CN117323993A - 一种用于催化臭氧氧化的催化剂及其制备方法和应用 - Google Patents
一种用于催化臭氧氧化的催化剂及其制备方法和应用 Download PDFInfo
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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Abstract
本申请公开了一种用于催化臭氧氧化的催化剂及其制备方法和应用,所述催化剂包括载体和负载于载体表面的活性组分;活性组分选自过渡金属元素单质或过渡金属元素氧化物;过渡金属元素的负载量为1~12wt%,过渡金属元素选自Ag、Fe、Mn或Pt中的至少一种;载体选自分子筛、拟薄水铝石或金属氧化物中的一种。包括以下步骤:a)将金属盐溶解于乙醇水溶液中,将载体逐渐加入过渡金属的乙醇盐溶液中,搅拌至干并研磨,获得前躯体;b)将获得的前躯体,经干燥,焙烧、还原,得到所述催化剂。制备的催化剂可对煤化工类含硅废水进行催化臭氧氧化处理,具有抗硅性能高、有机物去除效率高,臭氧利用率高,催化剂稳定性好,活性组分流失少等优点。
Description
技术领域
本申请涉及一种用于催化臭氧氧化的催化剂及其制备方法和应用,属于废水处理技术和环境功能材料领域。
背景技术
在煤气化生产过程中,对粗煤气冷却洗涤时将产生大量废水,该废水有机物浓度高、悬浮物含量高、色度深、可生化性差,属于难处的工业废水之一。污染物中的酚类物质被认为是煤化工废水中的主要污染物之一,传统的生物处理法不能有效地去除酚类。此外,生产过程产生的硅由煤炭燃烧后的炉渣降温接触水等带入水系统,导致废水含有微量总硅可达1000mg/L。通常的除硅方法有混凝、反渗透除硅、超滤除硅、电絮凝除硅、离子交换除硅等,但都无法有效降低胶体硅和可溶硅含量值(< 50mg/L),以至于影响后续水处理工序的正常运行。因此有效的抗硅除间甲酚的方法值得进一步研究。
这些年来,高级氧化法(AOPs)多被用于处理有机污染物,可以有效地提高了废水的可生化性能。其中,在多相催化臭氧氧化技术是在催化剂的作用下,臭氧分子转化生成活性氧(ROS),如羟基自由基(·OH)、超氧自由基(O2·-)和单线态氧(1O2),这些活性氧可以迅速、不加区别地矿化有机物为CO2和H2O,用于处理新兴污染物,如杀虫剂和除草剂,制药、邻苯二甲酸酯、染料、硝基苯、酚类,同时也用于煤气化废水的深度处理。然而,污染物长时间经过催化剂床层对催化剂的寿命也造成一定程度的影响。其中有研究表明,某煤气化废水中的残余硅长时间通过臭氧催化剂床层,使得在催化剂表面产生了硅酸盐沉淀,硅含量高达17wt.%,造成催化剂活性降低,逐渐失效。有研究表明硅是催化剂的常见催化毒物,当硅含量大于3wt.%时对催化剂影响是不可再生的。
综上,目前急需一种抗硅除有机物的催化剂用于臭氧氧化技术中处理煤化工含硅废水。
发明内容
本申请提供了一种催化剂,该催化剂具有抗硅性能高、有机物去除效率高,臭氧利用率高,催化剂稳定性好,活性组分流失少等优点。
根据本申请的一个方面,提供一种用于催化臭氧氧化的催化剂,所述催化剂包括载体和负载于载体表面的活性组分;
所述活性组分选自过渡金属元素单质或过渡金属元素氧化物;
所述催化剂中,所述过渡金属元素的负载量为1~12wt%,以所述过渡金属元素的质量计;
所述过渡金属元素选自Ag、Fe、Mn或Pt中的至少一种;
所述载体选自分子筛、拟薄水铝石或金属氧化物中的一种。
所述金属氧化物选自Al2O3、Co3O4、CeO2或TiO2中的至少一种。
根据本申请的另一个方面,提供一种上述的催化剂的制备方法,包括以下步骤:
将所述载体的表面与含有过渡金属盐的乙醇溶液等体积浸渍,搅拌、研磨、干燥、焙烧、造粒、还原,得到所述催化剂。
所述过渡金属盐选自所述过渡金属元素的硝酸盐和/或硫酸盐;
