CN116283267A - Method for preparing rare earth composite permanent magnetic ferrite by using recycles in rare earth tailings - Google Patents
Method for preparing rare earth composite permanent magnetic ferrite by using recycles in rare earth tailings Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 86
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 145
- 239000012141 concentrate Substances 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 35
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000001914 filtration Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 4
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 239000004227 calcium gluconate Substances 0.000 claims description 3
- 229960004494 calcium gluconate Drugs 0.000 claims description 3
- 235000013927 calcium gluconate Nutrition 0.000 claims description 3
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 22
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 15
- 229910052712 strontium Inorganic materials 0.000 description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 235000012501 ammonium carbonate Nutrition 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000005188 flotation Methods 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 108010007337 Azurin Proteins 0.000 description 3
- 108091005950 Azurite Proteins 0.000 description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 3
- 229910052923 celestite Inorganic materials 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
- C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
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- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
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Abstract
The invention relates to a method for preparing rare earth composite permanent magnetic ferrite by utilizing a recovery product in rare earth tailings, which comprises the following raw materials 2 O 3 、SrCO 3 、BaCO 3 、La 2 O 3 、Co 2 O 3 、CaCO 3 And SiO 2 ，SrCO 3 And BaCO 3 The rare earth tailings are used for carrying out beneficiation treatment to obtain strontium-barium-rare earth mixed symbiotic powder prepared from azure ore concentrate and strontianite ore concentrate. The process steps include batching, preparing a pre-sinter, preparing a second slurry, preparing a green body, and sintering. Through detection, under the condition that the mass percentages of the raw materials of strontium carbonate and barium carbonate are the same, the strontium-barium-rare earth mixed symbiotic powder and SrCO are adopted 3 Powder and BaCO 3 Compared with the powder, the powder can obviously improve the preparationThe comprehensive magnetic performance of the rare earth composite permanent magnetic ferrite. Meanwhile, the cost can be reduced, and the pollution and potential safety hazard to the environment and the occupation of the land caused by the rare earth tailings can be reduced.
Description
Technical Field
The invention belongs to the field of permanent magnetic ferrite preparation, and particularly relates to a preparation method of rare earth composite permanent magnetic ferrite.
Background
Strontium carbonate and barium carbonate are indispensable raw materials in the preparation of ferrite permanent magnet materials, and along with the continuous development of intelligent automation of the mechanical industry, the requirements for ferrite permanent magnet materials with high cost performance and high performance are increasingly greater, so that the consumption of the raw materials such as strontium carbonate and barium carbonate is increased. The strontium ore resources in China are characterized in that: the lean ore is more and the rich ore is less; single ore is less, mixed and associated ore is more. In China, the development and utilization of strontium ore are mainly carried out by single celestite strontium-rich ore, and after 1994, celestite ore enters an accelerated mining period, so far, except for a few areas, the fact that part of rich ore is still caused by the factors of high environmental protection requirement, difficult mining, low grade of raw ore, late development and the like, the rich ore is basically mined everywhere. Therefore, the prices of raw materials such as strontium carbonate, rare earth oxide and the like required by ferrite permanent magnetic materials are doubled in recent years, the production cost of enterprises is greatly increased, and the development pace of the magnetic material industry in China from large to strong is severely restricted.
On the other hand, a large amount of resources such as strontium ores and the like existing in a large amount of waste piled rare earth tailings are not recycled and comprehensively utilized, so that precious resources are wasted, a large amount of land is occupied by the tailings, and certain environmental and safety hazards exist. Therefore, the strontium resources in the rare earth tailings are recycled, and the associated strontium minerals are recycled, so that not only can the strontium carbonate and the barium carbonate with lower prices be provided for the preparation of ferrite permanent magnetic materials, but also huge economic benefits are created for enterprises, the tailings discharge can be effectively reduced, and the method has great significance in improving the environment and the sustainable development of resources.
