循环流化床高碱煤气化技术研发及应用进展

doi:10.16085/j.issn.1000-6613.2023-2195

摘要/Abstract

摘要：

系统回顾了循环流化床高碱煤气化技术的研发及应用历程，重点概况了在高碱煤基础理化特性、气化反应特性及碱金属的迁移特性、防结渣技术研究及循环流化床高碱煤气化工程应用四个方面的进展与成果。梳理了高碱煤的煤质特征、碱金属的赋存形态和含量、前处理方法对碱金属含量测定的影响，以及高碱煤的燃烧和成灰特性。总结了煤种、反应进程、气化温度、氧碳摩尔比、反应气氛等对高碱煤气化性能指标和气化灰结渣特性的影响。阐述了配煤、添加剂及更换床料等方法对预防高碱煤气化结渣的作用和反应机理，采用刚玉做床料实现了循环流化床高碱煤气化中试装置稳定运行。评述了循环流化床高碱煤气化技术的自主创新以及在工业燃气、合成气领域的成功应用。最后，从建立高碱煤气化用煤数据库、开发纯用高碱煤的气化技术、开发高效脱碱及原位耦合利用革新技术、探索高碱煤与其他物料协同利用技术并制备高性能材料四个方面展望了未来高碱煤气化技术的发展方向。

关键词: 高碱煤, 循环流化床, 气化, 钠迁移, 结渣

Abstract:

The development and application of circulating fluidized bed gasification with high-alkaline coal technology was systematically reviewed, with a focus on fundamental physicochemical properties, gasification reaction characteristics, alkali-metal migration behavior, anti-slagging technology research, and industrial demonstration of high-alkaline coal gasification. The characteristics of high-alkaline coal, the distribution and content of alkali metals, the influence of pretreatment methods on sodium content determination, and combustion and ash formation properties of high-alkaline coal were outlined. The effects of coal type, gasification temperature, oxygen-to-carbon molar ratio, reaction atmosphere, and reaction extent on gasification performance of high-alkaline coal and slagging characteristics of gasification residue were summarized. The role and reaction mechanisms of blending coals, additives, and replacing bed materials in preventing slagging during high-alkaline coal gasification were elucidated, leading to stable operation of a pilot-scale circulating fluidized bed gasification of high-alkaline coal by using corundum as bed material. The paper also reviewed the original innovation of circulating fluidized bed gasification of high-alkaline coal and its successful applications in production of industrial fuel gas and syngas. Finally, future directions for high-alkaline coal gasification technology were discussed from four perspectives: establishing a database for high-alkaline coal gasification, developing gasification technologies specifically for pure use of high-alkaline coal, developing efficient alkali removal and in-situ coupling utilization innovation technology, and exploring synergistic utilization techniques of high-alkaline coal with other materials to produce high-performance materials.

Key words: high-alkaline coal, circulating fluidized bed, gasification, migration of Na, slagging

中图分类号:

TQ53

张海霞, 朱治平, 张思源. 循环流化床高碱煤气化技术研发及应用进展[J]. 化工进展, 2024, 43(5): 2254-2278.

ZHANG Haixia, ZHU Zhiping, ZHANG Siyuan. Research and application progress of circulating fluidized bed gasification with high-alkaline coal[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2254-2278.

图/表 39

表1 高碱煤的工业分析和元素分析结果[13,42-43]

煤种	工业分析（质量分数）/%			元素分析（质量分数）/%						低位热值（LHV_ar） /MJ·kg^-1
煤种	A_d	V_d	FC_d	C_d	H_d	N_d	O_d	S_d	Cl_d	低位热值（LHV_ar） /MJ·kg^-1
ML	9.55	30.08	60.38	71.73	3.54	0.72	13.29	1.17	0.704	22.92
TCML	3.69	31.54	64.77	75.34	3.53	0.61	16.31	0.53	0.065	23.70
TCWCW	11.50	30.39	58.11	68.96	3.28	0.77	14.31	1.19	0.093	21.84
SHWCW	5.96	40.37	53.66	64.50	2.02	0.82	26.23	0.47	0.123	17.63
SEH	16.48	34.23	49.29	57.92	2.65	0.65	22.17	0.12	1.279	17.93
YH	8.40	27.64	63.96	72.91	3.73	0.50	13.99	0.46	0.054	24.28
YN	5.29	44.61	50.11	70.61	4.68	1.28	17.82	0.33	0.019	20.30
BK	43.53	25.64	30.83	41.94	3.00	1.32	9.42	0.78	0.022	14.98

表2 高碱煤的灰成分分析结果（质量分数，%）[13,42-43]

