CN107662946B - Preparation method of vanadium trioxide - Google Patents

Preparation method of vanadium trioxide Download PDF

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CN107662946B
CN107662946B CN201710685096.3A CN201710685096A CN107662946B CN 107662946 B CN107662946 B CN 107662946B CN 201710685096 A CN201710685096 A CN 201710685096A CN 107662946 B CN107662946 B CN 107662946B
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oxalic acid
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崔旭梅
陈孝娥
张贵刚
蓝德均
刘甜甜
左承阳
丁虎标
候冰雪
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Abstract

The invention discloses a preparation method of vanadium trioxide applicable to a vanadium battery, which comprises the following steps: and (3) carrying out liquid phase reduction on ammonium vanadate with the vanadium valence of +5 and oxalic acid or a solvate of oxalic acid in a reaction solvent, evaporating the reaction solution to dryness, and calcining to obtain the catalyst. The method takes cheap and easily-obtained + 5-valent ammonium vanadate as a raw material, and vanadium trioxide with the purity of up to 99 percent can be obtained by oxalic acid reduction and calcination. The production process has the advantages of simple operation, low energy consumption, safety and low equipment requirement, is suitable for industrial large-scale production, and can obviously reduce the production cost of vanadium trioxide.

Description

三氧化二钒的制备方法The preparation method of vanadium trioxide

技术领域technical field

本发明涉及三氧化二钒的制备方法,属于化工材料合成领域。The invention relates to a preparation method of vanadium trioxide, and belongs to the field of chemical material synthesis.

背景技术Background technique

三氧化二钒是一种重要的钒氧化物,广泛应用于高钒铁和钒氮合金生产、传感器、新型电子元器件以及电池生产等领域。其中,三氧化二钒在全钒液流电池电解液生产过程中具有很好的应用前景,原因是以三氧化二钒为还原剂还原五氧化二钒制备3.5价钒电解液的方法,其生产工艺简单,还原效果好,且不带入其它杂质,兼具化学还原法和电解法的优点,使钒电解液的生产成本得到降低,因此,此方法一经提出即受到相关行业的广泛关注。然而,由于目前三氧化二钒的制备成本高,产品纯度低,使这种生产钒电解液的方法受到了限制。Vanadium trioxide is an important vanadium oxide, which is widely used in the production of high vanadium iron and vanadium nitrogen alloys, sensors, new electronic components and battery production. Among them, vanadium trioxide has good application prospects in the production process of all-vanadium redox flow battery electrolyte, because the method for preparing 3.5-valent vanadium electrolyte by reducing vanadium pentoxide with vanadium The process is simple, the reduction effect is good, and other impurities are not introduced, and it has the advantages of chemical reduction and electrolysis, so that the production cost of vanadium electrolyte can be reduced. However, due to the high preparation cost and low product purity of vanadium trioxide at present, this method of producing vanadium electrolyte is limited.

目前,三氧化二钒主要由高价态钒化合物经还原制得。还原的方法包括外加固体还原剂(如,硫、碳粉、石墨等)还原,还原性气体(如,H2、CO等)还原,钒酸铵分解,氨气裂解还原等。其中,加石墨和碳等还原剂还原的方法生产工艺简单,但所需还原温度高,且产品中容易残留碳或带入其他杂质;H2或CO等还原气体还原效果好,产品纯度高,但是存在燃烧、爆炸或有毒气体泄露等危险;钒酸铵分解,产生的氨气裂解成H2和N2还原制备三氧化二钒的方法清洁、环保,无需添加任何还原剂,但是由于氨气裂解不完全,还原不充分,且对设备要求较高。除了以上几种主要的制备方法之外,还可在保护气体条件下煅烧含钒肼盐,以及加有机还原剂再通过水热合成或溶剂热等方法合成出粒径均匀细小的三氧化二钒,并在相关领域取得较好的应用效果,但是这些方法存在着对设备要求高、生产效率低等缺点,导致三氧化二钒的生产成本偏高。At present, vanadium trioxide is mainly obtained by reduction of high-valence vanadium compounds. The reduction methods include reduction with external solid reducing agents (eg, sulfur, carbon powder, graphite, etc.), reduction with reducing gases (eg, H 2 , CO, etc.), decomposition of ammonium vanadate, and reduction by ammonia cracking. Among them, the method of adding reducing agents such as graphite and carbon for reduction has a simple production process, but the required reduction temperature is high, and carbon is easily left in the product or other impurities are easily introduced; H2 or CO and other reducing gases have good reduction effects and high product purity. But there are dangers such as burning, explosion or toxic gas leakage; ammonium vanadate is decomposed, and the generated ammonia is cracked into H 2 and N 2 The method for reducing vanadium trioxide is clean and environmentally friendly, and does not need to add any reducing agent, but due to ammonia gas The cracking is incomplete, the reduction is insufficient, and the equipment requirements are high. In addition to the above several main preparation methods, vanadium-containing hydrazine salts can also be calcined under protective gas conditions, and organic reducing agents can be added to synthesize vanadium trioxide with uniform and fine particle size by hydrothermal synthesis or solvothermal methods. , and achieved good application results in related fields, but these methods have shortcomings such as high equipment requirements and low production efficiency, resulting in high production costs of vanadium trioxide.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供三氧化二钒的制备方法,以克服现有生产工艺成本较高、操作复杂的缺陷。The object of the present invention is to provide a preparation method of vanadium trioxide, to overcome the defects of higher cost and complicated operation of the existing production process.

