CN101358301A - Method for directly extracting vanadium from vanadium-titanium magnetite concentrate - Google Patents
Method for directly extracting vanadium from vanadium-titanium magnetite concentrate Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 58
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000012141 concentrate Substances 0.000 title claims abstract description 31
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 39
- 239000008188 pellet Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 29
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 13
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 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 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001948 sodium oxide Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 208000004434 Calcinosis Diseases 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 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 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- -1 vanadate ions Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及一种从钒钛磁铁精矿中提钒的方法，更具体地讲，涉及一种可以直接从钒钛磁铁精矿中提钒的方法。The invention relates to a method for extracting vanadium from vanadium-titanium magnetite concentrate, more specifically, relates to a method for directly extracting vanadium from vanadium-titanium magnetite concentrate.
背景技术 Background technique
目前，除了首先将钒钛磁铁精矿中的铁还原然后再从钒钛渣中提钒的方法之外，国内外已经对直接从钒钛磁铁精矿中提钒的方法进行了充分的研究。At present, in addition to the method of first reducing iron in vanadium-titanium magnetite concentrate and then extracting vanadium from vanadium-titanium slag, the method of directly extracting vanadium from vanadium-titanium magnetite concentrate has been fully studied at home and abroad.
国外从钒钛磁铁精矿中直接提钒的产业化工艺为：钠化球团→氧化钠化焙烧→粉料(或球团)水浸出→沉钒→多钒酸铵或偏钒酸铵。该工艺通过浸出液循环浸出的方式富集溶液中的钒浓度，虽然钒浓度可以富集到10～20g/l，但是需要大量的水来洗涤残渣中的可溶钒，从而使得使用水的量剧增。因此，为了便于操作，通常将浸出液中的钒浓度控制在10g/l左右。由于浸出液中的钒浓度较低，所以沉钒后产生大量的含氨氮的沉钒废水，环境污染严重。The industrialization process of directly extracting vanadium from vanadium-titanium magnetite concentrate in foreign countries is: sodium pellet → sodium oxide roasting → powder (or pellet) water leaching → vanadium precipitation → ammonium polyvanadate or ammonium metavanadate. This process enriches the concentration of vanadium in the solution by circulating the leaching solution. Although the concentration of vanadium can be enriched to 10-20g/l, a large amount of water is needed to wash the soluble vanadium in the residue, so that the amount of water used is severe. increase. Therefore, for the convenience of operation, the concentration of vanadium in the leaching solution is usually controlled at about 10g/l. Due to the low concentration of vanadium in the leaching solution, a large amount of vanadium-containing waste water containing ammonia nitrogen is produced after vanadium precipitation, which seriously pollutes the environment.
国内从钒钛磁铁精矿中直接提钒的工艺为：钠化球团→氧化钠化焙烧→球团水浸出→沉钒→多钒酸铵或偏钒酸铵。国内的工艺主要采用球团浸出的方式，从而获得浸出液中的钒浓度为7g/l左右。由于球团的浸出时间长，温度高，使得浸出工序能耗增大，并且沉钒产生大量的含氨氮的沉钒废水，造成一定的环境污染。The process of directly extracting vanadium from vanadium-titanium magnetite concentrate in China is: sodium pellet → sodium oxide roasting → pellet water leaching → vanadium precipitation → ammonium polyvanadate or ammonium metavanadate. The domestic process mainly adopts pellet leaching, so that the concentration of vanadium in the leaching solution is about 7g/l. Due to the long leaching time and high temperature of the pellets, the energy consumption of the leaching process increases, and the vanadium precipitation produces a large amount of vanadium precipitation wastewater containing ammonia nitrogen, which causes certain environmental pollution.
第CN1629326A号中国发明专利申请公开了一种含钒铁精矿球团提钒方法。该方法是在含钒铁精矿粉中加入适量的钠盐造球，然后焙烧成钠化球团；钠化球团经过水浸处理使其中的可溶性钒酸钠溶解在水中；将获得的钒酸钠溶液浓缩后加入硫酸混合、搅拌，使五氧化二钒沉淀出来，经过压滤、烘干制成粉状或溶化浇铸成片状的五氧化二钒的成品。在该工艺中，为了溶解可溶性钒酸钠，需要多次浸泡球团，因此，浸出工序时间长，从而增大了能耗。The Chinese invention patent application No. CN1629326A discloses a method for extracting vanadium from iron ore concentrate pellets containing vanadium. The method is to add an appropriate amount of sodium salt into vanadium-containing iron ore concentrate powder to form pellets, and then roast them into sodiumized pellets; the sodiumized pellets are subjected to water immersion treatment to dissolve the soluble sodium vanadate in water; the obtained vanadium After the sodium acid solution is concentrated, sulfuric acid is added to mix and stir to precipitate vanadium pentoxide, which is then filtered and dried to make a powder or melted and cast into a finished product of vanadium pentoxide. In this process, in order to dissolve the soluble sodium vanadate, the pellets need to be soaked many times, so the leaching process takes a long time, thereby increasing the energy consumption.
