多元醇液相重整反应的催化剂研究
摘要
近年来,由于化石资源的大量消耗,同时化石资源的利用导致的全球环境问题日益严重,因此急需寻找清洁可再生的替代能源。在众多新能源中,生物质的转化和利用由于生物质的可再生性而受到了高度的关注。
最近Dumesic等人提出了生物质液相催化重整(APR)工艺,该工艺以从生物质中提取的碳水化合物(乙二醇、甘油、葡萄糖或山梨醇)为原料,通过改变不同的催化剂和反应条件可以灵活制取氢气、低碳数烷烃、合成气等不同的产品,具有原料安全易得、低温操控、能量利用率高、CO2净排量为零等优点。因此,该工艺具有广阔的发展前景。
与其他第ⅧB族贵金属相比,Ni基催化剂不但价格低廉,而且具有较强的C-C键断裂能力和较高的水煤气变换反应(WGS)活性,所以其在APR反应中的应用受到了催化工作者的广泛关注。Co基催化剂同样具有价格优势,且Co基催化剂在生物质液相重整领域中研究较少。因此本文主要对Ni基和Co基催化剂上的乙二醇及丙三醇液相重整反应进行了研究,得到以下主要结果：
1. Sn-RQ NiMo催化剂上的乙二醇液相重整制氢研究
采用急冷法制备了骨架Ni-Mo催化剂(RQ Ni50-xMox)并应用于乙二醇液相重整制氢反应中。研究表明,Mo的加入显著提高了催化活性,并且活性随着Mo含量的增加而增加,但是H2选择性呈现下降趋势。结合XRD表征结果可知,随着Mo的加入,Ni2Al3相更易被抽提,活化后的催化剂晶粒减小,使更多的Ni暴露在表面上,有利于与反应物的接触,使催化剂活性增加。由于Mo的加入有利于甲烷化反应的进行,因此反应的H2选择性下降。文献工作表明,Sn修饰的Raney Ni催化剂虽然在乙二醇液相重整制氢反应中表现出了良好的H2选择性,但同时活性也有所降低。由于Mo的加入能够显著提高反应活性,因此我们分别用SnCl4、SnCl2以及Sn(n-C4H9)4作为锡源对RQ Ni47.8Mo2.2催化剂进行修饰。研究表明,Sn的加入使H2选择性得到大幅度的提高,且不同Sn源修饰的催化剂表现出的催化性能有所区别。在三种Sn源中,SnCl4修饰的催化剂具有最佳的催化性能：在Sn/Ni原子比为2%时,H2选择性即达到了91.1%；当Sn/Ni原子比达到5%时,H2选择性达到95%以上,同时基本消除了烷烃的生成。由H2-TPD结果可知,催化剂经Sn修饰后,表面活性位种类减少,从而有可能减少反应物分子在催化剂上的吸附模式,降低了副反应的发生。动力学研究发现,Sn的修饰作用主要体现在两方面,即抑制甲烷化反应和促进WGS反应的进行。对于同一种Sn源修饰的催化剂,其活性和Sn在催化剂中的分散情况有关,Sn的分散情况越好,则活性越高。对SnCl4修饰的RQ Ni和RQ Ni47.8Mo2.2催化剂进行了100h稳定性考察发现,RQ Ni47.8Mo2.2的初始活性和稳态活性均比Sn(IV)-RQNi催化剂高,且催化剂的H2选择性在反应过程中始终保持在99%以上,显示了良好的应用前景。
2. CoNi/Al2O3催化剂上的乙二醇液相重整制氢研究
Dumesic等人发现Ni/Al2O3催化剂虽然拥有较好的活性,但在498 K和2.58MPa的反应条件下,该催化剂因为烧结而迅速失活。文献报道CoNi双金属催化剂在甲烷二氧化碳重整制合成气反应中具有优秀的反应活性和稳定性以及抗烧结能力。我们以Co(NO3)6-6H2O、Ni(NO3)6·6H2O和γ-Al203为原料采用共浸渍方法制备了一系列不同Co/Ni原子比的CoNi/γ-Al2O3催化剂,并考察了其在乙二醇APR反应中的催化活性和选择性。研究表明,CoNi双金属催化剂与单金属催化剂相比,具有更加优秀的催化活性,同时不同的Co/Ni比对反应活性和选择性具有显著影响。随着Ni含量的增加,催化剂的活性和烷烃选择性先升高后降低,而H2选择性的变化规律与之相反。我们在Co67Ni33催化剂上得到了最佳的反应活性(以CO2生成速率表示)85.5μmol g-1 min-1,其H2和烷烃选择性分别为47%和33%。XRD结果表明,催化剂焙烧后形成了NixCo3-xO4的固熔体。TPR研究表明,CoNi双金属催化剂比单金属的Co和Ni催化剂更容易还原,说明固熔体的形成降低了金属与载体间的相互作用。从XAFS谱发现,CoNi双金属催化剂存在方向为Co→Ni的电子转移,并且其电子转移程度在Co67Ni33催化剂上最大。对Co100、Ni100和Co67Ni33催化剂进行稳定性考察发现,Col00和Ni100催化剂在反应条件下快速失活；Co67Ni33催化剂在反应150 h后,仍然保持了86%的初始反应活性,显示出了优秀的催化活性和稳定性。对反应前后的Co67Ni33催化剂进行表征,反应150 h后,催化剂的比表面积没有明显变化,反应后仍然保持了较好的分散度。TEM表明,Col00催化剂反应后严重烧结,其颗粒大于120nm.Ni100催化剂反应后比表面积从101 m2g-1下降到40 m2g-1,说明催化剂结构遭到破坏,造成Ni催化剂活性迅速降低。此外,我们还在CoNi/γ-Al2O3催化剂中添加第三金属Sn、Au、Pt来提高反应的H2选择性。研究表明,Sn的添加在大幅提高H2选择性的同时显著降低了催化剂的活性；少量Au的添加即可提高反应活性,但对H2选择性基本无影响;而Pt的添加使催化剂的活性和H2选择性同时提高。
