CN111410228A - Method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder - Google Patents
Method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 49
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims abstract description 45
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000460 chlorine Substances 0.000 claims abstract description 36
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 claims 1
- 125000005287 vanadyl group Chemical group 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 229910001021 Ferroalloy Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- -1 vanadyl oxychloride Chemical compound 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明属于化工冶金技术领域，具体涉及利用钒铁细粉制备高纯三氯氧钒的方法。本发明所要解决的技术问题是提供能够有效利用钒铁细粉制备高纯三氯氧钒的方法。该方法包括如下步骤：a、将钒铁细粉置于氯化反应器中，通入氮气，升温至300℃～600℃，通入氯气和氧气，调整氮气、氯气和氧气的总流速，进行氯化反应，反应过程中，将反应器内挥发的组分进行冷凝，得到三氯氧钒粗品；b、氯化反应结束后，停止通入氯气和氧气，再次调整氮气流速，待反应器冷却至室温后停止通入氮气；c、将三氯氧钒粗品蒸馏，冷凝，得到高纯三氯氧钒。本发明方法能够制备出高纯度的三氯氧钒产品，纯度可达99.9％以上，同时能够提高钒铁细粉中钒的氯化效率。The invention belongs to the technical field of chemical metallurgy, and in particular relates to a method for preparing high-purity vanadium oxychloride by using ferrovanadium fine powder. The technical problem to be solved by the present invention is to provide a method that can effectively utilize the ferrovanadium fine powder to prepare high-purity vanadium oxychloride. The method includes the following steps: a. placing the ferrovanadium fine powder in a chlorination reactor, feeding nitrogen gas, heating the temperature to 300°C to 600°C, feeding chlorine gas and oxygen gas, adjusting the total flow rate of nitrogen gas, chlorine gas and oxygen gas, and carrying out Chlorination reaction, in the reaction process, the volatilized components in the reactor are condensed to obtain the vanadium oxychloride crude product; b, after the chlorination reaction finishes, stop feeding chlorine and oxygen, adjust the nitrogen flow rate again, and wait for the reactor to cool After reaching room temperature, stop feeding with nitrogen; c. Distill the crude vanadyl trichloride and condense to obtain high-purity vanadium oxychloride. The method of the invention can prepare a high-purity vanadium oxychloride product, the purity can reach more than 99.9%, and at the same time, the chlorination efficiency of vanadium in the ferrovanadium fine powder can be improved.
Description
技术领域technical field
本发明属于化工冶金技术领域，具体涉及利用钒铁细粉制备高纯三氯氧钒的方法。The invention belongs to the technical field of chemical metallurgy, and in particular relates to a method for preparing high-purity vanadium oxychloride by using ferrovanadium fine powder.
背景技术Background technique
三氯氧钒是一类重要的化工中间体，是制备乙丙橡胶反应的催化剂或预催化剂，三氯氧钒可用作有机溶剂，是合成有机钒化合物的原料。此外，三氯氧钒也是制备高纯五氧化二钒的重要原料，以三氯氧钒为原料制备出的高纯五氧化二钒，产品纯度通常可达99.99％(4N)以上。随着化工、储能等行业不断发展，高纯三氯氧钒的需求量与日俱增，尤其在钒电池储能领域，以高纯三氯氧钒为原料制备出高纯五氧化二钒，再以高纯五氧化二钒为原料制备出低杂质钒电解液，可以达到提高钒电池电解液性能的技术目的。制备三氯氧钒的原料通常为氧化钒或含钒矿物，但上述物料制备出的粗三氯氧钒，通常需要经过复杂的精馏除杂过程方能制备出高纯度的三氯氧钒，不仅增加了制备成本，同时也会在一定程度上降低工艺可行性。Vanadium oxychloride is a kind of important chemical intermediate, and it is the catalyst or pre-catalyst for the preparation of ethylene-propylene rubber. Vanadium oxychloride can be used as an organic solvent and is the raw material for synthesizing organic vanadium compounds. In addition, vanadium oxychloride is also an important raw material for preparing high-purity vanadium pentoxide. The high-purity vanadium pentoxide prepared from vanadium oxychloride as a raw material usually has a product purity of more than 99.99% (4N). With the continuous development of chemical industry, energy storage and other industries, the demand for high-purity vanadium oxychloride is increasing day by day, especially in the field of vanadium battery energy storage, high-purity vanadium oxychloride is used as raw material to prepare high-purity vanadium pentoxide, and then High-purity vanadium pentoxide is used as raw material to prepare low-impurity vanadium electrolyte, which can achieve the technical purpose of improving the performance of vanadium battery electrolyte. The raw material for preparing vanadium oxychloride is usually vanadium oxide or vanadium-containing minerals, but the thick vanadium oxychloride prepared from the above-mentioned materials usually needs to go through a complex rectification and impurity removal process to prepare high-purity vanadium oxychloride, It not only increases the preparation cost, but also reduces the feasibility of the process to a certain extent.