In addition, the problems that the reactivity of raw materials is insufficient, the rare earth elements added in a small amount are unevenly mixed, the magnetic performance is reduced due to the addition of low-cost barium carbonate, and the like, which are caused by the fact that the magnetic performance cannot meet the requirements, are often encountered in the process of preparing the high-performance permanent magnetic ferrite, and the problems need to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing rare earth composite permanent magnetic ferrite by using a recovery material in rare earth tailings, so as to solve the problems of high acquisition cost of strontium carbonate, small addition amount of rare earth elements, uneven mixing and improvement of magnetic performance caused by the addition of low-cost barium carbonate, and reduce pollution and potential safety hazard of the rare earth tailings to the environment and occupation of land.
The invention relates to a method for preparing rare earth composite permanent magnetic ferrite by utilizing a recovery product in rare earth tailings, which comprises the following raw materials 2 O 3 、SrCO 3 、BaCO 3 、La 2 O 3 、Co 2 O 3 、CaCO 3 And SiO 2 The mass percentage of each raw material is Fe 2 O 3 82％～86％、SrCO 3 6％～10％、BaCO 3 0.2％～2％、La 2 O 3 3％～6％、Co 2 O 3 1％～3％、CaCO 3 0.2％～2％、SiO 2
0.05 to 0.3 percent of Fe 2 O 3 Iron red powder is adopted, la 2 O 3 By La 2 O 3 Powder of Co 2 O 3 Co is adopted 2 O 3 Powder of SiO 2 SiO is adopted 2 Powder of CaCO 3 By CaCO 3 Powder characterized in that the SrCO 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared from the azure ore concentrate and the strontianite ore concentrate is obtained by adopting rare earth tailings through beneficiation treatment, and the process comprises the following steps:
(1) Proportioning materials
Iron oxide red powder and La are metered according to the mass percentage of each component in the rare earth composite permanent magnetic ferrite raw material 2 O 3 Powder, co 2 O 3 Powder, siO 2 Powder, caCO 3 Powder and strontium-barium-rare earth mixed intergrowth powder;
(2) Preparation of presintered materials
Performing wet ball milling on the raw materials metered in the step (1) to form first slurry with the average particle size of suspended particles of 0.2-2 mu m, filtering the obtained first slurry, drying the wet material obtained by filtering to remove water, and presintering for 1-2 h at 1180-1200 ℃ in air atmosphere to obtain presintering material;
(3) Preparing a second slurry
Coarse crushing and sieving the pre-sintered material obtained in the step (2) to obtain pre-sintered material powder with an average particle size of 2-5 mu m, adding a surfactant, a secondary additive and water into the pre-sintered material powder, and performing wet ball milling to form second slurry with suspended particles with an average particle size of 0.8-0.9 mu m; the addition amount of the surfactant is 0.1-1% of the mass of the pre-sintering powder, and the addition amount of the secondary additive is 1.0-3.6% of the mass of the pre-sintering powder;
(4) Preparation of a green body
Filtering the second slurry obtained in the step (3) to remove water, controlling the water content of wet materials obtained after filtering to remove water to be 35-40%, and then adopting a wet pressing magnetic field to perform oriented pressing to form green bodies of the wet materials with the water content of 35-40%, wherein a pulse magnetic field is 6-8 KOE, and the pressing pressure is 7-9 MPa;
(5) Sintering
And (3) sintering the green body obtained in the step (4) in air at 1150-1180 ℃ for 0.5-2 h, and then cooling to room temperature along with a furnace to obtain the rare earth composite permanent magnetic ferrite.
In the step (3) of the method, the surfactant is at least one of calcium gluconate, sorbitol and polyethylene glycol; the secondary additive is CaCO 3 、SiO 2 、H 3 BO 3 、La 2 O 3 、SrCO 3 、Co 2 O 3 At least the first four of the powders, caCO 3 The addition amount of the powder is 0.2-1.2% of the mass of the pre-sintered powder, and SiO 2 The addition amount of the powder is 0.1 to 0.6 percent of the mass of the powder of the presintered material, H 3 BO 3 The addition amount of the powder is 0.1 to 0.6 percent of the mass of the powder of the presintered material, la 2 O 3 The addition amount of the powder is 0.2 to 0.6 percent of the mass of the powder of the presintered material, and SrCO 3 The addition amount of the powder is 0-2% of the mass of the pre-sintered powder, co 2 O 3 The addition amount of the powder is 0 to 0.6 percent of the mass of the powder of the presintered material.
