本文選題：煎炸廢油　切入點(diǎn)：預(yù)處理　出處：《合肥工業(yè)大學(xué)》2015年博士論文

【摘要】：全球經(jīng)濟(jì)的迅速發(fā)展加大了人類(lèi)對(duì)石油能源的需求。石油能源具有不可再生性,因此開(kāi)發(fā)有可持續(xù)來(lái)源的石油替代燃料具有重要的意義。柴油燃料是重要的石油能源產(chǎn)品之一,目前國(guó)內(nèi)外學(xué)者對(duì)替代性柴油的研究主要集中在酯交換反應(yīng)制備生物柴油,對(duì)于催化加氫制備加氫柴油的研究較少。加氫制備綠色柴油是以動(dòng)植物油脂或廢棄油脂為原料,通過(guò)催化加氫技術(shù)制備的新型燃料。原料油品質(zhì)。催化劑催化特性和產(chǎn)品的改性是加氫制備綠色柴油產(chǎn)業(yè)的關(guān)鍵因素。本文以煎炸廢油為原料,通過(guò)加氫催化制備綠色柴油,以實(shí)現(xiàn)煎炸廢油的轉(zhuǎn)化利用。確定煎炸廢油預(yù)處理工藝。作為催化加氫反應(yīng)的原料,煎炸廢油較深的顏色是影響加氫產(chǎn)物品質(zhì)的重要因素,研究采用分離除雜、脫膠、脫色、脫水的方法對(duì)煎炸廢油進(jìn)行預(yù)處理,并對(duì)煎炸廢油的脫色步驟進(jìn)行單因素及響應(yīng)曲面分析。得到最優(yōu)脫色工藝參數(shù)為：反應(yīng)溫度104℃,反應(yīng)時(shí)間46min,攪拌速率300 r/min,脫色劑用量16wt%,煎炸廢油脫色率可達(dá)75%。將處理前后的煎炸廢油進(jìn)行對(duì)比,酸值由18.7mg KOH/g下降至15.2mg KOH/g、水分由0.75%下降到痕量,磷脂含量由1.47%下降到0.12%,透光率由92%上升到98%,達(dá)到實(shí)驗(yàn)對(duì)原料的要求。利用設(shè)計(jì)的催化加氫裝置研究硫化法活化NiMo/Al2O3和CoMo/Al2O3催化劑對(duì)煎炸廢油的加氫催化規(guī)律,通過(guò)各因素全面實(shí)驗(yàn)考察反應(yīng)溫度、反應(yīng)壓力和液時(shí)空速對(duì)原料油轉(zhuǎn)化率及液體產(chǎn)物得率的影響。研究了兩種催化劑加氫產(chǎn)物的物理化學(xué)參數(shù),其中十六烷值達(dá)到90左右,高十六烷值有助于與石化燃料調(diào)配使用。產(chǎn)物中硫含量超過(guò)40 mg/Kg,冷濾點(diǎn)也超過(guò)EN590標(biāo)準(zhǔn),需進(jìn)行進(jìn)一步的改性。針對(duì)硫化催化劑催化產(chǎn)物的硫含量超標(biāo)問(wèn)題,用氫氣活化處理氧化態(tài)NiMo/Al2O3和CoMo/Al2O3催化劑。利用氫化活化催化劑對(duì)預(yù)處理的煎炸廢油進(jìn)行加氫催化,采用全面實(shí)驗(yàn)對(duì)兩種催化劑催化條件進(jìn)行優(yōu)化�？疾旆磻�(yīng)溫度、反應(yīng)壓力和液時(shí)空速對(duì)原料油轉(zhuǎn)化率及液體產(chǎn)物得率的影響。氫化活化處理的催化劑表現(xiàn)出良好的活性。通過(guò)對(duì)反應(yīng)產(chǎn)物的研究發(fā)現(xiàn),氫化活化催化劑改善了硫化活化的缺陷,所得產(chǎn)物的硫含量低于1mg/Kg,產(chǎn)物中異構(gòu)烷烴含量較高,無(wú)硫元素污染且具有更好的低溫特性。共浸漬法制備了負(fù)載型催化齊NiMoLa/Al2O3,采用一系列現(xiàn)代分析手段對(duì)催化劑的形貌,結(jié)構(gòu)和活性組分進(jìn)行分析,將其應(yīng)用于煎炸廢油的加氫催化反應(yīng),與NiMo/Al2O3和CoMo/Al2O3催化劑進(jìn)行了對(duì)比。得到了NiMoLa/Al2O3催化劑最優(yōu)制備條件為,La(NO3)3負(fù)載量6%,焙燒溫度500℃,焙燒時(shí)間4h；通過(guò)實(shí)驗(yàn)確定最佳催化條件為：反應(yīng)溫度340-360℃、反應(yīng)壓力4.0MPa、液時(shí)空速1.5h-1,H2/oil為100Nm3/m3,在獲得相似轉(zhuǎn)化率和目標(biāo)產(chǎn)物得率的情況下,所需的反應(yīng)條件更溫和；在200h的使用時(shí)間內(nèi),催化劑仍保持較高的催化活性。研究了煎炸廢油的催化反應(yīng)路徑,顯示的反應(yīng)順序應(yīng)為第一階段甘油三酯的飽和反應(yīng)；第二階段飽和甘油三酯的分解；第三階段脂肪酸的加氫脫水,加氫脫羰和脫羧反應(yīng)；第四階段烷烴產(chǎn)物的裂化和異構(gòu)化；其中氣體產(chǎn)物中還存在甲烷化和水煤氣變換反應(yīng)。通過(guò)催化不同類(lèi)型原料研究NiMoLa/Al2O3催化劑的適應(yīng)性和耐受性。結(jié)合產(chǎn)物的物理化學(xué)性質(zhì),氣相色譜和紅外吸收光譜分析得出：催化劑對(duì)脂肪酸有較好的耐受性,對(duì)同時(shí)含堿金屬離子和磷脂的原料油也有一定的催化效果,但對(duì)含有單一高含量堿金屬和磷脂的原料油耐受性較差；催化不同類(lèi)型脂肪酸酯所得產(chǎn)物的組成成分及性質(zhì)相差不大,催化劑有較好的原料適應(yīng)能力。最后,測(cè)定并改善NiMoLa/Al2O3催化劑加氫柴油組分的理化特性。與礦物柴油相比,加氫柴油組分的十六烷值可達(dá)93,酸值小于0.1,硫含量低于1mg/Kg,但產(chǎn)物中異構(gòu)烷烴含量在11.3-15.4%,產(chǎn)物的低溫特性較差,冷濾點(diǎn)較高。采用添加降凝劑、與低凝點(diǎn)礦物柴油混摻的方法來(lái)改善加氫柴油組分的低溫流動(dòng)性。兩種方法都能夠在一定程度上改善產(chǎn)品的低溫流動(dòng)性。在-20#柴油中添加5-30wt%的加氫柴油組分,混合燃料的凝點(diǎn)從-20℃上升到-14℃,冷濾點(diǎn)從-14℃上升到-3℃。選擇三種降凝劑改善混合燃料的低溫特性,選擇添加30wt%加氫柴油組分的混合燃料作為研究對(duì)象,效果最好的是Keroflux 6226,0.25‰的添加量能把混合燃料的凝點(diǎn)從-14℃降至-30℃,效果最差的是降凝劑B,1.0‰的添加量將混合燃料的凝點(diǎn)從-14℃降至-28℃。三種降凝劑降低冷濾點(diǎn)效果沒(méi)有降低凝點(diǎn)明顯。
