CN111085201A - 一种空气净化方法 - Google Patents
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Abstract
本发明公开了一种空气净化方法,属于空气净化技术领域,一种空气净化方法,采用金催化剂用于空气净化,金催化剂的活性组分为Au,载体为经过金属化合物助剂修饰的Al2O3,Au和Al2O3的质量百分比为(0.5~3.0):100,金催化剂表面的Au颗粒的平均粒径为3.2~3.6nm,Al2O3的粒径为2.0~3.0mm。本发明公开的空气净化方法,通过制备的金催化剂具有活性高、抗潮湿性能强、使用寿命长的特点,将其应用于空气净化领域中,在常温常湿环境中,可有效去除空气中的甲醛、CO、以及臭氧。
Description
技术领域
本发明属于空气净化领域,尤其涉及一种空气净化方法。
背景技术
自Haruta等(Haruta,M.Yamada,N.,J.Catal.,1989,115,301)发现高分散的Au催化剂对CO低温完全氧化反应具很高的催化活泩以后,Au催化剂引起众多研究者的关注。研究内容涉及Au催化剂的制备方法、载体的选用、在不同反应类型中的应用以及在相应反应中Au催化剂催化作用机理的探讨等。
现有负载型金催化剂制备工艺复杂,催化剂表面杂质难以去除,重现性差,难以工业化生产;金催化剂粒子在使用过程中较易团聚,稳定性较差,易失活,寿命短,难以良好地应用于空气净化领域,以达到去除空气中的甲醛、CO、以及臭氧的效果。
发明内容
为了克服现有技术的缺陷,本发明所要解决的技术问题在于提出一种新的空气净化方法,通过制备的金催化剂具有活性高、抗潮湿性能强、使用寿命长的特点,将其应用于空气净化领域中,在常温常湿环境中,可有效去除空气中的甲醛、CO、以及臭氧。
为达此目的,本发明采用以下技术方案:
本发明提供的一种空气净化方法,采用金催化剂用于空气净化,金催化剂的活性组分为Au,载体为经过金属化合物助剂修饰的Al2O3,Au和Al2O3的质量百分比为(0.5~3.0):100,金催化剂表面的Au颗粒的平均粒径为3.2~3.6nm,Al2O3的粒径为2.0~3.0mm。
优选地,空气净化是指净化空气中的甲醛、CO、臭氧中的一种或多种。
优选地,Al2O3为γ-Al2O3、α-Al2O3、χ-Al2O3或ρ-Al2O3中的一种。
优选地,Al2O3呈球状、柱状或粉状中的一种。
优选地,金催化剂由以下制备方法制备得到:S1:选取材料,选取Au作为活性组分,Al2O3作为载体,S2:修饰Al2O3,将S1中选取的Al2O3载体烘干后浸渍在金属化合物溶液中,0.8-1.2h后对浸渍处理后的Al2O3载体烘干,制得修饰的Al2O3载体,S3:制备金溶胶,在室温及搅拌下,将溴化铵类化合物的四氢呋喃溶液加入到HAuCl4的NaCl溶液中,并继续搅拌,待混合溶液分层后,加入烷基硫醇的四氢呋喃溶液,搅拌均匀后,将NaBH4的NaCl溶液加入至上述溶液中,在室温下反应1.8~2.2h后,分离获得有机相,将有机相蒸发,获得余液,加入醇溶液获得混合液,振荡静置,将该混合液进行离心分离,获得沉淀物,分别用纯水、醇溶液对沉淀物进行多次洗涤,获得金纳米团簇沉淀物,将获得的金纳米团簇沉淀物用正己烷溶解制成烷基硫醇单层保护金溶胶作为浸渍液,S4:制备催化剂前体,将金溶胶等容浸渍于修饰的Al2O3载体上,蒸发去除溶剂,并烘干,获得金催化剂前体,S5:活化催化剂前体,将金催化剂前体在400~450℃条件下,用含CO的空气混合气活化1.8~2.2h,即得负载型金催化剂。上述醇溶液为乙醇溶液。
优选地,步骤S1中,选取的载体的三氧化二铝质量分数≥95%,比表面积≥200m2/g,孔容≥0.45cm3/g,粒径2.0~3.0mm。
优选地,步骤S2中,两次的烘干温度均为110-130℃。
优选地,步骤S2中,金属化合物溶液中的金属为铁、铜、锰、铑、钌、铈、钼或钛中的一种。
优选地,步骤S3中,溴化铵类化合物为四丁基溴化铵或四正辛基溴化铵,四丁基溴化铵或四正辛基溴化铵的浓度范围:0.1~0.3mol/L,HAuCl4的浓度范围:0.02~0.04mol/L,烷基硫醇的浓度范围:0.03~0.05mo1/L,NaBH4的浓度范围:0.3~0.5mol/L。
优选地,步骤S3中,金纳米团簇的烷基硫醇为C8~C16烷基硫醇。
优选地,步骤S4中,烘干温度为60~80℃,烘干时间为2~3h。
