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

CHARACTERIZATION OF SULFUR COMPOUNDS IN LIQUID PRODUCTS FROM RESIDUE CONTACT CRACKING PROCESS BY COMPREHENSIVE TWO-DIMENSIONAL GC WITH TIME-OF-FLIGHT MS

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C_2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(C_1~C_3)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(C_4^+)取代苯并噻吩的分布占优势。

Sulfides including phenyl alkyl sulfides, thiophenols, thiophenes, benzothiophenes, dihydrobenzothiophenes, naphthothiophenes, tetrahydro-dibenzothiophenes, benzonaphthothiophenes, benzodithiophenes, dibenzothiophenes and thiopyrans,phenanthrothiophenes in the liquid products from residue contact cracking process were identified and characterized by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry（GC × GC-TOFMS）. Based on group separation and tile effect in GC × GC-TOFMS, the research was mainly focused on the carbon number distribution in thiophenes, benzothiophenes and dibenzothiophenes in liquid products. Addition, fifteen individual molecules of C2-DBTs which are extensively concerned in oil processing were specially determined and recognized. Combined with residue contact cracking process, the effect of the activity of the contact cracking agent on the types and carbon distributions of the sulfides in the liquid products was investigated. It is found that the sulfur molecule species were similar in liquid products from one residue with different contact agents,while contents and distribution mode of them varies a lot. As for carbon number distribution of sulfur compounds in liquid products, taking benzothiophenes（BTs）as example, alkyl（C1- C3）BTs with low carbon number dominate in their homologues distribution when using strong agent, while alkyl（C4＋ ）BTs with relatively high carbon number dominate on weak agent.