3. CoNi/Al2O3催化剂上的丙三醇液相重整反应研究
由于CoNi/Al2O3催化剂具有优秀的催化活性和稳定性,我们也将其应用于丙三醇液相重整反应中。研究表明,随着Ni含量的增加,催化剂的活性和选择性同样呈现火山型的变化规律,与乙二醇不同,我们在Co50Ni50催化剂上得到了最佳的反应活性(C02生成速率为150.6μmol g-1 min-1)和H2选择性(43.2%)。但是对Co67Ni33和Co50Ni50做了100 h稳定性考察后发现,Co67Ni33催化剂的稳态活性和稳定性均高于后者。表征结果表明,反应后C67Ni33催化剂具有比Co50Ni50催化剂更小的晶粒尺寸和更高的活性比表面积。由于丙三醇液相重整反应中有酸生产,因此催化剂金属活性组分的流失也是活性下降的一个重要因素。ICP结果表明,反应过程中两个催化剂上Co的流失(10-60 wppm)比Ni的流失(< 1 wppm)严重,说明Co的流失是催化剂活性下降的重要原因。而Co67Ni33催化剂中Co的流失小于Co50Ni50。反应100 h后Co67Ni33和Co50Ni50催化剂的Co/Ni比例发生改变,分别为60／40和39／61,从而对催化剂的活性和选择性造成影响。最后,我们通过对Co67Ni33催化剂上甲醇、乙醇、乙二醇和1,2-丙二醇四种主要液相产物的液相重整反应研究,讨论了CoNi/Al2O3催化剂上丙三醇可能的反应路径。丙三液相重整反应主要有两条路径：第一条路径为丙三醇液相重整生成H2,CO2和烷烃,另外一条路径是丙三醇脱水加氢后生成1,2-丙二醇,并且在较高的丙三醇转化率下,1,2-丙二醇可以继续反应生成气相产物和乙醇,后者可以和H2O反应生成乙酸。
此外,我们还对丙三醇直接液相重整制二醇的反应进行了研究。采用浸渍法制备了丫-Al203负载的Ru、Cu、Fe、Co、Ni催化剂,并对其进行筛选,发现丙三醇在Fe催化剂上不生成二醇；Ru和Ni催化剂虽然活性较高,但二醇选择性较差,这主要是因为Ru和Ni对于C-C键的断裂能力较强,使部分原料直接转化成气相产物。Co和Cu催化剂的活性较差,其产物中含有较多丙酮醇,这是因为Co和Cu的液相重整制氢能力较差,不能产生足够的H2和丙酮醇反应生成1,2-丙二醇。在Co和Cu催化剂中添加Ni可以提高二醇的得率,但过多Ni的加入会使大量原料直接重整生成气相产物。对于CuNi催化剂和CoNi催化剂,其最佳的Ni含量分别为75%和10%。
4. Co/ZnO催化剂上的乙二醇液相重整制氢研究
采用共沉淀法制备了不同Co/Zn比例的Co/ZnO催化剂,并将其应用于乙二醇液相重整制氢反应。XRD结果表明,焙烧后催化剂形成了ZnCo2O4的尖晶石物相；在723 K温度下还原后,催化剂的物相为金属Co和ZnO。由还原后催化剂的XPS谱可知,随Co/Zn比例的升高,催化剂表面金属Co的含量随之上升,这与测得的催化剂还原度变化趋势相一致。在乙二醇液相重整反应中,当Co/Zn比例从1：3上升到2：1,反应的H2选择性从89%下降到52%,且H2的TOF值从101.4h-1下降到27.9 h-1。反应的气相产物中出现了烯烃,这主要是因为Co是一种良好的费-托合成(FTS)反应的催化剂；反应的液相产物为甲醇,乙醇和乙酸。我们分别研究了Co/ZnO-21催化剂上甲醇、乙醇和乙酸的液相重整反应,并讨论了乙二醇在Co/ZnO催化剂上可能的反应路径。结果表明,在Co/ZnO催化剂上乙二醇除了发生文献报道的反应外,还应把乙醇在催化剂上生成乙酸和异丙醇以及通过FTS反应生成烯烃的途径考虑在内。
With decreased crude-oil reserves, enhanced demand for fuels worldwide, increased climate concerns about the use of fossil-based energy carriers, the focus has recently turned towards improved utilization of renewable energy resources. Biomass has attracted much attention, because it is an abundant and carbon-neutral renewable energy resource, which can be used for the production of biofuels and valuable chemicals.