[Abstract]:The rapid development of the global economy to increase the human energy demand for oil. The oil is not renewable energy, plays an important role in oil alternative fuel sources. Therefore the development of a sustainable diesel fuel oil is one of the important energy products, scholars at home and abroad for the generation of research mainly diesel biodiesel exchange reaction system in the study of ester, hydrogenation hydrogenation diesel less. Hydrogenation preparation is green diesel from vegetable oils and animal fats or waste oil as raw material, through the new fuel hydrogen preparation technology of catalytic hydrogenation. The catalytic characteristics of feedstock quality. And product modification is the key factor for preparing green diesel hydrogenation industry. Taking frying oil as raw material, preparation of green diesel through catalytic hydrogenation system, to achieve the transformation of frying oil by frying oil. Determine the pretreatment process. As catalytic hydrogenation The reaction of raw materials, deep fried oil color is an important factor affecting the hydrogenation product quality, research the separation and impurity removal, degumming, bleaching, dehydration pretreatment of frying oil, analysis of decolorization and steps of frying oil by single factor and response surface. The optimal parameters for the decolorization reaction temperature 104 C, reaction time 46min, stirring rate of 300 r/min, the dosage of decolorizing agent 16wt%, frying oil decolorization rate of 75%. was compared before and after treatment of the frying oil, acid value by 18.7mg KOH/g down to 15.2mg KOH/g, the water dropped from 0.75% to trace, the phospholipid content decreased from 1.47% to 0.12%, the light transmittance increased from 92% to 98%. To meet the requirements of raw materials of the experiment. The catalytic hydrogenation of NiMo/Al2O3 and activation of CoMo/Al2O3 catalyst for frying oil by catalytic hydrogenation device design of the curing method, through the comprehensive experiment The effects of reaction temperature, reaction pressure and liquid space velocity on the conversion rate of raw oil and liquid product yield were studied. The physical and chemical parameters of two kinds of catalysts for hydrogenation products, of which sixteen cetane number reached 90, sixteen higher octane help deployment and fossil fuel use. The 40 mg/Kg more than the sulfur content in the product also, cold filter point exceeds EN590 standards, the need for further modification. The sulfur content exceed the standard problem of the catalytic product sulfide catalyst, oxidation states of NiMo/Al2O3 and CoMo/Al2O3 catalysts for hydrogen activation. The activation catalyst for catalytic hydrogenation pretreatment of frying oil by hydrogenation, using two kinds of catalysts to optimize the comprehensive experiment. The influences of reaction temperature, reaction pressure and liquid space velocity on the conversion rate of raw oil and liquid product yield. The catalyst hydrogenation activation treatment showed good activity through the. The study of reaction products, improve the hydrogenation activation catalyst activation defects, the sulfur content of the product is less than 1mg/Kg, higher isoparaffin content in the product, no pollution and low temperature properties of sulfur has better. Prepared by CO impregnation of supported catalyst NiMoLa/ Al2O3, on the