煤种	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	TiO₂	SO₃	P₂O₅	K₂O	Na₂O
ML	23.28	9.26	18.26	10.95	2.72	0.54	18.58	0.54	0.86	7.86
TCML	3.73	6.16	5.37	33.45	5.42	0.41	29.34	0.00	0.45	7.28
TCWCW	20.81	10.54	29.70	11.36	4.51	0.60	14.91	0.04	0.89	2.71
SHWCW	17.24	11.90	5.76	28.74	5.34	0.60	19.58	0.05	0.38	3.92
SEH	41.98	17.59	6.78	19.39	2.49	1.08	1.82	0.18	0.66	4.38
YH	35.22	10.89	7.06	22.28	5.39	0.74	12.12	0.14	1.14	3.56
YN	42.73	16.95	5.15	10.11	4.20	1.02	9.88	0.29	1.21	8.46
BK	58.65	28.53	4.57	1.35	1.13	0.98	0.82	0.11	3.27	0.57

表3 高碱煤的灰熔融特征温度[13,42-43]

煤种	灰熔融特征温度（弱还原性）/℃
煤种	变形温度（DT）	软化温度（ST）	半球温度（HT）	流动温度（FT）
ML	1030	1060	1080	1100
TCML	1360	1370	1370	1380
TCWCW	1110	1130	1150	1170
SHWCW	1320	1320	1330	1340
SEH	1120	1130	1140	1150
YH	1170	1170	1180	1190
YN	1080	1100	1100	1120
BK	1470	>1500	—	—

表4 传统结渣判断指标[43-46]

判断指标	计算方式	判断标准及程度
判断指标	计算方式	轻度	中度	重度
ST/℃	GB/T 1574—1995	>1390	1260~1390	<1260
R_B/A		<0.206	0.206~0.400	>0.4
R_S/A		<1.87	1.87~2.65	>2.65
R_F/C		<0.30	0.3~3.0	>3.0

表5 结渣判断结果[43]

判断指标	煤种及判断结果
判断指标	TCML	YN	SEH	YH
ST/℃	1370	1100	1130	1170
R_B/A	5.05	0.48	0.56	0.84
R_S/A	0.61	2.52	2.39	3.23
R_F/C	0.16	0.51	0.35	0.32

图1 准东高碱煤及气化飞灰（QHH）中钠和钾的赋存形态[26]

图2 前处理方法对钠含量检测的影响[26]

表6 五种准东煤的着火温度和燃尽温度[19]

煤种	着火温度T_i/℃	燃尽温度T_f/℃
ML	386.5	487.0
TCML	398.7	452.3
TCWCW	387.0	452.1
SHWCW	380.0	441.4
SEH	337.1	457.9

图3 ML原煤和不同温度成灰的SEM照片[19]

图4 ML不同成灰温度下灰成分XRD谱图[19]1—NaCl；2—SiO2；3—CaSO4；4—CaCO3；5—Fe2O3；6—Al6Si2O18； 7—NaAlSi3O8；8—NaAlSiO4；9—Ca2SiO4

表7 5种准东高碱煤的气化特征温度及灰分收率[42]

煤种	气化起始温度T_i/℃	气化终止温度T_f/℃	气化反应速率峰值温度T_max/℃	灰分收率/%
ML	841.1	925.6	900.8	7.03
TCML	804.0	903.5	873.6	0.80
TCWCW	797.1	921.5	866.8	6.75
SHWCW	792.2	916.5	886.7	4.50
SEH	724.7	844.1	789.3	9.08

图5 不同准东高碱煤气化残留物的钠含量[42]

图6 不同煤种气化灰的微观形貌[42]

表8 气化残留物中可能存在的部分低温共熔体分子式及共熔温度[42]

低温共熔体分子式	共熔温度/℃
Na₂O·2SiO₂+SiO₂+Na₂O·3CaO·6SiO₂	725
Na₂O·2SiO₂+SiO₂	790
Na₂O·2SiO₂+Na₂O·SiO₂+2Na₂O·CaO·3SiO₂	821
Na₂O·SiO₂+Na₂O·2SiO₂	840
Na₂SO₄+NaCl	721
CaSO₄+Na₂SO₄	918
SiO₂+Al₂O₃+K₂O	695
CaO+Fe₂O₃	597
CaSO₄+CaS	850
CaSO₄+Na₂SO₄+K₂SO₄	845~933
FeS+FeO	940
SiO₂+Na₂O+K₂O	540
Fe₂O₃+SiO₂	577

图7 ML 950℃气化不同停留时间下所得灰产率和气化残留物的钠固留率[42]

图8 ML煤950℃不同停留时间气化灰的表观形貌图[42]

图9 ML 950℃不同气化时间气化灰物相分析[42]1—CaO；2—SiO2；3—Fe3O4；4—NaAlSiO4；5—NaAlSi3O8

图10 不同样品的SEM-EDS检测结果[43]

