CN117342618A - Basic manganese chloride and preparation method and application thereof - Google Patents
Basic manganese chloride and preparation method and application thereof Download PDFInfo
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 title claims abstract description 109
- 229910021380 Manganese Chloride Inorganic materials 0.000 title claims abstract description 107
- 239000011565 manganese chloride Substances 0.000 title claims abstract description 107
- 235000002867 manganese chloride Nutrition 0.000 title claims abstract description 107
- 229940099607 manganese chloride Drugs 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003513 alkali Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 14
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 59
- 239000000047 product Substances 0.000 claims description 48
- 239000011572 manganese Substances 0.000 claims description 45
- 229910052748 manganese Inorganic materials 0.000 claims description 44
- 239000000706 filtrate Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 33
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 27
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000005751 Copper oxide Substances 0.000 claims description 24
- 229910000431 copper oxide Inorganic materials 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
- 229910001431 copper ion Inorganic materials 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 235000019730 animal feed additive Nutrition 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007790 solid phase Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application relates to basic manganese chloride and a preparation method and application thereof. According to the preparation method of basic manganese chloride, the manganese chloride solution with the manganese ion concentration of 60 g/L-100 g/L and the ammonia nitrogen concentration of 5 g/L-15 g/L and the alkali solution with the hydroxide concentration of 100 g/L-150 g/L are selected, so that the reaction can be fully performed under the induction action of the ammonia nitrogen; and the alkali liquor concentration that this application used is lower, can avoid the product to reunite and the too high shortcoming that leads to of local concentration of alkali liquor product purity, and then makes the basic manganese chloride of this application preparation be granular, not agglomerate, and has the advantage that the particle diameter is big and the purity is high concurrently. On the other hand, the method limits the technological parameters of precipitation reaction, does not need to be protected by inert gas, and simultaneously can fully react without adding a surfactant and a catalyst, so that the method is simple in process. Thus, organic matters such as surfactant, catalyst and the like are avoided, and the produced wastewater is simple to treat, safe and environment-friendly.
Description
Technical Field
The application relates to the technical field of inorganic chemical product preparation, in particular to a preparation method of basic manganese chloride.
Background
Basic manganese chloride is a commonly used manganese compound which is not easily oxidized in air and is not easily absorbed by moisture and agglomerates, and is well absorbed in animals, so that the basic manganese chloride is widely used as pigment of enamel, paint and varnish, animal feed additive and the like.
Currently, the synthesis methods of basic manganese chloride mainly include solid-liquid synthesis methods and liquid-liquid synthesis methods. The solid-liquid synthesis method mainly comprises two types: (1) Adding manganese oxide solid into ammonium chloride solution to react in the presence of a surfactant to prepare basic manganese chloride; (2) In the presence of a catalyst, solid manganese hydroxide or solid manganese monoxide is added into a manganese chloride solution to react, so as to prepare basic manganese chloride. The solid-liquid synthesis method needs to react in the presence of a surfactant or a catalyst, and the produced basic manganese chloride has small particle size and is easy to generate static electricity and raise dust. The liquid-liquid synthesis method mainly utilizes the reaction of manganese chloride solution and strong alkali to prepare basic manganese chloride under the protection of nitrogen or inert gas, but in the liquid-liquid synthesis method, the required strong alkali concentration is higher, so that the agglomeration of products is easy to cause; and the partial concentration of hydroxide is higher, so that manganese hydroxide is easy to generate, and manganese dioxide is further generated by oxidation, and the purity of the final product is influenced.
Disclosure of Invention
Based on the above, the application provides basic manganese chloride and a preparation method and application thereof. The preparation method provided by the application can enable the prepared basic manganese chloride to be granular and not to agglomerate, and has the advantages of large grain size and high purity.
In a first aspect of the present application, there is provided a method for preparing basic manganese chloride, comprising the steps of:
manganese chloride solution and alkali liquor are mixed according to the proportion of 2-4: 1 is added into the reaction base solution in parallel flow mode,
carrying out precipitation reaction at the pH value of 6.5-8 and the temperature of 60-80 ℃ for 2-4 hours, and then carrying out solid-liquid separation and collecting basic manganese chloride solid;
wherein, the ammonia nitrogen concentration in the reaction base solution is 5 g/L-15 g/L;
in the manganese chloride solution, the concentration of manganese ions is 60 g/L-100 g/L, and the concentration of ammonia nitrogen is 5 g/L-15 g/L;
in the alkali liquor, the concentration of hydroxyl is 100 g/L-150 g/L.
