Basic manganese chloride and method for its preparation and use

Abstract

The application relates to a basic manganese chloride and a preparation method and application thereof. In the preparation method of the basic manganese chloride provided by the application, through selection of a manganese chloride solution with a manganese ion concentration of 60 g / L to 100 g / L and an ammonia nitrogen concentration of 5 g / L to 15 g / L, and an alkali liquor with a hydroxyl ion concentration of 100 g / L to 150 g / L, the reaction can be fully induced under the induction of ammonia nitrogen; the alkali liquor concentration used by the application is relatively low, the product agglomeration and the low product purity caused by the local high concentration of the alkali liquor can be avoided, and the basic manganese chloride prepared by the application is in a granular form, is not agglomerated, and has the advantages of large particle size and high purity. On the other hand, the process parameters of the precipitation reaction are limited, inert gas protection is not needed, the reaction can be fully carried out without addition of a surfactant and a catalyst, and the process is simple. In this way, the introduction of the surfactant and the catalyst and other organic matters is avoided, the wastewater treatment after production is simple, safe and environmentally friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic chemical product preparation, in particular to a preparation method of basic manganese chloride. BACKGROUND

[0002] Basic manganese chloride is a commonly used manganese compound, which is not easy to be oxidized in the air, and is not easy to absorb moisture and caking, and is better absorbed in the animal body, so it is widely used as a pigment for enamel, paint and varnish, and an animal feed additive, etc.

[0003] At present, the synthesis methods of basic manganese chloride mainly include solid-liquid synthesis method and liquid-liquid synthesis method. The solid-liquid synthesis method mainly includes two kinds: (1) adding manganese oxide solid to the ammonium chloride solution in the presence of a surfactant to prepare basic manganese chloride; (2) adding solid manganese hydroxide or solid manganese monoxide to the manganese chloride solution in the presence of a catalyst to prepare basic manganese chloride. The solid-liquid synthesis method needs to be carried out in the presence of a surfactant or a catalyst, and the particle size of the produced basic manganese chloride is small, which is easy to produce static electricity and dust. The liquid-liquid synthesis method mainly uses the reaction of manganese chloride solution and strong base to prepare basic manganese chloride under the protection of nitrogen or inert gas, but in the liquid-liquid synthesis method, the required concentration of strong base is high, which is easy to cause product agglomeration; and the local higher concentration of hydroxyl group is easy to generate manganese hydroxide, which is further oxidized to generate manganese dioxide, thereby affecting the purity of the final product. SUMMARY

[0004] Based on this, the present application provides a kind of basic manganese chloride and its preparation method and application.The preparation method provided in the present application can make the basic manganese chloride prepared into granular, not agglomerated, and has the advantages of large particle size and high purity.

[0005] The first aspect of the present application provides a preparation method of basic manganese chloride, comprising the following steps:

[0006] adding manganese chloride solution and lye into the reaction bottom liquid in a volume flow ratio of 2-4:1,

[0007] carrying out precipitation reaction under the conditions of pH 6.5-8 and temperature 60℃-80℃, and after 2h-4h of reaction, carrying out solid-liquid separation and collecting basic manganese chloride solid;

[0008] wherein, in the reaction bottom liquid, the ammonia nitrogen concentration is 5 g / L-15 g / L;

[0009] in the manganese chloride solution, the manganese ion concentration is 60 g / L-100 g / L, and the ammonia nitrogen concentration is 5 g / L-15 g / L;

[0010] The hydroxyl ion concentration in the lye is 100 g / L to 150 g / L.

[0011] In one embodiment, the preparation process of the manganese chloride solution comprises the following steps:

[0012] The solution is mixed with a manganese source, hydrochloric acid is added to adjust the pH to 0.5 to 1, and after 2 to 4 hours of reaction, solid-liquid separation is performed to prepare a first solid and a first filtrate; wherein the solution contains ammonia nitrogen and chloride ions; the pH of the first filtrate is adjusted to 3 to 4, manganese powder is added, and after 0.5 to 1 hours of reaction, solid-liquid separation is performed to prepare a second solid and a second filtrate;

[0013] An ammonia source is added to the second filtrate to prepare the manganese chloride solution with a manganese ion concentration of 60 g / L to 100 g / L and an ammonia nitrogen concentration of 5 g / L to 15 g / L.

[0014] In one embodiment, the ammonia nitrogen concentration in the solution is 2 g / L to 5 g / L, and the sodium chloride concentration is 50 g / L to 100 g / L.

