CN104383880B - 一种深度处理工业废水用合金活性焦催化填料的制备方法 - Google Patents

一种深度处理工业废水用合金活性焦催化填料的制备方法 Download PDF

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CN104383880B
CN104383880B CN201410727020.9A CN201410727020A CN104383880B CN 104383880 B CN104383880 B CN 104383880B CN 201410727020 A CN201410727020 A CN 201410727020A CN 104383880 B CN104383880 B CN 104383880B
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陈红
李响
薛罡
张文启
高品
刘亚男
刘振鸿
王成
张凡
张禾
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Donghua University
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Abstract

本发明公开了一种用于工业废水深度处理的合金活性焦催化填料的制备方法。填料制备原料包括：焦炭、多金属离子溶液、铁屑及碱等。先对废焦炭进行活化、烘干，形成固体活性焦。将此固体活性焦浸渍在多金属离子溶液中，加入废铁屑、碱，慢速搅拌至糊状，烘干烧结形成合金活性焦催化填料。此填料可增强臭氧、双氧水、活性污泥对污水有机物深度氧化处理效果，启动快，填料钝化及消耗速度缓慢。催化填料原料易得，组装方便，成本低廉。

Description

一种深度处理工业废水用合金活性焦催化填料的制备方法
技术领域
本发明涉及一种环境化工材料，具体涉及一种深度处理工业废水用合金活性焦催化填料的制备方法，属于环境污染治理技术领域。
背景技术
随着化学工业的迅猛发展，工业废水处理是缓解环境污染最有效的途径。为了贯彻国家节能减排方针，工业废水排放标准普遍提高(一级B标准：COD＜60mg/L；NH4 +-N＜8mg/L)。但是，化工废水水质复杂，特别是难降解物质多，现有的印染及化工废水处理工艺仅能将COD降解至140mg/L(中国给水排水，2011，27(15)32-34)，这对进一步深度处理带来极大难度。
针对工业废水深度处理技术尚无成型技术。目前，一般借鉴给水相关处理技术如高级氧化或还原技术进行工业废水深度处理，但均存在相应问题。如臭氧氧化，其臭氧发生和制氧等设备投资高、运行管理难度大(CN101700927B)；铁碳内电解技术，主要用于前端预处理提高污水的可生化性能，处理对象是原水，仅能将COD降解至1000mg/L(CN103253742A，CN102557201B)；通过优化填料配比，COD可降解至300mg/L(ZL200510029765.9)；通过磁性填料内电解技术，可以将COD降解至150mg/L(CN101671068B)。但要实现达标排放，技术难度相当大，至今尚且没有工业废水的深度处理技术，更没有适合工业废水深度处理的填料。
发明内容
本发明所要解决的技术问题是提供一种适合工业废水深度处理的填料，能应用于工业废水的深度处理技术，满足废水提标改造的需求。
为了解决上述问题，本发明提供了一种用于工业废水深度处理的合金活性焦催化填料的制备方法，其特征在于，包括以下步骤：
步骤1)：对废焦炭进行活化、烘干，形成固体活性焦；
步骤2)：将固体活性焦超声浸渍于含过渡金属离子的浸渍溶液中，向溶液中加入铁屑，再加入碱，缓慢加热，慢速搅拌至糊状；
步骤3)：将糊状物烘干后烧结，用带孔径的塑性网织布包裹成型，构成合金活性焦催化填料。
优选地，所述步骤1)的焦炭活化过程具体为：将废焦炭置于水热锅中，在50-90℃的温度条件下，加入浓HCl、双氧水，浓HCl与双氧水的体积比(以热水体积为基数)为0.5％∶0.1-1％，活化时间为0.5-2.5h，活化结束后在70-120℃下烘干，烘干时间为2-8h。
进一步地，所述步骤1)的焦炭活化过程具体为：将废焦炭置于水热锅中，在70℃的温度条件下加入浓HCl、双氧水，浓HCl与双氧水的体积比(以热水体积为基数)为0.5％∶0.5％活化时间为1.5h，活化结束后在95℃下烘干，优选95℃，烘干时间为5h。
优选地，所述步骤2)中超声的具体步骤为：在30-60kHz的频率条件下，浸渍时间为4-24h。
进一步地，所述步骤2)中超声的具体步骤为：在45kHz的频率条件下，浸渍时间为12h。
优选地，所述步骤2)中的过渡金属离子采用钴、镍、锰、锌及铜；浸渍溶液体积为固体活性焦吸水体积的1-6倍；各过渡金属离子重量百分比为(以固体活性焦干重为基准)：Co2+ 0.5-4.5％、Ni2+ 0.8-5.0％、Mn2+ 0.5-3.0％、Zn2+ 0.2-2.0％、Cu2+ 0.5-2.0％。
优选地，所述步骤2)中铁屑的投加量为固体活性焦质量的20-80％，碱用量为活性焦炭质量的2-8％；步骤2)的反应温度从室温加热至60℃，加热速度为0.5-5℃/min；慢速搅拌速度为20-100rpm。
进一步地，所述步骤2)中铁屑的投加量为固体活性焦质量的50％，碱用量为活性焦炭质量的5％；步骤2)的反应温度从室温加热至60℃，加热速度为3℃/min；慢速搅拌速度为60rpm。
优选地，所述步骤2)中的碱采用KOH、NaOH或Ca(OH)2。
优选地，所述步骤3)中糊状物的烘干温度为100-120℃，烘干时间为2-6h；烧结温度为300-500℃，烧结时间为4-12h。
进一步地，所述步骤3)中糊状物的烘干温度为110℃，烘干时间为4h；烧结温度为为400℃，烧结时间为8h。