In one embodiment, the preparation process of the manganese chloride solution comprises the following steps:
mixing the solution with a manganese source, adding hydrochloric acid to adjust the pH to 0.5-1, reacting for 2-4 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate; wherein the solution contains ammonia nitrogen and chloride ions; adjusting the pH value of the first filtrate to 3-4, adding manganese powder, reacting for 0.5-1 h, and then carrying out solid-liquid separation to prepare a second solid and a second filtrate;
and adding an ammonia source into the second filtrate to prepare the manganese chloride solution with the manganese ion concentration of 60 g/L-100 g/L and the ammonia nitrogen concentration of 5 g/L-15 g/L.
In one embodiment, the ammonia nitrogen concentration in the solution is 2 g/L-5 g/L, and the sodium chloride concentration is 50 g/L-100 g/L.
In one embodiment, the process for preparing the solution comprises the steps of:
taking copper oxide production mother liquor, wherein the ammonia nitrogen concentration in the copper oxide production mother liquor is 2 g/L-5 g/L, the sodium chloride concentration is 50 g/L-100 g/L, and the copper ion concentration is 1 g/L-3 g/L;
and removing copper ions in the copper oxide production mother liquor by an ion exchange resin method to ensure that the concentration of the copper ions is less than or equal to 2 mg/L, so as to prepare the solution.
In one embodiment, the copper oxide production mother liquor is a waste liquor generated in the process of producing a copper oxide product by using an acidic etching waste liquor and/or an alkaline etching waste liquor.
In one embodiment, the manganese source has one or more of the following characteristics:
(1) The manganese source is manganese slag;
(2) The manganese source comprises 40-45 parts of manganese and 0.02-0.05 part of lead in parts by weight.
In one embodiment, the ammonia source comprises one or more of ammonium chloride, aqueous ammonia, ammonium sulfate, ammonium nitrate, ammonium carbonate, and urea.
In a second aspect, the present application provides a basic manganese chloride obtained by the preparation method according to any one of the embodiments in the first aspect of the present application, where the basic manganese chloride has one or more of the following characteristics:
(1) The grain diameter D50 of the basic manganese chloride is more than or equal to 65 mu m;
(2) The purity of the basic manganese chloride is more than or equal to 97 percent.
In a third aspect of the present application there is provided an animal feed additive comprising the basic manganese chloride described in the second aspect of the present application.
In a fourth aspect of the present application there is provided a pigment comprising the manganese basic chloride described in the second aspect of the present application.
According to the preparation method of basic manganese chloride, a manganese chloride solution with the manganese ion concentration of 60 g/L-100 g/L and the ammonia nitrogen concentration of 5 g/L-15 g/L and an alkali solution with the hydroxide concentration of 100 g/L-150 g/L are selected, and the reaction can be fully performed under the induction action of the ammonia nitrogen; and the alkali liquor concentration that this application used is lower, can avoid the product to reunite and the too high shortcoming that leads to of local concentration of alkali liquor product purity, and then makes the basic manganese chloride of this application preparation be granular, not agglomerate, and has the advantage that the particle diameter is big and the purity is high concurrently.
On the other hand, the method limits the technological parameters of precipitation reaction, does not need to be protected by inert gas, and simultaneously can fully react without adding a surfactant and a catalyst, so that the method is simple in process. Thus, organic matters such as surfactant, catalyst and the like are avoided, and the produced wastewater is simple to treat, safe and environment-friendly.
Drawings
Fig. 1-2 are process flow charts of the preparation method of basic manganese chloride provided by the application;
fig. 3 to 4 are scanning electron microscope diagrams of basic manganese chloride prepared in example 1 of the present application;
FIG. 5 is an XRD pattern of basic manganese chloride prepared in example 1 of the present application;
FIG. 6 is a graph showing the particle size distribution of basic manganese chloride prepared in example 1 of the present application.
Detailed Description
The basic manganese chloride and the preparation method and application thereof are further fully and clearly described below with reference to specific examples. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, 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 in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Herein, "one or more" refers to any one, any two, or any two or more of the listed items.
In this application, "first aspect," "second aspect," "third aspect," "fourth aspect," "fifth aspect," etc. are for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature being indicated. Also, "first," "second," "third," "fourth," "fifth," etc. are for non-exhaustive list of descriptive purposes only and are not to be construed as limiting the number of closed forms.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise the open technical scheme of the listed characteristics.
