CN113101898A - 一种多孔颗粒状分子筛VOCs吸附剂及制备方法 - Google Patents
一种多孔颗粒状分子筛VOCs吸附剂及制备方法 Download PDFInfo
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Abstract
本公开涉及多孔颗粒状分子筛VOCs吸附剂的制备方法,其特征在于,添加HY分子筛粉末:50‑55份;高岭土:5‑10份;造孔剂助剂:1‑3份;造孔剂:1‑3份;通过浸渍‑空气气氛焙烧‑还原气氛焙烧‑氧化气氛焙烧后的CuNiO2/MS金属氧化物,经过浸泡在海藻酸钠和普鲁兰多糖的复合溶液中,利用超声处理10‑15s;本发明的有益效果是:通过浸渍‑空气气氛焙烧‑还原气氛焙烧‑氧化气氛焙烧后的CuNiO2/MS金属氧化物,经过还原处理再氧化处理,具有有较强的还原能力,易于再生;在助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道,避免了气体包裹导致结构应力集中导致吸附剂结构破碎;VOCs吸附剂涂覆有复合膜,通过短时间的微波处理,加强复合膜的阻遏和结合效果。
Description
技术领域:
本发明属于吸附剂技术领域,更具体地涉及一种多孔颗粒状分子筛VOCs吸附剂。
背景技术:
挥发性有机化合物(VOCs)是指在常压下,沸点50℃~260℃的各种有机化合物,VOCs按其化学结构,可以进一步分为:烷类、芳烃类、酯类、醛类和其他等。目前已鉴定出的有300多种。最常见的有苯、甲苯、二甲苯、苯乙烯、三氯乙烯、三氯甲烷、三氯乙烷、二异氰酸酯(TDI)、二异氰甲苯酯等。
在VOCs净化处理技术中,吸附法具有工艺简单、可操作性强、能耗低及安全环保等优势,是目前使用最广泛的VOCs净化方法。活性炭是吸附法净化处理VOCs的传统吸附剂。但是,由于活性炭的孔道结构和表面的吸附官能团性质不均一,使其对VOCs的吸附选择性不高;活性炭在吸附应用中内部毛细孔道结构容易堵塞从而降低吸附能力,再生难以彻底,对VOCs的吸附能力衰减快,使用寿命短,通常几个月(3-6个月)就需要更换新的活性炭;另外,活性炭在吸附净化VOCs的再生过程中由于脱附温度高而存在自燃现象,容易引起燃烧、爆炸等安全问题。
特别是现有的吸附剂在长期储存过程中,由于环境变差,吸附剂活性较强,导致了吸附剂没使用就失效。
发明内容:
为解决上述问题,克服现有技术的不足,本发明提供了一种多孔颗粒状分子筛VOCs吸附剂,能够有效的解决上述问题。
本发明解决上述技术问题的具体技术方案为:一种多孔颗粒状分子筛VOCs吸附剂,其特征在于,采用如下原料:按照质量份数包括:
HY分子筛粉末:50-55份;铝溶胶:5-10份;水:25-30份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;
所述VOCs吸附剂包含用于运送吸附气体的通道,通道由助剂和造孔剂助剂形成,助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道。
所述的造孔助剂为聚乙烯醇纤维丝;所述造孔剂为碳酸氢铵或碳酸铵。
所述的VOCs吸附剂涂覆有复合膜,所述复合膜为普鲁兰多糖和海藻酸钠复合膜。
所述的VOCs吸附剂使用前需要用水浸泡,并利用超声处理大于10min。
一种多孔颗粒状分子筛VOCs吸附剂的制备方法,制备所述的多孔颗粒状分子筛VOCs吸附剂,其特征在于,
(1)将HY分子筛粉末:50-55份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;按上述比例充分混合均匀得到混合料;
(2)将铝溶胶和水加入所得混合料,用制丸机制得颗粒状颗粒;
(3)所得颗粒经干燥、焙烧后得到该多孔颗粒状分子筛VOCs,干燥温度为80℃,干燥时间为12h,焙烧温度为500℃,焙烧时间为5h;冷却后得到分子筛VOCs吸附剂模体,
(4)将分子筛VOCs吸附剂模体采用浸渍法负载铜盐和镍盐,干燥,然后在空气气氛下焙烧,形成脱砷催化剂前驱体-CuO/NiO/MS;
(5)再在H2/N2还原气氛中750-850℃焙烧5-7h;
(6)在氧化气氛中750-850℃氧化5-7h,形成具有CuNiO2/MS金属氧化物固溶体的多孔颗粒状分子筛VOCs吸附剂;
(7)将得到的多孔颗粒状分子筛VOCs吸附剂浸泡在海藻酸钠和普鲁兰多糖的复合溶液中,普鲁兰多糖1.5份,海藻酸钠0.15份,用水补齐至100份,利用超声处理240-360W,超声频率为30-40khz,时间10-15s;
