CN113101891B - 一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用 - Google Patents

一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用 Download PDF

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CN113101891B
CN113101891B CN202110410712.0A CN202110410712A CN113101891B CN 113101891 B CN113101891 B CN 113101891B CN 202110410712 A CN202110410712 A CN 202110410712A CN 113101891 B CN113101891 B CN 113101891B
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zirconium phosphate
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梁栋
周慧晴
张晓雨
孟慧琴
张瑞琴
史雍何
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Abstract

本发明属金属碳基复合材料以及环境工程应用技术领域,为解决目前并没有磷酸锆材料表现出对酸性和碱性气体分子兼有容纳吸附功能,提供一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用。以三聚氰胺锆配合物与壳聚糖甲醛聚合物为前驱体,添加铜、锌、铈、锰金属盐溶液组分,加入磷酸得湿凝胶,湿凝胶填充在模具上或涂覆于空气滤材上,真空冷冻干燥和热解炭化,为高氮碳基磷酸锆广谱性气体吸附剂。对NH3、SO2和H2S等性质差异气体的容纳能力显著高于现有商品碳和多数广谱性吸附剂,制备过程相对温和、原料易得,适用于各种废气处理装置和空气过滤装置加工,使用时不易受温度、湿度、VOCs等环境因素影响,有良好的商业应用前景。

Description

一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用
技术领域
本发明属于金属碳基复合材料以及环境工程应用技术领域,具体涉及一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用,该气体吸附剂用于NH3、SO2和H2S的广谱性气体吸附材料。
背景技术
随着城市化程度提高和工业活动的加剧,有毒有害气体的排放、混合着空气雾霾和流行疫病的发生,日益影响人民群众的健康并受到环境卫生部门的关注。然而常规环境吸附材料与技术一般只针对一类或若干性质相似的污染物,在大气环境工程领域以及处理某些应急事故和个人防护时却要同时面临性质显著差异的多种气体,例如酸性二氧化硫/硫化氢与碱性氨气、无机气体与有机VOCs等共存,这就要求开发一种具有多功能广谱性的吸附剂,使材料上能携带多种吸附位点并协同作用于各种有毒有害气体污染物。
Gregory W. Peterson等人在研究一种MnOx干凝胶或气凝胶时(ACS AppliedMaterials & Interfaces, 2016, 8, 1184-1193)明确提出了广谱性气体吸附剂的概念(broad-spectrum sorbents),这种由NaMnO4和反丁烯二酸通过溶胶-凝胶法制备的凝胶状吸附剂,对NH3、SO2和H2S的吸附容量分别达到39、200和680 mg/g。M. Douglas LeVan等人将MCM-41分子筛的模板剂炭化得到介孔碳硅复合材料(carbon-silica composites),使负载30 wt% Cu(NO3)2之后对NH3和SO2的吸附容量分别达到4.0和0.45 mmol/g(Microporous &Mesoporous Materials, 2016, 221, 197-203),使负载ZnCO3之后对NH3和SO2的吸附容量分别达到4.2和0.59 mmol/g(Adsorption, 2017, 23: 87-99)。Jennifer V. Romero等人将ZnO/CuO/CuCl2负载到活性炭上,对SO2和NH3的吸附容量分别达到0.53和0.94 mmol/g(ACS Combinatorial Science, 2012, 14, 31-37),将CuO/ZnO/Mn3O4负载到活性炭上,对SO2和NH3的吸附容量分别达到1.2和0.7 mmol/g(ACS Combinatorial Science, 2013, 15,101−110)。
