CN116283267A - 利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法 - Google Patents
利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法 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
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- 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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Abstract
本发明所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,原料包括Fe2O3、SrCO3、BaCO3、La2O3、Co2O3、CaCO3和SiO2,SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶‑钡‑稀土混合共生物粉末。工艺步骤包括配料、制备预烧料、制备第二浆料、制备生坯和烧结。经检测,在原料碳酸锶、碳酸钡质量百分数相同的情况下,采用锶‑钡‑稀土混合共生物粉末与采用SrCO3粉末和BaCO3粉末相比,能明显提升所制备的稀土复合永磁铁氧体的综合磁性能。同时,能降低成本并减少稀土尾矿对环境造成的污染和安全隐患及对土地的占用。
Description
技术领域
本发明属于永磁铁氧体制备领域,特别涉及稀土复合永磁铁氧体的制备方法。
背景技术
碳酸锶、碳酸钡是铁氧体永磁材料制备中必不可少的原材料,随着机械工业智能自动化的不断发展,对高性价比高性能的铁氧体永磁材料的需求越来越大,这就加大的对碳酸锶、碳酸钡等原材料的消耗。而我国锶矿资源的特点是:贫矿多、富矿少;单一矿少、混合和伴生矿多。一直以来我国锶矿石的开发利用以单一天青石富锶矿为主,1994年后,天青石矿进入了加速开采期,迄今为止,除少数地区因其环保要求高、开采难、原矿品位总体不高、开发较晚等因素使得尚有部分富矿外,其余各处富矿基本采完。因此近年铁氧体永磁材料所需的碳酸锶、稀土氧化物等原料价格翻倍增长,企业的生产成本大幅增加,严重制约了我国磁性材料产业从大到强的发展步伐。
另一方面,目前大量废弃堆积的稀土尾矿中存在的大量锶矿等资源并未得到回收和综合利用,不仅浪费了宝贵的资源,而且尾矿占用大量土地,且存在一定的环境和安全隐患。因此,对稀土尾矿中的锶资源进行回收利用,将伴生锶矿物资源化,不仅可以为铁氧体永磁材料制备提供价格更低的碳酸锶、碳酸钡,给企业创造巨大的经济效益,还可以有效减少尾矿排放量,对改善环境和资源的可持续发展具有重大意义。
此外,在制备高性能永磁铁氧体过程中往往会遇到原料反应活性不够、少量添加的稀土元素混合不均匀、廉价碳酸钡的添加降低磁性能等导致磁性能达不到要求问题,也是需要解决的。
发明内容
本发明的目的在于克服现有技术的不足,提供一种利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,以解决碳酸锶购置成本高,稀土元素添加量少混合不均匀和廉价碳酸钡的添加影响磁性能提高的问题,并减少稀土尾矿对环境造成的污染和安全隐患及对土地的占用。
本发明所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,原料包括Fe2O3、SrCO3、BaCO3、La2O3、Co2O3、CaCO3和SiO2,各原料的质量百分数为Fe2O382%~86%、SrCO36%~10%、BaCO30.2%~2%、La2O33%~6%、Co2O31%~3%、CaCO30.2%~2%、SiO2
