WO2024124791A1 - Method for preparing refined vanadium oxytrichloride from vanadium-containing refined tailings - Google Patents
Method for preparing refined vanadium oxytrichloride from vanadium-containing refined tailings Download PDFInfo
- Publication number
- WO2024124791A1 WO2024124791A1 PCT/CN2023/093835 CN2023093835W WO2024124791A1 WO 2024124791 A1 WO2024124791 A1 WO 2024124791A1 CN 2023093835 W CN2023093835 W CN 2023093835W WO 2024124791 A1 WO2024124791 A1 WO 2024124791A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vanadium
- refined
- tailings
- oxychloride
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
Definitions
- the invention belongs to the field of metallurgy and chemical industry, and more specifically, relates to a method for preparing refined vanadium oxytrichloride by utilizing vanadium-containing refined tailings.
- Refined tailings are a type of solid waste produced by vanadium-titanium slag in the process of producing titanium dioxide chloride or titanium sponge.
- the vanadium content can reach 20%, which is a vanadium resource with great utilization value.
- vanadium, titanium and other impurities are mostly in the form of chloride/chloride oxides, chlorine and hydrogen chloride pollutants are easily generated, which makes it difficult to treat.
- the current treatment method is mainly to remove chlorine through oxidative roasting, and convert vanadium and titanium into oxides and then mix them with ordinary vanadium slag for treatment. This method has some problems such as high oxidative roasting temperature, a large amount of chlorine smoke generated during the roasting process that is difficult to handle, and difficulty in separating vanadium and titanium from the roasting product.
- Patent CN 104004920A discloses a method for extracting vanadium from titanium tetrachloride refined tailings, which involves high-temperature roasting of titanium tetrachloride refined tailings and leaching with sulfuric acid, and the vanadium leaching rate can reach more than 90%.
- the energy consumption in the roasting stage is high, and the consumption of leaching sulfuric acid is large.
- the leaching solution is highly acidic, making subsequent treatment difficult.
- Patent CN 108996547A discloses a method for extracting vanadium from titanium tetrachloride refined tailings by ultrasonic-assisted alkaline leaching. The method adopts an alkaline leaching process but requires the introduction of oxygen while performing the leaching process under ultrasonic assistance.
- Patents CN 106929696A and CN 107032400A disclose a method for extracting vanadium by ammonium leaching and alkali leaching of TiCl4 refined tailings, respectively. Both methods involve leaching the TiCl4 refined tailings after roasting, and obtaining a leachate which is purified, impurities removed, and vanadium precipitated to obtain vanadium pentoxide.
- Vanadium trichloride is an important chemical product used to manufacture high-purity vanadium pentoxide powder, catalysts, etc., and is used in many fields.
- the current vanadium trichloride production process mainly involves converting vanadium-containing ore into
- the vanadium-containing minerals include ammonium metavanadate, ammonium polyvanadate, vanadium pentoxide, vanadium slag, vanadium-containing refined tailings, etc.
- the chlorinating agents include chlorine gas, ferric chloride, etc.
- Patent CN110642294A discloses a method for preparing vanadium oxychloride by low-temperature chlorination of blast furnace slag, wherein blast furnace slag and a carbonaceous reducing agent are mixed, preheated, and then chlorine gas is introduced to react to obtain a vanadium oxychloride mixture.
- Patent CN112142107A discloses a method for preparing high-purity vanadium oxychloride from vanadium-containing refined tailings, wherein the refined tailings and petroleum coke are evenly mixed and subjected to chlorination reaction to obtain crude vanadium oxychloride, and the crude vanadium oxychloride is hydrolyzed and distilled to obtain high-purity vanadium oxychloride.
- Patent CN111410228A discloses a method for preparing high-purity vanadium oxytrichloride using ferrovanadium fine powder, wherein the ferrovanadium fine powder is placed in a chlorination reaction, chlorine is introduced and the temperature is raised to 300°C to 600°C, chlorine and oxygen are introduced to adjust nitrogen to carry out a chlorination reaction, volatiles are condensed to obtain a crude vanadium oxytrichloride, and the crude vanadium oxytrichloride is distilled and condensed to obtain high-purity vanadium oxytrichloride.
- the disclosed methods for preparing high-purity vanadium oxychloride all have the problem of high chlorination temperature, which not only makes the chlorination process difficult to control, but also causes a large number of impurities to be chlorinated at the same time, making the subsequent purification process complicated, or requiring high-purity vanadium-containing raw materials to reduce impurities, but also causing extremely high production costs of vanadium oxychloride. These problems lead to high production costs of vanadium oxychloride, affecting the development of its application.
- the present invention provides a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings.
- the method uses ordinary vanadium-containing refined tailings as raw materials to achieve chlorination and vanadium extraction at low temperature, solves the process control problems and simultaneous chlorination problems of impurities caused by high-temperature chlorination, and effectively reduces the production cost. Low energy consumption and equipment requirements, and the preparation of refined vanadium oxychloride.
- the present invention adopts the following technical solutions:
- the present invention provides a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings, comprising the following steps:
- the inert gas is one or more of argon, helium and nitrogen.
