本文選題：疏水性納米氧化鐵　切入點(diǎn)：煤直接液化　出處：《新疆大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：催化劑在煤直接液化(Direct Coal Liquefaction)反應(yīng)過程中起著至關(guān)重要的作用。高效的催化劑應(yīng)具備以下幾個(gè)特點(diǎn):與煤粉顆粒具有良好的接觸性、高的遞氫活性、高的催化裂解及催化加氫活性、相對(duì)低廉的制備成本或具有易再生、易回收的特點(diǎn)。而鐵基催化劑因?yàn)閾碛衼?lái)源廣泛、價(jià)格相對(duì)低廉、環(huán)境友好、相對(duì)較高的催化活性等特點(diǎn),成為最常用的煤直接液化催化劑。影響鐵基催化劑催化活性的因素主要包括顆粒尺寸和分散性。因此,制備小尺寸高分散性的鐵基催化劑在近幾十年來(lái)已經(jīng)受到了人們的廣泛關(guān)注。本論文通過二相溶劑熱法和“鐵鹽強(qiáng)迫水解/二相法”分別制備了疏水性納米Fe2O3和疏水性納米β-FeOOH催化劑。并對(duì)比了所得產(chǎn)物與商品Fe2O3在催化新疆西溝煤直接液化上的催化效果。主要研究?jī)?nèi)容和所得結(jié)論如下:一、以油胺(OAm)輔助二相溶劑熱法制備了油胺包覆型的疏水性Fe2O3納米粒子。通過調(diào)控油胺量成功獲得了不同粒徑分布的疏水性納米Fe2O3顆粒,結(jié)果表明,隨著油胺用量的增加,產(chǎn)物粒徑呈現(xiàn)出減小趨勢(shì)。TEM和XRD結(jié)果表明,當(dāng)體系中加入的Fe與油胺摩爾比為1:3、1:6和1:9時(shí),分別得到了平均粒徑分別為108 nm、64 nm和52 nm的Fe2O3納米粒子。FT-IR結(jié)果表明納米粒子表面存在油胺分子包覆層。二、開展了油胺包覆的疏水性納米Fe2O3的放大合成研究(將反應(yīng)物料整體放大3倍)。通過實(shí)驗(yàn)室初級(jí)放大制備得到了較高產(chǎn)量(250 mL單釜產(chǎn)物大約為0.22 g)的疏水性納米Fe2O3。XRD和TEM表征表明,經(jīng)過實(shí)驗(yàn)室初步放大,產(chǎn)物的形貌及物相沒有發(fā)生明顯改變。在反應(yīng)物料放大3倍的條件下,通過調(diào)控油胺量,可以獲得平均粒徑分別在96 nm,69 nm和53 nm左右的疏水性納米Fe2O3。通過進(jìn)一步分析XRD、TEM和FT-IR譜圖,確定了油胺輔助二相溶劑熱法制備的疏水性納米Fe2O3表面確實(shí)存在油胺分子包覆層。以所得產(chǎn)物和商品Fe2O3作為催化劑,對(duì)阜康西溝煤進(jìn)行了直接液化性能測(cè)試。結(jié)果顯示,當(dāng)液化體系中分別加入鐵含量為干基無(wú)灰煤的3.0 wt%的疏水性納米Fe2O3和商品Fe2O3催化劑時(shí),其轉(zhuǎn)化率、油產(chǎn)率和液化率分別達(dá)到了95.9 wt%、77.4 wt%和87.1 wt%(Fe/OAm=1:3);92.3 wt%、73.6 wt%和81.5 wt%(Fe/OAm=1:6);92.3 wt%、70.2 wt%和72.3 wt%(Fe/OAm=1:9);93.8%、67.6%和75.9%(商品Fe2O3)。液化結(jié)果表明,合成的三種疏水性納米Fe2O3催化劑的油產(chǎn)率相比于商品Fe2O3催化劑分別提高了14.5%、8.9%和3.8%。三、采用簡(jiǎn)單的水解法大批量制備了親水性β-FeOOH納米粒子,并用油酸鈉對(duì)其改性,獲得了疏水性β-FeOOH納米粒子。首先,通過鐵鹽的強(qiáng)迫水解,獲得了大批量(422 g)的親水性β-FeOOH納米粒子。其次,以油酸鈉作為改性劑,以兩相法制備了油酸(OA)包覆的疏水性β-FeOOH納米粒子。XRD和TEM結(jié)果表明,產(chǎn)物為長(zhǎng)約120 nm直徑50 nm的紡錘形β-FeOOH納米粒子。FT-IR結(jié)果表明,粒子表面包覆有油酸分子層。以親水性和疏水性β-FeOOH納米粒子作為催化劑,研究了其煤直接液化催化效果。結(jié)果顯示,其轉(zhuǎn)化率、油產(chǎn)率和液化率分別達(dá)到了86.4 wt%、57.7 wt%和69.0 wt%(空白);88.3 wt%、66.7 wt%和73.7 wt%(親水性β-FeOOH);92.6 wt%、73.8 wt%和80.8 wt%(疏水性β-FeOOH)。實(shí)驗(yàn)結(jié)果表明,通過鐵鹽水解和油酸包覆能實(shí)現(xiàn)親水性β-FeOOH納米粒子的大批量制備和疏水改性,并且產(chǎn)物對(duì)催化西溝煤直接液化展現(xiàn)了較好的液化效果。此外,由于該合成方案反應(yīng)條件溫和、操作簡(jiǎn)單和易于放大,故具有良好的工業(yè)應(yīng)用前景。
[Abstract]:The catalyst in direct coal liquefaction (Direct Coal Liquefaction) plays a crucial role in the reaction process. Efficient catalyst should have the following characteristics: have a good contact performance and delivery of coal particles, high catalytic activity, catalytic cracking and catalytic hydrogenation activity is high, relatively low cost of preparation or is easy to regenerate, the characteristics of easy recovery. The iron-based catalyst because they have a wide range of sources, the price is relatively cheap, environmentally friendly, relatively high catalytic activity and other characteristics, has become the most commonly used direct coal liquefaction catalyst. Factors influencing the iron-based catalyst of catalytic activity mainly include particle size and dispersity. Therefore, the preparation of small size and high dispersion of iron based catalyst has received widespread attention in recent years. This paper through the two-phase solvothermal method and Fe / two-phase forced hydrolysis method were used to prepare hydrophobic nano Fe preparation 2O3 and hydrophobic nano beta -FeOOH catalysts. And compared the products and commodities in Xinjiang Fe2O3 catalytic Xigou coal direct liquefaction on the catalytic effect. The main research contents and conclusions are as follows: first, using oil amine (OAm) hydrophobic Fe2O3 nanoparticles coated oil amine was prepared by phase assisted