In the present application, reference is made to numerical intervals, where the numerical intervals are considered to be continuous unless specifically stated, and include the minimum and maximum values of the range, and each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The percentage content referred to in the present application refers to mass percent for both solid-liquid and solid-solid phase mixing and volume percent for liquid-liquid phase mixing unless otherwise specified.
The percentage concentrations referred to in this application, unless otherwise indicated, refer to the final concentrations. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
As used herein, "ammonia nitrogen" refers to the compound nitrogen in the form of ammonia or ammonium ions, i.e., free ammonia (NH) 3 ) And ammonium ion (NH) 4 + ) Nitrogen in the form of nitrogen.
In a first aspect of the present application, there is provided a method for preparing basic manganese chloride, comprising the steps of:
s50, mixing a manganese chloride solution and alkali liquor according to a ratio of 2-4: 1, and adding the mixture into the reaction base solution in parallel flow;
carrying out precipitation reaction at the pH value of 6.5-8 and the temperature of 60-80 ℃ for 2-4 hours, and then carrying out solid-liquid separation and collecting basic manganese chloride solid;
wherein, the ammonia nitrogen concentration in the reaction base solution is 5 g/L-15 g/L;
in the manganese chloride solution, the concentration of manganese ions is 60 g/L-100 g/L, and the concentration of ammonia nitrogen is 5 g/L-15 g/L;
in the alkali liquor, the concentration of hydroxyl is 100 g/L-150 g/L.
It can be understood that in step S50 of the present application, the volume flow ratio of the manganese chloride solution to the alkali solution may be selected from 2 to 4: any number between 1. In particular, the volumetric flow ratio of the manganese chloride solution and the lye 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 the present application, the pH at which the precipitation reaction is performed may be selected from any value between 6.5 and 8. In particular, the pH at which the precipitation reaction is performed includes, but is not limited to, 6.5, 6.7, 6.9, 7, 7.3, 7.5, 7.8, 7.9, or 8. In the present application, the temperature at which the precipitation reaction is carried out may 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 the application, the time for carrying out the precipitation reaction is 2-4 hours. Specifically, the time for performing the precipitation reaction includes, but is not limited to, 2h, 2.1h, 2.5h, 3h, 3.5h, 3.8h, 3.9h, or 4h.
In the preparation method, the precipitation reaction temperature is controlled to be 60-80 ℃ and the pH is controlled to be 6.5-8, so that on one hand, the influence on the product purity caused by the generation of manganese dioxide due to the overhigh reaction temperature or overhigh pH can be avoided; on the other hand, the defect that the chlorine content in the product is low due to the too low reaction temperature or the basic manganese chloride cannot be synthesized due to the too low pH value can be avoided.
In addition, it is understood that in step S50, the concentration of manganese ions in the manganese chloride solution may be any value between 60g/L and 100g/L. Specifically, the manganese ion concentration includes, but is not limited to, 60g/L, 65 g/L, 70 g/L, 75 g/L, 80g/L, 85 g/L, 90 g/L, 91 g/L, 92 g/L, 93 g/L, 95 g/L, 98 g/L, or 100g/L. The ammonia nitrogen concentration can be any value between 5g/L and 15 g/L. Specifically, ammonia nitrogen concentrations include, but are not limited to, 5g/L, 6 g/L, 7 g/L, 8 g/L, 10g/L, 12 g/L, 13 g/L, or 15 g/L.
In the manganese chloride solution, the concentration of manganese ions is set to be 60 g/L-100 g/L, and the concentration of ammonia nitrogen is set to be 5 g/L-15 g/L, so that good compatibility between manganese element and ammonia nitrogen can be ensured; meanwhile, the concentration of ammonia nitrogen is more suitable for inducing the generation of basic manganese chloride, so that the phenomenon that the concentration of ammonia nitrogen is too low and the inducibility is insufficient is avoided, the product is easy to agglomerate, and the quality of the synthesized basic manganese chloride product is poor; and the ammonia nitrogen concentration is too high, resulting in the defect of low product conversion rate.
The concentration of hydroxyl in the alkali liquor can be any value between 100g/L and 150 g/L. Specifically, hydroxyl concentration includes, but is not limited to, 100g/L, 101 g/L, 103 g/L, 105 g/L, 107 g/L, 109 g/L, 110 g/L, 115 g/L, 120g/L, 125 g/L, 130 g/L, 135 g/L, 140 g/L, 145 g/L, or 150 g/L. It is understood that the alkali liquor is not particularly limited in this application, and may include, but is not limited to, aqueous potassium hydroxide solution, aqueous sodium hydroxide solution.
