CN113198475B - 一种铁合金催化剂的制备方法及其应用 - Google Patents
一种铁合金催化剂的制备方法及其应用 Download PDFInfo
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 19
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Abstract
本发明提供了一种铁合金催化剂的制备方法及其应用。所述铁合金催化剂是以多孔性载体为基体负载活性组分通过浸渍‑高温煅烧两步法制得。本发明结合浸渍法与高温煅烧两步制备出了铁合金催化剂,提高了过硫酸盐活化效率,提高了有机物降解效率;并通过该催化剂活化过硫酸盐氧化降解有机废水,该反应过程操作工艺简单、对废水pH适用范围宽泛、在常温常压下即可进行,无二次污染,可适用于各种有机废水的处理。
Description
技术领域
本发明属于水污染处理技术领域,特别涉及一种铁合金催化剂的制备方法及其应用。
背景技术
随着化学工业的迅速崛起,工业废水的排放量逐年增加,对水资源污染如酚类、多环芳烃及杂环类化合物等有机污染物的排放量始终居于前列。工业废水尤其是焦化行业废水有着高浓度且结构稳定的特点,这对我国宝贵的水资源造成了严重威胁,因此,如何有效地去除这些高浓度难降解有机废水已经成为水处理的热点问题。
非均相催化过硫酸盐技术是通过固体材料催化剂活化过硫酸盐得到硫酸根自由基矿化废水中的有机物。当前,过硫酸盐活化的方法大体包括热活化、碱活化、紫外光活化、过渡金属活化、电活化等。其中,碱活化过程对设备容易腐蚀;紫外光活化能耗大且难以处理较高色度的煤化工废水;而电活化处理过程中产生二次污染,在处理高盐废水中的有机物效率低且使用过程中受高盐环境中大量无机离子的影响。
发明内容
本发明的目的旨在基于现有技术中存在的不足,提供一种铁合金催化剂的制备方法及其应用。
为实现上述目的,本发明是通过以下技术方案来实现:
一种铁合金催化剂,其以多孔性载体为基体,负载铁合金纳米球,通过浸渍-高温煅烧两步法制备而成。
本发明提供了上述铁合金催化剂的制备方法,包括以下步骤:
步骤1,浸渍:将多孔性载体浸入浸渍液中,在25℃~80℃条件下浸渍0.5~24h后将载体捞出,置于40~90℃条件下干燥0.5~12h,得浸渍后的催化剂;
步骤2,高温煅烧:将浸渍后的催化剂置于管式炉中,在还原气氛中,于250℃~850℃下煅烧1h~9h,即得铁合金催化剂。
进一步,多孔性载体包括陶瓷材料、碳基载体、沸石、堇青石、Al2O3、多孔分子筛或者泡沫金属材料;所述碳基载体包括煤质活性炭、椰壳活性炭、合成材料活性炭、碳毡、碳纸、碳纤维、碳棒、碳纳米管或者碳布。
进一步,浸渍液中以Fe元素为主,含有Ni、Co、Cu、Ti、Ru、Mn及Sn中的二种及以上,Fe与其他金属元素的摩尔比为1:0.01~10。
进一步,所述金属盐为氯化盐、硫酸盐或硝酸盐。
进一步,所述多孔载体与浸渍溶液的质量比为1:0.1~100。
进一步,所述还原气氛为一种还原气体,或者还原气体与惰性气体的任意组合;所述还原气氛为一种还原气体,或者还原气体与惰性气体的任意组合;所述还原气体为H2,惰性气体为N2或Ar。如H2、H2/Ar=1:0.01~24、H2/N2=1:0.01~24或者H2/N2/Ar=1:1:0.01~24。
本发明还提供了上述铁合金催化剂用于活化过硫酸盐以降解有机污染物。
进一步,所述过硫酸盐为过硫酸钠、过硫酸钾或过硫酸铵;所述过硫酸盐与有机污染物的质量浓度比为20~200:1。
进一步,所述有机污染物来源于工业煤焦化废水、化工污水、药厂废水或生活污水;所述铁合金催化剂与有机污染物的质量浓度比为10~100:1,所述有机污染物的降解时间为30~180min。
与现有技术相比,本发明的有益效果如下:
(1)本发明不需要额外操作消耗能量,比如超声、紫外光照、加热等操作,在常温常压下反应即可降解,降低成本且操作简单,适用性强,具有更广阔的应用前景;
(2)本发明中所制备的催化剂结构稳定,不易被超硫酸根氧化分解,催化过程中,含重金属的活性组分溶出率低,有效解决目前该类催化剂催化过程带来重金属二次污染的问题;
(3)本发明提供的纳米金属球具有高比表面积,能与过硫酸盐充分接触反应,生成较多的硫酸根自由基提高催化反应效率。
附图说明
图1为实施例1过硫酸根分解速率曲线图;
图2为实施例1中水样COD降解速率曲线图;
图3为实施例1中煤质活性炭负载Fe-Ni-Cu/C金属催化剂未处理水样前的扫描电镜图;
图4为实施例1中煤质活性炭负载Fe-Ni-Cu/C金属催化剂对水样处理后的扫描电镜图;