The drying temperature of the wet material obtained by filtering in the step (2) of the method is 150-200 ℃ and the drying time is 2-3 h.
In the step (5) of the method, the temperature rising rate from room temperature to sintering temperature 1150-1180 ℃ is controlled at 40-400 ℃/h.
In the method, the method for obtaining the azurin ore concentrate and the strontianite concentrate by the ore dressing treatment of the rare earth tailings is disclosed in CN201910132753.0, and the specification of CN201910132753.0 is recorded: adding water into the rare earth ore dressing tailings for size mixing, and then, carrying out gravity separation to obtain gravity dressing concentrate and gravity dressing tailings; performing strong magnetic separation on the gravity concentrate to obtain magnetic ore and non-magnetic celestite concentrate; adding a flotation reagent into the gravity tailings for flotation roughing to obtain strontianite rough concentrate and flotation tailings; and carrying out flotation and concentration operation on strontianite rough concentrate to obtain strontianite concentrate and middling.
In the method, the strontium-barium-rare earth mixed symbiotic powder prepared by taking azurin concentrate and strontianite concentrate as raw materials adopts a method disclosed by CN 202211273348.9, and the process steps are as follows:
(1) The method comprises the steps of (1-2) mixing the azure ore concentrate powder and strontianite ore concentrate powder according to the mass ratio: 1, adding deionized water into the mixture to prepare ore pulp, controlling the mass concentration of mineral powder in the ore pulp to be 40-60%, adding dilute hydrochloric acid into the mixture to adjust the pH value to be 1.5-2, and reacting the mixture at room temperature for 15-30 min;
(2) Na is added into the acid washing ore pulp obtained in the step (1) 2 CO 3 Metathesis is carried out, na 2 CO 3 The addition amount of the catalyst is 1.1 to 1.3 times of the mole amount of strontium in the azurite concentrate powder and strontianite concentrate powder, the reaction temperature is 80 to 90 ℃, the reaction time is 4 to 5 hours, and the solid and the filtrate are obtained after the reaction time is reached;
(3) Adding deionized water into the solid obtained in the step (2), regulating the pH value to 2-3 by using hydrochloric acid or nitric acid, continuously reacting for 30-40 min, and then filtering to obtain leaching slag I and filtrate I;
(4) Adding ammonia water into the filtrate I obtained in the step (3) to adjust the pH value to 7-8, and then filtering to obtain leaching residue II and filtrate II;
(5) Adding ammonium carbonate or ammonium bicarbonate into the filtrate II obtained in the step (4), reacting until precipitation is completely separated out, and filtering to obtain a precipitate, wherein the addition amount of the ammonium carbonate or the ammonium bicarbonate is 0.9-1.0 times of the mole amount of strontium in the azurite concentrate powder and the strontianite concentrate powder;
(6) Washing the precipitate obtained in the step (5) with deionized water, and then filtering and drying to obtain strontium-barium-rare earth mixed symbiotic powder.
Through X-ray fluorescence spectrum analysis, the strontium-barium-rare earth mixed biological powder comprises the following substances in percentage by mass: srCO 3 80～94％，BaCO 3 1～15％，CaCO 3 1～2％，Na 2 O 0.1-0.55％，Cl 0.03～0.25％，CuO 0～0.08％，PbO0～0.055％，NiO 0～0.01％，ZnO 0～0.01％，Ga 2 O 3 0 to 0.008 percent and the balance of rare earth oxide.
The invention has the following beneficial effects:
1. due to the raw material SrCO of the method of the invention 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared from the azure ore concentrate and the strontianite ore concentrate is obtained by adopting the rare earth tailings through beneficiation treatment, and the preparation cost of the strontium-barium-rare earth mixed symbiotic powder is low, and the price is about one tenth of the price of strontium carbonate, so that the preparation cost of the composite permanent magnetic ferrite can be obviously reduced.