所述含有过渡金属盐的乙醇溶液中,所述过渡金属盐的含量为 0.5~20wt%,所述乙醇的含量为0.5~4%,其余为水;
所述干燥的温度为50~100℃;
所述干燥的时间为8~48h。
所述焙烧的温度为350~550℃;
可选地,所述焙烧的温度为400~500℃;
所述焙烧的时间为1~3h;
所述焙烧为马弗炉内空气焙烧。
所述还原的温度为300~700℃;
可选地,所述还原的温度为400~600℃;
所述还原的时间为0.5~2h;
所述还原的气氛为含氢气氛;所述含氢气氛中氢气的含量为 10~100wt%;
所述含氢气氛还包括非活性气体;
所述非活性气体选自氮气、氦气或氩气中的至少一种;
所述含氢气氛的气体流量为5~20mL/min;
可选地,所述含氢气氛的气体流量6~12mL/min。
所述搅拌和所述研磨为搅拌至干并研磨,用磁力搅拌搅拌至干,玛瑙研钵研磨至60~100目。
所述造粒,是将焙烧后得到的粉末经压实、敲碎、过筛。
其中,压实条件为3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品。
具体地,包括以下步骤:
a)将过渡金属盐溶解于乙醇水溶液中,将载体逐渐加入过渡金属乙醇盐溶液中,搅拌至干,研磨成粉状,获得前躯体;所述乙醇溶液中乙醇含量为0.5~4%。
b)将上述前躯体,经干燥,焙烧、造粒、还原,得到所述催化剂。
步骤a)中所述前躯体由过渡金属盐溶解在一定量乙醇水溶液中形成的盐溶液,将载体逐渐加入并搅拌至干并研磨得到;
其中,形成的过渡金属乙醇盐溶液加入水量为载体的饱和吸附量,且不低于乙醇盐溶液饱和溶解度的加水量。
根据本申请的另一个方面,提供一种上述催化剂在催化臭氧氧化中的应用。
根据本申请的另一个方面,提供一种催化臭氧氧化处理废水的方法,将含硅废水通入装有催化剂的反应器中,在含有臭氧的气氛中,反应;
所述催化剂选自上述的催化剂或根据上述的制备方法制备的催化剂。
所述含硅废水的COD为50~500mg/L;
所述含硅废水中的硅含量为50~100mg/L;
所述反应的温度为25~35℃;
所述反应的压力为0.1MPa~0.3MPa;
所述含硅废水的pH为5~10;
所述臭氧的用量与所述含硅废水中COD的比为O3(mg/L):COD(mg/L) =1.0~3.0;
所述含有臭氧的气氛中,臭氧的浓度为10~130mg/L;
所述含硅废水的体积空速为2~10h-1。
所述含硅废水来自煤化工工业。
本申请能产生的有益效果包括:
1、本申请所提供的催化剂,在催化臭氧氧化技术中具有较高的初活性,为工业应用提供新的可靠好用的催化剂。
2、本申请所提供的催化剂,在催化臭氧氧化技术中具有较高的抗硅性能,防止硅给催化剂带来的毒害作用,延长催化剂稳定性。
附图说明
图1从左到右依次为对比例3、对比例2、实施例5、实施例6、实施例2对TOC的去除率、间甲酚转化率以及抗硅性能对比图。
图2为实施例2和实施例8的XRD图。
具体实施方式
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料和催化剂均通过商业途径购买。
本申请的实施例中分析方法如下:
TOC(总有机碳)采用日本岛津公司生产的TOC-VCPH/CPN分析仪进行测定;pH采用雷磁PHS-3C精密pH计测定;间甲酚含量采用HPLC 高效液相色谱测定,色谱柱恒温25℃;使用固定床间歇反应评价装置评价所制备的催化剂在催化臭氧氧化技术中的应用。
采用硅钼蓝分光光度法来测定溶液中的硅含量,用硫酸钼酸铵做显色剂,草酸做掩蔽剂,硫酸亚铁铵做还原剂。测定条件在波长为815nm处, 5cm比色皿,检测范围在0~4ppm,根据测得的样品吸光度,通过标准曲线计算得到二氧化硅的含量。
实验采用的78ppm间甲酚废水水质:液相色谱峰面积1062, TOC:63.5mg/L;硅浓度G=87ppm,稀释20倍后吸光度=1.787;pH调至 4.6。间歇反应:常温常压,初始pH为4.6,O3(mg/L):COD(mg/L)=1.0~ 3.0,空速为2~10h-1,反应运行时间为5h。
