本文選題：金屬-有機骨架材料 + 羰基硫��； 參考：《催化學報》2017年08期

【摘要】：羰基硫(COS)廣泛存在于以煤、焦炭、渣油和天然氣等為原料生產(chǎn)的化工原料氣中,不僅腐蝕管道設(shè)備,使下游催化劑發(fā)生硫中毒,而且還會造成環(huán)境污染.因此,COS脫除具有重要意義.在各種方法中,催化水解COS(COS+H_2O→CO_2+H_2S)由于具有反應(yīng)條件溫和、轉(zhuǎn)化率高和副反應(yīng)少等優(yōu)點越來越受重視.其關(guān)鍵在于發(fā)展高效的催化劑.近年來,金屬-有機骨架材料(metal-organic frameworks,MOFs)由于其獨特的物理化學性質(zhì)引起人們廣泛關(guān)注.與傳統(tǒng)材料相比,MOFs不僅擁有超高的比表面積和規(guī)則的孔道結(jié)構(gòu),而且其結(jié)構(gòu)具有可設(shè)計性強和易調(diào)變等特點,是一類非常有潛力的多相催化劑.然而,目前MOFs在催化水解COS方面的研究應(yīng)用未見報道.此外,MOFs的合成方法主要有水/溶劑熱法、擴散法和微波輔助加熱法等.近年來新發(fā)展的電化學法具有合成效率高、操作方便和環(huán)境友好等優(yōu)點,在材料合成中顯示出巨大的優(yōu)越性,但利用電化學法合成MOFs相關(guān)研究還較少.本文采用快速溫和的電化學方法制備了典型的Cu-MOFs(HKUST-1).該方法可以有效縮短反應(yīng)時間,通過調(diào)節(jié)反應(yīng)電壓(15 30 V),在室溫下電解3 h,可得到一系列HKUST-1樣品.根據(jù)合成中設(shè)置的電壓值,樣品分別命名為HKUST-1-E15,HKUST-1-E20,HKUST-1-E25和HKUST-1-E30.XRD表征結(jié)果顯示,不同電壓下合成樣品的XRD譜圖與通過晶體數(shù)據(jù)擬合的HKUST-1圖出峰位置基本一致.SEM結(jié)果表明,合成電壓對樣品形貌的影響很大.HKUST-1-E15主要呈長棒狀結(jié)構(gòu),長約為15μm.隨著電壓的增大,HKUST-1-E20的形貌逐漸轉(zhuǎn)變?yōu)檩^短的四棱柱體.當電壓為25 V時,所得HKUST-1-E25呈八面體狀.進一步提高合成電壓,HKUST-1-E30顆粒變小,沒有特殊形貌,并出現(xiàn)明顯的團聚.COS水解測試結(jié)果顯示,不同電壓下合成樣品的活性差異大,這主要是由于樣品的形貌及比表面積差異引起的.其中,HKUST-1-E25樣品的活性較好.在150°C下,該樣品對COS的轉(zhuǎn)化率接近100%,比水熱法合成的HKUST-1-Hy的活性更高.在此基礎(chǔ)上,進一步對活性測試過程的條件進行優(yōu)化,發(fā)現(xiàn)當原料氣流速為30 mL/min,水溫為40°C時,催化劑的COS水解性能最優(yōu).此外,樣品的活性穩(wěn)定性測試結(jié)果顯示,相比傳統(tǒng)的氧化銅材料,HKUST-1是一類較穩(wěn)定的COS水解催化劑.
[Abstract]:Carbonyl sulfur (COS) is widely used in chemical raw gas produced from coal, coke, residuum and natural gas. It not only corrodes pipeline equipment and causes sulfur poisoning in downstream catalyst, but also causes environmental pollution. Therefore, the removal of COS is of great significance. Among the various methods, the catalytic hydrolysis of COS(COS H _ 2O CO_2 H _ 2s has attracted more and more attention due to its mild reaction conditions, high conversion rate and less side reactions. The key is to develop efficient catalysts. In recent years, metal-organic framework materials (metal-organic frameworks) have attracted wide attention due to their unique physical and chemical properties. Compared with traditional materials, MOFs not only have high specific surface area and regular pore structure, but also have the characteristics of high designability and easy to adjust, so they are a kind of potential heterogeneous catalysts. However, the application of MOFs in catalytic hydrolysis of COS has not been reported. In addition, the synthesis methods of MOFs mainly include hydrothermal method, diffusion method and microwave-assisted heating method. In recent years the newly developed electrochemical method has many advantages such as high synthesis efficiency convenient operation and environmental friendliness. It has shown great advantages in the synthesis of materials but there is little research on the synthesis of MOFs by electrochemical method. In this paper, the typical Cu-MOFsN HKUST-1 is prepared by a rapid and mild electrochemical method. This method can effectively shorten the reaction time. A series of HKUST-1 samples can be obtained by electrolysis at room temperature for 3 h by adjusting the voltage of the reaction. According to the voltage values set in the synthesis, the samples were named HKUST-1-E15 (HKUST-1-E20) HKUST-1-E25 and HKUST-1-E30.XRD characterization results showed that the XRD spectra of the synthesized samples at different voltages were basically consistent with the peak locations of the HKUST-1 diagrams fitted by crystal data. The synthesis voltage has great influence on the morphology of the sample. HKUST-1-E15 is a long rod structure with a length of about 15 渭 m. With the increase of voltage, the morphology of HKUST-1-E20 is gradually changed to a shorter tetrahedral cylinder. When the voltage is 25 V, the HKUST-1-E25 is octahedral. Further increasing the synthesis voltage, the HKUST-1-E30 particles become smaller and have no special morphology, and the results of hydrolytic test of obvious agglomeration. COS show that the activity of the synthesized samples varies greatly at different voltages. This is mainly due to the difference in the morphology and specific surface area of the sample. Among them, the activity of HKUST-1-E 25 was better. At 150 擄C, the conversion of COS was close to 100%, which was higher than that of HKUST-1-Hy synthesized by hydrothermal method. On this basis, the conditions of the activity test process were further optimized. It was found that the COS hydrolysis performance of the catalyst was optimal when the feed flow rate was 30 mL / min and the water temperature was 40 擄C. In addition, the results of activity stability test showed that HKUST-1 was a more stable COS hydrolysis catalyst than the traditional copper oxide material.
【作者單位】： 福州大學化肥催化劑國家工程研究中心;
【基金】：supported by the National Natural Science Foundation of China (21603034,21576051) the National High Technology Research and Development Program of China (863 Program,2015AA03A402)~~
【分類號】：O643.36

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