CN112916018B - 一种乙酸自热重整制氢的镨锆复合氧化物钴基催化剂 - Google Patents
一种乙酸自热重整制氢的镨锆复合氧化物钴基催化剂 Download PDFInfo
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Abstract
本发明涉及一种乙酸自热重整制取氢气的镨锆复合氧化物钴基催化剂。针对现有催化剂在乙酸自热重整反应中存在的催化剂结构的变化、烧结、积炭等失活问题,本发明采用溶胶‑凝胶法,制备了含有尖晶石相的Co3O4和Pr掺杂t‑ZrO2的Zr‑Pr‑O复合氧化物钴基催化剂,限制了活性组分的聚集与晶粒的长大,显著提高了催化剂的抗积炭、抗烧结能力和氢气产率。本发明的催化剂化学成分是(PrO1.5)a(ZrO2)b(CoO1.5)c,其中a为0‑0.19且不为0,b为0.43‑0.69,c为0.17‑0.21。
Description
技术领域
本发明涉及一种镨锆复合氧化物钴基催化剂在乙酸自热重整制氢过程中的应用,属于乙酸自热重整制取氢气的领域。
背景技术
氢气是一种清洁能源载体,也是重要的化工原料。目前氢气主要是通过煤炭、石油及天然气等不可再生化石资源转化而得,带来了大量温室气体排放。生物质作为可再生资源,具有来源丰富、环境友好等特点;生物质经快速热解可获得生物质油,而生物油的水相组分主要成分是乙酸,从而可经生物质衍生品乙酸催化重整规模化制取廉价氢气。
通常,在乙酸催化重整制氢过程中,由于水蒸气重整是强吸热反应,在反应过程中需要消耗大量能量,提高了制氢的成本;而乙酸部分氧化重整是一种放热反应,但是在部分氧化过程中,乙酸往往会发生深度氧化生成CO2和水,导致氢气的产率降低。
乙酸自热重整制氢(CH3COOH+1.4H2O+0.28O2→2CO2+3.44H2),结合了部分氧化重整和水蒸气重整的优点,即CH3COOH在催化剂的作用下脱氢、脱氧生成CH3COO*、CH3CO*、CH3*、CO*、C*等中间产物,进而转化为产物H2与CO、CO2等,也就是在蒸汽重整反应中引入少量氧气,利用反应物乙酸部分氧化放热为反应提供能量,使得整个反应过程实现了热平衡,具有显著优势。
催化剂的选择对乙酸自热重整制氢的高效运行尤为重要,而催化剂一般分为贵金属和过渡金属催化剂。贵金属催化剂包含Ru、Rh、Pt等,具有优良的催化活性和抗烧结、抗积碳能力,但是由于其价格昂贵,限制了应用。在过渡金属催化剂中,Co基催化剂由于具有活化C-C、C-H键的能力,对乙酸自热重整过程有较好的活性,受到了广泛的关注。
Co基催化剂在自热重整过程中,将反应物CH3COOH、H2O、O2在催化剂表面吸附活化为CH3COO*、CH3CO*、CH3*等中间体,然后进一步转化为H2、CO2、CO等;同时,也会伴随一些副反应,例如乙酸脱水和乙酸的酮基化反应、氢气与二氧化碳甲烷化反应,所生成的副产物进一步脱氢聚合,在催化剂表面上积碳,覆盖了活性中心,从而使得催化剂失活;并且,自热重整过程的催化剂床层前端温度较高,易发生烧结失活。因此,合适的催化剂组成和结构成为高效催化剂的关键。
为了提高Co基催化剂的抗烧结、抗积碳性能,提高Co金属的分散度,本发明利用溶胶-凝胶法制备了Co-Zr-Pr-O催化剂,获得了含有稳定的尖晶石相的Co3O4和Pr掺杂四方相ZrO2物相,构造了介孔结构的Zr-Pr-O复合氧化物钴基催化剂。
首先,本发明引入具有同时具有酸性/碱性的ZrO2载体,以其较高的供电子能力,其外层电子向活性组分Co偏移,抑制了活性组分Co的氧化,并增强水蒸气和乙酸在活性中心吸附,但是Co在ZrO2载体上容易发生烧结,分散度不高,晶粒也比较大。
