solutions are separated by utilizing a solvent extraction mode, so that the extraction efficiency is improved, the investment of an extraction system is reduced, and the efficient recovery of potassium, rubidium and cesium in the mixed alum after lithium extraction from lepidolite is realized.
Further, based on the first embodiment, a more complete embodiment of the method for recovering potassium, rubidium and cesium in the mixed alum is provided, referring to fig. 2, the mixed alum is obtained, and the mixed alum and the causticizing agent are mixed for solid phase reaction, so as to obtain a mixed material. Adding a leaching agent into the mixed material for leaching, wherein the leaching agent can be at least one of water, sulfate leaching liquid and mixed sulfate solution; filtering to remove solid slag of aluminum and calcium to obtain sulfate leaching solution. If the concentration of potassium in the sulfate leaching solution is less than or equal to 40g/L, the sulfate leaching solution is taken as a leaching agent, mixed alum is obtained again, a new mixed material is obtained, and then the sulfate leaching solution taken as the leaching agent is added into the new mixed material for reaction leaching until the concentration of potassium in the sulfate leaching solution is more than 40g/L, so that the enrichment of potassium in the sulfate leaching solution is realized. And then freezing and crystallizing the sulfate leaching solution, and removing filter residues through solid-liquid separation to obtain a mixed sulfate solution. And washing, filtering and drying filter residues to obtain potassium sulfate. Judging whether the mixed sulfate solution satisfies that the concentration of potassium is less than or equal to 40g/L, the concentration of rubidium is more than 100g/L, and the concentration of cesium is more than 40g/L; if not, enriching rubidium and cesium in the mixed sulfate solution, and re-reacting and leaching the mixed sulfate solution with the mixed material by taking the mixed sulfate solution as a leaching agent until the mixed sulfate solution meets the conditions that the concentration of potassium is less than or equal to 40g/L, the concentration of rubidium is more than 100g/L, and the concentration of cesium is more than 40g/L, so as to obtain an enriched solution. And adding an extractant and a diluent into the enrichment liquid to perform multistage extraction to obtain a first organic phase with a first preset stage number and a first raffinate. And adding a stripping agent into the first organic phase for stripping, collecting the water phase, and evaporating and crystallizing to obtain cesium salt. And (3) further adding an extractant and a diluent into the first raffinate, and performing multistage extraction again to obtain a second organic phase and a second raffinate. The second raffinate can be used as a leaching agent to react and leach with the mixed material again, so that the recycling of the reaction product is realized. Adding a stripping agent into the second organic phase for stripping, collecting the water phase, and evaporating and crystallizing to obtain rubidium salt; realizing the recovery of potassium, rubidium and cesium in the mixed alum.
In order that the details and operation of the embodiments of the present application may be clearly understood by those skilled in the art, and that the improved performance of the recovery method of potassium, rubidium and cesium in the mixed alum of the embodiments of the present application may be significantly reflected, the following examples are given to illustrate the above technical solutions.
Example 1
1) Obtaining mixed alum generated by lithium extraction of lepidolite, mixing 500g of mixed alum with 80g of calcium oxide, and carrying out solid phase reaction for 1h at 70 ℃ to obtain a mixed material; wherein, the potassium content in the mixed alum is 6.5 wt%, the rubidium content is 0.4 wt%, and the cesium content is 0.25 wt%; the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent is 1:1.7;
2) Adding 1500g of water into the mixed material, leaching in a leaching reaction kettle, reacting for 1h at 80 ℃ and then carrying out solid-liquid separation to obtain aluminum-calcium solid slag containing aluminum hydroxide and calcium sulfate and sulfate leaching liquid containing potassium, rubidium and cesium, wherein the potassium content in the sulfate leaching liquid is 21g/L, the rubidium content is 1.3g/L and the cesium content is 0.8g/L;
3) Re-executing the step 1) to obtain a mixed material, and returning the sulfate leaching solution obtained in the step 2) to the leaching reaction kettle in the step 2) for leaching for multiple times until the potassium content in the sulfate leaching solution is 50g/L, the rubidium content is 3g/L and the cesium content is 1.9g/L;
4) Freezing and crystallizing the sulfate leaching solution at 15 ℃, and performing solid-liquid separation after the freezing and crystallizing are completed to obtain potassium sulfate crystals and mixed sulfate solution, wherein the potassium content of the mixed sulfate solution is 30g/L, the rubidium content is 3.2g/L and the cesium content is 2.1g/L;
5) Re-executing the step 1) to obtain a mixed material, and returning the mixed sulfate solution obtained in the step 4) to the leaching reaction kettle in the step 2) for leaching for multiple times, so as to further enrich rubidium and cesium in the mixed sulfate solution until the potassium content in the mixed sulfate solution is 20g/L, the rubidium content is 110g/L and the cesium content is 50g/L, thereby obtaining an enrichment solution;
