CN114917916A - 一种高储氧量和高稳定性载氧体及其制备方法 - Google Patents
一种高储氧量和高稳定性载氧体及其制备方法 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000001301 oxygen Substances 0.000 title claims abstract description 142
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 142
- 238000003860 storage Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910019902 La0.8Sr0.2FeO3 Inorganic materials 0.000 claims abstract description 39
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 81
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 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 24
- 239000008247 solid mixture Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 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 14
- 235000015110 jellies Nutrition 0.000 claims description 14
- 239000008274 jelly Substances 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 14
- -1 lanthanum ions Chemical class 0.000 claims description 14
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910001427 strontium ion Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 64
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- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 11
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- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
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- 238000003786 synthesis reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
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- 229910052786 argon Inorganic materials 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
本发明涉及一种高储氧量和高稳定性载氧体及其制备方法,属于载氧体技术领域。本发明载氧体包括钙钛矿载体和活性组分,载氧体的通式为:x(Ni/CeO2)/La0.8Sr0.2FeO3,其中x为质量分数,0<x≤30%,载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10~20%。本发明载氧体在化学链甲烷重整反应中,能够显著降低反应温度,中温下(600~800℃)活化甲烷,降低反应能耗的同时防止保护活性组分防止载氧体失活,具有较强的稳定性。
Description
技术领域
本发明涉及一种高储氧量和高稳定性载氧体及其制备方法,属于化学链甲烷重整反应载氧体技术领域。
背景技术
甲烷干重整反应(DRM)同时利用CO2、CH4两种温室气体,其产物合成气(H2和CO)是一种宝贵的中间资源,可作为氢源,用于生产甲醇、氨等。
传统甲烷二氧化碳重整技术反应式为:
然而,在DRM反应中,高温(>800℃)反应物完全转化所需的催化剂选择上,这种能源密集型约束给重整催化剂带来了两个挑战:活性相的烧结和由大量副反应引发的碳中毒。
为了克服二氧化碳转化及甲烷干重整存在的问题,采用化学链燃烧技术(chemical looping combustion,CLC)将其耦合用于重整,即化学链干重整(chemicallooping dry reforming,CL-DRM)。CLR技术具有如下优点:(Ⅰ)不需要外部燃料为重整过程提供热量;(Ⅱ)不会产生二氧化碳排放,因为合成气中包含有所有的碳,环境友好;(Ⅲ)每单位燃料进料需要较少的蒸汽和较少的催化剂;(Ⅳ)较少考虑硫污染物,不会形成氮氧化物。
