CN112808260A - 一种球磨法制备铈锆固溶体的方法 - Google Patents
一种球磨法制备铈锆固溶体的方法 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- -1 hydroxide ions Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
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- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
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- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 claims description 2
- LRIHKZMLMWYPFS-UHFFFAOYSA-N azanium;hexadecanoate Chemical compound [NH4+].CCCCCCCCCCCCCCCC([O-])=O LRIHKZMLMWYPFS-UHFFFAOYSA-N 0.000 claims description 2
- BJOYVZZDDFVLPI-UHFFFAOYSA-N azanium;tetradecanoate Chemical compound [NH4+].CCCCCCCCCCCCCC([O-])=O BJOYVZZDDFVLPI-UHFFFAOYSA-N 0.000 claims description 2
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 2
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- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种球磨法制备铈锆固溶体的方法,涉及固溶体的制备技术领域。本发明所述球磨法制备铈锆固溶体的方法包括如下步骤:(1)制备金属盐溶液,在金属盐溶液中加入表面活性剂,搅拌;(2)制备沉淀剂分散液;(3)在沉淀剂分散液中加入球磨珠,然后加入金属盐和表面活性剂的混合液,进行球磨,得到悬浊液;(4)在悬浊液中加入分散剂,得到沉淀物;(5)对沉淀物进行干燥、焙烧,得到所述铈锆固溶体。本发明通过球磨处理,将大晶粒分散为小晶粒,制备出了晶粒大小均一的铈锆固溶体。
Description
技术领域
本发明涉及固溶体的制备技术领域,尤其涉及一种球磨法制备铈锆固溶体的方法。
背景技术
目前铈锆固溶体主要用于机动车尾气处理技术上。第一代催化剂助剂氧化铈的晶体主要为萤石结构,其中存在三价和四价铈离子,具有优异的的储放氧性能。但是氧化铈在高温时容易烧结,性能下降较大,所以第二代催化剂助剂,在氧化铈的基础上加入锆,利用锆的立方相稳定结构,和铈形成固溶体,有效提高了催化剂助剂的耐高温性能,同时增加了晶格中的氧空穴,提高了催化剂助剂的储氧性能。目前第三代催化剂助剂,在铈锆的基础上加入了不同的稀土元素进行改性,进一步提高了催化剂助剂的耐高温性能和储氧性能。
目前铈锆固溶体的制备工艺有固相法,共沉淀法和水热法等,其中固相法虽然能制得固溶体,但因其经过高温烧结,存在比表面积低的缺点,同时混合不均匀也将影响固溶体的固溶度。水热法是目前研究比较热门的制备方法之一,其优点在于制得的铈锆固溶体晶型生长均匀,比表面积高,但水热法存在对生产设备要求高,需要加热能耗大的缺点。共沉淀法工艺简单,容易操作,因其制得的产品固溶度高,生产设备简单而容易大规模化生产,深受市场欢迎,但沉淀法也同样存在制备的铈锆固溶体晶粒大,晶相分布不均匀等缺点。
现有技术生产的铈锆固溶体,存在因晶粒生长时间不同而晶相分布不均匀的问题。焙烧出来的一次颗粒的粒度集中度较差,需要进行机械粉碎处理,机械粉碎会破坏铈锆固溶体的孔结构,影响其比表面积等物理性能。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种简单的铈锆固溶体的球磨法制备方法,制备出的铈锆固溶体晶粒尺寸均匀,且具有较好的高温稳定性。
为实现上述目的,本发明所采取的技术方案为:一种球磨法制备铈锆固溶体的方法,包括如下步骤:
(1)将铈盐溶液、锆盐溶液和除铈以外的稀土元素盐溶液混合,加入表面活性剂,充分搅拌,得到溶液A;
(2)将沉淀剂分散在水中,得到溶液B;
