CN112916015B - 一种乙酸自热重整制氢的锶锆钙钛矿型钴基催化剂 - Google Patents
一种乙酸自热重整制氢的锶锆钙钛矿型钴基催化剂 Download PDFInfo
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- 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
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Abstract
本发明涉及一种乙酸自热重整制氢的锶锆钙钛矿型钴基催化剂及制备方法。本发明针对现有催化剂在乙酸自热重整过程中的失活问题,采用水热法制备了锶锆钙钛矿担载的钴基催化剂,形成的活性中心Sr‑Zr‑Co‑O能有效地吸附和活化乙酸、水和氧气等反应物,抑制了活性组分钴在高温条件下可能发生的迁移、聚集和氧化,提高了乙酸自热重整过程中氢气产率。本发明催化剂以氧化物表示的摩尔组成为:(SrO)a(ZrO2)b(CoO1.5)c,其中a为0.7‑1.2,b为0.95‑1.3,c为0.54‑0.56。
Description
技术领域
本发明涉及一种乙酸自热重整制氢的锶锆钙钛矿型钴基催化剂及其制备方法,属于乙酸自热重整制取氢气的领域。
背景技术
面对全球日益增长的能源需求,氢气作为一种清洁的能源载体,在传统能源替代方面具有较大的潜力。传统制氢方式是将天然气、煤等化石资源进行转化,带来了大量的二氧化碳排放。生物质分布广泛、可再生,被视为前景广阔的制氢原料。生物质经热解获得的生物质油是一种复杂的混合物,可分为有机相和水相,而乙酸是生物质油水相的主要成分,含量可达33%,故可将生物质衍生乙酸用于规模化制氢。
乙酸一般可经催化重整过程制取氢气,而根据原料CH3COOH、H2O、O2比例的不同,乙酸催化重整制氢一般可分为蒸汽重整反应CH3COOH+2H2O→2CO2+4H2、部分氧化反应CH3COOH+O2→2CO2+2H2以及自热重整反应CH3COOH+xO2+yH2O→aCO+bCO2+cH2。蒸汽重整是一个强吸热反应,需持续供热以维持反应进行,限制了其应用。部分氧化反应是一个放热反应,但此过程反应物乙酸往往会发生深度氧化,生成CO2和H2O,降低氢气的产率。作为对比,乙酸自热重整反应,结合了蒸汽重整和部分氧化的优势,引入适量的O2,利用乙酸部分氧化放热,使整个反应体系的热量供应得到平衡,显示了其优势。
在乙酸自热重整反应制氢过程中,高效的催化剂决定着过程的可行性。根据催化剂活性金属的不同,可分为贵金属催化剂和过渡金属催化剂。贵金属表现出较好的催化活性和选择性,但因其价格昂贵,其应用规模受到了限制。研究表明,Co、Ni等过渡金属在乙酸自热重整过程中,具有较好的催化性能;其中活性金属Co能有效促进乙酸分子的吸附活化,而获得较高的乙酸转化率和氢气产率。
Co基催化剂在乙酸自热重整过程中表现出活性较高,但随着反应的进行,O2或空气的存在会导致活性组分Co的氧化,使催化剂表面活性位点减少,降低对乙酸、水分子等反应物的活化转化能力。同时,乙酸分子在催化剂表面活化后,会脱羟产生CH3CO*,CH3CO*进一步脱羰、脱氢产生CH2CO*、CHx*等物种,其中CH3CO*和CHx*反应会产生副产物丙酮,而丙酮、乙烯酮等副产物会发生低聚形成包裹型碳物种,覆盖在活性中心上,导致催化剂积炭失活。此外,中间产物*CHx持续脱氢生成*C,若没有及时转移并气化*C物种,也将会在催化剂表面沉积而积炭,降低催化剂的活性。
为了解决Co基催化剂积炭、烧结和氧化等问题,本发明以Co为活性组分,加入Sr和Zr组分,采用水热法合成了以Sr-Zr-Co-O为活性中心的SrZrO3钙钛矿型钴基催化剂。在Sr-Zr-Co-O活性中心中,引入的Zr在氧气气氛下以Zr4+/Zr3+两种氧化态相互转换,能促进氧离子在氧化物晶格中的迁移,产生氧空位,有利于H2O和O2活化产生的活性氧物种传递转移到催化剂表面,气化乙酸活化产生的含碳物种CHx*/C*,提高催化剂抗积炭能力;碱土金属Sr的添加有利于提高催化剂表面碱性,抑制积碳的形成,且Sr会吸附产物CO2,促进水汽重整反应的正向进行,增加氢气产率,同时Sr具有较强的给电子效应,将调变活性组分Co的电子性质,使其在H2氛围中易被还原,提高催化剂抗氧化能力。