用于化学链干重整的载氧体常常选用晶体结构类似于钙钛氧化物(CaTiO3)的钙钛矿金属氧化物,记为ABO3,钙钛矿结构的高稳定性允许具有不同氧化状态的其他金属部分取代A位和B位阳离子,并由此产生结构缺陷,例如阴离子或阳离子空位。特别是,A位取代基的性质和数量可以稳定B阳离子的异常氧化状态和/或在固体中生成阴离子空位。因此,钙钛矿结构的广泛可变氧非化学计量(还原或氧化,ABO3)可以很容易地去除氧,同时仍然保持原始框架。
然而常用于CL-DRM反应的钙钛矿均需求高温(>800℃),并导致甲烷裂解使得积碳严重,并且未改性的钙钛矿载体氧空位浓度不足,循环反应性能不理想。
发明内容
针对目前CL-DRM反应中钙钛矿型氧化物需求高温且氧空位浓度不足的等问题,本发明提供一种高储氧量和高稳定性载氧体的制备方法,即采用溶胶凝胶法制备钙钛矿氧化物作为载体,将Ni/CeO2纳米颗粒均匀分散于钙钛矿载体表面,利用纳米氧化铈与钙钛矿之间相互作用,有效提高钙钛矿载体的氧空位浓度,进而提升载氧体氧迁移速率及其甲烷活化速率,提高载氧体反应性能。
一种高储氧量和高稳定性载氧体:载氧体包括钙钛矿载体和活性组分,载氧体的通式为:x(Ni/CeO2)/La0.8Sr0.2FeO3,其中x为质量分数,0<x≤30%,载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10~20%。
所述高储氧量和高稳定性载氧体的制备方法,具体步骤如下:
(1)按照La、Sr和Fe的化学计量比,将硝酸镧、硝酸锶和硝酸铁加入到去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度60~80℃下搅拌30~60min,然后加入乙二醇,搅拌至形成胶状物;
(3)胶状物干燥,然后在空气中匀速升温至温度800~850℃,恒温焙烧2~3h得到钙钛矿载体;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;
(5)将钙钛矿载体加入到前驱体溶液B中,在温度60~80℃下搅拌至去离子水完全蒸发得到固体混合物;或者将钙钛矿载体加入到前驱体溶液B中,逐滴滴加沉淀剂NH3·H2O使体系pH值为9.5~10.0,完全共沉淀后静置老化5~8h,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;或者将钙钛矿载体加入到前驱体溶液B中,再加入氢氧化钠溶液调节pH值为9.5~10.0,置于温度为100~110℃下水热处理20~24h,冷却至室温,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;
(6)固体混合物干燥,然后在空气中匀速升温至温度800~850℃,恒温焙烧2~3h得到载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3。
所述步骤(2)前驱体溶液A中镧离子、锶离子和铁离子的总摩尔量与柠檬酸的摩尔比为1:1.5~2。
所述步骤(2)中柠檬酸与乙二醇的摩尔比为1:1.5~2。
所述步骤(3)升温速率为2~5℃/min。
所述步骤(6)升温速率为2~5℃/min。
在甲烷还原阶段,化学链甲烷重整载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3在无氧条件下与甲烷反应,化学链甲烷重整载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3中的晶格氧将甲烷部分氧化生成合成气,同时化学链甲烷重整载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3被还原成x(Ni/Ce)/La0.8Sr0.2FeO3;在CO2氧化阶段,被还原后的化学链甲烷重整载氧体(Ni/Ce)/La0.8Sr0.2FeO3与二氧化碳反应,二氧化碳被还原成CO,(Ni/Ce)/La0.8Sr0.2FeO3被氧化成化学链甲烷重整载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3,实现载氧体的循环再生,恢复到与甲烷反应前的结构;
所述载氧体在化学链甲烷重整反应中,载氧体还原阶段的反应温度为600~800℃,载氧体氧化再生阶段的反应温度为600~800℃,载氧体还原阶段通入甲烷和氩气混合气,其中甲烷体积百分数为5%,其流量为30~50mL/min;载氧体氧化再生阶段通入二氧化碳和氩气混合气,其中二氧化碳体积百分数为5%,其流量为30~50mL/min。
本发明氧载体由Ni/CeO2与钙钛矿La0.8Sr0.2FeO3复合而成,通常情况下,Fe2+在LaSrFeO3钙钛矿氧化物中不稳定,由于CeO2-LaFeSrO3相互作用,LaFeSrO3上存在的CeO2纳米颗粒有利于Fe2+的形成,从而形成氧缺陷;而Fe2+物种与Ce3+的共存导致了氧缺陷的进一步形成,Ce与Fe的相互作用有利于氧空位浓度的提高。
