CN106179360A - 一种铜锌铝催化剂及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000611 Zinc aluminium Inorganic materials 0.000 claims 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明属于一氧化碳和水蒸气变换制氢领域和催化剂领域。涉及一种铜锌铝催化剂及其制备方法,本发明的铜锌铝催化剂包括如下重量百分比的组分:CuO 10~55%,ZnO 20~55%,Al2O3 5~30%;本发明的铜锌铝催化剂的制备方法包括沉淀剂溶解、加入有机溶剂、铜锌盐溶液配制、沉淀、加入铝源、过滤、洗涤、烘干、焙烧、造粒、压片等步骤,与传统共沉淀法相比,本发明的制备方法增加了在溶解沉淀剂的溶液中加入有机溶剂的步骤,且通过先沉淀铜锌沉淀物再沉淀铝沉淀物的工艺,制备的铜锌铝催化剂孔径为9~15nm,在CO低温变换制氢工艺中的应用中具有更高的活性和更好的耐热性。
Description
技术领域
本发明属于CO和水蒸气变换制氢和催化剂技术领域,具体涉及一种铜锌铝催化剂及其制备方法。
背景技术
通常在合成气制氢工艺中,CO变换分两个阶段进行,即:反应温度在350~400℃的高温变换阶段,以及反应温度在180~220℃的低温变换阶段。由于铜锌铝催化剂有较好低温变换活性,用于合成氨厂低温变换制氢工艺已有超过50年的历史。在传统工艺中,一般低温变换工艺出口的CO含量为0.1%~0.3%,该部分CO在后续工艺中需要进一步脱除以防止合成氨催化剂中毒。生产实践证明,如果低温变换工艺出口气中CO含量降低0.1%,H2和氨的产率可以增加1.1%~1.6%。因此,铜锌铝催化剂的活性及寿命对合成氨厂的效益有明显的影响,如何提高该催化剂性能也始终是一个重要的研究课题。且随着氢能源利用的发展,尤其是随着新一代燃料电池——聚合物电解质膜燃料电池(PEMFCs)的发展,用于制氢的铜锌铝催化剂也得到了更多课题组的重视。
工业上铜锌铝变换催化剂一般通过共沉淀法制备。传统的共沉淀法是指:在溶液中含有两种或多种阳离子,它们以均相存在于溶液中,加入沉淀剂,经沉淀反应后,可得到各种成分均一的沉淀。如英国专利1,296,211及1,296212提出的共沉淀法是以碳酸钠作沉淀剂,使铜锌铝硝酸盐混合液在确定的pH值及确定的沉淀温度条件下形成碳酸盐沉淀物,用蒸馏水洗净钠离子,然后经烘干焙烧,处理成铜锌铝氧化混合物,该法制备的催化剂孔径较小,催化剂活性较小且活性重复性差。
在机理上,目前大部分研究认为铜锌铝催化剂的变换活性与铜的分散度相关,分散度越高,则铜微晶越小,活性铜比表面越大,则活性越高。在铜锌铝催化剂制备过程中,多种因素如沉淀方式、沉淀过程中的pH值、搅拌速率、沉淀温度、陈化时间、助剂等都可以影响铜的分散度,进而影响铜锌铝催化剂活性。而有关其它因素对铜锌铝催化剂活性影响的报道较少,尤其是孔径对铜锌铝催化剂活性的影响。Sagata等(Int.J.HydrogenEnergy,2014,39,20639–20645)以模板法制备了有序介孔氧化铝,并考察了的孔径对铜锌铝催化剂活性的影响,其制备出的铜锌铝催化剂孔径在6nm以下。
提高铜锌铝催化剂的孔径,会在一定程度上降低铜锌铝催化剂比表面及活性铜的比表面,降低活性中心数量,但对反应物及产物的扩散更加有利,从而提高铜锌铝催化剂的性能。因此,制备大孔径的铜锌铝催化剂样品,对铜锌铝变换催化剂的发展有重要意义。尤其是应用于CO低温变换合成气制氢工艺,增加铜锌铝催化剂的孔径,催化活性相应增加,出口气中CO含量降低,H2和氨的产率随之增加,合成氨厂的效益有明显提升;但现有技术中传统的共沉淀法制备的铜锌铝催化剂孔径只有7~8nm,催化剂的活性较低。
发明内容
为了解决现有技术中存在的上述问题,本发明提供了一种铜锌铝催化剂及其制备方法,本发明的铜锌铝催化剂用于CO低温变换制氢工艺具有很高的CO变换反应活性。本发明要解决的技术问题通过以下技术方案实现的:
一种铜锌铝催化剂,包括如下重量百分比的组分:CuO 10~55%,ZnO20~55%,Al2O3 5~30%;所述催化剂的孔径为9~15nm。
一种权利要求1所述的铜锌铝催化剂的制备方法,所述方法步骤如下:
步骤一:沉淀剂溶解:将沉淀剂溶解于水中,得溶液I;
步骤二:加入有机溶剂:在所述溶液I中加入有机溶剂,得溶液II并将溶液II加热或冷却;
步骤三:铜锌盐溶液配制:将铜、锌可溶盐溶于水中,得溶液III;
步骤四:沉淀:在搅拌条件下将所述溶液III加到所述溶液II中沉淀,得到混合物;
步骤五:加入铝源:在所述步骤四的混合物中加入氢氧化铝或拟薄水铝石共沉淀,得到共沉淀混合物;
步骤六:过滤、洗涤、烘干、焙烧:将所述步骤五共沉淀混合物过滤、洗涤和烘干后焙烧,得到焙烧后产物;
步骤七:造粒、压片:将所述步骤六焙烧后产物经过造粒后,混合石墨进行压片,得成品催化剂。
进一步地,所述步骤一中沉淀剂为碳酸钠、碳酸氢钠、碳酸钾或碳酸氢铵、尿素、氨水中的一种或几种;所述沉淀剂浓度为0.2~2mol/L。
进一步地,所述步骤二中有机溶剂为甲醇、乙醇、乙二醇中的一种或多种;所述有机溶剂的量为溶液I体积的2~80%。
进一步地,所述步骤二中溶液II温度为0℃~85℃。
进一步地,所述步骤三中铜、锌可溶性盐为铜、锌硝酸盐或铜、锌乙酸盐。
进一步地,所述步骤三中溶液III的金属离子总浓度为0.01~0.5mol/L。
进一步地,所述步骤六中焙烧的温度为320~600℃,时间为1~10h。
进一步地,所述步骤七中石墨的含量为1~5%。
一种上述技术方案所述的铜锌铝催化剂或上述方案所述的方法制备的铜锌铝催化剂在CO低温变换制氢工艺中的应用。
与现有技术相比,本发明的具有的有益效果为:
1.本发明的铜锌铝催化剂孔径为9~15nm,远大于现有的铜锌铝催化剂7~8nm的孔径,根据大量实验证明,本发明更大孔径的铜锌铝催化剂用于CO低温变换反应时具有更高的反应活性和更好的耐热性。
2.本发明通过在溶解沉淀剂的溶液中加入有机溶剂,先沉淀铜锌沉淀物再沉淀铝沉淀物的特殊共沉淀法,制备的铜锌铝催化剂孔径为9~15nm,比传统共沉淀方法制备的催化剂孔径大,活性高,耐热性好。
具体实施方式
下面结合具体实施例对本发明做进一步详细地描述,但本发明的实施方式不限于此。
实施例1
取73.5g Na2CO3溶于800mL水中记为溶液I,向溶液I中加入甲醇200mL,得溶液II,将溶液II加热至55℃;称取72.9g Cu(NO3)2·3H2O,73.1gZn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III和加入溶液II中,边滴加边搅拌;沉淀完成后加入9.2gAl(OH)3,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合3%石墨,压片成型。成品中CuO含量46.6%,ZnO含量38.8%,Al2O3含量11.6%,平均孔径为12.7nm。
实施例2
取73.5g Na2CO3溶于650mL水中记为溶液I,向溶液I中加入甲醇350mL,得溶液II,将溶液II加热至55℃;称取72.9g Cu(NO3)2·3H2O,73.1gZn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III和加入溶液II中,边滴加边搅拌;沉淀完成后加入9.2gAl(OH)3,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合5%石墨,造粒、压片成型。成品中CuO含量45.6%,ZnO含量38.0%,Al2O3含量11.4%,平均孔径为11.5nm。
实施例3