6) After the pH of the enrichment solution is adjusted to 11, the enrichment solution is uniformly mixed with 4-sec-butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, wherein the volume ratio of the enrichment solution to the 4-sec-butyl-2 (alpha-methylbenzyl) phenol to the sulfonated kerosene is 1:0.2:0.5; shaking thoroughly, and extracting for 3 times; separating to obtain a first organic phase and a first raffinate;
7) Adding sulfuric acid solution accounting for 0.1mol/L of one fourth of the volume of the first organic phase into the first organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain cesium sulfate;
8) After the pH value of the first raffinate obtained in the step 6) is regulated to 11, the first raffinate, 4-sec-butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene are uniformly mixed, the volume ratio of the first raffinate, the 4-sec-butyl-2 (alpha-methylbenzyl) phenol and the sulfonated kerosene is 1:0.8:1.2, the first raffinate, the 4-sec-butyl-2 (alpha-methylbenzyl) phenol and the sulfonated kerosene are fully shaken, extraction is carried out for 3 times, and a second organic phase and a second raffinate are obtained through separation;
9) Adding sulfuric acid solution accounting for 0.1mol/L of one fourth of the volume of the second organic phase into the second organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain rubidium sulfate;
10 After the steps, the recovery rates of potassium, rubidium and cesium respectively reach 88%, 86% and 82%. Wherein, the purity of the potassium sulfate, the rubidium sulfate and the cesium sulfate reaches 99.0 percent.
Example 2
1) Obtaining mixed alum generated by lithium extraction of lepidolite, mixing 500g of mixed alum with 86g of calcium oxide, and carrying out solid phase reaction for 5 hours at 60 ℃ to obtain a mixed material; wherein, the potassium content in the mixed alum is 7.5 wt%, the rubidium content is 0.9 wt%, and the cesium content is 0.4 wt%; the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent is 1:1.5;
2) Adding 1500g of water into the mixed material and leaching the mixed material in a leaching reaction kettle, reacting for 0.5h at 90 ℃ and then carrying out solid-liquid separation to obtain aluminum-calcium solid slag containing aluminum hydroxide and calcium sulfate and sulfate leaching liquid containing potassium, rubidium and cesium, wherein the potassium content in the sulfate leaching liquid is 23.8g/L, the rubidium content is 2.8g/L and the cesium content is 1.3g/L;
3) Re-executing the step 1) to obtain a mixed material, and returning the sulfate leaching solution obtained in the step 2) to the leaching reaction kettle in the step 2) for leaching for multiple times until the potassium content in the sulfate leaching solution is 60g/L, the rubidium content is 7.9g/L and the cesium content is 3.6g/L;
4) Freezing and crystallizing the sulfate leaching solution at the temperature of minus 5 ℃, and carrying out solid-liquid separation after the freezing and crystallizing are finished to obtain potassium sulfate crystals and mixed sulfate solution, wherein the potassium content of the mixed sulfate solution is 30g/L, the rubidium content is 8.2g/L, and the cesium content is 3.8g/L;
5) Re-executing the step 1) to obtain a mixed material, and returning the mixed sulfate solution obtained in the step 4) to the leaching reaction kettle in the step 2) for leaching for multiple times, so as to further enrich rubidium and cesium in the mixed sulfate solution until the potassium content in the mixed sulfate solution is 20g/L, the rubidium content is 110g/L and the cesium content is 50g/L, thereby obtaining an enrichment solution;
6) After the pH value of the enrichment solution is adjusted to 11, the enrichment solution is uniformly mixed with 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, wherein the volume ratio of the enrichment solution to the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol to the sulfonated kerosene is 1:0.1:0.4; shaking thoroughly, and extracting for 2 times; separating to obtain a first organic phase and a first raffinate;
7) Adding hydrochloric acid solution accounting for 0.1mol/L of one fourth of the volume of the first organic phase into the first organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain cesium chloride;
8) After the pH value of the first raffinate obtained in the step 6) is regulated to 11, the first raffinate is uniformly mixed with 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, the volume ratio of the first raffinate to the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol to the sulfonated kerosene is 1:1.2:1.8, and the first raffinate is fully shaken for 2 times, extracted and separated to obtain a second organic phase and a second raffinate;
9) Adding hydrochloric acid solution accounting for 0.1mol/L of one fourth of the volume of the second organic phase into the second organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain rubidium chloride;
10 After the steps, the recovery rates of potassium, rubidium and cesium reach 86%, 88% and 84%, respectively. Wherein, the purity of the potassium sulfate, the rubidium chloride and the cesium chloride reaches 99.0 percent.
