CN115253587A - 一种有机废气电催化-生化联用净化的方法及装置 - Google Patents
一种有机废气电催化-生化联用净化的方法及装置 Download PDFInfo
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Abstract
本发明公开了一种有机废气电催化‑生化联用净化的方法,其是将除尘后的待处理有机废气通入到吸附/电催化净化系统,流量不稳定、低浓度的VOCs经过系统内的吸附/催化复合材料进行吸附富集,当达到起燃浓度后启用电阻丝进行快速增温点火,将大部分VOCs进行燃烧去除,之后形成含有SO2、NOx、CO2及少部分VOCs的尾气,尾气再进入到生物净化系统中,尾气中的硫硝碳及少部分未去除的VOCs经培养液捕集、生物填料吸附、微生物降解流程进行深度净化,最终实现超低排放,使用后更换的生物填料取出破碎,用于制作微生物营养土;本发明对有机废气及尾气中的硫硝碳进行深度去除,达到超低排放的目的。
Description
技术领域
本发明涉及烟气净化领域,具体涉及一种有机废气电催化-生化联用净化的方法及装置。
背景技术
随着我国工业化和城市化的快速发展,环境问题日益突出,挥发性有机物( VOCs)排入大气中,会产生严重的环境问题,如雾霾、光化学烟雾、破坏臭氧层导致全球变暖等,如何消减挥发性有机物(VOCs)成为社会广泛关注的问题。
目前对于VOCs的末端控制使用的治理技术主要包括两类:一是采用吸附的方法对高浓度废气进行回收,吸附剂有活性炭纤维和颗粒活性炭两种;二是采用吸附浓缩催化焚烧的方法对车间排出的低浓度废气进行净化。吸附剂有蜂窝活性炭和颗粒活性炭,净化效率一般在90%以上。有部分企业采用了国外的沸石转轮吸附浓缩装置,效果良好。国内目前在吸附材料沸石的改性方面还没有很好的解决方法。石油化工行业的生产装置复杂,因此,排放的污染物众多,成分复杂,浓度变化大。石化行业的污染物排放分为无组织排放和有组织连续排放。石化行业VOCs的有组织排放主要为生产工艺过程中的人为排放。工艺过程产生的有机废气无法彻底回收利用,尽管采用了焚烧、吸附、冷凝等方式处理,但仍有部分有机尾气排放到大气中。
生物法处理有机废气技术是为解决这类既无回收利用价值又扰民并污染环境的低浓度工业有机废气净化处理难题而开发的,属目前世界上工业废气净化领域的前沿热点技术。但是对非水溶性的VOCs去除效果较差,对于高浓度的VOCs抗冲击能力较差,限制了其在工业中的进一步应用。
发明内容
针对上述问题,本发明提出了一种有机废气电催化-生化联用净化的方法,利用吸附/电催化复合系统耦合生物净化系统对有机废气及尾气中的硫硝碳进行深度去除,最终达到对工业有机废气中硫硝尘的一体化高效去除的目的超低排放的目的。
为解决上述问题,本发明有机废气电催化-生化联用净化的方法,通过对现有的催化燃烧技术、生物净化技术进行创新,形成电催化-生化联用净化系统;具体是除尘后的待处理有机废气进入到吸附/电催化净化系统,流量不稳定、低浓度的VOCs经过系统内的吸附/催化复合材料进行吸附富集,当达到起燃浓度后启用电极上的电阻丝进行快速增温点火,将大部分VOCs进行燃烧去除,之后形成含有SO2、NOx、CO2及少部分VOCs的尾气,尾气再进入到生物净化系统中,尾气中的硫硝碳及少部分未去除的VOCs 经培养液捕集、生物填料吸附、微生物降解流程进行深度净化,最终实现超低排放,使用后更换的生物填料取出破碎,用于制作微生物营养土。
所述吸附/催化复合体是由海泡石、高岭土、滑石、蒙脱石、珍珠岩、高岭石、蛭石、羟基磷灰石、活性氧化铝、天然沸石分子筛、Y分子筛、X分子筛、MIL-101有机金属骨架、多孔碳基材料中的一种或多种作为载体,通过浸渍-烧结法、电沉积法、化学气相沉积法负载催化材料。
所述催化材料为非贵金属催化剂或复合催化剂;
