不同方法对煤气化粗渣中硅铝矿物的活化

doi:10.16085/j.issn.1000-6613.2024-0774

摘要/Abstract

摘要：

随着煤气化技术的快速发展，其副产物煤气化渣的产量也逐年增加，引发的环境问题日益突出。煤气化渣中硅铝矿物是其主要的存在成分，而复杂的硅铝结构对其资源化利用带来挑战。本文以产自宁东的煤气化粗渣为研究对象，采用碱熔活化法和亚熔盐活化法对其中的硅铝矿物进行活化，结合响应面法设计实验并建模分析，得到最优条件和各因素间的交互作用对活化效果的影响。结果表明，在碱熔活化作用下，硅活化率、铝活化率、活化产物浸提液中硅铝比最高分别可达到64.91%、34.14%和10；亚熔盐活化粗渣中，硅活化率、铝活化率、活化产物浸提液中硅铝比最高分别可达到63.14%、24.78%和23。两种活化过程中，影响粗渣中硅铝物种活化效果的主要因素均为碱渣比，且硅活化率和铝活化率随着碱渣比的增大而提高，各因素之间的交互作用对活化效果均存在一定影响，并发现粗渣中硅铝矿物在亚熔盐体系中存在SOD → FAU → CHA的晶体转化路径。本研究旨为粗渣中硅铝物种的高值化利用提供科学依据。

关键词: 环境, 活化, 沸石, 煤气化渣, 亚熔盐, 响应面法

Abstract:

With the rapid development of coal gasification technology, the production of its by-product, coal gasification slag, is also increasing year by year. The environmental problems caused by coal gasification are becoming increasingly prominent. The main components of coal gasification slag are silica-aluminum minerals, and the complex silica-aluminum structure poses a challenge to its resource utilization. This thesis took the coal gasification coarse slag from Ningdong as the research object, and used the alkali fusion activation method and sub-molten salt activation method to activate the silica-aluminum minerals therein. By combining with the response surfaced method to design the experiments and made models to analyze, the influence of the optimal conditions and the interactions among the factors on the activation effect could be seen. The results showed that, under the effect of alkali fusion activation, the activation rate of Si, the activation rate of Al and the molar rate of Si/Al in the activation product leaching solution could reach 64.91%, 34.14% and 10, respectively; in sub-molten salt activation of the coarse slag, the activation rate of Si, the activation rate of Al and the molar rate of Si/Al in the activation product leaching solution were 63.14%, 24.78% and 23, respectively; both in the processes of activation of coarse slag by alkali fusion and sub-molten salt activation, the primary factor affecting the activation effect of the silica-aluminum species in the coarse slag was the ratio of alkali and slag, and the activation rates of Si and Al increased with increasing of the ratio of alkali and slag. The interactions between the factors had some influence on the activation effect. It was also found that there was a crystal transformation pathway of SOD → FAU → CHA in the sub-molten salt system of silica-aluminum minerals in the coarse slag. The aim of this study was to provide a scientific basis for the high value utilization of silica-aluminum species in coarse slag.

Key words: environment, activation, zeolite, coal gasification slag, sub-molten salt activation, response surface method

中图分类号:

TQ536

马晶, 马玉龙, 朱莉, 乔松, 孙永刚, 吉文欣. 不同方法对煤气化粗渣中硅铝矿物的活化[J]. 化工进展, 2025, 44(7): 4251-4266.

MA Jing, MA Yulong, ZHU Li, QIAO Song, SUN Yonggang, JI Wenxin. Activation of silica-aluminium minerals of coal gasification coarse slag by different methods[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4251-4266.

图/表 21

参考文献 27

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样品	质量分数/%
SiO₂	42.39
Fe₂O₃	20.6
Al₂O₃	14.29
CaO	10.68
MgO	2.58
K₂O	2.47
SO₃	2.27
Na₂O	1.56
TiO₂	1.32

样品	质量分数/%
SiO₂	42.39
Fe₂O₃	20.6
Al₂O₃	14.29
CaO	10.68
MgO	2.58
K₂O	2.47
SO₃	2.27
Na₂O	1.56
TiO₂	1.32

