CN106040241B - 一种废弃物沼渣制备非均相Fenton催化剂的方法和应用 - Google Patents
一种废弃物沼渣制备非均相Fenton催化剂的方法和应用 Download PDFInfo
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Abstract
本发明公开了一种废弃物沼渣制备非均相Fenton催化剂的方法及应用,属于废弃物综合利用和水处理领域。包括以下步骤:废弃物沼渣通过清洗、干燥、粉碎、活化剂及过渡金属的盐溶液浸渍、微波活化、酸洗及筛分等步骤,制备出高比表面积的富含催化催化活性组分的沼渣基非均相Fenton催化剂。本发明的制备方法简单易操作、成本低廉,制备的催化剂在常温常压下催化Fenton氧化处理废水具有较宽的pH适用范围、高效的催化活性和稳定性,有效解决了废弃物沼渣高附加值资源化利用的难题,降低了Fenton催化剂制备成本,具有环境友好和可持续发展的技术特点和良好的工业化应用前景。
Description
技术领域
本发明涉及废弃物沼渣制备非均相Fenton催化剂的方法,应用于深度处理各种废水,属于废弃物综合利用和水处理领域。
背景技术
厌氧发酵技术将畜禽粪便、秸秆及污泥等废弃物进行高效能源化产生沼气,有效地解决了此类废弃物资源化利用的难题,取得了良好的经济和环境效益。但是,在沼气工程迅猛发展的同时,也产生了大量富含有机污染物和病源性微生物的厌氧消化残余物沼渣,其无害化和资源化利用成为制约厌氧发酵制沼气推广和应用的瓶颈。特别是畜禽粪便中,Cu和Zn等金属含量超标导致金属离子在沼渣中大量富集,超出我国农用土地污染物控制标准,如果长期作为肥料施用于农田将会导致严重的土壤污染,伴随着土壤圈的物质循环,对生态环境和人类健康产生巨大的危害。因此,亟需研发一种成本低廉,工艺简单,易推广且能够有效实现沼渣无害化与资源化高附加值利用的技术。
Fenton氧化技术原理是Fe2+ 作为H2O2的催化剂,在酸性条件下(pH 2~4),产生羟基自由基等氧化基团对水中污染物进行去除。该技术适用范围广、抗干扰能力强、最终分解产物是O2和H2O,不会产生二次污染,符合“绿色氧化”的理念,在工业废水处理领域被广泛应用。非均相Fenton是利用Fe3+离子负载于载体上,作为固体催化剂提高H2O2产生自由基的数量,强化对废水污染物的去除效能,弥补了传统Fenton矿化能力不足,产生铁泥和金属离子二次污染的问题,不需要严格控制pH值,催化剂易于分离,可重复回收使用,高效经济且无二次污染,具有广阔的市场应用前景。催化剂载体一般是多孔的固体物质,例如活性炭,活性炭纤维,沸石,树脂等,利用吸附和催化协同作用处理废水中污染物。然而,目前研制的催化剂往往存在制备工艺较为复杂,成本偏高,稳定性差,严重限制了该技术的推广与应用。
发明内容
本发明以废弃物沼渣为原料,通过一步合成法和微波活化等技术制备出高比表面积的富含催化活性组分的沼渣基非均相Fenton催化剂,有效解决沼渣无害化和高附加值资源化的难题,制备方法简单,成本低廉,易于回收,在废水处理过程具有良好的应用性,适宜工程化应用和推广。
所述的一种废弃物沼渣制备非均相Fenton催化剂的方法,其特征在于包括以下步骤:
1)将原料沼渣清洗、干燥并粉碎,待用;
2)将粉碎后的沼渣与活化剂及过渡金属的盐溶液通过一步合成法进行化学活化和浸渍处理,静置并收集固体沉淀物;
3)将固体沉淀物进行微波活化处理;
4)将微波活化后的样品进行酸洗;
5)将酸洗后的样品进行除杂和筛分,得沼渣基非均相Fenton催化剂。