本发明的有益效果是:
(1)本发明采用溶胶凝胶法制备钙钛矿氧化物作为载体,将Ni/CeO2纳米颗粒均匀分散于钙钛矿载体表面,构建了具有金属间相互作用的复合氧载体结构,产生晶格畸变并增加氧空位浓度,提高了抗积碳和抗烧结能力,从而获得高的合成气选择性和循环稳定性;
(2)本发明Ni金属的负载显著改善载氧体的反应活性,并降低材料的初始反应温度,使其适用于中温化学链干重整反应,Ni在纳米氧化铈的保护下,并没有出现烧结,复合氧载体多次循环后并未因此失活,仍能表现出优异的CH4活性;
(3)本发明载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3具有较高的CH4转化率(~88%)、CO选择性(~90%)、高的合成气产量且H2/CO比值十分接近理想值(~2),即能够高选择地产生高品质合成气,而且在多次周期性氧化还原循环中还具有优良的反应活性和循环稳定性;
(4)本发明复合载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3不仅能够将甲烷选择性氧化为H2/CO摩尔比十分接近理论值2的高品质合成气,还原的氧载体还能在二氧化碳氧化气氛中再生,同时利用两种温室气体。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:本实施例高储氧量和高稳定性载氧体包括钙钛矿载体和活性组分,载氧体为:10%(Ni/CeO2)/La0.8Sr0.2FeO3,即载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10%;
一种高储氧量和高稳定性载氧体的制备方法(浸渍法),具体步骤如下:
(1)按照La、Sr和Fe的化学计量比0.8:0.2:1,将硝酸镧、硝酸锶和硝酸铁加入到温度为80℃的去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度80℃下搅拌30min,然后加入乙二醇,搅拌至形成胶状物;其中前驱体溶液A中阳离子(镧离子、锶离子和铁离子)的总摩尔量与柠檬酸的摩尔比为1:1.5,柠檬酸与乙二醇的摩尔比为1:1.5;
(3)胶状物置于温度为100℃干燥12h,然后在空气中以3℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到钙钛矿载体,破碎、研磨、过筛至40-60目颗粒;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;其中硝酸镍中镍和硝酸铈中铈的摩尔比为1:9;
(5)将钙钛矿载体加入到前驱体溶液B中,在温度60℃下搅拌至去离子水完全蒸发得到固体混合物;
(6)固体混合物置于温度为100℃下干燥12h,然后在空气中以2℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到载氧体10%(Ni/CeO2)/La0.8Sr0.2FeO3;
对载氧体10%(Ni/CeO2)/La0.8Sr0.2FeO3进行催化活性测定,氧载体的活性通过比较合成气转化率,储氧量提升率是通过比较Ni/CeO2改性前后氧载体实际晶格氧消耗量测定,稳定性是通过循环测试来获得:在化学链甲烷重整反应中,载氧体还原阶段的反应温度为600-800℃,载氧体氧化再生阶段的反应温度为600-800℃,载氧体还原阶段通入甲烷和氩气混合气,其中甲烷体积百分数为5%,其流量为50mL/min;载氧体氧化再生阶段通入二氧化碳和氩气混合气,其中二氧化碳体积百分数为5%,其流量为40mL/min。
实施例2:本实施例高储氧量和高稳定性载氧体包括钙钛矿载体和活性组分,载氧体为:20%(Ni/CeO2)/La0.8Sr0.2FeO3,即载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占12%;
一种高储氧量和高稳定性载氧体的制备方法(浸渍法),具体步骤如下:
(1)按照La、Sr和Fe的化学计量比0.8:0.2:1,将硝酸镧、硝酸锶和硝酸铁加入到温度为70℃的去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度70℃下搅拌40min,然后加入乙二醇,搅拌至形成胶状物;其中前驱体溶液A中阳离子(镧离子、锶离子和铁离子)的总摩尔量与柠檬酸的摩尔比为1:1.8,柠檬酸与乙二醇的摩尔比为1:1.6;
(3)胶状物置于温度为110℃干燥15h,然后在空气中以4℃/min的升温速率匀速升温至温度820℃,恒温焙烧2.6h得到钙钛矿载体,破碎、研磨、过筛至40-60目颗粒;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;其中硝酸镍中镍和硝酸铈中铈的摩尔比为1.2:8.8;
(5)将钙钛矿载体加入到前驱体溶液B中,在温度70℃下搅拌至去离子水完全蒸发得到固体混合物;
