CN112588295B - 用于有机废水处理的催化剂及其制备方法 - Google Patents
用于有机废水处理的催化剂及其制备方法 Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J37/088—Decomposition of a metal salt
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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Abstract
本发明属于催化剂制备技术领域,具体涉及一种用于有机废水处理的催化剂及其制备方法。用于有机废水处理的催化剂结构式如下:MnxFeyMzOi,其中,M为钴、镍、铜、钒、钛、锌、铈、镧或锆中的一种或几种,x为0.2‑0.8,y为0.05‑0.6,z为0.01‑0.25,i为1‑2;催化剂的粒径为5‑100nm。本发明具有步骤简单,所制备的催化剂元素构成均一、性能高、容易放大的优点。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种用于有机废水处理的催化剂及其制备方法。
背景技术
有机废水是化工、制药、炼焦等行业排放的主要水体污染物,具有成分复杂、难降解、毒性强、对人体健康和生态环境危害大的特点。因此对生产过程中产生的有机废水进行彻底净化是相关行业保持可持续发展的重要保证。目前处理有机废水的主要方法有生物法、物理法和化学法,但生物法很难将有机废水的COD降到200ppm以下,且会产生污泥等固体废弃物;物理法虽效率较高,但所用吸附剂需要再生,效率较低,也会产生有毒的固体废弃物。针对以上缺点,化学法具有高效、净化彻底的优点。其中,固体催化臭氧氧化法是一种环保、高效的有机废水净化方法,提高该法效率的关键在于开发出高效的固体催化剂。
目前,制备该催化剂的方法主要有溶胶凝胶法、沉淀法、水热法、浸渍法等,所制备的催化剂主要包含锰、铁、钴、铈等元素。其制备过程通常包括反应、过滤、洗涤、干燥、焙烧、活化等几个步骤。同济大学的马鲁明等利用沉淀法制备了氧化铁催化剂用于催化臭氧氧化处理工业有机废水,TOC去除率达78.7%(Chemosphere 195(2018)336-343)。S.Contreras等利用共沉淀法制备了铜-铝复合氧化物用于催化臭氧氧化降解固醇酸废水,TOC去除率可达81.7%(Applied Catalysis B:Environmental 209(2017)523–529)。刘正乾等通过浸渍法制备了氧化锌/石墨催化剂用于催化臭氧氧化处理酞酸二乙酯废水,可使臭氧的利用率达到72.1%(Separation and Purification Technology 200(2018)51–58)。以上研究表明,现有的方法可制备出高效臭氧氧化催化剂。但这些方法也存在显著不足,如制备步骤繁琐,难以进行稳定的质量控制;在水溶液中进行沉淀、结晶,难以将掺杂元素均匀地分散到主催化剂的晶体中。因此这些方法进行工业放大时,往往很难使催化剂的性能达到实验室水平。
发明内容
本发明的目的是提供一种用于有机废水处理的催化剂,性能高、质地均匀、容易放大;本发明同时提供了用于有机废水处理的催化剂的制备方法,通过火焰喷射分解快速将催化剂前驱体制备成活性催化剂,步骤简单。
本发明所述的用于有机废水处理的催化剂,结构式如下:
MnxFeyMzOi
其中,M为钴、镍、铜、钒、钛、锌、铈、镧或锆中的一种或几种,x为0.2-0.8,y为0.05-0.6,z为0.01-0.25,i为1-2;催化剂的粒径为5-100nm。
本发明所述的用于有机废水处理的催化剂的制备方法,包括如下步骤:
(1)将锰的前驱体和铁的前驱体溶于溶剂中得到主催化剂前驱体溶液,然后将主催化剂前驱体溶液通过高压气体分散到甲烷-氧气火焰中燃烧、反应,经冷凝后,得到主催化剂纳米颗粒;
(2)将主催化剂纳米颗粒溶于溶剂中得到主催化剂溶液,然后将M的前驱体溶于主催化剂溶液中得到催化剂溶液,催化剂溶液通过高压气体分散到甲烷-氧气火焰中燃烧、反应,得到用于有机废水处理的催化剂。
