CN112044401A - 一种多孔有机笼吸附材料及其制备方法 - Google Patents
一种多孔有机笼吸附材料及其制备方法 Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 18
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- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
本发明公开了一种多孔有机笼吸附材料及其制备方法,所述吸附材料由偏铝酸钠、硅酸盐、氮化碳和助剂在水‑乙醇溶剂体系下合成的多孔有机笼状吸附材料,所述吸附材料的比表面积在3000~3800m2/g。本发明能在水——乙醇体系下合成,有效减少有机溶剂的使用,且反应时间不到12h,应用于苯、二甲苯等挥发性有机物的吸附。
Description
技术领域
本发明属于空气净化技术领域,特别是涉及一种多孔有机笼吸附材料。
背景技术
目前中国刚迈入人均GDP一万美金大关,随着人民生活水平的提高,国家对环境的要求越加严格,以挥发性有机物(Volatile Organic Compounds,VOCs)排放标准值而言,从1996年国家颁布的《大气污染物综合排放标准》GB16297-1996中VOCs(非甲烷总烃)排放标准值150mg/m3已经逐步降至各地不同行业的严格标准值,例如2015年上海《大气污染物综合排放标准》DB31/933—2015中限定非甲烷总烃排放标准值为70mg/m3,2020年河南《工业涂装工序挥发性有机物排放标准》DB41/1951-2020中限定非甲烷总烃排放标准值为50mg/m3,2019年北京《电子工业大气污染物排放标准》DB11/1631-2019中限定非甲烷总烃排放标准值为10mg/m3。而VOCs排放浓度的控制对治理技术的要求也是严之又严。
故目前VOCs的治理对吸附剂的要求也逐步提高,尤其对吸附剂的吸附容量、耐高温、疏水性提出了高要求。吸附剂的吸附容量决定着吸附剂的使用量和吸附效率;疏水性决定着吸附剂在亲水吸附和亲VOCs吸附的竞争程度。
现有VOCs吸附剂主要分为三种:一种是活性炭及其改性产物;一种是分子筛类,如ZSM-5、Y分子筛、β分子筛类;另一种是其他类多孔吸附物质,如金属有机骨架材料(MOFs)等有机笼吸附材料。
①活性炭是一种黑色多孔的固体炭质,由煤、果壳等通过粉碎、成型或用均匀的煤粒经炭化、活化生产。主要成分为碳,并含少量氧、氢、硫、氮、氯等元素。普通活性炭的比表面积在500~1700m2/g间。具有很强的吸附性能,为用途极广的一种工业吸附剂。虽然活性炭的比表面积大,对多种有机废气都具有广谱吸附作用,但是由于活性炭不耐高温,在实际应用中,有两种方式:一种是单纯吸附,不脱附,造成的是活性炭更换频繁,且活性炭作为危险废物处理成本较高,给企业带来了很大的经济压力;另一种是先吸附后升温脱附,但是脱附温度一般低于120℃,导致大量沸点大于100℃的有机物难以被脱附出来,以致于活性炭在工业废气治理中很快失效,且经常出现小型火灾事故,安全性得不到保障。
②分子筛是一种具有立方晶格的硅铝酸盐化合物。分子筛具有均匀的微孔结构,它的孔穴直径大小均匀,这些孔穴能把比其直径小的分子吸附到孔腔的内部,并对极性分子和不饱和分子具有优先吸附能力,因而能把极性程度不同,饱和程度不同,分子大小不同及沸点不同的分子分离开来,即具有“筛分”分子的作用,故称分子筛。由于分子筛具有吸附能力高,热稳定性强等其它吸附剂所没有的优点,使得分子筛获得广泛的应用。分子筛具有不可燃的特点,但是其对有机物的吸附容量相较活性炭略低。
③MOFs是金属有机骨架化合物(英文名称Metal organic Frameworks)的简称。是由无机金属中心(金属离子或金属簇)与桥连的有机配体通过自组装相互连接,形成的一类具有周期性网络结构的晶态多孔材料。MOFs是一种有机-无机杂化材料,也称配位聚合物(coordination polymer),它既不同于无机多孔材料,也不同于一般的有机配合物。兼有无机材料的刚性和有机材料的柔性特征。使其在现代材料研究方面呈现出巨大的发展潜力和诱人的发展前景。
尽管中国专利CN105399779A中公开了一种具有纳米笼结构的多酸基金属有机框架晶态材料及其制备方法和应用,指出其将硅钨酸、硝酸银、四氮哩和矿化剂溶解到蒸馏水中,调节pH值,再在温度为160℃下反应3天,可获得一种具有纳米笼结构的多酸基金属有机框架晶态材料,是要解决现有技术合成的纳米笼结构的晶态材料的难度大和降解罗丹明有机染料效果差的问题。该发明制备的POMOFs反应时间较长,不利于产业化,且目前仅在液体污染物中有应用,对气体污染物暂无应用。
