Biorefining of biocrude oil: recirculation of by-products and hydrothermal autocatalysis

doi:10.16085/j.issn.1000-6613.2020-2183

Abstract

Abstract:

Hydrothermal liquefaction (HTL) can simulate generation of crude oil under high temperature and high pressure. Bio-crude oil prepared by HTL can solve the problem of oil resource depletion in the future. However, the problem of disposal by-products during HTL restricts its sustainable development. One way to solve this problem is direct hydrothermal catalysis for bio-crude oil to reduce processing by-products and then integration of various technologies to in-situ convert by-products into resources. Based on this and according to biorefinery, a developing model integrating hydrothermal technologies to biorefinery of bio-crude oil was discussed in this paper. This model was based on analyzing the characteristics of hydrothermal by-products; then catalysts were prepared via hydrothermal synthesis of solid products, reusing of aqueous products, and separation or completely oxidization of gas products to produce organic acids; and finally, recirculation of hydrothermal by-products in this model was realized and biomass was autocatalyzed to produce biocrude oil again. This model conforms to the concept of green chemical industry and has important significance for accelerating the large-scale production of bio-crude oil and alleviating the energy crisis.

Key words: hydrothermal conversion, bio-crude oil, biorefinery, autocatalysis, biomass

摘要：

利用高温高压条件模拟石油生成的生物质水热液化技术可用于制备生物原油，以替代日益枯竭的石油资源，然而副产物处置问题制约了其可持续发展。解决该问题的方法首先是通过水热定向催化调控减少副产物，然后集成各种技术将副产物尽可能原位资源化。基于此并依据生物炼制的思想，本文对一种集成几种水热技术炼制生物原油的模式进行了讨论。依据生物质水热液化副产物的特性，通过对固体产物水热合成制备催化剂、水相产物回用产生有机酸、气体产物分离或彻底氧化后水热还原生产有机酸等，可实现副产物内循环并强化自催化生成生物原油。指出该模式符合绿色化工的理念，对于加快规模化生产可替代石油的生物原油、缓解能源危机具有重要的参考意义。

关键词: 水热技术, 生物原油, 生物炼制, 自催化, 生物质

CLC Number:

GAO Chuanrui, TIAN Chunyan, LI Zhihe, YI Weiming, YUAN Qiaoxia, FU Peng, ZHANG Yuchun, LI Zhiyu. Biorefining of biocrude oil: recirculation of by-products and hydrothermal autocatalysis[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5348-5359.

高传瑞, 田纯焱, 李志合, 易维明, 袁巧霞, 付鹏, 张玉春, 李治宇. 生物原油炼制：副产物内循环及水热自催化[J]. 化工进展, 2021, 40(10): 5348-5359.

