水相生物油原位汽化-催化重整制氢工艺优化

doi:10.16085/j.issn.1000-6613.2021-1674

化工进展 ›› 2022, Vol. 41 ›› Issue (3): 1340-1348.DOI: 10.16085/j.issn.1000-6613.2021-1674

• 可再生能源的开发利用 • 上一篇下一篇

水相生物油原位汽化-催化重整制氢工艺优化

张安东¹^,²(), 李志合¹^,²(), 王丽红¹^,², 王绍庆¹^,², 梁昌明¹^,², 万震¹^,²

^1.山东理工大学农业工程与食品科学学院，山东淄博 255000
^2.山东理工大学山东省清洁能源工程技术研究中心，山东淄博 255000

收稿日期:2021-08-05 修回日期:2021-09-01 出版日期:2022-03-23 发布日期:2022-03-28
通讯作者: 李志合
作者简介:张安东（1990—），男，博士研究生，主要从事生物油催化重整制氢研究。E-mail：936085286@qq.com。
基金资助:
国家重点研发计划(2019YFD1100600);国家自然科学基金(52176192);山东省自然科学基金(ZR2020ME185)

Optimization of in-situ gasification & catalytic reforming process for hydrogen production from aqueous bio-oil

ZHANG Andong¹^,²(), LI Zhihe¹^,²(), WANG Lihong¹^,², WANG Shaoqing¹^,², LIANG Changming¹^,², WAN Zhen¹^,²

^1.School of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, Shandong, China
^2.Shandong Research Center of Engineering and Technology for Clean Energy, Shandong University of Technology, Zibo 255000, Shandong, China

Received:2021-08-05 Revised:2021-09-01 Online:2022-03-23 Published:2022-03-28
Contact: LI Zhihe

摘要/Abstract

摘要：

为了“碳达峰，碳中和”的目标，开发以可再生能源为主体的绿色制氢技术势在必行。基于原位汽化策略，本文在自主研发的固定床/流化床催化重整一体式反应装置上开展水相生物油催化重整制氢对比实验。结果发现，在经原位汽化改进后的催化重整制氢工艺中，流化床内水相生物油转化效率（95%左右）明显高于固定床（80%左右），两种反应体系中的H₂选择性均能100%保持较长时间稳定，但在反应进行到100min左右时，固定床反应体系中出现了明显的催化剂积炭失活现象，而流化床体系中催化剂始终保持较高活性，未发现积炭生成。从反应后液相产物分析可以发现，流化床反应体系中水相生物油各组分接近完全转化，而固定床反应体系中除有少量乙酸和苯酚残留外，还有少量酮类物质产生（丙酮等）。因此，原位汽化策略可以有效促进水相生物油催化重整制氢过程，结合流化床中催化剂的流化效果，将极大促进生物质-生物油-氢气的产业链推广进程。

关键词: 水相生物油, 催化剂, 氢, 原位汽化, 流化床

Abstract:

Due to the component diversity of aqueous bio-oil, it faces the problems of uneven component gasification and low conversion efficiency of raw materials in the process of catalytic reforming for hydrogen production. In this study, the feeding system was optimized to make the aqueous bio-oil instantaneously vaporized in the reaction tube. On this basis, a set of catalytic reforming hydrogen production device integrating fixed bed and fluidized bed was designed and processed. A series of experiments were carried out to explore the conversion efficiency and hydrogen production effect of aqueous bio-oil in two reactors by in-situ gasification strategy. The results showed that the conversion efficiency of aqueous bio-oil in fluidized bed (about 95%) was significantly higher than that in fixed bed (about 80%), and the H₂ selectivity in both reaction systems could remain stable at 100% for a long time. The obvious deactivation of catalyst by carbon deposition occurred in the later stage (about 100min) of the fixed bed reaction system, while in the fluidized bed, the catalysts always maintained high activity without carbon deposition. Their liquid products were analyzed, and all the components of aqueous bio-oil were nearly completely transformed in fluidized bed, while a small amount of acetic acid and phenol remained for fixed bed and some ketones (acetone, etc.) were generated at the same time. These results prove that the in-situ gasification strategy greatly promotes the total component transformation of aqueous bio-oil. Combined with the fluidization effect of catalyst in fluidized bed, which can greatly enhance the catalytic conversion efficiency and stability, it will greatly promote the industrial chain process from biomass to bio-oil to hydrogen.

