CN113019313A - 一种用于燃烧中pm2.5脱除的复合吸附剂及其应用 - Google Patents
一种用于燃烧中pm2.5脱除的复合吸附剂及其应用 Download PDFInfo
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Abstract
本发明属于燃烧污染物处理相关技术领域,其公开了一种用于燃烧中PM2.5脱除的复合吸附剂及其应用,所述复合吸附剂包括硅铝基吸附剂和钙基吸附剂的混合物,其中,所述硅铝基吸附剂和钙基吸附剂的质量比为1∶9~9∶1,在燃烧的高温条件下,燃料中原子态无机质及易挥发重金属气化与所述复合吸附剂接触发生气固反应进而将所述无机质和重金属固化在所述复合吸附剂中,同时,所述硅铝基吸附剂和钙基吸附剂在高温下反应形成Si‑Al‑Ca共熔体熔融表面,PM2.5颗粒通过碰撞粘附于所述熔融表面实现PM2.5的捕集脱除。本申请的复合吸附剂可以通过气固反应以及生成的熔融表面,显著减少PM2.5的释放。
Description
技术领域
本发明属于燃烧污染物处理相关技术领域,更具体地,涉及一种用于燃烧中PM2.5脱除的复合吸附剂及其应用。
背景技术
固体燃料主要包括煤、生物质、城市生活垃圾和工业垃圾等,其燃烧会产生大量的污染物,例如,颗粒物、硫、氯以及重金属等,影响设备的运行,其排放到大气中将造成严重的大气污染,危害人体健康。
目前,固体燃料燃烧污染物控制主要通过在燃烧后端布置污染物脱除装置,例如,选择性催化还原脱硝设备、低温省煤器、静电除尘器、脱硫塔和湿式电除尘等,以上污染物脱除设备以单一污染物脱除为目标,且设备复杂、运行成本高。除尘器虽然对PM10脱除效率较高,但对PM2.5的脱除存在“穿透窗口”,脱除效率低,因此,强化对燃烧源PM2.5的脱除变得尤为重要。
燃烧固体燃料产生的污染物主要以气态污染物和固态污染物为主,气态污染物主要以PM2.5前躯体Na、K、S、Cl和有害易挥发的重金属为主,固体污染物主要以破碎为主的PM2.5、燃烧过程中由前驱体形成的PM2.5。目前,对燃料过程中PM2.5的脱除主要还是以单一吸附剂为主,单一吸附剂技术主要存在以下问题:1)单一吸附剂通过单一机理对污染物实现脱除,难以实现协同脱除,如高岭土通过捕获颗粒物前驱体Na、K实现颗粒物的脱除,石灰石通过钙硫反应脱除硫化物等,以上吸附剂对PM1都有较好的脱除效果,但对PM2.5效果较差;2)缺乏固体燃料种类适应性,高岭土实现对PM2.5的脱除仅对高碱燃料作用效果明显,石灰石仅对高硫燃料效果明显;3)吸附剂成本及制备工序难以工业化制约其发展,目前脱除效果较好的吸附剂成本较高,如镁基吸附剂和钛基吸附剂,而其他化学改性吸附剂制备工艺复杂,且难以实现燃烧过程中多污染物的脱除。现有的复合吸附剂仅仅针对燃煤PM2.5进行脱除且脱除效率较低,未见有同时对颗粒物、硫、氯及重金属的多污染物脱除且实现对不同固体燃料的适应性。因此,亟需设计一种制备简单、脱除效率高、脱除种类多、脱除成本低的PM2.5脱除吸附剂。
发明内容
针对现有技术的以上缺陷或改进需求,本发明提供了一种用于燃烧中PM2.5脱除的复合吸附剂及其应用,以解决现有的吸附剂脱除种类单一,脱除成本高,制备复杂的技术问题。
为实现上述目的,按照本发明的一个方面,提供了一种用于燃烧中PM2.5脱除的复合吸附剂,其特征在于,所述复合吸附剂包括硅铝基吸附剂和钙基吸附剂的混合物,其中,所述硅铝基吸附剂和钙基吸附剂的质量比为1∶9~9∶1,在燃烧的高温条件下,燃料中原子态无机质及易挥发重金属气化与所述复合吸附剂接触发生气固反应进而将所述无机质和重金属固化在所述复合吸附剂中,同时,所述硅铝基吸附剂和钙基吸附剂在高温下反应形成Si-Al-Ca共熔体熔融表面,PM2.5颗粒通过碰撞粘附于所述熔融表面实现PM2.5的捕集脱除。
优选地,所述硅铝基吸附剂包括高岭土、沸石、蛭石、蒙脱石、铝土矿、硅藻土、凹凸棒石、长石、云母、硅灰石、或石榴石中的一种或多种混合物。
优选地,所述钙基吸附剂包括石灰石、生石灰、白云石、石膏、磷灰石、钙长石、钙黄长石、氢氧化钙、碳酸钙、硫酸钙、醋酸钙、氯化钙中的一种或多种混合物。
