CN114471606A - 一种二氧化钛改性的锰钴尖晶石催化剂及其制备方法和应用 - Google Patents
一种二氧化钛改性的锰钴尖晶石催化剂及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical class [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 4
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种二氧化钛改性的锰钴尖晶石催化剂及其制备方法和应用,所述制备方法包括以下步骤:将TiO2分散于去离子水中,将Mn(NO3)2·4H2O和Co(NO3)2·6H2O、尿素CO(NH2)2和氟化铵NH4F溶于去离子水,两种溶液混合形成混合溶液,然后加热反应,待溶液颜色由白色变成灰色,离心,将沉淀物洗涤,干燥,煅烧,即得二氧化钛改性锰钴尖晶石催化剂。本发明方法简单、快捷,无二次污染,将该催化剂用于环己烯催化氧化,环己烯转化率为70~85%。
Description
技术领域
本发明属于锰钴尖晶石催化剂技术领域,具体涉及一种二氧化钛改性的锰钴尖晶石催化剂及其制备方法和应用。
背景技术
环己烯是一种廉价易得的工业原料,它的氧化产物具有各种结构:环己烯酮、环己二醇、环氧环己烷、2-环己烯醇等重要化学中间体。同时环己烯的氧化产物拥有非常活泼基团,它可以与胺、苯酚、醇和羧酸反应形成一系列高附加值的化合物,这使得设计环己烯的选择性氧化的催化剂尤为关键。
据文献报道,传统的环己烯氧化需要使用过氧酸,虽然收率高,但流程长、设备腐蚀严重等,同时还产生有害气体,难以满足当前绿色环保的生产需求。近年来,高级氧化技术在催化氧化方面表现出良好的性能,其机理主要取决于羟基自由基。羟基自由基是一种非选择性强氧化剂,另外,硫酸根自由基比羟基自由基具有更高的选择性和更长的半衰期。因此,硫酸根自由基在协同参与氧化反应时具有更好的催化效应。硫酸根自由基是通过分解过硫酸盐产生的。过硫酸盐主要分为过一硫酸盐和过二硫酸盐。然而,过硫酸盐在常温条件下难以活化产生自由基,所以需要其进行活化处理。通过制备有效的催化剂可以对过硫酸盐进行活化,协同过氧化氢高效催化氧化环己烯。
目前使用的催化剂大多为稀有金属催化剂,稀有金属催化剂在催化氧化方面有明显的成本高的、循环性能差。
发明内容
发明目的:为了解决现有技术存在问题,本发明提供了一种二氧化钛改性的锰钴尖晶石催化剂及其制备方法和应用,其制备方法操作简便、成本低廉,所得催化剂催化效果好。
技术方案:为了达到上述发明问题,本发明采取的技术方案如下:
一种二氧化钛改性的锰钴尖晶石催化剂的制备方法,包括以下步骤:
将TiO2分散于去离子水中,将Mn(NO3)2·4H2O和Co(NO3)2·6H2O、尿素CO(NH2)2和氟化铵NH4F溶于去离子水,两种溶液混合形成混合溶液,然后加热反应,待溶液颜色由白色变成灰色,离心,将沉淀物洗涤,干燥,煅烧,即得二氧化钛改性锰钴尖晶石催化剂。
优选的,所述Mn(NO3)2·4H2O、Co(NO3)2·6H2O、NH4F、CO(NH2)2的摩尔比为1:(1-3):(2-4):(5-7)。
优选的,所述混合溶液pH值9~11。
优选的,所述加热反应的温度为90-110℃,时间为4-8h;所述加热反应采用回流方式进行。
优选的,所述洗涤采用去离子水洗涤2-3次;所述干燥是在60~70℃减压干燥8~10h;所述煅烧的温度为200~800℃。
一种二氧化钛改性的锰钴尖晶石催化剂,由上述制备方法制得。
优选的,所述二氧化钛改性的锰钴尖晶石催化剂中,TiO2的质量分数为10~90%。
本发明还提供了所述的二氧化钛改性的锰钴尖晶石催化剂在环己烯催化氧化中的应用。
优选的,以环己烯、过一硫酸盐和H2O2为原料,以所述二氧化钛改性的锰钴尖晶石催化剂,在60~90℃下反应10~12h。
