CN115569666A - 一种高疏水性VOCs吸附催化剂 - Google Patents
一种高疏水性VOCs吸附催化剂 Download PDFInfo
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明公开了一种高疏水性VOCs吸附催化剂,涉及VOCs吸附处理和分子筛技术领域;由脱硅改性ZSM‑5分子筛和改性Y分子筛按照质量比10:5~40混合组成;本发明的高疏水性VOCs吸附催化剂,由高硅铝比的脱硅改性ZSM‑5分子筛和改性Y分子筛按照比例混合得到;高硅的ZSM‑5分子筛采用碱液和酸液交替处理,可以有效增加ZSM‑5分子筛的比表面积,增加孔容量和介孔体积,因而大幅度提高ZSM‑5分子筛对大分子VOCs的吸附能力;在高湿环境下对VOCs的吸附催化效果优异,避免了单一分子筛对某类VOCs分子的吸附能力差,提高了对VOCs分子的吸附能力和吸附饱和量。
Description
技术领域
本发明涉及VOCs吸附处理和分子筛技术领域,具体说是一种高疏水性VOCs吸附催化剂。
背景技术
挥发性有机化合物VOCs通常是易挥发性有机化合物,主要包括脂肪烃类、卤代烃类、芳香烃类、醇类、醛类、酯类、醚类、酮类、羧酸类、胺类以及含硫有机化合物等。VOCs主要来源于工业排放的废气以及交通工具所排放的废气。VOCs排入大气中后,有的会在太阳光的照射下,与氮氧化物(NOx)发生光化学反应,形成光化学烟雾,产生更严重的污染危害。除此之外,VOCs还直接危害人体健康,人体吸入芳香烃后,中枢神经受损,造成神经系统障碍,危及血液和造血器官,严重时还会有出血症状或感染败血症。因此,控制VOCs的排放具有重大意义。
中国专利CN108786719A公开了一种用于吸附VOCs材料及其制备方法。吸附材料由分子筛吸附剂和催化剂组成,分子筛吸附剂为ZSM-5/USY混合分子筛,催化剂为Pt/BN和CeO2-ZrO2混合物,制得的吸附材料,吸附量大,且在脱附过程中不发生积炭,易再生。
工业废气中VOCs的特点是风量大、浓度低、湿度大,因此对VOCs吸附催化剂的性能提出了更高的要求,中国专利CN110302830A公开了一种高湿度环境下的VOCs净化用分子筛基催化剂及其制备方法与应用。将分子筛浸渍与贵金属化合物水溶液中,分散处理后陈化,得到混合液;然后去除混合液中的水,得到固体物;然后煅烧固体物,得到高湿度环境下的VOCs净化用分子筛基催化剂。该催化剂VOCs吸附能力和抗湿性能优异,在高湿度条件下,室内VOCs催化速率依然很高,但是在制备过程中添加了贵金属物质或价格昂贵的催化剂,导致成本较高,不利于工业推广生产。
因此,目前亟待研发一种针对大风量、低浓度、湿度高工业废气VOCs的吸附催化剂,不仅吸附催化效果优异,而且制备过程易于操作,成本低廉,便于市场推广。
发明内容
为解决针对大风量、低浓度、湿度高工业废气VOCs的吸附催化剂的吸附催化效果差,制备过程中操作复杂,成本高,不利于市场推广的问题,本发明的目的是提供一种高疏水性VOCs吸附催化剂,在高湿度的环境下吸附催化效果优异,并且制备过程易于操作,成本低廉,便于市场推广。
本发明为实现上述目的,通过以下技术方案实现:
一种高疏水性VOCs吸附催化剂,由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:5~40混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将ZSM-5分子筛加入碱液中,在40~80℃下浸泡2~3小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入酸液中,在60~80℃下浸泡4~5小时,过滤,洗涤,在100~120℃下干燥,得到脱硅改性ZSM-5分子筛;所述ZSM-5分子筛的硅铝比为200~300;
ZSM-5分子筛、碱液和酸液的质量比为1:10~20:10~20;
所述碱液为摩尔浓度为1~3mol/L的氢氧化钠或氢氧化钾水溶液;
所述酸液为摩尔浓度为1~3mol/L的盐酸、磷酸或草酸;
所述改性Y分子筛按照以下步骤得到:
将Y分子筛、硅烷化试剂、促进剂和甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入钛酸四丁酯,搅拌1~2小时,然后在压力0.2~0.5MPa、温度50~60℃下反应2~3小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比大于5;
所述硅烷化试剂为三甲基氯硅烷、叔丁基二甲基氯硅烷或二叔丁基二氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比2~5:1混合组成;