所述的一种废弃物沼渣制备非均相Fenton催化剂的方法,其特征在于步骤1)中:沼渣产生原料包括畜禽粪便、农作物秸秆、餐厨垃圾、污泥的厌氧消化过程,或者产生于混合原料包括畜禽粪便/农作物秸秆、畜禽粪便/有机生活垃圾的厌氧消化过程,沼渣的干燥温度为80-90℃,干燥后粉碎至粉末状。
所述的一种废弃物沼渣制备非均相Fenton催化剂的方法,其特征在于步骤2)中:活化剂是KOH溶液,浓度为1-3 mol/L,浸渍比例为KOH溶液:干燥沼渣=1-3L:100g,过渡金属的盐溶液为过渡金属Fe的硝酸盐溶液或以Fe的硝酸盐溶液为基础复合Cu、Mn、Zn、Al的盐溶液一种以上的组合物,干燥沼渣与过渡金属的盐溶液进行浸渍处理,浸渍比例为干燥沼渣:过渡金属的盐溶液=100g:1-3L,金属盐在金属盐溶液中的含量为30-70%,一步合成法浸渍时间为1-3小时,浸渍过程中搅拌器以80-100 转/分钟进行混匀。
所述的一种废弃物沼渣制备非均相Fenton催化剂方法,其特征在于步骤2)中:过渡金属的盐溶液为以过渡金属Fe的硝酸盐溶液为基础复合Cu、Mn、Zn、Al的盐溶液一种以上的组合物,体积比为过渡金属Fe的硝酸盐溶液:其他过渡金属的硝酸盐溶液=5:1-3。
所述的一种废弃物沼渣制备非均相Fenton催化剂方法,其特征在于步骤3)中:微波活化处理的条件是微波热解温度为400-900℃,微波时间为10-40分钟,微波功率为250-400W;微波活化处理过程中采用氮气进行隔绝氧气保护,氮气流速为100-300 mL/min。
所述的一种废弃物沼渣制备非均相Fenton催化剂方法,其特征在于步骤4)中:采用H2SO4溶液进行酸洗,H2SO4溶液浓度为1-3 mol/L,冲洗至溶液pH值不再发生变化为止。
所述的废弃物沼渣制备非均相Fenton催化剂方法,其特征在于步骤5)中:酸洗后的样品采用纯净水继续冲洗杂质,干燥,然后筛分得到粒径为1-5 mm的沼渣基非均相Fenton催化剂。
所述任一方法所制备的非均相Fenton催化剂在非均相Fenton氧化处理废水中的应用,反应条件为:反应温度10-60 ℃,pH值为2-9,每次反应时间为20-90分钟,H2O2的投加量与废水COD的质量比为H2O2:COD=0.3-1.5:1,催化剂投加量为5-25 g/L。
所述的非均相Fenton催化剂在非均相Fenton氧化处理废水中的应用,其特征在于所述废水为造纸、煤化工和沼液废水等难降解有机废水或生化方法处理后未能达标排放的废水。
本发明具有以下有益效果:
1.本发明的制备方法简单,易操作,成本低,反应条件温和,适于工业化的生产。
2.本发明的方法制备的催化剂具有高效的催化活性和稳定性,不需要调节pH值,具有较宽的pH适用范围,适宜于工程化应用。
3.本发明制备催化剂以废弃物沼渣为物质基础,属于可持续发展的催化剂制备技术,有效解决了沼渣的高附加值利用问题,具有良好的经济和环境效益。
附图说明
图1是Fe/沼渣催化Fenton氧化深度处理沼液废水的效能图;
图2是Fe/沼渣催化Fenton氧化对沼液废水可生化性的影响图;
图3是Fe/沼渣连续催化Fenton氧化沼液废水的稳定性变化图;
图4是Fe-Mn/沼渣催化Fenton氧化深度处理造纸废水的效能图;
图5是 Fe-Mn/沼渣催化Fenton氧化对造纸废水可生化性的影响图;
图6是Fe-Mn/沼渣连续催化Fenton氧化造纸废水的稳定性变化图。
具体实施方式
为了更好地阐述本项发明,结合实施例进一步解释本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1
