WO2023087727A1 - 利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法 - Google Patents

利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法 Download PDF

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WO2023087727A1
WO2023087727A1 PCT/CN2022/102645 CN2022102645W WO2023087727A1 WO 2023087727 A1 WO2023087727 A1 WO 2023087727A1 CN 2022102645 W CN2022102645 W CN 2022102645W WO 2023087727 A1 WO2023087727 A1 WO 2023087727A1
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vanadium
leaching
solution
containing carbonated
residual liquid
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PCT/CN2022/102645
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French (fr)
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付自碧
饶玉忠
伍金树
吴优
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攀钢集团研究院有限公司
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Priority to ZA2022/09075A priority Critical patent/ZA202209075B/en
Publication of WO2023087727A1 publication Critical patent/WO2023087727A1/zh

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/22Obtaining vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the invention relates to the technical field of vanadium extraction metallurgy, in particular to a method for extracting vanadium by utilizing vanadium-containing carbonated leaching solution and recycling the vanadium-precipitated residual solution.
  • Vanadium slag is the main raw material for producing vanadium oxide, and the traditional industrialization process is sodium roasting-water leaching to extract vanadium.
  • the process of sodium roasting consumes a lot of sodium carbonate, and the process cost is relatively high; the content of sodium oxide in the tailings of vanadium extraction is about 6%, which is difficult to reuse; a large amount of solid waste vanadium chromium reduction filter cake and sodium sulfate will be produced in the water treatment process, which is environmentally friendly There are great hidden dangers.
  • a process idea of vanadium slag calcification roasting-carbonation leaching for vanadium extraction was proposed.
  • the main function of the leaching agent is carbonate, and the available reagents include ammonium carbonate, ammonium bicarbonate, sodium carbonate and sodium bicarbonate.
  • Ammonium carbonate and ammonium bicarbonate are easy to decompose under high temperature leaching conditions, the reagent consumption is large, and the solubility of ammonium metavanadate is relatively small.
  • the carbonation leaching solution studied above can recover vanadium by using ammonium salt vanadium precipitation, and the clinker leaching clinker by the upper layer circulation can realize the recycling of sodium, carbonate, and process water, but the temperature of vanadium precipitation is low, and a special refrigeration system is required; A large number of air bubbles will be generated during the feeding process, which will affect the stability control of the leaching process and equipment utilization efficiency; the leaching slurry contains a high concentration of ammonia, which will affect the operating environment and the recycling rate of ammonium salt during solid-liquid separation.
  • the patent application CN109837384A discloses a vanadium extraction process by sodium roasting, adding ammonium carbonate to the leaching solution to precipitate ammonium metavanadate, and the vanadium precipitation wastewater is deammonized by distillation And condense to obtain dilute ammonia water to realize the recycling of ammonium salt and sodium salt.
  • the purpose of the present invention is to overcome the low temperature of vanadium precipitation in the prior art and the need for a special refrigeration system, the supernatant liquid of vanadium precipitation needs a special deammonization process, the low utilization efficiency of leaching equipment when the supernatant liquid of vanadium precipitation directly leaches clinker, and the leaching process
  • a method for extracting vanadium by using vanadium-containing carbonated leaching solution and recycling the vanadium-precipitated residual solution is provided.
  • the present invention provides a method for utilizing vanadium-containing carbonated leaching solution to extract vanadium and recycle the vanadium-precipitated residual liquid, said method comprising the following steps:
  • the desorbent is a solution containing ammonium bicarbonate and sodium bicarbonate.
  • the vanadium-containing carbonation leaching solution is obtained from vanadium slag through calcification roasting-carbonation leaching and/or from vanadium slag through roasting-carbonation leaching.
  • the vanadium concentration in the vanadium-containing carbonated leaching solution is 1-25 g/L, and the sodium concentration is 5-25 g/L.
  • the concentration of vanadium in the vanadium-containing carbonated leaching solution is 5-25 g/L.
  • the pH value of the vanadium-containing carbonated leaching solution is 7.0-9.5.
  • the specific process of step a includes: flowing the vanadium-containing carbonated leachate through the HCO 3 -type anion exchange resin column from top to bottom, and the vanadium is adsorbed by the resin to obtain a vanadium-rich resin and an ion exchange residue.
