Composite basic manganese chloride, and preparation method and application thereof

Abstract

The application discloses composite basic manganese chloride and a preparation method and application thereof, and belongs to the technical field of inorganic chemical product preparation. The raw materials used in the preparation method are widely sourced, are lower in price, and the production process steps are simple, the yield is high, and thus the production cost is low. In addition, the preparation method contains a impurity removal step, the harmful ion content of the finally obtained basic manganese chloride product is extremely low, and after use, the product does not have adverse effects on animals and plants. Moreover, in the preparation process, a crystal nucleus agent and a surfactant are introduced, which not only can obtain a product with narrow and uniform particle size distribution, but also can introduce specific nutrient components in the product, can avoid the generation of high-valence manganese components in the drying process, and make the obtained product more easily absorbed and utilized by animals and plants, so that the obtained product can be better used as feed or plant fertilizer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of inorganic chemical product preparation, and particularly relates to a composite basic manganese chloride and a preparation method and application thereof. BACKGROUND

[0002] Although the content of manganese element in animal body is very small, only 2-3 mg / kg, it plays a very important physiological function as an important life element. Manganese element is usually one of the elements necessary for animal bone development and brain function, reproductive function. In the biological body, manganese element participates in carbohydrate, fat, protein metabolism. When poultry is deficient in manganese, it will lead to abnormal bone development, short and curved leg bones, and sick poultry limping; it will also lead to abnormal embryonic development of poultry, short and thick legs, short wings, head deformity, and poor embryonic development, thus reducing the hatching rate. When pigs, cattle and other livestock mammals are deficient in manganese, they will have growth and development inhibition, weight loss; reproductive dysfunction, poor mammary gland development in female animals, prolonged estrus, difficult to be pregnant, and abortion, stillbirth and weak fetus; newborn animals have movement disorder, weak and sick, tremor, ataxia, and slow growth; bone deformity, short tubular bone, and strong gait or lameness. The testes of male animals degenerate and lose reproductive function.

[0003] In the prior art, the problem of manganese deficiency in livestock is generally solved by adding a feed additive containing manganese to the feed. However, the absorption rate of manganese in the feed by livestock is low, only 3-4%, and most of the ingested manganese is excreted outside the body through feces. Moreover, when livestock eat high-calcium and high-phosphorus feed, the absorption of manganese is significantly reduced. The main sources of manganese in the animal feed additives and plant manganese fertilizers on the market can be divided into inorganic manganese and organic manganese. The inorganic manganese in the feed additive or plant manganese fertilizer can be selected from one or more of MnO, MnSO4, MnCl2, MnCO3, etc., but there is a big difference in the absorption and utilization of these manganese in animals or plants. The bioavailability of Mn in MnSO4 is better than that of MnO and MnCO3, and is close to that of MnCl2. Among them, the utilization rate of Mn in MnO is only about two-thirds of that of MnSO4, and the utilization rate of Mn in MnCO3 is only about one-third of that of MnSO4. In fact, most of the single manganese element in the animal stomach will synthesize manganese phytate to form a poorly soluble compound, which is difficult to digest and utilize. After Mn is combined with organic matter such as methionine, citric acid and other complexing agents, the utilization rate and absorption rate of manganese element will be improved. For example, methionine manganese can be directly absorbed in the intestinal tract of livestock and poultry and participate in metabolism. Therefore, when selecting a suitable manganese additive, on the one hand, the cost of addition should be considered, and on the other hand, the bioavailability should also be considered.

[0004] Although the bioavailability of organic manganese sources is higher than that of inorganic manganese sources, they are usually expensive and have low cost-effectiveness in the field of feed and plant micro-fertilizer. Currently, the easily available organic manganese sources on the market include manganese glycinate, manganese methionine, manganese hydroxy methionine, etc. These amino acid manganese products have good use effects, are easily absorbed by animal and plant bodies, and are less likely to interact with other components such as protein, starch and sugar in feed. Moreover, the impact of the excrement of animals after consuming the products on the environment is also small. However, the ligand of amino acid manganese is amino acid, which is expensive and has low cost advantage. Moreover, the manganese content is low, and the addition amount needs to be increased, so the cost pressure in the process of feed production is faced when using such products.

