本文選題：磷化鎳　切入點：加氫脫氧　出處：《東北石油大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：生物油作為一種可再生能源備受關(guān)注。然而,生物油中含氧組分占有較大比例,不可避免地導(dǎo)致生物油燃燒熱值降低,化學(xué)穩(wěn)定性變差,必須對其進(jìn)行加氫脫氧(HDO)精制。在傳統(tǒng)的程序升溫還原法基礎(chǔ)上,采用低溫還原法制備磷化鎳催化劑的方法,并制備了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為載體中TiO_2質(zhì)量分?jǐn)?shù))催化劑。采用XRD、H_2-TPR、BET、NH_3-TPD、XPS、TEM、CO吸附等技術(shù)對所制備的催化劑進(jìn)行了表征,并以苯并呋喃(BF)為模型化合物,考察了Al和Fe改性對Ni_2P/SBA-15催化劑結(jié)構(gòu)和HDO性能的影響,同時考察了TiO_2含量x對Ni_2P/x-TA抗水性能的影響,得到如下結(jié)果:(1)Al引入到SBA-15載體中,有助于形成粒徑更小、分散更均勻的Ni_2P活性相粒子,能夠有效抑制P的富集從而暴露出更多的Ni位點;Al改性提高催化劑酸性,B酸和L酸酸量分別提高了5.1μmol·g~(-1)和2.8μmol·g~(-1)。(2)在573 K、3 MPa、氫油比500(V/V)以及空速為4 h~(-1)的反應(yīng)條件下,Ni_2P/SBA-15催化劑的HDO產(chǎn)率僅為70.9%,改性過后Ni_2P/Al-SBA-15達(dá)到90.3%,提高了19.4%。(3)Fe的引入有利于形成小粒徑的Ni_2P活性相,且分散更加均勻。改性后的Ni_2P/Fe-SBA-15催化劑的加氫脫氧性能有所提高,這主要是第二金屬Fe的引入和活性位Ni相互作用的結(jié)果。(4)在573 K、3 MPa、氫油比500(V/V)以及空速為4 h~(-1)的反應(yīng)條件下,Fe改性后的Ni_2P/Fe-SBA-15最終的脫氧率為83%,與Ni_2P/SBA-15催化劑的脫氧率(70.9%)相比,提高了12.1%。(5)適量的TiO_2添加量有助于形成粒徑更小、分散更加均勻的Ni_2P粒子。當(dāng)x為50%時,Ni_2P/x-TA催化劑活性最好。原料中含水會導(dǎo)致催化劑的HDO活性明顯降低。對含水原料進(jìn)行HDO時,Ni_2P/50%-TA完全脫氧產(chǎn)物產(chǎn)率能達(dá)到80.3%,與不含Ti的Ni_2P/Al_2O_3催化劑(53.8%)相比高26.5%,疏水性TiO_2能明顯提高Ni_2P/50%-TA催化劑抗水中毒能力。
[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.
【學(xué)位授予單位】：東北石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TE667

【參考文獻(xiàn)】

相關(guān)期刊論文 前7條

1 王海彥;齊振東;鄢景森;魏民;;Ti摻雜對Ni_2P/SBA-15催化劑加氫脫氮催化性能的影響[J];石油學(xué)報(石油加工);2015年06期

2 宋華;張福勇;宋華林;代敏;萬霞;徐曉偉;;負(fù)載型磷化鎳催化劑的溶劑熱法制備及其加氫脫硫性能[J];燃料化學(xué)學(xué)報;2015年06期

3 宋華;徐曉偉;代敏;宋華林;;制備方法及載體類型對Ni_2P/TiO_2催化劑加氫脫硫性能的影響[J];燃料化學(xué)學(xué)報;2014年11期

4 劉洪濤;李福祥;;微孔-介孔復(fù)合分子篩的合成研究進(jìn)展[J];應(yīng)用化工;2012年05期

5 張亮;沈健;賈寶君;李春晶;王超;;Al-SBA-15介孔分子篩催化合成叔丁基苯酚[J];工業(yè)催化;2009年04期

6 李冬燕;余夕志;陳長林;徐南平;王延儒;;Ni_2P/TiO_2上噻吩加氫脫硫性能研究[J];高�；瘜W(xué)工程學(xué)報;2006年05期

7 魏昭彬,辛勤,Sham,E.L.,Grange,P.,Delwon,B.;TiO_2在Al_2O_3表面上分散狀態(tài)的AEM研究[J];物理化學(xué)學(xué)報;1990年04期

相關(guān)碩士學(xué)位論文 前2條

1 劉春艷;負(fù)載型Pt、Pd及Pt-Pd催化劑上苯并呋喃加氫脫氧反應(yīng)[D];大連理工大學(xué);2012年

2 何兵;負(fù)載型非晶態(tài)催化劑的制備及其加氫脫氧性能的研究[D];湘潭大學(xué);2012年

，

本文編號：1629632