(8)将超声处理的多孔颗粒状分子筛VOCs吸附剂在低温条件下利用真空干燥法干燥处理。
所述的铜盐为硝酸铜,镍盐为硝酸镍。
所述脱砷催化剂前驱体-CuO/NiO/MS中,CuO占脱砷催化剂质量的1-10%,NiO占脱砷催化剂质量的0.5-5%。
所述还原气氛为H2/N2还原气氛;氧化气氛为O2/He氧化气氛。
所述H2/N2还原气氛中H2的体积分数为5%,N2的体积分数为95%;所述O2/He氧化气氛中O2的体积分数为30%,He的体积分数为70%。
本发明的有益效果是:
通过浸渍-空气气氛焙烧-还原气氛焙烧-氧化气氛焙烧后的CuNiO2/MS金属氧化物,经过还原处理再氧化处理,具有有较强的还原能力,能够高效吸附VOCs有机废气,在高温焚烧过程中易于去除,该CuNiO2/MS金属氧化物易于再生;
在助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道,增加了吸附表面积,利用聚乙烯醇纤维丝有效地将造孔剂气体导出,避免了气体包裹导致结构应力集中导致吸附剂结构破碎;
VOCs吸附剂涂覆有复合膜,通过短时间的微波处理,加强复合膜的阻遏和结合效果,避免了VOCs吸附剂长期放置过程中因环境较差导致VOCs吸附剂失效的问题;并通过长时间的微波改变了海藻酸钠和普鲁兰多糖形成复合膜的阻遏效果,解除阻遏并溶于水中,无污染无残留。
具体实施方式:
在本发明的描述中具体细节仅仅是为了能够充分理解本发明的实施例,但是作为本领域的技术人员应该知道本发明的实施并不限于这些细节。另外,公知的结构和功能没有被详细的描述或者展示,以避免模糊了本发明实施例的要点。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。
本发明的具体实施方式:
多孔颗粒状分子筛VOCs吸附剂,其特征在于,采用如下原料:按照质量份数包括:
HY分子筛粉末:50-55份;铝溶胶:5-10份;水:25-30份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;
所述VOCs吸附剂包含用于运送吸附气体的通道,通道由助剂和造孔剂助剂形成,助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道。
所述的造孔助剂为聚乙烯醇纤维丝;所述造孔剂为碳酸氢铵或碳酸铵。
所述的VOCs吸附剂涂覆有复合膜,所述复合膜为普鲁兰多糖和海藻酸钠复合膜。
所述的VOCs吸附剂使用前需要用水浸泡,并利用超声处理大于10min。
一种多孔颗粒状分子筛VOCs吸附剂的制备方法,制备所述的多孔颗粒状分子筛VOCs吸附剂,其特征在于,
(1)将HY分子筛粉末:50-55份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;按上述比例充分混合均匀得到混合料;
(2)将铝溶胶和水加入所得混合料,用制丸机制得颗粒状颗粒;
(3)所得颗粒经干燥、焙烧后得到该多孔颗粒状分子筛VOCs,干燥温度为80℃,干燥时间为12h,焙烧温度为500℃,焙烧时间为5h;冷却后得到分子筛VOCs吸附剂模体,
(4)将分子筛VOCs吸附剂模体采用浸渍法负载铜盐和镍盐,干燥,然后在空气气氛下焙烧,形成脱砷催化剂前驱体-CuO/NiO/MS;
(5)再在H2/N2还原气氛中750-850℃焙烧5-7h;
(6)在氧化气氛中750-850℃氧化5-7h,形成具有CuNiO2/MS金属氧化物
固溶体的多孔颗粒状分子筛VOCs吸附剂;
(7)将得到的多孔颗粒状分子筛VOCs吸附剂浸泡在海藻酸钠和普鲁兰多糖的复合溶液中,普鲁兰多糖1.5份,海藻酸钠0.15份,用水补齐至100份,利用超声处理240-360W,超声频率为30-40khz,时间10-15s;
(8)将超声处理的多孔颗粒状分子筛VOCs吸附剂在低温条件下利用真空干燥法干燥处理。
所述的铜盐为硝酸铜,镍盐为硝酸镍。
所述脱砷催化剂前驱体-CuO/NiO/MS中,CuO占脱砷催化剂质量的1-10%,NiO占脱砷催化剂质量的0.5-5%。
所述还原气氛为H2/N2还原气氛;氧化气氛为O2/He氧化气氛。
所述H2/N2还原气氛中H2的体积分数为5%,N2的体积分数为95%;所述O2/He氧化气氛中O2的体积分数为30%,He的体积分数为70%。
为了更加直观的展现本发明的工艺优势,特以本发明的工艺条件和相同工艺采用等效替换的方法进行对比,
对比例一:
制备方法同实施例,所不同的是:本对比例的制备过程中,将本发明的浸渍-空气气氛焙烧-还原气氛焙烧-氧化气氛焙烧替换成浸渍-空气气氛焙烧;
吸附实验条件如下:填料厚度200mm,填料截面积300mm*300mm,风速2m/s,废气入口浓度300mg/m3,吸附结果见表1。
对比例二:
制备方法同实施例,所不同的是:本对比例的制备过程中,未添加调节剂造孔剂助剂聚乙烯醇纤维丝;
表1:不同工艺条件吸附效率和吸附风阻的测定
吸附剂 | 阻力 | 60min后出口浓度 |
实施例 | 1.17kpa | 13.98mg/m<sup>3</sup> |
对比例1 | 1.19kpa | 32.87mg/m<sup>3</sup> |
对比例2 | 2.21kpa | 17.65mg/m<sup>3</sup> |
由表1数据分析可知:
实施例与对比例1对比可知:本发明通过60min吸附后出口浓度仍然能保持较低的浓度,而对比例1通过60min吸附后出口浓度升高至32.87mg/m3,吸附效率较低;
实施例与对比例2对比可知:本发明和对比例2通过60min吸附后出口浓度都能保持较低的浓度,而对比例2产生的风阻较大,一定程度上影响了吸附效率;
将表1中的各个实施例和对比例的吸附剂吸附20次后,在氧化气氛中750-850℃氧化烧结5-7h,进行再生处理,再按照吸附实验条件如下:填料厚度200mm,填料截面积300mm*300mm,风速2m/s,废气入口浓度300mg/m3,吸附结果见表2:
表2:不同工艺条件再生前后吸附效率和吸附风阻的测定
由表2数据分析可知:
本发明的吸附剂再生前和再生后在吸附阻力和吸附效率上差异性不大,烧结过程中结构稳定不易破碎;
对比例1的吸附剂再生前和再生后的吸附剂在吸附阻力差异性不大,但是吸附效率上差异性较大,烧结过程中结构稳定不易破碎,这主要是由于没有经过还原处理再氧化处理,不具有有较强的还原能力,吸附VOCs废气效率较低,且没有经过还原处理再氧化处理CuNiO2/MS金属氧化物不易于再生,再生后的吸附效率更低。
对比例2的吸附剂再生前和再生后在吸附阻力和吸附效率上差异性不大,烧结过程中结构不稳定易破碎;这可能是由于本发明采用了助剂和造孔剂助剂,在热分解过程后留下用于运送吸附气体的通道,具有宏观尺度上的中空孔道和发达的孔隙结构,能有效吸附VOCs和降低阻力,利用聚乙烯醇纤维丝有效地将造孔剂气体导出,避免了气体包裹导致结构应力集中导致吸附剂结构破碎;
为了更加直观的展现本发明的涂覆复合膜的工艺优势,特以本发明的工艺条件和相同工艺采用等效替换的方法进行对比,
对比例三:
制备方法同实施例,所不同的是:本对比例的制备过程中,VOCs吸附剂未涂覆有复合膜;
对比例四:
制备方法同实施例三,所不同的是:本对比例的制备过程中,VOCs吸附剂涂覆复合膜时,超声时间10-15s替换成10min;
对比例五:
制备方法同实施例三,所不同的是:本对比例的制备过程中,VOCs吸附剂涂覆复合膜时,取消超声处理;
在含有VOCs废气环境中放置2个月,用水浸泡,并利用超声激活处理,低温晾干,并设置对照组即放置在洁净空气中放置2个月,用水浸泡,并利用超声激活处理,低温晾干,再按照吸附实验条件如下:填料厚度200mm,填料截面积300mm*300mm,风速2m/s,废气入口浓度300mg/m3,吸附结果见表3:
表3:不同工艺条件涂膜对吸附效率测定
(1)其中对比例3、对比例4、对比例5和本发明的实施例对比可知:对比例3、对比例4、对比例5的对照组浓度均低于实验组的浓度,而本发明的实验组和对照组的差异性不大;
这充分说明了本发明的涂膜工艺优于对比例3和对比例4;
(2)其中对比例3的实验组出口浓度远远大于本发明的出口浓度,这可能是由于对比例3中没有采用涂膜工艺,导致了空气中的VOCs废气被吸附剂吸附,失去活性,当未采用再生处理进行使用时,吸附能力极差;
(3)对比例4的出口浓度优于对比例3的实验组出口浓度,这充分说明了涂膜能够有效地抑制空气中的VOCs废气与吸附剂的接触;
(4)本发明的实施例优于对比例4的出口浓度、对比例4的出口浓度低于对比例5的出口浓度;这说明了通过短时间的微波处理,能够加强复合膜的阻遏和结合效果;
也说明了长时间的微波处理不仅不会加强复合膜的阻遏和结合效果,反而会导致复合膜结构的变化,影响了阻遏和结合效果,导致了空气中的部分的VOCs废气被吸附剂吸附,活性有所降低。
综上所述:
(1)本发明通过浸渍-空气气氛焙烧-还原气氛焙烧-氧化气氛焙烧后的CuNiO2/MS金属氧化物,经过还原处理再氧化处理,具有有较强的还原能力,能够高效吸附VOCs废气,在高温焚烧过程中易于去除,该CuNiO2/MS金属氧化物易于再生;
