Energy consumption of condensation-hydrogenation process to prepare alkanes from lignocellulose biomass
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摘要:
随着纤维素原料制备糠醛、5-羟甲基糠醛、乙酰丙酸平台化合物技术的日益成熟，平台化合物再利用技术成为国际热点。通过研究平台化合物自缩合与交叉缩合工艺特点，以及后续加氢制备合成航油烷烃的可行路径，设计了利用2条纤维素生物质平台化合物全组分制备航油的工艺，通过能耗分析与评价，确定了每条工艺路线中的主要能耗单元及主要输入的耗能物质。结果表明：糠醛-乙酰丙酸交叉缩合加氢工艺相比糠醛自缩合加氢工艺、5-羟甲基糠醛自缩合加氢工艺在热耗、氢耗等方面有明显优势。为实现秸秆的全组分利用，提出糠醛-乙酰丙酸交叉缩合加氢联合5-羟甲基糠醛自缩合加氢工艺，根据目前的工艺技术，航油收率可达19.6%。
Abstract:With the increasing maturity of technology for preparing furfural, 5-hydroxymethylfurfural, levulinic acid from lignocellulose biomass, platform compounds reuse technology has become an international hot spot. By studying the characteristics of the self-condensation and cross-condensation processes of platform compounds, as well as the feasible paths for subsequent hydrogenation to prepare synthetic jet fuel alkanes, two processes for preparing jet fuel with the full component use of lignocellulose biomass derived platform compounds were designed. Through energy consumption analysis and evaluation, the main energy consumption units and main input energy consumption materials in each process route were determined. Furfural-levulinic acid cross-condensation hydrogenation process compared with furfural self-condensation hydrogenation process and 5-hydroxymethyl furfural self-condensation hydrogenation process has obvious advantages in terms of heat consumption and hydrogen consumption. In order to realize the full-component utilization of straw, furfural-levulinic acid cross-condensation hydrogenation is combined with 5-hydroxymethylfurfural self-condensation hydrogenation process, and according to the current process technology, the jet fuel yield can reach 19.6%.
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Key words:
- platform compounds /
- condensation /
- hydrogenation /
- energy consumption analysis /
- alternative jet fuel
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图 1 ASPEN PLUS模拟的纤维素航油缩合-加氢工艺
Figure 1. Condensation-hydrogenation process simulated by ASPEN PLUS to prepare alkanes from lignocellulose biomass
图 3 三种催化糠醛二聚制备C10烷烃的路径
Figure 3. Three pathways of catalyzed dimerization of FF for preparation of C10 alkanes
图 4 糠醛借助甲基呋喃作为桥梁三聚制备C15烷烃
Figure 4. Methylfuran assisted trimerization of FF for preparation of C15 alkanes
图 5 四种催化5-羟甲基糠醛二聚制备C12烷烃的路径
Figure 5. Four pathways of catalyzed dimerization of HMF for preparation of C12 alkanes
图 9 糠醛及5-羟甲基糠醛的醇类衍生物聚合生成烷烃
Figure 9. Alcohols derived from FF/HMF oligomerize to prepare alkanes
图 10 糠醛、5-羟甲基糠醛与环酮聚合生成C15~C18环烷烃
Figure 10. Condensation of FF/HMF and cyclic ketones to produce C15~C18 cycloalkanes
图 11 LA-FF缩合和5-羟甲基糖醛自缩合结合的纤维素航油制备工艺
Figure 11. Preparation process of alkanes from lignocellulose biomass by LA-FF condensation and HMF self-condensation
图 12 糖醛自缩合和5-羟甲基糖醛自缩合结合的纤维素航油制备工艺
Figure 12. Preparation process of alkanes from lignocellulose biomass by self-condensation of FF and HMF
表 1 三种纤维素类生物质前驱体缩合-加氢制备航油烷烃的方法
Table 1. Three ways of alkanes production by condensation and hydrogenation of precursors derived from lignocellulose-derived chemicals
