CN114873643A - Method for preparing sodium molybdate from vanadium precipitation mother liquor based on ion exchange method and sodium molybdate - Google Patents
Method for preparing sodium molybdate from vanadium precipitation mother liquor based on ion exchange method and sodium molybdate Download PDFInfo
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- CN114873643A CN114873643A CN202210564323.8A CN202210564323A CN114873643A CN 114873643 A CN114873643 A CN 114873643A CN 202210564323 A CN202210564323 A CN 202210564323A CN 114873643 A CN114873643 A CN 114873643A
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- molybdenum
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- 238000000034 method Methods 0.000 title claims abstract description 96
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001556 precipitation Methods 0.000 title claims abstract description 56
- 239000012452 mother liquor Substances 0.000 title claims abstract description 55
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 235000015393 sodium molybdate Nutrition 0.000 title claims abstract description 44
- 239000011684 sodium molybdate Substances 0.000 title claims abstract description 44
- 238000005342 ion exchange Methods 0.000 title claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 157
- 239000011733 molybdenum Substances 0.000 claims abstract description 157
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000011347 resin Substances 0.000 claims abstract description 92
- 229920005989 resin Polymers 0.000 claims abstract description 92
- 238000001179 sorption measurement Methods 0.000 claims abstract description 49
- 238000003795 desorption Methods 0.000 claims abstract description 44
- 239000002585 base Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 238000004458 analytical method Methods 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- -1 tungsten ions Chemical class 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical class [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/60—Cleaning or rinsing ion-exchange beds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method and sodium molybdate, and the method comprises the following steps: (1) carrying out molybdenum adsorption on the vanadium precipitation mother liquor by adopting macroporous strong base resin to obtain adsorption tail liquor and molybdenum-loaded resin; (2) carrying out molybdenum desorption on the loaded molybdenum resin obtained in the step (1) by using alkali liquor to obtain desorption liquid and molybdenum-poor resin; the molybdenum-poor resin is directly recycled to step (1); (3) concentrating and crystallizing the analytic solution obtained in the step (2) to obtain sodium molybdate; wherein the pH value of the vanadium precipitation mother liquor in the step (1) is 6.5-7.5. The method provided by the invention improves the molybdenum content of the desorption solution, simplifies the process flow and reduces the operation difficulty.
Description
Technical Field
The invention belongs to the technical field of extraction of nonferrous metals, relates to a preparation method of sodium molybdate, and particularly relates to a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method and sodium molybdate.
Background
At present, in the process of recycling waste catalysts containing vanadium and molybdenum, methods for preparing sodium molybdate by extracting molybdenum from vanadium precipitation mother liquor mainly comprise three methods: (1) a solvent extraction method, which is to obtain sodium molybdate by extracting molybdenum in a tertiary amine kerosene solution in an acidic manner, back extracting in sodium hydroxide, precipitating molybdic acid, dissolving in sodium hydroxide, and concentrating and crystallizing; however, the method has the defects of long process flow, high reagent consumption, production of process acid wastewater, easy precipitation of molybdenum under an acid condition and the like. (2) A weak-base anion exchange method, which is to use sodium hydroxide to desorb molybdenum, precipitate molybdic acid, dissolve sodium hydroxide, concentrate and crystallize after adsorbing molybdenum by using weak-base anion exchange resin, so as to obtain sodium molybdate; the method has the same defects as the solvent extraction method except that the resin needs to be regenerated; (3) a strong-alkaline ion exchange method, which is to use strong-alkaline ion exchange resin to adsorb molybdenum and then use ammonium bicarbonate to desorb molybdenum and precipitate ammonium molybdate; however, this method has many disadvantages such as low saturation capacity of the resin used, low molybdenum content in the desorption solution, and the need to regenerate the resin for use.
CN 103421953A discloses a method for deep separation of vanadium and molybdenum, which comprises three steps of solution pH value pre-adjustment, ion state adjustment and resin ion exchange separation and analysis. Firstly, the solution of vanadium-containing molybdate is adjusted to proper pH value by sulfuric acid, the redox potential of the solution is adjusted by adding a reducing agent and an oxidizing agent, the valence state and the ionic state of vanadium and molybdenum are adjusted, vanadium is reduced from V (V) to V (IV), and VO is used 2+ The molybdenum exists in a hexavalent anion form, continuously passes through an exchange column of strongly basic anion exchange resin, the exchange speed is controlled by the contact time of 20-30min, the adsorption effect is judged according to the concentration of Mo in the effluent liquid, and the loaded resin is recycled after being analyzed. However, the strong-base anion exchange resin adopted by the method has poor oxidation resistance, the molybdenum content of the desorption solution is only 8.45-13.06g/L, and the saturation capacity is low.
