CN108745368A - 一种双钙钛矿催化剂及其制备方法与应用 - Google Patents
一种双钙钛矿催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 125
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 62
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 235000010333 potassium nitrate Nutrition 0.000 claims description 28
- 239000004323 potassium nitrate Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 235000010344 sodium nitrate Nutrition 0.000 claims description 27
- 239000004317 sodium nitrate Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011833 salt mixture Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 16
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 14
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 230000010718 Oxidation Activity Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical group [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 229910003433 La2NiMnO6 Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical group [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910019016 NaNO3—KNO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 rare earth metal salt Chemical class 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- RLDDBOUYRSPFAE-UHFFFAOYSA-N [Ti+4].[N+](=O)([O-])[O-].[Na+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [Ti+4].[N+](=O)([O-])[O-].[Na+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] RLDDBOUYRSPFAE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- 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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- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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Abstract
本发明涉及一种双钙钛矿催化剂及其制备方法与应用,属于催化剂技术领域。本发明双钙钛矿催化剂的化学通式为A2BB’O6,其中A为稀土金属元素La、Ce、Nd或Gd,B为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,B’为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,且B≠B’。本发明采用熔融盐法,在NaNO3和KNO3熔融盐体系中制备纳米规则形貌的双钙钛矿催化剂A2BB’O6。双钙钛矿催化剂在较低的温度和较宽的温度范围内可高效地将一氧化氮催化氧化为二氧化氮,本发明方法的工艺简单,易于操作,成本较低,易实现工业化生产。
Description
技术领域
本发明涉及一种双钙钛矿催化剂及其制备方法与应用,属于催化剂技术领域。
背景技术
在汽车尾气净化技术方面,NO被催化氧化为NO2不仅作为关键步骤,而且具有重要意义:在LNT(Lean-burn NOX Trap)阶段,NO被氧化为更容易储存的NO2;在SCR(SelectiveCatalytic Reduction)阶段,NO:NO2的比为1:1催化效率最优;微粒捕集器DPF中NO2的存在能够显著降低soot的起燃温度。目前普遍使用催化氧化NO的催化剂主要是以Pt为活性中心负载在A12O3等载体上,其中贵金属的负载量为2%〜3%。这种催化剂的使用成本较高,且贵金属在高温催化反应中会发生团聚而使催化性能下降。