上述与气体分子作用的均为金属氧化物或金属盐组分。如羟基、氨基、异氰酸、脲基、甲基丙烯酰氧丙基等通过嫁接方式引入到介孔MCM-41分子筛,证明有机官能团对酸性和碱性气体分子具有较好的吸附能力,对SO2和NH3的吸附容量最高达到0.85和7 mmol/g(Langmuir 2012, 28, 17450-17456)。
因此,当金属与有机骨架形成MOF材料(metal-organic framework)时,对气体污染物的吸附能力又有了显著改善。例如Gregory W. Peterson等人用均三苯甲酸和Cu(NO3)2合成的CuBTC,与美国3M公司的商品碳比较,在湿润条件下对NH3、AsH3和H2S的吸附能力均有所提高(Industry & Engineering Chemistry Research, 2015, 54, 3626-3633),用2-氨基对苯二甲酸与ZrOCl2合成UiO-66-NH2,对NH3和CNCl的吸附容量分别达到3.3和4.1 mmol/g(Industry & Engineering Chemistry Research, 2014, 53, 701-707)。ChristophJaniak等人用4,4-二甲酸-联吡啶/有机脲配体与锌形成MOF材料,对SO2和NH3的饱和吸附容量分别达到10.9和14.3 mmol/g,这也是近年来文献中报道最高的吸附数据(ACS AppliedMaterials & Interfaces, 2017, 9, 37419-37434)。
上述提及金属有机复合材料均表现出对性质相异气体分子的吸附能力,但是有机配体的价格以及苛刻的合成条件增加了MOFs材料规模生产和应用的成本。目前来看市场上主流吸附剂仍然是炭/碳基材料,一般是指活性炭或担载活性组分的活性炭材料,部分是改性的炭/碳纤维、碳纳米管等。炭/碳基材料由于其表面相对疏水性的特征,普遍用于工业废气及室内有机VOCs的处理,例如甲苯、甲醛等,但是在面临共存的SO2、NOX、NH3时吸附效果欠佳,有时无机气体还会抑制有机VOCs的吸附,例如纯的活性碳纤维(ACF)对SO2和NH3的饱和吸附量仅为9.4 mg/g和13.7 mg/g(中国卫生工程学,1995,4,13-17)。
事实上,工业活性炭经常浸渍铜、铁、锌、锆、镁、锰、钯、金等金属活性组分,才可满足对有毒有害气体处理的需要(中国专利,CN105251447A),但多种活性组分在活性炭表面又存在此消彼长的制约,使得普通的炭/碳基吸附剂难以对性质差异显著的气体污染物均达到优异的净化效果,故环境工程实践中经常要组合使用多种净化器。
氧化锆被认为是一种兼有酸性和碱性的两性氧化物,水合氧化锆和纳米氢氧化锆表面上丰富的Zr-OH为SO2和NOx提供了有利的吸附位(Applied Surface Science, 2012,258(15), 5778-5785),锆与对苯二甲酸等形成稳定的金属有机多孔聚合物(如Zr-MOF)可用于CO2/N2/CH4的有效分离(Progress in Natural Science: Materials International,2018, 28 (2),160-167),以硫酸、草酸、膦酸等有机酸进行处理,或与铝、铜、锌、铈等金属氧化物混合之后,也可以显著增强氧化锆对NH3的吸附能力,同时由锆元素衍生的改性吸附剂还具有明显的热稳定性和耐腐蚀性,因此锆化合物可被引入碳基广谱性吸附剂成为一种重要的活性组分。只是纳米氧化锆和氢氧化锆尽管具有两性的吸附能力、且成本较低,但是其吸附能力又容易受温度、pH、VOCs等工作环境的影响而发生不可逆的损失、甚至回收也比较困难。
