金屬基磺酸型固體酸催化劑催化纖維素降解制備5-羥甲基糠醛的研究
發(fā)布時(shí)間：2018-08-03 11:38
【摘要】：近年來(lái),化石能源的過(guò)度使用使得環(huán)境污染和能源短缺問(wèn)題日益嚴(yán)重,人類(lèi)對(duì)于新能源的需求越來(lái)越迫切。生物質(zhì)由于其具有來(lái)源廣泛、儲(chǔ)量豐富等優(yōu)點(diǎn),被認(rèn)為是最有前途的可再生資源之一。生物質(zhì)資源的開(kāi)發(fā)利用可以降低化石能源的消耗,有利于社會(huì)經(jīng)濟(jì)的可持續(xù)發(fā)展。纖維素是最為豐富的生物質(zhì)資源,以纖維素為原料,可以得到重要的平臺(tái)化合物5-羥甲基糠醛(HMF),進(jìn)而可以轉(zhuǎn)化為多種化學(xué)品。本論文設(shè)計(jì)并合成了多種負(fù)載型雙酸性固體酸催化劑,并將其用于催化纖維素降解制備5-羥甲基糠醛。利用紅外光譜、拉曼光譜、X射線(xiàn)衍射、N2吸附-脫附、掃描電鏡、透射電鏡等多種表征手段對(duì)催化劑的組成和結(jié)構(gòu)進(jìn)行了分析,并對(duì)纖維素降解制備HMF的反應(yīng)條件進(jìn)行了優(yōu)化。首先合成了介孔分子篩MSNP并對(duì)其進(jìn)行了磺酸化改性,然后以其為載體,以咪唑型離子液體為媒介,引入CrCl3,制備了具有雙重酸性的[pmim]CrCl4-MSNP-SO3H催化劑。將此催化劑用于纖維素降解制備HMF的實(shí)驗(yàn),考察了催化劑的用量、纖維素的初始濃度、反應(yīng)溫度和時(shí)間對(duì)HMF產(chǎn)率的影響。結(jié)果發(fā)現(xiàn)當(dāng)[pmim]CrCl4-MSNP-SO3H用量為0.05 g,纖維素初始量為0.01 g,反應(yīng)溫度為160oC,反應(yīng)時(shí)間為140 min時(shí),HMF產(chǎn)率可達(dá)39.1%。該體系具有較好的穩(wěn)定性,循環(huán)使用4次而沒(méi)有明顯的活性損失。為了進(jìn)一步提高HMF的產(chǎn)率,合成了三種介孔分子篩MSNP、MCM-41和SBA-15,利用嫁接法負(fù)載了含有布朗斯特酸性的吡啶型離子液體[PPy-SO3H]Cl,并引入了CrCl3,得到了具有布朗斯特酸和路易斯酸雙重酸性的催化劑。實(shí)驗(yàn)發(fā)現(xiàn),催化劑的載體對(duì)其催化活性有較大影響,其中以MSNP為載體時(shí)活性最佳。隨后,以[PPy-SO3H]CrCl4-MSNP為催化劑,探究了催化劑的用量、纖維素的初始濃度、反應(yīng)溫度和時(shí)間對(duì)HMF產(chǎn)率的影響。其中當(dāng)纖維素初始量為0.01 g,催化劑用量為0.05 g,反應(yīng)溫度為130oC,反應(yīng)時(shí)間為120 min時(shí),HMF產(chǎn)率高達(dá)61.5%。此外,該體系循環(huán)使用6次時(shí)仍然具有較好的活性。以葡萄糖和磺基水楊酸為原料,水熱法制備了含有磺酸基的碳微球CM-SO3H,并利用浸漬法負(fù)載了多種金屬氯化物,得到了具有雙重酸性的碳基固體酸催化劑MClx-CM-SO3H。探究了不同金屬氯化物對(duì)纖維素降解制備HMF的影響,發(fā)現(xiàn)負(fù)載CrCl3時(shí)活性最佳。隨后對(duì)催化劑的用量、纖維素的初始濃度、反應(yīng)溫度和時(shí)間對(duì)催化活性的影響進(jìn)行了考察,結(jié)果發(fā)現(xiàn),以0.01 g纖維素為反應(yīng)底物,加入0.05gCrCl3-CM-SO3H(負(fù)載量為40wt%),在140oC反應(yīng)120 min,HMF產(chǎn)率可達(dá)66.7%。此外,該體系具有一定的耐水性。
[Abstract]:In recent years, the problem of environmental pollution and energy shortage is becoming more and more serious due to the excessive use of fossil energy, and the demand for new energy is becoming more and more urgent. Biomass is considered to be one of the most promising renewable resources because of its wide range of sources and abundant reserves. The exploitation and utilization of biomass resources can reduce the consumption of fossil energy and contribute to the sustainable development of social economy. Cellulose is the most abundant biomass resource. With cellulose as the raw material, the important platform compound 5-hydroxymethylfurfural (HMF), can be transformed into many chemicals. In this paper, several supported double acid solid acid catalysts were designed and synthesized, which were used to catalyze the degradation of cellulose to 5 hydroxymethyl furfural. The composition and structure of the catalyst were analyzed by means of infrared spectroscopy, Raman spectroscopy, X-ray diffraction (XRD) N _ 2 adsorption and desorption, scanning electron microscopy (SEM) and transmission electron microscope (TEM), and the reaction conditions for the preparation of HMF by cellulose degradation were optimized. Mesoporous molecular sieve MSNP was synthesized and modified with sulfonic acid. Then the [pmim] CrCl4-MSNP-SO3H catalyst with double acidity was prepared by introducing CrCl3 into the imidazole ionic liquid as the carrier. The effects of the amount of catalyst, the initial concentration of cellulose, the reaction temperature and time on the yield of HMF were investigated. The results showed that when the dosage of [pmim] CrCl4-MSNP-SO3H was 0. 05 g, the initial amount of cellulose was 0. 01 g, the reaction temperature was 160 OC and the reaction time was 140 min, the yield of HMF could reach 39. 1%. The system has good stability and is recycled for 4 times without obvious loss of activity. In order to further improve the yield of HMF, Three kinds of mesoporous molecular sieve MSNPN MCM-41 and SBA-15 were synthesized. The pyridine ionic liquid [PPy-SO3H] Cl containing Brownst acid was supported by grafting method, and CrCl3 was introduced. The catalyst with the double acidity of Brownstearic acid and Lewis acid was obtained. It was found that the support of the catalyst had great influence on its catalytic activity, and the best one was when MSNP was used as the carrier. Then, using [PPy-SO3H] CrCl4-MSNP as catalyst, the effects of the amount of catalyst, initial concentration of cellulose, reaction temperature and time on the yield of HMF were investigated. When the initial amount of cellulose was 0.01 g, the amount of catalyst was 0.05 g, the reaction temperature was 130 OC and the reaction time was 120 min, the yield of HMF reached 61.5%. In addition, the system still has good activity when it is recycled for 6 times. Carbon microspheres containing sulfonic groups