CN101264933A - A method for deep purification and removal of trace tungsten from high-concentration molybdate solution - Google Patents

A method for deep purification and removal of trace tungsten from high-concentration molybdate solution Download PDF

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CN101264933A
CN101264933A CNA2008100310515A CN200810031051A CN101264933A CN 101264933 A CN101264933 A CN 101264933A CN A2008100310515 A CNA2008100310515 A CN A2008100310515A CN 200810031051 A CN200810031051 A CN 200810031051A CN 101264933 A CN101264933 A CN 101264933A
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tungsten
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molybdate solution
resin
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肖连生
龚柏藩
王学文
张贵清
刘能生
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Central South University
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Abstract

一种从高浓度钼酸盐溶液中深度净化除去微量钨的方法。本发明将含少量钨的钼酸盐溶液预先调整pH值,使钨酸根离子充分聚合成多钨酸根离子之后,通过盛装大孔型弱碱性阴离子交换树脂的吸附床,钨被优先吸附,从而达到从钼酸盐溶液中深度除钨的效果。A method for deep purification and removal of trace tungsten from high-concentration molybdate solution. In the present invention, the pH value of the molybdate solution containing a small amount of tungsten is pre-adjusted, and after the tungstate ions are fully polymerized into polytungstate ions, the tungsten is preferentially adsorbed through the adsorption bed of a macroporous weakly basic anion exchange resin, thereby To achieve the effect of deep removal of tungsten from molybdate solution.

Description

一种从高浓度钼酸盐溶液中深度净化除去微量钨的方法 A method for deep purification and removal of trace tungsten from high-concentration molybdate solution

技术领域technical field

本发明涉及一种从钼酸盐溶液中深度分离低含量钨的离子交换工艺。The invention relates to an ion exchange process for deep separation of low-content tungsten from molybdate solution.

背景技术Background technique

钼金属制品的加工性能以及电、化、物理性能很大程度上受制于金属钼中杂质成分含量,元素钨的影响尤为突出。为了获得具有优异性能的钼金属制品,必须制备高纯的钼中间化合物,如仲钼酸铵、四钼酸铵或二钼酸铵。有害杂质元素中,最难深度净化的当属常与钼共生的元素钨。因钨与钼乃相似元素,物化性质极其相近,且在弱酸性介质中,彼此能生成杂多酸根离子,因此,从宏量钼中分离微量钨具有相当难度。The processing performance and electrical, chemical and physical properties of molybdenum metal products are largely restricted by the content of impurity components in metal molybdenum, and the influence of element tungsten is particularly prominent. In order to obtain molybdenum metal products with excellent properties, it is necessary to prepare high-purity molybdenum intermediate compounds, such as ammonium paramolybdate, ammonium tetramolybdate or ammonium dimolybdate. Among the harmful impurity elements, the most difficult to deeply purify is tungsten, an element that often coexists with molybdenum. Because tungsten and molybdenum are similar elements, their physical and chemical properties are very similar, and they can form heteropolyacid ions with each other in a weakly acidic medium. Therefore, it is quite difficult to separate trace tungsten from macro molybdenum.

目前,从钼酸盐溶液分离微量钨的研究较为深入的方法是金属水合氧化物吸附钨,已有工业应用,但因方法自身的不足未能获得推广,因此国内绝大多数钼酸盐生产厂家没有微量钨深度净化的工艺。研究从宏量钼中分离微量钨的优异工艺是当务之急。At present, the more in-depth research on the separation of trace tungsten from molybdate solution is the adsorption of tungsten by metal hydrated oxides. There is no process of deep purification of trace tungsten. It is urgent to study an excellent process for separating trace tungsten from macromolybdenum.