[0015] In one embodiment, the preparation process of the solution comprises the following steps:

[0016] The copper oxide production mother liquor is taken, and the ammonia nitrogen concentration in the copper oxide production mother liquor is 2 g / L to 5 g / L, the sodium chloride concentration is 50 g / L to 100 g / L, and the copper ion concentration is 1 g / L to 3 g / L;

[0017] The copper ion in the copper oxide production mother liquor is removed by ion exchange resin method to make the copper ion concentration ≤2 mg / L, thereby preparing the solution.

[0018] In one embodiment, the copper oxide production mother liquor is a waste liquid generated during the production of copper oxide products using acidic etching waste liquid and / or alkaline etching waste liquid.

[0019] In one embodiment, the manganese source has one or more of the following characteristics:

[0020] (1) The manganese source is manganese slag;

[0021] (2) In terms of weight parts, the manganese content in the manganese source is 40 parts to 45 parts, and the lead content is 0.02 parts to 0.05 parts.

[0022] In one embodiment, the ammonia source includes one or more of ammonium chloride, ammonia water, ammonium sulfate, ammonium nitrate, ammonium carbonate, and urea.

[0023] In a second aspect, the application provides a basic manganese chloride prepared by the method of any one of the first aspect of the application, wherein the basic manganese chloride has one or more of the following characteristics:

[0024] (1) the basic manganese chloride has a particle size D50≥65 μm;

[0025] (2) the basic manganese chloride has a purity≥97%.

[0026] In a third aspect, the application provides an animal feed additive comprising the basic manganese chloride of the second aspect of the application.

[0027] In a fourth aspect, the application provides a pigment comprising the basic manganese chloride of the second aspect of the application.

[0028] In the method for preparing the basic manganese chloride provided by the application, the reaction is fully carried out by selecting a manganese chloride solution with a manganese ion concentration of 60 g / L to 100 g / L, an ammonia nitrogen concentration of 5 g / L to 15 g / L, and a hydroxyl ion concentration of 100 g / L to 150 g / L of alkali liquor, and under the induction of ammonia nitrogen. The low concentration of alkali liquor used in the application can avoid the disadvantages of product agglomeration and low product purity caused by the local high concentration of alkali liquor, and thus the basic manganese chloride prepared by the application is in the form of particles, is not agglomerated, and has the advantages of large particle size and high purity.

[0029] On the other hand, the application limits the process parameters of the precipitation reaction, does not need to be protected by inert gas, and at the same time, can fully react without adding surfactants and catalysts, and the process is simple. In this way, the introduction of organic matters such as surfactants and catalysts is avoided, the wastewater treatment after production is simple, safe and environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figures 1-2 A process flow chart of the method for preparing the basic manganese chloride provided by the application is shown in the figure;

[0031] Figures 3-4 A scanning electron microscope image of the basic manganese chloride prepared in Example 1 of the application is shown in the figure;

[0032] Figure 5 An XRD graph of the basic manganese chloride prepared in Example 1 of the application is shown in the figure;

[0033] Figure 6 A particle size distribution graph of the basic manganese chloride prepared in Example 1 of the application is shown in the figure. DETAILED DESCRIPTION

[0034] The following detailed description, in conjunction with specific embodiments, provides a more complete and clear account of the basic manganese chloride, its preparation method, and its applications. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0036] In this article, "one or more" refers to any one, two or more of the listed items.

[0037] In this application, terms such as "first aspect," "second aspect," "third aspect," "fourth aspect," and "fifth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," "fourth," and "fifth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0038] In this application, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions composed of the listed features.

[0039] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0040] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0041] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0042] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0043] In this application, "ammonia nitrogen" refers to combined nitrogen existing in the form of ammonia or ammonium ions, that is, in water as free ammonia (NH3) and ammonium ions (NH4). + Nitrogen exists in the form of ).

[0044] A first aspect of this application provides a method for preparing basic manganese chloride, comprising the following steps:

[0045] S50. Add manganese chloride solution and alkaline solution in parallel flow to the reaction substrate at a volume ratio of 2~4:1;

[0046] Precipitation reaction was carried out at pH 6.5-8 and temperature 60℃-80℃. After 2-4 hours of reaction, solid-liquid separation was performed, and basic manganese chloride solid was collected.

[0047] The ammonia nitrogen concentration in the reaction substrate is 5 g / L to 15 g / L.