图11 不同样品碱金属钠和钾的固留率[43]

图12 温度对煤气化性能指标的影响[16]

图13 不同温度条件下气化底渣和飞灰的微观形貌[16]

图14 气化温度对钠含量及钠固留率的影响[16]

图15 准东高碱煤气化灰中钠的赋存形态[53]FA—飞灰；BA—底渣

图16 O2/C摩尔比对SHWCW煤气化性能指标的影响[15]

图17 不同O2/C摩尔比条件下SHWCW煤气化底渣和飞灰XRD谱图[15]a—CaSO4；b—SiO2；c—CaO；d—CaCO3；e—Fe2O3；f—NaAlSi2O6；g—MgO；h—NaCl；i—Na2SO4；j—Al2O3；k—NaAlSiO4；l—Na2(MgSiO4)

图18 不同O2/C摩尔比条件下SHWCW煤气化底渣和飞灰的钠含量[15]

图19 不同O2/C摩尔比时SHWCW气化残留物中钠的固留率[15]

图20 氧煤比对YH煤气化飞灰组成的影响[43]

图21 反应气氛对煤气化性能的影响[53]

图22 富氧气氛下灰中Na的分布[53]

图23 蒸汽煤比对YH煤气化飞灰组成的影响[43]

图24 配煤比例对YN煤气灰微观形貌和元素组成的影响[43]

图25 不同样品中碱金属Na的固留率[31]O—YH；A—YH+高岭土；B—YH+勃姆石；C—YH+刚玉；D—YH+石英；E—YH+生蛭石；F—YH+熟蛭石

图26 不同气化灰样品XRD谱图[31]a—SiO2；b—CaO；c—MgO；d—Ca2Al2SiO7；e—NaAlSi3O8；f—CaAl2Si2O8；g—CaCO3；h—Ca3Al2Si3O12；i—Fe2O3；j—Al2O3；k—NaAlSiO4； l—Mg2SiO4；m—CaSO4；n—Ca(Fe,Mg)Si2O6；o—Na2SO4；p—Ca3SiO5；q—Ca3Mg(SiO4)2；r—(Na,Ca)Al(Si,Al)3O8

表9 煤灰组分与添加剂之间的主要反应[43]

主要产物	化学反应	ΔG/kJ·mol^-1	ΔH/kJ·mol^-1
CaO	CaCO₃ $→$ CaO + CO₂	-8.05	165.19
	2CaSO₄ + C $→$ 2CaO + 2SO₂ + CO₂	-64.67	560.30
NaAlSiO₄	Na₂SO₄ + Al₂O₃ + 2SiO₂ $→$ 2NaAlSiO₄ + SO₃	25.69	192.09
	Na₂O + Al₂O₃ + 2SiO₂ $→$ 2NaAlSiO₄	-355.54	-328.02
	Na₂O + 2AlOOH + 2SiO₂ $→$ 2NaAlSiO₄ + H₂O	-1038.36	-1305.73
	Na₂SO₄ + 2AlOOH + 2SiO₂ $→$ 2NaAlSiO₄ + SO₃ + H₂O	-657.12	-785.62
NaAlSi₃O₈	Na₂SO₄ + Al₂O₃ + 6SiO₂ $→$ 2NaAlSi₃O₈ + SO₃	-13.33	160.87
	Na₂O + Al₂O₃ + 6SiO₂ $→$ 2NaAlSi₃O₈	-394.57	-359.25
	Na₂O + 2AlOOH + 6SiO₂ $→$ 2NaAlSi₃O₈ + H₂O	-1077.38	-1336.96
	Na₂SO₄ + 2AlOOH + 6SiO₂ $→$ 2NaAlSi₃O₈ + SO₃ + H₂O	-696.15	-816.84
CaAl₂Si₂O₈	CaO + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈	-130.68	-107.27
	CaCO₃ + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈ + CO₂	-138.73	57.92
	CaSO₄ + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈ + SO₃	50.72	273.74
Ca₂Al₂SiO₇	2CaO + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇	-162.54	-131.07
	2CaCO₃ + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇ + 2CO₂	-178.64	199.31
	2CaSO₄ + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇ + 2SO₃	200.25	630.94
Ca₃Al₂Si₃O₁₂	3CaO + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂	-272.25	-337.06
	3CaCO₃ + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + 3CO₂	-296.40	158.52
	3CaSO₄ + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + 3SO₃	271.93	805.97
	3CaO + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O	-955.06	-1314.77
	3CaCO₃ + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O + 3CO₂	-979.21	-819.19
	3CaSO₄ + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O + 3SO₃	-410.89	-171.75
Mg₂SiO₄	2MgO + SiO₂ $→$ Mg₂SiO₄	-60.38	-67.06
Ca₃SiO₅	3CaO + SiO₂ $→$ Ca₃SiO₅	-125.99	-69.83
	3CaCO₃ + SiO₂ $→$ Ca₃SiO₅ + 3CO₂	-150.14	425.74
	3CaSO₄ + SiO₂ $→$ Ca₃SiO₅ + 3SO₃	418.1835	1073.19
	2AlOOH $→$ Al₂O₃ + H₂O	-682.81	-977.71

