CN117187598A - Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system - Google Patents
Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system Download PDFInfo
- Publication number
- CN117187598A CN117187598A CN202311035091.8A CN202311035091A CN117187598A CN 117187598 A CN117187598 A CN 117187598A CN 202311035091 A CN202311035091 A CN 202311035091A CN 117187598 A CN117187598 A CN 117187598A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- chamber
- resin
- electrodialysis
- liquid storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 110
- 239000011733 molybdenum Substances 0.000 title claims abstract description 110
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 52
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000004576 sand Substances 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 90
- 229920005989 resin Polymers 0.000 claims abstract description 90
- 238000002386 leaching Methods 0.000 claims abstract description 55
- 238000000605 extraction Methods 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- -1 molybdate anions Chemical class 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000013508 migration Methods 0.000 claims abstract description 12
- 230000005012 migration Effects 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005684 electric field Effects 0.000 claims abstract description 6
- 230000007646 directional migration Effects 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 51
- 238000003860 storage Methods 0.000 claims description 44
- 239000003957 anion exchange resin Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000003480 eluent Substances 0.000 claims description 26
- 238000011084 recovery Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- 230000005496 eutectics Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000000374 eutectic mixture Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 150000005838 radical anions Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000001962 electrophoresis Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000000523 sample Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000005370 electroosmosis Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- KTEXACXVPZFITO-UHFFFAOYSA-N molybdenum uranium Chemical compound [Mo].[U] KTEXACXVPZFITO-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for extracting molybdenum from lead-zinc tailing sand and an electrodialysis system, and belongs to the technical field of metal production by an electrophoresis method or an electrolysis method. In the method, the electric field force is utilized to promote the directional migration and separation of anions and cations of the leaching solution, the migration of silicic acid molecules in the leaching solution is blocked by controlling the selective permeability, the adsorption enrichment of molybdate anions is realized in the electrodialysis process, and meanwhile, the migration of molybdic acid molecules is inhibited; the process has simple operation, high extraction efficiency and strong cation interference resistance. The invention also provides an electrodialysis system used in the matching method, which adopts a single-stage four-chamber architecture, not only can realize the high-efficiency separation of silicon and molybdenum in the high-silicon low-molybdenum solution, but also can simultaneously realize the high-efficiency enrichment of molybdic acid radicals in the low-molybdenum solution, effectively eliminates the interference of cations such as calcium, magnesium, iron and the like, can effectively prevent and control the continuous migration of molybdenum entering the resin chamber to the electrode anode chamber, and strengthens the capacity of enriching molybdenum in the resin chamber.
Description
Technical Field
The invention relates to the technical field of metal production by an electrophoresis method or an electrolysis method, in particular to a method for extracting molybdenum from lead-zinc tailing sand and an electrodialysis system.
Background
Molybdenum is an extremely important and scarce strategic metal and has wide application in the fields of iron and steel, nuclear energy, petroleum processing, ammonia synthesis and the like, environmental protection, aerospace and the like. However, molybdenum resources are extremely lean, with an average content in the crust of the earth of only 0.001%. Therefore, the extraction and recovery of molybdenum from solid wastes such as minerals, catalysts, spent fuel and the like has important strategic significance.
Current major methods for leaching molybdenum from solid wastes include precipitation (e.g., CN112662874A and CN115747530 a), ion exchange adsorption (e.g., CN113215419A, CN114438320a and CN111876617 a), extraction (e.g., CN109763003A, CN114686706a and CN 115522052A), and the like. Since precipitation requires a sufficient amount to be of separation significance, it is generally suitable for the extraction of molybdenum from enriched liquids at higher concentrations. The ion exchange adsorption method and the extraction method can realize the enrichment of molybdenum, but the extraction method has higher cost of the extractant. The ion exchange adsorption method has higher enrichment efficiency and convenient and simple operation, so the method is more suitable for enriching molybdenum ions with smaller concentration and has higher cycle rate. However, the use of extraction and ion exchange alone for solutions with higher acidity, more heavy metal impurities and lower molybdenum content is not effective for the recovery of molybdenum (Deng Pan. Research on the extraction of molybdenum from arsenite reduction final solution containing low concentration of molybdenum [ D ]. University of jiang xi university, 2013.).