Recently, Dumesic and coworkers reported a process to generate hydrogen, alkanes and syngas by aqueous-phase reforming (APR) of oxygenated hydrocarbon, such as ethylene glycol, glycerol, glucose, and sorbitol. Compared with the existed steam reforming process, the APR process has the advantages of higher energy efficiency, lower operating temperature, and broader range of safe liquid feedstocks.
Ni shows high activity for C-C bond cleavage and moderate activity for water-gas shift (WGS) reaction among the VIIIB metals, and is less costly than Pt, so it has attracted much attention in the APR of polyols. Co-base catalysts, which also have cost superiority and moderate activity for C-C bond cleavage and WGS reaction, haven't been exploited in the field of APR of polyols. In the present work, we carried out the APR of ethylene glycol and glycerol over the Ni-based and Co-based catalysts, and obtained the following results.
1. Aqueous phase reforming of ethylene glycol to H2 over Sn-RQ NiMo catalysts
The rapidly quenched skeletal Ni-Mo (RQ Ni50-xMox) catalysts were prepared by alkali leaching of RQ Ni50-xMoxAl50 alloy and investigated in the APR of ethylene glycol. Addition of Mo to the RQ Ni catalyst improved the activity remarkably, but the H2 selectivity decreased with the increment of Mo content. Ni2Al3 phase was easier to be leached at the presence of Mo, which resulted in smaller Ni crystallite size. The reason for the decreased H2 selectivity is that Mo can improve the activity of the methanation reaction. It has been reported that addition of Sn to Raney Ni catalyst can improve the H2 selectivity but suppress the activity. Thus, we modified the RQ Ni47.8Mo2.2 catalyst with SnCl4, SnCl2 and Sn(n-C4H9)4. The addition of Sn to RQ catalyst drastically enhanced the H2 selectivity, and SnCl4 has the best modification efficiency. The selectivity to H2 reached 91.1%at Sn/Ni atomic ratio of 2%. Moreover, when the Sn/Ni atomic ratio was 5%, the selectivity to H2 was above 95%, while the formation of alkanes was substantially suppressed. H2-TPD results showed that the number of desorption peaks reduced after Sn modification, suggesting that the active sites over the catalysts became more uniform, which may have decreased the adsorption modes of the reactant and suppressed side reactions. According to the kinetic results of the APR of ethylene glycol, we concluded that the addition of Sn to RQ Ni47.8Mo2.2 improved the H2 selectivity by promoting the WGS reaction while suppressing the methanation reaction. For the catalysts modified by the same Sn species, higher dispersion of Sn in the catalysts resulted in higher catalytic activity. The stability tests over Sn(IV)-RQ Ni47.8Mo2.2 and Sn(IV)-RQ Ni catalysts showed that Sn(IV)-RQ Ni47.8Mo2.2 showed higher activity and stability than Sn(IV)-RQ Ni catalyst, and its H2 selectivity catalyst was above 99% during 100 h reaction, indicating that this catalyst is a good candidate in fuel-cell system.