CN 104628032A discloses a method for preparing high-purity ammonium metavanadate from a waste catalyst, which comprises the following steps: removing phosphorus, namely collecting the waste catalyst leachate in a leaching mode, filtering the leachate, then feeding the leachate into an ion exchange phosphorus removal system, and adsorbing phosphorus in the waste catalyst leachate by using resin; separating molybdenum and vanadium, feeding the solution containing molybdenum and vanadium after removing phosphorus into an ion exchange system, and performing molybdenum adsorption by using resin to separate molybdenum and vanadium; and (3) vanadium precipitation, namely pumping the vanadium-containing mother liquor subjected to phosphorus removal and molybdenum separation into a vanadium precipitation tank, and precipitating vanadium by using alkalescent ammonium salt to obtain a high-purity ammonium metavanadate product. However, the invention relates only to molybdenum adsorption and does not relate to the preparation of sodium molybdate.
CN 110724838A discloses a method for separating tungsten and molybdenum from a spent catalyst containing tungsten and molybdenum, comprising the following steps: (1) a mixed solution containing sodium tungstate and sodium molybdate; (2) separating and adsorbing tungsten ions by using D314-W alkalescent anion resin; (3) separating and adsorbing molybdenum ions by using D314 weak-base anion resin; (4) separating a small amount of molybdenum ions adsorbed in the high-adsorption tungsten resin; (5) resolving the high adsorption tungsten resin to finally obtain fixed sodium tungstate; (5) and (4) resolving the high adsorption molybdenum resin to finally obtain fixed molybdic acid. However, the weakly basic anion resin adopted in the method needs to be regenerated after being used, and has the defects of long process flow, high reagent consumption, generation of process acid wastewater, easy precipitation of molybdenum under an acid condition and the like.
Therefore, how to provide a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, which can improve the molybdenum content of the desorption solution, simplify the process flow and reduce the operation difficulty is the problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method and sodium molybdate.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, which comprises the following steps:
(1) carrying out molybdenum adsorption on the vanadium precipitation mother liquor by adopting macroporous strong base resin to obtain adsorption tail liquor and molybdenum-loaded resin;
(2) carrying out molybdenum desorption on the loaded molybdenum resin obtained in the step (1) by using alkali liquor to obtain desorption liquid and molybdenum-poor resin; the molybdenum-poor resin is directly recycled to step (1);
(3) concentrating and crystallizing the analytic solution obtained in the step (2) to obtain sodium molybdate;
the pH of the vanadium precipitation mother liquor in step (1) is 6.5-7.5, for example, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4 or 7.5, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
According to the invention, the macroporous strong base resin is adopted to adsorb molybdenum to the precipitated vanadium mother liquor, and then the alkali liquor is adopted to carry out molybdenum analysis, so that the analysis solution with the molybdenum concentration of more than 80g/L is obtained, the molybdenum content of the analysis solution is obviously improved, the precipitated vanadium mother liquor with the pH value of 6.5-7.5 is adopted, the ion exchange is directly carried out without pH adjustment, and the molybdenum cannot be separated out from the solution. In addition, the macroporous strong base resin adopted by the invention does not need transformation subsequently, thereby simplifying the process flow and reducing the operation difficulty.
Preferably, the macroporous strong base resin of step (1) comprises D401 and/or D231.
Preferably, the saturated adsorption capacity of the macroporous strong base resin in the step (1) is more than or equal to 80g/L, for example, 80g/L, 82g/L, 84g/L, 86g/L, 88g/L, 90g/L, 92g/L, 94g/L, 96g/L, 98g/L or 100g/L, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the molybdenum concentration of the vanadium precipitation mother liquor in the step (1) is 12-16g/L, such as 12g/L, 12.5g/L, 13g/L, 13.5g/L, 14g/L, 14.5g/L, 15g/L, 15.5g/L or 16g/L, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the molybdenum adsorption of step (1) is fed at a flow rate of 1.5-2.5BV/h, such as 1.5BV/h, 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2BV/h, 2.1BV/h, 2.2BV/h, 2.3BV/h, 2.4BV/h or 2.5BV/h, but not limited to the values listed, and other values not listed within this range are equally applicable.