- the vanadium-containing refined tailings is composed of components with the following contents: C: 9.8wt%; V: 15.23wt%; Ti: 14.44wt%; Cl: 41.32wt%; Fe: 0.20wt%; Si: 0.026wt%; Ca: 0.062wt%; Al: ⁇ 0.005wt%; S: 0.02wt%; P: 0.005wt%; Cr: ⁇ 0.005wt%.
- the temperature of the high temperature treatment is 500-800° C., and the insulation time is 30-120 min.
- step 2) the pre-treated refined tailings are cooled to 160-350°C.
- the reaction time is 30-90 min.
- the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
- the temperature of the low temperature condensation is -20°C to 5°C.
- the vanadium recovery rate is above 90% based on the total amount of vanadium in the vanadium-containing refined tailings.
- the obtained refined vanadium oxychloride has a Ti impurity content of 0.005%-0.02%, and a Fe impurity content of 0.002%-0.005%.
- the present invention has the following advantages compared with the prior art:
- the present invention adopts an ultra-low temperature chlorination process of inert gas pretreatment of vanadium-containing refined tailings, which has a low chlorination temperature, effectively reduces energy consumption, and reduces equipment requirements;
- the present invention realizes efficient chlorination extraction of vanadium and selective separation of vanadium and titanium through ultra-low temperature selective chlorination of vanadium, and prepares a high-purity vanadium oxychloride product.
- FIG1 shows a schematic flow diagram of a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings provided by the present invention.
- a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
- S104 Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
- the present invention uses common vanadium-containing refined tailings as raw materials to achieve vanadium extraction by chlorination at low temperature, solves the process control problems and simultaneous chlorination problems of impurities caused by high-temperature chlorination, effectively reduces energy consumption and equipment requirements, and prepares high-purity vanadium oxychloride.
- the inert gas is one or more of argon, helium and nitrogen.
- the vanadium-containing refined tailings are composed of the following components: C: 9.8wt%; V: 15.23wt%; Ti: 14.44wt%; Cl: 41.32wt%; Fe: 0.20wt%; Si: 0.026wt%; Ca: 0.062wt%; Al: ⁇ 0.005wt%; S: 0.02wt%; P: 0.005wt%; Cr: ⁇ 0.005wt%.
- step S101 the temperature of the high temperature treatment is 500-800°C, and the insulation time is 30-120 minutes.
- step S102 the pre-treated refined tailings are cooled to 160-350°C; and the reaction time is 30-90 minutes.
- the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
- step S103 the temperature of the low-temperature condensation is -20°C to 5°C.
- the vanadium recovery rate is above 90% based on the total amount of vanadium in the refined tailings.
- the Ti impurity content of the obtained refined vanadium oxychloride is 0.005%-0.02%, and the Fe impurity content is 0.002%-0.005%.
- a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
- Example 1 based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 95%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.02% and 0.002% respectively.
- a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
- Example 2 based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 90%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.005% and 0.003%, respectively.
- a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
- Example 3 based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 94%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.01% and 0.005% respectively.
- a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
- Example 4 based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 92%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.013% and 0.004%, respectively.
- the present invention adopts an ultra-low temperature chlorination process for inert gas pretreatment of vanadium-containing refined tailings, with a low chlorination temperature, which effectively reduces energy consumption and equipment requirements; the present invention also realizes efficient chlorination extraction of vanadium and selective separation of vanadium and titanium through ultra-low temperature selective chlorination of vanadium, and prepares a high-purity vanadium oxychloride product.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本发明属于冶金、化工领域，并且，更具体地，涉及一种利用含钒精制尾渣制备精三氯氧钒的方法。The invention belongs to the field of metallurgy and chemical industry, and more specifically, relates to a method for preparing refined vanadium oxytrichloride by utilizing vanadium-containing refined tailings.
精制尾渣是含钒钛渣在生产氯化钛白或海绵钛的过程产生的一种固废，其中钒含量可达20％，是一种极具利用价值的钒资源。但由于其中钒、钛及其他杂质多以氯化物/氯氧化物形式存在，易产生氯气、氯化氢污染物，处理难度较大。目前的处理方法主要是通过氧化焙烧，脱除其中的氯，并将钒、钛转化为氧化物后与普通钒渣混合处理。该方法存在氧化焙烧温度高，焙烧过程产生大量氯气烟尘难以处理，焙烧产物中钒钛分离困难等一些问题。Refined tailings are a type of solid waste produced by vanadium-titanium slag in the process of producing titanium dioxide chloride or titanium sponge. The vanadium content can reach 20%, which is a vanadium resource with great utilization value. However, since vanadium, titanium and other impurities are mostly in the form of chloride/chloride oxides, chlorine and hydrogen chloride pollutants are easily generated, which makes it difficult to treat. The current treatment method is mainly to remove chlorine through oxidative roasting, and convert vanadium and titanium into oxides and then mix them with ordinary vanadium slag for treatment. This method has some problems such as high oxidative roasting temperature, a large amount of chlorine smoke generated during the roasting process that is difficult to handle, and difficulty in separating vanadium and titanium from the roasting product.