优选地,步骤S5中,空气混合气中的CO含量为1.0%~1.5%。
优选地,步骤S3中,离心分离的转速为6000~10000转/min。
优选地,步骤S3中,获得余液后加入乙醇的量为200~500mL。
优选地,步骤S3中,正己烷溶剂与金纳米团簇沉淀物的用量比例为100mL:(95~101)mg。
优选地,步骤S4中,Al2O3载体与金胶溶液的用量比例为1g:(10~20)mL。
本发明的有益效果为:
1、通过本方法制备的金催化剂具有活性高、使用寿命长的特点,将其应用于空气净化领域中可有效去除空气中的甲醛、CO、以及臭氧。
2、通过本方法制备的金催化剂可在常温、常湿条件下去除甲醛、CO、以及臭氧。
3、通过本方法制备的金催化剂稳定性好、抗潮湿性能强。
4、通过载体的修饰以及金溶胶粒径的控制可阻止和延缓催化剂表面金粒子的团聚,有效防止金催化剂失活。
5、金催化剂前体在400~500℃条件下活化1.8~2.2h,减少活化时间并提高催化剂活性,甲醛、一氧化碳等污染物完全催化转化的空速可提高20~30%。
6、工艺流程合理、成本低、成品率高,可实现工业化生产。
附图说明
图1是本发明实施例一的金催化剂的TEM图。
图2是本发明实施例一的金催化剂表面Au纳米粒子粒径分布图。
图3是本发明实施例二的金催化剂的TEM图。
图4是本发明实施例三的金催化剂的TEM图。
图5是本发明实施例四的金催化剂的TEM图。
具体实施方式
现结合附图和具体实施方式对本发明进一步说明。
实施例一:
选用市售的球状的γ-Al2O3载体,载体的三氧化二铝质量分数≥95%,比表面积≥200m2/g,孔容≥0.45cm3/g,粒径2.0~3.0mm。球状的Al2O3载体相比于柱状和粉状的Al2O3载体具有更高的空速。
称取γ-Al2O3载体100g,置于烘箱中,在120℃下,烘干2h。将烘干后的γ-Al2O3载体浸入含10%六水合硝酸铈[Ce(N03)3·6H20]、10%柠檬酸的混合水溶液中,1h后置于烘箱中,在120℃下烘干,得到铈修饰的γ-Al2O3(简称载体A),作为载体备用。
采用十二烷基硫醇(简称为R12,分子式为R12H25SH)作为保护剂合成出十二烷基硫醇单层保护金纳米团簇(R12AuMPCs)。在室温及剧烈搅拌下,将100mL浓度0.1mol/L的(C4H9)4NBr的四氢呋喃溶液加入到58.6mL浓度3.5x10-2mol/L HAuCl4的NaCl饱和溶液中,并继续搅拌,待混合溶液分层后,加入145mL浓度0.035mo1/L C12H25SH的四氢呋喃溶液,搅拌均匀后,将60mL浓度0.35mol/L NaBH4的NaCl水溶液加入;继续搅拌2h后,用分液漏斗分离获得有机相,将有机相蒸发除去溶剂,获得余液,加入200mL乙醇获得混合液,振荡静置。将该混合液进行高速(8000转/min)离心分离,获得黑褐色沉淀物。分别用纯水、乙醇多次洗涤该沉淀物,以除去反应残留物等杂质,最后获得含404mg Au的金纳米团簇(R12AuMPCs)沉淀物。
将含404mg Au的十二烷基硫醇单层保护金纳米团簇(R12AuMPCs)在室温下溶于400mL正己烷溶剂中,配制成制备催化剂的浸渍液,浸渍20g载体A,搅拌均匀后旋蒸蒸发去除溶剂,置于烘箱中于80℃下烘干,制成金负载量约为2%的金催化剂前体。
金催化剂前体在400℃下,用含1.5%CO的空气混合气以20000mL·g-1·h-1的空速活化2h,即得金催化剂。金纳米粒子平均粒径3.4nm。
按此方法调节载体用量,可根据实际需要,制备金负载量分别为0.5%、1.0%、3.0%等的金催化剂。
催化剂活性评价:
1、去除甲醛
原料气组成为10ppm甲醛的空气混合气。评价催化剂用量100mg。在反应温度25℃,相对湿度60%,空速410000mL·g-1·h-1的条件下,甲醛经催化氧化后尾气浓度<0.06ppm,甲醛去除率≥99.4%。该活性已保持4500小时不变,寿命长,而且金纳米平均粒径保持不变,未见金纳米粒子团聚失活现象。
2、去除CO
原料气组成:1.5%CO的空气混合气。评价催化剂用量3000mg。在反应温度25℃,相对湿度60%的条件下,催化剂空速为14400mL·g-1·h-1,CO经催化氧化后尾气浓度<0.01ppm,CO去除率>99%。
3、实用测试
用上述方法制备250克催化剂,制作成催化剂模块,装入空气净化器进行实用测试。
(1)去除甲醛:空气净化器送上海环境保护产品质量监督检验总站检测甲醛去除率及洁净空气值(CADR),结果如表1和表2所示:
表1
表2(2)去除臭氧:将空气净化器放入10m3试验舱进行消除臭氧测试。臭氧由臭氧发生器产生,初始浓度为0.85mg/m3,在常温常湿条件下,开启空气净化器,臭氧去除率为62.3%。
催化剂TEM图、Au纳米分布图见附图说明的图1、图2。
实施例二:
称取市售的球状的γ-Al2O3载体100g,置于烘箱中,在120℃下,烘干2h。将烘干后的γ-Al2O3载体浸入含4.3%硝酸锰、10%柠檬酸的混合水溶液中,1h后置于烘箱中,在120℃下烘干,得到锰修饰的γ-Al2O3(简称载体B),作为载体备用。
采用实施例一所述方法制备催化剂的浸渍液浸渍20g载体B,搅拌均匀后旋蒸蒸发去除溶剂,置于烘箱中于80℃下烘干,制成金负载量约为2%的金催化剂前体。
金催化剂前体在400℃下,用含1.5%CO的空气混合气以20000mL·g-1·h-1的空速活化2h,即得金催化剂。金纳米粒子平均粒径3.64nm。
催化剂活性评价:
1、去除甲醛
原料气组成为6ppm甲醛的空气混合气,评价催化剂用量200mg。在反应温度25℃,相对湿度60%,空速380000mL·g-1·h-1的条件下,甲醛经催化氧化后尾气浓度<0.06ppm,甲醛去除率≥99%。该活性保持800小时不变,未见金纳米粒子团聚失活现象。
2、去除CO
原料气组成:1.5%CO的空气混合气。评价催化剂用量3000mg。在反应温度25℃,相对湿度60%的条件下,催化剂空速为13800mL·g-1·h-1,CO经催化氧化后尾气浓度<0.01ppm,CO去除率>99%。
实施例三:
采用辛烷基硫醇(简称为R8)代替十二烷基硫醇作为保护剂合成出辛烷基硫醇单层保护金纳米团簇(R8AuMPCs)。具体制备方法同实施例一。不同的基团制备出的纳米金,在颗粒度以及与载体的相互作用会有差别,最终会影响到催化剂的空速。主要根据催化剂的用途来决定基团的使用。
将含138mg Au的辛烷基硫醇单层保护金纳米团簇(R8AuMPCs)在室温下溶于140mL正己烷溶剂中,配制成制备催化剂的浸渍液,浸渍13.8g载体A,搅拌均匀后旋蒸蒸发去除溶剂,置于烘箱中于80℃下烘干,制成金负载量约为1%的金催化剂前体。
按实施例1的方法进行活化处理,即得辛烷基硫醇单层保护的金催化剂,该催化剂金负载量为1%。金纳米粒子平均粒径3.61nm。
催化剂活性评价:
原料气组成为8ppm甲醛的空气混合气,评价催化剂用量200mg。在反应温度25℃,相对湿度60%,空速180000mL·g-1·h-1条件下,甲醛经催化氧化后尾气浓度<0.06ppm,甲醛去除率99.3%。
实施例四:
按实施例一的方法,用四正辛基溴化铵(C32H68BrN)替代四丁基溴化铵。采用十二烷基硫醇(简称为R12,分子式为R12H25SH)作为保护剂合成出十二烷基硫醇单层保护金纳米团簇(R12AuMPCs)。在室温及剧烈搅拌下,将34mL浓度0.1mol/L的(C32H68BrN)的四氢呋喃溶液加入到20mL浓度3.5×10-2mol/L HAuCl4的NaCl饱和溶液中,并继续搅拌,待混合溶液分层后,加入49mL浓度0.035mol/L C12H25SH的四氢呋喃溶液,搅拌均匀后,将20mL浓度0.35mol/L NaBH4的NaCl水溶液加入;继续搅拌2h后,用分液漏斗分离提取有机相,将有机相蒸发除去溶剂,获得余液,加入70mL乙醇获得混合液,振荡静置。将该混合液进行高速(8000转/min)离心分离,获得黑褐色沉淀物。分别用纯水、乙醇多次洗涤该沉淀物,以除去反应残留物等杂质,最后获得含138mg Au的金纳米团簇(R12AuMPCs)沉淀物。
将含138mg Au的十二烷基硫醇单层保护金纳米团簇(R12AuMPCs)在室温下溶于138mL正己烷溶剂中,配制成制备催化剂的浸渍液,浸渍9g载体A,搅拌均匀后旋蒸蒸发去除溶剂,置于烘箱中于80℃下烘干,制成金负载量约为1.5%的金催化剂前体。
金催化剂前体在400℃下,用含1.5%CO的空气混合气以20000mL·g-1·h-1空速活化2h,即得金催化剂。金负载量为1.5%。金纳米粒子平均粒径2.86nm。
催化剂活性评价:
原料气组成为10ppm甲醛的空气混合气,评价催化剂用量100mg。在反应温度25℃,相对湿度60%,空速240000mL·g-1·h-1的条件下,甲醛经催化氧化后尾气浓度<0.06ppm,甲醛去除率≥99.4%。