0.05%~0.3%,所述Fe2O3采用铁红粉末,所述La2O3采用La2O3粉末,所述Co2O3采用Co2O3粉末,所述SiO2采用SiO2粉末,所述CaCO3采用CaCO3粉末,其特征在于所述SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶-钡-稀土混合共生物粉末,工艺步骤如下:
(1)配料
根据稀土复合永磁铁氧体原料中各组分的质量百分比计量铁红粉末、La2O3粉末、Co2O3粉末、SiO2粉末、CaCO3粉末和锶-钡-稀土混合共生物粉末;
(2)制备预烧料
将步骤(1)计量好的各原料采用湿法球磨形成悬浮颗粒平均粒径在0.2~2μm的第一料浆,再将所得第一料浆进行过滤,然后将过滤所得湿料进行干燥去除水分后在空气气氛中于1180~1200℃预烧1~2h,得到预烧料;
(3)制备第二料浆
将步骤(2)所得预烧料进行粗破碎并过筛,得到平均粒径在2~5μm的预烧料粉末,然后在预烧料粉末中添加表面活性剂、二次添加剂及水,采用湿法球磨形成悬浮颗粒平均粒径在0.8~0.9μm的第二料浆;所述表面活性剂的添加量为预烧料粉末质量的0.1~1%,所述二次添加剂的添加量为预烧料粉末质量的1.0~3.6%;
(4)制备生坯
将步骤(3)所得第二料浆过滤除水,控制过滤除水后所得湿料的含水率在35~40%,然后采用湿压磁场取向压制,使含水率在35~40%的湿料形成生坯,脉冲磁场为6~8KOe,压制压力为7~9MPa;
(5)烧结
将步骤(4)所得生坯在空气气氛中于1150~1180℃保温烧结0.5~2h,然后随炉冷却至室温,即得到稀土复合永磁铁氧体。
上述方法的步骤(3)中,所述表面活性剂为葡萄糖酸钙、山梨糖醇、聚乙二醇中的至少一种;所述二次添加剂为CaCO3、SiO2、H3BO3、La2O3、SrCO3、Co2O3粉末中的至少前四种,CaCO3粉末的添加量为预烧料粉末质量的0.2~1.2%,SiO2粉末的添加量为预烧料粉末质量的0.1~0.6%,H3BO3粉末的添加量为预烧料粉末质量的0.1~0.6%,La2O3粉末的添加量为预烧料粉末质量的0.2~0.6%,SrCO3粉末的添加量为预烧料粉末质量的0~2%,Co2O3粉末的添加量为预烧料粉末质量的0~0.6%。
上述方法的步骤(2)中过滤所得湿料的干燥温度为150~200℃,干燥时间为2~3h。
上述方法的步骤(5)中,从室温升至烧结温度1150~1180℃的升温速率控制在40~400℃/h。
上述方法中,稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿的方法见CN201910132753.0公开的方法,CN 201910132753.0说明书记载:对稀土选矿尾矿加水调浆后进行重选得到重选精矿和重选尾矿;对重选精矿进行强磁选得到磁性矿和非磁性天青石精矿;对重选尾矿加浮选药剂进行浮选粗选,得到菱锶矿粗精矿和浮选尾矿;对菱锶矿粗精矿进行浮选精选作业,得到菱锶矿精矿和中矿。
上述方法中,以天青矿精矿和菱锶矿精矿为原料制备锶-钡-稀土混合共生物粉末采用CN 202211273348.9公开的方法,工艺步骤如下:
(1)将天青矿精矿粉与菱锶矿精矿粉按质量比(1~2):1混合后加去离子水调制成矿浆,矿浆中矿粉的质量浓度控制在40~60%,然后加入稀盐酸调pH值至1.5~2,在室温下反应15~30min;
(2)在步骤(1)所得酸洗矿浆中加入Na2CO3进行复分解,Na2CO3的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的1.1~1.3倍,反应温度为80~90℃,反应时间为4~5h,反应时间到达后过滤,得固体物和滤液;
(3)将步骤(2)所得固体物加入去离子水,用盐酸或硝酸调节pH值至2~3,持续反应30~40min,然后过滤,得浸出渣Ⅰ和滤液Ⅰ;
(4)将步骤(3)所得滤液Ⅰ加入氨水调节pH值至7~8,然后过滤得到浸出渣Ⅱ和滤液Ⅱ;
