【摘要】：本文以辛酸作為生物質(zhì)熱解所得生物油的模型化合物,探討了催化加氫以及催化酯化這兩種生物油提質(zhì)手段對辛酸脫氧的影響。對于辛酸催化加氫,當(dāng)氫氣壓力為3MPa,反應(yīng)溫度為320oC,催化劑為5%Ni-ZrO2時,辛酸的轉(zhuǎn)化率最高為92.79%,主要產(chǎn)物是辛酸通過加氫生成辛醛-辛醛脫羰而產(chǎn)生的庚烷,其收率為69.68%;反應(yīng)過程中還有少量的輕烴、辛烷、辛醇、辛酸辛酯等產(chǎn)物產(chǎn)生。相同條件下,當(dāng)催化劑為摻雜10 wt.%Mo改性的10Mo/Ni-ZrO2時,辛酸的轉(zhuǎn)化率為100%,此時主要產(chǎn)物為辛烷,收率為77.07%;同時還有輕烴、庚烷、辛烯、辛醛、辛醇、辛酸辛酯等產(chǎn)生,收率分別為2.31%、10.67%、0.99%、3.56%、4.89%和1.10%。對Mo摻雜前后的鎳基催化劑進(jìn)行了N2吸附-脫附、TEM、XRD、H2-TPR、NH3-TPD以及H2-TPD表征,得出Mo的摻雜可以顯著增加催化劑的比表面積,增強催化劑的酸性,提高催化劑的H2吸附量,并使得ZrO2載體由立方型轉(zhuǎn)變?yōu)閱涡毙汀Ｒ陨献饔枚加欣谔岣哝嚮呋瘎┑拇呋钚?增強催化劑對H2的吸附性能,從而導(dǎo)致了反應(yīng)向辛醛加氫生成辛醇-辛醇脫水生成辛烯-辛烯加氫生成辛烷方向進(jìn)行,繼而導(dǎo)致了辛酸加氫主要產(chǎn)物由庚烷向辛烷的轉(zhuǎn)變。對于辛酸催化酯化,甲醇作為醇助劑,當(dāng)反應(yīng)溫度為160oC,甲醇/辛酸的摩爾比為4.5:1時,550oC焙燒得到的SO_4~(2-)/Al_2O_3的催化效果最好,辛酸的轉(zhuǎn)化率最高為92.56%,目標(biāo)產(chǎn)物-辛酸甲酯的最高收率為89.08%。同等條件下,當(dāng)催化劑為經(jīng)SiO2摻雜改性后的SO_4~(2-)/Al_2O_3-SiO2(Al/Si摩爾比為5:1),記做SAS-5時,辛酸的轉(zhuǎn)化率增加到99.11%,同時辛酸甲酯的收率上升為99.07%,沒有其他副產(chǎn)物產(chǎn)生。對改性前后的催化劑進(jìn)行了N2吸附-脫附、XRD、紅外、熱重、原位吡啶紅外吸附等一系列表征,得出摻雜SiO2后,使得催化劑的比表面積顯著增加,同時還會抑制Al2(SO4)3晶型的形成,并有利于催化劑表面SO42-的形成,增強催化劑的酸性;此外SiO2的摻雜還有利于增強SO42-與氧化鋁的相互作用,增強催化劑的穩(wěn)定性并延長使用壽命,使得SAS-5催化劑在循環(huán)使用了9次之后仍能保持較高的催化活性。循環(huán)使用后的催化劑的B酸位的量明顯下降,而L酸位的量變化不大,說明B酸位對于辛酸的催化酯化起著主要作用;同時,B酸位的流失也是催化劑失活的主要原因。
[Abstract]:In this paper, octanoic acid was used as a model compound of bio-oil from biomass pyrolysis, and the effects of catalytic hydrogenation and catalytic esterification on the deoxidation of octanoic acid were discussed. The product is heptane produced by decarbonylation of octanaldehyde to octanaldehyde in 69.68% yield, and a small amount of light hydrocarbons, octane, octanol, octanoate and other products are produced in the reaction process. The yields of light hydrocarbons, heptane, octene, octanaldehyde, octanol and octyl octoate were 2.31%, 10.67%, 0.99%, 3.56%, 4.89% and 1.10% respectively. ZrO2 supports were converted from cubic to monoclinic by increasing the acidity of the catalysts, increasing the H2 adsorption capacity of the catalysts. All the above actions were conducive to improving the catalytic activity of the nickel-based catalysts and enhancing the adsorption capacity of the catalysts for H2, resulting in the hydrogenation of octanol to octanol and the dehydration of octanol to octene and octene to octene. For the catalytic esterification of octanoic acid, methanol is used as alcohol promoter. When the reaction temperature is 160oC and the molar ratio of methanol to octanoic acid is 4.5:1, the catalytic effect of SO_4~ (2-) / Al_2O_3 from 550oC calcination is the best, and the conversion of octanoic acid is 92.56% and the target product-Al_2O_3 is the best. The highest yield of methyl octanoate is 89.08%. Under the same conditions, when the catalyst is SO_4 ~ (2-) / Al_2O_3-SiO_2 (Al/Si molar ratio is 5:1) modified by SiO_2 doping, the conversion of octanoic acid increases to 99.11% as SAS-5, and the yield of methyl octanoate increases to 99.07% without any by-products. A series of characterizations, such as adsorption-desorption, XRD, IR, TG, in-situ pyridine infrared adsorption, etc., show that doping SiO2 can significantly increase the specific surface area of the catalyst, inhibit the formation of Al2 (SO4) 3 crystal form, and facilitate the formation of SO42 - on the surface of the catalyst, enhance the acidity of the catalyst; in addition, SiO2 doping is also conducive to the enhancement of SO42 - and alumina. The stability of the SAS-5 catalyst was enhanced and its service life was prolonged by the interaction. The activity of the SAS-5 catalyst remained high after 9 cycles. The loss of acid sites is also the main reason for catalyst deactivation.
【學(xué)位授予單位】：中國石油大學(xué)(華東)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TE667

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