石煤氧压酸浸萃取提钒新工艺研究
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摘要
石煤属黑色炭质页岩,是一种含钒矿物,是我国除钒钛磁铁矿外另一种重要钒矿资源。我国的石煤资源十分丰富,遍布20余省,广泛分布于云南、贵州、湖南、浙江、江西、广西、甘肃、新疆等省(区)。石煤含钒总量约1.18亿吨,是我国钒钛磁铁矿中钒总量的7倍,超过世界其他国家钒储量的总和。因此,如何合理利用石煤中钒资源具有重大的研究意义。
我国石煤提钒的传统工艺为平窑钠化焙烧—水浸,该工艺流程主要包括钠盐氯化焙烧—水浸—酸沉粗钒—碱溶—铵盐沉钒—热解。传统工艺的主要缺点为：钒回收率低(<50%),生产成本高；食盐焙烧过程中所放出的Cl2、HCl等有害气体,以及生产过程中排出的废水、废渣等严重污染环境。伴随环境问题的日益增长,2003年国家强行取缔了该工艺,从而限制了我国石煤资源的利用。因此,新型高效环保工艺的研发迫在眉睫。
本文研发了一种新型、低耗、环保、高回收率的提钒工艺。文中对含钒石煤氧压酸浸萃取提钒新工艺进行了系统的研究。首先利用扫描电子显微镜、电子探针、能谱分析、X-射线衍射分析、热重分析等检测手段,研究贵州铜仁某地石煤矿中钒的矿物学特征；在此基础上,开展了探索性试验,然后进行了正交试验和条件试验,研究考察了影响钒浸取率的各种因素：浸出时间、浸出温度、浸出剂浓度、浸出液固比、矿石粒度、添加剂种类及用量等,试验结果表明在浸出时间3-4h、浸出温度150℃、硫酸用量25%-35%、液固比1.2：1、矿石粒度0.074mm、Po2为1.2MPa、添加剂用量3%-5%的条件下,经两段氧压酸浸后,钒的浸出率可达90%以上。
同时,本文还研究了石煤氧压酸浸液中萃钒除铁的工艺过程,从萃取和反萃的相比、试剂组成、pH值、澄清时间等方面进行了详细试验研究。研究表明：浸出液经酸回收、还原除铁处理后,采用10%P204+5%TBP+85%煤油萃取钒时,经六级逆流萃取后萃取率为95%以上；负载有机相用15%H2S04反萃时,经五级逆流反萃后反萃率可达99%以上。经萃取后,浸出液中的钒可富集到37g/L以上,铁可缩减至0.6g/L以下,反萃水相中钒铁质量比大于60,钒铁分离效果较好。
反萃液用氨水进行沉钒处理,得到的钒酸铵在550℃下煅烧3h即可得到V205含量为99.5%的粉状产品,钒的总回收率达80%左右。
本工艺具有流程短、操作简单、回收率高、成本低、污染少等优点,具有较好的经济效益、环境效益和社会效益。
Stone coal is black carbonaceous shale which contains vanadium. It is an alternative resource of vanadium in China, besides the vanadium and titanium magnetite ore. Our country is rich in stone coal resources, more than 20 around the province. This mineral extensively exists in Yunnan, Guizhou, Hunan, Zhejiang, Jiangxi, Guangxi, Gansu, Xinjiang, etc province or autonomous region. Total of vanadium reserves is about 118 million tons in stone coal vanadium mine, is 7 times of the vanadium total amount in China's vanadium and titanium magnetite, and is more than the sum of vanadium reserves in other countries. So how rationally to use the vanadium resources in the stone coal which has great significance.
In our country, sodium salt roasting and water leaching is the traditonal technology of extract vanadium from stone coal.The brief flowof the classical technology includes chloridizing roasting, water leaching, deposition vanadium, alkali dissolution, ammonium salt precipitation vanadium and thermal decomposition. This classical technology has two main problems, low recovery of vanadium (<50%), high cost of the product and serious environment pollution.Serious poisonous gases, HCl and Cl2, are produced in the roasting process because sodium chloride is used as an additive, and the waste water and solid residues. Increasing environmental concerns and legislation concerning environmental protection, China banned the application of this technology in 2003, thus, the utilization of stone coal was limited. Therefore, it is extremely urgent to research and develop a new higher recovery of vanadium and no pollution to environment technology of extracting vanadium from stone coal.