(5)将步骤(4)所得滤液Ⅱ加碳酸铵或碳酸氢铵,反应至沉淀完全析出,经过滤得到沉淀物,所述碳酸铵或碳酸氢铵的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的0.9~1.0倍;
(6)将步骤(5)所得沉淀物用去离子水洗涤,然后经过滤、烘干得到锶-钡-稀土混合共生物粉末。
经X射线荧光光谱分析,锶-钡-稀土混合共生物粉末中,所含物质及其质量分数为:SrCO380~94%,BaCO31~15%,CaCO31~2%,Na2O 0.1-0.55%,Cl 0.03~0.25%,CuO0~0.08%,PbO0~0.055%,NiO 0~0.01%,ZnO 0~0.01%,Ga2O30~0.008%,余量为稀土氧化物。
本发明具有以下有益效果:
1、由于本发明所述方法的原料SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶-钡-稀土混合共生物粉末,而锶-钡-稀土混合共生物粉末的制备成本低,价格约为碳酸锶价格的十分之一,因此可明显降低复合永磁铁氧体的制备成本。
2、由于锶-钡-稀土混合共生物粉末各元素间具有原子级别的混合共生的特点,因而在原料的混料过程中会促进各元素的均匀分布,特别是少量稀土元素的混生,进一步促进了微量稀土元素的均匀分布及有效固溶,改善其固溶进程,提高稀土元素的有效利用率,提高原料的反应活性,降低预烧的固相反应温度,有利于复合永磁铁氧体磁性能的提升。
3、碳酸钡价格远低于碳酸锶,基于此,往往希望通过碳酸钡替换部分碳酸锶来降低成本,但碳酸钡的替换量一般控制在5%左右,过多则使永磁铁氧体的磁性能明显降低,这是永磁铁氧体制备领域的常识。本发明所述方法的原料SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶-钡-稀土混合共生物粉末,该共生物粉末中碳酸钡占比可高达14wt%,明显高于纯碳酸钡的可添加量,但所制备的永磁铁氧体的综合磁性能明显提升,打破了对钡元素添加不利于磁性能提升的传统认知,为钡元素在制备高性能永磁铁氧体中的应用提供了一种全新思路。
4、本发明所述方法的原料SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶-钡-稀土混合共生物粉末,为稀土选矿尾矿的利用开拓了新的领域,有利于减少稀土尾矿对环境造成的污染和安全隐患及对土地的占用,不仅具有明显的经济效益,而且具有明显的社会效益。
具体实施方式
下面通过实施例对本发明所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法作进一步说明。
下述实施例中,铁红粉末、La2O3粉末、Co2O3粉末、CaCO3粉末和SiO2粉末均通过市场购买。
实施例1:制备锶-钡-稀土混合共生物粉末
本实施例中,原料天青矿精矿和菱锶矿精矿通过CN 201910132753.0所述方法对稀土选矿尾矿进行选矿处理得到。天青矿精矿中,含SrO:34.15wt%;菱锶矿精矿中,含SrO:39.45wt%。制备锶-钡-稀土混合共生物粉末的工艺步骤如下:
(1)将天青矿精矿粉与菱锶矿精矿粉按质量比2:1混合后加去离子水调制成矿浆,矿浆中矿粉的质量浓度控制在50%,然后加入稀盐酸调pH值至2,在室温下反应15min;
(2)在步骤(1)所得酸洗矿浆中加入Na2CO3进行复分解,Na2CO3的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的1.2倍(将Na2CO3用去离子水溶解后加入酸洗矿浆),在搅拌下于80℃反应4h,反应时间到达后过滤,得固体物和滤液;
(3)将步骤(2)所得固体物加入去离子水,用盐酸调节pH值至3,持续反应40min,然后过滤,得浸出渣Ⅰ和滤液Ⅰ;
(4)将步骤(3)所得滤液Ⅰ加入氨水调节pH值至8,然后过滤得到浸出渣Ⅱ和滤液Ⅱ;
(5)将步骤(4)所得滤液Ⅱ加碳酸铵,反应至沉淀完全析出,经过滤得到沉淀物,所述碳酸铵的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的0.9倍;