其中Y分子筛、硅烷化试剂、促进剂、甲苯和钛酸四丁酯的质量比为1:0.2~0.5:0.01~0.05:8~12:0.1~0.2。
优选的,所述碱液为摩尔浓度为2mol/L的氢氧化钠水溶液。
优选的,所述酸液为摩尔浓度为2mol/L的磷酸。
优选的,所述硅烷化试剂为三甲基氯硅烷。
优选的,由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:35混合组成。
优选的,所述ZSM-5分子筛的硅铝比为300。
本发明相比现有技术具有以下优点:
本发明的高疏水性VOCs吸附催化剂,由高硅铝比的脱硅改性ZSM-5分子筛和改性Y分子筛按照比例混合得到。在高湿环境下对VOCs的吸附催化效果优异,避免了单一分子筛对某类VOCs分子的吸附能力差,提高了对VOCs分子的吸附能力和吸附饱和量。
本发明的高疏水性VOCs吸附催化剂,一方面,高硅的ZSM-5分子筛的疏水性较强,但是ZSM-5分子筛的孔径较小,对大分子VOCs的吸附较弱,采用碱液和酸液交替处理,可以有效增加ZSM-5分子筛的比表面积,增加孔容量和介孔体积,因而大幅度提高ZSM-5分子筛对大分子VOCs的吸附能力;另一方面,Y分子筛的孔径较大,但是硅铝比较低,疏水性差,无法用于高湿环境下对VOCs吸附催化反应;采用本技术处理后得到的Y分子筛可以对其表面和内部孔径进行硅烷化处理,并且钛酸四丁酯水解会产生二氧化钛,并且在骨架中引入了Ti-O键,提高了Y分子筛的结晶度,增强了Y分子筛在高湿环境下的结构稳定性,并且部分二氧化钛也会附着在Y分子筛的内部,提高Y分子筛的比表面积。
具体实施方式
本发明的目的是提供一种高疏水性VOCs吸附催化剂,通过以下技术方案实现:
一种高疏水性VOCs吸附催化剂,由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:5~40混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将ZSM-5分子筛加入碱液中,在40~80℃下浸泡2~3小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入酸液中,在60~80℃下浸泡4~5小时,过滤,洗涤,在100~120℃下干燥,得到脱硅改性ZSM-5分子筛;所述ZSM-5分子筛的硅铝比为200~300;
ZSM-5分子筛、碱液和酸液的质量比为1:10~20:10~20;
所述碱液为摩尔浓度为1~3mol/L的氢氧化钠或氢氧化钾水溶液;
所述酸液为摩尔浓度为1~3mol/L的盐酸、磷酸或草酸;
所述改性Y分子筛按照以下步骤得到:
将Y分子筛、硅烷化试剂、促进剂和甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入钛酸四丁酯,搅拌1~2小时,然后在压力0.2~0.5MPa、温度50~60℃下反应2~3小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比大于5;
所述硅烷化试剂为三甲基氯硅烷、叔丁基二甲基氯硅烷或二叔丁基二氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比2~5:1混合组成;
其中Y分子筛、硅烷化试剂、促进剂、甲苯和钛酸四丁酯的质量比为1:0.2~0.5:0.01~0.05:8~12:0.1~0.2。
优选的,所述碱液为摩尔浓度为2mol/L的氢氧化钠水溶液。
优选的,所述酸液为摩尔浓度为2mol/L的磷酸。
优选的,所述硅烷化试剂为三甲基氯硅烷。
优选的,由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:35混合组成。
优选的,所述ZSM-5分子筛的硅铝比为300。
以下结合具体实施例来对本发明作进一步的描述。
本发明实施例中使用的Y分子筛为自产的硅铝比大于5的Y分子筛原粉,结晶度大于90%;也可采用市售的硅铝比大于5的Y分子筛,也能够起到同样效果。
本发明的硅铝比为二氧化硅和氧化铝的摩尔比。
实施例1
一种高疏水性VOCs吸附催化剂,由1kg脱硅改性ZSM-5分子筛和0.5kg改性Y分子筛混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将1kg硅铝比为200的ZSM-5分子筛加入10kg摩尔浓度1mol/L的氢氧化钠水溶液中,在80℃下浸泡2小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入10kg摩尔浓度为1mol/L的盐酸酸液中,在60℃下浸泡4小时,过滤,洗涤,在100℃下干燥,得到脱硅改性ZSM-5分子筛;