[0005] The bioavailability of trace elements is closely related to the compound state of the elements. Inorganic trace elements can dissolve in water or be oxidized by air and chemically react with other components in the air in the natural environment. In addition, inorganic trace elements are easily chemically reacted with other components in feed to form relatively stable compounds and are not easily absorbed by animals and plants. Therefore, the total bioavailability of trace elements in inorganic salts is generally less than 20%. In addition, due to the high toxicity of inorganic trace heavy metal elements, the addition amount in feed must be strictly controlled within the range permitted by the state.

[0006] Currently, considering the comprehensive cost-effectiveness, manganese used in feed additives and plant fertilizers mainly adopts manganese sulfate or manganese chloride. However, when using manganese sulfate as an additive in feed, the feed is prone to caking due to the hygroscopicity of manganese sulfate. In addition, manganese sulfate is usually oxidized by potassium permanganate or hydrogen peroxide to remove impurities in the production process. The synthesized manganese sulfate product may contain a small amount of manganese dioxide, potassium permanganate and other oxides. These oxides have high oxidation and catalytic properties, and are easily oxidized and reduced with other nutritional components in feed or plant fertilizer, such as protein, vitamin, divalent iron, fatty acid and other components, which affects the quality and shelf life of feed or fertilizer. Moreover, the content of sulfate is high, and the excrement of animals after absorption and utilization will contain a large amount of sulfate, which will cause soil compaction and accelerate soil salinization. As a new type of feed additive, alkali manganese chloride has good palatability, good stability, can effectively inhibit bacterial growth, has less environmental pollution, and has higher bioavailability than inorganic trace elements. However, the currently produced alkali manganese chloride still has problems such as low absorption efficiency and high residual high-valence manganese ions. SUMMARY

[0007] In view of the above prior art, the present application provides a composite alkali manganese chloride, a preparation method and application thereof, to solve the technical problems of low absorption efficiency and high residual high-valence manganese ions of the existing alkali manganese chloride.

[0008] In order to achieve the above object, the technical scheme adopted by the present application is to provide a preparation method of composite basic manganese chloride, comprising the following steps:

[0009] S1: dissolving the manganese-containing material in water or acid solution to prepare a solution with a manganese ion concentration of 75-130 g / L;

[0010] S2: adjusting the solution to weak acidity, then adding manganese metal to the solution, stirring and filtering, repeating the above operation several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ in the filtrate are all less than 0.002 g / L;

[0011] S3: adding a decontaminating agent to the filtrate obtained in S2, stirring and filtering, then adding ammonium sulfide to the obtained filtrate, continuing to stir and filter to obtain pure manganese solution;

[0012] S4: adding a crystal nucleus agent to the pure manganese solution, adjusting the pH of the pure manganese solution to 6-7, then introducing a precipitating agent into the pure manganese solution to perform a precipitation reaction until the D 50 particle size of the precipitated particles reaches 6-8 μm, stopping the precipitation reaction and stirring at 20-55 ℃ for 10-24 h;

[0013] S5: adding a surface modifier to the system obtained in S4, uniformly stirring, then flash drying at 250 ℃ to obtain the product.

[0014] On the basis of the above technical scheme, the present application can also be improved as follows.

[0015] Further, the manganese-containing material is industrial manganese chloride, industrial manganese carbonate or industrial manganese oxide; and the acid solution is hydrochloric acid solution.

[0016] Further, the pH of the solution after being adjusted to weak acidity in S2 is 6-6.5; the manganese metal is ultra-fine manganese powder, manganese particle, manganese block or manganese ingot; and the amount of manganese metal added is 1.5 times the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution.

[0017] Further, the decontaminating agent is at least one of manganese sulfide, manganese oxalate, manganese carbonate, manganese selenide, ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium oxalate, potassium oxalate, sodium silicate, potassium silicate, sodium selenate, potassium selenate, sodium phosphate, potassium phosphate and lithium phosphate; and the material solution ratio of the added decontaminating agent to the filtrate is 5 kg:1 m 3The stirring time after adding the impurity remover is 1 hour; the amount of ammonium sulfide added is 1.5 times the amount of zinc detected in the solution, and the stirring time after adding ammonium sulfide is 1~2 hours.