本申请另一方面提供了一种上述的用于燃烧中PM2.5脱除的复合吸附剂的应用,将所述复合吸附剂与固体燃料均匀混合。
优选地,所述固体燃料为煤、生物质、生活垃圾或工业垃圾中的一种或多种。
优选地,当所述固体燃料中灰分中钠、钾含量之和大于5%时且硫、氯、磷含量之和小于10%时,所述硅铝基吸附剂和钙基吸附剂比例为6∶4~9∶1;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为1∶9~4∶6;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和小于10%,或钠、钾含量之和大于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为4∶6~6∶4。
优选地,所述复合吸附剂与固体燃料均匀混合后还包括压块成型,混合后所述复合吸附剂的质量分数为1%~20%。
总体而言,通过本发明所构思的以上技术方案与现有技术相比,本发明提供的用于燃烧中PM2.5脱除的复合吸附剂及其应用具有如下有益效果:
1.本申请利用硅铝基吸附剂和钙基吸附剂形成复合吸附剂对固体燃料燃烧源污染物进行脱除,一方面可以通过气固反应吸附颗粒物前驱体Na、K、S、Cl和易挥发的重金属等,将气态污染物固化在复合吸附剂中,从而减少其排放;另一方面,高温下硅铝基吸附剂和钙基吸附剂发生化学反应生成Si-Al-Ca共熔体提供熔融表面,PM2.5颗粒之间的碰撞在熔融表面团聚,实现PM2.5向PM2.5+的迁移,减少PM2.5的释放。
2.本申请中硅铝基吸附剂和钙基吸附剂质量比范围为1∶9~9∶1,可以针对不同的固体燃料选择不同的质量比,本申请中的复合吸附剂不仅适用于煤,还可以用于生活垃圾、工业垃圾等的燃烧污染物的脱除,显著提高了复合吸附剂对固体燃料生成污染物的适用性,适用范围广。
3.本申请中的硅铝基吸附剂和钙基吸附剂均为廉价易得的原料,制作成本低,制作工艺简单。
附图说明
图1示意性示出了本实施例的复合吸附剂制备添加流程图;
图2示意性示出了本实施例的复合吸附剂高温下熔融SEM图;
图3示意性示出了本实施的PM2.5脱除效率。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明提供了一种用于燃烧中PM2.5脱除的复合吸附剂,所述复合吸附剂包括硅铝基吸附剂和钙基吸附剂的混合物,其中,所述硅铝基吸附剂和钙基吸附剂的质量比为1∶9~9∶1,在燃烧的高温条件下,燃料中原子态无机质与易挥发重金属气化与所述复合吸附剂接触发生气固反应进而将所述无机质和重金属固化在所述复合吸附剂中,同时,所述硅铝基吸附剂和钙基吸附剂在高温下反应形成Si-Al-Ca共熔体熔融表面(如图2所示),PM2.5颗粒通过碰撞粘附于所述熔融表面实现PM2.5的捕集脱除。
本实施例中,硅铝基吸附剂包括高岭土、沸石、蛭石、蒙脱石、铝土矿、硅藻土、凹凸棒石、长石、云母、硅灰石、或石榴石中的一种或多种混合物。钙基吸附剂包括石灰石、生石灰、白云石、石膏、磷灰石、钙长石、钙黄长石、氢氧化钙、碳酸钙、硫酸钙、醋酸钙、氯化钙中的一种或多种混合物。
本申请另一方面还提供了一种上述用于燃烧中PM2.5脱除的复合吸附剂的应用,如图1所示,将该复合吸附剂与固体燃料均匀混合,混合后所述复合吸附剂的质量分数为1%~20%。固体燃料可以为煤、生物质、生活垃圾、工业垃圾等。
在应用过程中首先将复合吸附剂与固体燃料进行研磨、筛分、压块或成型等预处理使得复合吸附剂与固体燃料均匀混合。将预处理后的混合物放入燃烧炉、电站锅炉、流化床锅炉、回转窑、链条炉排等固体燃料燃烧设备中进行燃烧。