(6)将步骤(5)所得沉淀物用去离子水洗涤,然后经过滤、在95℃烘干得到锶-钡-稀土混合共生物粉末。
经经X射线荧光光谱分析,锶-钡-稀土混合共生物粉末中,所含物质及其质量分数为:SrCO381%,BaCO314.12%,CaCO31.13%,Na2O 0.11%,PbO 0.055%,Cl 0.044%,Ga2O30.008%,余量为稀土氧化物。
实施例2:制备锶-钡-稀土混合共生物粉末
本实施例中,原料天青矿精矿和菱锶矿精矿通过CN 201910132753.0所述方法对稀土选矿尾矿进行选矿处理得到。天青矿精矿中,含SrO:36.88wt%;菱锶矿精矿中,含SrO:41.03wt%。制备锶-钡-稀土混合共生物粉末的工艺步骤如下:
(1)将天青矿精矿粉与菱锶矿精矿粉按质量比1:1混合后加去离子水调制成矿浆,矿浆中矿粉的质量浓度控制在55%,然后加入稀盐酸调pH值至1.5,在室温下反应30min;
(2)在步骤(1)所得酸洗矿浆中加入Na2CO3进行复分解,Na2CO3的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的1.2倍(将Na2CO3用去离子水溶解后加入酸洗矿浆),在搅拌下于80℃反应4h,反应时间到达后过滤,得固体物和滤液;
(3)将步骤(2)所得固体物加入去离子水,用盐酸调节pH值至3,持续反应40min,然后过滤,得浸出渣Ⅰ和滤液Ⅰ;
(4)将步骤(3)所得滤液Ⅰ加入氨水调节pH值至8,然后过滤得到浸出渣Ⅱ和滤液Ⅱ;
(5)将步骤(4)所得滤液Ⅱ加碳酸铵,反应至沉淀完全析出,经过滤得到沉淀物,所述碳酸铵的加入量为天青矿精矿粉和菱锶矿精矿粉中锶摩尔量的1.0倍;
(6)将步骤(5)所得沉淀物用去离子水洗涤,然后经过滤、在120℃烘干得到锶-钡-稀土混合共生物粉末。
经经X射线荧光光谱分析,锶-钡-稀土混合共生物粉末中,所含物质及其质量分数为:SrCO391%、BaCO32.98%,CaCO31.1%,Na2O 0.517%,ZnO 0.009%,Cl 0.183%,Ga2O30.008%,余量为稀土氧化物。
实施例3:制备稀土复合永磁铁氧体
本实施中,原料包括Fe2O3、SrCO3、BaCO3、La2O3、Co2O3、CaCO3和SiO2,各原料的质量百分数为Fe2O3:85.37%、SrCO3:7.9%、BaCO3:1.37%、La2O3:3.413%、Co2O3:1.494%、CaCO3:0.367%、SiO2:0.086%,所述Fe2O3采用铁红粉末,所述La2O3采用La2O3粉末,所述Co2O3采用Co2O3粉末,所述SiO2采用SiO2粉末,所述CaCO3采用CaCO3粉末,所述SrCO3和BaCO3采用实施例1制备的锶-钡-稀土混合共生物粉末,工艺步骤如下:
(1)配料
根据稀土复合永磁铁氧体原料中各组分的质量百分比计量铁红粉末1000g、La2O3粉末40g、Co2O3粉末17.5g、SiO2粉末1g、CaCO3粉末3g、锶-钡-稀土混合共生物粉末114.2g;
(2)制备预烧料
将步骤(1)计量好的各原料用滚筒球磨机湿法球磨形成悬浮颗粒平均粒径在1μm的第一料浆,再将所得第一料浆进行过滤,然后将过滤所得湿料在马弗炉中于200℃保温2h烘干水分,再在空气气氛中升温至1200℃预烧1h,得到预烧料;湿法球磨时,料:水:球=1:1.5:10(重量比),球磨机转速85r/min,球磨时间4h;
(3)制备第二料浆
将步骤(2)所得预烧料进行粗破碎并过120目筛,得到预烧料粉末,然后在预烧料粉末中添加表面活性剂、二次添加剂及水,采用湿法球磨形成悬浮颗粒平均粒径在0.85μm的第二料浆;表面活性剂为山梨糖醇,添加量为预烧料粉末质量的0.2%;二次添加剂为CaCO3、SiO2、H3BO3、La2O3、Co2O3,它们的添加量分别为预烧料粉末质量的1.0%(CaCO3)、0.3%(SiO2)、0.15%(H3BO3)、0.4%(La2O3)、0.2%(Co2O3);湿法球磨时,料:水:球=1:1.5:10(重量比),球磨机转速85r/min,球磨时间10h;
