WO2024016444A1 - Prussian white wastewater recycling method and use - Google Patents

Prussian white wastewater recycling method and use Download PDF

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WO2024016444A1
WO2024016444A1 PCT/CN2022/118002 CN2022118002W WO2024016444A1 WO 2024016444 A1 WO2024016444 A1 WO 2024016444A1 CN 2022118002 W CN2022118002 W CN 2022118002W WO 2024016444 A1 WO2024016444 A1 WO 2024016444A1
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wastewater
prussian white
solution
manganese
prussian
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French (fr)
Chinese (zh)
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李永光
李长东
徐学留
刘更好
阮丁山
蔡勇
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Definitions

  • the invention belongs to the technical field of battery material preparation, and specifically relates to a method and application of recycling Prussian white wastewater.
  • Prussian white belongs to the Prussian blue compound. Because it contains high sodium (Prussian blue only contains one sodium), it appears white, so it is called Prussian white. Prussian white is an important cathode material for sodium-ion batteries. The current production of Prussian white produces a large amount of wastewater, which contains a high concentration of ferricyanide. Although ferricyanide has low toxicity and a relatively stable structure, it is difficult to produce highly toxic cyanide. However, the wastewater discharge indicators stipulate that the total cyanide content is ⁇ 1 mg/L, and there is no distinction between types of cyanide.
  • Prussian white wastewater containing low-toxic ferricyanide also needs to be treated and discharged with a total cyanide content of ⁇ 1mg/L, which undoubtedly increases the difficulty and cost of Prussian white wastewater treatment.
  • Prussian white wastewater also contains a large amount of complexing agents, which not only increases the difficulty of treatment, but also causes a waste of resources in direct treatment.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recycling Prussian white wastewater, which can significantly reduce the total amount of wastewater, and produce Prussian white products with stable quality through wastewater recycling.
  • the first aspect of the present invention provides a method for recycling Prussian white wastewater.
  • a method for recycling Prussian white wastewater includes the following steps:
  • the Prussian white wastewater contains ferrocyanide salt, sulfate, nitrate or chloride salt.
  • concentration of the ferrocyanide salt in the Prussian white wastewater is 0.002-0.03mol/L
  • concentration of the sulfate is 0.2-0.8mol/L
  • concentration of the nitrate and chloride salt is The concentration is 0.4-1.6mol/L.
  • the concentration of ferrocyanide salt in the mixed solution A is 0.3-0.6 mol/L; further preferably, the concentration of ferrocyanide salt in the mixed solution A is 0.4 -0.6mol/L.
  • the manganese salt in the manganese salt solution is selected from at least one of manganese sulfate, manganese nitrate, manganese chloride or manganese oxalate.
  • the manganese salt solution is actually for slurry.
  • the concentration of manganese salt in the manganese salt solution is 0.4-2.0 mol/L; further preferably, the concentration of manganese salt in the manganese salt solution is 1.0-2.0 mol/L.
  • the salt concentration In solution preparation, the salt concentration must not exceed the solubility of the material and the salt dissolution efficiency must not be significantly reduced. The higher the solution concentration, the better, and the less wastewater will be generated.
  • Research has found that by controlling the concentration of ferrocyanide salt in mixed solution A to 0.3-0.6mol/L, and the concentration of manganese salt in the manganese salt solution to 0.4-2.0mol/L, while effectively reducing the amount of wastewater, It is conducive to the continuous and stable progress of the reaction and the preparation of Prussian white with stable quality.
  • the manganese salt solution is prepared with Prussian white wastewater or pure water.
  • the manganese salt solution can be prepared with pure water or waste water. Using pure water to prepare the manganese salt solution can effectively dilute the salt concentration in the wastewater; when used in conjunction with wastewater preparation, the Prussian white wastewater can be fully recycled while controlling the salt concentration in the wastewater.
  • the manganese salt solution Before preparing the manganese salt solution, first add manganese salt to the Prussian white wastewater, so that the excess ferrocyanide salt in the Prussian white wastewater can fully react with the manganese salt to obtain Prussian white slag, which can then be removed by filtration, which can effectively prevent the solution from appearing again. Precipitate to prevent clogging of metering pumps and reactor inlet pipes. The obtained Prussian white slag can be returned to the co-precipitation and aging process. Due to its small particle size, it is easy to dissolve and recrystallize without affecting the overall performance of the product.
  • the amount of manganese salt added for the first time is 2-3 times the amount of ferrocyanide salt in the Prussian white wastewater.
  • the manganese salt solution can be prepared alone or mixed with a complexing agent.
  • the complexing agent is selected from at least one of citric acid, maleic acid, citric acid, ethylenediaminetetraacetic acid, sodium citrate or ammonia.
  • the concentration of the complexing agent solution is 0.4-15 mol/L; further preferably, the concentration of the complexing agent solution is 0.4-3 mol/L.
  • the protective atmosphere is nitrogen.
  • step (2) the flow rates of the mixed solution A, the manganese salt solution and the complexing agent solution are controlled by a metering pump; the flow rate of the complexing agent solution is 0.1-0.1 of the flow rate of the manganese salt solution. 3 times.
  • step (2) the pH of the precipitation reaction is maintained at 6.5-9.5 by controlling the flow rate of the ferrocyanide salt. Further preferably, in step (2), by controlling the flow rate of the ferrocyanide salt, the pH of the precipitation reaction is maintained at 7.0-8.5.
  • the aging time is 3-48 hours.
  • the temperature of the precipitation reaction is 30-98°C; further preferably, the temperature of the precipitation reaction is 60-95°C.
  • a method for recycling Prussian white wastewater includes the following steps:
  • the second aspect of the present invention provides the application of the above-mentioned Prussian white wastewater recycling method in preparing Prussian white.
  • the method for recycling Prussian white wastewater is to filter the Prussian white wastewater to remove the filter residue, prepare a mixed solution A containing ferrocyanide salts and a manganese salt solution, and then perform a reaction to prepare Prussian white.
  • Continuous recycling of wastewater can significantly reduce the total amount of wastewater. Taking a 1000L reactor as an example, when only Prussian white wastewater is used to prepare sodium ferrocyanide solution, about 900L of mother liquor and about 300L of washing water are produced every day, and the total wastewater is about 1200L. 400L of wastewater is recovered each time for liquid preparation. The reuse rate can reach 33%.
  • the salt content in the wastewater will not increase indefinitely, but will remain stable after multiple cycles. When reusing the solution, the salt content will not exceed the solubility of the material.
  • the method for recycling Prussian white wastewater provided by the present invention can also effectively reduce the amount of complexing agent. Since the wastewater contains a large amount of complexing agent, when the wastewater is used to prepare the sodium ferrocyanide solution, the complexing agent re-enters the process flow and can continue to play a complexing role during the reaction process, thereby reducing the subsequent consumption of the complexing agent.
  • Usage amount The amount of reused complexing agent can reach 33-90% of the amount used in a single reaction.
  • the present invention recycles Prussian white wastewater to prepare Prussian white.
