銅基、鎳基催化劑非均相催化生物質(zhì)甘油制備乳酸及動力學(xué)研究
發(fā)布時(shí)間：2018-07-21 18:31
【摘要】：伴隨社會的迅速發(fā)展,能源的消耗量與日俱增,傳統(tǒng)化石能源能量儲備有限,不可避免的將加速化石能源消耗殆盡�；茉吹倪^度利用導(dǎo)致了地球環(huán)境極度惡化,因此尋求綠色可再生清潔能源已經(jīng)迫在眉睫。通過甲醇與動物植物油脂之間進(jìn)行的酯交換生成的生物柴油作為可再生能源的代表,目前已經(jīng)大規(guī)模量生產(chǎn)并應(yīng)用,這是因?yàn)槠淇稍偕�、對化石能源的可替代性以及可以減少溫室氣體排放,減少污染提高空氣質(zhì)量。然而隨著生物柴油用量激增,副產(chǎn)物甘油也會大量生產(chǎn)。因此,開發(fā)由甘油出發(fā)制備更具價(jià)值的化學(xué)品引起相關(guān)研究人員的注意。其中生物質(zhì)甘油轉(zhuǎn)化制備乳酸是甘油重要的利用途徑,因?yàn)槿樗峥梢宰鳛槎喾N生物可降解材料以及生物相容材料的前體。所以催化轉(zhuǎn)化甘油制備乳酸具有重要的理論研究、環(huán)境效益和經(jīng)濟(jì)價(jià)值。本文主要研究了堿性載體負(fù)載金屬銅,金屬納米銅以及石墨負(fù)載鎳等為催化劑,以生物質(zhì)甘油為原料,NaOH為堿源,催化制備乳酸。在反應(yīng)過程中探究了各實(shí)驗(yàn)參數(shù)如甘油濃度、NaOH濃度、實(shí)驗(yàn)溫度、實(shí)驗(yàn)時(shí)間及催化劑量等反應(yīng)因素對催化劑催化效果的影響,研究了催化劑結(jié)構(gòu)與催化活性的構(gòu)效關(guān)系。并以冪指數(shù)動力學(xué)方程為模型對實(shí)驗(yàn)數(shù)據(jù)進(jìn)行擬合,進(jìn)行了催化反應(yīng)動力學(xué)研究。取得研究結(jié)果如下。1.采用等孔體積浸漬法,制備了以MgO,ZrO2和HAP(羥基磷灰石)為載體,納米Cu0為活性組分的負(fù)載型銅基催化劑。在高壓反應(yīng)釜中,堿性條件下,以生物質(zhì)甘油為原料催化制備乳酸。研究發(fā)現(xiàn),具有強(qiáng)堿性位的MgO和HAP載體負(fù)載銅催化劑催化效果要高于弱堿強(qiáng)度的載體ZrO2負(fù)載銅催化劑。當(dāng)以Cu(16)/HAP為催化劑,以1.0 mol L~(-1)甘油和1.1 mol L~(-1)的NaOH在230 oC下反應(yīng)2 h,乳酸選擇性可達(dá)90%,甘油轉(zhuǎn)化率為91%。同時(shí)Cu(16)/HAP表現(xiàn)出很好的重復(fù)利用性能。以Cu(16)/HAP為催化劑,使用冪指數(shù)動力學(xué)模型對甘油濃度,NaOH濃度以及反應(yīng)溫度等對反應(yīng)的影響進(jìn)行了評價(jià),催化反應(yīng)活化能(Ea)為117.2 kJ mol L~(-1)。2.采用濕化學(xué)還原法,使用不同化學(xué)結(jié)構(gòu)的有機(jī)修飾劑制備了不同粒徑的納米銅。當(dāng)以聚乙二醇為修飾劑制備的具有最小粒徑的納米銅催化劑催化轉(zhuǎn)化甘油制備乳酸時(shí),其表現(xiàn)出很好的催化性能。以1.0 mol L~(-1)甘油和1.1 mol L~(-1)的NaOH為反應(yīng)物,在230 oC下反應(yīng)4 h,甘油轉(zhuǎn)化率為98.0%,乳酸選擇性為91.9%。以CuPEG(36.9 nm)和Cublank(118.3 nm)為催化劑,反應(yīng)活化能分別為76.3和86.5 kJ mol L~(-1)。納米銅粒徑的降低明顯降低了反應(yīng)活化能,加速了催化反應(yīng)。3.在NaOH水溶液中,超細(xì)石墨負(fù)載的鎳催化劑有效地催化甘油制備乳酸。研究發(fā)現(xiàn),NaOH和鎳納米顆粒協(xié)同催化甘油制備乳酸。當(dāng)甘油濃度為1.0 mol L~(-1),NaOH濃度為1.1 mol L~(-1),以Ni0.3/石墨為催化劑,在230 oC反應(yīng)3 h,反應(yīng)物轉(zhuǎn)化率和主產(chǎn)物選擇性分別為97.6%和92.2%。反應(yīng)活化能(Ea)為69.2 kJ mol L~(-1)。研究表明,銅基、鎳基催化劑具有良好的催化甘油制備乳酸活性,以生物質(zhì)甘油為原料催化制備乳酸具有替代傳統(tǒng)糖類發(fā)酵制備乳酸的可行性。
[Abstract]:With the rapid development of the society, the consumption of energy is increasing, the energy reserves of the traditional fossil energy are limited and the fossil energy will inevitably be depleted. The overutilization of fossil energy leads to the extreme deterioration of the earth's environment. Therefore, it is imminent to seek green renewable clean energy. Biodiesel generated by transesterification, as a representative of renewable energy, is now produced and applied with large moduli because of its renewability, substitutes for fossil fuels, reducing greenhouse gas emissions, reducing pollution and improving air quality. However, as the amount of biodiesel increases, the byproduct glycerol is also The development of a more valuable chemical from glycerol, therefore, has attracted the attention of relevant researchers. The conversion of biomass glycerin to lactic acid is an important use of glycerol, because lactic acid can be used as a precursor of biodegradable materials and biocompatible materials. It has important theoretical research, environmental benefit and economic value. In this paper, the basic carrier load metal copper, metal nanoscale copper and graphite loaded nickel are used as the catalyst, the biomass glycerol as the raw material and the NaOH as the base source, the lactic acid is prepared. In the reaction process, the experimental parameters such as glycerol concentration, NaOH concentration, and experimental temperature are explored. The influence of the reaction time and the amount of catalyst on the catalytic activity of the catalyst was studied. The structure effect