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CN116375494B - 一种多孔陶瓷球材料及其制备方法和应用 - Google Patents

一种多孔陶瓷球材料及其制备方法和应用 Download PDF

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CN116375494B
CN116375494B CN202310382990.9A CN202310382990A CN116375494B CN 116375494 B CN116375494 B CN 116375494B CN 202310382990 A CN202310382990 A CN 202310382990A CN 116375494 B CN116375494 B CN 116375494B
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metal
oxide
porous ceramic
ceramic ball
cerium
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CN116375494A (zh
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郭旭东
吴海霞
孟澜
李恒宇
高雪涛
兰学强
习梦杨
段宏剑
李正坤
高凡
贾宏韬
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Hebei University of Science and Technology
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    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02MSUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M27/00Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
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Abstract

本发明燃油催化剂技术领域,具体公开一种多孔陶瓷球材料及其制备方法和应用。所述多孔陶瓷球材料包括如下质量百分含量的组分:电气石60%~70%,碳酸钙10%~20%,改性铈锆复合氧化物1%~3%,镧改性铁氧化物4%~6%,铁尖晶石1%~4%,金属镝粉1%~2%和硫酸锌改性活性炭5%~13%。本发明提供的多孔陶瓷球材料具有比表面积大,吸附容量和孔隙率大的优点,具有优异的催化燃油分子燃烧的效果,且还能充分脱除燃油分子中的杂质和胶质物,改善燃油分子品质,减少发动机积炭,提高发动机的使用寿命,且多孔陶瓷球材料的制备工艺简单,操作方便,成本低廉,适合工业化规模生产应用。

Description

一种多孔陶瓷球材料及其制备方法和应用
技术领域
本发明涉及燃油催化剂技术领域,尤其涉及一种多孔陶瓷球材料及其制备方法和应用。
背景技术
燃油在贮存、运输过程中会发生氧化生成无法燃烧的胶质物,这些胶质物易沉积在油管、过滤器、汽化器喷管和喷油嘴的部位,影响发动机的正常使用。当这些胶质物和燃油一起进入发动机后,会逐渐沉积在活塞顶端,经过温灼烧而变硬,增加燃烧积炭,堵塞油路,造成供油量少、雾化效果差、可燃混合气体浓度低等不良结果,从而导致发动机动力下降。此外,积炭还会减少燃烧室面积,降低功率,设置会引起爆燃爆震,影响发动机的使用寿命。因此,减少胶炭的生成,保证发动机的正常工作,对于降低汽车维修成本、增加发动机的使用寿命具有十分重要的意义。