2. Aqueous phase reforming of ethylene glycol to H2 over CONi/Al2O3 catalysts
Dumesic et al. found that the Ni/Al2O3 catalyst deactivated rapidly under the APR condition. However, bimetallic supported Co-Ni catalysts displayed an excellent catalytic performance in carbon dioxide reforming of methane. We prepared the CoNi/y-Al2O3 catalysts by the coimpregnation method and studied their catalytic performance in the APR of ethylene glycol. We obtained the best acitivity over Co67Ni33 catalyst with H2 and alkane selectivity of 47% and 33%, respectively. The formation of spinel-type NixCo3-xO4 phase after calcination reduced the metal-support interaction, thus leading to higher reduction degree of bimetallic CoNi catalysts. The electron transfer of Co→Ni was found in the CoNi catalysts by XAFS, and the highest transfer degree was obtained on Co67Ni33 catalyst. The stability tests of Co100, Co67Ni33 and Ni100 catalysts showed that Co67Ni33 catalyst displayed the best activity and stability. Both Co100 and Ni100 catalysts deactivated quickly, while Co67Ni33 remained 86%of its initial activity after 150 h time on stream. After reaction the Co 100 catalyst was seriously sintered (dCo> 120 nm). The BET surface area of the Ni100 catalyst decreased drastically from 101 to 40 m2·g-1, indicating that the destruction of the structure resulted in the decreased activity. On the contrary, Co67Ni33 catalyst retained the structure and the metal dispersion after reaction. In addition, we added the third metal to Co67Ni33 catalyst to improve the H2 selectivity. The addition of Sn increased the H2 selectivity remarkably but drastically suppressed the activity. Adding Au to Co67Ni33 enhanced the activity but hardly influenced the selectivity. The addition of Pt can improve both H2 selectivity and activity.
3. Aqueous phase reforming of glycerol over CoNi/Al2O3 catalysts
We carried out the APR of glycerol on the CoNi/Al2O3 catalysts, which displayed an excellent catalytic performance in the APR of ethylene glycol. The Co/Ni ratio had a great influence on the activity, and the best activity and H2 selectivity were obtained on the Co50Ni50 catalyst. However, we found that the Co67Ni33 catalyst have superior stability to Co50Ni50. The characterization results showed that after reaction Co67Ni33 catalyst had smaller crystallite size and higher active surface area than Co50Ni50 catalyst. Since acid species were formed in the reaction, the leaching of the metal is another reason for the decreased activity. ICP results showed that the leaching of Co is much more serious than that of Ni, and the leaching of Co in Co67Ni33 is higher than that in the Co50Ni50 catalyst. Thus the Co/Ni ratio of the Co67Ni33 and Co50Ni50 catalysts after reaction turned into 60/40 and 39/61, respectively. The reaction pathway of glycerol was discussed based on the APR of methanol, ethanol, ethylene glycol and 1,2-dipropanol. The reaction pathway of glycerol can be divided into two parts:(1) Glycerol can be converted into H2, CO2 and alkanes by C-C cleavage followed by WGS or methanation/FTS reaction. (2) Glycerol can be converted into 1,2-dipropanol by dehydration to acetol and subsequent hydrogenation. 1,2-dipropanol will undergo further reaction to produce gas products and ethanol at high conversion levels. In addition, ethanol can be transformed into acetic acid under the reaction condition.
We also studied the catalytic conversion of glycerol into glycol by the APR process. We first investigated the APR of glycerol on M/Y-Al2O3 (M= Ru, Cu, Fe, Co, Ni) catalysts. For the Fe catalyst, no glycol was found in the APR of glycerol. Both Ni and Ru catalysts have good glycerol conversion but poor glycol selectivity. Since Ni and Ru show high activity to C-C cleavage, the selectivity to gas products is much higher than that of other catalysts. Co and Cu have low activity, and the main product on these two catalysts is acetol. The poor ability to convert acetol to 1,2-dipropanol may be attributed to the poor reforming activity of Co and Cu towards glycerol. Adding proper amount of Ni to the Co and Cu catalysts can improve the glycol yield, while suppressing the side reactions. The optimized content of Ni in CuNi and CoNi catalysts is 75% and 10%, respectively.
4. Aqueous phase reforming of ethylene glycol to H2 over Co/ZnO catalysts
Co/ZnO catalysts with different Co/Zn ratio were prepared by coprecipitation method and their catalytic performances were evaluated in the APR of ethylene glycol. The spinel type of ZnCo2O4 was formed after calcination at 723 K. After reduction, the Co/ZnO catalysts are composed of fcc Co and ZnO. XPS results shows that surface Co0 content increased with the increment of Co/Zn ratio, which is in good agreement with the reduction degree. When the Co/Zn ratio increased from 1/3 to 2/1, the H2 selectivity decreased from 89% to 52%, and the TOF of H2 decreased from 101.4 h"1 to 27.9 h-1. Since Co is a common catalyst in FTS reaction, Co/ZnO catalyst produced the alkenes in the APR of ethylene glycol. The liquid products contained methanol, ethanol, and acetic acid. Based on the results of the APR of methanol, ethanol and acetic acid on Co/ZnO-21 catalyst, we concluded that besides the reaction pathways of ethylene glycol with water over metallic catalysts proposed in the literature, reaction pathways from ethanol to acetic acid and 2-propanol and via the FTS reaction to alkenes should be taken into account over the Co/ZnO catalysts in APR of ethylene glycol.
