CN114797945A - 一种键合相类芬顿催化剂及其制备方法 - Google Patents
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Abstract
本发明属于类芬顿催化剂的技术领域,涉及一种键合相类芬顿催化剂及其制备方法,所述键合相类芬顿催化剂由改性MCM‑41介孔分子筛与活性组分二价铁离子进行配位作用得到。改性提高催化剂的活性,可以减少铁离子的流失,保证催化剂的高稳定性,进而得到高活性、高稳定性的键合相类芬顿催化剂。
Description
技术领域
本发明属于类芬顿催化剂的技术领域,具体涉及一种键合相类芬顿催化剂及其制备方法。
背景技术
近年来随着人类对资源,特别是石油石化类产品的需求量增加,含有烷基酚类化合物废水的排放量逐年增加,以双酚A为代表的烷基酚类环境激素的危害引起了广泛关注。双酚A(BPA),学名2,2-二(羟基苯基)丙烷,是世界上广泛使用的工业原料之一,用于生产环氧树脂、聚碳酸酯塑料、阻燃剂、抗氧化剂及农药等,有数据显示其在不同的水体中的残留从微克到毫克不等,在接近人体温度时析出浓度显著增大,极低的浓度进入人体即可诱发各种疾病。
环境激素是指外源性干扰生物和人体正常内分泌机能的化学物质,主要是由人类活动释放到环境中,并对人体和生物体内的正常激素功能施加影响,具有类似激素的作用,能导致生物的生殖能力下降、生殖器肿瘤、免疫力降低、并引起各种生理异常。为缓解环境激素污染使生物和人类健康受到的威胁,因此急需一种高效、稳定降解有机污染物的催化剂。
发明内容
为了解决上述问题,本发明提供了一种键合相类芬顿催化剂及其制备方法,通过酸改性提高催化剂的活性,同时通过将活性组分铁离子配位在改性MCM-41介孔分子筛上,实现减少铁离子的流失,保证催化剂的高稳定性,进而得到高活性、高稳定性的键合相类芬顿催化剂。
一种键合相类芬顿催化剂,所述键合相类芬顿催化剂由改性MCM-41介孔分子筛与活性组分二价铁离子进行配位作用得到,所述改性MCM-41介孔分子筛具有以下结构通式:
其中,Y选自醛基或羧基。
进一步地,所述改性MCM-41介孔分子筛结构为:
进一步地,所述改性MCM-41介孔分子筛由甲酸甲酯与硅烷化MCM-41介孔分子筛反应所得,反应方程式如下:
进一步地,所述活性组分二价铁离子的来源,选自硫酸亚铁、硝酸亚铁或氯化亚铁。
本发明的另一个目的,在于提供上述键合相类芬顿催化剂制备方法,其特征在于,包括如下步骤:
S1. 酸改性:将MCM-41介孔分子筛与氧化铝和水,共混加热,所得中间产物1用酸浸泡,得到中间产物2;
S2. 将所述中间产物2,与硅烷化试剂进行偶联反应,得到硅烷化MCM-41介孔分子筛,将所述硅烷化MCM-41介孔分子筛与甲酸甲酯反应,得到改性MCM-41介孔分子筛;
S3. 将所述改性MCM-41介孔分子筛与二价铁离子,在还原剂作用下配位,得到产物。
进一步地,所述硅烷化试剂为十八烷基三氯硅烷、十八烷基三甲氧基硅烷、苯基三氯硅烷、苯基三甲氧基硅烷、N-[3-(三甲氧基硅基)丙基]乙二胺等中的至少一种。
进一步地,所述二价铁离子的来源为硫酸亚铁溶液,所述硫酸亚铁溶液的摩尔浓度为0.02-0.08 mol/L。
进一步地,所述还原剂选自碘化钾、碘化钠、溴化钾或溴化钠。
进一步地,所述还原剂的浓度为0.02-0.08 mol/L。
进一步地,所述酸选自硫酸、硝酸或盐酸。
本发明具有以下有益效果:
1. 通过对MCM-41介孔分子筛酸改性,提高其酸性中心和酸强度,提高催化剂的活性,同时在降解废水时无需调介质呈酸性的条件,进而大大减少废水的处理成本,也减少了环境污染。
2. 通过硅烷化反应使形成更稳定的Si-O-C化学键,将特定的有机官能团嫁接到MCM-41介孔分子筛的孔道内或层间,制备出一系列有机官能化的改性MCM-41介孔分子筛,活性组分铁离子通过配位作用固载在改性MCM-41介孔分子筛上,从而减少铁离子的流失,保证催化剂的高稳定性。
3. 通过本发明的制备方法,可以安全地得到高活性、高稳定性的键合相类芬顿催化剂,可以大大降低活性组分二价铁离子的流失量,减少二次污染,保证催化剂的活性和重复利用率。
附图说明
图1是实施例1中改性MCM-41介孔分子筛和未改性的硅烷化MCM-41介孔分子筛的XRD谱图。
图2是实施例1中改性MCM-41介孔分子筛和得到的产物键合相类芬顿催化剂的XRD谱图。
图3是实施例1与对比例1所得到的催化剂对苯酚降解的效果图。
图4是实施例1中,不同硫酸亚铁溶液浓度下所得到的键合相类芬顿催化剂对苯酚降解的效果图。
具体实施方式
