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过渡金属助剂改性Ca-Zr催化剂上甲醇与碳酸丙烯酯制备碳酸二甲酯的研究

陈美娟 杨金海 赵宁 肖福魁

陈美娟, 杨金海, 赵宁, 肖福魁. 过渡金属助剂改性Ca-Zr催化剂上甲醇与碳酸丙烯酯制备碳酸二甲酯的研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60075-6
引用本文: 陈美娟, 杨金海, 赵宁, 肖福魁. 过渡金属助剂改性Ca-Zr催化剂上甲醇与碳酸丙烯酯制备碳酸二甲酯的研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60075-6
CHEN Mei-juan, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui. Preparation of dimethyl carbonate from methanol and propylene carbonate over Ca-Zr catalyst modified by transition metals[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60075-6
Citation: CHEN Mei-juan, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui. Preparation of dimethyl carbonate from methanol and propylene carbonate over Ca-Zr catalyst modified by transition metals[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60075-6

过渡金属助剂改性Ca-Zr催化剂上甲醇与碳酸丙烯酯制备碳酸二甲酯的研究

doi: 10.1016/S1872-5813(22)60075-6
基金项目: 山西省科技重大专项(202005D121002)和山西省中央引导地方科技发展资金项目(2020SW26)资助
详细信息
    通讯作者:

    E-mail: zhaoning@sxicc.ac.cn(13935170768)

    xiaofk@sxicc.ac.cn(13403457648)

  • 中图分类号: TQ225

Preparation of dimethyl carbonate from methanol and propylene carbonate over Ca-Zr catalyst modified by transition metals

Funds: The project was supported by Science and Technology Major Project of Shanxi Province (202005D121002), The Central Project Guide local science and technology for development (2020SW26)
  • 摘要: 研究了一系列由溶胶凝胶法制备的过渡金属助剂改性的Ca-Zr催化剂对甲醇与碳酸丙烯酯(PC)制备碳酸二甲酯(DMC)的低温反应性能的影响。反应结果表明,催化剂上DMC的选择性的顺序为Co-Ca-Zr>Cu-Ca-Zr> Ca-Zr >Fe-Ca-Zr> Ni-Ca-Zr>Zn-Ca-Zr。其中,用Co改性的催化剂在温度为35 ℃、时间为2 h、甲醇与PC物质的量比为15、催化剂用量为4%的反应条件下,PC转化率可达84.3%,DMC的选择性可达94.5%。采用XRD、FT-IR、XPS、CO2-TPD等手段对催化剂的性质进行了表征。结果表明,增加催化剂的碱性位强度可以提高PC的转化率,而增加催化剂表面的总碱性位含量会降低DMC的选择性。Co改性的Ca-Zr催化剂具有最低的碱性位含量,最高的强碱性位点比例,因此,具有最高的PC转化率和DMC选择性。
  • 图  1  催化剂的 XRD 谱图

    Figure  1  XRD patterns of the catalysts

    图  2  催化剂的红外光谱谱图

    Figure  2  FT-IR spectra of the catalysts

    图  3  催化剂的N2吸附-解吸等温曲线(a)和孔经分布(b)

    Figure  3  N2 adsorption-desorption isotherms (a) and pore distribution (b) of the catalysts

    图  4  催化剂的O 1s XPS谱图

    Figure  4  O 1s XPS spectra of the catalysts

    图  5  Fe-CZ的Fe 2p XPS谱图(a); Ni-CZ的Ni 2p XPS谱图(b); Cu-CZ的Cu 2p XPS谱图(c); Zn-CZ的Zn 2p XPS谱图(d); Co-CZ的Co 2p XPS谱图(e)

    Figure  5  Fe 2p XPS spectrum of Fe-CZ (a); Ni 2p XPS spectrum of Ni-CZ (b); Cu 2p XPS spectrum of Cu-CZ (c); Zn 2p XPS spectrum of Zn -CZ (d); Co 2p XPS spectrum of Co -CZ (e)