(6)固体混合物置于温度为110℃下干燥12h,然后在空气中以3℃/min的升温速率匀速升温至温度820℃,恒温焙烧3h得到载氧体20%(Ni/CeO2)/La0.8Sr0.2FeO3;
对载氧体20%(Ni/CeO2)/La0.8Sr0.2FeO3进行催化活性测定,测定方法同实施例1。
实施例3:本实施例高储氧量和高稳定性载氧体包括钙钛矿载体和活性组分,载氧体为:30%(Ni/CeO2)/La0.8Sr0.2FeO3,即载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占15%;
一种高储氧量和高稳定性载氧体的制备方法(浸渍法),具体步骤如下:
(1)按照La、Sr和Fe的化学计量比0.8:0.2:1,将硝酸镧、硝酸锶和硝酸铁加入到温度为60℃的去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度60℃下搅拌60min,然后加入乙二醇,搅拌至形成胶状物;其中前驱体溶液A中阳离子(镧离子、锶离子和铁离子)的总摩尔量与柠檬酸的摩尔比为1:2,柠檬酸与乙二醇的摩尔比为1:1.6;
(3)胶状物置于温度为120℃干燥10h,然后在空气中以3℃/min的升温速率匀速升温至温度850℃,恒温焙烧2h得到钙钛矿载体,破碎、研磨、过筛至40-60目颗粒;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;其中硝酸镍中镍和硝酸铈中铈的摩尔比为1.5:8.5;
(5)将钙钛矿载体加入到前驱体溶液B中,在温度70℃下搅拌至去离子水完全蒸发得到固体混合物;
(6)固体混合物置于温度为120℃下干燥10h,然后在空气中以5℃/min的升温速率匀速升温至温度850℃,恒温焙烧2h得到载氧体30%(Ni/CeO2)/La0.8Sr0.2FeO3;
对载氧体30%(Ni/CeO2)/La0.8Sr0.2FeO3进行催化活性测定,测定方法同实施例1。
实施例4:本实施例高储氧量和高稳定性载氧体包括钙钛矿载体和活性组分,载氧体为:20%(Ni/CeO2)/La0.8Sr0.2FeO3,即载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10%;
一种高储氧量和高稳定性载氧体的制备方法(共沉淀法),具体步骤如下:
(1)按照La、Sr和Fe的化学计量比0.8:0.2:1,将硝酸镧、硝酸锶和硝酸铁加入到温度为80℃的去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度80℃下搅拌30min,然后加入乙二醇,搅拌至形成胶状物;其中前驱体溶液A中阳离子(镧离子、锶离子和铁离子)的总摩尔量与柠檬酸的摩尔比为1:1.5,柠檬酸与乙二醇的摩尔比为1:1.5;
(3)胶状物置于温度为100℃干燥12h,然后在空气中以3℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到钙钛矿载体,破碎、研磨、过筛至40-60目颗粒;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;其中硝酸镍中镍和硝酸铈中铈的摩尔比为1:9;
(5)将钙钛矿载体加入到前驱体溶液B中,逐滴滴加沉淀剂NH3·H2O使体系pH值为9.5~10.0,完全共沉淀后静置老化6h,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;
(6)固体混合物置于温度为100℃下干燥12h,然后在空气中以2℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到载氧体10%(Ni/CeO2)/La0.8Sr0.2FeO3;
对载氧体20%(Ni/CeO2)/La0.8Sr0.2FeO3进行催化活性测定,测定方法同实施例1。
实施例5:本实施例高储氧量和高稳定性载氧体包括钙钛矿载体和活性组分,载氧体为:20%(Ni/CeO2)/La0.8Sr0.2FeO3,即载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10%;
一种高储氧量和高稳定性载氧体的制备方法(水热法),具体步骤如下:
(1)按照La、Sr和Fe的化学计量比0.8:0.2:1,将硝酸镧、硝酸锶和硝酸铁加入到温度为80℃的去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度80℃下搅拌30min,然后加入乙二醇,搅拌至形成胶状物;其中前驱体溶液A中阳离子(镧离子、锶离子和铁离子)的总摩尔量与柠檬酸的摩尔比为1:1.5,柠檬酸与乙二醇的摩尔比为1:1.5;
(3)胶状物置于温度为100℃干燥12h,然后在空气中以3℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到钙钛矿载体,破碎、研磨、过筛至40-60目颗粒;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;其中硝酸镍中镍和硝酸铈中铈的摩尔比为1:9;