序号	碱渣比	温度/℃	时间/h	响应值
序号	碱渣比	温度/℃	时间/h	硅活化率/%	铝活化率/%	硅铝比
1	2.0	500	4	53.08	23.15	6
2	2.0	500	2	62.57	33.27	5
3	1.5	600	1	48.81	17.06	7
4	2.0	700	2	66.37	26.11	6
5	2.5	600	3	92.75	40.96	6
6	1.0	500	4	25.69	10.67	6
7	1.5	600	3	30.71	20.83	4
8	1.5	600	3	32.17	24.32	3
9	1.5	800	3	35.67	10.80	8
10	1.5	600	5	47.61	16.63	7
11	1.0	700	2	21.62	6.14	9
12	0.5	600	3	10.18	3.75	7
13	1.5	600	3	20.98	21.67	2
14	2.0	700	4	58.62	16.84	9
15	1.0	700	4	24.14	6.70	9
16	1.5	400	3	42.54	18.37	6
17	1.5	600	3	31.30	19.84	4
18	1.0	500	2	27.58	5.06	12
19	1.5	600	3	31.47	22.16	4
20	1.5	600	3	30.17	20.83	5

序号	碱渣比	温度/℃	时间/h	响应值
序号	碱渣比	温度/℃	时间/h	硅活化率/%	铝活化率/%	硅铝比
1	2.0	500	4	53.08	23.15	6
2	2.0	500	2	62.57	33.27	5
3	1.5	600	1	48.81	17.06	7
4	2.0	700	2	66.37	26.11	6
5	2.5	600	3	92.75	40.96	6
6	1.0	500	4	25.69	10.67	6
7	1.5	600	3	30.71	20.83	4
8	1.5	600	3	32.17	24.32	3
9	1.5	800	3	35.67	10.80	8
10	1.5	600	5	47.61	16.63	7
11	1.0	700	2	21.62	6.14	9
12	0.5	600	3	10.18	3.75	7
13	1.5	600	3	20.98	21.67	2
14	2.0	700	4	58.62	16.84	9
15	1.0	700	4	24.14	6.70	9
16	1.5	400	3	42.54	18.37	6
17	1.5	600	3	31.30	19.84	4
18	1.0	500	2	27.58	5.06	12
19	1.5	600	3	31.47	22.16	4
20	1.5	600	3	30.17	20.83	5

序号	碱渣比	液固比	温度/℃	时间/h	响应值
序号	碱渣比	液固比	温度/℃	时间/h	硅活化率/%	铝活化率/%	硅铝比
1	1.6	0.50	250	3.25	50.22	15.05	8
2	2.0	0.75	200	2.5	52.34	23.5	6
3	0.4	0.75	200	2.5	14.9	1.25	30
4	1.2	0.25	200	2.5	47.43	13.1	9
5	1.6	1.00	150	1.75	54.84	19.51	7
6	1.6	0.50	150	3.25	64.83	17.25	9
7	1.6	1.00	150	3.25	51.05	22.13	6
8	1.2	0.75	200	4	46.24	8.3	14
9	0.8	1.00	250	1.75	36.98	9.25	10
10	1.6	0.50	250	1.75	55.17	18.96	7
11	1.2	0.75	200	2.5	46.68	9.57	12
12	1.6	1.00	250	1.75	59.38	24.31	6
13	1.2	0.75	200	1	44.93	9.87	11
14	0.8	1.00	150	3.25	34.96	3.96	22
15	1.2	0.75	300	2.5	51.02	16.04	6
16	1.2	1.25	200	2.5	41.22	17.1	6
17	1.2	0.75	200	2.5	53.22	8.34	16
18	0.8	0.50	150	3.25	41.14	4.71	22
19	0.8	1.00	150	1.75	24.92	5.23	12
20	1.2	0.75	200	2.5	48.77	13.7	9
21	0.8	0.50	150	1.75	25.94	2.72	24
22	1.6	1.00	250	3.25	55.65	25.25	6
23	1.6	0.50	150	1.75	63.63	17	9
24	1.2	0.75	200	2.5	56.05	11.75	12
25	0.8	0.50	250	3.25	33.75	3.7	23
26	1.2	0.75	100	2.5	43.44	8.83	12
27	1.2	0.75	200	2.5	49.89	7.43	17
28	1.2	0.75	200	2.5	56.68	11.24	13
29	0.8	1.00	250	3.25	43.44	9.33	12
30	0.8	0.50	250	1.75	40.57	6.16	17