就吸附机理而言,不仅锆自身可以参与化学吸附,与锆原子相邻的金属离子、酸根离子、羧基、羟基、氨基或其他有机官能团均可直接影响锆化合物对气体的吸附。近十年来磷酸锆吸附剂由于其稳定的层状结构、较高的比表面积和较强的离子交换能力而备受环境工程材料同行的重视(化学进展, 2014, 26(1): 87-99),Thomas Simons等人的研究表明磷酸锆对NH3有显著的响应、可用作微量氨气传感器,但对SO2等酸性气体不敏感(Sensorsand Actuators B-Chemical, 2015, 217, 175-180),Wang Qiang等人以钠、钾等碱金属掺杂磷酸锆有效提高了对CO2的选择吸附(Science of Advanced Materials, 2013, 5,469-474)。虽然磷酸锆吸附剂的结构稳定,不容易受温度、pH、VOCs等工作环境的影响,经常用于溶液离子交换吸附,与碳纳米管、碳纤维等碳基材料复合用于传感器、电极,或与聚苯胺、壳聚糖等聚合物复合用于阻燃材料,但据目前调研所得,尚未有磷酸锆材料表现出对酸性和碱性气体分子兼有容纳吸附功能的报道。
发明内容
本发明为了解决目前并没有磷酸锆材料表现出对酸性和碱性气体分子兼有容纳吸附功能的报道,提供了一种高氮碳基磷酸锆广谱性气体吸附剂及其制备方法和应用,该气体吸附剂为广谱性气体吸附剂,用于NH3、SO2和H2S的广谱性气体吸附材料。
本发明由如下技术方案实现的:一种高氮碳基磷酸锆广谱性气体吸附剂,以三聚氰胺锆配合物与壳聚糖甲醛聚合物为前驱体,添加铜、锌、铈、锰金属盐溶液组分,然后加入磷酸,得到湿凝胶,将湿凝胶填充在模具上或者涂覆于空气滤材上,经真空冷冻干燥和热解炭化,即为高氮碳基磷酸锆广谱性气体吸附剂。
制备所述的高氮碳基磷酸锆气体吸附剂的方法,具体步骤如下:
(1)25 g三聚氰胺于1500-2000 mL蒸馏水中加热至80-90℃溶解,加入提前用200mL蒸馏水溶解的8-16 g氧氯化锆和0.8-1.6 g金属盐溶液,800-1000 r/min搅拌生成微悬浮物,然后加入提前用1000 mL蒸馏水溶解10-15 g水溶性壳聚糖的溶液,静置反应0.5-1 h后加入16ml质量浓度为37%的甲醛溶液,用85%浓磷酸调节体系pH值为2.5-3,继续反应6-10h;过滤得到疏松湿凝胶,然后将湿凝胶填充于模具或涂覆于滤材上,-18℃-0℃冷冻36-48h;
(2)步骤(1)中冷冻成型的凝胶真空冷冻干燥36-48h,然后再浸入质量浓度为10%磷酸的无水乙醇溶液中继续静置反应2-3天,二者固液比为1/20-1/10,回收模具或空气滤材,用乙醇洗涤除去未反应磷酸,置于45-60℃真空干燥8-12 h,在氮气保护中加热到350-450℃热解2-6 h,升温速率为5-10℃/min,气体流速10-15 mL/min,至获得成型的黑褐色产品或相应的滤材。
所述金属盐溶液为摩尔比为1:1的铜/锌或铈/锰的可溶性盐溶液。
所述模具为玻璃或坩埚器皿;所述空气滤材为毛毡、纸质、化纤或碳纤维的空气滤材。
所述的高氮碳基磷酸锆气体吸附剂的应用,所述高氮碳基磷酸锆气体吸附剂在对NH3、SO2和H2S的气体污染物的吸附中的应用。
在温度范围25-55℃、湿度范围20-50%、有机VOCs共存的情况下,对NH3、SO2和H2S有害气体表现出强吸附能力。
相比现有广谱性碳基吸附剂及制备方法,本发明通过三聚氰胺金属配合物与壳聚糖甲醛树脂为前驱体,经磷酸处理和低温碳化,制得一种新型的广谱性碳基多孔吸附剂,其中主成分磷酸锆质量分数为40%-50%,有机氮含量为22%-28%,比表面积为137-215 m2/g,平均孔径为6.5-8.5 nm,对NH3、SO2和H2S等性质差异的气体污染物均表现出显著的吸附能力,吸附容量分别达到2.3-4.7 mmol/g、2.9-5.2 mmol/g和3.2-6.0 mmol/g,适用范围较宽,不易受温度、湿度、VOCs等环境因素影响。对NH3、SO2和H2S等性质差异气体的容纳能力显著高于现有商品碳和多数广谱性吸附剂,而且制备过程相对温和、原料易得,适用于各种废气处理装置和空气过滤装置的加工,使用时也不易受温度、湿度、VOCs等环境因素影响,具有良好的商业应用前景。
附图说明
图1为实施例2所得吸附剂的N2等温吸附线;
图2为实施例2所得吸附剂的孔径分布图;
图3为实施例2所得吸附剂的扫描电镜图;
图4为实施例2所得吸附剂的红外光谱和XRD谱图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例;基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:一种高氮碳基磷酸锆气体吸附剂,以三聚氰胺锆配合物与壳聚糖甲醛聚合物为前驱体,添加铜、锌、铈、锰金属盐溶液组分,然后加入磷酸,得到湿凝胶,将湿凝胶填充在模具上或者涂覆于空气滤材上,经真空冷冻干燥和热解炭化,即为高氮碳基磷酸锆气体吸附剂。