(4)制备生坯
将步骤(3)所得第二料浆过滤除水,控制过滤除水后所得湿料的含水率在35%,然后采用湿压磁场取向压制,使含水率在35%的湿料形成生坯,脉冲磁场为8KOe,压制压力为8MPa;
(5)烧结
将步骤(4)所得生坯在空气气氛中于1180℃保温烧结0.5h,然后随炉冷却至室温,即得到稀土复合永磁铁氧体。
对比例1
本对比例与实施例3的原料及各原料的质量百分数相同,工艺步骤及各工艺步骤的工艺参数相同。本对比例与实施例3不同之处是:所述SrCO3采用SrCO3粉末,所述BaCO3采用BaCO3粉末。
实施例4:制备稀土复合永磁铁氧体
本实施中,原料包括Fe2O3、SrCO3、BaCO3、La2O3、Co2O3、CaCO3和SiO2,各原料的质量百分数为Fe2O3:84.33%、SrCO3:6.52%、BaCO3:0.214%、La2O3:5.482%、Co2O3:1.77%、CaCO3:1.6%、SiO2:0.084%,所述Fe2O3采用铁红粉末,所述La2O3采用La2O3粉末,所述Co2O3采用Co2O3粉末,所述SiO2采用SiO2粉末,所述CaCO3采用CaCO3粉末,所述SrCO3和BaCO3采用实施例2制备的锶-钡-稀土混合共生物粉末,工艺步骤如下:
(1)配料
根据稀土复合永磁铁氧体原料中各组分的质量百分比计量铁红粉末1000g、La2O3粉末65g、Co2O3粉末21g、CaCO3粉末18g、SiO2粉末1g、锶-钡-稀土混合共生物粉末85g;
(2)制备预烧料
将步骤(1)计量好的各原料用滚筒球磨机湿法球磨形成悬浮颗粒平均粒径在0.9μm的第一料浆,再将所得第一料浆进行过滤,然后将过滤所得湿料在马弗炉中于150℃保温2h烘干水分,再在空气气氛中升温至1185℃预烧2h,得到预烧料;湿法球磨时,料:水:球=1:1.5:10(重量比),球磨机转速85r/min,球磨时间5h;
(3)制备第二料浆
将步骤(2)所得预烧料进行粗破碎并过120目筛,得到预烧料粉末,然后在预烧料粉末中添加表面活性剂、二次添加剂及水,采用湿法球磨形成悬浮颗粒平均粒径在0.9μm的第二料浆;表面活性剂为葡萄糖酸钙,添加量为预烧料粉末质量的0.5%;二次添加剂为CaCO3、SiO2、H3BO3、SrCO3、La2O3、Co2O3,它们的添加量分别为预烧料粉末质量的0.6%(CaCO3)、0.35%(SiO2)、0.1%(H3BO3)、0.2%(SrCO3)、0.3%(La2O3)、0.2%(Co2O3);湿法球磨时,料:水:球=1:1.5:10(重量比),球磨机转速85r/min,球磨时间9h;
(4)制备生坯
将步骤(3)所得第二料浆过滤除水,控制过滤除水后所得湿料的含水率在38%,然后采用湿压磁场取向压制,使含水率在38%的湿料形成生坯,脉冲磁场为7KOe,压制压力为8MPa;
(5)烧结
将步骤(4)所得生坯在空气气氛中于1160℃保温烧结1.5h,然后随炉冷却至室温,即得到稀土复合永磁铁氧体。
对比例2
本对比例与实施例4的原料及各原料的质量百分数相同,工艺步骤及各工艺步骤的工艺参数相同。本对比例与实施例4不同之处是:所述SrCO3采用SrCO3粉末,所述BaCO3采用BaCO3粉末。
对实施例3、4和对比例1、2制备的稀土复合永磁铁氧体按照GB/T3217-92国家标准进行磁性能测试,测试结果见下述表1。
表1磁性能测试结果
Br(mT) | HCB(KA/m) | HCJ(KA/m) | BH(max)(Kj/m3) | |
实施例3 | 422 | 280 | 344 | 33.5 |
对比例1 | 413 | 272 | 331 | 32 |
实施例4 | 435 | 303 | 395.4 | 35 |
对比例2 | 418.7 | 303 | 361.4 | 33 |