  • the concentration of ammonium bicarbonate in the desorbent is 100-160 g/L.
  • the concentration of sodium in the desorbent is 15-25 g/L.
  • the molar ratio of the NH 4 + in the ammonium bicarbonate added to the desorption liquid to the vanadium element in the desorption liquid is 1-1.1:1.
  • the leaching agent for the carbonation leaching is a solution containing sodium carbonate and/or sodium bicarbonate.
  • the ion-exchange resin is used as the carrier to realize the exchange of vanadate and bicarbonate, which avoids the refrigeration process required for ammonium salt vanadium precipitation in the traditional method and the influence of ammonium salt introduction on the sodium salt cycle leaching clinker process.
  • the desorption solution can be directly recycled as a desorption agent to realize the recycling of ammonium salts and save the deammonization process of the supernatant liquid required for the circulation of water and sodium salts in the existing process.
  • the invention provides a method for utilizing the vanadium-containing carbonated leaching solution to extract vanadium and to recycle the vanadium-precipitated residual liquid.
  • the method comprises the following steps:
  • the desorbent is a solution containing ammonium bicarbonate and sodium bicarbonate.
  • the HCO 3 -type anion exchange resin is used to separate vanadium and sodium from the vanadium-containing carbonated leaching solution, the vanadate group has a stronger binding capacity with the resin than HCO 3 - , and is adsorbed by the resin, while HCO 3 - is replaced into the solution,
  • the obtained ion-exchange residual liquid is sodium bicarbonate solution and contains a very small amount of sodium vanadate, which can be returned to the carbonation leaching process as a leaching agent to leach clinker obtained by calcification or blank roasting.
  • the vanadium-containing carbonated leaching solution is obtained from vanadium slag through calcification roasting and carbonation leaching.
  • the leaching agent of the carbonation leaching is a solution containing sodium carbonate and/or sodium bicarbonate.
  • the vanadium slag may come from vanadium-containing slag produced by extracting vanadium from vanadium-containing iron, secondary vanadium-containing resources, low-grade vanadium-containing materials, and the like.
  • the vanadium-containing carbonation leaching solution is obtained from vanadium slag through calcification roasting-carbonation leaching and/or from vanadium slag through roasting-carbonation leaching.
  • the vanadium concentration in the vanadium-containing carbonated leaching solution is 1-25 g/L, and the sodium concentration is 5-25 g/L.
  • the concentration of vanadium in the vanadium-containing carbonated leaching solution is 5-25 g/L.
  • the pH value of the vanadium-containing carbonated leaching solution is 7.0-9.5.
  • the specific process of step a includes: flowing the vanadium-containing carbonated leachate through the HCO 3 -type anion exchange resin column from top to bottom, and the vanadium is adsorbed by the resin to obtain a vanadium-rich resin and an ion exchange residue.
  • the concentration of ammonium bicarbonate in the desorbent is 100-160 g/L. Specifically, it may be 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L or 160g/L.
  • the concentration of sodium in the desorbent is 15-25 g/L. Specifically, it can be 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 22g/L, 23g/L, 24g/L or 25g/L.
  • the molar ratio of the NH 4 + in the ammonium bicarbonate added to the desorption liquid to the vanadium element in the desorption liquid is 1-1.1:1.
  • the vanadium-rich resin obtained in step a is desorbed using a solution containing ammonium bicarbonate and sodium bicarbonate as a desorbent.
  • the vanadate is replaced by the concentration difference between HCO3- and vanadate in the desorption solution.
  • the ion exchange resin can be converted into HCO 3 -type and can be recycled to adsorb vanadium; on the other hand, the vanadium-precipitated residual liquid obtained after vanadium-precipitated desorption liquid can be directly returned to step c to circulate and desorb vanadium-rich resin.
  • adding sodium bicarbonate in the desorbent can prolong the time for desorbing liquid crystallization to separate out ammonium metavanadate, avoiding the formation of ammonium metavanadate precipitation in the desorption process of vanadium-rich resin to block the resin pores; simultaneously control the sodium ion concentration 15 ⁇ 25g/L, the HCO 3 - concentration of the desorbent can be increased as much as possible, which is beneficial to the desorption of the vanadium-rich resin, and at the same time, it can avoid the influence of the subsequent vanadium precipitation effect on the high sodium ion concentration.
