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CN102430266A - Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide - Google Patents

Method for purifying liquid with vanadium and method for preparing ammonium metavanadate and vanadium oxide Download PDF

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CN102430266A
CN102430266A CN 201010501816 CN201010501816A CN102430266A CN 102430266 A CN102430266 A CN 102430266A CN 201010501816 CN201010501816 CN 201010501816 CN 201010501816 A CN201010501816 A CN 201010501816A CN 102430266 A CN102430266 A CN 102430266A
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vanadium
liquid
method
acid
exchange
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CN 201010501816
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CN102430266B (en )
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刘学文
周芳
彭一村
李千文
王永钢
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攀钢集团攀枝花钢钒有限公司
攀钢集团钢铁钒钛股份有限公司
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Abstract

The invention provides a method for purifying liquid with vanadium, comprising the following steps: contacting the liquid with vanadium with acid cation exchange resin for ion exchange; and separating the liquid with vanadium after being contacted from the acid cation exchange resin, wherein the liquid with vanadium comprises metal cations and acid group anions of the vanadium. The method can be easily operated, has a few steps and low cost, can be used for processing the high-concentration liquid with vanadium and reducing the combustion of precipitator, so the supernatant liquid of the precipitated vanadium can be directly recycled, the yield of the vanadium is improved, and the grade of the vanadium oxide is improved.

Description

一种含钒溶液的纯化方法及偏钒酸铵和氧化钒的制备方法 Vanadium containing solution and purification method for preparing ammonium metavanadate and vanadium oxide

技术领域 FIELD

[0001] 本发明涉及一种含钒溶液的纯化方法及偏钒酸铵和氧化钒的制备方法。 [0001] The present invention relates to a method for preparation and purification of ammonium metavanadate and vanadium oxide containing vanadium solution. 背景技术 Background technique

[0002] 钒是高熔点的稀有金属,具有很多优良的性能,在冶金、化工等行业有广泛的用途。 [0002] Vanadium is a high melting point metals, has many excellent performance in the metallurgical, chemical and other industries have a wide range of uses. 钒用于钢铁工业,在钢中加入0. 〜0.5%的钒与碳生成碳化物,细化基体晶粒,从而改善钢的性能;钒的高价氧化物是化学工业和石油工业中的重要催化剂;此外,在电子、 玻璃、印刷、电影、照相和陶瓷等工业,钒的化合物亦得到广泛应用。 Vanadium for the steel industry, in the steel was added 0.5 ~ 0.5% vanadium and carbon forming carbides, fine matrix grains, thereby improving properties of steel; high vanadium oxide is an important catalyst in the chemical and petroleum industries in ; in the electronic, glass, printing, film, photographic and ceramic industries, vanadium compounds has also been widely used. 并且,随着我国现代化建设的高速发展,钒和其化合物的需求越来越大,使用范围越来越广,其质量要求也越来越尚ο Furthermore, with the rapid development of China's modernization, the demand for vanadium compound and its growing use of increasingly wide range of quality requirements are increasingly still ο

[0003] 在沉钒的现有技术中:(1) 2003年李大标在“酸性铵盐沉钒条件实验研究”,《过程工程学报》,2003,NO. 3(1),P. 53〜56文献中,提出的沉钒方法是以含钒30g/L左右的溶液为原料,加硫酸铵后用硫酸调节PH至2. 2左右,加铵系数2. 2,沸水浴(95°C)中沉淀得到含Na 0.70%〜1.08%,S 0. 78%〜1. 20%的APV。 [0003] In the prior art vanadium precipitation in: (1) 2003 Lee marked "Experimental Study of acidic ammonium vanadium precipitation conditions", "Journal of Process Engineering", 2003, NO 3 (1), P 53~56.. Document, vanadium precipitation method proposed is based on vanadium about 30g / L of a solution containing raw materials with sulfuric acid after adding ammonium sulfate to adjust the PH to about 2.2, plus ammonium coefficient 2.2, boiling water bath (95 ° C) in the precipitate obtained containing Na 0.70% ~1.08%, S 0. 78% ~1. 20% of APV. 这种方法的缺点是:沉淀产物中杂质K、Na、S含量高,钒产品品位低。 A disadvantage of this method is that: the product precipitated impurities K, Na, S content is high, low grade vanadium products.

[0004] (2) 2007年彭毅等人在CNlOl 157478A中提出的沉钒方法是以传统的钠化焙烧-水浸工艺生产的含钒溶液为原料,先使钒与加入的钙化合物结合生成钒酸钙,然后用碳酸氢铵与钒酸钙反应,使钒转入溶液,而钙生成更难溶的碳酸钙,分离后的溶液在适当的PH和加热条件下生成多钒酸铵,所得产品中含S 0.04〜0.43%。 [0004] (2) 2007 Peng Yideng al CNlOl 157478A vanadium precipitation method is proposed in a conventional roasting sodium - flooding process for producing vanadium-containing solution as the raw material, the vanadium compound is added calcium binding generation vanadium, calcium, ammonium bicarbonate and then reacted with calcium vanadate, vanadium into solution, while the less soluble calcium carbonate generated, the solution generating multi-vanadate isolated under appropriate heating conditions and PH, the resulting products containing S 0.04~0.43%. 这种方法的缺点是:生产工序较长,产品中S含量高。 The disadvantage of this approach are: a longer production process, the product of high S content.