为了解决上述工艺存在的问题，需要一种可以减少浸出、洗涤时间和次数并节约用水量的直接提钒的方法。In order to solve the problems existing in the above process, a method for directly extracting vanadium that can reduce leaching and washing time and frequency and save water consumption is needed.
发明内容 Contents of the invention
本发明的目的在于提供一种从钒钛磁铁精矿中直接提钒的方法，该方法可以使净化后的余液循环利用，避免了含氨氮废水的产生，并节约用水，减少了能耗。The object of the present invention is to provide a method for directly extracting vanadium from vanadium-titanium magnetite concentrate, which can recycle the purified residual liquid, avoid the generation of ammonia nitrogen-containing waste water, save water and reduce energy consumption.
为了实现上述目的，本发明提供了一种从钒钛磁铁精矿中直接提钒的方法，该方法包括：一种从钒钛磁铁精矿直接提钒的方法，包括步骤：将硫酸钠加入钒钛磁铁精矿中，混合均匀后进行造球；将造球后的所得球团经高温氧化钠化焙烧；将焙烧后的球团磨成粉料，用水浸出洗涤；净化浸出液，从而使钒富集得到含钒溶液；向得到的含钒溶液中加入氯化钙沉淀钒酸钙。In order to achieve the above object, the present invention provides a method for directly extracting vanadium from vanadium-titanium magnetite concentrate, the method comprising: a method for directly extracting vanadium from vanadium-titanium magnetite concentrate, comprising the steps of: adding sodium sulfate to vanadium In the titanium magnetite concentrate, the pellets are mixed evenly; the obtained pellets are roasted by high-temperature sodium oxide; the roasted pellets are ground into powder, and washed with water; the leachate is purified to make the vanadium rich Collect to obtain a vanadium-containing solution; add calcium chloride to precipitate calcium vanadate in the obtained vanadium-containing solution.
优选地，在本发明的实施例中，将焙烧后的球团磨成粉料的步骤为采用湿球磨的方式。湿球磨所用的水为新水、净化后的余液、或者新水和余液的混合物。Preferably, in the embodiment of the present invention, the step of grinding the calcined pellets into powder is by means of wet ball milling. The water used in wet ball milling is new water, purified residual liquid, or a mixture of new water and residual liquid.
在本发明的实施例中，浸出洗涤用水为热水。浸出洗涤用水为新水、净化后的余液、或者新水和余液的混合物。In an embodiment of the present invention, the water for leaching and washing is hot water. The water used for leaching and washing is new water, purified residual liquid, or a mixture of new water and residual liquid.
在本发明的实施例中，净化浸出液使钒富集的步骤包括采用离子交换或萃取的方式来净化浸出液。离子交换方法采用阴离子交换树脂。阴离子交换树脂为SO4 2-型树脂或Cl-型树脂。离子交换或萃取后的余液返回湿球磨步骤和浸出洗涤步骤使用。循环使用离子交换或萃取后的余液时，根据余液中硫酸钠的浓度确定是否对溶液进行冷冻结晶并分离硫酸钠。In an embodiment of the present invention, the step of purifying the leachate to enrich vanadium includes using ion exchange or extraction to purify the leachate. The ion exchange method employs anion exchange resins. The anion exchange resin is SO 4 2- type resin or Cl - type resin. The residual liquid after ion exchange or extraction is returned to the wet ball milling step and the leaching washing step for use. When recycling the residual liquid after ion exchange or extraction, determine whether to freeze and crystallize the solution and separate sodium sulfate according to the concentration of sodium sulfate in the residual liquid.
附图说明 Description of drawings
图1是示出了根据本发明实施例的从钒钛磁铁精矿中直接提钒的方法的流程图。Fig. 1 is a flowchart showing a method for directly extracting vanadium from vanadium-titanium magnetite concentrate according to an embodiment of the present invention.
具体实施方式 Detailed ways
现在，将参照附图来详细描述本发明的具体实施例。Now, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.