(2)在助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道,增加了吸附表面积,利用聚乙烯醇纤维丝有效地将造孔剂气体导出,避免了气体包裹导致结构应力集中导致吸附剂结构破碎;
(3)VOCs吸附剂涂覆有复合膜,通过短时间的微波处理,加强复合膜的阻遏和结合效果,避免了VOCs吸附剂长期放置过程中因环境较差导致VOCs吸附剂失效的问题;并通过长时间的微波改变了海藻酸钠和普鲁兰多糖复合膜的阻遏效果,解除阻遏并溶于水中,无污染无残留。
Claims (9)
1.一种多孔颗粒状分子筛VOCs吸附剂,其特征在于,采用如下原料:按照质量份数包括:
HY分子筛粉末:50-55份;铝溶胶:5-10份;水:25-30份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;
所述VOCs吸附剂包含用于运送吸附气体的通道,通道由助剂和造孔剂助剂形成,助剂和造孔剂助剂在热分解过程后留下用于运送吸附气体的通道。
2.根据权利要求1所述的蜂窝状复合吸附剂,其特征在于所述的造孔助剂为聚乙烯醇纤维丝;所述造孔剂为碳酸氢铵或碳酸铵。
3.根据权利要求2所述的蜂窝状复合吸附剂,其特征在于所述的VOCs吸附剂涂覆有复合膜,所述复合膜为普鲁兰多糖和海藻酸钠复合膜。
4.根据权利要求3所述的蜂窝状复合吸附剂,其特征在于所述的VOCs吸附剂使用前需要用水浸泡,并利用超声处理大于10min。
5.一种多孔颗粒状分子筛VOCs吸附剂的制备方法,制备权利要求3或4所述的多孔颗粒状分子筛VOCs吸附剂,其特征在于,
(1)将HY分子筛粉末:50-55份;高岭土:5-10份;造孔剂助剂:1-3份;造孔剂:1-3份;按上述比例充分混合均匀得到混合料;
(2)将铝溶胶和水加入所得混合料,用制丸机制得颗粒状颗粒;
(3)所得颗粒经干燥、焙烧后得到该多孔颗粒状分子筛VOCs,干燥温度为80℃,干燥时间为12h,焙烧温度为500℃,焙烧时间为5h;冷却后得到分子筛VOCs吸附剂模体,
(4)将分子筛VOCs吸附剂模体采用浸渍法负载铜盐和镍盐,干燥,然后在空气气氛下焙烧,形成脱砷催化剂前驱体-CuO/NiO/MS;
(5)再在H2/N2还原气氛中750-850℃焙烧5-7h;
(6)在氧化气氛中750-850℃氧化5-7h,形成具有CuNiO2/MS金属氧化物
固溶体的多孔颗粒状分子筛VOCs吸附剂;
(7)将得到的多孔颗粒状分子筛VOCs吸附剂浸泡在海藻酸钠和普鲁兰多糖的复合溶液中,普鲁兰多糖1.5份,海藻酸钠0.15份,用水补齐至100份,利用超声处理240-360W,超声频率为30-40khz,时间10-15s;
(8)将超声处理的多孔颗粒状分子筛VOCs吸附剂在低温条件下利用真空干燥法干燥处理。
6.根据权利要求5所述的多孔颗粒状分子筛VOCs吸附剂的制备方法,其特征在于所述的铜盐为硝酸铜,镍盐为硝酸镍。
7.根据权利要求5所述的多孔颗粒状分子筛VOCs吸附剂的制备方法,其特征在于所述脱砷催化剂前驱体-CuO/NiO/MS中,CuO占脱砷催化剂质量的1-10%,NiO占脱砷催化剂质量的0.5-5%。
8.根据权利要求5所述的多孔颗粒状分子筛VOCs吸附剂的制备方法,其特征在于所述还原气氛为H2/N2还原气氛;氧化气氛为O2/He氧化气氛。
9.根据权利要求8所述的多孔颗粒状分子筛VOCs吸附剂的制备方法,其特征在于所述H2/N2还原气氛中H2的体积分数为5%,N2的体积分数为95%;所述O2/He氧化气氛中O2的体积分数为30%,He的体积分数为70%。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113368813A (zh) * | 2021-07-28 | 2021-09-10 | 山东亮剑环保新材料有限公司 | 一种利用赤泥制备蜂窝状分子筛吸附剂的方法 |
CN114260017A (zh) * | 2021-12-27 | 2022-04-01 | 山东亮剑环保新材料有限公司 | 一种催化燃烧VOCs的复合金属催化剂及其制备方法 |
CN114345400A (zh) * | 2021-11-24 | 2022-04-15 | 中国科学院大连化学物理研究所 | 一种过渡金属-分子筛催化剂及改性方法和应用 |