Example 3
1) Obtaining mixed alum generated by lithium extraction of lepidolite, mixing 500g of mixed alum with 75g of calcium oxide, and carrying out solid phase reaction for 0.5h at 90 ℃ to obtain a mixed material; wherein, the potassium content in the mixed alum is 6.5 wt%, the rubidium content is 0.4 wt%, and the cesium content is 0.25 wt%; the ratio of the total amount of potassium, rubidium and cesium in the mixed alum to the amount of the causticizing agent is 1:1.6;
2) Adding 1500g of water into the mixed material, leaching in a leaching reaction kettle, reacting for 2 hours at 60 ℃ and then carrying out solid-liquid separation to obtain aluminum-calcium solid slag containing aluminum hydroxide and calcium sulfate and sulfate leaching liquid containing potassium, rubidium and cesium, wherein the potassium content in the sulfate leaching liquid is 21g/L, the rubidium content is 1.3g/L and the cesium content is 0.8g/L;
3) Re-executing the step 1) to obtain a mixed material, and returning the sulfate leaching solution obtained in the step 2) to the leaching reaction kettle in the step 2) for leaching for multiple times until the potassium content in the sulfate leaching solution is 41g/L, the rubidium content is 2.6g/L and the cesium content is 1.6g/L;
4) Freezing and crystallizing the sulfate leaching solution at 25 ℃, and performing solid-liquid separation after the freezing and crystallizing are completed to obtain potassium sulfate crystals and mixed sulfate solution, wherein the potassium content of the mixed sulfate solution is 30g/L, the rubidium content is 2.7g/L and the cesium content is 1.8g/L;
5) Re-executing the step 1) to obtain a mixed material, returning the mixed sulfate solution obtained in the step 4) to the leaching reaction kettle in the step 2) for leaching for multiple times, and further enriching rubidium and cesium in the mixed sulfate solution until the potassium content in the mixed sulfate solution is 35g/L, the rubidium content is 101g/L and the cesium content is 41g/L, wherein the solution is an enriched solution;
6) After the pH of the enrichment solution is adjusted to 13, the enrichment solution is uniformly mixed with 4-sec-butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, wherein the volume ratio of the enrichment solution to the 4-sec-butyl-2 (alpha-methylbenzyl) phenol to the sulfonated kerosene is 1.2:0.5:0.7; shaking thoroughly, and extracting for 5 times; separating to obtain a first organic phase and a first raffinate;
7) Adding 2mol/L nitric acid solution accounting for one fourth of the volume of the first organic phase into the first organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain cesium nitrate;
8) After the pH value of the first raffinate obtained in the step 6) is regulated to 11, the first raffinate, 4-sec-butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene are uniformly mixed, the volume ratio of the first raffinate, the 4-sec-butyl-2 (alpha-methylbenzyl) phenol and the sulfonated kerosene is 1:0.6:1.2, the first raffinate, the 4-sec-butyl-2 (alpha-methylbenzyl) phenol and the sulfonated kerosene are fully shaken, extraction is carried out for 5 times, and a second organic phase and a second raffinate are obtained through separation;
9) Adding 2mol/L nitric acid solution accounting for one fourth of the volume of the second organic phase into the second organic phase for back extraction, and evaporating and crystallizing the separated water phase to obtain rubidium nitrate;
10 After the steps, the recovery rates of potassium, rubidium and cesium reach 89%, 88% and 85% respectively. Wherein, the purity of the potassium sulfate, the rubidium nitrate and the cesium nitrate reaches 99.0 percent.
Comparative example 1
The experimental procedure and raw material ratios were the same as in example 1, except that: omitting the step of solid-phase reaction for 1h at 70 ℃ in the step 1) to obtain a mixed material, directly mixing the mixed alum, calcium oxide and water for liquid-phase reaction, and returning the mixed sulfate solution to the leaching reaction kettle for direct mixing with the mixed alum and calcium oxide when enriching rubidium and cesium in the mixed sulfate solution, and executing the subsequent steps.