Figures/Tables 7

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催化剂	原料	过程条件	产率提升	对生物原油催化效果						参考文献
催化剂	原料	过程条件	产率提升	C	H	O	N	S	HHV	参考文献
均相催化剂
氢氧化钾	玉米芯	340℃，60min	+49%^TO	-22%	-9%	+67%	+33%	N/A	N/A	［39］
碳酸钾	木屑	280℃，15min	+136%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［40］
碳酸钠	水葫芦		-50%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［27］
	微绿球藻	300℃，60min	-21%^TO	+4%	-4%	-92%	+2%	+70%	-0.9%	［26］
	泡桐	300℃，10min	+18%^HO	+5%	+2%	-13%	N/A	N/A	+7%	［41］
	螺旋藻	350℃，60min	-11%^TO	+3%	+17%	-16%	-34%	+0.5%	-5%	［28］
			+29％^HO	-2%	+11%	+16%	-14%	-3%	+3%	［29］
甲酸		380℃，120min	+28%^TO	-1%	-12%	+18%	-27%	N/A	-7%	［28］
盐酸	纤维素	300℃，0min	+21%^LO	N/A	N/A	N/A	N/A	N/A	N/A	［30］
乙酸	小球藻蛋白	300℃，20min，8.5MPa	降低^LO	-7%	+81%	+3%	-10%	N/A	+18%	［32］
非均相催化剂
铁粉	泡桐	340℃，10min	+51%^HO	+10%	+20%	-29%	N/A	N/A	+20%	［41］
硼酸钙石粉	山毛榉	300℃，0min	+89%^HO	+4%	-4%	-6%	N/A	N/A	+3%	［42］
沸石			+29%^TO	-8%	-7%	+3%	+4%	-12%	-8%	［43］
Pt/Al₂O₃			-12%^TO	+9%	+16%	-37%	-12%	N/A	+11%	［44］
Ni/Al₂O₃			-47%^TO	+13%	+7%	-46%	-12%	N/A	+11%
Co/Mo/Al₂O₃			-26%^TO	+13%	+1%	-51%	+12%	N/A	+9%
CoMo/γ-Al₂O₃	微绿球藻	350℃，60min	+54%^TO	+1%	+1%	-7%	+3%	-31%	+1%	［43］
Ni/SiO₂-Al₂O₃			+44%^TO	0	0	-6%	-11%	-100%	-1%
Pt/C			+34%^TO	+1%	+6%	-8%	-3%	-14%	+3%
Ru/C			+43%^TO	-4%	+1%	+2%	-17%	-63%	-3%
Pd/C			+63%^TO	-3%	+6%	-2%	-7%	-38%	+0.3%
			+4%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［45］
Pt/C		280℃，30min	+6%^HO	N/A	N/A	N/A	N/A	N/A	N/A
Pd/Al₂O₃	小球藻		+8%^HO	N/A	N/A	N/A	N/A	N/A	N/A
Ce/HZSM-5		300℃，20min	+47%^LO	+15%	+52%	-10%	-97%	N/A	+40%	［46］
HZSM-5			+3%^LO	+4%	+25%	-2%	-38%	N/A	+15%
	螺旋藻	380℃，120min	+7%^TO	-0.07%	-5%	-0.8%	+9%	N/A	-2%	［28］
Ni-Mo/Al₂O₃	微绿球藻	340℃，30min	+41%^TO	+1%	+5%	-9%	-6%	N/A	+3%	［47］
Ni-Cu/γ-Al₂O₃	纸铝塑	330℃，30min	+54%^HO	+5%	-1%	-21%	N/A	N/A	+7%	［48］
FeHZSM-5	玉米秸秆	340℃，30min	+25%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［49］

催化剂	原料	过程条件	产率提升	对生物原油催化效果						参考文献
催化剂	原料	过程条件	产率提升	C	H	O	N	S	HHV	参考文献
均相催化剂
氢氧化钾	玉米芯	340℃，60min	+49%^TO	-22%	-9%	+67%	+33%	N/A	N/A	［39］
碳酸钾	木屑	280℃，15min	+136%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［40］
碳酸钠	水葫芦		-50%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［27］
	微绿球藻	300℃，60min	-21%^TO	+4%	-4%	-92%	+2%	+70%	-0.9%	［26］
	泡桐	300℃，10min	+18%^HO	+5%	+2%	-13%	N/A	N/A	+7%	［41］
	螺旋藻	350℃，60min	-11%^TO	+3%	+17%	-16%	-34%	+0.5%	-5%	［28］
			+29％^HO	-2%	+11%	+16%	-14%	-3%	+3%	［29］
甲酸		380℃，120min	+28%^TO	-1%	-12%	+18%	-27%	N/A	-7%	［28］
盐酸	纤维素	300℃，0min	+21%^LO	N/A	N/A	N/A	N/A	N/A	N/A	［30］
乙酸	小球藻蛋白	300℃，20min，8.5MPa	降低^LO	-7%	+81%	+3%	-10%	N/A	+18%	［32］
非均相催化剂
铁粉	泡桐	340℃，10min	+51%^HO	+10%	+20%	-29%	N/A	N/A	+20%	［41］
硼酸钙石粉	山毛榉	300℃，0min	+89%^HO	+4%	-4%	-6%	N/A	N/A	+3%	［42］
沸石			+29%^TO	-8%	-7%	+3%	+4%	-12%	-8%	［43］
Pt/Al₂O₃			-12%^TO	+9%	+16%	-37%	-12%	N/A	+11%	［44］
Ni/Al₂O₃			-47%^TO	+13%	+7%	-46%	-12%	N/A	+11%
Co/Mo/Al₂O₃			-26%^TO	+13%	+1%	-51%	+12%	N/A	+9%
CoMo/γ-Al₂O₃	微绿球藻	350℃，60min	+54%^TO	+1%	+1%	-7%	+3%	-31%	+1%	［43］
Ni/SiO₂-Al₂O₃			+44%^TO	0	0	-6%	-11%	-100%	-1%
Pt/C			+34%^TO	+1%	+6%	-8%	-3%	-14%	+3%
Ru/C			+43%^TO	-4%	+1%	+2%	-17%	-63%	-3%
Pd/C			+63%^TO	-3%	+6%	-2%	-7%	-38%	+0.3%
			+4%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［45］
Pt/C		280℃，30min	+6%^HO	N/A	N/A	N/A	N/A	N/A	N/A
Pd/Al₂O₃	小球藻		+8%^HO	N/A	N/A	N/A	N/A	N/A	N/A
Ce/HZSM-5		300℃，20min	+47%^LO	+15%	+52%	-10%	-97%	N/A	+40%	［46］
HZSM-5			+3%^LO	+4%	+25%	-2%	-38%	N/A	+15%
	螺旋藻	380℃，120min	+7%^TO	-0.07%	-5%	-0.8%	+9%	N/A	-2%	［28］
Ni-Mo/Al₂O₃	微绿球藻	340℃，30min	+41%^TO	+1%	+5%	-9%	-6%	N/A	+3%	［47］
Ni-Cu/γ-Al₂O₃	纸铝塑	330℃，30min	+54%^HO	+5%	-1%	-21%	N/A	N/A	+7%	［48］
FeHZSM-5	玉米秸秆	340℃，30min	+25%^HO	N/A	N/A	N/A	N/A	N/A	N/A	［49］

