CN106381387B - A kind of method that high-purity phosphoric acid manganese is prepared from low grade rhodochrosite leachate - Google Patents
A kind of method that high-purity phosphoric acid manganese is prepared from low grade rhodochrosite leachate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 27
- CCQLOTNQWSBPLX-UHFFFAOYSA-N manganese phosphoric acid Chemical compound [Mn].OP(O)(O)=O CCQLOTNQWSBPLX-UHFFFAOYSA-N 0.000 title 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 16
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 12
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 8
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- 229910052748 manganese Inorganic materials 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/377—Phosphates of heavy metals of manganese
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
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Abstract
本发明公开了一种从低品位菱锰矿浸出液制备高纯磷酸锰的方法，属于湿法冶金领域。低品位菱锰矿浸出液杂质含量较高，除杂技术难度高，工艺复杂，本发明的从低品位菱锰矿浸出液制备高纯磷酸锰的方法工艺流程短，主要包括以下两步：第一步是将磷酸钠加入到菱锰矿的硫酸浸出液中，控制溶液的pH值在3~3.5之间，充分搅拌，过滤去除沉淀物，得到初级净化硫酸锰溶液；第二步是在初级净化硫酸锰溶液中继续加入磷酸钠，控制溶液最终的pH值在4.0~4.5之间，充分搅拌，过滤并反复洗涤，得到高纯磷酸锰产物。本发明工艺操作简单、容易控制，制备的磷酸锰纯度高，从经济、技术和环境等角度评价的可行性高，为低品位菱锰矿的开发应用提供了新途径。
The invention discloses a method for preparing high-purity manganese phosphate from low-grade rhodochrosite leaching solution, belonging to the field of hydrometallurgy. The low-grade rhodochrosite leaching solution has a relatively high impurity content, and the impurity removal technology is difficult and complicated. The method for preparing high-purity manganese phosphate from the low-grade rhodochrosite leaching solution of the present invention has a short process flow and mainly includes the following two steps: the first step is to Add sodium phosphate to the sulfuric acid leaching solution of rhodochrosite, control the pH value of the solution between 3 and 3.5, stir fully, filter and remove the precipitate, and obtain the primary purified manganese sulfate solution; the second step is to continue in the primary purified manganese sulfate solution Sodium phosphate is added to control the final pH value of the solution between 4.0 and 4.5, fully stirred, filtered and washed repeatedly to obtain a high-purity manganese phosphate product. The process of the invention is simple in operation and easy to control, the prepared manganese phosphate has high purity, and has high feasibility evaluated from the perspectives of economy, technology and environment, etc., and provides a new way for the development and application of low-grade rhodochrosite.
Description
技术领域technical field
本发明涉及湿法冶金领域，特别提供了一种从低品位菱锰矿浸出液制备高纯磷酸锰的方法。The invention relates to the field of hydrometallurgy, and in particular provides a method for preparing high-purity manganese phosphate from low-grade rhodochrosite leaching solution.
背景技术Background technique
我国的锰矿资源储量丰富，但是品位普遍较低，目前菱锰矿的平均品位低于14%，远低于富锰矿的国际标准。传统的冶金行业主要采用电解锰技术生产电解锰和电解二氧化锰产品，并以此作为其他高纯锰制品的原料进行生产应用。但是，菱锰矿原矿品位降低、杂质种类复杂、含量高，电解效率低、成本居高不下，而且电解废液中含有大量的重金属离子，对环境构成了严重的威胁。my country's manganese ore reserves are abundant, but the grade is generally low. At present, the average grade of rhodochrosite is lower than 14%, which is far lower than the international standard of manganese-rich ore. The traditional metallurgical industry mainly uses electrolytic manganese technology to produce electrolytic manganese and electrolytic manganese dioxide products, and use them as raw materials for other high-purity manganese products for production and application. However, the grade of rhodochrosite raw ore is reduced, the types of impurities are complex, the content is high, the electrolysis efficiency is low, the cost remains high, and the electrolysis waste liquid contains a large amount of heavy metal ions, which poses a serious threat to the environment.