Preferably, the adsorption endpoint of the molybdenum adsorption in the step (1) is as follows: the molybdenum concentration of the effluent is the same as that of the vanadium precipitation mother liquor.
Preferably, step (1) further comprises washing the molybdenum-loaded resin.
Preferably, the washing solution used for washing comprises deionized water.
Preferably, the washing is carried out using a wash liquor in an amount of 3 to 5BV, for example 3BV, 3.2BV, 3.4BV, 3.6BV, 3.8BV, 4BV, 4.2BV, 4.4BV, 4.6BV, 4.8BV or 5BV, but not limited to the values recited, other values not recited in this range being equally applicable.
Preferably, the wash feed flow rate is from 1.5 to 2.5BV/h, and may be, for example, 1.5BV/h, 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2BV/h, 2.1BV/h, 2.2BV/h, 2.3BV/h, 2.4BV/h or 2.5BV/h, but is not limited to the values recited, and other values not recited within this range are equally applicable.
Preferably, the alkali solution in step (2) comprises sodium hydroxide solution.
Preferably, the concentration of the lye of step (2) is 18 to 22 wt.%, and may be, for example, 18 wt.%, 18.5 wt.%, 19 wt.%, 19.5 wt.%, 20 wt.%, 20.5 wt.%, 21 wt.%, 21.5 wt.% or 22 wt.%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the feed flow rate for molybdenum desorption in step (2) is 0.3 to 0.7BV/h, and may be, for example, 0.3BV/h, 0.35BV/h, 0.4BV/h, 0.45BV/h, 0.5BV/h, 0.55BV/h, 0.6BV/h, 0.65BV/h or 0.7BV/h, but is not limited to the values recited, and other values not recited in this range are equally applicable.
Preferably, the desorption volume of molybdenum desorption in step (2) is 4-6BV, for example, 4BV, 4.2BV, 4.4BV, 4.6BV, 4.8BV, 5BV, 5.2BV, 5.4BV, 5.6BV, 5.8BV or 6BV, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the molybdenum concentration of the analysis solution in step (2) is 80g/L or more, for example, 80g/L, 82g/L, 84g/L, 86g/L, 88g/L, 90g/L, 92g/L, 94g/L, 96g/L, 98g/L or 100g/L, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the concentration and crystallization in the step (3) are further followed by filtration and drying in sequence.
Preferably, the filtrate obtained by filtration is returned to the analysis solution for concentration and crystallization.
As a preferred technical solution of the first aspect of the present invention, the method comprises the steps of:
(1) carrying out molybdenum adsorption on the vanadium precipitation mother liquor by adopting macroporous strong base resin, wherein the feeding flow rate is 1.5-2.5BV/h, and stopping feeding when the molybdenum concentration of the effluent liquid is the same as that of the vanadium precipitation mother liquor to obtain adsorption tail liquor and loaded molybdenum resin; the macroporous strong base resin comprises D401 and/or D231, and the saturated adsorption capacity is more than or equal to 80 g/L; the pH value of the vanadium precipitation mother liquor is 6.5-7.5, and the concentration of molybdenum is 12-16 g/L; then, washing the obtained molybdenum-loaded resin by using deionized water, wherein the using amount of the deionized water is 3-5BV, and the feeding flow rate of the washing is 1.5-2.5 BV/h;
(2) carrying out molybdenum analysis on the loaded molybdenum resin obtained in the step (1) by adopting a sodium hydroxide solution with the concentration of 18-22 wt%, wherein the feeding flow rate is 0.3-0.7BV/h, and the analysis volume is 4-6BV, so as to obtain analysis liquid with the molybdenum concentration being more than or equal to 80g/L and molybdenum-poor resin; the molybdenum-poor resin is directly recycled to step (1);
(3) sequentially carrying out concentration crystallization, filtration and drying on the analytic solution obtained in the step (2) to obtain sodium molybdate; and returning the filtrate obtained by filtering to the analysis solution for concentration and crystallization.
