K/Ca催化木屑水蒸气气化制取富氢合成气

doi:10.3969/j.issn.0253-2417.2023.01.002

Abstract

Abstract:

KOH/dolomite composite catalyst was used to catalyze steam gasification in a fixed-bed gasifier with pine sawdust as raw material. The effects of catalyst preparation conditions, reaction temperature, steam flow rate and catalyst dosage on the evaluation indexes of gasification characteristics such as gasification synthesis hydrogen content, gas yield, hydrogen yield and carbon conversion rate were investigated. SEM, XRD and pore structure analysis of the K/Ca composite catalyst were carried out. The results showed that K element was well loaded on dolomite. The K/Ca composite catalyst prepared by KOH mass fraction of 6%, K/Ca molar ratio of 2∶1 and calcination at 900 ℃ had the best catalytic performance. When the gasification temperature increased from 600 to 750 ℃, the H₂ volume fraction increased from 40.70% to 59.09%, and the hydrogen yield rate increased from 16.38 to 90.64 g/kg. However, the catalyst activity decreased owing to the continuous increase of temperature, and the H₂ volume fraction and hydrogen yield decreased as well. When the steam flow rate increased from 0.4 to 1.0 mL/min, the H₂ volume fraction increased from 52.75% to 59.09%, and the hydrogen yield increased from 68.14 to 90.64 g/kg. Further increase of steam flow would lead to heat loss in the system, which would reduce the H₂ volume fraction and hydrogen production rate. When the mass ratio of catalyst to raw material was 0.3 g/g, the volume fraction of H₂ was 59.09% and the yield rate of hydrogen was 90.64 g/kg. When the mass ratio increased to 0.6 g/g, the volume fraction of H₂ decreased to 58.50%, and the hydrogen production rate increased to 103.18 g/kg. When the mass ratio of biomass continuously increased, above growth became significantly slow, that was, the catalytic reaction basically reached equilibrium. With the consideration of the various aspects, the optimal conditions of K/Ca composite catalyst for pine sawdust steam gasification were as follows: reaction temperature of 750 ℃, water vapor flow rate of 1.0 mL/min, and mass ratio of catalyst to raw material of 0.6 g/g. At this time, volume fraction of H₂ in product gas was 58.50%, hydrogen production rate was 103.18 g/kg, the low calorific value was 10.94 MJ/m³, and carbon conversion was 83.25%.

Key words: biomass, gasification, catalyst, hydrogen-rich syngas

CLC Number:

TQ35
TK6

Jurong REN, Yunhong SU, Yunjuan SUN, Hao YING, Zhongzhi YANG, Le XU. K/Ca Catalytic Steam Gasification of Sawdust for Production of Hydrogen-rich Syngas[J]. Chemistry and Industry of Forest Products, 2023, 43(1): 15-24.