The alkali-melting anions of the lead-zinc tailing mainly comprise silicate and carbonate, and are converted into silicic acid and carbonic acid or CO after acidification 2 Escape in the air. The cationic component in the acidified solution is more complex, and the heavy metal ion types are more. The leached molybdic acid radicals usually exist in a weak acid form under the weak acid condition, and although the adsorption of molybdenum can be realized by using anion exchange resin, for tailing leaching liquor with a large amount of silicate radicals, the performance of the ion exchange resin is greatly influenced by silicic acid pollution under the weak acid condition, so that the direct application of an ion exchange method for enriching molybdenum is limited, and in addition, the adsorption capacity of macroporous anion resin to molybdenum is reduced along with the reduction of pH, so that the application in the field is further limited.
Chinese patent document (CN 110104688A) discloses a molybdenum removal method for ammonium tungstate feed liquid, which is based on WDA918 resin with high adsorption capacity, but for low-concentration molybdenum solutionThe adsorption effect is poor, while the 201 multiplied by 7 resin has low adsorption capacity, is easy to leak, and has stable adsorption effect on low-concentration molybdenum solution. Based on the characteristics, the invention adds MoO 4 2- Sulfur to MoS 4 2- Adsorption of high concentration MoS with WDA918 resin 4 2- Adsorption of low concentration MoS with 201X 7 resin 4 2- 。
Chinese patent literature (CN 103866122A) discloses a uranium molybdenum ore microorganism leaching and uranium molybdenum enrichment and separation method, wherein 201X 7 resin is adopted to enrich uranium molybdenum and then the uranium molybdenum is eluted in a cascade manner, the uranium molybdenum recovery rate is more than 80%, and the 201X 7 resin can be used for enriching molybdenum.
Electrodialysis is widely applied in the field of valuable metal recovery, but has not been applied in molybdenum extraction, and electrodialysis has good separation performance on anions and cations, but is greatly affected by ion composition of a sample solution, so that the separation method is reasonably designed based on the characteristics of components of leaching liquor in application. The single stage electrodialysis enrichment capacity is relatively low, often achieved using multi-stage extraction. In addition, if molybdate anions are directly migrated to the anode chamber under the action of electric field force, the recycling of the anode chamber solution can be influenced, and the continuous enhancement of the acidity of the anode chamber also can influence the adsorption efficiency of molybdenum, so that the interference of the electrolyte solution on the purity of molybdenum is greatly enhanced, and the complexity of a separation process is increased.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, there is provided a method for extracting molybdenum from lead-zinc tailings with high extraction efficiency and strong resistance to cationic interference, comprising the steps of:
leaching the lead-zinc tailings to obtain leaching liquor containing silicate ions and molybdate ions; extracting the leaching liquor by electrodialysis, and promoting the directional migration and separation of anions and cations of the leaching liquor by electric field force; controlling the selective permeability to block migration of silicic acid molecules in the leaching solution; the adsorption enrichment of molybdate anions is realized in the electrodialysis process, and meanwhile, the migration of molybdate molecules is inhibited; and (3) eluting the molybdenum acid radical anions after adsorption and enrichment, and recovering eluent to finish the extraction of molybdenum.
Preferably, the method for leaching lead-zinc tailings comprises the following steps: eutectic melting lead-zinc tailings and alkaline substances, and cooling to form a eutectic mixture; the eutectic mixture is acidified and insoluble substances are separated to obtain leaching liquor.
Further preferably, the mass ratio of the eutectic lead-zinc tailings to the alkaline substance is 1:0.3 to 1; the eutectic temperature is 400-680 ℃.
Still further, the alkaline substance includes at least one of sodium hydroxide, potassium hydroxide, and sodium carbonate.
Further preferably, the pH of the resulting leaching solution after the acidification treatment is between 2 and 3.
Further, hydrochloric acid or sulfuric acid is adopted for the acidification treatment.
The concentration of silicate ions and molybdate ions in the leaching solution obtained by leaching the lead-zinc tailings under the preferred condition is higher, and the leaching process of the lead-zinc tailings is not limited to the form of the preferred method on the basis of meeting the requirement of the method for extracting molybdenum.