relationship of the catalyst structure and the catalytic activity was studied. The experimental data were fitted with the power exponent kinetic equation as the model, and the catalytic reaction kinetics was studied. The results are as follows:.1. is prepared by the impregnation method of equal pore volume. The supported copper based catalyst with MgO, ZrO2 and HAP (hydroxyapatite) as the carrier and the nano Cu0 as the active component. In the high pressure reactor, the lactic acid was prepared with biomass glycerol as the catalyst under the alkaline condition. It was found that the catalytic effect of the MgO and HAP supported copper catalyst with strong alkali position was higher than the carrier ZrO2 negative of the weak alkali strength. Copper catalyst. When Cu (16) /HAP was used as the catalyst, the NaOH of 1 mol L~ (-1) glycerol and 1.1 mol L~ (-1) were reacted 2 h under 230 oC. The selectivity of lactic acid was 90%. The conversion rate of glycerol was equal to 91%. simultaneously (16). The effect of reaction temperature and the reaction temperature were evaluated. The catalytic activation energy (Ea) was 117.2 kJ mol L~ (-1).2. using wet chemical reduction method. The nano copper with different particle sizes was prepared by the organic modifier of different chemical structures. The nano copper catalyst with the minimum particle size prepared with polyethylene glycol as the modifier was used to catalyze the conversion of glycerol. When the lactic acid was prepared, it showed good catalytic performance. With 1 mol L~ (-1) glycerin and 1.1 mol L~ (-1) NaOH as reactant, the reaction was 4 h under 230 oC, the conversion rate of glycerol was 98%, the selectivity of lactic acid was CuPEG (36.9 nm) and 118.3 (118.3). The reaction activation energy was 76.3 and 86.5, respectively. The reduction obviously reduced the activation energy and accelerated the catalytic reaction.3. in NaOH aqueous solution. The nickel catalyst supported by superfine graphite was used to catalyze the preparation of lactic acid in glycerol effectively. It was found that NaOH and Ni nanoparticles co catalyzed glycerol preparation of lactic acid. The concentration of glycerol was 1 mol L~ (-1), NaOH concentration was 1.1 mol L~ (-1), and Ni0.3/ graphite was used as catalyst. The reaction rate and the selectivity of the main product were 97.6% and the 92.2%. reaction activation energy (Ea) was 69.2 kJ mol L~ (-1) at 230 oC, respectively. The study showed that the copper based catalyst had good catalytic activity for the preparation of lactic acid in glycerol, and the preparation of lactic acid with biomass glycerin as raw material could replace the traditional saccharide fermentation to prepare lactic acid. Feasibility.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TQ225.4
本文編號：2136443
[Abstract]:With the rapid development of the society, the consumption of energy is increasing, the energy reserves of the traditional fossil energy are limited and the fossil energy will inevitably be depleted. The overutilization of fossil energy leads to the extreme deterioration of the earth's environment. Therefore, it is imminent to seek green renewable clean energy. Biodiesel generated by transesterification, as a representative of renewable energy, is now produced and applied with large moduli because of its renewability, substitutes for fossil fuels, reducing greenhouse gas emissions, reducing pollution and improving air quality. However, as the amount of biodiesel increases, the byproduct glycerol is also The development of a more valuable chemical from glycerol, therefore, has attracted the attention of relevant