本文選題：ZSM-35分子篩 + 晶粒��； 參考：《東北石油大學(xué)》2017年碩士論文

【摘要】：本文成功的合成了大小晶粒ZSM-35分子篩催化劑并對其進(jìn)行正丁烯骨架異構(gòu)化反應(yīng)。結(jié)合XRD、SEM、BET、TG等表征手段,對不同晶粒ZSM-35分子篩催化劑失活現(xiàn)象進(jìn)行分析研究。以L-ZSM-35為原粉,通過使用草酸與檸檬酸分別對L-ZSM-35分子篩進(jìn)行脫鋁,探究了其失活現(xiàn)象。考察了鋁粘結(jié)劑以及硅粘結(jié)劑對L-ZSM-35分子篩失活的影響。探究了L-ZSM-35分子篩在工業(yè)條件下的失活與再生現(xiàn)象得到結(jié)果如下:(1)小晶粒ZSM-35分子篩顯示了較好的催化性能,在WHSV=7、常壓的條件下,小晶粒ZSM-35分子篩的評價時間達(dá)到146 h,異丁烯的收率超過40%、異丁烯選擇性超過90%。同時,小晶粒分子篩具有較慢的積碳速度以及較大的積碳容量,積碳量可達(dá)12%以上。(2)根據(jù)分子篩失活的特點(diǎn)將積碳系統(tǒng)的分為兩部分:反應(yīng)第一階段積碳和反應(yīng)第二階段積碳。盡管第一階段積碳的積碳量比較大,占總積碳量的80%以上,但主要作用是覆蓋一些非選擇性的酸位點(diǎn)。而第二階段積碳的積碳量比較少,約占總積碳量的20%,卻是導(dǎo)致失活的關(guān)鍵。(3)當(dāng)草酸處理分子篩的濃度為3 mol/L、檸檬酸處理分子篩濃度為1 mol/L時L-ZSM-35分子篩催化效果最好,異丁烯收率均超過40%、異丁烯選擇性超過90%,評價時間超過65 h。脫酸處理有效的降低了分子篩的積碳量,增加了到第二階段的積碳容量。(4)經(jīng)二氧化硅粘結(jié)改性后的L-ZSM-35分子篩催,評價化效果良好,異丁烯收率均超過40%、異丁烯選擇性超過90%,評價時間超過60 h。外接孔道越大,越有利于延緩分子篩失活。(5)工業(yè)丁烯中含有的致毒物質(zhì)是一種永久致毒物質(zhì),會導(dǎo)致分子篩不可再生,且再生時間越長,再生效果越好。
[Abstract]:In this paper, large and small grain ZSM-35 molecular sieve catalysts were successfully synthesized and isomerization of n-butene was carried out. The deactivation of ZSM-35 molecular sieve catalysts with different grains was studied by means of XRDX SEM-BETTG and other characterization methods. The dealination of L-ZSM-35 molecular sieve was investigated by using oxalic acid and citric acid as raw powder. The effects of aluminum binder and silicon binder on the deactivation of L-ZSM-35 molecular sieve were investigated. The results of deactivation and regeneration of L-ZSM-35 molecular sieve under industrial conditions were as follows: (1) small grain ZSM-35 molecular sieve showed good catalytic performance. The evaluation time of small grain ZSM-35 molecular sieve is 146h, the yield of isobutene is more than 40 and the selectivity of isobutene is more than 90. At the same time, the small grain molecular sieve has a slow carbon deposition rate and a large carbon accumulation capacity, which can reach more than 12%.) according to the characteristics of molecular sieve deactivation, the carbon deposition system is divided into two parts: the first stage of the reaction and the second stage of the reaction. Although the carbon accumulation in the first stage is relatively large, accounting for more than 80% of the total carbon deposition, the main function is to cover some non-selective acid sites. However, in the second stage, the carbon deposition was relatively small, accounting for about 20% of the total carbon deposition, but it was the key factor leading to inactivation.) when the concentration of oxalic acid was 3 mol / L, the citric acid concentration was 1 mol/L, the catalytic effect of L-ZSM-35 zeolite was the best, and the catalytic effect of L-ZSM-35 zeolite was the best when the concentration of oxalic acid was 3 mol / L and citric acid was 1 mol/L. The yield of isobutene was over 40, the selectivity of isobutene was over 90, and the evaluation time was over 65 h. The deacidification treatment can effectively reduce the carbon accumulation of molecular sieve and increase the carbon accumulation capacity of the second stage. The L-ZSM-35 molecular sieve modified by silica binds is used to catalyze the molecular sieve, and the evaluation effect is good. The yield of isobutene was over 40, the selectivity of isobutene was over 90 and the evaluation time was more than 60 hours. The larger the external pore channel, the more favorable to delay the deactivation of molecular sieve. 5) the toxic substance contained in the industrial butene is a permanent toxic substance, which will lead to the non-regeneration of molecular sieve, and the longer the regeneration time, the better the regeneration effect.
【學(xué)位授予單位】：東北石油大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O623.121
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本文編號：1960708