CN113522281A - 一种结构化自热重整制氢催化剂及其制备方法 - Google Patents
一种结构化自热重整制氢催化剂及其制备方法 Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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Abstract
本发明公开了一种结构化自热重整制氢催化剂及其制备方法,包括基底、加固层、载体层、助剂层和活性组分层,基底为铁铬铝合金丝网,加固层主要是在基底表面原位形成的α‑Al2O3,载体层是在加固层表面原位生长的氧化铝,助剂层是在加固层和载体层表面负载的含有稀土金属的固溶体涂层,活性组分层是负载在助剂层表面的贵金属、过渡金属中的至少一种。制备方法依次经过制备基底、原位形成加固层、原位生长载体层、负载助剂层、负载活性组分层。本发明中选用铁铬铝丝网作为基底,能有效保证催化剂床层的温度均一性,防止催化剂积碳、局部高温烧结失活;结构化催化剂器件紧凑,压降低,能有效保证制氢效率;催化剂活性组分局部浓度高,活性高。
Description
技术领域
本发明涉及催化剂及其制备方法,尤其涉及一种结构化自热重整制氢催化剂及其制备方法。
背景技术
传统三大非再生资源(煤、石油、天然气)正在以逐年递增的趋势消耗,当代人们在享受丰富便捷的社会物质文明的同时,21世纪的人们不得不共同面临着生态环境恶化和石油资源短缺的两个重大问题。为了迫切地解决此两大问题,世界各国都致力于寻找新的替代能源。目前,已被开发的能源有太阳能、风能、水能、核能、海洋能、生物能等,但是它们受地理、气候、季节、时间等条件限制,不具备能量集中、可储、可输、可分散使用的优点。科学家们达成共识:氢能是21世纪最理想的一种替代能源。氢气作为一种高密度的能量载体,具有来源广泛(烃、水等)、清洁高效(无污染有害物质)、可循环再生使用、适应储运/应用的各种环境等特点。目前,常见的制氢方法有:烃类重整法、烃类分解法、醇类重整法、煤气化法、电解水发、光解水法等,化石燃料制氢是工业上制氢的主要途径,有90%的氢气来源于化石燃料。
化石燃料制氢的主要方法有:水蒸气重整制氢、部分氧化重整制氢、自热重整制氢、等离子体重整制氢等。水蒸气重整反应为吸热反应,需加热设施,在实际应用中受到极大限制,特别在微型化制氢方面难以实现装置小型化;部分氧重整为强放热反应,不需要外界供热,但是存在催化剂床层因局部温度过高导致催化剂烧结的缺点,同时,部分氧重整是靠燃烧掉部分氢气为重整体系提供热量,导致氢气产率较低;自热重整反应是把水蒸气重整反应和部分氧化重整反应结合在一起,利用部分氧化重整反应提供热量同时进行水蒸气重整反应,燃料、水和氧气的混合重整制氢技术(自热重整制氢技术)被认为是最理想的重整制氢方式,产氢率介于水蒸气重整和部分氧重整之间。
催化反应过程对自热重整制氢催化剂的活性和稳定性具有很高的要求,与常规催化剂(钙钛矿型、纳米颗粒型、负载型)相比,结构化催化剂具有相对浓度高、床层压降低、传质系数高、易于工程放大等优点,可以在反应过程中保持良好的活性和稳定性,提高目的产物的选择性和催化效率,成为了催化领域的研究热点。
发明内容
本发明的目的是制备一种适用于未来燃料处理器设备的高活性、高选择性和高稳定性的结构化自热重整制氢催化剂。具体地,本发明采用以下技术方案:
一种结构化自热重整制氢催化剂,包括基底、加固层、载体层、助剂层和活性组分层,基底为铁铬铝合金丝网,加固层主要是在基底表面原位形成的α-Al2O3,载体层是在加固层表面原位生长的氧化铝,助剂层是在加固层和载体层表面负载的含有稀土金属的固溶体涂层,活性组分层是负载在助剂层表面的贵金属、过渡金属中的至少一种。
为了解决自热重整制氢过程中催化床层的热不均匀现象,本发明选用导热性能优异的铁铬铝合金丝网作为催化剂基底,同时该载体还易于成型和制备小型化制氢装置和工业应用的制氢器件。
