新型納米級Cu基催化劑的合成及性能研究
發(fā)布時間:2018-04-23 21:35
本文選題:CO + 甲醇 ; 參考:《西安石油大學》2017年碩士論文
【摘要】:甲醇是重要的有機化工原料以及C1化學的基礎物質(zhì),在有機合成、染料、農(nóng)藥、涂料及國防等工業(yè)領域被廣泛應用。近幾年在科學技術的不斷發(fā)展下,甲醇的用途拓展迅猛,并且逐漸成為一種潛在的車用燃料以及電池燃料。我國的能源特點是富煤、缺油,一次能源以煤為主的格局將長期延續(xù)下去,汽、柴油等液體燃料的短缺現(xiàn)象將日趨嚴重,發(fā)展替代燃料特別是煤基潔凈替代燃料勢在必行,而大力發(fā)展煤基醇類(主要是甲醇)代用燃料在中國是完全合乎國情、現(xiàn)實可行的。上世紀60年代以來,合成甲醇催化劑在國內(nèi)外的研究領域受到重視,雖然從合成氣出發(fā)合成甲醇已經(jīng)實現(xiàn)工業(yè)化,但相較于國外研究而言,國內(nèi)Cu基催化劑還存在較大差距。本文結(jié)合反應機理、反應熱力學和動力學研究了不同組分、制備參數(shù)對CO催化加氫制備甲醇的影響,采用共沉淀法制備不同Cu含量、Zn/Al比、助劑Mn含量的催化劑樣品,采用微型固定床反應器對其進行活性評價,與催化劑樣品的XRD、BET、H_2-TPR、NH3-TPD、SEM、TEM、FTIR等表征結(jié)果進行關聯(lián),確定當催化劑Cu:Zn:Al:Mn摩爾比為1:2:2:0.05,經(jīng)復頻超聲(低頻22kHz、高頻40kHz)處理,溶液濃度為1.5mol/L,pH為7.5,焙燒溫度為550℃、焙燒時間為7h時,催化劑活性較優(yōu)。實驗結(jié)合CO加氫反應動力學及熱力學,確定反應工藝的主要影響因素為反應壓力、反應溫度、空速及H_2/CO,通過對篩選的活性及選擇性較優(yōu)催化劑進行活性評價,確定優(yōu)化反應條件為:反應溫度250℃,反應壓力6.0MPa,H_2/CO比2.5,液時空速5000h-1,在該反應條件下,CO轉(zhuǎn)化率達到98.50%,甲醇選擇性可達到96.51%,并且催化劑性能穩(wěn)定,使用壽命較長。
[Abstract]:Methanol is an important organic chemical raw material and basic material of C1 chemistry. It is widely used in organic synthesis, dyes, pesticides, coatings and national defense industries. In recent years, with the development of science and technology, the use of methanol has expanded rapidly, and gradually become a potential fuel for vehicles and fuel cells. The energy characteristics of our country are rich in coal and lack of oil. The pattern of primary energy based on coal will continue for a long time. The shortage of liquid fuels such as steam and diesel will become more and more serious. It is imperative to develop alternative fuels, especially coal based clean alternative fuels. The development of coal-based alcohols (mainly methanol) substitute fuels in China is fully in line with the national conditions and practical. Since the 1960s, methanol synthesis catalysts have been paid more attention in the domestic and foreign research fields. Although methanol synthesis from syngas has been industrialized, there is still a big gap between domestic and foreign research. Based on the reaction mechanism, thermodynamics and kinetics, the effects of different components and preparation parameters on the catalytic hydrogenation of CO to methanol were studied in this paper. The samples of different Cu content Zn / Al ratio and mn content of auxiliaries were prepared by coprecipitation method. The microscale fixed-bed reactor was used to evaluate its activity, which was correlated with the characterization results of XRDD-BETH _ 2-TPR-NH _ 3-TPD _ 3-TPDH _ (TM) T _ (TM) T _ (T) IR. It was determined that when the molar ratio of catalyst Cu:Zn:Al:Mn was 1: 2: 2: 0.05, the catalyst was treated by complex frequency ultrasound (low frequency 22 kHz, high frequency 40 kHz). When the solution concentration was 1.5 mol / L, pH was 7.5, calcination temperature was 550 鈩,
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