(3)将球磨珠加入溶液B中,再将溶液A加入溶液B中,搅拌,得到悬浊液C;
(4)滤出球磨珠,向悬浊液C中加入分散剂,搅拌30~60min,得到沉淀物D;
(5)将沉淀物D经压滤、洗涤、焙烧和过筛后,得到所述铈锆固溶体;
所述步骤(3)中,球磨珠的体积为球磨过程所在容器体积的30~35%,球磨珠的直径为2~40mm。使用两种尺寸的球磨珠进行球磨,分别为大珠和小珠,大珠的直径至少为小珠直径的1.37倍,所有大珠的体积为所有小珠体积的2.5~3.5倍。利用大小两种球磨珠的组合,如图1所示大珠之间的缝隙由小珠填充,如此可以提升研磨效果,通过计算,大珠的直径应至少为小珠直径的1.37倍。
优选地,所述步骤(1)中,表面活性剂的质量为铈锆固溶体质量的5~20%,溶液A中金属离子的浓度为0.4~1mol/L;所述步骤(2)中,沉淀剂包含氢氧化钠、碳酸钠、碳酸铵、氨水中的至少一种,溶液B中氢氧根离子的浓度为溶液A中金属离子浓度的5~10倍;所述步骤(4)中,分散剂的质量为铈锆固溶体质量的5~50%。
优选地,所述步骤(3)中,溶液A加入到溶液B中耗时10~30min。
优选地,所述步骤(5)中,沉淀物D以60~80℃干燥6~10h,再以700~900℃焙烧4~10h。
优选地,所述铈盐溶液包含硝酸铈溶液、硝酸铈铵溶液、氯化铈溶液、硝酸高铈溶液中的至少一种;所述锆盐溶液包含硝酸锆溶液、氯氧化锆溶液中的至少一种;所述除铈以外的稀土元素盐溶液为稀土元素硝酸盐溶液、稀土元素氯盐溶液中的至少一种。
优选地,所述表面活性剂为聚乙二醇、聚丙二醇、异丙醇中的至少一种;其中,所述聚乙二醇的重均分子量为200~4000,所述聚丙二醇的重均分子量为200~2000。
优选地,所述溶液B中氢氧根离子的浓度为3~7mol/L。
优选地,所述球磨珠材质包含玛瑙、氧化锆、聚四氟乙烯中的至少一种。
优选地,所述分散剂包含十二烷基三甲基溴化铵、十六烷基三甲基溴化铵、十二烷基二甲基苄基溴化铵、十二酸、十二酸铵、十四酸、十四酸铵、十六酸、十六酸铵、十八酸、油酸、十二烷基甜菜碱中的至少一种。
相比于现有技术,本发明的有益效果为:本发明采用球磨法制备铈锆固溶体,通过球磨处理,能将大的晶粒分散成小晶粒,消除因晶粒生长时间不同而导致的晶粒大小不一的影响。焙烧出来的铈锆固溶体,只需要经过过筛处理就可得到成品,不再需要经过机械破碎,减少破碎对铈锆固溶体孔结构的影响。以本发明所述方法制备的样品过筛后的一次颗粒集中度高。
附图说明
图1为球磨时大小球磨珠的堆积示意图;
图2为实施例1制备的铈锆固溶体的粒径分布图;
图3为对比例1制备的铈锆固溶体的粒径分布图;
图4为对比例2制备的铈锆固溶体的粒径分布图;
图5为对比例3制备的铈锆固溶体的粒径分布图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合附图和具体实施例对本发明作进一步说明。
实施例1
本发明所述球磨法制备铈锆固溶体的方法的一种实施例,本实施例制备的铈锆固溶体的质量为500g,本实施例所述制备方法包括如下步骤:
(1)按照氧化物重量比为:CeO2:ZrO2:La2O3:Nd2O3=45:45:5:5量取硝酸铈铵溶液、硝酸锆溶液、硝酸镧溶液、硝酸钕溶液,每种金属盐溶液中金属离子的浓度均为2mol/L,然后加入纯水,配制成8L金属离子浓度为0.429mol/L的混合溶液,再加入25g聚乙二醇400,搅拌均匀,得到溶液A;
(2)配制6L NH3·H2O浓度为5.148mol/L的氨水溶液,为溶液B,置于50L反应釜中持续搅拌;
(3)向反应釜中加入12.5L直径为14mm的玛瑙球磨珠和4.2L直径为10mm的玛瑙球磨珠;将溶液A加入溶液B中,溶液A完全加入溶液B中的时间为20min,搅拌,得到悬浊液C;
(4)滤出球磨珠后,向悬浊液中加入200g十四酸,继续搅拌30min得到沉淀物D;
(5)将沉淀物D压滤、洗涤干净后,在80℃下进行烘干,时间为6h,将烘干后的物质用700℃焙烧4h,过筛后得到所述铈锆固溶体。
对比例1
一种球磨法制备铈锆固溶体的方法,本方法制备的铈锆固溶体的质量为500g,与实施例1的区别仅在于,球磨所用的球磨珠均为10mm的玛瑙球磨珠,体积约为17L。
对比例2
一种球磨法制备铈锆固溶体的方法,本方法制备的铈锆固溶体的质量为500g,与实施例1的区别仅在于,步骤(3)中未添加球磨珠,反应完,得到沉淀物D后再加入球磨珠进行球磨,球磨珠的尺寸及用量也与实施例1相同。
对比例3