图5为实施例4中椰壳活性炭负载Fe-Cu-Co/C金属催化剂反应前后的X射线衍射图。
具体实施方式
以下所述实例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但并不限制本发明专利的保护范围,凡采用等同替换或等效变换的形式所获得的技术方案,均应落在本发明的保护范围之内。
实施例1
本实施例提供一种Fe-Ni-Cu/C金属催化剂的制备方法,包括以下步骤;
步骤1:将Fe(NO3)3·9H2O、Ni(NO3)3·6H2O、Cu(NO3)3·6H2O按摩尔比Fe/Ni/Cu=8:1:1混合溶解在100mL蒸馏水中,搅拌得到均一的金属盐溶液;将10g煤质活性炭加入上述金属盐溶液中,在40℃条件下不断搅拌使其充分浸渍,浸渍24h后,置于烘箱80℃下干燥8h,得到浸渍后的催化剂;
步骤2:将浸渍后的催化剂置于管式炉中,在N2/H2=7/1的还原气氛下进行高温煅烧,煅烧温度为650℃,煅烧时间为4h,即得Fe-Ni-Cu/C金属催化剂。
采用某焦化厂二沉池出水作为目标污染物,以该污水COD的降解程度代表有机废水的处理效率,向待处理水样中加入上述制得的Fe-Ni-Cu/C金属催化剂及过硫酸钠,充分反应60min;过硫酸钠的初始浓度为50ppm;Fe-Ni-Cu/C催化剂的浓度为5g/L;间隔时间取样,并对所取样品中过硫酸根浓度及COD浓度进行测试,即可知道催化剂对水样COD降解情况。
由图1与图2的过硫酸根分解速率及水样COD降解速率曲线可知,过硫酸钠在10次反应过程中分解速率达到98%以上,充分反映催化剂与过硫酸钠充分反应生成硫酸根自由基,对焦化污水的降解率集中保持在50%。
图3为催化剂使用前的SEM图谱,从图中可以明显看出,使用前催化剂孔道分布均匀,比表面积大。图4为催化剂使用后的SEM图谱,由图可知,多个尺寸为100-200nm的规则正方体小晶块叠加在一起,该正方体晶块就是CuO晶体,进一步证实使用后单质Cu被氧化为CuO。
实施例2
本实施例提供一种Fe-Co-Mn/C金属催化剂的制备方法,包括以下步骤;
步骤1:将Fe(NO3)3·9H2O、Co(NO3)3·6H2O、MnCl2·6H2O按摩尔比Fe/Ni/Cu=10:1:5混合溶解在100mL蒸馏水中,搅拌得到均一的金属盐溶液;将5g堇青石加入上述金属盐溶液中,在30℃条件下不断搅拌使其充分浸渍,浸渍14h结束后,置于烘箱60℃下干燥12h,得到浸渍后的催化剂;
步骤2:将浸渍后的催化剂置于管式炉中,在N2/H2=10/1的还原气氛下进行高温煅烧,煅烧温度为250℃,煅烧时间为9h,即得Fe-Co-Mn/C金属催化剂。
实施例3
本实施例提供一种Fe-Ti-Sn/C金属催化剂的制备方法,包括以下步骤;
步骤1:将FeCl3·6H2O、TiCl4和SnCl2按摩尔比Fe/Ti/Sn=10:1:5混合溶解在100mL蒸馏水中,搅拌得到均一的金属盐溶液;将8g分子筛ZMS-5加入上述金属盐溶液中,在80℃条件下不断搅拌使其充分浸渍,浸渍0.5h结束后,置于烘箱90℃下干燥6h,得到浸渍后的催化剂;
步骤2:将浸渍后的催化剂置于管式炉中,在N2/H2=5/1的还原气氛下进行高温煅烧,煅烧温度为850℃,煅烧时间为2h,即得Fe-Ti-Sn/C金属催化剂。
实施例4
本实施例提供一种Fe-Cu-Co/C金属催化剂的制备方法,包括以下步骤;
步骤1:将Fe(NO3)3·9H2O、Cu(NO3)3·6H2O和Co(NO3)3·6H2O按摩尔比称取Fe/Cu/Co=1:0.13:0.03混合溶解在100mL蒸馏水中,搅拌得到均一的金属盐溶液;将15g椰壳活性炭加入上述金属盐溶液中,在70℃条件下不断搅拌使其充分浸渍,浸渍12h结束后,置于烘箱70℃下干燥9h,得到浸渍后的催化剂;
步骤2:将浸渍后的催化剂置于管式炉中,在N2/H2=24/1的还原气氛下进行高温煅烧,煅烧温度为750℃,煅烧时间为6h,即得Fe-Cu-Co/C金属催化剂。
采用某焦化厂二沉池出水作为目标污染物,以该污水COD的降解程度代表有机废水的处理效率,向待处理水样中加入上述制得的Fe-Cu-Co/C金属催化剂、过硫酸钠与过硫酸钾按质量比为2:1混合加入,充分反应120min;过硫酸盐的初始浓度为5000ppm;Fe-Cu-Sn/C催化剂的浓度为8g/L;间隔时间取样,并对所取样品中过硫酸根浓度及COD浓度进行测试,即可知道催化剂对水样COD降解情况。