Preferably, the electrodialysis has a single-stage potential difference of 5-20V and a current density of 250-1500A/m 2 Electrodialysis time is 2-5 h.
Preferably, the concentration of the electrolyte of the anode and cathode of the electrodialysis is 0.01-0.2 mol/L.
Further preferably, the electrolyte of the anode and the cathode of the electrodialysis adopts sodium chloride aqueous solution or sodium sulfate aqueous solution.
Preferably, the adsorption enrichment is performed by 201 x 7 strongly basic type I anion exchange resin.
Further preferably, the molybdate anions are eluted by adopting sodium hydroxide aqueous solution after adsorption enrichment, the concentration of the molybdate anions is 0.1 to 1mol/L, and the eluent of 1 to 6BV is recovered.
In a second aspect of the invention there is provided an electrodialysis system for extracting molybdenum from lead zinc tailings sand for use in the electrodialysis process of the first aspect of the invention for extracting molybdenum:
the electrodialysis system comprises an electrodialysis device, a liquid storage system, a regeneration system and a recovery system;
the electrodialysis device consists of a single-stage or multi-stage electrodialysis unit; the electrodialysis unit sequentially comprises an electrode positive chamber, a resin chamber, a sample chamber and an electrode negative chamber, wherein each anode in the electrodialysis unit is connected in parallel and is connected with the positive electrode of a power supply, and each cathode in the electrodialysis unit is connected in parallel and is connected with the negative electrode of the power supply; the electrode positive chamber, the resin chamber and the sample chamber are separated by an acid-base resistant homogeneous anion exchange membrane, and the sample chamber and the electrode negative chamber are separated by an acid-base resistant homogeneous cation exchange membrane for controlling the selective permeability of electrodialysis; the resin chamber contains anion exchange resin for adsorbing molybdenum;
the liquid storage system comprises a leaching liquid storage tank, a first liquid storage tank and a second liquid storage tank; the leaching solution is stored in a leaching solution liquid storage tank and is used for conveying the leaching solution to a sample chamber of the first-stage electrodialysis unit; electrolyte used for electrodialysis is reserved in a first liquid storage tank and used for conveying electrolyte for an electrode positive chamber and an electrode negative chamber; the second liquid storage tank is used for conveying the acid liquor to the resin chamber to keep the acidity unchanged;
the regeneration system comprises a resin regeneration tank and a resin column; the anion exchange resin in the resin chamber is stored in a resin regeneration tank after being adsorbed, and then alkali liquor is added for elution to obtain eluent and regenerated anion exchange resin; the resin column contains anion exchange resin, the low-concentration molybdenum which is not adsorbed by the resin chamber in the electrodialysis device is adsorbed, and eluent and regenerated anion exchange resin can be obtained after elution;
the recovery system comprises a liquid outlet box and a molybdenum recovery box; the solution flowing out of the sample chamber of the electrodialysis device is stored in a liquid outlet box and can be used for recycling white carbon black and iron; and storing the eluent obtained by eluting the anion exchange resin in a molybdenum recovery box to finish the extraction of molybdenum, and preparing a molybdenum product.
Preferably, in the resin chamber, the solid-liquid volume ratio of the anion exchange resin is 4:3 to 6:1.
preferably, in the second liquid storage tank, the pH value of the acid liquid is 1-2.5.
Further preferably, the acid solution is sulfuric acid or hydrochloric acid.
Based on the process and the system provided by the first aspect and the second aspect of the invention, the design thought and the extraction process of the invention are as follows:
the invention uses anion-cation exchange membrane in electrodialysis method to block migration of silicic acid molecules, uses electric field force to promote directional migration and separation of anions and cations, and realizes adsorption and enrichment of condensed molybdate anions (Mo) by 201X 7 strong-alkaline I-type anion exchange resin by regulating and controlling pH value 7 O 24 6- Or H 2 Mo 7 O 24 4- ) Meanwhile, the migration of molecules existing in molybdic acid to the electrode positive chamber is inhibited, the migration of anions of strong acid in the resin chamber to the electrode positive chamber is promoted, and the solid waste recycling technology of silicon-molybdenum separation and molybdenum enrichment is realized.