(5)将钙钛矿载体加入到前驱体溶液B中,再加入氢氧化钠溶液调节pH值为9.5~10.0,置于温度为100~110℃下水热处理22h,冷却至室温,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;
(6)固体混合物置于温度为100℃下干燥12h,然后在空气中以2℃/min的升温速率匀速升温至温度800℃,恒温焙烧3h得到载氧体10%(Ni/CeO2)/La0.8Sr0.2FeO3;
对载氧体20%(Ni/CeO2)/La0.8Sr0.2FeO3进行催化活性测定,测定方法同实施例1;
实施例1~5载氧体催化活性见表1,活性测定是以各物质的转化率及选择性来说明,储氧催化剂的循环稳定性,通常长期的反应测试可得,储氧量提升通过实际晶格氧消耗量结果计算得到;
表1实施例1~5载氧体催化活性
从表1可知,实施例2、4、5甲烷转化率较高,浸渍法中活性组分Ni/CeO2纳米颗粒含量为20%时,复合氧载体的甲烷活性优势明显,循环稳定性更好;实施例1~3的催化活性可以看出,当Ni/CeO2负载后,复合氧载体的反应活性有较大提升,活性组分Ni/CeO2纳米颗粒含量为30%时,催化活性比活性组分Ni/CeO2纳米颗粒含量为20%时的催化活性低,Ni/CeO2负载有效提高了氧释放性能,当表面氧被消耗时,位于氧化物亚表面或体相氧可以立即迁移到表面,为甲烷氧化提供更多晶格氧;使得整体反应更趋向于甲烷的部分氧化,甲烷部分氧化得到加强,CO选择性有所提高,但进一步的Ni/CeO2负载会使得氧空位的覆盖,导致氧空位浓度的降低;
从实施例2、4、5的催化活性可知,负载方式的不同会对反应催化性能产生影响,水热法(实施例5)的甲烷转化率达到了92%,储氧量提升达到了52%,循环性能良好,纳米CeO2的负载明显提升氧释放速率,促进CH4的部分氧化,有效提高CO选择性的同时降低了积碳的生成,利用水热法负载的CeO2粒径更小,而纳米CeO2粒径越小,其Ni颗粒分散度更高,且甲烷反应性越强;Ni在纳米氧化铈的保护下,并没有出现烧结,复合氧载体多次循环后并未因此失活,仍能表现出优异的CH4活性;
Ni/CeO2均匀分散在的钙钛矿载体表面,并通过占据空位诱导氧空位的增加,氧空位浓度对决定反应活性起着重要作用;高储氧的复合氧载体x(Ni/CeO2)/La0.8Sr0.2FeO3具有良好的甲烷催化性能、循环稳定性和氧释放能力。
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)
1.一种高储氧量和高稳定性载氧体,其特征在于:载氧体包括钙钛矿载体和活性组分,载氧体的通式为:x(Ni/CeO2)/La0.8Sr0.2FeO3,其中x为质量分数,0<x≤30%,载氧体的钙钛矿载体为La0.8Sr0.2FeO3,活性组分为Ni/CeO2纳米颗粒,以Ni/CeO2纳米颗粒中Ni和Ce的总摩尔量为100%计,Ni占10~20%。
2.权利要求1所述高储氧量和高稳定性载氧体的制备方法,其特征在于:具体步骤如下:
(1)按照La、Sr和Fe的化学计量比,将硝酸镧、硝酸锶和硝酸铁加入到去离子水中,搅拌溶解得到前驱体溶液A;
(2)将柠檬酸加入至前驱体溶液A中,在温度60~80℃下搅拌30~60min,然后加入乙二醇,搅拌至形成胶状物;
(3)胶状物干燥,然后在空气中匀速升温至温度800~850℃,恒温焙烧2~3h得到钙钛矿载体;
(4)将硝酸镍和硝酸铈溶解于去离子水中,得到前驱体溶液B;
(5)将钙钛矿载体加入到前驱体溶液B中,在温度60~80℃下搅拌至去离子水完全蒸发得到固体混合物;或者将钙钛矿载体加入到前驱体溶液B中,逐滴滴加沉淀剂NH3·H2O使体系pH值为9.5~10.0,完全共沉淀后静置老化5~8h,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;或者将钙钛矿载体加入到前驱体溶液B中,再加入氢氧化钠溶液调节pH值为9.5~10.0,置于温度为100~110℃下水热处理20~24h,冷却至室温,固液分离,依次采用去离子水和乙醇洗涤固体沉淀得到固体混合物;
(6)固体混合物干燥,然后在空气中匀速升温至温度800~850℃,恒温焙烧2~3h得到载氧体x(Ni/CeO2)/La0.8Sr0.2FeO3。
3.根据权利要求2所述高储氧量和高稳定性载氧体的制备方法,其特征在于:步骤(2)前驱体溶液A中镧离子、锶离子和铁离子的总摩尔量与柠檬酸的摩尔比为1:1.5~2。
4.根据权利要求2所述高储氧量和高稳定性载氧体的制备方法,其特征在于:步骤(2)中柠檬酸与乙二醇的摩尔比为1:1.5~2。
5.根据权利要求2所述高储氧量和高稳定性载氧体的制备方法,其特征在于:步骤(3)升温速率为2~5℃/min。
6.根据权利要求2所述高储氧量和高稳定性载氧体的制备方法,其特征在于:步骤(6)升温速率为2~5℃/min。
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