WO2018024083A1 - Method using highly concentrated vanadium solution for manufacturing ammonium polyvanadate - Google Patents

Method using highly concentrated vanadium solution for manufacturing ammonium polyvanadate Download PDF

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WO2018024083A1
WO2018024083A1 PCT/CN2017/092659 CN2017092659W WO2018024083A1 WO 2018024083 A1 WO2018024083 A1 WO 2018024083A1 CN 2017092659 W CN2017092659 W CN 2017092659W WO 2018024083 A1 WO2018024083 A1 WO 2018024083A1
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Prior art keywords
vanadium
solution
ammonium
polyvanadate
high concentration
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PCT/CN2017/092659
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French (fr)
Chinese (zh)
Inventor
郭继科
彭一村
付自碧
王英
黄可行
殷兆迁
刘学文
蒋霖
冉俊
王俊
潘少彦
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攀钢集团攀枝花钢铁研究院有限公司
攀钢集团攀枝花钢钒有限公司
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Priority to NZ747853A priority Critical patent/NZ747853A/en
Priority to RU2018145366A priority patent/RU2701564C1/en
Publication of WO2018024083A1 publication Critical patent/WO2018024083A1/en
Priority to ZA2018/07309A priority patent/ZA201807309B/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention belongs to the field of chemical industry, and particularly relates to a method for preparing ammonium polyvanadate with high concentration vanadium solution.
  • vanadium is mainly recovered from the sodium halide vanadium solution by the acidic ammonium salt vanadium precipitation process, which is widely used at home and abroad due to its advantages of fast vanadium precipitation, high product purity, high vanadium rate and low ammonium salt consumption.
  • the main disadvantages and limitations of acidic ammonium salt vanadium are as follows: the concentration of vanadium is limited by the concentration of sodium sulfate in the solution. The vanadium and sodium in the solution exist in a certain ratio.
  • the prior art provides a low-cost and high-efficiency vanadium precipitation method, comprising the steps of: a, taking a vanadium immersion liquid, adding sulfuric acid; b, adding ammonium sulfate to the vanadium immersion liquid after a step of adding acid; c, Step b: Add ammonium sulfate solution, pass steam, adjust the pH value of the solution to 1.8-2.5, stir evenly, then let stand and separate, separate to obtain supernatant and precipitate; d, the supernatant fraction obtained in step c Return to the vanadium infusion instead of sulfuric acid and some ammonium sulfate.
  • the concentration of the solution is only 25g/L, the concentration of vanadium is low, and the reaction temperature needs to be greater than 90 ° C, the reaction time is about 1 h, and the ammonium salt is added in a large amount.
  • the object of the present invention is to provide a high concentration vanadium solution vanadium with low production cost and high vanadium precipitation efficiency. method.
  • the technical solution of the present invention to solve the technical problem is to provide a method for preparing a polyoxonium vanadate with a high concentration vanadium solution, comprising the following steps:
  • the water is heated to 80 ⁇ 90 ° C, the vanadium-containing powder material is added, and the pH is adjusted to 2.0 ⁇ 3.0;
  • step c the solution obtained in step a is slowly added to the solution obtained in step b, and the pH is ensured to be 2.0-3.0 when added, and stirred while being added;
  • step a After the solution of step a is added, the reaction is continued for 5 to 30 minutes, filtered and washed with water to obtain ammonium polyvanadate.
  • the high-concentration vanadium liquid in the step a refers to a vanadium liquid having a total vanadium content of 40-110 g/L in the vanadium solution.
  • the ammonium salt in the step a is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium hydrogencarbonate.
  • the vanadium-containing powder material in the step b is at least one of ammonium polyvanadate, ammonium metavanadate, vanadium pentoxide or vanadium pentoxide.
  • the particle size of the vanadium-containing powder material in step b is all over 120 mesh sieve.
  • the vanadium-containing powder material in the step b is added in an amount of 16 to 20 times the product of the TV content of the high concentration vanadium solution and the high concentration vanadium solution volume.
  • the pH adjustment in steps a and b is adjusted with sulfuric acid.
  • the slow addition speed in the step c is 15-25 mL/min.
  • the stirring speed in the step c is 400 to 500 r/min.
  • the slow addition described in the step c is slowly dripping using a peristaltic pump.
  • the water in the step b may be replaced by the vanadium-doped supernatant, and the Na 2 O content in the vanadium-preserving supernatant is ⁇ 60 g/L.
  • the beneficial effects of the invention are as follows: the invention firstly raises the high concentration vanadium liquid to 65 ° C to 85 ° C, and adjusts the pH value to 6.5-8.5, and then adds the ammonium salt powder, and adds it to the pH of 2.0-3.0.
  • the reaction is carried out in a solution prepared with a vanadium-containing powder material, which effectively solves the problem of vanadium precipitation in a high-concentration vanadium solution, and can increase the total vanadium content in the vanadium-vanadium-vanadium solution to 40-110 g/L.
  • the process of the invention is simple, sinking The vanadium rate is high and the product impurity content is low.
  • the vanadium-bearing wastewater can be reduced by 50%/t V 2 O 5 or more, the working efficiency can be greatly improved, and the production cost is obviously reduced.
  • the invention provides a method for preparing ammonium polyvanadate with high concentration vanadium solution, comprising the following steps:
  • the water is heated to 80 ⁇ 90 ° C, the vanadium-containing powder material is added, and the pH is adjusted to 2.0 ⁇ 3.0;
  • step c the solution obtained in step a is slowly added to the solution obtained in step b, and the pH is ensured to be 2.0-3.0 when added, and stirred while being added;
  • step a After the solution of step a is added, the reaction is continued for 5 to 30 minutes, filtered and washed with water to obtain ammonium polyvanadate.
  • the high concentration vanadium liquid of the invention refers to a vanadium liquid with a total vanadium content of 40-110 g/L in the vanadium solution, and the high concentration vanadium liquid is limited by the concentration of sodium sulfate in the solution, and the vanadium and sodium in the solution are in a certain ratio.
  • it is easy to produce precipitates such as hydrolysate or heteropoly acid, and there are many precipitates, and the dissolution rate is much smaller than the precipitation rate.