In the extraction process, lead-zinc tailings and alkali are subjected to acidification and separation after eutectic melting, so as to obtain a solution containing condensed molybdate and silicic acid, namely leaching solution;
the leaching solution is stored in a leaching solution liquid storage tank, and when the system works, the solution of the electrode positive chamber and the electrode negative chamber of each level of electrodialysis unit comes from a first liquid storage tank and continuously and circularly flows among the electrode positive chamber, the electrode negative chamber and the first liquid storage tank;
the solution in the first stage sample chamber comes from the leaching solution liquid storage tank, flows to the next stage sample chamber step by step after electroosmosis, flows out to the liquid outlet tank after reaching the last stage sample chamber, and can be used for recovering white carbon black and iron;
the solution in the last stage of resin chamber comes from the second liquid storage tank, flows to the previous stage of resin chamber step by step after electroosmosis, reaches the first stage of resin chamber and flows out to the resin column; the acid liquor in the second liquid storage tank can ensure that hydrogen ions of the solution do not migrate to keep the acidity unchanged when the acid liquor flows gradually upwards in a first stage in a resin chamber between two negative films, so that molybdenum migrated to the chamber exists as condensed ions or molybdic acid molecules, wherein molybdenum anions are fully contacted with the resin under the stirring effect to replace chloride ions or sulfate radicals to be preferentially adsorbed by the resin, and the chloride ions or sulfate radicals migrate to an anode chamber through the negative film under the electric field force;
discharging the anion exchange resin into a resin regeneration tank from the bottom after the adsorption capacity of the resin chamber is nearly saturated, eluting with alkali liquor, collecting eluent and storing in a molybdenum recovery tank, and recovering the regenerated anion exchange resin for repeated adsorption;
the solution in the resin chamber flows step by step and finally reaches the resin column, the resin column is filled with regenerated anion exchange resin, the low-concentration molybdenum which is not adsorbed by the resin chamber is adsorbed by the anion exchange resin, the eluent is collected after the elution by alkali liquor, and the eluent is also stored in a molybdenum recovery box to finish the extraction of molybdenum, so that the molybdenum product is prepared.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a method for extracting molybdenum from lead-zinc tailing sand, which is simple and convenient in process operation, high in extraction efficiency and strong in cation interference resistance.
The invention provides an electrodialysis system for extracting molybdenum from lead-zinc tailing sand, which adopts a single-stage four-chamber architecture and is used for an electrodialysis method, so that not only can the high-efficiency separation of silicon and molybdenum in a high-silicon low-molybdenum solution (silicon-rich solution) be realized, but also the high-efficiency enrichment of molybdic acid radicals in the low-molybdenum solution can be realized, and the interference of cations such as calcium, magnesium, iron and the like can be effectively eliminated. The continuous migration of molybdenum entering the resin chamber to the electrode positive chamber can be effectively prevented, and the molybdenum enrichment capacity of the resin chamber is enhanced.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of lead-zinc tailings employed in the examples;
fig. 2 is a flow chart of the process of the invention for extracting molybdenum from lead-zinc tailings.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples:
the lead zinc tailings are from water market of Yunnan province, and the X-ray diffraction pattern of the raw material is shown in figure 1, and the lead zinc tailings contain substances such as silicon dioxide, calcium carbonate, magnesium calcium carbonate and the like.
