• •
胡德政1,2(), 王榕1, 王世栋1, 杨文菲1, 张宏伟1, 袁珮1,2(
)
收稿日期:
2024-01-23
修回日期:
2024-04-24
出版日期:
2024-07-01
通讯作者:
袁珮
作者简介:
胡德政(1998—),男,硕士研究生,853491951@qq.com
基金资助:
Dezheng HU1,2(), Rong WANG1, Shidong WANG1, Wenfei YANG1, Hongwei ZHANG1, Pei YUAN1,2(
)
Received:
2024-01-23
Revised:
2024-04-24
Online:
2024-07-01
Contact:
Pei YUAN
摘要:
C9石油树脂 (C9PR) 是由乙烯裂解副产物C9馏分聚合而成的热塑性树脂,经加氢改性后可以制得色度浅、抗氧化稳定性高、相容性好的高附加值氢化石油树脂(HC9PR)。但C9PR分子量大、空间位阻高且原料中含有硫化物等杂质易使催化剂中毒失活,因此加氢难度极大。为了同时实现C9PR的加氢和脱杂,采用化学还原法结合球磨法制备了非晶态NiP@γ-Al2O3催化剂。表征结果显示,该催化剂具有较大的比表面积、富含Niδ+活性物种、较多的活性位数量,并对C=C键具有较强的吸附能力。对其进行C9PR加氢性能评价,结果显示非晶态NiP@γ-Al2O3催化剂表现出优异的加氢活性(加氢度98.35%)和脱硫活性(硫含量从122.8 μg/g降低至8 μg/g),明显优于利用程序升温还原法结合球磨法制备的不同晶型磷化镍催化剂。此外,经过连续100 h的反应,该催化剂仍能保持较高的加氢度,表明其具有良好的稳定性。
中图分类号:
胡德政, 王榕, 王世栋, 杨文菲, 张宏伟, 袁珮. 兼具加氢和脱硫活性的富含Niδ+非晶态NiP@γ-Al2O3催化剂的构筑及其用于石油树脂加氢的性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240106.
Dezheng HU, Rong WANG, Shidong WANG, Wenfei YANG, Hongwei ZHANG, Pei YUAN. Construction of amorphous NiP@γ-Al2O3 catalyst rich in Niδ+ for petroleum resin hydrogenation with enhanced hydrogenation and desulfurization activity[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240106.
图2 γ-Al2O3、非晶态NiP@γ-Al2O3、不同晶型催化剂N2吸附-脱附等温曲线和孔径分布
Fig. 2 N2 adsorption-desorption curves and pore size distributions of γ-Al2O3, amorphous NiP@γ-Al2O3 and different crystalline catalysts
Sample | BET surface area /(m2·g-1) | Pore volume /(cm3·g-1) | Pore diameter /nm |
---|---|---|---|
γ-Al2O3 | 320 | 0.88 | 15.8 |
非晶态NiP@γ-Al2O3 | 255 | 0.47 | 6.9 |
Ni2P@γ-Al2O3 | 241 | 0.53 | 6.3 |
Ni12P5@γ-Al2O3 | 214 | 0.45 | 9.3 |
Ni3P@γ-Al2O3 | 213 | 0.65 | 10.9 |
表1 γ-Al2O3载体、非晶态NiP@γ-Al2O3和不同晶型催化剂的织构性质
Table 1 Textural properties of γ-Al2O3, amorphous NiP@γ-Al2O3 and different crystalline catalysts
Sample | BET surface area /(m2·g-1) | Pore volume /(cm3·g-1) | Pore diameter /nm |
---|---|---|---|
γ-Al2O3 | 320 | 0.88 | 15.8 |
非晶态NiP@γ-Al2O3 | 255 | 0.47 | 6.9 |
Ni2P@γ-Al2O3 | 241 | 0.53 | 6.3 |
Ni12P5@γ-Al2O3 | 214 | 0.45 | 9.3 |
Ni3P@γ-Al2O3 | 213 | 0.65 | 10.9 |
图3 非晶态NiP@γ-Al2O3和不同晶型磷化镍催化剂的Ni 2p和P 2p XPS谱图
Fig. 3 Ni 2p XPS spectra and P 2p XPS spectra of amorphous NiP@γ-Al2O3 and different crystalline catalysts