原料	操作条件	pH	TOC/mg·L^-1	TN/mg·L^-1	参考文献
小球藻	260～300℃，30～90min	7.77～8.29	N/A	11000～37000	［62］
天然蓝藻	340℃，60min	N/A	37.22	2215	［63］
核桃壳	280℃，30min	N/A	22900	N/A	［64］
团集江蓠	350℃，15min	N/A	2800	6400	［65］
细江蓠	350℃，15min	N/A	1750	2100	［65］
微绿球藻	350℃，20min	8.28	25.78	10.18	［26］
等鞭金藻	350℃，20min	6.8	17.24	8.08	［26］
锯末	250℃，60min	8.12	N/A	N/A	［66］

原料	操作条件	pH	TOC/mg·L^-1	TN/mg·L^-1	参考文献
小球藻	260～300℃，30～90min	7.77～8.29	N/A	11000～37000	［62］
天然蓝藻	340℃，60min	N/A	37.22	2215	［63］
核桃壳	280℃，30min	N/A	22900	N/A	［64］
团集江蓠	350℃，15min	N/A	2800	6400	［65］
细江蓠	350℃，15min	N/A	1750	2100	［65］
微绿球藻	350℃，20min	8.28	25.78	10.18	［26］
等鞭金藻	350℃，20min	6.8	17.24	8.08	［26］
锯末	250℃，60min	8.12	N/A	N/A	［66］

原料	操作条件	循环次数	检测出的有机酸	回用效果	参考文献
白杨木	400℃，7.1～11.1h	3	N/A	第1~3批次处理产油率上升，第4批次产率降低。水相中无机物和水溶性有机物随批次累积，灰分沉积率从6.2增长到12.6%。TOC含量从54.1g/L增加到136.2g/L	［67］
玉米秸秆	300℃，30min	3	乙酸、丙酸	有机酸含量富集，促进酚酮类转化，生物原油产率提高了3.89%，固体产物中碳含量提高了0.8%	［68］
刚毛藻江蓠	350℃，15min	2	N/A	随着循环次数的增加，气体产物和液体产物的总量下降，固体沉积率下降，产油率分别增加了8.1%和8.89%	［65］
干酒糟	350℃，20min	9	乙酸、乙酰丙酸、异丁酸、异戊酸	当循环第8次的时候，生物原油的产率从39.4%大幅增加到54.5%，同时循环后的水相体积更小，浓度更高。循环9次，生物原油的含氧量降低了52%。TOC和TN的浓度随循环次数逐渐增大	［58］
海藻-锯末	250℃，60min	1	乙酸、2-己酸	水相循环后，产油率由11.1%降到了9.2%，固体残渣生成增加，从31.3%~38.9%。通过回用能大幅度消减过程副产物	［66］
大麦秸秆	300℃，15min	3	乳酸，乙酸，2-羟基异丁酸， 2-丁烯二酸，2-羟基-3-甲基戊酸	循环3次后，产油率由34.9%增长到38.4%。循环前后生物原油的元素并无太大差异，热值有略微提升。水相有机物主要聚合为固体残渣导致循环后的固体残渣产率是未循环的两倍。固体残渣的碳含量随循环次数增加而增加，氧含量则相反，热值显著增加	［71］