且由于机动车燃油中含有较大的分子团,容易出现燃烧不充分,导致其尾气中含有大量可燃性有害气体,如一氧化碳CO、氮氧化合物NOx和碳氢化合物等问题,不仅会导致燃油能源的浪费,还会导致较为严重的环境污染问题。为了达到节油、减少积炭、净化尾气的目的,现已研制出不少燃料油添加剂。目前的燃油添加剂主要是向燃油中添加多种有机物助剂,使发动机内部燃油快速分解,减少积碳产生,但是这种催化剂减低发动机性能;其次,这些添加剂在燃烧过程中会产生一氧化碳、二氧化硫等污染环境的气体,造成环境污染,环保性较差。
发明内容
鉴于此,本发明提供一种多孔陶瓷球材料及其制备方法和应用。本发明以电气石为主要原料,加入碳酸钙、铈锆复合氧化物、改性铁氧化物、铁尖晶石、稀土金属镝和改性活性炭,制备得到多孔陶瓷材料,将其作为燃油催化剂,可促使燃油更完全燃烧,增强燃油燃烧效率,且还能抑制积炭生成,延长发动机的使用寿命,降低用车保养费用
为解决上述技术问题,本发明提供的技术方案是:
一种多孔陶瓷球材料,包括如下质量百分含量的组分:电气石60%~70%,碳酸钙10%~20%,改性铈锆复合氧化物1%~3%,镧改性铁氧化物4%~6%,铁尖晶石1%~4%,金属镝粉1%~2%和硫酸锌改性活性炭5%~13%;
所述改性铈锆复合氧化物为金属镧、金属镨、金属钇、金属钙和氢氧化铁改性铈锆复合氧化物。
相对于现有技术,本发明提供的多孔陶瓷球材料,电气石、镧改性铁氧化物和铁尖晶石可通过辐射远红外线降低燃油分子的团聚状态,同时三者协同可有效降低燃油分子的表面张力,减小油滴雾化液滴粒径,提高雾化质量,促进燃油的充分燃烧;铈锆复合氧化物具有优异的储氧和释氧功能,与电气石协同作用,可显著提高燃油的含氧量,使经过远红外线裂解的燃油小分子燃烧更充分;硫酸锌改性活性炭,具有大量的微孔结构,且化学性质稳定,能够充分吸附燃油中的胶质物和杂质,改善燃油品质,且硫酸锌改性活性炭能够提高多孔陶瓷球材料耐老化性,从而提高多孔陶瓷球材料的使用寿命;稀土金属镝,可加快电石气、镧改性铁氧化物和铁尖晶石裂解燃油分子的反应速率,使得燃油分子充分裂解,进而促进燃油分子的充分燃烧。本发明通过各组分的协同作,可对经过多孔陶瓷球材料的燃油进行高效的吸附净化、增加燃油的含氧量,使得燃油分子充分裂解,从而提高燃油的燃烧效率,降低有害气体的排放量,同时,还能有效抑制积碳的产生,增加发动机的使用寿命,具有较高的实际应用价值。
示例性的,所述电气石的粒径为2mm~5mm。
示例性的,所述铁尖晶石的粒径为7mm~15mm。
示例性的,所述改性铈锆复合氧化物的粒径为700μm~900μm。
示例性的,所述镧改性铁氧化物的粒径为100μm~120μm。
示例性的,所述硫酸锌改性活性炭的粒径为0.25mm~0.35mm。
优选的,所述铈锆复合氧化物的制备方法包括如下步骤:
将氢氧化铈和氢氧化锆混合均匀,依次加入金属镧、金属镨、金属钇、金属钙和氢氧化铁,混合均匀,于500℃~550℃焙烧2.0h~2.5h,得所述改性铈锆复合氧化物。
优选的,所述氢氧化铈和氢氧化锆的质量比为1.25~1.50:1。
优选的,所述金属镧的加入量为氢氧化铈质量的4.8%~5.0%,所述金属镨的加入量为氢氧化铈质量的4.8%~5.0%,所述金属钇的加入量为氢氧化铈质量的9.6%~10.0%,所述金属钙的加入量为氢氧化铈质量的0.045%~0.05%,所述氢氧化铁的加入量为氢氧化铈质量的0.045%~0.05%。