与Pt、Ru、Pd等贵金属催化剂相比,钙钛矿材料具备价格低廉、结构稳定、催化活性良好及高温下热力学性能稳定等特点,在尾气催化净化领域具有良好的发展潜力。但是,由于其低温起燃的特性不佳、比表面积低以及成分复杂难以批量制备的不足,限制了钙钛矿材料优势的发挥和实际的应用。
发明内容
针对上述现有技术存在的问题及不足,本发明提供一种双钙钛矿催化剂及其制备方法与应用,本发明双钙钛矿催化剂的化学通式为A2BB’O6,其中A为稀土金属元素La、Ce、Nd或Gd,B为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,B’为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,且B≠B’。双钙钛矿催化剂可在较低的温度下和较宽的温度范围内高效地将一氧化氮催化氧化为二氧化氮,其成本低,对一氧化氮催化氧化的转化率可达到70%以上,更适应高温下NO的催化氧化。
所述双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐、B盐和B’盐加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐为稀土金属元素La、Ce、Nd或Gd的硝酸盐,B为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga的硝酸盐,B’为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga的硝酸盐,且B≠B’;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;
(3)步骤(2)所得混合盐以2~10℃/min的升温速率匀速升温至400~800℃并焙烧3~10h,然后以2~3℃/min的降温速率匀速降温至室温;
(4)将步骤(3)所得焙烧产物采用温度为70~80℃的去离子水洗涤3次以上,然后干燥即得双钙钛矿催化剂;
进一步地,所述A盐、B盐和B’盐的总摩尔量与硝酸钾和硝酸钠的总摩尔量的比为1:(20~60);
进一步地,所述A盐、B盐和B’盐的摩尔比为2:1:1;
进一步地,所述硝酸钾与硝酸钠的摩尔比为1:(1~1.5)。
本发明的熔盐体系选取NaNO3-KNO3二元混合盐体系,标准气压下,NaNO3的熔点为308℃,KNO3的熔点为344℃,在NaNO3与KNO3的最低共熔点的配比组成摩尔分数NaNO3/(NaNO3+KNO3)为47%时的最低共熔点为225℃,即在温度为225℃时开始形成熔盐共熔物。NaNO3-KNO3二元混合盐体系不溶于无水乙醇,不干扰其他金属混合盐在无水乙醇中混合均匀;在高温熔盐状态下,使双钙钛矿催化剂的固相合成反应在熔盐共熔物分解的部分氧气氧化气氛中进行,有利于金属氧化物的形成;在固相合成反应结束后,NaNO3-KNO3二元混合盐体系组分易溶于水,可快速清除双钙钛矿催化剂的熔融盐体系组分。
双钙钛矿催化剂可用于催化氧化NO,可以在较低的温度下和较宽的温度范围内高效地将一氧化氮催化氧化为二氧化氮,具有很好的热稳定性,能长时间保持较高的催化活性,明显提高汽车尾气中氮氧化物的去除效率。
本发明的有益效果是:
(1)本发明方法采用硝酸钾和硝酸钠作为混合熔融盐,在混合熔融盐中焙烧即得双钙钛矿催化剂A2BB’O6,其制备方法简单,易于操作,适合大规模工业化应用;
(2)本发明双钙钛矿催化剂为双钙钛矿型结构,结构稳定,不易相变,因而具有优异的热稳定性,寿命长,能长时间保持较高的催化活性;主要包括稀土金属盐、过渡族金属盐、碱金属盐等,不涉及贵金属的使用,成本较低;
(3)本发明双钙钛矿催化剂可用于催化氧化NO,可以在较低的温度下和较宽的温度范围内高效地将一氧化氮催化氧化为二氧化氮,具有很好的热稳定性,能长时间保持较高的催化活性,明显提高汽车尾气中氮氧化物的去除效率。
附图说明
图1为实施例1的La2CoMnO6双钙钛矿催化剂的XRD图谱;
图2为实施例1~4双钙钛矿催化剂催化氧化一氧化氮的转化率-温度变化曲线。
具体实施方式
下面结合具体实施方式,对本发明作进一步说明。
实施例1:本实施例双钙钛矿催化剂为La2CoMnO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸钴)和B’盐(B’盐为硝酸锰)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸锰)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸锰)的总摩尔量与硝酸钾和硝酸钠的总摩尔量的比为1:30;硝酸钾和硝酸钠的摩尔比为1:1;
(3)步骤(2)所得混合盐以2℃/min的升温速率匀速升温至700℃并焙烧6h,然后以2℃/min的降温速率匀速降温至室温;
(4)采用温度为80℃的去离子水洗涤3次步骤(3)所得焙烧产物,然后干燥即得La2CoMnO6双钙钛矿催化剂;
本实施例的La2CoMnO6双钙钛矿催化剂的XRD图谱如图1所示,从图1可知,纯相的La2CoMnO6的谱图,在2θ为23°、32°、40°、47°、52°、58°、68°和78°处出现了钙钛矿结构的特征衍射峰,没有杂相峰的出现,证明形成了单相的稀土双钙钛矿复合金属氧化物结构。根据德拜谢乐公式(Debye-Scherrer equation),我们可以算出纳米样品的平均晶粒尺寸,德拜谢乐公式的具体表达式为:D=kλ/(βcosθ),其中k为谢乐常数,数值为0.89,λ为入射X射线的波长,β为衍射峰的半高全宽(FWHM),θ为衍射角。扣除仪器展宽因素之后,我们计算得到La2CoMnO6双钙钛矿催化剂的平均晶粒尺寸为15nm;