最近Dumesic等人提出了生物质液相催化重整(APR)工艺,该工艺以从生物质中提取的碳水化合物(乙二醇、甘油、葡萄糖或山梨醇)为原料,通过改变不同的催化剂和反应条件可以灵活制取氢气、低碳数烷烃、合成气等不同的产品,具有原料安全易得、低温操控、能量利用率高、CO2净排量为零等优点。因此,该工艺具有广阔的发展前景。
与其他第ⅧB族贵金属相比,Ni基催化剂不但价格低廉,而且具有较强的C-C键断裂能力和较高的水煤气变换反应(WGS)活性,所以其在APR反应中的应用受到了催化工作者的广泛关注。Co基催化剂同样具有价格优势,且Co基催化剂在生物质液相重整领域中研究较少。因此本文主要对Ni基和Co基催化剂上的乙二醇及丙三醇液相重整反应进行了研究,得到以下主要结果：
1. Sn-RQ NiMo催化剂上的乙二醇液相重整制氢研究
采用急冷法制备了骨架Ni-Mo催化剂(RQ Ni50-xMox)并应用于乙二醇液相重整制氢反应中。研究表明,Mo的加入显著提高了催化活性,并且活性随着Mo含量的增加而增加,但是H2选择性呈现下降趋势。结合XRD表征结果可知,随着Mo的加入,Ni2Al3相更易被抽提,活化后的催化剂晶粒减小,使更多的Ni暴露在表面上,有利于与反应物的接触,使催化剂活性增加。由于Mo的加入有利于甲烷化反应的进行,因此反应的H2选择性下降。文献工作表明,Sn修饰的Raney Ni催化剂虽然在乙二醇液相重整制氢反应中表现出了良好的H2选择性,但同时活性也有所降低。由于Mo的加入能够显著提高反应活性,因此我们分别用SnCl4、SnCl2以及Sn(n-C4H9)4作为锡源对RQ Ni47.8Mo2.2催化剂进行修饰。研究表明,Sn的加入使H2选择性得到大幅度的提高,且不同Sn源修饰的催化剂表现出的催化性能有所区别。在三种Sn源中,SnCl4修饰的催化剂具有最佳的催化性能：在Sn/Ni原子比为2%时,H2选择性即达到了91.1%；当Sn/Ni原子比达到5%时,H2选择性达到95%以上,同时基本消除了烷烃的生成。由H2-TPD结果可知,催化剂经Sn修饰后,表面活性位种类减少,从而有可能减少反应物分子在催化剂上的吸附模式,降低了副反应的发生。动力学研究发现,Sn的修饰作用主要体现在两方面,即抑制甲烷化反应和促进WGS反应的进行。对于同一种Sn源修饰的催化剂,其活性和Sn在催化剂中的分散情况有关,Sn的分散情况越好,则活性越高。对SnCl4修饰的RQ Ni和RQ Ni47.8Mo2.2催化剂进行了100h稳定性考察发现,RQ Ni47.8Mo2.2的初始活性和稳态活性均比Sn(IV)-RQNi催化剂高,且催化剂的H2选择性在反应过程中始终保持在99%以上,显示了良好的应用前景。
2. CoNi/Al2O3催化剂上的乙二醇液相重整制氢研究
Dumesic等人发现Ni/Al2O3催化剂虽然拥有较好的活性,但在498 K和2.58MPa的反应条件下,该催化剂因为烧结而迅速失活。文献报道CoNi双金属催化剂在甲烷二氧化碳重整制合成气反应中具有优秀的反应活性和稳定性以及抗烧结能力。我们以Co(NO3)6-6H2O、Ni(NO3)6·6H2O和γ-Al203为原料采用共浸渍方法制备了一系列不同Co/Ni原子比的CoNi/γ-Al2O3催化剂,并考察了其在乙二醇APR反应中的催化活性和选择性。研究表明,CoNi双金属催化剂与单金属催化剂相比,具有更加优秀的催化活性,同时不同的Co/Ni比对反应活性和选择性具有显著影响。随着Ni含量的增加,催化剂的活性和烷烃选择性先升高后降低,而H2选择性的变化规律与之相反。我们在Co67Ni33催化剂上得到了最佳的反应活性(以CO2生成速率表示)85.5μmol g-1 min-1,其H2和烷烃选择性分别为47%和33%。XRD结果表明,催化剂焙烧后形成了NixCo3-xO4的固熔体。TPR研究表明,CoNi双金属催化剂比单金属的Co和Ni催化剂更容易还原,说明固熔体的形成降低了金属与载体间的相互作用。从XAFS谱发现,CoNi双金属催化剂存在方向为Co→Ni的电子转移,并且其电子转移程度在Co67Ni33催化剂上最大。对Co100、Ni100和Co67Ni33催化剂进行稳定性考察发现,Col00和Ni100催化剂在反应条件下快速失活；Co67Ni33催化剂在反应150 h后,仍然保持了86%的初始反应活性,显示出了优秀的催化活性和稳定性。对反应前后的Co67Ni33催化剂进行表征,反应150 h后,催化剂的比表面积没有明显变化,反应后仍然保持了较好的分散度。TEM表明,Col00催化剂反应后严重烧结,其颗粒大于120nm.Ni100催化剂反应后比表面积从101 m2g-1下降到40 m2g-1,说明催化剂结构遭到破坏,造成Ni催化剂活性迅速降低。此外,我们还在CoNi/γ-Al2O3催化剂中添加第三金属Sn、Au、Pt来提高反应的H2选择性。研究表明,Sn的添加在大幅提高H2选择性的同时显著降低了催化剂的活性；少量Au的添加即可提高反应活性,但对H2选择性基本无影响;而Pt的添加使催化剂的活性和H2选择性同时提高。