  • the formed hydrolyzate consumes vanadate and ammonium in the solution, and the vanadium precipitation rate Low, and because the vanadium concentration is too high, the nucleation of pre-vanadium is too much, the crystal particle size is not uniform, the adsorption is strong, and the impurities are entrained and adsorbed into the product, which is difficult to wash, resulting in low purity of the product.
  • the vanadium effect of high concentration vanadium solution is mainly affected by the reaction temperature and pH, and the reaction temperature requirement is greater than 80 ° C.
  • the high concentration vanadium liquid is heated to the reaction temperature in advance, which is favorable for the reaction; meanwhile, the pH needs to be adjusted after the temperature rise.
  • the high concentration vanadium solution regulates the pH below 65 ° C, a large amount of transient hydrolysis precipitates are formed.
  • the present invention first raises the high concentration vanadium liquid to 65-85 ° C; in addition, the high concentration vanadium solution When the vanadium is extracted, the ammonium salt needs to be added.
  • the present invention raises the high-concentration vanadium liquid to 65-85 °C.
  • the pH value of the high concentration vanadium solution of the invention is 6.5-8.5, which avoids the direct adjustment of the vanadium-doped solution from alkaline to acidic process, and firstly adjusts the solution to be weakly alkaline. After adding the ammonium salt, it participates in the vanadium precipitation reaction, avoiding the high concentration of the vanadium liquid from the alkaline adjustment to the acidic hydrolysis, and the formation of sodium polyvanadate and polyvanadate, so that the obtained polyvanadate has high purity.
  • the present invention also adds a quantity of vanadium-containing powder material to the diluent water, the vanadium-containing powder material being one or more of ammonium polyvanadate, ammonium metavanadate, vanadium pentoxide or vanadium pentoxide.
  • the vanadium-containing powder material is too small, can not sink the ammonium polyvanadate, there are other precipitates produced, the vanadium-containing powder material is too much, the solution is viscous, can not be stirred, and can not sink the ammonium polyvanadate.
  • the inventors have obtained experimental results that the vanadium-containing powder material is added in the amount of 16 to 20 times the volume of the high concentration vanadium solution and the volume of the high concentration vanadium solution.
  • the vanadium-containing powder material needs to participate in the crystallization reaction as a microcrystalline nucleus, and promote the precipitation of ammonium polyvanadate product, and the particle size requirement is all over 120 mesh sieve.
  • the invention adopts water to dilute the high concentration vanadium solution, and can also use the vanadium precipitation supernatant, but the Na 2 O content of the vanadium precipitation supernatant is required to be ⁇ 60 g/L. When this standard is met, even the vanadium content and oxidation in the vanadium precipitation solution are satisfied.
  • the sodium content is high and the process of the invention still precipitates acceptable polyvanadate and is calcined to yield a qualified vanadium pentoxide product.
  • the invention adopts a peristaltic pump to slowly add a high concentration vanadium solution with an ammonium salt to a solution containing a vanadium-containing powder material, and the slow addition speed is 15-25 mL/min, while stirring, the stirring speed is 400-500r. /min.
  • Adopt The slow addition of the peristaltic pump can reduce the instantaneous concentration of the high concentration vanadium solution and reduce the driving force for the formation of hydrolyzate. After the high concentration vanadium solution enters the solution of step a, the hydrogen ions act as the driving force, the reaction crystallization speed is fast, and the ammonium polyvanadate precipitate is formed immediately.
  • the instantaneous vanadium concentration is very low, the sodium ion concentration is limited, and the ammonium ion in the solution replaces the polyvanadate.
  • the hydrogen ion velocity in the salt is much higher than the sodium ion displacement hydrogen ion velocity, and the binding force between the ammonium ion and the polyvanadate ion is much higher than the sodium ion and its binding force, so the formation of the hydrolyzate is difficult, and the feed rate is controlled.
  • the vanadium precipitation rate is 99.57%
  • the polyvanadate ammonium TV is 50.40%
  • the Na 2 O+K 2 O is 0.097%
  • the S is 0.045%
  • the polyvanadate is calcined to obtain the vanadium pentoxide product
  • five V 2 O 5 in the vanadium oxide product is 98.99%
  • Na 2 O is 0.119%
  • K 2 O is 0.135%
  • Si is 0.101%
  • Fe is 0.054%
  • S is 0.010%
  • P is 0.020%
  • As ⁇ 0.010 % the obtained vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
  • the vanadium precipitation rate is 99.63%
  • the TV of the polyvanadate is 50.41%
  • the Na 2 O+K 2 O is 0.093%
  • the S is 0.045%.
  • the ammonium polyvanadate is calcined to obtain the vanadium pentoxide product, vanadium pentoxide.
  • the product has V 2 O 5 of 99.16%, Na 2 O of 0.119%, K 2 O of 0.143%, Si of 0.109%, Fe of 0.053%, S of 0.011%, P of 0.024%, and As ⁇ 0.010%.
  • Vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
  • the vanadium precipitation rate is 99.42%
  • the multi-vanadate ammonium TV is 50.25%
  • the Na 2 O+K 2 O is 0.101%
  • the S is 0.073%
  • the poly-vanadate ammonium is calcined to obtain the vanadium pentoxide product.
  • V 2 O 5 in the vanadium oxide product is 99.12%
  • Na 2 O is 0.125%
  • K 2 O is 0.343%
  • Si 0.092%
  • Fe is 0.043%
  • S 0.019%
  • P 0.035%
  • As ⁇ 0.010 % the obtained vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
  • the vanadium pentoxide product is obtained.
  • the V 2 O 5 in the vanadium pentoxide product is 95.31% and 94.22%, respectively, and the Na 2 O is 3.55% and 4.59%, respectively, and the K 2 O is 0.51%, 0.55%, Si is 0.331%, 0.356%, Fe is 0.045%, 0.041%, S is respectively 0.095%, 0.167%, P is 0.030%, 0.032%, and As is ⁇ 0.010%, the obtained vanadium pentoxide.
  • the product is far from the standard YB/T5304-2011 requirements.