  • the materials used are the same as those used in the original reaction. No new impurities are introduced and will not have a negative impact on the reaction.
  • Prussian white products prepared through wastewater reuse are consistent with Prussian white products prepared by normal production processes. Their morphology and particle size distribution are normal, and their specific surface area and tap density are basically the same as normal products.
  • the sodium-ion batteries prepared using them are also It has good specific capacity and excellent product performance.
  • Figure 1 is a process flow diagram for the recycling of Prussian white wastewater in Embodiment 1;
  • Figure 2 is an SEM image of the Prussian white product prepared in Example 1;
  • Figure 3 is an SEM image of the Prussian white product produced in Comparative Example 1.
  • the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources, or can be obtained by existing known methods.
  • a method for recycling Prussian white wastewater including the following steps:
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
  • the above-mentioned Prussian white wastewater can be recycled indefinitely, but in practice it will be limited by the size of the wastewater storage tank. After the recycling reaches stability, the concentration of sodium ferrocyanide in the Prussian white wastewater is about 0.02 mol/L, and the concentration of sodium sulfate is about 0.25 mol/L, which does not interfere with the liquid preparation in step (1) at all.
  • a method for recycling Prussian white wastewater including the following steps:
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 800L pure water. Mix the washing water with the mother liquor to obtain 2500L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
  • a method for recycling Prussian white wastewater including the following steps:
  • (1) Prepare solution: filter 1200L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.02mol/L, and the concentration of sodium nitrate is about 0.9mol/L) through a precision filter to remove the residue in the wastewater , and then mixed and stirred with 300kg sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4 mol/L. Then use pure water to prepare a mixed solution of manganese nitrate and citric acid, in which the concentration of manganese nitrate is 2mol/L and the concentration of citric acid is 0.4mol/L.
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 600L pure water. Mix the washing water with the mother liquor to obtain 2300L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
  • a method for recycling Prussian white wastewater including the following steps:
  • a mixed solution of diamine tetraacetic acid in which the concentration of manganese sulfate is 1.5mol/L and the concentration of ethylenediaminetetraacetic acid is 0.3mol/L.
  • the filter residue is returned to the co-precipitation and aging process for reuse.
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
  • a method for recycling Prussian white wastewater including the following steps:
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
  • Comparative Example 1 adopts conventional methods to prepare Prussian white products, that is, pure water is used for liquid preparation, and waste water is not reused.
  • step (3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water; The filter cake is dried to obtain a Prussian white product.
  • Particle size (D10, D50, D90) is detected with a dry particle size analyzer.
  • the physical and chemical parameters of the Prussian white product prepared in Example 1 are almost consistent with the Prussian white product prepared by the normal production process in Comparative Example 1. Its particle size distribution is normal, the morphology is normal, and the specific surface area and tap density are the same as those of the normal product. Basically the same, the sodium-ion battery prepared using it also has good specific capacity. It can be seen that the use of the method provided by the present invention to recycle Prussian white wastewater to prepare Prussian white will not affect the quality of the product. The sodium ion battery prepared by using the method also has a high specific capacity and excellent product performance.

Abstract

The present invention relates to the technical field of battery material preparation. Disclosed are a Prussian white wastewater recycling method and a use. The method comprises: filtering Prussian white wastewater to remove filter residues, and then mixing same with a ferrocyanide salt to obtain a mixed solution A; preparing a manganese salt solution and a complexing agent solution; carrying out a precipitation reaction in a protective atmosphere, aging, filtering to obtain a filter residue and a filtrate, and then washing and drying the filter residue to obtain Prussian white; and collecting the filtrate and wastewater generated during washing to obtain new Prussian white wastewater, and repeating the process one or more times by using the new Prussian white wastewater. The method can greatly reduce the total amount of wastewater and effectively reduce the usage amount of a complexing agent; the Prussian white prepared by recycling wastewater has normal morphology and particle size distribution, the specific surface area and the tap density are consistent with those of a normal product, and a sodium ion battery prepared by using the Prussian white also has good specific capacity and excellent product performance.

Description

一种普鲁士白废水循环使用的方法和应用A method and application of Prussian white wastewater recycling 技术领域Technical field
本发明属于电池材料制备技术领域，具体涉及一种普鲁士白废水循环使用的方法和应用。The invention belongs to the technical field of battery material preparation, and specifically relates to a method and application of recycling Prussian white wastewater.
背景技术Background technique
普鲁士白属于普鲁士蓝类化合物，由于含有高钠(普鲁士蓝只含一个钠)，呈现白色，所以称为普鲁士白。普鲁士白是重要的钠离子电池正极材料。目前普鲁士白的生产中会产生大量废水，这种废水含有较高浓度的铁氰根。虽然铁氰根的毒性低，结构相对较稳定，很难产生出剧毒的氰化物，但在废水的排放指标中，规定总氰含量<1mg/L，并没有对氰根种类进行区分。因此含有低毒性的铁氰根的普鲁士白废水也需要按总氰含量<1mg/L进行处理和排放，这无疑增加了普鲁士白废水处理的难度和成本。此外，普鲁士白废水中还含有大量的络合剂，不仅增加处理难度，而且直接处理造成资源的浪费。Prussian white belongs to the Prussian blue compound. Because it contains high sodium (Prussian blue only contains one sodium), it appears white, so it is called Prussian white. Prussian white is an important cathode material for sodium-ion batteries. The current production of Prussian white produces a large amount of wastewater, which contains a high concentration of ferricyanide. Although ferricyanide has low toxicity and a relatively stable structure, it is difficult to produce highly toxic cyanide. However, the wastewater discharge indicators stipulate that the total cyanide content is <1 mg/L, and there is no distinction between types of cyanide. Therefore, Prussian white wastewater containing low-toxic ferricyanide also needs to be treated and discharged with a total cyanide content of <1mg/L, which undoubtedly increases the difficulty and cost of Prussian white wastewater treatment. In addition, Prussian white wastewater also contains a large amount of complexing agents, which not only increases the difficulty of treatment, but also causes a waste of resources in direct treatment.
因此，亟需提供一种普鲁士白废水合理利用或处理的方法，减少废水处理的难度和成本。Therefore, there is an urgent need to provide a method for rational utilization or treatment of Prussian white wastewater to reduce the difficulty and cost of wastewater treatment.
发明内容Contents of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种普鲁士白废水循环使用的方法，能够大幅度减少废水总量，通过废水循环使用能够制备出质量稳定的普鲁士白产品。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recycling Prussian white wastewater, which can significantly reduce the total amount of wastewater, and produce Prussian white products with stable quality through wastewater recycling.
本发明第一方面提供了一种普鲁士白废水循环使用的方法。The first aspect of the present invention provides a method for recycling Prussian white wastewater.