非贵金属催化剂为CuOx、MnOx、CeO2、Co3O4、Cr2O3、NiO、TiOx中的一种,复合催化剂为M-TiO2、MOx-RuO2、MOx-石墨烯-RuO2、MOx-石墨烯-TiO2中的一种,其中M为Zr、Sn、La、Mn。
所述电极为镍铬合金、铁铬铝合金、多孔镍网、多孔钛网、多孔铜网、泡沫镍、泡沫铜制成电极基体,采用电沉积的方法将钴基双金属催化剂、单原子催化剂、氮改性碳基材料负载到电极基体上,并从电极基体周围延伸出电阻丝,电阻丝均匀分布在吸附/催化复合体内。
所述电沉积方法具体实施包括恒电位和恒电流沉积,对于不导电材料,采用恒电位沉积,电压大小为1V~360V;对于表面较为粗糙的基体负载催化剂时候,选择恒电流沉积,电流大小为1mA~10A。
生物净化系统中填充有生物填料,生物填料上负载有由微生物菌剂1-3重量份、营养液1-3重量份、吸收液10-35重量份组成的混合物,其中吸收液为5%稀氨水、2%氢氧化钙溶液、5%二甲基亚砜溶液,3%异戊醇溶液,5% C1~C10烷烃有机溶剂中一种或几种;生物填料选自火山岩、多孔陶瓷、生物质、泥煤、堆肥、木屑、土壤腐泥煤、碎树皮、改性活性炭、改性硅藻土。
本发明另一目的是提供完成上述方法的装置,其包过滤单元、吸附/电催化系统、生物净化系统,过滤单元通过管道与2个以上的吸附/电催化系统连接,吸附/电催化系统底部的出气口通过引风机与生物净化系统下部连接,吸收液循环池通过管道与生物净化系统内的喷淋装置连通,喷淋装置设置在生物净化系统内的生物填料层的上方,菌种及营养元素补充池通过管道连通至生物填料层的上方,空气泵与菌种及营养元素补充池连通,生物净化系统底部通过管道与吸收液循环池连通,生物净化系统顶部设置有排放口,气体管道上设置有控制法兰,液体管道上设置有阀门,过滤单元通过管道与生物净化系统连接。
所述吸附/电催化净化系统内设置有吸附/催化复合体层,电极设置在吸附/催化复合体内,从电极上延伸出若干电阻丝均匀分布在吸附/催化复合体内,电极与电源连接,电源为直流电源,电压范围在0.1~10kV,接入电源后通过电压调控保持吸附/电催化净化系统内温度在300~1200℃。
本发明方法的优点和技术效果:
1)解决了传统催化燃烧处理技术因气体流量及浓度波动大,装置运行不稳定的问题,同时也解决了生物法对非甲烷总烃等非水溶性VOCs去除效率差的问题;
2)采用电催化燃烧的方式,装置启动速度快,催化效果好;创新后的生物处理系统不仅能对有机废气进行去除,同时也能对硫硝碳进行深度捕集,且处理后的生物填料可用作微生物营养土,创造可观的利用价值。
附图说明
图1是有机废气电催化-生化联用净化的流程示意图;
1-有机废气进气口;2-过滤单元;3-吸附/电催化系统;4-生物净化系统;5-排放口;6-电源;7-电极;8-吸附/催化复合材料层;9-引风机;10-吸收液循环池;11-生物填料层;12-喷淋装置;13-菌种及营养元素补充池;14-空气泵;15-控制法兰;16-阀门。
具体实施方式
下面通过附图和实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容;如图1所示,下述实施例中使用的装置包过滤单元2、吸附/电催化系统3、生物净化系统4,过滤单元2通过管道与2个以上的吸附/电催化系统3连接,吸附/电催化系统3底部的出气口通过引风机9与生物净化系统4下部连接,吸收液循环池10通过管道与生物净化系统4内的喷淋装置12连通,喷淋装置12设置在生物净化系统内的生物填料层的上方,菌种及营养元素补充池13通过管道连通至生物填料层的上方,空气泵14与菌种及营养元素补充池13连通,生物净化系统4底部通过管道与吸收液循环池10连通,生物净化系统4顶部设置有排放口5,气体管道上设置有控制法兰15,液体管道上设置有阀门16;吸附/电催化净化系统内设置有吸附/催化复合体层8,电极7设置在吸附/催化复合体内,电极与电源6连接,电源为直流电源;过滤单元2通过管道、引风机9与生物净化系统4连接;
