CN112569941B - 高分散钴基氨氮净化臭氧催化剂的制备方法及其产品和应用 - Google Patents
高分散钴基氨氮净化臭氧催化剂的制备方法及其产品和应用 Download PDFInfo
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 51
- 239000010941 cobalt Substances 0.000 title claims abstract description 51
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 51
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000006185 dispersion Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 238000000034 method Methods 0.000 claims abstract description 30
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- 230000000536 complexating effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012018 catalyst precursor Substances 0.000 claims description 25
- 239000008188 pellet Substances 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
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- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000000149 chemical water pollutant Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 238000010170 biological method Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公布了一种高分散钴基氨氮净化臭氧催化剂的制备方法及其产品和应用,活性氧化铝小球为整体式载体,以钴作为活性组分。利用超声浸渍法和钴与氨氮络合原理,在制备过程中有效去除与载体相互作用弱的钴,实现了钴基整体式催化剂的高分散。本专利所得催化剂活性高,大大降低了整体式催化剂用量,并实现在低浓度臭氧条件下,室温选择性催化氧化氨氮生成氮气。本专利制备方法简单,易于规模化生产,具有很好的应用前景。
Description
技术领域
本发明涉及一种氨氮催化净化方法,具体涉及一种高分散钴基氨氮净化臭氧催化剂的制备方法及其产品和应用。
背景技术
氨氮是厨房垃圾异味来源之一。蛋白质经过微生物的作用,分解成肽和氨基酸,进一步分解成的低级氨和氨气。氨氮是饮用水的主要污染物之一。氨氮在水体中硝化产生硝酸盐和亚硝酸盐,长期饮用可诱发高铁血红蛋白症和产生致癌的亚硝胺。氨氮亦广泛存在于生活污水和工业污水中,排入河流中会危害水生生物,造成水体富营养化和黑臭水。因此,氨氮净化技术意义重大。
目前的氨氮净化技术有吹脱法、吸附法、生物法、折点加氯法、湿式氧化法、及高级氧化法。吹脱法使用范围窄,只适用于氨氮浓度高于100mg/L的废水。吸附法易达到饱和,需重复再生。生物法受水的温度、水质因素影响很大,净化效果不稳定。折点加氯法易产生有毒害作用的副产物。湿式氧化法需要高温高压条件,不易操作、治理费用较高。高级氧化法可在室温、常压条件下将氨氮选择性氧化为氮气。尤其是臭氧催化法,引入的臭氧很容易分解为氧气,大大降低或避免了二次污染,具有很大的应用前景。
当前研究表明,尽管很多过渡金属氧化物或稀土氧化物均具有臭氧催化氧化活性。但依然存在制备为整体式催化剂后,催化效率较低,直接导致催化剂用量较大,增加了臭氧催化氧化处理成本。其次,当前催化剂臭氧利用率较低,需要引入大量臭氧,大大增加了运行成本。
发明内容
本发明目的在于提供一种高分散钴基氨氮净化臭氧催化剂的制备方法。
本发明的再一目的在于:提供一种上述方法制备的高分散钴基氨氮净化臭氧催化剂产品。
本发明的又一目的在于:提供一种上述产品的应用。