所述改性Y分子筛按照以下步骤得到:
将1kgY分子筛、0.2kg硅烷化试剂、0.01kg促进剂和8kg甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入0.1kg钛酸四丁酯,搅拌1小时,然后在压力0.2MPa、温度50℃下反应2小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比为5.2;
所述硅烷化试剂为三甲基氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比2:1混合组成。
实施例2
一种高疏水性VOCs吸附催化剂,由1kg脱硅改性ZSM-5分子筛和4kg改性Y分子筛混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将1kg硅铝比为300的ZSM-5分子筛加入20kg摩尔浓度为3mol/L的氢氧化钾水溶液中,在80℃下浸泡2小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入20kg摩尔浓度为3mol/L的磷酸中,在80℃下浸泡4小时,过滤,洗涤,在120℃下干燥,得到脱硅改性ZSM-5分子筛;
所述改性Y分子筛按照以下步骤得到:
将5kgY分子筛、2.5kg硅烷化试剂、0.25kg促进剂和60kg甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入1kg钛酸四丁酯,搅拌2小时,然后在压力0.5MPa、温度60℃下反应2小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比为5.5;
所述硅烷化试剂为叔丁基二甲基氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比5:1混合组成。
实施例3
一种高疏水性VOCs吸附催化剂,由1kg脱硅改性ZSM-5分子筛和1kg改性Y分子筛混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将1kg硅铝比为220的ZSM-5分子筛加入12kg摩尔浓度为1.5mol/L的氢氧化钠水溶液中,在50℃下浸泡2.5小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入14kg摩尔浓度为2.5mol/L的草酸水溶液中,在65℃下浸泡4.5小时,过滤,洗涤,在105℃下干燥,得到脱硅改性ZSM-5分子筛;
所述改性Y分子筛按照以下步骤得到:
将1kgY分子筛、0.3kg硅烷化试剂、0.02kg促进剂和9kg甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入0.12kg钛酸四丁酯,搅拌1.5小时,然后在压力0.3MPa、温度52℃下反应2.5小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比为5.4;
所述硅烷化试剂为二叔丁基二氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比3:1混合组成。
实施例4
一种高疏水性VOCs吸附催化剂,由1kg脱硅改性ZSM-5分子筛和2kg改性Y分子筛混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将1kg硅铝比为250的ZSM-5分子筛加入18kg摩尔浓度为2mol/L的氢氧化钾水溶液中,在70℃下浸泡2小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入14kg摩尔浓度为2mol/L的磷酸中,在80℃下浸泡5小时,过滤,洗涤,在100~120℃下干燥,得到脱硅改性ZSM-5分子筛;
所述改性Y分子筛按照以下步骤得到:
将2kgY分子筛、0.6kg硅烷化试剂、0.08kg促进剂和18kg甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入0.3kg钛酸四丁酯,搅拌1.5小时,然后在压力0.3MPa、温度55℃下反应2.5小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比为5.5;
所述硅烷化试剂为二叔丁基二氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比2:1混合组成。
实施例5
