【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程中,會破壞催化劑的酸性活性中心,導致催化劑中毒失活,使得產(chǎn)出的汽柴油收率降低。同時,高含量的氮化物及硫化物易導致產(chǎn)品油氧化安定性差,燃燒后造成嚴重的環(huán)境污染。針對這一不利現(xiàn)象,目前國內(nèi)外主要采用對焦化蠟油進行吸附脫氮,加氫脫氮,酸法脫氮,絡合萃取脫氮等處理工藝。為了簡化脫氮工藝,節(jié)約生產(chǎn)成本,本研究團隊提出原位定向脫氮技術,即在延遲焦化工藝過程中加入脫氮劑,在重質原料油焦化過程中直接脫除氮化物,進入下道工序。本文根據(jù)結構導向集總的方法建立了描述重質原料油分子組成的模擬矩陣。通過編寫反應規(guī)則及構建整個延遲焦化的反應網(wǎng)絡,建立了關于DN-3脫氮劑的反應動力學方程組。同時以原料油分子組成矩陣作為初值,采用四階龍格庫塔法進行數(shù)值求解,從而獲得了模擬延遲焦化的產(chǎn)物分布。本文設計了新型DN-5脫氮劑,同時考察了其在分餾塔底油模擬延遲焦化實驗中的脫氮脫硫效果。在無需添加溶劑、相容劑并且省去了預焦化過程的前提下,進一步降低了脫氮劑的添加量,節(jié)約了生產(chǎn)成本。結果表明,DN-5添加量為3wt%時,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%.
【學位授予單位】：華東理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TE624.5

【參考文獻】

相關期刊論文 前10條

1 何仲文;裘志浩;殷強鋒;石堯麒;周長路;辛忠;;原位定向焦化脫氮劑的篩選與應用[J];現(xiàn)代化工;2016年10期

2 倪騰亞;劉紀昌;沈本賢;孫輝;;基于結構導向集總的渣油分子組成矩陣構建模型[J];石油煉制與化工;2015年07期

3 李澤坤;;高氮原料催化裂化轉化研究[J];石油煉制與化工;2015年05期

4 韓璐;周亞松;魏強;羅怡;王靖宇;;NiW/Al_2O_3催化劑酸性與加氫活性的調(diào)變及對重油加氫脫氮性能的影響[J];燃料化學學報;2014年10期

5 田立達;沈本賢;劉紀昌;;基于結構導向集總模擬渣油分子組成[J];石化技術與應用;2012年05期

6 秦麗華;萬書寶;郭立艷;賈云剛;;焦化蠟油絡合脫氮-蠟催組合工藝研究[J];化工科技市場;2009年02期

7 史權;趙鎖奇;徐春明;侯讀杰;;傅立葉變換離子回旋共振質譜儀在石油組成分析中的應用[J];質譜學報;2008年06期

8 郭立艷;萬書寶;趙光輝;秦麗華;;焦化蠟油絡合脫氮用作催化裂化摻煉進料的研究[J];石油煉制與化工;2008年10期

9 袁起民;王屹亮;李春義;楊朝合;山紅紅;;焦化蠟油兩段提升管催化裂化研究[J];中國石油大學學報(自然科學版);2007年01期

10 陳國強;劉少兵;產(chǎn)圣;;催化裂化抗堿氮劑的研究[J];煉油技術與工程;2006年06期

，

本文編號：2422550