[0005] (3)2007年贾绍才等人在CN101182036A中提出的沉钒方法是采用硫酸铝净化钒溶液,用盐酸调节钒溶液PH值,滤液加入氯化铵反应3〜4天,离心脱水后灼烧6〜8小时,得到五氧化二钒产品。 [0005] (3) 2007 vanadium precipitation method was Jiashao CN101182036A et al is employed in the purification of vanadium aluminum sulfate solution, the PH value was adjusted with hydrochloric acid of vanadium, ammonium chloride and the filtrate was added 3 to 4 days, after centrifugal dewatering burning burn 6 ~ 8 hours to obtain vanadium pentoxide product. 这种方法的缺点是:生产周期长,劳动效率低;废水中氯离子浓度高,处理难度大。 The disadvantage of this approach are: long production cycle and low labor efficiency; high chloride ion concentration in the wastewater, a large processing difficult.

[0006] (4) 1992年邓庆云等人在CN1065494A中提出的沉钒方法是用含钒溶液和碱性淋洗液间隔地通过大孔径弱碱性阴离子交换树脂床,收集含钒浓度高达60〜100g/L的溶液, 然后接氧化钒生产工艺。 [0006] (4) The method of vanadium precipitation 1992 Deng Qingyun et al in CN1065494A eluent is a vanadium-containing solution and the basic interval exchange resin bed through the large aperture weakly basic anion collected vanadium concentrations up 60~ 100g / L solution, and then vanadium oxide production process.

[0007] (5) 1998年欧阳昌伦等人在0附23520认中提出的沉钒方法是用网篮装着的大孔弱碱性阴离子交换树脂直接浸入浸出的含钒矿浆中吸附钒,然后用碱液解吸钒,树脂用稀硫酸溶液再生后返回吸附,含钒解吸液再接现有工艺提取五氧化二钒。 [0007] (5) 1998 macroporous vanadium precipitation method Changlun Ouyang et al recognize the attachment 023520 basket is filled with a vanadium-containing weakly basic anion exchange resin slurry directly immersed vanadium leaching adsorption, and vanadium desorption with lye, with a dilute sulfuric acid solution to return the resin regenerated after the adsorption, desorption solution containing vanadium pentoxide followed by conventional extraction process.

[0008] (6) 2006年洪声在CN101003855A中提出的沉钒方法是将焙烧熟料经湿式磨矿至细度小于0. 1mm,保持矿浆浓度25〜40%,矿浆进入水浸搅拌槽,向搅拌槽中加入矿重7〜 15%的阴离子型树脂对矿浆中的钒离子进行吸附,吸附饱和的树脂用碱液解吸;将解吸液再分别接铵盐沉钒。 [0008] (6) of vanadium precipitation method presented in the 2006 Hong sound CN101003855A clinker is calcined by a wet grinding to a fineness of less than 0. 1mm, holding 25~40% pulp density, flooding into the slurry agitation tank, was added to a stirred tank mine July to 15% weight of anionic resin vanadium ions in the pulp adsorption, adsorption and desorption with saturated resin with lye; the desorption solution and then were then ammonium vanadium precipitation.

[0009] 上述(4)、(5)、(6)方法的缺点是:a.采用阴离子交换树脂对钒进行富集的同时, 也对其它的杂质阴离子进行富集,沉淀时杂质也一起进入钒产品,钒产品品位低,一般不高于98. 5% ;b.钒溶液浓度不能太高,一般不能高于30g/L,浓度越高,杂质含量越高。 [0009] (4) above, (5), the disadvantages (6) The method is:. A simultaneous use of anion exchange resin vanadium enrichment, but also anionic impurities other enrichment, precipitation with impurities into the vanadium products, low quality vanadium product, generally not higher than 98. 5%;. b vanadium concentration of the solution is not too high, generally not greater than 30g / L, the higher the concentration, the higher the impurity content.

[0010] 另外,以上所有方法共同的缺点是:用过量的铵盐进行沉钒,铵盐加入量大,成本高,废水中氨含量高,处理难度大;废水不能直接回用,降低了钒的收率。 [0010] Further, a common drawback of all the above methods are: vanadium precipitation carried out with an excess of an ammonium salt, an ammonium salt added volume, high cost, high ammonia content in waste water, a large processing difficulty; wastewater can not be directly reused, reducing the vanadium It yields.

[0011] 因此,迫切期望一种能够处理高浓度含钒溶液且能够获得高品位钒产品的方法。 [0011] Accordingly, there is a desire for a process capable of high concentration vanadium solution can be obtained, and high quality method of vanadium products.

发明内容 SUMMARY

[0012] 本发明的目的是为了克服现有含钒溶液的纯化方法存在的所得钒产品品位低、钒溶液浓度不能太高的问题,提供一种能够获得高品位钒产品且能够纯化高浓度钒溶液的纯化方法及偏钒酸铵和氧化钒的制备方法。 [0012] The object of the present invention is to overcome the low quality of the resulting product of vanadium, the vanadium concentration of the solution is not too high purification methods of the prior problems of the vanadium-containing solution, to provide a high quality vanadium product can be obtained and can be purified in a high concentration of vanadium the method of purification and preparation of the solution of ammonium metavanadate and vanadium oxide.