发明内容Contents of the invention

本发明的目的旨在提供一种从宏量钼中分离除去微量钨,且效果好,工艺简单,稳定可靠,不会造成污染的一种从高浓度钼酸盐溶液中深度净化除去微量钨的方法The purpose of the present invention is to provide a method for removing trace tungsten from high-concentration molybdenum solution with good effect, simple process, stable and reliable, and no pollution. method

本发明的目的是通过下述方式实现:The purpose of the present invention is to realize in the following way:

本发明的方法为:(1)预处理:将钼酸盐溶液加入无机酸,调整溶液pH值至7.0~8.5,并存放5-12小时;(2)将经过预处理的钼酸盐溶液匀速通过装有阴离子交换树脂的吸附床,钼酸盐溶液中除钨吸附过程接触时间在30~120min之间,连续进料至WO3穿漏为吸附终点。The method of the present invention is: (1) pretreatment: add molybdate solution to mineral acid, adjust the pH value of the solution to 7.0~8.5, and store for 5-12 hours; Through the adsorption bed equipped with anion exchange resin, the contact time of the adsorption process for removing tungsten in the molybdate solution is between 30 and 120 minutes, and the continuous feeding until WO 3 leakage is the adsorption end point.

钼酸盐溶液中的钼含量范围为50~250g/l,三氧化钨与钼的质量比为5×10-4~2×10-2The molybdenum content in the molybdate solution ranges from 50 to 250 g/l, and the mass ratio of tungsten trioxide to molybdenum is 5×10 -4 to 2×10 -2 .

所述的阴离子交换树脂优选大孔型弱碱性阴离子交换树脂,树脂使用时为Cl-型。The anion exchange resin is preferably a macroporous weakly basic anion exchange resin, and the resin is Cl - type when used.

负钨树脂用碱性溶液解析,钠盐体系用1~2mol/lNaOH溶液解析,铵盐体系用5~6mol/l的氨水解析。The negative tungsten resin is analyzed with alkaline solution, the sodium salt system is analyzed with 1-2mol/l NaOH solution, and the ammonium salt system is analyzed with 5-6mol/l ammonia water.

解析后的树脂,用4~6%的HCl溶液再生,并水洗涤至出液pH=3~5后用于下一轮吸附。The analyzed resin is regenerated with 4-6% HCl solution, and washed with water until the pH of the effluent is 3-5, and then used for the next round of adsorption.

本发明的工艺其具体实施过程为:Its specific implementation process of technique of the present invention is:

1、溶液的预处理:钼酸盐溶液在搅拌条件下缓缓加入无机酸,调整溶液pH值至7.0~8.5,使钨酸根缩合成同多酸根大离子,并尽量使钼仍以单分子形式存在,一般钼酸钠溶液可用盐酸,钼酸铵溶液可用硝酸,pH值调整到位的钼酸盐溶液存放5-12小时或稍微加温以缩短存放时间。1. Pretreatment of the solution: Slowly add inorganic acid to the molybdate solution under stirring conditions, adjust the pH value of the solution to 7.0-8.5, make the tungstate condense into isopolyacid ions, and try to keep the molybdenum in the form of a single molecule Generally, hydrochloric acid can be used for sodium molybdate solution, nitric acid can be used for ammonium molybdate solution, and the molybdate solution with pH adjusted in place can be stored for 5-12 hours or slightly warmed to shorten the storage time.

2、阴离子交换树脂按常规预处理之后,转化成Cl-型,转型过程宜在交换柱中进行。用于交换除钨的树脂为大孔型弱碱性阴离子交换树脂,用4-6%HCl转型后的树脂用水洗至出液pH3~5待用。2. After the anion exchange resin is pretreated according to the routine, it is transformed into Cl - type, and the transformation process should be carried out in the exchange column. The resin used for exchanging and removing tungsten is a macroporous weakly basic anion exchange resin, and the resin transformed with 4-6% HCl is washed with water until the pH of the effluent is 3-5 for use.