  • the vanadium precipitation residual liquid obtained in step d can be returned to step c for use as a desorbent, and the ion exchange residual liquid obtained in step a can be used in the carbonation leaching process, and vanadium is removed from the resin in step c
  • the resin obtained after desorption can continue to be recycled for the adsorption of vanadium, which can reduce the generation of waste water and save the cost of vanadium extraction.
  • the vanadium-containing carbonated leaching solution used in the following examples is from vanadium-containing converter vanadium-containing slag through calcification roasting and carbonation leaching (leaching agent is a mixed solution of sodium carbonate and sodium bicarbonate), the main components and pH value are as shown in the table 1.
  • the concentration of ammonium bicarbonate in the desorbent is 120g/L, and the concentration of sodium bicarbonate is 80g/L.
  • the concentration of ammonium bicarbonate in the desorbent is 120g/L, and the concentration of sodium bicarbonate is 70g/L.
  • the concentration of ammonium bicarbonate in the desorbent is 150g/L, and the concentration of sodium bicarbonate is 80g/L.
  • vanadium precipitation rate (weight of ammonium metavanadate ⁇ vanadium content)/(desorption liquid volume ⁇ vanadium concentration) ⁇ 100%
  • Example 1 Example 2
  • Example 3 Vanadium precipitation rate/% 83.20 79.05 85.25

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Abstract

本发明涉及钒的提取冶金技术领域,具体涉及一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法。所述方法包括以下步骤:a:将含钒碳酸化浸出液与HCO3 -型阴离子交换树脂接触,得到富钒树脂和离子交换余液;b:将离子交换余液返回碳酸化浸出工序使用;c:将富钒树脂与解吸剂接触,得到解吸液;d:向解吸液中加入碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液;e;将沉钒余液返回步骤c使用;其中,所述解吸剂为含有碳酸氢铵和碳酸氢钠的溶液。该方法以离子交换树脂为载体实现钒酸根与碳酸氢根的交换,简化了碳酸化浸出液回收钒及介质循环的工艺过程;整个工艺过程在常温下进行,降低能源消耗。

Description

利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法 技术领域
本发明涉及钒的提取冶金技术领域,具体涉及一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法。
背景技术