Key words: aqueous bio-oil, catalyst, hydrogen, in-situ gasification, fluidized-bed

中图分类号:

张安东, 李志合, 王丽红, 王绍庆, 梁昌明, 万震. 水相生物油原位汽化-催化重整制氢工艺优化[J]. 化工进展, 2022, 41(3): 1340-1348.

ZHANG Andong, LI Zhihe, WANG Lihong, WANG Shaoqing, LIANG Changming, WAN Zhen. Optimization of in-situ gasification & catalytic reforming process for hydrogen production from aqueous bio-oil[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1340-1348.

图/表 8

参考文献 27

1	GUPTA S, MONDAL P, BORUGADDA V B, et al. Advances in upgradation of pyrolysis bio-oil and biochar towards improvement in bio-refinery economics: a comprehensive review[J]. Environmental Technology & Innovation, 2021, 21: 101276.
2	KAN T, STREZOV V, EVANS T, et al. Catalytic pyrolysis of lignocellulosic biomass: a review of variations in process factors and system structure[J]. Renewable and Sustainable Energy Reviews, 2020, 134: 110305.
3	KUMAR R, STREZOV V. Thermochemical production of bio-oil: a review of downstream processing technologies for bio-oil upgrading, production of hydrogen and high value-added products[J]. Renewable and Sustainable Energy Reviews, 2021, 135: 110152.
4	HU X, GHOLIZADEH M. Progress of the applications of bio-oil[J]. Renewable and Sustainable Energy Reviews, 2020, 134: 110124.
5	陈爱苹. 生物油轻质组分水相重整制氢的研究[D]. 杭州: 浙江大学, 2017.
	CHEN Aiping. Study on aqueous-phase reforming of low-boiling fraction of bio-oil for hydrogen production[D]. Hangzhou: Zhejiang University, 2017.
6	毕冬梅, 张凯真, 易维明, 等. 白云石基多孔陶瓷负载Al₂O₃催化生物质热解试验[J]. 农业机械学报, 2019, 50(10): 315-322.
	BI Dongmei, ZHANG Kaizhen, YI Weiming, et al. Catalytic pyrolysis of biomass with porous ceramic loading aluminum oxide[J]. Transactions of the Chinese Society for Agricultural Machinery, 2019, 50(10): 315-322.
7	BRIDGWATER A V. Review of fast pyrolysis of biomass and product upgrading[J]. Biomass and Bioenergy, 2012, 38: 68-94.
8	王治斌, 孙来芝, 陈雷, 等. 生物油水蒸气催化重整制氢研究进展[J]. 化工进展, 2021, 40(1): 151-163.
	WANG Zhibin, SUN Laizhi, CHEN Lei, et al. Progress in hydrogen production by steam catalytic reforming of bio-oil[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 151-163.
9	SETIABUDI H D, AZIZ M A A, ABDULLAH S, et al. Hydrogen production from catalytic steam reforming of biomass pyrolysis oil or bio-oil derivatives: a review[J]. International Journal of Hydrogen Energy, 2020, 45(36): 18376-18397.
10	ARANDIA A, REMIRO A, DE OAR-ARTETA L, et al. Reaction conditions effect and pathways in the oxidative steam reforming of raw bio-oil on a Rh/CeO₂-ZrO₂ catalyst in a fluidized bed reactor[J]. International Journal of Hydrogen Energy, 2017, 42(49): 29175-29185.
11	RUOCCO C, PALMA V, RICCA A. Hydrogen production by oxidative reforming of ethanol in a fluidized bed reactor using a PtNi/CeO₂SiO₂ catalyst[J]. International Journal of Hydrogen Energy, 2019, 44(25): 12661-12670.
12	VICENTE J, MONTERO C, EREÑA J, et al. Coke deactivation of Ni and Co catalysts in ethanol steam reforming at mild temperatures in a fluidized bed reactor[J]. International Journal of Hydrogen Energy, 2014, 39(24): 12586-12596.
13	ZHANG A D, LIANG C M, WANG L H, et al. Study on the trigger mechanism and carbon behavior of catalytic reforming of wood vinegar[J]. International Journal of Hydrogen Energy, 2020, 45(29): 14669-14678.