3、吸附除钨:经预处理好的钼酸盐溶液,以一定的流速匀速通过装载Cl-型大孔弱碱性阴离子交换树脂的交换床,吸附流速(Q,L/min)由交换床装载的树脂体积(VR,L)和吸附接触时间(T,min,)确定,即Q=VR/T,从高钼低钨的钼酸盐溶液中除钨吸附过程接触时间范围在30~120min之间,连续进料至WO3穿漏为吸附终点,收集的交后液为净化除钨合格液,漏穿点按净化要求而定,视料液中钨的浓度及净化液WO3/Mo(质量比)控制要求,每次交换作业可处理10~30倍树脂床层体积的料液。3. Tungsten removal by adsorption: The pretreated molybdate solution passes through the exchange bed loaded with Cl - type macroporous weakly basic anion exchange resin at a constant flow rate, and the adsorption flow rate (Q, L/min) is determined by the exchange bed The loaded resin volume (V R , L) and the adsorption contact time (T, min,) are determined, that is, Q=V R /T, and the contact time range of the adsorption process for tungsten removal from the molybdate solution with high molybdenum and low tungsten is within 30 Between ~120min, continuous feeding until WO 3 leakage is the end point of adsorption, and the collected post-transition liquid is the qualified liquid for purifying tungsten removal. The leakage point is determined according to the purification requirements, depending on the concentration of tungsten in the material liquid and the purification liquid WO 3 /Mo (mass ratio) control requirements, each exchange operation can handle 10 to 30 times the resin bed volume of the feed liquid.

4、钨(钼)的解吸:用碱性溶液极易从负载树脂中将钨钼完全解析下来,钠盐体系解析剂用1~2mol/lNaOH溶液,铵盐体系用5~6mol/l的氨水解析,与钨一起被吸附的钼损失(可回收)。为投入总钼量的4%以下4. Desorption of tungsten (molybdenum): It is very easy to completely desorb tungsten and molybdenum from the loaded resin with an alkaline solution. The desorption agent for the sodium salt system uses 1-2mol/l NaOH solution, and the ammonium salt system uses 5-6mol/l ammonia water Analytically, the molybdenum lost (recoverable) is adsorbed together with the tungsten. Less than 4% of the total molybdenum input

树脂再生;解析后的树脂用约3倍树脂体积的4-6%的HCl溶液再生,随后用水洗涤至出液pH=3~5用于下一轮吸附。Resin regeneration: The analyzed resin is regenerated with 4-6% HCl solution about 3 times the volume of the resin, and then washed with water until the pH of the effluent is 3-5 for the next round of adsorption.

本发明研究成功的工艺是离子交换工艺。藉助含钨钼酸盐溶液中,杂质钨与宏量钼生成同多酸盐条件的微小差别及选择合适的离子交换树脂,钨优先吸附,获得了深度分离钨的效果。含钨达1%(钨与钼的质量比)的钼酸盐溶液经深度分离后,钨按常规工艺制成的多钼酸铵,钨含量可降至0.02%以下。The successfully researched technique of the present invention is the ion exchange technique. With the help of the small difference in the conditions of polyacid salt formation of impurity tungsten and macromolybdenum in the tungsten-containing molybdate solution and the selection of a suitable ion exchange resin, tungsten is preferentially adsorbed, and the effect of deep separation of tungsten is obtained. After deep separation of the molybdate solution containing 1% tungsten (mass ratio of tungsten to molybdenum), the ammonium polymolybdate made from tungsten according to the conventional process can reduce the tungsten content to less than 0.02%.

本发明借助于在弱碱和中性介质条件下使钨聚合生成同多酸根离子,而钼基本上仍以单钼酸根离子形式存在,选择合适的阴离子交换树脂,在大量钼存在的情况下能优先吸附多钨酸根离子,达到钼钨分离的目的。该工艺适于从含少量钨的钼酸铵或钼酸钠溶液中分离钨,溶液中的钼含量范围为50~250g/l,三氧化钨与钼的质量比为5×10-4~2×10-2The present invention relies on the polymerization of tungsten to generate isopolyacid ions under the conditions of weak base and neutral medium, while molybdenum basically still exists in the form of monomolybdate ions, and a suitable anion exchange resin can be selected in the presence of a large amount of molybdenum. Prioritize the adsorption of polytungstate ions to achieve the purpose of separating molybdenum and tungsten. This process is suitable for separating tungsten from ammonium molybdate or sodium molybdate solution containing a small amount of tungsten. The molybdenum content in the solution ranges from 50 to 250 g/l, and the mass ratio of tungsten trioxide to molybdenum is 5×10 -4 ~2 ×10 -2 ,