Abstract

The present invention relates to the field of chemical engineering, and specifically relates to a method using highly concentrated vanadium solution for manufacturing ammonium polyvanadate. The invention addresses the issues of the prior art including the limitation of using only a low concentration vanadium solution to perform vanadium precipitation, long manufacturing process, high production cost, and the like. Provided is a method using a highly concentrated vanadium solution for vanadium precipitation with a low production cost and high vanadium precipitation efficiency. The method comprises: adjusting the highly concentrated vanadium solution to a suitable temperature and pH, adding an ammonium salt, then slowly adding a powdered material comprising vanadium into the solution to perform a reaction, and obtaining the ammonium polyvanadate after the reaction is complete. The technical solution effectively addresses the issue of vanadium precipitation with a highly concentrated vanadium solution, and can increase total vanadium content in the vanadium solution for vanadium precipitation to 40-110 g/L. The method has a simple technique, high vanadium precipitation, and low contaminant content in the product. When compared to the prior art using an acidic ammonium salt for vanadium precipitation, the invention can reduce vanadium precipitation wastewater by 50%/t V2O5. The method can significantly increase operational efficiency and significantly reduce production costs.

Description

高浓度钒液制备多钒酸铵的方法Method for preparing polyvanadate by high concentration vanadium solution 技术领域Technical field
本发明属于化工领域，具体涉及一种高浓度钒液制备多钒酸铵的方法。The invention belongs to the field of chemical industry, and particularly relates to a method for preparing ammonium polyvanadate with high concentration vanadium solution.
背景技术Background technique
目前，主要采用酸性铵盐沉钒工艺从钠化钒液中回收钒，因其沉钒速度快、产品纯度高、沉钒率高、铵盐消耗较低等优势，被国内外广泛采用。酸性铵盐沉钒的主要弊端与局限性表现为以下几点，主要为沉钒浓度受到溶液中硫酸钠盐浓度的限制，溶液中的钒与钠以一定比例存在，在调节pH过程中，容易产生水解物或杂多酸等沉淀，沉淀物较多，溶解速度远小于沉淀速度，形成的水解物消耗掉了溶液中的钒酸根与铵根，沉钒率低，并由于钒浓度过高，沉钒前期成核过多，晶体颗粒大小不均匀，吸附性强，杂质被夹带、吸附进产品中，难以洗涤，致使产品纯度低等。故，目前工业上采用酸性铵盐沉钒的钠化钒液钒浓度瓶颈为30g/L左右(以TV计)。At present, vanadium is mainly recovered from the sodium halide vanadium solution by the acidic ammonium salt vanadium precipitation process, which is widely used at home and abroad due to its advantages of fast vanadium precipitation, high product purity, high vanadium rate and low ammonium salt consumption. The main disadvantages and limitations of acidic ammonium salt vanadium are as follows: the concentration of vanadium is limited by the concentration of sodium sulfate in the solution. The vanadium and sodium in the solution exist in a certain ratio. Precipitation of hydrolyzate or heteropoly acid, resulting in more precipitates, the dissolution rate is much smaller than the precipitation rate, the formed hydrolyzate consumes vanadate and ammonium in the solution, the vanadium precipitation rate is low, and the vanadium concentration is too high, In the early stage of vanadium precipitation, the nucleation was too much, the crystal particle size was not uniform, and the adsorption was strong. The impurities were entrained and adsorbed into the product, which was difficult to wash, resulting in low purity of the product. Therefore, at present, the bottleneck of vanadium and vanadium in the industrial use of acidic ammonium salt vanadium is about 30g/L (in terms of TV).
现有技术中提供了一种低成本高效沉钒方法，包括以下步骤：a、取钒浸液，加入硫酸；b、向a步骤加酸处理后的钒浸液中加入硫酸铵；c、将b步骤加入硫酸铵后的溶液，通入蒸汽，调节溶液pH值为1.8～2.5，搅拌均匀后静置分层，分离，得到上清液和沉淀；d、将c步骤得到的上清液部分返回到钒浸液中，代替硫酸和部分硫酸铵。该方法调配合格液浓度仅为25g/L，沉钒浓度低，且存在反应温度需大于90℃，反应时间需1h左右，铵盐加入量较多等问题。The prior art provides a low-cost and high-efficiency vanadium precipitation method, comprising the steps of: a, taking a vanadium immersion liquid, adding sulfuric acid; b, adding ammonium sulfate to the vanadium immersion liquid after a step of adding acid; c, Step b: Add ammonium sulfate solution, pass steam, adjust the pH value of the solution to 1.8-2.5, stir evenly, then let stand and separate, separate to obtain supernatant and precipitate; d, the supernatant fraction obtained in step c Return to the vanadium infusion instead of sulfuric acid and some ammonium sulfate. The concentration of the solution is only 25g/L, the concentration of vanadium is low, and the reaction temperature needs to be greater than 90 ° C, the reaction time is about 1 h, and the ammonium salt is added in a large amount.
发明内容Summary of the invention
针对上述现有技术中存在的只能对低浓度钒液沉钒、工艺路线长、生产成本高等问题,本发明的目的在于提供一种生产成本低、沉钒效率高的高浓度钒液沉钒方法。In view of the above problems existing in the prior art, which can only form vanadium in a low concentration vanadium solution, a long process route, high production cost, etc., the object of the present invention is to provide a high concentration vanadium solution vanadium with low production cost and high vanadium precipitation efficiency. method.
本发明解决技术问题的技术方案为：提供一种高浓度钒液制备多钒酸铵的方法，包括以下步骤：The technical solution of the present invention to solve the technical problem is to provide a method for preparing a polyoxonium vanadate with a high concentration vanadium solution, comprising the following steps:
a、取高浓度钒液，升温至65～85℃，调节pH值至6.5～8.5，加入铵盐，搅拌至完全溶解；a, take a high concentration of vanadium solution, raise the temperature to 65 ~ 85 ° C, adjust the pH to 6.5 ~ 8.5, add ammonium salt, stir until completely dissolved;
b、将水升温至80～90℃，加入含钒粉末物料，并调节pH值至2.0～3.0；b, the water is heated to 80 ~ 90 ° C, the vanadium-containing powder material is added, and the pH is adjusted to 2.0 ~ 3.0;
c、将步骤a中所得溶液缓慢加入步骤b所得溶液中，加入时保证pH值为2.0～3.0，边加边搅拌；c, the solution obtained in step a is slowly added to the solution obtained in step b, and the pH is ensured to be 2.0-3.0 when added, and stirred while being added;
d、待步骤a溶液加完后，继续反应5～30min，过滤、水洗，得到多钒酸铵。 d. After the solution of step a is added, the reaction is continued for 5 to 30 minutes, filtered and washed with water to obtain ammonium polyvanadate.
