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摘要: 通过液相离子交换法制备了Cu（Ⅰ）Y、NiY、CeY分子筛，以XRD、低温N2吸附-脱附、NH3-TPD、吡啶红外Py-FTIR等方法对其进行物性表征。利用固定床技术、WK-2D微库伦仪及硫化学发光检测GC-SCD色谱评价了改性分子筛对于硫含量300 μg/g模拟油（含硫化合物二丙硫醚、环己硫醇和1-庚硫醇与壬烷配制）及HDS汽油的吸附脱硫性能。结果表明，吸附剂对模拟油和HDS燃料油品中硫醇硫醚具有吸附效果，且改性后的分子筛在吸附脱硫过程中，强的B酸对于吸附脱硫有负作用，会使油品中硫醇硫醚发生催化反应，聚合的大分子硫化物遮盖及阻塞吸附活性位点，从而使吸附剂不能够完全地吸附硫化物，造成吸附硫容较小，而弱L酸无催化活性对吸附脱硫有正面影响。Abstract: Samples of Cu (Ⅰ) Y, NiY and CeY were prepared by modifying a NaY type zeolite with a liquid ion-exchange method and characterized by means of XRD, ICP-MS, pyridine Py-FTIR, NH3-TPD and low temperature N2 adsorption-desorption.Use of micro coulombmeter WK-2D, sulfide luminescence detecting chromatography GC-SCD and fixed bed technology to evaluate the desulfurization performance of the samples for a 300 μg/g sulfur content model oil (dipropyl sulfide, cyclohexanol mercaptan and 1-heptyl mercaptan are prepared with nonane, etc.) and a hydrodesulfurization (HDS) gasoline. Results show that Cu (Ⅰ) Y has good adsorption desulfurization performance on those different oils. In the liquid ion-exchange process, the modified Y zeolite's surface acidity has greatly changed. The strong surface Bronsted (B) acidity of modified Y zeolite has negative effects on adsorption desulfurization through catalyzing mercaptan and thioether to form bigger molecules, which cover the surface of Y zeolite and block the adsorption activity sites, resulting in lower sulfur adsorption capacity of the catalyst. The weak surface Lewis (L) acidity has positive effects on adsorption desulfurization.
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Key words:
- Y zeolite /
- mercaptan /
- sulfide /
- adsorption desulfurization /
- catalyze /
- surface acidity
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图 1 NaY、NiY、CeY及Cu(Ⅰ)Y分子筛的XRD谱图
Figure 1 XRD patterns of the NaY, NiY, CeY and Cu(Ⅰ)Y samples used
图 2 改性分子筛的Py-FTIR谱图
Figure 2 Py-FTIR characterization of the samples
a: blank; b: 150 ℃; c: 400 ℃
图 4 HDS油经吸附剂处理前后的GC-SCD-1谱图
Figure 4 GC-SCD-1 chromatograms of HDS oil treated by different adsorbents
A: C1-3-thiol; B: thiophene(TP); C: 2-methylthiophene(2-MTP); D: 3-methylthiophene(3-MTP); E: C5-thiol; F: 2, 5-dimethylthiophene(2, 5-DMTP); G: 2, 3-dimethylthiophene(2, 3-DMTP); H: di-n-propylsulfide; I: cyclohexanethiol; J: 2-ethyl-5-methylthiophene(2-E-5-MDMTP); K: heptanethiol; L: C4-thiophene
图 5 改性分子筛对二丙硫醚、环己硫醇及1-庚硫醇模拟油的动态吸附穿透曲线
Figure 5 Breakthrough curves of the model oils in the modified Y zeolite
(a): dipropyl sulfide; (b): 1-heptyl mercaptan; (c): cyclohexanol mercaptan
图 6 吸附剂吸附饱和经溶液萃取后萃取液的GC-SCD谱图
Figure 6 GC-SCD chromatograms after solution extraction
(a): dipropyl sulfide; (b): 1-heptyl mercaptan
a: CuY; b: NiY; c: CeY; d: NaY表 1 改性Y型分子筛的结构参数
Table 1 Textural parameters of the samples
Sorbent Exchange degree of Na+ vp/(cm3·g-1) A/(m2·g-1) Average pore diameter d/nm NaY - 0.360 874 0.70 CeY 91 0.307 607 0.68 NiY 74 0.333 654 0.69 Cu(Ⅰ)Y 68 0.336 721 0.69 
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表 2 改性金属Y对不同模拟油的静态脱除
Table 2 Desulfurization capacity of the modified Y zeolites for different model oils
Sorbent η/(mg·g-1) di-n-propyl sulfide cyclohexanethiol 1-heptanethiol NaY 2.95 2.92 2.94 CeY 13.617 10.85 15.86 NiY 15.72 17.86 25.34 Cu(Ⅰ)Y 46.783 27.38 39.07
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表 3 HDS燃料油中主要硫化物的含量及脱除率
Table 3 Contents and desulfurization rate of main sulfur compounds in the HDS gasoline
Retention time t/min Sulfur compound Sulfur compound Desulfurization rate η/% NaY NiY Cu(Ⅰ)Y CeY 3.778-4.562 C1-3 sulfide 3.9 55.7 78.4 100 100 5.60 TP 2.0 22.5 16.6 63.4 42.7 9.16 C5-sulfide 3.1 21.9 98.2 100 99.1 9.76 2-MTHF 0.7 55.9 100 100 100 10.77 2, 5-DMTP 3.9 13.7 14.1 46.2 43.1 11.21 di-n-propylsulfide 1.0 14.6 67.3 97.6 100 14.10 cyclohexanethiol 1.1 12.7 80.1 97.2 100 14.70 2-E-5-MDMTP 5.3 16.7 15.6 18.8 20.2 18.02 heptanethiol 2.3 10.2 98.1 100 100
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表 4 改性分子筛动态穿透硫容
Table 4 Adsorptive sulfur capacity of the modified Y zeolites at the breakthrough point of 1 μg/g
Sorbent Cs/(mg·g-1) thiophene di-n-propyl sulfide cyclohexanethiol 1-heptanethiol NaY 2.15 2.41 2.34 2.44 CeY 3.66 11.15 8.67 12.49 NiY 7.66 13.22 7.09 21.07 Cu(Ⅰ)Y 15.43 25.05 13.54 22.66
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