近年来，锰资源的需求不仅仅是局限于钢铁工业锰系铁合金的生产领域，由于一些新兴的材料行业如磁性材料工业和以锂离子二次电池工业为代表的新能源产业迅速发展，对高纯锰产品的需求量与日俱增，这些新兴产业的迅猛发展对锰矿资源产品结构调整、深加工材料的精细化发展提出了迫切的要求。In recent years, the demand for manganese resources is not limited to the production of manganese-based ferroalloys in the iron and steel industry. Due to the rapid development of some emerging material industries such as the magnetic material industry and the new energy industry represented by the lithium-ion secondary battery industry, the demand for high The demand for pure manganese products is increasing day by day, and the rapid development of these emerging industries has put forward urgent requirements for the adjustment of the product structure of manganese ore resources and the refined development of deep-processing materials.
因此，近年来应用非电解工艺制备高纯锰产品的技术发展迅速。本发明基于化学耦合一体化工艺设计思路，提出了一种从低品位菱锰矿直接制备高纯磷酸锰的短流程低能耗方法，其工艺成本低、绿色无污染，且产品纯度高。Therefore, the technology of preparing high-purity manganese products by non-electrolytic process has developed rapidly in recent years. Based on the idea of chemical coupling and integrated process design, the present invention proposes a short-process and low-energy-consumption method for directly preparing high-purity manganese phosphate from low-grade rhodochrosite. The process has low process cost, is green and pollution-free, and has high product purity.
发明内容Contents of the invention
本发明的目的在于从杂质含量较高的低品位菱锰矿浸出液直接制备高纯磷酸锰，实现锰资源的高效绿色开发以及短流程高纯锰制品的生产。The purpose of the present invention is to directly prepare high-purity manganese phosphate from low-grade rhodochrosite leaching solution with high impurity content, so as to realize the efficient and green development of manganese resources and the production of short-process high-purity manganese products.
一种从低品位菱锰矿浸出液制备高纯磷酸锰的方法，以品位≤14%的菱锰矿的硫酸浸出液作为原料，采用磷酸钠作为pH调节剂和沉淀剂，方法主要包括以下两步：其过程主要包括两步：第一步是在菱锰矿的硫酸浸出液中加入磷酸钠，控制溶液的pH值为3~3.5，过滤去除浸出液中的沉淀，得到初级净化硫酸锰溶液；第二步是在初级净化硫酸锰溶液中继续加入磷酸钠，控制最终的pH值在4.0~4.5之间，过滤并反复洗涤，得到高纯磷酸锰产品。A method for preparing high-purity manganese phosphate from a low-grade rhodochrosite leaching solution, using the sulfuric acid leaching solution of rhodochrosite with a grade ≤ 14% as a raw material, and using sodium phosphate as a pH regulator and a precipitating agent. The method mainly includes the following two steps: the process It mainly includes two steps: the first step is to add sodium phosphate to the sulfuric acid leaching solution of rhodochrosite, control the pH value of the solution to 3~3.5, filter and remove the precipitate in the leaching solution, and obtain the primary purified manganese sulfate solution; the second step is to Continue to add sodium phosphate to the purified manganese sulfate solution, control the final pH value between 4.0 and 4.5, filter and wash repeatedly to obtain high-purity manganese phosphate products.
其中，操作温度在20~80℃范围内，菱锰矿的硫酸浸出液浓度为75~120g/L，磷酸钠溶液浓度为10~20g/L。Among them, the operating temperature is in the range of 20-80°C, the concentration of the sulfuric acid leaching solution of rhodochrosite is 75-120g/L, and the concentration of sodium phosphate solution is 10-20g/L.