进一步优选的,所述环己烯的浓度为0.5~2mol/L;过一硫酸盐(PMS)投加量为5~20mmoL/L;H2O2的浓度为25-35%,投加量1~2.5mmol/L;二氧化钛改性的锰钴尖晶石催化剂投加量为0.5~2g/L。。
有益效果:与现有技术相比,本发明具有以下优势:
1)操作简便:本发明提供的方法为制备的TiO2改性的MnCo2O4尖晶石催化剂,操作非常简便。
2)提供了更多的反应位点:本发明提供的方法所制备的TiO2改性MnCo2O4尖晶石可以通过调节TiO2的组分含量选择性的制备具有较高结晶度和较高比表面积的尖晶石,为催化反应提供了更多的反应位点。
3)成本低:本发明所制备的TiO2改性的MnCo2O4尖晶石催化剂具有优异的催化反应性能,与过一硫酸盐PMS和过氧化氢协同作用,然后用气相色谱法检测可以在12h使环己烯的转化率到达80%左右,环己烯酮的选择性达到75%左右。
附图说明
图1为实施例1所得MnCo2O4-TiO2的XRD图谱。
具体实施方式
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
一种TiO2改性的MnCo2O4尖晶石催化剂,该方法为:室温下将190mgTiO2溶于40mL去离子水,超声分散30min,将
10.5mgMn(NO3)2·4H2O,23.2mgCo(NO3)2·6H2O,14.5mgCO(NH2)2和4.5mgNH4F溶于10ml去离子水,并与TiO2分散液充分混合后,在100℃搅拌条件下,冷凝回流4h。待溶液颜色由白色变成灰色,离心,沉淀物用蒸馏水洗涤3次,60℃下减压干燥10h,经过300℃煅烧2.5h,即得TiO2改性的MnCo2O4尖晶石催化剂MnCo2O4-TiO2,其XRD图谱如图1所示。取上述催化剂8mg投加到2mol/L环己烯乙腈体系中,PMS投加量为1mmol/L,过氧化氢投加量1mol/L,在80℃条件下12h催化氧化后,用气相色谱法检测反应后体系中环己烯的转化率为72%,环己烯酮的选择性为75%。
实施例2
一种TiO2改性的MnCo2O4尖晶石催化剂,该方法为:室温下将190mgTiO2溶于40mL去离子水,超声分散30min,将
10.5mgMn(NO3)2·4H2O,23.2mgCo(NO3)2·6H2O,14.5mgCO(NH2)2和9mgNH4F溶于10ml去离子,并与TiO2分散液充分混合后,在100℃搅拌条件下,冷凝回流6h。待溶液颜色由白色变成灰色,离心,沉淀物用蒸馏水洗涤3次,60℃下减压干燥10h,经过300℃煅烧2.5h即得TiO2改性的MnCo2O4尖晶石催化剂。取上述催化剂10mg投加到2mol/L环己烯乙腈体系中,PMS投加量为1mmol/L,在80℃条件下12h催化氧化后,用气相色谱法检测反应后体系中环己烯的转化率为74%,环己烯酮的选择性为69%。
实施例3
一种TiO2改性的MnCo2O4尖晶石催化剂,该方法为:室温下将180mgTiO2溶于40mL去离子水,超声分散30min,将
21mgMn(NO3)2·4H2O,46.4mgCo(NO3)2·6H2O,29mgCO(NH2)2和9mgNH4F溶于10ml去离子水,并与TiO2分散液充分混合后,在100℃搅拌条件下,冷凝回流8h。待溶液颜色由白色变成灰色,离心,沉淀物用蒸馏水洗涤3次,60℃下减压干燥10h,经过300℃煅烧2.5h即得TiO2改性的MnCo2O4尖晶石催化剂。取上述催化剂6mg投加到2mol/L环己烯乙腈体系中,PMS投加量为1mmol/L,在80℃条件下12h催化氧化后,用气相色谱法检测反应后体系中环己烯的转化率为76%,环己烯酮的选择性为78%。
实施例4
一种TiO2改性的MnCo2O4尖晶石催化剂,该方法为:室温下将180mgTiO2溶于40mL去离子水,超声分散30min,将
