【摘要】：延遲焦化-催化裂化聯(lián)合工藝是目前渣油利用的主要路線。但是,由于延遲焦化后焦化蠟油含氮量高,氮化物尤其是堿性氮化物在催化裂化過(guò)程中,會(huì)破壞催化劑的酸性活性中心,導(dǎo)致催化劑中毒失活,使得產(chǎn)出的汽柴油收率降低。同時(shí),高含量的氮化物及硫化物易導(dǎo)致產(chǎn)品油氧化安定性差,燃燒后造成嚴(yán)重的環(huán)境污染。針對(duì)這一不利現(xiàn)象,目前國(guó)內(nèi)外主要采用對(duì)焦化蠟油進(jìn)行吸附脫氮,加氫脫氮,酸法脫氮,絡(luò)合萃取脫氮等處理工藝。為了簡(jiǎn)化脫氮工藝,節(jié)約生產(chǎn)成本,本研究團(tuán)隊(duì)提出原位定向脫氮技術(shù),即在延遲焦化工藝過(guò)程中加入脫氮?jiǎng)?在重質(zhì)原料油焦化過(guò)程中直接脫除氮化物,進(jìn)入下道工序。本文根據(jù)結(jié)構(gòu)導(dǎo)向集總的方法建立了描述重質(zhì)原料油分子組成的模擬矩陣。通過(guò)編寫(xiě)反應(yīng)規(guī)則及構(gòu)建整個(gè)延遲焦化的反應(yīng)網(wǎng)絡(luò),建立了關(guān)于DN-3脫氮?jiǎng)┑姆磻?yīng)動(dòng)力學(xué)方程組。同時(shí)以原料油分子組成矩陣作為初值,采用四階龍格庫(kù)塔法進(jìn)行數(shù)值求解,從而獲得了模擬延遲焦化的產(chǎn)物分布。本文設(shè)計(jì)了新型DN-5脫氮?jiǎng)?同時(shí)考察了其在分餾塔底油模擬延遲焦化實(shí)驗(yàn)中的脫氮脫硫效果。在無(wú)需添加溶劑、相容劑并且省去了預(yù)焦化過(guò)程的前提下,進(jìn)一步降低了脫氮?jiǎng)┑奶砑恿?節(jié)約了生產(chǎn)成本。結(jié)果表明,DN-5添加量為3wt%時(shí),焦化蠟油中氮化物含量由3120.0ppm降低至1450.3 ppm,總氮脫除率為53.5%。其中,堿性氮化物含量由1088.0 ppm降低至342.0 ppm,堿氮脫除率為68.6%。氮化物含量已滿足催化裂化生產(chǎn)的常規(guī)要求。此外,DN-5對(duì)硫化物亦具有一定的脫除效果,硫化物脫除率為20%左右。
[Abstract]:The combined process of delayed coking and catalytic cracking is the main route of residue utilization at present. However, because of the high nitrogen content of coking gas oil after delayed coking, nitride, especially basic nitride, will destroy the acidic active center of catalyst, lead to deactivation of catalyst poisoning, and reduce the yield of gasoline and diesel oil. At the same time, high content of nitride and sulfides can lead to poor oxidation stability of oil and serious environmental pollution after combustion. In view of this disadvantage, adsorption denitrification, hydrodenitrification, acid denitrification, complexation extraction and denitrification are mainly used at home and abroad. In order to simplify denitrification process and save production cost, the research team proposed in situ directional denitrification technology, that is, adding denitrification agent in delayed coking process, removing nitride directly in the process of heavy feedstock coking, and entering the next process. In this paper, a simulation matrix for describing the molecular composition of heavy feedstock oil is established based on the structural directed set method. The reaction kinetics equations of DN-3 denitrifier were established by writing the reaction rules and constructing the whole network of delayed coking reaction. At the same time, using the molecular composition matrix of feedstock as the initial value, the fourth order Runge-Kutta method is used to solve the problem, and the product distribution of the simulated delayed coking is obtained. In this paper, a new DN-5 denitrification agent was designed, and the effect of denitrification and desulphurization in the simulated delayed coking experiment of the bottom oil of the fractionator was also investigated. Without adding solvent and compatibilizer and without the precoking process, the addition of denitrification agent is further reduced and the production cost is saved. The results showed that the nitride content in coking wax oil decreased from 3120.0ppm to 53.5% total nitrogen removal rate of 1450.3 ppm, when the addition of DN-5 was 3 wt%. The content of basic nitride decreased from 1088.0 ppm to 342.0 ppm,. The removal rate of alkaline nitrogen was 68.6%. Nitride content has met the conventional requirements of FCC production. In addition, DN-5 also has a certain removal effect on sulfides, and the removal rate of sulphide is about 20%.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TE624.5

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