Sample | Ni speciesa | P speciesa | CO uptakesb/(μmol·g-1) | C2H4-TPD peak areac | |||
---|---|---|---|---|---|---|---|
Niδ+/% | Ni2+/% | Satellite/% | Pδ-/% | P-O/% | |||
非晶态NiP@γ-Al2O3 | 36.51 | 37.44 | 26.06 | 58.44 | 41.56 | 21.67 | 1.00 |
Ni2P@γ-Al2O3 | 12.06 | 45.76 | 42.17 | 47.15 | 52.85 | 11.43 | 0.69 |
Ni12P5@γ-Al2O3 | 9.92 | 50.42 | 39.66 | 46.64 | 53.36 | 6.92 | 0.62 |
Ni3P@γ-Al2O3 | 16.44 | 48.47 | 35.09 | 56.85 | 43.15 | 16.42 | 0.89 |
表2 非晶态NiP@γ-Al2O3,Ni2P@γ-Al2O3,Ni12P5@γ-Al2O3和Ni3P@γ-Al2O3催化剂的性质表征结果
Table 2 Properties of amorphous NiP@γ-Al2O3, Ni2P@γ-Al2O3, Ni12P5@γ-Al2O3 and Ni3P@γ-Al2O3 catalysts.
Sample | Ni speciesa | P speciesa | CO uptakesb/(μmol·g-1) | C2H4-TPD peak areac | |||
---|---|---|---|---|---|---|---|
Niδ+/% | Ni2+/% | Satellite/% | Pδ-/% | P-O/% | |||
非晶态NiP@γ-Al2O3 | 36.51 | 37.44 | 26.06 | 58.44 | 41.56 | 21.67 | 1.00 |
Ni2P@γ-Al2O3 | 12.06 | 45.76 | 42.17 | 47.15 | 52.85 | 11.43 | 0.69 |
Ni12P5@γ-Al2O3 | 9.92 | 50.42 | 39.66 | 46.64 | 53.36 | 6.92 | 0.62 |
Ni3P@γ-Al2O3 | 16.44 | 48.47 | 35.09 | 56.85 | 43.15 | 16.42 | 0.89 |
图4 非晶态NiP@γ-Al2O3,Ni2P@γ-Al2O3,Ni12P5@γ-Al2O3和Ni3P@γ-Al2O3催化剂的乙烯-TPD图
Fig. 4 C2H4-TPD profiles of amorphous NiP@γ-Al2O3, Ni2P@γ-Al2O3, Ni12P5@γ-Al2O3 and Ni3P@γ-Al2O3 catalysts.
Sample | 溴值/(g·(100g)-1) | 色度 | 硫含量/(μg/g) | 加氢度/% |
---|---|---|---|---|
C9PR | 5.06 | 5.6# | 122.80 | -- |
Blank | 3.65 | 4.3# | 102.80 | 27.86 |
非晶态NiP@γ-Al2O3 | 0.08 | 0.3# | 8.0 | 98.35 |
Ni2P@γ-Al2O3 | 0.63 | 0.7# | 28.60 | 87.58 |
Ni12P5@γ-Al2O3 | 0.94 | 2.7# | 28.53 | 81.37 |
Ni3P@γ-Al2O3 | 0.30 | 1.0# | 28.02 | 94.05 |
表3 C9PR和HC9PR的溴值、Gardner色度、硫含量及加氢度数据
Table 3 The bromine value, Gardner color, sulfur content and hydrogenation degree of raw C9PR and HC9PR products
Sample | 溴值/(g·(100g)-1) | 色度 | 硫含量/(μg/g) | 加氢度/% |
---|---|---|---|---|
C9PR | 5.06 | 5.6# | 122.80 | -- |
Blank | 3.65 | 4.3# | 102.80 | 27.86 |
非晶态NiP@γ-Al2O3 | 0.08 | 0.3# | 8.0 | 98.35 |
Ni2P@γ-Al2O3 | 0.63 | 0.7# | 28.60 | 87.58 |
Ni12P5@γ-Al2O3 | 0.94 | 2.7# | 28.53 | 81.37 |
Ni3P@γ-Al2O3 | 0.30 | 1.0# | 28.02 | 94.05 |
Sample | 溴值/(g·(100g)-1) | 色度 | 硫含量/(μg/g) | 加氢度/% |
