CN113769756A - 一种新型铁锰氧化物催化剂及其应用 - Google Patents
一种新型铁锰氧化物催化剂及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims abstract description 8
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000623 carbamazepine Drugs 0.000 claims abstract description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000012425 OXONE® Substances 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 15
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 27
- 230000015556 catabolic process Effects 0.000 description 21
- 238000006731 degradation reaction Methods 0.000 description 21
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 229940126601 medicinal product Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/08—Heat treatment
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Abstract
本发明公开了一种用于水处理的新型铁锰氧化物催化剂,其特征是以硝酸铁、硝酸锰、柠檬酸和乙二醇为原料,通过溶胶‑凝胶法合成铁锰前驱体复合物,经煅烧得到一种新型铁锰氧化物催化剂。本发明所提供的这种用于水处理的新型铁锰氧化物催化剂能够在中性pH条件下高效活化过一硫酸氢钾复合盐,深度降解废水中的医药品污染物卡马西平,性能显著优于传统的铁锰基催化剂;本发明提供的这种用于水处理的新型铁锰氧化物催化剂具有催化活性高、稳定性好和环境友好的优势,特别适用于医药废水的深度处理。
Description
技术领域
本发明涉及医药化工废水深度处理技术领域,尤其涉及一种新型铁锰氧化物催化剂及其应用。
背景技术
医药品作为新兴污染物在水体中广泛检出,多数药物具有生物毒性、难降解性及假持久性,严重威胁水环境安全和人类健康。废水中医药品污染物的深度处理是当前污水处理研究领域的热点和难点之一,因此,发展有效的医药废水深度处理技术对水资源保护和社会可持续发展具有重要意义。高级氧化技术通过产生高活性的自由基(例如羟基自由基(HO·)和硫酸根自由基(SO4 ·-))降解水体中的难降解有机污染物,具有氧化能力强、反应速率快和处理效果好等优势。相比于HO·,SO4 ·-具有较长的寿命和相当的氧化还原电位,对污染物具有更好的选择性。因此,基于SO4 ·-的高级氧化技术成为近年来的研究热点,而缺乏高效稳定且环境友好的过硫酸盐催化材料是限制该技术应用的主要瓶颈。因此,发展高催化活性和高稳定性的环境友好型催化剂,将能够推动SO4 ·-高级氧化技术的发展,有望为医药废水的深度处理提供一种有效途径。
发明内容
本发明的目的是为了解决上述技术的不足而提供一种具有催化活性高、稳定性好和环境友好的优势,适用于医药废水的深度处理过程的新型铁锰氧化物催化剂及其应用。
为了达到上述目的,本发明提供的一种新型铁锰氧化物催化剂,其特征在于:以硝酸铁、硝酸锰、柠檬酸和乙二醇为原料,通过溶胶-凝胶法合成铁锰前驱体复合物,经煅烧得到;所述硝酸铁与硝酸锰的摩尔比为1:3-5,铁锰离子、柠檬酸与乙二醇的摩尔比为1:1:0.72,通过溶胶-凝胶法制得铁锰前驱体复合物;将所制得铁锰前驱体复合物在空气氛围下500℃-600℃煅烧2小时,获得新型铁锰氧化物催化剂。