2. Because the strontium-barium-rare earth mixed co-biological powder has the characteristic of atomic level mixing symbiosis among elements, the uniform distribution of the elements, particularly the mixed generation of a small amount of rare earth elements, is promoted in the mixing process of raw materials, the uniform distribution and effective solid solution of trace rare earth elements are further promoted, the solid solution process of the trace rare earth elements is improved, the effective utilization rate of the rare earth elements is improved, the reactivity of the raw materials is improved, the solid phase reaction temperature of presintering is reduced, and the improvement of the magnetic performance of the composite permanent magnetic ferrite is facilitated.
3. The price of barium carbonate is far lower than that of strontium carbonate, and on the basis of the price, the cost is often expected to be reduced by replacing part of strontium carbonate by barium carbonate, but the replacement amount of barium carbonate is generally controlled to be about 5%, and the magnetic property of the permanent magnetic ferrite is obviously reduced if the replacement amount of barium carbonate is excessive, which is common knowledge in the field of permanent magnetic ferrite preparation. The raw material SrCO of the method 3 And BaCO 3 The rare earth tailings are adopted to obtain strontium-barium-rare earth mixed symbiotic powder prepared from azure ore concentrate and strontianite ore concentrate through mineral separation treatment, wherein the proportion of barium carbonate in the symbiotic powder can be up to 14wt%, and the ratio is obviously higher than that of pure barium carbonate which can be addedThe addition amount, however, the comprehensive magnetic property of the prepared permanent magnetic ferrite is obviously improved, the traditional cognition that the addition of the barium element is unfavorable for the improvement of the magnetic property is broken, and a brand new idea is provided for the application of the barium element in the preparation of the high-performance permanent magnetic ferrite.
4. The raw material SrCO of the method 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared from the azure ore concentrate and the strontianite ore concentrate is obtained by adopting the rare earth tailings through the beneficiation treatment, so that a new field is developed for the utilization of the rare earth tailings, the pollution and the potential safety hazard of the rare earth tailings to the environment and the occupation of the land are reduced, and the method has obvious economic benefit and obvious social benefit.
Detailed Description
The method for preparing the rare earth composite permanent magnetic ferrite by utilizing the recyclate in the rare earth tailings is further described below by way of examples.
In the following examples, iron oxide red powder and La 2 O 3 Powder, co 2 O 3 Powder, caCO 3 Powder and SiO 2 Powders are all commercially available.
Example 1: preparation of strontium-barium-rare earth mixed co-biological powder
In the embodiment, the raw materials of azure ore concentrate and strontianite concentrate are obtained by carrying out mineral separation treatment on rare earth mineral separation tailings by a method described by CN 201910132753.0. The azure ore concentrate contains SrO:34.15wt%; strontianite concentrate contains SrO:39.45wt%. The process steps for preparing the strontium-barium-rare earth mixed biological powder are as follows:
(1) The method comprises the following steps of (1) mixing the azure ore concentrate powder and strontianite ore concentrate powder according to a mass ratio of 2:1, adding deionized water to prepare ore pulp, controlling the mass concentration of mineral powder in the ore pulp to be 50%, adding dilute hydrochloric acid to adjust the pH value to 2, and reacting for 15min at room temperature;
(2) Na is added into the acid washing ore pulp obtained in the step (1) 2 CO 3 Metathesis is carried out, na 2 CO 3 The addition amount of the iron ore concentrate powder is 1.2 times of the mole amount of strontium in the azure ore concentrate powder and the strontianite ore concentrate powder (Na is used 2 CO 3 With deionized waterAdding acid washing ore pulp after dissolution), reacting for 4 hours at 80 ℃ under stirring, and filtering after the reaction time is up to obtain solid matters and filtrate;
(3) Adding deionized water into the solid obtained in the step (2), regulating the pH value to 3 by using hydrochloric acid, continuously reacting for 40min, and filtering to obtain leaching slag I and filtrate I;
(4) Adding ammonia water into the filtrate I obtained in the step (3) to adjust the pH value to 8, and then filtering to obtain leaching residue II and filtrate II;
(5) Adding ammonium carbonate into the filtrate II obtained in the step (4), reacting until precipitation is completely separated out, and filtering to obtain a precipitate, wherein the addition amount of the ammonium carbonate is 0.9 time of the mole amount of strontium in the azure ore concentrate powder and the strontianite ore concentrate powder;
(6) Washing the precipitate obtained in the step (5) by deionized water, and then filtering and drying at 95 ℃ to obtain strontium-barium-rare earth mixed symbiotic powder.
