石油炼制与化工 ›› 2017, Vol. 48 ›› Issue (4): 92-98.

• 分析与评定 • 上一篇    下一篇

采用全二维气相色谱-飞行时间质谱表征渣油接触裂化液体产物中含硫化合物

蔡新恒,龙军,张书红,周建,田松柏,刘泽龙,刘颖荣   

  1. 中国石化石油化工科学研究院
  • 收稿日期:2016-09-27 修回日期:2016-11-24 出版日期:2017-04-12 发布日期:2017-03-20
  • 通讯作者: 蔡新恒 E-mail:caixh.ripp@sinopec.com
  • 基金资助:
    国家重点基础研究发展规划“973”项目

CHARACTERIZATION OF SULFUR COMPOUNDS IN LIQUID PRODUCTS FROM RESIDUE CONTACT CRACKING PROCESS BY COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY COUPLED WITH TIME-OF-FLIGHT MASS SPECTROMETRY

    

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  • Received:2016-09-27 Revised:2016-11-24 Online:2017-04-12 Published:2017-03-20
  • Supported by:
     

摘要: 采用全二维气相色谱-飞行时间质谱(GC×GC-TOFMS)方法对渣油接触裂化液体产物中的含硫化合物进行分子水平表征,鉴定出苯硫醚、苯硫酚、噻吩类、苯并噻吩类、二氢苯并噻吩类、二苯并噻吩类、萘噻吩类、四氢二苯并噻吩类、苯并萘噻吩类、菲噻吩类、苯并二噻吩类及噻喃类等含硫分子。通过GC×GC-TOFMS的族分离和瓦片效应重点研究了渣油接触裂化液体产物中的噻吩类、苯并噻吩类及二苯并噻吩类化合物的碳数分布,并对油品加工过程中较关注的C2烷基取代二苯并噻吩类化合物进行了单体分子识别。结合渣油接触裂化工艺考察了接触剂活性对渣油接触裂化液体产物中的含硫化合物的分子类型分布及碳数分布的影响,结果表明,同种渣油在不同接触剂作用下接触裂化的液体产物中含硫化合物的分子类型分布基本相似,但含量分布存在明显差异。对于碳数分布,以苯并噻吩类为例,采用强微反活性的接触剂时,液体产物中的低碳数烷基(C1~C3)取代苯并噻吩的分布占优势,而采用弱活性接触剂时,产物中较高碳数烷基(C4+)取代苯并噻吩的分布占优势。

关键词: 全二维气相色谱, 飞行时间质谱, 渣油, 含硫化合物, 接触裂化, 分子表征

Abstract: Sulfur compounds in liquid products from residue contact cracking process were characterized by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS), results showing that there were sulfur species identified such as phenyl alkyl sulfides, thiophenols, thiophenes, benzothiophenes, dihydro-benzothiophenes, dibenzothiophenes, naphthothiophenes, tetrahydro-dibenzothiophenes, benzonaphthothiophenes, phenanthrothiophenes, benzodithiophenes and thiopyrans. Based on group separation and tile effect in GC×GC-TOFMS, carbon number distribution characteristics of thiophenes, benzothiophenes and dibenzothiophenes in liquid products were studied, in addition, 15 individual molecules of C2-DBTs which got extensive concern in oil processing were determined and recognized. Combined with residue contact cracking process, it was found that micro-reactor activities of contact agents had evident influence on molecular species and carbon number distribution of sulfur compounds in liquid products from residue cracking, and to be specific, sulfur molecule species were similar in products from one residue on different contact agents, while contents and distribution mode of them varied a lot. As for carbon number distribution of sulfur compounds in liquid products, taking benzothiophenes (BTs) for example, low carbon number alkyl (C1-C3) BTs dominated in their homologues distribution when using strong agent, while relatively high carbon number alkyl (C4+) BTs dominated on weak agent.

Key words: comprehensive two-dimensional gas chromatography, time-of-flight mass spectrometry, residue, sulfur compound, contact cracking, molecular characterization

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