morphology of the catalysts by using a series of modern analysis methods the structure, and the active component of catalytic hydrogenation reaction is applied to the frying oil, compared with NiMo/Al2O3 and CoMo/Al2O3 catalysts were obtained. The optimal preparation conditions for NiMoLa/Al2O3 catalyst, La (NO3) 3 loading 6%, 500 C of roasting temperature, roasting time is 4H; the optimal catalytic conditions as the reaction temperature is 340-360 DEG C, reaction pressure 4.0MPa, liquid space velocity 1.5h-1, H2/oil 100Nm3/m3, in similar conversion rate and target product yield under the condition of reaction required A more moderate; in the use of 200H time, the catalyst still maintain high catalytic activity. The catalytic reaction path of frying oil, reaction order display should be the first stage of the reaction of saturated triglycerides; second stage decomposition saturated triglycerides; hydrogenation dehydration stage third fatty acid hydrogenation, decarbonylation and removal decarboxylation; fourth stage alkane cracking and isomerization products; methane and water gas shift reaction exists in product gas. Through different types of catalytic material research NiMoLa/Al2O3 catalyst adaptability and tolerance. Combined with the physical and chemical properties of the product, the absorption spectra of gas chromatography and infrared: catalyst for fatty acid tolerance well, have a catalytic effect on raw oil and alkali metal ions and phospholipids, but the single containing higher content of alkali metal and raw phospholipid Feed oil poor tolerance; the composition and properties of fatty acid ester catalyzed by different types of the products are similar, the catalyst with better material adaptability. Finally, determine and improve the physical and chemical properties of NiMoLa/Al2O3 catalyst for hydrogenation of diesel components. Compared with diesel, diesel hydrogenation component sixteen octane can reach 93, acid value less than 0.1, the sulfur content of less than 1mg/Kg, but the content of isoparaffin products in 11.3-15.4%, poor low temperature characteristics of products, cold filter point higher. By adding depressant, to improve the low-temperature fluidity of diesel oil with hydrogen component and low pour point mineral diesel mixed method. The two methods can improve the low temperature fluidity the product in a certain extent. The addition of 5-30wt% in diesel hydrogenation group -20# in diesel fuel mixture, pour point increased from -20 DEG to -14 DEG, cold filter point increased from -14 DEG to -3 DEG. Three kinds of improved mixed depressant Low temperature fuel characteristics, selection of blended fuel adding 30wt% hydrogenation diesel components as the research object, the best is Keroflux 6226,0.25% of the amount can be added to the mixed fuel pour point from -14 to -30 DEG C, the difference is depressant B, adding 1% of the mixed fuel from freezing -14 DEG C to -28 DEG C. Three kinds of depressant reduced cold filter point effect is not obvious to reduce the pour point.

【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TE667

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