[0018] Furthermore, the nucleating agent is at least one of the following: manganese selenoamino acid, manganese methionine, manganese oxalate, manganese citrate, manganese gluconate, manganese methionine, and manganese protein salt.

[0019] Furthermore, the mass ratio of the added nucleating agent to the manganese-containing material is 0.5~1:500.

[0020] Furthermore, the precipitant is at least one of ammonia gas, liquid ammonia, ammonia water, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0021] Furthermore, the surface modifier is at least one of glucose, sucrose, citric acid, ascorbic acid, amino acids, unsaturated fatty acids, salicylic acid, ethylene glycol, glycerol, ethyl acetate, and butanone; the mass ratio of the added surface modifier to the nucleating agent is 3 to 3.1:1.

[0022] The beneficial effects of adopting the above technical solution in this invention are: In the impurity removal step, this invention removes Fe... 3+ And Al 3+ The method is based on the low solubility product of Fe(OH)3 and Al(OH)3 ions. By adjusting the pH value, they are precipitated and separated. The Fe element is present in the solution. 2+ and Fe 3+ The component can be oxidized using oxygen in the air, causing the Fe in the system to... 2+ ions are converted to Fe 3+ The ions are then separated by obtaining a precipitate within their pH range.

[0023] In the impurity removal step, this invention removes or reduces the Cu content in the system by adding metallic manganese materials such as manganese powder, manganese blocks, manganese ingots, and manganese granules. 2+ Sb 3+ Cr 3+ As 3+ Pb 2+ Cd 2+ Hg 2+ The main principle of plasma content is Mn 2+ The electrode potentials of the ions mentioned above differ, and Mn is used... 0 / Mn 2+ Charge transfer between them occurs through a redox reaction, using metallic Mn to reduce and displace Cu in the solution. 2+ Sb 3+ Cr 3+ As 3+ Pb 2+ Cd2+ Hg 2+ plasma.

[0024] In the impurity removal process, at least one of the impurity removal agents (manganese sulfide, manganese oxalate, manganese carbonate, manganese selenide, ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium oxalate, potassium oxalate, sodium silicate, potassium silicate, sodium selenate, potassium selenate, sodium phosphate, potassium phosphate, lithium phosphate) is added to the system. The basic principle is to use the low solubility and low solubility of specific metal ions, carbonates, oxalates, silicates, hydroxides, etc. to carry out chemical precipitation reaction, so that the metal ions to be separated are precipitated, and the purpose of purification is achieved. The amount of impurity removal agent is determined based on the ion content in the raw material solution. In the impurity removal process, in order to ensure the removal effect of impurity ions, the amount of impurity removal agent is usually increased by 1%~20% based on the theoretical calculation.

[0025] In the process of preparing basic manganese chloride, a crystal nucleus agent is used. The purpose of using the crystal nucleus agent is to make the basic manganese chloride obtained by the reaction grow on the crystal nucleus, on the one hand to reduce the nucleation barrier of the basic manganese chloride, on the other hand to well control the agglomeration phenomenon in the reaction system, and to promote the forward reaction, so that the yield of the target product is higher, and the particles of the target product are more uniform, thereby obtaining a basic manganese chloride product with narrow and uniform particle size distribution. In addition, the addition of the crystal nucleus agent can also introduce specific nutrients into the basic manganese chloride product, making it easier for plants and animals to absorb and utilize, so that the obtained product can be better used as feed or plant fertilizer.

[0026] In the process of preparing basic manganese chloride, a precipitant is also used. The precipitant can be selected from one or more of liquid ammonia, ammonia water, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. The amount is calculated according to the stoichiometric ratio, and the actual amount added is usually reduced by 1%~10% based on the theoretical calculation. The present application obtains Mn2(OH)3Cl by controlling the pH value, stirring speed, reaction temperature and other condition parameters, and the chemical reaction equation is:

[0027] 2MnCl2+3NH3·H2O=Mn2(OH)3Cl↓+3NH4Cl

[0028] In order to avoid the direct generation of Mn(OH)2 in a large amount of strong alkali environment, the amount of manganese chloride is usually slightly excessive, so as to reduce the generation of by-product Mn(OH)2, so as to make the purity and yield of the target product basic manganese chloride higher.