具体制备方法为:
(1)称取25 g三聚氰胺于1500mL蒸馏水中加热至90℃溶解,加入提前用200 mL蒸馏水溶解8 g氧氯化锆和1.6 g其他金属盐的溶液,以800r/min剧烈搅拌生成微悬浮物,随后加入提前用1000 mL蒸馏水溶解10g的水溶性壳聚糖溶液,反应0.5 h后加入16毫升37%甲醛溶液,用85%浓磷酸调节体系pH值约3,继续反应6 h、过滤得到疏松的湿凝胶,使填充于模具或涂覆于滤材上、转移至-18℃-0℃冷柜中冷冻;
(2)冷冻成型的凝胶经真空冷冻干燥36h,再浸入10%磷酸的无水乙醇溶液中继续反应2天,二者固液比为1/10,回收模具或滤材、用乙醇洗涤除去未反应磷酸,置于45℃真空干燥8h,在氮气保护中加热到350℃热解2h,升温速率为5℃/min,气体流速15 mL/min,直到获得成型的黑褐色产品或相应的滤材。
其他金属盐为摩尔比为1:1的铜和锌的可溶性盐,模具可以为任意形状和尺寸的玻璃或坩埚器皿;滤材如毛毡、纸质、化纤和碳纤维等均为常规滤材。
实施例2:一种高氮碳基磷酸锆气体吸附剂,三聚氰胺于1600 mL蒸馏水中加热至80℃溶解,蒸馏水溶解12 g氧氯化锆和1.2 g其他金属盐的溶液,以900 r/min剧烈搅拌生成微悬浮物,随后加入提前用用1000 mL蒸馏水溶解12 g的水溶性壳聚糖溶液,用85%浓磷酸调节体系pH值约2.8,继续反应8 h、冷冻成型的凝胶经真空冷冻干燥40 h,再浸入10%磷酸的无水乙醇溶液中继续反应2天,二者固液比为1/15,置于50℃真空干燥10 h,在氮气保护中加热到400℃热解3 h,升温速率为8℃/min,气体流速12 mL/min,其他方法同实施例1所述方法。
实施例3:一种高氮碳基磷酸锆气体吸附剂,三聚氰胺于1800 mL蒸馏水中加热至85℃溶解,入10%磷酸的无水乙醇溶液中继续反应3天,二者固液比为1/15,置于55℃真空干燥10 h,在氮气保护中加热到400℃热解4 h,升温速率为8℃/min,气体流速12 mL/min,其他金属盐为摩尔比为1:1的铈和锰的可溶性盐,其他方法同实施例2所述方法。
实施例4:三聚氰胺于2000 mL蒸馏水中加热至90℃溶解,蒸馏水溶解16 g氧氯化锆和0.8 g其他金属盐的溶液,以1000 r/min剧烈搅拌生成微悬浮物,蒸馏水溶解15 g的水溶性壳聚糖溶液,反应1 h后加入16毫升37%甲醛溶液,用85%浓磷酸调节体系pH值约2.5,继续反应10 h;冷冻成型的凝胶经真空冷冻干燥48 h,再浸入10%磷酸的无水乙醇溶液中继续反应3天,二者固液比为1/20,用乙醇洗涤除去未反应磷酸,置于60℃真空干燥12 h,在氮气保护中加热到450℃热解6 h,升温速率为10℃/min,气体流速10 mL/min,其他金属盐为摩尔比为1:1的铈和锰的可溶性盐,其他方法同实施例1所述方法。
实验例1:碳基吸附剂的评价过程参考煤炭行业标准《MT/T 998-2006 活性炭吸附SO2饱和容量的试验方法》、《MT/T 997-2006 活性炭吸附NH3穿透容量和穿透时间的试验方法》和《MT/T 998-2006 活性炭吸附H2S穿透容量和穿透时间的试验方法》。
其中:一定质量的活性炭,在规定条件下通入体积含量为2%的SO2/H2S/NH3/气体,吸附3h后,测定活性炭吸附SO2/H2S/NH3后的增量,其增量部分与测试前活性炭的质量比,称为该气体的饱和吸附容量。
称量空的吸附管(内径20 mm),记为质量m1,将活性炭粉末过筛控制在2-3 mm,填入吸附管,使样品填装高度为10 cm,记为质量m2,同时升温空气浴温度到120℃和加湿器水温到80℃,控制SO2/H2S/NH3体积含量为2%,将样品管接入混合气体,使气体流量200 ml/min,吸附3h后,取出吸附管,放入干燥器,放冷后称重并记为质量m3。按如上步骤平行两次取平均值,误差小于等于10%。
饱和吸附容量 W (mg/g) = [1000*(m3-m2)]/(m2-m1);
饱和吸附容量V (mmol/g) = W /M,其中M为气体分子质量(g/mol)。
经检测,实施例1-4所得吸附剂的结构与组成特征见表1。
表1示例中吸附剂的结构与组成特征
Figure DEST_PATH_IMAGE001
注:磷酸锆含量根据ICP测试计算,有机氮含量由元素分析得到,比表面积和平均孔径用氮吸附仪表征。
