本文關鍵詞： 乙烷氧氯化 氯化鐵 助劑作用 載體效應 氯乙烯時空產(chǎn)率　出處：《內(nèi)蒙古大學》2017年碩士論文　論文類型：學位論文

【摘要】：聚氯乙烯是世界五大通用塑料之一,被廣泛應用于許多領域。氯乙烯作為聚氯乙烯的單體,可以通過乙炔氫氯化,乙烯氧氯化,乙烷氧氯化三種工藝生產(chǎn)。乙炔氫氯化最明顯的缺點是高能耗,高污染。在發(fā)達國家,乙炔氫氯化已經(jīng)被乙烯氧氯化取代。雖然乙烯氧氯化在石油資源豐富的國家有一定的優(yōu)勢,但世界范圍內(nèi)的石油資源日漸緊缺,也導致乙烯氧氯化的成本在不斷的攀升。乙烷氧氯化采用乙烷為原料,生產(chǎn)工藝簡單。乙烷氧氯化是最經(jīng)濟,最環(huán)保的生產(chǎn)工藝。但缺乏高性能催化劑限制了乙烷氧氯化在工業(yè)上的應用。因而乙烷氧氯化催化劑的研究十分重要。本論文以氯化鐵為活性組分,采用浸漬法制備了一系列氯化鐵基乙烷氧氯化催化劑。對常見的堿金屬和堿土金屬進行篩選,從中選出最好的堿金屬/堿土金屬助劑。詳細研究了氯化鉀助劑的助劑效應以及不同混合載體對氯化鐵基乙烷氧氯化催化劑的載體效應。利用正交試驗研究了不同反應條件對催化劑性能的影響。結(jié)合X射線粉末衍射(XRD)、氮氣物理吸附、X射線光電子能譜(XPS)、氫氣程序升溫還原(H2-TPR)、穆斯堡爾譜(Mossbauer spectrum)、拉曼光譜(Raman spectrum)等表征手段的測試結(jié)果,得到以下結(jié)論:1.對常見的堿金屬和堿土金屬進行篩選,從中選出最好的堿金屬/堿土金屬助劑。發(fā)現(xiàn)堿金屬鹽/堿土金屬鹽助劑對氯化鐵基乙烷氧氯化催化劑有顯著的影響。添加助劑后的催化劑乙烷轉(zhuǎn)化率明顯提高,氯乙烯選擇性同樣明顯升高。并且,氯化鉀助劑的助劑作用最為明顯。2.詳細研究了氯化鉀助劑對氯化鐵基乙烷氧氯化催化劑的助劑效應。發(fā)現(xiàn)催化劑的乙烷轉(zhuǎn)化率和氯乙烯選擇性均隨著鉀鐵摩爾比x(0≤x≤2)的增加而增加。催化劑的活性明顯提高以及各種表征手段的結(jié)果證明了催化劑活性組分的變化(FeCl3→KFeCl4)。在此基礎上,本文嘗試提出部分反應機理,認為KFeCl4比FeCl3具有更高的氯氣釋放能力,最終導致了催化劑性能的提高。3.詳細研究了不同載體混合對氯化鐵基乙烷氧氯化催化劑的載體效應。發(fā)現(xiàn)二氧化鈰/二氧化鋯-氧化鋁混合載體催化劑中,二氧化鋯-氧化鋁混合載體催化劑表現(xiàn)更佳。多種表征手段,如XRD、XPS、拉曼光譜等,證明了二氧化鋯和氧化鋁之間發(fā)生相互作用,部分Al3+進入二氧化鋯晶格,導致二氧化鋯晶胞塌縮。這種相互作用有利于乙烷氧氯化活性的提高。4.對催化性能最好的FeK2和Zr50催化劑進行了正交試驗。發(fā)現(xiàn)不同乙烷流量、不同進料比和不同溫度對乙烷轉(zhuǎn)化率和氯乙烯選擇性都有影響,并最終影響氯乙烯時空產(chǎn)率。其中,乙烷流量與HC1流量之比對乙烷轉(zhuǎn)化率、氯乙烯選擇性和時空產(chǎn)率都有明顯影響。氯化氫過量與否、過量多少對乙烷氧氯化反應十分重要。
[Abstract]:Polyvinyl chloride (PVC) is one of the five universal plastics in the world and has been widely used in many fields. As a monomer of PVC, it can be chlorinated by hydrogen acetylene and oxychlorination of ethylene. Ethane oxychlorination is produced by three processes. The most obvious disadvantages of acetylene hydrochlorination are high energy consumption, high pollution. In developed countries. Hydrogen chlorination of acetylene has been replaced by ethylene oxychlorination. Although ethylene oxychlorination has some advantages in oil-rich countries, oil resources in the world are increasingly scarce. It also leads to the rising cost of ethane oxychlorination. Ethane oxychlorination using ethane as raw material, the production process is simple. Ethane oxychlorination is the most economical. The most environmentally friendly production process. However, the lack of high performance catalyst limits the industrial application of ethane oxychlorination. Therefore, the study of ethane oxychlorination catalyst is very important. In this paper, ferric chloride is used as the active component. A series of ferric chloride ethane oxychlorination catalysts were prepared by impregnation method. The common alkali metals and alkaline earth metals were screened. The best alkali metal / alkali earth metal promoter was selected. The promoter effect of potassium chloride promoter and the support effect of different mixed support on ferric chloride ethoxy chlorination catalyst were studied in detail. Effect of the same reaction conditions on the performance of the catalyst-combined X-ray powder diffraction (XRD). XRD). Nitrogen is physically adsorbed by X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H2-TPRN), Mossbauer spectrum (Mossbauer spectrum). The results of Raman spectroscopy and other characterization methods obtained the following conclusions: 1. Screening of common alkali metals and alkaline earth metals. The best alkali metal / alkali earth metal promoter was selected. It was found that the alkali metal salt / alkali earth metal additive had a significant effect on the catalyst of ferric chloride ethane oxygen chlorination. . Vinyl chloride selectivity was also significantly increased. And. The promoter effect of potassium chloride promoter on ferric chloride ethane oxychlorination catalyst was studied in detail. It was found that the conversion of ethane and the selectivity of vinyl chloride of the catalyst were with potassium iron friction. Erbix (. The increase of 0 鈮，

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