本发明提供了三氧化二钒的制备方法,包括如下步骤:钒价态为+5价的钒酸铵与草酸或草酸的溶剂合物在反应溶剂中进行液相还原,蒸干反应液,煅烧,即得。The present invention provides a method for preparing vanadium trioxide, which comprises the following steps: performing liquid phase reduction of ammonium vanadate whose vanadium valence is +5 and oxalic acid or a solvate of oxalic acid in a reaction solvent, evaporating the reaction solution to dryness, and calcining , that is.

进一步地,所述钒价态为+5价的钒酸铵为偏钒酸铵或多钒酸铵。Further, the ammonium vanadate whose vanadium valence state is +5 is ammonium metavanadate or ammonium polyvanadate.

进一步地,所述钒酸铵中钒的摩尔量与草酸的摩尔量比例为1:(1.5~3)。Further, the molar ratio of vanadium in the ammonium vanadate to the molar ratio of oxalic acid is 1:(1.5-3).

进一步优选地,所述钒酸铵中钒的摩尔量与草酸的摩尔量比例为1:(1.5~2.5)。Further preferably, the molar ratio of vanadium in the ammonium vanadate to the molar ratio of oxalic acid is 1:(1.5-2.5).

进一步地,所述钒酸铵中钒的摩尔量:反应溶剂的体积为5~12mol/L。Further, the molar amount of vanadium in the ammonium vanadate: the volume of the reaction solvent is 5-12 mol/L.

进一步优选地,所述钒酸铵中钒的摩尔量:反应溶剂的体积为8.5~10mol/L。Further preferably, the molar amount of vanadium in the ammonium vanadate: the volume of the reaction solvent is 8.5-10 mol/L.

进一步地,反应温度为80~100℃。Further, the reaction temperature is 80-100°C.

进一步优选地,反应温度为80~90℃。Further preferably, the reaction temperature is 80-90°C.

进一步地,煅烧在保护气氛中进行。Further, calcination is carried out in a protective atmosphere.

进一步地,所述保护气氛为氮气、氦气、氩气、氨气、CO、气态烷烃中一种或两种以上的混合物。Further, the protective atmosphere is one or a mixture of two or more of nitrogen, helium, argon, ammonia, CO, and gaseous alkanes.

进一步优选地,所述保护气氛为氮气。Further preferably, the protective atmosphere is nitrogen.

进一步地,煅烧温度为700~1000℃。Further, the calcination temperature is 700-1000°C.

进一步优选地,煅烧温度为700~900℃。Further preferably, the calcination temperature is 700-900°C.

进一步地,煅烧时间为1.5~5h。Further, the calcination time is 1.5-5h.

进一步优选地,煅烧时间为2~4h。Further preferably, the calcination time is 2-4h.

进一步地,所述反应溶剂为水。Further, the reaction solvent is water.

进一步地,所述草酸的溶剂合物为草酸二水合物。Further, the solvate of oxalic acid is oxalic acid dihydrate.

进一步地,煅烧前先进行干燥;干燥过程中,为防止前驱体干燥后结块,每隔10-20min需对前驱体进行机械搅拌。Further, drying is performed before calcination; in the drying process, in order to prevent the precursor from agglomerating after drying, the precursor needs to be mechanically stirred every 10-20 minutes.