Example 1
Performance study of molybdenum extraction by electrodialysis system:
preparing a sulfuric acid acidified sample solution with the molybdenum content of 959.5mg/L by using molybdenum salts such as sodium molybdate or ammonium molybdate tetrahydrate and the like, taking 50mL of the solution as leaching liquor, and storing the leaching liquor in a leaching liquor liquid storage tank for later use; molybdenum is extracted by adopting an electrodialysis system, and a single-stage electrodialysis unit is adopted in the embodiment; na of 0.2mol/L 2 SO 4 The aqueous solution is stored in a first liquid storage tank, and sulfuric acid with the pH value of 1-2.5 is added into a second liquid storage tank; when the system carries out electrodialysis, the single-stage potential difference is 20V, and the current density is 250-1500A/m 2 Electrodialysis time was 2.5h; in the process, na in the first liquid storage tank 2 SO 4 The aqueous solution flows into the electrode positive chamber and the electrode negative chamber and continuously and circularly flows among the electrode positive chamber, the electrode negative chamber and the first liquid storage tank; leaching liquor in the leaching liquor liquid storage tank flows into the sample chamber, and flows out to the liquid outlet tank after electroosmosis; the sulfuric acid in the second liquid storage tank flows into a resin chamber, and the solid-to-liquid ratio of 201X 7 strong-base type I anion exchange resin and liquid in the resin chamber is 1:1, after electroosmosis, the solution in the resin chamber flows out to a resin column which is also filled with 201X 7 strong alkaline I-type anion exchange resin to finish further adsorption; discharging the anion exchange resin in the resin chamber into a resin regeneration tank from the bottom, eluting with 1mol/L sodium hydroxide aqueous solution, collecting 4BV eluent, and storing in a molybdenum recovery tank; similarly, the anion exchange resin in the resin column is eluted by the same method, and the obtained eluent is still stored in a molybdenum recovery box to finish the extraction of molybdenum.
In order to examine the extraction effect of the method of this example, the molybdenum content of the extract in each step was examined in the course of the process in combination with an inductively coupled plasma emission spectrometer (ICP-OES). The 201X 7 strong-base type I anion exchange resin in the resin chamber is eluted by 1mol/L sodium hydroxide aqueous solution, the molybdenum content of the obtained eluent is 224.7mg/L, and the molybdenum content of low-concentration molybdenum which is adsorbed and eluted by the resin chamber effluent solution through a resin column is 36.78mg/L. Measuring the volumes of the eluents from two sources, and calculating to obtain the extraction quality of the molybdenum corresponding to the electrodialysis; simultaneously calculating the initial mass of molybdenum in the leaching solution; the recovery rate of molybdenum can be obtained through the mass ratio. In this example, the total recovery of molybdenum was 58.5%, with a resin enrichment of 56.2% (from the anion exchange resin in the resin compartment), a solution enrichment of 2.3% (from the anion exchange resin in the resin column), and a resin enrichment of 96.1%.
Example 2
The method for extracting molybdenum from lead-zinc tailing sand comprises the following steps:
(1) Lead-zinc tailings and sodium hydroxide are mixed according to the mass ratio of 1: mixing 0.3-1, completing eutectic melting at 400-680 ℃, and then cooling to normal temperature to obtain a eutectic mixture;
(2) Dissolving the eutectic mixture in sulfuric acid and acidifying to pH 2-3, stirring uniformly, centrifuging to separate precipitate to obtain 50mL of leaching liquor containing condensed molybdate and silicic acid, and storing the leaching liquor in a leaching liquor liquid storage tank for later use;
(3) Molybdenum is extracted by adopting an electrodialysis system, and a single-stage electrodialysis unit is adopted in the embodiment; na of 0.2mol/L 2 SO 4 The aqueous solution is stored in a first liquid storage tank, and sulfuric acid with the pH value of 1-2.5 is added into a second liquid storage tank; when the system carries out electrodialysis, the single-stage potential difference is 15V, and the current density is 250-1500A/m 2 Electrodialysis time was 2.5h; in the process, na in the first liquid storage tank 2 SO 4 The aqueous solution flows into the electrode positive chamber and the electrode negative chamber and continuously and circularly flows among the electrode positive chamber, the electrode negative chamber and the first liquid storage tank; leaching liquor in the leaching liquor liquid storage tank flows into the sample chamber, and flows out to the liquid outlet tank after electroosmosis; the sulfuric acid in the second liquid storage tank flows into a resin chamber, and the solid-to-liquid ratio of 201X 7 strong-base I-type anion exchange resin and liquid in the resin chamber is 1:1, the solution in the resin chamber flows out to a resin column which is also provided with 201X 7 strong alkaline I-type anion exchange resin after electroosmosis to finish further adsorption; discharging the anion exchange resin in the resin chamber into a resin regeneration tank from the bottom, eluting with 1mol/L sodium hydroxide aqueous solution, collecting 1BV eluent and storing in a molybdenum recovery tank; similarly, the anion exchange resin in the resin column is eluted by the same method, and the obtained eluent is still stored in a molybdenum recovery box to finish the extraction of molybdenum.