步骤(1)中所述的锰的前驱体为锰酸盐、高锰酸盐、锰的硝酸盐、锰的碳酸盐、锰的乙酸盐、锰的柠檬酸盐、锰的草酸盐或锰的2-乙基己酸盐中的一种。
步骤(1)中所述的铁的前驱体为铁的锰酸盐、高锰酸盐、硝酸盐、碳酸盐、乙酸盐、柠檬酸盐、草酸盐或2-乙基己酸盐中的一种。
步骤(1)中所述的溶剂为水、乙醇、乙酸乙酯、苯、甲苯或二甲苯中的一种。
步骤(1)中所述的主催化剂前驱体溶液的浓度为0.05-2.5mol/L。
步骤(1)中所述的高压气体为氧气,高压气体的压强为0.1-1MPa。
步骤(1)中所述的主催化剂前驱体溶液通过高压气体分散到甲烷-氧气火焰中的流速为2-30mL/min。
步骤(1)中所述的甲烷的流量为0.5-3.5L/min,高压气体的流量为1-3L/min,甲烷和高压气体的流量比为1:2-5。
步骤(1)中将主催化剂前驱体溶液通过高压气体(即分散氧气)分散到甲烷-氧气火焰中燃烧、反应,在喷头周围保护氧气形成的气墙保护下,经冷凝后,得到主催化剂纳米颗粒;其中,保护氧气的流量为2-6L/min。
步骤(2)中所述的溶剂为水、乙醇、乙酸乙酯、苯、甲苯或二甲苯中的一种。
步骤(2)中所述的主催化剂溶液中主催化剂纳米颗粒的含量为1-20wt.%。
步骤(2)中所述的M的前驱体为M的硝酸盐、碳酸盐、乙酸盐、柠檬酸盐、草酸盐或2-乙基己酸盐中的一种。
步骤(2)中所述的高压气体为氧气,高压气体的压强为0.1-1MPa。
步骤(2)中所述的催化剂溶液通过高压气体分散到甲烷-氧气火焰中的流速为2-30mL/min。
步骤(2)中所述的甲烷的流量为0.5-3.5L/min,高压气体的流量为1-3L/min,甲烷和高压气体的流量比为1:2-5。
步骤(2)中所述的用于有机废水处理的催化剂通过收集器收集。
步骤(2)中催化剂溶液通过高压气体(即分散氧气)分散到甲烷-氧气火焰中燃烧、反应,在喷头周围保护氧气形成的气墙保护下,经冷凝后,得到用于有机废水处理的催化剂;其中,保护氧气的流量为2-6L/min。
本发明制得的催化剂可用于臭氧氧化处理有机废水。
本发明催化剂的催化机理如下:
水中溶解的臭氧被吸附到催化剂表面,臭氧和催化剂表面的羟基或氢氧根离子反应,产生羟基自由基,羟基自由基与水中的有机物或吸附在催化剂表面的有机物反应,将其彻底氧化降解为CO2和H2O。
本发明的有益效果如下:
本发明针对制备固体催化剂的传统湿化学法存在步骤繁琐、催化剂质量难以稳定控制、工业放大过程困难的问题,提供了一种利用火焰喷射分解法快速制备用于臭氧氧化处理有机废水催化剂的方法。本发明可将溶有催化剂前驱体的溶液通过高压气体分散到火焰中,直接反应获得主催化剂纳米颗粒,然后将其直接用溶剂收集,由于纳米颗粒尺寸小于100nm,可在溶剂中形成凝胶,再加入掺杂金属的前驱体,再次经过火焰喷射分解反应,从而使掺杂金属在主催化剂表面形成活性位点,使其催化活性高,该法具有步骤简单,所制备的催化剂元素具有构成均一、性能高、容易放大的优点。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)将5g高锰酸钾和3g硝酸亚铁溶于50mL去离子水中,然后用微量注射泵以5mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.9L/min,保护氧气的流量为4.2L/min,分散氧气的流量为2.2L/min,分散氧气的压强为0.15MPa。火焰中生成的主催化剂纳米颗粒由带有玻璃滤网的收集器收集。
(2)主催化剂纳米颗粒经水冷管冷却后由100mL水收集,得到水悬浮液。将0.5g硝酸铈、0.3g硝酸镍和0.2g硝酸钴溶于上述水悬浮液中,然后用微量注射泵以10mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.8L/min,分散氧气的流量为1.8L/min,氧气的压强为0.17MPa,通过收集器收集,得到催化剂Mn0.6Fe0.32Ce0.03Ni0.03Co0.02O1.62,经XRD测试,利用谢乐公式计算,获得其晶粒直径为26.3nm。