为了解决以上问题,本发明创造性地引入了Pr,形成了Pr掺杂四方相二氧化锆(t-ZrO2)的Zr-Pr-O复合氧化物载体负载钴基催化剂。由于Pr3+的离子半径(0.99nm)大于Zr4+的离子半径(0.72nm),形成的Zr-Pr-O复合氧化物中,离子半径更大的Pr3+进入ZrO2晶格之中,单斜相的m-ZrO2转变为四方相t-ZrO2,使得晶格常数变大,并形成了晶格畸变,并使得负载活性组分Co3O4的电子云与ZrO2缺陷位中的电子云发生重叠,调变了Co与Zr-Pr-O复合氧化物的电负性,获得了大量氧空位,并提高了储氧能力;同时,活性组分Co与Zr-Pr-O载体形成强相互作用,有效阻止Co3O4晶粒的生长,稳定了Co-Zr-Pr-O活性中心,避免了活性组分的聚集,提高了催化剂抗烧结能力,并促使Co高度分散在了Zr-Pr-O复合氧化物载体上,增加了催化剂表面金属Co的活性位点,提高了催化剂表面对水的吸附强度和对乙酸的吸附活化,促进CH3COO*、CH3CO*等中间产物的形成和转化,获得H2、CO2目标产物,提高了催化剂的活性。
可见,本发明创制的Pr掺杂t-ZrO2的Zr-Pr-O复合氧化物钴基催化剂,利用了Zr-Pr之间的协同效应,有效提高储氧、氧转移性能与电子转移能力,催化剂中大量形成的氧空位能够有效诱导乙酸自热重整反应物中H2O与O2的吸附活化;同时在催化剂中Pr3+与Zr4+的相互作用下形成了Lewis碱位,进一步增加了催化剂整体碱度,抑制了乙酸酮基化反应的进行,并增强了对CO2的吸附活化作用,促进含碳产物的气化,减少了积碳;该Zr-Pr复合氧化物钴基催化剂对于H2O的活化也促进了水煤气反应以提高氢气产率。本发明催化剂应用于乙酸自热重整反应的活性测试结果也表明了其优异的活性、选择性和稳定性。
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中活性低、稳定性差、积碳多和不耐烧结,导致催化剂失活的问题,提供一种结构稳定、耐烧结、抗积炭、活性稳定的新型催化剂。本发明用Co作为活性组分,引入Pr、Zr组分,采用溶胶-凝胶法合成了含有尖晶石相的Co3O4和Pr掺杂t-ZrO2的Zr-Pr-O复合氧化物钴基催化剂。将本发明催化剂用于乙酸自热重整制氢反应中,在反应温度为650℃的情况下,乙酸(HAc)转化率接近100%,氢气产率稳定在2.75mol-H2/mol-HAc左右。
本发明技术方案:
本发明针对乙酸自热重整的特点,以溶胶-凝胶法制得了Pr掺杂t-ZrO2的Zr-Pr-O复合氧化物钴基催化剂,通过引入Pr、Zr,提高了活性组分的分散度,并具有抗烧结、抗积碳和热稳定性特点。本发明的组成是(PrO1.5)a(ZrO2)b(CoO1.5)c,其中a为0-0.19且不为0,b为0.43-0.69,c为0.17-0.21;重量百分组成为:氧化镨(PrO1.5)含量为0%-30.7%且不为0%,氧化锆(ZrO2)含量为53.5%-86.0%,氧化钴(CoO1.5)含量为14.0%-16.0%,且各组分重量百分比组成之和为100%。
具体的制备及反应方法的步骤如下:
1)配制金属硝酸盐的混合溶液:根据催化剂中各组分摩尔比例(PrO1.5)a(ZrO2)b(CoO1.5)c,其中a为0-0.19且不为0,b为0.43-0.69,c为0.17-0.21,分别称取一定量的硝酸钴、硝酸镨、硝酸氧锆加入去离子水配制成硝酸盐混合溶液;
2)根据柠檬酸与金属阳离子物质的量的总和的摩尔比为1:1,称取一定量的柠檬酸,加入去离子水配制成柠檬酸溶液;于70℃水浴搅拌条件下,将金属盐溶液缓慢滴加到柠檬酸溶液中,反应络合0.5h;根据乙二醇和柠檬酸的摩尔比为1:1,称取适量的乙二醇,缓慢滴加乙二醇,形成溶胶,维持70℃水浴搅拌3h,形成凝胶,然后置于105℃的烘箱中干燥12h;