本实施例的La2CoMnO6双钙钛矿催化剂的NO催化氧化活性评价实验在自制的圆柱状的反应器中进行,其中圆柱状的反应器的直径为6 mm,长度为550 mm,将500mg的A位掺杂型La2CoMnO6双钙钛矿催化剂置于反应器中心位置,两端用石英棉塞住;在进行催化反应之前,将催化剂在10%O2/N2(500ml/min)气氛下升温至温度为300℃稳定1h,然后在相同气氛下降温至温度为100℃,待温度稳定后,通入总流量为500 mL/min的含有500 ppm NO、10%O2的N2平衡气,空速(GHSV)为30000 h-1;在温度为150℃下稳定30~60min至出口NO浓度不再变化为止;在相同气氛下,将催化剂以10℃/min的升温速率升至温度为450℃,初始浓度测定后,调节温控仪设定值,使反应器达到所需的试验温度,测试温度范围为150℃~400℃,每隔25℃取一个测试点,在每个测试点各保持15分钟,出口NOX(NO、NO2)浓度由42i-HL型高浓度氮氧化物分析仪分析;La2CoMnO6双钙钛矿催化剂催化NO氧化成NO2的转化率如图2所示,从图2可知,La2CoMnO6双钙钛矿催化剂的最髙转化率为80%,最髙转化率所对应的温度为280℃;该双钙钛矿催化剂对NO的催化氧化性能完全符合热力学平衡,即热力学平衡下NO氧化成NO2的转化率达到最大值以后,随着温度的升高,转化率逐渐降低,故存在最髙转化率。
实施例2:本实施例双钙钛矿催化剂为La2FeMnO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸铁)和B’盐(B’盐为硝酸锰)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸铁)和B’盐(硝酸锰)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸铁)和B’盐(硝酸锰)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:30;硝酸钾和硝酸钠的摩尔比为1:1.4;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为78℃的去离子水洗涤4次步骤(3)所得焙烧产物,然后干燥即得La2FeMnO6双钙钛矿催化剂;
本实施例的La2FeMnO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,La2FeMnO6双钙钛矿催化剂的催化NO氧化成NO2的转化率如图2所示,从图2可知,La2FeMnO6双钙钛矿催化剂的最髙转化率为73%,最髙转化率所对应的温度为300℃。
实施例3:本实施例双钙钛矿催化剂为La2NiMnO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸镍)和B’盐(B’盐为硝酸锰)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸镍)和B’盐(硝酸锰)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸镍)和B’盐(硝酸锰)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:20;硝酸钾和硝酸钠的摩尔比为1:1.5;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为70℃的去离子水洗涤5次步骤(3)所得焙烧产物,然后干燥即得La2NiMnO6双钙钛矿催化剂;
本实施例的La2NiMnO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,La2NiMnO6双钙钛矿催化剂的催化NO氧化成NO2的转化率如图2所示,从图2可知,La2NiMnO6双钙钛矿催化剂的最髙转化率为70%,最髙转化率所对应的温度为312℃。
实施例4:本实施例双钙钛矿催化剂为La2CuMnO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸铜)和B’盐(B’盐为硝酸锰)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸铜)和B’盐(硝酸锰)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸铜)和B’盐(硝酸锰)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:40;硝酸钾和硝酸钠的摩尔比为1:1.4;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为76℃的去离子水洗涤6次步骤(3)所得焙烧产物,然后干燥即得La2CuMnO6双钙钛矿催化剂;
本实施例的La2CuMnO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,La2CuMnO6双钙钛矿催化剂的催化NO氧化成NO2的转化率如图2所示,从图2可知,La2CuMnO6双钙钛矿催化剂的最髙转化率为64%,最髙转化率所对应的温度为335℃。
