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渣油加氢反应样品中含铁和含钙化合物溶解性能研究

王现元 张涛 张龙力 赵愉生 边钰清 杨朝合

王现元, 张涛, 张龙力, 赵愉生, 边钰清, 杨朝合. 渣油加氢反应样品中含铁和含钙化合物溶解性能研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60053-1
引用本文: 王现元, 张涛, 张龙力, 赵愉生, 边钰清, 杨朝合. 渣油加氢反应样品中含铁和含钙化合物溶解性能研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60053-1
WANG Xian-yuan, ZHANG Tao, ZHANG Long-li, ZHAO Yu-sheng, BIAN Yu-qing, YANG Chao-he. Study on the dissolution performance of ferrum and calcium compounds in residue hydrogenation reaction samples[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60053-1
Citation: WANG Xian-yuan, ZHANG Tao, ZHANG Long-li, ZHAO Yu-sheng, BIAN Yu-qing, YANG Chao-he. Study on the dissolution performance of ferrum and calcium compounds in residue hydrogenation reaction samples[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60053-1

渣油加氢反应样品中含铁和含钙化合物溶解性能研究

doi: 10.1016/S1872-5813(21)60053-1
基金项目: 国家自然科学基金(21576292)资助
详细信息
    作者简介:

    王现元:1044097546@qq.com

    通讯作者:

    Tel: 0532-86983374, E-mail: llzhang@upc.edu.cn

  • 中图分类号: TE622.1

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

Funds: The project was supported by the National Natural Science Foundation of China (21576292)
More Information
  • 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。
  • 图  1  溶剂抽提法分三组分流程图

    Figure  1.  Three-components flow chart of solvent extraction

    图  2  各形态铁、钙的含量测定流程图

    Figure  2.  Flow chart for determination of ferrum and calcium content of various forms

    图  3  加氢系列油样A的组分含量变化

    Figure  3.  Variations of the components content of hydrogenated oil sample A

    图  4  渣油中铁、钙化合物的主要形态

    Figure  4.  Main forms of ferrum and calcium compounds in residue oil

    表  1  加氢系列油样A的基础物性参数

    Table  1.   Basic properties of hydrogenated oil sample A

    Analysis itemCrude oilVacuum residueHydrogenation feedstockHydrogenation products
    Density(20 ℃)/(g·cm−3)0.850.960.950.93
    CSP*/(g·g−1)3.104.283.363.03
    Acid value/(mg·g−1)0.260.320.420.03
    Molecular weight/(g·mol−1)$ {\rm{9}}{{.31 \times 1}}{{\rm{0}}^{\rm{2}}}$$ {\rm{1}}{{.98 \times 1}}{{\rm{0}}^{\rm{3}}}$$ {\rm{1}}{\rm{.21 \times 1}}{{\rm{0}}^{\rm{3}}} $$ {\rm{9}}{\rm{.58 \times 1}}{{\rm{0}}^{\rm{2}}}$
    Dipole moment/Debye2.804.904.002.40
    C/wt%85.586.386.287.0
    H/wt%13.112.512.212.8
    N/wt%0.180.430.370.24
    S/wt%0.771.341.080.61
    V/($ {\text{μ}{\rm{g}}} \cdot {{\rm{g}}^{{\rm{ - 1}}}} $)15.639.133.76.60
    Ni/($ {\text{μ}{\rm{g}}} \cdot {{\rm{g}}^{{\rm{ - 1}}}} $)6.122.117.24.00
    Fe/($ {\text{μ}{\rm{g}}} \cdot {{\rm{g}}^{{\rm{ - 1}}}} $)34.211282.472.7
    Ca/($ {\text{μ}{\rm{g}}} \cdot {{\rm{g}}^{{\rm{ - 1}}}}$)10.861.243.132.1
    *: Drops of diffusion method
    下载: 导出CSV

    表  2  实验试剂一览表

    Table  2.   List of experiment reagents

    ReagentSpecificationManufacturer
    Petroleum ether
    (60−90 ℃)
    Analytic reagentShanghai Woke Biotechnology Co., Ltd
    MethylbenzeneAnalytic reagentSinopharm chemical reagent Co., Ltd
    N-eptaneAnalytic reagentXilong Chemical Co., Ltd
    CyclohexaneAnalytic reagentSinopharm chemical reagent Co. Ltd
    ActetoneAnalytic reagentTianjin Fuyu Fine Chemicals Co. Ltd
    Hydrochloric
    acid
    Guaranteed reagentSinopharm chemical reagent Co. Ltd
    下载: 导出CSV