本发明目的通过下述方案实现:一种高分散钴基氨氮净化臭氧催化剂的制备方法,该催化剂以活性氧化铝小球为整体式载体,以钴作为活性组分,其特征在于利用超声浸渍法和钴与氨氮络合原理,在制备过程中有效去除与载体相互作用弱的钴,实现了钴基整体式催化剂的高分散,包括以下步骤:
(1)载体活化,将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
(2)活性组分负载,采用活化后的活性氧化铝小球作为整体式载体,硝酸钴溶液为钴源。利用等体积超声浸渍法进行活性组分钴的负载,并利用高浓度氨氮废水进行表面处理;去离子水洗涤干燥后,得催化剂前驱体;
(3)活性组分再分散与晶化,将上述催化剂前驱体焙烧处理进行活性组分再分散与晶化,得氨氮净化臭氧催化剂。
钴的理论担载量,以四氧化三钴计,为7%-12%;所述等体积超声浸渍法具体为,等体积浸渍后,超声处理30-60min,开放条件下40℃反应24h,70-110℃干燥;所述高浓度氨氮废水进行表面处理具体为,采用3倍体积、氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;所述催化剂前驱体焙烧处理具体为,将上述催化剂前驱体利用空气气氛,在400-600℃处理3-5h,升温速率2℃/min。
本发明提供一种高分散钴基氨氮净化臭氧催化剂,根据上述任一所述方法制备得到。
本发明提供一种臭氧催化剂用于氨氮催化净化的应用。
在工业废水、垃圾渗滤液以及由氨气引起的异味处理等氨氮净化中的应用。
分别采用实施例中的氨氮净化臭氧催化剂,进行氨氮选择性氧化能力测试。测试条件如下:氯化铵为氮源配制100mg/L模拟氨氮废水,催化剂投加量为25g/L,臭氧浓度为80ppm,O3/O2流量为240mL/min,反应时间5h。
本发明制备了一种高分散钴基氨氮净化臭氧催化剂,所得催化剂具有很高的活性,大大降低了整体式催化剂用量,并实现在低浓度臭氧条件下,室温选择性催化氧化氨氮生成氮气。活性氧化铝小球作为整体式载体,通过超声浸渍法实现钴在载体缺陷位的高度分散;高浓度氨氮废水进行表面处理,利用钴与氨氮络合原理去除与载体相互作用弱的钴。二者相互协同实现高分散钴基氨氮净化臭氧催化剂选择性氧化氨氮性能的显著提高。本专利制备方法简单,易于规模化生产,具有很好的应用前景。
本发明具有以下优点:
本发明催化剂具有很高的活性,大大降低了整体式催化剂用量,并实现在低浓度臭氧条件下,室温选择性催化氧化氨氮生成氮气;本发明利用超声浸渍法和钴与氨氮络合原理,在制备过程中可效去除与载体相互作用弱的钴,实现了钴基整体式催化剂的高分散;本发明采用等体积超声浸渍和氨氮废水进行表面处理,制备过程不产生废液,工艺简单环保,易于规模化生产,具有很好的应用前景。
具体实施方式
下面对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1:
一种高分散钴基氨氮净化臭氧催化剂,以活性氧化铝小球为整体式载体,以钴作为活性组分,其特征在于,利用超声浸渍法和钴与氨氮络合原理,在制备过程中有效去除与载体相互作用弱的钴,以实现钴基整体式催化剂的高分散,按以下步骤制备:
第一步,载体活化,将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
第二步,活性组分负载,采用活化后的活性氧化铝小球作为整体式载体,硝酸钴溶液为钴源,将6.34g六水硝酸钴溶于10g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍30min,开放条件下40℃反应24h,110℃干燥,得催化剂前驱体;
第三步,活性组分再分散与晶化,将上述催化剂前驱体以2℃/min的升温速率升温至600℃焙烧处理3h,得氨氮净化臭氧催化剂,记作7CoAl6C。
实施例2:
一种高分散钴基氨氮净化臭氧催化剂,与实施例1步骤近似,按以下步骤制备:
第一步,载体活化,将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
第二步,活性组分负载,将6.34g六水硝酸钴溶于10g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍30min,开放条件下40℃反应24h,70℃干燥;采用100mL氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;
第三步,活性组分再分散与晶化,将上述催化剂前驱体以2℃/min的升温速率升温至400℃焙烧处理3h,进行活性组分再分散与晶化,得氨氮净化臭氧催化剂,记作7CoAl4C。
实施例3:
一种高分散钴基氨氮净化臭氧催化剂,与实施例1步骤近似,按以下步骤制备:
第一步,载体活化:将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用。
第二步,进行活性组分负载:将9.05g六水硝酸钴溶于9g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍60min,开放条件下40℃反应24h,70℃干燥,得催化剂前驱体;采用100mL氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;
第三步,将上述催化剂前驱体以2℃/min的升温速率升温至400℃焙烧处理3h,进行活性组分再分散与晶化,得氨氮净化臭氧催化剂,记作10CoAl4C。
实施例4:
一种高分散钴基氨氮净化臭氧催化剂,与实施例1步骤近似,按以下步骤制备:
第一步,将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
第二步,将10.86g六水硝酸钴溶于8g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍60min,开放条件下40℃反应24h,70℃干燥;采用100mL氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;
第三步,将上述催化剂前驱体以2℃/min的升温速率升温至400℃焙烧处理3h,进行活性组分再分散与晶化,得氨氮净化臭氧催化剂,记作12CoAl4C。
应用例:
分别采用实施例1-4中的氨氮净化臭氧催化剂,进行氨氮选择性氧化能力测试。测试条件如下:氯化铵为氮源配制100mg/L模拟氨氮废水,催化剂投加量为25g/L,臭氧浓度为10mg/L,O3/O2流量为240mL/min,反应时间5h。为了进行对比,单独臭氧氧化活性也进行了测试。测试结果如下表所示:
Claims (6)
1.一种高分散钴基氨氮净化臭氧催化剂的制备方法,以活性氧化铝小球为整体式载体,以钴作为活性组分,其特征在于,利用超声浸渍法和钴与氨氮络合原理,在制备过程中有效去除与载体相互作用弱的钴,以实现钴基整体式催化剂的高分散,按以下步骤制备:
第一步,载体活化,将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
第二步,活性组分负载,将6.34g六水硝酸钴溶于10g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍30min,开放条件下40℃反应24h,70℃干燥;采用100mL氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;
第三步,活性组分再分散与晶化,在空气气氛中,将上述催化剂前驱体以2℃/min的升温速率升温至400℃焙烧处理3h,进行活性组分再分散与晶化,得氨氮净化臭氧催化剂,记作7CoAl4C。
2.一种高分散钴基氨氮净化臭氧催化剂的制备方法,以活性氧化铝小球为整体式载体,以钴作为活性组分,其特征在于,利用超声浸渍法和钴与氨氮络合原理,在制备过程中有效去除与载体相互作用弱的钴,以实现钴基整体式催化剂的高分散,按以下步骤制备:
第一步,载体活化:将活性氧化铝小球利用0.1mol/L的盐酸溶液等体积浸渍24h,去离子水洗涤至中性,110℃烘干,备用;
第二步,进行活性组分负载:将9.05g六水硝酸钴溶于9g去离子水中,充分混合得硝酸钴溶液;将25g处理后的活性氧化铝小球与硝酸钴溶液混合,超声浸渍60min,开放条件下40℃反应24h,70℃干燥,得催化剂前驱体;采用100mL氨氮浓度为2000-4000mg/L的高浓度氨氮废水进行催化剂前驱体表面处理,并在密封条件下40℃反应24h,去离子水洗涤3次,70℃干燥,得催化剂前驱体;
第三步,在空气气氛中,将上述催化剂前驱体以2℃/min的升温速率升温至400℃焙烧处理3h,进行活性组分再分散与晶化,得氨氮净化臭氧催化剂,记作10CoAl4C。
3.一种高分散钴基氨氮净化臭氧催化剂,其特征在于根据权利要求1或2所述方法制备得到。
4.一种根据权利要求3所述高分散钴基氨氮净化臭氧催化剂用于氨氮催化净化的应用。
5.一种根据权利要求4所述的高分散钴基氨氮净化臭氧催化剂的应用,其特征在于:用于工业废水、垃圾渗滤液的氨氮净化。
6.一种根据权利要求4所述的高分散钴基氨氮净化臭氧催化剂的应用,其特征在于:用于由氨气引起的异味处理的氨氮净化。
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