【作者】 李辉；

【导师】 于英民； 时敬涛；

【作者基本信息】 中国石油大学(华东) ， 化学工程（专业学位）， 2021， 硕士

【摘要】 溶剂脱沥青作为一种高效的重油加工技术,具有萃取深度大、精制效果好和工艺组合灵活等特点,被广泛应用于各大炼厂中。为了提高重质油的加工深度和高值化利用,本研究首先以催化裂化(FCC)油浆为原料,使用溶剂脱沥青工艺进行萃取,然后将得到的脱沥青油(DAO)经高温反应制备针状焦,再以长庆石化生产的脱油沥青(DOA)为原料,采用萃取-调和工艺制备出合格的50号和70号A等级石油道路沥青产品。以S70为萃取剂,采用常压萃取工艺对FCC油浆进行精制,考察了萃取温度、溶剂质量比和萃取级数对DAO性质的影响,发现当温度为80℃、溶剂比2:1和级数为2时制得的DAO中灰分含量最少,可以满足针状焦原料的质量标准。以正丁烷为萃取剂,采用超临界萃取工艺对FCC油浆进行萃取和组分切割,使用元素分析、四组分、红外光谱和氢核磁等方法对FCC油浆和DAO进行分析,发现油浆经超临界工艺萃取后,DAO中灰分、杂原子和多环芳烃的含量更少,芳香环系取代率得到提高,更加适合作为针状焦的制备原料。将FCC油浆和DAO进行焦化实验,使用偏光显微镜对生焦性质进行评价,发现原料组成和工艺条件均对生焦内部的组织结构影响明显。相对而言,灰分和杂原子含量低、芳烃较高的原料更易在合适的工艺下制得偏光性质好的生焦产品。将超临界萃取油制备的两种生焦在1300℃条件进行煅烧,并使用X射线衍射仪和电子显微镜对焦化产品的结构进行表征,发现高温煅烧可以促进生焦结构的进一步发展,最终得到片层排布紧密有序、纤维化明显的煅烧石油焦,但由于煅烧温度较低,目前制备的仍为易石墨化的针状焦产品。以长庆石化生产的DOA和FCC油浆为原料,采用萃取-调和工艺制备满足《JTG F40-2004公路沥青路面施工技术规范》要求的A等级石油道路沥青产品。DOA经常压溶剂脱沥青工艺萃取后,制得的精制沥青(RDAO)中重质组分含量降低,四组分分布得到改善。当外加0.5wt%的改性剂A101和1.5wt%的丁苯橡胶(SBR),在调和温度180℃～200℃,FCC油浆:RDAO=50:50和调和温度170℃～180℃,FCC油浆:减压渣油:RDAO=41.03:8.16:50.81两个条件下分别可以制得合格的50号和70号A等级石油道路沥青产品。更多还原

【Abstract】 As an efficient heavy oil processing technology,solvent deasphalting has the characteristics of high extraction depth,good refining effect,and flexible process combination,and is widely used in major refineries.In order to improve the processing depth and high-value utilization of heavy oil,this paper first uses FCC slurry as raw material and uses solvent deasphalting process for extraction and refining.The resulting deasphalted oil(DAO)was subjected to high-temperature thermal condensation to prepare needle coke products.Finally,Deoiled Asphalt(DOA)produced by Changqing petrochemical is used as the raw material,and the qualified 50#and 70#A-grade petroleum road asphalt products are prepared by the extraction and blending process.Using S70 as the extractant,the FCC slurry was extracted by atmospheric extraction process,and the effects of extraction temperature,solvent ratio and extraction on the properties of DAO.The study found that when the extraction temperature is 80°C,the solvent ratio is 2and the number of extraction stages is 2.The ash content in the DAO obtained is the least,which can meet the standards of needle coke raw materials.Using n-butane as the extractant,the supercritical extraction process was used to extract and cut the components of the FCC slurry.Using elemental analysis,heavy oil four-component,FTIR and ~1H-NMR methods to analyze FCC slurry and DAO,it can be found that after the slurry is extracted and refined,the content of ash,heteroatoms,and polycyclic aromatic hydrocarbons in DAO is less,and the aromatic ring substitution rate has also been improved.It is more suitable as a raw material for the preparation of needle coke.The FCC slurry and DAO were subjected to coking experiments,and a polarized microscope was used to evaluate the raw coke samples and raw oil.It shows that the raw material composition and process conditions have a significant impact on the properties of the raw coke.Relatively speaking,raw materials with low ash and heteroatom content and higher aromatics are easier to produce coke products with better polarizing properties under a suitable process.Two kinds of mesophase coke by supercritical extraction raw materials were calcined at 1300℃,and the structure of the calcined coke was characterized by XRD and SEM.It shows that the calcination process can promote the further development of the internal structure of the mesophase coke and make the the amorphous carbon is transformed to the crystalline carbon.In the calcined coke,more slices are arranged tightly and layered structure with obvious fibrosis.However,due to the lower calcining temperature,the needle coke products that are currently prepared are still easy to graphitize.Using Changqing DOA and FCC slurry as raw materials,the A-grade petroleum road asphalt product that meets the requirements of“JTG F40-2004 Technical Specification for Highway Asphalt Pavement Construction”standard is prepared by the extraction-blending process.After DOA atmospheric solvent deasphalting process is extracted,the heavy components in the refined asphalt(RDAO)obtained are significantly reduced.When 0.5wt%A101 and 1.5 wt%SBR are added,at the blending temperature of 180℃～200℃,FCC slurry:RDAO=50:50 and the temperature at 170℃～180℃,FCC slurry:Vacuum residue:RDAO=41.03:8.16:50.81 conditions,which can produce qualified 50#and 70#A-grade petroleum road asphalt products.更多还原