3)将步骤2)中所得干燥的样品于管式炉中,以10℃/min的加热速度升温至700℃,并保持4h后,得到具有尖晶石相的Co3O4和Pr掺杂t-ZrO2的Zr-Pr-O复合氧化物钴基催化剂,其典型结构如X射线衍射图(附图1)所示,其典型BJH孔径分布如附图2所示,该催化剂经还原后样品的X射线衍射图如附图3所示,形成了具有介孔结构的Co高度分散在Zr-Pr-O复合氧化物载体上的、具有Co-Zr-Pr-O活性中心的钴基催化剂;
4)将所得催化剂于反应前在600-800℃的温度下在H2中还原1h,反应用氮气为载气,通入摩尔比为乙酸/水/氧气=1/(1.3-5.0)/(0.2-0.5)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)本发明催化剂采用溶胶-凝胶法制备了具有介孔结构的Zr-Pr-O复合氧化物钴基催化剂,含有尖晶石相的Co3O4和Pr掺杂的四方相的t-ZrO2,经过H2还原后其活性成分钴高度分散,增加了钴粒子和Zr-Pr-O复合氧化物载体上的相互作用,促进了反应物CH3COOH、H2O、O2和产物CO2、H2的传递和扩散,从而提高了催化活性。
2)本发明催化剂形成了介孔结构,其BJH孔径分布图如附图2所示,其多孔结构有利于产物分子和反应物分子的扩散与传递,并且有利于活性组分钴的分散,提高催化剂的催化活性;并且其孔道结构可以抑制乙酸自热重整制氢的积碳前驱体乙烯酮的聚合,从而抑制积炭,也提高了反应产物H2以及CO/CO2的选择性。
3)由于引入了稀土金属Pr进入ZrO2,形成了Pr掺杂的四方相t-ZrO2结构;在此结构中,由于Pr与ZrO2的协同作用,Pr的添加提高载体整体的Lewis碱度,有效活化了CH3CO*与CH3*,抑制丙酮的产生;Pr和ZrO2复合氧化物中形成了晶格中的大量氧空位,有效促进O*物种迁移,与乙酸的活化产物C*、CO*结合生成CO与CO2,而OH*物种则继续活化O2,形成更多的O*物种,显著减少了碳物种沉积,所以本发明的Zr-Pr-O复合氧化物钴基催化剂具有优异的抗积碳性能。
4)本发明的Zr-Pr-O复合氧化物钴基催化剂形成了Co-Zr-Pr-O活性中心,抗烧结能力与活性组分分散度显著提高;这是由于Pr3+的离子半径大于Zr4+的离子半径,这就使得当离子半径更大的Pr3+进入ZrO2晶格之中,m-ZrO2转变为t-ZrO2,即从单斜相变为了四方相,造成了晶格膨胀,使得Co3O4的电子云与ZrO2缺陷位中的电子云发生重叠,调变了Co与Zr-Pr-O复合氧化物的电负性,使活性组分与载体形成强相互作用,稳定了Co-Zr-Pr-O活性中心,避免了活性组分的聚集,提高了催化剂抗烧结能力;Pr的加入阻止了活性组分Co晶粒的生长,这使得活性中心Co能够高度分散在了Zr-Pr-O复合氧化物载体上,从而增加了催化剂表面钴位点的数量,提高了催化剂表面对水的吸附强度和对乙酸的吸附活化,形成CH3COO*、CH3CO*等中间产物,进而转化为H2、CO2,提高了催化剂的活性。
5)本发明在焙烧后形成的Zr-Pr-O复合氧化物钴基催化剂,利用了Zr-Pr之间的协同效应,促进活性组分钴形成了Co-Zr-Pr-O活性中心,在乙酸转化过程中,能够诱导乙酸进行高效的吸附转化,且有效抑制酮基化反应,从而抑制丙酮、乙烯酮和甲烷等副产物的产生,具有抗积碳、耐烧结、活性稳定、氢气产率高等特点。
附图说明
图1:本发明催化剂的X射线衍射图
图2:本发明催化剂的BJH孔径分布图
图3:本发明催化剂还原后的X射线衍射图
具体实施方式
参照例一