一种球磨法制备铈锆固溶体的方法,本方法制备的铈锆固溶体的质量为500g,与实施例1的区别仅在于,14mm的玛瑙球磨珠的体积与10mm的玛瑙球磨珠的体积分别约为10.5L和6.5L。
1)粒度测试
采用激光粒度仪对实施例1和对比例1~3制备的铈锆固溶体的粒径分布情况进行测试,测试结果如表1所示,粒径分布图如图2~5所示。
表1
项目 | D10(μm) | D50(μm) | D90(μm) |
实施例1 | 3.035 | 6.946 | 14.186 |
对比例1 | 2.223 | 9.573 | 26.808 |
对比例2 | 2.306 | 11.157 | 27.800 |
对比例3 | 2.044 | 8.361 | 22.091 |
2)高温稳定性
将实施例1和对比例1~3的新鲜态铈锆固溶体用马弗炉于1000℃老化4小时,采用气体吸附(氮气吸附法)比表面积测定法测试新鲜态和老化态的比表面积。测试结果如表2所示。
表2
由上述结果可知,以本发明所述球磨法制备的铈锆固溶体,其粒径分布范围相对较窄,制备的铈锆固溶体的粒径更为均一,其高温稳定性相对更好。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,但并不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种球磨法制备铈锆固溶体的方法,其特征在于,包括如下步骤:
(1)将铈盐溶液、锆盐溶液和除铈以外的稀土元素盐溶液混合,加入表面活性剂,充分搅拌,得到溶液A;
(2)将沉淀剂分散在水中,得到溶液B;
(3)将球磨珠加入溶液B中,再将溶液A加入溶液B中,搅拌,得到悬浊液C;
(4)滤出球磨珠,向悬浊液C中加入分散剂,搅拌30~60min,得到沉淀物D;
(5)将沉淀物D经压滤、洗涤、焙烧和过筛后,得到所述铈锆固溶体;
所述步骤(3)中,球磨珠的体积为球磨过程所在容器体积的30~35%,球磨珠的直径为2~40mm。
2.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,使用两种尺寸的球磨珠进行球磨,分别为大珠和小珠,大珠的直径至少为小珠直径的1.37倍,所有大珠的体积为所有小珠体积的2.5~3.5倍。
3.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述步骤(1)中,表面活性剂的质量为铈锆固溶体质量的5~20%,溶液A中金属离子的浓度为0.4~1mol/L;所述步骤(2)中,沉淀剂包含氢氧化钠、碳酸钠、碳酸铵、氨水中的至少一种,溶液B中氢氧根离子的浓度为溶液A中金属离子浓度的5~10倍;所述步骤(4)中,分散剂的质量为铈锆固溶体质量的5~50%。
4.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述步骤(3)中,溶液A加入到溶液B中耗时10~30min。
5.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述步骤(5)中,沉淀物D以60~80℃干燥6~10h,再以700~900℃焙烧4~10h。
6.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述铈盐溶液包含硝酸铈溶液、硝酸铈铵溶液、氯化铈溶液、硝酸高铈溶液中的至少一种;所述锆盐溶液包含硝酸锆溶液、氯氧化锆溶液中的至少一种;所述除铈以外的稀土元素盐溶液为稀土元素硝酸盐溶液、稀土元素氯盐溶液中的至少一种。
7.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述表面活性剂为聚乙二醇、聚丙二醇、异丙醇中的至少一种;其中,所述聚乙二醇的重均分子量为200~4000,所述聚丙二醇的重均分子量为200~2000。
8.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述溶液B中氢氧根离子的浓度为3~7mol/L。
9.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述球磨珠材质包含玛瑙、氧化锆、聚四氟乙烯中的至少一种。
10.如权利要求1所述的球磨法制备铈锆固溶体的方法,其特征在于,所述分散剂包含十二烷基三甲基溴化铵、十六烷基三甲基溴化铵、十二烷基二甲基苄基溴化铵、十二酸、十二酸铵、十四酸、十四酸铵、十六酸、十六酸铵、十八酸、油酸、十二烷基甜菜碱中的至少一种。
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