具体地，一种普鲁士白废水循环使用的方法，包括以下步骤：Specifically, a method for recycling Prussian white wastewater includes the following steps:
(1)将普鲁士白废水过滤去滤渣，然后与亚铁氰化盐混合，制得混合溶液A；配制锰盐溶液和络合剂溶液；(1) Filter the Prussian white wastewater to remove the filter residue, and then mix it with ferrocyanide salt to prepare mixed solution A; prepare a manganese salt solution and a complexing agent solution;
(2)于保护气氛下将所述混合溶液A、锰盐溶液和络合剂溶液混合，发生沉淀反应得浆料，然后将所述浆料陈化，过滤得滤渣和滤液，再将所述滤渣洗涤、干燥，制得普鲁士白；收集所述滤液和所述洗涤过程产生的废水得新的普鲁士白废水；(2) Mix the mixed solution A, the manganese salt solution and the complexing agent solution under a protective atmosphere, and a precipitation reaction occurs to obtain a slurry. Then the slurry is aged, filtered to obtain the filter residue and filtrate, and then the The filter residue is washed and dried to obtain Prussian white; the filtrate and the wastewater generated by the washing process are collected to obtain new Prussian white wastewater;
(3)利用所述新的普鲁士白废水重复一次或多次步骤(1)-(2)的过程。(3) Repeat steps (1)-(2) one or more times using the new Prussian white wastewater.
优选地，在步骤(1)中，所述普鲁士白废水中包含亚铁氰化盐、硫酸盐、硝酸盐或氯化 盐。进一步优选地，所述普鲁士白废水中所述亚铁氰化盐的浓度为0.002-0.03mol/L，所述硫酸盐的浓度为0.2-0.8mol/L，所述硝酸盐和氯化盐的浓度为0.4-1.6mol/L。Preferably, in step (1), the Prussian white wastewater contains ferrocyanide salt, sulfate, nitrate or chloride salt. Further preferably, the concentration of the ferrocyanide salt in the Prussian white wastewater is 0.002-0.03mol/L, the concentration of the sulfate is 0.2-0.8mol/L, and the concentration of the nitrate and chloride salt is The concentration is 0.4-1.6mol/L.
优选地，在步骤(1)中，所述混合溶液A中亚铁氰化盐的浓度为0.3-0.6mol/L；进一步优选地，所述混合溶液A中亚铁氰化盐的浓度为0.4-0.6mol/L。Preferably, in step (1), the concentration of ferrocyanide salt in the mixed solution A is 0.3-0.6 mol/L; further preferably, the concentration of ferrocyanide salt in the mixed solution A is 0.4 -0.6mol/L.
优选地，在步骤(1)中，所述锰盐溶液中锰盐选自硫酸锰、硝酸锰、氯化锰或草酸锰中的至少一种，当选用草酸锰时，所述锰盐溶液实际为浆料。Preferably, in step (1), the manganese salt in the manganese salt solution is selected from at least one of manganese sulfate, manganese nitrate, manganese chloride or manganese oxalate. When manganese oxalate is selected, the manganese salt solution is actually for slurry.
优选地，在步骤(1)中，所述锰盐溶液中锰盐的浓度为0.4-2.0mol/L；进一步优选地，所述锰盐溶液中锰盐的浓度为1.0-2.0mol/L。Preferably, in step (1), the concentration of manganese salt in the manganese salt solution is 0.4-2.0 mol/L; further preferably, the concentration of manganese salt in the manganese salt solution is 1.0-2.0 mol/L.
溶液配制中，控制盐浓度不超过物料的溶解度并且不明显降低盐溶解效率的情况下，配液浓度越高越好，产生的废水量就越少。研究发现，通过控制混合溶液A中亚铁氰化盐的浓度为0.3-0.6mol/L，所述锰盐溶液中锰盐的浓度为0.4-2.0mol/L，在有效减少废水量的同时，有利于反应的持续稳定进行，制备出质量稳定的普鲁士白。In solution preparation, the salt concentration must not exceed the solubility of the material and the salt dissolution efficiency must not be significantly reduced. The higher the solution concentration, the better, and the less wastewater will be generated. Research has found that by controlling the concentration of ferrocyanide salt in mixed solution A to 0.3-0.6mol/L, and the concentration of manganese salt in the manganese salt solution to 0.4-2.0mol/L, while effectively reducing the amount of wastewater, It is conducive to the continuous and stable progress of the reaction and the preparation of Prussian white with stable quality.
优选地，在步骤(1)中，所述锰盐溶液采用普鲁士白废水或纯水进行配制。Preferably, in step (1), the manganese salt solution is prepared with Prussian white wastewater or pure water.
锰盐溶液可以用纯水配液，也可以用废水配液。采用纯水配制所述锰盐溶液，可以有效稀释废水中的盐浓度；与采用废水配液配合使用，能够在控制废水中盐浓度的同时使普鲁士白废水得到充分循环使用。The manganese salt solution can be prepared with pure water or waste water. Using pure water to prepare the manganese salt solution can effectively dilute the salt concentration in the wastewater; when used in conjunction with wastewater preparation, the Prussian white wastewater can be fully recycled while controlling the salt concentration in the wastewater.
优选地，当采用普鲁士白废水进行配制时，包括如下步骤：Preferably, when using Prussian white wastewater for preparation, the following steps are included:
向普鲁士白废水中第一次加入锰盐，过滤去滤渣，然后第二次加入锰盐，制得所述锰盐溶液。Add manganese salt to the Prussian white wastewater for the first time, filter out the filter residue, and then add manganese salt for the second time to prepare the manganese salt solution.
在配制锰盐溶液之前，先向普鲁士白废水中加入锰盐，使普鲁士白废水中过量的亚铁氰化盐与锰盐充分反应得到普鲁士白渣，然后通过过滤去除，能够有效避免溶液再次出现沉淀，防止堵塞计量泵和反应釜进液管。得到的普鲁士白渣能够返投回共沉淀、陈化工序中，由于粒度小，很容易溶解再结晶，不会影响产品整体性能。Before preparing the manganese salt solution, first add manganese salt to the Prussian white wastewater, so that the excess ferrocyanide salt in the Prussian white wastewater can fully react with the manganese salt to obtain Prussian white slag, which can then be removed by filtration, which can effectively prevent the solution from appearing again. Precipitate to prevent clogging of metering pumps and reactor inlet pipes. The obtained Prussian white slag can be returned to the co-precipitation and aging process. Due to its small particle size, it is easy to dissolve and recrystallize without affecting the overall performance of the product.
优选地，所述第一次加入锰盐的物质的量为所述普鲁士白废水中亚铁氰化盐的物质的量的2-3倍。Preferably, the amount of manganese salt added for the first time is 2-3 times the amount of ferrocyanide salt in the Prussian white wastewater.
优选地，当采用纯水配制锰盐溶液时，所述锰盐溶液可以单独配液，也可以与络合剂配制成混合溶液。Preferably, when pure water is used to prepare the manganese salt solution, the manganese salt solution can be prepared alone or mixed with a complexing agent.
优选地，在步骤(1)中，所述络合剂选自柠檬酸、马来酸、枸杞酸、乙二胺四乙酸、柠檬酸钠或氨水中的至少一种。Preferably, in step (1), the complexing agent is selected from at least one of citric acid, maleic acid, citric acid, ethylenediaminetetraacetic acid, sodium citrate or ammonia.