14	FU P, ZHANG A D, LUO S, et al. Comparative study on the catalytic steam reforming of biomass pyrolysis oil and its derivatives for hydrogen production[J]. RSC Advances, 2020, 10(22): 12721-12729.
15	张安东. 生物油及其典型组分重整制氢实验研究[D]. 淄博: 山东理工大学, 2015.
	ZHANG Andong. Study of hydrogen production by reforming of bio-oil and its model compounds[D]. Zibo: Shandong University of Technology, 2015.
16	刘守光, 刘悦, 刘一默, 等. 介孔Ni/MgO催化剂催化水蒸气重整生物质油制氢[J]. 燃料化学学报, 2020, 48(4): 424-431.
	LIU Shouguang, LIU Yue, LIU Yimo, et al. Hydrogen production by steam reforming of bio-oils over mesoporous Ni/MgO catalyst[J]. Journal of Fuel Chemistry and Technology, 2020, 48(4): 424-431.
17	MIAO Z W, HU Z F, JIANG E C, et al. Hydrogen-rich syngas production by chemical looping reforming on crude wood vinegar using Ni-modified HY zeolite oxygen carrier[J]. Fuel, 2020, 279: 118547.
18	MEGÍA P J, VIZCAÍNO A J, RUIZ-ABAD M, et al. Coke evolution in simulated bio-oil aqueous fraction steam reforming using Co/SBA-15[J]. Catalysis Today, 2021, 367: 145-152.
19	ZENG X, WANG F, HAN Z N, et al. Assessment of char property on tar catalytic reforming in a fluidized bed reactor for adopting a two-stage gasification process[J]. Applied Energy, 2019, 248: 115-125.
20	梁昌明, 张安东, 李志合, 等. 镍基催化剂催化木醋液重整制氢实验研究[J]. 燃料化学学报, 2021, 49(2): 168-177.
	LIANG Changming, ZHANG Andong, LI Zhihe, et al. Hydrogen production from wood vinegar reforming over cobalt modified nickel-based catalyst[J]. Journal of Fuel Chemistry and Technology, 2021, 49(2): 168-177.
21	刘嘉辉, 孙道安, 杜咏梅, 等. 芳烃蒸汽催化重整制氢研究进展[J]. 化工进展, 2021, 40(9): 4782-4790.
	LIU Jiahui, SUN Dao’an, DU Yongmei, et al. Progress on hydrogen production from catalytic steam reforming of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4782-4790.
22	CHEN G Y, TAO J Y, LIU C X, et al. Hydrogen production via acetic acid steam reforming: a critical review on catalysts[J]. Renewable and Sustainable Energy Reviews, 2017, 79: 1091-1098.
23	ZADEH SAHRAEI O ALI, LARACHI F, ABATZOGLOU N, et al. Hydrogen production by glycerol steam reforming catalyzed by Ni-promoted Fe/Mg-bearing metallurgical wastes[J]. Applied Catalysis B: Environmental, 2017, 219: 183-193.
24	ZHANG A D, LI Z H, YI W M, et al. Study the reaction mechanism of catalytic reforming of acetic acid through the instantaneous gas production[J]. International Journal of Hydrogen Energy, 2019, 44(39): 21279-21289.
25	MONTERO C, OCHOA A, CASTAÑO P, et al. Monitoring NiO and coke evolution during the deactivation of a Ni/La₂O₃-αAl₂O₃ catalyst in ethanol steam reforming in a fluidized bed[J]. Journal of Catalysis, 2015, 331: 181-192.
26	OCHOA A, BILBAO J, GAYUBO A G, et al. Coke formation and deactivation during catalytic reforming of biomass and waste pyrolysis products: a review[J]. Renewable and Sustainable Energy Reviews, 2020, 119: 109600.
27	林俊明, 岑洁, 李正甲, 等. Ni基重整催化剂失活机理研究进展[J]. 化工进展, 2022, 41（1）： 201-209.
	LIN Junming, CEN Jie, LI Zhengjia, et al. Development on deactivation mechanism of Ni-based reforming catalysts[J]. Chemical Industry and Engineering Progress, 2022, 41（1）： 201-209.