本发明提供了三氧化二钒的制备方法。该方法以廉价易得的+5价钒酸铵为原料,经草酸还原,煅烧,即可得到纯度高达99%的三氧化二钒,收率100%(不计转移损失)。本发明生产工艺操作简便,能耗低,安全,对设备要求不高,适合工业化大规模生产,能够显著降低三氧化二钒的生产成本。此外,该方法得到的V2O3适用于制备全钒液流电池的电解液,将其置于有效面积为100cm2的钒电池中进行充放电循环40次,电池的库仑效率保持在96%以上,能量效率保持在80%以上,且库伦效率和能量效率几乎无衰减。在全钒液流电池电解液生产过程中具有广阔的应用前景。The invention provides a preparation method of vanadium trioxide. The method uses cheap and readily available +5-valent ammonium vanadate as a raw material, and through oxalic acid reduction and calcination, vanadium trioxide with a purity of up to 99% can be obtained, and the yield is 100% (excluding transfer loss). The production process of the invention has the advantages of simple operation, low energy consumption, safety, low equipment requirements, suitable for industrialized large-scale production, and can significantly reduce the production cost of vanadium trioxide. In addition, the V 2 O 3 obtained by this method is suitable for the preparation of electrolytes for all-vanadium redox flow batteries. It was placed in a vanadium battery with an effective area of 100 cm 2 for 40 charge-discharge cycles, and the coulombic efficiency of the battery remained at 96%. Above, the energy efficiency is maintained above 80%, and the Coulomb efficiency and the energy efficiency are hardly attenuated. It has broad application prospects in the production process of all-vanadium redox flow battery electrolyte.

附图说明Description of drawings

图1为本发明三氧化二钒生产工艺示意图;Fig. 1 is vanadium trioxide production process schematic diagram of the present invention;

图2为对比例1中偏钒酸铵与草酸摩尔配比为1:0.5反应所得产物的XRD衍射谱图;Fig. 2 is the XRD diffractogram of ammonium metavanadate and oxalic acid molar ratio of 1:0.5 reaction products obtained in Comparative Example 1;

图3为对比例1中偏钒酸铵与草酸摩尔配比为1:1反应所得产物的XRD衍射谱图;Fig. 3 is the XRD diffractogram of ammonium metavanadate and oxalic acid molar ratio of 1:1 reaction products obtained in Comparative Example 1;

图4为对比例2中于400℃煅烧所得产物的XRD衍射谱图;Fig. 4 is the XRD diffraction pattern of the product obtained by calcining at 400°C in Comparative Example 2;

图5为对比例2中于450℃煅烧所得产物的XRD衍射谱图;Fig. 5 is the XRD diffractogram of the product obtained by calcining at 450°C in Comparative Example 2;

图6为对比例2中于500℃煅烧所得产物的XRD衍射谱图;Fig. 6 is the XRD diffractogram of the product obtained by calcining at 500°C in Comparative Example 2;

图7为对比例2中于550℃煅烧所得产物的XRD衍射谱图;Fig. 7 is the XRD diffractogram of the product obtained by calcination at 550°C in Comparative Example 2;

图8为对比例2中于600℃煅烧所得产物的XRD衍射谱图;Fig. 8 is the XRD diffraction pattern of the product obtained by calcination at 600°C in Comparative Example 2;

图9为对比例2中于650℃煅烧所得产物的XRD衍射谱图;Fig. 9 is the XRD diffraction pattern of the product obtained by calcination at 650°C in Comparative Example 2;

图10为对比例2中于700℃煅烧所得产物的XRD衍射谱图;Fig. 10 is the XRD diffraction pattern of the product obtained by calcination at 700°C in Comparative Example 2;

图11为试验例1中电池充放电库仑效率和能量效率图;Fig. 11 is a diagram showing the coulombic efficiency and energy efficiency of battery charging and discharging in Test Example 1;

图12为试验例2中偏钒酸铵与草酸摩尔配比为1:1.5反应所得产物的XRD衍射谱图;Figure 12 is the XRD diffractogram of the product obtained from the reaction of ammonium metavanadate and oxalic acid in the molar ratio of 1:1.5 in Test Example 2;

图13为试验例2中偏钒酸铵与草酸摩尔配比为1:2反应所得产物的XRD衍射谱图;Fig. 13 is the XRD diffractogram of ammonium metavanadate and oxalic acid molar ratio of 1:2 reaction products obtained in Test Example 2;

图14为试验例2中偏钒酸铵与草酸摩尔配比为1:2.5反应所得产物的XRD衍射谱图;Figure 14 is the XRD diffractogram of the product obtained by the reaction of ammonium metavanadate and oxalic acid in the molar ratio of 1:2.5 in Test Example 2;

图15为试验例2中偏钒酸铵与草酸摩尔配比为1:3反应所得产物的XRD衍射谱图。Figure 15 is the XRD diffraction pattern of the product obtained by the reaction of ammonium metavanadate and oxalic acid in a molar ratio of 1:3 in Test Example 2.

