【摘要】：多酸負(fù)載于高比表面積的介孔載體上做異相催化劑一直是多酸催化領(lǐng)域的研究熱點(diǎn)。本論文用氨基修飾法將磷鎢酸(簡(jiǎn)記為HPW)負(fù)載到毫米級(jí)的介孔γ-氧化鋁微球表面制備了HPW-NH2-Al2O3和HPW-NH2-C8-Al2O3,用水熱合成法將HPW、硅鎢酸(簡(jiǎn)記為HSiW)負(fù)載到毫米級(jí)的介孔γ-氧化鋁微球表面制備了HPW@HKUST-1@Al2O3和HSiW@HKUST-1@Al2O3。通過(guò)IR、XRD、XRF、ICP、SEM、NH3-TPD和TG-DTA等測(cè)試手段對(duì)這些負(fù)載型催化劑進(jìn)行表征,結(jié)果表明雜多酸成功負(fù)載到了γ-Al2O3載體上,且催化劑保持了介孔結(jié)構(gòu)。另外,對(duì)以上催化劑的催化性能分別進(jìn)行了研究。研究結(jié)果主要有以下幾個(gè)方面：(1)利用兩種硅烷偶聯(lián)劑—正辛基三甲氧基硅烷和3-氨丙基三乙氧基硅烷修飾介孔γ-氧化鋁微球,再將HPW負(fù)載到γ-Al2O3微球中,制備了多酸負(fù)載型催化劑HPW-NH2-C8-Al2O3和HPW-NH2-Al2O3。 HPW-NH2-C8-Al2O3和HPW-NH2-Al2O3兩種催化劑的酸催化活性用乙酸乙酯的水解反應(yīng)來(lái)考察,實(shí)驗(yàn)結(jié)果表明0.2 g催化劑在65℃條件下的催化乙酸乙酯的水解效率分別為4.45%和8.27%,催化活性分別為245.4μmol·gacid-1·min-1和182.0μmol·gacid-1·min-1,采用UV-Vis測(cè)試兩種催化劑在第一次使用時(shí)的溶脫率分別為2.17%和7.79%,而且兩種催化劑在重復(fù)使用6次后催化效率分別降低了13.9%和62.9%。從實(shí)驗(yàn)結(jié)果可見(jiàn),雖然催化劑HPW-NH2-Al2O3在第一次使用時(shí)催化效率和催化活性均高于HPW-NH2-C8-Al2O3,但是其重復(fù)使用效果遠(yuǎn)不如HPW-NH2-C8-Al2O3,該結(jié)果證明了正辛基基團(tuán)在氧化鋁表面形成的疏水空腔對(duì)磷鎢酸具有保護(hù)作用。通過(guò)對(duì)比可以知道,HPW-NH2-C8-Al2O3催化劑是一種機(jī)械強(qiáng)度高、化學(xué)性質(zhì)穩(wěn)定、價(jià)格低廉、重復(fù)使用極其簡(jiǎn)便的優(yōu)良催化劑。(2)通過(guò)氨基陽(yáng)離子的靜電引力作用,將HPW負(fù)載到氨基修飾的γ-Al2O3載體表面制備了多酸負(fù)載型催化劑HPW-NH2-Al2O3。將HPW-NH2-Al2O3應(yīng)用于模擬油的萃取結(jié)合催化氧化脫硫?qū)嶒?yàn)中,結(jié)果表明60 mg的HPW-NH2-Al2O3可以在2h內(nèi)將20 mL含硫量為350 ppmws的DBT正辛烷模擬油的含硫量降到2.8 ppmws,且催化劑易回收,重復(fù)使用5次后氧化脫硫效率由最初的99.2%僅降低到94.7%,表明這種HPW-NH2-Al2O3催化劑是一種優(yōu)秀的除硫催化劑且可重復(fù)使用。(3)通過(guò)水熱合成法在球型γ-Al2O3載體上負(fù)載了高分散的HKUST-1和多金屬氧酸(簡(jiǎn)記為HPAs),制備了負(fù)載型多酸催化劑HPW@HKUST-1@Al2O3和HSiW@HKUST-1@Al2O3。將復(fù)合物作為酸催化劑用于乙酸乙酯和乙酸丁酯的酯化反應(yīng),實(shí)驗(yàn)結(jié)果表明,兩種催化劑對(duì)酯化反應(yīng)的催化選擇性均為100%,其中對(duì)于合成乙酸乙酯的酯化反應(yīng),在酸醇比為2、反應(yīng)溫度為75℃的條件下用0.25 g催化劑反應(yīng)2 h,HPW@HKUST-1@Al2O3催化劑的催化效率為92.3%HSiW@HKUST-1@Al2O3催化劑的催化效率為95.1%；而對(duì)于合成乙酸正丁酯的酯化反應(yīng),在酸醇比為2,反應(yīng)溫度為110℃的條件下用0.4g催化劑反應(yīng)8h,HPW@HKUST-1@Al2O3催化劑的催化效率為82.7%,HSiW@HKUST-1@Al2O3催化劑的催化效率為84.9%。從實(shí)驗(yàn)結(jié)果可以看出,HSiW@HKUST-1@Al2O3催化劑的酸催化活性高于HPW@HKUST-1@Al2O3,且乙酸乙酯的酯合成效率高于乙酸丁酯。兩種催化劑重復(fù)使用6次,催化效率均保持不變。HPW@HKUST-1@Al2O3和HSiW@HKUST-1@Al2O3兩種催化劑的抗壓強(qiáng)度較γ-Al2O3分別提高了60.0%和57.9%,表明球型γ-Al2O3起到載體的作用的同時(shí)還可以穩(wěn)定HKUST-1和多酸的結(jié)構(gòu),防止其被破壞。
[Abstract]:The heterogeneous catalyst supported on the mesoporous support with high specific surface area has been a hot spot in the field of multi-acid catalysis. HPW-NH2-Al2O3 and HPW-NH2-C8-Al2O3 were prepared on the surface of mesoporous silica-alumina microspheres loaded with phosphotungstic acid (abbreviated as HPW) on the surface of millimeter-grade mesoporous silica-alumina microspheres by the amino-modification method, and the HPW was prepared by hydrothermal synthesis. The HPW@HKUST-1 @ Al2O3 and HSiW@HKUST-1 @ Al2O3 are prepared on the surface of the mesoporous silica-alumina microsphere loaded to the millimeter level by using silicotungstic acid (abbreviated as HSiW). The supported catalysts are characterized by IR, XRD, XRF, ICP, SEM, NH3-TPD and TG-DTA. The results show that the heteropoly acid is successfully loaded on the Al-Al2O3 carrier, and the catalyst keeps the mesoporous structure. In addition, the catalytic performance of the above catalysts was studied. The results of the study were as follows: (1) Using two silane coupling agents, n-octyltrimethoxysilane and 3-aminopropyltriethoxysilane to modify the mesoporous silica-alumina microspheres, the HPW-loaded catalyst HPW-NH2-C8-Al2O3 and HPW-NH2-Al2O3 were prepared. The catalytic activity of the two catalysts HPW-NH2-C8-Al2O3 and HPW-NH2-Al2O3 was investigated by the hydrolysis reaction of ethyl acetate. The experimental results showed that the