颜色	ρ/kg·m^-3	pH	含水率/%	元素分析/%				H/C^②
颜色	ρ/kg·m^-3	pH	含水率/%	N	C	H	O^①	H/C^②
棕黑色	1045	2.13	85.56	1.04	14.33	13.36	71.37	11.19

颜色	ρ/kg·m^-3	pH	含水率/%	元素分析/%				H/C^②
颜色	ρ/kg·m^-3	pH	含水率/%	N	C	H	O^①	H/C^②
棕黑色	1045	2.13	85.56	1.04	14.33	13.36	71.37	11.19

类别	名称	相对峰面积比/%
水	水	25.89
酯类	乙酸甲酯	2.36
酯类	丁内酯	1.09
酸类	乙酸	17.97
	丙酸	1.96
	丁酸	0.59
	2-甲基丙酸酸酐	2.41
酮类	丙酮	0.64
	1-羟基，2-丙酮	7.25
	3-羟基，2-丁酮	0.58
	环戊酮	0.56
	1-羟基，2-丁酮	1.53
	1-乙酰氧基，2-丙酮	0.50
	2-甲基环戊酮	0.73
	2-呋喃基乙烯酮	0.51
	3-甲基环戊酮	0.74
	五氢呋喃酮	0.64
	2-羟基-3-甲基环戊酮	2.69
	3-甲基五氢呋喃酮	0.55
	2-羟基-3-乙基环戊酮	0.80
	环戊基乙酮	0.57
	5-异丙基二氢呋喃酮	1.03
	1-(4-羟基-3-甲氧基苯基)-丙酮	0.53
醇类	乙二醇	1.52
醛类	5-甲基糠醛	0.74
酚类	苯酚	3.39
	2-甲基苯酚	2.70
	4-甲基苯酚	0.63
	2-甲氧基苯酚	1.91
	2-甲氧基-4-甲基苯酚	0.91
	2，5-双甲基苯酚	0.50
	2-甲氧基4-乙基苯酚	0.63
	2，6-二甲氧基苯酚	2.24
	3-甲氧基甲基，4-甲氧基苯酚	0.70
	对苯二酚	0.57
糖类	3，4-脱水-D-半乳糖	0.88
	1，4∶3，6-二脱水-α-D-吡喃葡萄糖	1.16
	1，6-脱水-α-D-葡萄糖（左旋葡聚糖）	5.33
其他	吡啶	0.52

类别	名称	相对峰面积比/%
水	水	25.89
酯类	乙酸甲酯	2.36
酯类	丁内酯	1.09
酸类	乙酸	17.97
	丙酸	1.96
	丁酸	0.59
	2-甲基丙酸酸酐	2.41
酮类	丙酮	0.64
	1-羟基，2-丙酮	7.25
	3-羟基，2-丁酮	0.58
	环戊酮	0.56
	1-羟基，2-丁酮	1.53
	1-乙酰氧基，2-丙酮	0.50
	2-甲基环戊酮	0.73
	2-呋喃基乙烯酮	0.51
	3-甲基环戊酮	0.74
	五氢呋喃酮	0.64
	2-羟基-3-甲基环戊酮	2.69
	3-甲基五氢呋喃酮	0.55
	2-羟基-3-乙基环戊酮	0.80
	环戊基乙酮	0.57
	5-异丙基二氢呋喃酮	1.03
	1-(4-羟基-3-甲氧基苯基)-丙酮	0.53
醇类	乙二醇	1.52
醛类	5-甲基糠醛	0.74
酚类	苯酚	3.39
	2-甲基苯酚	2.70
	4-甲基苯酚	0.63
	2-甲氧基苯酚	1.91
	2-甲氧基-4-甲基苯酚	0.91
	2，5-双甲基苯酚	0.50
	2-甲氧基4-乙基苯酚	0.63
	2，6-二甲氧基苯酚	2.24
	3-甲氧基甲基，4-甲氧基苯酚	0.70
	对苯二酚	0.57
糖类	3，4-脱水-D-半乳糖	0.88
	1，4∶3，6-二脱水-α-D-吡喃葡萄糖	1.16
	1，6-脱水-α-D-葡萄糖（左旋葡聚糖）	5.33
其他	吡啶	0.52

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	杨建平. 降低HPPO装置反应系统原料消耗的PSE[J]. 化工进展, 2023, 42(S1): 21-32.
[8]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	葛全倩, 徐迈, 梁铣, 王凤武. MOFs材料在光电催化领域应用的研究进展[J]. 化工进展, 2023, 42(9): 4692-4705.
[12]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[13]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[14]	史柯柯, 刘木子, 赵强, 李晋平, 刘光. 镁基储氢材料的性能及研究进展[J]. 化工进展, 2023, 42(9): 4731-4745.
[15]	刘木子, 史柯柯, 赵强, 李晋平, 刘光. 固体储氢材料的研究进展[J]. 化工进展, 2023, 42(9): 4746-4769.

水相生物油原位汽化-催化重整制氢工艺优化

Optimization of in-situ gasification & catalytic reforming process for hydrogen production from aqueous bio-oil

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 27

相关文章 15

编辑推荐

Metrics

本文评价