优选地，在步骤(1)中，所述络合剂溶液的浓度为0.4-15mol/L；进一步优选地，所述络合剂溶液的浓度为0.4-3mol/L。Preferably, in step (1), the concentration of the complexing agent solution is 0.4-15 mol/L; further preferably, the concentration of the complexing agent solution is 0.4-3 mol/L.
优选地，在步骤(2)中，所述保护气氛为氮气。Preferably, in step (2), the protective atmosphere is nitrogen.
优选地，在步骤(2)中，通过计量泵控制所述混合溶液A、锰盐溶液和络合剂溶液的流量；所述络合剂溶液的流量是所述锰盐溶液的流量的0.1-3倍。Preferably, in step (2), the flow rates of the mixed solution A, the manganese salt solution and the complexing agent solution are controlled by a metering pump; the flow rate of the complexing agent solution is 0.1-0.1 of the flow rate of the manganese salt solution. 3 times.
优选地，在步骤(2)中，通过控制所述亚铁氰化盐的流量，保持所述沉淀反应的pH为6.5-9.5。进一步优选地，在步骤(2)中，通过控制所述亚铁氰化盐的流量，保持所述沉淀反应的pH为7.0-8.5。Preferably, in step (2), the pH of the precipitation reaction is maintained at 6.5-9.5 by controlling the flow rate of the ferrocyanide salt. Further preferably, in step (2), by controlling the flow rate of the ferrocyanide salt, the pH of the precipitation reaction is maintained at 7.0-8.5.
优选地，在步骤(2)中，所述陈化的时间为3-48h。Preferably, in step (2), the aging time is 3-48 hours.
优选地，在步骤(2)中，所述沉淀反应的温度为30-98℃；进一步优选地，所述沉淀反应的温度为60-95℃。Preferably, in step (2), the temperature of the precipitation reaction is 30-98°C; further preferably, the temperature of the precipitation reaction is 60-95°C.
更为具体地，一种普鲁士白废水循环使用的方法，包括以下步骤：More specifically, a method for recycling Prussian white wastewater includes the following steps:
(1)将普鲁士白废水过滤去滤渣，然后与亚铁氰化盐混合，制得亚铁***浓度为0.3-0.6mol/L的混合溶液A；配制浓度为0.4-2mol/L的锰盐溶液和浓度为0.4-15mol/L的络合剂溶液；(1) Filter the Prussian white wastewater to remove the filter residue, and then mix it with ferrocyanide salt to prepare a mixed solution A with a sodium ferrocyanide concentration of 0.3-0.6 mol/L; prepare manganese with a concentration of 0.4-2 mol/L Salt solution and complexing agent solution with a concentration of 0.4-15mol/L;
(2)向反应釜中加入纯水，开启搅拌，升高温度至30-98℃，通入保护气体，将所述亚铁***溶液、锰盐溶液和络合剂溶液用计量泵同时泵入反应釜中，所述络合剂溶液的流量是所述锰盐溶液的流量的0.1-3倍，对应的用量摩尔比为0.1-20倍，反应釜中发生沉淀反应得浆料，控制亚铁氰化盐的流量，保持所述沉淀反应时pH值为6.5-9.5，然后将所述浆料陈化3-48h，再经过滤得滤渣和滤液，将所述滤渣洗涤、干燥，制得所述普鲁士白；收集所述滤液和所述洗涤过程产生的废水得新的普鲁士白废水，将新的普鲁士白废水继续进行步骤(1)的过程。(2) Add pure water to the reaction kettle, start stirring, raise the temperature to 30-98°C, introduce protective gas, and use a metering pump to add the sodium ferrocyanide solution, manganese salt solution and complexing agent solution simultaneously Pump into the reaction kettle, the flow rate of the complexing agent solution is 0.1-3 times the flow rate of the manganese salt solution, and the corresponding molar ratio of the amount is 0.1-20 times. A precipitation reaction occurs in the reaction kettle to obtain a slurry. Control The flow rate of ferrocyanide salt is maintained at a pH value of 6.5-9.5 during the precipitation reaction. The slurry is then aged for 3-48 hours, and then filtered to obtain the filter residue and filtrate. The filter residue is washed and dried to prepare The Prussian white is obtained; the filtrate and the wastewater generated by the washing process are collected to obtain new Prussian white wastewater, and the new Prussian white wastewater is continued to the process of step (1).
本发明第二方面提供了上述普鲁士白废水循环使用的方法在制备普鲁士白中的应用。The second aspect of the present invention provides the application of the above-mentioned Prussian white wastewater recycling method in preparing Prussian white.
相对于现有技术，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
(1)本发明提供的普鲁士白废水循环使用的方法，通过将普鲁士白废水过滤去滤渣，配 制含亚铁氰化盐的混合溶液A和锰盐溶液，然后进行反应制备普鲁士白，对产生的废水不断循环使用，可以大幅度减少废水总量。以1000L反应釜为例，在仅采用普鲁士白废水配制亚铁***溶液的情况下，每天产生的母液约900L，洗涤水约300L，总计废水约1200L，每次回收400L废水进行配液，回用率可以达到33％。同时，由于纯水和洗涤水的加入，废水中的盐含量不会无限提高，而是在多次循环使用后保持稳定，在回用配液时，盐含量不会超过物料的溶解度。(1) The method for recycling Prussian white wastewater provided by the present invention is to filter the Prussian white wastewater to remove the filter residue, prepare a mixed solution A containing ferrocyanide salts and a manganese salt solution, and then perform a reaction to prepare Prussian white. Continuous recycling of wastewater can significantly reduce the total amount of wastewater. Taking a 1000L reactor as an example, when only Prussian white wastewater is used to prepare sodium ferrocyanide solution, about 900L of mother liquor and about 300L of washing water are produced every day, and the total wastewater is about 1200L. 400L of wastewater is recovered each time for liquid preparation. The reuse rate can reach 33%. At the same time, due to the addition of pure water and washing water, the salt content in the wastewater will not increase indefinitely, but will remain stable after multiple cycles. When reusing the solution, the salt content will not exceed the solubility of the material.
(2)本发明提供的普鲁士白废水循环使用的方法，还能够有效减少络合剂的用量。由于废水中含有大量的络合剂，在采用废水配制亚铁***溶液时，络合剂重新进入工艺流程，在反应过程中可以继续起到络合作用，从而减少后续的络合剂的使用量，回用的络合剂用量可以达到单次反应用量的33-90％。(2) The method for recycling Prussian white wastewater provided by the present invention can also effectively reduce the amount of complexing agent. Since the wastewater contains a large amount of complexing agent, when the wastewater is used to prepare the sodium ferrocyanide solution, the complexing agent re-enters the process flow and can continue to play a complexing role during the reaction process, thereby reducing the subsequent consumption of the complexing agent. Usage amount: The amount of reused complexing agent can reach 33-90% of the amount used in a single reaction.