本发明提供的一种新型铁锰氧化物催化剂的应用,其特征是用于活化过一硫酸氢钾复合盐并对水中医药品污染物卡马西平的优化处理,其优化处理条件为:待处理的污水调整pH值范围6-8,新型铁锰氧化物催化剂投加量0.3-0.5g L-1,过一硫酸氢钾复合盐投加量3-7mmol L-1。
本发明得到的新型铁锰氧化物催化剂能够在中性pH条件下高效活化过一硫酸氢钾复合盐,深度降解废水中的医药品污染物卡马西平,性能显著优于传统的铁锰基催化剂。
本发明提供的一种新型铁锰氧化物催化剂具有以下优点:
(1)本发明提供的新型铁锰氧化物催化剂制备方法简单,制得催化剂属于多孔材料,孔隙丰富,比表面积大,表面富含Fe3+、Mn3+和Mn4+等活性位。
(2)本发明提供的新型铁锰氧化物催化剂能够在中性pH条件下高效活化过一硫酸氢钾复合盐,深度降解废水中的医药品污染物卡马西平,性能显著优于传统的铁锰基催化剂。
(3)该催化剂具有催化活性高、稳定性好和环境友好的优势,适用于医药废水的深度处理过程。
附图说明
图1是本发明新型铁锰氧化物催化剂表征结果图:
其中:图1(a)为新型FeMnO催化剂的X射线衍射图(XRD);图1(b)为新型FeMnO催化剂的扫描电镜(SEM)图片;图1(c)为新型FeMnO催化剂的N2吸-脱附等温线;图1(d1)为新型FeMnO催化剂Fe离子的X射线光电子能谱图(XPS);图1(d2)为新型FeMnO催化剂Mn离子的X射线光电子能谱图(XPS);
图2新型FeMnO催化剂和传统铁锰基材料催化活性对比图;
图3铁锰比例对新型FeMnO催化剂催化活性的影响;
图4煅烧温度对新型FeMnO催化剂催化活性的影响;
图5新型FeMnO催化剂投加量对医药品目标物降解效果的影响;
图6过一硫酸氢钾复合盐投加量对医药品目标物降解效果的影响;
图7溶液pH对医药品目标物降解效果的影响。
具体实施方式
为了便于清晰了解本发明的技术手段,下面结合具体实施例,对本发明的具体实施方式作进一步详细描述,以下实施例用于进一步说明本发明能实现的技术效果,并非限制本发明的保护范围。
实施例:
本实施例提供的一种新型铁锰氧化物催化剂:以硝酸铁、硝酸锰、柠檬酸和乙二醇为原料,通过溶胶-凝胶法合成铁锰前驱体复合物,经煅烧得到;所述硝酸铁与硝酸锰的摩尔比为1:3-5,铁锰离子、柠檬酸与乙二醇的摩尔比为1:1:0.72,在80℃条件下搅拌3h,制得溶胶;将制得的溶胶置于真空干燥箱中,在110℃条件下干燥,制得铁锰前驱体复合物;将所制得铁锰前驱体复合物在空气氛围下经500-600℃煅烧2小时,获得新型铁锰氧化物催化剂。
本实施例采用上述获得的新型铁锰氧化物催化剂进行如下应用实验:
实验在100mL反应瓶中进行,向含有医药品(卡马西平)的废水溶液中加入确定量的上述实施例提供的新型铁锰氧化物催化剂(以下简称新型FeMnO催化剂)和过一硫酸氢钾复合盐开始反应,并在预设时间点取样分析,具体操作如下:
(1)用30mmol L-1硼酸缓冲溶液控制废水pH在6-8。
(2)加入FeMnO催化剂,超声1min,振荡15min以达到材料对污染物的吸-脱附平衡。
(3)加入过一硫酸氢钾复合盐开始反应,并在预设时间取样分析。
新型FeMnO催化剂的表征:
图1(a)为新型FeMnO催化剂的X射线衍射图(XRD);图1(b)为新型FeMnO催化剂的扫描电镜(SEM)图片;图1(c)为新型FeMnO催化剂的N2吸-脱附等温线;图1(d1)为新型FeMnO催化剂Fe离子的X射线光电子能谱图(XPS);图1(d2)为新型FeMnO催化剂Mn离子的X射线光电子能谱图(XPS)。由XRD表征结果可知,该催化剂的特征衍射峰与Fe2O3和Mn2O3的标准图谱接近;SEM结果显示该催化剂属于多孔材料,孔隙丰富;BET分析结果显示该催化剂的比表面积为36.776m2 g-1,孔体积达到0.3364cm3 g-1;XPS分析结果表明该催化剂表面富含Fe3+、Mn3+和Mn4+,与XRD分析结果一致。
