【摘要】：隨著原料油的日益重質(zhì)化以及低碳烯烴需求量的不斷增加,ZSM-5分子篩作為催化裂解催化劑中提高低碳烯烴收率及選擇性的活性組分已得到廣泛的工業(yè)應(yīng)用。ZSM-11分子篩具有與ZSM-5分子篩相似的結(jié)構(gòu)及組成,但其相關(guān)研究主要集中在輕烴芳構(gòu)化、甘油制丙烯腈等方面,而有關(guān)該分子篩催化裂解性能的文獻(xiàn)報(bào)道較少。因此,本文對(duì)ZSM-11分子篩的催化裂解性能進(jìn)行了系統(tǒng)地研究。本文采用XRD、SEM、低溫氮?dú)馕�、FT-IR以及NH3-TPD等方法對(duì)硅鋁比為36的ZSM-5(LTB-2)、ZSM-11(LQM-1)進(jìn)行結(jié)構(gòu)性質(zhì)表征及對(duì)比,表征結(jié)果顯示相比于ZSM-5,ZSM-11孔道較短,孔道交叉處空間大,比表面積大且含有較多介孔,但酸量及B酸比例下降。以撫順VGO及勝華VGO為原料,在500℃,劑油比為5條件下,使用固定床微反以及ZDT-1型中試裝置對(duì)兩者性能進(jìn)行考察,結(jié)果表明:兩種分子篩擁有相近的重油轉(zhuǎn)化能力及低碳烯烴選擇性,且ZSM-11分子篩在提高汽油辛烷值的同時(shí),還能減少汽油損失,說明ZSM-11分子篩具有多產(chǎn)低碳烯烴兼產(chǎn)高辛烷值汽油的性能。在提升管中試裝置上,以勝華VGO為原料,考察了模擬工業(yè)條件下LQM-1催化劑的活性衰減規(guī)律,結(jié)果表明:在反應(yīng)溫度540℃,劑油比為8,水油比為0.2,再生劑溫度為700℃,停留時(shí)間為1.8s的條件下,連續(xù)運(yùn)轉(zhuǎn)60h過程中,LQM-1催化的相對(duì)結(jié)晶度、比表面積以及酸量均降低;原料轉(zhuǎn)化率略有下降,維持在86%以上,干氣及焦炭收率降低,汽柴油收率維持穩(wěn)定;液化氣收率增加4.36個(gè)百分點(diǎn),液化氣中丙烯收率由15.33%增至18.37%,丁烯收率則由11.22%增加到14.24%。此外,干氣、液化氣以及汽油中烯烴的選擇性也有不同程度的提高。在提升管中試裝置上,以勝華VGO為原料,考察了劑油比、反應(yīng)溫度以及停留時(shí)間對(duì)LQM-1催化劑裂解性能的影響,結(jié)果表明:綜合考慮目的產(chǎn)物收率及選擇性,在反應(yīng)溫度為540℃,劑油比7~9,停留時(shí)間2.0s條件下可獲得最佳產(chǎn)物分布。該條件下原料轉(zhuǎn)化率可達(dá)87.44%,其中干氣及焦炭收率分別為7.5%和3.41%,液化氣收率為40.94%,丙烯收率為20.61%,且丙烯選擇性達(dá)到最大值50.34%,汽油收率為24.62%。
[Abstract]:With the increasingly heavy quality of feedstock and the increasing demand for low carbon olefins, ZSM-5 molecular sieve has been widely used as an active component in catalytic cracking catalyst to improve the yield and selectivity of low olefins. ZSM-11 molecular sieve has similar structure and composition to ZSM-5 molecular sieve. However, the related studies mainly focus on the aromatization of light hydrocarbons and the preparation of acrylonitrile from glycerol, but there are few reports on the catalytic cracking performance of this molecular sieve. Therefore, the catalytic cracking performance of ZSM-11 molecular sieve was studied systematically. In this paper, the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio of 36 are characterized by XRD,SEM, low temperature nitrogen adsorption, FT-IR and NH3-TPD. The results show that the structure and properties of ZSM-5 (LTB-2) and ZSM-11 (LQM-1) with Si-Al ratio 36 are compared with those of ZSM-5,. The ZSM-11 pore is short, the pore cross space is large, the specific surface area is large and contains more mesoporous, but the acid content and B acid ratio decrease. Using Fushun VGO and Victory VGO as raw materials, under the condition of 500 鈩，

本文編號(hào)：2309348