CN114410971A - Method for separating vanadium and titanium from titanium tetrachloride refining tailings - Google Patents
Method for separating vanadium and titanium from titanium tetrachloride refining tailings Download PDFInfo
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- CN114410971A CN114410971A CN202111512407.9A CN202111512407A CN114410971A CN 114410971 A CN114410971 A CN 114410971A CN 202111512407 A CN202111512407 A CN 202111512407A CN 114410971 A CN114410971 A CN 114410971A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 120
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 41
- 239000010936 titanium Substances 0.000 title claims abstract description 41
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000002893 slag Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910010270 TiOCl2 Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 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
- 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
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1227—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using an oxygen containing agent
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of metallurgical chemical industry, and discloses a method for separating vanadium and titanium from titanium tetrachloride refining tailings. The method comprises the following steps: (1) roasting the titanium tetrachloride refined tailings at the temperature of 100-300 ℃ for 5-30min to obtain roasted slag; (2) adding water into the roasting slag obtained in the step (1) for stirring and leaching, and then carrying out solid-liquid separation to obtain vanadium-containing leaching solution and leaching residue; (3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystal, standing, and filtering to obtain vanadium-containing purified liquid and filter residue, wherein the TiO is2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is (0.001-0.05): 1. The method realizes the purpose of adding vanadium in the titanium tetrachloride refining tailingsSelective separation of titanium.
Description
Technical Field
The invention relates to the field of metallurgical chemical industry, in particular to a method for separating vanadium and titanium from titanium tetrachloride refining tailings.
Background
In the process of preparing titanium white by chlorination method, because titanium is chloridized and vanadium is chloridized and enters into the crude titanium tetrachloride liquid, in order to remove impurities such as vanadium, the crude titanium tetrachloride liquid needs to be vanadium-removed, and the obtained solid residue is generally called titanium tetrachloride refined tailings. The titanium tetrachloride refined tailings contain less than or equal to 30 wt% of vanadium, less than or equal to 35 wt% of titanium, less than or equal to 20 wt% of carbon, less than or equal to 50 wt% of chlorine and about 1 wt% of other impurity elements, and are high-quality vanadium extraction raw materials by analyzing the types and contents of impurities. However, because vanadium (vanadium exists mainly in the form of chloride or oxychloride), titanium and other impurities mostly exist in the form of chloride, the vanadium-titanium composite material has strong corrosivity, is easy to decompose or oxidize, has a low boiling point of chloride, is easy to volatilize and lose, and causes low resource utilization rate. Research shows that the chlorides of vanadium and titanium are similar in property, so that not only is effective separation difficult in a conventional distillation method, but also the problems of long flow and high vanadium loss rate generally exist in a chemical method, so that the process technology for extracting vanadium from refined tailings with high efficiency and low cost and preparing high-purity vanadium products is relatively lacked at present.
Patent applications CN 106929696A and CN 107032400A respectively disclose TiCl4The method for extracting vanadium by ammonium leaching and alkaline leaching of refined tailings adopts TiCl4And (4) leaching the refined tailings after roasting treatment to obtain leachate, and purifying the leachate to remove impurities and precipitate vanadium to obtain vanadium pentoxide. Patent application CN 104004920A discloses a method for extracting vanadium from titanium tetrachloride refined tailings, wherein the titanium tetrachloride refined tailings are subjected to high-temperature roasting and sulfuric acid leaching, and the vanadium leaching rate can reach more than 90%. Patent application CN 108996547a discloses a method for extracting vanadium from titanium tetrachloride refining tailings by ultrasonic-assisted alkali leaching, which adopts an alkali leaching process, but needs to be carried out by introducing oxygen while being assisted by ultrasonic.
The above patents all have the problems of high energy consumption in the roasting stage and volatilization of chloride at high temperature. Leaching with strong acids or strong bases tends to result in leachate with higher levels of impurities and residual acid/base requires additional processing costs.
Patent application CN 110683579A discloses a method for producing high-purity vanadium pentoxide from titanium tetrachloride refining vanadium-removing tailings, wherein the refining vanadium-removing tailings are subjected to seven procedures of pretreatment, chlorination, dust removal, leaching and the like to obtain high-purity vanadium pentoxide powder. The pretreatment stage also needs high-temperature oxidizing roasting, adopts a chlorination mode to achieve better vanadium-titanium separation effect, has complex overall process flow,
disclosure of Invention
The invention aims to solve the problems that vanadium and titanium in titanium tetrachloride refined tailings are difficult to effectively separate by a distillation method, the chemical method has long process and high vanadium loss rate in the prior art, and provides a method for separating vanadium and titanium from titanium tetrachloride refined tailings, which realizes the selective separation of vanadium and titanium.