researchers. The conversion of biomass glycerin to lactic acid is an important use of glycerol, because lactic acid can be used as a precursor of biodegradable materials and biocompatible materials. It has important theoretical research, environmental benefit and economic value. In this paper, the basic carrier load metal copper, metal nanoscale copper and graphite loaded nickel are used as the catalyst, the biomass glycerol as the raw material and the NaOH as the base source, the lactic acid is prepared. In the reaction process, the experimental parameters such as glycerol concentration, NaOH concentration, and experimental temperature are explored. The influence of the reaction time and the amount of catalyst on the catalytic activity of the catalyst was studied. The structure effect relationship of the catalyst structure and the catalytic activity was studied. The experimental data were fitted with the power exponent kinetic equation as the model, and the catalytic reaction kinetics was studied. The results are as follows:.1. is prepared by the impregnation method of equal pore volume. The supported copper based catalyst with MgO, ZrO2 and HAP (hydroxyapatite) as the carrier and the nano Cu0 as the active component. In the high pressure reactor, the lactic acid was prepared with biomass glycerol as the catalyst under the alkaline condition. It was found that the catalytic effect of the MgO and HAP supported copper catalyst with strong alkali position was higher than the carrier ZrO2 negative of the weak alkali strength. Copper catalyst. When Cu (16) /HAP was used as the catalyst, the NaOH of 1 mol L~ (-1) glycerol and 1.1 mol L~ (-1) were reacted 2 h under 230 oC. The selectivity of lactic acid was 90%. The conversion rate of glycerol was equal to 91%. simultaneously (16). The effect of reaction temperature and the reaction temperature were evaluated. The catalytic activation energy (Ea) was 117.2 kJ mol L~ (-1).2. using wet chemical reduction method. The nano copper with different particle sizes was prepared by the organic modifier of different chemical structures. The nano copper catalyst with the minimum particle size prepared with polyethylene glycol as the modifier was used to catalyze the conversion of glycerol. When the lactic acid was prepared, it showed good catalytic performance. With 1 mol L~ (-1) glycerin and 1.1 mol L~ (-1) NaOH as reactant, the reaction was 4 h under 230 oC, the conversion rate of glycerol was 98%, the selectivity of lactic acid was CuPEG (36.9 nm) and 118.3 (118.3). The reaction activation energy was 76.3 and 86.5, respectively. The reduction obviously reduced the activation energy and accelerated the catalytic reaction.3. in NaOH aqueous solution. The nickel catalyst supported by superfine graphite was used to catalyze the preparation of lactic acid in glycerol effectively. It was found that NaOH and Ni nanoparticles co catalyzed glycerol preparation of lactic acid. The concentration of glycerol was 1 mol L~ (-1), NaOH concentration was 1.1 mol L~ (-1), and Ni0.3/ graphite was used as catalyst. The reaction rate and the selectivity of the main product were 97.6% and the 92.2%. reaction activation energy (Ea) was 69.2 kJ mol L~ (-1) at 230 oC, respectively. The study showed that the copper based catalyst had good catalytic activity for the preparation of lactic acid in glycerol, and the preparation of lactic acid with biomass glycerin as raw material could replace the traditional saccharide fermentation to prepare lactic acid. Feasibility.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TQ225.4
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