取73.5g Na2CO3溶于500mL水中记为溶液I,向溶液I中加入甲醇500mL,记为溶液II,将溶液II加热至55℃;称取72.9g Cu(NO3)2·3H2O,73.1g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入9.2g Al(OH)3,过滤、洗涤、烘干后,320℃下焙烧10h,焙烧后产物经过造粒后,再混合1%石墨,造粒、压片成型。成品中CuO含量47.5%,ZnO含量39.6%,Al2O3含量11.9%,平均孔径为10.3nm。
实施例4
取95.6g K2CO3溶于800mL水中记为溶液I,向溶液I中加入甲醇200mL,记为溶液II,将溶液II冷却至10℃;称取66.8g Cu(NO3)2·3H2O,80.4g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入8.6g拟薄水铝石,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合3%石墨,造粒、压片成型。成品中CuO含量42.7%,ZnO含量42.7%,Al2O3含量11.6%,平均孔径为13.2nm。
实施例5
取110.0g NH4HCO3溶于2500mL水中记为溶液I,向溶液I中加入乙醇500mL,记为溶液II,将溶液II冷却至0℃;称取66.8g Cu(NO3)2·3H2O,80.4g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入8.6g拟薄水铝石,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合3%石墨,造粒、压片成型。成品中CuO含量42.7%,ZnO含量42.7%,Al2O3含量11.6%,平均孔径为14.1nm。
实施例6
取116.4g NaHCO3溶于800mL水中记为溶液I,向溶液I中加入乙二醇200mL,记为溶液II,将溶液II加热至70℃;称取66.8gCu(NO3)2·3H2O,80.4g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入8.6g拟薄水铝石,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合3%石墨,造粒、压片成型。成品中CuO含量42.7%,ZnO含量42.7%,Al2O3含量11.6%,平均孔径为12.5nm。
实施例7
取102.5g Na2CO3溶于800mL水中记为溶液I,向溶液I中加入乙二醇200mL,记为溶液II,将溶液II加热至85℃;称取16.1g Cu(NO3)2·3H2O,104.2g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入22.8g拟薄水铝石,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合5%石墨,造粒、压片成型。成品中CuO含量10.0%,ZnO含量55.0%,Al2O3含量30.0%,平均孔径为14.1nm。
实施例8
取102.5g Na2CO3溶于800mL水中记为溶液I,向溶液I中加入乙醇200mL,记为溶液II,将溶液II加热至85℃;称取86.1g Cu(NO3)2·3H2O,37.8g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入16.1g拟薄水铝石,过滤、洗涤、烘干后,350℃下焙烧5h,焙烧后产物经过造粒后,再混合3%石墨,造粒、压片成型。成品中CuO含量55.0%,ZnO含量20.0%,Al2O3含量21.9%,平均孔径为15.0nm。
实施例9
取83.1g尿素溶于980mL水中记为溶液I,向溶液I中加入乙醇20mL,记为溶液II,将溶液II加热至85℃;称取59.5g Cu(CH3COO)2·H2O,63.9g Zn(CH3COO)2·2H2O溶于500mL水中,记为溶液III;将溶液III加入溶液II中,边滴加边搅拌;沉淀完成后加入3.7g拟薄水铝石,过滤、洗涤、烘干后,600℃下焙烧1h,焙烧后产物经过造粒后,再混合3%石墨,造粒、压片成型。成品中CuO含量46.0%,ZnO含量46.0%,Al2O3含量5.0%,平均孔径为9.0nm。