[0029] The alkali manganese chloride is prepared by adding a surfactant into the system, and the surfactant is used to prevent uncontrollable agglomeration of Mn2(OH)3Cl crystal grains obtained in the reaction, and to avoid oxidation of Mn2(OH)3Cl by oxygen in the air in the drying process, so that high-valence manganese components such as Mn 3+ , Mn 4+ are generated, thereby affecting application and nutritional components in subsequent feed proportioning.

[0030] The application further discloses a composite alkali manganese chloride prepared by the preparation method. 50 The D 90 particle size of the composite alkali manganese chloride is 5-10 microns, the Mn element content is 53.0wt%-56.8wt%, the Cl element content is 16.5wt%-19.5wt%, the H2O content is 1wt-5wt%, the Ca element content is 0.01wt%-0.05wt%, the Se element content is 0.0001wt%-0.0005wt%, the P element content is 0.0001wt%-0.0003wt%, the Zn element content is 0.0015wt%-0.002wt%, and the Cr, Pb, Cd, As and Hg element contents are all lower than 0.00003wt%.

[0031] The application further discloses application of the composite alkali manganese chloride, and the composite alkali manganese chloride is used as an animal feed additive or a plant fertilizer additive.

[0032] The application has the following beneficial effects:

[0033] 1. The preparation method in the application can use one of industrial-grade manganese chloride, a solution containing manganese chloride prepared by leaching a rhodochrosite or a manganese carbonate ore with hydrochloric acid, a reaction product of crude manganese carbonate and hydrochloric acid, a reaction product of crude manganese oxide and hydrochloric acid, or a mixed solution as raw material for production, so that the raw material source is wider, the price is lower, and the production cost is smaller.

[0034] 2. The method in the application has simple production process steps, low cost and high yield, and the method contains a step of removing impurities, so that the harmful ion content of the finally obtained alkali manganese chloride product is extremely low.

[0035] 3. The alkali manganese chloride prepared by the method has nanoscale primary crystal grains and micron-level secondary particles, the secondary particles are uniform in particle size, have narrow particle size distribution, good dispersion flowability, are easy to dry, do not contain crystal water, are not easy to be hardened in long-term heavy pressure storage, and are beneficial to storage and transportation.

[0036] 4. The basic manganese chloride Mn 2+ The content of the basic manganese chloride obtained by the method is high, the content of impurity ions is low, and the basic manganese chloride is rich in other life elements. The basic manganese chloride is not only green and environmentally friendly, but also rich in nutritional components, and can be used as animal feed or plant fertilizer. In addition, a surface modifier is added in the process of preparing the basic manganese chloride, and the obtained product can still be stable at a high temperature of 280°C and is not easy to be oxidized. The product can withstand the temperature during the processing and granulation of the feed or plant fertilizer, and will not be denatured during the granulation. In addition, the addition of the surface modifier can introduce nutritional components such as glucose, sucrose, citric acid, ascorbic acid, amino acid, unsaturated fatty acid, salicylic acid, ethylene glycol, glycerol, ethyl acetate and the like into the obtained basic manganese chloride product, which is more beneficial to the absorption of animals and plants.

[0037] 5. The basic manganese chloride obtained by the method has a relatively higher manganese concentration (the theoretical value can reach 55.97 wt%), which is higher than 32.5 wt% of the manganese chloride monohydrate. The addition amount (calculated based on the manganese element) of the basic manganese chloride in the feed or plant fertilizer can be reduced, and more other functional auxiliary products can be added under the same addition level of manganese content.

[0038] 6. The basic manganese chloride obtained by the method has a very low content of Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ and the like, and does not contain KMnO4, MnO2, Mn3O4 and the like. The basic manganese chloride can effectively prevent the oxidation and destruction of other nutritional components in the animal feed or plant fertilizer.

[0039] 7. The basic manganese chloride obtained by the method is environmentally friendly, safe, efficient, environmentally friendly, rich in nutritional components and easy to store, and is a new type of feed additive. DETAILED DESCRIPTION

[0040] The specific embodiments of the application will be described in detail below with reference to the examples.