钒铁冶炼过程中，制备出的钒铁合金经冷却、拆炉后，需对合金饼进行破碎，破碎过程中产生大量的钒铁碎屑，由于其粒径通常较小，不能满足钒铁产品粒径标准，故这部分钒铁合金碎屑只能通过回炉重熔的方式回用，不仅能耗较高、成本增加；同时，在回炉加料的过程中，部分超细粒径(平均粒径小于100μm)钒铁合金细粉容易被抽进除尘系统，一定程度上造成了钒的损失。因此，如何对这部分钒铁细粉进行充分有效利用，将会影响到钒铁冶炼系统的生产效率与经济性。目前，鲜有关于钒铁合金细粉回收利用的报道。In the ferro-vanadium smelting process, after the prepared ferro-vanadium alloy is cooled and dismantled, the alloy cake needs to be crushed, and a large amount of ferro-vanadium debris is generated during the crushing process. Therefore, this part of vanadium ferroalloy scraps can only be reused by remelting, which not only consumes a lot of energy but also increases costs; ) Vanadium ferroalloy fine powder is easily pumped into the dust removal system, causing vanadium loss to a certain extent. Therefore, how to fully and effectively utilize this part of the ferrovanadium fine powder will affect the production efficiency and economy of the ferrovanadium smelting system. At present, there are few reports on the recycling of vanadium ferroalloy fine powder.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是提供能够有效利用钒铁细粉制备高纯三氯氧钒的方法。The technical problem to be solved by the present invention is to provide a method that can effectively utilize the ferrovanadium fine powder to prepare high-purity vanadium oxychloride.
本发明解决上述技术问题采用的技术方案是提供了利用钒铁细粉制备高纯三氯氧钒的方法。该方法包括如下步骤：The technical scheme adopted by the present invention to solve the above-mentioned technical problems is to provide a method for preparing high-purity vanadium oxychloride by utilizing ferrovanadium fine powder. The method includes the following steps:
a、将钒铁细粉置于氯化反应器中，通入氮气，升温至300℃～600℃，通入氯气和氧气，调整氮气、氯气和氧气的总流速，进行氯化反应，反应过程中，将反应器内挥发的组分进行冷凝，得到三氯氧钒粗品；a. Place the ferrovanadium fine powder in the chlorination reactor, feed nitrogen, heat up to 300 ℃～600 ℃, feed chlorine and oxygen, adjust the total flow rate of nitrogen, chlorine and oxygen, and carry out chlorination reaction, the reaction process In, the volatilized components in the reactor are condensed to obtain the vanadium oxychloride crude product;
b、氯化反应结束后，停止通入氯气和氧气，再次调整氮气流速，待反应器冷却至室温后停止通入氮气；b. After the chlorination reaction finishes, stop feeding chlorine and oxygen, adjust the nitrogen flow rate again, and stop feeding nitrogen after the reactor is cooled to room temperature;
c、将三氯氧钒粗品蒸馏，冷凝，得到高纯三氯氧钒。c, the crude product of vanadium oxychloride is distilled and condensed to obtain high-purity vanadium oxychloride.
进一步地，步骤a中，所述钒铁细粉的粒度为5μm～200μm，钒铁细粉中钒含量为40％～85％。Further, in step a, the particle size of the ferrovanadium fine powder is 5 μm˜200 μm, and the vanadium content in the ferrovanadium fine powder is 40%˜85%.
进一步地，步骤a中，所述通入氮气的流速为0.01m/s～0.03m/s。Further, in step a, the flow rate of the nitrogen gas introduced is 0.01m/s～0.03m/s.
进一步地，步骤a中，氯化反应的时间为60min～120min。Further, in step a, the time of the chlorination reaction is 60min～120min.
