石油学报(石油加工)
石油學報(石油加工)
석유학보(석유가공)
ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)
2014年
6期
1052-1058
,共7页
葛传长%龙东辉%乔文明%凌立成
葛傳長%龍東輝%喬文明%凌立成
갈전장%룡동휘%교문명%릉립성
乙烯渣油%平均分子结构%热稳定%热解行为%机理
乙烯渣油%平均分子結構%熱穩定%熱解行為%機理
을희사유%평균분자결구%열은정%열해행위%궤리
ethylene tar%average molecular structure%thermal stability%pyrolysis behavior%mechanism
以乙烯渣油为原料,采用1 H‐NMR、13C‐NMR表征渣油组分中各类型H、C的分布,并联合基质辅助激光解吸电离飞行时间质谱、元素分析设计了乙烯渣油的平均分子结构模型,同时采用热重技术研究了其热稳定和热反应性,利用管弹式反应器研究了乙烯渣油在320℃、350℃和420℃N2保护下的热转化反应特征。结果表明,乙烯渣油的平均相对分子质量约为247,芳香度为0.76,平均分子结构中烷基侧链与环烷结构并存;当温度为320℃和350℃时,乙烯渣油的热转化以裂解反应为主,产物主要为轻质油和气体,无焦生成,且液相产物芳香度随温度升高逐渐增大;而温度为420℃时,缩聚反应加剧并有固体焦生成,液相产物芳香 H(C)与脂肪H(C)的原子比也随之升高。
以乙烯渣油為原料,採用1 H‐NMR、13C‐NMR錶徵渣油組分中各類型H、C的分佈,併聯閤基質輔助激光解吸電離飛行時間質譜、元素分析設計瞭乙烯渣油的平均分子結構模型,同時採用熱重技術研究瞭其熱穩定和熱反應性,利用管彈式反應器研究瞭乙烯渣油在320℃、350℃和420℃N2保護下的熱轉化反應特徵。結果錶明,乙烯渣油的平均相對分子質量約為247,芳香度為0.76,平均分子結構中烷基側鏈與環烷結構併存;噹溫度為320℃和350℃時,乙烯渣油的熱轉化以裂解反應為主,產物主要為輕質油和氣體,無焦生成,且液相產物芳香度隨溫度升高逐漸增大;而溫度為420℃時,縮聚反應加劇併有固體焦生成,液相產物芳香 H(C)與脂肪H(C)的原子比也隨之升高。
이을희사유위원료,채용1 H‐NMR、13C‐NMR표정사유조분중각류형H、C적분포,병연합기질보조격광해흡전리비행시간질보、원소분석설계료을희사유적평균분자결구모형,동시채용열중기술연구료기열은정화열반응성,이용관탄식반응기연구료을희사유재320℃、350℃화420℃N2보호하적열전화반응특정。결과표명,을희사유적평균상대분자질량약위247,방향도위0.76,평균분자결구중완기측련여배완결구병존;당온도위320℃화350℃시,을희사유적열전화이렬해반응위주,산물주요위경질유화기체,무초생성,차액상산물방향도수온도승고축점증대;이온도위420℃시,축취반응가극병유고체초생성,액상산물방향 H(C)여지방H(C)적원자비야수지승고。
The average molecular structure of the ethylene tar was studied by a combination method of elemental analysis ,1 H NMR ,13 C NMR and matrix‐assisted laser desorption and ionization time‐of‐flight mass spectrometry(MALDI‐TOF‐MS) .The thermal stability and thermal reaction of the ethylene tar was analyzed by thermogravimetric method .The pyrolysis behavior of the ethylene tar was investigated at temperature of 320℃ , 350℃ and 420℃ in a tube bomb reactor under N2 atmosphere .Results showed that in the average molecular structure of ethylene tar there were both naphthenic ring and alkyl substitutions , with an average molecular mass of 247 and the aromaticity value of 0.76 .During the pyrolysis process of ethylene tar , the cracking reaction was dominated at the temperature of 320℃ and 350℃to produce light oils and gases with no coke‐like products .The aromaticity value of the liquid product increased steadily with the increase of temperature .While the pyrolysis temperature increased to 420℃ , the condensation reaction was intensified in the system , resulting in formation of solid coke and higher atomic ratio of aromatic H to aliphatic H , as well as aromatic C to aliphatic C .