Figures/Tables 10

Table 1

Fig.1

Fig.2

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

References 29

1	ISLAM M W. A review of dolomite catalyst for biomass gasification tar removal[J/OL]. Fuel, 2020, 267: 117095[2021-11-10]. https://doi.org/10.1016/j.fuel.2020.117095.
2	于蓬, 王健, 郑金凤, 等. 氢能利用与发展综述[J]. 汽车实用技术, 2019, (24): 22- 25.
	YU P , WANG J , ZHENG J F , et al. A review of hydrogen energy utilization and development[J]. Automobile Practical Technology, 2019, (24): 22- 25.
3	王敏. 国内外新能源制氢发展现状及未来趋势[J]. 化学工业, 2018, (36): 13- 18.
	WANG M . The status quo and trend of producing hydrogen from new energy[J]. Chemical Industry, 2018, (36): 13- 18.
4	NOROUZI O , SAFARI F , JAFARIAN S , et al. Hydrothermal gasification performance of Enteromorpha intestinalis as an algal biomass for hydrogen-rich gas production using Ru promoted Fe-Ni/-Al₂O₃ nano catalysts[J]. Energy Conversion and Management, 2017, 141, 63- 71. doi: 10.1016/j.enconman.2016.04.083
5	JI G , XU X , YANG H , et al. Enhanced hydrogen production from sawdust decomposition using hybrid-functional Ni-CaO-Ca₂SiO₄ materials[J]. Environmental Science & Technology, 2017, 51 (19): 11484- 11492.
6	KONG M , FEI J , WANG S , et al. Influence of supports on catalytic behavior of nickel catalysts in carbon dioxide reforming of toluene as a model compound of tar from biomass gasification[J]. Bioresource Technology, 2011, 102 (2): 2004- 2008. doi: 10.1016/j.biortech.2010.09.054
7	贾爽, 应浩, 孙云娟, 等. 生物质热解与气化制氢研究进展[J]. 现代化工, 2015, 35 (1): 53- 57.
	JIA S , YING H , SUN Y J , et al. Research progress of biomass pyrolysis and gasification to produce hydrogen[J]. The Modern Chemical Industry, 2015, 35 (1): 53- 57.
8	贾爽, 应浩, 徐卫, 等. 生物质炭水蒸气气化制取富氢合成气[J]. 化工进展, 2018, 37 (4): 1402- 1407.
	JIA S , YING H , XU W , et al. Steam gasification of biochar to produce hydrogen-rich syngas[J]. Chemical Progress, 2018, 37 (4): 1402- 1407.
9	孙宁, 应浩, 徐卫, 等. 松木屑催化气化制取富氢燃气[J]. 化工进展, 2017, 36 (6): 2158- 2163.
	SUN N , YING H , XU W , et al. Catalytic gasification of pine sawdust to produce hydrogen-rich gas[J]. Chemical Progress, 2017, 36 (6): 2158- 2163.
10	CAO L, YU I K M, XIONG X, et al. Biorenewable hydrogen production through biomass gasification: A review and future prospects[J/OL]. Environmental Research, 2020, 186: 109547[2021-11-10]. https://doi.org/10.1016/j.envres.2020.109547.
11	NING S Y , JIA S , YING H , et al. Hydrogen-rich syngas produced by catalytic steam gasification of corncob char[J]. Biomass and Bioenergy, 2018, 117, 131- 136.
12	TAN R S, ABDULLAH T A T, JOHARI A, et al. Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: A review[J/OL]. Frontiers in Energy, 2020, 14(3): 545[2021-11-10]. https://doi.org/10.1007/s11708-020-0800-2.
13	SAID M , CASSAYRE L , DIRION J , et al. Influence of nickel on biomass pyro-gasification: Coupled thermodynamic and experimental investigations[J]. Industrial & Engineering Chemistry Research, 2018, 57 (30): 9788- 9797.
14	武宏香, 赵增立, 张伟, 等. 碱/碱土金属对纤维素热解特性的影响[J]. 农业工程学报, 2012, 28 (4): 215- 220.
	WU H X , ZHAO Z L , ZHANG W , et al. Effects of alkali/alkaline earth metals on pyrolysis properties of cellulose[J]. Transactions of the Chinese Society of Agricultural Engineering, 2012, 28 (4): 215- 220.
15	刘琨琨. 基于白云石负载铁铈催化剂生物质催化气化实验研究[D]. 包头: 内蒙古科技大学, 2020.
	LIU K K. Experimental research on biomass catalytic gasification based on Fe-Ce/Dol catalyst[D]. Baotou: Inner Mongolia University of Science and Technology, 2020.
16	JIANG M , HU J , WANG J . Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char: Effect of hydrothermal pretreatment[J]. Fuel, 2013, 109, 14- 20.
17	PERANDER M , DEMARTINI N , BRINK A , et al. Catalytic effect of Ca and K on CO₂ gasification of spruce wood char[J]. Fuel, 2015, 150, 464- 472.
18	曾志伟. 碱金属K对生物质水蒸气催化气化增强制氢特性影响研究[D]. 武汉: 华中科技大学, 2016.
	ZENG Z W. Influence of potassium salts on hydrogen production from the enhanced steam gasification of biomass[D]. Wuhan: Huazhong University of Science and Technology, 2016.
19	SU S , CHI Y Q , CHANG R X , et al. Analysis of the catalytic steam gasification mechanism of biomass[J]. International Journal of Hydrogen Energy, 2015, 40 (2): 935- 940.
20	ESFAHANI R A M , OSMIERI L , SPECCHIA S , et al. H₂-rich syngas production through mixed residual biomass and HDPE waste via integrated catalytic gasification and tar cracking plus bio-char upgrading[J]. Chemical Engineering Journal, 2017, 308, 578- 587.
21	张丽奇. 基于新型复合催化剂的生物质催化热解实验研究[D]. 包头: 内蒙古科技大学, 2019.
	ZHANG L Q. Experimental study on catalytic pyrolysis of biomass based on novel composite catalyst[D]. Baotou: Inner Mongolia University of Science and Technology, 2019.
22	YANG L M , LYU P M , YUAN Z H , et al. Synthesis of biodiesel by different carriers supported KOH catalyst[J]. Advanced Materials Research, 2012, 581/582, 197- 201.
23	KIM J H, LEE G, PARK J E, et al. Limitation of K₂CO₃ as a chemical agent for upgrading activated carbon[J/OL]. Processes, 2021, 9(6): 1000[2021-11-10]. https://doi.org/10.3390/pr9061000.
24	WU X M, ZHU F F, QI J J, et al. Challenge of biodiesel production from sewage sludge catalyzed by KOH, KOH/activated carbon, and KOH/CaO[J/OL]. Frontiers of Environmental Science & Engineering, 2017, 11(2): 3[2021-11-10]. https://doi.org/10.1007/s11783-017-0913-y.
25	YAN F , ZHANG L G , HU Z Q , et al. Hydrogen-rich gas production by steam gasification of char derived from cyanobacterial blooms(CDCB) in a fixed-bed reactor: Influence of particle size and residence time on gas yield and syngas composition[J]. International Journal of Hydrogen Energy, 2010, 35 (19): 10212- 10217.
26	RICHARDSON Y , DROBEK M , JULBE A , et al. Biomass gasification to produce syngas[J]. Biomass Gasifiers for Syngas Production, 2015, (1): 209- 247.
27	王永刚, 谢克昌, 凌开来, 等. 碱金属催化剂在煤气化过程中的作用机理[J]. 太原工业大学学报, 1988, (3): 52- 62.
	WANG Y G , XIE K C , LIN K L , et al. Mechanism of alkali metal catalyst in coal gasification process[J]. Journal of Taiyuan University of Technology, 1988, (3): 52- 62.
28	DU C S , LIU L , QIU P H . Variation of char reactivity during catalytic gasification with steam: Comparison among catalytic gasification by ion-exchangeable Na, Ca, and Na/Ca mixture[J]. Energy & Fuels, 2018, 32 (1): 142- 153.
29	S′PIEWAK K, CZERSKI G, PORADA S. Effect of K, Na and Ca-based catalysts on the steam gasification reactions of coal. Part Ⅱ: Composition and amount of multi-component catalysts[J/OL]. Chemical Engineering Science, 2021, 229: 116023[2021-11-10]. https://doi.org/10.1016/j.ces.2020.116023.