In order to achieve the above object, the present invention provides a method for separating vanadium and titanium from titanium tetrachloride refining tailings, comprising the steps of:
(1) roasting the titanium tetrachloride refined tailings at the temperature of 100-300 ℃ for 5-30min to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1) for stirring and leaching, and then carrying out solid-liquid separation to obtain vanadium-containing leaching solution and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystal, standing, and filtering to obtain vanadium-containing purified liquid and filter residue, wherein the TiO is2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is (0.001-0.05): 1.
Preferably, in the step (1), the content of vanadium in the titanium tetrachloride refined tailings is 10 to 30 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 10 to 35 wt%.
Preferably, in the step (1), the content of chlorine in the titanium tetrachloride refined tailings is 10 to 50 wt%.
Preferably, in step (1), the atmosphere of the calcination is an oxygen-containing atmosphere.
Preferably, in step (1), the oxygen-containing atmosphere is air and/or oxygen.
Preferably, in the step (2), the liquid-solid ratio of the water to the roasting slag is 1-10 mL/g.
Preferably, in step (2), the temperature of the agitation leaching is 50-95 ℃.
Preferably, in the step (2), the time of agitation leaching is 30-120 min.
Preferably, in step (3), the temperature of the standing is 25 to 50 ℃.
Preferably, in step (3), the standing time is 3 to 7 days.
The method realizes the selective separation of vanadium and titanium in the titanium tetrachloride refining tailings. The finally obtained vanadium-containing purification solution can be used for preparing high-purity vanadium product raw materials, and the chlorine content in the filter residue is less than or equal to 0.1 weight percent, and can be directly used as a titanium-rich material.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for separating vanadium and titanium from titanium tetrachloride refined tailings, which comprises the following steps:
(1) roasting the titanium tetrachloride refined tailings at the temperature of 100-300 ℃ for 5-30min to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1) for stirring and leaching, and then carrying out solid-liquid separation to obtain vanadium-containing leaching solution and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystal, standing, and filtering to obtain vanadium-containing purified liquid and filter residue, wherein the TiO is2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is (0.001-0.05): 1.
In the invention, in the step (1), vanadium in the titanium tetrachloride refined tailings mainly exists in the forms of vanadium trichloride and vanadium oxytrichloride, the content of vanadium in the titanium tetrachloride refined tailings is 10-30 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 10-35 wt%. Specifically, the content of vanadium in the titanium tetrachloride refined tailings may be 10 wt%, 12.5 wt%, 15 wt%, 17.5 wt%, 20 wt%, 22.5 wt%, 25 wt%, 27.5 wt%, or 30 wt%, and the content of titanium may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or 35 wt%.
In the invention, in the step (1), the content of chlorine in the titanium tetrachloride refined tailings is 10 to 50 wt%. Specifically, the content of chlorine in the titanium tetrachloride refined tailings may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%.
In the present invention, in the step (1), the atmosphere of the calcination is an oxygen-containing atmosphere. Preferably, in step (1), the oxygen-containing atmosphere is air and/or oxygen.
In a specific embodiment, in the step (1), the roasting temperature may be 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃ or 300 ℃, and the roasting time may be 5min, 7.5min, 10min, 12.5min, 15min, 17.5min, 20min, 22.5min, 25min, 27.5min or 30 min.
In the invention, in the step (2), the liquid-solid ratio of the water to the roasting slag is 1-10 mL/g. Specifically, the liquid-solid ratio of the water to the roasting slag may be 1mL/g, 2mL/g, 3mL/g, 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, or 10 mL/g.
Preferably, in step (2), the temperature of the agitation leaching is 50-95 ℃. Specifically, the temperature of the agitation leaching may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, in the step (2), the stirring leaching time is 30-120 min. Specifically, the time of agitation leaching may be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, or 120 min.
In the present invention, the TiO is2The average diameter of the seed crystal is 0.6-0.7 μm TiO2And (3) granules.
In a specific embodiment, in step (3), the TiO2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution may be 0.001:1, 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05: 1.
Preferably, in step (3), the temperature of the standing is 25 to 50 ℃. Specifically, the temperature of the standing may be 25 ℃, 27 ℃, 30 ℃, 33 ℃, 35 ℃, 37 ℃, 40 ℃, 43 ℃, 45 ℃, 47 ℃ or 50 ℃.
Preferably, in step (3), the standing time is 3 to 7 days. Specifically, the standing time may be 3 days, 4 days, 5 days, 6 days, or 7 days.