[0048] In the manganese chloride solution, the concentration of manganese ions is 60 g / L to 100 g / L, and the concentration of ammonia nitrogen is 5 g / L to 15 g / L;

[0049] The hydroxide concentration in the alkaline solution is 100 g / L to 150 g / L.

[0050] Understandably, in step S50 of this application, the volumetric flow rate ratio of manganese chloride solution to alkali solution can be selected from any value between 2 and 4:1. Specifically, the volumetric flow rate ratio of manganese chloride solution to alkali solution includes, but is not limited to, 2:1, 2.1:1, 2.5:1, 2.8:1, 2.9:1, 3:1, 3.5:1, 3.8:1, 3.9:1, or 4:1. In this application, the pH for the precipitation reaction can be selected from any value between 6.5 and 8. Specifically, the pH for the precipitation reaction includes, but is not limited to, 6.5, 6.7, 6.7, 6.9, 7, 7.3, 7.5, 7.8, 7.9, or 8. In this application, the temperature for the precipitation reaction can be selected from any value between 60℃ and 80℃. Specifically, the temperature includes, but is not limited to, 60℃, 62℃, 65℃, 68℃, 70℃, 72℃, 75℃, 78℃, or 80℃. In this application, the precipitation reaction time is 2h to 4h. Specifically, the precipitation reaction time includes, but is not limited to, 2h, 2.1h, 2.5h, 3h, 3.5h, 3.8h, 3.9h, or 4h.

[0051] In the above preparation method, the precipitation reaction temperature is controlled between 60℃ and 80℃, and the pH is controlled between 6.5 and 8. On the one hand, this can avoid the generation of manganese dioxide due to excessively high reaction temperature or pH, which would affect the purity of the product; on the other hand, it can avoid the disadvantages of low chlorine content in the product due to excessively low reaction temperature, or the inability to synthesize basic manganese chloride due to excessively low pH.

[0052] Additionally, it is understood that in step S50, the manganese ion concentration in the manganese chloride solution can be any value between 60 g / L and 100 g / L. Specifically, the manganese ion concentration includes, but is not limited to, 60 g / L, 65 g / L, 70 g / L, 75 g / L, 80 g / L, 85 g / L, 90 g / L, 91 g / L, 92 g / L, 93 g / L, 95 g / L, 98 g / L, or 100 g / L. The ammonia nitrogen concentration can be any value between 5 g / L and 15 g / L. Specifically, the ammonia nitrogen concentration includes, but is not limited to, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 10 g / L, 12 g / L, 13 g / L, or 15 g / L.

[0053] In this application, the manganese ion concentration in the manganese chloride solution is set to 60 g / L ~ 100 g / L, and the ammonia nitrogen concentration is set to 5 g / L ~ 15 g / L. This ensures good compatibility between manganese and ammonia nitrogen. At the same time, the ammonia nitrogen concentration is more suitable for inducing the formation of basic manganese chloride, avoiding the disadvantages of too low ammonia nitrogen concentration, which leads to insufficient induction and easy product agglomeration, resulting in poor quality of the synthesized basic manganese chloride product; and too high ammonia nitrogen concentration, which leads to low product conversion rate.

[0054] In the alkaline solution, the hydroxide concentration can be any value between 100 g / L and 150 g / L. Specifically, the hydroxide concentration includes, but is not limited to, 100 g / L, 101 g / L, 103 g / L, 105 g / L, 107 g / L, 109 g / L, 110 g / L, 115 g / L, 120 g / L, 125 g / L, 130 g / L, 135 g / L, 140 g / L, 145 g / L, or 150 g / L. It is understood that in this application, the alkaline solution is not particularly limited and may include, but is not limited to, aqueous solutions of potassium hydroxide and sodium hydroxide.

[0055] Maintaining a hydroxide concentration of 100 g / L to 150 g / L in the alkali solution can prevent excessively high local concentrations, thereby avoiding product agglomeration or the formation of manganese dioxide and effectively ensuring product purity. Furthermore, it can prevent problems such as slow production rates and the generation of large amounts of wastewater caused by excessively low alkali concentrations.

[0056] In this application, the ammonia nitrogen concentration in the reaction substrate can be any value between 5 g / L and 15 g / L. Specifically, the ammonia nitrogen concentration in the reaction substrate includes, but is not limited to, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 10 g / L, 12 g / L, 13 g / L, or 15 g / L. The ammonia nitrogen concentration in the reaction substrate is between 5 g / L and 15 g / L, which allows it to induce a precipitation reaction between the manganese chloride solution and the alkaline solution. No surfactant or catalyst needs to be added during the reaction, and no inert gas is required for protection.