图1是示出了根据本发明实施例的从钒钛磁铁精矿中直接提钒的方法的流程图。Fig. 1 is a flowchart showing a method for directly extracting vanadium from vanadium-titanium magnetite concentrate according to an embodiment of the present invention.
参照图1，在步骤S100，首先将钒钛磁铁精矿和硫酸钠按一定量的配比混合均匀，而硫酸钠的配比量根据钒钛磁铁精矿中的钒、硅含量确定。Referring to Fig. 1, in step S100, at first, the vanadium-titanium magnetite concentrate and sodium sulfate are uniformly mixed in a certain proportion, and the proportioning amount of sodium sulfate is determined according to the vanadium and silicon content in the vanadium-titanium magnetite concentrate.
在步骤S101，将混合均匀的钒钛磁铁精矿和硫酸钠的混合物造球。造球后的球团的直径为大约8～12mm。In step S101, the uniformly mixed mixture of vanadium-titanium magnetite concentrate and sodium sulfate is pelletized. The pellets after pelletizing have a diameter of about 8 to 12 mm.
在步骤S102，将球团在大约1250℃下进行焙烧，然后保温大约60分钟，使钒钛磁铁精矿中的钒与硫酸钠反应生成钒酸钠。In step S102, the pellets are roasted at about 1250° C., and then kept for about 60 minutes, so that the vanadium in the vanadium-titanium magnetite concentrate reacts with sodium sulfate to form sodium vanadate.
在步骤S103，将焙烧后的热球团在湿球磨中进行破碎，这样能提高后续的浸出温度，降低能耗。In step S103, the calcined hot pellets are crushed in a wet ball mill, which can increase the subsequent leaching temperature and reduce energy consumption.
在湿球磨中进行破碎的介质可以是新水，也可以是后续净化工序后的余液(将在后面进行描述)，或者也可以是新水与所述余液的混合物。The medium for crushing in the wet ball mill can be new water, or the residual liquid after the subsequent purification process (to be described later), or a mixture of new water and the residual liquid.
在步骤S104，将湿球磨后的粉料用水浸出洗涤，使焙烧后的可溶性钒酸钠溶于水中，浸出洗涤后的不溶物为提钒残渣(步骤S1042)，而钒钛磁铁精矿中的钛和铁包含在提钒残渣中。在步骤S104中，可以使用热水来浸出洗涤。并且，在该步骤中使用的水可以是新水，也可以是后续净化工序后的余液(将在后面进行描述)，或者也可以是新水与所述余液的混合物。In step S104, the powder after the wet ball milling is leached and washed with water, so that the soluble sodium vanadate after roasting is dissolved in water, and the insoluble matter after leaching and washing is the vanadium extraction residue (step S1042), and the vanadium-titanium magnetite concentrate Titanium and iron are contained in the vanadium extraction residue. In step S104, hot water may be used for leaching and washing. And, the water used in this step can be new water, also can be the residual liquid (will be described later) after subsequent purification process, or also can be the mixture of new water and described residual liquid.
在步骤S105，将经过浸出洗涤后所得到的溶液用离子交换树脂进行净化并富集钒，或者采用萃取的方式进行净化并富集钒。离子交换树脂可以采用阴离子交换树脂，例如SO4 2-型树脂或Cl-型树脂，优选的为SO4 2-型树脂。例如，可以使用717树脂。萃取剂可以是N-263萃取剂。In step S105, the solution obtained after leaching and washing is purified with ion exchange resin and enriched in vanadium, or purified and enriched in vanadium by means of extraction. The ion exchange resin can be anion exchange resin, such as SO 4 2- type resin or Cl - type resin, preferably SO 4 2- type resin. For example, 717 resin can be used. The extractant can be N-263 extractant.
经离子交换后的余液(溶液)可以返回到步骤S103(步骤S1031)和S104(步骤S1041)，即，经离子交换后的余液可用作湿球磨的介质和用于浸出洗涤球磨后的粉料。The residual liquid (solution) after ion exchange can be returned to steps S103 (step S1031) and S104 (step S1041), that is, the residual liquid after ion exchange can be used as a medium for wet ball milling and for leaching and washing after ball milling. Powder.
当余液中的硫酸钠浓度达到一定量时，可以对余液进行冷却结晶，分离出硫酸钠。分离出的结晶硫酸钠可用于步骤S100(步骤S1011)。When the concentration of sodium sulfate in the residual liquid reaches a certain amount, the residual liquid can be cooled and crystallized to separate sodium sulfate. The separated crystalline sodium sulfate can be used in step S100 (step S1011).