制备的磷酸锰纯度高，杂质总含量低于0.05%，其中铁的含量低于0.04%；铝的含量低于0.01%；重金属的含量低于0.01%；钙、镁的含量低于0.01%。The prepared manganese phosphate has high purity, and the total impurity content is less than 0.05%, wherein the content of iron is less than 0.04%, the content of aluminum is less than 0.01%, the content of heavy metal is less than 0.01%, and the content of calcium and magnesium is less than 0.01%.
本发明的优点及有益技术效果：（1）制备过程中只添加了磷酸钠，发挥其作为pH调节剂和沉淀剂的作用，因此在整个制备过程中从外部未向低品位菱锰矿浸出液中引入重金属离子和毒性药剂；（2）本发明的方法第一步去除了低品位菱锰矿浸出液中的铁和铝杂质，同时也去除了通过吸附作用存在于沉淀物表面的重金属离子，第二步在溶液中原位沉淀生成磷酸锰，而钠、钙、镁等以杂质离子形式残留在溶液中，实现锰与其他杂质离子的高效分离；（3）本发明基于溶度——pH值等系统理论分析，确定磷酸钠控制反应体系的pH值得同时作为沉淀剂，实现了体系除杂与高纯材料制备的耦合一体化，突破了“先除杂后制备”的高纯材料的传统工艺，完成了高纯锰产品的短流程低能耗制备。（4）本发明方法制备得到的磷酸锰纯度高、杂质含量少，可作为下游锰相关产品的精细原料。Advantages and beneficial technical effects of the present invention: (1) During the preparation process, only sodium phosphate is added to play its role as a pH regulator and precipitant, so no low-grade rhodochrosite leaching solution is introduced from the outside during the entire preparation process Heavy metal ions and toxic agents; (2) the first step of the method of the present invention removes the iron and aluminum impurities in the low-grade rhodochrosite leachate, and also removes the heavy metal ions present on the surface of the sediment by adsorption. In-situ precipitation in the solution produces manganese phosphate, while sodium, calcium, magnesium, etc. remain in the solution in the form of impurity ions, so as to realize the efficient separation of manganese and other impurity ions; (3) The present invention is based on the theoretical analysis of the solubility-pH value system , determined the pH value of the reaction system controlled by sodium phosphate and used as a precipitant at the same time, realized the coupling integration of system impurity removal and high-purity material preparation, broke through the traditional process of "removing impurities first and then preparing" high-purity materials, and completed the high-purity Short process and low energy consumption preparation of pure manganese products. (4) The manganese phosphate prepared by the method of the present invention has high purity and less impurity content, and can be used as a fine raw material for downstream manganese-related products.
附图说明Description of drawings
图1是实施例1合成的高纯磷酸锰的XRD图谱。Fig. 1 is the XRD collection of patterns of the high-purity manganese phosphate synthesized in embodiment 1.
图2是实施例2合成的高纯磷酸锰的ICP分析结果与菱锰矿浸出液杂质含量的对比柱形图。Fig. 2 is the comparison column chart of the ICP analysis result of the high-purity manganese phosphate synthesized in Example 2 and the impurity content of rhodochrosite leachate.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细描述。应当理解，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
相反，本发明涵盖任何由权利要求定义的在本发明的精髓和范围上做的替代、修改、等效方法以及方案。进一步，为了使公众对本发明有更好的了解，在下文对本发明的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本发明。On the contrary, the invention covers any alternatives, modifications, equivalent methods and schemes within the spirit and scope of the invention as defined by the claims. Further, in order to make the public have a better understanding of the present invention, some specific details are described in detail in the detailed description of the present invention below. The present invention can be fully understood by those skilled in the art without the description of these detailed parts.