催化剂性能的评价通过以下方法进行:称取催化剂0.5g,投放到500mLCOD为550ppm的制药废水中,在搅拌的情况下通入臭氧,臭氧的流量为10g/h,每隔10min取一次水样,离心将催化剂分离后,按照国标GB119189测量其COD。结果表明反应0.5小时,COD的去除率在78%,反应1小时,COD的去除率为89.5%。
COD的去除率计算方法:
实施例2
(1)将10g2-乙基己酸锰和4g乙酸铁溶于50mL二甲苯中,然后用微量注射泵以5mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.5L/min,保护氧气的流量为4.2L/min,分散氧气的流量为1.8L/min,分散氧气的压强为0.16MPa。火焰中生成的主催化剂纳米颗粒由带有玻璃滤网的收集器收集。
(2)主催化剂纳米颗粒经水冷管冷却后由100mL甲苯收集,得到甲苯悬浮液。将0.5g1-草酸铈、0.3g2-乙基己酸锆和0.2g乙酸氧钒溶于上述甲苯悬浮液中,然后用微量注射泵以10mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.8L/min,分散氧气的流量为1.8L/min,分散氧气的压强为0.17MPa,通过收集器收集,得到催化剂Mn0.72Fe0.25Ce0.01Zr0.005V0.02O1.76,经XRD测试,利用谢乐公式计算,获得其晶粒直径为31.6nm。
催化剂的评价方法如实施例1,反应0.5小时,COD的去除率为76%,反应1小时,COD的去除率为84%。
实施例3
(1)将7g柠檬酸锰和3g乙酸铁溶于50mL甲苯中,然后用微量注射泵以5mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.2L/min,分散氧气的流量为2.2L/min,分散氧气的压强为0.16MPa。火焰中生成的主催化剂纳米颗粒由带有玻璃滤网的收集器收集。
(2)主催化剂纳米颗粒经水冷管冷却后由100mL乙醇收集,得到乙醇悬浮液。将0.5g1-草酸铈、0.3g2-硝酸锆和0.2g2-草酸氧钒溶于上述乙醇悬浮液中,然后用微量注射泵以10mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.8L/min,分散氧气的流量为1.8L/min,分散氧气的压强为0.17MPa,通过收集器收集,得到催化剂Mn0.46Fe0.46Ce0.03Zr0.02V0.03O1.56,经XRD测试,利用谢乐公式计算,获得其晶粒直径为47.2nm。
催化剂的评价方法如实施例1,反应0.5小时,COD的去除率为78%,反应1小时,COD的去除率为85%。
实施例4
(1)将6.5g2-乙基己酸锰和2.5g2-乙基己酸铁溶于50mL甲苯中,然后用微量注射泵以10mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.2L/min,分散氧气的流量为2.4L/min,分散氧气的压强为0.18MPa。火焰中生成的主催化剂纳米颗粒由带有玻璃滤网的收集器收集。
(2)主催化剂纳米颗粒经水冷管冷却后由100mL乙酸乙酯收集,得到乙酸乙酯悬浮液。将0.5g1-柠檬酸钛、0.3g1-乙酸钴和0.2g2-乙基己酸氧钒溶于上述乙酸乙酯悬浮液中,然后用微量注射泵以10mL/min的流速注射到分散氧气中,然后在喷头周围保护氧气形成的气墙保护下将其分散到甲烷-氧气火焰中燃烧、反应,甲烷的流量为1.8L/min,保护氧气的流量为4.8L/min,分散氧气的流量为1.8L/min,分散氧气的压强为0.17MPa,通过收集器收集,得到催化剂Mn0.76Fe0.12Ti0.07Co0.04V0.01O1.87,经XRD测试,利用谢乐公式计算,获得其晶粒直径为38.2nm。
催化剂的评价方法如实施例1,反应0.5小时,COD的去除率为73%,反应1小时,COD的去除率为83%。
对比例1