---|---|---|---|---|
C9PR | 5.06 | 5.6# | 122.80 | -- |
10% 非晶态NiP@γ-Al2O3 | 0.12 | 0.8# | 25.0 | 97.65 |
20% 非晶态NiP@γ-Al2O3 | 0.08 | 0.3# | 8.0 | 98.35 |
30% 非晶态NiP@γ-Al2O3 | 0.02 | 0.2# | 0 | 99.10 |
表4 C9PR与HC9PR的物性参数
Table 4 Characteristic of raw C9PR and HC9PR products
Sample | 溴值/(g·(100g)-1) | 色度 | 硫含量/(μg/g) | 加氢度/% |
---|---|---|---|---|
C9PR | 5.06 | 5.6# | 122.80 | -- |
10% 非晶态NiP@γ-Al2O3 | 0.12 | 0.8# | 25.0 | 97.65 |
20% 非晶态NiP@γ-Al2O3 | 0.08 | 0.3# | 8.0 | 98.35 |
30% 非晶态NiP@γ-Al2O3 | 0.02 | 0.2# | 0 | 99.10 |
图9 不同反应条件对30% 非晶态NiP@γ-Al2O3催化剂的C9PR加氢性能的影响 (加氢反应条件固定,考察单一变量:温度220 °C、压力5 MPa、液时空速 1.5 h-1、氢脂比 600:1)
Fig. 9 Effect of different reaction conditions on the C9PR hydrogenation performance of 30% amorphous NiP@γ-Al2O3 catalyst (hydrogenation reaction conditions were fixed and a single variable was examined: temperature of 220 °C, pressure of 5 MPa, LHSV of 1.5 h-1, VRHO of 600:1)
Sample | Ni0/% | Niδ+/% | Ni2+/% | Satellite/% | Pδ-/% | P-O/% |
---|---|---|---|---|---|---|
Fresh NiP@γ-Al2O3 | - | 39.96 | 34.26 | 25.78 | 53.68 | 46.32 |
Spent NiP@γ-Al2O3 | 4.58 | 23.89 | 36.87 | 34.66 | 40.53 | 59.47 |
表5 反应前后NiP@γ-Al2O3催化剂中的各物种组成占比
Table 5 Elemental composition ratio of fresh and spent NiP@γ-Al2O3 catalysts.
Sample | Ni0/% | Niδ+/% | Ni2+/% | Satellite/% | Pδ-/% | P-O/% |
---|---|---|---|---|---|---|
Fresh NiP@γ-Al2O3 | - | 39.96 | 34.26 | 25.78 | 53.68 | 46.32 |
Spent NiP@γ-Al2O3 | 4.58 | 23.89 | 36.87 | 34.66 | 40.53 | 59.47 |
图12 反应前后30% 非晶态NiP@γ-Al2O3催化剂的N2吸附-脱附等温曲线和孔径分布
Fig.12 N2 adsorption-desorption curves and pore size distributions of fresh and spent NiP@γ-Al2O3 catalysts
Sample | BET surface area /(m2·g-1) | Pore volume /(cm3·g-1) | Pore diameter /nm | |
---|---|---|---|---|
Fresh NiP@γ-Al2O3 | 230 | 0.47 | 7.9 | |
Spent NiP@γ-Al2O3 | 128 | 0.30 | 3.9/7.9 |
表6 反应前后30% 非晶态NiP@γ-Al2O3催化剂的织构性质
Table 6 Textural properties of fresh and spent NiP@γ-Al2O3 catalysts
Sample | BET surface area /(m2·g-1) | Pore volume /(cm3·g-1) | Pore diameter /nm | |
---|---|---|---|---|
Fresh NiP@γ-Al2O3 | 230 | 0.47 | 7.9 | |
Spent NiP@γ-Al2O3 | 128 | 0.30 | 3.9/7.9 |
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