渣油加氢反应样品中含铁和含钙化合物溶解性能研究

Study of the dissolution performance of ferrum and calcium compounds in residue hydrogenation reaction samples

  • 摘要: 以某原油及其对应的减压渣油、加氢原料和加氢产品为研究对象,通过柱色谱分离法和溶剂抽提法,对油样中铁和钙化合物在组分中的含量、分布以及存在形态进行了研究。研究结果表明,柱色谱分离过程中,油样中的含铁或钙的化合物在色谱柱上产生吸附,损失了58%的铁化合物和76%的钙化合物;溶剂抽提法能够有效减少组分中金属元素的损失。原油中97%以上的铁和钙分布在减压渣油馏分中,减压渣油中60%−90%的铁和钙分布在胶质、沥青质组分中。渣油加氢反应过程中,铁、钙化合物主要是从胶质中得到脱除,整体脱除率接近30%,铁化合物更易结合在沥青质中而难以脱除。原油经过常减压蒸馏后,油溶性铁相对分布由95.6%降低为64.7%,水溶性铁相对分布由4.4%升高为35.3%。经过加氢反应后,38%左右的油溶性铁在反应中转化为水溶性铁,30%左右的油溶性钙在反应中转化为水溶性钙。

     

    Abstract: The content, distribution and forms of the ferrum or calcium compounds in a crude oil, the corresponding vacuum residue (VR), hydrogenation feedstock and hydrogenation products were studied. The separation method was studied by column chromatography and solvent extraction method. This work indicated that in the process of column chromatographic separation, some ferrum or calcium compounds in the oil samples were irreversibly adsorbed on the chromatographic column, resulting in the loss of 58% of the ferrum compounds and 76% of calcium compounds. The solvent extraction method could effectively reduce the loss of the metal components and was suitable for the study of the content of metal elements. More than 97% of the ferrum or calcium compounds were distributed in the VR fraction. The 60% to 90% of the ferrum or calcium compounds were distributed in the resin and asphaltene components. During the hydrogenation reaction, the ferrum or calcium compounds in vacuum residue were mainly removed from the resin components, and the overall removal ratio was close to 30%. The ferrum compounds prefered to bond in the asphaltene components and were difficult to remove. Through the process of atmospheric distillation and vacuum distillation of the crude oil, the relative distribution of the oil-soluble ferrum compounds decreased from 95.6% to 64.7%, and the relative distribution of the water-soluble ferrum compounds increased from 4.4% to 35.3%. Through the process of the hydrogenation reaction, 38% of the oil-soluble ferrum compounds were converted into the water-soluble ferrum compounds and 30% of the oil-soluble calcium compounds were converted into the water-soluble calcium compounds in the reaction.

     

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