序号 No.	反应类型reaction type	反应式reaction equation	焓变/(kJ·mol^-1) enthalpy change
1	热解反应pyroilsis	生物质→ C+焦油+热解气
2	焦油裂解反应tar cracking	焦油→ aH₂+bCH₄+cCO+dCO₂+eH₂O+C_mH_n
3	炭气化反应char steam gasification	C+H₂O(g)→ H₂+CO	118.9
4	炭气化反应char steam gasification	C+H₂O(g)→ H₂+CO₂	90.2
5	CO₂还原反应reduction reaction of CO₂	C+CO₂→ 2CO	173.8
6	甲烷化反应methanation	C+2H₂→ 4CH₄	-74.8
7	水气转化反应water-gas shifting	CO+H₂O(g)→ H₂+CO₂	-40.9
8	甲烷水蒸气重整反应steam reforming of CH₄	CH₄+H₂O(g)→ 3H₂+CO	206.3
9	甲烷水蒸气重整反应steam reforming of CH₄	CH₄+2H₂O(g)→ 4H₂+CO₂	165.0
10	碳氢化合物蒸气重整反应hydrocarbon vapor reforming	C_mH_n+2nH₂O(g)→(2n+m/2)H₂+nCO₂

催化剂类型¹⁾ catalyst	比表面积/(m²·g^-1) specific surface area	孔容积/(cm³·g^-1) pore volume	平均孔径/nm mean pore size
白云石dolomite	4.552 1	0.022 211	19.52
K/Ca-900	7.779 7	0.008 395	4.32
K/Ca-25	0.082 8	0.000 334	16.11

