水/二氧化碳气氛下酒糟催化气化反应特性的研究

doi:10.19964/j.issn.1006-4990.2022-0243

摘要/Abstract

摘要：

在固定床气化装置中，以赤泥为催化剂、水/二氧化碳为气化剂对酒糟进行气化实验。研究了赤泥添加量、气化温度和V（水）/V（二氧化碳）对酒糟气化活性的影响，并对水/二氧化碳共气化协同机理进行了探讨。结果表明：当赤泥添加量为20%（质量分数）时气化活性最佳；升高气化温度有利于提高气化反应活性；随着V（水）/V（二氧化碳）的增大，合成气产量、n（氢气）/n（一氧化碳）均增加，分别达到270.7 mmol/g和6.67；在水/二氧化碳混合气氛下共气化反应产生了明显的协同效应，协同因子在60%水-40%二氧化碳（体积分数）时达到峰值。拉曼光谱、扫描电子显微镜及比表面积分析表明：水/二氧化碳混合气氛下酒糟焦无定形碳和非晶碳结构的破坏程度比在纯水或二氧化碳中更严重，验证了二氧化碳和水在酒糟气化中存在协同效应；二氧化碳更容易在酒糟焦表面发生气化反应，形成大量微孔使其比表面积增加；水炭渗透力较强有利于形成中孔；在水/二氧化碳混合气氛下，二氧化碳与水产生的交互作用促进了孔结构的发育，使酒糟焦的微孔发展为中孔和大孔并促使气化反应向酒糟颗粒内部发展，这是协同效应产生的主要原因。

关键词: 酒糟, 协同效应, 水/二氧化碳, 催化气化, 赤泥

Abstract:

The gasification experiments on distillers′ grain was conducted in a fixed-bed gasification plant with red mud as the catalyst and H₂O/CO₂ as the gasification agent.The effects of red mud addition，gasification temperature and H₂O/CO₂ ratio on the gasification characteristics of the distillers′ grain were investigated and the synergistic mechanism of H₂O/CO₂co-gasification was discussed.The results showed that the gasification activity was best when red mud addition was 20%（mass fraction）.The increased gasification temperature was beneficial to the gasification reaction activity.When V（H₂O）/V（CO₂） was increased，the syngas yield and n（H₂）/n（CO） was also increased，up to 270.7 mmol/g and 6.67.The co-gasification under H₂O/CO₂ mixed atmosphere produced significant synergistic effect，and the synergistic factor was peaked at 60% H₂O-40% CO₂（volume fraction）.Raman，SEM and BET analysis showed that the amorphous carbon and amorphous carbon structure of the distillers′ grain coke in the H₂O/CO₂mixed atmosphere was more severely damaged than that in pure H₂O or CO₂，which verified that CO₂and H₂O existed the synergistic effect of in the distillers′ grain gasification.CO₂ was more prone to gasification on the surface of distiller′s grains coke，forming a large number of micropores to increase the specific surface area.Carbon with H₂O had stronger permeability to facilitate the formation of mesopores.In H₂O/CO₂ mixed atmosphere，the interaction between CO₂ and H₂O made the micropores of distiller′s grains coke to develop into mesopores and macropores and promoted the gasification reaction to the interior of distillers′ grains granule，which triggered the synergistic effect.

Key words: distillers′^grains, synergistic effect, H₂O/CO₂, catalytic gasification, red mud

中图分类号:

O643.3

李松鸿,周松华,赵爱明,董文燕,姜春燕,曹阳,敖先权. 水/二氧化碳气氛下酒糟催化气化反应特性的研究[J]. 无机盐工业, 2023, 55(2): 132-140.

LI Songhong,ZHOU Songhua,ZHAO Aiming,DONG Wenyan,JIANG Chunyan,CAO Yang,AO Xianquan. Study on catalytic gasification reaction of distillers′grains under H₂O/CO₂ atmosphere[J]. Inorganic Chemicals Industry, 2023, 55(2): 132-140.

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工业分析，w/%					元素分析，w/%
M_ad	V_d	A_d	F_cd		C	H	N	S	O*
9.44	69.47	5.00	16.09		60.10	4.82	3.26	0.28	31.09

不同气氛下的样品	理论反应性指数	实际反应性指数	协同因子
100%CO₂	0.014 6	0.014 6	1.000
20%H₂O-80%CO₂	0.015 1	0.021 4	1.418
40%H₂O-60%CO₂	0.015 8	0.024 2	1.535
60%H₂O-40%CO₂	0.016 4	0.028 1	1.712
80%H₂O-20%CO₂	0.016 9	0.026 4	1.562
100%H₂O	0.017 5	0.017 5	1.000

样品	S_BET （m²·g^-1）	S_micro （m²·g^-1）	V_micro （cm³·g^-1）	V_meso （cm³·g^-1）	L_mpps/ nm	V_total （cm³·g^-1）
100%CO₂	661	290	0.125	0.193	4.617	0.376
100%H₂O	623	265	0.116	0.387	7.007	0.503
60%H₂O-40%CO₂	576	238	0.092	0.413	8.262	0.567
80%H₂O-20%CO₂	615	255	0.112	0.361	6.215	0.516

不同气氛下的气化半焦	A_D3/A_G	A_D1/A_G
100%CO₂	3.583	5.345
100%H₂O	2.076	4.416
60%H₂O-40%CO₂	1.398	2.818
80%H₂O-20%CO₂	1.866	3.099

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