所述铁铬铝合金丝网是由波浪状丝网和平整丝网交替放置后制成的,波浪状丝网是将平整丝网折成波浪状而形成的。铁铬铝合金丝网粗0.1mm-1mm,丝网孔径10-100目。波浪状丝网的每个褶子约2-5个网格。在制备催化剂前,需要根据使用需求将丝网制成合适的形状,如圆柱型、方柱形。基底主要作为制备结构化器件的成型部分,同时提供加固层原料。将铁铬铝合金丝网做成结构化器件的作用有:①铁铬铝合金丝网具有高导热性,可以最大限度地减少柴油制热重整(ATR)过程中催化床层的热不均匀性现象,降低催化剂积碳和失活概率;②降压底,单位时间内流通量大,可最大限度地保证氢气的产量。
加固层主要是在基底表面原位形成的α-Al2O3,另外加固层可能还包括在基底表面原位形成的α-Fe2O3,其主要作用是:提高基底和载体层、助剂层之间的相互用作和催化剂器件的热稳定性,改善金属丝基底和活性氧化物涂层之间因热膨胀系数差异表现出的机械强度低、热稳定性差、使用寿命短等问题。
所述载体层为δ-Al2O3、γ-Al2O3、κ-Al2O3、η-Al2O3、θ-Al2O3、χ-Al2O3中的一种或多种,优选载体层为η-Al2O3;载体层的厚度为1-50μm,比表面积10-300m2/g,催化剂中载体层的质量百分含量为4-10wt%。载体层的主要作用是:①提高活性氧化物涂层(助剂层和活性组分层)和金属基底间的相互作用力,②提高氧转化率,以助于柴油重整过程中的炼焦过程。
助剂层是在载体层和加固层表面。含有稀土金属的固溶体涂层含有钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥中的一种或多种稀土金属元素,催化剂中助剂层的质量百分含量为3-12wt%。助剂层使用的含有稀土金属的固溶体涂层优选为铈锆固溶体。以纯氧化铝作为载体的柴油重整催化剂时,Rh(铑)、Rh-Pt活性中心的引入会加快催化反应过程中的结焦现象。而Rh-Ce催化剂体系能有效提高催化剂的稳定性,同时Ce的高晶格氧迁移率、低酸度和强金属载体相互作用,使得重烃快速气化,最大限度地减少了碳质沉积物的形成。氧化铈和氧化锆掺杂氧化铝具有协同作用,除了保持较高的储氧能力和较高的比表面积外,还能减缓氧化物的高温相变现象,提高催化剂抗硫能力,因此利用铈锆固溶体作为助剂层优选方案之一。
活性组分层是负载在助剂层表面的大颗粒贵金属、过渡金属中的至少一种,活性组分层的主要作用是催化C-C、C-H键的断裂。其中贵金属、过渡金属包括钌、铑、钯、铂、锇、铱、银、锰、钴、镍、钼、钇。活性组分层中的贵金属在催化剂中的质量百分数含量为0.01-1wt%,或者活性组分层中的过渡金属在催化剂中的质量百分含量为0.1%-12%;活性组分层的质量为载体层和助剂层质量之和的0.05-5wt%。
本发明还提供了结构化自热重整制氢催化剂的制备方法,该方法包括以下步骤:
(1)制备基底
准备两份铁铬铝合金丝网,一份为波浪状丝网,一份为平整丝网,然后交替放置,再制成所需的形状,得到基底;所需的形状可能是圆柱、长方体、正方体等;
(2)制备加固层
将基底置于马弗炉中在空气流速0-300sccm、900-1300℃焙烧3-10小时,使得基底上原位形成加固层;
(3)原位生长载体层
在反应容器的底部均匀铺上铝箔,向反应容器内加入碱液,然后将形成了加固层的基底置于碱液中进行沉积反应,得到原位生长了载体层的结构化器件;
(4)负载助剂层
将结构化器件在稀土金属溶液中反复“浸渍-高温焙烧”,使结构化器件上负载助剂层;
(5)负载活性组分层
配制含有贵金属或过渡金属的溶液,或者配制同时含有贵金属和过渡金属的溶液,在溶液中加入弱碱或者强碱弱酸盐,将步骤(4)得到的结构化器件置于溶液中,在30-100℃沉降反应2-48h,然后冲洗至中性,干燥,用氢气还原,即得到结构化自热重整制氢催化剂。