称取7.972g的ZrO(NO3)2·2H2O、2.921g的Co(NO3)2·6H2O,加入10ml去离子水,配制成溶液#1;称取9.353g的柠檬酸于250ml烧杯中,加入10ml去离子水,用磁力搅拌器搅拌溶解,配制成溶液#2;将柠檬酸溶液#2置于70℃的水浴条件下搅拌,将硝酸盐溶液#1缓慢滴加到柠檬酸溶液中,反应络合0.5h;称取2.763g乙二醇溶液,缓慢滴加到前述混合溶液,维持70℃水浴搅拌3h,形成凝胶,置于105℃干燥箱中烘12h,后在750℃下焙烧4h,得到CDUT-CZ催化剂。该催化剂的摩尔组成为(ZrO2)0.68(CoO1.5)0.2,重量百分比组成为:氧化锆为84.9%,氧化钴为15.1%。
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。将催化剂研磨并压片,然后筛分成小颗粒,并将20-40目的颗粒称取0.1-0.2g,装入反应器中,在600℃-800℃的温度下在H2中还原1h;然后将乙酸-水的混合溶液以恒流泵注入汽化器经汽化后,混合氧气,并以氮气为内标气体,形成摩尔比为CH3COOH/H2O/O2=1/(1.3-5.0)/(0.2-0.5)的反应原料气,将此原料气导入反应床层,反应条件为600-800℃、常压、空速10000-35000ml/(g-catalyst·h),反应尾气采用气相色谱仪在线分析。
该CDUT-CZ催化剂经乙酸自热重整反应进行活性考察,还原温度为700℃、反应空速为11000ml/(g-catalyst·h)、反应温度为650℃、进料摩尔比为CH3COOH/H2O/O2=1/4.0/0.28。该催化剂乙酸转化率稳定在100%,氢气产率在1.75mol-H2/mol-HAc左右,二氧化碳选择性在56%左右,一氧化碳选择性在44%左右,副产物丙酮选择性在0.1%左右。对催化剂进行氮低温物理吸附表征,结果为:比表面积为2.1m2/g、孔体积为0.02cm3/g、平均孔径为17.4nm。
实施例一
称取1.451g的Pr(NO3)3·6H2O、6.939g的ZrO(NO3)2·2H2O和2.921g的Co(NO3)2·6H2O,加入10ml去离子水,配制成溶液#1;称取9.117g的柠檬酸于250ml烧杯中,加入10ml去离子水,用磁力搅拌器搅拌溶解,配制成溶液#2;将柠檬酸溶液#2置于70℃的水浴条件下搅拌,将硝酸盐溶液#1缓慢滴加到柠檬酸溶液中,反应络合0.5h;称取2.693g乙二醇溶液,缓慢滴加到前述混合溶液,维持70℃水浴搅拌3h,形成凝胶,置于105℃干燥箱中烘12h,后在750℃下焙烧4h,得到含有尖晶石相Co3O4和Pr掺杂四方相ZrO2的Co-Zr-Pr-O复合氧化物钴基催化剂,即CDUT-CZP-I催化剂,其氧化物典型晶型结构如附图1所示,其孔结构特征如附图2所示,其还原后样品的典型晶型结构如附图3所示,形成了Co物种高度分散在Pr掺杂的t-ZrO2的、含Co-Zr-Pr-O活性中心的复合氧化物催化剂;该催化剂的摩尔组成为(PrO1.5)0.067(ZrO2)0.60(CoO1.5)0.2,重量百分比组成为:氧化镨为11.0%,氧化钴为15.1%,氧化锆为73.9%。
该CDUT-CZP-I催化剂经乙酸自热重整反应进行活性考察,还原温度为700℃、反应空速为11000mL/(g-catalyst·h)、反应温度为650℃、进料摩尔比为CH3COOH/H2O/O2=1/4.0/0.28。该催化剂乙酸转化率稳定在100%,氢气产率在2.75mol-H2/mol-HAc左右,二氧化碳选择性在57%左右,一氧化碳选择性在48%左右,没有副产物丙酮,催化活性保持稳定,未见失活;对CDUT-CZP-I催化剂进行氮低温物理吸附表征,结果为:比表面积为8.7m2/g、孔体积为0.06cm3/g、平均孔径为12.9nm。对还原后的催化剂进行表征,如附图3还原后XRD谱图所示,催化剂活性组分Co高度分散在Zr-Pr-O复合氧化物载体上,价态稳定,没有聚结,未发现积炭物种。由结果可知,本发明的催化剂在乙酸自热重整反应中,具有抗积碳、耐烧结、氢气产率高、结构稳定等优点。
