摻雜鑭的固體酸制備及其催化合成生物柴油的應(yīng)用研究
發(fā)布時間：2018-07-23 14:14
【摘要】：近年來,隨著人們生活質(zhì)量的提高,對環(huán)境要求越來越高,希望在低碳、低污染環(huán)境中生活、學(xué)習(xí)和工作。生物柴油作為一種環(huán)保、可再生的生物質(zhì)能源,可直接代替石油等礦物能源,對環(huán)境保護(hù)和資源節(jié)約具有重要意義。目前,地溝油可與甲醇經(jīng)堿催化可合成綠色能源生物柴油;但地溝油酸值太高,合成生物柴油過程中,地溝油中的游離脂肪酸易與堿性物質(zhì)發(fā)生皂化反應(yīng),極大地影響了生物柴油的產(chǎn)率。因此,亟需解決高酸值問題。固體酸催化劑可以降低地溝油的酸值,且較均相酸性催化劑具有易分離、對設(shè)備腐蝕程度小,對合成生物柴油起著巨大作用。本論文以高酸值地溝油為原料,重點(diǎn)研究了固體酸的制備與表征、酯化反應(yīng)合成酯化油及酯交換反應(yīng)合成生物柴油整個應(yīng)用過程。本論文研究成果有助于促進(jìn)生物柴油產(chǎn)業(yè)技術(shù)水平的進(jìn)步和產(chǎn)品質(zhì)量的提高,創(chuàng)造良好的經(jīng)濟(jì)效益和環(huán)境效應(yīng)。主要研究內(nèi)容如下:(1)本論文以活性炭為基質(zhì)、TiO_2和La_2O_3為改性劑、濃硫酸為活化劑,采用高溫磺化法制備復(fù)合型稀土改性固體酸SO_4~(2-)/C-TiO_2-La_2O_3。探討La_2O_3的質(zhì)量分?jǐn)?shù)、磺化反應(yīng)溫度、磺化反應(yīng)時間對固體酸催化劑制備條件的影響。通過實(shí)驗(yàn)結(jié)果表明,固體酸催化劑制備SO_4~(2-)/C-TiO_2-La_2O_3的最佳工藝條件為:La_2O_3的質(zhì)量分?jǐn)?shù)為3%(以活性炭質(zhì)量計,下同)、磺化溫度為200℃、磺化時間為10 h。(2)采用掃描電鏡(SEM)、透射電鏡(TEM)、紅外光譜(FT-IR)、X射線衍射(XRD)、比表面積(BET)、能譜分析(EDS)、熱重分析(DTG)分別對固體酸進(jìn)行表征分析。固體酸SO_4~(2-)/C-TiO_2-La_2O_3最佳制備條件:La_2O_3的質(zhì)量分?jǐn)?shù)為3%、磺化時間為10 h、磺化溫度為200℃;固體酸SO_4~(2-)/C-TiO_2-La_2O_3的比表面積最大、粒徑最小,分別為53.82 m2/g和156.91 nm;固體酸SO_4~(2-)/C-TiO_2-La_2O_3的酸位中心數(shù)量最多;固體酸SO_4~(2-)/C-TiO_2-La_2O_3中的O、S、Ti、La原子比其他三種固體酸多;固體酸SO_4~(2-)/C-TiO_2-La_2O_3熱穩(wěn)定性最強(qiáng)。(3)通過比較四種固體酸SO_4~(2-)/C、SO_4~(2-)/C-TiO_2、SO_4~(2-)/C-La_2O_3、SO_4~(2-)/C-TiO_2-La_2O_3的催化活性,固體酸SO_4~(2-)/C-TiO_2-La_2O_3的催化活性相對其他三種固體酸要高一些,因此,選擇固體酸SO_4~(2-)/C-TiO_2-La_2O_3為催化劑,催化經(jīng)處理過的地溝油與甲醇發(fā)生酯化反應(yīng),酯化率作為衡量對象,考察固體酸SO_4~(2-)/C-TiO_2-La_2O_3的質(zhì)量分?jǐn)?shù)、反應(yīng)時間、反應(yīng)溫度、甲醇與地溝油的比對酯化率的影響。結(jié)果指明:固體酸SO_4~(2-)/C-TiO_2-La_2O_3的質(zhì)量分?jǐn)?shù)為2.5%(以地溝油的質(zhì)量計,下同)、酯化反應(yīng)的時間為4 h、酯化反應(yīng)的溫度為65℃、甲醇與地溝油的質(zhì)量比為1:5,在此條件下酯化率最大,達(dá)到95.64%,將地溝油的酸值從18.97mg(KOH)/g下降至1.10 mg(KOH)/g,得到酯化油,酯化油為后續(xù)的酯交換反應(yīng)使用。(4)以堿性催化劑NaOH為酯交換反應(yīng)的催化劑,將NaOH與甲醇配制成NaOH-甲醇溶液,與酯化油在一定的條件下發(fā)生酯交換反應(yīng),以粗品生物柴油得率為考察目標(biāo),探討催化劑NaOH的質(zhì)量分?jǐn)?shù)(以酯化油質(zhì)量計,下同)、酯交換反應(yīng)時間、酯交換反應(yīng)溫度、甲醇與酯化油的質(zhì)量比四個因素對粗品生物柴油層得率的影響。結(jié)果表明,合成生物柴油的最佳條件是:催化劑NaOH的質(zhì)量分?jǐn)?shù)為0.4%、酯交換反應(yīng)的時間為1 h、酯交換反應(yīng)的溫度為65℃、醇油質(zhì)量比為3:20,此時粗品生物柴油的得率為95.90%。(5)檢測產(chǎn)品生物柴油的凝點(diǎn)為-2℃、運(yùn)動粘度為5.0 mm2/s、銅片腐蝕度為1級、密度為878 Kg/m3、閉口閃點(diǎn)為160℃、膠質(zhì)為1000 mg/100mL、酸值為0.28 mg(KOH)/g、硫含量為0.02%(W/W)、十六烷值為44,其性能基本符合國標(biāo)。因此,合成的生物柴油具有一定的研究價值和使用價值。