步骤(3)所述碱液是氢氧化钠溶液、氢氧化钾溶液或者偏铝酸钠溶液,优选为偏铝酸钠溶液;碱液中OH-的浓度为0.1-1.0mol/L,铝箔的质量与碱液的体积之比为0.001-0.1g/mL,铝箔与铁铬铝合金丝网的质量之比为0.01-1.0;沉积反应时间为5-48h。铝箔尺寸优选3mm×3mm~50mm×50mm。结构化器件底面与反应容器底部的距离为20-40mm,结构化器件顶面与碱液液面的距离为20-40mm。载体层的原位为生长η-Al2O3,优先选用碱液NaAlO2与铝箔反应,能降低反应过程氢气产生量70%,有效防止大批量生产时因为氢气的产生而导致的安全事故,同时该法在合金丝网表面沉积的氢氧化铝为单一晶相的拜水铝石,经600℃焙烧后为单一晶相η-Al2O3。
步骤(4)所述稀土金属溶液为稀土金属硝酸盐、稀土金属醋酸盐中的一种或几种的混合物;稀土金属溶液中稀土金属元素的总浓度为0.1-5.0mol/L;步骤(4)的焙烧温度为600-1100℃。根据本发明的一个优选实施方式,步骤(4)所述稀土金属溶液为硝酸氧锆、乙酸锆中的至少一种与乙酸铈、硝酸铈中的至少一种配制的混合溶液,溶液中铈与锆的质量之比为1-5,溶液中铈与锆的总浓度为0.1-5.0mol/L;浸渍时间为1-10min/次,浸渍次数1-8次。
步骤(5)所述含有贵金属和过渡金属的溶液、含有贵金属或过渡金属的溶液是利用贵金属盐和/或过渡金属盐配制的溶液,贵金属盐是四氨合氯化铂水合物、氯铂酸钾、乙二胺氯化铂、硝酸铂、三氯化铑、三氯化钌、氯化铱、氯化锇中的任意一种或几种;步骤(5)所述弱碱或强碱弱酸盐是碳酸氢钠、碳酸钠、氨水中一种。弱碱或强碱弱酸盐的质量与贵金属盐、过渡金属盐的总质量之比为0.1-4:1。冲洗采用60-90℃热水冲洗,干燥后,用氢气在150-350℃条件下还原10min-2h。
与现有技术相比,本发明至少具有以下有益效果:
1.本发明中选用铁铬铝丝网作为基底,能有效保证催化剂床层的温度均一性,防止催化剂积碳、局部高温烧结失活。
2.本发明选用铁铬铝丝网作为基底,结构化催化剂器件紧凑,压降低,能有效保证制氢效率。
3.本发明活性组分局部浓度高,活性高。
附图说明
图1为结构化自热重整制氢催化剂的结构示意图。
从图1可以看出,结构化自热重整制氢催化剂从内到外依次包括了基底1、加固层2、载体层3、助剂层4和活性组分层5五个组成部分。
图2为结构化自热重整制氢催化剂的基底结构示意图。
图3为原位生长η-Al2O3装置简图。
图4为原位生长η-Al2O3前的形成了加固层的基底。
图5为原位生长η-Al2O3后的基底局部放大图。
图6为实施例1原位生长氧化铝后高温焙烧前样品表面负载层的XRD。
图7为实施例2铁铬铝合金丝网表面处理后样品的衰减全反射红外结果。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
各实施例的铁铬铝合金丝网都采用波浪状丝网和平整丝网交替放置,再卷制成柱状,即形成基底,其结构示意图如图2所示。
实施例1
⑴铁铬铝合金丝网表面处理制备加固层:①将铁铬铝合金丝网(Fe75Cr20Al5)制成Φ18*45mm(质量约12g)的小圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干,每个小圆柱称重并编号;②置于高温马弗炉中在空气流速100sccm、900℃条件下焙烧10h;
⑵原位生长载体层氧化铝:按照图3所示的装置简图,①将焙烧后的铁铬铝合金丝网圆柱4个(合计质量47g)均匀悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm,且不同圆柱间要间隔至少1mm;②称取1.3g铝箔(m(Al)/V(H2O)=0.011),并剪成15×15mm的方片均匀铺于烧杯底部;③称取14g偏铝酸钠溶于470ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢倒入烧杯中,静置原位生长反应24h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于100℃烘箱烘干后(高温焙烧前样品表面负载层的XRD结果如图6所示),600℃焙烧2h,称重;原位生长η-Al2O3前、后的基底如图3、4所示。从图6可以看出,原位生长的是纯相的拜三水铝石,经过高温焙烧,可形成纯相的η-Al2O3。