其中,,当所述固体燃料中灰分中钠、钾含量之和大于5%时且硫、氯、磷含量之和小于10%时,所述硅铝基吸附剂和钙基吸附剂比例为6∶4~9∶1,对于该高碱金属固体燃料,复合吸附剂以硅铝基吸附剂为主,混配钙基吸附剂,以优化硅铝基吸附剂对碱金属的吸附,从而减少PM2.5的生成,同时吸附重金属,配比钙基吸附剂,以吸附硫、氯等物质,同时硅铝基吸附剂和钙基吸附剂生成Si-Al-Ca共熔体可以提供熔融表面,通过颗粒碰撞减少PM2.5的生成;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为1∶9~4∶6,对于该高硫氯的固体燃料,复合吸附剂以钙基吸附剂为主,混配硅铝基吸附剂,增强复合吸附剂对硫氯的脱除,同时实现对重金属的脱除,并提供熔融表面减少PM2.5的生成;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和小于10%,或钠、钾含量之和大于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为4∶6~6∶4,针对该低碱金属低硫氯或高碱金属高硫氯的固体燃料,通过混合硅铝基吸附剂和钙基吸附剂形成复合吸附剂使熔融表面增加,降低以破碎为主的PM2.5的生成,同时硅铝基吸附剂和钙基吸附剂提供对重金属和硫、氯的脱除。通过以上定向调配原则,实现复合吸附剂对固体燃料燃烧污染物的普适性,使得不同固体燃料均可以达到较高的脱除效率。
实施例1
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按5∶5混合制备复合吸附剂。
将复合吸附剂按煤基质量的3%添加到固体燃料煤中,煤粉粒径小于100μm,随后送入沉降炉中进行燃烧实验,燃烧温度为1300℃,空气气氛;
燃烧后利用低压撞击器(DLPI)收集燃烧后的颗粒物,得到PM2.5生成浓度;
将上述收集到的PM2.5进行微波消解,水洗得到待测溶液,使用ICP-MS测定消解液中元素浓度,用IC测定水洗液中阴离子浓度。
通过以上分析,与未进行吸附处理的对照组相比,本实验中的复合吸附剂可以将PM2.5的质量浓度减少39.39%。
实施例2
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按7∶3混合制备复合吸附剂。
将复合吸附剂按煤基质量的3%添加到固体燃料煤中,煤粉粒径小于100μm,随后送入沉降炉中进行燃烧实验,燃烧温度为1300℃,空气气氛;
燃烧后利用低压撞击器(DLPI)收集燃烧后的颗粒物,得到PM2.5生成浓度;
将上述收集到的PM2.5进行微波消解,水洗得到待测溶液,使用ICP-MS测定消解液中元素浓度,用IC测定水洗液中阴离子浓度。
通过以上分析,与未进行吸附处理的对照组相比,本实验中的复合吸附剂可以将PM2.5的质量浓度减少24.76%。
实施例3
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按1∶9混合制备复合吸附剂。
将复合吸附剂按煤基质量的3%添加到固体燃料煤中,煤粉粒径小于100μm,随后送入沉降炉中进行燃烧实验,燃烧温度为1300℃,空气气氛;
燃烧后利用低压撞击器(DLPI)收集燃烧后的颗粒物,得到PM2.5生成浓度;
将上述收集到的PM2.5进行微波消解,水洗得到待测溶液,使用ICP-MS测定消解液中元素浓度,用IC测定水洗液中阴离子浓度。
通过以上分析,与未进行吸附处理的对照组相比,本实验中的复合吸附剂可以将PM2.5的质量浓度减少16.52%。
实施例4
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按9∶1混合制备复合吸附剂。
将复合吸附剂按煤基质量的3%添加到固体燃料煤中,煤粉粒径小于100μm,随后送入沉降炉中进行燃烧实验,燃烧温度为1300℃,空气气氛;
燃烧后利用低压撞击器(DLPI)收集燃烧后的颗粒物,得到PM2.5生成浓度;
将上述收集到的PM2.5进行微波消解,水洗得到待测溶液,使用ICP-MS测定消解液中元素浓度,用IC测定水洗液中阴离子浓度。
通过以上分析,与未进行吸附处理的对照组相比,本实验中的复合吸附剂可以将PM2.5的质量浓度减少19.58%。
实施例5
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按以下表1中的比例制备混合制备复合吸附剂,将该复合吸附剂加入到灰成分中钠含量为7.73%、钾含量为0.81%、硫含量为6.54%、氯含量为1.63%的煤中。
表1