优选地，所述步骤3)中塑性网织布采用尼龙材料、PE材料或PVC材料，其网孔目数为10-50目。
采用本发明提供的制备方法制成的填料可用于工业废水深度处理。
与现有技术相比，本发明的有益效果是：
(1)本发明制备的合金活性焦催化填料可显著增强多金属催化还原能力，增强活性炭吸附能力，缩短了停留时间。用于深度处理，填料耗失缓慢，运营成本低；
(2)填料组装简便，生产周期短，原材料便宜易得，强度及硬度适中，使用过程中可以任意投放至曝气池，不用刻意摆置，降低人工操作成本；
(3)COD降解至60mg/L以下。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，作详细说明如下。
实施例1
一种深度处理工业废水用合金活性焦催化填料的制备方法：
(1)称取500g废焦炭，置于含1L水的水热锅中，温度控制在50℃，加入浓HCl 5mL、双氧水1mL，水热活化2.5h，活化后在70℃下烘干，干燥8h，形成固体活性焦。
(2)配置400mL浸渍溶液，其中含Co2+ 2.5g、Ni2+ 4.0g、Mn2+ 2.5g、Zn2+ 1.0g、Cu2+2.5g。将固体活性焦置于浸渍溶液中，在30kHz超声24h，再向溶液中添加废铁屑100g，再加入Ca(OH)2 10g，以0.5℃/min的加热速度将溶液加热至60℃，在20rpm下搅拌至糊状。
(3)将糊状物在100℃下烘干，干燥6h，300℃下烧结12h。采用网孔目数为10目的尼龙材料包裹成型，构成合金活性焦催化填料。
利用上述制备的合金活性焦催化填料对2L工业废水二级生化出水(COD浓度为120-140mg/L)进行深度处理，将出水与填料混合曝气，溶解氧控制为2mg/L，曝气时间为6h。曝气结束后投加70mg/L石灰及250mg/L硫酸铝，固液分离后，重复上述该步骤2次，处理后上清液COD为60mg/L。曝气过程中可选择性使用臭氧、双氧水、活性污泥的一种，深度处理效率进一步提高。
实施例2
一种深度处理工业废水用合金活性焦催化填料的制备方法：
(1)称取500g废焦炭，置于含1L水的水热锅中，温度控制在90℃，加入浓HCl 5mL、双氧水10mL，水热活化0.5h，活化后在120℃下烘干，干燥2h，形成固体活性焦。
(2)配置2400mL浸渍溶液，其中含Co2+ 22.5g、Ni2+ 25.0g、Mn2+ 15.0g、Zn2+ 10.0g、Cu2+ 10.0g。将固体活性焦置于浸渍溶液中，在60kHz超声4h，再向溶液中添加废铁屑400g，再向溶液中加入KOH40g，以5℃/min的加热速度将溶液加热至60℃，在100rpm下搅拌至糊状。
(3)将糊状物在120℃下烘干，干燥2h，500℃下烧结4h。采用网孔目数为50目的PE材料包裹成型，构成合金活性焦催化填料。
利用上述制备的合金活性焦催化填料对2L工业废水二级生化出水(COD浓度为120-140mg/L)进行深度处理，将出水与填料混合曝气，溶解氧控制为2mg/L，曝气时间为6h，曝气时，以工业废水体积为基准附加臭氧(投加量10mg/L)进行高级氧化处理。曝气结束后投加70mg/L石灰及250mg/L硫酸铝，固液分离后，重复上述该步骤2次，处理后上清液COD为55mg/L。
实施例3
一种深度处理工业废水用合金活性焦催化填料的制备方法：
(1)称取500g废焦炭，置于含1L水的水热锅中，温度控制在70℃，加入浓HCl 5mL、双氧水5mL，水热活化1.5h，活化后在95℃下烘干，干燥5h，形成固体活性焦。
(2)配置1200mL浸渍溶液，其中含Co2+ 12.5g、Ni2+ 15.0g、Mn2+ 7.5g、Zn2+ 5.0g、Cu2+ 7.0g。将固体活性焦置于浸渍溶液中，在45kHz超声12h，再向溶液中添加废铁屑250g，再向溶液中加入NaOH 25g，以3℃/min的加热速度将溶液加热至60℃，在60rpm下搅拌至糊状。
(3)将糊状物在110℃下烘干，干燥4h，400℃下烧结8h。采用网孔目数为30目的PVC材料包裹成型，构成合金活性焦催化填料。
利用上述制备的合金活性焦催化填料对2L工业废水二级生化出水(COD浓度为120-140mg/L)进行深度处理，将出水与填料混合曝气，溶解氧控制为2mg/L，曝气时间为6h，曝气时，以工业废水体积为基准投加双氧水(10mg/L)进行高级氧化处理。曝气结束后投加70mg/L石灰及250mg/L硫酸铝，固液分离后，重复上述该步骤2次，处理后上清液COD为50mg/L。
实施例4
一种深度处理工业废水用合金活性焦催化填料的制备方法：
(1)称取500g废焦炭，置于含1L水的水热锅中，温度控制在60℃，加入浓HCl 5mL、双氧水1mL，水热活化1.5h，活化后在80℃下烘干，干燥6h，形成固体活性焦。
(2)配置800mL浸渍溶液，其中含Co2+ 5.0g、Ni2+ 9.0g、Mn2+ 5.0g、Zn2+ 5.0g、Cu2+ 5.0g。将固体活性焦置于浸渍溶液中，在45kHz超声12h，再向溶液中添加废铁屑250g，再向溶液中加入Ca(OH)2 30g，以2℃/min的加热速度将溶液加热至60℃，在40rpm下搅拌至糊状。
(3)将糊状物在110℃下烘干，干燥5h，350℃下烧结6h。采用网孔目数为20目的尼龙材料包裹成型，构成合金活性焦催化填料。
利用上述制备的合金活性焦催化填料对2L工业废水二级生化出水(COD浓度为120-140mg/L)进行深度处理，将出水与填料混合曝气，溶解氧控制为2mg/L，曝气时间为6h，曝气时，以工业废水体积为基准接种活性污泥(接种量为废水体积的40％)进行深度处理。曝气结束后投加70mg/L石灰及250mg/L硫酸铝，固液分离后，重复上述该步骤2次，处理后上清液COD为55mg/L。