⑶负载助剂层:①称取Ce(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++Ce3+)=1.0mol/L,n(Ce3+/Zr2+)=3的混合溶液,将⑵步骤中的圆柱置于铈锆溶液中,全部浸没1min后取出,然后置于700℃马弗炉焙烧10min,取出冷却后称重,重复浸渍焙烧2次,冷却后称重。
⑷负载活性组分:称取0.5g氯铂酸钾溶于60℃280mL的蒸馏水中,称取碳酸钠0.2g,溶于前述溶液中。将步骤⑶的4个圆柱均匀悬挂于烧杯中,60℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得结构化自热重整制氢催化剂,称重计算负载率。其结构示意图如图1所示,从内到外依次包括了基底1、加固层2、载体层3、助剂层4和活性组分层5五个组成部分。
实施例2
⑴铁铬铝合金丝网表面处理:①将铁铬铝合金丝网(Fe75Cr20Al5)制成Φ18*45mm(质量约12g)的小圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干;②置于高温马弗炉中在空气流速100sccm、1000℃条件下焙烧10h(铁铬铝合金丝网表面处理后样品的衰减全反射红外结果如图7所示);从图7可以看出,基底经过1000℃高温焙烧10h后,基底表面原位生长了一层α-Al2O3。
⑵原位生长氧化铝:①将焙烧后的铁铬铝合金丝网圆柱4个(合计质量46g)均匀悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm,且不同圆柱间要间隔至少1mm;②称取4.8g铝箔(m(Al)/V(H2O)=0.008),并剪成10×10mm的方片均匀铺于烧杯底部;③称取6g氢氧化钾溶于600ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢导入烧杯中,静置原位生长反应20h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于100℃烘箱烘干后,500℃焙烧3h,称重;
⑶负载助剂层:①称取La(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++La3+)=2.0mol/L,n(La3+/Zr2+)=3的混合溶液,将⑵步骤中的圆柱置于镧锆溶液中,全部浸没1min后取出,然后置于800℃马弗炉焙烧10min,取出冷却后称重,重复浸渍焙烧1次,冷却后称重。
⑷负载活性组分:称取0.4gRhCl3·3H2O溶于50℃200mL的蒸馏水中,称取25%氨水1g,溶于前述溶液中。将⑶步骤的4个圆柱均匀悬挂于烧杯中,50℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得结构化自热重整制氢催化剂,称重计算负载率。
实施例3
⑴铁铬铝合金丝网表面处理:①将铁铬铝合金丝网合金(Fe75Cr20Al5)制成Φ80*120mm(质量约470g)的大圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干;②置于高温马弗炉中在空气流速100sccm、1100℃条件下焙烧10h;
⑵原位生长氧化铝:①将焙烧后的铁铬铝合金丝网圆柱悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm;②称取25g铝箔(m(Al)/V(H2O)=0.011),并剪成40×40mm的方片均匀铺于烧杯底部;③称取33g96%的氢氧化钠溶于2200ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢导入烧杯中,室温静置原位生长反应24h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于120℃烘箱烘干后,700℃焙烧2h,称重;
