Hydrodeoxygenation of soybean oil methyl esters to alkane biodiesel over the PdMoP/γ-Al2O3 catalyst
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摘要: 采用等体积浸渍法将Pd、Mo和P元素负载在γ-Al2O3上制得PdMoP/γ-Al2O3催化剂，通过XRD、NH3-TPD、XPS、Py-FTIR、氮吸附和STEM-EDS等手段对催化剂进行了表征，以大豆油甲酯为原料考察了催化剂的催化加氢脱氧性能，并进行了加氢脱氧工艺条件的优化。结果表明，Pd、Mo、P三种元素相结合能够有效地调节催化剂的酸性；Mo元素可降低催化剂的强酸酸性；P元素可增强催化剂的弱酸酸性，使得催化剂弱酸的B/L值减小、强酸的B/L值略有增大。经优化后的加氢工艺条件为：315 ℃、1.5 MPa、WHSV为0.5 h-1、H2/esters体积比为1100，大豆油甲酯的转化率达到98.4%，C15-18烷烃收率达到91.5%。
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关键词:
- 加氢脱氧 /
- PdMoP/γ-Al2O3催化剂 /
- 酸性调节 /
- 大豆油甲酯 /
- 烷烃类生物柴油
Abstract: The PdMoP/γ-Al2O3 catalyst was prepraed through loading the Pd, Mo, and P elements on the γ-Al2O3 support by incipient impregnation method and characterized by XRD, NH3-TPD, XPS, Py-FTIR, nitrogen physisorption and STEM-EDS. The catalytic performance of PdMoP/γ-Al2O3 in the hydrodeoxygenation of soybean oil methyl ester to alkane biodiesel was invetigqated and the operation conditions were optimized. The results show that a combination of Pd, Mo and P elements can effectively adjust the catalyst acidity; Mo can reduce strong acidity, whereads P can enhance weak acidity, leading to a decrease in the B/L ratio of weak acid sites and a slight increase in the B/L ratio of strong acid sites. The optimized hydrodeoxygenation conditions are 315 ℃, 1.5 MPa, WHSV=0.5 h-1, and V(hydrogen)/V(esters)=1100; under such conditions, the conversion of soybean oil methyl esters reaches 98.4% and the C15-18 alkane yield is 91.5%. -
图 1 催化剂的N2吸附-脱附等温线和孔径分布
Figure 1 N2 adsorption-desorption isotherms and pore size distribution of various catalysts
图 4 催化剂P、P-M、P-M-P在200 ℃(实线)和350 ℃(虚线)的吡啶吸附红外光谱谱图
Figure 4 Py-FTIR spectra of various catalysts (P, P-M and P-M-P) at 200 ℃ (solid line) and 350 ℃ (dashed line)
图 5 催化剂P-M-P的XPS光谱谱图
Figure 5 XPS spectra of the P-M-P catalyst
(a): Pd 3d; (b): Mo 3d; (c): P 2p
图 7 催化剂的性能评价
Figure 7 Performance of various catalysts in the hydrodeoxygenation of soybean oil methyl esters to alkane biodiesel
图 8 PMP催化剂的性能评价
Figure 8 Catalytic performance of PMP in the hydrodeoxygenation of soybean oil methyl esters to alkane biodiesel
表 1 催化剂的性能
Table 1 Textural properties of various catalysts
Catalyst ABET/(m2·g-1) Aext/(m2·g-1) Amic/(m2·g-1) vmiso/(mL·g-1) vmeso/(mL·g-1) P 247.10 247.10 0.00 0.088 0.382 M-P 211.33 211.33 0.00 0.074 0.353 P-P 224.54 224.54 0.00 0.078 0.332 P-M 197.86 197.86 0.00 0.085 0.263 P-M-P 184.40 184.40 0.00 0.068 0.241 
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表 2 催化剂的NH3-TPD定量分析
Table 2 Quantitative analysis results of NH3-TPD of various catalysts
Catalyst P M-P P-P P-M-P Peak temperature t/℃ 165.2 294.6 628.3 167.5 644.0 165.9 618.3 164.5 633.3 Quantity/(mmol·g-1) 0.2686 0.2489 0.0538 0.4577 0.0257 0.4775 0.0486 0.4130 0.0350
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表 3 通过Py-FTIR测得催化剂P、P-M和P-M-P的酸度
Table 3 Acidic properties of the P, P-M and P-M-P catalysts determined by Py-FTIR
Sample Amounts of various acid sites /(μmol·g-1) total acid sites measured at 200 ℃ medium and strong acid sites measured at 350 ℃ B L B+L B/L B L B+L B/L P 36.95 236.20 273.15 0.1564 35.80 98.60 134.40 0.3631 P-M 23.96 193.45 217.41 0.1239 22.67 77.12 99.79 0.2940 P-M-P 21.32 188.17 209.50 0.1133 18.47 61.88 80.36 0.2985
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