KOH质量分数/% mass fraction of KOH solution	合成气组分体积分数/% volume fraction of gas				Q_LHV/ (MJ·m^-3)	产气率/ (L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
KOH质量分数/% mass fraction of KOH solution	H₂	CH₄	CO	CO₂	Q_LHV/ (MJ·m^-3)	产气率/ (L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
0	44.13	7.96	20.03	25.09	11.92	0.85	32.52	47.38
2	55.36	5.76	19.34	17.72	11.63	1.79	85.94	78.15
4	56.60	4.73	19.87	17.22	11.32	1.82	92.13	80.07
6	57.54	5.13	17.97	17.63	11.42	1.80	92.36	76.98
8	56.77	5.63	18.79	16.89	11.73	1.80	90.91	77.74

n(K)∶n(Ca)	合成气组分体积分数/% volume fraction of gas					Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
n(K)∶n(Ca)	H₂	CH₄	CO	CO₂	C_mH_n	Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
1∶3	50.83	7.28	18.68	20.37	4.41	12.26	1.32	59.77	63.97
1∶2	52.32	5.49	16.83	22.53	2.83	11.53	1.38	64.63	65.12
1∶1	52.40	5.79	16.06	23.25	2.49	11.34	1.55	72.45	73.47
2∶1	56.14	4.81	16.77	20.12	2.15	11.27	1.76	88.29	77.04
3∶1	54.96	4.58	15.04	23.43	1.99	10.74	1.64	80.31	74.08

催化剂 catalyst	合成气组分体积分数/% volume fraction of gas					Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
催化剂 catalyst	H₂	CH₄	CO	CO₂	C_mH_n	Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
无催化剂without catalyst	44.13	7.96	20.03	25.09	2.79	11.92	0.85	32.52	47.38
白云石dolomite	49.91	6.91	17.05	23.43	2.70	11.73	1.26	55.96	63.10
K/Ca-750	53.40	4.51	17.94	22.02	2.14	11.00	1.66	79.32	77.83
K/Ca-800	54.23	4.09	15.58	24.13	1.96	10.53	1.72	83.11	78.95
K/Ca-850	54.24	4.14	15.24	24.39	1.99	10.53	1.73	83.59	79.35
K/Ca-900	56.14	4.81	16.77	20.12	2.15	11.27	1.76	88.29	77.04

K/Ca Catalytic Steam Gasification of Sawdust for Production of Hydrogen-rich Syngas

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 29

Related Articles 15

Recommended Articles

Metrics

Comments

About Journal

Guide for Authors

Journal Online

相关单位

Contacts Us

反应温度/℃ temperature	合成气组分体积分数/% volume fraction of gas					Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
反应温度/℃ temperature	H₂	CH₄	CO	CO₂	C_mH_n	Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
600	40.70	4.33	27.15	18.86	3.64	13.59	0.44	16.39	25.53
700	54.91	4.59	11.55	26.80	2.14	10.39	1.36	67.17	60.70
750	59.09	3.81	13.27	21.94	1.89	10.62	1.72	90.64	70.22
800	56.14	4.81	16.77	20.12	2.15	11.27	1.76	88.29	77.04
850	56.82	4.39	21.51	15.40	1.88	11.61	1.66	84.10	71.65

水蒸气流量/ (mL·min^-1) steam flow rate	合成气组分体积分数/% volume fraction of gas					Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
水蒸气流量/ (mL·min^-1) steam flow rate	H₂	CH₄	CO	CO₂	C_mH_n	Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
0.4	52.75	6.12	16.64	21.87	2.62	11.65	1.43	68.14	66.65
0.7	52.91	5.41	14.71	24.55	2.42	11.04	1.63	76.76	76.41
1.0	59.09	3.81	13.27	21.94	1.89	10.62	1.72	90.64	70.22
1.3	58.94	4.25	15.55	19.23	2.03	11.14	1.61	84.56	65.89

催化剂用量/(g·g^-1) dosage of catalyst	合成气组分体积分数/% volume fraction of gas					Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
催化剂用量/(g·g^-1) dosage of catalyst	H₂	CH₄	CO	CO₂	C_mH_n	Q_LHV/ (MJ·m^-3)	产气率/(L·g^-1) gas production rate	产氢率/(g·kg^-1) hydrogen production rate	碳转化率/% carbon conversion
0	41.63	11.46	31.46	13.62	1.82	13.73	0.76	29.43	25.53
0.3	59.09	3.81	13.27	21.94	1.89	10.62	1.72	90.64	70.22
0.6	58.50	4.06	15.64	19.91	1.90	10.94	1.99	103.18	83.25
0.9	60.00	3.80	15.27	19.09	1.84	10.93	2.00	106.65	80.54
1.2	61.06	3.80	15.52	17.99	1.80	10.99	1.97	107.27	76.99