(3)本发明循环使用普鲁士白废水制备普鲁士白，所用的物料均与原初反应的物料相同，并未引入新的杂质，不会对反应产生恶劣影响。通过废水回用制备出的普鲁士白产品，与正常生产工艺制备的普鲁士白产品一致，其形貌、粒度分布正常，比表面积和振实密度与正常产品基本一致，利用其制备的钠离子电池也具有良好的比容量，产品性能优良。(3) The present invention recycles Prussian white wastewater to prepare Prussian white. The materials used are the same as those used in the original reaction. No new impurities are introduced and will not have a negative impact on the reaction. Prussian white products prepared through wastewater reuse are consistent with Prussian white products prepared by normal production processes. Their morphology and particle size distribution are normal, and their specific surface area and tap density are basically the same as normal products. The sodium-ion batteries prepared using them are also It has good specific capacity and excellent product performance.
附图说明Description of drawings
图1为实施例1中普鲁士白废水循环使用的工艺流程图；Figure 1 is a process flow diagram for the recycling of Prussian white wastewater in Embodiment 1;
图2为实施例1制得的普鲁士白产品的SEM图；Figure 2 is an SEM image of the Prussian white product prepared in Example 1;
图3为对比例1制得的普鲁士白产品的SEM图。Figure 3 is an SEM image of the Prussian white product produced in Comparative Example 1.
具体实施方式Detailed ways
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。In order to allow those skilled in the art to understand the technical solution of the present invention more clearly, the following examples are listed for description. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources, or can be obtained by existing known methods.
实施例1Example 1
一种普鲁士白废水循环使用的方法，包括以下步骤：A method for recycling Prussian white wastewater, including the following steps:
(1)配制溶液：将400L普鲁士白废水(废水中亚铁***浓度约为0.01mol/L，硫酸钠浓度约为0.2mol/L)通过精密过滤器过滤，除掉废水中的残渣，然后与100kg亚铁***混 合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A；再分别配制浓度为1.5mol/L硫酸锰溶液和浓度为2mol/L柠檬酸钠溶液。(1) Prepare the solution: Filter 400L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.01mol/L, the concentration of sodium sulfate is about 0.2mol/L) through a precision filter to remove the residue in the wastewater. Then mix and stir with 100kg sodium ferrocyanide to obtain a mixed solution A with a concentration of sodium ferrocyanide of 0.4mol/L; then prepare a manganese sulfate solution with a concentration of 1.5mol/L and a sodium citrate solution with a concentration of 2mol/L. solution.
(2)反应制备普鲁士白：向1000L反应釜中加入200L纯水，开启搅拌，升高温度至90℃，通入氮气，将混合溶液A、硫酸锰溶液、柠檬酸钠溶液用计量泵同时泵入反应釜中，硫酸锰溶液的流量为15L/h，柠檬酸钠溶液的流量是硫酸锰溶液流量的1.5倍，溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为8.2，将反应后的物料陈化16h，得反应浆料。(2) Preparation of Prussian White by reaction: Add 200L pure water to the 1000L reaction kettle, start stirring, raise the temperature to 90°C, pass in nitrogen, and pump mixed solution A, manganese sulfate solution, and sodium citrate solution simultaneously with a metering pump into the reaction kettle, the flow rate of the manganese sulfate solution is 15L/h, the flow rate of the sodium citrate solution is 1.5 times the flow rate of the manganese sulfate solution, the solution undergoes a precipitation reaction in the reaction kettle, control the flow rate of the mixed solution A, and keep the reaction pH at 8.2. Aging the reacted materials for 16 hours to obtain reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用300L纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到1200L废水，将废水收集在废水槽中，回到步骤(1)继续过滤循环使用；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
以上方法的工艺流程图如图1所示。The process flow chart of the above method is shown in Figure 1.
理论上，上述普鲁士白废水可以无限循环使用，但在实际中会受限于废水储罐容积的大小。在循环使用达到稳定后，普鲁士白废水中亚铁***浓度约为0.02mol/L，硫酸钠的浓度约为0.25mol/L，完全不干扰步骤(1)中的配液。Theoretically, the above-mentioned Prussian white wastewater can be recycled indefinitely, but in practice it will be limited by the size of the wastewater storage tank. After the recycling reaches stability, the concentration of sodium ferrocyanide in the Prussian white wastewater is about 0.02 mol/L, and the concentration of sodium sulfate is about 0.25 mol/L, which does not interfere with the liquid preparation in step (1) at all.
实施例2Example 2
一种普鲁士白废水循环使用的方法，包括以下步骤：A method for recycling Prussian white wastewater, including the following steps:
(1)配制溶液：将1000L普鲁士白废水(废水中亚铁***浓度约为0.02mol/L，硫酸钠浓度约为0.3mol/L)通过精密过滤器过滤，除掉废水中的残渣，然后与250kg亚铁***混合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A。将420L普鲁士白废水与3.5kg硫酸锰混合、搅拌，使废水中过量的亚铁***与硫酸锰充分反应得到少量普鲁士白，再将废水过滤得滤液，采用该滤液配制浓度为1mol/L的硫酸锰溶液，滤渣则返回共沉淀和陈化工序再次利用。最后采用纯水配制浓度为2mol/L的柠檬酸钠溶液。(1) Prepare the solution: Filter 1000L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.02mol/L, and the concentration of sodium sulfate is about 0.3mol/L) through a precision filter to remove the residue in the wastewater. Then mix and stir with 250 kg of sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4 mol/L. Mix and stir 420L Prussian white wastewater with 3.5kg manganese sulfate to fully react with excess sodium ferrocyanide and manganese sulfate in the wastewater to obtain a small amount of Prussian white. Then filter the wastewater to obtain a filtrate. Use this filtrate to prepare a concentration of 1mol/L of manganese sulfate solution, and the filter residue is returned to the co-precipitation and aging process for reuse. Finally, use pure water to prepare a sodium citrate solution with a concentration of 2 mol/L.
(2)反应制备普鲁士白：向2000L反应釜中加入400L纯水，开启搅拌，升高温度至95℃，通入氮气，将混合溶液A、硫酸锰溶液、柠檬酸钠溶液用计量泵同时泵入反应釜中，硫酸锰溶液的流量为20L/h，柠檬酸钠溶液的流量为5L/h。溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为8.5，将反应后的物料陈化8h，得反应浆料。(2) Preparation of Prussian white by reaction: Add 400L pure water to the 2000L reaction kettle, start stirring, raise the temperature to 95°C, pass in nitrogen, and pump mixed solution A, manganese sulfate solution, and sodium citrate solution simultaneously with a metering pump Into the reaction kettle, the flow rate of the manganese sulfate solution is 20L/h, and the flow rate of the sodium citrate solution is 5L/h. The solution undergoes a precipitation reaction in the reaction kettle. Control the flow rate of the mixed solution A to keep the reaction pH at 8.5. Aging the reacted material for 8 hours to obtain a reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用800L 纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到2500L废水，将废水收集在废水槽中，回到步骤(1)继续过滤循环使用；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 800L pure water. Mix the washing water with the mother liquor to obtain 2500L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
实施例3Example 3
一种普鲁士白废水循环使用的方法，包括以下步骤：A method for recycling Prussian white wastewater, including the following steps:
(1)配制溶液：将1200L普鲁士白废水(废水中亚铁***浓度约为0.02mol/L，硝酸钠的浓度约为0.9mol/L)通过精密过滤器过滤，除掉废水中的残渣，然后与300kg亚铁***混合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A。再采用纯水配制硝酸锰与柠檬酸混合溶液，其中，硝酸锰浓度为2mol/L，柠檬酸浓度为0.4mol/L。(1) Prepare solution: filter 1200L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.02mol/L, and the concentration of sodium nitrate is about 0.9mol/L) through a precision filter to remove the residue in the wastewater , and then mixed and stirred with 300kg sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4 mol/L. Then use pure water to prepare a mixed solution of manganese nitrate and citric acid, in which the concentration of manganese nitrate is 2mol/L and the concentration of citric acid is 0.4mol/L.