钒渣是生产氧化钒的主要原料,传统的产业化工艺是钠化焙烧-水浸提钒。该工艺钠化焙烧消耗大量碳酸钠,工艺成本较高;提钒尾渣氧化钠含量6%左右,二次利用困难;水处理过程中会产生大量固废钒铬还原滤饼和硫酸钠,环保隐患大。为降低氧化钒的生产成本,消除环保隐患,提出了钒渣钙化焙烧-碳酸化浸出提钒的工艺思路。
在碳酸化浸出过程中,浸出剂中主要起作用的是碳酸根,可用试剂包括碳酸铵、碳酸氢铵、碳酸钠和碳酸氢钠等。碳酸铵、碳酸氢铵在高温浸出条件下易分解,试剂消耗大,且偏钒酸铵溶解度相对较小,为避免浸出过程中形成偏钒酸铵沉淀影响钒浸出率,需控制较大的浸出液固比,导致浸出液钒浓度降低,相应的后续沉钒率也低,影响设备作业效率,不宜选用。因此,碳酸化浸出试剂多选用碳酸钠和碳酸氢钠。
从碳酸化浸出液中回收钒多采用铵盐沉钒,《钒渣空白焙烧清洁提钒工艺探讨》中公开了碳酸氢钠浸出液添加碳酸铵、碳酸氢铵在10~15℃温度条件下沉钒回收钒的方法,上层液直接循环浸出熟料;《高钙高磷钒渣制备氧化钒工艺研究》中公开了碳酸钠浸出液添加-碳酸氢铵、碳酸铵在10~20℃沉钒的方法,并将残渣、偏钒酸铵洗水混合后蒸发浓缩处理,得到的浓缩液与沉钒上层液一起循环浸出熟料。上述研究的碳酸化浸出液采用铵盐沉钒可以回收钒,上层液循环浸出熟料可以实现钠、碳酸根、工艺水的循环利用, 但沉钒温度低,需要专门制冷系统;上层液循环浸出熟料时会产生大量气泡影响浸出过程的稳定控制和设备利用效率;浸出浆料含氨浓度高,固液分离时影响操作岗位环境和铵盐循环利用率。
为解决沉钒上层液循环浸出熟料时铵盐带来的不利影响,专利申请CN109837384A公开了一种钠化焙烧提钒工艺,浸出液添加碳酸铵沉淀偏钒酸铵,沉钒废水经蒸馏脱氨并冷凝获得稀氨水,实现铵盐、钠盐的循环利用。
现有文献公开了碳酸化浸出液铵盐沉钒、沉钒上层液直接或者脱氨后循环浸出熟料的方法,存在沉钒温度低,需要专门制冷系统;沉钒上层液需要专门脱氨工艺过程;或者沉钒上层液直接浸出熟料时浸出设备利用效率低、浸出过程控制稳定性差、氨回收利用率低等问题。目前未见解决上述问题的相关报道。
发明内容
本发明的目的是为了克服现有技术存在的沉钒温度低、需要专门制冷系统,沉钒上层液需要专门脱氨工艺过程,沉钒上层液直接浸出熟料时浸出设备利用效率低、浸出过程控制稳定性差、氨回收利用率低等问题,提供一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法。
为了实现上述目的,本发明提供一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,所述方法包括以下步骤:
a:将含钒碳酸化浸出液与HCO 3 -型阴离子交换树脂接触,得到富钒树脂和离子交换余液;
b:将离子交换余液返回碳酸化浸出工序使用;
c:将富钒树脂与解吸剂接触,得到解吸液;
d:向解吸液中加入碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液;
e;将沉钒余液返回步骤c使用;
其中,所述解吸剂为含有碳酸氢铵和碳酸氢钠的溶液。
优选地,在步骤a中,所述含钒碳酸化浸出液由钒渣通过钙化焙烧-碳酸化浸出得到和/或由钒渣通过焙烧-碳酸化浸出得到。
优选地,在步骤a中,所述含钒碳酸化浸出液中钒的浓度为1~25g/L,钠的浓度为5~25g/L。
优选地,所述含钒碳酸化浸出液中钒的浓度为5~25g/L。
优选地,所述含钒碳酸化浸出液的pH值为7.0-9.5。
优选地,所述步骤a的具体过程包括:将含钒碳酸化浸出液从上至下流经HCO 3 -型阴离子交换树脂柱,钒被树脂吸附,得到富钒树脂和离子交换余液。
优选地,在步骤c中,所述解吸剂中碳酸氢铵的浓度为100~160g/L。
优选地,所述解吸剂中钠的浓度为15~25g/L。
优选地,在步骤d中,向解吸液中加入的碳酸氢铵中的NH 4 +与解吸液中的钒元素的摩尔比为1-1.1:1。
优选地,所述碳酸化浸出的浸出剂为含有碳酸钠和/或碳酸氢钠的溶液。
在本发明的有益效果为:
(1)以离子交换树脂为载体实现钒酸根与碳酸氢根的交换,避免了传统方法中铵盐沉钒需要的制冷过程和铵盐引入对钠盐循环浸出熟料过程的影响。
(2)解吸液沉钒后可以直接循环作为解吸剂使用,实现铵盐的循环利用,省去现有工艺中为了实现水、钠盐循环需要的上层液脱氨过程。
(3)简化了碳酸化浸出液回收钒及介质循环的工艺过程;整个工艺过程在常温下进行,降低能源消耗。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明提供一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,所述方法包括以下步骤:
a:将含钒碳酸化浸出液与HCO 3 -型阴离子交换树脂接触,得到富钒树脂和离子交换余液;