[0057] This application does not limit the type of reaction substrate, as long as it contains 5 g / L to 15 g / L of ammonia nitrogen. The types of reaction substrate include, but are not limited to, ammonium chloride solution, ammonia water, ammonium sulfate solution, ammonium nitrate solution, ammonium carbonate solution, and basic manganese chloride production mother liquor.

[0058] In one specific example, after the precipitation reaction is completed, the process also includes steps S601~S603 for treating the mother liquor from the production of basic manganese chloride:

[0059] S601. Add an alkaline compound to the basic manganese chloride production mother liquor to precipitate manganese, and prepare manganese precipitated solid phase and first wastewater;

[0060] S602. The first wastewater is passed through a membrane system to recover ammonia nitrogen, and ammonium salt products and second wastewater are prepared;

[0061] S603. The second wastewater is concentrated by evaporation to prepare chloride salt products.

[0062] Specifically, in step S601, the alkaline compound includes one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate. In this case, in step S603, the prepared chloride product is a sodium chloride product.

[0063] Understandably, the manganese precipitate solid phase prepared in step S601 can be used to adjust the pH of the first filtrate in step S30 below. The ammonium salt product prepared in step S602 can be used to replenish the ammonia nitrogen in the manganese chloride solution.

[0064] In one example, the preparation process of the manganese chloride solution includes the following steps:

[0065] S20. The solution is mixed with a manganese source, and hydrochloric acid is added to adjust the pH to 0.5-1. After reacting for 2-4 hours, the solid and liquid are separated to prepare a first solid and a first filtrate; wherein the solution contains ammonia nitrogen and chloride ions;

[0066] S30. Adjust the pH of the first filtrate to 3-4, add manganese powder, react for 0.5-1 hour, then separate the solid and liquid to prepare the second solid and the second filtrate;

[0067] S40. Add an ammonia source to the second filtrate to prepare the manganese chloride solution with a manganese ion concentration of 60 g / L to 100 g / L and an ammonia nitrogen concentration of 5 g / L to 15 g / L.

[0068] Understandably, the "solution" mentioned in this application contains not only ammonia nitrogen but also chloride ions, thus enabling it to provide an ammonia source and a chloride source for the preparation of basic manganese chloride.

[0069] In one example, in step S20, the manganese source contains 40 to 45 parts by weight of manganese and 0.02 to 0.05 parts by weight of lead.

[0070] In one specific example, in step S20, the manganese source is manganese slag. More specifically, the manganese source is manganese slag produced after the production of manganese monoxide. The main chemical composition of the manganese slag is shown in Table 1 below.

[0071] Table 1

[0072]

[0073] In one example, in step S20, the mass ratio of the solution to the manganese source is 4 to 6:1. Specifically, the mass ratio of the solution to the manganese source includes, but is not limited to, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1.

[0074] In step S20 of this application, the pH value adjusted by adding hydrochloric acid can be any value between 0.5 and 1. Specifically, the pH includes, but is not limited to, 0.5, 0.6, 0.7, 0.8, 0.9, or 1. The reaction time can be any value between 2 hours and 4 hours. Specifically, the reaction time includes, but is not limited to, 2 hours, 2.3 hours, 2.5 hours, 2.7 hours, 2.9 hours, 3 hours, 3.5 hours, or 4 hours.

[0075] In step S20, the pH is adjusted to 0.5~1 with hydrochloric acid and the reaction is carried out for 2h~4h. On the one hand, this ensures that the manganese in the manganese source is completely converted into a free state and exists in the first filtrate. On the other hand, since the manganese slag contains acid-insoluble substances, the acid-insoluble substances can exist in the first solid after the reaction through solid-liquid separation.

[0076] In one example, in step S20, the ammonia nitrogen concentration in the solution is 2 g / L to 5 g / L, and the sodium chloride concentration is 50 g / L to 100 g / L. It is understood that the ammonia nitrogen concentration in the solution includes, but is not limited to, 2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, or 5 g / L. The sodium chloride concentration includes, but is not limited to, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L, or 100 g / L.

[0077] In step S30, adding manganese powder can remove other metal impurity ions, such as lead ions, present in the first filtrate by displacement, thereby reducing the impurity content in the filtrate and ensuring the quality of subsequent products.

