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淖毛湖煤热解重油直接转化制备芳烃化合物研究

黄澎 吴艳 马博文 毛学锋 刘敏

黄澎, 吴艳, 马博文, 毛学锋, 刘敏. 淖毛湖煤热解重油直接转化制备芳烃化合物研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60039-7
引用本文: 黄澎, 吴艳, 马博文, 毛学锋, 刘敏. 淖毛湖煤热解重油直接转化制备芳烃化合物研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60039-7
HUANG Peng, WU Yan, MA Bo-wen, MAO Xue-feng, LIU Min. Study on direct conversion of naomaohu coal pyrolysis heavy oil to aromatics[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60039-7
Citation: HUANG Peng, WU Yan, MA Bo-wen, MAO Xue-feng, LIU Min. Study on direct conversion of naomaohu coal pyrolysis heavy oil to aromatics[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60039-7

淖毛湖煤热解重油直接转化制备芳烃化合物研究

doi: 10.1016/S1872-5813(21)60039-7
基金项目: 国家重点研发计划(2016YFB0600305)资助
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    Tel: 010-84262941, E-mail: squallok@qq.com

  • 中图分类号: TQ523;TE624

Study on direct conversion of naomaohu coal pyrolysis heavy oil to aromatics

Funds: The project was supported by the National Key Research and Development Project (2016YFB0600305)
  • 摘要: 采用实沸点蒸馏对新疆淖毛湖煤热解焦油进行了馏分分离,对其中> 320 ℃重质馏分进行四组分分析可以发现,胶质含量28.84%,沥青质含量35.12%,属于加氢中很难以转化的组分;13C-NMR结果显示,重油中芳香碳相对摩尔占比71.16%,说明重质馏分中芳香族化合物占主体地位。采用悬浮床+固定床联合裂化工艺处理重质馏分,并对产物油进行分析,结果显示,沥青质胶质等几乎完全转化,< 180 ℃石脑油收率66.95%,> 180 ℃柴油馏分收率17.84%,硫、氮、氧等杂原子得到深度脱除。对< 180 ℃石脑油进行催化重整,环烷烃减少了60.23%,芳香烃增加了65.8%,说明重整过程中主要发生了环烷烃脱氢芳化反应,正构烷烃减少了13.42%,说明同时伴有正构烷烃异构化和环化反应。催化重整产物油中苯、甲苯、二甲苯及乙苯的含量较多,分别为11.97%、23.15%、21.43%、3.48%。煤热解重油直接转化过程中煤基本结构单元的传递性得到了显著的体现。
  • 图  1  悬浮床+固定床工艺流程示意图

    Figure  1.  Process flow chart of suspended bed and fixed bed

    图  2  重整流程示意图

    Figure  2.  Flowchart of hydroforming

    1: compressor; 2: raw material tank; 3: feed pump; 4: preheater; 5: reforming reactor; 6: separator

    图  3  热解重油四组分分析

    Figure  3.  Analysis of heavy oil fraction components

    图  4  重油馏分13C-NMR谱图

    Figure  4.  13C-NMR spectrum of heavy oil

    图  5  加氢裂化全流程物料平衡

    Figure  5.  Material balance in hydrocracking process

    图  6  催化重整前后族组成的变化分析

    Figure  6.  Analysis of group composition before and after catalytic reforming

    (a): n-paraffins; (b): i-paraffins; (c): Naphthene; (d): Aromatics

    图  7  芳烃脱氢反应

    Figure  7.  Dehydrogenation and aromatizing reactions

    图  8  链烷烃环化脱氢反应

    Figure  8.  cyclization and dehydrogenation reactions

    图  9  异构化反应

    Figure  9.  isomerization reaction

    图  10  重整油中主要芳烃化合物含量对比

    Figure  10.  Main benzene compounds content of the reformed oil

    图  11  全流程物料平衡

    Figure  11.  Material Balance

    图  12  煤焦油生产芳烃技术路线图

    Figure  12.  Technical route to produce aromatic hydrocarbon from coal tar

    表  1  淖毛湖煤焦油及重质馏分性质

    Table  1.   Properties of coal tar and heavy oil

    PropertiesSample
    coal tar> 320 ℃ heavy oil
    Density/(kg·cm−31.0211.059
    H w/%8.988.07
    C w/%84.2785.43
    S w/%0.090.11
    N w/%0.881.23
    H/C1.281.13
    下载: 导出CSV