In a second aspect, the present invention provides sodium molybdate prepared according to the method of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the macroporous strong base resin is adopted to adsorb molybdenum to the vanadium precipitation mother liquor, and then the alkali liquor is adopted to carry out molybdenum analysis, so that the analysis solution with the molybdenum concentration as high as more than 80g/L is obtained, and the molybdenum content of the analysis solution is obviously improved;
(2) the method adopts the vanadium precipitation mother liquor with the pH value of 6.5-7.5, directly carries out ion exchange without pH adjustment, and does not precipitate molybdenum in the solution;
(3) the macroporous strong base resin adopted by the invention does not need transformation subsequently, thereby simplifying the process flow and reducing the operation difficulty.
Drawings
FIG. 1 is a flow chart of a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, as shown in fig. 1, the method includes the following steps:
(1) loading 50mL of macroporous strong base resin D401 into an organic glass column with the inner diameter of 10mm and the height of 600mm, feeding vanadium precipitation mother liquor with the pH value of 6.7 and the molybdenum concentration of 12.92g/L from the upper part of the glass column for molybdenum adsorption at the feeding flow rate of 2BV/h (100mL/h), and when the feeding amount reaches 1550mL, leading the molybdenum concentration of effluent liquid to be the same as that of the vanadium precipitation mother liquor, leading the resin to be saturated, and stopping feeding to obtain adsorption tail liquor and loaded molybdenum resin; then, washing the obtained loaded molybdenum resin by using deionized water, wherein the using amount of the deionized water is 4BV (200mL), the washing feeding flow rate is 2BV/h (100mL/h), the obtained washing liquid and the adsorption tail liquid are combined and uniformly mixed, the total volume is 1750mL, the analyzed molybdenum concentration is 9.01g/L, and the saturated adsorption capacity of the resin is 85.2g/L through calculation;
(2) molybdenum analysis is carried out on the loaded molybdenum resin obtained in the step (1) by adopting a sodium hydroxide solution with the concentration of 20 wt%, the feeding flow rate is 0.5BV/h (25mL/h), the analysis volume is 6BV (300mL), feeding and sampling are carried out in batches according to the volume of 1BV (50mL) each time, and the molybdenum concentration of the analysis solution is analyzed and detailed in Table 1;
TABLE 1
| Batches of | 1 | 2 | 3 | 4 | 5 | 6 |
| Volume (mL) | 50 | 50 | 50 | 50 | 50 | 50 |
| Molybdenum concentration (g/L) | 1.32 | 82.34 | 0.89 | 0.49 | 0.13 | 0.03 |
As can be seen from Table 1: the sodium hydroxide solution with the concentration of 20 wt% can effectively resolve molybdenum in the resin. The molybdenum resolution was 99.81% when the resolution volume was 4BV (200mL) by calculation; when the desorption volume is 6BV (300mL), the molybdenum desorption rate is 100 percent; directly recycling the lean molybdenum resin obtained after the desorption to the step (1);
(3) combining and uniformly mixing the analytic solutions of the first 2 batches obtained in the step (2) to obtain 100mL of analytic solution, and sequentially carrying out concentration crystallization, filtration and drying to obtain sodium molybdate; and returning the filtrate obtained by filtering to the analysis solution for concentration and crystallization.
Example 2
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, as shown in fig. 1, the method includes the following steps:
(1) loading 50mL of macroporous strong base resin D401 into an organic glass column with the inner diameter of 10mm and the height of 600mm, feeding vanadium precipitation mother liquor with the pH value of 7.0 and the molybdenum concentration of 13.07g/L from the upper part of the glass column for molybdenum adsorption at the feeding flow rate of 2BV/h (100mL/h), and when the feeding amount reaches 1550mL, leading the molybdenum concentration of effluent liquid to be the same as that of the vanadium precipitation mother liquor, leading the resin to be saturated, and stopping feeding to obtain adsorption tail liquor and loaded molybdenum resin; then, washing the obtained loaded molybdenum resin by using deionized water, wherein the using amount of the deionized water is 4BV (200mL), the washing feeding flow rate is 2BV/h (100mL/h), the obtained washing liquid and the adsorption tail liquid are combined and uniformly mixed, the total volume is 1750mL, the analyzed molybdenum concentration is 9.09g/L, and the saturated adsorption capacity of the resin is calculated to be 87.02 g/L;
(2) molybdenum analysis is carried out on the molybdenum-loaded resin obtained in the step (1) by adopting sodium hydroxide solution with the concentration of 20 wt%, the feeding flow rate is 0.5BV/h (25mL/h), the analysis volume is 6BV (300mL), feeding and sampling are carried out in batches according to the volume of 1BV (50mL) each time, the molybdenum concentration of the analysis solution is analyzed, and the details are shown in Table 2
TABLE 2
| Batches of | 1 | 2 | 3 | 4 | 5 | 6 |
| Volume (mL) | 50 | 50 | 50 | 50 | 50 | 50 |
| Molybdenum concentration (g/L) | 2.13 | 83.58 | 0.81 | 0.35 | 0.12 | 0.03 |
As can be seen from Table 1: the sodium hydroxide solution with the concentration of 20 wt% can effectively resolve molybdenum in the resin. The molybdenum resolution was 99.83% when the resolution volume was 4BV (200mL) by calculation; when the desorption volume is 6BV (300mL), the molybdenum desorption rate is 100 percent; directly recycling the lean molybdenum resin obtained after the desorption to the step (1);
(3) combining and uniformly mixing the analytic solutions of the first 2 batches obtained in the step (2) to obtain 100mL of analytic solution, and sequentially carrying out concentration crystallization, filtration and drying to obtain sodium molybdate; and returning the filtrate obtained by filtering to the analysis solution for concentration and crystallization.