一种高疏水性VOCs吸附催化剂,由1kg脱硅改性ZSM-5分子筛和3.5kg改性Y分子筛混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将1kg硅铝比为300的ZSM-5分子筛加入15kg摩尔浓度为2mol/L的氢氧化钠水溶液中,在60℃下浸泡2.5小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入15kg摩尔浓度为2mol/L的盐酸中,在70℃下浸泡4.5小时,过滤,洗涤,在110℃下干燥,得到脱硅改性ZSM-5分子筛;
所述改性Y分子筛按照以下步骤得到:
将4kgY分子筛、1.6kg硅烷化试剂、0.16kg促进剂和40kg甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入0.6kg钛酸四丁酯,搅拌1.5小时,然后在压力0.4MPa、温度55℃下反应2.5小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比为5.8;
所述硅烷化试剂为三甲基氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比4:1混合组成。
本发明实施例1~5的原料和所得高疏水性VOCs吸附催化剂的物化性质如表1所示。其中ZSM-5分子筛和Y型分子筛的数据为实施例1~5所用原料,即ZSM-5分子筛、Y分子筛各取100g后混合后进行测试的数值。
表1 原料和高疏水性VOCs吸附催化剂的性能比对表
由表1的结果可以看出,经过本发明脱硅改性后的ZSM-5分子筛和改性Y分子筛在复配后其孔径、比表面积和孔容均增加明显,并且分子筛的接触角显著增加,可以看出吸附材料整体的疏水性能显著增加。
对实施例5中所得脱硅改性ZSM-5分子筛和改性Y分子筛的性能进行检测,研究本技术对ZSM-5分子筛和Y分子筛性能的影响,结果如表2所示。
表2 实施例5中所得脱硅改性ZSM-5分子筛和改性Y分子筛的性能结果
由表2的结果可以看出,ZSM-5分子筛经过本发明的技术处理后,平均孔径、比表面积和孔容明显增大,但是对接触角的影响不大,也即不会改善ZSM-5分子筛的疏水性能;Y分子筛经过硅烷化和钛酸四丁酯处理后,Y分子筛的比表面积和接触角明显增大,这是因为常规技术中的硅烷化改性只能改性分子筛的表面,而本技术通过静置、加温加压处理,硅烷化试剂能够进入Y分子筛的孔道内,对Y分子筛的内部孔径进行硅烷化改性,并且钛酸四丁酯水解会产生二氧化钛,在Y分子筛中引入Ti-O键,并且部分二氧化钛也会附着在Y分子筛的内部,提高Y分子筛的比表面积。
对实施例1~5所得高疏水性VOCs吸附催化剂的VOCs吸附-脱附性能测试在微型固定床反应器中进行,催化剂的装填量为1g,VOCs的吸附温度为40oC,空气为载气,反应空速为20000h-1,相对湿度控制在60%,控制各种VOCs的浓度分别为:甲苯200ppm、甲醛400ppm、苯乙烯100ppm、乙酸乙酯800ppm。将1kgZSM-5分子筛和3.5kgY分子筛混合组成对比例催化剂进行相同的试验和所得实施例中吸附性能评价相同操作,吸附性能结果见表3。
表3 实施例与对比例催化剂对甲苯、甲醛、苯乙烯和乙酸乙酯饱和吸附量
由表3的结果可以看出,本发明所得高疏水性VOCs吸附催化剂对VOCs分子中甲苯、甲醛、苯乙烯和乙酸乙酯的吸附效果明显优于未处理ZSM-5分子筛和Y分子筛复配后的催化剂;碱处理和酸处理后的ZSM-5分子筛比表面积和介孔体积增大,增强了对大分子VOCs的吸附能力,同时,对Y分子筛进行硅烷化和钛氧键表面处理后,增强了疏水性,减少了水分子与VOCs分子的竞争吸附。
增加检测过程中的VOCs的吸附温度和相对湿度,采用实施例5的高疏水性VOCs吸附催化剂进行VOCs吸附检测,结果如表4所示。
表4不同温度和湿度下对甲苯、甲醛、苯乙烯和乙酸乙酯饱和吸附量
由表4的结果可以看出,随着温度和湿度的增加,高疏水性VOCs吸附催化剂对甲苯、甲醛、苯乙烯和乙酸乙酯的吸附效果逐渐降低,但是本发明的高疏水性VOCs吸附催化剂在温度60℃,湿度85%时,仍然具有较高的饱和吸附量,因此吸附催化剂的疏水效果和吸附效果优异。
Claims (6)
1.一种高疏水性VOCs吸附催化剂,其特征在于:由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:5~40混合组成;
所述脱硅改性ZSM-5分子筛按照以下步骤得到:
将ZSM-5分子筛加入碱液中,在40~80℃下浸泡2~3小时,过滤,洗涤,然后将处理后的ZSM-5分子筛加入酸液中,在60~80℃下浸泡4~5小时,过滤,洗涤,在100~120℃下干燥,得到脱硅改性ZSM-5分子筛;所述ZSM-5分子筛的硅铝比为200~300;