The aim of this paper is to research and develop a new process of extracting vanadium from stone coal, characterized by higher recovery of vanadium and which was environmentally-friendly. The new technology on vanadium extraction from stone-coal by sulfuric acid oxygen pressure leaching and solvent extraction was studied in this paper. Firstly, the mineralogy of the stone-coal from Tongren of Guizhou was investigated by various determination methods, scanning electronic microscope, electron probe analysis, energy spectrum analysis,Ⅹ-ray diffraction, thermogravimetric analysis, and so on. Based on the mineralogy, the investigative test was carried out. Then orthogonal and conditional experiments were designed. The effects of leaching time, leaching temperature, leaching agent concentration, leaching L/S, granularity of material, additive consumption, which were the influential factors of extraction of vanadium, were investigated. The results showed that under the conditions of leaching time for 3-4h, temperature at 150℃, sulfuric acid consumption was 25%-35%, ratio of liquid-solid was 1.2:1, the granularity was 0.074mm, Po2 was 1.2MPa and additive consumption was 3%-5%, vanadium leaching percent was over 90% by the method of two-step reverse flow oxygen pressurized acid leaching.
At the same time, the technological process of extracting vanadium from the stone-coal oxygen pressure acid-leaching solution is reseached in this paper. Some parameters of extraction and anti-extraction, such as organic phase to aqueous phase (O/A), the composition of solvent, pH and the setting time, are optimized by a series of tests. The results show that after Pretreatment of acid recovery, removing iron by reduction process, adjusting pH to oxygen pressure acid leached solution, the extraction percent can be up to 95% under the conditions of 6-stage counter-flow extraction with 10%P204+5%TBP+85%coal oil, and the stripping efficiency will exceed 99% when 15%H2SO4 solution is taken as the stripping agent. By way of extraction, the concentration of vanadium can be raised to 37g/L or more, and the concentration of iron can be reduced to 0.6g/L or less. The mass ratio of V and Fe can be up to 60 in aqueous phase of stripping, the effect of separation is well.
Ammonia was added to stripping liquor to precipitate vanadium, and then the precipitates (ammonium mult-vanadate) was calcined at 550℃for 3 h. The powdery V2O5 product with 99.5% in V2O5 content was obtained by this flowsheet. The total recovery efficiency of vanadium was about 80%.
The advantages of this process are:short route, simple operation, high coefficient of recovery and with better economic efficiency, society benefits and environment acceptability.
我国石煤提钒的传统工艺为平窑钠化焙烧—水浸,该工艺流程主要包括钠盐氯化焙烧—水浸—酸沉粗钒—碱溶—铵盐沉钒—热解。传统工艺的主要缺点为：钒回收率低(<50%),生产成本高；食盐焙烧过程中所放出的Cl2、HCl等有害气体,以及生产过程中排出的废水、废渣等严重污染环境。伴随环境问题的日益增长,2003年国家强行取缔了该工艺,从而限制了我国石煤资源的利用。因此,新型高效环保工艺的研发迫在眉睫。
本文研发了一种新型、低耗、环保、高回收率的提钒工艺。文中对含钒石煤氧压酸浸萃取提钒新工艺进行了系统的研究。首先利用扫描电子显微镜、电子探针、能谱分析、X-射线衍射分析、热重分析等检测手段,研究贵州铜仁某地石煤矿中钒的矿物学特征；在此基础上,开展了探索性试验,然后进行了正交试验和条件试验,研究考察了影响钒浸取率的各种因素：浸出时间、浸出温度、浸出剂浓度、浸出液固比、矿石粒度、添加剂种类及用量等,试验结果表明在浸出时间3-4h、浸出温度150℃、硫酸用量25%-35%、液固比1.2：1、矿石粒度0.074mm、Po2为1.2MPa、添加剂用量3%-5%的条件下,经两段氧压酸浸后,钒的浸出率可达90%以上。
同时,本文还研究了石煤氧压酸浸液中萃钒除铁的工艺过程,从萃取和反萃的相比、试剂组成、pH值、澄清时间等方面进行了详细试验研究。研究表明：浸出液经酸回收、还原除铁处理后,采用10%P204+5%TBP+85%煤油萃取钒时,经六级逆流萃取后萃取率为95%以上；负载有机相用15%H2S04反萃时,经五级逆流反萃后反萃率可达99%以上。经萃取后,浸出液中的钒可富集到37g/L以上,铁可缩减至0.6g/L以下,反萃水相中钒铁质量比大于60,钒铁分离效果较好。
反萃液用氨水进行沉钒处理,得到的钒酸铵在550℃下煅烧3h即可得到V205含量为99.5%的粉状产品,钒的总回收率达80%左右。
本工艺具有流程短、操作简单、回收率高、成本低、污染少等优点,具有较好的经济效益、环境效益和社会效益。
Stone coal is black carbonaceous shale which contains vanadium. It is an alternative resource of vanadium in China, besides the vanadium and titanium magnetite ore. Our country is rich in stone coal resources, more than 20 around the province. This mineral extensively exists in Yunnan, Guizhou, Hunan, Zhejiang, Jiangxi, Guangxi, Gansu, Xinjiang, etc province or autonomous region. Total of vanadium reserves is about 118 million tons in stone coal vanadium mine, is 7 times of the vanadium total amount in China's vanadium and titanium magnetite, and is more than the sum of vanadium reserves in other countries. So how rationally to use the vanadium resources in the stone coal which has great significance.