[Abstract]:In recent years, with the improvement of people's quality of life, the demand for the environment is getting higher and higher, hoping to live, study and work in low carbon and low pollution environment. As a kind of environmental protection and renewable biomass energy, biodiesel can directly replace petroleum and other mineral energy. It is of great significance to environmental protection and resource conservation. In the process of synthetic biodiesel, the free fatty acids in the gutter oil are easily saponified with the basic substances, which greatly affects the yield of biodiesel. Therefore, the high acid value problem is urgently needed. The solid acid catalyst can reduce the acid value of the gutter oil and is more than the same. The homogeneous acid catalyst is easy to be separated and has a small corrosion degree to the equipment. It plays a great role in the synthesis of biodiesel. This paper focuses on the preparation and characterization of solid acid, esterification synthesis of esterified oil and ester exchange reaction to synthesize biodiesel oil. Improving the technological level of biodiesel industry and improving the quality of products to create good economic and environmental effects. The main contents are as follows: (1) this paper uses activated charcoal as matrix, TiO_2 and La_2O_3 as modifier, concentrated sulfuric acid as activator, and the preparation of compound rare earth modified solid acid SO_4~ (2-) /C-TiO_2-La by high temperature sulfonated method The effect of the mass fraction of La_2O_3, the temperature of sulfonation reaction and the time of sulfonation reaction on the preparation conditions of solid acid catalyst were investigated by _2O_3.. The optimum process conditions for the preparation of SO_4~ (2-) /C-TiO_2-La_2O_3 by solid acid catalyst were as follows: the mass fraction of La_2O_3 was 3% (with the activated carbon mass meter, the same below), the sulfonation temperature was 200, and the sulfonation was sulfonated. The time was 10 h. (2) by scanning electron microscope (SEM), transmission electron microscope (TEM), infrared spectroscopy (FT-IR), X ray diffraction (XRD), specific surface area (BET), energy spectrum analysis (EDS) and thermogravimetric analysis (DTG), respectively. The optimum preparation conditions for solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 were 3%, 10 sulfonated and sulfonated. The specific surface area of solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 is the largest and the particle size is the lowest, 53.82 m2/g and 156.91 nm respectively. The solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 