多孔微球镍锌复合型吸附剂反应吸附脱硫性能研究

王海彦; 关纵驰; 康蕾; 郝明阳

多孔微球镍锌复合型吸附剂反应吸附脱硫性能研究

辽宁石油化工大学, 辽宁抚顺 113001

详细信息

通讯作者:
王海彦, Tel:13941336296, E-mail:fswhy@126.com

中图分类号: TQ624.431
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- 文章访问数: 118
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- 被引次数: 0
出版历程
- 收稿日期: 2017-05-10
- 修回日期: 2017-08-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Study on adsorption desulfurization performance of porous microsphere nickel zinc composite adsorbent

Liaoning Shihua University, Fushun 113001, China

摘要

摘要: 考察了葡萄糖量对氧化锌微球形貌的影响，分别采用等体积浸渍法和水热法制备含Ni质量分数为5%的NiO/ZnO微球吸附剂，使用N₂吸附-脱附、扫描电子显微镜（SEM）、X射线衍射（XRD）等手段对NiO/ZnO微球吸附剂进行结构和形貌分析，并研究了制备方法对NiO/ZnO微球吸附剂物化性质的影响，再将其经H₂还原后制得Ni/ZnO微球吸附剂，在模型汽油中使用噻吩作为含硫化合物，通过固定床反应器进行反应吸附脱硫性能研究。实验表明，与等体积浸渍法制备的负载型NiO/ZnO微球吸附剂相比，水热法制备的复合型NiO-ZnO微球吸附剂的比表面积和孔体积分别高达（40.45 m²/g）和（0.096 cm³/g），还原后所得复合型Ni-ZnO微球吸附剂具有更好的脱硫活性，在吸附温度350℃、压力1.0 MPa、进料液体积空速6 h^-1及氢气与模拟油体积比为60的条件下，可以将模拟油中的硫质量含量从1.5×10^-4降至10^-5以下。并且拥有很好的再生能力，经过多次再生后仍保持很高的脱硫率，具有潜在的工业应用价值。
- 复合材料 /
- 微球 /
- 吸附剂 /
- 吸附脱硫 /
- 氧化锌 /
- 介孔结构
Abstract: The effects of glucose on the morphology of the microspheres of zinc oxide were first studied, and then 5% NiO/ZnO microspheric adsorbents were prepared by impregnation method and hydrothermal synthesis. The morphology and structure of NiO/ZnO microspheres were analyzed by N₂ adsorption, scanning electron microscopy (SEM), X-ray diffraction (XRD) methods, and the effects of the preparation method of NiO/ZnO microspheric adsorbents on the physicochemical properties were examined. Furthermore, Ni/ZnO microsphere adsorbent was prepared by reduction with H₂, over which the performance of adsorption desulfurization was tested in a fixed bed reactor by using thiophene as the sulfur compounds in model gasoline.The results show that the specific surface area and pore volume of the NiO-ZnO microspheric adsorbents prepared by hydrothermal method are as high as 40.45 m²/g and 0.096 cm³/g, respectively, in contrast to the ones prepared by the impregnation method, and the composite Ni-ZnO microspheric adsorbents exhibit a favorable desulfurization activity. Under the conditions including a temperature of 350℃, a pressure of 1.0 MPa, a volume space velocity of 6 h^-1, and a hydrogen to simulated oil volume ratio of 60, the sulphur contents in simulated oil decrease from 1.5×10^-4 to less than 10^-5. Also, the adsorbents boast a good regeneration capacity and a potential application value in industry.
- composites /
- microsphere /
- adsorbent /
- adsorption desulfurization /
- zincoxide /
- mesoporous structure

HTML全文

图 1 葡萄糖量对ZnO微球形貌影响的SEM照片

Figure 1 Effect of Glucose on Morphology of ZnO Microspheres

(a): Zn (AC)₂ /glucose mass ratio 1:1; (b): Zn (AC)₂ /glucose mass ratio 1:3

下载: 全尺寸图片幻灯片

图 2 三种吸附剂的SEM照片

Figure 2 SEM images of three adsorbents

C1, C2: pure ZnO microspheres adsorbent; D1, D2: supported NiO/ZnO microsphere adsorbent; E1, E2: composite NiO-ZnO microsphere adsorbent

下载: 全尺寸图片幻灯片

图 3 三种吸附剂的N₂ 吸附-脱附等温曲线(a)以及相应的BJH孔径分布曲线(b)

Figure 3 N₂ adsorption-desorption isotherm (a) of the three adsorbents and the corresponding BJH pore size distribution curve (b)

a: pure ZnO microspheres adsorbent; b: supported NiO/ZnO microsphere adsorbent; c: composite NiO-ZnO microsphere adsorbent

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图 4 三种吸附剂的XRD谱图

Figure 4 XRD patterns of three adsorbents

a: pure ZnO microspheres adsorbent; b: supported NiO/ZnO microsphere adsorbent; c: composite NiO-ZnO microsphere adsorbent

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图 5 吸附剂的EDX能谱照片

Figure 5 EDX spectra of adsorbents

F: composite NiO-ZnO microsphere adsorbent; G: supported NiO/ZnO microsphere adsorbent

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图 6 反应吸附脱硫率随反应时间的变化

Figure 6 Study on adsorption desulfurization performance

a:composite NiO-ZnO microsphere adsorbent; b: supported NiO/ZnO microsphere adsorbent

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图 7 复合型NiO-ZnO微球吸附剂稳定性实验

Figure 7 Stability experiment of composite NiO-ZnO microspheres adsorbent

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图 8 水热法合成的复合型Ni-ZnO微球吸附剂再生性能

Figure 8 Regeneration performance of complex Ni-ZnO microspheres adsorbent synthesized by hydrothermal method

a: first cycle; b: second cycle; c: third cycle; d: fourth cycle; e: fifth cycle

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表 1 不同样品的BET比表面积和孔体积

Table 1 BET specific surface area and pore volume of different samples

Sample A_BET/(m²·g^-1) v_p/(cm³·g^-1)

ZnO 37.76 0.083

Supported NiO/ZnO 35.92 0.075

Composite NiO-ZnO 40.45 0.096

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