神府煤热解-活化耦合反应产物特性及机制研究

刘源; 贺新福; 张亚刚; 杨伏生; 任秀彬; 周安宁

神府煤热解-活化耦合反应产物特性及机制研究

基金项目:

国家自然科学基金 51174279

教育部博士学科专项基金 20116121110005

陕西省13115科技创新工程重大科技专项 2008ZDKG-53

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中图分类号: TQ530.2
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出版历程
- 收稿日期: 2015-09-20
- 修回日期: 2015-11-17

Mechanism and product characteristics of pyrolysis-activation coupling reaction of Shenfu coal

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Corresponding author: Tel: 13609282106, E-mail: psu564@139.com

摘要

摘要: 利用两段式固定床反应装置, 研究了神府煤热解-活化耦合产物的特性, 探讨了热解温度及活化剂 (H₂O (g)、CO₂和H₂O (g)/CO₂) 对产物性能的影响, 揭示了热解-活化耦合反应机制。结果表明, 热解温度对半焦的CO₂化学反应性影响较小; 采用热解-活化两段耦合工艺, 可使神府煤热解的焦油产率明显提高, 产率最高为17.8%;不同活化剂对两段耦合过程产生的混合煤气 (mixture coal gases, MCG) 和焦油产率影响为H₂O (g)>H₂O (g)/CO₂>CO₂, 其焦油组分均以饱和分和芳香分为主; 采用H₂O (g)/CO₂(1:1) 活化剂, 可有效提高活性炭的比表面积, 其BET比表面积为845.37 m²/g。热解-活化耦合机制主要为活化段产生的合成气 (synthesis gases, SG) 为热解段煤的加氢热解提供了氢源, 丰富的氢自由基促进了煤的加氢热解反应, 改变了耦合过程的产物分布和特性。
- 神府煤 /
- 热解-活化 /
- 耦合反应 /
- 活性炭 /
- 焦油组成
Abstract: The characteristics of products from Shenfu coal pyrolysis-activation coupling reaction were investigated in a two-stage fixed bed reactor.The effect of pyrolysis temperature and activating agents (H₂O (g), CO₂ and H₂O (g)/CO₂) on the characteristics of products was analyzed.The mechanism of pyrolysis-activation coupling reaction was revealed.The results show that the pyrolysis temperature has little effect on the CO₂ chemical reactivity of the chars.The tar yield of Shenfu coal pyrolysis is significantly increased by using pyrolysis-activation coupling process, and the tar yield is up to 17.8%.The effect of different activating agents on the yield of mixed coal gases (MCG) and tar is in the order of H₂O (g)>H₂O (g)/CO₂>CO₂ and the main components of tar are saturates and aromatics.The specific surface area of activated carbon can be effectively improved by using H₂O (g)/CO₂ as the activating agents, and the BET specific surface area reaches to 845.37 m²/g.The mechanism of pyrolysis-activation coupling process is that the synthesis gases (SG) from the activation section can provide hydrogen source for coal hydropyrolysis in pyrolysis section, and the rich hydrogen radicals can promote the reaction and change the product distribution and properties.
- Shenfu coal /
- pyrolysis-activation /
- coupling reaction /
- activated carbon /
- tar composition

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图 1 煤热解-活化耦合工艺流程示意图

Figure 1. Flow chart of the coal pyrolysis-activation coupling

1: gas cylinder; 2: commingler; 3: preheater; 4: control cabinet; 5: furnace; 6: tubular reactor; 7: gas/liquid separator;8: refrigeration cycle; 9: soap bubble flow-meter; 10: dryer; 11: gas chromatograph; 12: heating belt; 13: steam generator

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图 2 煤热解-活化耦合反应示意图

Figure 2. Schematic diagram of the coal pyrolysis-activation coupling reactions

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图 3 不同热解温度半焦的CO₂反应性能

Figure 3. CO₂ reactivity of char at different pyrolysis temperatures

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图 4 样品的SEM照片

Figure 4. SEM photos of samples

(a): Char_(N₂-700); (b): AC (H₂O); (c): AC (H₂O/CO₂); (d): AC (CO₂)

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图 5 活化剂对热解-活化耦合产物产率的影响

Figure 5. Effect of activating agents on yields of products from pyrolysis-activation coupling process

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图 6 活化剂对热解-活化耦合气体产物组成的影响

Figure 6. Effect of activating agents on composition of MCG from pyrolysis-activation coupling process