b:将离子交换余液返回碳酸化浸出工序使用;
c:将富钒树脂与解吸剂接触,得到解吸液;
d:向解吸液中加入碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液;
e;将沉钒余液返回步骤c使用;
其中,所述解吸剂为含有碳酸氢铵和碳酸氢钠的溶液。
在本发明中,使用HCO 3 -型阴离子交换树脂从含钒碳酸化浸出液中分离钒与钠,钒酸根与树脂结合能力比HCO 3 -强,被树脂吸附,而HCO 3 -被置换进入溶液,得到的离子交换余液为碳酸氢钠溶液并且含有极少量钒酸钠,可以返回碳酸化浸出工序作为浸出剂浸出钙化或空白焙烧得到的熟料。
在优选的实施方式中,在步骤a中,所述含钒碳酸化浸出液由钒渣通过钙化焙烧和碳酸化浸出得到。进一步优选地,所述碳酸化浸出的浸出剂为含有碳酸钠和/或碳酸氢钠的溶液。
在本发明中,所述钒渣可以来自含钒铁水提钒产生的含钒炉渣、二次含钒资源和低品位含钒物料等。
在优选的实施方式中,在步骤a中,所述含钒碳酸化浸出液由钒渣通过钙化焙烧-碳酸化浸出得到和/或由钒渣通过焙烧-碳酸化浸出得到。
优选地,在步骤a中,所述含钒碳酸化浸出液中钒的浓度为1~25g/L,钠的浓度为5~25g/L。
进一步优选地,所述含钒碳酸化浸出液中钒的浓度为5~25g/L。
优选地,所述含钒碳酸化浸出液的pH值为7.0-9.5。
优选地,所述步骤a的具体过程包括:将含钒碳酸化浸出液从上至下流经HCO 3 -型阴离子交换树脂柱,钒被树脂吸附,得到富钒树脂和离子交换余液。
在优选的实施方式中,在步骤c中,所述解吸剂中碳酸氢铵的浓度为100~160g/L。具体的,可以为100g/L、110g/L、120g/L、130g/L、140g/L、150g/L或160g/L。
在优选的实施方式中,所述解吸剂中钠的浓度为15~25g/L。具体的,可以为15g/L、16g/L、17g/L、18g/L、19g/L、20g/L、21g/L、22g/L、23g/L、24g/L或25g/L。
优选地,在步骤d中,向解吸液中加入的碳酸氢铵中的NH 4 +与解吸液中的钒元素的摩尔比为1-1.1:1。
在本发明中,对于步骤a得到的富钒树脂使用含有碳酸氢铵和碳酸氢钠的溶液作为解吸剂进行解吸,一方面利用HCO 3 -与钒酸根浓度差将钒酸根置换到解吸液中,同时离子交换树脂转变为HCO 3 -型可以循环用于吸附钒;另一方面解吸液沉钒后得到的沉钒余液可以直接返回步骤c循环解吸富钒树脂。
在本发明中,解吸剂中加入碳酸氢钠可以了延缓解吸液结晶析出偏钒酸铵的时间,避免富钒树脂解吸过程中形成偏钒酸铵沉淀堵塞树脂孔;同时控制钠离子浓度15~25g/L,可以尽可能提高解吸剂的HCO 3 -浓度,利于富钒树脂的解吸,同时避免钠离子浓度过高影响后续的沉钒效果。
在本发明中,可以将步骤d得到的沉钒余液返回步骤c中作为解吸剂进行使用,可以将步骤a得到的离子交换余液用于碳酸化浸出过程,步骤c中将钒从树脂上解吸后得到的树脂可以继续循环用于吸附钒,可以减少废水的产生并且节约提钒成本。
以下将通过实施例对本发明进行详细描述,但本发明的保护范围并不局限于此。
以下实施例使用的含钒碳酸化浸出液由来自含钒铁水转炉提钒的钒渣通过钙化焙烧和碳酸化浸出(浸出剂为碳酸钠和碳酸氢钠的混合溶液),主要成分和pH值如表1所示。
表1含钒碳酸化浸出液主要成分/g·L -1
编号 TV Na P Si CO 3 2-+HCO 3 - pH
实施例1 5.62 8 0.01 0.03 10.67 8.92
实施例2 13.7 19.50 0.02 0.07 26.01 9.03
实施例3 8.96 12.75 0.02 0.05 17.01 9.01
实施例1
a:将2000mL含钒碳酸化浸出液按400mL/h速度从上至下流经HCO 3 -型D201阴离子交换树脂桩,钒被树脂吸附,得到富钒树脂和离子交换余液(TV<0.1g/L);
b:将离子交换余液返回碳酸化浸出工序使用;
c:将富钒树脂与500mL解吸剂接触,得到解吸液(500mL,TV=27.85g/L);
d:向解吸液中加入18g碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液(TV=4.68g/L);
e;将沉钒余液返回步骤c使用;
其中,所述解吸剂中碳酸氢铵的浓度为120g/L,碳酸氢钠的浓度为80g/L。
实施例2
a:将1000mL含钒碳酸化浸出液按200mL/h速度从上至下流经HCO 3 -型D301阴离子交换树脂桩,钒被树脂吸附,得到富钒树脂和离子交换余液(TV<0.1g/L);
b:将离子交换余液返回碳酸化浸出工序使用;
c:将富钒树脂与600mL解吸剂接触,得到解吸液(600mL,TV=22.72g/L);