该工艺的优点在于:The advantages of this process are:

1、工艺简单,无需特殊试剂,投资省。1. The process is simple, no special reagents are needed, and the investment is low.

2、与无机吸附剂吸附钨相比,本工艺不引入含有害杂质元素的化学试剂,不会因除钨工序的加入而造成对钼最终产品的污染。2. Compared with the adsorption of tungsten by inorganic adsorbent, this process does not introduce chemical reagents containing harmful impurity elements, and will not cause pollution to the final molybdenum product due to the addition of tungsten removal process.

3、方便使用,原料不同工艺相异的多钼酸铵生产厂家均可方便使用,在沉淀结晶多钼酸铵工序之前插入除钨交换作业就行,原工艺可不作任何变动。3. It is convenient to use. It is easy to use by manufacturers of ammonium polymolybdate with different raw materials and different processes. It is enough to insert tungsten removal and exchange operation before the process of precipitation and crystallization of ammonium polymolybdate, and the original process does not need to be changed.

4、除钨效果好,稳定可靠,如处理钨与钼质量比达1%的钼酸铵溶液,一次交换过程净化液的钨钼比可降低至0.04%以下,共吸附钼量在4%以下,属可回收损失。4. The tungsten removal effect is good, stable and reliable. For example, if the ammonium molybdate solution with a mass ratio of tungsten and molybdenum reaches 1%, the tungsten-molybdenum ratio of the purification solution in one exchange process can be reduced to less than 0.04%, and the total amount of molybdenum adsorbed is less than 4%. , is a recoverable loss.

具体实施方式Detailed ways

下面结合实施例对从钼酸盐溶液中净化除钨的交换工艺作进一步说明。The exchange process for purifying and removing tungsten from molybdate solution will be further described below in combination with examples.

实施例1Example 1

原料为辉钼矿焙砂氨浸液经(NH4)2S净化除杂后的钼酸铵溶液,用浓硝酸调整pH至8.0后,溶液中含钼121.73g/l,三氧化钨1.379g/l,吸附树脂为大孔弱碱性阴离子交换树脂(编号S18),柱上吸附,交换柱Φ20×250mm,接触时间80分钟,通过8倍树脂床层体积料液后的交后液,含钼121.73g/l,三氧化钨0.101g/l,此时三氧化钨的去除率为92.5%。The raw material is the ammonium molybdate solution purified by (NH 4 ) 2 S to remove impurities from the ammonia immersion solution of molybdenite calcine. After adjusting the pH to 8.0 with concentrated nitric acid, the solution contains 121.73g/l of molybdenum and 1.379g of tungsten trioxide. /l, the adsorption resin is a macroporous weakly basic anion exchange resin (code S 18 ), adsorbed on the column, the exchange column Φ20 × 250mm, the contact time is 80 minutes, and the liquid after passing through 8 times of the resin bed volume feed liquid, It contains 121.73g/l of molybdenum and 0.101g/l of tungsten trioxide. At this time, the removal rate of tungsten trioxide is 92.5%.