专利CN 104004920A公开了一种从四氯化钛精制尾渣中提钒的方法，将四氯化钛精制尾渣进行高温焙烧、硫酸浸出，钒浸出率可达90％以上。但焙烧阶段能耗较高，且浸出硫酸耗量大，浸出液呈强酸性，后续处理难度大。Patent CN 104004920A discloses a method for extracting vanadium from titanium tetrachloride refined tailings, which involves high-temperature roasting of titanium tetrachloride refined tailings and leaching with sulfuric acid, and the vanadium leaching rate can reach more than 90%. However, the energy consumption in the roasting stage is high, and the consumption of leaching sulfuric acid is large. The leaching solution is highly acidic, making subsequent treatment difficult.
专利CN 108996547A公开了一种四氯化钛精制尾渣超声辅助碱浸提钒的方法，采用碱浸工艺，但需要在超声辅助同时通入氧气进行。Patent CN 108996547A discloses a method for extracting vanadium from titanium tetrachloride refined tailings by ultrasonic-assisted alkaline leaching. The method adopts an alkaline leaching process but requires the introduction of oxygen while performing the leaching process under ultrasonic assistance.
专利CN 106929696A和CN 107032400A分别公开了一种TiCl4精制尾渣铵浸和碱浸提钒的方法，均采用将TiCl4精制尾渣焙烧处理后进行浸出，得到浸出液经净化除杂沉钒工序制得五氧化二钒。Patents CN 106929696A and CN 107032400A disclose a method for extracting vanadium by ammonium leaching and alkali leaching of TiCl4 refined tailings, respectively. Both methods involve leaching the TiCl4 refined tailings after roasting, and obtaining a leachate which is purified, impurities removed, and vanadium precipitated to obtain vanadium pentoxide.
三氯氧钒是一种重要的化工产品，用于制造高纯五氧化二钒粉末、催化剂等，在许多领域均有应用。目前的三氯氧钒生产工艺主要是将含钒矿 物氯化得到，含钒矿物包括偏钒酸铵、多钒酸铵、五氧化二钒、钒渣、含钒精制尾渣等，氯化剂有氯气、氯化铁等。Vanadium trichloride is an important chemical product used to manufacture high-purity vanadium pentoxide powder, catalysts, etc., and is used in many fields. The current vanadium trichloride production process mainly involves converting vanadium-containing ore into The vanadium-containing minerals include ammonium metavanadate, ammonium polyvanadate, vanadium pentoxide, vanadium slag, vanadium-containing refined tailings, etc. The chlorinating agents include chlorine gas, ferric chloride, etc.
文献《基于铁氯化物的高钒渣氯化提钒技术》提出了一种可以同时高效回收钒、铁、钛的综合利用工艺，以FeCl3为氯化剂，在温度900K～1100K、反应时间2h制得三氯氧钒，提钒率达到38％。The document "Chlorination Extraction Technology of High Vanadium Slag Based on Iron Chloride" proposes a comprehensive utilization process that can simultaneously and efficiently recover vanadium, iron, and titanium. Using FeCl3 as the chlorinating agent, vanadium trichloride is produced at a temperature of 900K~1100K and a reaction time of 2h, and the vanadium extraction rate reaches 38%.
专利CN110642294A公开了一种高炉渣低温氯化制备三氯氧钒的方法，将高炉渣和碳质还原剂混合，预热然后通入氯气进行反应，得到三氯氧钒混合物。Patent CN110642294A discloses a method for preparing vanadium oxychloride by low-temperature chlorination of blast furnace slag, wherein blast furnace slag and a carbonaceous reducing agent are mixed, preheated, and then chlorine gas is introduced to react to obtain a vanadium oxychloride mixture.
专利CN112142107A公开了一种含钒精制尾渣制备高纯三氯氧钒的方法，利用精制尾渣和石油焦混合均匀，进行氯化反应得到三氯氧钒粗品，将三氯氧钒粗品进行水解、蒸馏获得高纯三氯氧钒。Patent CN112142107A discloses a method for preparing high-purity vanadium oxychloride from vanadium-containing refined tailings, wherein the refined tailings and petroleum coke are evenly mixed and subjected to chlorination reaction to obtain crude vanadium oxychloride, and the crude vanadium oxychloride is hydrolyzed and distilled to obtain high-purity vanadium oxychloride.
专利CN111410228A公开了一种利用钒铁细粉制备高纯三氯氧钒的方法，将钒铁细粉至于氯化反应其中，通入氯气并升温至300℃～600℃，通入氯气和氧气调整氮气进行氯化反应，将挥发分冷凝得到三氯氧钒粗品，三氯氧钒粗品进行蒸馏冷凝得到高纯三氯氧钒。Patent CN111410228A discloses a method for preparing high-purity vanadium oxytrichloride using ferrovanadium fine powder, wherein the ferrovanadium fine powder is placed in a chlorination reaction, chlorine is introduced and the temperature is raised to 300°C to 600°C, chlorine and oxygen are introduced to adjust nitrogen to carry out a chlorination reaction, volatiles are condensed to obtain a crude vanadium oxytrichloride, and the crude vanadium oxytrichloride is distilled and condensed to obtain high-purity vanadium oxytrichloride.
