农林业固废超临界水热化学制氢进展——反应系统及应用

郭烈锦; 黄勇; 王乐; 葛晖; 杜明明; 刘兆峥; 陈渝楠

doi:10.7652/xjtuxb202302001

您当前的位置：

首页 >

文章列表页 >

农林业固废超临界水热化学制氢进展——反应系统及应用

专题新能源与储能 | 更新时间：2025-07-09

- 农林业固废超临界水热化学制氢进展——反应系统及应用
- Review of Thermochemical Conversion of Agriculture and Forestry Waste for Hydrogen Production in Supercritical Water—Reaction Systems and Applications
- 西安交通大学学报 2023年57卷第2期页码：1-11
- 作者机构：
  
  西安交通大学动力工程多相流国家重点实验室,西安,710049
- 作者简介：
  
  : 2022-08-31。作者简介: 郭烈锦(1963—),男,教授,博士生导师,中国科学院院士。基金项目: 国家自然科学基金资助项目(51888103)。
- 基金信息：
  
  : 2022-08-31。作者简介: 郭烈锦(1963—),男,教授,博士生导师,中国科学院院士。基金项目: 国家自然科学基金资助项目(51888103)。
- DOI：10.7652/xjtuxb202302001
  中图分类号： TK421.4
- 网络首发：2023-02-10，
  
  纸质出版：2023
- 稿件说明：
移动端阅览
郭烈锦, 黄勇, 王乐, 等. 农林业固废超临界水热化学制氢进展——反应系统及应用[J]. 西安交通大学学报, 2023,57(2):1-11.

GUO Liejin, HUANG Yong, WANG Le, et al. Review of Thermochemical Conversion of Agriculture and Forestry Waste for Hydrogen Production in Supercritical Water—Reaction Systems and Applications[J]. 2023, 57(2): 1-11.
郭烈锦, 黄勇, 王乐, 等. 农林业固废超临界水热化学制氢进展——反应系统及应用[J]. 西安交通大学学报, 2023,57(2):1-11. DOI： 10.7652/xjtuxb202302001.

GUO Liejin, HUANG Yong, WANG Le, et al. Review of Thermochemical Conversion of Agriculture and Forestry Waste for Hydrogen Production in Supercritical Water—Reaction Systems and Applications[J]. 2023, 57(2): 1-11. DOI： 10.7652/xjtuxb202302001.

摘要

超临界水热化学制氢技术能够将农林业固废中的生物质有机成分转化成氢能

是一种高效、经济和清洁的农林业固废能源化利用技术。本文主要从反应系统的角度出发

对超临界水热化学制氢技术进行了深入的分析。对不同类型反应系统的研究表明

间歇式反应器便于实现反应温度、压力以及反应时间的控制

但因难以扩大生产规模和无法实现热回收而不适合工业化推广; 连续式反应系统具有反应性能好、经济效益高等优点

是农林废弃物超临界水热化学制氢技术从实验室走向工业化应用的必由之路。对于连续式系统

反应器材质以耐高温、耐高压和耐腐蚀的哈氏合金或铬镍铁合金为主; 系统压力输送采用恒流泵和背压阀相结合的设计控制系统内部压力; 超临界水的加热采用带嵌入式热电偶的接触式电阻加热方式可以实现系统快速和可控地升温; 反应物料直接输送进热态超临界水中可以显著减少焦炭焦油的生成。对于不同的农林业固废

超临界水热化学制氢技术均能实现生物质向氢能的转化

但反应规律存在很大差异性

其中木质纤维素生物质废弃物的纤维素含量越高反应越容易进行

而禽畜粪便废弃物还要考虑重金属等污染物的转化问题。未来研究重点方向为:反应器的防腐蚀问题

反应器堵塞和盐沉积问题

系统在线排渣问题

针对工业化系统的建模设计、经济衡算以及与其他系统耦合的问题。

Abstract

Supercritical hydrothermal chemical hydrogen production technology converts biomass organic components in agroforestry solid waste into hydrogen energy. It is an efficient

economical and clean way to make use of energy in agroforestry solid waste. This paper carries out an in-depth analysis on this technology mainly from the perspective of reaction systems. According to studies on various types of reaction systems

it is concluded that it is easy to implement control over reaction temperature

reaction pressure

and reaction time with batch reactor. However

considering the difficulty in scaling up the production and recovering the thermal energy

it is not practical to use this type of reactor in industrial applications. Boasting advantages of good reaction performance and high economic benefits