Through X-ray fluorescence spectrum analysis, the strontium-barium-rare earth mixed biological powder comprises the following substances in percentage by mass: srCO 3 81％，BaCO 3 14.12％，CaCO 3 1.13％，Na 2 O 0.11％，PbO 0.055％，Cl 0.044％，Ga 2 O 3 0.008% and the balance of rare earth oxide.
Example 2: preparation of strontium-barium-rare earth mixed co-biological powder
In the embodiment, the raw materials of azure ore concentrate and strontianite concentrate are obtained by carrying out mineral separation treatment on rare earth mineral separation tailings by a method described by CN 201910132753.0. The azure ore concentrate contains SrO:36.88wt%; strontianite concentrate contains SrO:41.03wt%. The process steps for preparing the strontium-barium-rare earth mixed biological powder are as follows:
(1) Mixing the azurin concentrate powder and strontianite concentrate powder according to a mass ratio of 1:1, adding deionized water to prepare ore pulp, controlling the mass concentration of the ore powder in the ore pulp to be 55%, adding dilute hydrochloric acid to adjust the pH value to 1.5, and reacting for 30min at room temperature;
(2) Na is added into the acid washing ore pulp obtained in the step (1) 2 CO 3 Metathesis is carried out, na 2 CO 3 The addition amount of the ore concentrate powder is azurite concentrate powder and strontianite concentrate1.2 times the molar amount of strontium in the powder (Na 2 CO 3 Dissolving with deionized water, adding acid washing ore pulp), reacting for 4 hours at 80 ℃ under stirring, and filtering after the reaction time is up to obtain solid matters and filtrate;
(3) Adding deionized water into the solid obtained in the step (2), regulating the pH value to 3 by using hydrochloric acid, continuously reacting for 40min, and filtering to obtain leaching slag I and filtrate I;
(4) Adding ammonia water into the filtrate I obtained in the step (3) to adjust the pH value to 8, and then filtering to obtain leaching residue II and filtrate II;
(5) Adding ammonium carbonate into the filtrate II obtained in the step (4), reacting until precipitation is completely separated out, and filtering to obtain a precipitate, wherein the addition amount of the ammonium carbonate is 1.0 time of the mole amount of strontium in the azure ore concentrate powder and the strontianite ore concentrate powder;
(6) Washing the precipitate obtained in the step (5) by deionized water, and then filtering and drying at 120 ℃ to obtain strontium-barium-rare earth mixed symbiotic powder.
Through X-ray fluorescence spectrum analysis, the strontium-barium-rare earth mixed biological powder comprises the following substances in percentage by mass: srCO 3 91％、BaCO 3 2.98％，CaCO 3 1.1％，Na 2 O 0.517％，ZnO 0.009％，Cl 0.183％，Ga 2 O 3 0.008% and the balance of rare earth oxide.