The concentration of hydroxyl in the alkali liquor is between 100g/L and 150g/L, so that the local concentration of the alkali liquor is prevented from being too high, further, the agglomeration of products or the generation of manganese dioxide can be avoided, and the purity of the products can be effectively ensured; further, the problems of slow production rate of products and large amount of wastewater generated due to the too low concentration of alkali liquor can be prevented.
In the reaction base solution, the ammonia nitrogen concentration can be any value between 5g/L and 15 g/L. Specifically, the ammonia nitrogen concentration in the reaction base solution includes, but is not limited to, 5g/L, 6 g/L, 7 g/L, 8 g/L, 10g/L, 12 g/L, 13 g/L or 15 g/L. The concentration of ammonia nitrogen in the reaction base solution is between 5g/L and 15g/L, so that the reaction base solution can induce the manganese chloride solution and the alkali liquor to perform precipitation reaction, and a surfactant and a catalyst are not required to be added in the reaction process, and inert gas is not required to be introduced for protection.
In the present application, the type of the reaction base solution is not limited, and the reaction base solution may contain 5g/L to 15g/L ammonia nitrogen. The types of reaction base solutions 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 solution.
In one specific example, after the precipitation reaction is completed, the method further comprises steps S601 to S603 of processing the basic manganese chloride production mother liquor:
s601, adding an alkaline compound into the basic manganese chloride production mother liquor to precipitate manganese, and preparing a manganese precipitation solid phase and first wastewater;
s602, recycling ammonia nitrogen from the first wastewater through a membrane system to prepare an ammonium salt product and second wastewater;
s603, evaporating and concentrating the second wastewater to prepare a chloride salt product.
Specifically, in step S601, the alkaline compound includes one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate. At this time, in step S603, the prepared chloride salt product is a sodium chloride product.
It will be appreciated that in step S601, the prepared manganese precipitation solid phase can be used to adjust the pH of the first filtrate in S30 described below. In step S602, the prepared ammonium salt product can be used to supplement ammonia nitrogen in the manganese chloride solution.
In one example, the preparation process of the manganese chloride solution comprises the following steps:
s20, mixing the solution with a manganese source, adding hydrochloric acid to adjust the pH to 0.5-1, reacting for 2-4 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate; wherein the solution contains ammonia nitrogen and chloride ions;
s30, adjusting the pH value of the first filtrate to 3-4, adding manganese powder, reacting for 0.5-1 h, and performing solid-liquid separation to prepare a second solid and a second filtrate;
s40, adding an ammonia source into the second filtrate to prepare the manganese chloride solution with the manganese ion concentration of 60 g/L-100 g/L and the ammonia nitrogen concentration of 5 g/L-15 g/L.
It will be appreciated that the "solution" referred to herein contains not only ammonia nitrogen but also chloride ions; thereby enabling it to provide an ammonia source and a chlorine source for the preparation of basic manganese chloride.
In one example, in step S20, the manganese source contains 40-45 parts by weight of manganese and 0.02-0.05 parts by weight of lead.
In a specific example thereof, in step S20, the manganese source is manganese slag. More specifically, the manganese source is manganese slag generated after the production of manganese monoxide. Wherein the main chemical components of the manganese slag are shown in the following table 1.
TABLE 1
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.
in step S20, the pH adjusted by adding hydrochloric acid may be any value between 0.5 and 1. Specifically, pH includes, but is not limited to, 0.5, 0.6, 0.7, 0.8, 0.9, or 1. The reaction time can be selected from any value between 2h and 4h. Specifically, the reaction time includes, but is not limited to, 2h, 2.3h, 2.5h, 2.7h, 2.9h, 3h, 3.5h, or 4h.
In the step S20, the pH is regulated to 0.5-1 by hydrochloric acid, and the reaction is carried out for 2-4 hours, on one hand, the manganese in the manganese source can be ensured to be completely converted into a free state to exist in the first filtrate; on the other hand, since the manganese slag contains acid-insoluble substances, the acid-insoluble substances may be present in the first solid by solid-liquid separation after the reaction.