为了更清楚地说明本发明的技术方案,列举如下实施例。实施例中所出现的原料、反应和后处理手段,除非特别声明,均为市面上常见原料,以及本领域技术人员所熟知的技术手段。
实施例1
称取2g的MCM-41介孔分子筛在220℃鼓风干燥箱内活化2 h,加入0.1g的氧化铝和去离子水,80℃水浴加热,回流时间5 h,回流产物进行抽滤、洗涤,并在110℃下干燥2 h,得到中间产物1,再用6g/L的硫酸浸泡,进而得到中间产物2。
取1g中间产物2于250℃干燥箱下活化2 h。将活化后的中间产物2加入100 ml甲苯中,搅拌均匀,然后加入20 mL的N-[3-(三甲氧基硅基)丙基]乙二胺和25 ml无水乙醇的混合物,连续搅拌,加热120 V回流12 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,得到硅烷化MCM-41介孔分子筛备用。
硅烷化反应的化学方程式如下:
取1g硅烷化MCM-41介孔分子筛加入100 mL乙醇中,再加入过量的甲酸甲酯,搅拌混合均匀后回流12 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,分别得到改性MCM-41介孔分子筛备用。
其中,甲酸甲酯与硅烷化MCM-41介孔分子筛偶联反应,醛基(-CHO)嫁接至硅烷化MCM-41介孔分子筛上,反应方程式如下:
配制浓度为0.045 mol/L的硫酸亚铁溶液以及0.045 mol/L的碘化钾溶液;在100ml具塞锥形瓶中加入0.5 g预处理后的改性MCM-41介孔分子筛及50 mL硫酸亚铁溶液,加入转子;放入水浴中,在水温60℃下于磁力搅拌30 min后,缓慢将碘化钾溶液滴入,滴入速度控制为2秒/滴,并且要边滴加边搅拌,继续搅拌30 min,抽滤,用蒸馏水进行洗涤,恒温真空干燥箱烘干,得到产物键合相类芬顿催化剂。
对改性MCM-41介孔分子筛和未改性的硅烷化MCM-41介孔分子筛进行XRD表征对比,如图1所示。在2°附近有明显的MCM-41介孔分子筛的衍射峰,表明嫁接前后没有造成介孔结构的坍塌。
对产物键合相类芬顿催化剂和改性MCM-41介孔分子筛进行XRD表征对比,如图2所示。在17.5°、35.4°、52.5°存在Fe2O3的特征峰,在36.4°、37.4°、44.7°存在Fe3O4的特征峰,表明铁离子成功配位到改性MCM-41介孔分子筛上。
实施例2
称2g的MCM-41介孔分子筛在220℃鼓风干燥箱内活化2 h,加入0.1的氧化铝和去离子水,80℃水浴加热,回流时间4 h,回流产物进行抽滤、洗涤,并在110℃下干燥2 h,得到中间产物1,再用6g/L的硫酸浸泡,进而得到中间产物2。
取1g中间产物2于250℃干燥箱下活化1.5 h。将活化后的中间产物2加入100 ml甲苯中,搅拌均匀,然后加入20 mL的N-[3-(三甲氧基硅基)丙基]乙二胺和25 ml无水乙醇的混合物,连续搅拌,加热120 V回流11 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,得到硅烷化MCM-41介孔分子筛备用。
取适量硅烷化MCM-41介孔分子筛加入100 mL乙醇中,再加入过量的甲酸甲酯,搅拌混合均匀后回流11 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,分别得到改性MCM-41介孔分子筛备用。
配制浓度为0.030 mol/L的硫酸亚铁溶液以及0.045 mol/L的碘化钾溶液;在100ml具塞锥形瓶中加入0.5 g预处理后的改性MCM-41介孔分子筛及50 mL硫酸亚铁溶液,加入转子;放入水浴中,在水温60℃下于磁力搅拌30 min后,缓慢将碘化钾溶液滴入,滴入速度控制为3秒/滴,并且要边滴加边搅拌,继续搅拌30 min,抽滤,用蒸馏水进行洗涤,恒温真空干燥箱烘干,得到产物键合相类芬顿催化剂。
实施例3
称取2g的MCM-41介孔分子筛在220℃鼓风干燥箱内活化2 h,加入0.1g的氧化铝和去离子水,80℃水浴加热,回流时间4 h,回流产物进行抽滤、洗涤,并在110℃下干燥2 h,得到中间产物1,再用6g/L的硫酸浸泡,进而得到中间产物2。
取1g中间产物2于250℃干燥箱下活化2.5 h。将活化后的中间产物2加入100 ml甲苯中,搅拌均匀,然后加入20 mL的N-[3-(三甲氧基硅基)丙基]乙二胺和25 ml无水乙醇的混合物,连续搅拌,加热120 V回流10 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,得到硅烷化MCM-41介孔分子筛备用。