将原料沼渣进行清洗,80 ℃烘干后进行粉碎至粉末状,与浓度为3 mol/L的KOH溶液和含量为50%的硝酸铁溶液进行一步合成法处理,浸渍比例为KOH:干燥沼渣:硝酸铁溶液=3L:100g:1L,浸渍时间为2小时,搅拌器以80 转/分钟进行混匀,静置1小时后收集固体沉淀物,然后将固体沉淀物在微波炉内高温活化,热解温度为700 ℃,微波功率为350 W,微波活化过程中采用氮气进行隔绝氧气保护,氮气流速为150 mL/min,微波活化时间为30分钟,活化后样品采用浓度为2 mol/L的H2SO4溶液酸洗至pH值不发生变化后,纯净水进行冲洗,去除杂质,烘干,筛分得到粒径为5-10 mm的沼渣基非均相Fenton催化剂,待用。
由表1可以得知,制备的沼渣负载过渡金属Fe的非均相Fenton催化剂(Fe/沼渣)具有高的比表面积,孔隙以微孔为主,催化剂较高的吸附性能,Fe的负载量约为10.8 wt%。
表1 制备的催化剂表面特征与金属负载量
参数 | 干燥沼渣 | Fe/沼渣 | Fe-Mn/沼渣 |
比表面积(m²/g) | 8.6 | 315.5 | 277.1 |
中大孔(cm³/g) | 0.009 | 0.134 | 0.121 |
微孔(cm³/g) | 0.012 | 0.242 | 0.207 |
Fe(wt%) | 0.7 | 10.8 | 7.9 |
Mn(wt%) | - | - | 4.7 |
该催化剂应用于催化Fenton氧化深度处理沼液废水,该废水为某大型猪场沼气池经厌氧消化后的沼液废水,废水的水质为:COD浓度为325 mg/L左右,BOD5浓度90 mg/L左右,可生化性差,pH值为原水7左右,污染物浓度未达到国家到《畜禽养殖业污染排放标准》以及《农田灌溉水质标准》,非均相催化Fenton技术参数为:反应温度30 ℃,原水pH值为7左右, H2O2浓度为120 mg/L,催化剂投加量为10 g/L,搅拌器100转/分钟进行混合,反应时间为60分钟。
试验结果如图1和2所示,Fe/沼渣催化Fenton深度处理沼液废水,COD去除率达到81 %,远高于单独臭氧氧化的43 %,可生化性得到显著提高,BOD5/COD值由原水的0.27提高至0.45,高于单独氧化的0.33,达到了国家城镇污水处理厂污染物排放标准。
由图3可知,Fe/沼渣连续催化Fenton氧化沼液废水40次,每次1小时,总计400小时,其催化活性并未发生明显改变,Fe离子的流失极少,证实制备的催化剂具有良好的稳定性和安全性,适宜工业化推广应用。
实施例2
将原料沼渣进行清洗,80 ℃烘干后进行粉碎至粉末状,与浓度为3 mol/L的KOH溶液、含量均为50%的硝酸铁和硝酸锰的混合溶液进行一步合成法处理,浸渍比例为KOH溶液:干燥沼渣:混合金属盐溶液=3L:100g:1L,其中硝酸铁溶液与硝酸锰溶液混合体积比为3:1,浸渍时间为3小时,搅拌器以80 转/分钟进行混匀,静置1小时后收集固体沉淀物,然后将收集到的固体沉淀物在微波炉内高温活化,热解温度为700 ℃,微波功率为350 W,微波活化过程中采用氮气进行隔绝氧气保护,氮气流速为150 mL/min,微波活化时间为30分钟,采用浓度为2 mol/L的H2SO4溶液酸洗至pH值不发生变化为止,然后采用纯净水进行冲洗,去除杂质,烘干,筛分得到粒径为5-10 mm的沼渣基非均相Fenton催化剂,待用。
由表1可以得知,制备的沼渣负载过渡金属Fe和Mn非均相Fenton催化剂(Fe-Mn/沼渣)具有高的比表面积,孔隙以微孔为主,催化剂具有较高的吸附性能,Fe和Mn的负载量分别约为7.9 和4.7 wt%,总计12.6 wt%。