hydrolysis efficiency of the catalyst was 4.45% and 8.27%, respectively, and the catalytic activity was 245.4. mu.mol 路 gacid-1 路 min-1 and 182.0. mu.mol 路 gacid-1 路 min-1, respectively. The dissolution rate of the two catalysts was 2.17% and 7.79%, respectively, and the catalytic efficiency of the two catalysts decreased by 13.9% and 62.9% after 6 times of re-use. It can be seen from the experimental results that, although the catalytic efficiency and catalytic activity of the catalyst HPW-NH2-Al2O3 are higher than that of the HPW-NH2-C8-Al2O3 at the time of the first use, the reuse effect of the catalyst is much lower than that of the HPW-NH2-C8-Al2O3, and the result shows that the hydrophobic cavity formed by the n-octyl group on the surface of the aluminum oxide has a protective effect on the phosphotungstic acid. By comparison, it is known that the HPW-NH2-C8-Al2O3 catalyst is an excellent catalyst with high mechanical strength, stable chemical property, low price and extremely simple and convenient re-use. (2) the HPW-NH2-Al2O3 is prepared by loading the HPW on the surface of the amino-modified Al-Al2O3 carrier by the electrostatic attraction of the amino cation. The application of HPW-NH2-Al2O3 in the extraction and catalytic oxidation of simulated oil shows that 60 mg of HPW-NH2-Al2O3 can reduce the sulfur content of 20 mL of DBT n-octane simulated oil with a sulfur content of 350 ppmws to 2.8 ppmws in 2 hours, and the catalyst is easy to recover. After 5 times of re-use, the oxidation desulfurization efficiency was only reduced to 94.7% from the original 99.2%, indicating that the HPW-NH2-Al2O3 catalyst is an excellent sulfur removal catalyst and can be used repeatedly. and (3) loading a highly dispersed HKUST-1 and a polyoxoacid (abbreviated as HPAs) on a spherical Al-Al2O3 carrier by a hydrothermal synthesis method, and preparing a supported catalyst HPW@HKUST-1 @ Al2O3 and HSiW@HKUST-1 @ Al2O3. The composite is used as an acid catalyst for esterification reaction of ethyl acetate and butyl acetate, The experimental results show that the catalytic selectivity of the two catalysts to the esterification reaction is 100%, in which, for the esterification reaction of the synthetic ethyl acetate, the reaction temperature of the two catalysts is 2, the reaction temperature is 75 DEG C, and the reaction is carried out with 0.25 g of the catalyst for 2 hours, The catalytic efficiency of the HPW@HKUST-1 @ Al2O3 catalyst is 92.3%, the catalytic efficiency of the Al2O3 catalyst is 95.1%, and for the esterification reaction for synthesizing n-butyl acetate, the catalytic efficiency of the HPW@HKUST-1 @ Al2O3 catalyst is 82.7% under the condition that the acid alcohol ratio is 2, the reaction temperature is 110 DEG C, the reaction temperature is 110 DEG C, and the catalytic efficiency of the HSiW@HKUST-1 @ Al2O3 catalyst is 82.7%, The catalytic efficiency of the HSiW@HKUST-1 @ Al2O3 catalyst is 84.9%. It can be seen from the experimental results that the catalytic activity of the HSiW@HKUST-1 @ Al2O3 catalyst is higher than that of the HPW@HKUST-1 @ Al2O3, and the ester synthesis efficiency of the ethyl acetate is higher than that of the butyl acetate. The two catalysts are used for 6 times, the catalytic efficiency is kept unchanged, and the compressive strength of the two catalysts of the .HPW@HKUST-1 @ Al2O3 and the HSiW@HKUST-1 @ Al2O3 is increased by 60.0% and 57.9%, respectively, and the structure of the HKUST-1 and the carbon dioxide can be stabilized at the same time, Preventing it from being damaged.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB33;O643.36