其中，上述高浓度钒液沉钒方法中，步骤a中所述高浓度钒液是指钒液中总钒含量为40～110g/L的钒液。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the high-concentration vanadium liquid in the step a refers to a vanadium liquid having a total vanadium content of 40-110 g/L in the vanadium solution.
其中，上述高浓度钒液沉钒方法中，步骤a中所述铵盐为硫酸铵、氯化铵、硝酸铵、碳酸铵或碳酸氢铵中的至少一种。In the above high-concentration vanadium solution vanadium precipitation method, the ammonium salt in the step a is at least one of ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium hydrogencarbonate.
其中，上述高浓度钒液沉钒方法中，步骤a中所述铵盐的加入量为按加铵系数为0.6～2.5添加；优选的，所述加铵系数为0.8～1.2，加铵系数K＝铵盐质量/(高浓度钒液中TV含量×高浓度钒液体积)。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the ammonium salt added in the step a is added according to the ammonium addition coefficient of 0.6 to 2.5; preferably, the ammonium addition coefficient is 0.8 to 1.2, and the ammonium addition coefficient is K. = ammonium salt mass / (TV content in high concentration vanadium solution × high concentration vanadium solution volume).
其中，上述高浓度钒液沉钒方法中，步骤b中所述含钒粉末物料为多钒酸铵、偏钒酸铵、五氧化二钒或三氧化二钒中的至少一种。Wherein the high-concentration vanadium solution vanadium precipitation method, the vanadium-containing powder material in the step b is at least one of ammonium polyvanadate, ammonium metavanadate, vanadium pentoxide or vanadium pentoxide.
其中，上述高浓度钒液沉钒方法中，步骤b中所述含钒粉末物料的粒度为全部过120目筛。Wherein, in the above high-concentration vanadium solution vanadium precipitation method, the particle size of the vanadium-containing powder material in step b is all over 120 mesh sieve.
其中，上述高浓度钒液沉钒方法中，步骤b中所述含钒粉末物料加入量为高浓度钒液中TV含量与高浓度钒液体积乘积的16～20倍。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the vanadium-containing powder material in the step b is added in an amount of 16 to 20 times the product of the TV content of the high concentration vanadium solution and the high concentration vanadium solution volume.
其中，上述高浓度钒液沉钒方法中，步骤a、b中所述调节pH用硫酸调节。Wherein, in the above high-concentration vanadium solution vanadium precipitation method, the pH adjustment in steps a and b is adjusted with sulfuric acid.
其中，上述高浓度钒液沉钒方法中，步骤c中所述缓慢加入的速度为15～25mL/min。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the slow addition speed in the step c is 15-25 mL/min.
其中，上述高浓度钒液沉钒方法中，步骤c中所述搅拌速度400～500r/min。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the stirring speed in the step c is 400 to 500 r/min.
其中，上述高浓度钒液沉钒方法中，步骤c中所述缓慢加入为使用蠕动泵缓慢滴加。Among them, in the above high-concentration vanadium solution vanadium precipitation method, the slow addition described in the step c is slowly dripping using a peristaltic pump.
其中，上述高浓度钒液沉钒方法中，步骤b中水可用沉钒上清液代替，所述沉钒上清液中Na2O含量≤60g/L。Wherein, in the high-concentration vanadium solution vanadium precipitation method, the water in the step b may be replaced by the vanadium-doped supernatant, and the Na 2 O content in the vanadium-preserving supernatant is ≤60 g/L.
本发明的有益效果为：本发明先将高浓度钒液升温至65℃～85℃，并调节pH值至6.5～8.5，再配加铵盐粉末，将其加入到pH为2.0～3.0的添加有含钒粉末物料配制的溶液中进行反应，有效的解决了高浓度钒液的沉钒问题，能将沉钒钒液中的总钒含量提高到40～110g/L，本发明工艺简单，沉钒率高，产品杂质含量低，相对于现有酸性铵盐沉钒工艺，可降低沉钒废水量50％/t V2O5以上，作业效率可大幅提高，降低生产成本效果明显。The beneficial effects of the invention are as follows: the invention firstly raises the high concentration vanadium liquid to 65 ° C to 85 ° C, and adjusts the pH value to 6.5-8.5, and then adds the ammonium salt powder, and adds it to the pH of 2.0-3.0. The reaction is carried out in a solution prepared with a vanadium-containing powder material, which effectively solves the problem of vanadium precipitation in a high-concentration vanadium solution, and can increase the total vanadium content in the vanadium-vanadium-vanadium solution to 40-110 g/L. The process of the invention is simple, sinking The vanadium rate is high and the product impurity content is low. Compared with the existing acid ammonium salt vanadium precipitation process, the vanadium-bearing wastewater can be reduced by 50%/t V 2 O 5 or more, the working efficiency can be greatly improved, and the production cost is obviously reduced.
具体实施方式detailed description
本发明提供一种高浓度钒液制备多钒酸铵的方法，包括以下步骤：The invention provides a method for preparing ammonium polyvanadate with high concentration vanadium solution, comprising the following steps:
a、取高浓度钒液，升温至65～85℃，调节pH值至6.5～8.5，加入铵盐，搅拌至完全溶解；a, take a high concentration of vanadium solution, raise the temperature to 65 ~ 85 ° C, adjust the pH to 6.5 ~ 8.5, add ammonium salt, stir until completely dissolved;
b、将水升温至80～90℃，加入含钒粉末物料，并调节pH值至2.0～3.0； b, the water is heated to 80 ~ 90 ° C, the vanadium-containing powder material is added, and the pH is adjusted to 2.0 ~ 3.0;
c、将步骤a中所得溶液缓慢加入步骤b所得溶液中，加入时保证pH值为2.0～3.0，边加边搅拌；c, the solution obtained in step a is slowly added to the solution obtained in step b, and the pH is ensured to be 2.0-3.0 when added, and stirred while being added;
d、待步骤a溶液加完后，继续反应5～30min，过滤、水洗，得到多钒酸铵。d. After the solution of step a is added, the reaction is continued for 5 to 30 minutes, filtered and washed with water to obtain ammonium polyvanadate.