进一步优选的,所述氢氧化铈的粒径为700μm~750μm,所述氢氧化锆的粒径为800μm~850μm,所述金属镧、金属镨、金属钇和金属钙的粒径均为200μm~235μm,所述氢氧化铁的粒径为700μm~725μm。
优选的铈锆复合氧化物具有优异的释氧和储氧功能,可为燃油燃烧提供充分的氧气,促进燃油分子更彻底地燃烧,提高燃油的经济性,并减少汽车尾气一氧化碳、碳氢化合物等污染物的排放;且制备得到的铈锆复合氧化物还可发射远红外线,破坏碳氢分子燃料间的氢键,减少碳氢燃油分子间的缔合度,生成小分子碳氢燃料,进一步促进燃油分子的彻底燃烧;同时,优选的铈锆复合氧化物还具有优异的抗老化性能,能够提高多孔陶瓷球材料的使用寿命。
优选的,所述镧改性铁氧化物的制备方法包括如下步骤:
向四氧化三铁中依次加入三氧化二铁和金属镧混合均匀,于磁场中压制成型后,再于惰性气氛下,1000℃~1200℃烧结3h~6h,得所述镧改性铁氧化物。
优选的,所述三氧化二铁的加入量为四氧化三铁质量的20%~30%。
优选的,所述金属镧的加入量为四氧化三铁与三氧化二铁总质量的5%~10%。
优选的,所述磁场的强度为2T~3T。
优选的,所述四氧化三铁和三氧化二铁的粒径均为100μm~120μm,所述金属镧的粒径为300nm~600nm。
优选的镧改性铁氧化物,具有更强的磁性和辐射远红外线的能力,可通过辐射远红外线降低燃油分子的团聚状态,降低燃油分子的表面张力,降低油滴雾化液滴粒径,提高雾化质量,增强汽车动力。
优选的,所述铁尖晶石的制备方法包括如下步骤:
将氧化镁、三氧化二铁、氧化铝和金属钇混合均匀,向混合物中加水,压制成型,干燥,于2860℃~3500℃熔融,冷却,粉碎,得所述铁尖晶石。
进一步优选的,所述氧化镁与氧化铝的质量比为1:2.3~2.9。
进一步优选的,所述三氧化二铁与氧化铝的质量比为1:2.1~2.6。
进一步优选的,所述金属钇的加入量为氧化镁、三氧化二铁和氧化铝总质量的5%~7%。
加入特定含量的金属钇粉可以促进熔融效果,并增强制备得到的多孔陶瓷球材料性能的稳定性。
进一步优选的,熔融时间为12h~15h。
进一步优选的,所述氧化镁、氧化铁和氧化铝的粒径均为80μm~100μm,金属钇的粒径为50μm~70μm。
示例性的,将熔融后的物质于室温冷却1~2天,然后进行粉碎,粉碎至粒径7mm~15mm。
上述方法制备得到的铁尖晶石与电气石和改性铈锆复合氧化物协同作用,可进一步降低燃油分子的团聚状态,增强远红外线的辐射效果,提高雾化效果,促进燃油的充分燃烧。
优选的,所述硫酸锌改性活性炭的制备方法包括如下步骤:
步骤a,将干燥的椰壳碳粉粉碎,在氢气氛围下,于650℃~750℃焙烧4h~5h,得预处理椰壳碳粉;
步骤b,将所述预处理椰壳碳粉加入硫酸锌溶液中,于50℃~80℃浸渍1.5h~3h,过滤,干燥,粉碎,得所述硫酸锌改性活性炭。
进一步优选的,所述硫酸锌溶液的浓度为3mol/L~5mol/L,其与所述预处理椰壳碳粉的质量比为1:0.25~0.35。
示例性的,步骤a中,将椰壳碳粉粉碎至0.15mm~0.25mm。
示例性的,步骤a中,氢气的通入流量为500mL/min~600mL/min。
示例性的,步骤b中,粉碎至粒径为0.25mm~0.35mm。
本发明通过氢气流动的氛围使得氢气分子贯穿椰壳碳粉的内部孔径,与碳分子充分接触并与碳分子间形成化学键合,抑制碳粉自身的氧化,使得制备的椰壳碳粉具有较大的比表面积和发达的孔道结构,且后续通过硫酸锌浸渍对椰壳碳粉进行改性,显著提高了改性活性炭的吸附能力,使得改性改性活性炭充分吸附燃油中的杂质和胶质物,大大减少发动机中的积炭,提高发动机的使用寿命;同时,通过硫酸锌改性活性炭,可使活性炭的化学性质更稳定,避免活性炭与燃油分子发生反应。