[0078] Understandably, in step S30, removing lead ion impurities requires the addition of an excess of manganese powder. In one example, in step S30, the molar ratio of added manganese powder to the molar ratio of lead content in the first filtrate is 1.5 to 2:1. Specifically, the molar ratio of manganese powder to the molar ratio of lead content in the first filtrate includes, but is not limited to, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1.

[0079] In step S30, the pH of the first filtrate can be adjusted to any value between 3 and 4. Specifically, the pH of the first filtrate includes, but is not limited to, 3, 3.2, 3.5, 3.8, or 4. The reaction time after adding manganese powder includes, but is not limited to, 0.5h, 0.6h, 0.8h, 0.9h, or 1h.

[0080] In one example, in step S40, the ammonia source includes one or more of ammonium chloride, ammonia water, ammonium sulfate, ammonium nitrate, ammonium carbonate, and urea.

[0081] In one example, the preparation process of the solution includes the following step S10:

[0082] S10. Take the copper oxide production mother liquor, wherein the concentration of ammonia nitrogen in the copper oxide production mother liquor is 2g / L~5g / L, the concentration of sodium chloride is 50g / L~100g / L, and the concentration of copper ions is 1g / L~3g / L;

[0083] The copper ions in the copper oxide production mother liquor are removed using an ion exchange resin method to achieve a copper ion concentration ≤2 mg / L, and the solution is prepared accordingly.

[0084] In one example, in step S10, the copper oxide production mother liquor is a waste liquid generated during the production of copper oxide products using acidic etching waste liquid and / or alkaline etching waste liquid. The main chemical components of the waste liquid are shown in Table 2 below.

[0085] Table 2

[0086]

[0087] In addition, in step S10 of this application, the prepared solution can also be mixed with potassium hydroxide or sodium hydroxide to prepare an alkaline solution with a concentration of 100g / L to 150g / L, and used in step S50.

[0088] In this application, a solution is prepared from the copper oxide production mother liquor generated during the production of copper oxide products using acidic and / or alkaline etching waste liquor. In step S20, this solution is mixed with manganese slag, so that the acid-insoluble substances from step S20 and other impurities in the manganese slag are present in the first solid. After rinsing, the first solid can be used as a raw material for cement production. In step S30, the second solid produced after solid-liquid separation can be used as a smelting raw material.

[0089] This application utilizes the wastewater generated during the production of copper oxide products from acidic and / or alkaline etching wastewater to provide ammonia and chlorine sources; and uses manganese slag as a manganese source, which can fully utilize valuable resources in industrial waste in a safe and environmentally friendly manner. Simultaneously, ammonia nitrogen is used as an inducer to achieve a complete reaction without the need for surfactants and catalysts. Furthermore, under reaction conditions of pH 6.5–8, temperature 60–80°C, and reaction time 2–4 hours, a low-concentration manganese chloride solution and alkaline solution are prepared for the reaction, avoiding the disadvantages of product agglomeration and low product purity due to excessively high local concentrations of alkaline solution. This results in the prepared basic manganese chloride being granular, non-agglomerated, and possessing both large particle size and high purity.

[0090] It should be understood that, although Figures 1-2 The steps in the flowchart are shown sequentially as indicated by the arrows, but these steps are not necessarily executed in the order indicated by the arrows. Unless otherwise specified herein, there is no strict order in which these steps are executed, and they can be performed in other orders. Figures 1-2 At least some of the steps in the process may include multiple steps or multiple stages. These steps or stages are not necessarily completed at the same time, but may be executed at different times. The execution order of these steps or stages is not necessarily sequential, but may be executed in turn or alternately with other steps or at least some of the steps or stages in other steps.

[0091] A second aspect of this application provides a basic manganese chloride obtained by the preparation method described in any example of the first aspect of this application.

[0092] In one example, the particle size D50 of the basic manganese chloride is ≥65 μm. The particle size D50 of the basic manganese chloride prepared in this application is ≥65 μm, which is higher than 45 μm in related products, and therefore it is less prone to generating static electricity and dust.

[0093] In one example, the purity of the basic manganese chloride is ≥97%.

[0094] A third aspect of this application provides an animal feed additive, comprising the basic manganese chloride described in the second aspect of this application.

[0095] A fourth aspect of this application provides a pigment comprising the basic manganese chloride described in the second aspect of this application.