continuous reaction system is the only way to usher supercritical hydrothermal chemical hydrogen production with agroforestry solid waste from laboratory to industrial applications. The reactor in continuous reaction systems is mainly made of Hastelloy or Inconel alloy resistant to high temperature

high pressure and corrosion. The combination of constant current pumps and back pressure valve is used for internal pressure control of the system. Contact resistive heating with embedded thermocouples is adopted for heating of supercritical water to achieve a rapid and controllable temperature rise of the system. The formation of coke tar is significantly reduced as the reaction material is sent into the hot supercritical water directly. Supercritical hydrothermal chemical hydrogen production technology enables conversion of biomass in various agroforestry solid wastes into hydrogen

but with significant difference in reaction characteristics depending on the waste type. For lignocellulose biomass waste

high cellulose content is favorable to reaction process. As to livestock manure waste

the conversion of pollutants such as heavy metals must be considered. Further studies on this topic will focus on corrosion prevention of reactor

blockage and salt deposition in reactor

online slag removal of reaction system

and modeling design

economic balance and coupling to other systems in industrial architecture.

关键词

Keywords

references

BP. Statistical review of world energy 2021: 70th edition [EB/OL]. [2022-08-01]. https://www.bp.com/content/dam/bp/business-sites/en/global/corporate/pdfs/energy-economics/statistical-review/bp-stats-review-2021-full-report.pdf.

陈冠益, 高文学, 马文超. 生物质制氢技术的研究现状与展望 [J]. 太阳能学报, 2006, 27(12): 1276-1284.

CHEN Guanyi, GAO Wenxue, MA Wenchao. Review on hydrogen-rich gas production from biomass [J]. Acta Energiae Solaris Sinica, 2006, 27(12): 1276-1284.

LUQUE R, HERRERO-DAVILA L, CAMPELO J M, et al. Biofuels: a technological perspective [J]. Energy Environmental Science, 2008, 5(1): 542-564.

ACHARYA B, DUTTA A, BASU P. Chemical-looping gasification of biomass for hydrogen-enriched gas production with in-process carbon dioxide capture [J]. Energy Fuels, 2009, 23(10): 5077-5083.

NANDA S, REDDY S N, MITRA S K, et al. The progressive routes for carbon capture and sequestration [J]. Energy Science Engineering, 2016, 4(2): 99-122.

YU Yun, LOU Xia, WU Hongwei. Some recent advances in hydrolysis of biomass in hot-compressed, water and its comparisons with other hydrolysis methods [J]. Energy Fuels, 2008, 22(1): 46-60.

POTIC B, KERSTEN S R A, PRINS W, et al. A high-throughput screening technique for conversion in hot compressed water [J]. Industrial Engineering Chemistry Research, 2004, 43(16): 4580-4584.

ONDZE F, BOUTIN O, RUIZ J-C, et al. Supercritical water gasification of beet residues: from batch to continuous reactor [J]. Chemical Engineering Science, 2015, 123: 350-358.

KARIMI A, KAZEMI N, TAVAKOLI O, et al. Catalytic supercritical water gasification of black liquor along with lignocellulosic biomass [J]. International Journal of Hydrogen Energy, 2022, 47(38): 16729-16740.

CHEN Yunan, YI Lei, WEI Wenwen, et al. Hydrogen production by sewage sludge gasification in supercritical water with high heating rate batch reactor [J]. Energy, 2022, 238: 121740.

CAO Wen, WEI Wenwen, JIN Hui, et al. Optimize hydrogen production from chicken manure gasification in supercritical water by experimental and kinetics study [J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107591.

GUTIÉRREZ ORTIZ F J, LÓPEZ-GUIRAO F, JIMÉNEZ-ESPADAFOR F J, et al. Heat transfer limitations in supercritical water gasification [J]. Energies, 2022, 15(1): 177.

GOODWIN A K, RORRER G L. Conversion of xylose and xylose-phenol mixtures to hydrogen-rich gas by supercritical water in an isothermal microtube flow reactor [J]. Energy Fuels, 2009, 23(7): 3818-3825.

GOODWIN A K, RORRER G L. Reaction rates for supercritical water gasification of xylose in a micro-tubular reactor [J]. Chemical Engineering Journal, 2010, 163(1/2): 10-21.

KRUSE A, MEIER D, RIMBRECHT P, et al. Gasification of pyrocatechol in supercritical water in the presence of potassium hydroxide [J]. Industrial Engineering Chemistry Research, 2000, 39(12): 4842-4848.