d:向解吸液中加入22g碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液(TV=4.76g/L);
e;将沉钒余液返回步骤c使用;
其中,所述解吸剂中碳酸氢铵的浓度为120g/L,碳酸氢钠的浓度为70g/L。
实施例3
a:将2000mL含钒碳酸化浸出液(TV=8.96g/L、pH=9.01)按200mL/h速度从上至下流经HCO 3 -型D301阴离子交换树脂桩,钒被树脂吸附,得到富钒树脂和离子交换余液(TV<0.1g/L);
b:将离子交换余液返回碳酸化浸出工序使用;
c:将富钒树脂与800mL解吸剂接触,得到解吸液(800mL,TV=22.23g/L);
d:向解吸液中加入29g碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液(TV=3.28g/L);
e;将沉钒余液返回步骤c使用;
其中,所述解吸剂中碳酸氢铵的浓度为150g/L,碳酸氢钠的浓度为80g/L。
测试例
对实施例中步骤d中得到的偏钒酸铵中的含钒量进行检测,计算出钒的 沉淀率,且沉钒余液可以循环用于解吸含钒树脂,其中的钒元素未损失。结果如表2所示。
计算公式为:钒沉淀率=(偏钒酸铵重量×钒含量)/(解吸液体积×钒浓度)×100%
表2
  实施例1 实施例2 实施例3
钒沉淀率/% 83.20 79.05 85.25
由表2可知,采用本发明所述的方法,实现了碳酸化浸出液中钒的回收,且过程中产生的离子交换余液可以循环用于浸出含钒熟料,沉钒余液可以循环解吸富钒树脂,减少了废水的产生和试剂的消耗。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。

Claims (10)

  1. 一种利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,所述方法包括以下步骤:
    a:将含钒碳酸化浸出液与HCO 3 -型阴离子交换树脂接触,得到富钒树脂和离子交换余液;
    b:将离子交换余液返回碳酸化浸出工序使用;
    c:将富钒树脂与解吸剂接触,得到解吸液;
    d:向解吸液中加入碳酸氢铵进行沉钒,过滤得到偏钒酸铵和沉钒余液;
    e;将沉钒余液返回步骤c使用;
    其中,所述解吸剂为含有碳酸氢铵和碳酸氢钠的溶液。
  2. 根据权利要求1所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,在步骤a中,所述含钒碳酸化浸出液由钒渣通过钙化焙烧-碳酸化浸出得到和/或由钒渣通过焙烧-碳酸化浸出得到。
  3. 根据权利要求1或2所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,在步骤a中,所述含钒碳酸化浸出液中钒的浓度为1~25g/L,钠的浓度为5~25g/L。
  4. 根据权利要求3所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,所述含钒碳酸化浸出液中钒的浓度为5~25g/L。
  5. 根据权利要求3或4所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,所述含钒碳酸化浸出液的pH值为7.0-9.5。
  6. 根据权利要求1或2所述的利用含钒碳酸化浸出液提钒和沉钒余液 循环利用的方法,其特征在于,所述步骤a的具体过程包括:将含钒碳酸化浸出液从上至下流经HCO 3 -型阴离子交换树脂柱,钒被树脂吸附,得到富钒树脂和离子交换余液。
  7. 根据权利要求1所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,在步骤c中,所述解吸剂中碳酸氢铵的浓度为100~160g/L。
  8. 根据权利要求1或6所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,所述解吸剂中钠的浓度为15~25g/L。
  9. 根据权利要求1所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,在步骤d中,向解吸液中加入的碳酸氢铵中的NH 4 +与解吸液中的钒元素的摩尔比为1-1.1:1。
  10. 根据权利要求2所述的利用含钒碳酸化浸出液提钒和沉钒余液循环利用的方法,其特征在于,所述碳酸化浸出的浸出剂为含有碳酸钠和/或碳酸氢钠的溶液。
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