实施例1:
在橡胶生产过程中会产生大量高VOCs、含H2S、SO2等有毒气体的有机废气,该烟气中SO2浓度为800mg/m3,VOCs浓度为300mg/m3,H2S浓度为200mg/m3,烟气温度为150℃;在实际操作中,烟气经收集系统收集后,由引风机将烟气由有机废气进气口1引入耐高温化纤毡过滤单元2内过滤除层后,进入到吸附/电催化净化系统3中,系统内吸附/催化复合体是由MIL-101有机金属骨架作为载体,采用恒电流沉积,电流大小为3A,负载的催化材料为CuOx、MnOx,电极为多孔镍网制成,采用恒电流(电流大小为5A)电沉积的方法将Cu-Co双金属催化剂负载到电极上,并从电极周围延伸出若干电阻丝均匀分布在吸附/催化复合体内;有机废气在此系统内首先被吸附富集,达到起燃浓度以后接入直流电源,电压为5kV,接入电源后通过电压调控保持装置内温度在600℃保持稳定;使吸附的有机废气充分燃烧,之后富含硫硝碳及少部分VOCs的尾气进入到生物净化系统中,生物净化系统中填充有火山岩填料层11,吸收液34重量份从吸收液循环池10由喷淋装置12喷洒到火山岩填料层上,微生物菌剂3重量份、营养液3重量份从菌种及营养元素补充池13输送到火山岩填料层上,其中微生物菌剂(高效微生物菌种JYS-01)、营养液(IDN-C)均为市售常规产品,吸收液是由5%稀氨水、5%二甲基亚砜溶液按体积比1:1混合而成,尾气进入到生物处理系统内,经培养液捕集→生物填料吸附→微生物降解进行深度净化,实现超低排放,生物净化系统4底部汇集的吸收液回流至吸收液循环池10中,处理后的火山岩取出破碎制的微生物营养土;
实施例2:
在焦化生产过程中会产生大量高VOCs、含H2S、SO2、NOx等有毒气体的有机废气,该烟气中SO2浓度为800mg/m3,VOCs浓度为300mg/m3,H2S浓度为200mg/m3,NOx浓度为100mg/m3。在实际操作中,烟气经收集系统收集后,由引风机将烟气由有机废气进气口1引入PTFE针刺毡过滤单元2内过滤除层后,烟气进入到吸附/电催化净化系统中,系统内的吸附/催化复合体是天然沸石分子筛作为载体,采用恒电位沉积,电压大小为5V,负载的催化材料为Co3O4,快速增温电极为多孔钛网制成,采用恒电流(电流大小为3A)电沉积的方法将Ag催化剂负载到电极上,并从电极周围延伸出电阻丝均匀分布在吸附/催化复合体内;有机废气在此系统内首先被吸附富集,达到起燃浓度以后接入直流电源,电压为10kV,接入电源后通过电压调控保持装置内温度在800℃保持稳定;使吸附的有机废气充分燃烧,之后富含硫硝碳及少部分VOCs的尾气进入到生物处理系统中,生物净化系统中填充有土壤腐泥煤层11,土壤腐泥煤层上负载有由微生物菌剂3重量份、营养液3重量份、吸收液25重量份组成的混合物,其中微生物菌剂(环微EBD菌剂)、营养液(复合碳源)均为市售常规产品,吸收液是由2%氢氧化钙溶液、5%二甲基亚砜溶液按质量比1:1混合而成,尾气进入到生物处理系统内,经培养液捕集→生物填料吸附→微生物降解进行深度净化,实现超低排放,处理后的土壤腐泥煤取出破碎制的微生物营养土。
实施例3:
在石油化工生产过程中会产生低浓度的VOCs及恶臭气体,本实施例中气体经过耐高温石棉过滤单元2后通过引风机9进入生物净化系统4进行净化;此时有机废气中主要VOCs浓度为50mg/m3,H2S、NH3等恶臭气体浓度为20mg/m3,在实际操作中,烟气经收集系统收集后,由引风机直接将烟气引入到生物净化体系内,,生物净化系统中填充有多孔陶瓷填料层,多孔陶瓷填料层上负载有由微生物菌剂2重量份、营养液2重量份、吸收液33重量份组成的混合物,其中微生物菌剂(复合菌种)、营养液(葡萄糖)均为市售常规产品,吸收液是由3%异戊醇溶液、5%丙烷溶液(按体积比1:1)混合而成,有机废气进入到生物处理系统内,经培养液捕集→生物填料吸附→微生物降解进行深度净化,实现超低排放,处理后的改性硅藻土取出破碎制取微生物营养土。