图5为该Fe-Cu-Co/C金属催化剂反应前后X射线粉末衍射分析,由图可知,反应前催化剂在2θ为43.41°、50.56°、74.30°分别对应Cu合金的(111)、(200)及(220)晶面,催化剂以合金铜为主。在2θ为44.66°处对应(110)晶面和65.02°的一个弱峰是α-Fe0的典型衍射峰,剩余衍射峰表明存在立方FeO为主要的氧化铁形式,证实反应前的催化剂是Fe、Cu、Co掺杂型的形态。催化剂使用之后,合金铜被氧化为Cu2O,对应(113)晶面,催化剂中铁离子(Fe0及Fe2+)与双氧水发生反应生成Fe3+,以Fe2O3为主要形式存在,在33.2°处对应γ-Fe2O3,在39.3°处对应α-Fe2O3。而催化剂在使用后2θ为36.5°、42.4°、61.51°、73.69°及77.56°处分别对应Co的(111)、(200)、(220)、(311)、(222)晶面,以单质Co形式存在,催化剂在使用之后各金属之间不再掺杂,以金属氧化物的形态出现,金属间的协同作用消失,导致分解过硫酸盐生成硫酸根自由基的速度减弱,对焦化废水中有机物的降解减慢。
Claims (9)
1.一种铁合金催化剂,其特征在于:所述催化剂以多孔性载体为基体,负载铁合金纳米球,通过浸渍-高温煅烧两步法制备而成;
所述多孔性载体包括陶瓷材料、碳基载体、沸石、堇青石、Al2O3、多孔分子筛或者泡沫金属材料;所述碳基载体包括煤质活性炭、椰壳活性炭、合成材料活性炭、碳毡、碳纸、碳纤维、碳棒、碳纳米管或者碳布;
所述铁合金纳米球以Fe元素为主,含有Ni、Co、Cu、Ti、Mn及Sn中的任意两种及以上;
所述催化剂用于活化过硫酸盐以降解有机污染物,所述有机污染物来源于工业煤焦化废水、化工污水、药厂废水或生活污水。
2.一种铁合金催化剂的制备方法,其特征在于,包括以下步骤:
步骤1,浸渍:将多孔性载体浸入浸渍液中,在25℃~80℃条件下浸渍0.5~24h后将载体捞出,置于40~90℃条件下干燥0.5~12h,得浸渍后的催化剂;
步骤2,高温煅烧:将浸渍后的催化剂置于管式炉中,在还原气氛中,于250℃~850℃下煅烧1h~9h,即得铁合金催化剂;
所述多孔性载体包括陶瓷材料、碳基载体、沸石、堇青石、Al2O3、多孔分子筛或者泡沫金属材料;所述碳基载体包括煤质活性炭、椰壳活性炭、合成材料活性炭、碳毡、碳纸、碳纤维、碳棒、碳纳米管或者碳布;
所述浸渍液中以Fe元素为主,含有Ni、Co、Cu、Ti、Mn及Sn中的任意两种及以上;
所述催化剂用于活化过硫酸盐以降解有机污染物,所述有机污染物来源于工业煤焦化废水、化工污水、药厂废水或生活污水。
3. 根据权利要求2所述的一种铁合金催化剂的制备方法,其特征在于: Fe与其他金属元素的摩尔比为1:0.01~10。
4.根据权利要求2所述的一种铁合金催化剂的制备方法,其特征在于:所述浸渍液中金属盐为氯化盐、硫酸盐或硝酸盐。
5.根据权利要求2所述的一种铁合金催化剂的制备方法,其特征在于:所述多孔载体与浸渍溶液的质量比为1:0.1~100。
6.根据权利要求2所述的一种铁合金催化剂的制备方法,其特征在于:所述还原气氛为一种还原气体,或者还原气体与惰性气体的任意组合;所述还原气体为H2,惰性气体为N2或Ar。
7.一种权利要求1所述的铁合金催化剂的应用,其特征在于,所述铁合金催化剂用于活化过硫酸盐以降解有机污染物。
8.根据权利要求7所述的一种铁合金催化剂的应用,其特征在于,所述过硫酸盐为过硫酸钠、过硫酸钾或过硫酸铵。
9.根据权利要求7所述的一种铁合金催化剂的应用,其特征在于:所述有机污染物来源于工业煤焦化废水、化工污水、药厂废水或生活污水。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106391095A (zh) * | 2016-10-18 | 2017-02-15 | 合肥学院 | 多孔磁性沸石载金属催化剂及其制备方法与应用 |
CN106955667A (zh) * | 2017-03-31 | 2017-07-18 | 中国科学院城市环境研究所 | 一种活性炭负载纳米零价铁和银金属簇的复合材料及其制备方法 |
CN107999060A (zh) * | 2017-12-13 | 2018-05-08 | 西安凯立新材料股份有限公司 | 一种处理难降解有机废水的负载钌催化剂及其制备方法 |
CN108404973A (zh) * | 2018-02-12 | 2018-08-17 | 华东理工大学 | 一种zsm-5负载的双金属催化剂及其制备方法与应用 |
CN108722344A (zh) * | 2018-04-13 | 2018-11-02 | 安徽工程大学 | 一种负载纳米零价铁铜双金属分子筛、制备方法及其除磷的应用 |