[0096] The following are specific examples. Unless otherwise specified, all raw materials used in the examples are commercially available products. The manganese slag used in the following examples and comparative examples all comes from manganese product manufacturers, and the various indicators of the manganese slag are shown in Table 1 above. The solutions used in the following examples and comparative examples are all prepared from copper oxide production mother liquor generated during the production of copper oxide products using acidic and alkaline etching waste liquid as raw material. The various indicators of the copper oxide production mother liquor are shown in Table 2 above.

[0097] Example 1

[0098] Example 1 of this application provides a basic manganese chloride and its preparation method, including the following steps:

[0099] (1) Take the copper oxide production mother liquor, remove copper ions using ion exchange resin method, so that the copper ion concentration is ≤2 mg / L, and prepare a solution.

[0100] (2) Take 400 kg of solution (the concentration of ammonia nitrogen in the solution is 3 g / L and the concentration of chloride ions is 80 g / L); add 100 kg of manganese slag, adjust and maintain the pH at 0.5 with hydrochloric acid with a volume concentration of 31%, react for 2 h, and then separate the solid and liquid to prepare the first solid and the first filtrate.

[0101] (3) Add the manganese precipitate solid phase generated in step (6) to the first filtrate, adjust the pH to 3, add manganese powder, and the molar ratio of the added manganese powder to the molar ratio of the lead content in the first filtrate is 1.5:1. After reacting for 0.5 h, the solid and liquid are separated to prepare the second solid and the second filtrate.

[0102] (4) Add ammonium chloride solid to the second filtrate to prepare a manganese chloride solution with a manganese ion concentration of 100 g / L and an ammonia nitrogen concentration of 5 g / L;

[0103] (5) Take 500L of the solution prepared in step (1), add sodium hydroxide solid, and prepare an alkaline solution with a concentration of 100g / L; take 500L of the solution prepared in step (1), add ammonium chloride solid, and prepare a reaction base solution with an ammonia nitrogen concentration of 5g / L. Heat the solution to 60℃ and maintain the reaction temperature, and add the manganese chloride solution and alkaline solution prepared in step (4) above. Control the reaction pH to 6.5, and the volume flow ratio of manganese chloride solution and alkaline solution to 4:1. After reacting for 4 hours, separate the solid and liquid, wash and dry the solid phase, and prepare basic manganese chloride.

[0104] (6) After solid-liquid separation in step (5), sodium hydroxide solid is added to the liquid phase to precipitate manganese and prepare manganese precipitate solid phase and first wastewater; the first wastewater is used to recover ammonia nitrogen through a membrane system to prepare ammonium chloride product and second wastewater; the second wastewater is concentrated by evaporation to prepare sodium chloride product.

[0105] Example 2

[0106] Example 2 of this application provides a basic manganese chloride and its preparation method, including the following steps:

[0107] (1) Take the copper oxide production mother liquor, remove copper ions using ion exchange resin method, so that the copper ion concentration is ≤2 mg / L, and prepare a solution.

[0108] (2) Take 600 kg of solution (the concentration of ammonia nitrogen in the solution is 3 g / L and the concentration of chloride ions is 80 g / L); add 100 kg of manganese slag, adjust and maintain the pH at 1 with hydrochloric acid with a volume concentration of 31%, react for 4 h, and then separate the solid and liquid to prepare the first solid and the first filtrate.

[0109] (3) Add the manganese precipitate solid phase generated in step (6) to the first filtrate, adjust the pH to 4, add manganese powder, and the molar ratio of the added manganese powder to the molar ratio of the lead content in the first filtrate is 2:1. After reacting for 1 hour, the solid and liquid are separated to prepare the second solid and the second filtrate.

[0110] (4) Add ammonium chloride solid to the second filtrate to prepare a manganese chloride solution with a manganese ion concentration of 60 g / L and an ammonia nitrogen concentration of 15 g / L;

[0111] (5) Take 500L of the solution prepared in step (1), add sodium hydroxide solid, and prepare an alkaline solution with a concentration of 150g / L; take 500L of the solution prepared in step (1), add ammonium chloride solid, and prepare a reaction base liquid with an ammonia nitrogen concentration of 15g / L. Heat the solution to 80℃ and maintain the reaction temperature, and add the manganese chloride solution and alkaline solution prepared in step (4) above. Control the reaction pH to 8, and the volume flow ratio of manganese chloride solution and alkaline solution to 2:1. After reacting for 2 hours, separate the solid and liquid, wash and dry the solid phase, and prepare basic manganese chloride.