因此,本发明催化剂经焙烧后的氧化物以SrZrO3钙钛矿为骨架,形成了Sr-Zr的协同效应,同时形成了Co3O4尖晶石相,并具有介孔结构;此催化剂经还原活化后,活性组分Co高度分散于SrZrO3钙钛矿结构中,形成了Sr-Zr-Co-O活性中心,增加了钴粒子与钙钛矿载体的接触面积,更利用了SrZrO3钙钛矿良好的热稳定性,对钴粒子起到很好的限域作用,有效防止钴金属粒子在乙酸自热重整过程中的高温下迁移烧结,提高了催化剂的抗烧结能力和热稳定性。更重要的是,形成的Sr-Zr-Co-O活性中心,促进了反应物CH3COOH、H2O、O2的活化转化和产物CO2、H2的传递和扩散,提高催化活性。在乙酸自热重整制氢过程中,反应物CH3COOH、H2O和O2为Sr-Zr-Co-O活性中心所吸附,通过反应物CH3COOH→CH3COO*→CH3CO*、H2O*→OH*→O*和O2→O*等过程,活化形成CH3CO*、OH*和O*物种,而CH3CO*在Sr-Zr-Co-O活性中心上进一步脱羰基、脱氢形成CHx*和C*等物种,抑制CH3CO*聚合形成丙酮。同时,OH*和O*在Sr-Zr-Co-O活性位的脱氢过程中起协同作用,并通过活性中心中Zr4+/Zr3+物种及Sr2+物种促进O*物种的传递和转移,促进催化剂表面CHx*/C*的氧化,抑制积炭的形成。此外,此催化剂形成了介孔结构有利于乙酸自热重整反应物和产物分子的传递和扩散,有利于活性组分Co的分散,提高催化剂的催化活性;同时,孔道结构通过限域效应限制积炭前驱体的聚合,抑制积炭。因此,本发明催化剂,在乙酸自热重整反应中表现出较好的热稳定性、抗积炭、抗氧化能力。
发明内容
本发明所要解决的技术问题是,针对现有催化剂在乙酸自热重整反应催化剂结构的变化和活性组分的氧化及烧结,导致催化剂失活的问题,提供一种结构稳定、耐烧结、抗积炭、活性稳定的新催化剂。本发明以Co为活性组分,引入Zr和Sr,经水热合成含Co3O4尖晶石、形成Sr-Zr-Co-O活性中心的以SrZrO3钙钛矿结构为主体的介孔结构催化剂。将本发明催化剂用于乙酸自热重整制氢反应,在反应温度700℃下,乙酸转换率稳定在100%,氢气产率达2.7mol-H2/mol-HAc。
本发明技术方案:
本发明针对乙酸自热重整的特点,以水热法制备了锶锆钙钛矿型结构的钴基催化剂,通过Sr、Zr的引入,形成Sr-Zr-Co-O活性中心的以SrZrO3钙钛矿结构为主体的介孔结构催化剂,提高了氢气产率和乙酸转化率。本发明催化剂以氧化物表示的摩尔组成是(SrO)a(ZrO2)b(CoO1.5)c,其中a为0.7-1.2,b为0.95-1.3,c为0.54-0.56;按照重量百分比组成为:氧化锶为26.6-41.2%,二氧化锆为44.9-58.6%,氧化钴为13.9-17.7%,且各组分重量百分比组成之和为100%。
具体的制备方法和反应的步骤如下:
1)分别称量取一定量的正丙醇锆和三乙醇胺于烧杯中,在室温下搅拌混合24h,形成稳定的锆-三乙醇胺络合物;在持续搅拌下将一定量的Sr(OH)2·8H2O、六水硝酸钴和1,3-丙二醇加入上述络合物中,在室温下搅拌90min获得混合溶液。
2)将步骤1)配制的溶液转入聚四氟乙烯内衬的高压反应釜中,并置于140℃的烘箱内72h;待高压反应釜冷却至室温后,过滤收集沉淀物并用去离子水洗涤至中性,然后将沉淀物置于105℃的烘箱中干燥12h,得到催化剂前驱体。
3)将干燥后的前驱体置于管式炉中部,以10℃/min的升温速率从室温升至700℃,保持焙烧4h,得到以SrZrO3钙钛矿结构为主体的钴基催化剂,其典型结构如X射线衍射图(附图1)所示,其介孔结构分布如附图2所示。
