镍金属催化剂芳烃加氢抗硫性的研究
摘要
以镍为活性组元，系统地研究了镍基芳烃加氢金属催化剂的抗硫性能。采用固定床连续流动微反评价装置，以噻吩为毒物，甲苯加氢为探针反应，考察了催化剂的催化活性。深入地研究了制备方法、前体组分、活性组分含量、助催化剂、载体表面的酸碱性及工艺条件等对催化剂的芳烃加氢活性和抗硫性能的影响，运用XRD、TPR、BET、DSC、XPS、CO-IR、PY-IR等表征手段对催化剂的表面性质、结构形态及活性中心进行了探讨，结果表明，上述因素对提高催化剂的抗硫性能均有一定的作用。同时，采用200~#和260~#溶剂油为原料，对催化剂进行了应用研究，工业试验表明，该催化剂具有高效芳烃加氢活性和高抗硫性能，在较缓和的工业操作条件下，能生产出质量合格的低芳烃环保型溶剂油，达到了工业生产的要求。
首先，对Ni／Al_2O_3催化剂的制备方法进行了对比研究。结果表明，制备方法主要影响了NiO的晶粒大小以及Ni在催化剂中的存在状态和分布，从而影响了催化剂的抗硫性能。以浸渍法制备的催化剂效果最好，活性最高。在制备方法上，催化剂的活性差异主要在于活性组分Ni与载体Al_2O_3之间的相互作用及其结构形态的不同。研究还进一步表明，焙烧温度对催化剂的活性有着重要影响。高温焙烧(550℃以上)加强了NiO与Al_2O_3的相互作用，易形成NiAl_2O_4尖晶石结构，丧失芳烃加氢活性；低温焙烧(350℃以下)不利于活性组分原料的完全分解，并影响了活性组分在载体上的分散度。实验得出：450℃焙烧，460～480℃还原为催化剂制备的最佳处理条件。
其次，系统地考察了助催化剂对Ni／Al_2O_3催化剂性能的影响。研究表明，碱土金属(Mg)、Ti和稀土的添加有利于提高催化剂的芳烃加氢和抗硫性能，其中以Mg效果最好。在Ni-Mg／Al_2O_3催化剂中，Mg具有给电子作用，能使Ni的电子云密度升高，NiO的电子结合能发生负的化学位移，能提高金属Ni的分散度，从而提高了催化剂的热稳定性和抗硫性能，并延长了催化剂的使用寿命。
最后，考察了载体表面的酸碱性对催化剂催化性能的影响。催化
剂样品的PY一IR、CO一IR谱图表明，催化剂的芳烃加氢和抗硫能力主
要与载体表面的B酸有关，与L酸无关。载体表面的B酸对Ni原子
簇具有电子诱导作用，使之呈现“电子缺乏”性质。缺电子的Ni原
子簇可以减弱硫在金属表面的吸附强度，从而提高了催化剂的抗硫
性。
反应条件对催化剂活性的影响表现在增大反应压力、提高反应温
度以及降低反应空速有利于芳烃加氢反应的进行，催化剂的抗硫能力
也相应得到提高。工业试验表明，该催化剂用于溶剂汕加氢脱芳烃最
适宜的工业操作条件为:压力2.OMPa、温度190一220℃、LHsv 1.oh一‘。
本研究结果为负载型芳烃加氢金属催化剂的基础研究和工业运
用提供理论依据。
The sulfur tolerance of nickel metal catalysts in aromatic hydrogenation has been studied systematically on the base of nickel active unit in this paper. The catalytic activities of Ni/Al2O3 were investigated by the probe reaction of hydrogenation of toluene using thiophene as poison in fixed-bed continuous-flow micro-reaction equipment. And it is studied deeply on the influences of the catalyst's performance on aromatic hydrogenation and the sulfur resisted by different preparation .methods, promoters, content of active parts, assistant catalyst , supports' acidity or alkalescence and reaction conditions. The catalysts' surface characteristic and configuration and activity center were discussed by means of XRD, TPR, BET, DSC, XPS, PY-IR, COIR. The results indicated that the factors discussed above have certain effects on Ni/Al2O3. At the same time, the industrial applied
studies on Ni/Al2O3 were carried out with 200 and 260 solvent oil. The industrial test results showed these catalysts with high aromatic hydrogenation and high sulfur tolerance can produce low aromatic environmental solvent oil with good quality under abirritant conditions.