该催化剂用于催化Fenton氧化深度处理造纸废水,废水取自造纸废水生化处理二沉池出水,废水的水质为:COD浓度为215 mg/L左右,BOD5浓度为22 mg/L左右,可生化性差,BOD5/COD为0.1,pH值为6,属于难降解工业废水,非均相催化Fenton氧化技术参数为:反应温度30 ℃,pH值为原水6左右,H2O2浓度为120 mg/L,催化剂投加量为10 g/L,搅拌器100转/分钟进行混合,反应时间为60分钟。
试验结果如图4和5所示,Fe-Mn/沼渣催化Fenton深度处理造纸废水,COD去除率达到77 %,远高于单独臭氧氧化的36 %,可生化性得到显著提高,BOD5/COD值由原水的0.1提高至0.43,远高于单独氧化的0.23,达到了国家城镇污水处理厂污染物排放一级标准的A标准。
由图6可知,Fe-Mn/沼渣连续催化Fenton氧化造纸废水40次,每次1小时,总计400小时,其催化活性并未发生明显改变,Fe和Mn离子的流失极少,证实制备的催化剂具有良好的稳定性和安全性,适宜工业化推广应用。
Claims (3)
1.一种废弃物沼渣制备非均相Fenton催化剂的方法,其特征在于包括以下步骤:
1)将原料沼渣清洗、干燥并粉碎,待用;沼渣产生原料包括畜禽粪便、农作物秸秆、餐厨垃圾、污泥的厌氧消化过程,或者产生于混合原料包括畜禽粪便/农作物秸秆、畜禽粪便/有机生活垃圾的厌氧消化过程,沼渣的干燥温度为80-90℃,干燥后粉碎至粉末状;
2)将粉碎后的沼渣与活化剂及过渡金属的盐溶液通过一步合成法进行化学活化和浸渍处理,静置并收集固体沉淀物;活化剂是KOH溶液,浓度为1-3 mol/L,浸渍比例为KOH溶液:干燥沼渣=1-3L:100g,过渡金属的盐溶液为过渡金属Fe的硝酸盐溶液或以Fe的硝酸盐溶液为基础复合Cu、Mn、Zn、Al的盐溶液一种以上的组合,干燥沼渣与过渡金属的盐溶液进行浸渍处理,浸渍比例为干燥沼渣:过渡金属的盐溶液=100g:1-3L,金属盐在金属盐溶液中的含量为30-70%,活化剂和金属盐一步合成法浸渍时间为1-3小时,浸渍过程中搅拌器以80-100 转/分钟进行混匀;过渡金属的盐溶液为以Fe的硝酸盐溶液为基础复合Cu、Mn、Zn、Al的盐溶液一种以上的组合物,体积比为过渡金属Fe的硝酸盐溶液:其他过渡金属的盐溶液=5:1-3;
3)将固体沉淀物进行微波活化处理,微波活化处理的条件是微波热解温度为400-900℃,微波时间为10-40分钟,微波功率为250-400W;微波活化处理过程中采用氮气进行隔绝氧气保护,氮气流速为100-300 mL/min;
4)将微波活化后的样品进行酸洗,具体为:采用H2SO4溶液进行酸洗,H2SO4溶液浓度为1-3 mol/L,冲洗至溶液pH值不再发生变化为止;
5)将酸洗后的样品进行除杂和筛分,得沼渣基非均相Fenton催化剂,具体为酸洗后的样品采用纯净水继续冲洗杂质,干燥,然后筛分得到粒径为1-5 mm的沼渣基非均相Fenton催化剂。
2.一种根据权利要求1所述方法所制备的非均相Fenton催化剂在非均相Fenton氧化处理废水中的应用,反应条件为:反应温度10-60 ℃,pH值为2-9,每次反应时间为20-90分钟,H2O2的投加量与废水COD的质量比为H2O2:COD=0.3-1.5:1,催化剂投加量为5-25 g/L。
3.根据权利要求2所述的催化剂在非均相Fenton氧化处理废水中的应用,其特征在于所述废水为造纸、煤化工和沼液废水等难降解有机废水或生化方法处理后未能达标排放的废水。
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