SINAG A, KRUSE A, MANIAM P. Hydrothermal conversion of biomass and different model compounds [J]. The Journal of Supercritical Fluids, 2012, 71: 80-85.

CASTELLO D, KRUSE A, FIORI L. Low temperature supercritical water gasification of biomass constituents: glucose/phenol mixtures [J]. Biomass and Bioenergy, 2015, 73: 84-94.

ADAR E, INCE M, BILGILI M S. Supercritical water gasification of sewage sludge by continuous flow tubular reactor: a pilot scale study [J]. Chemical Engineering Journal, 2020, 391: 123499.

CAO Changqing, GUO Liejin, CHEN Yunan, et al. Hydrogen production from supercritical water gasification of alkaline wheat straw pulping black liquor in continuous flow system [J]. International Journal of Hydrogen Energy, 2011, 36(21): 13528-13535.

MATSUMURA Y, MINOWA T. Fundamental design of a continuous biomass gasification process using a supercritical water fluidized bed [J]. International Journal of Hydrogen Energy, 2004, 29(7): 701-707.

钟文琪, 李蔚玲, 金保昇. 黑液超临界水低温气化装置及其气化方法: CN201310234351.4 [P]. 2013-06-13.

LU Y J, JIN H, GUO L J, et al. Hydrogen production by biomass gasification in supercritical water with a fluidized bed reactor [J]. International Journal of Hydrogen Energy, 2008, 33(21): 6066-6075.

LIAO Bo, GUO Liejin, LU Youjun, et al. Solar receiver/reactor for hydrogen production with biomass gasification in supercritical water [J]. International Journal of Hydrogen Energy, 2013, 38(29): 13038-13044.

JIN Hui, LU Youjun, LIAO Bo, et al. Hydrogen production by coal gasification in supercritical water with a fluidized bed reactor [J]. International Journal of Hydrogen Energy, 2010, 35(13): 7151-7160.

CHEN Jingwei, LU Youjun, GUO Liejin, et al. Hydrogen production by biomass gasification in supercritical water using concentrated solar energy: system development and proof of concept [J]. International Journal of Hydrogen Energy, 2010, 35(13): 7134-7141.

GUO Liejin, JIN Hui, LU Youjun. Supercritical water gasification research and development in China [J]. The Journal of Supercritical Fluids, 2015, 96: 144-150.

TANG Xingying, WANG Shuzhong, QIAN Lili, et al. Corrosion behavior of nickel base alloys, stainless steel and titanium alloy in supercritical water containing chloride, phosphate and oxygen [J]. Chemical Engineering Research and Design, 2015, 100: 530-541.

CAPUTO G, RUBIO P, SCARGIALI F, et al. Experimental and fluid dynamic study of continuous supercritical water gasification of glucose [J]. The Journal of Supercritical Fluids, 2016, 107: 450-461.

GONZÁLEZ G, SALVADÓ J, MONTANÉ D. Reactions of vanillic acid in sub-and supercritical water [J]. The Journal of Supercritical Fluids, 2004, 31(1): 57-66.

RAMAYYA S, BRITTAIN A, DEALMEIDA C, et al. Acid-catalysed dehydration of alcohols in supercritical water [J]. Fuel, 1987, 66(10): 1364-1371.

XU Xiaodong, MATSUMURA Y, STENBERG J, et al. Carbon-catalyzed gasification of organic feedstocks in supercritical water [J]. Industrial Engineering Chemistry Research, 1996, 35(8): 2522-2530.

FAIRES K B. Gasification of in-forest biomass residues [D]. Seattle: University of Washington, 2013.

NANDA S, REDDY S N, HUNTER H N, et al. Supercritical water gasification of fructose as a model compound for waste fruits and vegetables [J]. The Journal of Supercritical Fluids, 2015, 104: 112-121.

MOLINO A, MIGLIORI M, MACRÌ D, et al. Glucose gasification in super-critical water conditions for both syngas production and green chemicals with a continuous process [J]. Renewable Energy, 2016, 91: 451-455.

LEMMON E W, HUBER M L, MCLINDEN M O. NIST standard reference database 23: reference fluid thermodynamic and transport properties-REFPROP, version 9.1 [EB/OL]. [2022-08-01]. https://www.nist.gov/publications/nist-standard-reference-database-23-reference-fluid-thermodynamic-and-transport?pub_id=912382.

WAGNER W, PRUB A. The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use [J]. Journal of Physical and Chemical Reference Data, 2002, 31(2): 387-535.