由于在步骤S100中，加入了硫酸钠，并且硫酸钠的溶解度随溶液温度的变化而变化较大，所以在循环使用余液的过程中，可以通过结晶的方式去除硫酸钠。因此，在根据本发明的实施例的方法中，优选的阴离子交换树脂为SO4 2-型树脂。Since sodium sulfate is added in step S100, and the solubility of sodium sulfate varies greatly with the temperature of the solution, sodium sulfate can be removed by crystallization during the process of recycling the residual liquid. Therefore, in the method according to the embodiment of the present invention, the preferred anion exchange resin is SO 4 2- type resin.
在步骤S106，利用解吸剂对离子交换树脂进行解吸，或者对萃取后的溶液进行反萃取。例如，解吸剂可为氢氧化钠，反萃剂可为氢氧化钠和氯化钠的混合溶液。In step S106, the ion exchange resin is desorbed with a desorbent, or the extracted solution is back-extracted. For example, the desorbent can be sodium hydroxide, and the stripping agent can be a mixed solution of sodium hydroxide and sodium chloride.
钒在浸出液体系中主要以HVO4 2-的形式存在，与离子交换树脂(R代表有机基团)发生的反应为：Vanadium mainly exists in the form of HVO 4 2- in the leach solution system, and the reaction with the ion exchange resin (R represents an organic group) is as follows:
树脂吸附：HVO4 2-+R2SO4(有机相)＝R2HVO4(有机相)+SO4 2- Resin adsorption: HVO 4 2- + R 2 SO 4 (organic phase) = R 2 HVO 4 (organic phase) + SO 4 2-
树脂解吸：2R2HVO4(有机相)+4OH-＝4ROH(有机相)+V2O7 4-+H2OResin desorption: 2R 2 HVO 4 (organic phase) + 4OH - = 4ROH (organic phase) + V 2 O 7 4- + H 2 O
树脂转型：2ROH(有机相)+SO4 2-＝R2SO4(有机相)+2OH- Resin transformation: 2ROH (organic phase) + SO 4 2- ＝ R 2 SO 4 (organic phase) + 2OH -
浸出液在萃取过程中发生的反应(R代表有机基团)为：The reaction of the leachate during the extraction process (R represents an organic group) is:
萃取反应：HVO4 2-+2RCl(有机相)＝R2HVO4(有机相)_+2Cl- Extraction reaction: HVO 4 2- +2RCl (organic phase) = R 2 HVO 4 (organic phase)_+2Cl -
反萃反应：2R2HVO4(有机相)+4Cl-＝4RCl(有机相)+V2O7 4-+H2OStripping reaction: 2R 2 HVO 4 (organic phase) + 4Cl - = 4RCl (organic phase) + V 2 O 7 4- + H 2 O
2R2HVO4(有机相)+4OH-＝4ROH(有机相)+V2O7 4-+H2O2R 2 HVO 4 (organic phase)+4OH - ＝4ROH (organic phase)+V 2 O 7 4- +H 2 O
在步骤S107，向解吸后的溶液或反萃取后的溶液中加入氯化钙，使溶液中的钒酸根离子与钙离子反应，然后在步骤S108，得到沉淀物钒酸钙。In step S107, calcium chloride is added to the desorbed solution or the stripped solution, so that the vanadate ions in the solution react with calcium ions, and then in step S108, precipitated calcium vanadate is obtained.
在步骤S108，进行固液分离，得到钒酸钙和废弃的溶液。对废弃的溶液进行废水处理(步骤S1081)，而得到的钒酸钙则用于冶炼钒铁(步骤S1082)。In step S108, solid-liquid separation is performed to obtain calcium vanadate and a discarded solution. Wastewater treatment is performed on the discarded solution (step S1081), and the obtained calcium vanadate is used for smelting ferrovanadium (step S1082).
下面将给出根据本发明的从钒钛磁铁精矿中直接提钒的方法的具体的实施例。Specific examples of the method for directly extracting vanadium from vanadium-titanium magnetite concentrate according to the present invention will be given below.