将5g高锰酸钾、3g硝酸亚铁、0.5g硝酸铈、0.3g硝酸镍和0.2g硝酸钴溶于30mL去离子水中,在搅拌的情况下滴入20mL含2g葡萄糖的水溶液,用NaOH水溶液将pH调为10。滴加完毕后,在搅拌的情况下,陈化12h,然后将沉淀过滤出,在100℃下干燥12h,然后在550℃下,空气气氛中焙烧5h,获得具有活性的催化剂Mn0.6Fe0.32Ce0.03Ni0.03Co0.02O1.62,经XRD测试,利用谢乐公式计算,获得其晶粒直径为284.5nm。
催化剂的评价方法如实施例1,反应0.5小时,COD的去除率为43%,反应1小时,COD的去除率为51%。
Claims (7)
1.一种用于有机废水处理的催化剂的制备方法,其特征在于所述催化剂结构式如下:
MnxFeyMzOi
其中,M为钴、镍、铜、钒、钛、锌、铈、镧或锆中的一种或几种,x为0.2-0.8,y为0.05-0.6,z为0.01-0.25,i为1-2;催化剂的粒径为5-100nm;
所述用于有机废水处理的催化剂的制备方法,包括如下步骤:
(1)将锰的前驱体和铁的前驱体溶于溶剂中得到主催化剂前驱体溶液,然后将主催化剂前驱体溶液通过高压气体分散到甲烷-氧气火焰中燃烧、反应,经冷凝后,得到主催化剂纳米颗粒;
(2)将主催化剂纳米颗粒溶于溶剂中得到主催化剂溶液,然后将M的前驱体溶于主催化剂溶液中得到催化剂溶液,催化剂溶液通过高压气体分散到甲烷-氧气火焰中燃烧、反应,得到用于有机废水处理的催化剂;
步骤(1)中所述的甲烷的流量为0.5-3.5L/min,高压气体的流量为1-3L/min,甲烷和高压气体的流量比为1:2-5;
步骤(2)中所述的甲烷的流量为0.5-3.5L/min,高压气体的流量为1-3L/min,甲烷和高压气体的流量比为1:2-5。
2.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(1)中所述的锰的前驱体为锰酸盐、高锰酸盐、锰的硝酸盐、锰的碳酸盐、锰的乙酸盐、锰的柠檬酸盐、锰的草酸盐或锰的2-乙基己酸盐中的一种,铁的前驱体为铁的锰酸盐、高锰酸盐、硝酸盐、碳酸盐、乙酸盐、柠檬酸盐、草酸盐或2-乙基己酸盐中的一种。
3.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(1)中所述的溶剂为水、乙醇、乙酸乙酯、苯、甲苯或二甲苯中的一种。
4.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(1)中所述的主催化剂前驱体溶液的浓度为0.05-2.5mol/L,高压气体为氧气,高压气体的压强为0.1-1MPa,主催化剂前驱体溶液通过高压气体分散到甲烷-氧气火焰中的流速为2-30mL/min。
5.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(2)中所述的溶剂为水、乙醇、乙酸乙酯、苯、甲苯或二甲苯中的一种。
6.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(2)中所述的主催化剂溶液中主催化剂纳米颗粒的含量为1-20wt.%,高压气体为氧气,高压气体的压强为0.1-1MPa,催化剂溶液通过高压气体分散到甲烷-氧气火焰中的流速为2-30mL/min。
7.根据权利要求1所述的用于有机废水处理的催化剂的制备方法,其特征在于步骤(2)中所述的M的前驱体为M的硝酸盐、碳酸盐、乙酸盐、柠檬酸盐、草酸盐或2-乙基己酸盐中的一种。
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CN107051468B (zh) * | 2017-02-24 | 2019-08-23 | 河北科技大学 | 负载多金属氧化物臭氧催化氧化催化剂的制备方法及应用 |
CN112547087A (zh) * | 2020-12-16 | 2021-03-26 | 北京北方节能环保有限公司 | 一种铁/猛酸镧催化剂的制备方法及应用 |
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