LEE I G, KIM M S, IHM S K. Gasification of glucose in supercritical water [J]. Industrial Engineering Chemistry Research, 2002, 41(5): 1182-1188.

ELLIOTT D C, PHELPS M R, SEALOCK L J Jr, et al. Chemical processing in high-pressure aqueous environments: 4 continuous-flow reactor process development experiments for organics destruction [J]. Industrial Engineering Chemistry Research, 1994, 33(3): 566-574.

AIDA T M, SATO Y, WATANABE M, et al. Dehydration of d-glucose in high temperature water at pressures up to 80 MPa [J]. The Journal of Supercritical Fluids, 2007, 40(3): 381-388.

PINKARD B R, GORMAN D J, RASMUSSEN E G, et al. Kinetics of formic acid decomposition in subcritical and supercritical water: a Raman spectroscopic study [J]. International Journal of Hydrogen Energy, 2019, 44(60): 31745-31756.

KLINGLER D, BERG J, VOGEL H. Hydrothermal reactions of alanine and glycine in sub- and supercritical water [J]. The Journal of Supercritical Fluids, 2007, 43(1): 112-119.

HELLING R K, TESTER J W. Oxidation kinetics of carbon monoxide in supercritical water [J]. Energy Fuels, 1987, 1(5): 417-423.

DINARO J L, TESTER J W, HOWARD J B, et al. Experimental measurements of benzene oxidation in supercritical water [J]. AIChE Journal, 2000, 46(11): 2274-2284.

AIDA T M, SHIRAISHI N, KUBO M, et al. Reaction kinetics of D-xylose in sub- and supercritical water [J]. The Journal of Supercritical Fluids, 2010, 55(1): 208-216.

HENDRY D, VENKITASAMY C, WILKINSON N, et al. Exploration of the effect of process variables on the production of high-value fuel gas from glucose via supercritical water gasification [J]. Bioresource Technology, 2011, 102(3): 3480-3487.

HELLING R K, TESTER J W. Oxidation of simple compounds and mixtures in supercritical water: carbon monoxide, ammonia and ethanol [J]. Environmental Science Technology, 1988, 22(11): 1319-1324.

REDDY S N, NANDA S, DALAI A K, et al. Supercritical water gasification of biomass for hydrogen production [J]. International of Hydrogen Energy, 2014, 39(13): 6912-6926.

D'JESS P, BOUKIS N, KRAUSHAAR-CZARNETZKI B, et al. Gasification of corn and clover grass in supercritical water [J]. Fuel, 2006, 85(7/8): 1032-1038.

NANDA S, REDDY S N, VO D V N, et al. Catalytic gasification of wheat straw in hot compressed(subcritical and supercritical)water for hydrogen production [J]. Energy Science Engineering, 2018, 6(5): 448-459.

KANG Kang, AZARGOHAR R, DALAI A K, et al. Hydrogen production from lignin, cellulose and waste biomass via supercritical water gasification: catalyst activity and process optimization study [J]. Energy Conversion and Management, 2016, 117: 528-537.

WANG Cui, JIN Hui, FENG Huifang, et al. Study on gasification mechanism of biomass waste in supercritical water based on product distribution [J]. International Journal of Hydrogen Energy, 2020, 45(52): 28051-28061.

YANIK J, EBALE S, KRUSE A, et al. Biomass gasification in supercritical water: part 1 effect of the nature of biomass [J]. Fuel, 2007, 86(15): 2410-2415.

BOUKIS N, GALLA U, MÜLLER H, et al. Biomass gasification in supercritical water: experimental progress achieved with the VERENA pilot plant [C/OL]//15th European Biomass Conference Exhibition [2022-07-01]. https://www.ikft.kit.edu/downloads/boukis-pub6.pdf.

KUMAR A, REDDY S N. In Situ sub-and supercritical water gasification of nano-nickel(Ni2+)impregnated biomass for H2 production [J]. Industrial Engineering Chemistry Research, 2019, 58(12): 4780-4793.

CAO Wen, GUO Liejin, YAN Xuecheng, et al. Assessment of sugarcane bagasse gasification in supercritical water for hydrogen production [J]. International Journal of Hydrogen Energy, 2018, 43(30): 13711-13719.

NANDA S, ISEN J, DALAI A K, et al. Gasification of fruit wastes and agro-food residues in supercritical water [J]. Energy Conversion and Management, 2016, 110: 296-306.