取适量硅烷化MCM-41介孔分子筛加入100 mL乙醇中,再加入过量的甲酸甲酯,搅拌混合均匀后回流10 h;抽滤,用无水乙醇多次洗涤后置于真空干燥箱内抽真空烘干,分别得到改性MCM-41介孔分子筛备用。
配制浓度为0.060 mol/L的硫酸亚铁溶液以及0.045 mol/L的碘化钾溶液;在100ml具塞锥形瓶中加入0.5 g预处理后的改性MCM-41介孔分子筛及50 mL硫酸亚铁溶液,加入转子;放入水浴中,在水温60℃下于磁力搅拌30 min后,缓慢将碘化钾溶液滴入,滴入速度控制为1秒/滴,并且要边滴加边搅拌,继续搅拌30 min,抽滤,用蒸馏水进行洗涤,恒温真空干燥箱烘干,得到产物键合相类芬顿催化剂。
对比例1
对比例1与实施例1的所用成分、成分用量和浓度、制备步骤均相同,其唯一区别在于,对比例1为未经S2步骤制备的Fe-MCM-41催化剂,其制备过程如下:
a. 酸改性:将MCM-41介孔分子筛与氧化铝和水,共混加热,所得中间产物1用酸浸泡,得到中间产物2;
b. 将所述中间产物2与硫酸亚铁溶液,在碘化钾溶液作用下配位,得到对比例1。
测试例1
选苯酚水溶液为测试物,反应条件为:常压、50℃、苯酚的起始浓度为100 mg/L、液固比为500:1,未调节pH值。实施例1及对比例1所得到的催化剂的降解效果对比如图3所示,对苯酚降解率数据如表1所示,这表明经过步骤S2改性后的催化剂的降解效果更好,有机官能团的嫁接提高了催化剂的活性。
表1 催化剂对苯酚降解率
样品编号 | 对苯酚降解率(%) |
实施例1 | 88.2 |
对比例1 | 66.1 |
测试例2
实施例1所得到的催化剂对苯酚的降解效果如图4所示,对苯酚降解率数据如表2所示;其中,硫酸亚铁溶液浓度为0.045 mol/L和0.060 mol/L得到的催化剂的降解反应速率很接近,随着溶液浓度的增加,催化剂的活性增强;但随着反应的进行,配位使用硫酸亚铁溶液浓度为0.045 mol/L得到的催化剂降解效果更好。
表2 催化剂降解性能评价结果
硫酸亚铁溶液浓度(mol/L) | 240 min后对苯酚降解率(%) |
0.045 | 78.0 |
0.030 | 72.9 |
0.060 | 73.0 |
测试例3
反应240 min后,采用原子吸收法,对实施例1与对比例1两种催化剂体系反应后的溶液中铁离子浓度进行测定,对比两种催化剂体系稳定性;测试数据如表3所示,本发明方法得出的催化剂中铁离子的溶出浓度低于欧盟标准的2 ppm,不会对后续生物处理或环境生态造成重金属污染,同时也说明了本发明制备得到的键合相类芬顿催化剂中,铁离子更好地固载在改性MCM-41介孔分子筛上,具有更好的稳定性能。催化剂的重复使用实验,将进行过反应的催化剂离心分离,进行回收,用于第二次实验,如此反复,循环10次,重复使用10次后,催化剂对苯酚降解效率仍有87.5%,说明了所制备催化剂具备优良重复利用性。
表3 催化剂稳定性评价结果
样品编号 | 铁离子的溶出浓度(ppm) |
对比例1 | 4.350 |
实施例1 | 0.087 |
由此可得,本发明可以通过酸改性提高催化剂的活性,同时通过将活性组分铁离子配位在改性MCM-41介孔分子筛上,实现减少铁离子的流失,保证催化剂的高稳定性,进而得到高活性、高稳定性的键合相类芬顿催化剂。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经组合形成本领域技术人员可以理解的其他实施方式。
Claims (10)
4.根据权利要求1所述一种键合相类芬顿催化剂,其特征在于,所述活性组分二价铁离子的来源,选自硫酸亚铁、硝酸亚铁或氯化亚铁。
5.权利要求1-4任一项所述键合相类芬顿催化剂制备方法,其特征在于,包括如下步骤:
S1. 酸改性:将MCM-41介孔分子筛与氧化铝和水,共混加热,所得中间产物1用酸浸泡,得到中间产物2;
S2. 将所述中间产物2,与硅烷化试剂进行偶联反应,得到硅烷化MCM-41介孔分子筛,将所述硅烷化MCM-41介孔分子筛与甲酸甲酯反应,得到改性MCM-41介孔分子筛;
S3. 将所述改性MCM-41介孔分子筛与二价铁离子,在还原剂作用下配位,得到产物。
6.根据权利要求5所述一种键合相类芬顿催化剂制备方法,其特征在于,所述硅烷化试剂为十八烷基三氯硅烷、十八烷基三甲氧基硅烷、苯基三氯硅烷、苯基三甲氧基硅烷、N-[3-(三甲氧基硅基)丙基]乙二胺等中的至少一种。