进一步地，步骤a中，所述调整氮气、氯气和氧气的总流速为0.02m/s～0.08m/s。Further, in step a, the adjusted total flow rate of nitrogen gas, chlorine gas and oxygen gas is 0.02m/s～0.08m/s.
进一步地，步骤a中，所述通入氯气与氧气的摩尔比为2～3:1；氯气占氮气、氯气和氧气混合气体体积分数的20％～50％。Further, in step a, the molar ratio of the introduced chlorine gas and oxygen gas is 2-3:1; the chlorine gas accounts for 20%-50% of the volume fraction of the mixed gas of nitrogen, chlorine and oxygen.
进一步地，步骤a中，氯化反应过程中的尾气采用30％的氢氧化钠水溶液吸收。Further, in step a, the tail gas in the chlorination reaction process is absorbed by 30% sodium hydroxide aqueous solution.
进一步地，步骤b中，所述再次调整氮气的流速为0.01m/s～0.03m/s。Further, in step b, the flow rate of the nitrogen gas is adjusted again to be 0.01m/s～0.03m/s.
进一步地，步骤c中，所述蒸馏至所得产物为三氯氧钒粗品质量的90％～95％。Further, in step c, the distillation until the obtained product is 90% to 95% of the quality of the crude vanadyl trichloride.
优选地，所述蒸馏的温度为125℃～130℃。Preferably, the temperature of the distillation is 125°C to 130°C.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明方法以钒铁合金细粉为原料，通过氯化工艺，能够制备出高纯度的三氯氧钒产品，纯度可达99.9％以上，不仅能提升产品的附加值，同时实现了钒铁冶炼系统含钒二次资源的回收利用，能够提高钒铁细粉的氯化效率。本发明方法以钒铁合金细粉为原料，在氯气、氧气及氮气混合气氛中进行原料的氯化，将钒氯化成为粗三氯氧钒，然后对得到的粗三氯氧钒进行蒸馏，制备出高纯三氯氧钒，整个流程简单易行、工艺流程短，应用前景好。The method of the invention uses the vanadium ferroalloy fine powder as the raw material, and through the chlorination process, a high-purity vanadium oxychloride product can be prepared, and the purity can reach more than 99.9%, which can not only improve the added value of the product, but also realize the ferrovanadium smelting system. The recovery and utilization of secondary resources containing vanadium can improve the chlorination efficiency of ferrovanadium fine powder. The method of the invention uses the vanadium ferroalloy fine powder as the raw material, chlorination of the raw material is carried out in a mixed atmosphere of chlorine, oxygen and nitrogen, the vanadium is chlorinated into crude vanadium oxychloride, and then the obtained crude vanadium oxychloride is distilled to prepare To produce high-purity vanadium oxychloride, the whole process is simple and easy to implement, the process flow is short, and the application prospect is good.
具体实施方式Detailed ways
针对现有技术的缺陷，本发明以钒铁细粉为原料，在氯气、氧气、氮气混合气氛中通过氯化工艺，将钒铁细粉中的钒氯化为粗品三氯氧钒，后经过简单蒸馏，有效去除粗品三氯氧钒中的杂质从而制备出高纯三氯氧钒产品。该方法步骤简单、便于操作，且制备出的粗品三氯氧钒分离纯化效率高，相应的三氯氧钒产品纯度高，有利于其应用性能、及附加值的提升。通过该方法，实现了钒铁细粉的高效、高值利用，形成了一种钒铁细粉回收利用工艺方法。同时，该方法流程可行性高，易于实现工业化应用，具有较高的应用价值。In view of the defects of the prior art, the present invention uses the ferrovanadium fine powder as a raw material, and passes through a chlorination process in a mixed atmosphere of chlorine, oxygen and nitrogen to chlorinate the vanadium in the ferrovanadium fine powder into crude vanadium oxychloride, and then pass through a chlorination process. Simple distillation can effectively remove impurities in the crude vanadyl trichloride to prepare high-purity vanadium oxychloride products. The method has simple steps and is easy to operate, and the prepared crude product vanadyl trichloride has high separation and purification efficiency, and the corresponding vanadium oxychloride product has high purity, which is beneficial to the improvement of its application performance and added value. Through the method, the efficient and high-value utilization of the ferrovanadium fine powder is realized, and a technical method for recycling and utilizing the ferrovanadium fine powder is formed. At the same time, the method has high process feasibility, is easy to realize industrial application, and has high application value.