[0041] Example 1

[0042] A composite basic manganese chloride is prepared by the following steps:

[0043] (1) 500 kg of industrial grade crude manganese chloride (MnCl2·4H2O) (purity 95%) is added to a glass steel storage tank (volume 3m 3 ) containing 1.75 t of water, and stirred to completely dissolve. The content of impurity ions in the obtained solution is analyzed and tested, and the specific content is as follows:

[0044] Ca 2+ : 0.6 g / L; Zn 2+ : 0.2 g / L; Cu 2+ : 0.03 g / L; Fe 3+ : 0.02 g / L; Al 3+ : 0.06 g / L; Sb 3+ : 0.005 g / L; Cr 3+ : 0.005 g / L; As 3+ : 0.005 g / L; Pb 2+ : 0.005 g / L; Cd 2+ : 0.015 g / L; Hg 2+ < 0.001 g / L; pH 4.0-4.5;

[0045] S2: adjust the pH value of the solution to 6.3, then add 1.5 times the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution into the solution under stirring, stir for 1 h and filter; repeat the above operation several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ in the solution are all less than 0.002 g / L;

[0046] S3: add manganese carbonate to the filtrate after filtering in S2, the ratio of manganese carbonate to the filtrate is 5 kg: 1 m 3 , stir for 1 h and filter;

[0047] S4: add ammonium sulfide which is 1.5 times the total amount of Zn 2+ and other heavy metal ions detected in the solution to the filtrate obtained in S3, continue to stir for 1 h and then filter for standby use;

[0048] S5: add 1 kg of selenoamino acid manganese microcrystals as crystal nuclei to the filtrate obtained in S4, wherein the selenoamino acid manganese microcrystals are prepared by gradient multiple chelation reaction of commercially available selenoamino acid and manganese ions[1]; adjust the pH value of the system to 6.5, then pass ammonia gas under stirring, monitor the growth process of the precipitate particles, and stop passing ammonia gas when the D 50 particle size of the precipitate particles is 6 μm, continue to stir at room temperature for 24 h;

[0049] S6: 3 kg of citric acid was added to the stirred system, and after stirring uniformly, flash drying was carried out at a temperature of 250°C to obtain basic manganese chloride Mn2(OH)3Cl.

[0050] The basic manganese chloride obtained in this example was tested by particle size analysis to obtain D 50 The particle size was about 6 μm, and D 90 The particle size was less than 13 μm; the primary grain size was about 70 nm by scanning electron microscope analysis, and the Mn element content was 54.7 wt%, the Cl element content was 18.4 wt%, the free water content was 4 wt%, the Ca element content was 0.05 wt%, the Se element content was 0.0003 wt%, the P element content was 0.0001 wt%, the Zn element content was 0.0017 wt%, the Cr element content was 0.00002 wt%, the Pb element content was 0.00003 wt%, the Cd element content was 0.000007 wt%, the As element content was 0.000005 wt%, and the Hg element content was 0.000002 wt% by component analysis; and the KMnO4, MnO2, Mn3O4 and other phases were not contained by XRD analysis.

[0051] Example 2

[0052] A composite basic manganese chloride was prepared by the following steps:

[0053] (1) 500 Kg of industrial-grade manganese carbonate (purity 98%) was added to a glass-steel storage tank (volume 3 m 3 ) containing 1 t of water and 1.05 t of hydrochloric acid with a concentration of 30 wt%, and stirring was carried out until no bubbles were generated, and the impurity ion content in the obtained solution was analyzed and tested as follows:

[0054] Ca 2+ : 1.1 g / L; Zn 2+ : 0.12 g / L; Cu 2+ : 0.004 g / L; Fe 3+ : 0.02 g / L; Al 3+ : 0.02 g / L; Sb 3+ : 0.002 g / L; Cr 3+ : 0.003 g / L; As 3+ : 0.003 g / L; Pb 2+ : 0.003 g / L; Cd 2+ : 0.015 g / L; Hg 2+ : <0.001 g / L; SO4 2- : 0.55 g / L; pH 3.0~3.5;