本发明所述高浓度钒液是指钒液中总钒含量为40～110g/L的钒液，高浓度钒液会受到溶液中硫酸钠盐浓度的限制，溶液中的钒与钠以一定比例存在，在调节pH过程中，容易产生水解物或杂多酸等沉淀，沉淀物较多，溶解速度远小于沉淀速度，形成的水解物消耗掉了溶液中的钒酸根与铵根，沉钒率低，并由于钒浓度过高，沉钒前期成核过多，晶体颗粒大小不均匀，吸附性强，杂质被夹带、吸附进产品中，难以洗涤，致使产品纯度低。The high concentration vanadium liquid of the invention refers to a vanadium liquid with a total vanadium content of 40-110 g/L in the vanadium solution, and the high concentration vanadium liquid is limited by the concentration of sodium sulfate in the solution, and the vanadium and sodium in the solution are in a certain ratio. In the process of adjusting pH, it is easy to produce precipitates such as hydrolysate or heteropoly acid, and there are many precipitates, and the dissolution rate is much smaller than the precipitation rate. The formed hydrolyzate consumes vanadate and ammonium in the solution, and the vanadium precipitation rate Low, and because the vanadium concentration is too high, the nucleation of pre-vanadium is too much, the crystal particle size is not uniform, the adsorption is strong, and the impurities are entrained and adsorbed into the product, which is difficult to wash, resulting in low purity of the product.
高浓度钒液沉钒效果主要受到反应温度和pH的影响，反应温度要求大于80℃，本发明中提前将高浓度钒液加热到反应温度，利于反应的进行；同时，升温后需要调控pH，高浓度钒液在低于65℃以下调控pH时，有大量瞬时水解沉淀物形成，为了减少沉淀物的产生，本发明先将高浓度钒液升温至65～85℃；此外，高浓度钒液提钒时需加入铵盐，温度太高，氨气容易逸出，工作环境恶劣，铵盐损失严重，为了提高沉钒效率，本发明将高浓度钒液升温至65～85℃。The vanadium effect of high concentration vanadium solution is mainly affected by the reaction temperature and pH, and the reaction temperature requirement is greater than 80 ° C. In the present invention, the high concentration vanadium liquid is heated to the reaction temperature in advance, which is favorable for the reaction; meanwhile, the pH needs to be adjusted after the temperature rise. When the high concentration vanadium solution regulates the pH below 65 ° C, a large amount of transient hydrolysis precipitates are formed. In order to reduce the generation of precipitates, the present invention first raises the high concentration vanadium liquid to 65-85 ° C; in addition, the high concentration vanadium solution When the vanadium is extracted, the ammonium salt needs to be added. The temperature is too high, the ammonia gas easily escapes, the working environment is bad, and the ammonium salt is seriously lost. In order to improve the vanadium-bearing efficiency, the present invention raises the high-concentration vanadium liquid to 65-85 °C.
为了使制备得到的多钒酸铵杂质更少，本发明调节高浓度钒液的pH值为6.5～8.5，避免了沉钒溶液从碱性直接调至酸性过程，先调控溶液为弱碱性，加入铵盐后参与沉钒反应，避免了高浓度钒液从碱性直接调至酸性出现水解，生成多聚钒酸铵钠和多聚钒酸，从而得到的多钒酸铵纯度高。In order to make the prepared polyvanadate impurity less, the pH value of the high concentration vanadium solution of the invention is 6.5-8.5, which avoids the direct adjustment of the vanadium-doped solution from alkaline to acidic process, and firstly adjusts the solution to be weakly alkaline. After adding the ammonium salt, it participates in the vanadium precipitation reaction, avoiding the high concentration of the vanadium liquid from the alkaline adjustment to the acidic hydrolysis, and the formation of sodium polyvanadate and polyvanadate, so that the obtained polyvanadate has high purity.
本发明还在稀释剂水中加入了一定量的含钒粉末物料，所述含钒粉末物料为多钒酸铵、偏钒酸铵、五氧化二钒或三氧化二钒中一种或几种。含钒粉末物料过少，沉不了多钒酸铵，有其他沉淀物产生，含钒粉末物料过多，溶液粘稠，搅不动，也沉不了多钒酸铵。发明人经过试验得出，含钒粉末物料加入量为高浓度钒液中TV含量×高浓度钒液体积的16～20倍时，沉钒效果最好。此外，含钒粉末物料需要作为微小晶核参与结晶反应，促进沉淀多钒酸铵产品，其粒度要求全部过120目筛。本发明采用水稀释高浓度钒液，也可以使用沉钒上清液，但需要沉钒上清液的Na2O含量≤60g/L，当满足这个标准时，即使沉钒溶液中钒含量与氧化钠含量均高，此发明方法仍可以沉淀出合格的多钒酸铵，并且煅烧得到合格的五氧化二钒产品。The present invention also adds a quantity of vanadium-containing powder material to the diluent water, the vanadium-containing powder material being one or more of ammonium polyvanadate, ammonium metavanadate, vanadium pentoxide or vanadium pentoxide. The vanadium-containing powder material is too small, can not sink the ammonium polyvanadate, there are other precipitates produced, the vanadium-containing powder material is too much, the solution is viscous, can not be stirred, and can not sink the ammonium polyvanadate. The inventors have obtained experimental results that the vanadium-containing powder material is added in the amount of 16 to 20 times the volume of the high concentration vanadium solution and the volume of the high concentration vanadium solution. In addition, the vanadium-containing powder material needs to participate in the crystallization reaction as a microcrystalline nucleus, and promote the precipitation of ammonium polyvanadate product, and the particle size requirement is all over 120 mesh sieve. The invention adopts water to dilute the high concentration vanadium solution, and can also use the vanadium precipitation supernatant, but the Na 2 O content of the vanadium precipitation supernatant is required to be ≤60 g/L. When this standard is met, even the vanadium content and oxidation in the vanadium precipitation solution are satisfied. The sodium content is high and the process of the invention still precipitates acceptable polyvanadate and is calcined to yield a qualified vanadium pentoxide product.