【共引文獻(xiàn)】

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2 王亞軍;陸科呈;馮長(zhǎng)根;;多金屬氧酸鹽在染料廢水光催化降解中的應(yīng)用[J];安全與環(huán)境學(xué)報(bào);2011年05期

3 朱雅婷;于潁;龔文朋;徐玉林;楊水金;;H_3PW_(12)O_(40)/SiO_2催化一鍋法合成4-苯基-6-甲基-5-乙氧羰基-3,4-二氫嘧啶-2(H)-酮[J];寶雞文理學(xué)院學(xué)報(bào)(自然科學(xué)版);2014年03期

4 Xi Xinguo;Zhang Jiling;Jiang Ruiyu;Xu Qi;;Application of Modified Attapulgite Clay as the Adsorbent in Gasoline Desulfurization[J];China Petroleum Processing & Petrochemical Technology;2014年03期

5 Liu Ni;Zhang Minghui;Wang Danhong;;Solvothermal Synthesis of V_2O_3 Catalysts for Oxidative Desulfurization of Dibenzothiophene[J];China Petroleum Processing & Petrochemical Technology;2014年03期

6 唐南方;趙小平;蔣宗軒;李燦;;分子氧為氧化劑磷釩酸鹽為催化劑超深度氧化脫除柴油中的二苯并噻吩[J];催化學(xué)報(bào);2014年09期

7 趙磊;田永勝;王光輝;邱江華;周勇;;CMC對(duì)HPMo/SiO_2結(jié)構(gòu)及其催化模型油氧化脫硫性能的影響[J];材料導(dǎo)報(bào);2014年24期

8 呂寶蘭;葉明琰;徐玉林;楊水金;;H_3PW_(12)O_(40)/TiO_2-SiO_2催化合成3,4-二氫嘧啶-2(1H)-酮衍生物[J];遼東學(xué)院學(xué)報(bào)(自然科學(xué)版);2015年01期

9 謝東;何其慧;蘇陽(yáng)洋;王童薇;許仁富;胡柏星;;MCM-41分子篩負(fù)載亞硒核過(guò)氧鎢酸鹽催化劑催化二苯并噻吩氧化脫硫（英文）[J];催化學(xué)報(bào);2015年08期

10 陳發(fā)旺;胡長(zhǎng)文;;多金屬氧簇催化研究進(jìn)展[J];化學(xué)進(jìn)展;2011年01期

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1 張銘;基于多酸材料的合成表征及其在燃油氧化脫硫中的應(yīng)用[D];江蘇大學(xué);2013年

2 林志榮;脈沖電場(chǎng)對(duì)醇酸常溫酯化反應(yīng)影響研究[D];華南理工大學(xué);2013年

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6 黃歡;吸附脫硫以及反應(yīng)吸附脫硫吸附劑的制備、表征及性能研究[D];華東理工大學(xué);2015年

7 胡小夫;金屬有機(jī)框架組裝雜多酸復(fù)合材料及其氧化脫硫性能[D];中國(guó)石油大學(xué)（華東）;2013年

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1 杜強(qiáng);摻雜稀土固體酸的制備及催化性能[D];四川師范大學(xué);2013年

2 顧婷婷;雜多酸（鹽）催化劑在酯化反應(yīng)中的應(yīng)用[D];聊城大學(xué);2014年

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