实施例1-4中所得吸附剂的环境参数与吸附数据见表2。
表2示例中吸附剂的环境参数与吸附数据
Figure 672222DEST_PATH_IMAGE002
注:甲醛为共存VOC的代表,定量加入到加湿器中与水蒸气混合,使其中甲醛含量为0.1-0.3 mg/m3
实施例中所制备中吸附剂的结构与组成特征见表1。从表1中可以看出,本发明所提及吸附剂均为结合磷酸锆的高氮碳基材料,有较高的比表面积和介孔特征。
附图1和图2分别是实施例2中所得吸附剂的氮吸附曲线和孔径分布图,图3为实施例2所得吸附剂的扫描电镜图,从中可以看出吸附剂的响应区间主要在中高压区,内部平均以6 nm的中孔为主,其比表面积约为192 m2/g,微观形貌呈现不规则多孔疏松状。
根据附图4中红外谱图,N-H基团的拉伸振动在3430 cm-1附近出现一个宽峰,与氢键结合的N-H证明在3180 cm-1附近发生弱吸附,而1400 cm-1处的峰可看作是N-H的弯曲振动,O-P-O碎片的变形和不对称拉伸振动会在1035 cm-1和930 cm-1处出现两个典型的特征峰,750 cm-1的弱峰归属于P-O键的对称拉伸振动,最后在1635 cm-1处的峰代表了在碳质骨架中伸展的芳香族C=C。同时根据XRD的表征看出该材料并没有出现显著的锆盐晶体衍射峰,可以认为是无定形结构特征。
实施例中所制备的吸附剂的环境参数与吸附数据见表2。从表2中可以看出,本发明所提及吸附剂在温度范围25-55 ℃、湿度范围20-50%以及代表性VOCs(如甲醛)共存的情况下,对NH3\SO2\H2S等性质各异的有害气体均表现出较强的吸附能力,各环境参数基本涵盖了中国北方日照资源丰富地区的气候特征,证明本发明所提及吸附剂不仅对多种气体有广谱性净化功能,也有广泛的环境适应性,其吸附能力不易受温度、湿度、VOCs等环境因素影响,因此具有较好的商业应用价值。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (6)

1.一种高氮碳基磷酸锆广谱性气体吸附剂,其特征在于:以三聚氰胺锆配合物与壳聚糖甲醛聚合物为前驱体,添加铜、锌、铈、锰金属盐溶液组分,然后加入磷酸,得到湿凝胶,将湿凝胶填充在模具上或者涂覆于空气滤材上,经真空冷冻干燥和热解炭化,即为高氮碳基磷酸锆广谱性气体吸附剂。
2.制备权利要求1所述的高氮碳基磷酸锆广谱性气体吸附剂的方法,其特征在于:具体步骤如下:
(1)25 g三聚氰胺于1500-2000 mL蒸馏水中加热至80-90℃溶解,加入提前用200 mL蒸馏水溶解的8-16 g氧氯化锆和0 .8-1 .6 g金属盐溶液,800-1000 r/min搅拌生成微悬浮物,然后加入提前用1000 mL蒸馏水溶解10~15 g水溶性壳聚糖的溶液,静置反应0 .5-1 h后加入16ml质量百分比浓度为37%的甲醛溶液,用85%浓磷酸调节体系pH值为2 .5-3,继续反应6-10 h;过滤得到疏松湿凝胶,然后将湿凝胶填充于模具或涂覆于空气滤材上, -18℃-0℃冷冻36-48h;
(2)步骤(1)中冷冻成型的凝胶真空冷冻干燥36-48h,然后再浸入质量百分比浓度10%磷酸的无水乙醇溶液中继续静置反应2-3天,二者固液比为1/20-1/10,回收模具或空气滤材,用乙醇洗涤除去未反应磷酸,置于45-60℃真空干燥8-12 h,在氮气保护中加热到350-450℃热解2-6 h,升温速率为5-10℃/min,气体流速10-15 mL/min,至获得成型的黑褐色产品或相应的滤材。
3.根据权利要求2所述的制备高氮碳基磷酸锆广谱性气体吸附剂的方法,其特征在于:所述金属盐溶液为摩尔比为1:1的铜/锌或铈/锰的可溶性盐溶液。
4.根据权利要求2所述的制备高氮碳基磷酸锆广谱性气体吸附剂的方法,其特征在于:所述模具为玻璃或坩埚器皿;所述空气滤材为毛毡、纸质、化纤或碳纤维的空气滤材。
5.权利要求1所述的高氮碳基磷酸锆广谱性气体吸附剂的应用,其特征在于:所述高氮碳基磷酸锆气体吸附剂在对NH3、SO2和H2S的气体污染物的吸附中的应用。
6.根据权利要求5所述的高氮碳基磷酸锆广谱性气体吸附剂的应用,其特征在于:在温度范围25-55℃、湿度范围20-50%、有机VOCs共存的情况下,对NH3、SO2和H2S有害气体表现出强吸附能力。
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