具体实施方式Detailed ways

本发明具体实施方式中使用的原料、设备均为已知产品,通过购买市售产品获得。The raw materials and equipment used in the specific embodiments of the present invention are all known products, which are obtained by purchasing commercially available products.

本发明提供了三氧化二钒的制备方法,包括如下步骤(生产工艺示意图见图1):The invention provides a preparation method of vanadium trioxide, comprising the following steps (see Fig. 1 for a schematic diagram of the production process):

1)将偏钒酸铵或多钒酸铵与草酸混合(混合比例为,钒的摩尔量:草酸的摩尔量=1:1.5~1:2.5),加入到温度为80~90℃的去离子水中(钒的摩尔量:水的体积为8.5~10mol/L),进行液相还原;1) Mix ammonium metavanadate or ammonium polyvanadate with oxalic acid (the mixing ratio is, the molar amount of vanadium: the molar amount of oxalic acid=1: 1.5~1: 2.5), add to the deionization temperature that the temperature is 80~90 ℃ In water (molar amount of vanadium: the volume of water is 8.5~10mol/L), carry out liquid phase reduction;

2)待偏钒酸铵或多钒酸铵完全溶解后,加热至沸腾,将溶液浓缩蒸干,得到前驱体;2) after ammonium metavanadate or ammonium polyvanadate is completely dissolved, heated to boiling, the solution is concentrated and evaporated to dryness to obtain a precursor;

3)将所得前驱体在氮气保护和温度为700~900℃的条件下焙烧2~4h,并在氮气保护下冷却至室温,即得三氧化二钒。3) calcining the obtained precursor under the protection of nitrogen and the temperature of 700-900 DEG C for 2-4 hours, and cooling to room temperature under the protection of nitrogen to obtain vanadium trioxide.

该生产工艺中,得到主要成分是(NH4)2(VO)2(C2O4)3和草酸混合物的前驱体,由于碳含量多,煅烧分解时的还原效果好;而且,中间产物分解能产生氨气,氨气本身具有还原性,起到了保护作用,能够使中间产物得到更好的还原。基于上述原因,本发明制备工艺具有明显优点:①能够高纯度、高收率地得到三氧化二钒,而且工艺稳定性强,所得产品质量稳定;②所得三氧化二钒非常适合用于制备钒电解液,电池的充放电效率良好,证明其应用效果佳。In this production process, a precursor whose main components are (NH 4 ) 2 (VO) 2 (C 2 O 4 ) 3 and oxalic acid mixture is obtained. Due to the high carbon content, the reduction effect during calcination and decomposition is good; Ammonia gas is produced, and the ammonia gas itself has reducibility and plays a protective role, which can better reduce the intermediate product. Based on the above reasons, the preparation process of the present invention has obvious advantages: 1. vanadium trioxide can be obtained with high purity and high yield, and the process stability is strong, and the quality of the obtained product is stable; 2. the obtained vanadium trioxide is very suitable for preparing vanadium Electrolyte, the battery has good charge and discharge efficiency, which proves that its application effect is good.

此外,本发明进一步对制备工艺中各参数条件进行了考察,结果发现,草酸用量和煅烧温度的相互配合对产品具有明显影响。当钒与草酸的摩尔量配比低于1:1.5时,很难得到三氧化二钒;相应地,在煅烧温度低于700℃的条件下,即使反复调整草酸用量,三氧化二钒的纯度也难以达到要求。在两者的特定配合下,最终将产品纯度提高至99%以上,除生产过程中的转移损失外,钒的收率无其它任何损失。In addition, the present invention further investigates various parameters and conditions in the preparation process, and it is found that the interaction between the amount of oxalic acid and the calcination temperature has a significant impact on the product. When the molar ratio of vanadium and oxalic acid is lower than 1:1.5, it is difficult to obtain vanadium trioxide; correspondingly, under the condition that the calcination temperature is lower than 700 ℃, even if the amount of oxalic acid is repeatedly adjusted, the purity of vanadium trioxide is It is also difficult to meet the requirements. Under the specific combination of the two, the product purity is finally increased to more than 99%, and the yield of vanadium has no other losses except the transfer loss during the production process.