In order to examine the extraction effect of the method of this example, the molybdenum content of the extract in each step was examined in the course of the process in combination with an inductively coupled plasma emission spectrometer (ICP-OES). In the step (2), the molybdenum content of the obtained leaching solution is 3.26mg/L, and in addition, the total silicon content of the leaching solution is 2130mg/L and the iron content of the leaching solution is 16.0g/L by adopting a hydrofluoric acid conversion spectrophotometry; in the step (3), the 201X 7 strong basic type I anion exchange resin in the resin chamber is eluted by 1mol/L sodium hydroxide aqueous solution to obtain an eluent with the molybdenum content of 4.04mg/L, and the low-concentration molybdenum which is adsorbed and eluted by the resin chamber effluent solution through a resin column has the molybdenum content of 0.071mg/L; silicon or iron was detected in the above eluents. Measuring the volumes of the eluents from two sources, and calculating to obtain the extraction quality of the molybdenum corresponding to the electrodialysis; simultaneously calculating the initial mass of molybdenum in the leaching solution; the recovery rate of molybdenum can be obtained through the mass ratio. In this example, the total recovery of molybdenum was 63.3%, with a resin enrichment of 62.0% (from the anion exchange resin of the resin compartment), a solution enrichment of 1.3% (from the anion exchange resin of the resin column), and a resin enrichment of 97.9%.
Example 3
The method for extracting molybdenum from lead-zinc tailing sand comprises the following steps:
(1) 50mL of the extract obtained in example 2 was stored in an extract tank;
(2) As shown in fig. 2, molybdenum is extracted by an electrodialysis system, and the leaching solution is added into a sample chamber 1 of an electrodialysis device for 2-stage electrodialysis in the embodiment; na of 0.2mol/L 2 SO 4 The aqueous solution is stored in a first liquid storage tank, and sulfuric acid with the pH value of 1-2.5 is added into a second liquid storage tank; when the system carries out electrodialysis, the single-stage potential difference is 10V, and the current density is 250-1500A/m 2 Electrodialysis time is 3h; in the process, na in the first liquid storage tank 2 SO 4 The aqueous solution flows into the electrode positive chamber and the electrode negative chamber of the electrodialysis unit and continuously and circularly flows among the electrode positive chamber, the electrode negative chamber and the first liquid storage tank; the leaching liquor in the leaching liquor liquid storage tank flows into the first-stage sample chamber, flows into the second-stage sample chamber step by step after electroosmosis, and flows out to the liquid outlet after electroosmosisA case; the sulfuric acid in the second liquid storage tank flows into the second-stage resin chamber, the solution in the second-stage resin chamber flows into the first-stage resin chamber after electroosmosis, and the solid-liquid ratio of 201X 7 strong-alkaline I-type anion exchange resin to liquid in the resin chamber is 1:1, the solution after electroosmosis flows out from a first-stage resin chamber to a resin column which is also provided with 201 multiplied by 7 strong-alkaline I-type anion exchange resin, and further adsorption is finished; discharging the anion exchange resin in the resin chamber into a resin regeneration tank from the bottom, eluting with 1mol/L sodium hydroxide aqueous solution, collecting 1BV eluent, storing in a molybdenum recovery tank, and recovering the anion exchange resin for recycling after eluting; similarly, the anion exchange resin in the resin column is eluted by the same method, and the obtained eluent is still stored in a molybdenum recovery box to finish the extraction of molybdenum.