本发明还提供了一种多孔陶瓷球材料的制备方法,包括如下步骤:
按照设计配比称取各组分,将称取的电气石、碳酸钙、铈锆复合氧化物、镧改性铁氧化物、铁尖晶石、金属镝粉和硫酸锌改性活性炭混合均匀,造粒,干燥,得球坯;
将所述球坯置于马弗炉中,先以3℃/min~5℃/min的速率升温至500℃~600℃,然后以9℃/min~11℃/min的速率升温至1200℃~1500℃,保温2h~4h,冷却,得所述多孔陶瓷球材料。
示例性的,所述球坯的粒径为20mm~30mm。
示例性的,所述干燥方式具体为:先自然风干20h~24h,然后再于110℃~120℃干燥10h~12h。
本发明提供的多孔陶瓷球材料的制备方法,制备得到的多孔陶瓷球材料具有比表面积大,吸附容量和孔隙率大的优点,具有优异的催化燃油分子燃烧的效果,且还能充分脱除燃油分子中的杂质和胶质物,改善燃油分子品质,减少发动机积炭,提高发动机的使用寿命,且多孔陶瓷球材料的制备工艺简单,操作方便,成本低廉,适合工业化规模生产应用。
本发明还提供了上述任一项所述的多孔陶瓷球材料作为燃油催化剂的应用,将所述多孔陶瓷球材料置于汽车燃油催化器内,并将所述汽车燃油催化器安装于汽车燃油滤清器进油口的前端。
示例性的,每一燃油催化器内放置40~45个所述多孔陶瓷球材料。
本发明制备的多孔陶瓷球材料应用时只需要将其直接置于汽车燃油催化器内即可,然后将燃油催化器安装于汽车滤清器进油口的前端,多孔陶瓷球材料对流经的燃油进行吸附净化,聚合燃油中的胶质物,增加燃油含氧量,释放远红外线裂解燃油分子和降低燃油的表面张力,经过催化的燃油进入油路喷射至气缸内,使得燃油与空气充分混合,促进燃油的充分燃烧,减少有害气体的排放;当胶质物的聚合分子超过活性炭的吸附能力时,聚合的胶质分子会被燃油冲刷,从改性活性炭表面脱落,随油路流入汽车滤清器内,被汽车滤清器过滤截停,防止进入内燃机燃烧形成积炭,影响发动机的效能,且燃油催化器安装简便,不改变发动机燃烧室的结构和性能,也不会额外产生一氧化碳、二氧化硫等污染环境的气体,是一种绿色环保高效的燃油催化剂材料,具有广阔的应用前景。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
为了更好的说明本发明,下面通过实施例做进一步的举例说明。
实施例1
本发明实施例提供一种多孔陶瓷球材料,包括如下质量百分含量的组分:电气石70%,碳酸钙10%,改性铈锆复合氧化物1%,镧改性铁氧化物4%,铁尖晶石1%,金属镝粉1%和硫酸锌改性活性炭13%。
上述多孔陶瓷球材料的制备方法,具体包括如下步骤:
(1)改性铈锆复合氧化物的制备:
将氢氧化铈粉末与氢氧化锆粉末按照质量比1.25:1混合均匀,将金属单质粉末镧、镨、钇分别按照氢氧化铈质量的4.8%、5%、10%加入上述混合物中,混合均匀,然后将氢氧化铁和金属单质钙粉分别按照氢氧化铈质量的0.05%、0.05%加入混合物中,混合均匀,将所得固体混合物放入石英坩埚中,于500℃焙烧2.5h,冷却,粉碎至粒径为700μm~900μm,得改性铈锆复合氧化物。
(2)镧改性铁氧化物的制备:
向四氧化三铁粉末中加入三氧化二铁粉末,加入量为四氧化三铁质量的30%,再向混合物中加入金属单质镧粉,加入量为四氧化三铁和三氧化二铁总质量的5%,在2T的磁场中压制成型,然后置于真空烧结炉中,于1200℃烧结3h,冷却,粉碎至粒径为100μm~120μm,得镧改性铁氧化物。
(3)铁尖晶石的制备:
将氧化镁粉与氧化铝粉按照质量比1:2.9混合均匀,将三氧化二铁加入上述混合物中混合均匀,三氧化二铁与氧化铝的质量比为1:2.1,得混合物料;然后加入所述混合物料总质量7%的金属钇粉,放入干粉搅拌机中搅拌1h,再放入压球机中加水密压成型,然后放入电热鼓风干燥箱中于120℃干燥1h,将干燥后的成型物料放入熔炼炉中,于3500℃熔融12h,然后室温冷却2天,粉碎至粒径7mm~15mm,得铁尖晶石。
(4)硫酸锌改性活性炭的制备:
将椰壳碳粉用蒸馏水清洗,过滤,于110℃干燥2h,粉碎至粒径为0.15-0.25mm的颗粒,然后在氢气流速600mL/min的氛围下,于750℃焙烧4h,得预处理椰壳碳粉;然后将所述预处理椰壳碳粉置于3mol/L硫酸锌溶液中,预处理椰壳碳粉与硫酸锌的质量比为0.25:1,在50℃浸渍3h,过滤,于110℃干燥24h,粉碎至粒径为0.25-0.35mm的颗粒,得硫酸锌改性活性炭。
(5)多孔陶瓷球材料的制备:
按照设计配比称取各组分,将称取的电气石、碳酸钙、铈锆复合氧化物、镧改性铁氧化物、铁尖晶石、金属镝粉和硫酸锌改性活性炭混合均匀,放入球形颗粒成型机中,采用滚动成型法造粒,得到粒径为20-30mm的球形颗粒,自然风干20h,再置于120℃电热鼓风干燥箱中干燥10h,得球坯;
将所述球坯置于马弗炉中,先以3℃/min的速率升温至500℃,然后以9℃/min的速率升温至1200℃,保温4h,随炉冷却,得所述多孔陶瓷球材料。
实施例2
本发明实施例提供一种多孔陶瓷球材料,包括如下质量百分含量的组分:电气石60%,碳酸钙20%,改性铈锆复合氧化物3%,镧改性铁氧化物6%,铁尖晶石4%,金属镝粉2%和硫酸锌改性活性炭5%。
上述多孔陶瓷球材料的制备方法,具体包括如下步骤:
(1)改性铈锆复合氧化物的制备:
将氢氧化铈粉末与氢氧化锆粉末按照质量比1.5:1混合均匀,将金属单质粉末镧、镨、钇分别按照氢氧化铈质量的5%、4.9%、9.6%加入上述混合物中,混合均匀,然后将氢氧化铁和金属单质钙粉分别按照氢氧化铈质量的0.045%、0.048%加入混合物中,混合均匀,将所得固体混合物放入石英坩埚中,于550℃焙烧2h,冷却,粉碎至粒径为700μm~900μm,得改性铈锆复合氧化物。
(2)镧改性铁氧化物的制备:
向四氧化三铁粉末中加入三氧化二铁粉末,加入量为四氧化三铁质量的20%,再向混合物中加入金属单质镧粉,加入量为四氧化三铁和三氧化二铁总质量的10%,在3T的磁场中压制成型,然后置于真空烧结炉中,于1000℃烧结6h,冷却,粉碎至粒径为100μm~120μm,得镧改性铁氧化物。
(3)铁尖晶石的制备:
将氧化镁粉与氧化铝粉按照质量比1:2.3混合均匀,将三氧化二铁加入上述混合物中混合均匀,三氧化二铁与氧化铝的质量比为1:2.6,得混合物料;然后加入所述混合物料总质量5%的金属钇粉,放入干粉搅拌机中搅拌0.5h,再放入压球机中加水密压成型,然后放入电热鼓风干燥箱中于100℃干燥1.5h,将干燥后的成型物料放入熔炼炉中,于2860℃熔融15h,然后室温冷却1天,粉碎至粒径7mm~15mm,得铁尖晶石。
(4)硫酸锌改性活性炭的制备:
将椰壳碳粉用蒸馏水清洗,过滤,于120℃干燥1h,粉碎至粒径为0.15-0.25mm的颗粒,然后在氢气流速500mL/min的氛围下,于650℃焙烧5h,得预处理椰壳碳粉;然后将所述预处理椰壳碳粉置于5mol/L硫酸锌溶液中,预处理椰壳碳粉与硫酸锌的质量比为0.35:1,在80℃浸渍1.5h,过滤,于120℃干燥20h,粉碎至粒径为0.25-0.35mm的颗粒,得硫酸锌改性活性炭。
(5)多孔陶瓷球材料的制备:
按照设计配比称取各组分,将称取的电气石、碳酸钙、铈锆复合氧化物、镧改性铁氧化物、铁尖晶石、金属镝粉和硫酸锌改性活性炭混合均匀,放入球形颗粒成型机中,采用滚动成型法造粒,得到粒径为20-30mm的球形颗粒,自然风干24h,再置于110℃电热鼓风干燥箱中干燥12h,得球坯;
将所述球坯置于马弗炉中,先以5℃/min的速率升温至600℃,然后以11℃/min的速率升温至1500℃,保温2h,随炉冷却,得所述多孔陶瓷球材料。
实施例3
本发明实施例提供一种多孔陶瓷球材料,包括如下质量百分含量的组分:电气石65%,碳酸钙15%,改性铈锆复合氧化物2%,镧改性铁氧化物5%,铁尖晶石3%,金属镝粉2%和硫酸锌改性活性炭8%。
上述多孔陶瓷球材料的制备方法,具体包括如下步骤:
(1)改性铈锆复合氧化物的制备:
将氢氧化铈粉末与氢氧化锆粉末按照质量比1.4:1混合均匀,将金属单质粉末镧、镨、钇分别按照氢氧化铈质量的4.9%、4.8%、9.8%加入上述混合物中,混合均匀,然后将氢氧化铁和金属单质钙粉分别按照氢氧化铈质量的0.048%、0.045%加入混合物中,混合均匀,将所得固体混合物放入石英坩埚中,于530℃焙烧2.5h,冷却,粉碎至粒径为700μm~900μm,得改性铈锆复合氧化物。
(2)镧改性铁氧化物的制备:
向四氧化三铁粉末中加入三氧化二铁粉末,加入量为四氧化三铁质量的25%,再向混合物中加入金属单质镧粉,加入量为四氧化三铁和三氧化二铁总质量的8%,在2.5T的磁场中压制成型,然后置于真空烧结炉中,于1100℃烧结4h,冷却,粉碎至粒径为100μm~120μm,得镧改性铁氧化物。
(3)铁尖晶石的制备:
将氧化镁粉与氧化铝粉按照质量比1:2.5混合均匀,将三氧化二铁加入上述混合物中混合均匀,三氧化二铁与氧化铝的质量比为1:2.3,得混合物料;然后加入所述混合物料总质量6%的金属钇粉,放入干粉搅拌机中搅拌1h,再放入压球机中加水密压成型,然后放入电热鼓风干燥箱中于120℃干燥1h,将干燥后的成型物料放入熔炼炉中,于3000℃熔融14h,然后室温冷却1天,粉碎至粒径7mm~15mm,得铁尖晶石。
(4)硫酸锌改性活性炭的制备:
将椰壳碳粉用蒸馏水清洗,过滤,于120℃干燥1h,粉碎至粒径为0.15-0.25mm的颗粒,然后在氢气流速550mL/min的氛围下,于700℃焙烧4.5h,得预处理椰壳碳粉;然后将所述预处理椰壳碳粉置于4mol/L硫酸锌溶液中,预处理椰壳碳粉与硫酸锌的质量比为0.3:1,在65℃浸渍2h,过滤,于120℃干燥20h,粉碎至粒径为0.25-0.35mm的颗粒,得硫酸锌改性活性炭。
(5)多孔陶瓷球材料的制备:
按照设计配比称取各组分,将称取的电气石、碳酸钙、铈锆复合氧化物、镧改性铁氧化物、铁尖晶石、金属镝粉和硫酸锌改性活性炭混合均匀,放入球形颗粒成型机中,采用滚动成型法造粒,得到粒径为20-30mm的球形颗粒,自然风干24h,再置于120℃电热鼓风干燥箱中干燥10h,得球坯;
将所述球坯置于马弗炉中,先以4℃/min的速率升温至550℃,然后以10℃/min的速率升温至1350℃,保温3h,随炉冷却,得所述多孔陶瓷球材料。
对比例1-对比例3
本对比例提供一种多孔陶瓷球材料,其原料组成以及制备方法均与实施例1-3相同,不同的仅是将实施例1-3中的硫酸锌改性活性炭分别替换为对应等量的硝酸铜改性活性炭,所述硝酸铜改性活性炭的制备方法如下:
将椰壳碳粉用蒸馏水清洗,过滤,于120℃干燥1h,粉碎至粒径为0.15-0.25mm的颗粒,然后在氢气流速550mL/min的氛围下,于700℃焙烧4.5h,得预处理椰壳碳粉;然后将所述预处理椰壳碳粉置于4mol/L硝酸铜溶液中,预处理椰壳碳粉与硫酸锌的质量比为0.3:1,在65℃浸渍2h,过滤,于120℃干燥20h,粉碎至粒径为0.25-0.35mm的颗粒,得硝酸铜改性活性炭。