Claims (8)
1.一种有机废气电催化-生化联用净化的方法,其特征在于:除尘后的待处理有机废气进入到吸附/电催化净化系统,流量不稳定、低浓度的VOCs经过系统内的吸附/催化复合材料进行吸附富集,当达到起燃浓度后启用电阻丝进行快速增温点火,将大部分VOCs进行燃烧去除,之后形成含有SO2、NOx、CO2及少部分VOCs的尾气,尾气再进入到生物净化系统中,尾气中的硫硝碳及少部分未去除的VOCs 经培养液捕集、生物填料吸附、微生物降解流程进行深度净化,最终实现超低排放,使用后更换的生物填料取出破碎,用于制作微生物营养土。
2.根据权利要求1所述的有机废气电催化-生化联用净化的方法,其特征在于:吸附/催化复合体是以海泡石、高岭土、滑石、蒙脱石、珍珠岩、高岭石、蛭石、羟基磷灰石、活性氧化铝、天然沸石分子筛、Y分子筛、X分子筛、MIL-101有机金属骨架、多孔碳基材料中的一种或多种作为载体,通过浸渍-烧结法、电沉积法、化学气相沉积法负载催化材料。
3.根据权利要求2所述的有机废气电催化-生化联用净化的方法,其特征在于:催化材料为非贵金属催化剂或复合催化剂。
4.根据权利要求3所述的有机废气电催化-生化联用净化的方法,其特征在于:非贵金属催化剂选自CuOx、MnOx、CeO2、Co3O4、Cr2O3、NiO、TiOx中的一种,复合催化剂为M-TiO2、MOx-RuO2、MOx-石墨烯-RuO2、MOx-石墨烯-TiO2中的一种,其中M为Zr、Sn、La、Mn。
5.根据权利要求1所述的有机废气电催化-生化联用净化的方法,其特征在于:电极为镍铬合金、铁铬铝合金、多孔镍网、多孔钛网、多孔铜网、泡沫镍、泡沫铜制成电极基体,采用电沉积的方法将钴基双金属催化剂、单原子催化剂、氮改性碳基材料负载到电极基体上,并从电极基体周围延伸出电阻丝,电阻丝均匀分布在吸附/催化复合体内。
6. 根据权利要求3所述的有机废气电催化-生化联用净化的方法,其特征在于:生物净化系统中填充有生物填料,生物填料上负载有由微生物菌剂1-3重量份、营养液1-3重量份、吸收液10-35重量份组成的混合物,其中吸收液为5%稀氨水、2%氢氧化钙溶液、5%二甲基亚砜溶液,3%异戊醇溶液,5% C1~C10烷烃有机溶剂中一种或几种;生物填料选自火山岩、多孔陶瓷、生物质、泥煤、堆肥、木屑、土壤腐泥煤、碎树皮、改性活性炭、改性硅藻土。
7.完成权利要求1所述的有机废气电催化-生化联用净化的方法的装置,其特征在于:包过滤单元(2)、吸附/电催化系统(3)、生物净化系统(4),过滤单元(2)通过管道与2个以上的吸附/电催化系统(3)连接,吸附/电催化系统(3)底部的出气口通过引风机(9)与生物净化系统(4)下部连接,吸收液循环池(10)通过管道与生物净化系统(4)内的喷淋装置(12)连通,喷淋装置(12)设置在生物净化系统内的生物填料层的上方,菌种及营养元素补充池(13)通过管道连通至生物填料层的上方,空气泵(14)与菌种及营养元素补充池(13)连通,生物净化系统(4)底部通过管道与吸收液循环池(10)连通,生物净化系统(4)顶部设置有排放口(5),气体管道上设置有控制法兰(15),液体管道上设置有阀门(16),过滤单元(2)通过管道与生物净化系统(4)连接。
8.根据权利要求7所述的装置,其特征在于:吸附/电催化净化系统内设置有吸附/催化复合体层,电极设置在吸附/催化复合体内,从电极上延伸出若干电阻丝均匀分布在吸附/催化复合体内,电极与电源连接,电源为直流电源,电压范围在0.1~10kV,接入电源后通过电压调控保持吸附/电催化净化系统内温度在300~1200℃。
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