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

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References 29

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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

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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

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