[0112] (6) The liquid phase generated after solid-liquid separation in step (5) is used to prepare manganese precipitated solid phase and first wastewater; the first wastewater is used to recover ammonia nitrogen through a membrane system to prepare ammonium chloride product and second wastewater; the second wastewater is concentrated by evaporation to prepare sodium chloride product.

[0113] Example 3

[0114] Example 3 of this application provides a basic manganese chloride and its preparation method, including the following steps:

[0115] (1) Take the copper oxide production mother liquor, remove copper ions using ion exchange resin method, so that the copper ion concentration is ≤2 mg / L, and prepare a solution.

[0116] (2) Take 500 kg of solution (the concentration of ammonia nitrogen in the solution is 3 g / L and the concentration of chloride ions is 80 g / L); add 100 kg of manganese slag, adjust and maintain the pH at 0.8 with hydrochloric acid with a volume concentration of 31%, react for 3 h, and then separate the solid and liquid to prepare the first solid and the first filtrate.

[0117] (3) Add the manganese precipitate solid phase generated in step (6) to the first filtrate, adjust the pH to 3.5, add manganese powder, and the molar ratio of the added manganese powder to the molar ratio of the lead content in the first filtrate is 1.8:1. After reacting for 0.8h, the solid and liquid are separated to prepare the second solid and the second filtrate.

[0118] (4) Add ammonium chloride solid to the second filtrate to prepare a manganese chloride solution with a manganese ion concentration of 80 g / L and an ammonia nitrogen concentration of 10 g / L;

[0119] (5) Take 500L of the solution prepared in step (1), add sodium hydroxide solid, and prepare an alkaline solution with a concentration of 120g / L; take 500L of the solution prepared in step (1), add ammonium chloride solid, and prepare a reaction base liquid with an ammonia nitrogen concentration of 10g / L. Heat the solution to 70℃ and maintain the reaction temperature, and add the manganese chloride solution and alkaline solution prepared in step (4) above. Control the reaction pH to 7, and the volume flow ratio of manganese chloride solution and alkaline solution to 3:1. After reacting for 3 hours, separate the solid and liquid, wash and dry the solid phase, and prepare basic manganese chloride.

[0120] (6) The liquid phase generated after solid-liquid separation in step (5) is used to prepare manganese precipitated solid phase and first wastewater; the first wastewater is used to recover ammonia nitrogen through a membrane system to prepare ammonium chloride product and second wastewater; the second wastewater is concentrated by evaporation to prepare sodium chloride product.

[0121] Comparative Example 1

[0122] Comparative Example 1 is basically the same as Example 1, except that in step (5), the concentration of the alkaline solution is 200 g / L.

[0123] Comparative Example 2

[0124] Comparative Example 2 is basically the same as Example 1, except that in step (5), a manganese chloride solution with an ammonia nitrogen concentration of 25 g / L is prepared.

[0125] Comparative Example 3

[0126] Comparative Example 3 is basically the same as Example 1, except that the reaction temperature in step (5) is 50°C.

[0127] Comparative Example 4

[0128] Comparative Example 4 is basically the same as Example 1, except that in step (5), the pH of the reaction is 10.

[0129] Comparative Example 5

[0130] Comparative Example 5 is basically the same as Example 1, except that in step (5), the volume flow ratio of manganese chloride solution and alkaline solution is 6:1.

[0131] The test methods or test standards for the products in the examples and comparative examples are as follows:

[0132] (1) Morphology: Observation and measurement were performed using a scanning electron microscope (SEM). The SEM images of the basic manganese chloride product prepared in step (5) of Example 1 are shown below. Figures 3-4 As shown.

[0133] (2) Crystal structure: X-ray diffraction (XRD) was used for testing and analysis. The XRD pattern of the basic manganese chloride product prepared in step (5) of Example 1 is shown below. Figure 5 As shown.

[0134] (3) Particle size: Tested using a laser particle size analyzer (model: LS-800). The particle size distribution of the basic manganese chloride product prepared in step (5) of Example 1 is shown below. Figure 6 As shown.

[0135] (4) Purity of products and content of other components in the examples and comparative examples: tested according to the group standard "Basic Manganese Chloride" (T-CPCIF 0164-2021).

[0136] The corresponding detection indicators are shown in Table 3.