实施例二
称取2.810g的Pr(NO3)3·6H2O、5.976g的ZrO(NO3)2·2H2O和2.912g的Co(NO3)2·6H2O,加入10ml去离子水,配制成溶液#1;称取8.892g的柠檬酸于250ml烧杯中,加入10ml去离子水,用磁力搅拌器搅拌溶解,配制成溶液#2;将柠檬酸溶液#2置于70℃的水浴条件下搅拌,将硝酸盐溶液#1缓慢滴加到柠檬酸溶液中,反应络合0.5h;称取2.627g乙二醇溶液,缓慢滴加到前述混合溶液,维持70℃水浴搅拌3h,形成凝胶,置于105℃干燥箱中烘12h,后在750℃下焙烧4h,得到含有尖晶石相Co3O4和Pr掺杂四方相ZrO2的Zr-Pr-O复合氧化物钴基催化剂,即CDUT-CZP-II催化剂;该催化剂的摩尔组成为(PrO1.5)0.12(ZrO2)0.53(CoO1.5)0.2,重量百分比组成为:氧化镨为21.3%,氧化钴为15.0%,氧化锆为63.7%。
该CDUT-CZP-II催化剂经乙酸自热重整反应进行活性考察,还原温度700℃、反应空速为11000mL/(g-catalyst·h)、反应温度为650℃、进料摩尔比为CH3COOH/H2O/O2=1/4.0/0.28。该催化剂乙酸转化率稳定在100%附近,氢气产率在2.4mol-H2/mol-HAc左右,二氧化碳选择性在60%左右,一氧化碳选择性在45%左右,未见副产物丙酮,催化剂活性保持稳定,未见失活;对CDUT-CZP-II催化剂进行氮低温物理吸附表征,结果为:比表面积为10.2m2/g、孔体积为0.06cm3/g、平均孔径为11.1nm。
Claims (3)
1.一种镨锆复合氧化物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0.1-0.2g催化剂于600-800℃ 的H2气氛中还原1h,通入摩尔比为CH3COOH/H2O/O2= 1/(1.3-5.0)/(0.2-0.5)的混合气体,通过催化剂床层进行乙酸自热重整反应,反应温度为600-800℃ ;所述催化剂的制备方法如下:根据化学组成,将硝酸钴、硝酸氧锆和硝酸镨溶于去离子水配制成金属盐溶液;根据柠檬酸与金属阳离子物质的量的总和的摩尔比为1:1,配制柠檬酸溶液;于70℃ 水浴搅拌条件下,将金属盐溶液缓慢滴加到柠檬酸溶液中,反应络合0.5h,形成混合溶液;按乙二醇和柠檬酸的摩尔比为1:1,称取乙二醇并缓慢滴入到前述混合溶液中,维持70℃ 水浴搅拌3h,形成凝胶,然后于105℃ 干燥12h,并于管式炉中以10℃ /min的加热速度升温至700℃ ,保持4h,得到具有尖晶石相Co3O4和Pr掺杂四方相ZrO2的Co-Zr-Pr-O复合氧化物钴基催化剂,其化学组成是(PrO1.5)a(ZrO2)b(CoO1.5)c,其中a为0-0.19,b为0.43-0.69,c为0.17-0.21;按照氧化物计的重量百分比组成为:氧化镨含量为0%-30.7%且不为0%,氧化锆含量为53.5%-86.0%,氧化钴含量为14.0%-16.0%,且各组分重量百分比组成之和为100%。
2.根据权利要求1所述的镨锆复合氧化物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为:氧化锆为73.9%,氧化钴为15.1%,氧化镨为11.0%。
3.根据权利要求1所述的镨锆复合氧化物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为:氧化锆为63.7%,氧化钴为15.0%,氧化镨为21.3%。
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