Firstly, a series of Ni/Al2O3 catalysts were prepared by different methods. Resistance of these nickel metal catalysts to sulfur poison has been investigated by performing hydrogenation of toluene. It showed that obvious effects on hydrogenation activity and sulfur resisted lie in granularity of NiO crystalline and state of Ni in Ni/Al2O3 catalyst. The catalyst prepared by impregnant method was the best. The difference of catalytic activities obviously displayed on the interaction between Ni and A12O3 carrier. The results also indicated that calcined temperature had the same important roles in nickel metal catalyst. The high calcined temperature enhanced the interaction between NiO and Al2O3, and it is
favored to form NiAl2O4, which has no hydrogenation activity and sulfur resisted. While the low calcined temperature, the decompound and reduction of Ni has decreased. The best preparation conditions of the catalyst were to have it calcined at 450 C and reducted at 460~480 C.
Secondly, systematic studies on the effects of catalysts property by assistant catalysts were carried out by adding Mg and Ti and earth to Ni/Al2O3 catalyst. It showed that catalytic activities increased with Mg or Ti. Among these promoters, the catalyst containing Mg was the best. The action of Mg promoter on catalyst has been discussed by means of XPS, BET. The results showed that Mg favored the sulfur resisted, which could enlarge the active surface area and increase the electronic cloud density of the nickel atom, and so could make catalysts life long.
Finally, the catalyst performance modified by carrier was discussed. A series of Nickel catalysts which have been characterized by pyridine-adsorbed and CO-adsorbed infrared spectra supported by Y -Al2O3, SiO2-Al2O3, Sep and Y-type Zeolite have been prepared. Resistance of these nickel catalysts to sulfur poison has been investigated by reaction of hydrogenation for toluene. The existence of electron-dificiency Ni species was confirmed and correlated to acidity of catalysts and catalytic behaviors. It was found that the stronger the acidity, the higher the electron deficiency, the better the sulfur resistance. Acidity characterization indicated that Bronsted acid sites of the catalyst favored the sulfur resistance but Lewis acid sites did not.
The effects of reaction conditions on catalysts performance were investigated by industrial test. The results showed increasing pressure and temperature and decreasing the LHSV were better for catalyst in aromatic hydrogenation and sulfur tolerance. The best handling conditions for Ni/Al2O3 were at 1.0MPa, 190-220 C, LHSV 1.0h-1.
首先，对Ni／Al_2O_3催化剂的制备方法进行了对比研究。结果表明，制备方法主要影响了NiO的晶粒大小以及Ni在催化剂中的存在状态和分布，从而影响了催化剂的抗硫性能。以浸渍法制备的催化剂效果最好，活性最高。在制备方法上，催化剂的活性差异主要在于活性组分Ni与载体Al_2O_3之间的相互作用及其结构形态的不同。研究还进一步表明，焙烧温度对催化剂的活性有着重要影响。高温焙烧(550℃以上)加强了NiO与Al_2O_3的相互作用，易形成NiAl_2O_4尖晶石结构，丧失芳烃加氢活性；低温焙烧(350℃以下)不利于活性组分原料的完全分解，并影响了活性组分在载体上的分散度。实验得出：450℃焙烧，460～480℃还原为催化剂制备的最佳处理条件。
其次，系统地考察了助催化剂对Ni／Al_2O_3催化剂性能的影响。研究表明，碱土金属(Mg)、Ti和稀土的添加有利于提高催化剂的芳烃加氢和抗硫性能，其中以Mg效果最好。在Ni-Mg／Al_2O_3催化剂中，Mg具有给电子作用，能使Ni的电子云密度升高，NiO的电子结合能发生负的化学位移，能提高金属Ni的分散度，从而提高了催化剂的热稳定性和抗硫性能，并延长了催化剂的使用寿命。
最后，考察了载体表面的酸碱性对催化剂催化性能的影响。催化
剂样品的PY一IR、CO一IR谱图表明，催化剂的芳烃加氢和抗硫能力主
要与载体表面的B酸有关，与L酸无关。载体表面的B酸对Ni原子
簇具有电子诱导作用，使之呈现“电子缺乏”性质。缺电子的Ni原
子簇可以减弱硫在金属表面的吸附强度，从而提高了催化剂的抗硫
性。
反应条件对催化剂活性的影响表现在增大反应压力、提高反应温
度以及降低反应空速有利于芳烃加氢反应的进行，催化剂的抗硫能力
也相应得到提高。工业试验表明，该催化剂用于溶剂汕加氢脱芳烃最
适宜的工业操作条件为:压力2.OMPa、温度190一220℃、LHsv 1.oh一‘。
本研究结果为负载型芳烃加氢金属催化剂的基础研究和工业运
用提供理论依据。