实施例中,所有催化剂评价时研磨成粉末进行。
实施例1
1)将0.0321g AgNO3溶解于6mL2 wt%乙醇水溶液中,将2.0055g ZSM5(46)(SiO2/Al2O3摩尔比46)分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件500℃还原1h,得到1Ag/ZSM5(46)-H500,1Ag 代表Ag在载体ZSM5(46)上负载的质量分数为1%,H500代表H2条件下 500℃还原,以下实施例同理。
实施例2
1)将0.3154g AgNO3溶解于6mL 2wt%乙醇水溶液中,将2.0024gβ40 分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件400℃还原1h,得到10Ag/β40-H400。
图2为实施例2的XRD图,从图中可以看出Ag颗粒比较均匀的分散在载体表面。
实施例3
1)将0.0315g AgNO3溶解于6mL 2wt%乙醇水溶液中,将2.0072g β62.3(SiO2/Al2O3摩尔比62.3)载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件500℃还原1h,得到1Ag/β62.3-H500。
实施例4
1)将0.3182g AgNO3溶解于6mL 2wt%乙醇水溶液中,将ALOOH 载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件400℃还原1h,得到10Ag/ALOOH-H400。
实施例5
1)将0.3182g AgNO3溶解于6mL 2wt%乙醇水溶液中,将β40分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;得到10Ag/β40-未还原。
实施例6
1)将0.3130g AgNO3溶解于6mL 2wt%乙醇水溶液中,将β40分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后10%H2/Ar条件400℃还原1h,得到10Ag/β40-H400(10%H2)。
实施例7
1)将0.3820g AgNO3溶解于6mL 2wt%乙醇水溶液中,将β40分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后10%H2/Ar条件400℃还原1h,得到12Ag/β40-H400(10%H2)。
实施例8
1)将0.0315g AgNO3溶解于6mL 2wt%乙醇水溶液中,将2.0024gβ40 分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件400℃还原1h,得到1Ag/β40-H400。
图2为实施例8的XRD图,从图中可以看出活性组分以Ag单质的形式负载在载体表面。
实施例9
1)将0.0317g AgNO3溶解于6mL 2wt%乙醇水溶液中,将1.9992gβ40 分子筛载体逐渐加入AgNO3溶液中,磁力搅拌至干,研磨至60~100目;
2)置于干燥箱内80℃烘干12h;再于马弗炉内450℃空气焙烧2h;
3)将焙烧后得到的粉末3~4Mpa保持20~60秒,敲碎后20~40目过筛,保留20~40目样品;
4)最后纯氢气条件700℃还原1h,得到1Ag/β40-H700。
实施例1至9制备得到的催化剂进行催化臭氧氧化废水处理测试,测试条件和结果如表1所示,实验10~12分别为不加催化剂以及两种工业催化剂的对比实验结果。
表1催化臭氧氧化实验结果