After the steps, the recovery rates of potassium, rubidium and cesium are respectively 70%, 65% and 60%.
Comparative example 2
The experimental procedure and raw material ratios were the same as in example 2, except that: the extraction steps in steps 6) and 8) are carried out only once.
After the steps, the recovery rates of potassium, rubidium and cesium are 85%, 75% and 70% respectively.
Comparative example 3
The experimental procedure and raw material ratios were the same as in example 2, except that: after the mixed sulfate solution is obtained in the step 4), the step 6) is directly executed without enriching rubidium and cesium in the mixed sulfate solution, wherein the potassium content in the mixed sulfate solution is 30g/L, the rubidium content is 3.3g/L and the cesium content is 2.1g/L.
After the steps, the recovery rates of potassium, rubidium and cesium are 85%, 75% and 70% respectively.
According to the above examples 1 to 3 and comparative examples 1 to 3, the recovery methods of potassium, rubidium and cesium in the mixed alum of the present application are improved compared with those of comparative examples 1 to 3; the investment of an extraction system can be reduced, and the high-efficiency recovery of potassium, rubidium and cesium in the mixed alum after lithium extraction from lepidolite is realized.
The foregoing is merely a preferred embodiment of the present application and is not intended to limit the scope of the patent application, but rather, various modifications and variations can be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the scope of the patent protection of the present application.
Claims (10)
1. The method for recovering potassium, rubidium and cesium in the mixed alum is characterized in that the mixed alum is a byproduct after lithium extraction from lepidolite, and the method comprises the following steps:
obtaining mixed alum;
mixing the mixed alum and a causticizing agent for solid phase reaction to obtain a mixed material, and adding a leaching agent into the mixed material for leaching to obtain sulfate leaching liquid;
freezing and crystallizing the sulfate leaching solution, and carrying out solid-liquid separation to obtain mixed sulfate solution and potassium sulfate;
enriching rubidium and cesium in the mixed sulfate solution to obtain an enrichment solution;
carrying out multistage extraction on the enrichment liquid, and collecting a first organic phase with a first preset stage number and a second organic phase with a second preset stage number, wherein the first preset stage number is smaller than the second preset stage number;
back-extracting the first organic phase to obtain cesium salt;
and carrying out back extraction on the second organic phase to obtain rubidium salt.
2. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein said step of enriching rubidium and cesium in said mixed sulfate solution comprises:
and under the condition that the concentration of the mixed sulfate solution does not reach a preset concentration threshold, taking the mixed sulfate solution as a leaching agent, and returning to execute the step of acquiring the mixed alum until the concentration of the mixed sulfate solution reaches the preset concentration threshold, executing the step of carrying out multistage extraction on the enriched liquid, and collecting a first organic phase with a first preset level and a second organic phase with a second preset level.
3. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein the reaction temperature of the solid phase reaction is 60-90 ℃ and the solid phase reaction time is 0.5-5 h;
and/or, the causticizing agent comprises: at least one of calcium oxide and calcium hydroxide.
4. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein the leaching reaction temperature is 60-90 ℃ and the leaching reaction time is 0.5-2 h;
and/or the reaction temperature of the freezing crystallization is-5-25 ℃.
5. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein after said step of multi-stage extraction of said enriched liquid, further comprising:
collecting raffinate after the second predetermined number of extractions;
the raffinate is used as the leaching agent.
6. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein said extracting agent used in said multistage extraction comprises: at least one of 4-sec-butyl-2 (α -methylbenzyl) phenol and 4-tert-butyl-2 (α -methylbenzyl) phenol;
and/or the diluents used for the multistage extraction include: sulfonated kerosene;
and/or, the stripping agent used for the stripping comprises: at least one of sulfuric acid, hydrochloric acid and nitric acid.
7. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein said multistage extraction has an extraction stage number of 4 to 10.
8. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein the ratio of the total amount of potassium, rubidium and cesium in said mixed alum to the amount of said causticizing agent is 1 (1.5-1.7).
9. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein the concentration of potassium in said sulfate leaching solution is greater than 40g/L.
10. The method for recovering potassium, rubidium and cesium from mixed alum according to claim 1, wherein the concentration of potassium in said enriched solution is less than or equal to 40g/L, the concentration of rubidium is greater than 100g/L, and the concentration of cesium is greater than 40g/L.
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