has the largest number of acid sites, and the O of solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 is more than the other three kinds of solid acids. Solid acids are more than solid acids. (3) by comparing the catalytic activity of four solid acids SO_4~ (2-) /C, SO_4~ (2-) /C-TiO_2, SO_4~ (2-) /C-La_2O_3, SO_4~ (2-) /C-TiO_2-La_2O_3, the catalytic activity of solid acids is higher than that of the other three solid acids. The effect of the esterification reaction and the esterification rate on the esterification rate of SO_4~ (2-) /C-TiO_2-La_2O_3 of solid acid, reaction time, reaction temperature, and the ratio of methanol to gutter oil were investigated. The results indicated that the mass fraction of solid acid SO_4~ (2-) / C-TiO_2-La_2O_3 was 2.5% (with the quality of gutter oil, The esterification reaction time is 4 h, the esterification reaction temperature is 65, the mass ratio of methanol to the gutter oil is 1:5, and the esterification rate is maximum, reaching 95.64%. The acid value of the gutter oil decreases from 18.97mg (KOH) /g to 1.10 Mg (KOH) /g. The esterified oil is obtained and the ester oil is used for the subsequent ester exchange reaction. (4) the alkaline catalyst NaOH is the ester. The catalyst of the exchange reaction was made up of NaOH and methanol into a NaOH- methanol solution, and the esterified oil was transesterified under certain conditions. The mass fraction of the catalyst NaOH (with the esterified oil mass, the same below), the ester exchange reaction time, the transesterification reaction temperature, the methanol and the quality of the esterified oil were investigated. The effect of four factors on the yield of crude biodiesel is measured. The results show that the optimum conditions for the synthesis of biodiesel are as follows: the mass fraction of the catalyst NaOH is 0.4%, the time of the transesterification is 1 h, the temperature of the transesterification is 65, the mass ratio of the alcohol oil is 3:20, and the yield of the crude biodiesel is 95.90%. (5) for the detection of the bio diesel fuel. The oil condensation point is -2 C, the moving viscosity is 5 mm2/s, the copper plate corrosion degree is 1, the density is 878 Kg/m3, the closing flash point is 160 C, the gum is 1000 mg/100mL, the acid value is 0.28 Mg (KOH) /g, the sulfur content is 0.02% (W/W), and the sixteen alkanes value is 44. The performance of the synthetic biodiesel has certain research value and use value.