solvothermal method. The regulation of oil amine quantity was successfully obtained with different particle size distribution of hydrophobic Fe2O3 nanoparticles. The results show that with the increase of oil amine content, particle size showed a decrease of.TEM and XRD results show that, when added to the system of Fe and oil amine 1 molar ratio of:3,1:6 and 1:9, respectively, the average particle size were 108 nm, Fe2O3 64 nm and 52.FT-IR nanoparticles results show that nm nanoparticles are oil amine molecules coating. Two, carried out the research of hydrophobic nano Fe2O3 coated oil amine amplification (Synthesis of the reaction mass overall amplification 3 Times). Through laboratory primary amplification were prepared with high yield (250 mL single reactor product is about 0.22 g) hydrophobic nano Fe2O3.XRD and TEM characterization showed that after preliminary laboratory amplification, morphology and product phase showed no change. 3 times larger in terms of the reaction materials, by regulating the amount of oil amine can be obtained, the average particle size was 96 nm, hydrophobic nano Fe2O3. 69 nm and 53 nm through the further analysis of XRD, TEM and FT-IR spectra, the oil amine assisted two-phase solvent thermal preparation of hydrophobic nano Fe2O3 surface exists oil amine molecules coating layer. The products and goods as Fe2O3 the catalyst of Fukang Xigou coal for direct liquefaction performance test. The results show that when the iron content were added for liquefaction system dry ash free coal 3 wt% hydrophobic nano Fe2O3 and commercial Fe2O3 catalyst, the conversion rate , oil yield and liquefaction rate reached 95.9 wt%, 77.4 wt% and 87.1 wt% (Fe/OAm=1:3); 92.3 wt%, 73.6 wt% and 81.5 wt% (Fe/OAm=1:6); 92.3 wt%, 70.2 wt% and 72.3 wt% (Fe/OAm=1:9); 93.8%, 67.6% and 75.9% (Fe2O3). The results show that the liquefaction, compared to three synthetic the hydrophobic nano Fe2O3 catalyst on the oil yield of commercial Fe2O3 catalysts were increased by 14.5%, 8.9% and three 3.8%., using a simple hydrolysis preparation of hydrophilic beta -FeOOH nanoparticles, and the modification by sodium oleate, the hydrophobic beta -FeOOH nanoparticles. Firstly, by forced hydrolysis of ferric salts, the mass (422 g) hydrophilic beta -FeOOH nanoparticles. Secondly, using sodium oleate as modifier to phase were prepared by oleic acid (OA) coated with hydrophobic beta -FeOOH nanoparticles.XRD and TEM results showed that the product was about 120 nm long and 50 nm diameter spindle shaped -FeOOH nano beta .FT-IR nanoparticles results show that particles coated with oleic acid. The molecular layer of hydrophilic and hydrophobic beta -FeOOH nanoparticles as catalyst on the catalytic effect of direct coal liquefaction. The results showed that the conversion rate, oil yield and liquefaction rate reached 86.4 wt%, 57.7 wt% and 69 wt% (blank); 88.3 wt% 66.7, wt% and 73.7 wt% (hydrophilic beta -FeOOH); 92.6 wt%, 73.8 wt% and 80.8 wt% (hydrophobic beta -FeOOH). The experimental results show that the ferric hydrolysis and oleic acid coated mass business to achieve hydrophilic beta -FeOOH nanoparticles and preparation of hydrophobic modification, and the product of catalytic Xigou coal direct liquefaction show the liquefaction effect is good. In addition, the synthesis scheme of mild reaction conditions, simple operation and easy amplification, so it has good prospects for industrial applications.

【學(xué)位授予單位】：新疆大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ138.11;TB383.1

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本文編號(hào)：1584029