were prepared by hydrothermal method from glucose and sulfosalicylic acid, and various metal chlorides were loaded by impregnation method. The double acidic carbon-based solid acid catalyst MClx-CM-SO3H was obtained. The effects of different metal chlorides on the preparation of HMF by cellulose degradation were investigated. It was found that the activity of CrCl3 was the best when loaded. The effects of the amount of catalyst, the initial concentration of cellulose, the reaction temperature and time on the catalytic activity were investigated. It was found that the yield of 0.05gCrCl3-CM-SO3H could reach 66.7% at 120 min after 140oC reaction with 0.01g cellulose as substrate and 40 wt% loading. In addition, the system has a certain water resistance.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.36;TQ251.11
本文編號(hào)：2161625
[Abstract]:In recent years, the problem of environmental pollution and energy shortage is becoming more and more serious due to the excessive use of fossil energy, and the demand for new energy is becoming more and more urgent. Biomass is considered to be one of the most promising renewable resources because of its wide range of sources and abundant reserves. The exploitation and utilization of biomass resources can reduce the consumption of fossil energy and contribute to the sustainable development of social economy. Cellulose is the most abundant biomass resource. With cellulose as the raw material, the important platform compound 5-hydroxymethylfurfural (HMF), can be transformed into many chemicals. In this paper, several supported double acid solid acid catalysts were designed and synthesized, which were used to catalyze the degradation of cellulose to 5 hydroxymethyl furfural. The composition and structure of the catalyst were analyzed by means of infrared spectroscopy, Raman spectroscopy, X-ray diffraction (XRD) N _ 2 adsorption and desorption, scanning electron microscopy (SEM) and transmission electron microscope (TEM), and the reaction conditions for the preparation of HMF by cellulose degradation were optimized. Mesoporous molecular sieve MSNP was synthesized and modified with sulfonic acid. Then the [pmim] CrCl4-MSNP-SO3H catalyst with double acidity was prepared by introducing CrCl3 into the imidazole ionic liquid as the carrier. The effects of the amount of catalyst, the initial concentration of cellulose, the reaction temperature and time on the yield of HMF were investigated. The results showed that when the dosage of [pmim] CrCl4-MSNP-SO3H was 0. 05 g, the initial amount of cellulose was 0. 01 g, the reaction temperature was 160 OC and the reaction time was 140 min, the yield of HMF could reach 39. 1%. The system has good stability and is recycled for 4 times without obvious loss of activity. In order to further improve the yield of HMF, Three kinds of mesoporous molecular sieve MSNPN MCM-41 and SBA-15 were synthesized. The pyridine ionic liquid [PPy-SO3H] Cl containing Brownst acid was supported by grafting method, and CrCl3 was introduced. The catalyst with the double acidity of Brownstearic acid and Lewis acid was obtained. It was found that the support of the catalyst had great influence on its catalytic activity, and the best one was when MSNP was used as the carrier. Then, using [PPy-SO3H] CrCl4-MSNP as catalyst, the effects of the amount of catalyst, initial concentration of cellulose, reaction temperature and time on the yield of HMF were investigated. When the initial amount of cellulose was 0.01 g, the amount of catalyst was 0.05 g, the reaction temperature was 130 OC and the reaction time was 120 min, the yield of HMF reached 61.5%. In addition, the system still has good activity when it is recycled for 6 times. Carbon microspheres containing sulfonic groups were prepared by hydrothermal method from glucose and sulfosalicylic acid, and various metal chlorides were loaded by impregnation method. The double acidic carbon-based solid acid catalyst MClx-CM-SO3H was obtained. The effects of different metal chlorides on the preparation of HMF by cellulose degradation were investigated. It was found that the activity of CrCl3 was the best when loaded. The effects of the amount of catalyst, the initial concentration of cellulose, the reaction temperature and time on the catalytic activity were investigated. It was found that the yield of 0.05gCrCl3-CM-SO3H could reach 66.7% at 120 min after 140oC reaction with 0.01g cellulose as substrate and 40 wt% loading. In addition, the system has a certain water resistance.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.36;TQ251.11
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