实施例1:新型FeMnO催化剂和传统铁锰基材料催化活性对比
图2为新型FeMnO催化剂和传统铁锰基材料(Fe3O4和Mn2O3)催化活性对比图。由图2可见,经过1h反应时间,Fe3O4和Mn2O3活化过一硫酸氢钾复合盐对目标医药品的降解率仅分别达到70%和15%;而本发明公开的新型FeMnO催化剂活化过一硫酸氢钾复合盐在20min时对目标医药品的降解率达到100%。该结果表明本发明公开的新型FeMnO催化剂具有良好的催化活性。
实施例2:铁锰比例和煅烧温度对新型FeMnO催化剂催化活性的影响
图3和图4为铁锰比例和煅烧温度对新型FeMnO催化剂催化活性的影响。由图3可见,当铁锰比例从1:0.5增大至1:3时,目标物降解效果显著提升;进一步增大铁锰比例至1:5,目标物降解效果提升较小,表明当铁锰比例在1:3-5条件下获得的FeMnO催化剂催化活性较高,故本发明优选铁锰比例为1:3-5。由图4可见,当煅烧温度从400℃增大至500℃时,目标物降解效果显著提升;进一步提高煅烧温度至600℃,目标物降解速率有所提升,降解效果相差不大,表明煅烧温度在500℃-600℃条件下获得的FeMnO催化剂催化活性较高,故本发明优选煅烧温度为500℃-600℃。
实施例3:新型FeMnO催化剂和过一硫酸氢钾复合盐投加量对医药品目标物降解效果的影响
图5和图6为新型FeMnO催化剂和过一硫酸氢钾复合盐投加量对医药品目标物降解效果的影响。由图5可见,目标物降解效果随着催化剂投加量的增加而显著提升。当FeMnO催化剂的投加量从0.1g L-1增加到0.5g L-1时,目标物降解效率快速增大,这是因为增加催化剂投加量能提供更多的活性位点,提高SO4 ·-的产生速率,促进污染物的降解。依据图5结果,本发明优选FeMnO催化剂的投加量为0.3-0.5g L-1。由图6可见,当过一硫酸氢钾复合盐投加量从1mmol L-1增加到3mmol L-1时,目标物降解效率显著提升,这是因为增加过一硫酸氢钾复合盐投加量能提高SO4 ·-的产生速率,进而获得较高的污染物降解效率。依据图6结果,本发明优选过一硫酸氢钾复合盐投加量为3-7mmol L-1。
实施例4:溶液pH对医药品目标物降解效果的影响
图7为溶液pH对医药品目标物降解效果的影响。由图可看出在pH6-8范围内,新型FeMnO催化剂活化过一硫酸氢钾复合盐对废水中医药品目标物均具有较好的处理效果,其中,pH为8的条件下获得的降解效果最好。此外,当pH达到9时,目标污染物的降解效果受到明显抑制,这是因为该催化剂在碱性条件下表面带负电荷,导致其对过一硫酸氢钾复合盐具有静电斥力,进而抑制过一硫酸氢钾复合盐的活化。依据图7结果,本发明优选反应pH条件为6-8。
通过上述实施例(1)、(2)、(3)和(4)的结果分析,说明本发明限定技术方案制备的新型FeMnO催化剂具有优异的催化活性,在中性pH条件下能够高效活化过一硫酸氢钾复合盐降解废水中医药品污染物卡马西平,在医药化工废水深度处理领域具有良好的应用前景。
以上仅是本发明的优选实施方式,并不用于限制本发明。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (2)
1.一种新型铁锰氧化物催化剂,其特征在于:以硝酸铁、硝酸锰、柠檬酸和乙二醇为原料,通过溶胶-凝胶法合成铁锰前驱体复合物,经煅烧得到;所述硝酸铁与硝酸锰的摩尔比为1:3-5,铁锰离子、柠檬酸与乙二醇的摩尔比为1:1:0.72,通过溶胶-凝胶法制得铁锰前驱体复合物;将所制得铁锰前驱体复合物在空气氛围下经500℃-600℃煅烧2小时,获得新型铁锰氧化物催化剂。
2.一种根据权利要求1所述的新型铁锰氧化物催化剂的应用,其特征是用于活化过一硫酸氢钾复合盐并对水中医药品污染物卡马西平的优化处理,其优化处理条件为:待处理的污水调整pH值范围6-8,新型铁锰氧化物催化剂投加量0.3-0.5g L-1,过一硫酸氢钾复合盐投加量3-7mmol L-1。
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