具体的，本发明利用钒铁细粉制备高纯三氯氧钒的方法，包括如下步骤：Specifically, the present invention utilizes the ferrovanadium fine powder to prepare the method for high-purity vanadium oxychloride, comprising the following steps:
a、将粒度为5μm～200μm，钒含量为40％～85％的钒铁细粉置于氯化反应器中，通入氮气，氮气的流速为0.01m/s～0.03m/s，升温至300℃～600℃，通入氯气和氧气，调整氮气、氯气和氧气的总流速为0.02m/s～0.08m/s，其中，通入氯气与氧气的摩尔比为2～3:1；氯气占氮气、氯气和氧气混合气体体积分数的20％～50％，进行氯化反应，反应过程中，将反应器内挥发的组分进行冷凝，得到三氯氧钒粗品，氯化反应的时间为60min～120min；a. Place the ferrovanadium fine powder with a particle size of 5 μm to 200 μm and a vanadium content of 40% to 85% in a chlorination reactor, feed nitrogen, and the flow rate of nitrogen is 0.01m/s to 0.03m/s. 300℃～600℃, feed chlorine and oxygen, adjust the total flow rate of nitrogen, chlorine and oxygen to be 0.02m/s～0.08m/s, wherein, the molar ratio of chlorine and oxygen is 2～3:1; It accounts for 20% to 50% of the volume fraction of the mixed gas of nitrogen, chlorine and oxygen, and performs chlorination reaction. During the reaction, the volatile components in the reactor are condensed to obtain a crude product of vanadium oxychloride. The time of the chlorination reaction is: 60min～120min;
b、氯化反应结束后，停止通入氯气和氧气，再次调整氮气的流速为0.01m/s～0.03m/s，待反应器冷却至室温后停止通入氮气；b. After the chlorination reaction is completed, stop feeding chlorine and oxygen, adjust the flow rate of nitrogen to be 0.01m/s～0.03m/s again, and stop feeding nitrogen after the reactor is cooled to room temperature;
c、将三氯氧钒粗品在125℃～130℃蒸馏，蒸馏至所得产物为三氯氧钒粗品质量的90％～95％，冷凝，得到高纯三氯氧钒。c, distilling the vanadium oxychloride crude product at 125 DEG C to 130 DEG C, distilling until the obtained product is 90%-95% of the quality of the vanadyl trichloride crude product, and condensing to obtain high-purity vanadium oxychloride.
在本发明步骤a中，将氯化反应过程中的尾气采用30％的氢氧化钠水溶液吸收，吸收后的溶液可以作为制备氯化钠及次氯酸钠的原料。In step a of the present invention, the tail gas in the chlorination reaction process is absorbed by a 30% aqueous sodium hydroxide solution, and the absorbed solution can be used as a raw material for preparing sodium chloride and sodium hypochlorite.
在本发明步骤a中，为了将反应器中的空气排出，同时便于反应器内热场的稳定，将钒铁细粉置于氯化反应器后通入氮气。升温至300℃～600℃，调整氮气流速是为了调节氯气的体积分数，起稀释作用。In the step a of the present invention, in order to discharge the air in the reactor and at the same time facilitate the stability of the thermal field in the reactor, the ferrovanadium fine powder is placed in the chlorination reactor and introduced into nitrogen. The temperature is raised to 300 ℃ ~ 600 ℃, and the nitrogen flow rate is adjusted to adjust the volume fraction of chlorine gas and play a diluting role.
本发明通过控制氯化温度、氯化时间以及氯气含量可以使钒高效率氯化，可以最大程度地抑制铁的氯化。将氯化温度控制在300℃～600℃，有利于钒的选择性氯化，若温度过高，会使钒铁细粉中的钒、铁均被氯化，增加氯气的消耗，同时后续蒸馏效率会降低；若温度过低，氯化反应慢，钒、铁均不能被氯化。By controlling the chlorination temperature, the chlorination time and the chlorine gas content, the present invention can make the vanadium chlorinated with high efficiency, and can restrain the chlorination of iron to the greatest extent. The chlorination temperature is controlled at 300℃～600℃, which is conducive to the selective chlorination of vanadium. If the temperature is too high, both vanadium and iron in the ferrovanadium fine powder will be chlorinated, which will increase the consumption of chlorine gas, and at the same time, the subsequent distillation will be carried out. The efficiency will be reduced; if the temperature is too low, the chlorination reaction will be slow, and neither vanadium nor iron can be chlorinated.