The sulfur tolerance of nickel metal catalysts in aromatic hydrogenation has been studied systematically on the base of nickel active unit in this paper. The catalytic activities of Ni/Al2O3 were investigated by the probe reaction of hydrogenation of toluene using thiophene as poison in fixed-bed continuous-flow micro-reaction equipment. And it is studied deeply on the influences of the catalyst's performance on aromatic hydrogenation and the sulfur resisted by different preparation .methods, promoters, content of active parts, assistant catalyst , supports' acidity or alkalescence and reaction conditions. The catalysts' surface characteristic and configuration and activity center were discussed by means of XRD, TPR, BET, DSC, XPS, PY-IR, COIR. The results indicated that the factors discussed above have certain effects on Ni/Al2O3. At the same time, the industrial applied
studies on Ni/Al2O3 were carried out with 200 and 260 solvent oil. The industrial test results showed these catalysts with high aromatic hydrogenation and high sulfur tolerance can produce low aromatic environmental solvent oil with good quality under abirritant conditions.
Firstly, a series of Ni/Al2O3 catalysts were prepared by different methods. Resistance of these nickel metal catalysts to sulfur poison has been investigated by performing hydrogenation of toluene. It showed that obvious effects on hydrogenation activity and sulfur resisted lie in granularity of NiO crystalline and state of Ni in Ni/Al2O3 catalyst. The catalyst prepared by impregnant method was the best. The difference of catalytic activities obviously displayed on the interaction between Ni and A12O3 carrier. The results also indicated that calcined temperature had the same important roles in nickel metal catalyst. The high calcined temperature enhanced the interaction between NiO and Al2O3, and it is
favored to form NiAl2O4, which has no hydrogenation activity and sulfur resisted. While the low calcined temperature, the decompound and reduction of Ni has decreased. The best preparation conditions of the catalyst were to have it calcined at 450 C and reducted at 460~480 C.
Secondly, systematic studies on the effects of catalysts property by assistant catalysts were carried out by adding Mg and Ti and earth to Ni/Al2O3 catalyst. It showed that catalytic activities increased with Mg or Ti. Among these promoters, the catalyst containing Mg was the best. The action of Mg promoter on catalyst has been discussed by means of XPS, BET. The results showed that Mg favored the sulfur resisted, which could enlarge the active surface area and increase the electronic cloud density of the nickel atom, and so could make catalysts life long.
Finally, the catalyst performance modified by carrier was discussed. A series of Nickel catalysts which have been characterized by pyridine-adsorbed and CO-adsorbed infrared spectra supported by Y -Al2O3, SiO2-Al2O3, Sep and Y-type Zeolite have been prepared. Resistance of these nickel catalysts to sulfur poison has been investigated by reaction of hydrogenation for toluene. The existence of electron-dificiency Ni species was confirmed and correlated to acidity of catalysts and catalytic behaviors. It was found that the stronger the acidity, the higher the electron deficiency, the better the sulfur resistance. Acidity characterization indicated that Bronsted acid sites of the catalyst favored the sulfur resistance but Lewis acid sites did not.
The effects of reaction conditions on catalysts performance were investigated by industrial test. The results showed increasing pressure and temperature and decreasing the LHSV were better for catalyst in aromatic hydrogenation and sulfur tolerance. The best handling conditions for Ni/Al2O3 were at 1.0MPa, 190-220 C, LHSV 1.0h-1.
引文
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