[0013] 在已知现有的技术中,均采用阴离子交换树脂与含钒溶液进行交换,使钒离子吸附在阴离子交换树脂上,再通过洗脱液将钒离子洗脱下来以达到纯化的目的。 [0013] In the known prior art, the anion exchange resin are used and exchanged vanadium-containing solution, so that the vanadium ions are adsorbed on the anion exchange resin, then through the eluate eluted vanadium ions to achieve purification purposes . 但是,采用阴离子交换树脂对钒进行富集的同时,也对其它的杂质阴离子进行富集,沉淀时杂质也一起进入钒产品,钒产品品位低,同时钒溶液浓度不能太高,浓度越高,杂质含量越高。 However, while the use of anion exchange resin vanadium enrichment, but also to other anion impurities enriched precipitation of vanadium impurities went into products, low quality vanadium product, but not too high a vanadium concentration of the solution, the higher the concentration, The higher the impurity content. 同时,由于钠化焙烧-水浸工艺生产的含钒溶液中成分复杂,使用现有的沉钒技术制备高品位的氧化钒,程序复杂,步骤长,而且,由于需加铵盐去置换溶液中与钒结合的金属阳离子,使钒与氨结合生成沉淀,一价阳离子与钒的结合性最好,一价阳离子越多,加的铵盐就越多,因此铵盐加入量大。 Meanwhile, since the sodium roasting - flooding process for producing a composition containing a solution of a complex of vanadium, vanadium oxide prepared using a conventional high-grade vanadium precipitation techniques, complicated procedures, step length, and, since the displacement to be added to a solution of an ammonium salt bound to the metal cation vanadium, vanadium combine with ammonia to form a precipitate, and the binding of monovalent cations is preferably vanadium, more monovalent cations, the more added salt, an ammonium salt is added so large.

[0014] 本发明人意外的发现,将钠化焙烧-水浸工艺生产的含钒溶液与酸性阳离子交换树脂接触,进行离子交换,酸性阳离子交换树脂中的氢离子进入钒溶液,而钒溶液中的金属阳离子则被酸性阳离子交换树脂截留,从而实现金属阳离子与钒的同多酸根离子的分离, 再利用沉淀剂使钒沉淀,将钒沉淀物高温焙烧后可得到高品位氧化钒。 [0014] The present inventors have surprisingly found that sodium roasting - flooding process for producing vanadium-containing solution is contacted with an acidic cation exchange resin, ion exchange, acid cation exchange resins hydrogen ions into the vanadium solution and the solution of the vanadium metal cations were entrapped acidic cation exchange resin, in order to achieve separation of multi-ion with metal cations and vanadium, vanadium precipitation agent recycling precipitated vanadium precipitate after high temperature firing to obtain a high quality vanadium oxide. 该方法简单易于操作,步骤少,成本低,可处理高浓度的含钒溶液,同时还可以减少沉淀剂的消耗,使沉钒上清液直接回用,提高了钒的收率,还提高了氧化钒的品位。 The method is simple and easy to operate, less steps, low cost, processing vanadium-containing solution with high concentration, but also can reduce the consumption of precipitant, so that reuse of the supernatant of vanadium precipitation, increasing the yield of vanadium, also increases grade vanadium oxide.

[0015] 由此,本发明提供一种含钒溶液的纯化方法,其特征在于,该方法包括将含钒溶液与酸性阳离子交换树脂接触,进行阳离子交换,并使接触后的含钒溶液与酸性阳离子交换树脂分离,所述含钒溶液含有金属阳离子和钒的同多酸根离子。 [0015] Accordingly, the present invention provides a method for purification of vanadium-containing solution, characterized in that the method comprising the vanadium-containing solution is contacted with an acidic cation exchange resin, cation exchange, and vanadium-containing solution after contact with the acidic separating the cation exchange resin, with multiple ion solution containing metal cations of vanadium and vanadium-containing.

[0016] 本发明还提供了一种偏钒酸铵的制备方法,该方法包括将含钒的同多酸根离子的钒溶液进行纯化,并将纯化得到的含钒溶液用PH值调节剂调节pH值为大于7. 5至小于等于9之后与铵沉淀剂接触,得到偏钒酸铵沉淀,其特征在于,所述将含钒的同多酸根离子的钒溶液进行纯化的方法为上述含钒溶液的纯化方法。 [0016] The present invention further provides a method for preparing ammonium metavanadate, the vanadium solution comprising ions of isopoly vanadium containing purified, and the vanadium-containing solution to give a PH adjusting the pH adjusting agent value of greater than 7.5 to less then 9 contacted with a precipitating agent, ammonium, ammonium metavanadate precipitate obtained, characterized in that the solution of the vanadium-containing vanadium ions with the plurality of the above-described method of purifying a solution containing vanadium purification methods.

[0017] 本发明还提供了一种氧化钒的制备方法,该方法包括制备偏钒酸铵,并将偏钒酸铵焙烧,其特征在于,所述制备偏钒酸铵的方法为本发明提供的上述偏钒酸铵的制备方法。 [0017] The present invention further provides a method for preparing vanadium oxide, which method comprises preparing ammonium metavanadate, ammonium metavanadate and calcined, characterized in that the preparation of ammonium metavanadate present invention provides the method of preparing the ammonium metavanadate.