⑶负载助剂层:①称取Ce(NO3)3·6H2O、Y(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++Ce3++Y3+)=1.5mol/L,
n((Ce3++Y3+)/Zr2+)=3,n(Ce3+/Y3+)=3的混合溶液,将步骤⑵中的圆柱置于上述混合溶液中,全部浸没1min后取出,然后置于800℃马弗炉焙烧5min,取出冷却后称重,重复浸渍焙烧2次,冷却后称重。
⑷负载活性组分:称取3.5g三氯化钌水合物溶于60℃750mL的蒸馏水中,称取碳酸钠1.0g,溶于前述溶液中。将⑶步骤的圆柱悬挂于烧杯中,60℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得结构化自热重整制氢催化剂,称重计算负载率。
实施例4
⑴铁铬铝合金丝网表面处理:①将铁铬铝合金丝网(Fe75Cr20Al5)制成Φ18*45mm(质量约12g)的小圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干;②置于高温马弗炉中在空气流速100sccm、1000℃条件下焙烧10h;
⑵原位生长氧化铝:①将焙烧后的铁铬铝合金丝网圆柱4个(合计质量46g)均匀悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm,且不同圆柱间要间隔至少1mm;②称取4.8g铝箔(m(Al)/V(H2O)=0.008),并剪成10×10mm的方片均匀铺于烧杯底部;③称取6g氢氧化钾溶于600ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢导入烧杯中,静置原位生长反应20h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于100℃烘箱烘干后,600℃焙烧3h,称重;
⑶负载助剂层:①称取La(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++La3+)=2.0mol/L,n(La3+/Zr2+)=3的混合溶液,将⑵步骤中的圆柱置于镧锆溶液中,全部浸没1min后取出,然后置于800℃马弗炉焙烧10min,取出冷却后称重,重复浸渍焙烧1次,冷却后称重。
⑷负载活性组分:称取14g硝酸钴溶于60℃280mL的蒸馏水中,称取碳酸钠5g,溶于前述溶液中。将步骤⑶的4个圆柱均匀悬挂于烧杯中,55℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得结构化自热重整制氢催化剂,称重计算负载率。
实施例5
⑴铁铬铝合金丝网表面处理:①将铁铬铝合金丝网(Fe75Cr20Al5)制成Φ18*45mm(质量约12g)的小圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干;②置于高温马弗炉中在空气流速100sccm、1000℃条件下焙烧10h;
⑵原位生长氧化铝:①将焙烧后的铁铬铝合金丝网圆柱4个(合计质量46g)均匀悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm,且不同圆柱间要间隔至少1mm;②称取4.8g铝箔(m(Al)/V(H2O)=0.008),并剪成10×10mm的方片均匀铺于烧杯底部;③称取6g氢氧化钾溶于600ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢导入烧杯中,静置原位生长反应20h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于100℃烘箱烘干后,600℃焙烧3h,称重;