从上述表1可以看出,在原料碳酸锶、碳酸钡质量百分数相同的情况下,碳酸锶和碳酸钡采用锶-钡-稀土混合共生物粉末能明显提升稀土复合永磁铁氧体的综合磁性能,实施例3、实施例4制备的稀土复合永磁铁氧体能达到高性能铁氧体永磁9材及以上材质的磁性能使用要求。
Claims (5)
1.一种利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,原料包括Fe2O3、SrCO3、BaCO3、La2O3、Co2O3、CaCO3和SiO2,各原料的质量百分数为Fe2O382%~86%、SrCO36%~10%、BaCO30.2%~2%、La2O33%~6%、Co2O31%~3%、CaCO30.2%~2%、SiO2
0.05%~0.3%,所述Fe2O3采用铁红粉末,所述La2O3采用La2O3粉末,所述Co2O3采用Co2O3粉末,所述SiO2采用SiO2粉末,所述CaCO3采用CaCO3粉末,其特征在于所述SrCO3和BaCO3采用稀土尾矿通过选矿处理得到天青矿精矿和菱锶矿精矿制备的锶-钡-稀土混合共生物粉末,工艺步骤如下:
(1)配料
根据稀土复合永磁铁氧体原料中各组分的质量百分比计量铁红粉末、La2O3粉末、Co2O3粉末、SiO2粉末、CaCO3粉末和锶-钡-稀土混合共生物粉末;
(2)制备预烧料
将步骤(1)计量好的各原料采用湿法球磨形成悬浮颗粒平均粒径在0.2~2μm的第一料浆,再将所得第一料浆进行过滤,然后将过滤所得湿料进行干燥去除水分后在空气气氛中于1180~1200℃预烧1~2h,得到预烧料;
(3)制备第二料浆
将步骤(2)所得预烧料进行粗破碎并过筛,得到平均粒径在2~5μm的预烧料粉末,然后在预烧料粉末中添加表面活性剂、二次添加剂及水,采用湿法球磨形成悬浮颗粒平均粒径在0.8~0.9μm的第二料浆;所述表面活性剂的添加量为预烧料粉末质量的0.1~1%,所述二次添加剂的添加量为预烧料粉末质量的1.0~3.6%;
(4)制备生坯
将步骤(3)所得第二料浆过滤除水,控制过滤除水后所得湿料的含水率在35~40%,然后采用湿压磁场取向压制,使含水率在35~40%的湿料形成生坯,脉冲磁场为6~8KOe,压制压力为7~9MPa;
(5)烧结
将步骤(4)所得生坯在空气气氛中于1150~1180℃保温烧结0.5~2h,然后随炉冷却至室温,即得到稀土复合永磁铁氧体。
2.根据权利要求1所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,其特征在于步骤(3)中,所述表面活性剂为葡萄糖酸钙、山梨糖醇、聚乙二醇中的至少一种;所述二次添加剂为CaCO3、SiO2、H3BO3、La2O3、SrCO3、Co2O3粉末中的至少前四种,CaCO3粉末的添加量为预烧料粉末质量的0.2~1.2%,SiO2粉末的添加量为预烧料粉末质量的0.1~0.6%,H3BO3粉末的添加量为预烧料粉末质量的0.1~0.6%,La2O3粉末的添加量为预烧料粉末质量的0.2~0.6%,SrCO3粉末的添加量为预烧料粉末质量的0~2%,Co2O3粉末的添加量为预烧料粉末质量的0~0.6%。
3.根据权利要求1或2所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,其特征在于步骤(2)中,过滤所得湿料的干燥温度为150~200℃,干燥时间为2~3h。
4.根据权利要求1或2所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,其特征在于步骤(5)中,从室温升至烧结温度1150~1180℃的升温速率控制在40~400℃/h。
5.根据权利要求3所述利用稀土尾矿中的回收物制备稀土复合永磁铁氧体的方法,其特征在于步骤(5)中,从室温升至烧结温度1150~1180℃的升温速率控制在40~400℃/h。
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