[0018] 由于本发明提供的含钒溶液的纯化方法使用的酸性阳离子交换树脂不吸附含钒溶液中的钒的同多酸根离子,而与容易被交换的钾、钠等金属阳离子进行交换,因此可处理高浓度的含钒溶液。 [0018] Since an acidic cation purification of vanadium-containing solution of the present invention provides the use of exchange resins is not adsorbed isopoly acid ion containing vanadium vanadium solution, and exchanged with potassium, sodium and other metal cation it is easily exchanged, so It can treat high-concentration vanadium solution. 另外,由于阳离子树脂吸附了含钒溶液中的钠离子、钾离子以及其它阳离子,使得经过离子交换后的含钒溶液中的钠离子、钾离子以及其它阳离子的含量非常少, 另外,本发明中,在调PH值时就采用氨水,而现有的工艺中全加硫酸铵,这一点减少了硫的加入量,最终能够得到钾、钠、硫含量低、高品位的氧化钒。 Further, since the cationic resin adsorbed sodium vanadium-containing solution, potassium ions, and other cations such as sodium ions vanadium-containing solution is subjected to ion exchange in the content of potassium ions, and other cations very small, further, the present invention , when the PH value is adjusted using ammonia, and the whole process of the conventional ammonium sulfate, which reduces the amount of sulfur, can be obtained finally potassium, sodium, low sulfur content, high quality vanadium oxide.

[0019] 综上所述,本发明的方法与已有的沉钒技术相比,具有如下明显的优点:[0020] 1、可处理高浓度含钒溶液; [0019] In summary, the method of the present invention as compared with conventional vanadium precipitation technique has the following significant advantages: [0020] 1, can handle a high concentration of vanadium-containing solution;

[0021] 2、沉淀时采用低铵沉钒,加铵系数(以硫酸铵计)为1-1. 3,沉钒上清液中氨氮浓度低、含盐量少,可直接回用,提高了钒的收率; [0021] 2, low precipitation, ammonium vanadium precipitation, plus ammonium coefficients (in terms of ammonium sulfate) 1-1. 3, vanadium precipitation low ammonia concentration in the supernatant, a small amount of salt, can be directly reused, improved yield of vanadium;

[0022] 3、氧化钒中钾、钠、硫含量低,提高了产品品位。 [0022] 3, vanadium oxide, potassium, sodium, low sulfur content, improved product quality.

具体实施方式 detailed description

[0023] 本发明提供了一种含钒溶液的纯化方法,其特征在于,该方法包括将含钒溶液与酸性阳离子交换树脂接触,进行阳离子交换,并使含钒溶液与酸性阳离子交换树脂分离,所述含钒溶液含有金属阳离子和钒的同多酸根离子。 [0023] The present invention provides a method for purifying the vanadium-containing solution, characterized in that the method comprising the vanadium-containing solution is contacted with an acidic cation exchange resin, cation exchange, and vanadium-containing solution with an acidic cation exchange resin was separated, the vanadium-containing ions with a solution containing a plurality of metal cations and vanadium.

[0024] 由于本发明的含钒溶液的纯化方法是通过使含钒溶液中的金属阳离子与酸性阳离子交换树脂中的氢离子发生离子交换,因此所述酸性阳离子交换树脂可以是各种酸性阳离子交换树脂,只要能够实现上述功能即可。 [0024] Since the purification process of the vanadium-containing solution of the present invention are prepared by reacting a hydrogen-containing ionic resins in the ion exchange vanadium metal cations in solution with an acidic cation exchange, and therefore the acidic cation exchange resin may be various acidic cation exchange resin, as long as the above-described functions can be achieved. 优选情况下,所述酸性阳离子交换树脂为强酸性阳离子交换树脂。 Preferably, the acidic cation exchange resin is a strongly acidic cation exchange resin. 进一步优选为强酸性苯乙烯系阳离子交换树脂。 More preferably a styrene-based strongly acidic cation exchange resin.

[0025] 本发明的含钒溶液的纯化方法,其中,所述酸性阳离子交换树脂的总交换容量为4. 35mmol H+/ 克-5mmol H+/ 克。 [0025] The purification process of the present invention the vanadium-containing solution, wherein the acidic cation exchange resin of the total exchange capacity is 4. 35mmol H + / g -5mmol H + / g.

[0026] 根据本发明的一种优选实施方式,所述含钒溶液与酸性阳离子交换树脂接触的方式为使所述含钒溶液通过酸性阳离子交换树脂床层,并且所述含钒溶液与阳离子交换树脂接触的时间为l-50min。 [0026] According to a preferred embodiment of the invention, a solution containing vanadium embodiment acidic cation exchange resin as the vanadium-containing solution through the resin bed acid cation exchange, and the vanadium-containing solution with a cation exchange the contact time of the resin for l-50min.

[0027] 由于本发明的含钒溶液的纯化方法是通过使含钒溶液中的金属阳离子与酸性阳离子交换树脂进行离子交换来实现的,因此含钒溶液中的金属阳离子浓度没有特别的限制,只要符合离子交换的条件即可,具体地。 [0027] Since purification of vanadium-containing solution of the present invention is obtained by containing a metal cation vanadium solution with an acidic cation exchange resin ion exchange achieved, the metal cation concentration of the vanadium-containing solution is not particularly limited, as long as to meet the conditions of ion exchange, in particular. 可以为在含钒溶液中金属阳离子的浓度为0-5 摩尔/升。 May be a solution containing a vanadium concentration of the metal cation is 0-5 mol / l. 该含钒溶液通过酸性阳离子交换树脂床层后的含钒溶液中金属阳离子的浓度低于0. 054摩尔/升。 The vanadium-containing solution of the vanadium-containing resin bed acid cation exchange solution concentration of the metal cations is less than 0.054 mol / liter. 所述金属阳离子包括钠离子和/或钾离子。 The metal cations include sodium and / or potassium ions.