[1]	CHENG Qin, SHEN Juanzhang, CAI Yanyan, YE Jun, WU Ziyang, TAN Weihong. Carbon Stable Isotope Fractionation of 5-Hydroxymethylfurfural from Hydrothermal Liquefaction [J]. Chemistry and Industry of Forest Products, 2023, 43(1): 63-71.
[2]	ZHENG Yunwu, WANG Jida, LI Donghua, LIU Can, DING Zhangshuai, ZHENG Zhifeng. A Review on Recent Advances in Catalytic Conversion of Biomass for Selective Production of Bio-aviation Fuels [J]. Chemistry and Industry of Forest Products, 2023, 43(1): 140-154.
[3]	Xueqin LI, Peng LIU, Youqing WU, Tingzhou LEI, Shiyong WU, Sheng HUANG. Development Status and Prospect of Biomass Gasification Technology [J]. Chemistry and Industry of Forest Products, 2022, 42(5): 113-121.
[4]	Shuo WANG, Yonggui WANG, Zefang XIAO, Yanjun XIE. Recent Progress in Preparation and Application of Bio-based Hydrogels [J]. Chemistry and Industry of Forest Products, 2022, 42(5): 122-136.
[5]	Fang WANG, Hongdan ZHANG. Application of Aspen Plus in Lignocellulosic Biomass Pretreatment for Ethanol Production: A Review [J]. Chemistry and Industry of Forest Products, 2022, 42(4): 119-130.
[6]	Shuai WANG, Xing TANG, Yong SUN, Xianhai ZENG, Lu LIN. Optimization and Kinetics of Hydrolysis of 5-Chloromethylfurfural to 5-Hydroxymethylfurfural [J]. Chemistry and Industry of Forest Products, 2022, 42(3): 65-74.
[7]	Yifei DU, Yue PU, Liping ZHANG, Qiang ZHAO, Xianliang SONG. Power Generation Performance of Lignin in Direct Biomass Fuel Cell [J]. Chemistry and Industry of Forest Products, 2022, 42(3): 75-82.
[8]	Yuxin LU, Lingang LU. Thermal Properties and Thermal Decomposition Kinetics of Tannic Acid [J]. Chemistry and Industry of Forest Products, 2022, 42(3): 83-89.
[9]	Yupeng LIU, Peipei KUANG, Ying CHEN, Jifu WANG, Chunpeng WANG, Fuxiang CHU. Research Progress of Biomass-based Stimulus-responsive Hydrogels [J]. Chemistry and Industry of Forest Products, 2022, 42(3): 126-134.
[10]	Tingting YU, Zongze LYU, Xiang LI, Jindong HU, Peiyan LI, Zhiguo LI. Preparation and Electrochemical Properties of Bamboo Based Ultra-thick Carbonaceous Electrode Materials [J]. Chemistry and Industry of Forest Products, 2022, 42(2): 10-18.
[11]	Xing LIU, Zhu YIN, Beili LU, Fengzhen WU, Biao HUANG. Preparation of Biomass-derived Fe-N-C Porous Carbon Material and Its Catalytic Reduction of Nitrobenzene [J]. Chemistry and Industry of Forest Products, 2022, 42(2): 63-70.
[12]	Qin WANG, Hongmei WANG, Aihua ZHANG, Zhihong XIAO, Changzhu LI. KNO₃-Loaded Mesoporous Carbon Catalyzed Transesterification Reaction of Cornus wilsoniana Oil [J]. Chemistry and Industry of Forest Products, 2021, 41(6): 83-89.
[13]	Mengyu LI, Peng YANG, Chun CHANG, Zhiyong CHEN, Jiande SONG. Research Progress in High-value Utilization of Furfural Residue [J]. Chemistry and Industry of Forest Products, 2021, 41(6): 117-126.
[14]	Haonan CHEN, Ting YU, Yali ZHOU, Xiping LEI, Xiaolin GUAN. Research Progress on Electrode Materials from Activated Carbon-based Supercapacitors [J]. Chemistry and Industry of Forest Products, 2021, 41(5): 113-125.
[15]	Hengyi SHU, Zhifeng ZHENG, Shouqing LIU, Hongzhou HE, Yuanbo HUANG. Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate [J]. Chemistry and Industry of Forest Products, 2021, 41(3): 11-18.