实施例1Example 1
菱锰矿的硫酸浸出液浓度为100g/L，量取25ml的浸出液置于反应容器中，加入浓度为20g/L的磷酸钠溶液，直至反应容器中溶液的pH约为3.5，磁力搅拌1h，过滤，得到初级硫酸锰溶液；继续加入浓度为20g/L的磷酸钠溶液，控制溶液pH达到约为4.0，25℃磁力搅拌2h，过滤，洗涤，烘干，得到磷酸锰。The sulfuric acid leaching solution concentration of rhodochrosite is 100g/L, measures the leaching solution of 25ml and is placed in reaction vessel, adds the sodium phosphate solution that concentration is 20g/L, until the pH of solution in reaction vessel is about 3.5, magnetic stirring 1h, filter, Obtain primary manganese sulfate solution; continue to add sodium phosphate solution with a concentration of 20g/L, control the pH of the solution to about 4.0, stir magnetically at 25°C for 2 hours, filter, wash, and dry to obtain manganese phosphate.
得到的磷酸锰中杂质总含量低于0.05%，其中铁的含量低于0.04%；铝的含量低于0.01%；重金属的含量低于0.01%；钙、镁的含量低于0.01%。The total content of impurities in the obtained manganese phosphate is less than 0.05%, wherein the content of iron is less than 0.04%, the content of aluminum is less than 0.01%, the content of heavy metals is less than 0.01%, and the content of calcium and magnesium is less than 0.01%.
图1是合成的高纯磷酸锰的XRD图谱，没有观察到明显的杂质衍射峰，说明得到的磷酸锰纯度较高；另外衍射峰形相对较窄且很尖锐，说明磷酸锰的结晶程度较高。Figure 1 is the XRD spectrum of the synthesized high-purity manganese phosphate, no obvious impurity diffraction peaks are observed, indicating that the obtained manganese phosphate is of high purity; in addition, the diffraction peak shape is relatively narrow and sharp, indicating that the crystallization degree of manganese phosphate is relatively high .
实施例2Example 2
菱锰矿的硫酸浸出液浓度为80g/L，量取25ml的浸出液置于反应容器中，加入浓度为15g/L的磷酸钠溶液，直至反应容器中溶液的pH约为3.0，磁力搅拌1h，过滤，得到初级硫酸锰溶液；继续加入浓度为15g/L的磷酸钠溶液，控制溶液pH达到约为4.5，70℃磁力搅拌2h，过滤，洗涤，烘干，得到磷酸锰。The concentration of the sulfuric acid leaching solution of rhodochrosite is 80g/L, measure the leaching solution of 25ml and be placed in the reaction vessel, add the sodium phosphate solution that concentration is 15g/L, until the pH of solution in the reaction vessel is about 3.0, magnetic stirring 1h, filter, Obtain primary manganese sulfate solution; continue to add sodium phosphate solution with a concentration of 15g/L, control the pH of the solution to about 4.5, stir magnetically at 70°C for 2 hours, filter, wash, and dry to obtain manganese phosphate.
图2是合成的高纯磷酸锰的ICP分析结果与菱锰矿浸出液杂质含量的对比柱形图。通过本发明方法合成的磷酸锰中杂质总含量为0.048%，低于0.05%；其中杂质铁的含量为0.034%，低于0.04%；而铝、钙、镁及重金属的含量分别为0.004%、0.002%、0.006%和0.002%，均低于0.01%，证实了通过本发明方法合成了高纯磷酸锰。Fig. 2 is a comparison bar chart of the ICP analysis result of the synthesized high-purity manganese phosphate and the impurity content of the rhodochrosite leach solution. The total content of impurities in the manganese phosphate synthesized by the inventive method is 0.048%, less than 0.05%; wherein the content of impurity iron is 0.034%, less than 0.04%; and the contents of aluminum, calcium, magnesium and heavy metals are respectively 0.004%, 0.004%, 0.002%, 0.006% and 0.002%, all lower than 0.01%, confirmed that high-purity manganese phosphate was synthesized by the method of the present invention.
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| CN112374929A (en) * | 2020-09-30 | 2021-02-19 | 宁夏天元锰材料研究院(有限公司) | Production process for continuously purifying electrolytic manganese neutral solution and co-producing compound fertilizer |
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