按照与实施例3相同的方法制备得到多孔陶瓷球材料。
对比例4-对比例6
本对比例提供一种多孔陶瓷球材料,其原料组成以及制备方法均与实施例1-3相同,不同的仅是将实施例1-3的镧改性铁氧化物分别替换为对应等量的铜改性铁氧化物,所述铜改性铁氧化物的制备方法如下:
向四氧化三铁粉末中加入三氧化二铁粉末,加入量为四氧化三铁质量的25%,再向混合物中加入金属单质铜粉,加入量为四氧化三铁和三氧化二铁总质量的8%,在2.5T的磁场中压制成型,然后置于真空烧结炉中,于1100℃烧结4h,冷却,粉碎至粒径为100μm~120μm,得铜改性铁氧化物。
按照与实施例3相同的方法制备得到多孔陶瓷球材料。
性能测试
采用行驶0公里的轿车,以汽油为原料,采用低怠速进行测试。将实施例和对比例制备得到的多孔陶瓷球材料置于汽车燃油催化器内,并将所述汽车燃油催化器安装于汽车燃油滤清器进油口的前端,每个燃油催化器内放40个多孔陶瓷球,并设置不加入多孔陶瓷球作为对照组。
实施后原地怠速30分钟当场测试一次,然后每个月测试一次连续测试4个月,并于1年后再进行一次追踪测试。
测试仪器是采用符合GB18285-2005和GB3847-2005标准的佛山分析仪器有限公司的佛分FGA4100汽车排气分析仪进行测试,测试结果如表1-表试验一
采用三辆行驶0公里的雅阁230TURBO1.5T轿车,其中两辆分别放置40个实施例1和对比例1制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表1
试验二
采用三辆行驶0公里的传祺GS41.5T轿车,其中两辆分别放置40个实施例2和对比例2制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表2
试验三
采用三辆行驶0公里的奔驰G500,排量4.0V8发动机,其中两辆分别放置40个实施例3和对比例3制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表3
试验四
采用三辆行驶0公里的福特福克斯,排量1.8,其中两辆分别放置40个实施例1和对比例4制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表4
试验五
采用三辆行驶0公里的广汽丰田汉兰达2.7,其中两辆分别放置40个实施例2和对比例5制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表5
试验六
采用三辆行驶0公里的美国进口jeep自由人,排量3.7V6发动机,其中两辆分别放置40个实施例3和对比例6制备的多孔陶瓷球,另外一个不放置多孔陶瓷球。
表6
上述实施例和对比例中所用的物料的粒径如下:
所述氢氧化铈的粒径为700μm~750μm,所述氢氧化锆的粒径为800μm~850μm,所述金属镧、金属镨、金属钇和金属钙的粒径均为200μm~235μm,所述氢氧化铁的粒径为700μm~725μm;所述四氧化三铁和三氧化二铁的粒径均为100μm~120μm,所述金属镧的粒径为300nm~600nm;所述氧化镁、氧化铁和氧化铝的粒径均为80μm~100μm,金属钇的粒径为50μm~70μm。
采用上述粒径范围内制备的物质均能达到基本相当的技术效果。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。

Claims (9)