实施例1Example 1
取攀枝花钒钛磁铁精矿2kg(粒度：-200目67％；主要成分：V2O5 0.769％，TFe 58.66％，FeO 27.08％，SiO2 1.52％，TiO2 11.09％，MgO 1.63％，MnO0.432％，Al2O3 3.43％)，在其中加入0.12kg无水硫酸钠，混匀后造球，球团大小为8～10mm，球团在马弗炉内升温至1250℃后保温60min；将焙烧后的球团磨成粉料用热水浸出后，获得TV＝1.895g/l的浸出液4L，其中，TV表示全钒量，即金属钒的含量；浸出液采用717树脂吸附、氢氧化钠解吸，获得TV＝24.3g/l的解吸液300ml；向解吸液加入16g氯化钙沉淀钒酸钙，获取23.4gTV＝30.8％的钒酸钙。Take 2kg of Panzhihua vanadium-titanium magnetite concentrate (particle size: -200 mesh 67%; main components: V 2 O 5 0.769%, TFe 58.66%, FeO 27.08%, SiO 2 1.52%, TiO 2 11.09%, MgO 1.63%, MnO0 .432%, Al 2 O 3 3.43%), add 0.12kg of anhydrous sodium sulfate to it, mix well and make pellets. ; Grind the roasted pellets into powder and leaching with hot water to obtain 4L of leaching solution with TV=1.895g/l, wherein, TV represents the amount of total vanadium, i.e. the content of metal vanadium; the leaching solution adopts 717 resin adsorption, hydrogen oxidation Sodium was desorbed to obtain 300ml of desorption solution with TV=24.3g/l; 16g of calcium chloride was added to the desorption solution to precipitate calcium vanadate to obtain 23.4g of TV=30.8% calcium vanadate.
实施例2Example 2
取攀枝花钒钛磁铁精矿2.5kg(粒度：-200目67％；主要成分：V2O50.769％，TFe 58.66％，FeO 27.08％，SiO2 1.52％，TiO2 11.09％，MgO 1.63％，MnO 0.432％，Al2O3 3.43％)在其中加入0.15kg无水硫酸钠，混匀后造球，球团大小为8～12mm；球团在马弗炉内升温至1250℃后保温60min；将焙烧后的球团磨成粉料用热水浸出后，获得TV＝2.07g/l的浸出液4.58L；浸出液采用717树脂吸附、氢氧化钠解吸，获得TV＝25.2g/l的解吸液361ml；向解吸液加入20g氯化钙沉淀钒酸钙，获取29.7g TV＝30.2％的钒酸钙。Take 2.5kg of Panzhihua vanadium-titanium magnetite concentrate (particle size: -200 mesh 67%; main components: V 2 O 5 0.769%, TFe 58.66%, FeO 27.08%, SiO 2 1.52%, TiO 2 11.09%, MgO 1.63%, MnO 0.432%, Al 2 O 3 3.43%), add 0.15kg of anhydrous sodium sulfate, mix well and make pellets, the size of the pellets is 8-12mm; the pellets are heated to 1250°C in the muffle furnace and then kept for 60 minutes; Grind the roasted pellets into powder and leaching with hot water to obtain 4.58L of leaching solution with TV=2.07g/l; the leaching solution is adsorbed with 717 resin and desorbed with sodium hydroxide to obtain 361ml of desorption solution with TV=25.2g/l ; Add 20g of calcium chloride to precipitate calcium vanadate to the desorption solution to obtain 29.7g of TV=30.2% calcium vanadate.
实施例3Example 3
取攀枝花白马钒钛磁铁精矿1.7kg(粒度：-200目67％；主要成分：V2O50.769％，TFe 58.66％，FeO 27.08％，SiO2 1.52％，TiO2 11.09％，MgO 1.63％，MnO 0.432％，Al2O3 3.43％)在其中加入0.10kg无水硫酸钠，混匀后造球，球团大小为8～12mm；球团在马弗炉内升温至1250℃后保温60min；将焙烧后的球团磨成粉料用热水浸出后，获得TV＝1.86g/l的浸出液3.46L；浸出液采用N-263萃取，氢氧化钠、氯化钠反萃，获得TV＝23.6g/l的反萃液361ml；向解吸液加入20g氯化钙沉淀钒酸钙，获取20.8g TV＝29.4％的钒酸钙。Take 1.7kg of Panzhihua Baima vanadium-titanium magnetite concentrate (particle size: -200 mesh 67%; main components: V 2 O 5 0.769%, TFe 58.66%, FeO 27.08%, SiO 2 1.52%, TiO 2 11.09%, MgO 1.63% , MnO 0.432%, Al 2 O 3 3.43%), add 0.10kg of anhydrous sodium sulfate to it, mix well and make pellets, the size of the pellets is 8-12mm; the pellets are heated to 1250°C in the muffle furnace and then kept for 60min ; Grind the roasted pellets into powder and leaching with hot water to obtain 3.46L of leaching solution with TV=1.86g/l; extracting the leaching solution with N-263, back-extracting with sodium hydroxide and sodium chloride to obtain TV=23.6 361ml of the stripping liquid of g/l; Add 20g calcium chloride precipitation calcium vanadate to the stripping liquid, obtain the calcium vanadate of 20.8g TV=29.4%.