实施例5:本实施例双钙钛矿催化剂为La2CoAlO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸钴)和B’盐(B’盐为硝酸铝)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸铝)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸铝)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:50;硝酸钾和硝酸钠的摩尔比为1:1.3;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为72℃的去离子水洗涤3次步骤(3)所得焙烧产物,然后干燥即得La2CoAlO6双钙钛矿催化剂;
本实施例的La2CoAlO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,La2CoAlO6双钙钛矿催化剂的催化NO氧化成NO2的最髙转化率为60%,最髙转化率所对应的温度为325℃。
实施例6:本实施例双钙钛矿催化剂为La2CoGaO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸镧)、B盐(B盐为硝酸钴)和B’盐(B’盐为硝酸镓)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸镓)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸镧)、B盐(硝酸钴)和B’盐(硝酸镓)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:60;硝酸钾和硝酸钠的摩尔比为1:1.1;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为75℃的去离子水洗涤5次步骤(3)所得焙烧产物,然后干燥即得La2CoGaO6双钙钛矿催化剂;
本实施例的La2CoGaO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,La2CoGaO6双钙钛矿催化剂的催化NO氧化成NO2的最髙转化率为62%,最髙转化率所对应的温度为335℃。
实施例7:本实施例双钙钛矿催化剂为Nd2CoAlO6;
一种双钙钛矿催化剂的制备方法,具体步骤如下:
(1)将A盐(A盐为硝酸钕)、B盐(B盐为硝酸钴)和B’盐(B’盐为硝酸铝)加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐(硝酸钕)、B盐(硝酸钴)和B’盐(硝酸铝)的摩尔比为2:1:1;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;其中A盐(硝酸钕)、B盐(硝酸钴)和B’盐(硝酸铝)的总摩尔量与与硝酸钾和硝酸钠的总摩尔量的比为1:45;硝酸钾和硝酸钠的摩尔比为1:1.2;
(3)步骤(2)所得混合盐以3℃/min的升温速率匀速升温至800℃并焙烧4h,然后以2.5℃/min的降温速率匀速降温至室温;
(4)采用温度为70℃的去离子水洗涤4次步骤(3)所得焙烧产物,然后干燥即得Nd2CoAlO6双钙钛矿催化剂;
本实施例的Nd2CoAlO6双钙钛矿催化剂的NO催化氧化活性评价实验与实施例1相同,Nd2CoAlO6双钙钛矿催化剂的催化NO氧化成NO2的最髙转化率为67%,最髙转化率所对应的温度为315℃。
以上对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (6)
1.一种双钙钛矿催化剂,其特征在于:化学通式为A2BB’O6,其中A为稀土金属元素La、Ce、Nd或Gd,B为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,B’为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga,且B≠B’。
2.权利要求1所述双钙钛矿催化剂,其特征在于,具体步骤如下:
(1)将A盐、B盐和B’盐加入到无水乙醇中研磨至溶解得到乙醇金属盐溶液,其中A盐为稀土金属元素La、Ce、Nd或Gd的硝酸盐,B为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga的硝酸盐,B’为Co、Fe、Ni、Cu、Mn、Zn、Al或Ga的硝酸盐,且B≠B’;
(2)在步骤(1)所得乙醇金属盐溶液、硝酸钾和硝酸钠混合均匀,干燥挥发乙醇得到混合盐;
(3)步骤(2)所得混合盐以2~10℃/min的升温速率匀速升温至400~800℃并焙烧3~10h,然后以2~3℃/min的降温速率匀速降温至室温;
(4)将步骤(3)所得焙烧产物采用温度为70~80℃的去离子水洗涤3次以上,然后干燥即得双钙钛矿催化剂。
3.根据权利要求2所述双钙钛矿催化剂的制备方法,其特征在于:A盐、B盐和B’盐的总摩尔量与硝酸钾和硝酸钠的总摩尔量的比为1:(20~60)。
4.根据权利要求2所述双钙钛矿催化剂的制备方法,其特征在于:A盐、B盐和B’盐的摩尔比为2:1:1。
5.根据权利要求2所述双钙钛矿催化剂的制备方法,其特征在于:硝酸钾与硝酸钠的摩尔比为1:(1~1.5)。
6.权利要求1所述双钙钛矿催化剂在催化氧化NO中的应用。
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