磷化镍催化剂加氢脱氧性能的研究

发布时间：2018-03-18 12:44

本文选题：磷化镍　切入点：加氢脱氧　出处：《东北石油大学》2017年硕士论文　论文类型：学位论文

【摘要】：生物油作为一种可再生能源备受关注。然而,生物油中含氧组分占有较大比例,不可避免地导致生物油燃烧热值降低,化学稳定性变差,必须对其进行加氢脱氧(HDO)精制。在传统的程序升温还原法基础上,采用低温还原法制备磷化镍催化剂的方法,并制备了Ni_2P/SBA-15、Ni_2P/Al-SBA-15、Ni_2P/Fe-SBA-15和Ni_2P/TiO_2-Al_2O_3(Ni_2P/x-TA,x为载体中TiO_2质量分数)催化剂。采用XRD、H_2-TPR、BET、NH_3-TPD、XPS、TEM、CO吸附等技术对所制备的催化剂进行了表征,并以苯并呋喃(BF)为模型化合物,考察了Al和Fe改性对Ni_2P/SBA-15催化剂结构和HDO性能的影响,同时考察了TiO_2含量x对Ni_2P/x-TA抗水性能的影响,得到如下结果:(1)Al引入到SBA-15载体中,有助于形成粒径更小、分散更均匀的Ni_2P活性相粒子,能够有效抑制P的富集从而暴露出更多的Ni位点;Al改性提高催化剂酸性,B酸和L酸酸量分别提高了5.1μmol·g~(-1)和2.8μmol·g~(-1)。(2)在573 K、3 MPa、氢油比500(V/V)以及空速为4 h~(-1)的反应条件下,Ni_2P/SBA-15催化剂的HDO产率仅为70.9%,改性过后Ni_2P/Al-SBA-15达到90.3%,提高了19.4%。(3)Fe的引入有利于形成小粒径的Ni_2P活性相,且分散更加均匀。改性后的Ni_2P/Fe-SBA-15催化剂的加氢脱氧性能有所提高,这主要是第二金属Fe的引入和活性位Ni相互作用的结果。(4)在573 K、3 MPa、氢油比500(V/V)以及空速为4 h~(-1)的反应条件下,Fe改性后的Ni_2P/Fe-SBA-15最终的脱氧率为83%,与Ni_2P/SBA-15催化剂的脱氧率(70.9%)相比,提高了12.1%。(5)适量的TiO_2添加量有助于形成粒径更小、分散更加均匀的Ni_2P粒子。当x为50%时,Ni_2P/x-TA催化剂活性最好。原料中含水会导致催化剂的HDO活性明显降低。对含水原料进行HDO时,Ni_2P/50%-TA完全脱氧产物产率能达到80.3%,与不含Ti的Ni_2P/Al_2O_3催化剂(53.8%)相比高26.5%,疏水性TiO_2能明显提高Ni_2P/50%-TA催化剂抗水中毒能力。
[Abstract]:As a kind of renewable energy, bio-oil has attracted much attention. However, the oxygen component in bio-oil occupies a large proportion, which inevitably leads to the decrease of combustion calorific value and the deterioration of chemical stability of bio-oil. On the basis of the traditional temperature programmed reduction method, the low temperature reduction method was used to prepare nickel phosphide catalyst. In addition, Ni2P / SBA-15 / Ni2P / Al-SBA-15 / Ni2P / Fe-SBA-15 and Ni2P- / TiO2-Al2O2-S / T _ 2P / TiO2-Al _ 2O _ 2O _ 3-S _ 2P / SBA-15 / Ni2P / SBA-15 / Ni2P / TiO2-Al _ 2O _ 2O _ 3-S / T _ 2P / SBA-15 / Ni2P / SBA-15 / Ni2P / SBA-15 / Ni2P / TiO2-Al _ 2O _ 2O _ 3 / Ni2P / SBA-15 / Ni2P / SBA-15 / Ni2P / SBA-15 / Ni2P / TiO2-Al _ 2O _ 2-S _ 2O _ 3 / T _ 2P / SBA-15 / Ni2P / SBA-@@. The effects of Al and Fe modification on the structure and HDO properties of Ni_2P/SBA-15 catalysts were investigated. The effects of TiO_2 content x on the water resistance of Ni_2P/x-TA were also investigated. More evenly dispersed Ni_2P active phase particles, It can effectively inhibit the enrichment of P and expose more Ni sites to improve the acid acid content of the catalyst. The acid content of B acid and L acid increased by 5.1 渭 mol 路gou-1) and 2.8 渭 mol 路gou-1g ~ (-1) 路L ~ (-1), respectively. Under the reaction conditions of 573kg ~ (3) MPA, 500V / V) of hydrogen to oil ratio and 4 h ~ (-1) of space velocity, Ni _ 2P / SBA-15 catalyst was used to catalyze the growth of Ni _ 2P ~ (-1) -1.The catalytic activity of Ni _ 2P / SBA-15 was obtained by using Ni _ 2P / SBA-15 as catalyst. The HDO yield of the agent was only 70.90.After the modification, the Ni_2P/Al-SBA-15 reached 90.33, which increased the amount of 19.4kyn, and increased the amount of 19.4% of Ni_2P, which was beneficial to the formation of the active phase of Ni_2P with small particle size. And the dispersion is more uniform. The hydrogenation deoxidation performance of the modified Ni_2P/Fe-SBA-15 catalyst is improved. This is mainly due to the effect of the introduction of the second metal Fe and the interaction of active site Ni. 4) under the reaction conditions of 573 Ku 3 MPa, 500 V / V / V of hydrogen / oil ratio and 4 h / L space velocity, the final deoxidation rate of the modified Ni_2P/Fe-SBA-15 is 83%, which is compared with that of the Ni_2P/SBA-15 catalyst (70.9%). The addition of appropriate amount of TiO_2 helps to form a smaller particle size. When x = 50, the activity of Ni _ 2P _ (x-TA) catalyst is the best. The water content in the raw material will result in a significant decrease in the HDO activity of the catalyst. When HDO is applied to the water-containing raw material, the yield of Ni2P / 50-TA completely deoxidized product can reach 80.3%. The Ni_2P/Al_2O_3 catalyst of Ti (53.8%) was 26.5% higher than that of Ni_2P/50%-TA catalyst, and hydrophobic TiO_2 could obviously improve the water poisoning resistance of Ni_2P/50%-TA catalyst.
【学位授予单位】：东北石油大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TE667

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