中国专利CN111454249A公开了一种金属有机笼状化合物的制备方法及其应用,指出其采用以过渡金属盐中的Zn2+作为节点,以L作为配体反应制得金属有机笼状化合物,其合成路线如下:Zn2++L→Zn-L;所述配体L为H2ZPA;所述过渡金属盐选自高氯酸锌、硝酸锌、四氟硼酸锌或三氟甲磺酸锌中的一种。该金属有机笼状化合物用来在光照温和的条件下,高效催化环丁酮制丁内脂及硫醚选择性氧化制亚砜。该金属有机笼状化合物合成步骤需采用乙醚、乙酸、甲醇、二氯甲烷等多种有机溶剂搅拌、洗涤,生产过程容易产生大量有机废气,且暂不知其对VOCs的吸附效果。
发明内容
本发明主要解决的技术问题是提供一种多孔有机笼吸附材料及其制备方法,能在水——乙醇体系下合成,有效减少有机溶剂的使用,且反应时间不到12h,应用于苯、二甲苯等挥发性有机物的吸附。
为解决上述技术问题,本发明采用的一个技术方案是:一种多孔有机笼吸附材料,所述吸附材料由偏铝酸钠、硅酸盐、氮化碳和助剂在水-乙醇溶剂体系下合成的多孔有机笼状吸附材料。
进一步地说,所述吸附材料的比表面积在3000~3800m2/g。
本发明为解决其技术问题所采用的进一步技术方案是:
所述的多孔有机笼吸附材料的制备方法,包括以下步骤:
S1:在容器中先后加入100~300ml去离子水、100~300ml乙醇,5~10mmol/L偏铝酸10-18ml、3.5~8mmol/L硅酸盐10-20ml,得到混合液;
S2:通过乙酸和氢氧化钠调控混合液的pH值,使其保持在2~4之间;
S3:在90℃下以3000~5000r/min的转速持续2小时;
S4:在混合液中加入10~12mmol/L的氮化碳、0.1~0.5wt%的助剂,继续在90℃下以1500~3000r/min的转速持续2小时;
S5:过滤,得到白色带淡黄色流体;
S6:将白色带淡黄色流体反复水洗3次,至烘箱120℃烘2h;
S7:在马弗炉中450℃焙烧4h,焙烧期间保持10~100mL/min的空气通气量,焙烧直至粉体变为纯白色即得多孔有机笼状吸附材料。
进一步地说,所述步骤S1中去离子水和乙醇的添加比例为1.1。
进一步地说,所述步骤S1中偏铝酸钠和硅酸盐的添加比例为1:0.7~1:0.8。
进一步地说,所述步骤S2中的pH值为2.5~3.5。
进一步地说,所述步骤S4中的氮化碳为BT石墨相氮化碳。
进一步地说,所述马费炉的升温程序为4个步骤:
①120~250℃,每分钟升温1~3℃;
②250℃保温1h;
③250~350℃,每分钟升温1~3℃;
④350℃保温1h;
⑤350~450℃,每分钟升温1~3℃;
⑥450℃保温4h。
进一步地说,所述助剂为聚乙二醇、聚乙烯醇和羧甲基纤维素中的至少一种。
本发明的有益效果至少具有以下几点:
1、本发明该材料兼具Y型分子筛的中孔优势和氮化碳对VOCs一定的催化分解作用,可有效提高对VOCs的吸附容量(部分易分解的VOCs被原位分解);
2、本发明该材料兼具超大的比表面积(3000~3800m2/g)和耐高温(450℃)的特性,使得该材料可以反复吸附脱附VOCs;
3、本发明采用水相溶剂,有机溶剂只采用了少量乙醇,有效减少了VOCs的排放;
4、本发明采用梯度升温方式,有效提高了多孔有机笼结构成型的稳定性,使得产率稳定在98%以上,且补充空气的方式使得多孔有机笼材料中的残留助剂可以焚烧干净,没有残留。
具体实施方式
下面对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
实施例1:一种多孔有机笼吸附材料,所述吸附材料由偏铝酸钠、硅酸盐、氮化碳和助剂在水-乙醇溶剂体系下合成的多孔有机笼状吸附材料。所述吸附材料的比表面积在3800m2/g。
所述吸附材料的制备方法包括:
S1:在容器中先后加入100ml去离子水、100ml乙醇(99.5wt%分析纯),5~10mmol/L偏铝酸钠10ml、3.5~8mmol/L硅酸盐10ml,得到混合液,其中,去离子水和乙醇的使用比例为1:1,偏铝酸钠和硅酸盐的使用比例为1:0.75,偏铝酸钠的浓度为5mmol/L;
S2:通过乙酸和氢氧化钠调控混合液的pH值,使其保持在2.5;
S3:在90℃下以3000r/min的转速持续2小时;
S4:在混合液中加入10mmol/L的氮化碳3ml、0.2wt%聚乙二醇1ml,继续在90℃下以1500r/min的转速持续2小时;,其中,氮化碳为BT石墨相氮化碳(99wt%);
S5:过滤,得到白色带淡黄色流体;
S6:将白色带淡黄色流体反复水洗3次,至烘箱120℃烘2h;