In one example, in the step S20, the ammonia nitrogen concentration in the solution is 2 g/L-5 g/L, and the sodium chloride concentration is 50 g/L-100 g/L. It will be appreciated that ammonia nitrogen concentrations in the solution include, but are not limited to, 2g/L, 2.5 g/L, 3g/L, 3.5 g/L, 4 g/L, 4.5 g/L, or 5 g/L. Sodium chloride concentrations include, but are not limited to, 50g/L, 60g/L, 70 g/L, 80g/L, 90 g/L, or 100g/L.
In step S30, the manganese powder is added to remove other metal impurity ions, such as lead ions, in the first filtrate by replacement, so as to reduce the impurity content in the filtrate and ensure the quality of subsequent products.
It will be appreciated that in step S30, the lead ion impurities are removed, and an excess of manganese powder is required. In one example, in step S30, the molar ratio of manganese powder to the molar ratio of lead content in the first filtrate is 1.5-2: 1. specifically, the molar ratio of manganese powder to the lead content of 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.
in step S30, the pH of the first filtrate may be adjusted to be 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 the manganese powder includes, but is not limited to, 0.5h, 0.6h, 0.8h, 0.9h, or 1h.
In one example, in step S40, the ammonia source includes one or more of ammonium chloride, aqueous ammonia, ammonium sulfate, ammonium nitrate, ammonium carbonate, and urea.
In one example, the preparation process of the solution includes the following step S10:
s10, taking copper oxide production mother liquor, wherein the ammonia nitrogen concentration in the copper oxide production mother liquor is 2 g/L-5 g/L, the sodium chloride concentration is 50 g/L-100 g/L, and the copper ion concentration is 1 g/L-3 g/L;
and removing copper ions in the copper oxide production mother liquor by an ion exchange resin method to ensure that the concentration of the copper ions is less than or equal to 2 mg/L, so as to prepare the solution.
In one example, in step S10, the copper oxide production mother liquor is a waste liquor generated in the process of producing a copper oxide product using an acidic etching waste liquor and/or an alkaline etching waste liquor, and the main chemical components of the waste liquor are shown in the following table 2.
TABLE 2
In addition, in the step S10, potassium hydroxide or sodium hydroxide can be added into the prepared solution to prepare alkali liquor with the concentration of 100 g/L-150 g/L, and the alkali liquor can be used in the step S50.
In the application, the solution is prepared by utilizing the copper oxide production mother liquor generated in the process of producing the copper oxide product by utilizing the acid etching waste liquor and/or the alkaline etching waste liquor; and in step S20, the mixture is mixed with the manganese slag, so that the acid insoluble matters in step S20 and other impurities in the manganese slag are present in the first solid, and the first solid can be used as a cement production raw material after rinsing. In step S30, the second solid produced after the solid-liquid separation can be used as a smelting raw material.
The method utilizes the acid etching waste liquid and/or the alkaline etching waste liquid to provide an ammonia source and a chlorine source for the waste liquid generated after the process of producing the copper oxide product; and the manganese slag is used as a manganese source, so that valuable resources in industrial wastes can be fully utilized, and the method is safe and environment-friendly. Meanwhile, ammonia nitrogen is used as an inducer, and full reaction is realized under the condition that a surfactant and a catalyst are not required to be added. Further, under the matching of reaction conditions of pH of 6.5-8, temperature of 60-80 ℃ and reaction time of 2-4 h, preparing a manganese chloride solution with lower concentration and alkali liquor for reaction, and avoiding the defects of low product purity caused by agglomeration of products and overhigh local concentration of the alkali liquor, so that the alkali manganese chloride prepared by the method is granular and free from agglomeration, and has the advantages of large particle size and high purity.
It should be understood that, although the steps in the flowcharts of fig. 1 to 2 are sequentially shown as indicated by arrows, the steps are not necessarily sequentially performed in the order indicated by the arrows. The steps are not strictly limited to the order of execution unless explicitly recited herein, and the steps may be executed in other orders. Moreover, at least a portion of the steps in fig. 1-2 may include a plurality of steps or stages, which are not necessarily performed at the same time, but may be performed at different times, and the order of performing the steps or stages is not necessarily sequential, but may be performed in turn or alternately with at least a portion of the steps or stages in other steps or others.
In a second aspect of the present application, there is provided a basic manganese chloride obtained by the method of preparation as exemplified in any one of the first aspects of the present application.
In one example, the particle size D50 of the basic manganese chloride is greater than or equal to 65 mu m. The particle size D50 of the basic manganese chloride prepared by the method is more than or equal to 65 mu m and is higher than 45 mu m in related products, so that static electricity and dust are not easy to generate.