平台化合物 类别 缩合过程 加氢过程 综合收率/% 参考文献 缩合收率/% 催化剂 温度/℃ 产物烷烃碳数 理论氢耗/g 加氢收率/% 催化剂 温度/℃ FF Zn催化FF二聚 98.51 还原剂Zn 50 10 0.103 61.26 Pt/C 300 60.35 [11] HMF TPT催化HMF二聚 95 TPT 60 12 0.103 49.92 Pd/C 250 47.42 [4] FF、LA LA-FF交叉缩合 79.21 NaOH 50 15、10 0.111 52.23 Ru/C
Ru/Al2O3300 41.37 [22-23] 注：缩合收率=缩合产物质量/平台化合物的质量×100%；加氢收率=烷烃质量/缩合产物质量×100%；理论氢耗=每克缩合产物加氢过程理论耗氢质量；综合收率=缩合收率×加氢收率×100%。 
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表 2 基于ASPEN PLUS模拟的各缩合-加氢路径的能耗情况
Table 2. Energy consumption of different pathways in condensation and hydrogenation by ASPEN PLUS simulation
路径 缩合单元 反应物组成/% 产物组成/% 反应条件 化学反应热/(kJ·mol-1) 热负荷/(J·g-1) LA-FF
缩合加氢FF 1.85 C10中间体 0.17 50℃ 1atm -106.35(参考组分：LA) 9 020.25 LA 1.12 C15中间体 2.17 NaOH 1.13 其他 97.66 H2O 95.9 FF自缩
合加氢FF 5.78 C10中间体 5.69 50℃ 1atm 413.35(参考组分：FF) 9 886.19 Zn 3.94 其他 94.31 NaOH 9.03 H2O 81.25 HMF自缩
合加氢HMF 100 C12中间体 95 60℃ 1atm 81.44(参考组分：HMF) 1 451.1 TPT 其他 5 KOtBu 路径 加氢单元 反应物组成/% 产物组成/% 反应条件 化学反应热/(kJ·mol-1) 热负荷/(J·g-1) LA-FF
缩合加氢含氧中间体 32.23 C10烷烃 1.17 300℃ 4 MPa -1 186.01(参考组分：含氧中间体) 2 836.74 甲醇 64.24 C15烷烃 15.67 催化剂 其他 83.16 H2 3.53 FF自缩合加氢 含氧中间体 1.9 C10烷烃 1.16 300℃ 10 MPa -1 317.28
(参考组分：含氧中间体)112 654.2 水 97.9 其他 98.84 Pt/C 固体酸 H2 0.2 HMF自缩合加氢 含氧中间体 0.59 C12烷烃 0.29 250℃ 4.2 MPa -1 105.91(参考组分：含氧中间体) 61 555.36 醋酸 99.35 其他 99.71 Pd/C La(OTf)3 H2 0.06 路径 泵单元 余热收集单元 电功/(J·g-1) 缩合副产物余热/(J·g-1) 加氢产物余热/(J·g-1) LA-FF缩合加氢 62.99 -7 780.66 -6 962.93 FF自缩合加氢 2 825.2 -2 287.26 -94 188.84 HMF自缩合加氢 4 289.59 -7.56 -58 110.59 注：表中各单元能耗基准为各路径生成每克航油产物所消耗的能量，正值表示吸热，负值表示放热；1 atm=1.013 25×105 Pa。
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表 3 基于航油产物的各缩合-加氢路径能耗汇总
Table 3. Energy consumption of different pathways in condensation and hydrogenation based on alkanes products
基准 路径 反应热耗/kJ 电耗/J (反应热耗+电耗)/J 余热收集/J 加氢氢耗/g 基于每克航油产物 LA-FF
缩合加氢考虑C10与C15 11 856.99 62.99 11 919.98 -14 743.59 0.142 3 只考虑C10 171 165.14 909.31 172 074.45 -212 835.52 2.054 3 只考虑C15 12 739.48 67.68 12 807.16 -15 840.93 0.152 9 FF自缩合加氢 122 540.42 2 825.20 125 365.62 -96 476.10 0.141 7 HMF自缩合加氢 63 006.46 4 289.59 67 296.05 -58 118.15 0.153 8 基于每焦耳航油产物 LA-FF
缩合加氢考虑C10与C15 0.27 0.001 4 0.27 -0.34 只考虑C10 3.87 0.020 6 3.89 -4.81 只考虑C15 0.29 0.001 5 0.29 -0.36 FF自缩合加氢 2.77 0.063 9 2.83 -2.18 HMF自缩合加氢 1.43 0.097 2 1.53 -1.32 / 注：LA-FF缩合加氢路径航油产物同时包含C10和C15烷烃，表中给出了只考虑C10或C15航油的情况；LHVC10=44.24 kJ/g, LHVC12=44.11 kJ/g, LHVC15=43.98 kJ/g。
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表 4 各种工艺缩合-加氢过程的能耗指标
Table 4. Energy consumption indexes of condensation and hydrogenation of various processes
工艺 航油产率 热耗+电耗 氢耗 基于每克秸秆/g 基于每克秸秆/J 基于每克秸秆/kJ 基于每克航油/kJ 基于每焦耳航油/J 基于每克秸秆/g 基于每克航油/g 基于每焦耳航油/g LA-FF缩合 0.094 2 4 144.79 1.12 11.92 0.27 0.013 4 0.142 3 3.234 3 FF自缩合 0.085 6 3 785.62 10.73 125.37 2.83 0.012 1 0.141 7 3.202 7 HMF自缩合 0.145 9 6 436.19 9.82 67.30 1.53 0.022 4 0.153 8 3.487 8 LA-FF缩合与HMF自缩合结合 0.196 0 8 634.23 7.97 40.68 0.92 0.029 1 0.148 3 3.366 1 FF自缩合与HMF自缩合结合 0.231 5 10 221.82 20.55 88.76 2.01 0.034 6 0.149 4 3.382 3
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