⑶负载助剂层:①称取Ce(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++Ce3+)=1.5mol/L,n(Ce3+/Zr2+)=4的混合溶液,将⑵步骤中的圆柱置于铈锆溶液中,全部浸没1min后取出,然后置于800℃马弗炉焙烧10min,取出冷却后称重,重复浸渍焙烧2次,冷却后称重。
⑷负载活性组分:称取12.6g氯化镍溶于60℃280mL的蒸馏水中,称取碳酸钠10.3g,溶于前述溶液中。将步骤⑶的4个圆柱均匀悬挂于烧杯中,50℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得结构化自热重整制氢催化剂,称重计算负载率。
对比例1
⑴铁铬铝合金丝网表面处理:①将铁铬铝合金丝网(Fe75Cr20Al5)制成Φ18*45mm(质量约12g)的小圆柱,分别用弱碱溶液、弱酸溶液、无水乙醇超声清洗30min,再置于100℃烘箱中烘干,每个小圆柱称重并编号;
⑵原位生长氧化铝:按照图3所示的装置简图,①将焙烧后的铁铬铝合金丝网圆柱4个(合计质量48g)均匀悬挂于烧杯中,圆柱下沿距离烧杯底部和反应液面均30mm,且不同圆柱间要间隔至少1mm;②称取1.28g铝箔(m(Al)/V(H2O)=0.011),并剪成15×15mm的方片均匀铺于烧杯底部;③称取14g偏铝酸钠溶于470ml的蒸馏水中,制成透明澄清的碱溶液,将碱溶液缓慢倒入烧杯中,静置原位生长反应24h;④用100℃蒸馏水漂洗2次,再置于100℃蒸馏水中老化30min,置于100℃烘箱烘干后,600℃焙烧2h,称重。
⑶负载助剂层:①称取Ce(NO3)3·6H2O和ZrO(NO3)2·2H2O作为原料,配制总离子浓度C(Zr2++Ce3+)=1.0mol/L,n(Ce3+/Zr2+)=3的混合溶液,将⑵步骤中的圆柱置于铈锆溶液中,全部浸没1min后取出,然后置于700℃马弗炉焙烧10min,取出冷却后称重,重复浸渍焙烧2次,冷却后称重。
⑷负载活性组分:称取0.5g氯铂酸钾溶于60℃280mL的蒸馏水中,称取碳酸钠0.2g,溶于前述溶液中。将步骤⑶的4个圆柱均匀悬挂于烧杯中,60℃静置沉淀20h。用80℃热水冲洗3遍,100℃烘箱干燥4h,200℃用氢气还原1h,即得对比例1产物。
试验例1
⑴各催化剂层附着力评价:分别取实施例1和对比例1制备的样品(四个圆柱中随机选一个)称重,并记录质量m1(g);再将样品置于水热老化装置中,于800℃老化48h,然后称重,并记录质量m2(g);计算失重率WI(%):
W1:附着力实验前制备催化剂样品的质量;
W2:附着力实验后制备催化剂样品的质量;
W0:基底的质量。
测试结果如表1所示:
对比例1没有将基底置于马弗炉焙烧,因此没有在基底表面没有引入加固层,而直接进行后续的载体层、助剂层和活性组分层的负载实验,经过实施例1和对比例1的附着力评价实验发现,引入加固层能非常显著的提高催化剂各负载层与基底之间的附着力,有效延长催化剂的寿命。
试验例2
将实施例1-2、实施例4-5制备的四种结构化自热重整制氢催化剂置于自热重整制氢催化剂评价装置(ATR)和配套气相色谱在线分析催化剂催化柴油重整制氢能力。催化剂尺寸-组成、评价条件和评价结果如表2、表3和表4所示。
表2催化剂尺寸及组成汇总表
表3自热重整制氢催化剂评价条件
表4不同催化剂的评价结果
对不同实施例制备样品进行柴油自热重整制氢催化反应评价实验,通过评价结果可以看出,本发明制备的样品对柴油重整具有较强的催化活性,柴油转化率,氢气、二氧化碳、一氧化碳、甲烷气体的选择性的具体结果和实施例样品的具体组分相关甚紧。各施例样品在评价试验后,进行了XRD、Raman、TPR等表征,结果显示没有明显积炭和烧结现象,催化剂热稳定性良好。