    表  2  淖毛湖煤焦油蒸馏

    Table  2.   Coal tar distillation results

    t / ℃Distillate yield w/%Cumulative yield w/%
    < 23014.4114.41
    230−2807.8922.30
    275−3007.7930.09
    280−3207.2237.31
    320−3504.8442.15
    > 35057.85100.00
    下载: 导出CSV

    表  3  联合裂化工艺反应条件

    Table  3.   Reaction conditions of combined cracking process

    Suspended bed reactor
    t /℃p/MPaspace velocity /h−1gas-liquid ratio (v/vcatalyst amount w/%recycle ratio
    450190.720000.030.15
    Fixed bed reactor
    t /℃p/MPagas-liquid ratio (v/vspace velocity /h−1
    refining reactorcracking reactor
    35039015.012000.5
    下载: 导出CSV

    表  4  悬浮床加氢裂化催化剂主要性质

    Table  4.   Properties of suspended hydrocracking catalyst

    FeaturesAnalysis method
    AppearanceYellow
    powder
    Purity w/%> 99HPLC/ICP
    Particle size/mm< 0.1
    Mo w/%27−29SH/T0749
    S w/%24−28SH/T0749
    Melting point/℃≮ 250GB/T2539
    下载: 导出CSV

    表  5  固定床加氢裂化催化剂主要性质

    Table  5.   Properties of fixed-bed hydrocracking catalyst

    CatalystRefiningCracking
    Composition w/%
    NiO2.8−4.35.1−7.5
    MoO321.6−24.2
    WO319.6−24.8
    Carrierγ-Al2O3γ-Al2O3-SiO2
    Shapeclovercylinder
    Surface area A/(m2·g−1≮190≮170
    Mechanical strength/(N·mm−1≮18≮18
    下载: 导出CSV

    表  6  重整催化剂性质

    Table  6.   Properties of reforming catalyst

    Composition
    w/%
    CarrierSurface area A/
    (m2·g−1
    Pore
    volume/
    (mL·g−1
    mechanical
    strength/
    (N·mm−1
    PtReClγ-Al2O3> 1800.45−0.55> 10
    下载: 导出CSV

    表  7  四组分的元素分析

    Table  7.   Four-component element analysis

    FractionElement analysis w/%
    HCO*NS
    Saturated8.2984.396.211.020.09
    Aromatic8.1785.115.660.990.07
    Colloid8.0187.163.381.340.11
    Asphaltene7.6587.533.411.270.14
      *: by difference
    下载: 导出CSV

    表  8  重油13C-NMR谱图归属及相对含量

    Table  8.   13C-NMR spectrum attribution and relative content of heavy oil

    Chemical shift δPeak attributionRelative molar ratio / %
    0−170visible carbon100
    10−70Aliphatic carbon28.84
    1.10−28methyl carbon, naphthenic carbon14.63
    1.228−70methylene, quaternary, α carbon on aromatic carbon14.21
    2100−170Aromatic carbon71.16
    2.1100−130secondary carbon linked by aromatic rings,
    tertiary carbon, aromatic carbon with protons
    33.01
    2.3130−150aromatic carbon linked to carbon bond37.57
    2.6150−170aromatic carbon linked to heteroatoms (N, S)0.58
    170−188carboxyl carbon
    188−220carbonyl carbon
    下载: 导出CSV

    表  9  加氢裂化产物性质分析

    Table  9.   Properties of hydrocracking products

    Properties< 180 ℃> 180 ℃
    Dnsity/(kg·m−3770.1876.1
    Bromine value0
    Refractive index1.42231.4633
    Aromatic potential w/%71.8
    Cetane number39
    Freezing point/℃−41
    Average molecular weight110190
    Elemental analysis w/%C86.2387.06
    H13.7712.94
    H/C1.921.78
    Trace analysis/(mg·kg−1N1.05.1
    Snd*1.1
      *not detected
    下载: 导出CSV

    表  10  催化重整试验

    Table  10.   The experimental result of catalytic reforming

    Parameter Value
    Input w/%
    Naphtha100
    Output w/%
    Reformed oil91.12
    H23.56
    C1−45.32
    Total100.00
    下载: 导出CSV
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  • 收稿日期:  2020-12-28
  • 修回日期:  2021-01-24
  • 网络出版日期:  2021-03-30

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