CN115007166A (zh) * | 2022-06-23 | 2022-09-06 | 山东亮剑环保新材料有限公司 | 一种颗粒状催化燃烧co催化剂的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001046878A (ja) * | 1999-06-04 | 2001-02-20 | Ne Chemcat Corp | ガス処理剤及びその製造方法並びにガス精製方法、ガス精製器及びガス精製装置 |
CN102372305A (zh) * | 2010-08-13 | 2012-03-14 | 范晓星 | 介孔钨酸盐光催化材料及其制备方法 |
US20180193790A1 (en) * | 2015-08-19 | 2018-07-12 | Nanjing University | Method for improving adsorption capability of fixed bed and application method thereof in organic waste gas treatment |
CN111408351A (zh) * | 2020-03-13 | 2020-07-14 | 山东亮剑环保新材料有限公司 | 一种稀土吸附剂的生产方法 |
CN111672533A (zh) * | 2020-06-28 | 2020-09-18 | 北京化工大学 | 一种脱砷催化剂及其制备方法 |
CN112337431A (zh) * | 2020-10-21 | 2021-02-09 | 萍乡市捷龙环保科技有限公司 | 一种高效苯系VOCs气体吸附分子筛及制备方法 |
-
2021
- 2021-04-16 CN CN202110409805.1A patent/CN113101898A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001046878A (ja) * | 1999-06-04 | 2001-02-20 | Ne Chemcat Corp | ガス処理剤及びその製造方法並びにガス精製方法、ガス精製器及びガス精製装置 |
CN102372305A (zh) * | 2010-08-13 | 2012-03-14 | 范晓星 | 介孔钨酸盐光催化材料及其制备方法 |
US20180193790A1 (en) * | 2015-08-19 | 2018-07-12 | Nanjing University | Method for improving adsorption capability of fixed bed and application method thereof in organic waste gas treatment |
CN111408351A (zh) * | 2020-03-13 | 2020-07-14 | 山东亮剑环保新材料有限公司 | 一种稀土吸附剂的生产方法 |
CN111672533A (zh) * | 2020-06-28 | 2020-09-18 | 北京化工大学 | 一种脱砷催化剂及其制备方法 |
CN112337431A (zh) * | 2020-10-21 | 2021-02-09 | 萍乡市捷龙环保科技有限公司 | 一种高效苯系VOCs气体吸附分子筛及制备方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113368813A (zh) * | 2021-07-28 | 2021-09-10 | 山东亮剑环保新材料有限公司 | 一种利用赤泥制备蜂窝状分子筛吸附剂的方法 |
CN114345400A (zh) * | 2021-11-24 | 2022-04-15 | 中国科学院大连化学物理研究所 | 一种过渡金属-分子筛催化剂及改性方法和应用 |
CN114345400B (zh) * | 2021-11-24 | 2023-03-14 | 中国科学院大连化学物理研究所 | 一种过渡金属-分子筛催化剂及改性方法和应用 |
CN114260017A (zh) * | 2021-12-27 | 2022-04-01 | 山东亮剑环保新材料有限公司 | 一种催化燃烧VOCs的复合金属催化剂及其制备方法 |
CN115007166A (zh) * | 2022-06-23 | 2022-09-06 | 山东亮剑环保新材料有限公司 | 一种颗粒状催化燃烧co催化剂的制备方法 |
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