本说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术;以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解;其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种空气净化方法,其特征在于,采用金催化剂用于空气净化;
所述金催化剂的活性组分为Au,载体为经过金属化合物助剂修饰的Al2O3;
Au和Al2O3的质量百分比为(0.5~3.0):100;
金催化剂表面的Au颗粒的平均粒径为3.2~3.6nm;
Al2O3的粒径为2.0~3.0mm。
2.根据权利要求1所述的空气净化方法,其特征在于,
所述的空气净化是指净化空气中的甲醛、CO、臭氧中的一种或多种。
3.根据权利要求1所述的空气净化方法,其特征在于,
所述Al2O3为γ-Al2O3、α-Al2O3、χ-Al2O3或ρ-Al2O3中的一种。
4.根据权利要求1所述的空气净化方法,其特征在于,
所述金催化剂由以下制备方法制备得到:
S1:选取材料,选取Au作为活性组分,Al2O3作为载体;
S2:修饰Al2O3,将S1中选取的Al2O3载体烘干后浸渍在金属化合物溶液中,0.8-1.2h后对浸渍处理后的Al2O3载体烘干,制得修饰的Al2O3载体;
S3:制备金溶胶,在室温及搅拌下,将溴化铵类化合物的四氢呋喃溶液加入到HAuCl4的NaCl溶液中,并继续搅拌,待混合溶液分层后,加入烷基硫醇的四氢呋喃溶液,搅拌均匀后,将NaBH4的NaCl溶液加入至上述溶液中,在室温下反应1.8~2.2h后,分离获得有机相,将有机相蒸发,获得余液,加入醇溶液获得混合液,振荡静置,将该混合液进行离心分离,获得沉淀物,分别用纯水、醇溶液对沉淀物进行多次洗涤,获得金纳米团簇沉淀物,将获得的金纳米团簇沉淀物用正己烷溶解制成烷基硫醇单层保护金溶胶作为浸渍液;
S4:制备催化剂前体,将所述金溶胶等容浸渍于所述修饰的Al2O3载体上,蒸发去除溶剂,并烘干,获得金催化剂前体;
S5:活化催化剂前体,将所述金催化剂前体在400~450℃条件下,用含CO的空气混合气活化1.8~2.2h,即得负载型金催化剂。
5.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S1中,选取的载体的三氧化二铝质量分数≥95%,比表面积≥200m2/g,孔容≥0.45cm3/g,粒径2.0~3.0mm。
6.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S2中,两次的烘干温度均为110-130℃。
7.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S2中,金属化合物溶液中的金属为铁、铜、锰、铑、钌、铈、钼或钛中的一种。
8.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S3中,所述溴化铵类化合物为四丁基溴化铵或四正辛基溴化铵,四丁基溴化铵或四正辛基溴化铵的浓度范围:0.1~0.3 mol/L,HAuCl4的浓度范围:0.02~0.04 mol/L,烷基硫醇的浓度范围:0.03~0.05 mo1/L,NaBH4的浓度范围:0.3~0.5 mol/L,所述金纳米团簇的烷基硫醇为C8~C16烷基硫醇。
9.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S4中,烘干温度为60~80℃,烘干时间为2~3h。
10.根据权利要求4所述的空气净化方法,其特征在于,
所述步骤S5中,空气混合气中的CO含量为1.0%~1.5%。
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CN103301853A (zh) * | 2013-06-20 | 2013-09-18 | 武汉大学 | 一种去除一氧化碳、甲醛和乙烯的金催化剂及制备与应用 |
CN107715872A (zh) * | 2017-10-31 | 2018-02-23 | 中国石油大学(华东) | 一种超高比表面介孔氧化铝负载金纳米催化剂(Au/γ‑Al2O3)的合成方法 |
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