[0028] 如前所述,本发明的含钒溶液的纯化方法能够处理较现有技术更高浓度的含钒溶液,具体地,以钒元素计,所述含钒溶液中钒的浓度可以为10-100克/升,优选为40-60克/升。 [0028] As described above, the purification method of the vanadium-containing solution of the present invention is capable of handling a higher concentration than the prior art vanadium-containing solution, in particular, calculated as elemental vanadium, vanadium-containing vanadium concentration in solution may be 10-100 g / l, preferably 40-60 g / liter.

[0029] 根据本发明的含钒溶液的纯化方法,其中,所述含钒溶液可以为各种来源的含钒溶液,本发明优选为由钠化焙烧-水浸工艺生产的含钒溶液。 [0029] The purification method of the present invention, the vanadium-containing solution, wherein the vanadium-containing solution may be various sources of vanadium-containing solution, preferably the present invention are the sodium roasting - flooding process for producing vanadium-containing solution.

[0030] 本发明还提供一种偏钒酸铵的制备方法,该方法包括将含钒的同多酸根离子的钒溶液进行纯化,并将纯化得到的含钒溶液用PH值调节剂调节pH值为大于7. 5至小于等于9 之后与铵沉淀剂接触,得到偏钒酸铵沉淀,其特征在于,所述将含钒的同多酸根离子的钒溶液进行纯化的方法为上述含钒溶液的纯化方法。 [0030] The present invention further provides a process for the preparation of ammonium metavanadate, which method comprises vanadium with a solution containing multiple ions of vanadium was purified, and the vanadium-containing solution to give pH was adjusted using PH adjusting agent of greater than 7.5 to less then 9 contacted with a precipitating agent, ammonium, ammonium metavanadate precipitate obtained, characterized in that the solution of the vanadium-containing vanadium ions with the plurality of the above-described method for the purification of vanadium-containing solution purification methods.

[0031] 上述pH值调节剂可以为本领域所公知的各种pH值调节剂,本发明优选为液氨、氨水、碳酸氢铵和碳酸铵中的一种或几种。 [0031] The pH adjusting agents known in the art may be present in various pH adjusting agent, the present invention is preferably one or more of liquid ammonia, aqueous ammonia, ammonium carbonate and ammonium bicarbonate in.

[0032] 根据上述偏钒酸铵的制备方法,其中,所述铵沉淀剂可以为硫酸铵、氯化铵、碳酸氢铵、碳酸铵、液氨和氨水中的一种或几种。 [0032] The preparation method of the ammonium metavanadate, wherein the precipitating agent may be ammonium sulfate, ammonium chloride, ammonium bicarbonate, ammonium carbonate, ammonia and one or more of ammonia.

[0033] 根据上述偏钒酸铵的制备方法,其中,加铵系数可以为1-1. 3,优选为1-1. 2。 [0033] The preparation method of the ammonium metavanadate, wherein the coefficients may be applied ammonium 1-1. 3, preferably 1-1. 2. 所述加铵系数(以硫酸铵计),按以下方式计算: The added ammonium coefficients (in terms of ammonium sulfate), calculated as follows:

[0034] G = Knh4+. V. C[0035] G为硫酸铵加入量,单位为kg ;V为溶液的体积,单位为m3 ;C为以钒元素计含钒溶液的浓度,单位为kg/m3 ;KNH4+为加铵系数。 . [0034] G = Knh4 + V. C [0035] G is an amount of ammonium sulfate is added, in units of kg; V is the volume of the solution in units of m3; C at a concentration of vanadium as calculated as elemental vanadium-containing solution, in kg / m3; KNH4 + is added ammonium coefficient. 在本发明中由于钒溶液中金属阳离子被酸性阳离子交换树脂所吸附,钒溶液中金属阳离子少,加入的氨就直接与钒结合,不需要多加铵盐提高溶液中的氨含量去与其它的阳离子竞争、置换,因此加铵系数小。 In the present invention, since the solution of the vanadium metal cations are adsorbed acidic cation-exchange resins, metal cation less vanadium solution, ammonia is added directly in combination with vanadium, ammonium salts do not need to pay more to improve the ammonia content of the solution with other cations to competition, displacement, and therefore small plus ammonium coefficient. 由于加铵系数小, 沉钒上清液中氨氮浓度低、含盐量少,可直接回用,提高了钒的收率。 Due to the small coefficient plus ammonium, vanadium precipitation low ammonia concentration in the supernatant, a small amount of salt, can be directly reused, increasing the yield of vanadium.

[0036] 本发明还提供了一种氧化钒的制备方法,该方法包括制备偏钒酸铵,并将偏钒酸铵焙烧,其特征在于,所述制备偏钒酸铵的方法为上述偏钒酸铵的制备方法。 [0036] The present invention further provides a method for preparing vanadium oxide, which method comprises preparing ammonium metavanadate, ammonium metavanadate and calcined, characterized in that the method of ammonium metavanadate is prepared above metavanadate preparation ammonium. 所述焙烧的条件可以为本领域所公知的条件,例如:焙烧温度可以为500-600°C,焙烧时间可以为6-8小时。 The firing conditions may be art known conditions, for example: the firing temperature may be 500-600 ° C, the calcination time may be 6-8 hours. 冷却后得到高纯度的五氧化二钒。 After cooling to obtain high purity vanadium pentoxide.