本发明采用蠕动泵将配加铵盐的高浓度钒液缓慢加入到加有含钒粉末物料的溶液中，缓慢加入的速度为15～25mL/min，边加边搅拌，搅拌速度为400～500r/min。采用 蠕动泵缓慢加入的方式可以降低高浓度钒液的瞬时浓度，降低水解物形成的推动力。高浓度钒液进入步骤a的溶液后，氢离子做推动力，反应结晶速度快，立即形成多钒酸铵沉淀，瞬时钒浓度很低，钠离子浓度有限，溶液中铵根离子置换多钒酸盐中的氢离子速度远远大于钠离子置换氢离子速度，且铵根离子与多钒酸根离子的结合力远远高于钠离子与其结合力，故水解物形成较困难，同时控制进液速度、加酸速度、搅拌速度等，控制溶液中反应的扩散速度，以避免沉淀物作为晶种被后形成的多钒酸铵包裹现象，从而控制了水解及对应包裹、夹带吸附等现象，能够制备得到纯度高、杂质少的多钒酸铵。The invention adopts a peristaltic pump to slowly add a high concentration vanadium solution with an ammonium salt to a solution containing a vanadium-containing powder material, and the slow addition speed is 15-25 mL/min, while stirring, the stirring speed is 400-500r. /min. Adopt The slow addition of the peristaltic pump can reduce the instantaneous concentration of the high concentration vanadium solution and reduce the driving force for the formation of hydrolyzate. After the high concentration vanadium solution enters the solution of step a, the hydrogen ions act as the driving force, the reaction crystallization speed is fast, and the ammonium polyvanadate precipitate is formed immediately. The instantaneous vanadium concentration is very low, the sodium ion concentration is limited, and the ammonium ion in the solution replaces the polyvanadate. The hydrogen ion velocity in the salt is much higher than the sodium ion displacement hydrogen ion velocity, and the binding force between the ammonium ion and the polyvanadate ion is much higher than the sodium ion and its binding force, so the formation of the hydrolyzate is difficult, and the feed rate is controlled. , acid addition speed, stirring speed, etc., to control the diffusion rate of the reaction in the solution, in order to avoid the precipitation of the precipitate as a polymorphic ammonium vanadate formed by the seed crystal, thereby controlling the hydrolysis and corresponding encapsulation, entrainment adsorption and the like, can be prepared Ammonium polyvanadate with high purity and low impurities is obtained.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的示例范围之中。The specific embodiments of the present invention are further described below in conjunction with the embodiments, and are not intended to limit the invention.
实施例1 用本发明技术方案制备多钒酸铵Example 1 Preparation of ammonium polyvanadate by the technical scheme of the invention
实施例1反应原料的主要化学成分见下表1。The main chemical components of the reaction materials of Example 1 are shown in Table 1 below.
表1 反应原料的主要化学成分Table 1 Main chemical constituents of the reaction raw materials
物料materials TVTV Na2ONa 2 O PP CrCr SiO2 SiO 2
高浓度钒液/g·L-1 High concentration vanadium solution / g · L -1 60.0060.00 71.0171.01 0.020.02 2.212.21 2.522.52
上清液/g·L-1 Supernatant /g·L -1 0.140.14 42.6042.60 // // //
多钒酸铵粉末/％Polyvanadate powder /% 48.4748.47 0.220.22 // // //
取高浓度钒液(TV＝60.00g/L)267mL，升温至75℃，调pH为7.30，按照加铵系数1.0配加硫酸铵；取上清液133mL，升温至85℃，加入多钒酸铵粉末2.88g，调pH为2.30；用蠕动泵逐渐滴加高浓度钒液至上清液中，滴加时间为14min，滴加完后继续搅拌反应5min，然后过滤、洗涤，获得多钒酸铵34.32g，沉钒率为99.57％，多钒酸铵中TV为50.40％，Na2O+K2O为0.097％，S为0.045％，多钒酸铵煅烧后获得五氧化二钒产品，五氧化二钒产品中V2O5为98.99％，Na2O为0.119％，K2O为0.135％，Si为0.101％，Fe为0.054％，S为0.010％，P为0.020％，As＜0.010％，所得五氧化二钒满足标准YB/T5304-2011的要求。Take high concentration vanadium solution (TV=60.00g/L) 267mL, raise the temperature to 75 °C, adjust the pH to 7.30, add ammonium sulfate according to the ammonium addition coefficient of 1.0; take the supernatant 133mL, heat up to 85 °C, add polyvanadate 2.88 g of ammonium powder, adjusted to pH 2.30; gradually add high concentration vanadium solution to the supernatant with a peristaltic pump, the dropping time is 14 min, stir the reaction for 5 min after the addition, then filter and wash to obtain ammonium polyvanadate. 34.32g, the vanadium precipitation rate is 99.57%, the polyvanadate ammonium TV is 50.40%, the Na 2 O+K 2 O is 0.097%, the S is 0.045%, the polyvanadate is calcined to obtain the vanadium pentoxide product, five V 2 O 5 in the vanadium oxide product is 98.99%, Na 2 O is 0.119%, K 2 O is 0.135%, Si is 0.101%, Fe is 0.054%, S is 0.010%, P is 0.020%, and As<0.010 %, the obtained vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
实施例2 用本发明技术方案制备多钒酸铵Example 2 Preparation of ammonium polyvanadate by the technical scheme of the invention
实施例2反应原料的主要化学成分见下表2。 The main chemical components of the reaction materials of Example 2 are shown in Table 2 below.