因此，由目前研究可以看出，四氯化钛精制尾渣提钒均存在一定问题，主要是由于除钒泥浆中钒钛大部分是氯化物形式存在，到精制尾渣中钒钛分离困难，含钒浸出液中杂质含量较高。而公开的制备高纯三氯氧钒的方法均存在氯化温度较高的问题，不仅导致氯化过程难以控制，同时导致大量杂质同时被氯化，使得后续净化流程复杂，或者需要高纯的含钒原料以减少杂质，但同时造成三氯氧钒极高的生产成本。这些问题导致三氯氧钒生产成本较高，影响了其应用的发展。Therefore, it can be seen from the current research that there are certain problems in extracting vanadium from titanium tetrachloride refined tailings, mainly because most of the vanadium and titanium in the vanadium removal slurry exist in the form of chlorides, and it is difficult to separate vanadium and titanium in the refined tailings, and the impurity content in the vanadium-containing leaching solution is relatively high. The disclosed methods for preparing high-purity vanadium oxychloride all have the problem of high chlorination temperature, which not only makes the chlorination process difficult to control, but also causes a large number of impurities to be chlorinated at the same time, making the subsequent purification process complicated, or requiring high-purity vanadium-containing raw materials to reduce impurities, but also causing extremely high production costs of vanadium oxychloride. These problems lead to high production costs of vanadium oxychloride, affecting the development of its application.
因此，现有技术有待改进。Therefore, the prior art needs to be improved.
发明内容Summary of the invention
针对现有技术的不足，本发明提供了一种利用含钒精制尾渣制备精三氯氧钒的方法，以普通含钒精制尾渣为原料，即可实现低温下的氯化提钒生产，解决了高温氯化带来的过程控制问题和杂质同时氯化问题，有效降 低能耗和设备要求，并制备出精三氯氧钒。In view of the shortcomings of the prior art, the present invention provides a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings. The method uses ordinary vanadium-containing refined tailings as raw materials to achieve chlorination and vanadium extraction at low temperature, solves the process control problems and simultaneous chlorination problems of impurities caused by high-temperature chlorination, and effectively reduces the production cost. Low energy consumption and equipment requirements, and the preparation of refined vanadium oxychloride.
为了解决上述技术问题，本发明采用以下技术方案：In order to solve the above technical problems, the present invention adopts the following technical solutions:
根据本发明的方面，本发明提供一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤：According to aspects of the present invention, the present invention provides a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings, comprising the following steps:
1)将含钒精制尾渣在惰性气体下进行高温处理，并保温持续一段时间，得到预处理精制尾渣；1) subjecting the vanadium-containing refined tailings to high temperature treatment under an inert gas and keeping the temperature for a period of time to obtain pretreated refined tailings;
2)将预处理精制尾渣冷却，并持续通入氧气和氯气的混合气体进行反应；2) cooling the pre-treated refined tailings, and continuously introducing a mixed gas of oxygen and chlorine to react;
3)将反应后的混合气体排出并进行低温冷凝，得到冷凝液体，即得到粗三氯氧钒；3) discharging the mixed gas after the reaction and condensing it at low temperature to obtain a condensed liquid, that is, obtaining crude vanadium oxychloride;
4)将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。4) Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
在本发明的一个实施例中，在步骤1)中，惰性气体是氩气、氦气和氮气中的一种或多种。In one embodiment of the present invention, in step 1), the inert gas is one or more of argon, helium and nitrogen.
在本发明的一个实施例中，含钒精制尾渣由以下含量的组分组成：C：9.8wt％；V：15.23wt％；Ti：14.44wt％；Cl：41.32wt％；Fe：0.20wt％；Si：0.026wt％；Ca：0.062wt％；Al：＜0.005wt％；S：0.02wt％；P：0.005wt％；Cr：＜0.005wt％。In one embodiment of the present invention, the vanadium-containing refined tailings is composed of components with the following contents: C: 9.8wt%; V: 15.23wt%; Ti: 14.44wt%; Cl: 41.32wt%; Fe: 0.20wt%; Si: 0.026wt%; Ca: 0.062wt%; Al: <0.005wt%; S: 0.02wt%; P: 0.005wt%; Cr: <0.005wt%.
在本发明的一个实施例中，在步骤1)中，高温处理的温度为500-800℃，保温持续的时间为30-120min。In one embodiment of the present invention, in step 1), the temperature of the high temperature treatment is 500-800° C., and the insulation time is 30-120 min.
在本发明的一个实施例中，在步骤2)中，将预处理精制尾渣冷却至160-350℃。In one embodiment of the present invention, in step 2), the pre-treated refined tailings are cooled to 160-350°C.
在本发明的一个实施例中，反应的时间为30-90min。In one embodiment of the present invention, the reaction time is 30-90 min.
在本发明的一个实施例中，混合气体中氧气与氯气的体积比为1:1-10:1。In one embodiment of the present invention, the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
在本发明的一个实施例中，在步骤3)中，低温冷凝的温度为-20℃～5℃。 In one embodiment of the present invention, in step 3), the temperature of the low temperature condensation is -20°C to 5°C.
在本发明的一个实施例中，按含钒精制尾渣中钒总量计，钒收率在90％以上。In one embodiment of the present invention, the vanadium recovery rate is above 90% based on the total amount of vanadium in the vanadium-containing refined tailings.