由实验结果可知,负载银的MCM-41、Co3O4、CeO2、TiO2、Al2O3、 ALOOH对模型废水TOC的去除率在10%~20%,间甲酚去除率为 60%~97%,负载银的Co3O4、TiO2和Al2O3,对硅有一定的吸附性。
由第6、7组实验对比得出,12%Ag负载量比10%Ag负载量催化剂的抗硅性差,吸硅率达49.25%;
由第2、8、9组实验对比得出,β40分子筛负载Ag具有较好的活性及抗硅性,增加Ag负载量,TOC略有提高,还原温度升高,TOC略有提高,对间甲酚及硅的吸附没有太大的影响。
图1从左到右依次为对比例3、对比例2、实施例5、实施例6、实施例2对TOC的去除率、间甲酚转化率以及抗硅性能对比图。从图中可以看出,工业红色小球Fe/Al2O3、KD-607-2活性均没有10Ag/β40-未还原高, H2还原可提高10Ag/β40的抗硅性,还原H2的浓度可进一步提高TOC的去除率。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种用于催化臭氧氧化的催化剂,其特征在于,
所述催化剂包括载体和负载于载体表面的活性组分;
所述活性组分选自过渡金属元素单质或过渡金属元素氧化物;
所述催化剂中,所述过渡金属元素的负载量为1~12wt%,以所述过渡金属元素的质量计;
所述过渡金属元素选自Ag、Fe、Mn或Pt中的至少一种;
所述载体选自分子筛、拟薄水铝石或金属氧化物中的一种。
2.根据权利要求1所述的催化剂,其特征在于,
所述金属氧化物选自Al2O3、Co3O4、CeO2或TiO2中的至少一种。
3.一种权利要求1或2所述的催化剂的制备方法,其特征在于,
包括以下步骤:
将所述载体与含有过渡金属盐的乙醇溶液等体积浸渍,干燥、焙烧、还原,得到所述催化剂。
4.根据权利要求3所述的制备方法,其特征在于,
所述过渡金属盐选自所述过渡金属元素的硝酸盐和/或硫酸盐;
优选地,所述含有过渡金属盐的乙醇溶液中,所述过渡金属盐的含量为0.5~20wt%,所述乙醇的含量为0.5~4wt%,其余为水。
5.根据权利要求3所述的制备方法,其特征在于,
所述干燥的温度为50~100℃;
优选地,所述干燥的时间为8~48h。
6.根据权利要求3所述的制备方法,其特征在于,
所述焙烧的温度为350~550℃;
优选地,所述焙烧的温度为400~500℃;
优选地,所述焙烧的时间为1~3h。
7.根据权利要求3所述的制备方法,其特征在于,
所述还原的温度为300~700℃;
优选地,所述还原的温度为400~600℃;
优选地,所述还原的时间为0.5~2h;
优选地,所述还原的气氛为含氢气氛;
优选地,所述含氢气氛中氢气的含量为10~100wt%;
优选地,所述含氢气氛还包括非活性气体;
优选地,所述非活性气体选自氮气、氦气或氩气中的至少一种;
优选地,所述含氢气氛的气体流量为5~20mL/min;
优选地,所述含氢气氛的气体流量6~12mL/min。
8.一种催化臭氧氧化处理废水的方法,其特征在于,
将含硅废水通入装有催化剂的反应器中,在含有臭氧的气氛中,反应;
所述催化剂选自权利要求1或2所述的催化剂或根据权利要求3~7任一项所述的制备方法制备的催化剂。
9.根据权利要求8所述的方法,其特征在于,
所述含硅废水的COD为50~500mg/L;
优选地,所述含硅废水中的硅含量为50~100mg/L;
优选地,所述反应的温度为25~35℃;
优选地,所述反应的压力为0.1MPa~0.3MPa;
优选地,所述含硅废水的pH为5~10;
优选地,所述臭氧的用量与所述含硅废水中COD的比为O3(mg/L):COD(mg/L)=1.0~3.0;
优选地,所述含有臭氧的气氛中,臭氧的浓度为10~130mg/L;
优选地,所述含硅废水的体积空速为2~10h-1。
10.根据权利要求8所述的方法,其特征在于,
所述含硅废水来自煤化工工业。
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