4)将步骤3)制得催化剂50-300mg装入固定床反应器,先在流量为20-40mL/min的H2氛围内600-800℃还原1h,进行活化处理,后经氮气吹扫,通入经汽化后的摩尔比为乙酸/水/氧气/氮气=1.0/(2.5-5.0)/(0.2-0.5)(2.5-4.5)的混合气体,通过催化剂床层进行反应,反应温度为600℃-800℃。
本发明的有益效果:
1)本发明催化剂采用Co作为活性组分,引入Sr和Zr,采用水热法制备出了以Sr-Zr-Co-O为活性中心、以SrZrO3钙钛矿结构为主体的钴基催化剂;本发明钙钛矿结构具有较好的催化活性和化学稳定性,同时SrZrO3钙钛矿结构的形成可以提高活性组分Co的分散度,减少组分Co的聚集生长,提高催化剂抗烧结能力。
2)本发明所得SrZrO3钙钛矿结构上的锆以Zr4+/Zr3+两种氧化态相互转换,能促进氧离子在氧化物晶格中的迁移,产生氧空位,使得锶锆钙钛矿晶格中的氧迁移到锶锆钙钛矿表面,氧化乙酸自热重整过程中催化剂表面产生的丙酮、乙烯酮及CHx*等物种,减少积炭量;结构中Sr具有较强的给电子效应,它的引入可以改变Co的电子性质,提高活性组分Co的抗氧化性,同时有利于稳定Zr3+缺陷,改善催化剂结构和电子性能,进一步提高催化剂的抗氧化能力;同时,Sr作为Lewis碱可提高催化剂表面的碱性,抑制积炭的形成。
3)本发明所得的锶锆钙钛矿结构形成的活性中心Sr-Zr-Co-O能有效诱导乙酸、水和氧气等反应物吸附活化为OH*/O*物种,促进O*物种的迁移和传递,加快与制氢过程中产生的CHx*/C*物种生成CO与CO2的反应,减少积炭量,同时能促进乙酸活化产生的CH3CO*物种进一步脱CO*和H*生成CHx*物种,抑制其转化为副产物丙酮,从而抑制丙酮聚合产生的积碳。
4)本发明催化剂形成了显著的介孔结构,有利于乙酸自热重整过程中反应物和产物分子的传递和扩散,有利于活性组分Co的分散,提高催化剂的催化活性;同时,孔道结构可以限制乙酸衍生的积炭前驱体的聚合,起到抑制积炭的作用。
5)经乙酸自热重整反应结果显示,本发明催化剂在乙酸转化过程中,能够诱导乙酸的高效转化,有效抑制丙酮、乙烯酮、甲烷等副产物的产生,具有耐烧结、抗积碳、活性稳定等特点。
附图说明
图1:本发明催化剂的X射线衍射谱图
图2:本发明催化剂的BJH孔径分布图
具体实施方式
参照例一
称取3.667g的正丙醇锆,放入装有1.3mL三乙醇胺的烧杯中,在室温下搅拌混合24h,形成稳定的锆-三乙醇胺络合物;在持续搅拌下将1.792g的六水硝酸钴和5.7mL的1,3-丙二醇加入上述络合物中,在室温下搅拌90min获得混合溶液;将此溶液转入聚四氟乙烯内衬的高压反应釜中,并置于140℃的烘箱内72h;待高压反应釜冷却至室温后,过滤收集沉淀物并用去离子水洗涤至中性,然后将沉淀物置于105℃的烘箱中干燥12h;将样品放入管式炉中,以10℃/min的升温速率升至700℃,并在该温度下焙烧4h后得到催化剂CDUT-ZC,该催化剂以氧化物的摩尔组成为(ZrO2)1.85(CoO1.5)0.55,以氧化物计的重量百分比为:二氧化锆的含量为84.7%,氧化钴的含量为15.3%。
乙酸自热重整反应活性评价在连续流动固定床反应器中进行,将催化剂压片、研磨筛分为20-40目的颗粒,分别称取200mg的催化剂颗粒和200mg石英砂均匀混合后装入反应管中,在600-800℃、20-40mL/min的H2流中还原1h;将乙酸和水的混合溶液用高压恒流泵引入汽化器经汽化后,混合氧气,并以氮气为内标气体,形成摩尔比为乙酸/水/氧气/氮气=1.0/(2.5-5.0)/(0.2-0.5)/(2.5-4.5)的反应原料气,并将此原料气通入反应床层进行自热重整反应,反应条件为常压、空速10000-30000mL/(g-catalyst·h),反应产物采用气相色谱仪进行在线分析。
该CDUT-ZC催化剂在乙酸自热重整反应中进行活性评价,在温度600℃、空速15000mL/(g-catalyst·h)、CH3COOH/H2O/O2/N2=1.00/4.00/0.28/3.90,在10h活性测试中,乙酸的初始转化率为92%,氢气的初始产率为1.60mol-H2/mol-HAc,但随着反应的进行,乙酸转化率不断波动,而氢气产率降低至1.40mol-H2/mol-HAc,同时,二氧化碳和一氧化碳的选择性分别达到55%和40%,甲烷的选择性高达4%。对CDUT-ZC催化剂进行氮气低温物理吸附表征,测得催化剂表面积为2.11m2/g,孔体积为0.020cm3/g,孔径为17.13nm。