In one example, the basic manganese chloride has a purity of 97% or more.
In a third aspect of the present application there is provided an animal feed additive comprising the basic manganese chloride described in the second aspect of the present application.
In a fourth aspect of the present application there is provided a pigment comprising the manganese basic chloride described in the second aspect of the present application.
The following are specific examples, and all materials used in the examples are commercially available products unless otherwise specified. The manganese slags used in the following examples and comparative examples were derived from manganese product manufacturers, and various indexes of the manganese slags are shown in the above table 1. The solutions used in the following examples and comparative examples were prepared from the copper oxide production mother liquor produced in the production of copper oxide products from acid and alkaline etching waste solutions, and the respective indexes of the copper oxide production mother liquor are shown in the above-mentioned Table 2.
Example 1
Embodiment 1 of the present application provides an alkali manganese chloride and a preparation method thereof, comprising the following steps:
(1) Copper ions are removed from copper oxide production mother liquor by an ion exchange resin method, so that the concentration of the copper ions is less than or equal to 2 mg/L, and a solution is prepared.
(2) Taking 400 kg solution (ammonia nitrogen concentration in the solution is 3g/L, chloride ion concentration is 80 g/L); adding 100kg of manganese slag, regulating and maintaining the pH value to 0.5 by using hydrochloric acid with the volume concentration of 31%, reacting for 2 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate;
(3) Adding the manganese precipitation solid phase generated in the step (6) into the first filtrate, adjusting the pH to 3, adding manganese powder, and enabling the molar ratio of the manganese powder to the molar ratio of the lead content in the first filtrate to be 1.5:1, after reacting for 0.5h, carrying out solid-liquid separation to prepare a second solid and a second filtrate;
(4) Adding ammonium chloride solid into the second filtrate to prepare a manganese chloride solution with the manganese ion concentration of 100g/L and the ammonia nitrogen concentration of 5 g/L;
(5) Taking 500L of the solution prepared in the step (1), adding sodium hydroxide solid, and preparing 100g/L of alkali liquor; adding 500L of the solution prepared in the step (1) into ammonium chloride solid to prepare reaction base solution with ammonia nitrogen concentration of 5g/L, heating to 60 ℃ and maintaining the reaction temperature, adding the manganese chloride solution prepared in the step (4) and alkali liquor in parallel flow, controlling the reaction pH to be 6.5, and controlling the volume flow ratio of the manganese chloride solution to the alkali liquor to be 4:1, after reacting for 4 hours, separating solid from liquid, washing and drying the solid phase, and preparing the basic manganese chloride.
(6) Adding sodium hydroxide solid into a liquid phase generated after solid-liquid separation in the step (5) to precipitate manganese, and preparing a manganese-precipitated solid phase and first wastewater; recycling ammonia nitrogen from the first wastewater through a membrane system to prepare an ammonium chloride product and second wastewater; evaporating and concentrating the second wastewater to prepare a sodium chloride product.
Example 2
Embodiment 2 of the present application provides an alkali manganese chloride and a preparation method thereof, comprising the following steps:
(1) Copper ions are removed from copper oxide production mother liquor by an ion exchange resin method, so that the concentration of the copper ions is less than or equal to 2 mg/L, and a solution is prepared.
(2) 600 kg solution (ammonia nitrogen concentration in the solution is 3g/L, chloride ion concentration is 80 g/L) is taken; adding 100kg of manganese slag, regulating and maintaining the pH value to 1 by using hydrochloric acid with the volume concentration of 31%, reacting for 4 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate;
(3) Adding the manganese precipitation solid phase generated in the step (6) into the first filtrate, adjusting the pH to 4, adding manganese powder, wherein the molar ratio of the manganese powder to the lead content in the first filtrate is 2:1, after reacting for 1h, carrying out solid-liquid separation to prepare a second solid and a second filtrate;
(4) Adding ammonium chloride solid into the second filtrate to prepare a manganese chloride solution with the manganese ion concentration of 60g/L and the ammonia nitrogen concentration of 15 g/L;
(5) Taking 500L of the solution prepared in the step (1), adding sodium hydroxide solid, and preparing 150g/L of alkali liquor; adding 500L of the solution prepared in the step (1) into ammonium chloride solid to prepare reaction base solution with ammonia nitrogen concentration of 15g/L, heating to 80 ℃ and maintaining the reaction temperature, adding the manganese chloride solution prepared in the step (4) and alkali liquor in parallel flow, controlling the reaction pH to be 8, and controlling the volume flow ratio of the manganese chloride solution to the alkali liquor to be 2:1, after reacting for 2 hours, separating solid from liquid, washing and drying the solid phase, and preparing the basic manganese chloride.
