CN113318728A - 一种三维有序大孔钨铈锆复合氧化物催化剂及其制备方法和应用 - Google Patents
一种三维有序大孔钨铈锆复合氧化物催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- KCZDRKPSIWVTAF-UHFFFAOYSA-N [W].[Zr].[Ce] Chemical compound [W].[Zr].[Ce] KCZDRKPSIWVTAF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 13
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 38
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003546 flue gas Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 25
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
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- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims 1
- 230000003100 immobilizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 9
- 150000001340 alkali metals Chemical class 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Abstract
本发明涉及一种三维有序大孔结构的钨铈锆复合氧化物催化剂及其制备方法和应用,属于环境催化和大气污染控制技术领域。该催化剂以三维有序大孔铈锆复合氧化物为载体,三氧化钨为活性组分。三氧化钨与铈锆复合氧化物间的协同效应以及三维有序大孔结构明显提高了催化剂的脱硝活性和抗碱金属性能。本发明的三维有序大孔钨铈锆复合氧化物催化剂,在250~500℃范围内,空速为124000h‑1时,NOx转化率均在90%以上。本发明的催化剂可用于固定源烟气及柴油车尾气中NOx的高效脱除。
Description
技术领域
本发明涉及一种三维有序大孔钨铈锆复合氧化物催化剂及其制备和应用。该催化剂适用于热电厂、冶炼厂和工业炉窑等固定源烟气以及柴油车尾气中NOx的消除,属于环境催化和大气污染控制技术领域。
背景技术
氮氧化物作为一种典型的致霾污染物,其控制对于改善大气环境质量具有重要意义。氨气选择性催化还原(NH3-SCR)技术作为NOx脱除的有效手段,其核心是高性能脱硝催化剂。目前,工业应用的NH3-SCR脱硝催化剂主要是V2O5-WO3(MoO3)/TiO2,该催化剂存在如下问题:活性温度窗口窄,只有在300~400℃范围内NOx可被脱除;活性组份V2O5具有生物毒性;催化剂抗碱金属性能差;在高温下载体TiO2易发生相变,催化剂热稳定性差。因此,亟需研发活性温度窗口宽、抗碱金属性能强的环境友好型NH3-SCR脱硝催化剂。
本发明制备了一种三维有序大孔钨铈锆复合氧化物催化剂,表现出良好的NOx脱除活性和抗碱金属性能。
发明内容
本发明的目的是提供一种活性温度窗口宽、抗碱金属性能强的环境友好型NH3-SCR脱硝催化剂及其制备方法。在三维有序大孔钨铈锆复合氧化物催化剂中,三氧化钨高度分散于铈锆复合氧化物表面,且三氧化钨与铈锆复合氧化物之间存在强的协同效应,该协同效应以及三维有序大孔结构使催化剂具有优异的脱硝活性和强的抗碱金属性能。从而制得一种环境友好、脱硝活性高且温度窗口宽、抗碱金属性能强的复合氧化物脱硝催化剂。
本发明的目的是通过以下技术方案实现的:
采用三维有序大孔铈锆复合氧化物为载体,三氧化钨为活性组分,其组成表示为WO3/CexZryO2(3DOM),其中WO3的质量百分含量为5~15%,Ce的摩尔百分含量0.10≤x≤0.67,Zr的摩尔百分含量0.33≤y≤0.90。
本发明提供了一种制备三维有序大孔钨铈锆复合氧化物催化剂的方法,其特征在于该方法依次包括以下步骤:
(1)聚甲基丙烯酸甲酯(PMMA)模板制备:取一定量的甲基丙烯酸甲酯,加入到三口烧瓶中;称取过硫酸钾,溶于去离子水中,置于70~90℃水浴中恒温预热,然后将其加入三口烧瓶中,反应50~60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
(2)取一定量的硝酸铈和氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取一定量步骤(1)中的PMMA,将其倒入上述溶液中,浸渍1~2h后,抽滤,并在100~120℃下烘干,然后将样品在500~600℃焙烧4~8h,制得三维有序大孔的铈锆复合氧化物;
(3)取一定量的偏钨酸铵溶液加入到步骤(2)所得的铈锆复合氧化物中,搅拌4~6小时,制得浆料;
(4)将步骤(3)中所得浆料在120℃条件下烘干12~24小时,然后在500~600℃条件下焙烧4~8小时制得WO3/CexZryO2(3DOM)催化剂。