[0037] 本发明中,沉钒率是指钒沉淀后得到的沉淀物中含钒量与沉淀前溶液中总的含钒量之比。 [0037] In the present invention, vanadium precipitation rate refers to the amount of vanadium in the solution before precipitation of the total amount of the vanadium-containing vanadium ratio of the resulting precipitate-containing precipitate.

[0038] 下面结合实施例对本发明进行进一步说明。 [0038] The present invention will be further described in conjunction with embodiments.

[0039] 实施例1 [0039] Example 1

[0040] 将2L含钒40. 46g/L、钠31. 5g/L、钾0. 64g/L、温度40°C的钠化焙烧-水浸工艺生产的含钒溶液通过重量为IOOOg的大孔强酸性苯乙烯系阳离子交换树脂(D001大孔强酸性苯乙烯系阳离子交换树脂、交换容量彡4. 35mmolH+/克,江苏省临海树脂科技有限公司)床层,含钒溶液与离子交换树脂的接触交换时间为2min,交换后钒溶液中含钒40. 25g/L、钠1. 2妆/1、钾< 0. 01g/L、pH = 1. 05,向交换后的钒溶液中加入氨水调节pH至7. 5,再加入碳酸氢铵进行沉钒,控制加铵系数(以硫酸铵计)为1,沉钒率为77. 2%。 [0040] A 2L vanadium 40. 46g / L, sodium 31. 5g / L, potassium 0. 64g / L, sodium roasting temperature of 40 ° C - flooding process for producing vanadium-containing solution is passed through a large weight IOOOg styrene based strongly acidic macroporous cation exchange resin (styrene-D001 macroporous strongly acidic cation exchange resin, the exchange capacity San 4. 35mmolH + / g resin Jiangsu Ltd. sea) bed of vanadium-containing solution with an ion exchange resin exchange the contact time 2min, vanadium in the vanadium-containing solution after the exchange 40. 25g / L, sodium makeup 1.2 / 1, K <0. 01g / L, pH = 1. 05, aqueous ammonia was added to the solution after exchange of vanadium pH was adjusted to 7.5, then add vanadium precipitation ammonium bicarbonate, ammonium plus control coefficients (in terms of ammonium sulfate) 1, vanadium precipitation rate was 77.2%. 将沉淀出的偏钒酸铵过滤洗涤后在电煅炉内在500-600°C下灼烧6-8小时,冷却后得到五氧化二钒产品。 The precipitated ammonium metavanadate was filtered and washed calcined for 6-8 hours at 500-600 ° C calcined in the electric furnace, and cooled to obtain vanadium pentoxide product. 得到的五氧化二钒产品中含V2O5 :99. 58重量%,Nei2O < 0.01重量%,K2O < 0.01重量%,S < 0. 01 重量%。 The product obtained contains vanadium pentoxide V2O5:. 99 58 wt%, Nei2O <0.01 wt%, K2O <0.01 wt%, S <0. 01 wt%.

[0041] 对比例1 [0041] Comparative Example 1

[0042] 将2L含钒40. 46g/L、钠31. 5g/L、钾0. 64g/L、温度40°C的钠化焙烧-水浸工艺生产的含钒溶液加入硫酸调节PH至7. 5,再加入碳酸氢铵进行沉钒,控制钒溶液中阳离子加铵系数(以硫酸铵计)为1,沉钒率为15.8%。 [0042] A 2L vanadium 40. 46g / L, sodium 31. 5g / L, potassium 0. 64g / L, sodium roasting temperature of 40 ° C - flooding process for producing vanadium-containing sulfuric acid was added to adjust the PH 7 5, ammonium bicarbonate was added vanadium precipitation, the control vanadium solution was added ammonium cation coefficients (in terms of ammonium sulfate) 1, vanadium precipitation was 15.8%. 将沉淀出的偏钒酸铵过滤洗涤后在电煅炉内在500-600°C下灼烧6-8小时,冷却后得到五氧化二钒产品。 The precipitated ammonium metavanadate was filtered and washed calcined for 6-8 hours at 500-600 ° C calcined in the electric furnace, and cooled to obtain vanadium pentoxide product. 得到的五氧化二钒产品中含V2O5 :98. 25 重量%,Nei2O :0. 60 重量%,K2O :0. 21 重量%,S :0. 30 重量%。 The product obtained contains vanadium pentoxide V2O5:. 98 25% by weight, Nei2O:. 0 60 wt%, K2O:. 0 21 wt%, S:. 0 30 wt%.