表2 反应原料的主要化学成分Table 2 Main chemical components of the reaction raw materials
物料materials TVTV Na2ONa 2 O PP CrCr SiO2 SiO 2
高浓度钒液/g·L-1 High concentration vanadium solution / g · L -1 68.5568.55 80.3580.35 0.030.03 2.672.67 2.882.88
水/g·L-1 Water / g · L -1 0.0010.001 0.020.02 // // //
五氧化二钒粉末/％Vanadium pentoxide powder /% 99.0199.01 0.100.10 // // //
取高浓度钒液(TV＝68.55g/L)350mL，升温至75℃，调pH为7.30，按照加铵系数1.2配加氯化铵；取水50mL，升温至85℃，加入五氧化二钒粉末4.80g，调pH为2.30；用蠕动泵逐渐滴加高浓度钒液至水溶液中，滴加时间为18min，滴加完后继续搅拌反应10min，然后过滤、洗涤，获得多钒酸铵50.61g，沉钒率为99.63％，多钒酸铵中TV为50.41％，Na2O+K2O为0.093％，S为0.045％，多钒酸铵煅烧后获得五氧化二钒产品，五氧化二钒产品中V2O5为99.16％，Na2O为0.119％，K2O为0.143％，Si为0.109％，Fe为0.053％，S为0.011％，P为0.024％，As＜0.010％，所得五氧化二钒满足标准YB/T5304-2011的要求。Take high concentration vanadium solution (TV=68.55g/L) 350mL, raise the temperature to 75 °C, adjust the pH to 7.30, add ammonium chloride according to the ammonium addition coefficient of 1.2; take 50mL of water, heat up to 85 °C, add vanadium pentoxide powder 4.80g, adjust the pH to 2.30; gradually add high concentration vanadium solution to the aqueous solution by peristaltic pump, the dropping time is 18min, continue to stir the reaction for 10min after the addition, then filter and wash to obtain 50.61g of ammonium polyvanadate. The vanadium precipitation rate is 99.63%, the TV of the polyvanadate is 50.41%, the Na 2 O+K 2 O is 0.093%, and the S is 0.045%. The ammonium polyvanadate is calcined to obtain the vanadium pentoxide product, vanadium pentoxide. The product has V 2 O 5 of 99.16%, Na 2 O of 0.119%, K 2 O of 0.143%, Si of 0.109%, Fe of 0.053%, S of 0.011%, P of 0.024%, and As <0.010%. Vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
实施例3 用本发明技术方案制备多钒酸铵Example 3 Preparation of ammonium polyvanadate by the technical scheme of the invention
实施例3反应原料的主要化学成分见下表3。The main chemical components of the reaction materials of Example 3 are shown in Table 3 below.
表3 反应原料的主要化学成分Table 3 Main chemical components of the reaction raw materials
物料materials TVTV Na2ONa 2 O PP CrCr SiO2 SiO 2
高浓度钒液/g·L-1 High concentration vanadium solution / g · L -1 97.3297.32 121.87121.87 0.050.05 4.244.24 3.223.22
上清液/g·L-1 Supernatant /g·L -1 0.140.14 42.6042.60 // // //
偏钒酸铵粉末/％Ammonium metavanadate powder /% 43.4443.44 0.010.01 // // //
取高浓度钒液(TV＝97.32g/L)328mL，升温至75℃，调pH为7.30，按照加铵系数0.80配加硫酸铵；取上清液72mL，升温至85℃，加入偏钒酸铵粉末6.40g，调pH为2.30；用蠕动泵逐渐滴加高浓度钒液至上清液中，滴加时间为20min，滴加完后继续搅拌反应30min，然后过滤、洗涤，获得多钒酸铵67.38g，沉钒率为99.42％，多钒酸铵中TV为50.25％，Na2O+K2O为0.101％，S为0.073％，多钒酸铵煅烧后获得五氧化二钒产品，五氧化二钒产品中V2O5为99.12％，Na2O为0.125％，K2O为0.343％，Si为0.092％，Fe为0.043％，S为0.019％，P为0.035％，As＜0.010％，所得五氧化二钒满足标准YB/T5304-2011的要求。Take high concentration vanadium solution (TV=97.32g/L) 328mL, raise the temperature to 75 °C, adjust the pH to 7.30, add ammonium sulfate according to the ammonium addition coefficient of 0.80; take the supernatant 72mL, heat up to 85 °C, add metavanadic acid The ammonium powder was 6.40g, and the pH was adjusted to 2.30. The high concentration vanadium solution was gradually added to the supernatant solution by a peristaltic pump, and the dropping time was 20 min. After the completion of the dropwise addition, the reaction was stirred for 30 min, and then filtered and washed to obtain ammonium polyvanadate. 67.38g, the vanadium precipitation rate is 99.42%, the multi-vanadate ammonium TV is 50.25%, the Na 2 O+K 2 O is 0.101%, the S is 0.073%, and the poly-vanadate ammonium is calcined to obtain the vanadium pentoxide product. V 2 O 5 in the vanadium oxide product is 99.12%, Na 2 O is 0.125%, K 2 O is 0.343%, Si is 0.092%, Fe is 0.043%, S is 0.019%, P is 0.035%, and As<0.010 %, the obtained vanadium pentoxide meets the requirements of the standard YB/T5304-2011.
对比例4～5Comparative Example 4 to 5
取实施例1中的高浓度钒液，用上清液稀释至TV＝40g/L、用生产水稀释至45g/L， 采用常规两步法酸性铵盐沉钒(首先，稀释后的溶液升温至65℃，调溶液pH为6.00，按加铵系数K＝1.80加入硫酸铵粉末；其次，调pH至2.30，升温至沸腾，搅拌沉钒60min)，过滤、洗涤、烘干后所得多钒酸铵中TV分别为46.35％、48.40％，Na2O分别为2.47％、3.51％，S分别为0.14％、0.16％，沉钒率分别为98.22％、96.35％，产品质量差且在调控pH过程中，水解与粘壁现象严重。Take the high concentration vanadium solution in Example 1, dilute to the TV = 40g / L with the supernatant, dilute to 45g / L with the production water, use the conventional two-step method of ammonium salt precipitation vanadium (first, the diluted solution is heated To 65 ° C, adjust the pH of the solution to 6.00, add ammonium sulfate powder according to the ammonium addition coefficient K = 1.80; secondly, adjust the pH to 2.30, warm to boiling, stir vanadium 60min), filter, wash, dry to obtain polyvanadate The TVs in ammonium were 46.35% and 48.40%, respectively, and Na 2 O was 2.47% and 3.51%, respectively, S was 0.14% and 0.16%, respectively. The vanadium precipitation rates were 98.22% and 96.35%, respectively. The product quality was poor and the pH was regulated. Among them, hydrolysis and sticking are serious.