(2)反应制备普鲁士白：向2000L反应釜中加入350L纯水，开启搅拌，升高温度至70℃，通入氮气，将混合溶液A、硝酸锰与柠檬酸的混合溶液用计量泵同时泵入反应釜中，硝酸锰与柠檬酸的混合溶液的流量为15L/h。溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为7.2，将反应后的物料陈化24h，得反应浆料。(2) Preparation of Prussian white by reaction: Add 350L pure water to the 2000L reaction kettle, start stirring, raise the temperature to 70°C, pass in nitrogen, and pump mixed solution A, manganese nitrate and citric acid simultaneously with a metering pump Into the reaction kettle, the flow rate of the mixed solution of manganese nitrate and citric acid is 15L/h. The solution undergoes a precipitation reaction in the reaction kettle. Control the flow rate of the mixed solution A to keep the reaction pH at 7.2. Aging the reacted material for 24 hours to obtain a reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用600L纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到2300L废水，将废水收集在废水槽中，回到步骤(1)继续过滤循环使用；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 600L pure water. Mix the washing water with the mother liquor to obtain 2300L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
实施例4Example 4
一种普鲁士白废水循环使用的方法，包括以下步骤：A method for recycling Prussian white wastewater, including the following steps:
(1)配制溶液：将500L普鲁士白废水(废水中亚铁***浓度约为0.02mol/L，硫酸钠浓度约为0.4mol/L)通过精密过滤器过滤，除掉废水中的残渣，然后与125kg亚铁***混合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A。将150L普鲁士白废水通与1.2kg硫酸锰混合、搅拌，使废水中过量的亚铁***与硫酸锰充分反应得到少量普鲁士白，再将废水过滤得滤液，用该滤液配制硫酸锰与乙二胺四乙酸的混合溶液，其中，硫酸锰浓度为1.5mol/L，乙二胺四乙酸浓度为0.3mol/L。滤渣则返回共沉淀和陈化工序再次利用。(1) Prepare the solution: Filter 500L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.02mol/L, and the concentration of sodium sulfate is about 0.4mol/L) through a precision filter to remove the residue in the wastewater. Then mix and stir with 125kg sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4 mol/L. Mix and stir 150L Prussian white wastewater with 1.2kg manganese sulfate to fully react with excess sodium ferrocyanide and manganese sulfate in the wastewater to obtain a small amount of Prussian white. Then filter the wastewater to obtain a filtrate, and use the filtrate to prepare manganese sulfate and ethanol. A mixed solution of diamine tetraacetic acid, in which the concentration of manganese sulfate is 1.5mol/L and the concentration of ethylenediaminetetraacetic acid is 0.3mol/L. The filter residue is returned to the co-precipitation and aging process for reuse.
(2)反应制备普鲁士白：向1000L反应釜中加入300L纯水，开启搅拌，升高温度至75℃，通入氮气，将混合溶液A、硫酸锰与乙二胺四乙酸的混合溶液用计量泵同时泵入反应釜中，硫酸锰与乙二胺四乙酸的混合溶液的流量为9L/h。溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为7.0，将反应后的物料陈化24h，得反应浆料。(2) Reaction to prepare Prussian white: Add 300L pure water to the 1000L reaction kettle, start stirring, raise the temperature to 75°C, pass in nitrogen, and mix the mixed solution A, manganese sulfate and ethylenediaminetetraacetic acid with a metering The pump simultaneously pumps into the reaction kettle, and the flow rate of the mixed solution of manganese sulfate and ethylenediaminetetraacetic acid is 9L/h. The solution undergoes a precipitation reaction in the reaction kettle. Control the flow rate of the mixed solution A to keep the reaction pH at 7.0. Aging the reacted material for 24 hours to obtain a reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用300L纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到1200L废水，将废水收集在废水槽中，回到步骤(1)继续过滤循环使用；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
实施例5Example 5
一种普鲁士白废水循环使用的方法，包括以下步骤：A method for recycling Prussian white wastewater, including the following steps:
(1)配制溶液：将400L普鲁士白废水(废水中亚铁***浓度约为0.01mol/L，硫酸钠浓度约为0.5mol/L)通过精密过滤器过滤，除掉废水中的残渣，然后与100kg亚铁***混合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A。再分别采用纯水配制浓度为1mol/L硫酸锰溶液、浓度为2mol/L柠檬酸钠溶液。(1) Prepare the solution: Filter 400L Prussian white wastewater (the concentration of sodium ferrocyanide in the wastewater is about 0.01mol/L, the concentration of sodium sulfate is about 0.5mol/L) through a precision filter to remove the residue in the wastewater. Then mix and stir with 100 kg of sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4 mol/L. Then use pure water to prepare a manganese sulfate solution with a concentration of 1 mol/L and a sodium citrate solution with a concentration of 2 mol/L.
(2)反应制备普鲁士白：向1000L反应釜中加入300L纯水，开启搅拌，升高温度至60℃，通入氮气，将混合溶液A、硫酸锰溶液、柠檬酸钠溶液用计量泵同时泵入反应釜中，柠檬酸钠溶液的流量与硫酸锰溶液的流量相同，都是10L/h。溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为8.5，将反应后的物料陈化16h，得反应浆料。(2) Preparation of Prussian White by reaction: Add 300L pure water to the 1000L reaction kettle, start stirring, raise the temperature to 60°C, pass in nitrogen, and pump mixed solution A, manganese sulfate solution, and sodium citrate solution simultaneously with a metering pump Into the reaction kettle, the flow rate of the sodium citrate solution is the same as that of the manganese sulfate solution, both 10L/h. The solution undergoes a precipitation reaction in the reaction kettle. Control the flow rate of the mixed solution A to keep the reaction pH at 8.5. Aging the reacted material for 16 hours to obtain a reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用300L纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到1200L废水，将废水收集在废水槽中，回到步骤(1)继续过滤循环使用；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water. Collect the waste water in the waste water tank, return to step (1) to continue filtration and recycling; dry the filter cake to obtain a Prussian white product.