在本发明的一个实施例中，得到的精三氯氧钒中Ti杂质含量为0.005％-0.02％，Fe杂质含量为0.002％-0.005％。In one embodiment of the present invention, the obtained refined vanadium oxychloride has a Ti impurity content of 0.005%-0.02%, and a Fe impurity content of 0.002%-0.005%.
通过采用上述技术方案，本发明相比于现有技术具有如下优点：By adopting the above technical solution, the present invention has the following advantages compared with the prior art:
(1)本发明采用将含钒精制尾渣惰性气体预处理-超低温氯化工艺，氯化温度低，有效降低能耗，并减少设备要求；(1) The present invention adopts an ultra-low temperature chlorination process of inert gas pretreatment of vanadium-containing refined tailings, which has a low chlorination temperature, effectively reduces energy consumption, and reduces equipment requirements;
(2)本发明通过超低温钒选择性氯化，实现钒的高效氯化提取和钒钛选择性分离，并制备出高纯三氯氧钒产品。(2) The present invention realizes efficient chlorination extraction of vanadium and selective separation of vanadium and titanium through ultra-low temperature selective chlorination of vanadium, and prepares a high-purity vanadium oxychloride product.
图1示出了本发明提供的利用含钒精制尾渣制备精三氯氧钒的方法的流程示意图。FIG1 shows a schematic flow diagram of a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings provided by the present invention.
应当理解，在示例性实施例中所示的本发明的实施例仅是说明性的。虽然在本发明中仅对少数实施例进行了详细描述，但本领域技术人员很容易领会在未实质脱离本发明主题的教导情况下，多种修改是可行的。相应地，所有这样的修改都应当被包括在本发明的范围内。在不脱离本发明的主旨的情况下，可以对以下示例性实施例的设计、操作条件和参数等做出其他的替换、修改、变化和删减。It should be understood that the embodiments of the present invention shown in the exemplary embodiments are only illustrative. Although only a few embodiments are described in detail in the present invention, it is easy for those skilled in the art to appreciate that multiple modifications are feasible without actually departing from the teaching of the subject matter of the present invention. Accordingly, all such modifications should be included within the scope of the present invention. Without departing from the gist of the present invention, other replacements, modifications, changes and deletions may be made to the design, operating conditions and parameters of the following exemplary embodiments.
如图1所示，一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤：As shown in FIG1 , a method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
S101：将含钒精制尾渣在惰性气体下进行高温处理，并保温持续一段时间，得到预处理精制尾渣；S101: subjecting the vanadium-containing refined tailings to high-temperature treatment under an inert gas and keeping the temperature for a period of time to obtain pretreated refined tailings;
S102：将预处理精制尾渣冷却，并持续通入氧气和氯气的混合气体进行反应；S102: cooling the pre-treated refined tailings, and continuously introducing a mixed gas of oxygen and chlorine to react;
S103：将反应后的混合气体排出并进行低温冷凝，得到冷凝液体，即 得到粗三氯氧钒；S103: The mixed gas after the reaction is discharged and condensed at low temperature to obtain a condensed liquid, that is, Obtaining crude vanadium oxychloride;
S104：将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。S104: Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
本发明以普通含钒精制尾渣为原料，即可实现低温下的氯化提钒生产，解决了高温氯化带来的过程控制问题和杂质同时氯化问题，有效降低能耗和设备要求，并制备出高纯三氯氧钒。The present invention uses common vanadium-containing refined tailings as raw materials to achieve vanadium extraction by chlorination at low temperature, solves the process control problems and simultaneous chlorination problems of impurities caused by high-temperature chlorination, effectively reduces energy consumption and equipment requirements, and prepares high-purity vanadium oxychloride.
在上述技术方案中，在步骤S101中，惰性气体是氩气、氦气和氮气中的一种或多种。In the above technical solution, in step S101, the inert gas is one or more of argon, helium and nitrogen.
在上述技术方案中，含钒精制尾渣由以下含量的组分组成：C：9.8wt％；V：15.23wt％；Ti：14.44wt％；Cl：41.32wt％；Fe：0.20wt％；Si：0.026wt％；Ca：0.062wt％；Al：＜0.005wt％；S：0.02wt％；P：0.005wt％；Cr：＜0.005wt％。In the above technical scheme, the vanadium-containing refined tailings are composed of the following components: C: 9.8wt%; V: 15.23wt%; Ti: 14.44wt%; Cl: 41.32wt%; Fe: 0.20wt%; Si: 0.026wt%; Ca: 0.062wt%; Al: <0.005wt%; S: 0.02wt%; P: 0.005wt%; Cr: <0.005wt%.
在上述技术方案中，在步骤S101中，高温处理的温度为500-800℃，保温持续的时间为30-120min。In the above technical solution, in step S101, the temperature of the high temperature treatment is 500-800°C, and the insulation time is 30-120 minutes.
在上述技术方案中，在步骤S102中，将预处理精制尾渣冷却至160-350℃；反应的时间为30-90min。In the above technical solution, in step S102, the pre-treated refined tailings are cooled to 160-350°C; and the reaction time is 30-90 minutes.
在上述技术方案中，混合气体中氧气与氯气的体积比为1:1-10:1。In the above technical solution, the volume ratio of oxygen to chlorine in the mixed gas is 1:1-10:1.
