催化油浆和煤焦油中固含物脱除及高附加值利用研究
发布时间：2019-06-14 21:28
【摘要】：流化催化裂化(FCC)油浆和煤焦油都是具有高沸点的炼油和炼焦装置副产物,富含稠环芳香结构,可以作为制备针状焦和其它高附加值化学品的原料,前提是必须高效脱除其中的固体颗粒。本研究针对这两种裂解重油固含物的脱除和脱固裂解重油的高附加值利用进行研究,为裂解重油高附加值利用技术开发奠定基础。首先,本文采用静电分离的手段对FCC油浆进行了净化处理。采用自行建立的一套静电分离装置,考察了原料性质、操作条件以及装置材质特性等因素对FCC油浆静电脱固效率的影响,初步探索多级静电分离对其净化效果的影响。由结果可知,在试验温度区间内,所选FCC油浆的粘度、电导率以及介电常数都满足静电分离要求。FCC油浆中的固含物主要有催化剂粉末、焦粉以及少量的金属锑;FCC油浆体系中的介电常数和电导率大小顺序为:固体杂质FCC油浆;无机物质有机焦粉。静电分离装置的材质对FCC油浆净化效果的影响较大,其中铜电极的净化效果优于铁电极;在一定条件下,电极尺寸越大、填料的粒径越小,净化效果越好。对于操作条件,随着电压的升高,FCC油浆的净化效果呈现先增大后减小的趋势,最佳的电压范围为12至13kV;另外,净化时间越长、温度越高,FCC油浆的净化效果越好,理想的操作条件为20至25min、130至150℃。采用多级静电分离的方法可以明显提高催化剂粉末的净化效果,但对焦粉的净化效果有限,简单多级静电试验最好不要超过两级。其次,采用助剂沉降分离和离心沉降的方法对煤焦油进行了净化处理。考察了助剂类型、用量以及试验条件对煤焦油净化效果的影响,并初步设计了煤焦油的净化工艺路线。由结果可以看出,该煤焦油中固含物主要由缩合度很高的有机物组成,且具有类似于炭黑的晶体结构。红外谱图分析可知固含物中可能存在醇羟基或酚羟基结构,且具有多环芳香结构。助剂沉降过程中优选出的稀释剂为轻油与洗油的混合物(质量比1:1),优选的剂油比为0.3:1。优选出的固含物粘结助剂为洗油和正构烷烃A的混合物,二者质量比为0.5:1;优选的剂油比为0.3:1。有机醇B对沉降体系中固体表面有较好的修饰作用。另外,加入少量的絮凝剂可以促进固含物的聚沉,试验优选的絮凝剂为F,其最佳用量为1μg g-1。试验中优选的沉降温度为75℃左右,沉降时间为24h。沉降试验后,采用离心沉降脱除煤焦油残留的细小颗粒,试验中优选的离心力为4000g、离心时间为5min。净化后的煤焦油固含量可降至0.1%以下,净化效率达98%。建立的助剂沉降法脱除煤焦油固含物的工艺流程,其操作简单,成本低,非常适用于实际生产中的连续及自动化操作,可进行推广使用。最后,以煤焦油为例,研究了裂解重油高附加值利用新途径,深入探讨了裂解重油中富芳馏分化学储氢特性及其在劣质重油热过程中释氢提质作用。考察了煤焦油中各馏分段的化学储氢能力,深入探讨了各馏分加氢后对委内瑞拉减压渣油热改质过程中生焦诱导期和产物性质的影响,以及对延迟焦化产物物料组成及成焦形态的影响。由结果可知,试验中反应温度350℃、初始氢压7.0MPa、反应时间60min下c馏分的临氢产物具有良好的供氢能力,因而优选为储氢剂C用于后续劣质重油热过程中释氢提质研究。选取委内瑞拉减压渣油实验减黏裂化效果,优选得到的试验条件为:5%储氢剂掺入比、400℃、40min,与空白减黏裂化效果相比较,使用储氢剂使得生焦诱导期延长9min、生成油的黏度降低14%和安定性增加。对于煤焦油炭化反应,优选的工艺条件为500℃、1.5MPa、2h。在此反应条件下,c馏分成焦具有较好光学针状结构且焦炭的收率较高,具有制备针状焦的潜在可行性。在分别与煤焦油沥青组分和委内瑞拉减渣混合炭化过程中,储氢剂C比c馏分更有利于改善生成焦的形貌,同时降低焦炭的收率,改善效果更为明显。
[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，
本文编号：2499712
[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，
本文编号：2499712
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