【摘要】：流化催化裂化(FCC)油漿和煤焦油都是具有高沸點的煉油和煉焦裝置副產(chǎn)物,富含稠環(huán)芳香結(jié)構(gòu),可以作為制備針狀焦和其它高附加值化學(xué)品的原料,前提是必須高效脫除其中的固體顆粒。本研究針對這兩種裂解重油固含物的脫除和脫固裂解重油的高附加值利用進(jìn)行研究,為裂解重油高附加值利用技術(shù)開發(fā)奠定基礎(chǔ)。首先,本文采用靜電分離的手段對FCC油漿進(jìn)行了凈化處理。采用自行建立的一套靜電分離裝置,考察了原料性質(zhì)、操作條件以及裝置材質(zhì)特性等因素對FCC油漿靜電脫固效率的影響,初步探索多級靜電分離對其凈化效果的影響。由結(jié)果可知,在試驗溫度區(qū)間內(nèi),所選FCC油漿的粘度、電導(dǎo)率以及介電常數(shù)都滿足靜電分離要求。FCC油漿中的固含物主要有催化劑粉末、焦粉以及少量的金屬銻;FCC油漿體系中的介電常數(shù)和電導(dǎo)率大小順序為:固體雜質(zhì)FCC油漿;無機(jī)物質(zhì)有機(jī)焦粉。靜電分離裝置的材質(zhì)對FCC油漿凈化效果的影響較大,其中銅電極的凈化效果優(yōu)于鐵電極;在一定條件下,電極尺寸越大、填料的粒徑越小,凈化效果越好。對于操作條件,隨著電壓的升高,FCC油漿的凈化效果呈現(xiàn)先增大后減小的趨勢,最佳的電壓范圍為12至13kV;另外,凈化時間越長、溫度越高,FCC油漿的凈化效果越好,理想的操作條件為20至25min、130至150℃。采用多級靜電分離的方法可以明顯提高催化劑粉末的凈化效果,但對焦粉的凈化效果有限,簡單多級靜電試驗最好不要超過兩級。其次,采用助劑沉降分離和離心沉降的方法對煤焦油進(jìn)行了凈化處理�？疾炝酥鷦╊愋�、用量以及試驗條件對煤焦油凈化效果的影響,并初步設(shè)計了煤焦油的凈化工藝路線。由結(jié)果可以看出,該煤焦油中固含物主要由縮合度很高的有機(jī)物組成,且具有類似于炭黑的晶體結(jié)構(gòu)。紅外譜圖分析可知固含物中可能存在醇羥基或酚羥基結(jié)構(gòu),且具有多環(huán)芳香結(jié)構(gòu)。助劑沉降過程中優(yōu)選出的稀釋劑為輕油與洗油的混合物(質(zhì)量比1:1),優(yōu)選的劑油比為0.3:1。優(yōu)選出的固含物粘結(jié)助劑為洗油和正構(gòu)烷烴A的混合物,二者質(zhì)量比為0.5:1;優(yōu)選的劑油比為0.3:1。有機(jī)醇B對沉降體系中固體表面有較好的修飾作用。另外,加入少量的絮凝劑可以促進(jìn)固含物的聚沉,試驗優(yōu)選的絮凝劑為F,其最佳用量為1μg g-1。試驗中優(yōu)選的沉降溫度為75℃左右,沉降時間為24h。沉降試驗后,采用離心沉降脫除煤焦油殘留的細(xì)小顆粒,試驗中優(yōu)選的離心力為4000g、離心時間為5min。凈化后的煤焦油固含量可降至0.1%以下,凈化效率達(dá)98%。建立的助劑沉降法脫除煤焦油固含物的工藝流程,其操作簡單,成本低,非常適用于實際生產(chǎn)中的連續(xù)及自動化操作,可進(jìn)行推廣使用。最后,以煤焦油為例,研究了裂解重油高附加值利用新途徑,深入探討了裂解重油中富芳餾分化學(xué)儲氫特性及其在劣質(zhì)重油熱過程中釋氫提質(zhì)作用�？疾炝嗣航褂椭懈黟s分段的化學(xué)儲氫能力,深入探討了各餾分加氫后對委內(nèi)瑞拉減壓渣油熱改質(zhì)過程中生焦誘導(dǎo)期和產(chǎn)物性質(zhì)的影響,以及對延遲焦化產(chǎn)物物料組成及成焦形態(tài)的影響。由結(jié)果可知,試驗中反應(yīng)溫度350℃、初始?xì)鋲?.0MPa、反應(yīng)時間60min下c餾分的臨氫產(chǎn)物具有良好的供氫能力,因而優(yōu)選為儲氫劑C用于后續(xù)劣質(zhì)重油熱過程中釋氫提質(zhì)研究。選取委內(nèi)瑞拉減壓渣油實驗減黏裂化效果,優(yōu)選得到的試驗條件為:5%儲氫劑摻入比、400℃、40min,與空白減黏裂化效果相比較,使用儲氫劑使得生焦誘導(dǎo)期延長9min、生成油的黏度降低14%和安定性增加。對于煤焦油炭化反應(yīng),優(yōu)選的工藝條件為500℃、1.5MPa、2h。在此反應(yīng)條件下,c餾分成焦具有較好光學(xué)針狀結(jié)構(gòu)且焦炭的收率較高,具有制備針狀焦的潛在可行性。在分別與煤焦油瀝青組分和委內(nèi)瑞拉減渣混合炭化過程中,儲氫劑C比c餾分更有利于改善生成焦的形貌,同時降低焦炭的收率,改善效果更為明顯。
[Abstract]:The fluid catalytic cracking (FCC) oil slurry and coal tar are the by-products of oil refining and coking units with high boiling points, and are rich in the aromatic structure of the fused ring and can be used as raw materials for preparing needle coke and other high-value-added chemicals, provided that the solid particles in the oil slurry and the coal tar have to be efficiently removed. The purpose of this study is to study the removal of these two kinds of cracked heavy oil solids and the high added value of the desolid heavy oil, and to lay the foundation for the technology development of high added value of heavy oil. First, this paper purifies the FCC slurry by means of electrostatic separation. The effect of the material properties, operating conditions and the material properties of the device on the electrostatic removal efficiency of the FCC slurry is investigated by a set of self-established electrostatic separation device. The effect