Claims (9)

1.一种用于工业废水深度处理的合金活性焦催化填料的制备方法，其特征在于，包括以下步骤：
步骤1）：对废焦炭进行活化、烘干，形成固体活性焦；
步骤2）：将固体活性焦超声浸渍于含过渡金属离子的浸渍溶液中，向溶液中加入铁屑，再加入碱，缓慢加热，慢速搅拌至糊状；
步骤3）：将糊状物烘干后烧结，用带孔径的塑性网织布包裹成型，构成合金活性焦催化填料；所述步骤1）的焦炭活化过程具体为：将废焦炭置于水热锅中，在50-90℃的温度条件下，加入浓HCl、双氧水，浓HCl与双氧水的体积比为0.5%:0.1-1%，该体积比以热水体积为基数，活化时间为0.5-2.5h，活化结束后在70-120℃下烘干，烘干时间为2-8h；
所述步骤2）中的过渡金属离子采用钴、镍、锰、锌及铜；浸渍溶液体积为固体活性焦吸水体积的1-6倍；各过渡金属离子重量百分比为：Co2+ 0.5-4.5%、Ni2+ 0.8-5.0%、Mn2+ 0.5-3.0%、Zn2+ 0.2-2.0%、Cu2+ 0.5-2.0%，该重量百分比以固体活性焦干重为基准；
所述步骤2）中铁屑的投加量为固体活性焦质量的20-80%，碱用量为活性焦炭质量的2-8%；步骤2）的反应温度从室温加热至60℃，加热速度为0.5-5℃/min；慢速搅拌速度为20-100rpm。
2.如权利要求1所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤1）的焦炭活化过程具体为：将废焦炭置于水热锅中，在70℃的温度条件下加入浓HCl、双氧水，浓HCl与双氧水的体积比为0.5%:0.5%，该体积比以热水体积为基数，活化时间为1.5h，活化结束后在95℃下烘干，烘干时间为5h。
3.如权利要求1所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤2）中超声的具体步骤为：在30-60kHz的频率条件下，浸渍时间为4-24h。
4.如权利要求3所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤2）中超声的具体步骤为：在45kHz的频率条件下，浸渍时间为12h。
5.如权利要求1所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤2）中铁屑的投加量为固体活性焦质量的50%，碱用量为活性焦炭质量的5%；步骤2）的反应温度从室温加热至60℃，加热速度为3℃/min；慢速搅拌速度为60rpm。
6.如权利要求1或5所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤2）中的碱采用KOH、NaOH或Ca(OH)2。
7.如权利要求1所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤3）中糊状物的烘干温度为100-120℃，烘干时间为2-6h；烧结温度为300-500℃，烧结时间为4-12h。
8.如权利要求7所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤3）中糊状物的烘干温度为110℃，烘干时间为4h；烧结温度为为400℃，烧结时间为8h。
9.如权利要求1、7-8任意一项所述的合金活性焦催化填料的制备方法，其特征在于，所述步骤3）中塑性网织布采用尼龙材料、PE材料或PVC材料，其网孔目数为10-50目。
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