According to the method, vanadium leaching rate can reach more than 90% through a water leaching process by carrying out short-time oxidizing roasting pretreatment on titanium tetrachloride refining tailings, the impurity content in the leaching solution is reduced, the consumption of acid-base reagents in leaching and purifying processes is effectively reduced, the efficient and low-cost extraction of vanadium is realized, and TiO is added to the leaching solution2And standing after the seed crystal to realize that the removal rate of the vanadium-containing leaching solution titanium reaches more than 80 percent, the vanadium loss is less than or equal to 0.5 percent, and the selective separation of vanadium and titanium is realized. Finally obtaining vanadium-containing purified liquid, namely, adopting an extraction process to prepare a high-purity vanadium product, wherein the chlorine content in the filter residue is less than or equal to 0.1 weight percent, and the filter residue can be directly used as a titanium-rich material.
The method realizes the high-efficiency and low-cost recovery of vanadium resources and the selective separation of vanadium and titanium, effectively removes chlorine in the titanium tetrachloride refined tailings, and solves the problem of environmental pollution of the refined tailings.
The present invention will be described in detail below by way of examples, but the method of the present invention is not limited thereto.
In the following examples and comparative examples, the titanium tetrachloride refined tailings used were obtained from crude titanium tetrachloride solution by a fatty acid vanadium removal process, the titanium tetrachloride refined tailings contained 10 to 30 wt% of vanadium, 10 to 50 wt% of chlorine, and 10 to 35 wt% of titanium, and TiO was used2The seed crystal comes fromTiCl of water4Hydrolysis to produce TiOCl2And HCl in water, followed by neutralization with sodium hydroxide to produce TiO2The suspension is finally washed to obtain TiO2Seed crystals with an average diameter of 0.6-0.7 μm.
Example 1
(1) Roasting 100g of titanium tetrachloride refined tailings (the content of vanadium in the titanium tetrachloride refined tailings is 10 wt%, the content of chlorine in the titanium tetrachloride refined tailings is 10 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 14 wt%) at 300 ℃ for 5min in an oxygen atmosphere to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1), wherein the liquid-solid ratio of the water to the roasting slag is 5mL/g, stirring and leaching at 50 ℃ for 30min, and then carrying out solid-liquid separation to obtain vanadium-containing leachate and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystals, TiO2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is 0.001:1, standing for 3 days at 25 ℃, and then filtering to obtain vanadium-containing purified liquid and filter residue;
the vanadium-containing purified liquid can be further subjected to an extraction process to obtain a high-purity vanadium product.
Example 2
(1) Roasting 100g of titanium tetrachloride refined tailings (the content of vanadium in the titanium tetrachloride refined tailings is 20 wt%, the content of chlorine in the titanium tetrachloride refined tailings is 41 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 10 wt%) at 200 ℃ for 15min in the atmosphere of air to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1), wherein the liquid-solid ratio of the water to the roasting slag is 5mL/g, stirring and leaching for 90min at 50 ℃, and then carrying out solid-liquid separation to obtain vanadium-containing leachate and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystals, TiO2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is 0.01:1, standing for 5 days at 30 ℃, and then filtering to obtain vanadium-containing purified liquid and filter residue;
the vanadium-containing purified liquid can be further subjected to an extraction process to obtain a high-purity vanadium product.
Example 3
(1) Roasting 100g of titanium tetrachloride refined tailings (the content of vanadium in the titanium tetrachloride refined tailings is 18 wt%, the content of chlorine in the titanium tetrachloride refined tailings is 26 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 12 wt%) at 100 ℃ for 30min in air to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1), wherein the liquid-solid ratio of water to the roasting slag is 10mL/g, stirring and leaching for 120min at 95 ℃, and then carrying out solid-liquid separation to obtain vanadium-containing leachate and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystals, TiO2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is 0.05:1, standing for 7 days at 50 ℃, and then filtering to obtain vanadium-containing purified liquid and filter residue;
the vanadium-containing purified liquid can be further subjected to an extraction process to obtain a high-purity vanadium product.
Comparative example 1
(1) Adding water into 100g of titanium tetrachloride refined tailings (the content of vanadium in the titanium tetrachloride refined tailings is 10 wt%, the content of chlorine in the titanium tetrachloride refined tailings is 10 wt%, and the content of titanium in the titanium tetrachloride refined tailings is 14 wt%), wherein the liquid-solid ratio of the water to the titanium tetrachloride refined tailings is 5mL/g, stirring and leaching the mixture at 50 ℃ for 30min, and then carrying out solid-liquid separation to obtain vanadium-containing leachate and leaching residues;
(2) adding TiO into the vanadium-containing leaching solution obtained in the step (1)2Seed crystals, TiO2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is 0.001:1, standing for 3 days at 25 ℃, and then filtering to obtain vanadium-containing purified liquid and filter residue;
comparative example 2
The method is carried out according to the method of the embodiment 1, except that in the step (1), the roasting temperature is 350 ℃, and the vanadium-containing purified liquid and the filter residue are obtained.