对比例1Comparative example 1
对比例1采用常规方法制备普鲁士白产品，即采用纯水配液，不回用废水。Comparative Example 1 adopts conventional methods to prepare Prussian white products, that is, pure water is used for liquid preparation, and waste water is not reused.
具体步骤如下：Specific steps are as follows:
(1)配制溶液：将400L纯水与100kg亚铁***混合、搅拌，得到亚铁***浓度为0.4mol/L的混合溶液A；再分别配制浓度为1.5mol/L硫酸锰溶液和浓度为2mol/L柠檬酸钠溶液。(1) Prepare solution: Mix and stir 400L pure water and 100kg sodium ferrocyanide to obtain a mixed solution A with a sodium ferrocyanide concentration of 0.4mol/L; then prepare a manganese sulfate solution with a concentration of 1.5mol/L. And the concentration is 2mol/L sodium citrate solution.
(2)反应制备普鲁士白：向1000L反应釜中加入200L纯水，开启搅拌，升高温度至90℃，通入氮气，将混合溶液A、硫酸锰溶液、柠檬酸钠溶液用计量泵同时泵入反应釜中，硫酸锰溶液的流量为15L/h，柠檬酸钠溶液的流量是硫酸锰溶液流量的1.5倍，溶液在反应釜中发生沉淀反应，控制混合溶液A的流量，保持反应pH为8.2，将反应后的物料陈化16h，得反应浆料。(2) Preparation of Prussian White by reaction: Add 200L pure water to the 1000L reaction kettle, start stirring, raise the temperature to 90°C, pass in nitrogen, and pump mixed solution A, manganese sulfate solution, and sodium citrate solution simultaneously with a metering pump into the reaction kettle, the flow rate of the manganese sulfate solution is 15L/h, the flow rate of the sodium citrate solution is 1.5 times the flow rate of the manganese sulfate solution, the solution undergoes a precipitation reaction in the reaction kettle, control the flow rate of the mixed solution A, and keep the reaction pH at 8.2. Aging the reacted materials for 16 hours to obtain reaction slurry.
(3)过滤洗涤：将步骤(1)得到的反应浆料用压滤机过滤，收集过滤滤液，再用300L纯水洗涤压滤机中的滤饼，洗涤水与母液混合，得到1200L废水；将滤饼干燥，制得普鲁士白产品。(3) Filtration and washing: Filter the reaction slurry obtained in step (1) with a filter press, collect the filtrate, and then wash the filter cake in the filter press with 300L pure water. Mix the washing water with the mother liquor to obtain 1200L waste water; The filter cake is dried to obtain a Prussian white product.
产品效果测试Product effect testing
将实施例1-5和对比例1制备的普鲁士白产品进行性能测试。具体测试内容如下：The Prussian white products prepared in Examples 1-5 and Comparative Example 1 were subjected to performance testing. The specific test content is as follows:
(1)采用扫描电子显微镜分析实施例1和对比例1制备的普鲁士白产品。图2和图3分贝为实施例1、对比例1制备的普鲁士白的SEM图。有图2和图3可知，两种产品的形貌一致，没有明显区别，本发明提供普鲁士白废水循环使用的方法，能够循环使用废水配液，对产品的形貌没有起到明显的劣化作用，该方法可行性强、工业应用价值高。(1) Scanning electron microscopy was used to analyze the Prussian white products prepared in Example 1 and Comparative Example 1. Figures 2 and 3 are SEM images of the Prussian white prepared in Example 1 and Comparative Example 1. It can be seen from Figure 2 and Figure 3 that the appearance of the two products is consistent and there is no obvious difference. The present invention provides a method for recycling Prussian white wastewater, which can recycle the wastewater for liquid preparation without causing obvious deterioration in the appearance of the product. , this method has strong feasibility and high industrial application value.
(2)粒度(D10、D50、D90)用干法粒度仪检测。(2) Particle size (D10, D50, D90) is detected with a dry particle size analyzer.
(3)比表面积(BET)用BSD3H-2000A物理吸附仪测试。(3) Specific surface area (BET) was tested with BSD3H-2000A physical adsorption instrument.
(4)振实密度(TD)用BT-302振实密度测试仪测试。(4) Tap density (TD) is tested with BT-302 tap density tester.
(5)比容量测试：将实施例1-5和对比例1制备的普鲁士白产品制成正极片，以金属钠做负极，NaPF 6的碳酸乙烯酯(EC)/碳酸二乙酯(DEC)溶液做电解液，在手套箱中装配成扣式半电池。测试电池在2-4V、0.1C充放电时的放电容量。 (5) Specific capacity test: The Prussian white products prepared in Examples 1-5 and Comparative Example 1 were made into positive electrode sheets, with metallic sodium as the negative electrode, NaPF 6 ethylene carbonate (EC)/diethyl carbonate (DEC) The solution is used as electrolyte and assembled into a button half cell in a glove box. Test the discharge capacity of the battery when charging and discharging at 2-4V and 0.1C.
测试结果如表1所示。The test results are shown in Table 1.
表1实施例样品的数据Table 1 Data of Example Samples
Figure PCTCN2022118002-appb-000001
Figure PCTCN2022118002-appb-000001
由表1可知，实施例1制备的普鲁士白产品的理化参数几乎与对比例1中正常生产工艺制备的普鲁士白产品一致，其粒度分布正常、形貌正常，比表面积和振实密度与正常产品基 本一致，利用其制备的钠离子电池也具有良好的比容量。由此可见，采用本发明提供的方法循环利用普鲁士白废水制备普鲁士白，不会影响产品的质量，利用其制备的钠离子电池也具有较高的比容量，产品性能优良。As can be seen from Table 1, the physical and chemical parameters of the Prussian white product prepared in Example 1 are almost consistent with the Prussian white product prepared by the normal production process in Comparative Example 1. Its particle size distribution is normal, the morphology is normal, and the specific surface area and tap density are the same as those of the normal product. Basically the same, the sodium-ion battery prepared using it also has good specific capacity. It can be seen that the use of the method provided by the present invention to recycle Prussian white wastewater to prepare Prussian white will not affect the quality of the product. The sodium ion battery prepared by using the method also has a high specific capacity and excellent product performance.

Claims (10)

  1. 一种普鲁士白废水循环使用的方法，其特征在于，包括以下步骤：A method for recycling Prussian white wastewater, which is characterized by including the following steps:
    (1)将普鲁士白废水过滤去滤渣，然后与亚铁氰化盐混合，制得混合溶液A；配制锰盐溶液和络合剂溶液；(1) Filter the Prussian white wastewater to remove the filter residue, and then mix it with ferrocyanide salt to prepare mixed solution A; prepare a manganese salt solution and a complexing agent solution;
    (2)于保护气氛下将所述混合溶液A、锰盐溶液和络合剂溶液混合，发生沉淀反应得浆料，然后将所述浆料陈化，过滤得滤渣和滤液，再将所述滤渣洗涤、干燥，制得普鲁士白；收集所述滤液和所述洗涤过程产生的废水得新的普鲁士白废水；(2) Mix the mixed solution A, the manganese salt solution and the complexing agent solution under a protective atmosphere, and a precipitation reaction occurs to obtain a slurry. Then the slurry is aged, filtered to obtain the filter residue and filtrate, and then the The filter residue is washed and dried to obtain Prussian white; the filtrate and the wastewater generated by the washing process are collected to obtain new Prussian white wastewater;
    (3)利用所述新的普鲁士白废水重复一次或多次步骤(1)-(2)的过程。(3) Repeat steps (1)-(2) one or more times using the new Prussian white wastewater.