JIN Hui, LU Youjun, GUO Liejin, et al. Hydrogen production by supercritical water gasification of biomass with homogeneous and heterogeneous catalyst [J]. Advances in Condensed Matter Physics, 2014, 2014: 160565.

NANDA S, GONG Miao, HUNTER H N, et al. An assessment of pinecone gasification in subcritical, near-critical and supercritical water [J]. Fuel Processing Technology, 2017, 168: 84-96.

GÜNGÖREN MADENOGLU T, BOUKIS N, SAGLAM M, et al. Supercritical water gasification of real biomass feedstocks in continuous flow system [J]. International Journal of Hydrogen Energy, 2011, 36(22): 14408-14415.

DING Ning, AZARGOHAR R, DALAI A K, et al. Catalytic gasification of cellulose and pinewood to H2 in supercritical water [J]. Fuel, 2014, 118: 416-425.

SELVI GÖKKAYA D, SERT M, SAGLAM M, et al. Hydrothermal gasification of the isolated hemicellulose and sawdust of the white poplar(Populus alba L.)[J]. The Journal of Supercritical Fluids, 2020, 162: 104846.

CAO Wen, CAO Changqing, GUO Liejin, et al. Hydrogen production from supercritical water gasification of chicken manure [J]. International Journal of Hydrogen Energy, 2016, 41(48): 22722-22731.

NANDA S, DALAI A K, GÖKALP I, et al. Valorization of horse manure through catalytic supercritical water gasification [J]. Waste Management, 2016, 52: 147-158.

YOUSSEF E A, ELBESHBISHY E, HAFEZ H, et al. Sequential supercritical water gasification and partial oxidation of hog manure [J]. International Journal of Hydrogen Energy, 2010, 35(21): 11756-11767.

NANDA S, AZARGOHAR R, KOZINSKI J A, et al. Characteristic studies on the pyrolysis products from hydrolyzed Canadian lignocellulosic feedstocks [J]. BioEnergy Research, 2014, 7(1): 174-191.

YOSHIDA T, OSHIMA Y, MATSUMURA Y. Gasification of biomass model compounds and real biomass in supercritical water [J]. Biomass and Bioenergy, 2004, 26(1): 71-78.

DEMIRBAS A. Hydrogen-rich gas from fruit shells via supercritical water extraction [J]. International Journal of Hydrogen Energy, 2004, 29(12): 1237-1243.

NANDA S, MOHANTY P, PANT K K, et al. Characterization of North American lignocellulosic biomass and biochars in terms of their candidacy for alternate renewable fuels [J]. BioEnergy Research, 2013, 6(2): 663-677.

NANDA S, DALAI A K, KOZINSKI J A. Supercritical water gasification of timothy grass as an energy crop in the presence of alkali carbonate and hydroxide catalysts [J]. Biomass and Bioenergy, 2016, 95: 378-387.

HASANAH U, SETIAJI B, TRIYONO, et al. The chemical composition and physical properties of the light and heavy tar resulted from coconut shell pyrolysis [J]. The Journal of Pure and Applied Chemistry Research, 2012, 1(1): 26-32.

MARRONE P A, HONG G T. Corrosion control methods in supercritical water oxidation and gasification processes [J]. The Journal of Supercritical Fluids, 2009,51(2):82-103.

郭烈锦,程泽宁,金辉,等. 一种可实现残渣富集的超临界水气化炉装置: CN201610570687.1 [P]. 2016-12-21.

HANTOKO D, YAN Mi, KANCHANATIP E, et al. Supercritical water gasification of sewage sludge and combined cycle for H2 and power production: a thermodynamic study [J]. International Journal of Hydrogen Energy, 2019, 44(45): 24459-24470.

GUO Shenghui, REN Changyifan, WANG Yu, et al. Thermodynamic modeling and analysis of the heat integration and power generation in pig manure supercritical water gasification system [J]. Energy Conversion and Management, 2021, 248: 114809.

LIU Shanke, YANG Yan, YU Lijun, et al. Thermodynamic and environmental analysis of solar-driven supercritical water gasification of algae for ammonia synthesis and power production [J]. Energy Conversion and Management, 2021, 243: 114409.

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

生物质与煤超临界水气化制氢的实验研究

生物质/煤超临界水气化制氢的主要影响因素

高含量煤在超临界水中气化制氢的实验研究

超临界水中花生壳气化制氢催化剂的筛选与研究

原生生物质在超临界水流化床系统中气化制氢