多钒酸铵煅烧后获得五氧化二钒产品，五氧化二钒产品中V2O5分别为95.31％、94.22％，Na2O分别为3.55％、4.59％，K2O分别为0.51％、0.55％，Si分别为0.331％、0.356％，Fe分别为0.045％、0.041％，S分别为0.095％、0.167％，P分别为0.030％、0.032％，As均＜0.010％，所得五氧化二钒产品离标准YB/T5304-2011要求相差较远。After the calcination of ammonium polyvanadate, the vanadium pentoxide product is obtained. The V 2 O 5 in the vanadium pentoxide product is 95.31% and 94.22%, respectively, and the Na 2 O is 3.55% and 4.59%, respectively, and the K 2 O is 0.51%, 0.55%, Si is 0.331%, 0.356%, Fe is 0.045%, 0.041%, S is respectively 0.095%, 0.167%, P is 0.030%, 0.032%, and As is <0.010%, the obtained vanadium pentoxide. The product is far from the standard YB/T5304-2011 requirements.
由实施例和对比例可知，使用本发明技术方案进行沉钒，能将沉钒钒液浓度提高到40～110g/L，沉钒率达到99％以上，得到的多钒酸铵TV含量高，Na2O+K2O、S含量少，煅烧后的五氧化二钒产品满足YB/T5304-2011的要求。 It can be seen from the examples and the comparative examples that using the technical scheme of the present invention to carry out vanadium precipitation can increase the concentration of vanadium-vanadium and vanadium solution to 40-110 g/L, and the vanadium-precipitating rate can reach 99% or more, and the obtained polyvanadate TV has high TV content. The content of Na 2 O+K 2 O and S is small, and the calcined vanadium pentoxide product satisfies the requirements of YB/T5304-2011.

Claims (10)

  1. 高浓度钒液制备多钒酸铵的方法，其特征在于，包括以下步骤：A method for preparing ammonium polyvanadate by a high concentration vanadium solution, comprising the steps of:
    a、取高浓度钒液，升温至65～85℃，调节pH值至6.5～8.5，加入铵盐，搅拌至完全溶解；a, take a high concentration of vanadium solution, raise the temperature to 65 ~ 85 ° C, adjust the pH to 6.5 ~ 8.5, add ammonium salt, stir until completely dissolved;
    b、将水升温至80～90℃，加入含钒粉末物料，并调节pH值至2.0～3.0；b, the water is heated to 80 ~ 90 ° C, the vanadium-containing powder material is added, and the pH is adjusted to 2.0 ~ 3.0;
    c、将步骤a中所得溶液缓慢加入步骤b所得溶液中，加入时保证pH值为2.0～3.0，边加边搅拌；c, the solution obtained in step a is slowly added to the solution obtained in step b, and the pH is ensured to be 2.0-3.0 when added, and stirred while being added;
    d、待步骤a溶液加完后，继续反应5～30min，过滤、水洗，得到多钒酸铵。d. After the solution of step a is added, the reaction is continued for 5 to 30 minutes, filtered and washed with water to obtain ammonium polyvanadate.
  2. 根据权利要求1所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤a中所述高浓度钒液是指钒液中总钒含量为40～110g/L的钒液。The method for preparing ammonium polyvanadate according to the high concentration vanadium solution according to claim 1, wherein the high concentration vanadium liquid in the step a refers to a vanadium liquid having a total vanadium content of 40 to 110 g/L in the vanadium solution.
  3. 根据权利要求1或2所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤a中所述铵盐为硫酸铵、氯化铵、硝酸铵、碳酸铵或碳酸氢铵中的至少一种。The method for preparing ammonium polyvanadate according to the high concentration vanadium solution according to claim 1 or 2, wherein the ammonium salt in the step a is ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium hydrogencarbonate. At least one of them.
  4. 根据权利要求1～3任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤a中所述铵盐的加入量按加铵系数0.6～2.5添加。The method for preparing ammonium polyvanadate according to any one of claims 1 to 3, wherein the ammonium salt is added in an amount of 0.6 to 2.5 in the step a.
  5. 根据权利要求1～4任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤b中所述含钒粉末物料为多钒酸铵、偏钒酸铵、五氧化二钒或三氧化二钒中的至少一种。The method for preparing ammonium polyvanadate according to any one of claims 1 to 4, wherein the vanadium-containing powder material in step b is ammonium polyvanadate, ammonium metavanadate, pentoxide At least one of vanadium or vanadium pentoxide.
  6. 根据权利要求1～5任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤b中所述含钒粉末物料的粒度为全部过120目筛。The method for preparing ammonium polyvanadate by the high concentration vanadium solution according to any one of claims 1 to 5, wherein the particle size of the vanadium-containing powder material in the step b is all over a 120 mesh sieve.
  7. 根据权利要求1～6任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤b中所述含钒粉末物料加入量为高浓度钒液中TV含量与高浓度钒液体积乘积的16～20倍。The method for preparing ammonium polyvanadate by using the high concentration vanadium solution according to any one of claims 1 to 6, wherein the vanadium-containing powder material in the step b is added to the TV content and the high concentration in the high concentration vanadium solution. The volume fraction of vanadium solution is 16 to 20 times.
  8. 根据权利要求1～7任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤c中所述缓慢加入的速度为15～25mL/min。The method for preparing ammonium polyvanadate according to any one of claims 1 to 7, wherein the slow addition speed in step c is 15 to 25 mL/min.
  9. 根据权利要求1～8任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤c中所述搅拌速度400～500r/min。The method for preparing ammonium polyvanadate according to any one of claims 1 to 8, wherein the stirring speed in the step c is 400 to 500 r/min.
  10. 根据权利要求1～9任一项所述的高浓度钒液制备多钒酸铵的方法，其特征在于：步骤b中水可用沉钒上清液代替，所述沉钒上清液中Na2O含量≤60g/L。 The method for preparing ammonium polyvanadate according to the high concentration vanadium solution according to any one of claims 1 to 9, wherein the water in the step b is replaced by a vanadium precipitation supernatant, and the vanadium precipitation supernatant is Na 2 . O content ≤ 60g / L.
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