  2. 根据权利要求1所述的方法，其特征在于，在步骤(1)中，所述普鲁士白废水中包含亚铁氰化盐、硫酸盐、硝酸盐或氯化盐。The method according to claim 1, characterized in that, in step (1), the Prussian white wastewater contains ferrocyanide salt, sulfate, nitrate or chloride salt.
  3. 根据权利要求1所述的方法，其特征在于，在步骤(1)中，所述混合溶液A中亚铁氰化盐的浓度为0.3-0.6mol/L；所述锰盐溶液中锰盐的浓度为0.4-2.0mol/L；所述络合剂溶液的浓度为0.4-15mol/L。The method according to claim 1, characterized in that, in step (1), the concentration of ferrocyanide salt in the mixed solution A is 0.3-0.6 mol/L; the concentration of the manganese salt in the manganese salt solution is The concentration is 0.4-2.0 mol/L; the concentration of the complexing agent solution is 0.4-15 mol/L.
  4. 根据权利要求3所述的方法，其特征在于，在步骤(1)中，所述锰盐溶液中锰盐选自硫酸锰、硝酸锰、氯化锰或草酸锰中的至少一种。The method according to claim 3, characterized in that in step (1), the manganese salt in the manganese salt solution is selected from at least one of manganese sulfate, manganese nitrate, manganese chloride or manganese oxalate.
  5. 根据权利要求1所述的方法，其特征在于，在步骤(1)中，所述锰盐溶液采用普鲁士白废水或纯水进行配制；当采用普鲁士白废水进行配制时，包括如下步骤：The method according to claim 1, characterized in that, in step (1), the manganese salt solution is prepared with Prussian white wastewater or pure water; when it is prepared with Prussian white wastewater, it includes the following steps:
    向普鲁士白废水中第一次加入锰盐，过滤去滤渣，然后第二次加入锰盐，制得所述锰盐溶液。Add manganese salt to the Prussian white wastewater for the first time, filter out the filter residue, and then add manganese salt for the second time to prepare the manganese salt solution.
  6. 根据权利要求5所述的方法，其特征在于，所述第一次加入锰盐的物质的量为所述普鲁士白废水中亚铁氰化盐的物质的量的2-3倍。The method according to claim 5, characterized in that the amount of manganese salt added for the first time is 2-3 times the amount of ferrocyanide salt in the Prussian white wastewater.
  7. 根据权利要求3所述的方法，其特征在于，在步骤(1)中，所述络合剂选自柠檬酸、马来酸、枸杞酸、乙二胺四乙酸、柠檬酸钠或氨水中的至少一种。The method according to claim 3, characterized in that, in step (1), the complexing agent is selected from the group consisting of citric acid, maleic acid, lycic acid, ethylenediaminetetraacetic acid, sodium citrate or ammonia water. At least one.
  8. 根据权利要求1所述的方法，其特征在于，在步骤(2)中，通过计量泵控制所述混合溶液A、锰盐溶液和络合剂溶液的流量；所述络合剂溶液的流量是所述锰盐溶液的流量的0.1-3倍。The method according to claim 1, characterized in that, in step (2), the flow rates of the mixed solution A, the manganese salt solution and the complexing agent solution are controlled by a metering pump; the flow rate of the complexing agent solution is The flow rate of the manganese salt solution is 0.1-3 times.
  9. 根据权利要求1所述的方法，其特征在于，在步骤(2)中，通过控制所述混合溶液A的流量，保持所述沉淀反应的pH为6.5-9.5。The method according to claim 1, characterized in that, in step (2), by controlling the flow rate of the mixed solution A, the pH of the precipitation reaction is maintained at 6.5-9.5.
  10. 权利要求1-9中任一项所述的普鲁士白废水循环使用的方法在制备普鲁士白中的应用。Application of the Prussian white wastewater recycling method described in any one of claims 1 to 9 in the preparation of Prussian white.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106171A (en) * 1985-08-14 1987-01-07 四川永川天然气化工研究所 Method of production of sodium ferrocyanide without wastewater
CN102030401A (en) * 2010-11-12 2011-04-27 中冶焦耐(大连)工程技术有限公司 Method for decyanating coking wastewater
CN105776655A (en) * 2016-03-07 2016-07-20 紫金矿业集团股份有限公司 Method for producing copper concentrates and prussian blue by means of mine copper cyanide wastewater
KR20170098529A (en) * 2016-02-22 2017-08-30 한국전기연구원 Prussian white positive electrode active material and a manufacturing method thereof using Taylor vortex
CN109399771A (en) * 2018-07-26 2019-03-01 内蒙古太平矿业有限公司 A kind of method for innocent treatment of the waste water of dump leaching containing cyanogen
CN110002465A (en) * 2019-03-29 2019-07-12 华中科技大学 A kind of white analog positive electrode in Prussia, preparation method and application
CN112209409A (en) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery
CN113830792A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Anhydrous prussian white material, preparation method and application
CN113839032A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Low-cost Prussian white material, and preparation method and application thereof
CN114853033A (en) * 2022-06-06 2022-08-05 华中科技大学 Prussian white synthesis process and application

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106171A (en) * 1985-08-14 1987-01-07 四川永川天然气化工研究所 Method of production of sodium ferrocyanide without wastewater
CN102030401A (en) * 2010-11-12 2011-04-27 中冶焦耐(大连)工程技术有限公司 Method for decyanating coking wastewater
KR20170098529A (en) * 2016-02-22 2017-08-30 한국전기연구원 Prussian white positive electrode active material and a manufacturing method thereof using Taylor vortex
CN105776655A (en) * 2016-03-07 2016-07-20 紫金矿业集团股份有限公司 Method for producing copper concentrates and prussian blue by means of mine copper cyanide wastewater
CN109399771A (en) * 2018-07-26 2019-03-01 内蒙古太平矿业有限公司 A kind of method for innocent treatment of the waste water of dump leaching containing cyanogen
CN110002465A (en) * 2019-03-29 2019-07-12 华中科技大学 A kind of white analog positive electrode in Prussia, preparation method and application
CN112209409A (en) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery
CN113830792A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Anhydrous prussian white material, preparation method and application
CN113839032A (en) * 2021-09-15 2021-12-24 杭州思拓瑞吉科技有限公司 Low-cost Prussian white material, and preparation method and application thereof
CN114853033A (en) * 2022-06-06 2022-08-05 华中科技大学 Prussian white synthesis process and application

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