对比例
取73.5g Na2CO3溶于1000mL水中记为溶液I,加热至55℃;称取72.9g Cu(NO3)2·3H2O,73.1g Zn(NO3)2·6H2O溶于500mL水中,记为溶液III;将溶液III和加入溶液I中,边滴加边搅拌;沉淀完成后加入9.2g Al(OH)3,过滤、洗涤、烘干后,350℃下焙烧5h,混合3%石墨,造粒、压片成型。成品中CuO含量46.6%,ZnO含量38.8%,Al2O3含量11.6%,平均孔径为7.9nm。
本发明9个实施例及对比例制备的铜锌铝催化剂的相关性能测试结果如表1所示。
表1铜锌铝催化剂性能测试结果
表中所述工业化样品为某公司铜锌铝变换催化剂,其标明含量为CuO38.9%,ZnO39.5%,Al2O3 10.1%,其余为水及石墨。
表1中铜锌铝催化剂活性检测条件为:催化剂破碎为粒度0.425mm~0.85mm,装填量3.00mL,固定床反应器、常压、原料气体组成为:CO 4~5%,CO2约2%,其余为H2和N2,空速为8000h-1,水碳比为6。催化剂使用前需进行还原,还原条件为原料气空速500h-1,20℃/min从室温升至200℃然后恒温2h。催化剂耐热条件为400℃耐热5h。
从表1中可以看出,本发明的大孔径铜锌铝样品的活性要明显高于工业化铜锌铝样品和对比例铜锌铝样品,某些铜锌铝样品如实施例1、2、4、8所制备的样品其400℃耐热5h后的活性甚至要高于工业化铜锌铝样品和对比例铜锌铝样品耐热前的活性。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明的保护范围。
Claims (10)
1.一种铜锌铝催化剂,其特征在于:包括如下重量百分比的组分:CuO 10~55%,ZnO20~55%,Al2O3 5~30%;所述催化剂的孔径为9~15nm。
2.一种权利要求1所述的铜锌铝催化剂的制备方法,其特征在于:所述方法步骤如下:
步骤一:沉淀剂溶解:将沉淀剂溶解于水中,得溶液I;
步骤二:加入有机溶剂:在所述溶液I中加入有机溶剂,得溶液II,并将溶液II加热或冷却至所需反应温度;
步骤三:铜锌盐溶液配制:将铜、锌可溶盐溶于水中,得溶液Ⅲ;
步骤四:沉淀:在搅拌条件下将所述溶液Ⅲ滴加到所述溶液II中沉淀,得到混合物;
步骤五:加入铝源:在所述步骤四的混合物中加入氢氧化铝或拟薄水铝石共沉淀,得到共沉淀混合物;
步骤六:过滤、洗涤、烘干、焙烧:将所述步骤五共沉淀混合物过滤、洗涤和烘干后焙烧,得到焙烧后产物;
步骤七:造粒、压片:将所述步骤六焙烧后产物经过造粒后,混合石墨进行压片,得成品催化剂。
3.根据权利要求2所述的制备方法,其特征在于:所述步骤一中沉淀剂为碳酸钠、碳酸氢钠、碳酸钾或碳酸氢铵、尿素、氨水中的一种或多种;所述沉淀剂浓度为0.2~2mol/L。
4.根据权利要求2所述的制备方法,其特征在于:所述步骤二中有机溶剂为甲醇、乙醇、乙二醇中的一种或多种;所述有机溶剂的量为溶液I体积的2~80%。
5.根据权利要求2所述的制备方法,其特征在于:所述步骤二中溶液II温度为0℃~85℃。
6.根据权利要求2所述的制备方法,其特征在于:所述步骤三中铜、锌可溶性盐为铜、锌硝酸盐或铜、锌乙酸盐。
7.根据权利要求2所述的制备方法,其特征在于:所述步骤三中溶液Ⅲ的金属离子总浓度为0.01~0.5mol/L。
8.根据权利要求2所述的制备方法,其特征在于:所述步骤六中焙烧的温度为320~600℃,时间为1~10h。
9.根据权利要求2所述的制备方法,其特征在于:所述步骤七中石墨的含量为1~5%。
10.一种权利要求1所述的铜锌铝催化剂或权利要求2~9任一项所述的方法制备的铜锌铝催化剂在CO低温变换制氢工艺中的应用。
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