21mgMn(NO3)2·4H2O,46.4mgCo(NO3)2·6H2O,29mgCO(NH2)2和18mgNH4F溶于10ml去离子水,并与TiO2分散液充分混合后,在100℃搅拌条件下,冷凝回流4h。待溶液颜色由白色变成灰色,离心,沉淀物用蒸馏水洗涤3次,60℃下减压干燥10h,经过300℃煅烧2.5h即得TiO2改性的MnCo2O4尖晶石催化剂。取上述催化剂8mg投加到2mol/L环己烯乙腈体系中,PMS投加量为1mmol/L,在80℃条件下12h催化氧化后,用气相色谱法检测反应后体系中环己烯的转化率为77%,环己烯酮的选择性为75%。
实施例5
一种TiO2改性的MnCo2O4尖晶石催化剂,该方法为:室温下将180mgTiO2溶于40mL去离子水,超声分散30min,将
21mgMn(NO3)2·4H2O,46.4mgCo(NO3)2·6H2O,29mgCO(NH2)2和18mgNH4F溶于10ml去离子水,并与TiO2分散液充分混合后,在100℃搅拌条件下,冷凝回流4h。待溶液颜色由白色变成灰色,离心,沉淀物用蒸馏水洗涤3次,60℃下减压干燥10h,,经过300℃煅烧2.5h即得TiO2改性的MnCo2O4尖晶石催化剂。取上述催化剂8mg投加到2mol/L环己烯乙腈体系中,PMS投加量为2mmol/L,在80℃条件下12h催化氧化后,用气相色谱法检测反应后体系中环己烯的转化率为80%,环己烯酮的选择性为75%。
本发明中制备的Mn(NO3)2·4H2O、Co(NO3)2·6H2O、CO(NH2)2、NH4F是与之相配比的质量,优选方案为实施例中方案。
本发明提供了一种思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
1.一种二氧化钛改性的锰钴尖晶石催化剂的制备方法,其特征在于,包括以下步骤:
将TiO2分散于去离子水中,将Mn(NO3)2·4H2O、Co(NO3)2·6H2O、尿素CO(NH2)2和氟化铵NH4F溶于去离子水,两种溶液混合形成混合溶液,然后加热反应,待溶液颜色由白色变成灰色,离心,将沉淀物洗涤,干燥,煅烧,即得二氧化钛改性锰钴尖晶石催化剂。
2.根据权利要求1所述的二氧化钛改性的锰钴尖晶石催化剂的制备方法,其特征在于,所述Mn(NO3)2·4H2O、Co(NO3)2·6H2O、NH4F、CO(NH2)2的摩尔比为1:(1-3):(2-4):(5-7)。
3.根据权利要求1所述的二氧化钛改性的锰钴尖晶石催化剂的制备方法,其特征在于,所述混合溶液pH值9~11。
4.根据权利要求1所述的二氧化钛改性的锰钴尖晶石催化剂的制备方法,其特征在于,所述加热反应的温度为90-110℃,时间为4-8h;所述加热反应采用回流方式进行。
5.根据权利要求1所述的二氧化钛改性的锰钴尖晶石催化剂的制备方法,其特征在于,所述洗涤采用去离子水洗涤2-3次;所述干燥是在60~70℃减压干燥8~10h;所述煅烧的温度为200~800℃。
6.一种二氧化钛改性的锰钴尖晶石催化剂,由权利要求1-5任一项所述制备方法制得。
7.根据权利要求6所述的二氧化钛改性的锰钴尖晶石催化剂,其特征在于,所述二氧化钛改性的锰钴尖晶石催化剂中,TiO2的质量分数为10~90%。
8.权利要求6或7所述的二氧化钛改性的锰钴尖晶石催化剂在环己烯催化氧化中的应用。
9.根据权利要求8所述的应用,其特征在于,以环己烯、过一硫酸盐和H2O2为原料,以所述二氧化钛改性的锰钴尖晶石催化剂,在60~90℃下反应10~12h。
10.根据权利要求9所述的应用,其特征在于,所述环己烯的浓度为0.5~2mol/L;过一硫酸盐(PMS)投加量为5~20mmoL/L;H2O2的浓度为25-35%,投加量1~2.5mmol/L;二氧化钛改性的锰钴尖晶石催化剂投加量为0.5~2g/L。
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