Example 3
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, as shown in fig. 1, the method includes the following steps:
(1) loading 50mL of macroporous strong base resin D401 into an organic glass column with the inner diameter of 10mm and the height of 600mm, feeding vanadium precipitation mother liquor with the pH value of 7.5 and the molybdenum concentration of 15.47g/L from the upper part of the glass column for molybdenum adsorption at the feeding flow rate of 2BV/h (100mL/h), and when the feeding amount reaches 1300mL, leading the molybdenum concentration of effluent liquid to be the same as that of the vanadium precipitation mother liquor, leading the resin to be saturated, stopping feeding, and obtaining adsorption tail liquor and loaded molybdenum resin; then, washing the obtained loaded molybdenum resin by using deionized water, wherein the using amount of the deionized water is 4BV (200mL), the washing feeding flow rate is 2BV/h (100mL/h), the obtained washing liquid and the adsorption tail liquid are combined and uniformly mixed, the total volume is 1500mL, the analyzed molybdenum concentration is 10.6g/L, and the saturated adsorption capacity of the resin is 84.22g/L through calculation; 1
(2) Molybdenum analysis is carried out on the molybdenum-loaded resin obtained in the step (1) by adopting sodium hydroxide solution with the concentration of 20 wt%, the feeding flow rate is 0.5BV/h (25mL/h), the analysis volume is 6BV (300mL), feeding and sampling are carried out in batches according to the volume of 1BV (50mL) each time, the molybdenum concentration of the analysis solution is analyzed, and the details are shown in Table 3
TABLE 3
| Batches of | 1 | 2 | 3 | 4 | 5 | 6 |
| Volume (mL) | 50 | 50 | 50 | 50 | 50 | 50 |
| Molybdenum concentration (g/L) | 1.63 | 81.34 | 0.74 | 0.37 | 0.11 | 0.03 |
As can be seen from Table 1: the sodium hydroxide solution with the concentration of 20 wt% can effectively resolve molybdenum in the resin. The molybdenum resolution was 99.83% when the resolution volume was 4BV (200mL) by calculation; when the desorption volume is 6BV (300mL), the molybdenum desorption rate is 100 percent; directly recycling the lean molybdenum resin obtained after the desorption to the step (1);
(3) combining and uniformly mixing the analytic solutions of the first 2 batches obtained in the step (2) to obtain 100mL of analytic solution, and sequentially carrying out concentration crystallization, filtration and drying to obtain sodium molybdate; and returning the filtrate obtained by filtering to the analysis solution for concentration and crystallization.
Example 4
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the feeding flow rate for molybdenum adsorption in step (1) is changed to 1.5BV/h (75mL/h), and thus, the details are not repeated herein.
The resin was saturated when the feed rate of molybdenum adsorption reached 1300mL in this example, as compared to example 1.
Example 5
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the feeding flow rate for molybdenum adsorption in step (1) is changed to 2.5BV/h (125mL/h), and thus, the details are not repeated herein.
The resin was saturated when the feed rate of molybdenum adsorption reached 1800mL in this example, compared to example 1.
Example 6
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the feeding flow rate for molybdenum adsorption in step (1) is changed to 0.5BV/h (25mL/h), and thus, the details are not repeated herein.
The resin was saturated when the feed rate of molybdenum adsorption reached 900mL in this example, as compared to example 1.
Example 7
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the feeding flow rate for molybdenum adsorption in step (1) is changed to 3BV/h (150mL/h), and thus, the details are not repeated herein.
The resin was saturated at a feed rate of 2000mL for molybdenum adsorption in this example, as compared to example 1.
Example 8
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the concentration of sodium hydroxide in step (2) is changed to 18 wt%, and thus, details are not repeated herein.
Compared with the example 1, in the molybdenum desorption process of the obtained molybdenum-loaded resin by the sodium hydroxide solution, when the desorption volume is 4BV (200mL), the molybdenum desorption rate is 99.2 percent; when the desorption volume was 6BV (300mL), the molybdenum desorption was 100%.
Example 9
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the concentration of sodium hydroxide in step (2) is changed to 22 wt%, and thus, details are not repeated herein.
Compared with the example 1, in the molybdenum desorption process of the obtained molybdenum-loaded resin by the sodium hydroxide solution, when the desorption volume is 4BV (200mL), the molybdenum desorption rate is 99.6 percent; when the desorption volume was 6BV (300mL), the molybdenum desorption was 100%.
Example 10
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the concentration of sodium hydroxide in step (2) is changed to 16 wt%, and thus, details are not repeated herein.
Compared with the example 1, in the molybdenum desorption process of the obtained loaded molybdenum resin by the sodium hydroxide solution, when the desorption volume is 4BV (200mL), the molybdenum desorption rate is 92 percent; when the desorption volume was 6BV (300mL), the molybdenum desorption was 95%.
Example 11
This example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, in which the steps and conditions are the same as those in example 1 except that the concentration of sodium hydroxide in step (2) is changed to 24 wt%, and thus, details are not repeated herein.
Compared with the example 1, in the molybdenum desorption process of the obtained molybdenum-loaded resin by the sodium hydroxide solution, when the desorption volume is 4BV (200mL), the molybdenum desorption rate is 99.6 percent; the molybdenum resolution was 100% when the resolution volume was 6BV (300 mL).
Comparative example 1
The comparative example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method, except that the resin in the step (1) is changed into weak-base anion resin D314, correspondingly, the pH value of the vanadium precipitation mother liquor is adjusted to 2, and the rest steps and conditions are the same as those in the example 1, so that the details are not repeated.
The saturated adsorption capacity of the resin used in the comparative example is 40g/L through calculation; in the process of molybdenum analysis of the obtained molybdenum-loaded resin by adopting a sodium hydroxide solution with the concentration of 20 wt%, when the analysis volume is 4BV (200mL), the molybdenum analysis rate is 98%; the molybdenum resolution was 99% when the resolution volume was 6BV (300 mL).
Compared with example 1, since the operation condition of the resin used in this comparative example is strong acid, molybdic acid and the substituted hydrogen ion are adsorbed during the adsorption process, and the resin must be changed to hydrogen form after the alkali solution is resolved to continue the adsorption.
Comparative example 2
The comparative example provides a method for preparing sodium molybdate from vanadium precipitation mother liquor based on a solvent extraction method, and the method comprises the following steps: adjusting the pH value of the vanadium precipitation mother liquor to 2, mixing and stirring the vanadium precipitation mother liquor with an N235 extracting agent (trioctyl decyl tertiary amine) for 5min, standing, after oil-water is completely separated, performing back extraction by using a sodium hydroxide solution to obtain a concentrated sodium molybdate solution, and transforming the extracting agent for reuse.
Compared with example 1, the solution of the comparative example needs to be adjusted to be strong acid, so that molybdenum is easy to form molybdic acid precipitate, the extractant is emulsified, oil-water phase separation is difficult, and material loss is serious. In addition, alkali is required to be added for the treatment of the acidic wastewater to adjust the acidic wastewater to be neutral, so that the consumption of reagents is high, and the cost is high; and an oil removing process is required, the flow is complicated, and the operation difficulty is high.
Therefore, the method comprises the steps of firstly adopting macroporous strong base resin to adsorb molybdenum to the vanadium precipitation mother liquor, and then adopting alkali liquor to carry out molybdenum analysis to obtain analysis liquid with the molybdenum concentration being higher than 80g/L, so that the molybdenum content of the analysis liquid is obviously improved; the method adopts the vanadium precipitation mother liquor with the pH value of 6.5-7.5, directly carries out ion exchange without pH adjustment, and does not precipitate molybdenum in the solution; in addition, the macroporous strong base resin adopted by the invention does not need transformation subsequently, thereby simplifying the process flow and reducing the operation difficulty.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing sodium molybdate from vanadium precipitation mother liquor based on an ion exchange method is characterized by comprising the following steps:
(1) carrying out molybdenum adsorption on the vanadium precipitation mother liquor by adopting macroporous strong base resin to obtain adsorption tail liquor and molybdenum-loaded resin;
(2) carrying out molybdenum desorption on the loaded molybdenum resin obtained in the step (1) by using alkali liquor to obtain desorption liquid and molybdenum-poor resin; the molybdenum-poor resin is directly recycled to step (1);
(3) concentrating and crystallizing the analytic solution obtained in the step (2) to obtain sodium molybdate;
wherein the pH value of the vanadium precipitation mother liquor in the step (1) is 6.5-7.5.
2. The process of claim 1 wherein step (1) the macroporous strong base resin comprises D401 and/or D231;
preferably, the saturated adsorption capacity of the macroporous strong base resin in the step (1) is more than or equal to 80 g/L.
3. The method according to claim 1 or 2, wherein the molybdenum concentration of the vanadium precipitation mother liquor in the step (1) is 12-16 g/L.
4. The process according to any one of claims 1 to 3, wherein the feed flow rate for molybdenum adsorption in step (1) is from 1.5 to 2.5 BV/h;
preferably, the adsorption endpoint of the molybdenum adsorption in the step (1) is as follows: the molybdenum concentration of the effluent is the same as that of the vanadium precipitation mother liquor.
5. The method according to any one of claims 1 to 4, wherein step (1) further comprises washing the loaded molybdenum resin;
preferably, the washing solution adopted for washing comprises deionized water;
preferably, the dosage of the washing liquid used for washing is 3-5 BV;
preferably, the feed flow rate for the wash is 1.5-2.5 BV/h.
6. The method according to any one of claims 1 to 5, wherein the lye of step (2) comprises a sodium hydroxide solution;
preferably, the concentration of the lye of step (2) is 18 to 22 wt%.
7. The process according to any one of claims 1 to 6, wherein the feed flow rate for molybdenum desorption in step (2) is 0.3 to 0.7 BV/h;
preferably, the desorption volume of the molybdenum desorption in the step (2) is 4-6 BV;
preferably, the concentration of molybdenum in the desorption solution in the step (2) is more than or equal to 80 g/L.
8. The method according to any one of claims 1 to 7, wherein the concentration crystallization in the step (3) is followed by filtration and drying which are carried out in sequence;
preferably, the filtrate obtained by filtration is returned to the analysis solution for concentration and crystallization.
9. Method according to any of claims 1-8, characterized in that the method comprises the steps of:
(1) carrying out molybdenum adsorption on the vanadium precipitation mother liquor by adopting macroporous strong base resin, wherein the feeding flow rate is 1.5-2.5BV/h, and stopping feeding when the molybdenum concentration of the effluent liquid is the same as that of the vanadium precipitation mother liquor to obtain adsorption tail liquor and loaded molybdenum resin; the macroporous strong base resin comprises D401 and/or D231, and the saturated adsorption capacity is more than or equal to 80 g/L; the pH value of the vanadium precipitation mother liquor is 6.5-7.5, and the concentration of molybdenum is 12-16 g/L; then, washing the obtained molybdenum-loaded resin by using deionized water, wherein the using amount of the deionized water is 3-5BV, and the feeding flow rate of the washing is 1.5-2.5 BV/h;
(2) carrying out molybdenum analysis on the loaded molybdenum resin obtained in the step (1) by adopting a sodium hydroxide solution with the concentration of 18-22 wt%, wherein the feeding flow rate is 0.3-0.7BV/h, and the analysis volume is 4-6BV, so as to obtain analysis liquid with the molybdenum concentration being more than or equal to 80g/L and molybdenum-poor resin; the molybdenum-poor resin is directly recycled to step (1);
(3) sequentially carrying out concentration crystallization, filtration and drying on the analytic solution obtained in the step (2) to obtain sodium molybdate; and returning the filtrate obtained by filtering to the analysis solution for concentration and crystallization.
10. Sodium molybdate prepared according to the process of any one of claims 1 to 9.
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