CN109529894A (zh) * | 2018-12-05 | 2019-03-29 | 浙江工商大学 | 一种活化过硫酸盐用催化剂及其催化过硫酸盐去除污染物的应用 |
CN110368941A (zh) * | 2019-07-29 | 2019-10-25 | 东华理工大学 | 一种孔隙里沉积还原铁纳米颗粒的烧结活性炭棒及制备方法和应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0259093A (ja) * | 1988-08-25 | 1990-02-28 | Nippon Steel Corp | 亜鉛−鉄合金電気メッキ廃液処理方法 |
JP4127102B2 (ja) * | 2003-04-01 | 2008-07-30 | 東ソー株式会社 | 有機ハロゲン化合物で汚染された被処理物の無害化処理方法 |
CN102583690A (zh) * | 2012-03-02 | 2012-07-18 | 中国海洋大学 | 一种废水中硝基苯类有机污染物的处理方法 |
CN104119845B (zh) * | 2014-08-05 | 2017-02-15 | 吉林大学 | 抗高温油田钻井液用降滤失剂及制备方法 |
CN105461042A (zh) * | 2015-12-22 | 2016-04-06 | 镇江市自来水公司 | 炭基纳米铁合金水处理材料的制备方法 |
US11370022B2 (en) * | 2017-11-28 | 2022-06-28 | Politecnico Di Torino | Method for the synthesis of a zero-valent metal micro- and nanoparticles in the presence of a noble metal |
CN108355610A (zh) * | 2018-02-09 | 2018-08-03 | 河南工业大学 | 一种介孔碳负载零价铁复合材料的制备及应用于活化过硫酸盐降解磺胺二甲基嘧啶的方法 |
CN111203179A (zh) * | 2020-01-15 | 2020-05-29 | 清创人和生态工程技术有限公司 | 一种可再生含酚有机废水催化吸附材料的制备方法及应用 |
-
2021
- 2021-04-29 CN CN202110476242.8A patent/CN113198475B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106391095A (zh) * | 2016-10-18 | 2017-02-15 | 合肥学院 | 多孔磁性沸石载金属催化剂及其制备方法与应用 |
CN106955667A (zh) * | 2017-03-31 | 2017-07-18 | 中国科学院城市环境研究所 | 一种活性炭负载纳米零价铁和银金属簇的复合材料及其制备方法 |
CN107999060A (zh) * | 2017-12-13 | 2018-05-08 | 西安凯立新材料股份有限公司 | 一种处理难降解有机废水的负载钌催化剂及其制备方法 |
CN108404973A (zh) * | 2018-02-12 | 2018-08-17 | 华东理工大学 | 一种zsm-5负载的双金属催化剂及其制备方法与应用 |
CN108722344A (zh) * | 2018-04-13 | 2018-11-02 | 安徽工程大学 | 一种负载纳米零价铁铜双金属分子筛、制备方法及其除磷的应用 |
CN109529894A (zh) * | 2018-12-05 | 2019-03-29 | 浙江工商大学 | 一种活化过硫酸盐用催化剂及其催化过硫酸盐去除污染物的应用 |
CN110368941A (zh) * | 2019-07-29 | 2019-10-25 | 东华理工大学 | 一种孔隙里沉积还原铁纳米颗粒的烧结活性炭棒及制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
氧化铁纳米结构的水热/溶剂热合成及其催化性能的表征;张怡;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080915;B014-19 * |
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