In order to examine the extraction effect of the method of this example, the molybdenum content of the extract in each step was examined in the course of the process in combination with an inductively coupled plasma emission spectrometer (ICP-OES). The raw material sources and preparation processes of the leaching solution of this example are the same as those of example 1; in the step (2), the 201X 7 strongly basic type I anion exchange resin in the resin chamber is eluted with 1mol/L sodium hydroxide aqueous solution to obtain an eluent with a molybdenum content of 2.96mg/L; and (3) combining low-concentration molybdenum adsorbed and eluted by the resin column from the effluent solution of the resin chamber with high-concentration molybdenum eluted by the anion exchange resin in the resin chamber, and detecting that the molybdenum content of the combined eluent is 1.88mg/L, wherein no silicon or iron is detected in the eluent. The total extraction quality of molybdenum is obtained by measuring the volumes of the combined eluents, and the total recovery rate of the molybdenum in the embodiment is finally calculated to be 92.2 percent which is higher than that of the embodiment 2, so that the process can realize the high-efficiency separation of silicon and molybdenum of the high-silicon low-molybdenum solution, can simultaneously realize the high-efficiency enrichment of molybdic acid radicals in the low-molybdenum solution, effectively eliminates the interference of cations such as calcium, magnesium, iron and the like, can effectively prevent the continuous migration of molybdenum entering the resin chamber to the electrode cation chamber, and strengthens the capability of enriching the molybdenum in the resin chamber.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. A method for extracting molybdenum from lead-zinc tailings sand, comprising the steps of:
leaching the lead-zinc tailings to obtain leaching liquor containing silicate ions and molybdate ions; extracting the leaching liquor by electrodialysis, and promoting the directional migration and separation of anions and cations of the leaching liquor by electric field force; controlling the selective permeability to block migration of silicic acid molecules in the leaching solution; the adsorption enrichment of molybdate anions is realized in the electrodialysis process, and meanwhile, the migration of molybdate molecules is inhibited; and (3) eluting the molybdenum acid radical anions after adsorption and enrichment, and recovering eluent to finish the extraction of molybdenum.
2. The method according to claim 1, characterized in that the method of leaching lead-zinc tailings is as follows: eutectic melting lead-zinc tailings and alkaline substances, and cooling to form a eutectic mixture; the eutectic mixture is acidified and insoluble substances are separated to obtain leaching liquor.
3. The method according to claim 2, characterized in that: the mass ratio of the eutectic lead-zinc tailings to the alkaline substances is 1:0.3 to 1, and the eutectic temperature is 400 to 680 ℃; after the acidification treatment, the pH value of the obtained leaching solution is 2-3.
4. The method according to claim 1, characterized in that: the electrodialysis has single-stage potential difference of 5-20V and current density of 250-1500A/m 2 Electrodialysis time is 2-5 h.
5. The method according to claim 1, characterized in that: the concentration of the electrolyte is 0.01-0.2 mol/L.
6. The method according to claim 1, characterized in that: the adsorption enrichment is performed by 201×7 strongly basic type I anion exchange resin.
7. The method according to claim 6, wherein: and eluting the molybdic acid anions by adopting a sodium hydroxide aqueous solution after adsorption enrichment, wherein the concentration of the sodium hydroxide aqueous solution is 0.1-1 mol/L, and recovering eluent of 1-6 BV.
8. An electrodialysis system for extracting molybdenum from lead zinc tailings sand, characterized in that:
the electrodialysis system comprises an electrodialysis device, a liquid storage system, a regeneration system and a recovery system;
the electrodialysis device consists of a single-stage or multi-stage electrodialysis unit; the electrodialysis unit sequentially comprises an electrode positive chamber, a resin chamber, a sample chamber and an electrode negative chamber, wherein each anode in the electrodialysis unit is connected in parallel and is connected with the positive electrode of a power supply, and each cathode in the electrodialysis unit is connected in parallel and is connected with the negative electrode of the power supply; the electrode positive chamber, the resin chamber and the sample chamber are separated by an acid-base resistant homogeneous anion exchange membrane, and the sample chamber and the electrode negative chamber are separated by an acid-base resistant homogeneous cation exchange membrane; the resin chamber contains anion exchange resin;
the liquid storage system comprises a leaching liquid storage tank, a first liquid storage tank and a second liquid storage tank; the leaching solution is stored in a leaching solution liquid storage tank, and is conveyed to a sample chamber of the first-stage electrodialysis unit; electrolyte used for electrodialysis is stored in a first liquid storage tank, and electrolyte is conveyed to an electrode positive chamber and an electrode negative chamber; the second liquid storage tank is used for storing acid liquid and conveying the acid liquid to the resin chamber;
the regeneration system comprises a resin regeneration tank and a resin column; the anion exchange resin in the resin chamber is stored in a resin regeneration tank after being adsorbed; the resin column contains anion exchange resin, and low-concentration molybdenum which is not adsorbed by the resin chamber in the electrodialysis device is adsorbed;
the recovery system comprises a liquid outlet box and a molybdenum recovery box; the solution flowing out from the sample chamber of the electrodialysis device is stored in a liquid outlet box; the eluent obtained by eluting the anion exchange resin is stored in a molybdenum recovery box.