目前,尚未见通过+5价钒酸铵与草酸反应制备三氧化二钒的报道。相较于现有制备工艺外加固体还原剂(如,硫、碳粉、石墨等)或还原性气体(如,H2、CO等)等还原方法,本发明具有生产成本低、操作简便、安全等显著优势。At present, there is no report on the preparation of vanadium trioxide by the reaction of +5-valent ammonium vanadate with oxalic acid. Compared with the existing preparation process by adding a solid reducing agent (eg, sulfur, carbon powder, graphite, etc.) or reducing gas (eg, H 2 , CO, etc.) and other reduction methods, the present invention has the advantages of low production cost, simple operation, and safety. and other significant advantages.

实施例1采用本发明工艺制备三氧化二钒Embodiment 1 adopts the technology of the present invention to prepare vanadium trioxide

1)将分析纯偏钒酸铵与分析纯二水合草酸混合(混合比例为,钒的摩尔量:草酸的摩尔量=1:1.5),分批加入到温度为80℃的去离子水中(钒的摩尔量:水的体积=10mol/L),进行液相还原;1) Mix analytically pure ammonium metavanadate with analytically pure dihydrate oxalic acid (the mixing ratio is, the molar amount of vanadium: the molar amount of oxalic acid=1:1.5), and adding it in batches into deionized water (vanadium) at a temperature of 80° C. The molar amount of: the volume of water=10mol/L), carry out liquid phase reduction;

2)待偏钒酸铵完全溶解后,加热至沸腾,将溶液浓缩蒸干,得到前驱体;2) after the ammonium metavanadate is completely dissolved, heated to boiling, the solution is concentrated and evaporated to dryness to obtain a precursor;

3)将所得前驱体在160℃下干燥后,在氮气保护和温度为700℃的条件下焙烧2.5h,并在氮气保护下冷却至室温。最后制得三氧化二钒的纯度为98.8%。3) After drying the obtained precursor at 160° C., calcining for 2.5 h under nitrogen protection and at a temperature of 700° C., and cooling to room temperature under nitrogen protection. The purity of vanadium trioxide finally obtained is 98.8%.

实施例2采用本发明工艺制备三氧化二钒Embodiment 2 adopts the technology of the present invention to prepare vanadium trioxide

1)将分析纯偏钒酸铵与分析纯二水合草酸混合(混合比例为,钒的摩尔量:草酸的摩尔量=1:2),分批加入到温度为95℃的去离子水中(钒的摩尔量:水的体积=9mol/L),进行液相还原;1) Mix analytically pure ammonium metavanadate with analytically pure dihydrate oxalic acid (the mixing ratio is, the molar amount of vanadium: the molar amount of oxalic acid=1:2), and adding it in batches into deionized water (vanadium) at a temperature of 95° C. The molar weight: the volume of water=9mol/L), carry out liquid phase reduction;

2)待偏钒酸铵完全溶解后,加热至沸腾,将溶液浓缩蒸干,得到前驱体;2) after the ammonium metavanadate is completely dissolved, heated to boiling, the solution is concentrated and evaporated to dryness to obtain a precursor;

3)将所得前驱体在100℃下干燥,在氮气保护和温度为750℃的条件下焙烧3h,并在氮气保护下冷却至室温。最后制得三氧化二钒的纯度为99.2%。3) The obtained precursor was dried at 100°C, calcined for 3 hours under nitrogen protection and at a temperature of 750°C, and cooled to room temperature under nitrogen protection. The purity of vanadium trioxide finally obtained is 99.2%.

实施例3采用本发明工艺制备三氧化二钒Embodiment 3 adopts the technology of the present invention to prepare vanadium trioxide

1)将分析纯偏钒酸铵与分析纯二水合草酸混合(混合比例为,钒的摩尔量:草酸的摩尔量=1:2.5),分批加入到温度为85℃去离子水中(钒的摩尔量:水的体积=10mol/L),进行液相还原;1) Mix analytically pure ammonium metavanadate with analytically pure dihydrate oxalic acid (the mixing ratio is, the molar amount of vanadium: the molar amount of oxalic acid=1:2.5), and adding in batches is that the temperature is 85 ℃ of deionized water (vanadium Molar weight: volume of water=10mol/L), carry out liquid phase reduction;

2)待偏钒酸铵完全溶解后,加热至沸腾,将溶液浓缩蒸干,得到前驱体;2) after the ammonium metavanadate is completely dissolved, heated to boiling, the solution is concentrated and evaporated to dryness to obtain a precursor;

3)将所得前驱体在200℃下干燥,在氮气保护和温度为800℃的条件下焙烧2h,并在氮气保护下冷却至室温。最后制得三氧化二钒的纯度为99.4%。3) The obtained precursor was dried at 200°C, calcined for 2 h under nitrogen protection and at a temperature of 800°C, and cooled to room temperature under nitrogen protection. The purity of vanadium trioxide finally obtained is 99.4%.