实施例一
称取3.667g的正丙醇锆,放入装有1.3mL的三乙醇胺的烧杯中,在室温下搅拌混合24h,形成稳定的锆-三乙醇胺络合物;在持续搅拌下将2.974g的Sr(OH)2·8H2O、1.792g的六水硝酸钴和5.7mL的1,3-丙二醇加入上述络合物中,在室温下搅拌90min获得混合溶液;将此溶液转入聚四氟乙烯内衬的高压反应釜中,并置于140℃的烘箱内72h;待高压反应釜冷却至室温后,过滤收集沉淀物并用去离子水洗涤至中性,然后将沉淀物置于105℃的烘箱中干燥12h;将样品放入管式炉中,以10℃/min的升温速率升至700℃,并在该温度下焙烧4h后,得到CDUT-SZC催化剂,即获得含Co3O4尖晶石、形成Sr-Zr-Co-O活性中心的以SrZrO3钙钛矿结构为主体的介孔结构催化剂,其典型结构如X射线衍射图(附图1)所示,典型介孔BJH孔径分布如附图2所示;该催化剂以氧化物表示的摩尔组成为(SrO)1.0(ZrO2)1.0(CoO1.5)0.55,以氧化物计的重量百分比组成为:氧化锶为38.6%,二氧化锆为46.0%,氧化钴为15.4%。
该CDUT-SZC催化剂在乙酸自热重整反应中进行活性评价,在温度600℃、空速15000mL/(g-catalyst·h)、CH3COOH/H2O/O2/N2=1.00/4.00/0.28/3.90时,该催化剂在乙酸自热重整反应中表现出良好的催化活性和稳定性,反应过程中乙酸的转化率稳定在100%左右,H2产率达到2.70mol-H2/mol-HAc,二氧化碳、一氧化碳的选择性分别为60%和45%,而丙酮等副产物未被检测到。对还原后的CDUT-SZC催化剂进行表征,结果表明还原形成的钴金属粒子高度分散于SrZrO3钙钛矿结构中;反应后的催化剂表征结果表明,该催化剂无显著积炭,且活性组分Co于SrZrO3钙钛矿结构上保持稳定。低温氮气吸附表征表明,催化剂表面积为5.22m2/g,孔体积为0.030cm3/g,孔径为9.22nm,显示催化剂的比表面和孔体积升高,有利于为催化反应提供更多的活性位,提高催化活性。
Claims (2)
1.一种锶锆钙钛矿型钴基催化剂在乙酸自热重整制氢过程中的应用,其特征在于:将50-300mg催化剂于600-800℃、20-40mL/min的H2中还原1h,进行活化处理;随后通入乙酸/水/氧气/氮气的摩尔比=1.0/(2.5-5.0)/(0.2-0.5)(2.5-4.5)的混合气体,在催化剂床层进行自热重整反应,反应温度为600-800℃;所述催化剂由以下方法制备而成:称量取一定量的正丙醇锆和三乙醇胺,搅拌混合形成锆-三乙醇胺络合物,在持续搅拌下将一定量的氢氧化锶、六水硝酸钴和1,3-丙二醇加入上述络合物中形成混合溶液,将此溶液转入聚四氟乙烯内衬高压反应釜中,放入140℃的烘箱保持72h,冷却、过滤并用去离子水洗涤,将所得沉淀物于105℃干燥12h,然后于管式炉中以10℃/min的升温速率升至700℃,并在该温度下焙烧4h后,得到以Sr-Zr-Co-O为活性中心的SrZrO3钙钛矿结构钴基催化剂,以氧化物表示的摩尔组成是(SrO)a(ZrO2)b(CoO1.5)c,其中a为0.7-1.2,b为0.95-1.3,c为0.54-0.56;以氧化物计的重量百分比组成为:氧化锶为26.6-41.2%,二氧化锆为44.9-58.6%,氧化钴为13.9-17.7%,且各组分重量百分比组成之和为100%。
2.根据权利要求1所述的锶锆钙钛矿型钴基催化剂在乙酸自热重整制氢过程中的应用,其特征在于:所述催化剂以氧化物的重量百分比组成为:二氧化锆为46.0%,氧化锶为38.6%,氧化钴为15.4%。
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