【學(xué)位授予單位】：江西理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TE667;TQ426
本文編號：2139669
[Abstract]:In recent years, with the improvement of people's quality of life, the demand for the environment is getting higher and higher, hoping to live, study and work in low carbon and low pollution environment. As a kind of environmental protection and renewable biomass energy, biodiesel can directly replace petroleum and other mineral energy. It is of great significance to environmental protection and resource conservation. In the process of synthetic biodiesel, the free fatty acids in the gutter oil are easily saponified with the basic substances, which greatly affects the yield of biodiesel. Therefore, the high acid value problem is urgently needed. The solid acid catalyst can reduce the acid value of the gutter oil and is more than the same. The homogeneous acid catalyst is easy to be separated and has a small corrosion degree to the equipment. It plays a great role in the synthesis of biodiesel. This paper focuses on the preparation and characterization of solid acid, esterification synthesis of esterified oil and ester exchange reaction to synthesize biodiesel oil. Improving the technological level of biodiesel industry and improving the quality of products to create good economic and environmental effects. The main contents are as follows: (1) this paper uses activated charcoal as matrix, TiO_2 and La_2O_3 as modifier, concentrated sulfuric acid as activator, and the preparation of compound rare earth modified solid acid SO_4~ (2-) /C-TiO_2-La by high temperature sulfonated method The effect of the mass fraction of La_2O_3, the temperature of sulfonation reaction and the time of sulfonation reaction on the preparation conditions of solid acid catalyst were investigated by _2O_3.. The optimum process conditions for the preparation of SO_4~ (2-) /C-TiO_2-La_2O_3 by solid acid catalyst were as follows: the mass fraction of La_2O_3 was 3% (with the activated carbon mass meter, the same below), the sulfonation temperature was 200, and the sulfonation was sulfonated. The time was 10 h. (2) by scanning electron microscope (SEM), transmission electron microscope (TEM), infrared spectroscopy (FT-IR), X ray diffraction (XRD), specific surface area (BET), energy spectrum analysis (EDS) and thermogravimetric analysis (DTG), respectively. The optimum preparation conditions for solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 were 3%, 10 sulfonated and sulfonated. The specific surface area of solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 is the largest and the particle size is the lowest, 53.82 m2/g and 156.91 nm respectively. The solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 has the largest number of acid sites, and the O of solid acid SO_4~ (2-) /C-TiO_2-La_2O_3 is more than the other three kinds of solid acids. Solid acids are more than solid acids. (3) by comparing the catalytic activity of four solid acids SO_4~ (2-) /C, SO_4~ (2-) /C-TiO_2, SO_4~ (2-) /C-La_2O_3, SO_4~ (2-) /C-TiO_2-La_2O_3, the catalytic activity of solid acids is higher than that of the other three solid acids. The effect of the esterification reaction and the esterification rate on the esterification rate of SO_4~ (2-) /C-TiO_2-La_2O_3 of solid acid, reaction time, reaction temperature, and the ratio of methanol to gutter oil were investigated. The results indicated that the mass fraction of solid acid SO_4~ (2-) / C-TiO_2-La_2O_3 was 2.5% (with the quality of gutter oil, The esterification reaction time is 4 h, the esterification reaction temperature is 65, the mass ratio of methanol to the gutter oil is 1:5, and the esterification rate is maximum, reaching 95.64%. The acid value of the gutter oil decreases from 18.97mg (KOH) /g to 1.10 Mg (KOH) /g. The esterified oil is obtained and the ester oil is used for the subsequent ester exchange reaction. (4) the alkaline catalyst NaOH is the ester. The catalyst of the exchange reaction was made up of NaOH and methanol into a NaOH- methanol solution, and the esterified oil was transesterified under certain conditions. The mass fraction of the catalyst NaOH (with the esterified oil mass, the same below), the ester exchange reaction time, the transesterification reaction temperature, the methanol and the quality of the esterified oil were investigated. The effect of four factors on the yield of crude biodiesel is measured. The results show that the optimum conditions for the synthesis of biodiesel are as follows: the mass fraction of the catalyst NaOH is 0.4%, the time of the transesterification is 1 h, the temperature of the transesterification is 65, the mass ratio of the alcohol oil is 3:20, and the yield of the crude biodiesel is 95.90%. (5) for the detection of the bio diesel fuel. The oil condensation point is -2 C, the moving viscosity is 5 mm2/s, the copper plate corrosion degree is 1, the density is 878 Kg/m3, the closing flash point is 160 C, the gum is 1000 mg/100mL, the acid value is 0.28 Mg (KOH) /g, the sulfur content is 0.02% (W/W), and the sixteen alkanes value is 44. The performance of the synthetic biodiesel has certain research value and use value.
【學(xué)位授予單位】：江西理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TE667;TQ426
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