3. CoNi/Al2O3催化剂上的丙三醇液相重整反应研究
由于CoNi/Al2O3催化剂具有优秀的催化活性和稳定性,我们也将其应用于丙三醇液相重整反应中。研究表明,随着Ni含量的增加,催化剂的活性和选择性同样呈现火山型的变化规律,与乙二醇不同,我们在Co50Ni50催化剂上得到了最佳的反应活性(C02生成速率为150.6μmol g-1 min-1)和H2选择性(43.2%)。但是对Co67Ni33和Co50Ni50做了100 h稳定性考察后发现,Co67Ni33催化剂的稳态活性和稳定性均高于后者。表征结果表明,反应后C67Ni33催化剂具有比Co50Ni50催化剂更小的晶粒尺寸和更高的活性比表面积。由于丙三醇液相重整反应中有酸生产,因此催化剂金属活性组分的流失也是活性下降的一个重要因素。ICP结果表明,反应过程中两个催化剂上Co的流失(10-60 wppm)比Ni的流失(< 1 wppm)严重,说明Co的流失是催化剂活性下降的重要原因。而Co67Ni33催化剂中Co的流失小于Co50Ni50。反应100 h后Co67Ni33和Co50Ni50催化剂的Co/Ni比例发生改变,分别为60／40和39／61,从而对催化剂的活性和选择性造成影响。最后,我们通过对Co67Ni33催化剂上甲醇、乙醇、乙二醇和1,2-丙二醇四种主要液相产物的液相重整反应研究,讨论了CoNi/Al2O3催化剂上丙三醇可能的反应路径。丙三液相重整反应主要有两条路径：第一条路径为丙三醇液相重整生成H2,CO2和烷烃,另外一条路径是丙三醇脱水加氢后生成1,2-丙二醇,并且在较高的丙三醇转化率下,1,2-丙二醇可以继续反应生成气相产物和乙醇,后者可以和H2O反应生成乙酸。
此外,我们还对丙三醇直接液相重整制二醇的反应进行了研究。采用浸渍法制备了丫-Al203负载的Ru、Cu、Fe、Co、Ni催化剂,并对其进行筛选,发现丙三醇在Fe催化剂上不生成二醇；Ru和Ni催化剂虽然活性较高,但二醇选择性较差,这主要是因为Ru和Ni对于C-C键的断裂能力较强,使部分原料直接转化成气相产物。Co和Cu催化剂的活性较差,其产物中含有较多丙酮醇,这是因为Co和Cu的液相重整制氢能力较差,不能产生足够的H2和丙酮醇反应生成1,2-丙二醇。在Co和Cu催化剂中添加Ni可以提高二醇的得率,但过多Ni的加入会使大量原料直接重整生成气相产物。对于CuNi催化剂和CoNi催化剂,其最佳的Ni含量分别为75%和10%。
4. Co/ZnO催化剂上的乙二醇液相重整制氢研究
采用共沉淀法制备了不同Co/Zn比例的Co/ZnO催化剂,并将其应用于乙二醇液相重整制氢反应。XRD结果表明,焙烧后催化剂形成了ZnCo2O4的尖晶石物相；在723 K温度下还原后,催化剂的物相为金属Co和ZnO。由还原后催化剂的XPS谱可知,随Co/Zn比例的升高,催化剂表面金属Co的含量随之上升,这与测得的催化剂还原度变化趋势相一致。在乙二醇液相重整反应中,当Co/Zn比例从1：3上升到2：1,反应的H2选择性从89%下降到52%,且H2的TOF值从101.4h-1下降到27.9 h-1。反应的气相产物中出现了烯烃,这主要是因为Co是一种良好的费-托合成(FTS)反应的催化剂；反应的液相产物为甲醇,乙醇和乙酸。我们分别研究了Co/ZnO-21催化剂上甲醇、乙醇和乙酸的液相重整反应,并讨论了乙二醇在Co/ZnO催化剂上可能的反应路径。结果表明,在Co/ZnO催化剂上乙二醇除了发生文献报道的反应外,还应把乙醇在催化剂上生成乙酸和异丙醇以及通过FTS反应生成烯烃的途径考虑在内。
With decreased crude-oil reserves, enhanced demand for fuels worldwide, increased climate concerns about the use of fossil-based energy carriers, the focus has recently turned towards improved utilization of renewable energy resources. Biomass has attracted much attention, because it is an abundant and carbon-neutral renewable energy resource, which can be used for the production of biofuels and valuable chemicals.