实施例6
本实施例中选取高岭土作为硅铝基吸附剂,选取石灰石作为钙基吸附剂,将高岭土和石灰石按以下表2中的比例制备混合制备复合吸附剂,将该复合吸附剂以燃料质量3%加入到灰成分中钠含量为4.19%、钾含量为0.28%、硫含量为27.46%、氯含量为1.80%的煤中。
高岭土和石灰石比例 | 1∶9 | 3∶7 | 4∶6 |
PM<sub>2.5</sub>脱除效率 | 33.46% | 27.58% | 24.21% |
单一吸附剂高岭土PM<sub>2.5</sub>脱除效率 | 8.23% | ||
单一吸附剂石灰石PM<sub>2.5</sub>脱除效率 | 23.36% |
表2
实施例7
本实施例中选取高岭土作为硅铝基吸附剂;选取石灰石作为钙基吸附剂,将高岭土和石灰石按以下表3中的比例制备混合制备复合吸附剂,将该复合吸附剂以燃料质量3%加入到灰成分中钠含量为0.99%、钾含量为1.50%、硫含量为7.26%、氯含量为0.26%的煤中。
高岭土和石灰石比例 | 4∶6 | 5∶5 | 6∶4 |
PM<sub>2.5</sub>脱除效率 | 29.49% | 39.39% | 37.27% |
单一吸附剂高岭土PM<sub>2.5</sub>脱除效率 | 21.37% | ||
单一吸附剂石灰石PM<sub>2.5</sub>脱除效率 | 15.28% |
表3
综上可知,如图3及表1~表3所示,本申请的复合吸附剂可以显著降低燃料燃烧后PM2.5的排放,主要原因是本申请的复合吸附剂一方面可以通过气固反应吸附颗粒物前驱体Na、K、S、Cl和易挥发的重金属等,将气态污染物固化在复合吸附剂中,从而减少其排放;另一方面,高温下硅铝基吸附剂和钙基吸附剂发生化学反应生成Si-Al-Ca共熔体提供熔融表面,PM2.5颗粒之间的碰撞在熔融表面团聚,实现PM2.5向PM2.5+的迁移,减少PM2.5的释放。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种用于燃烧中PM2.5脱除的复合吸附剂,其特征在于,所述复合吸附剂包括硅铝基吸附剂和钙基吸附剂的混合物,其中,所述硅铝基吸附剂和钙基吸附剂的质量比为1∶9~9∶1,在燃烧的高温条件下,燃料中原子态无机质及易挥发重金属气化与所述复合吸附剂接触发生气固反应进而将所述无机质和重金属固化在所述复合吸附剂中,同时,所述硅铝基吸附剂和钙基吸附剂在高温下反应形成Si-Al-Ca共熔体熔融表面,PM2.5颗粒通过碰撞粘附于所述熔融表面实现PM2.5的捕集脱除。
2.根据权利要求1所述的复合吸附剂,其特征在于,所述硅铝基吸附剂包括高岭土、沸石、蛭石、蒙脱石、铝土矿、硅藻土、凹凸棒石、长石、云母、硅灰石、石榴石中的一种或多种混合物。
3.根据权利要求1所述的复合吸附剂,其特征在于,所述钙基吸附剂包括石灰石、生石灰、白云石、石膏、磷灰石、钙长石、钙黄长石、氢氧化钙、碳酸钙、硫酸钙、醋酸钙、氯化钙中的一种或多种混合物。
4.一种权利要求1~3任意一项所述的用于燃烧中PM2.5脱除的复合吸附剂的应用,其特征在于,将所述复合吸附剂与固体燃料均匀混合,以用于固体燃料燃烧中PM2.5的脱除。
5.根据权利要求4所述的应用,其特征在于,所述固体燃料为煤、生物质、生活垃圾、工业垃圾中的一种或多种。
6.根据权利要求4所述的应用,其特征在于,当所述固体燃料中灰分中钠、钾含量之和大于5%时且硫、氯、磷含量之和小于10%时,所述硅铝基吸附剂和钙基吸附剂比例为6∶4~9∶1;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为1∶9~4∶6;当所述固体燃料中灰分中钠、钾含量之和小于5%且硫、氯、磷含量之和小于10%,或钠、钾含量之和大于5%且硫、氯、磷含量之和大于10%时,所述硅铝基吸附剂和钙基吸附剂比例为4∶6~6∶4。
7.根据权利要求4所述的应用,其特征在于,所述复合吸附剂与固体燃料均匀混合后还包括压块成型,混合后所述复合吸附剂的质量分数为1%~20%。
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