9. Electrodialysis system according to claim 8, characterized in that: in the resin chamber, the solid-liquid volume ratio of the anion exchange resin is 4:3 to 6:1.
10. electrodialysis system according to claim 8, characterized in that: in the second liquid storage tank, the pH value of the acid liquid is 1-2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311035091.8A CN117187598A (en) | 2023-08-16 | 2023-08-16 | Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311035091.8A CN117187598A (en) | 2023-08-16 | 2023-08-16 | Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117187598A true CN117187598A (en) | 2023-12-08 |
Family
ID=88998804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311035091.8A Pending CN117187598A (en) | 2023-08-16 | 2023-08-16 | Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117187598A (en) |
-
2023
- 2023-08-16 CN CN202311035091.8A patent/CN117187598A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104831064B (en) | Acidleach-cyclone electrolytic cell technology technique of high efficiente callback copper from lead copper matte is pressed with oxygen | |
| CN111926180B (en) | Method for extracting ion adsorption type rare earth | |
| CN100572286C (en) | Utilize arsenic-containing waste water to prepare the method for white arsenic | |
| CN105174556B (en) | A kind of method of peracid high ferro heavy metal wastewater thereby sub-prime resource reclaim | |
| WO2015162902A1 (en) | Method and equipment for recovering valuable components from waste dry batteries | |
| CN108950219B (en) | Gradient extraction and comprehensive utilization method of valuable metals in titanium white waste acid | |
| CN103073061A (en) | Method for extracting tungsten and molybdenum in high molybdenum scheelite | |
| CN106868544B (en) | A method of the selective removal univalent anion impurity from sulfuric acid system electrolyte | |
| CN106744721A (en) | The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid | |
| CN105671323A (en) | Method for comprehensively recycling copper and rhenium from rhenium-rich residues | |
| CN105950865B (en) | A method of the separation and Extraction vanadium chromium from high-chromic vanadium leachate | |
| CN108342583A (en) | A method of recycling rhenium and molybdenum from calcining molybdenum ore concentrate collected ash | |
| CN113512652B (en) | Method for extracting gallium metal from coal-series solid waste | |
| CN110724838A (en) | Method for separating tungsten and molybdenum from waste catalyst containing tungsten and molybdenum | |
| CN103498050A (en) | Chromium recovery method in electrolytic manganese chromium wastewater treatment process | |
| CN107354300B (en) | A method of the enriching rhenium from Copper making spent acid | |
| CN110643811B (en) | Clean smelting process for nickel-molybdenum ore by full-wet method | |
| CN102634819A (en) | Method for preparing electrolytic manganese/electrolytic manganese dioxide through leaching manganese oxide by sulfur dioxide | |
| CN110642414B (en) | Control method for efficiently separating vanadium-chromium wastewater by using modified chelate resin | |
| CN117187598A (en) | Method for extracting molybdenum from lead-zinc tailing sand and electrodialysis system | |
| CN105983707B (en) | A method of high-purity rhenium powder is prepared from rhenium-containing high arsenic-and copper-bearing sulfide | |
| CN106283108A (en) | A kind of spent ion exchange resin is the method for deep copper removal from nickle electrolysis anode solution | |
| CN105861814A (en) | Clean metallurgic method for preparing ammonium molybdate from molybdenite concentrates | |
| CN103397182B (en) | Method for efficiently recycling bismuth from monomer bismuth ore | |
| CN102660756B (en) | High-purity manganese metal and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |