CN107312942B - The method of extraction and separation vanadium and chromium from vanadium chromium slag pickle liquor - Google Patents
The method of extraction and separation vanadium and chromium from vanadium chromium slag pickle liquor Download PDFInfo
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- CN107312942B CN107312942B CN201710537785.XA CN201710537785A CN107312942B CN 107312942 B CN107312942 B CN 107312942B CN 201710537785 A CN201710537785 A CN 201710537785A CN 107312942 B CN107312942 B CN 107312942B
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- 239000011651 chromium Substances 0.000 title claims abstract description 85
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 71
- 238000000605 extraction Methods 0.000 title claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 58
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002893 slag Substances 0.000 title claims abstract description 26
- 235000021110 pickles Nutrition 0.000 title claims abstract description 19
- 238000000926 separation method Methods 0.000 title abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 21
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 17
- -1 1-octyl-3-methyl-imidazolium tetrafluoroborate Chemical group 0.000 claims description 16
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002386 leaching Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 10
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical group CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 claims 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000011001 backwashing Methods 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000003960 organic solvent Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- FSXANJBLYFVXEU-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCCCCCCCN1CN(C)C=C1 FSXANJBLYFVXEU-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- ILQHIGIKULUQFQ-UHFFFAOYSA-N 1-dodecyl-3-methylimidazolium Chemical group CCCCCCCCCCCCN1C=C[N+](C)=C1 ILQHIGIKULUQFQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- WHTNETGIQWPQFF-UHFFFAOYSA-N [Br].CN1CN(C=C1)CCCCCCCC Chemical compound [Br].CN1CN(C=C1)CCCCCCCC WHTNETGIQWPQFF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002891 organic anions Chemical class 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/37—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing boron, silicon, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of method that the present invention provides extraction and separation vanadium and chromium in the chromium slag pickle liquor from vanadium, including：S1, using extract liquor by vanadium chromium slag pickle liquor pentavalent vanadium and Cr VI be extracted into separated from the water after organic phase, obtain the organic phase of load vanadium chromium；S2, the organic phase of the load vanadium chromium in step S1 is stripped using back washing agent, after back extraction, is obtained containing chromium back extraction extraction raffinate, ammonium metavanadate or ammonium poly-vanadate precipitation and regeneration of ionic liquid；S3, it the ammonium metavanadate or ammonium poly-vanadate that are obtained in step S2 is deposited at 550 DEG C -600 DEG C calcining obtains barium oxide；S4, the Cr that will be stripped in step S2 in extraction raffinate6+Reduction generates Cr3+, chromium is precipitated with precipitation form after adjusting chromium pH, and calcining obtains Cr2O3.The method of the present invention extraction efficiency is high, and rapid, no emulsion is layered after extraction, and ionic liquid has good lipophilic-hydrophobic property, in long-chain alcohol have preferable dissolubility, and with water base it is immiscible, can reduce because water phase carry secretly or dissolve generate organic phase loss.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for extracting and separating vanadium and chromium from a vanadium-chromium slag pickle liquor.
Background
In modern industrial technology, vanadium and chromium are important valuable metal elements and are widely applied to metallurgical industry and chemical industry. Heavy metal vanadium and chromium ions contained in the vanadium-chromium slag pickle liquor have good water solubility and migration capacity, and can be dissolved out and permeate into underground water body to cause serious pollution to the environment and human if being stockpiled in open air for a long time. In addition, vanadium and chromium are important rare metals, and have wide application in aviation, automobiles, shipbuilding and defense industry.
At present, the methods for separating vanadium and chromium mainly comprise a chemical precipitation method, an ion exchange method, an electrolytic method and an extraction method. For example, one of the existing chinese patents discloses a precipitation method for separating vanadium and chromium, but the extraction rate of chromium is not high, and the purity of the product is low due to the entrainment of impurities. In addition, the existing literature discloses that vanadium and chromium are separated by an ion exchange method and an electrolytic method, and although automation is convenient to realize, the pretreatment requirement is high and energy waste is serious, so that the process is complex.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for extracting and separating vanadium and chromium from a vanadium-chromium slag pickle liquor.
The technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a method for extracting and separating vanadium and chromium from a vanadium-chromium slag pickle liquor, which comprises the following steps:
s1, extracting pentavalent vanadium and hexavalent chromium in the vanadium-chromium slag acid leaching solution to an organic phase by using the extraction liquid, and then separating the organic phase from a water phase to obtain a vanadium-chromium-loaded organic phase;
s2, back-extracting the organic phase loaded with vanadium and chromium in the step S1 by using a back-extraction agent, and obtaining lower-layer chromium-containing back-extraction raffinate (aqueous solution), ammonium metavanadate or ammonium polyvanadate precipitate and regenerated ionic liquid after the back-extraction is finished;
s3, calcining the ammonium metavanadate or ammonium polyvanadate precipitate obtained in the step S2 at 550-600 ℃ to obtain vanadium oxide;
s4, Cr in the strip raffinate obtained in the step S26+Reduction to form Cr3+Adjusting the pH of the chromium, precipitating the chromium in a precipitation form, and calcining to obtain the Cr2O3And (3) powder.
Optionally, before step S1, the method further includes:
s0, adjusting the pH value of the pretreated vanadium-chromium slag pickle liquor to 2-5;
correspondingly, S1, extracting the pentavalent vanadium and the hexavalent chromium in the immersion liquid obtained in the step S0 to an organic phase by using the extraction liquid, and then separating the organic phase from the water phase to obtain the vanadium-chromium-loaded organic phase.
Optionally, step S0 includes:
adding inorganic acid and ammonia water (the ammonia water is used for adjusting the pH value of the extraction reaction) into the pre-oxidized acid leaching solution of the vanadium-chromium slag, so that the pH value of the leaching solution is within the range of 2-5; or,
in step S0, the inorganic acid is sulfuric acid, hydrochloric acid, or phosphoric acid.
Alternatively, the extract in step S1 is obtained by dissolving an extracting agent in a diluent;
the diluent is alcohol with 5 carbon atoms.
Alternatively, the extractant is 1-octyl-3-methyl-imidazolium tetrafluoroborate [ Omim [ ]]BF4
Or,
the extractant is 1-decyl-3-methyl-imidazole tetrafluoroborate [ Deim]BF4；
Or,
the extractant is 1-dodecyl-3-methylimidazolium tetrafluorideBorate [ Domim ]]BF4。
Optionally, the stripping agent in the step S2 is 0.5-1.25 mol/L NH4Br solution.
Optionally, in step S1, a one-stage extraction method or a multi-stage extraction method is used to extract the pentavalent vanadium and hexavalent chromium in the immersion liquid obtained in step S0.
Optionally, in step S2, the organic phase loaded with vanadium and chromium in step S1 is stripped by using a one-stage stripping or multi-stage stripping manner;
alternatively, the extract is a 10.0g/L to 50.0g/L solution of ionic liquid-pentanol.
Optionally, the extraction liquid is an ionic liquid-organic phase solution prepared from 1-octyl-3-methyl-imidazole tetrafluoroborate and amyl alcohol;
or,
the extract is 1-decyl-3-methyl-imidazole tetrafluoroborate [ Deim ]]BF4Preparing ionic liquid-organic phase solution with amyl alcohol;
or,
the extract liquid is 1-dodecyl-3-methylimidazolium tetrafluoroborate [ Domim ]]BF4Ionic liquid-organic phase solution prepared with amyl alcohol.
Has the advantages that:
the invention is based on that an extractant such as 1-octyl-3-methyl-imidazole tetrafluoroborate is used for treating Cr under the acidic to weakly acidic conditions with the pH value of 2-52O7 2-And VO3 -Has strong extraction capability, firstly, Cr in the acid leaching solution containing vanadium and chromium2O7 2-And VO3 -Extracting to an organic phase, after extraction is finished, carrying out back extraction on the organic phase loaded with metal ions by using ammonium bromide, wherein vanadium is preferentially combined with ammonium salt to generate ammonium metavanadate or ammonium polyvanadate precipitate, and chromium exists in a back extraction raffinate; the metal ions either form a precipitate or are returned to the aqueous phase,the extractant is regenerated to generate the novel ionic liquid 1-octyl-3-methylimidazole-bromine salt.
The method has the advantages of high extraction efficiency, balanced time period, rapid layering after extraction, no emulsification phenomenon and simple operation, and the ionic liquid has good oleophylic and hydrophobic properties and is basically immiscible with water, so that the loss of organic phase caused by entrainment or dissolution of water phase can be reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic view of a preparation operation scheme of the present invention;
FIG. 2 is a schematic scanning electron micrograph of vanadium oxide according to example 2 of the present invention;
FIG. 3 is an X-ray diffraction pattern of vanadium oxide in example 2 of the present invention;
FIG. 4 is a graph showing an experiment after the ignition of the chromium precipitates in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Currently, the extraction method is widely applied to separation of various substances due to the advantages of less energy consumption, simple operation, high product purity, low energy consumption, small environmental pollution and the like, and has good industrial application prospect.
The ionic liquid is a kind of organic salts which are composed of organic cations and organic or inorganic anions and are liquid at or near room temperature, and compared with the traditional volatile organic solvent, the ionic liquid has the characteristics of low volatility, high thermal and chemical stability, wide electrochemical window, high ionic conductivity and the like, so that the ionic liquid has wide application and research prospects in the fields of organic synthesis, biology, energy, lithium ion batteries, catalysis and the like. The research time of the ionic liquid applied to the extraction and separation of metal ions is only a few years, but the ionic liquid has attracted people's attention, and the research on the application of the ionic liquid extractant to the separation of vanadium and chromium has not been reported.
In the leaching solution of vanadium-chromium slag in the following examples, H is present+、Fe3+、VO3 -、Cr2O7 2-、SO4 2-、Na+、Ca2+Or Cl-According to the theory of soft and hard acid-base, most of the free ions belong to hard acid or hard base, but the most critical two elements of vanadium and chromium are VO3 -、Cr2O7 2-The 'soft base' form exists, which is the most essential difference between vanadium and chromium and other ions and is the most important theoretical basis for separating and extracting vanadium and chromium. The 'soft acid' property of organic cation in the ionic liquid reacts with VO3 -、Cr2O7 2-The soft alkali has stronger binding capacity and is the most important theoretical basis for the application of the ionic liquid as the extracting agent.
Example 1
The embodiment provides a method for extracting and separating vanadium and chromium from a vanadium-chromium slag pickle liquor, as shown in fig. 1, the method comprises the following steps:
s0, 100.0ml of pre-oxidized vanadium-chromium slag acid leaching solution (containing 2.5g/L of vanadium and 0.16g/L of chromium), and adjusting the pH value of the leaching solution to 3 by adopting 10-50 wt% of sulfuric acid.
The pre-oxidation in the step is the vanadium-chromium slag acid leaching solution which pre-oxidizes the low-valence vanadium and the low-valence chromium in the vanadium-chromium slag acid leaching solution into pentavalent vanadium and hexavalent chromium. For example, the oxidant can be hydrogen peroxide, sodium hypochlorite or potassium permanganate.
S1, adding 100.0ml of extraction liquid into the pickle liquor in the step S0, extracting the pentavalent vanadium and the hexavalent chromium obtained in the step S0 into an organic phase at normal temperature, and then separating the organic phase from a water phase to obtain a vanadium-chromium-loaded organic phase, wherein the extraction rate of a single vanadium stage is 85.02%, and the extraction rate of a single chromium stage is 87.17%.
The extract liquid is ionic liquid-amyl alcohol solution which is prepared by taking 1-octyl-3-methyl-imidazole tetrafluoroborate as an extracting agent and taking n-amyl alcohol as an organic solvent and contains 40.0g/L of the extracting agent.
In order to prevent the oxidation-reduction reaction of the high-valence metal in long-term contact with the organic solvent with reducing ability, the organic solvent with reducing ability such as kerosene and sulfonated kerosene should be avoided, so the organic solvent n-amyl alcohol with strong anti-reducing ability is selected.
The step S1 can be realized by multi-stage extraction. The multistage extraction in this example is: the feed liquid and the raffinate are contacted with a fresh extracting agent, so that the extraction rate is high. The multi-stage extraction is to ensure that metal ions in the pickle liquor are all extracted, and if the primary extraction rate is higher, a multi-stage extraction process is not needed.
S2, using 50.0ml of 0.75mol/L NH4And (4) back-extracting the organic phase loaded with vanadium and chromium in the step S1 by using a Br ammonium bromide solution, and separating to obtain lower-layer chromium-containing back raffinate (namely an aqueous solution), ammonium metavanadate or ammonium polyvanadate precipitate and regenerated ionic liquid (namely 1-octyl-3-methylimidazole-bromide).
In this step, vanadium is combined with ammonium ions in preference to ammonium ions to form ammonium metavanadate or ammonium polyvanadate precipitates.
S3, calcining the ammonium metavanadate or ammonium polyvanadate precipitate obtained in the step S2 at 550-600 ℃ to obtain vanadium oxide.
In this step, different calcination conditions can produce vanadium oxides of different valence states.
S4, adjusting the pH of the chromium-containing strip liquor in the step S2 to about 2 according to the Cr in the strip liquor6+According to stoichiometric amount, adding excessive NaHSO30.15g to ensure that hexavalent chromium is completely reduced, and stirring the solution at normal temperature until the pH value of the solution is maintained to be about 2, namely Cr6+Complete reduction to form Cr3+Adjusting the pH value of the chromium to 8.0, precipitating the chromium in a precipitation form, and calcining to obtain the Cr2O3As shown in fig. 4, trivalent chromium was further recovered, and the final vanadium recovery was 73.34% and chromium was 75.67%.
Cr2O7 2-+3HSO3-+5H+→2Cr3++3SO4 2-+4H2O(1.8<pH<2.2)
Fig. 4 is a study means for obtaining information such as the composition of a material, the structure or form of an atom or molecule in the material by analyzing a diffraction pattern of the material by X-ray diffraction detected by an XRD apparatus which is exclusively used in schools. The X-ray diffraction spectrum is obtained by scanning the entire diffraction region at an angle of 2 θ by an X-ray diffractometer, and exists as an angle change as an abscissa of the X-ray diffraction spectrum. The intensities of the diffraction peaks at different diffraction angles (2 theta, not theta) are taken as the ordinate, thus constituting the XRD spectrum. In this example, after the sample was measured, the data was processed and the sample was chromium oxide.
Example 2
In the embodiment, vanadium and chromium are extracted and separated by adopting the sodium-treatment roasted vanadium-chromium slag pickle liquor. The method comprises the following steps:
s0, 100.0ml of pre-oxidized vanadium-chromium slag acid leaching solution (containing 2.5g/L of vanadium and 0.16g/L of chromium), and adjusting the pH value of the leaching solution to 4 by adopting 10-50 wt% of sulfuric acid.
S1, adding 120.0ml of extraction liquid into the pickle liquor in the step S0, extracting the pentavalent vanadium and the hexavalent chromium obtained in the step S0 into an organic phase at normal temperature, and then separating the organic phase from a water phase to obtain a vanadium-chromium-loaded organic phase, wherein the extraction rate of a single vanadium stage is 88.59%, and the extraction rate of a single chromium stage is 90.48%.
The extract liquid is ionic liquid-amyl alcohol solution which is prepared by taking 1-decyl-3-methyl-imidazole tetrafluoroborate as an extractant and n-amyl alcohol as an organic solvent and contains 45.0g/L of the extractant.
S2, carrying out back extraction on the organic phase loaded with the vanadium and the chromium in the step S1 by adopting 1.0mol/L ammonium bromide solution, and obtaining lower-layer chromium-containing back raffinate (aqueous solution), ammonium metavanadate or ammonium polyvanadate precipitate and regenerated ionic liquid, namely 1-octyl-3-methylimidazole-bromide after the back extraction is finished.
And S3, calcining the ammonium metavanadate or ammonium polyvanadate precipitate obtained in the step S2 at 550 ℃ to obtain vanadium oxide.
As shown in fig. 2 and 3.
Specifically, in the present embodiment, the atomic percentage of the vanadium oxide in step S3 is as follows.
The atomic percentages are measured by a scanning electron microscope device, and are data given by the device, the table is also a result given after the machine measurement, and the product is vanadium oxide obtained by analyzing the atomic percentages.
S4, adjusting the pH of the chromium-containing strip liquor in the step S2 to about 2 according to the Cr in the strip liquor6+According to stoichiometric amount, adding excessive NaHSO30.18g to ensure that hexavalent chromium is completely reduced, and stirring the solution at normal temperature until the pH value of the solution is maintained to be about 2, namely Cr6+Complete reduction to form Cr3+Adjusting the pH value of the chromium to 8.0, precipitating the chromium in a precipitation form, and calcining to obtain the Cr2O3And trivalent chromium can be recovered, the final recovery rate of vanadium is 78.68%, and the final recovery rate of chromium is 82.95%.
Example 3
In the embodiment, vanadium and chromium are extracted and separated by adopting the sodium-treatment roasted vanadium-chromium slag pickle liquor. The method comprises the following steps:
s0, 100.0ml of pre-oxidized pickle liquor (containing 2.5g/L of vanadium and 0.16g/L of chromium), and adjusting the pH value of the leach liquor to 4.5 by adopting 10-50 wt% of sulfuric acid.
S1, adding 150.0ml of extraction liquid into the pickle liquor in the step S0, extracting the pentavalent vanadium and the hexavalent chromium obtained in the step S0 into an organic phase at normal temperature, and then separating the organic phase from a water phase to obtain a vanadium-chromium-loaded organic phase, wherein the extraction rate of the single vanadium stage is 90.02%, and the extraction rate of the single chromium stage is 92.84%.
The extract liquid is ionic liquid-amyl alcohol solution which is prepared by taking 1-dodecyl-3-methyl-imidazole tetrafluoroborate as an extracting agent and taking n-amyl alcohol as an organic solvent and contains 50.0g/L of the extracting agent.
S2, carrying out back extraction on the organic phase loaded with the vanadium and the chromium in the step S1 by adopting 1.25mol/L ammonium bromide solution, and obtaining lower-layer chromium-containing back raffinate (aqueous solution), ammonium metavanadate or ammonium polyvanadate precipitate and regenerated ionic liquid, namely 1-octyl-3-methylimidazole-bromide after the back extraction is finished;
s3, calcining the ammonium metavanadate or ammonium polyvanadate precipitate obtained in the step S2 at 580 ℃ to obtain vanadium oxide;
s4, adjusting the pH of the chromium-containing strip liquor in the step S2 to about 2 according to the Cr in the strip liquor6+According to stoichiometric amount, adding excessive NaHSO30.2g to ensure that hexavalent chromium is completely reduced, and stirring the solution at normal temperature until the pH value of the solution is maintained to be about 2, namely Cr6+Complete reduction to form Cr3+Adjusting the pH value of the chromium to 8.0, precipitating the chromium in a precipitation form, and calcining to obtain Cr2O3And trivalent chromium can be further recovered, and the final recovery rate of vanadium is 80.05%, and the final recovery rate of chromium is 85.78%.
In the conventional art, extractive separation is a process in which a leach solution is brought into intimate contact with another immiscible solvent to allow some solute or solutes in the solution to enter the solvent and separate them from other interfering components in the solution. At present, research on vanadium/chromium separation by extraction, such as an amine extractant system, a three-phase extraction system, a two-aqueous-phase extraction system and the like, has been carried out to achieve the purpose of vanadium/chromium separation. The extraction separation has the advantages of large separation coefficient of vanadium/chromium, short process flow, simple and convenient operation, low cost and the like. Therefore, the vanadium/chromium extraction separation technology is certainly one of the most main methods for developing and utilizing vanadium-chromium slag in the future, and the development of related researches has important significance.
In the metal ion extraction system, the ionic liquid is only used as a green solvent to serve as a 'corner matching' effect, but the possibility of industrial application is extremely low due to the high cost of the ionic liquid. Therefore, no relevant research report is found for applying the ionic liquid as an extracting agent to vanadium/chromium extraction separation in the form of a 'principal angle'. Although as many as ten ions exist in the vanadium-chromium slag leaching solution, the ions exist in a free state, and the anions and cations of the ionic liquid also exist in a free state, so that an environmental basis is provided for the application of the ionic liquid to the extraction separation of vanadium/chromium by using the 'main angle' identity of an 'extractant'. From a new scientific perspective, the application of the ionic liquid as an extracting agent in a main angle mode in a vanadium/chromium separation system is explored, so that the method realizes the great inverse attack from the 'main angle' identity of a 'green solvent' to the 'main angle' identity of the 'extracting agent'.
In the embodiment of the invention, the ionic liquid is used as an extracting agent, is dissolved in n-amyl alcohol to form an extraction liquid, changes the traditional role of the green solvent of the ionic liquid, is applied to the resource utilization of the vanadium-chromium slag by taking the new role of the main angle of the extracting agent, breaks through the bottleneck restriction of the cost of the industrial application of the ionic liquid, and expands the application field of the ionic liquid.
The technical principles of the present invention have been described above in connection with specific embodiments, which are intended to explain the principles of the present invention and should not be construed as limiting the scope of the present invention in any way. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive efforts, which shall fall within the scope of the present invention.
Claims (10)
1. A method for extracting and separating vanadium and chromium from a vanadium-chromium slag pickle liquor is characterized by comprising the following steps:
s1, extracting pentavalent vanadium and hexavalent chromium in the acid leaching solution of the vanadium-chromium slag into an organic phase by using an extraction liquid, and then separating the organic phase from a water phase to obtain a vanadium-chromium-loaded organic phase, wherein the extraction liquid is an ionic liquid-pentanol solution; s2, back-extracting the organic phase loaded with vanadium and chromium in the step S1 by using a back-extraction agent, and obtaining lower-layer chromium-containing back-extraction raffinate, ammonium metavanadate or ammonium polyvanadate precipitate and regenerated ionic liquid after the back-extraction is finished;
s3, calcining the ammonium metavanadate or ammonium polyvanadate precipitate obtained in the step S2 at 550-600 ℃ to obtain vanadium oxide;
s4, Cr in the strip raffinate obtained in the step S26+Reduction to form Cr3+Adjusting the pH of the chromium, precipitating the chromium in a precipitation form, and calcining to obtain the Cr2O3And (3) powder.
2. The method according to claim 1, wherein before step S1, the method further comprises:
s0, adjusting the pH value of the pretreated vanadium-chromium slag pickle liquor to 2-5;
correspondingly, S1, extracting the pentavalent vanadium and the hexavalent chromium in the immersion liquid obtained in the step S0 to an organic phase by using the extraction liquid, and then separating the organic phase from the water phase to obtain the vanadium-chromium-loaded organic phase.
3. The method according to claim 2, wherein step S0 includes:
adding inorganic acid and ammonia water into the pre-oxidized acid leaching solution of the vanadium-chromium slag to enable the pH value of the leaching solution to be within 2-5;
wherein the inorganic acid is one of sulfuric acid, hydrochloric acid or phosphoric acid.
4. The method according to claim 1 or 2, wherein the extract in step S1 is obtained by dissolving an extractant in a diluent;
the diluent is alcohol with 5 carbon atoms.
5. A process according to claim 4, characterized in that the extractant is 1-octyl-3-methyl-imidazolium tetrafluoroborate [ Omim ™ ]]BF4；
Or,
the extractant is 1-decyl-3-methyl-imidazole tetrafluoroborate [ Deim]BF4；
Or,
the extractant is 1-dodecyl-3-methylimidazole tetrafluoroborate[Domim]BF4。
6. The method according to claim 1 or 2, wherein the stripping agent in step S2 is 0.5-1.25 mol/L NH4Br solution.
7. The method according to claim 2, wherein the extraction of pentavalent vanadium and hexavalent chromium in the immersion liquid obtained in step S0 is performed by a one-stage extraction method or a multi-stage extraction method in step S1.
8. The process according to claim 1 or 2, characterized in that the organic phase loaded with vanadium and chromium in step S1 is stripped in step S2 by using a one-stage stripping or multi-stage stripping method.
9. The method according to claim 1 or 2, wherein the extraction solution is a solution of ionic liquid-pentanol of 10.0g/L to 50.0 g/L.
10. The method of claim 9, wherein the extraction solution is an ionic liquid-organic phase solution of 1-octyl-3-methyl-imidazolium tetrafluoroborate in pentanol;
or,
the extract was 1-decyl-3-methyl-imidazolium tetrafluoroborate [ Deim ]]BF4Preparing ionic liquid-organic phase solution with amyl alcohol;
or,
the extract liquid is 1-dodecyl-3-methylimidazolium tetrafluoroborate [ Domim ]]BF4Ionic liquid-organic phase solution prepared with amyl alcohol.
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| CN109207724B (en) * | 2018-09-12 | 2020-12-29 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for simultaneously extracting and separating vanadium and chromium from vanadium and chromium-containing solution |
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| CN106048261A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting vanadium from acidic solution by using ionic liquid [OMIM]BF4 |
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