(6) Preparing a manganese precipitation solid phase and first wastewater from a liquid phase generated after solid-liquid separation in the step (5); recycling ammonia nitrogen from the first wastewater through a membrane system to prepare an ammonium chloride product and second wastewater; evaporating and concentrating the second wastewater to prepare a sodium chloride product.
Example 3
Embodiment 3 of the present application provides an alkali manganese chloride and a preparation method thereof, comprising the following steps:
(1) Copper ions are removed from copper oxide production mother liquor by an ion exchange resin method, so that the concentration of the copper ions is less than or equal to 2 mg/L, and a solution is prepared.
(2) Taking 500 kg solution (ammonia nitrogen concentration in the solution is 3g/L, chloride ion concentration is 80 g/L); adding 100kg of manganese slag, regulating and maintaining the pH value to 0.8 by using hydrochloric acid with the volume concentration of 31%, reacting for 3 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate;
(3) Adding the manganese precipitation solid phase generated in the step (6) into the first filtrate, adjusting the pH to 3.5, adding manganese powder, and adding the manganese powder to the first filtrate in a molar ratio of 1.8:1, after reacting for 0.8h, carrying out solid-liquid separation to prepare a second solid and a second filtrate;
(4) Adding ammonium chloride solid into the second filtrate to prepare a manganese chloride solution with the manganese ion concentration of 80g/L and the ammonia nitrogen concentration of 10 g/L;
(5) Taking 500L of the solution prepared in the step (1), adding sodium hydroxide solid, and preparing 120g/L of alkali liquor; adding 500L of the solution prepared in the step (1) into ammonium chloride solid to prepare reaction base solution with ammonia nitrogen concentration of 10g/L, heating to 70 ℃ and maintaining the reaction temperature, adding the manganese chloride solution prepared in the step (4) and alkali liquor in parallel flow, controlling the reaction pH to be 7, and controlling the volume flow ratio of the manganese chloride solution to the alkali liquor to be 3:1, after 3 hours of reaction, separating solid from liquid, washing and drying the solid phase, and preparing the basic manganese chloride.
(6) Preparing a manganese precipitation solid phase and first wastewater from a liquid phase generated after solid-liquid separation in the step (5); recycling ammonia nitrogen from the first wastewater through a membrane system to prepare an ammonium chloride product and second wastewater; evaporating and concentrating the second wastewater to prepare a sodium chloride product.
Comparative example 1
Comparative example 1 is essentially the same as example 1, the main difference being that in step (5) the concentration of the lye is 200g/L.
Comparative example 2
Comparative example 2 is substantially the same as example 1, except that in step (5), a manganese chloride solution having an ammonia nitrogen concentration of 25g/L is prepared.
Comparative example 3
Comparative example 3 is substantially the same as example 1, except that in step (5), the reaction is carried out at a temperature of 50 ℃.
Comparative example 4
Comparative example 4 is substantially the same as example 1, except that in step (5), the reaction is carried out at a pH of 10.
Comparative example 5
Comparative example 5 is essentially the same as example 1, the main difference being that in step (5) the volume flow ratio of manganese chloride solution to lye is 6:1.
the test methods or test criteria for the products of the examples and comparative examples are:
(1) Morphology: observations and measurements were made using Scanning Electron Microscopy (SEM). Scanning electron microscope images of the basic manganese chloride product prepared in the step (5) of the embodiment 1 are respectively shown in fig. 3-4.
(2) The crystal form structure: the test analysis was performed using an X-ray diffractometer (XRD). The XRD pattern of the basic manganese chloride product prepared in step (5) of example 1 is shown in FIG. 5.
(3) Particle size: the test was performed 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 in fig. 6.
(4) Purity of the products and other component contents in examples and comparative examples: detection was performed according to the body standard basic manganese chloride (T-CPCIF 0164-2021).
The corresponding detection indexes are shown in table 3.