在上述技术方案中，在步骤S103中，低温冷凝的温度为-20℃～5℃。In the above technical solution, in step S103, the temperature of the low-temperature condensation is -20°C to 5°C.
在上述技术方案中，按精制尾渣中钒总量计，钒收率在90％以上。In the above technical solution, the vanadium recovery rate is above 90% based on the total amount of vanadium in the refined tailings.
在上述技术方案中，得到的精三氯氧钒中Ti杂质含量为0.005％-0.02％，Fe杂质含量为0.002％-0.005％。In the above technical solution, the Ti impurity content of the obtained refined vanadium oxychloride is 0.005%-0.02%, and the Fe impurity content is 0.002%-0.005%.
下面通过具体实施例来对本发明的上述技术方案进行详细地说明。The above technical solution of the present invention is described in detail below through specific embodiments.
本发明采用的含钒精制尾渣主要成分分析如下表1所示：The main components of the vanadium-containing refined tailings used in the present invention are analyzed as shown in Table 1 below:
表1含钒精制尾渣主要成分分析wt％
Table 1 Analysis of main components of vanadium-containing refined tailings wt%
实施例1Example 1
一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤： A method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
(1)将含钒精制尾渣在氩气下升温至500℃，并保温120min，得到预处理精制尾渣；(1) heating the vanadium-containing refined tailings to 500° C. under argon and keeping the temperature for 120 minutes to obtain pretreated refined tailings;
(2)将预处理精制尾渣冷却至160℃，并按照氧气与氯气的体积比为10:1持续通入氧气和氯气的混合气体，反应30min；(2) cooling the pre-treated refined tailings to 160° C., and continuously introducing a mixed gas of oxygen and chlorine at a volume ratio of 10:1 for 30 minutes;
(3)将反应后的混合气体排出并在5℃下进行低温冷凝，得到冷凝液体，即得到粗三氯氧钒；(3) discharging the mixed gas after the reaction and condensing it at a low temperature of 5° C. to obtain a condensed liquid, that is, crude vanadium oxychloride;
(4)将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。(4) Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
通过上述实施例1，按照精制尾渣中钒总量计，钒收率达到95％，制备的精三氯氧钒产品中Ti、Fe杂质含量分别为0.02％、0.002％。According to the above Example 1, based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 95%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.02% and 0.002% respectively.
实施例2Example 2
一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤：A method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
(1)将含钒精制尾渣在氮气下升温至800℃，并保温30min，得到预处理精制尾渣；(1) heating the vanadium-containing refined tailings to 800° C. under nitrogen and keeping the temperature for 30 minutes to obtain pretreated refined tailings;
(2)将预处理精制尾渣冷却至250℃，并按照氧气与氯气的体积比为1:1持续通入氧气和氯气的混合气体，反应90min；(2) cooling the pre-treated refined tailings to 250° C., and continuously introducing a mixed gas of oxygen and chlorine at a volume ratio of 1:1, and reacting for 90 minutes;
(3)将反应后的混合气体排出并在0℃下进行低温冷凝，得到冷凝液体，即得到粗三氯氧钒；(3) discharging the mixed gas after the reaction and condensing it at 0° C. to obtain a condensed liquid, that is, crude vanadium oxychloride;
(4)将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。(4) Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
通过上述实施例2，按照精制尾渣中钒总量计，钒收率达到90％，制备的精三氯氧钒产品中Ti、Fe杂质含量分别为0.005％、0.003％。According to the above Example 2, based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 90%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.005% and 0.003%, respectively.
实施例3Example 3
一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤：A method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
(1)将含钒精制尾渣在氩气和氦气两种按体积比1:1混合气体下升温至650℃，并保温60min，得到预处理精制尾渣；(1) heating the vanadium-containing refined tailings to 650° C. in a mixed gas of argon and helium in a volume ratio of 1:1, and keeping the temperature for 60 minutes to obtain pretreated refined tailings;
(2)将预处理精制尾渣冷却至200℃，并按照氧气与氯气的体积比为5:1持续通入氧气和氯气的混合气体，反应60min； (2) cooling the pre-treated refined tailings to 200° C., and continuously introducing a mixed gas of oxygen and chlorine at a volume ratio of 5:1 for 60 minutes;
(3)将反应后的混合气体排出并在-20℃下进行低温冷凝，得到冷凝液体，即得到粗三氯氧钒；(3) discharging the mixed gas after the reaction and condensing it at -20°C to obtain a condensed liquid, that is, crude vanadium oxychloride;
(4)将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。(4) Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
通过上述实施例3，按照精制尾渣中钒总量计，钒收率达到94％，制备的精三氯氧钒产品中Ti、Fe杂质含量分别为0.01％、0.005％。According to the above Example 3, based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 94%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.01% and 0.005% respectively.