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图 7 煤热解反应-活化反应耦合机制示意图

Figure 7. Schematic diagram of coupling mechanism of coal pyrolysis-activation reaction

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表 1 神府煤的工业分析和元素分析

Table 1. Proximate and ultimate analyses of Shenfu coal

Proximate analysis w_ad/%				Ultimate analysis w_daf/%					H/C	O/C
M	A	V	FC^*	C	H	N	O^*	S	H/C	O/C
5.98	7.26	36.75	50.01	79.86	4.88	0.89	14.09	0.28	0.73	0.13
^*: by difference

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表 2 半焦的工业分析、元素分析和结构参数

Table 2. Proximate analysis, ultimate analysis and structural parameters of chars

Sample	Proximate analysis w_ad/%				Ultimate analysis w_daf/%					H/C	O/C	Structural parameters
Sample	M	A	V	FC^*	C	H	N	O^*	S	(mol ratio)		f_a	2(R-1)/C	R
Char_(N₂-500)	1.31	7.98	10.84	79.87	89.02	1.32	0.87	8.53	0.26	0.18	0.07	0.868	0.954	4.900
Char_(N₂-550)	1.29	8.29	8.21	82.21	89.81	1.22	0.55	8.19	0.23	0.16	0.07	0.886	0.951	4.936
Char_(N₂-600)	1.29	8.48	7.44	82.79	88.67	1.29	0.78	8.99	0.27	0.17	0.08	0.904	0.922	4.775
Char_(N₂-650)	1.25	8.72	5.38	84.65	89.51	1.15	0.61	8.49	0.24	0.18	0.07	0.915	0.931	4.855
Char_(N₂-700)	1.23	9.12	4.73	84.92	89.99	1.01	0.73	8.02	0.25	0.18	0.07	0.913	0.952	4.982
Char_(N₂-750)	1.19	9.24	4.24	85.33	90.07	0.93	0.66	8.12	0.22	0.16	0.06	0.917	0.959	5.019
^*: by difference; f_a: aromaticity factor; 2(R-1)/C: ring condensation index; R: even ring condensation number

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表 3 半焦和活性炭的比表面积和孔结构

Table 3. Surface area and pore structure parameters of char and activated carbons

Sample	BET surface area A/(m²·g^-1)			Pore volume v/(cm³·g^-1)		Pore size d/nm
Sample	BET surface area	micropore surface area	external surface area	total pore volume	micropore pore volume	average pore size
Char	31.82	28.12	3.70	0.059	0.009	53.25
AC (H₂O)	725.19	637.14	88.05	0.219	0.079	3.93
AC (H₂O/CO₂)	845.37	741.59	103.78	0.243	0.061	4.86
AC (CO₂)	591.67	530.22	61.45	0.287	0.058	5.72

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表 4 活化剂对SG中气体产量的影响

Table 4. Effect of activating agents on yield of gases in SG

Activating agents	H₂/(mmol·g^-1)	CH₄/(mmol·g^-1)	CO /(mmol·g^-1)	CO₂/(mmol·g^-1)
H₂O (g)	50.29	1.92	1.15	19.17
H₂O (g)/CO₂	20.33	1.51	9.32	36.64
CO₂	2.86	0.98	17.46	50.71

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表 5 活化剂对热解-活化耦合焦油组成的影响

Table 5. Effect of activating agents on component of tar from pyrolysis-activation coupling process

Activation agent	Content w/%
Activation agent	saturates	aromatics	rein	asphaltene
H₂O (g)	32.70	49.69	12.85	4.76
H₂O (g)/CO₂	31.26	50.32	13.70	4.72
CO₂	29.97	51.08	13.94	5.01

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表 6 神府煤热解-活化耦合反应主要反应及产物

Table 6. Main reactions and product composition of Shenfu coal pyrolysis-activation coupling process

Reaction zone	Product composition	Gas composition	Chemical reaction^{[24, 25]}
Activation zone	activated carbon	H₂, CH₄, CO, CO₂	C (s)+H₂O (g) ↔ H₂(g)+CO (g)-131.5 kJ/mol
			C (s)+2H₂O (g) ↔2 H₂(g)+CO₂(g)-88.0 kJ/mol
			C (s)+CO₂(g) ↔ 2CO (g)-172.7 kJ/mol
			CO (s)+H₂O (g) ↔H₂(g)+CO₂(g)+40.6 kJ/mol
Pyrolysis zone	tar, gas, char	H₂, CH₄, CO, CO₂, C_2-4	cracking reaction
			secondary reaction
			crosslinking reaction
			polycondensation

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