本发明与现有技术相比,具有以下优点及突出性效果:不采用有毒性的活性组分V2O5,通过制备三维有序大孔结构并发挥三氧化钨与铈锆复合氧化物间的协同效应,有效提高了催化剂的活性和抗碱金属性能,在250~500℃范围内,空速为124000h-1时,NOx转化率均在90%以上。
附图说明
图1是10%WO3/Ce0.5Zr0.5O2(3DOM)催化剂的SEM图。
具体实施方式
下面结合实施例对本发明的技术方案做进一步的说明:
实施例1:5%WO3/Ce0.5Zr0.5O2(3DOM)催化剂的制备
a)取113mL甲基丙烯酸甲酯,加入到三口烧瓶中;称取0.4g过硫酸钾,溶于去离子水中,置于70℃水浴中恒温预热,然后将其加入三口烧瓶中,反应50分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
b)取43.4g硝酸铈和32.2g氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取10g步骤a)中的PMMA,将其倒入上述溶液中,浸渍1h后,抽滤,并在100℃下烘干,然后将样品在600℃焙烧4h,制得三维有序大孔的铈锆复合氧化物;
c)取0.95mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌4小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干12小时,然后在500℃条件下焙烧8小时,制得5%WO3/Ce0.5Zr0.5O2(3DOM)催化剂。
实施例2:10%WO3/Ce0.5Zr0.5O2(3DOM)催化剂的制备
a)取113mL甲基丙烯酸甲酯,加入到三口烧瓶中;称取0.4g过硫酸钾,溶于去离子水中,置于90℃水浴中恒温预热,然后将其加入三口烧瓶中,反应60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
b)取43.4g硝酸铈和32.2g氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取10g步骤a)中的PMMA,将其倒入上述溶液中,浸渍2h后,抽滤,并在120℃下烘干,然后将样品在500℃焙烧4h,制得三维有序大孔的铈锆复合氧化物;
c)取2mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌6小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干24小时,然后在500℃条件下焙烧4小时,制得10%WO3/Ce0.5Zr0.5O2(3DOM)催化剂。
实施例3:15%WO3/Ce0.5Zr0.5O2(3DOM)催化剂的制备
a)取113mL甲基丙烯酸甲酯,加入到三口烧瓶中;称取0.4g过硫酸钾,溶于去离子水中,置于80℃水浴中恒温预热,然后将其加入三口烧瓶中,反应60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
b)取43.4g硝酸铈和32.2g氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取10g步骤a)中的PMMA,将其倒入上述溶液中,浸渍2h后,抽滤,并在100℃下烘干,然后将样品在600℃焙烧4h,制得三维有序大孔的铈锆复合氧化物;
c)取3.16mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌6小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干24小时,然后在550℃条件下焙烧6小时,制得15%WO3/Ce0.5Zr0.5O2(3DOM)催化剂。
实施例4:10%WO3/Ce0.9Zr0.1O2(3DOM)催化剂的制备
a)取113mL甲基丙烯酸甲酯,加入到三口烧瓶中;称取0.4g过硫酸钾,溶于去离子水中,置于90℃水浴中恒温预热,然后将其加入三口烧瓶中,反应60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
b)取78.2g硝酸铈和6.5g氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取15g步骤a)中的PMMA,将其倒入上述溶液中,浸渍2h后,抽滤,并在120℃下烘干,然后将样品在500℃焙烧4h,制得三维有序大孔的铈锆复合氧化物;
c)取2mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌6小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干24小时,然后在550℃条件下焙烧8小时,制得10%WO3/Ce0.9Zr0.1O2(3DOM)催化剂。
实施例5:10%WO3/Ce0.67Zr0.33O2(3DOM)催化剂的制备
a)取113mL甲基丙烯酸甲酯,加入到三口烧瓶中;称取0.4g过硫酸钾,溶于去离子水中,置于80℃水浴中恒温预热,然后将其加入三口烧瓶中,反应60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