实施例4采用本发明工艺制备三氧化二钒Embodiment 4 adopts the technology of the present invention to prepare vanadium trioxide

1)将分析纯偏钒酸铵与分析纯二水合草酸混合(混合比例为,钒的摩尔量:草酸的摩尔量=1:3),分批加入到温度为90℃的去离子水中(钒的摩尔量:水的体积=8.5mol/L),进行液相还原;1) Mix analytically pure ammonium metavanadate with analytically pure dihydrate oxalic acid (the mixing ratio is, the molar amount of vanadium: the molar amount of oxalic acid=1:3), and adding it in batches into deionized water (vanadium) at a temperature of 90° C. The molar amount of : the volume of water=8.5mol/L), carry out liquid phase reduction;

2)待偏钒酸铵完全溶解后,加热至沸腾,将溶液浓缩蒸干,得前驱体;2) after the ammonium metavanadate is completely dissolved, heated to boiling, the solution is concentrated and evaporated to dryness to obtain the precursor;

3)将所得前驱体在180℃下干燥,在氮气保护和温度为900℃的条件下焙烧3h,并在氮气保护下冷却至室温。最后制得三氧化二钒的纯度为99.0%。3) The obtained precursor was dried at 180 °C, calcined for 3 h under nitrogen protection and at a temperature of 900 °C, and cooled to room temperature under nitrogen protection. The purity of vanadium trioxide finally obtained is 99.0%.

对比例1制备工艺中草酸用量对产品的影响Influence of the amount of oxalic acid on the product in the preparation process of Comparative Example 1

本实验将偏钒酸铵与草酸分别在1:0.5、1:1摩尔配比下反应,制备出的前驱体于氮气保护条件下700℃下焙烧,得到产物,具体工艺条件同实施例1。对所得产物进行XRD衍射分析,分析结果如图2、3所示。In this experiment, ammonium metavanadate and oxalic acid were reacted in molar ratios of 1:0.5 and 1:1 respectively, and the prepared precursor was calcined at 700°C under nitrogen protection to obtain a product. The specific process conditions were the same as those in Example 1. The obtained product was subjected to XRD diffraction analysis, and the analysis results are shown in Figures 2 and 3.

对图2、3的XRD图谱分析可知,当偏钒酸铵与草酸的摩尔配比为1:0.5、1:1时,所得产物的主要成分为VO2、V3O5,而并非目标物质V2O3The analysis of the XRD patterns of Figures 2 and 3 shows that when the molar ratio of ammonium metavanadate and oxalic acid is 1:0.5 and 1:1, the main components of the obtained product are VO 2 and V 3 O 5 , rather than the target substance. V 2 O 3 .

此外,对比试验还在偏钒酸铵:草酸摩尔比1:3的基础上进一步加大草酸用量,结果在不提高煅烧温度的前提下,焙烧所得产物中的无定型碳含量随着草酸加入量的增加而增加,XRD衍射出现无定形碳衍射峰杂峰越来越明显,说明所得产物的纯度显著降低。In addition, the comparative test also further increased the amount of oxalic acid on the basis of ammonium metavanadate: the oxalic acid molar ratio of 1:3, and the result did not increase the calcination temperature. With the increase of , the stray peaks of amorphous carbon diffraction peaks appear more and more obvious in XRD diffraction, indicating that the purity of the obtained product is significantly reduced.

以上试验结果表明,草酸用量对终产品会产生明显影响,在本发明制备工艺确定的用量范围内,即钒酸铵中钒的摩尔量与草酸的摩尔量比例为1:(1.5~3)时,可以高收率地制备得到高纯度的目标产物V2O3The above test results show that the amount of oxalic acid will have a significant impact on the final product. Within the dosage range determined by the preparation process of the present invention, that is, when the molar ratio of vanadium in the ammonium vanadate to the molar ratio of oxalic acid is 1: (1.5~3) , high-purity target product V 2 O 3 can be prepared in high yield.