Example 3: preparation of rare earth composite permanent magnetic ferrite
In the present embodiment, the raw materials include Fe 2 O 3 、SrCO 3 、BaCO 3 、La 2 O 3 、Co 2 O 3 、CaCO 3 And SiO 2 The mass percentage of each raw material is Fe 2 O 3 ：85.37％、SrCO 3 ：7.9％、BaCO 3 ：1.37％、La 2 O 3 ：3.413％、Co 2 O 3 ：1.494％、CaCO 3 ：0.367％、SiO 2 :0.086%, fe 2 O 3 Iron red powder is adopted, la 2 O 3 By La 2 O 3 Powder of Co 2 O 3 Co is adopted 2 O 3 Powder of SiO 2 SiO is adopted 2 Powder of CaCO 3 By CaCO 3 Powder of SrCO 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared in the example 1 is adopted, and the process steps are as follows:
(1) Proportioning materials
1000g of iron oxide red powder and 1000g of La of the rare earth composite permanent magnetic ferrite raw material are metered according to the mass percentage of each component 2 O 3 40g of powder, co 2 O 3 17.5g of powder, siO 2 1g of powder, caCO 3 3g of powder and 114.2g of strontium-barium-rare earth mixed co-biological powder;
(2) Preparation of presintered materials
Performing wet ball milling on the raw materials metered in the step (1) by using a roller ball mill to form first slurry with suspended particles having an average particle size of 1 mu m, filtering the first slurry, drying moisture in a muffle furnace at 200 ℃ for 2h, and pre-sintering for 1h at the temperature of 1200 ℃ in an air atmosphere to obtain a pre-sintered material; during wet ball milling, the following materials: water: ball=1:1.5:10 (weight ratio), ball mill rotation speed 85r/min, ball milling time 4h;
(3) Preparing a second slurry
Coarse crushing the pre-sintered material obtained in the step (2) and sieving the pre-sintered material with a 120-mesh sieve to obtain pre-sintered material powder, adding a surfactant, a secondary additive and water into the pre-sintered material powder, and performing wet ball milling to form second slurry with suspended particles having an average particle size of 0.85 mu m; the surfactant is sorbitol, and the addition amount is 0.2% of the mass of the pre-sintered powder; the secondary additive is CaCO 3 、SiO 2 、H 3 BO 3 、La 2 O 3 、Co 2 O 3 They are added in an amount of 1.0% of the mass of the pre-sintered powder (CaCO) 3 )、0.3％(SiO 2 )、0.15％(H 3 BO 3 )、0.4％(La 2 O 3 )、0.2％(Co 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the During wet ball milling, the following materials: water: ball=1:1.5:10 (weight ratio), ball mill rotation speed 85r/min, ball milling time 10h;
(4) Preparation of a green body
Filtering the second slurry obtained in the step (3) to remove water, controlling the water content of wet materials obtained after the filtering and the removing of water to be 35%, and then adopting a wet pressing magnetic field to perform oriented pressing to form green bodies of the wet materials with the water content of 35%, wherein a pulse magnetic field is 8KOE, and the pressing pressure is 8MPa;
(5) Sintering
And (3) sintering the green body obtained in the step (4) in an air atmosphere at 1180 ℃ for 0.5h, and then cooling to room temperature along with a furnace to obtain the rare earth composite permanent magnetic ferrite.
Comparative example 1
The comparative example was identical to the raw materials and the mass percentages of the raw materials of example 3, the process steps and the process parameters of the process steps were identical. This comparative example differs from example 3 in that: the SrCO 3 By SrCO 3 Powder of BaCO 3 By BaCO 3 And (3) powder.
Example 4: preparation of rare earth composite permanent magnetic ferrite
In the present embodiment, the raw materials include Fe 2 O 3 、SrCO 3 、BaCO 3 、La 2 O 3 、Co 2 O 3 、CaCO 3 And SiO 2 The mass percentage of each raw material is Fe 2 O 3 ：84.33％、SrCO 3 ：6.52％、BaCO 3 ：0.214％、La 2 O 3 ：5.482％、Co 2 O 3 ：1.77％、CaCO 3 ：1.6％、SiO 2 :0.084%, said Fe 2 O 3 Iron red powder is adopted, la 2 O 3 By La 2 O 3 Powder of Co 2 O 3 Co is adopted 2 O 3 Powder of SiO 2 SiO is adopted 2 Powder of CaCO 3 By CaCO 3 Powder of SrCO 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared in the example 2 is adopted, and the process steps are as follows:
(1) Proportioning materials
1000g of iron oxide red powder and 1000g of La of the rare earth composite permanent magnetic ferrite raw material are metered according to the mass percentage of each component 2 O 3 65g of powder, co 2 O 3 21g of powder, caCO 3 18g of powder, siO 2 1g of powder and 85g of strontium-barium-rare earth mixed biological powder;
(2) Preparation of presintered materials
Performing wet ball milling on the raw materials metered in the step (1) by using a roller ball mill to form first slurry with the average particle size of suspended particles of 0.9 mu m, filtering the obtained first slurry, then drying moisture of the wet material obtained by filtering in a muffle furnace at the temperature of 150 ℃ for 2 hours, and then heating to 1185 ℃ in air atmosphere for presintering for 2 hours to obtain a presintered material; during wet ball milling, the following materials: water: ball=1:1.5:10 (weight ratio), ball mill rotation speed 85r/min, ball milling time 5h;
(3) Preparing a second slurry
Coarse crushing the pre-sintered material obtained in the step (2) and sieving the pre-sintered material with a 120-mesh sieve to obtain pre-sintered material powder, adding a surfactant, a secondary additive and water into the pre-sintered material powder, and performing wet ball milling to form second slurry with suspended particles having an average particle size of 0.9 mu m; the surfactant is calcium gluconate, and the addition amount is 0.5% of the mass of the pre-sintered powder; the secondary additive is CaCO 3 、SiO 2 、H 3 BO 3 、SrCO 3 、La 2 O 3 、Co 2 O 3 They are added in an amount of 0.6% of the mass of the pre-sintered powder (CaCO) 3 )、0.35％(SiO 2 )、0.1％(H 3 BO 3 )、0.2％(SrCO 3 )、0.3％(La 2 O 3 )、0.2％(Co 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the During wet ball milling, the following materials: water: ball=1:1.5:10 (weight ratio), ball mill rotation speed 85r/min, ball milling time 9h;
(4) Preparation of a green body
Filtering the second slurry obtained in the step (3) to remove water, controlling the water content of wet materials obtained after the filtering to remove water to be 38%, and then adopting a wet pressing magnetic field to perform oriented pressing to form green bodies of the wet materials with the water content of 38%, wherein the pulse magnetic field is 7KOE, and the pressing pressure is 8MPa;
(5) Sintering
And (3) sintering the green body obtained in the step (4) in air at 1160 ℃ for 1.5h, and then cooling to room temperature along with a furnace to obtain the rare earth composite permanent magnetic ferrite.
Comparative example 2
The comparative example was identical to the raw materials and the mass percentages of the raw materials of example 4, the process steps and the process parameters of the process steps were identical. This comparative example differs from example 4 in that: the SrCO 3 By SrCO 3 Powder of BaCO 3 By BaCO 3 And (3) powder.
The rare earth composite permanent magnetic ferrites prepared in examples 3 and 4 and comparative examples 1 and 2 were subjected to magnetic performance test according to the national standard GB/T3217-92, and the test results are shown in the following Table 1.
TABLE 1 magnetic property test results
| Br(mT) | HCB(KA/m) | HCJ(KA/m) | BH(max)(Kj/m3) | |
| Example 3 | 422 | 280 | 344 | 33.5 |
| Comparative example 1 | 413 | 272 | 331 | 32 |
| Example 4 | 435 | 303 | 395.4 | 35 |
| Comparative example 2 | 418.7 | 303 | 361.4 | 33 |
From table 1, it can be seen that, under the condition that the mass percentages of the raw materials of strontium carbonate and barium carbonate are the same, the strontium carbonate and the barium carbonate adopt the strontium-barium-rare earth mixed symbiotic powder to obviously improve the comprehensive magnetic performance of the rare earth composite permanent magnetic ferrite, and the rare earth composite permanent magnetic ferrite prepared in the embodiment 3 and the embodiment 4 can meet the use requirement of the magnetic performance of the high-performance ferrite permanent magnetic 9 material and above.
