基于釩取代的Keggin型鉬磷酸的石墨烯雜化材料及催化氧化脫硫活性研究
發(fā)布時間：2018-09-03 09:10
【摘要】：本論文中采用兩種方法制備了基于釩取代Keggin型鉬磷酸(H_5PV_2Mo_(10)O_(40)簡稱:POVM)的石墨烯雜化材料,系統(tǒng)研究了該材料在燃料油脫硫反應(yīng)中的催化活性。主要內(nèi)容及創(chuàng)新性研究如下:1.利用乙二胺還原氧化石墨烯得到胺功能化的石墨烯雜化物,將其浸泡在多酸的水溶液中制備了多酸石墨烯雜化材料(POVM-rGO-1)。在材料的合成過程中,通過調(diào)節(jié)乙二胺和多酸的用量,可以控制材料表面胺基的數(shù)量以及多酸的擔(dān)載量。經(jīng)實(shí)驗(yàn)發(fā)現(xiàn),將50mgGO分散在10mL水中,加入0.1mL乙二胺還原,而后將rGO浸泡在20mg/mL,10mL的多酸水溶液中可以得到催化效果最好的材料(POVM-rGO-1a)。雖然催化劑可以較好的分散在油相中,但是在加入過氧化氫之后,催化劑出現(xiàn)團(tuán)聚現(xiàn)象。這可能有兩方面原因,一方面,催化劑表面的胺基基團(tuán)和過氧化氫之間形成氫鍵;另一方面,多酸具有極強(qiáng)的親水性,而過氧化氫溶液中含有大量水。這兩種原因?qū)е麓呋瘎└菀拙奂谶^氧化氫相,而過氧化氫相的強(qiáng)極性使其不能在油相中良好的分散,因此也破壞了催化劑在油相中的分散�；诖朔N情況,在體系中加入了萃取劑乙腈,形成了萃取-催化氧化脫硫體系。乙腈可以從油相中萃取一部分的硫化物,并且過氧化氫和催化劑都更容易分散在極性較強(qiáng)的乙腈相中。當(dāng)乙腈中的硫化物被氧化為相應(yīng)的砜時,隨著攪拌的過程,會再次萃取一部分硫化物,直至達(dá)到完全脫硫。10mL,500ppm的模擬油中加入5m L的乙腈,0.05g催化劑(POVM-rGO-1a),0.5mL 30%過氧化氫,在60℃油浴中攪拌30min轉(zhuǎn)化率達(dá)到100%。催化劑可以使用離心方法分離,重復(fù)使用5次依然保持較高的活性。2.采用光還原的方法,利用乙二醇還原POVM得到的雜多藍(lán)來還原氧化石墨烯,得到材料(POVM-rGO-2)。以氧氣為氧化劑,異丁醛為犧牲試劑,80℃時,5h,0.1g的POVM-rGO-2可以催化10mL的500ppm的模擬油實(shí)現(xiàn)完全脫硫。
[Abstract]:In this paper, graphene hybrid materials based on vanadium substituted Keggin molybdenum phosphoric acid (HAP5PV2Mo10 O40) were prepared and their catalytic activity in desulfurization of fuel oil was systematically studied. The main contents and innovative research are as follows: 1. The graphene hybrid material (POVM-rGO-1) was prepared by using ethylenediamine to reduce graphene oxide to amine-functionalized graphene hybrid material, which was immersed in aqueous solution of polyacid. The amount of amino groups on the surface and the loading of polyacids can be controlled by adjusting the amount of ethylenediamine and polyacid during the synthesis of the materials. It was found that the best catalytic material (POVM-rGO-1a) could be obtained by dispersing 50mgGO in 10mL water adding 0.1mL ethylenediamine and then immersing rGO in 20mg / mL 10 mL polyacid solution. Although the catalyst can be well dispersed in the oil phase, but after the addition of hydrogen peroxide, the catalyst appears agglomeration. There may be two reasons for this: on the one hand, hydrogen bonds are formed between the amine groups on the surface of the catalyst and hydrogen peroxide; on the other hand, polyacids have a strong hydrophilicity, and hydrogen peroxide solution contains a lot of water. These two reasons cause the catalyst to concentrate in the hydrogen peroxide phase more easily, and the strong polarity of the hydrogen peroxide phase makes it can not be well dispersed in the oil phase, thus destroying the dispersion of the catalyst in the oil phase. In this case, the extractant acetonitrile was added to the system to form an extraction-catalytic oxidation desulfurization system. Acetonitrile can extract part of sulfides from oil phase, and hydrogen peroxide and catalyst are more easily dispersed in highly polar acetonitrile phase. When the sulfides in acetonitrile are oxidized to corresponding sulfone, some sulfides will be extracted again with the stirring process, until the amount of acetonitrile 0.05g catalyst (POVM-rGO-1a) of 0.5 mL 30% hydrogen peroxide is added to the simulated oil of complete desulphurization. The conversion rate of 30min agitated in 60 鈩，
本文編號：2219532
[Abstract]:In this paper, graphene hybrid materials based on vanadium substituted Keggin molybdenum phosphoric acid (HAP5PV2Mo10 O40) were prepared and their catalytic activity in desulfurization of fuel oil was systematically studied. The main contents and innovative research are as follows: 1. The graphene hybrid material (POVM-rGO-1) was prepared by using ethylenediamine to reduce graphene oxide to amine-functionalized graphene hybrid material, which was immersed in aqueous solution of polyacid. The amount of amino groups on the surface and the loading of polyacids can be controlled by adjusting the amount of ethylenediamine and polyacid during the synthesis of the materials. It was found that the best catalytic material (POVM-rGO-1a) could be obtained by dispersing 50mgGO in 10mL water adding 0.1mL ethylenediamine and then immersing rGO in 20mg / mL 10 mL polyacid solution. Although the catalyst can be well dispersed in the oil phase, but after the addition of hydrogen peroxide, the catalyst appears agglomeration. There may be two reasons for this: on the one hand, hydrogen bonds are formed between the amine groups on the surface of the catalyst and hydrogen peroxide; on the other hand, polyacids have a strong hydrophilicity, and hydrogen peroxide solution contains a lot of water. These two reasons cause the catalyst to concentrate in the hydrogen peroxide phase more easily, and the strong polarity of the hydrogen peroxide phase makes it can not be well dispersed in the oil phase, thus destroying the dispersion of the catalyst in the oil phase. In this case, the extractant acetonitrile was added to the system to form an extraction-catalytic oxidation desulfurization system. Acetonitrile can extract part of sulfides from oil phase, and hydrogen peroxide and catalyst are more easily dispersed in highly polar acetonitrile phase. When the sulfides in acetonitrile are oxidized to corresponding sulfone, some sulfides will be extracted again with the stirring process, until the amount of acetonitrile 0.05g catalyst (POVM-rGO-1a) of 0.5 mL 30% hydrogen peroxide is added to the simulated oil of complete desulphurization. The conversion rate of 30min agitated in 60 鈩，
本文編號：2219532
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