[0055] S2: adjust the pH value of the solution to 6.3, then add 1.5 times of the total amount of detected iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury in the solution into the solution under stirring, stir for 2 h and filter; repeat the above operation for several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ in the solution are all less than 0.002 g / L;

[0056] S3: add manganese oxalate into the filtrate after filtering in S2, the ratio of added manganese oxalate to the filtrate is 5 kg: 1 m 3 , stir for 1 h and filter;

[0057] S4: add 1.5 times of the total amount of detected Zn 2+ and other heavy metal ions in the solution into the filtrate obtained in S3, continue to stir for 1.5 h, then filter and reserve;

[0058] S5: add 0.75 kg of commercially available methionine manganese microcrystal as crystal nucleus into the filtrate obtained in S4; adjust the pH value of the system to 6.5, then pass ammonia gas under stirring, monitor the growth process of the precipitated particles in the system, and stop passing ammonia gas when the D 50 particle size of the precipitated particles is about 7.5 μm, continue to stir at 55℃ for 10 h;

[0059] S6: add 2.3 kg of ascorbic acid into the stirred system, then perform flash drying at a temperature of 250℃ after uniform stirring, to obtain basic manganese chloride Mn2(OH)3Cl.

[0060] The basic manganese chloride obtained in the example is tested by particle size analysis, and the D 50 particle size is about 7.5 μm, and the D 90The particle size is less than 14 μm; the primary crystal grain size is about 83 nm by scanning electron microscope analysis; the Mn element content is 54.3 wt%, the Cl element content is 18.1 wt%, the free water content is 4.1 wt%, the Ca element content is 0.01 wt%, the Se element content is 0.0001 wt%, the P element content is 0.0001 wt%, the Zn element content is 0.0018 wt%, the Cr element content is 0.000018 wt%, the Pb element content is 0.000023 wt%, the Cd element content is 0.0000065 wt%, the As element content is 0.000005 wt%, and the Hg element content is 0.0000018 wt% by composition analysis; and the solution does not contain KMnO4, MnO2, Mn3O4 and other phases by XRD analysis.

[0061] Comparative Example 1

[0062] A composite basic manganese chloride is prepared by the following steps:

[0063] (1) 500 Kg of industrial grade crude manganese chloride (MnCl2·4H2O) (purity 95%) is added to a glass steel storage tank (volume 3 m 3 ) containing 1.75 t of water, and stirred to completely dissolve, and the impurity ion content in the obtained solution is analyzed and tested, as follows:

[0064] Ca 2+ : 0.6 g / L; Zn 2+ : 0.2 g / L; Cu 2+ : 0.03 g / L; Fe 3+ : 0.02 g / L; Al 3+ : 0.06 g / L; Sb 3+ : 0.005 g / L; Cr 3+ : 0.005 g / L; As 3+ : 0.005 g / L; Pb 2+ : 0.005 g / L; Cd 2+ : 0.015 g / L; Hg 2+ <0.001 g / L; pH 4.0~4.5;

[0065] S2: the pH value of the solution is adjusted to 6.3, and then the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution is added to the solution under stirring, and the solution is stirred for 1 h and filtered; the above operation is repeated several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb2+ , Cd 2+ , Hg 2+ are all less than 0.002 g / L;

[0066] S3: manganese carbonate is added to the filtrate after filtration in S2, the material liquid ratio of the added manganese carbonate to the filtrate is 5 kg: 1 m 3 After stirring for 1 h, filtration is performed;

[0067] S4: ammonium sulfide is added to the filtrate obtained in S3, the total amount of Zn 2+ and other heavy metal ions detected in the solution is 1.5 times, stirring is continued for 1 h, and then filtration is performed for standby;

[0068] S5: under stirring, 81 m 3 of ammonia gas is introduced into the filtrate obtained in S4, and then stirring is continued at room temperature for 24 h;

[0069] S6: the system after stirring is subjected to flash drying at a temperature of 250°C, to obtain basic manganese chloride Mn2(OH)3Cl.