ZSM-5分子筛、碱液和酸液的质量比为1:10~20:10~20;
所述碱液为摩尔浓度为1~3mol/L的氢氧化钠或氢氧化钾水溶液;
所述酸液为摩尔浓度为1~3mol/L的盐酸、磷酸或草酸;
所述改性Y分子筛按照以下步骤得到:
将Y分子筛、硅烷化试剂、促进剂和甲苯加入到高压反应釜中,混合均匀,在搅拌下向其中加入钛酸四丁酯,搅拌1~2小时,然后在压力0.2~0.5MPa、温度50~60℃下反应2~3小时,过滤,滤饼用去离子水洗涤,干燥,得到改性Y分子筛;所述Y分子筛的硅铝比大于5;
所述硅烷化试剂为三甲基氯硅烷、叔丁基二甲基氯硅烷或二叔丁基二氯硅烷;
所述促进剂为三乙醇胺和碳酸铵按照质量比2~5:1混合组成;
其中Y分子筛、硅烷化试剂、促进剂、甲苯和钛酸四丁酯的质量比为1:0.2~0.5:0.01~0.05:8~12:0.1~0.2。
2.根据权利要求1所述的一种高疏水性VOCs吸附催化剂,其特征在于:所述碱液为摩尔浓度为2mol/L的氢氧化钠水溶液。
3.根据权利要求1所述的一种高疏水性VOCs吸附催化剂,其特征在于:所述酸液为摩尔浓度为2mol/L的磷酸。
4.根据权利要求1所述的一种高疏水性VOCs吸附催化剂,其特征在于:所述硅烷化试剂为三甲基氯硅烷。
5.根据权利要求1所述的一种高疏水性VOCs吸附催化剂,其特征在于:由脱硅改性ZSM-5分子筛和改性Y分子筛按照质量比10:35混合组成。
6.根据权利要求1所述的一种高疏水性VOCs吸附催化剂,其特征在于:所述ZSM-5分子筛的硅铝比为300。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1135527A (ja) * | 1997-07-23 | 1999-02-09 | Mitsubishi Gas Chem Co Inc | メチルアミン類の製造法 |
CN104628011A (zh) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | 一种zsm-5的改性处理方法 |
US20180169636A1 (en) * | 2015-08-18 | 2018-06-21 | Bp Corporation North America Inc. | Desilicated zsm-5 catalysts for xylene isomerization |
CN110237808A (zh) * | 2019-05-26 | 2019-09-17 | 天津大学 | 一种y分子筛的硅烷化改性方法 |
CN115228431A (zh) * | 2022-08-08 | 2022-10-25 | 南通斐腾新材料科技有限公司 | 一种ZSM-5和NaY分子筛的疏水改性方法 |
-
2022
- 2022-11-30 CN CN202211515280.0A patent/CN115569666B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1135527A (ja) * | 1997-07-23 | 1999-02-09 | Mitsubishi Gas Chem Co Inc | メチルアミン類の製造法 |
CN104628011A (zh) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | 一种zsm-5的改性处理方法 |
US20180169636A1 (en) * | 2015-08-18 | 2018-06-21 | Bp Corporation North America Inc. | Desilicated zsm-5 catalysts for xylene isomerization |
CN110237808A (zh) * | 2019-05-26 | 2019-09-17 | 天津大学 | 一种y分子筛的硅烷化改性方法 |
CN115228431A (zh) * | 2022-08-08 | 2022-10-25 | 南通斐腾新材料科技有限公司 | 一种ZSM-5和NaY分子筛的疏水改性方法 |
Non-Patent Citations (1)
Title |
---|
吕双春;葛云丽;赵倩;李轩;纪娜;宋春风;马德刚;刘庆岭;: "高硅分子筛的合成及其在VOCs吸附去除领域的应用", 环境化学, no. 07, pages 1492 - 1505 * |
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