Study on durability of online catalytic upgrading of bio-oil based on Ru/HZSM-5
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摘要: 采用Ru/HZSM-5在线催化提质生物油,通过综合品质指数(TQI),分析生物油产率和理化特性变化,并对生物油化学组成及催化剂结焦情况进行分析。结果表明,使用新鲜催化剂所得生物油产率和理化特性均较高,TQI从0.15升至6.45;随着使用次数的增加,TQI先小幅升高至6.68,而后快速下降至1.25,第4次使用后TQI仅为0.27。初期少量结焦反应使强酸位点部分钝化,提升了芳构化性能,当催化剂使用2次时,生物油中烃类相对含量达53.79%,其中,轻质脂肪烃相对含量为16.87%,单环芳香烃相对含量为32.65%;当使用4次时,烃类相对含量仅为9.32%,催化层丧失提质作用,并对热解气产生2次裂解或聚合等不利影响。前2次使用,催化剂焦炭主要是附着在表面的低温热解焦炭;当使用3次时,低温热解焦炭和高温催化焦炭均显著增多,催化剂活性急剧下降;继续使用使焦炭小幅增加,且以热解焦炭增加为主。Abstract: Ru/HZSM-5 was prepared and used to upgrade bio-oil online and the changes of bio-oil yield and physicochemical properties were analyzed through the total quality index ( TQI ). The changes of the chemical compositions of the bio-oils were compared; simultaneously, the coking situation of the catalyst was characterized. The results showed that the yield and physicochemical properties of bio-oil obtained by using fresh catalyst were high, and the TQI increased from 0.15 to 6.45; with the increase of using times, the TQI first increased slightly to 6.68, then decreased rapidly to 1.25, and reduced to only 0.27 after the fourth usage. In the initial stage, a small amount of coking reactions made the strong acid sites partially passivated, which improved the aromatization performance. When the catalyst was used twice, the relative content of hydrocarbons in the bio-oil reached 53.79%, of which the relative content of light aliphatic hydrocarbons was 16.87%, and the relative content of monocyclic aromatic hydrocarbons was 32.65%. After the fourth usage, the relative content of hydrocarbons in the bio-oil was only 9.32%, and the catalyst layer basically lost the upgrading effect, and had adverse effects on pyrolysis vapors such as secondary cracking or polymerization. Before the third usage, the low-temperature pyrolytic coke attached to the catalyst surface was dominant. After the third usage, the low-temperature pyrolytic coke and high-temperature catalytic coke increased significantly, and the catalyst activity decreased sharply. Continuous usage of catalyst slightly increased coke, of which the pyrolytic coke increased mainly.
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Key words:
- bio-oil /
- catalytic upgrading /
- Ru/HZSM-5 /
- fuel-grade /
- coking deactivation
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图 1 生物油在线催化提质实验系统
1: temperature controller; 2: catalytic reactor; 3: filter; 4: globe valve A; 5: globe valve B; 6: globe valve C; 7: gas collector; 8: vacuum pump; 9: pressure stabilizing tube; 10: cooling tower; 11: bio-oil collector; 12: cold trap; 13: pyrolysis reactor
Figure 1 Experimental system for online catalytic upgrading of bio-oil
表 1 催化剂的酸性和纹理性质
Table 1 Acidity and texture properties of catalysts
Catalyst B acid/
(μmol·g−1)L acid/
(μmol·g−1)SDFT/
(m2·g−1)vDFT/
(cm3·g−1)Smicro/
(m2·g−1)vmicro/
(cm3·g−1)Average pore width/nm HZSM-5 141.78 33.55 437.15 0.23 324.18 0.12 0.98 Ru/HZSM-5 172.46 17.10 305.00 0.19 230.49 0.08 1.02 表 2 生物油产率、理化特性和TQI的变化
Table 2 Change of bio-oil yields, physicochemical properties and TQI values
Bio-oil Yield/% Vyield pH value VpH HHV
/(MJ·kg−1)VHHV Carbon residue/% wC Oxygen content/% wO TQI BO-0 43.25 1.13 2.22 0.51 18.08 0.69 16.72 1.84 50.86 1.46 0.15 BO-1 32.08 0.84 6.20 1.42 32.81 1.26 3.35 0.37 22.09 0.63 6.45 BO-2 35.47 0.93 6.12 1.40 32.90 1.26 3.55 0.39 21.98 0.63 6.68 BO-3 38.84 1.02 4.44 1.02 26.26 1.01 7.89 0.87 33.93 0.97 1.25 BO-4 41.69 1.09 2.87 0.66 20.08 0.77 14.02 1.54 45.67 1.31 0.27 表 3 BO-0与BO-4中相同化合物含量对比
Table 3 Comparison of the contents of the same compounds in BO-0 and BO-4
No Compound name Structure Formula BO-0/% BO-4/% 1 2-cyclopenten-1-one, 2-methyl- C6H8O 1.70 1.87 2 ethanone, 1-(2-furanyl)- C6H6O2 1.32 1.20 3 2-cyclopenten-1-one, 3,4-dimethyl- C7H10O 3.28 2.03 4 1,2-cyclopentanedione, 3-methyl- C6H8O2 7.94 6.51 5 phenol, 2-methoxy- C7H8O2 11.94 8.90 6 2-cyclopenten-1-one, 3-ethyl-2-hydroxy- C7H10O2 3.30 3.19 7 phenol, 2-methoxy-4-methyl- C8H10O2 1.44 3.03 8 phenol, 4-ethyl-2-methoxy- C9H12O2 1.58 0.91 9 phenol, 2,6-dimethoxy- C8H10O3 22.41 21.46 10 homovanillyl alcohol C9H12O3 2.77 4.07 表 4 不同使用时间后催化剂的结焦量
Table 4 Coke contents of the catalysts after different usage time
Catalyst Fitting/℃ Peak temperature/℃ Peak area/% Coefficient R2 main acromion main acromion total SC-1 384−674 494 604 1.27 0.27 1.54 0.9660 SC-2 383−674 494 603 1.73 0.37 2.10 0.9661 SC-3 352−768 522 664 7.31 1.96 9.27 0.9975 SC-4 308−707 483 613 8.13 2.18 10.31 0.9935 -
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