本发明步骤b中，氯化反应结束后，停止通入氯气和氧气，再次调整氮气流速为0.01m/s～0.03m/s是为了使反应器降温，并将反应器内的残余产物排出。In the step b of the present invention, after the chlorination reaction is completed, the feeding of chlorine and oxygen is stopped, and the nitrogen flow rate is adjusted to 0.01m/s～0.03m/s again in order to cool the reactor and discharge the residual product in the reactor.
下面将通过具体的实施例对本发明作进一步地详细阐述。The present invention will be described in further detail below through specific embodiments.
实施例1Example 1
将500g钒铁细粉置于刚玉坩埚中，钒铁细粉粒度为5μm～200μm，含钒量为40％，将坩埚置于石英氯化反应器中，并向反应器内通入0.01m/s的氮气，然后将反应器置于管式炉内升温加热；当炉温达到并恒定在600℃时，重新调节反应器内氮气流量，并向反应器内通入氯气及氧气，使反应器内氮气、氯气及氧气的总气速保持在0.02m/s，氯气与氧气的摩尔比为2:1，氯气在混合气体(氯气、氮气和氧气)中的体积分数为50％；氯化反应过程中，将氯化反应器内挥发出的组分进行冷凝收集得到三氯氧钒粗品，尾气采用30％的氢氧化钠水溶液吸收净化；反应120min后停止通入氯气及氧气，调整通入的氮气流量为0.01m/s，将反应器冷却至室温后停止通入氮气，取出未反应完的钒铁细粉，计算得到钒、铁的氯化率分别为95.02％、40.34％；将氯化得到的三氯氧钒粗品在125℃下蒸馏15min，蒸馏至所得产物为三氯氧钒粗品质量的90％，得到的三氯氧钒产品纯度为99.90％。Put 500g of ferro-vanadium fine powder in a corundum crucible, the particle size of ferro-vanadium fine powder is 5μm～200μm, the content of vanadium is 40%, the crucible is placed in a quartz chlorination reactor, and 0.01m/ s nitrogen, and then place the reactor in a tube furnace to heat up; when the furnace temperature reaches and is constant at 600 °C, the nitrogen flow in the reactor is readjusted, and chlorine and oxygen are introduced into the reactor to make the reactor The total gas velocity of nitrogen, chlorine and oxygen in the interior is kept at 0.02m/s, the molar ratio of chlorine to oxygen is 2:1, and the volume fraction of chlorine in the mixed gas (chlorine, nitrogen and oxygen) is 50%; chlorination reaction During the process, the volatilized components in the chlorination reactor were condensed and collected to obtain the crude vanadium oxychloride, and the tail gas was absorbed and purified with a 30% aqueous sodium hydroxide solution; after 120 min of reaction, the introduction of chlorine and oxygen was stopped, and the introduced gas was adjusted. The nitrogen flow rate was 0.01m/s. After cooling the reactor to room temperature, nitrogen was stopped, and the unreacted ferrovanadium fine powder was taken out. The chlorination rates of vanadium and iron were calculated to be 95.02% and 40.34%, respectively; The obtained crude vanadyl trichloride was distilled at 125° C. for 15 min, and the obtained product was distilled to 90% of the quality of the crude vanadyl trichloride, and the obtained product of vanadyl oxychloride had a purity of 99.90%.