对比例2制备工艺中煅烧温度对产品的影响Influence of calcination temperature on product in preparation process of comparative example 2

根据实施例1制备前驱体,将前驱体至于管式炉中,通入氮气保护,分别于400℃、450℃、500℃、550℃、600℃、650℃、700℃焙烧4h,焙烧完成后,继续通氮气,直至炉温降到室温。对所得产物进行XRD衍射分析,分析结果如图4~10所示。The precursor was prepared according to Example 1. The precursor was placed in a tube furnace, protected by nitrogen, and calcined at 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 650 °C, and 700 °C for 4 hours. , continue to pass nitrogen until the furnace temperature drops to room temperature. The obtained product was subjected to XRD diffraction analysis, and the analysis results are shown in Figures 4-10.

从图4~10可以看出,随着焙烧温度的不断升高,V2O3的衍射峰越来越明显,杂峰越来越弱。说明在低于700℃温度下焙烧时,前驱体分解不完全,产物中无定形碳的含量较多,产品纯度不高;煅烧温度高于700℃时,前驱体分解彻底,其中的碳对钒的还原能力较强,能够得到高纯度的V2O3It can be seen from Figures 4 to 10 that with the continuous increase of the calcination temperature, the diffraction peaks of V 2 O 3 become more and more obvious, and the impurity peaks become weaker and weaker. It shows that when the calcination temperature is lower than 700℃, the decomposition of the precursor is incomplete, the content of amorphous carbon in the product is large, and the purity of the product is not high; The reducing ability is strong, and high-purity V 2 O 3 can be obtained.

以下通过试验例证明本发明的有益效果。The beneficial effects of the present invention are demonstrated below through test examples.

试验例1以本发明三氧化二钒为原料制备钒电池Test Example 1 Preparation of vanadium battery with vanadium trioxide of the present invention as raw material

将五氧化二钒与根据本发明实施例1制备的三氧化二钒按摩尔比为4.2:1的比例混合,加入6mol/L的硫酸,于90℃下反应120min,冷却至室温后,过滤,测定滤液中三价钒和五价钒的含量(V+3:V+5=1.04:1),加入去离子水调节溶液中H2SO4浓度为3mol/L,总钒浓度为2mol/L。取等量该电解液分别置于钒电池的正负极储液罐中(钒电池的有效面积为100cm2),以40mA/cm2的电流密度进行恒流充放电循环40次,电池的能量效率和库伦效率如图11所示。Vanadium pentoxide was mixed with vanadium trioxide prepared according to Example 1 of the present invention in a molar ratio of 4.2:1, 6 mol/L sulfuric acid was added, the reaction was carried out at 90 ° C for 120 min, after cooling to room temperature, filtered, Measure the content of trivalent vanadium and pentavalent vanadium in the filtrate (V +3 :V +5 =1.04:1), add deionized water to adjust the H 2 SO 4 concentration in the solution to be 3mol/L, and the total vanadium concentration to be 2mol/L . Get an equal amount of this electrolyte and place it in the positive and negative electrode storage tanks of the vanadium battery respectively (the effective area of the vanadium battery is 100cm 2 ), with a current density of 40mA/cm , carry out constant current charge - discharge cycle 40 times, the energy of the battery Efficiency and Coulombic efficiency are shown in Figure 11.

从图11可以看出,电池的库仑效率保持在96%以上,能量效率保持在80%以上,且库伦效率和能量效率几乎无衰减,说明该电解液的性能良好。It can be seen from Figure 11 that the coulombic efficiency of the battery is maintained above 96%, the energy efficiency is maintained above 80%, and the coulombic efficiency and energy efficiency are almost not attenuated, indicating that the electrolyte has good performance.

以上试验结果表明,采用本发明方法制备出的V2O3适用于制备全钒液流电池的电解液,其纯度能够达到制备钒电池的要求,加之生产成本明显降低,有利于以三氧化二钒为还原剂还原五氧化二钒制备3.5价钒电解液的方法得到进一步推广应用。The above test results show that the V 2 O 3 prepared by the method of the present invention is suitable for preparing the electrolyte of all-vanadium redox flow batteries, and its purity can meet the requirements for preparing vanadium batteries. The method of preparing 3.5-valent vanadium electrolyte by reducing vanadium pentoxide with vanadium as reducing agent has been further popularized and applied.

试验例2本发明制备工艺的验证试验Test Example 2 Verification test of the preparation process of the present invention

偏钒酸铵与草酸分别在1:1.5、1:2、1:2.5、1:3摩尔配比下反应,制备出的前驱体于氮气保护条件下700℃下焙烧,得到还原产物,工艺条件同实施例1。所得产物进行XRD衍射分析,分析结果如图12~15所示。Ammonium metavanadate and oxalic acid were reacted in molar ratios of 1:1.5, 1:2, 1:2.5, and 1:3, respectively, and the prepared precursor was calcined at 700 °C under nitrogen protection to obtain a reduced product. The process conditions Same as Example 1. The obtained product was subjected to XRD diffraction analysis, and the analysis results are shown in Figures 12-15.