of the multi-stage electrostatic separation on the purification effect of the FCC slurry is studied. It can be seen from the results that the viscosity, the conductivity and the dielectric constant of the selected FCC slurry in the test temperature range meet the requirements for electrostatic separation. The solid contents in the FCC slurry are mainly catalyst powder, coke powder and a small amount of metallic antimony. The order of the dielectric constant and the electric conductivity in the FCC slurry system is: solid impurity FCC slurry; inorganic matter organic coke powder. The effect of the material of the electrostatic separation device on the purification effect of the FCC oil slurry is large, and the purification effect of the copper electrode is superior to that of the iron electrode; under certain conditions, the larger the size of the electrode, the smaller the particle size of the filler, and the better the purification effect. For operating conditions, with the increase of the voltage, the purification effect of the FCC slurry is first increased, and the best voltage range is 12 to 13 kV; in addition, the longer the purification time, the higher the purification effect, the better the purification effect of the FCC slurry, and the ideal operating condition is 20 to 25 min, and 130 to 150 DEG C. The method of multi-stage electrostatic separation can obviously improve the purification effect of the catalyst powder, but the purification effect of the focusing powder is limited, and the simple multistage electrostatic test is preferably not more than two stages. Secondly, the coal tar is subjected to a purification treatment by adopting an auxiliary sedimentation separation and a centrifugal sedimentation method. The effect of assistant type, dosage and test conditions on the purification effect of coal tar was investigated, and the process route of coal tar was designed. As a result, it can be seen that the solid content in the coal tar is mainly composed of organic matter with high degree of condensation and has a crystal structure similar to that of carbon black. In that analysis of the infrared spectrum, the hydroxyl or phenolic hydroxyl structure of the alcohol can be present in the solid content, and the structure has a polycyclic aromatic structure. The diluent used in the settling process of the auxiliary agent is a mixture of light oil and wash oil (mass ratio of 1:1), and the preferred oil ratio is 0.3:1. The preferred solid-containing binding aid is a mixture of the wash oil and the n-alkane A, the mass ratio of which is 0.5:1, and the preferred oil-to-oil ratio is 0.3:1. And the organic alcohol B has good modification effect on the solid surface in the sedimentation system. In addition, a small amount of a flocculant can be added to promote the precipitation of the solid, and the preferred flocculant is F, and the optimum amount is 1. mu. g-1. The settling time is about 75 鈩，

本文編號：2499712