[0070] In the present comparative example, no crystal nucleus agent and surface modifier are added, the obtained basic manganese chloride is subjected to particle size analysis test, and the D 50 particle size is about 18 μm, the D 90 particle size is about 35 μm; the primary crystal grain size is about 310 nm by scanning electron microscope analysis, the Mn element content is 56.3 wt%, the Cl element content is 16.7 wt%, and the free water content is 6.2 wt% by composition analysis; about 19.0 wt% of MnO2, Mn3O4 and other phases are analyzed by XRD.

[0071] Comparative Example 2

[0072] A composite basic manganese chloride is prepared by the following steps:

[0073] (1) 500 kg of industrial-grade manganese carbonate (purity of 98%) is added into a glass steel storage tank (volume of 3 m 3 ) containing 1 t of water and 1.05 t of hydrochloric acid with a concentration of 30 wt%, stirring is performed until no bubbles are generated, and the impurity ion content in the obtained solution is analyzed and tested, and the details are as follows:

[0074] Ca 2+ : 1.1 g / L; Zn 2+ : 0.12 g / L; Cu 2+ : 0.004 g / L; Fe 3+ : 0.02 g / L; Al 3+ : 0.02 g / L; Sb 3+ : 0.002 g / L; Cr3+ : 0.003 g / L; As 3+ : 0.003 g / L; Pb 2+ : 0.003 g / L; Cd 2+ : 0.015 g / L; Hg 2+ : <0.001 g / L; SO4 2- : 0.55 g / L; pH 3.0~3.5;

[0075] S2: The pH value of the solution is adjusted to 6.3, and then the superfine manganese powder 1.5 times the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution is added under stirring, and stirred for 2 h and then filtered; the above operation is repeated for several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ in the solution are all less than 0.002 g / L;

[0076] S3: Manganese oxalate is added to the filtrate after filtering in S2, and the ratio of manganese carbonate added to the filtrate is 5 kg: 1 m 3 , and stirred for 1 h and then filtered;

[0077] S4: Ammonium sulfide 1.5 times the total amount of heavy metal ions such as Zn 2+ detected in the solution is added to the filtrate obtained in S3, and stirred for 1.5 h and then filtered for standby;

[0078] S5: Under stirring, 81 m 3 of ammonia gas is introduced into the filtrate obtained in S4, and then stirred at 55℃ for 10 h;

[0079] S6: The system after stirring is flash dried at a temperature of 250℃ to obtain basic manganese chloride Mn2(OH)3Cl.

[0080] In the present comparative example, no crystal nucleus agent and surface modifier are added, and the obtained basic manganese chloride has a D 50 particle size of about 22 μm, a D 90 particle size of about 43 μm; the primary grain size is about 330 nm by scanning electron microscope analysis; the Mn element content is 55.4 wt%, the Cl element content is 17.1 wt%, and the free water content is 7.1 wt% by composition analysis; and about 12.9 wt% of MnO2, Mn3O4 and other phases are obtained by XRD analysis.

[0081] By comparing the examples with the comparative examples, it can be known that by adding metal manganese and impurity removing agent into the reaction system, the harmful ions in the reaction system can be effectively removed, and the finally obtained product will not have adverse effects on animals and plants; and in the preparation process, a crystal nucleus agent and a surfactant are also added into the system; wherein, the crystal nucleus agent can well control the agglomeration phenomenon in the reaction system, and can promote the forward reaction, so that the yield of the target product is higher, and the particles of the target product are more uniform, thereby obtaining the basic manganese chloride product with narrow and uniform particle size distribution range; in addition, the addition of the crystal nucleus agent can also introduce specific nutrient components into the basic manganese chloride product, so that it is more easily absorbed and utilized by animals and plants, so that the obtained product can be better used as feed or plant fertilizer; the surfactant not only can prevent uncontrollable agglomeration between Mn2(OH)3Cl crystal grains obtained by the reaction, but also can avoid oxidation of Mn2(OH)3Cl by oxygen in the air during the drying process, thereby producing high-valence state manganese components such as Mn 3+ , Mn 4+ , thereby affecting its application and nutrient components in subsequent feed proportioning, and at the same time, the surfactant will adhere to the surface of the product after drying, which is more conducive to the absorption of animals or plants. The composite basic manganese chloride prepared by the present application has very low harmful ion content and does not contain high-valence manganese, and can be applied to animal feed and plant fertilizer additives.

