本文選題：鈷基催化劑 + 載體��； 參考：《浙江工業(yè)大學(xué)》2016年碩士論文

【摘要】：費(fèi)托合成(Fischer-Tropsch Synthesis,簡(jiǎn)稱FTS)是將生物質(zhì)、煤、天然氣等氣化的合成氣(CO+H_2)催化轉(zhuǎn)化為清潔的液體燃料及高附加值化學(xué)品的重要途徑,被認(rèn)為是解決我國(guó)能源供應(yīng)不足的最有效途徑之一。鈷基催化劑因其具有良好的催化活性和高碳烴的選擇性,不易失活和積碳,水煤氣變換反應(yīng)活性低等特點(diǎn),被認(rèn)為是費(fèi)托合成反應(yīng)最具有發(fā)展前途的催化劑之一。本文采用等體積浸漬法制備了費(fèi)托合成負(fù)載型鈷基催化劑,在固定床反應(yīng)器上評(píng)價(jià)催化劑的催化活性,以CO轉(zhuǎn)化率和C_5-C_(11)汽油餾分烴選擇性為催化劑催化活性的評(píng)價(jià)指標(biāo),篩選出催化活性較好的催化劑,并對(duì)催化劑進(jìn)行了BET、XRD、FT-IR、TPR、TPD等手段的表征。本論文的具體研究工作和主要結(jié)論如下:(1)分別考察了氧化物載體(SiO_2)、碳材料載體(CNTs)、純硅分子篩載體(MCM-41、SBA-15)以及酸性分子篩載體(Hβ、HY、HZSM-5、mordenite)對(duì)費(fèi)托合成鈷基催化劑催化活性的影響。結(jié)果表明:穩(wěn)定狀態(tài)下Co/SBA-15催化劑的CO轉(zhuǎn)化率最高,為92.6%。穩(wěn)定狀態(tài)下Co/HZSM-5催化劑的C_5-C_(11)烴選擇性最高,為48.3%。以CO轉(zhuǎn)化率、C_5-C_(11)汽油餾分烴選擇性為催化劑催化活性的評(píng)價(jià)指標(biāo),篩選出了催化劑對(duì)CO轉(zhuǎn)化率最高的載體為SBA-15,對(duì)C_5-C_(11)汽油餾分烴選擇性最高的載體為HZSM-5。(2)考察了載體HZSM-5硅鋁比(SiO_2/Al_2O_3=25、38、50、80和200)以及合成Co/HZSM-5催化劑的焙燒溫度對(duì)負(fù)載型鈷基催化劑費(fèi)托合成反應(yīng)活性的影響。結(jié)果表明:相比Co/HZSM-5(SiO_2/Al_2O_3=25、38、50和80)催化劑,Co/HZSM-5(SiO_2/Al_2O_3=200)催化劑表現(xiàn)出相對(duì)最高的CO轉(zhuǎn)化率和C_5-C_(11)烴選擇性,分別為84.1%、52.8%。以HZSM-5(SiO_2/Al_2O_3=200)為載體,發(fā)現(xiàn)不同焙燒溫度合成的Co/HZSM-5催化劑對(duì)費(fèi)托合成活性也具有明顯的影響。對(duì)比Co/HZSM-5(300℃、400℃、500℃)催化劑,Co/HZSM-5(400℃)催化劑表現(xiàn)出相對(duì)最高的CO轉(zhuǎn)化率和C_5-C_(11)烴選擇性,分別為84.1%、52.8%。(3)在前期研究的基礎(chǔ)上,篩選出其中催化劑催化性能較優(yōu)的兩個(gè)載體為SBA-15和HZSM-5。以不同硅鋁比的HZSM-5分子篩(SiO_2/Al_2O_3=50、80、200)與SBA-15組成的復(fù)合載體作為新的載體,分別考察了HZSM-5不同硅鋁比、SBA-15與HZSM-5不同質(zhì)量比對(duì)復(fù)合催化劑費(fèi)托反應(yīng)活性的影響。結(jié)果表明:相比Co/SZ-50-4、Co/SZ-80-4催化劑,Co/SZ-200-4催化劑表現(xiàn)出相對(duì)較高的CO轉(zhuǎn)化率和C_5-C_(11)烴選擇性,分別為93.0%、51.8%。對(duì)比Co/SZ-200-1、Co/SZ-200-2、Co/SZ-200-3、Co/SZ-200-4催化劑,Co/SZ-200-4催化劑的CO轉(zhuǎn)化率和C_5-C_(11)烴選擇性最高,分別為93.0%、51.8%。(4)穩(wěn)定狀態(tài)下催化劑的C5~C11烴收率為:Co/SZ-200-4Co/HZSM-5-200Co/SBA-15,依次為48.2%、44.4%、38.2%,其中Co/SZ-200-4催化劑的C5~C11烴收率最高,為48.2%。對(duì)比Co/HZSM-5-200和Co/SBA-15催化劑,以復(fù)合載體為新的載體制備的Co/SZ-200-4催化劑的C5~C11烴收率明顯提高。
[Abstract]:Fischer-Tropsch Synthesis (FTS) is an important way to catalyze the conversion of biomass, coal, natural gas and other gasified syngas to clean liquid fuel and high value-added chemicals. It is considered to be one of the most effective ways to solve the shortage of energy supply in China. Cobalt based catalysts are considered as one of the most promising catalysts for Fischer synthesis because of their good catalytic