实施例4Example 4
一种利用含钒精制尾渣制备精三氯氧钒的方法，包含以下步骤：A method for preparing refined vanadium oxychloride using vanadium-containing refined tailings comprises the following steps:
(1)将含钒精制尾渣在氮气和氦气两种按体积比1:1混合气体下升温至700℃，并保温100min，得到预处理精制尾渣；(1) heating the vanadium-containing refined tailings to 700° C. in a mixed gas of nitrogen and helium in a volume ratio of 1:1, and keeping the temperature for 100 minutes to obtain pretreated refined tailings;
(2)将预处理精制尾渣冷却至350℃，并按照氧气与氯气的体积比为5:1持续通入氧气和氯气的混合气体，反应100min；(2) cooling the pre-treated refined tailings to 350° C., and continuously introducing a mixed gas of oxygen and chlorine at a volume ratio of 5:1 for 100 min;
(3)将反应后的混合气体排出并在-10℃下进行低温冷凝，得到冷凝液体，即得到粗三氯氧钒；(3) discharging the mixed gas after the reaction and condensing it at -10°C to obtain a condensed liquid, that is, crude vanadium oxychloride;
(4)将粗三氯氧钒过滤去除固体杂质，得到精三氯氧钒。(4) Filter the crude vanadium oxychloride to remove solid impurities to obtain refined vanadium oxychloride.
通过上述实施例4，按照精制尾渣中钒总量计，钒收率达到92％，制备的精三氯氧钒产品中Ti、Fe杂质含量分别为0.013％、0.004％。According to the above Example 4, based on the total amount of vanadium in the refined tailings, the vanadium yield reaches 92%, and the impurity contents of Ti and Fe in the prepared refined vanadium oxychloride product are 0.013% and 0.004%, respectively.
总之，本发明采用将含钒精制尾渣惰性气体预处理-超低温氯化工艺，氯化温度低，有效降低能耗，并减少设备要求；本发明还通过超低温钒选择性氯化，实现钒的高效氯化提取和钒钛选择性分离，并制备出高纯三氯氧钒产品。In summary, the present invention adopts an ultra-low temperature chlorination process for inert gas pretreatment of vanadium-containing refined tailings, with a low chlorination temperature, which effectively reduces energy consumption and equipment requirements; the present invention also realizes efficient chlorination extraction of vanadium and selective separation of vanadium and titanium through ultra-low temperature selective chlorination of vanadium, and prepares a high-purity vanadium oxychloride product.
以上所述仅为本发明的较佳实施例，并非用来限定本发明的实施范围；如果不脱离本发明的精神和范围，对本发明进行修改或者等同替换，均应涵盖在本发明权利要求的保护范围当中。 The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of implementation of the present invention. If the present invention is modified or replaced by equivalents without departing from the spirit and scope of the present invention, it should be included in the protection scope of the claims of the present invention.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211601395.1A CN115947370B (en) | 2022-12-13 | 2022-12-13 | Method for preparing refined vanadium oxychloride from vanadium-containing refined tailings |
| CN202211601395.1 | 2022-12-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024124791A1 true WO2024124791A1 (en) | 2024-06-20 |
Family
ID=87286953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2023/093835 Ceased WO2024124791A1 (en) | 2022-12-13 | 2023-05-12 | Method for preparing refined vanadium oxytrichloride from vanadium-containing refined tailings |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115947370B (en) |
| WO (1) | WO2024124791A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292180B (en) * | 2021-11-19 | 2024-04-26 | 攀钢集团攀枝花钢铁研究院有限公司 | A method for preparing high-purity vanadyl oxalate by extraction |
| CN115947370B (en) * | 2022-12-13 | 2024-06-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing refined vanadium oxychloride from vanadium-containing refined tailings |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1832735A1 (en) * | 1988-12-26 | 1996-08-20 | Березниковский филиал Всесоюзного научно-исследовательского и проектного института титана | Method for production of pure titanium tetrachloride and vanadium oxytrichloride |
| WO2016119720A1 (en) * | 2015-01-30 | 2016-08-04 | 中国科学院过程工程研究所 | System and method for highly effective chlorination and vanadium extraction from vanadium slag |
| CN110683580A (en) * | 2018-07-06 | 2020-01-14 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination |
| CN111410228A (en) * | 2020-03-31 | 2020-07-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder |
| CN112142107A (en) * | 2020-09-29 | 2020-12-29 | 攀钢集团研究院有限公司 | Method for preparing high-purity vanadium oxychloride from vanadium-containing refined tailings |
| CN112646972A (en) * | 2020-11-13 | 2021-04-13 | 北京科技大学 | Method for separating vanadium and chromium from vanadium and chromium-containing material through chlorination-selective oxidation |
| CN114380332A (en) * | 2021-12-28 | 2022-04-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for purifying crude vanadium oxychloride |
| CN115947370A (en) * | 2022-12-13 | 2023-04-11 | 攀钢集团攀枝花钢铁研究院有限公司 | A method for preparing refined vanadium oxytrichloride by utilizing vanadium-containing refined tailings |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1936988C3 (en) * | 1969-07-21 | 1974-01-03 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of vanadium oxitrichloride |
| CN103025899A (en) * | 2010-05-19 | 2013-04-03 | Tng有限公司 | Method for extracting and recovering vanadium |
| CN106676289B (en) * | 2017-01-17 | 2018-10-26 | 中国科学院过程工程研究所 | A method of preparing high purity vanadic anhydride using vanadium-containing material |
| CN107055598A (en) * | 2017-04-20 | 2017-08-18 | 河南佰利联新材料有限公司 | A kind of crude titanic chloride solution refines production method |