[0043] 实施例2 [0043] Example 2

[0044] 将2L含钒45. 75g/L、钠29. 3g/L、钾0. 61g/L、温度50°C的钠化焙烧-水浸工艺生产的含钒溶液通过IOOOg的大孔强酸性苯乙烯系阳离子交换树脂(D001大孔强酸性苯乙烯系阳离子交换树脂、交换容量> 4. 35mmolH+/克,江苏省临海树脂科技有限公司)床层,含钒溶液与离子交换树脂的接触交换时间为20min,交换后钒溶液中含钒45. 43g/L、钠0. 518/1、钾< 0. 01g/L、pH = 1. 03,向交换后的钒溶液中加入氨水调节pH至8. 0,再加入碳酸氢铵进行沉钒,控制加铵系数(以硫酸铵计)为1. 2,沉钒率为92. 5%。 [0044] A 2L vanadium 45. 75g / L, sodium 29. 3g / L, potassium 0. 61g / L, sodium roasting temperature of 50 ° C - flooding process for producing vanadium-containing solution was passed through a macroporous strong IOOOg acidic styrene cation exchange resin (styrene-D001 macroporous strongly acidic cation exchange resin, the exchange capacity> 4. 35mmolH + / g resin Jiangsu Ltd. sea) bed of vanadium-containing solution is contacted with an ion exchange resin exchange time was 20min, after an exchange of vanadium in the vanadium-containing solution 45. 43g / L, 0. 518/1 sodium, potassium <0. 01g / L, pH = 1. 03, vanadium was added to the aqueous ammonia solution to adjust the pH of the exchange 8.0, then add vanadium precipitation ammonium bicarbonate, ammonium plus control coefficient (ammonium sulfate basis) of 1.2, 92.5% vanadium deposition rate. 将沉淀出的偏钒酸铵过滤洗涤后在电煅炉内在500-600°C下灼烧6-8小时,冷却后得到五氧化二钒产品。 The precipitated ammonium metavanadate was filtered and washed calcined for 6-8 hours at 500-600 ° C calcined in the electric furnace, and cooled to obtain vanadium pentoxide product. 得到的五氧化二钒产品中含V2O5 :99. 76重量%,Na2O < 0. 01重量%,K2O < 0. 01重量%, S < 0. 01 重量%。 The product obtained contains vanadium pentoxide V2O5:. 99 76 wt%, Na2O <0. 01 wt%, K2O <0. 01 wt%, S <0. 01 wt%.

[0045] 实施例3[0046] 将2L含钒57. 38g/L、钠34. 50g/L、钾0. 67g/L、温度30°C的钠化焙烧-水浸工艺生产的含钒溶液通过IOOOg的大孔强酸性苯乙烯系阳离子交换树脂(D001大孔强酸性苯乙烯系阳离子交换树脂、交换容量> 4. 35mmolH+/克,江苏省临海树脂科技有限公司)床层,含钒溶液与离子交换树脂的接触交换时间为50min,交换后钒溶液中含钒56. 86g/L、钠0. 2妝/1、钾< 0. 01g/L、pH = 1. 01,向交换后的钒溶液中加入氨水调节pH至8. 5,再加入碳酸氢铵进行沉钒,控制加铵系数(以硫酸铵计)为1. 3,沉钒率为98. 2%。 Flooding process for producing vanadium-containing solution - [0045] 57. 38g / L, sodium 34. 50g / L, potassium 0. 67g / L, sodium roasting temperature of 30 ° C in Example 3 [0046] A 2L vanadium macroporous strongly acidic styrenic cation-exchange resin IOOOg (D001 styrene macroporous strongly acidic cation exchange resin, the exchange capacity> 4. 35mmolH + / g resin Jiangsu Ltd. sea) bed of vanadium-containing solution ion exchange resin in contact with the exchange time was 50min, after an exchange of vanadium in the vanadium-containing solution 56. 86g / L, sodium makeup 0.2 / 1, K <0. 01g / L, pH = 1. 01, after the exchange of the vanadium was added ammonia to adjust the pH to 8.5, then add vanadium precipitation ammonium bicarbonate, ammonium plus control coefficient (ammonium sulfate basis) of 1.3, 98.2% vanadium deposition rate. 将沉淀出的偏钒酸铵过滤洗涤后在电煅炉内在500-600°C下灼烧6-8小时,冷却后得到五氧化二钒产品。 The precipitated ammonium metavanadate was filtered and washed calcined for 6-8 hours at 500-600 ° C calcined in the electric furnace, and cooled to obtain vanadium pentoxide product. 得到的五氧化二钒产品中含V2O5 :99. 85重量%,Na2O < 0. 01重量%,K2O < 0. 01重量%, S < 0. 01 重量%。 The product obtained contains vanadium pentoxide V2O5:. 99 85 wt%, Na2O <0. 01 wt%, K2O <0. 01 wt%, S <0. 01 wt%.

[0047] 实施例4 [0047] Example 4

[0048] 按照实施例1的方案进行,不同的是将大孔强酸性苯乙烯系阳离子交换树脂替换为JK008均孔强酸性苯乙烯系阳离子交换树脂(JK008均孔强酸性苯乙烯系阳离子交换树脂、交换容量彡4. 35mmolH+/克,江苏省临海树脂科技有限公司),得到的五氧化二钒产品中含V205 :98. 85 重量%,Na20 :0. 09 重量%,K20 :0. 02 重量%,S < 0. 01 重量%。 [0048] carried out according to the protocol of Example 1, except that the styrene macroporous strongly acidic cation exchange resin was replaced JK008 average pore strong acid styrene cation exchange resin (strongly acidic macroporous styrene-JK008 both cation exchange resin exchange capacity San 4. 35mmolH + / g resin Jiangsu sea Ltd.), the product obtained contains vanadium pentoxide V205:. 98 85 wt%, Na20:. 0 09 wt%, K20:. 0 02 wt. %, S <0. 01 wt%.

[0049] 由上可见,采用本发明的方法可直接处理高浓度含钒溶液;在沉淀时采用低铵沉钒,加铵系数(以硫酸铵计)为1-1.3 ;氧化钒中钾、钠、硫含量低,提高了产品品位。 [0049] seen from the above, the method of the present invention can be processed directly vanadium-containing solution of high concentration; low ammonium vanadium precipitation during precipitation, plus ammonium coefficients (in terms of ammonium sulfate) 1-1.3; vanadium oxide, potassium, sodium low sulfur content, improved product quality. 因此, 本发明的方法制备氧化钒具有简单易于操作、成本低、提高了钒的收率和钒产品质量,带来了很好的经济效益和社会效益,具有很好的应用前景。 Thus, a process for preparing vanadium oxide according to the present invention has a simple and easy operation, low cost, improve the yield of vanadium and vanadium product quality, it has brought about good economic and social benefits, has good application prospect.