b)取58.2g硝酸铈和21.3g氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取15g步骤a)中的PMMA,将其倒入上述溶液中,浸渍2h后,抽滤,并在100℃下烘干,然后将样品在500℃焙烧8h,制得三维有序大孔的铈锆复合氧化物;
c)取2mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌6小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干24小时,然后在550℃条件下焙烧8小时,制得10%WO3/Ce0.67Zr0.33O2(3DOM)催化剂。
实施例6:1%K-10%WO3/Ce0.5Zr0.5O2(3DOM)催化剂的制备
a)取2.14ml 0.1mol/L的硝酸钾溶液,加入去离子水,搅拌均匀;再取1g 10%WO3/Ce0.5Zr0.5O2(3DOM)(制备方法同实施例2相同)加入到该溶液中,搅拌6小时,制得浆料;
b)将步骤a)中制得的浆料在120℃条件下烘干12小时,然后将样品在马弗炉中500℃焙烧4小时,制得1%K-10%WO3/Ce0.5Zr0.5O2(3DOM)催催化剂。
实施例7(参比):共沉淀法制备10%WO3/Ce0.5Zr0.5O2(CP)催化剂
a)取4.34g硝酸铈和3.22g氧氯化锆溶于去离子水中,滴加氨水至pH=10得到沉淀物;
b)将步骤a)所得的沉淀物抽滤、洗涤,在120℃下干燥12小时,然后将样品在500℃焙烧4h,制得铈锆复合氧化物;
c)取2mL 0.02mol/L偏钨酸铵溶液加入到1g步骤b)所得的铈锆复合氧化物中,搅拌6小时,制得浆料;
d)将步骤c)中所得浆料在120℃条件下烘干24小时,然后在500℃条件下焙烧4小时,制得10%WO3/Ce0.5Zr0.5O2(CP)催化剂。
实施例8(参比):1%K-10%WO3/Ce0.5Zr0.5O2(CP)催化剂的制备
a)取2.14ml 0.1mol/L的硝酸钾溶液,加入去离子水,搅拌均匀;再取1g 10%WO3/Ce0.5Zr0.5O2(CP)(制备方法同实施例7相同)加入到该溶液中,搅拌6小时,制得浆料;
b)将步骤a)中制得的浆料在120℃条件下烘干12小时,然后将样品在马弗炉中500℃焙烧4小时,制得1%K-10%WO3/Ce0.5Zr0.5O2(CP)催催化剂。
实施例9:催化剂的制备方法与实施例1相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
实施例10:催化剂的制备方法与实施例2相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
实施例11:催化剂的制备方法与实施例3相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
表1.催化剂活性及抗碱金属性能
实施例12:催化剂的制备方法与实施例4相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
实施例13:催化剂的制备方法与实施例5相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
实施例14:催化剂的制备方法与实施例6相同,将0.12g催化剂置于连续流动固定床反应器中,反应气组成为500ppm NO,500ppm NH3,5%O2,用氮气做平衡气,反应气的流速为300ml/min,空速为124000h-1。活性评价温度范围为200-500℃,不同温度下,催化剂还原NOx的转化率见表1。
Claims (3)
1.一种用于氨选择性催化还原氮氧化物的三维有序大孔钨铈锆复合氧化物催化剂,其特征在于:该催化剂以三维有序大孔铈锆复合氧化物为载体,三氧化钨为活性组分,其组成表示为WO3/CexZryO2(3DOM),其中WO3的质量百分含量为5~15%,Ce的摩尔百分含量0.10≤x≤0.67,Zr的摩尔百分含量0.33≤y≤0.90。
2.一种制备如权利要求1所述的钨铈锆复合氧化物催化剂的方法,其特征在于该方法依次包括以下步骤:
(1)聚甲基丙烯酸甲酯(PMMA)模板制备:取一定量的甲基丙烯酸甲酯,加入到三口烧瓶中;称取过硫酸钾,溶于去离子水中,置于70~90℃水浴中恒温预热,然后将其加入三口烧瓶中,反应50~60分钟;然后将三口烧瓶中的溶液倒入盛有1500mL去离子水的烧杯中,同时不断搅拌;然后将所得乳浊液离心分离,取出固体层,并在80℃干燥,得到PMMA模板;
(2)取一定量的硝酸铈和氧氯化锆,将其溶于甲醇与乙二醇的混合溶液中,然后称取一定量步骤(1)中的PMMA,将其倒入上述溶液中,浸渍1~2h后,抽滤,并在100~120℃下烘干,然后将样品在500~600℃焙烧4~8h,制得三维有序大孔的铈锆复合氧化物;
(3)取一定量的偏钨酸铵溶液加入到步骤(2)所得的铈锆复合氧化物中,搅拌4~6小时,制得浆料;
(4)将步骤(3)中所得浆料在120℃条件下烘干12~24小时,然后在500~600℃条件下焙烧4~8小时制得WO3/CexZryO2(3DOM)催化剂。
3.如权利要求1所述三维有序大孔钨铈锆复合氧化物催化剂的应用,其特征在于,用于固定源烟气和柴油车尾气中NOx的消除。
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