尽管这里参照本发明的解释性实施例对本发明进行了描述,但是,应该理解,本领域技术人员可以设计出很多其他的修改和实施方式,这些修改和实施方式将落在本申请公开的原则范围和精神之内。
Claims (10)
1.一种结构化自热重整制氢催化剂,其特征在于,包括基底、加固层、载体层、助剂层和活性组分层,基底为铁铬铝合金丝网,加固层主要是在基底表面原位形成的α-Al2O3,载体层是在加固层表面原位生长的氧化铝,助剂层是在加固层和载体层表面负载的含有稀土金属的固溶体涂层,活性组分层是负载在助剂层表面的贵金属、过渡金属中的至少一种。
2.根据权利要求1所述的结构化自热重整制氢催化剂,其特征在于,所述铁铬铝合金丝网是由波浪状丝网和平整丝网交替放置后制成的,波浪状丝网是将平整丝网折成波浪状而形成的。
3.根据权利要求1所述的结构化自热重整制氢催化剂,其特征在于,所述载体层为δ-Al2O3、γ-Al2O3、κ-Al2O3、η-Al2O3、θ-Al2O3、χ-Al2O3中的一种或多种;催化剂中载体层的质量百分含量为4-10wt%。
4.根据权利要求1所述的结构化自热重整制氢催化剂,其特征在于,所述含有稀土金属的固溶体涂层含有钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥中的一种或多种稀土金属元素,催化剂中助剂层的质量百分含量为3-12wt%。
5.根据权利要求4所述的结构化自热重整制氢催化剂,其特征在于,所述含有稀土金属的固溶体涂层为铈锆固溶体。
6.根据权利要求1所述的结构化自热重整制氢催化剂,其特征在于,所述贵金属、过渡金属包括钌、铑、钯、锇、铱、铂、银、锰、钴、镍、钼、钇;活性组分层中的贵金属在催化剂中的质量百分含量为0.01-1wt%;或者活性组分层中的过渡金属在催化剂中的质量百分含量为0.1%-12%。
7.权利要求1-6任意一项所述的结构化自热重整制氢催化剂的制备方法,其特征在于,包括以下步骤:
(1)制备基底
准备两份铁铬铝合金丝网,一份为波浪状丝网,一份为平整丝网,然后交替放置,再制成所需的形状,得到基底;
(2)制备加固层
将基底置于马弗炉中在空气流速0-300sccm、900-1300℃焙烧3-10小时,使得基底上原位形成加固层;
(3)原位生长载体层
在反应容器的底部均匀铺上铝箔,向反应容器内加入碱液,然后将形成了加固层的基底置于碱液中进行沉积反应,得到原位生长了载体层的结构化器件;
(4)负载助剂层
将结构化器件在稀土金属溶液中“浸渍-高温焙烧”,使结构化器件上负载助剂层;
(5)负载活性组分层
配制含有贵金属或过渡金属的溶液,或者配制同时含有贵金属和过渡金属的溶液,在溶液中加入弱碱或者强碱弱酸盐,将步骤(4)得到的结构化器件置于溶液中,在30-100℃沉降反应2-48h,然后冲洗至中性,干燥,用氢气还原,即得到结构化自热重整制氢催化剂。
8.根据权利要求7所述的结构化自热重整制氢催化剂,其特征在于,步骤(3)所述碱液是氢氧化钠溶液、氢氧化钾溶液或者偏铝酸钠溶液;碱液中OH-的浓度为0.1-1.0mol/L,铝箔的质量与碱液的体积之比为0.001-0.1g/mL,铝箔与铁铬铝合金丝网的质量之比为0.01-1.0;沉积反应时间为5-48h。
9.根据权利要求7所述的结构化自热重整制氢催化剂,其特征在于,步骤(4)所述稀土金属溶液为稀土金属硝酸盐、稀土金属醋酸盐中的一种或几种的混合物;稀土金属溶液中稀土金属元素的总浓度为0.1-5.0mol/L;步骤(4)的焙烧温度为600-1100℃。
10.根据权利要求7所述的结构化自热重整制氢催化剂,其特征在于,步骤(5)所述含有贵金属和过渡金属的溶液、含有贵金属或过渡金属的溶液是利用贵金属盐和/或过渡金属盐配制的溶液,贵金属盐是四氨合氯化铂水合物、氯铂酸钾、乙二胺氯化铂、硝酸铂、三氯化铑、三氯化钌、氯化铱、氯化锇中的任意一种或几种;步骤(5)所述弱碱或强碱弱酸盐是碳酸氢钠、碳酸钠、氨水中一种。
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