S7:在马弗炉中450℃焙烧4h,焙烧期间保持10~100mL/min的空气通气量,焙烧直至粉体变为纯白色即得多孔有机笼状吸附材料。
焙烧温度需从120摄氏度采用梯度升温方式到450℃,升温程序为4个步骤:
①120~250℃,每分钟升温1~3℃;
②250℃保温1h;
③250~350℃,每分钟升温1~3℃;
④350℃保温1h;
⑤350~450℃,每分钟升温1~3℃;
⑥450℃保温4h。
实施例2:一种多孔有机笼吸附材料,所述吸附材料由偏铝酸钠、硅酸盐、氮化碳和助剂在水-乙醇溶剂体系下合成的多孔有机笼状吸附材料。所述吸附材料的比表面积在3000m2/g。
所述吸附材料的制备方法包括:
S1:在容器中先后加入150ml去离子水、150ml乙醇(99.5wt%分析纯),5~10mmol/L偏铝酸钠15ml、3.5~8mmol/L硅酸盐10ml,得到混合液,其中,去离子水和乙醇的使用比例为1:1,偏铝酸钠和硅酸盐的使用比例为1:0.8,偏铝酸钠的浓度为7mmol/L;
S2:通过乙酸和氢氧化钠调控混合液的pH值,使其保持在2.8;
S3:在90℃下以3500r/min的转速持续2小时;
S4:在混合液中加入12mmol/L的氮化碳5ml、0.1wt%聚乙二醇3ml,继续在90℃下以2500r/min的转速持续2小时;,其中,氮化碳为BT石墨相氮化碳(99wt%),添加浓度为12mmol/L;
S5:过滤,得到白色带淡黄色流体;
S6:将白色带淡黄色流体反复水洗3次,至烘箱120℃烘2h;
S7:在马弗炉中450℃焙烧4h,焙烧期间保持10~100mL/min的空气通气量,焙烧直至粉体变为纯白色即得多孔有机笼状吸附材料。
焙烧温度需从120摄氏度采用梯度升温方式到450℃,升温程序为4个步骤:
①120~250℃,每分钟升温1~3℃;
②250℃保温1h;
③250~350℃,每分钟升温1~3℃;
④350℃保温1h;
⑤350~450℃,每分钟升温1~3℃;
⑥450℃保温4h。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种多孔有机笼吸附材料,其特征在于:所述吸附材料由偏铝酸钠、硅酸盐、氮化碳和助剂在水-乙醇溶剂体系下合成的多孔有机笼状吸附材料。
2.根据权利要求1所述的多孔有机笼吸附材料,其特征在于:所述吸附材料的比表面积在3000~3800m2/g。
3.根据权利要求1所述的多孔有机笼吸附材料的制备方法,其特征在于:包括以下步骤:
S1:在容器中先后加入100~300ml去离子水、100~300ml乙醇,5~10mmol/L偏铝酸钠10-20ml、3.5~8mmol/L硅酸盐10-18ml,得到混合液;
S2:通过乙酸和氢氧化钠调控混合液的pH值,使其保持在2~4之间;
S3:在90℃下以3000~5000r/min的转速持续2小时;
S4:在混合液中加入10~12mmol/L的氮化碳、0.1~0.5wt%的助剂,继续在90℃下以1500~3000r/min的转速持续2小时;
S5:过滤,得到白色带淡黄色流体;
S6:将白色带淡黄色流体反复水洗3次,至烘箱120℃烘2h;
S7:在马弗炉中450℃焙烧4h,焙烧期间保持10~100mL/min的空气通气量,焙烧直至粉体变为纯白色即得多孔有机笼状吸附材料。
4.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述步骤S1中去离子水和乙醇的添加比例为1.1。
5.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述步骤S1中偏铝酸钠和硅酸盐的添加比例为1:0.7~1:0.8。
6.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述步骤S2中的pH值为2.5~3.5。
7.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述步骤S4中的氮化碳为BT石墨相氮化碳。
8.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述马费炉的升温程序为4个步骤:
①120~250℃,每分钟升温1~3℃;
②250℃保温1h;
③250~350℃,每分钟升温1~3℃;
④350℃保温1h;
⑤350~450℃,每分钟升温1~3℃;
⑥450℃保温4h。
9.根据权利要求3所述的多孔有机笼吸附材料的制备方法,其特征在于:所述助剂为聚乙二醇、聚乙烯醇和羧甲基纤维素中的至少一种。
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