对图12~15的XRD图谱分析可知,这几种产物的主要成分均为V2O3The analysis of the XRD patterns in Figs. 12-15 shows that the main components of these products are all V 2 O 3 .

以上试验结果表明,本发明制备工艺稳定可靠,所得产品质量稳定。The above test results show that the preparation process of the present invention is stable and reliable, and the quality of the obtained product is stable.

Claims (12)

1.三氧化二钒的制备方法,其特征是:包括如下步骤:钒价态为+5价的钒酸铵与草酸或草酸的溶剂合物在反应溶剂中进行液相还原,蒸干反应液,煅烧,即得;所述钒酸铵中钒的摩尔量与草酸的摩尔量比例为1:(1.5~3);液相还原的温度为80~100℃;煅烧温度为700~1000℃;所述草酸的溶剂合物为草酸二水合物;煅烧在保护气氛中进行。1. the preparation method of vanadium trioxide, it is characterized in that: comprise the steps: the solvate of ammonium vanadate and oxalic acid or oxalic acid that vanadium valence state is +5 valence carries out liquid phase reduction in reaction solvent, evaporated to dryness reaction solution , calcining to obtain; the molar ratio of vanadium in the ammonium vanadate to the molar ratio of oxalic acid is 1: (1.5~3); the temperature of liquid-phase reduction is 80~100 ℃; the calcination temperature is 700~1000 ℃; The solvate of oxalic acid is oxalic acid dihydrate; calcination is carried out in a protective atmosphere. 2.如权利要求1所述的制备方法,其特征是:所述钒价态为+5价的钒酸铵为偏钒酸铵或多钒酸铵。2. preparation method as claimed in claim 1 is characterized in that: the ammonium vanadate that described vanadium valence state is +5 valence is ammonium metavanadate or ammonium polyvanadate. 3.如权利要求1所述的制备方法,其特征是:所述钒酸铵中钒的摩尔量与草酸的摩尔量比例为1:(1.5~2.5)。3 . The preparation method according to claim 1 , wherein the molar ratio of vanadium in the ammonium vanadate to the molar ratio of oxalic acid is 1:(1.5~2.5). 4 . 4.如权利要求1~3任意一项所述的制备方法,其特征是:所述钒酸铵中钒的摩尔量:反应溶剂的体积为5~12mol/L。4. The preparation method according to any one of claims 1 to 3, wherein the molar amount of vanadium in the ammonium vanadate: the volume of the reaction solvent is 5 to 12 mol/L. 5.如权利要求1~3任意一项所述的制备方法,其特征是:所述钒酸铵中钒的摩尔量:反应溶剂的体积为8.5~10mol/L。5. The preparation method according to any one of claims 1 to 3, wherein the molar amount of vanadium in the ammonium vanadate: the volume of the reaction solvent is 8.5 to 10 mol/L. 6.如权利要求1所述的制备方法,其特征是:液相还原的温度为80~90℃。6 . The preparation method according to claim 1 , wherein the temperature of the liquid phase reduction is 80-90° C. 7 . 7.如权利要求1所述的制备方法,其特征是:所述保护气氛为氮气、氦气、氩气、氨气、CO、气态烷烃中一种或两种以上的混合物。7. The preparation method of claim 1, wherein the protective atmosphere is a mixture of one or more of nitrogen, helium, argon, ammonia, CO, and gaseous alkanes. 8.如权利要求1所述的制备方法,其特征是:所述保护气氛为氮气。8. The preparation method of claim 1, wherein the protective atmosphere is nitrogen. 9.如权利要求1所述的制备方法,其特征是:煅烧温度为700~900℃。9. The preparation method of claim 1, wherein the calcination temperature is 700-900°C. 10.如权利要求1、7~9任意一项所述的制备方法,其特征是:煅烧时间为1.5~5h。10. The preparation method according to any one of claims 1, 7 to 9, wherein the calcination time is 1.5 to 5 hours. 11.如权利要求1、7~9任意一项所述的制备方法,其特征是:煅烧时间为2~4h。11. The preparation method according to any one of claims 1, 7 to 9, wherein the calcination time is 2 to 4 hours. 12.如权利要求1所述的制备方法,其特征是:所述反应溶剂为水。12. The preparation method of claim 1, wherein the reaction solvent is water.
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