TABLE 3 Table 3
As can be seen from figures 3-4, the basic manganese chloride product prepared by the method is independently shaped into particles and is free from caking. FIG. 5 shows that the product prepared in example 1 of the present application has a molecular formula Mn 2 (OH) 3 Cl. As can be seen from FIG. 6, the particle size D50 of the product prepared in example 1 was 70.94 μm, and the particle size distribution was relatively uniform. As can be seen from Table 3, the examples of the present application1-the purity of the basic manganese chloride prepared in the embodiment 3 is more than or equal to 97.3 percent and 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 alkali liquor used in comparative example 1 has too high concentration, so that the purity of the prepared product is lower, and the particle size of the prepared product is also smaller; the ammonia nitrogen content in the manganese chloride solution used in the comparative example 2 is too high, the purity of the prepared basic manganese chloride cannot meet the requirements of the group standard, and in the actual production and preparation process, the conversion rate of the product of the comparative example 2 is lower and is lower than 50%; the product conversion rate in the embodiment 1 to the embodiment 3 is more than or equal to 70 percent; the temperature, pH and volume flow ratio of the reaction in comparative examples 3-5 do not meet the requirements, so that the purity of the prepared basic manganese chloride and the particle size of the product are low.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be indicated by the appended claims, and the description may be used to interpret the contents of the claims.
Claims (10)
1. The preparation method of the basic manganese chloride is characterized by comprising the following steps:
manganese chloride solution and alkali liquor are mixed according to the proportion of 2-4: 1, and adding the mixture into the reaction base solution in parallel flow;
carrying out precipitation reaction at the pH value of 6.5-8 and the temperature of 60-80 ℃ for 2-4 hours, and then carrying out solid-liquid separation and collecting basic manganese chloride solid;
wherein, the ammonia nitrogen concentration in the reaction base solution is 5 g/L-15 g/L;
in the manganese chloride solution, the concentration of manganese ions is 60 g/L-100 g/L, and the concentration of ammonia nitrogen is 5 g/L-15 g/L;
in the alkali liquor, the concentration of hydroxyl is 100 g/L-150 g/L.
2. The method for preparing basic manganese chloride according to claim 1, wherein the preparation process of the manganese chloride solution comprises the following steps:
mixing the solution with a manganese source, adding hydrochloric acid to adjust the pH to 0.5-1, reacting for 2-4 hours, and then carrying out solid-liquid separation to prepare a first solid and a first filtrate; wherein the solution contains ammonia nitrogen and chloride ions;
adjusting the pH value of the first filtrate to 3-4, adding manganese powder, reacting for 0.5-1 h, and then carrying out solid-liquid separation to prepare a second solid and a second filtrate;
and adding an ammonia source into the second filtrate to prepare the manganese chloride solution with the manganese ion concentration of 60 g/L-100 g/L and the ammonia nitrogen concentration of 5 g/L-15 g/L.
3. The method for preparing basic manganese chloride according to claim 2, wherein the ammonia nitrogen concentration in the solution is 2g/L to 5g/L, and the sodium chloride concentration is 50g/L to 100g/L.
4. A method of preparing basic manganese chloride according to claim 3 wherein said solution is prepared by the steps of:
taking copper oxide production mother liquor, wherein the ammonia nitrogen concentration in the copper oxide production mother liquor is 2 g/L-5 g/L, the sodium chloride concentration is 50 g/L-100 g/L, and the copper ion concentration is 1 g/L-3 g/L;
and removing copper ions in the copper oxide production mother liquor by an ion exchange resin method to ensure that the concentration of the copper ions is less than or equal to 2 mg/L, so as to prepare the solution.
5. The method for preparing basic manganese chloride according to claim 4, wherein the mother liquor for producing copper oxide is a waste liquor produced in the production of copper oxide product by using an acidic etching waste liquor and/or an alkaline etching waste liquor.
6. The method for preparing basic manganese chloride according to any one of claims 2 to 5, wherein the manganese source has one or more of the following characteristics:
(1) The manganese source is manganese slag;
(2) The manganese source comprises 40-45 parts of manganese and 0.02-0.05 part of lead in parts by weight.
7. The method for preparing basic manganese chloride according to any one of claims 2 to 5, wherein the ammonia source comprises one or more of ammonium chloride, aqueous ammonia, ammonium sulfate, ammonium nitrate, ammonium carbonate and urea.
8. The basic manganese chloride prepared by the preparation method of any one of claims 1 to 7, wherein the basic manganese chloride has one or more of the following characteristics:
(1) The grain diameter D50 of the basic manganese chloride is more than or equal to 65 mu m;
(2) The purity of the basic manganese chloride is more than or equal to 97 percent.
9. An animal feed additive comprising the basic manganese chloride according to claim 8.
10. A pigment comprising the basic manganese chloride according to claim 8.
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