7.根据权利要求5所述一种键合相类芬顿催化剂制备方法,其特征在于,所述二价铁离子的来源为硫酸亚铁溶液,所述硫酸亚铁溶液的摩尔浓度为0.02-0.08 mol/L。
8.根据权利要求5所述一种键合相类芬顿催化剂制备方法,其特征在于,所述还原剂选自碘化钾、碘化钠、溴化钾或溴化钠。
9.根据权利要求8所述一种键合相类芬顿催化剂制备方法,其特征在于,所述还原剂的浓度为0.02-0.08 mol/L。
10.根据权利要求5所述一种键合相类芬顿催化剂制备方法,其特征在于,所述酸选自硫酸、硝酸或盐酸。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241406A (zh) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | 用于吸附重金属离子的羧基化mcm-41介孔分子筛及制法 |
CN102703412A (zh) * | 2012-06-06 | 2012-10-03 | 华东理工大学 | 固定生物酶的顺磁性的醛基介孔分子筛及其制备方法 |
CN103537313A (zh) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | 苯羟基化制苯酚的催化剂及其制备方法 |
CN108043458A (zh) * | 2018-01-05 | 2018-05-18 | 中国石油大学(华东) | 一种固定化非均相芬顿催化剂的制备方法及其应用 |
CN108722473A (zh) * | 2018-06-04 | 2018-11-02 | 中国中化股份有限公司 | 一种加氢裂化催化剂的制备方法 |
CN110624597A (zh) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | 一种有机官能团功能化mcm分子筛的制备方法 |
CN110627084A (zh) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | 一种有机官能团功能化mcm分子筛的制备方法 |
-
2022
- 2022-04-11 CN CN202210370971.XA patent/CN114797945A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241406A (zh) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | 用于吸附重金属离子的羧基化mcm-41介孔分子筛及制法 |
CN102703412A (zh) * | 2012-06-06 | 2012-10-03 | 华东理工大学 | 固定生物酶的顺磁性的醛基介孔分子筛及其制备方法 |
CN103537313A (zh) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | 苯羟基化制苯酚的催化剂及其制备方法 |
CN108043458A (zh) * | 2018-01-05 | 2018-05-18 | 中国石油大学(华东) | 一种固定化非均相芬顿催化剂的制备方法及其应用 |
CN108722473A (zh) * | 2018-06-04 | 2018-11-02 | 中国中化股份有限公司 | 一种加氢裂化催化剂的制备方法 |
US20210205801A1 (en) * | 2018-06-04 | 2021-07-08 | Fu Zhou University | Method for preparing hydrocracking catalyst |
CN110624597A (zh) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | 一种有机官能团功能化mcm分子筛的制备方法 |
CN110627084A (zh) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | 一种有机官能团功能化mcm分子筛的制备方法 |
Non-Patent Citations (2)
Title |
---|
刘文静等: "铁系-酸改性MCM-41异相芬顿催化剂用于苯酚降解的研究", 《山东化工》 * |
周仁贤等: "MCM-41分子筛固载羧基钯(Ⅱ)配合物催化剂的制备、表征和催化性能(Ⅰ)", 《化工学报》 * |
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