    图  6  催化剂的CO2-TPD谱图

    Figure  6  CO2-TPD profiles of the catalysts

    图  7  催化剂的催化性能

    Figure  7  Catalytic performance of the catalysts (60 ℃, 5 h, methanol to PC molar ratio of 15, and catalyst dosage of 4%)

    图  8  DMC的选择性与催化剂的碱量(a)以及强碱性位点所占比例(b)的关系

    Figure  8  Relationship between DMC selectivity and the amount of basic sites of catalyst (a) and the proportion of strong basic sites (b)

    图  9  Co-CZ催化剂上反应条件的优化

    Figure  9  Optimization of reaction conditions over Co-CZ catalyst. molar ratio of reactants(a); catalyst content (w% of PC) (b); reaction time(c); reaction temperature (d)

    表  1  催化剂的织构参数

    Table  1  Texture properties of the catalysts

    CatalystSBET A/(m2·g−1)Pore volume v/(cm3·g−1)aAverage pore size d/nmb
    CZ 7.5 3.0 × 10−2 16.0
    Fe-CZ 10.2 5.0 × 10−2 19.8
    Co-CZ 3.1 1.3 × 10−2 16.4
    Ni-CZ 7.3 1.9 × 10−2 10.7
    Cu-CZ 1.1 0.3 × 10−2 11.2
    Zn-CZ 3.5 1.5 × 10−2 17.1
    a: total pore volume measured at p/p0 = 0.99, b: the pore diameter calculated from the desorption branch of the isotherm using the BJH method
    下载: 导出CSV

    表  2  催化剂的结合能值

    Table  2  Binding energy values of the catalysts

    CatalystBinding energy/eV
    Ca 2pZr 3dO 1s
    CZ350.7; 347.0181.7; 184.0529.5; 531.6
    Fe-CZ350.2; 346.4181.0; 183.3529.2; 531.5
    Co-CZ350.2; 346.5181.3; 183.6529.2; 531.3
    Ni-CZ350.9; 346.7181.3; 183.7529.5; 531.4
    Cu-CZ350.4; 346.7181.4; 183.7529.5; 531.4
    Zn-CZ350.3; 346.6181.4; 183.7529.5; 531.4
    下载: 导出CSV

    表  3  催化剂的总碱位数量和各碱性位点所占比例

    Table  3  Base number and the proportion of base sites of the catalysts

    Catalystα peak/%β peak/%γ peak/%Total basicity/
    (mmol·g−1)
    CZ2.456.041.61.57
    Fe-CZ4.143.952.01.66
    Co-CZ3.527.469.10.66
    Ni-CZ2.373.024.73.24
    Cu-CZ2.979.317.81.25
    Zn-CZ2.961.635.51.08
    下载: 导出CSV

    表  4  合成DMC的催化剂性能

    Table  4  Comparation of the catalytic performance for DMC synthesis

    CatalystReaction
    time t /h
    Reaction
    tem. t /℃
    PC con.
    x /%
    DMC sel.
    s /%
    Ref.
    CaZr 5 60 85.7 86.5 this work
    CaFeZr 5 60 84.8 82.7 this work
    CaCoZr 5 60 84.9 92.2 this work
    CaNiZr 5 60 84.0 82.1 this work
    CaCuZr 5 60 84.9 88.9 this work
    CaZnZr 5 60 84.3 82.0 this work
    CaO 2 60 ~55.0 - [4]
    ZrO2 6 140 14.0 50.0 [30]
    CaCo 2 60 71.6 72.9 [11]
    CaAl 2 60 53.7 92.8 [13]
    CaMgAl 2 60 55.3 96.3 [13]
    MgAl 4 65 10.7 20.9 [31]
    FeMgAl 4 65 66.2 82.6 [31]
    CuMgAl 4 65 63.8 81.5 [31]
    下载: 导出CSV
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  • 收稿日期:  2022-10-14
  • 录用日期:  2022-11-08
  • 修回日期:  2022-11-07
  • 网络出版日期:  2022-12-13

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