Claims (5)
1. Method for preparing rare earth composite permanent magnetic ferrite by using recycles in rare earth tailings, wherein the raw materials comprise Fe 2 O 3 、SrCO 3 、BaCO 3 、La 2 O 3 、Co 2 O 3 、CaCO 3 And SiO 2 The mass percentage of each raw material is Fe 2 O 3 82％～86％、SrCO 3 6％～10％、BaCO 3 0.2％～2％、La 2 O 3 3％～6％、Co 2 O 3 1％～3％、CaCO 3 0.2％～2％、SiO 2
0.05 to 0.3 percent of Fe 2 O 3 Iron red powder is adopted, la 2 O 3 By La 2 O 3 Powder of Co 2 O 3 Co is adopted 2 O 3 Powder of SiO 2 SiO is adopted 2 Powder ofCaCO as described 3 By CaCO 3 Powder characterized in that the SrCO 3 And BaCO 3 The strontium-barium-rare earth mixed symbiotic powder prepared from the azure ore concentrate and the strontianite ore concentrate is obtained by adopting rare earth tailings through beneficiation treatment, and the process comprises the following steps:
(1) Proportioning materials
Iron oxide red powder and La are metered according to the mass percentage of each component in the rare earth composite permanent magnetic ferrite raw material 2 O 3 Powder, co 2 O 3 Powder, siO 2 Powder, caCO 3 Powder and strontium-barium-rare earth mixed intergrowth powder;
(2) Preparation of presintered materials
Performing wet ball milling on the raw materials metered in the step (1) to form first slurry with the average particle size of suspended particles of 0.2-2 mu m, filtering the obtained first slurry, drying the wet material obtained by filtering to remove water, and presintering for 1-2 h at 1180-1200 ℃ in air atmosphere to obtain presintering material;
(3) Preparing a second slurry
Coarse crushing and sieving the pre-sintered material obtained in the step (2) to obtain pre-sintered material powder with an average particle size of 2-5 mu m, adding a surfactant, a secondary additive and water into the pre-sintered material powder, and performing wet ball milling to form second slurry with suspended particles with an average particle size of 0.8-0.9 mu m; the addition amount of the surfactant is 0.1-1% of the mass of the pre-sintering powder, and the addition amount of the secondary additive is 1.0-3.6% of the mass of the pre-sintering powder;
(4) Preparation of a green body
Filtering the second slurry obtained in the step (3) to remove water, controlling the water content of wet materials obtained after filtering to remove water to be 35-40%, and then adopting a wet pressing magnetic field to perform oriented pressing to form green bodies of the wet materials with the water content of 35-40%, wherein a pulse magnetic field is 6-8 KOE, and the pressing pressure is 7-9 MPa;
(5) Sintering
And (3) sintering the green body obtained in the step (4) in air at 1150-1180 ℃ for 0.5-2 h, and then cooling to room temperature along with a furnace to obtain the rare earth composite permanent magnetic ferrite.
2. The method for preparing rare earth composite permanent magnetic ferrite by utilizing the recycled material in the rare earth tailings, which is characterized in that in the step (3), the surfactant is at least one of calcium gluconate, sorbitol and polyethylene glycol; the secondary additive is CaCO 3 、SiO 2 、H 3 BO 3 、La 2 O 3 、SrCO 3 、Co 2 O 3 At least the first four of the powders, caCO 3 The addition amount of the powder is 0.2-1.2% of the mass of the pre-sintered powder, and SiO 2 The addition amount of the powder is 0.1 to 0.6 percent of the mass of the powder of the presintered material, H 3 BO 3 The addition amount of the powder is 0.1 to 0.6 percent of the mass of the powder of the presintered material, la 2 O 3 The addition amount of the powder is 0.2 to 0.6 percent of the mass of the powder of the presintered material, and SrCO 3 The addition amount of the powder is 0-2% of the mass of the pre-sintered powder, co 2 O 3 The addition amount of the powder is 0 to 0.6 percent of the mass of the powder of the presintered material.
3. The method for preparing rare earth composite permanent magnetic ferrite by using the recycled material in the rare earth tailings according to claim 1 or 2, wherein in the step (2), the drying temperature of the wet material obtained by filtration is 150-200 ℃ and the drying time is 2-3 h.
4. The method for preparing rare earth composite permanent magnetic ferrite by using the reclaimed materials in the rare earth tailings according to claim 1 or 2, wherein in the step (5), the temperature rising rate from room temperature to sintering temperature 1150-1180 ℃ is controlled to be 40-400 ℃/h.
5. The method for preparing rare earth composite permanent magnetic ferrite by using the recycled material in the rare earth tailings according to claim 3, wherein in the step (5), the temperature rising rate from room temperature to the sintering temperature of 1150-1180 ℃ is controlled to be 40-400 ℃/h.
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