Comparative example 3
The method is implemented according to the method in the embodiment 1, except that in the step (1), the roasting time is 3min, and the vanadium-containing purified liquid and the filter residue are obtained.
Comparative example 4
The method is implemented according to the method described in the embodiment 3, except that in the step (1), the roasting time is 40min, and the vanadium-containing purified liquid and the filter residue are obtained.
Comparative example 5
The method is carried out according to the method of the embodiment 3, except that in the step (1), the roasting temperature is 50 ℃, and the vanadium-containing purified liquid and the filter residue are obtained.
Comparative example 6
The procedure is as described in example 1, except that, in step (3), TiO is added2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is 0.0005: 1, obtaining vanadium-containing purified liquid and filter residue.
Test example
Respectively detecting the concentration of vanadium, the concentration of titanium and the concentration of chlorine in the vanadium-containing purified liquid, the content of vanadium, the content of titanium and the content of chlorine in filter residue in the examples and the comparative examples, and calculating the leaching rate of vanadium, the removal rate of titanium and the loss of vanadium, wherein the results are shown in table 1;
the method for calculating the leaching rate of vanadium comprises the following steps: weight m of vanadium in roasting slag1Weight m of vanadium in leaching residue2Vanadium leaching rate σ1＝(1-m2/m1)×100％；
In comparative example 1, since the calcination was not performed, the leaching rate of vanadium in comparative example 1 was calculated by: weight m of vanadium in titanium tetrachloride refined tailings1Weight m of vanadium in leaching residue2Vanadium leaching rate σ1＝(1-m2/m1)×100％；
The calculation method of the titanium removal rate comprises the following steps: weight m of titanium in vanadium-containing leaching solution3The weight m of titanium in the vanadium-containing purification solution4Titanium removal rate σ2＝(1-m4/m3)×100％；
The method for calculating the loss rate of vanadium comprises the following steps: weight m of vanadium in vanadium-containing leaching solution5The weight m of vanadium in the vanadium-containing purification solution6Loss ratio of vanadium σ3＝(1-m6/m5)×100％。
TABLE 1
The results in table 1 show that by adopting the method of the invention, the leaching rate of vanadium reaches more than 90%, chlorine in the titanium tetrachloride refined tailings is effectively removed, so that chlorine mainly enters the purification solution, the chlorine content in the filter residue is extremely low, the titanium removal rate reaches more than 80%, the vanadium loss is less than or equal to 0.5%, the titanium removal rate is high, the vanadium loss is small, and meanwhile, the chlorine content in the filter residue is less than or equal to 0.1 wt%, and the filter residue can be directly used as a titanium-rich material, so that the high-efficiency selective separation of vanadium and titanium in the titanium tetrachloride refined tailings is realized.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for separating vanadium and titanium from titanium tetrachloride refined tailings, which is characterized by comprising the following steps:
(1) roasting the titanium tetrachloride refined tailings at the temperature of 100-300 ℃ for 5-30min to obtain roasted slag;
(2) adding water into the roasting slag obtained in the step (1) for stirring and leaching, and then carrying out solid-liquid separation to obtain vanadium-containing leaching solution and leaching residue;
(3) adding TiO into the vanadium-containing leaching solution obtained in the step (2)2Seed crystal, standing, and filtering to obtain vanadium-containing purified liquid and filter residue, wherein the TiO is2The weight ratio of the seed crystal to the titanium element in the vanadium-containing leaching solution is (0.001-0.05): 1.
2. The method according to claim 1, wherein in the step (1), the content of vanadium in the titanium tetrachloride refining tailings is 10 to 30% by weight, and the content of titanium is 10 to 35% by weight.
3. The method according to claim 1 or 2, wherein in the step (1), the content of chlorine in the titanium tetrachloride refining tailings is 10 to 50% by weight.
4. The method according to claim 1, wherein in step (1), the atmosphere for the calcination is an oxygen-containing atmosphere.
5. The method according to claim 4, wherein in step (1), the oxygen-containing atmosphere is air and/or oxygen.
6. The method as claimed in claim 1, wherein in step (2), the liquid-solid ratio of the water to the roasting slag is 1-10 mL/g.
7. The method according to claim 1 or 6, wherein in step (2), the temperature of the agitation leaching is 50-95 ℃.
8. The method as claimed in claim 7, wherein the agitation leaching time is 30-120min in the step (2).
9. The method according to claim 1, wherein, in the step (3), the temperature of the standing is 25 to 50 ℃.
10. The method according to claim 1 or 9, wherein in step (3), the standing time is 3 to 7 days.
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