表9 煤灰组分与添加剂之间的主要反应[43]

主要产物	化学反应	ΔG/kJ·mol^-1	ΔH/kJ·mol^-1
CaO	CaCO₃ $→$ CaO + CO₂	-8.05	165.19
	2CaSO₄ + C $→$ 2CaO + 2SO₂ + CO₂	-64.67	560.30
NaAlSiO₄	Na₂SO₄ + Al₂O₃ + 2SiO₂ $→$ 2NaAlSiO₄ + SO₃	25.69	192.09
	Na₂O + Al₂O₃ + 2SiO₂ $→$ 2NaAlSiO₄	-355.54	-328.02
	Na₂O + 2AlOOH + 2SiO₂ $→$ 2NaAlSiO₄ + H₂O	-1038.36	-1305.73
	Na₂SO₄ + 2AlOOH + 2SiO₂ $→$ 2NaAlSiO₄ + SO₃ + H₂O	-657.12	-785.62
NaAlSi₃O₈	Na₂SO₄ + Al₂O₃ + 6SiO₂ $→$ 2NaAlSi₃O₈ + SO₃	-13.33	160.87
	Na₂O + Al₂O₃ + 6SiO₂ $→$ 2NaAlSi₃O₈	-394.57	-359.25
	Na₂O + 2AlOOH + 6SiO₂ $→$ 2NaAlSi₃O₈ + H₂O	-1077.38	-1336.96
	Na₂SO₄ + 2AlOOH + 6SiO₂ $→$ 2NaAlSi₃O₈ + SO₃ + H₂O	-696.15	-816.84
CaAl₂Si₂O₈	CaO + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈	-130.68	-107.27
	CaCO₃ + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈ + CO₂	-138.73	57.92
	CaSO₄ + Al₂O₃ + 2SiO₂ $→$ CaAl₂Si₂O₈ + SO₃	50.72	273.74
Ca₂Al₂SiO₇	2CaO + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇	-162.54	-131.07
	2CaCO₃ + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇ + 2CO₂	-178.64	199.31
	2CaSO₄ + Al₂O₃ + SiO₂ $→$ Ca₂Al₂SiO₇ + 2SO₃	200.25	630.94
Ca₃Al₂Si₃O₁₂	3CaO + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂	-272.25	-337.06
	3CaCO₃ + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + 3CO₂	-296.40	158.52
	3CaSO₄ + Al₂O₃ + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + 3SO₃	271.93	805.97
	3CaO + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O	-955.06	-1314.77
	3CaCO₃ + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O + 3CO₂	-979.21	-819.19
	3CaSO₄ + 2AlOOH + 3SiO₂ $→$ Ca₃Al₂Si₃O₁₂ + H₂O + 3SO₃	-410.89	-171.75
Mg₂SiO₄	2MgO + SiO₂ $→$ Mg₂SiO₄	-60.38	-67.06
Ca₃SiO₅	3CaO + SiO₂ $→$ Ca₃SiO₅	-125.99	-69.83
	3CaCO₃ + SiO₂ $→$ Ca₃SiO₅ + 3CO₂	-150.14	425.74
	3CaSO₄ + SiO₂ $→$ Ca₃SiO₅ + 3SO₃	418.1835	1073.19
	2AlOOH $→$ Al₂O₃ + H₂O	-682.81	-977.71

图27 添加剂对YH煤气化灰颗粒的微观结构及表面元素含量[31,43]

图28 YH煤气化底渣和返料器样品的晶相结构[43]○ SiO2；◆ CaSO4；□ Al2O3；△ Na2SiO3；◁ Na2SO4；▷ NaAl11O17；/// Fe2O3；● NaAlSiO4；▼ Na2CO3；▶ (K, Na)AlSi3O；★ NaCaMgAl(Si2O6)2

图29 350t/d的循环流化床煤气化工业示范装置系统工艺流程图[13]①—提升管；②—旋风分离器；③—返料器；④—空气预热器；⑤—余热锅炉；⑥—二级旋风除尘器；⑦—煤气冷却器；⑧—布袋除尘器；⑨—点火燃烧器；⑩—气化炉鼓风机；—返料风机；—冷渣机；—螺旋给料机；—油箱；—水泵；—煤气加压机

图30 Na2O-Al2O3-SiO2三元相图分析[13]

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