Recently, Dumesic and coworkers reported a process to generate hydrogen, alkanes and syngas by aqueous-phase reforming (APR) of oxygenated hydrocarbon, such as ethylene glycol, glycerol, glucose, and sorbitol. Compared with the existed steam reforming process, the APR process has the advantages of higher energy efficiency, lower operating temperature, and broader range of safe liquid feedstocks.
Ni shows high activity for C-C bond cleavage and moderate activity for water-gas shift (WGS) reaction among the VIIIB metals, and is less costly than Pt, so it has attracted much attention in the APR of polyols. Co-base catalysts, which also have cost superiority and moderate activity for C-C bond cleavage and WGS reaction, haven't been exploited in the field of APR of polyols. In the present work, we carried out the APR of ethylene glycol and glycerol over the Ni-based and Co-based catalysts, and obtained the following results.
1. Aqueous phase reforming of ethylene glycol to H2 over Sn-RQ NiMo catalysts
The rapidly quenched skeletal Ni-Mo (RQ Ni50-xMox) catalysts were prepared by alkali leaching of RQ Ni50-xMoxAl50 alloy and investigated in the APR of ethylene glycol. Addition of Mo to the RQ Ni catalyst improved the activity remarkably, but the H2 selectivity decreased with the increment of Mo content. Ni2Al3 phase was easier to be leached at the presence of Mo, which resulted in smaller Ni crystallite size. The reason for the decreased H2 selectivity is that Mo can improve the activity of the methanation reaction. It has been reported that addition of Sn to Raney Ni catalyst can improve the H2 selectivity but suppress the activity. Thus, we modified the RQ Ni47.8Mo2.2 catalyst with SnCl4, SnCl2 and Sn(n-C4H9)4. The addition of Sn to RQ catalyst drastically enhanced the H2 selectivity, and SnCl4 has the best modification efficiency. The selectivity to H2 reached 91.1%at Sn/Ni atomic ratio of 2%. Moreover, when the Sn/Ni atomic ratio was 5%, the selectivity to H2 was above 95%, while the formation of alkanes was substantially suppressed. H2-TPD results showed that the number of desorption peaks reduced after Sn modification, suggesting that the active sites over the catalysts became more uniform, which may have decreased the adsorption modes of the reactant and suppressed side reactions. According to the kinetic results of the APR of ethylene glycol, we concluded that the addition of Sn to RQ Ni47.8Mo2.2 improved the H2 selectivity by promoting the WGS reaction while suppressing the methanation reaction. For the catalysts modified by the same Sn species, higher dispersion of Sn in the catalysts resulted in higher catalytic activity. The stability tests over Sn(IV)-RQ Ni47.8Mo2.2 and Sn(IV)-RQ Ni catalysts showed that Sn(IV)-RQ Ni47.8Mo2.2 showed higher activity and stability than Sn(IV)-RQ Ni catalyst, and its H2 selectivity catalyst was above 99% during 100 h reaction, indicating that this catalyst is a good candidate in fuel-cell system.