实施例2Example 2
将200g钒铁细粉置于刚玉坩埚中，钒铁合金细粉粒度为5μm～200μm，含钒量为85％，将坩埚置于石英氯化反应器中，并向反应器内通入0.03m/s的氮气，然后将反应器置于管式炉内升温加热；当炉温达到并恒定在300℃时，重新调节反应器内氮气流量，并向反应器内通入氯气及氧气，使反应器内氮气、氯气及氧气的总气速保持在0.05m/s，氯气与氧气的摩尔比为3:1，氯气在混合气体(氯气、氮气和氧气)中的体积分数为30％；氯化反应过程中，将氯化反应器内挥发出的组分进行冷凝收集得到三氯氧钒粗品，尾气采用30％的氢氧化钠水溶液吸收净化；反应60min后停止通入氯气及氧气，调整通入的氮气流量为0.03m/s，将反应器冷却至室温后停止通入氮气，取出未反应完的钒铁细粉，计算得到钒、铁的氯化率分别为96.78％、11.28％；将氯化得到的三氯氧钒粗品在130℃下蒸馏10min，蒸馏至所得产物为三氯氧钒粗品质量的95％，得到的三氯氧钒产品纯度为99.98％。Put 200g of ferrovanadium fine powder in a corundum crucible, the particle size of vanadium ferroalloy fine powder is 5μm～200μm, and the vanadium content is 85%, put the crucible in a quartz chlorination reactor, and pass 0.03m/ s nitrogen, and then place the reactor in a tube furnace to heat up; when the furnace temperature reaches and is constant at 300 °C, the nitrogen flow in the reactor is readjusted, and chlorine and oxygen are introduced into the reactor to make the reactor The total gas velocity of nitrogen, chlorine and oxygen in the interior is kept at 0.05m/s, the molar ratio of chlorine and oxygen is 3:1, and the volume fraction of chlorine in the mixed gas (chlorine, nitrogen and oxygen) is 30%; chlorination reaction During the process, the components volatilized in the chlorination reactor were condensed and collected to obtain a crude vanadium oxychloride product, and the tail gas was absorbed and purified with a 30% aqueous sodium hydroxide solution; after 60 minutes of reaction, the introduction of chlorine and oxygen was stopped, and the introduced gas was adjusted. The nitrogen flow rate was 0.03m/s. After cooling the reactor to room temperature, nitrogen was stopped, and the unreacted ferrovanadium fine powder was taken out. The chlorination rates of vanadium and iron were calculated to be 96.78% and 11.28%, respectively; The obtained crude vanadyl trichloride was distilled at 130° C. for 10 min, until the obtained product was 95% of the quality of the crude vanadyl trichloride, and the purity of the obtained vanadyl trichloride product was 99.98%.
实施例3Example 3
将300g钒铁细粉置于刚玉坩埚中，钒铁合金细粉粒度为5μm～200μm，含钒量为50％，将坩埚置于石英氯化反应器中，并向反应器内通入0.02m/s的氮气，然后将反应器置于管式炉内升温加热；当炉温达到并恒定在500℃时，重新调节反应器内氮气流量，并向反应器内通入氯气及氧气，使反应器内氮气、氯气及氧气的总气速保持在0.08m/s，氯气与氧气的摩尔比为2.5:1，氯气在混合气体(氯气、氮气和氧气)中的体积分数为20％；氯化反应过程中，将氯化反应器内挥发出的组分进行冷凝收集得到三氯氧钒粗品，尾气采用30％的氢氧化钠水溶液吸收净化；反应90min后停止通入氯气及氧气，调整通入的氮气流量为0.02m/s，将反应器冷却至室温后停止通入氮气，取出未反应完的钒铁细粉，计算得到钒、铁的氯化率分别为96.02％、19.86％；将氯化得到的三氯氧钒粗品在127℃下蒸馏12min，蒸馏至所得产物为三氯氧钒粗品质量的92％，得到的三氯氧钒产品纯度为99.95％。Place 300g of ferrovanadium fine powder in a corundum crucible, the particle size of vanadium ferroalloy fine powder is 5μm～200μm, and the vanadium content is 50%. s nitrogen, and then place the reactor in a tube furnace to heat up and heat; when the furnace temperature reaches and is constant at 500 ° C, the nitrogen flow in the reactor is re-adjusted, and chlorine and oxygen are introduced into the reactor to make the reactor The total gas velocity of nitrogen, chlorine and oxygen in the interior is kept at 0.08m/s, the molar ratio of chlorine to oxygen is 2.5:1, and the volume fraction of chlorine in the mixed gas (chlorine, nitrogen and oxygen) is 20%; chlorination reaction During the process, the volatilized components in the chlorination reactor were condensed and collected to obtain the crude vanadium oxychloride, and the tail gas was absorbed and purified with a 30% aqueous sodium hydroxide solution; after 90 minutes of reaction, the introduction of chlorine and oxygen was stopped, and the introduced gas was adjusted. The nitrogen flow rate was 0.02m/s. After cooling the reactor to room temperature, nitrogen was stopped, and the unreacted ferrovanadium fine powder was taken out. The chlorination rates of vanadium and iron were calculated to be 96.02% and 19.86%, respectively; The obtained crude vanadyl trichloride product was distilled at 127° C. for 12 min, and the obtained product was distilled to 92% of the quality of the crude vanadyl trichloride product, and the purity of the obtained vanadyl trichloride product was 99.95%.
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| 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 |
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| 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 |
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