[0082] Although the specific embodiments of the present application are described in detail in combination with the examples, it should not be understood as limiting the protection scope of the present patent. Various modifications and changes made by those skilled in the art within the scope described in the claims are still within the protection scope of the present patent.

Claims

1. A composite basic manganese chloride characterized in that: The composite basic manganese chloride does not contain KMnO4, MnO2 and Mn3O4, and the D 50 The particle size is 6-8 μm, the D 90 The particle size is less than 15 μm, the Mn element content is 53.0wt%-56.8wt%, the Cl element content is 16.5wt%-19.5wt%, the H2O content is 1wt-5wt%, the Ca element content is 0.01wt%-0.05wt%, the Se element content is 0.0001wt%-0.0005wt%, the P element content is 0.0001wt%-0.0003wt%, the Zn element content is 0.0015wt%-0.002wt%, and the Cr, Pb, Cd, As and Hg element contents are all lower than 0.00003wt%; and the preparation method of the composite basic manganese chloride comprises the following steps: S1: dissolving manganese-containing material in water or acid solution to prepare a solution with a manganese ion concentration of 75-130 g / L; the manganese-containing material is industrial manganese chloride, industrial manganese carbonate or industrial manganese oxide; S2: adjust the pH of the solution to 6-6.5, then add manganese metal to the solution, stir, filter, repeat the above operation several times until the Fe 3+ , Al 3+ , Cu 2+ , Sb 3+ , Cr 3+ , As 3+ , Pb 2+ , Cd 2+ , Hg 2+ contents in the filtrate are all less than 0.002 g / L; S3: adding a decontaminant to the filtrate obtained in S2, stirring, filtering, then adding ammonium sulfide to the obtained filtrate, continuing to stir and filter, to obtain a pure manganese solution; the decontaminant is at least one of manganese sulfide, manganese oxalate, manganese carbonate, ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium oxalate, potassium oxalate; the ratio of the decontaminant to the filtrate is 5 kg: 1 m 3 ; the stirring time after adding the decontaminant is 1 h; the added ammonium sulfide is 1.5 times the detected zinc in the solution; the stirring time after adding the ammonium sulfide is 1-2 h; S4: adding a crystal nucleus agent to the purified manganese liquid, adjusting the pH of the purified manganese liquid to 6-7, then introducing a precipitant into the purified manganese liquid to perform a precipitation reaction until the D 50 particle size reaches 6-8 μm, stopping the precipitation reaction and stirring at 20-55 °C for 10-24 h; the crystal nucleus agent is at least one of selenoamino acid manganese, methionine manganese, manganese citrate, and manganese gluconate; the mass ratio of the added crystal nucleus agent to the manganese-containing material is 0.5-1:500; S5: adding a surface modifier to the system obtained in S4, uniformly mixing, and then flash drying at 250 DEG C to obtain the product; the surface modifier is at least one of glucose, sucrose, citric acid, ascorbic acid, amino acid, unsaturated fatty acid, salicylic acid, ethylene glycol, glycerol, ethyl acetate and butanone; the mass ratio of the added surface modifier to the crystal nucleus agent is 3-3.1:

1.

2. The composite basic manganese chloride according to claim 1, characterized in that: The acid solution is a hydrochloric acid solution.

3. The composite basic manganese chloride according to claim 1, characterized in that: The metallic manganese is manganese particles; the amount of the metallic manganese added is 1.5 times the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution.

4. The composite basic manganese chloride according to claim 1, characterized in that: The metallic manganese is ultrafine manganese powder; the amount of the metallic manganese added is 1.5 times the total amount of iron, aluminum, copper, antimony, chromium, arsenic, lead, cadmium and mercury detected in the solution.

5. The composite basic manganese chloride according to claim 1, characterized in that: The precipitant is at least one of ammonia gas, liquid ammonia, aqueous ammonia, sodium hydroxide, potassium hydroxide and lithium hydroxide.

6. Use of the composite basic manganese chloride according to claim 1, characterized in that The composite basic manganese chloride is used as an animal feed additive or a plant fertilizer additive.