2. Aqueous phase reforming of ethylene glycol to H2 over CONi/Al2O3 catalysts
Dumesic et al. found that the Ni/Al2O3 catalyst deactivated rapidly under the APR condition. However, bimetallic supported Co-Ni catalysts displayed an excellent catalytic performance in carbon dioxide reforming of methane. We prepared the CoNi/y-Al2O3 catalysts by the coimpregnation method and studied their catalytic performance in the APR of ethylene glycol. We obtained the best acitivity over Co67Ni33 catalyst with H2 and alkane selectivity of 47% and 33%, respectively. The formation of spinel-type NixCo3-xO4 phase after calcination reduced the metal-support interaction, thus leading to higher reduction degree of bimetallic CoNi catalysts. The electron transfer of Co→Ni was found in the CoNi catalysts by XAFS, and the highest transfer degree was obtained on Co67Ni33 catalyst. The stability tests of Co100, Co67Ni33 and Ni100 catalysts showed that Co67Ni33 catalyst displayed the best activity and stability. Both Co100 and Ni100 catalysts deactivated quickly, while Co67Ni33 remained 86%of its initial activity after 150 h time on stream. After reaction the Co 100 catalyst was seriously sintered (dCo> 120 nm). The BET surface area of the Ni100 catalyst decreased drastically from 101 to 40 m2·g-1, indicating that the destruction of the structure resulted in the decreased activity. On the contrary, Co67Ni33 catalyst retained the structure and the metal dispersion after reaction. In addition, we added the third metal to Co67Ni33 catalyst to improve the H2 selectivity. The addition of Sn increased the H2 selectivity remarkably but drastically suppressed the activity. Adding Au to Co67Ni33 enhanced the activity but hardly influenced the selectivity. The addition of Pt can improve both H2 selectivity and activity.
3. Aqueous phase reforming of glycerol over CoNi/Al2O3 catalysts
We carried out the APR of glycerol on the CoNi/Al2O3 catalysts, which displayed an excellent catalytic performance in the APR of ethylene glycol. The Co/Ni ratio had a great influence on the activity, and the best activity and H2 selectivity were obtained on the Co50Ni50 catalyst. However, we found that the Co67Ni33 catalyst have superior stability to Co50Ni50. The characterization results showed that after reaction Co67Ni33 catalyst had smaller crystallite size and higher active surface area than Co50Ni50 catalyst. Since acid species were formed in the reaction, the leaching of the metal is another reason for the decreased activity. ICP results showed that the leaching of Co is much more serious than that of Ni, and the leaching of Co in Co67Ni33 is higher than that in the Co50Ni50 catalyst. Thus the Co/Ni ratio of the Co67Ni33 and Co50Ni50 catalysts after reaction turned into 60/40 and 39/61, respectively. The reaction pathway of glycerol was discussed based on the APR of methanol, ethanol, ethylene glycol and 1,2-dipropanol. The reaction pathway of glycerol can be divided into two parts:(1) Glycerol can be converted into H2, CO2 and alkanes by C-C cleavage followed by WGS or methanation/FTS reaction. (2) Glycerol can be converted into 1,2-dipropanol by dehydration to acetol and subsequent hydrogenation. 1,2-dipropanol will undergo further reaction to produce gas products and ethanol at high conversion levels. In addition, ethanol can be transformed into acetic acid under the reaction condition.
We also studied the catalytic conversion of glycerol into glycol by the APR process. We first investigated the APR of glycerol on M/Y-Al2O3 (M= Ru, Cu, Fe, Co, Ni) catalysts. For the Fe catalyst, no glycol was found in the APR of glycerol. Both Ni and Ru catalysts have good glycerol conversion but poor glycol selectivity. Since Ni and Ru show high activity to C-C cleavage, the selectivity to gas products is much higher than that of other catalysts. Co and Cu have low activity, and the main product on these two catalysts is acetol. The poor ability to convert acetol to 1,2-dipropanol may be attributed to the poor reforming activity of Co and Cu towards glycerol. Adding proper amount of Ni to the Co and Cu catalysts can improve the glycol yield, while suppressing the side reactions. The optimized content of Ni in CuNi and CoNi catalysts is 75% and 10%, respectively.
4. Aqueous phase reforming of ethylene glycol to H2 over Co/ZnO catalysts
Co/ZnO catalysts with different Co/Zn ratio were prepared by coprecipitation method and their catalytic performances were evaluated in the APR of ethylene glycol. The spinel type of ZnCo2O4 was formed after calcination at 723 K. After reduction, the Co/ZnO catalysts are composed of fcc Co and ZnO. XPS results shows that surface Co0 content increased with the increment of Co/Zn ratio, which is in good agreement with the reduction degree. When the Co/Zn ratio increased from 1/3 to 2/1, the H2 selectivity decreased from 89% to 52%, and the TOF of H2 decreased from 101.4 h"1 to 27.9 h-1. Since Co is a common catalyst in FTS reaction, Co/ZnO catalyst produced the alkenes in the APR of ethylene glycol. The liquid products contained methanol, ethanol, and acetic acid. Based on the results of the APR of methanol, ethanol and acetic acid on Co/ZnO-21 catalyst, we concluded that besides the reaction pathways of ethylene glycol with water over metallic catalysts proposed in the literature, reaction pathways from ethanol to acetic acid and 2-propanol and via the FTS reaction to alkenes should be taken into account over the Co/ZnO catalysts in APR of ethylene glycol.
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