    表  3  实验仪器一览表

    Table  3.   List of experiment equipments

    Instrument nameTypeManufacturer
    Automatic rapid
    crude oil distillation
    apparatus
    SDM-06ABeijing Opwiye Technology Co., Ltd
    AASControAA700Jena analytical
    instruments ag
    Steam pressure penetratorK700Knauer
    CHSN
    elemental analyzer
    VARIO EL ⅢGerman company elementar
    Automatic acid
    value tester
    SY-3000ATaizhou jiangyan analysis instrument factory
    下载: 导出CSV

    表  4  A原油中金属铁和钙随馏程的分布

    Table  4.   Distribution of the metal ferreum and calcium with distillation range in crude oil A

    SampleFraction content
    /wt%
    Fe content/
    (μg·g−1)
    Relative distribution
    /%
    Ca content/
    (μg·g−1)
    Relative distribution
    /%
    Crude oil10034.210010.8100
    gasoline fraction28.10.220.180.010.03
    diesel fraction20.70.530.320.010.02
    vacuum gas oil27.62.602.100.310.79
    Vacuum residure23.611297.461.299.16
    下载: 导出CSV

    表  5  不同分离方法所得组分中铁和钙的含量

    Table  5.   Contents of the ferrum and calcium compounds in the components obtained by different separation methods

    Separation methodComponentComponent content/wt%Ca content/(μg·g−1)recovery ratio/%Fe content/(μg·g−1)recovery ratio/%
    Column chromatographySaturated + Aromatic73.72.332.814.753.13
    Resin24.2NN14731.8
    Asphaltene2.159620.43767.05
    Metal recovery rate/%23.241.9
    Solvent
    extraction
    Saturation + Aromatic73.111.113.342.727.9
    Resin24.715160.924453.8
    Asphaltene2.2085630.878115.3
    Metal recovery ratioe/%10597.0
    N: The instrument is not detected
    下载: 导出CSV

    表  6  金属铁在加氢系列油样A组分中的分布变化

    Table  6.   Distribution variations of the metallic ferrum compounds in components of hydrogenated oil sample A

    Oil (Saturated+ Aromatic)ResinAsphaltene
    SampleTotal Fe content/(μg·g−1)Fe content/
    (μg·g−1)
    Relative distribution/%Fe content/
    (μg·g−1)
    Relative distribution/%Fe content/
    (μg·g−1)
    Relative distribution/%
    Crude oil34.220.158.337237.26694.50
    Vacuum residue11242.728.824455.578115.7
    Hydrogenation feedstock82.420.419.027160.581220.5
    Hydrogenation products72.721.926.223944.799229.1
    下载: 导出CSV

    表  7  金属钙在加氢系列油样A组分中的分布变化

    Table  7.   Distribution variations of the metallic calcium compounds in component of hydrogenated oil sample A

    Saturated + AromaticResinAsphaltene
    SampleTotal Ca content/(μg·g−1)Ca content/
    (μg·g−1)
    Relative distribution/%Ca content/
    (μg·g−1)
    Relative distribution/%Ca content/
    (μg·g−1)
    Relative distribute on/%
    Crude oil10.84.1737.917053.44248.70
    Vacuum residue61.211.112.715158.185629.2
    Hydrogenation feedstock43.113.424.211248.655527.2
    Hydrogenation products32.115.738.089.033.647928.4
    下载: 导出CSV

    表  8  加氢系列油样A中铁化合物的溶解性能

    Table  8.   Dissolution performance of the ferrum compounds in hydrogenated oil sample A

    Total FeOil-soluble FeWater-soluble FePetrleum acid FePorphyrin Fe and
    non-porphyrin Fe
    SampleContent/
    (μg·g−1)
    Content/
    (μg·g−1)
    Relative distribution/%Content/
    (μg·g−1)
    Relative distribution/%Content/
    (μg·g−1)
    Relative distribution/%Content/
    (μg·g−1)
    Relative distribution/%
    Crude oil34.232.795.61.504.4019.757.513.138.2
    Vacuum residue11272.464.739.635.344.439.628.125.0
    Hydrogenation feedstock82.466.781.015.719.025.530.941.350.1
    Hydrogenation products72.731.443.241.356.86.609.1024.834.1
    下载: 导出CSV

    表  9  加氢系列油样A中钙化合物的溶解性能

    Table  9.   Dissolution performance of the calcium compounds in hydrogenated oil sample A

    SampleTotal CaOil-soluble calciumWater-soluble calcium
    Content/(μg·g−1)Content/(μg·g−1)Relative distribution/%Content/(μg·g−1)Relative distribution/%
    Crude oil10.86.7062.04.1038.0
    Vacuum residue61.258.695.72.604.30
    Hydrogenation feedstock43.131.372.711.827.3
    Hydrogenation products32.110.031.122.168.9
    下载: 导出CSV
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