1.一种多孔陶瓷球材料,其特征在于,包括如下质量百分含量的组分:电气石60%~70%,碳酸钙10%~20%,改性铈锆复合氧化物1%~3%,镧改性铁氧化物4%~6%,铁尖晶石1%~4%,金属镝粉1%~2%和硫酸锌改性活性炭5%~13%;
所述改性铈锆复合氧化物为金属镧、金属镨、金属钇、金属钙和氢氧化铁改性铈锆复合氧化物;
所述镧改性铁氧化物的制备方法包括如下步骤:
向四氧化三铁中依次加入三氧化二铁和金属镧混合均匀,于磁场中压制成型后,再于惰性气氛下,1000℃~1200℃烧结3h~6h,得所述镧改性铁氧化物。
2.如权利要求1所述的多孔陶瓷球材料,其特征在于,所述铈锆复合氧化物的制备方法包括如下步骤:
将氢氧化铈和氢氧化锆混合均匀,依次加入金属镧、金属镨、金属钇、金属钙和氢氧化铁,混合均匀,于500℃~550℃焙烧2.0h~2.5h,得所述改性铈锆复合氧化物。
3.如权利要求2所述的多孔陶瓷球材料,其特征在于,所述氢氧化铈和氢氧化锆的质量比为1.25~1.50:1;和/或
所述金属镧的加入量为氢氧化铈质量的4.8%~5.0%,所述金属镨的加入量为氢氧化铈质量的4.8%~5.0%,所述金属钇的加入量为氢氧化铈质量的9.6%~10.0%,所述金属钙的加入量为氢氧化铈质量的0.045%~0.05%,所述氢氧化铁的加入量为氢氧化铈质量的0.045%~0.05%;和/或
所述氢氧化铈的粒径为700μm~750μm,所述氢氧化锆的粒径为800μm~850μm,所述金属镧、金属镨、金属钇和金属钙的粒径均为200μm~235μm,所述氢氧化铁的粒径为700μm~725μm。
4.如权利要求1所述的多孔陶瓷球材料,其特征在于,所述三氧化二铁的加入量为四氧化三铁质量的20%~30%;和/或
所述金属镧的加入量为四氧化三铁与三氧化二铁总质量的5%~10%;和/或
所述磁场的强度为2T~3T;和/或
所述四氧化三铁和三氧化二铁的粒径均为100μm~120μm,所述金属镧的粒径为300nm~600nm。
5.如权利要求1所述的多孔陶瓷球材料,其特征在于,所述铁尖晶石的制备方法包括如下步骤:
将氧化镁、三氧化二铁、氧化铝和金属钇混合均匀,向所得混合物中加水,压制成型,干燥,于2860℃~3500℃熔融,冷却,粉碎,得所述铁尖晶石。
6.如权利要求1所述的多孔陶瓷球材料,其特征在于,所述硫酸锌改性活性炭的制备方法包括如下步骤:
步骤a,将干燥的椰壳碳粉粉碎,在氢气氛围下,于650℃~750℃焙烧4h~5h,得预处理椰壳碳粉;
步骤b,将所述预处理椰壳碳粉加入硫酸锌溶液中,于50℃~80℃浸渍1.5h~3h,过滤,干燥,粉碎,得所述硫酸锌改性活性炭。
7.如权利要求6所述的多孔陶瓷球材料,其特征在于,所述硫酸锌溶液的浓度为3mol/L~5mol/L,其与所述预处理椰壳碳粉的质量比为1:0.25~0.35。
8.权利要求1-7任一项所述的多孔陶瓷球材料的制备方法,其特征在于,包括如下步骤:
按照设计配比称取各组分,将称取的电气石、碳酸钙、铈锆复合氧化物、镧改性铁氧化物、铁尖晶石、金属镝粉和硫酸锌改性活性炭混合均匀,造粒,干燥,得球坯;
将所述球坯置于马弗炉中,先以3℃/min~5℃/min的速率升温至500℃~600℃,然后以9℃/min~11℃/min的速率升温至1200℃~1500℃,保温2h~4h,冷却,得所述多孔陶瓷球材料。
9.权利要求1~7任一项所述的多孔陶瓷球材料作为燃油催化剂的应用,其特征在于,将所述多孔陶瓷球材料置于汽车燃油催化器内,并将所述汽车燃油催化器安装于汽车燃油滤清器进油口的前端。
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