Claims (13)

1. 一种含钒溶液的纯化方法,其特征在于,该方法包括将含钒溶液与酸性阳离子交换树脂接触,进行离子交换,并使接触后的含钒溶液与酸性阳离子交换树脂分离,所述含钒溶液含有金属阳离子和钒的同多酸根离子。 CLAIMS 1. A method of purifying a solution containing vanadium, characterized in that the method comprising the vanadium-containing solution is contacted with an acidic cation exchange resin, ion exchange, and the vanadium-containing solution is contacted with the acidic cation exchange resin separation, the multi-containing ions with a metal cation-containing solution of vanadium and vanadium.
2.根据权利要求1所述的方法,其中,所述酸性阳离子交换树脂为强酸性阳离子交换树脂。 The method according to claim 1, wherein said acidic cation exchange resin is a strongly acidic cation exchange resin.
3.根据权利要求2所述的方法,其中,所述强酸性阳离子交换树脂为强酸性苯乙烯系阳离子交换树脂。 3. The method according to claim 2, wherein the strong acid cation exchange resin is a styrene strongly acidic cation exchange resin.
4.根据权利要求1-3中任意一项所述的方法,其中,所述酸性阳离子交换树脂的总交换容量彡4. SSmmolH+/克。 4. A method according to any one of claims 1-3 claims, wherein the total exchange capacity of the acidic cation exchange resins San 4. SSmmolH + / g.
5.根据权利要求1-4中任意一项所述方法,其中,在步骤(1)中,所述含钒溶液与酸性阳离子交换树脂接触的条件使得接触后的含钒溶液中金属阳离子的浓度低于0. 054摩尔/升。 5. A method a according to any of claims 1-4, wherein, in step (1), the condition of the vanadium-containing solution with an acidic cation exchange resin such that the concentration of the vanadium-containing solution in contact with metal cations less than 0.054 moles / liter.
6.根据权利要求5所述的方法,其中,所述含钒溶液与阳离子交换树脂接触的时间为l_50mino 6. The method according to claim 5, wherein the vanadium-containing solution and the time for the cation exchange resin l_50mino
7.根据权利要求1所述的方法,其中,所述含钒溶液中金属阳离子的浓度为0-5摩尔/ 升,所述金属阳离子包括钠离子和/或钾离子。 7. The method according to claim 1, wherein the concentration of the vanadium-containing solution is a metal cation of 0-5 mol / l, the metal cation comprises sodium ions and / or potassium ions.
8.根据权利要求1所述的方法,其中,以钒元素计,所述含钒溶液中钒的浓度为10-100克/升。 8. The method according to claim 1, wherein, calculated as elemental vanadium, vanadium in the vanadium concentration was 10 to 100 g / liter.
9.根据权利要求1或8所述的方法,其中,所述含钒溶液为由钠化焙烧-水浸工艺生产的含钒溶液。 9. The method of claim 1 or claim 8, wherein the vanadium-containing solution by sodium roasting - flooding process for producing vanadium-containing solution.
10. 一种偏钒酸铵的制备方法,该方法包括将含钒的同多酸根离子的钒溶液进行纯化, 并将纯化得到的含钒溶液用PH值调节剂调节PH值为大于7. 5至小于等于9之后与铵沉淀剂接触,得到偏钒酸铵沉淀,其特征在于,所述将含钒的同多酸根离子的钒溶液进行纯化的方法为权利要求1-9中任意一项所述的方法。 10. A method for the preparation of ammonium metavanadate, which method comprises vanadium-containing vanadium ions in a solution with multiple purification, and give a vanadium-containing solution is adjusted PH PH adjusting agent is greater than 7.5 after less than or equal to 9 in contact with the precipitating agent, ammonium, ammonium metavanadate precipitate obtained, characterized in that the vanadium solution with multiple ion containing vanadium purifying method as claimed in any one of claims 1-9 the method described below.
11.根据权利要求10所述的方法,其中,pH值调节剂为液氨、氨水、碳酸氢铵和碳酸铵中的一种或几种;所述铵沉淀剂为硫酸铵、氯化铵、碳酸氢铵、碳酸铵、液氨和氨水中的一种或几种。 11. The method according to claim 10, wherein, pH adjusting agent is one or more of liquid ammonia, aqueous ammonia, ammonium carbonate and ammonium hydrogencarbonate; and the precipitating agent is ammonium sulfate, ammonium chloride, one or more ammonium bicarbonate, ammonium carbonate, ammonia and ammonia water.
12.根据权利要求10所述的方法,其中,加铵系数为1-1.3。 12. The method according to claim 10, wherein the coefficient of plus ammonium 1-1.3.
13. 一种氧化钒的制备方法,该方法包括制备偏钒酸铵,并将偏钒酸铵焙烧,其特征在于,所述制备偏钒酸铵的方法为权利要求10-12中任意一项所述的方法。 13. A method for preparing vanadium oxide, which method comprises preparing ammonium metavanadate, ammonium metavanadate and calcined, characterized in that the method of ammonium metavanadate is prepared according to any one of claims 10-12 the method of claim.
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