In our country, sodium salt roasting and water leaching is the traditonal technology of extract vanadium from stone coal.The brief flowof the classical technology includes chloridizing roasting, water leaching, deposition vanadium, alkali dissolution, ammonium salt precipitation vanadium and thermal decomposition. This classical technology has two main problems, low recovery of vanadium (<50%), high cost of the product and serious environment pollution.Serious poisonous gases, HCl and Cl2, are produced in the roasting process because sodium chloride is used as an additive, and the waste water and solid residues. Increasing environmental concerns and legislation concerning environmental protection, China banned the application of this technology in 2003, thus, the utilization of stone coal was limited. Therefore, it is extremely urgent to research and develop a new higher recovery of vanadium and no pollution to environment technology of extracting vanadium from stone coal.
The aim of this paper is to research and develop a new process of extracting vanadium from stone coal, characterized by higher recovery of vanadium and which was environmentally-friendly. The new technology on vanadium extraction from stone-coal by sulfuric acid oxygen pressure leaching and solvent extraction was studied in this paper. Firstly, the mineralogy of the stone-coal from Tongren of Guizhou was investigated by various determination methods, scanning electronic microscope, electron probe analysis, energy spectrum analysis,Ⅹ-ray diffraction, thermogravimetric analysis, and so on. Based on the mineralogy, the investigative test was carried out. Then orthogonal and conditional experiments were designed. The effects of leaching time, leaching temperature, leaching agent concentration, leaching L/S, granularity of material, additive consumption, which were the influential factors of extraction of vanadium, were investigated. The results showed that under the conditions of leaching time for 3-4h, temperature at 150℃, sulfuric acid consumption was 25%-35%, ratio of liquid-solid was 1.2:1, the granularity was 0.074mm, Po2 was 1.2MPa and additive consumption was 3%-5%, vanadium leaching percent was over 90% by the method of two-step reverse flow oxygen pressurized acid leaching.
At the same time, the technological process of extracting vanadium from the stone-coal oxygen pressure acid-leaching solution is reseached in this paper. Some parameters of extraction and anti-extraction, such as organic phase to aqueous phase (O/A), the composition of solvent, pH and the setting time, are optimized by a series of tests. The results show that after Pretreatment of acid recovery, removing iron by reduction process, adjusting pH to oxygen pressure acid leached solution, the extraction percent can be up to 95% under the conditions of 6-stage counter-flow extraction with 10%P204+5%TBP+85%coal oil, and the stripping efficiency will exceed 99% when 15%H2SO4 solution is taken as the stripping agent. By way of extraction, the concentration of vanadium can be raised to 37g/L or more, and the concentration of iron can be reduced to 0.6g/L or less. The mass ratio of V and Fe can be up to 60 in aqueous phase of stripping, the effect of separation is well.
Ammonia was added to stripping liquor to precipitate vanadium, and then the precipitates (ammonium mult-vanadate) was calcined at 550℃for 3 h. The powdery V2O5 product with 99.5% in V2O5 content was obtained by this flowsheet. The total recovery efficiency of vanadium was about 80%.
The advantages of this process are:short route, simple operation, high coefficient of recovery and with better economic efficiency, society benefits and environment acceptability.
引文
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