activity, high hydrocarbon selectivity, low activity of water gas shift reaction and so on. In this paper, supported cobalt based catalyst for Fischer synthesis was prepared by equal volume impregnation method. The catalytic activity of the catalyst was evaluated in a fixed bed reactor. The catalytic activity of the catalyst was evaluated by using CO conversion and the selectivity of C _ 5-C _ (11) gasoline fraction as the catalytic activity. The catalyst with good catalytic activity was screened and characterized by BET-XRDX FT-IRT-TPR-TPD. The specific research work and main conclusions of this thesis are as follows: (1) the effects of oxide support SiO2H, carbon material carrier CNTsN, pure silica molecular sieve carrier MCM-41 SBA-15) and acidic molecular sieve carrier HYYHZSM-5mordenite on the catalytic activity of Cobalt based catalyst for Fischer synthesis were investigated. The results showed that the CO conversion of Co/SBA-15 catalyst was the highest, 92.6g under stable condition. The selectivity of C _ S _ 5-C _ S _ (11) for Co/HZSM-5 catalyst is the highest at 48.3% under stable condition. The selectivity of CO conversion to C _ 5-C _ S _ (11) gasoline fraction was taken as the evaluation index of the catalytic activity of the catalyst. The carrier with the highest CO conversion was SBA-15, and the carrier with the highest hydrocarbon selectivity for gasoline fraction was HZSM-5.02) the carrier HZSM-5 SiO2 / Al _ 2O _ 2O _ 2 / Al _ 2O _ 2O _ 3O _ 2O _ 3 / Si _ 2O _ 3 / S _ 2O _ 3O _ 2O _ 3 and the calcination temperature of the synthetic Co/HZSM-5 catalyst were used to investigate the effect of calcination temperature on the supported cobalt-based catalyst. The effect of Fischer on the activity of synthetic reaction. The results show that compared with Co/ HZSM-5SiO _ (2 / S) / S _ 2AlS _ 2O _ 3 / S _ 3 / S _ 3 / T _ 3) catalyst Co/ H _ ZSM-5 / Si _ 2O _ 3 _ T _ (2 / 20) catalyst shows the highest CO conversion and C _ 5-C _ (11) hydrocarbon selectivity, respectively, which are 84.1and 52.8%, respectively, in comparison with the Co/ HZSM-5 / S _ (20) / C _ (5) C _ (11) C _ (5) C _ (11). On the basis of HZSM-5SiOS _ 2 / Al _ 2O _ 2O _ 3 / 200), it was found that Co/HZSM-5 catalysts with different calcination temperatures also had a significant effect on the activity of Fischer synthesis. Compared with the Co/HZSM-5(300 鈩，

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