从以上三个实施例可以看出，实施例1和2采用离子交换树脂对浸出液进行净化。而实施例3采用萃取的方式对浸出液进行净化。另外，树脂吸附和萃取后的余液均可以循环用作湿球磨的介质和浸出洗涤时的所用水。It can be seen from the above three examples that examples 1 and 2 use ion exchange resins to purify the leachate. However, Example 3 uses extraction to purify the leachate. In addition, the residual liquid after resin adsorption and extraction can be recycled as the medium of wet ball milling and the water used in leaching and washing.
因此，根据本发明实施例的从钒钛磁铁精矿直接提钒的方法可以大大减少水浸和残渣的洗涤次数；浸出液经离子交换或萃取后返回浸出循环使用，既降低了浸出洗涤新水用量，又提高了沉钒溶液中的钒浓度，减少了废水的产生；同时还避免了含氨氮废水的产生，大大减轻了传统工艺的环境污染问题。Therefore, the method for directly extracting vanadium from vanadium-titanium magnetite concentrate according to the embodiment of the present invention can greatly reduce the number of times of water leaching and residue washing; the leaching solution is returned to leaching for recycling after ion exchange or extraction, which not only reduces the amount of fresh water used for leaching and washing , and increased the concentration of vanadium in the vanadium precipitation solution, reducing the generation of waste water; at the same time, it also avoided the generation of waste water containing ammonia nitrogen, greatly reducing the environmental pollution problems of traditional processes.
将清楚的是，在不脱离本发明的精神或范围的情况下，可以对本发明做出各种修改和变形。因此，如果对本发明的修改和变形落入权利要求及其等同物的范围内，则本发明意图覆盖这些修改和变形。It will be apparent that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. Thus, it is intended that the present invention covers the modifications and variations of the present invention if they come within the scope of the claims and their equivalents.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925720A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Method for extracting vanadium from shale containing vanadium |
| CN104388679A (en) * | 2014-09-30 | 2015-03-04 | 边悟 | Method for extracting vanadium from vanadium-containing raw material |
| CN105695732A (en) * | 2016-03-01 | 2016-06-22 | 攀钢集团攀枝花钢钒有限公司 | Fine vanadium slag pelleting and roasting method and production system thereof |
| CN106995879A (en) * | 2017-04-05 | 2017-08-01 | 东北大学 | A kind of low-grade Oxidation Leaching of sodium containing chromic vanadium-titanium ferroferrite extraction vanadium method |
| CN109722531A (en) * | 2019-02-15 | 2019-05-07 | 四川大裂谷钒业有限公司 | Vanadium titano-magnetite process for extracting vanadium |
| CN119736488A (en) * | 2024-12-31 | 2025-04-01 | 中南大学 | A method for improving the leaching rate of vanadium from vanadium-titanium iron concentrate by acid leaching |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925720A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Method for extracting vanadium from shale containing vanadium |
| CN102925720B (en) * | 2012-11-14 | 2015-02-04 | 武汉理工大学 | Method for extracting vanadium from shale containing vanadium |
| CN104388679A (en) * | 2014-09-30 | 2015-03-04 | 边悟 | Method for extracting vanadium from vanadium-containing raw material |
| CN105695732A (en) * | 2016-03-01 | 2016-06-22 | 攀钢集团攀枝花钢钒有限公司 | Fine vanadium slag pelleting and roasting method and production system thereof |
| CN106995879A (en) * | 2017-04-05 | 2017-08-01 | 东北大学 | A kind of low-grade Oxidation Leaching of sodium containing chromic vanadium-titanium ferroferrite extraction vanadium method |
| CN109722531A (en) * | 2019-02-15 | 2019-05-07 | 四川大裂谷钒业有限公司 | Vanadium titano-magnetite process for extracting vanadium |
| CN119736488A (en) * | 2024-12-31 | 2025-04-01 | 中南大学 | A method for improving the leaching rate of vanadium from vanadium-titanium iron concentrate by acid leaching |
| CN119736488B (en) * | 2024-12-31 | 2025-10-17 | 中南大学 | Method for improving acid leaching vanadium leaching rate of vanadium-titanium-iron concentrate |
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