实施例2Example 2

原料液同实施例1,pH=7.5,交前液中含钼120.71g/l,三氧化钨1.371g/l,吸附树脂为大孔弱碱性阴离子交换树脂(编号863),柱上吸附,交换柱Φ20×250mm,接触时间60分钟,前十倍树脂床层体积流出液三氧化钨平均浓度为0.054g/l,三氧化钨的去除率可达96%,由该混合液酸沉出的钼酸铵结晶,钨含量为0.0156%。The raw material solution is the same as in Example 1, pH=7.5, containing 120.71g/l of molybdenum and 1.371g/l of tungsten trioxide in the solution before handing over, and the adsorption resin is a macroporous weakly basic anion exchange resin (number 863 ), which is adsorbed on the column , exchange column Φ20×250mm, contact time 60 minutes, the average concentration of tungsten trioxide in the effluent of the first ten times the volume of the resin bed is 0.054g/l, the removal rate of tungsten trioxide can reach 96%, and the mixed solution is acid-precipitated Ammonium molybdate crystals with a tungsten content of 0.0156%.

实施例3Example 3

钼酸铵晶体用氨水溶解后,调整溶液pH值至7.2,钼酸铵溶液(钼120.7g/l,三氧化钨0.174g/l,)进行吸附除钨,吸附柱及树脂同实施例2,吸附的接触时间为40分钟,前21倍树脂床层体积流出液三氧化钨平均浓度为0.016g/l,三氧化钨去除率为90.8%。After ammonium molybdate crystal is dissolved with ammoniacal liquor, adjust solution pH value to 7.2, ammonium molybdate solution (molybdenum 120.7g/l, tungsten trioxide 0.174g/l,) carries out adsorption and removes tungsten, and adsorption column and resin are with embodiment 2, The contact time of adsorption is 40 minutes, the average concentration of tungsten trioxide in the effluent of the first 21 times of resin bed volume is 0.016g/l, and the removal rate of tungsten trioxide is 90.8%.

Claims (6)

1, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution is characterized in that, (1) pre-treatment: molybdate solution is added mineral acid, adjust pH value of solution value to 7.0~8.5, and deposited 5-12 hour; (2) will be through pretreated molybdate solution at the uniform velocity by the adsorption bed of anionite-exchange resin be housed, remove tungsten adsorption process duration of contact in the molybdate solution between 30~120min, continuously feeding is to WO 3Leakage is the absorption terminal point.
2, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution according to claim 1,, it is characterized in that the molybdenum content range in the molybdate solution is 50~250g/l, the mass ratio of tungstic oxide and molybdenum is 5 * 10 -4~2 * 10 -2
3, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution according to claim 1,, it is characterized in that molybdate solution comprises ammonium molybdate solution and sodium molybdate solution.
4, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution according to claim 1,, it is characterized in that described anionite-exchange resin is the macroporous type weak base anion-exchange resin, when using, resin is Cl -Type.
5, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution according to claim 1,, it is characterized in that negative tungsten resin is resolved with basic solution, the sodium salt system is resolved with 1~2mol/lNaOH solution, and the ammonium salt system is resolved with the ammoniacal liquor of 5~6mol/l.
6, a kind of method that deep purifying is removed micro-tungsten from high-concentration molybdenate solution according to claim 5,, it is characterized in that, the resin after the parsing, the HCl solution regeneration with 4~6%, and water washing is used for next round absorption to fluid pH=3~5.
CN2008100310515A 2008-04-11 2008-04-11 Deep purification method for removing micro-tungsten from high-concentration molybdenate solution Expired - Fee Related CN101264933B (en)

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CN103906709A (en) * 2011-08-26 2014-07-02 环保金属有限公司 Method for recovering technical-grade molybdenum from diluted acid leacing solutions (PLS) that have a high arsenic concentration and originate from metallurgical waste
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CN102329962A (en) * 2011-10-17 2012-01-25 中南大学 Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution
CN102329962B (en) * 2011-10-17 2014-04-09 中南大学 Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution
CN102676810B (en) * 2012-05-22 2013-08-21 中南大学 Method for separating and recycling vanadium and chromium from vanadate-chromate-containing solution
CN102676810A (en) * 2012-05-22 2012-09-19 中南大学 Method for separating and recycling vanadium and chromium from vanadate-chromate-containing solution
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