| CN110683579B (en) * | 2018-07-06 | 2020-12-11 | 中国科学院过程工程研究所 | A kind of method for producing high-purity vanadium pentoxide by refining and removing vanadium tailings from titanium tetrachloride |
| CN109868370B (en) * | 2019-04-19 | 2020-09-29 | 重庆科技学院 | A kind of recovery method of valuable metal in vanadium chromium slag |
| CN110642294A (en) * | 2019-10-30 | 2020-01-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium oxychloride by low temperature chlorination of blast furnace slag |
| CN110937630A (en) * | 2019-12-20 | 2020-03-31 | 大连博融新材料有限公司 | Preparation method of vanadium oxytrichloride |
-
2022
- 2022-12-13 CN CN202211601395.1A patent/CN115947370B/en active Active
-
2023
- 2023-05-12 WO PCT/CN2023/093835 patent/WO2024124791A1/en not_active Ceased
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1832735A1 (en) * | 1988-12-26 | 1996-08-20 | Березниковский филиал Всесоюзного научно-исследовательского и проектного института титана | Method for production of pure titanium tetrachloride and vanadium oxytrichloride |
| WO2016119720A1 (en) * | 2015-01-30 | 2016-08-04 | 中国科学院过程工程研究所 | System and method for highly effective chlorination and vanadium extraction from vanadium slag |
| CN110683580A (en) * | 2018-07-06 | 2020-01-14 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination |
| CN111410228A (en) * | 2020-03-31 | 2020-07-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder |
| CN112142107A (en) * | 2020-09-29 | 2020-12-29 | 攀钢集团研究院有限公司 | Method for preparing high-purity vanadium oxychloride from vanadium-containing refined tailings |
| CN112646972A (en) * | 2020-11-13 | 2021-04-13 | 北京科技大学 | Method for separating vanadium and chromium from vanadium and chromium-containing material through chlorination-selective oxidation |
| CN114380332A (en) * | 2021-12-28 | 2022-04-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for purifying crude vanadium oxychloride |
| CN115947370A (en) * | 2022-12-13 | 2023-04-11 | 攀钢集团攀枝花钢铁研究院有限公司 | A method for preparing refined vanadium oxytrichloride by utilizing vanadium-containing refined tailings |
Non-Patent Citations (1)
| Title |
|---|
| AIRAN ZHOU, LU PING: "Study on the Track and Recycle of Vanadium in the Titanium Extraction from Blast Furnace Slag", IRON STEEL VANADIUM TITANIUM, vol. 36, no. 2, 15 May 2015 (2015-05-15), pages 63 - 67, XP093182053 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947370B (en) | 2024-06-14 |
| CN115947370A (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130279B (en) | A kind of method of chlorination production high purity vanadic anhydride | |
| CN115947370B (en) | Method for preparing refined vanadium oxychloride from vanadium-containing refined tailings | |
| CN114349048B (en) | Method for preparing high-purity vanadyl sulfate solution by recycling titanium tetrachloride refined tailings | |
| CN110683580B (en) | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination | |
| CN110683579B (en) | A kind of method for producing high-purity vanadium pentoxide by refining and removing vanadium tailings from titanium tetrachloride | |
| WO2014125275A1 (en) | Method for producing titanium oxide and iron oxide | |
| JPH06102546B2 (en) | Extraction and purification of titanium products from titanium-containing minerals | |
| CN109868370B (en) | A kind of recovery method of valuable metal in vanadium chromium slag | |
| CN115537548B (en) | Method for recovering iron and vanadium-titanium resources in vanadium-titanium magnetite through gradient reduction separation | |
| CN115232960B (en) | Processing methods of mixed rare earth concentrates and uses of quartz | |
| CN116287737B (en) | A method for realizing the recycling of titanium, vanadium, iron, calcium, silicon, sulfur and nitrogen | |
| CN112390285A (en) | Method for recovering vanadium-titanium series waste catalyst | |
| RU2829472C1 (en) | Method of preparing purified vanadium oxotrichloride from vanadium-containing refined tails | |
| CN112410569A (en) | Method for recovering vanadium from acidic vanadium-containing underflow slag | |
| WO2024198185A1 (en) | Method for improving yield of titanium-rich material for boiling chlorination, and use thereof | |
| CN113584319B (en) | Method for extracting germanium from smoke dust | |
| CN108975393A (en) | The method for preparing titanium dioxide using high-titanium blast furnace slag | |
| CN114293019A (en) | A kind of method that utilizes titanium tetrachloride refining tailings to extract vanadium | |
| CN115896483B (en) | A method for extracting vanadium by roasting vanadium-containing refined tailings | |
| CN117626012B (en) | Hydrochloric acid treatment process for mixed rare earth concentrate | |
| CN115821071B (en) | Treatment method of titanium tetrachloride vanadium-removing slurry | |
| US20240110259A1 (en) | Method for co-producing blister copper by enriching germanium and indium from a copper sulfide ore | |
| JPS6314826A (en) | Titanium ore smelting method | |
| CN117684010A (en) | Methods for recovering iron, vanadium and titanium in slag | |
| CN116200592A (en) | Method for separating iron, vanadium and titanium in vanadium titano-magnetite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23902004 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 23902004 Country of ref document: EP Kind code of ref document: A1 |