Distribution and Form of Iron and Calcium Compounds Before and After Residue Hydrogenation Under Different Space Velocities

The distribution and form of iron and calcium compounds were studied using hydrogenation feedstock and hydrogenation products with different space velocities as the research object.The content of metallic elements,such as calcium and iron in hydrogenation feedstock,and extract samples were determined via flame atomic absorption spectrometry.The water-soluble iron and calcium species in oil samples were determined by an IC2010 high-throughput ion chromatograph.Nearly 60%-80%of the iron or calcium compounds were mainly concentrated in resins and asphaltenes.Iron and calcium compounds mainly exist in the form of oil-soluble metal species in hydrogenation feedstock and hydrogenation products.Under certain conditions of reaction temperature,pressure,and volume ratio of hydrogen to oil,when the reaction space velocity was 0.6 h^(−1),about 30%of the iron or calcium compounds were converted from oil-soluble to water-soluble species after hydrogenation.When the reaction space velocity was decreased from 1.70 to 0.60 h^(−1),the proportion of iron compounds converted from oil-soluble to water-soluble increased from 8.4%to 28%.Moreover,the proportion of calcium compounds converted from oil-soluble to water-soluble increased from 10%to 37%.This denotes that with decreasing reaction space velocity,the ratio of oil-soluble to water-soluble species increases.Water-soluble iron and calcium compounds are present in the form of inorganic salts,such as chlorate and sulfate.This study helps in understanding the removal mechanism of iron and calcium compounds and optimizing the operating conditions of residue hydrogenation.

Reaction Process of Heavy Hydrocarbons Hydrogenation in Ebullated Bed

The properties and structural changes of unconverted oil(UCO)obtained from ebullated bed hydrogenation at different residue conversion rates were analyzed to clarify the reaction process of heavy components.Meanwhile,the processing routes of UCO,delayed coking,and solvent deasphalting,were investigated.The results showed that with the increase of conversion,the impurity removal rate increased;meanwhile the contents of sulfur and metal in UCO decreased,while the contents of nitrogen and residual carbon increased,and the colloidal stability of UCO became worse.The structural parameters of UCO indicated that the change in molecular structure of heavy oil mainly covered the opening of cycloalkanes ring,hydrogenation saturation of aromatic rings and dealkylation reaction during hydrogenation in the ebullated bed;the aromatic structure was basically unchanged at high conversion,and was mainly due to the ring opening of cycloalkanes and the fracture reaction of alkyl side chains.The coking route of UCO showed that low sulfur petroleum coke with different grades could be prepared by adjusting the conversion in ebullated bed to produce UCOs with different properties.The coke generating coefficient and sulfur transfer coefficient in UCO coking process were higher than those in residue coking.The properties of deasphalted oil(DAO)of UCO were significantly improved and could be used as FCC or hydrocracking feedstock.The DAO yield of UCO feedstock at high conversion was higher,and its sulfur content was lower and CCR value was higher.