[0137] Table 3

[0138]

[0139] Depend on Figures 3-4 It can be seen that the basic manganese chloride product prepared in this application is in the form of independently formed granules and does not clump together. Figure 5As can be seen, the molecular formula of the product prepared in Example 1 of this application is Mn2(OH)3Cl. Through... Figure 6 As can be seen, the particle size D50 of the product prepared in Example 1 is 70.94 μm, and the particle size distribution is relatively uniform. Table 3 shows that the purity of the basic manganese chloride prepared in Examples 1-3 of this application is ≥97.3%, which is higher than the requirements of the group standard; the content of other metal elements is also far lower than the requirements of the group standard. The concentration of the alkali solution used in Comparative Example 1 was too high, resulting in lower purity and smaller particle size of the prepared product; the ammonia nitrogen content in the manganese chloride solution used in Comparative Example 2 was too high, and the purity of the basic manganese chloride prepared in it could not meet the requirements of the group standard. Furthermore, the product conversion rate of Comparative Example 2 was also low, below 50%, during the actual production process; while the product conversion rate in Examples 1-3 of this application was ≥70%; the reaction temperature, pH, and volumetric flow rate ratio of Comparative Examples 3-5 did not meet the requirements, resulting in lower purity and lower particle size of the prepared basic manganese chloride.

[0140] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0141] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing basic manganese chloride, characterized in that, Includes the following steps: The manganese chloride solution and the alkaline solution were added to the reaction substrate in a parallel flow at a volume ratio of 2 to 4:

1. Precipitation reaction was carried out at pH 6.5-8 and temperature 60℃-80℃. After 2-4 hours of reaction, solid-liquid separation was performed, and basic manganese chloride solid was collected. The ammonia nitrogen concentration in the reaction substrate is 5 g / L to 15 g / L. In the manganese chloride solution, the concentration of manganese ions is 60 g / L to 100 g / L, and the concentration of ammonia nitrogen is 5 g / L to 15 g / L; The alkali solution has a hydroxide concentration of 100 g / L to 150 g / L; the alkali solution includes one or more of potassium hydroxide aqueous solution and sodium hydroxide aqueous solution.

2. The method for preparing basic manganese chloride according to claim 1, characterized in that, The preparation process of the manganese chloride solution includes the following steps: The solution was mixed with a manganese source, and hydrochloric acid was added to adjust the pH to 0.5-1. After reacting for 2-4 hours, the solid and liquid were separated to prepare a first solid and a first filtrate. The solution contained ammonia nitrogen and chloride ions. Adjust the pH of the first filtrate to 3-4, add manganese powder, react for 0.5-1 hour, then separate the solid and liquid to prepare the second solid and the second filtrate. An ammonia source is added to the second filtrate to prepare the manganese chloride solution with a manganese ion concentration of 60 g / L to 100 g / L and an ammonia nitrogen concentration of 5 g / L to 15 g / L.

3. The method for preparing basic manganese chloride according to claim 2, characterized in that, The solution contains ammonia nitrogen at a concentration of 2 g / L to 5 g / L and sodium chloride at a concentration of 50 g / L to 100 g / L.

4. The method for preparing basic manganese chloride according to claim 3, characterized in that, The preparation process of the solution includes the following steps: Take the copper oxide production mother liquor, wherein the concentration of ammonia nitrogen in the copper oxide production mother liquor is 2 g / L~5 g / L, the concentration of sodium chloride is 50 g / L~100 g / L, and the concentration of copper ions is 1 g / L~3 g / L; The copper ions in the copper oxide production mother liquor are removed using an ion exchange resin method to achieve a copper ion concentration ≤2 mg / L, and the solution is prepared accordingly.

5. The method for preparing basic manganese chloride according to claim 4, characterized in that, The copper oxide production mother liquor is the waste liquid generated during the production of copper oxide products using acidic etching waste liquid and / or alkaline etching waste liquid.

6. The method for preparing basic manganese chloride according to any one of claims 2 to 5, characterized in that, The manganese source has one or more of the following characteristics: (1) The manganese source is manganese slag; (2) By weight, the manganese source contains 40 to 45 parts of manganese and 0.02 to 0.05 parts of lead.

7. The method for preparing basic manganese chloride according to any one of claims 2 to 5, characterized in that, The ammonia source includes one or more of ammonium chloride, ammonia water, ammonium sulfate, ammonium nitrate, ammonium carbonate, and urea.

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