生物质中矿物质在气化条件下的演变行为研究

曹琴; 黄胜; 吴诗勇; 吴幼青; 高晋生

生物质中矿物质在气化条件下的演变行为研究

华东理工大学资源与环境工程学院煤气化及能源化工教育部重点实验室, 上海 200237

基金项目:

国家自然科学基金 21506060

详细信息

中图分类号: TQ53
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出版历程
- 收稿日期: 2015-12-02
- 修回日期: 2016-03-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-06-10

Evolution behaviors of mineral matters in biomass under gasification conditions

Resources and Environment Engineering Institute, Key Laboratory of Coal Gasification and Energy Chemical of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

More Information

Corresponding author: Tel: 021-64252037, E-mail: wyq@ecust.edu.cn

摘要

摘要: 以稻秸秆和玉米秸秆为原料, 考察了弱还原性气氛以及550-1300℃生物质中矿物质的变化, 并采用FactSage软件对生物质中矿物质在高温下的演变行为进行了模拟。结果表明, 生物质灰中Na和K元素的存在形式相对稳定, 部分以气态氯化物的形式挥发出去, 部分存在于低熔点硅酸盐或硫酸盐中; Si元素与Ca、Fe、Mg和Al四种元素形成的硅酸盐的变化形式较多, 主要形成辉石、橄榄石和黄长石三类物质, 随着温度的升高, 部分辉石会转化为橄榄石与黄长石, 此三类物质相互作用易形成熔点较低的共熔体而导致矿物质的熔融。方石英和莫来石是导致稻秸秆流动温度高于玉米秸秆的主要原因, 莫来石最终转化为斜铁辉石、铁尖晶石和钙长石等熔点较低的矿物质。
- 生物质 /
- 矿物质 /
- 熔融特征温度 /
- XRD /
- FactSage
Abstract: The composition and reaction of mineral matters in rice straw and corn stalk were investigated in weak reducing atmosphere at temperature range of 550-1300℃. The FactSage was also used to simulate the evolution behaviors of mineral matters under high temperatures. The results show that the existing form of Na and K in biomass is relatively stable, including volatilized chlorides, silicates and sulphates with a lower melting point. The silicates made up of Si, Ca, Mg, Fe and Al have various forms, mainly including pyroxene, olivine and melilite. Pyroxene is transformed into olivine and melilite with the increasing of temperature. The interaction of the three kinds of materials could result in the generation of eutectics which could lead to the melting of mineral matters in biomass. The formation of cristobalite and mullite leads to a higher flow temperature of rice straw ash than corn stalk ash, the mullite ultimately is transformed into low melting point materials like clinoferrosilite, iron spinel and anorthite.
- biomass /
- mineral matter /
- ash fusion temperature /
- XRD /
- FactSage

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图 1 不同热处理温度下稻秸秆灰的XRD谱图

Figure 1 XRD patterns of the rice straw ash produced at different temperatures

Q: quartz [SiO₂]; C: cristobalite [SiO₂]; Sy: sylvine [KCl]; Co: calcium oxide [CaO]; Wh: whitlockite [Ca₃(PO₄)₂]; N: nepheline [NaAlSiO₄]; Mo: monticellite [CaMgSiO₄]; E: enstatite [MgSiO₃]; Ce: clinoenstatite [MgSiO₃]; Cf: clinoferrosilite [FeSiO₃]; A: akermanite [Ca₂MgSi₂O₇]; Si: sillimanite [Al₂SiO₅]; K: kaliophilite [KAlSiO₄]; Cs: calcium silicate [CaSiO₃]; G: gehlenite [CaAl₂SiO₇]; Cor: cordierite [Mg₂Al₄Si₅O₁₈]; Mu: mullite [Al₆Si₂O₁₃]

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图 2 不同热处理温度下玉米秸秆灰的XRD谱图

Figure 2 XRD patterns of the corn stalk ash produced at different temperatures

Q: quartz [SiO₂]; C: cristobalite[SiO₂]; Sy: sylvine [KCl]; K: kalsilite [KAlSiO₄]; Co: calcium oxide [CaO]; Wo: wollastonite [CaSiO₃]; Pas: potassium aluminum silicate eutectic [K_0.85Al_0.85Si_0.15O₂]; Wh: whitlockite [Ca₃(PO₄)₂]; Ds: disodium sulfate[Na₂SO₄]; Ps: potassium silicate[K₂Si₂O₅]; Fo: forsterite[Mg₂SiO₄]; Fa: fayalite[Fe₂SiO₄]; D: diopside[CaMgSi₂O₆]; Ce: clinoenstatite[MgSiO₃]; Cf: clinoferrosilite[FeSiO₃]

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图 3 稻秸秆灰的FactSage模拟图

Figure 3 FactSage simulation of rice straw ash

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图 4 玉米秸秆灰的FactSage模拟图

Figure 4 FactSage simulation of corn stalk ash

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表 1 生物质的工业分析与元素分析

Table 1 Proximate and ultimate analysis of biomass

Sample	Proximate analysis w_d/%			Ultimate analysis w_d/%
Sample	A	V	FC	C	H	S_t	N
DJG	20.14	72.81	7.05	43.91	5.75	0.15	1.37
YMJG	4.27	72.00	23.73	46.91	5.24	0.12	1.28

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表 2 生物质灰的组成

Table 2 Ash analysis of biomass

Sample	Component w/%
Sample	Na₂O	K₂O	CaO	MgO	Fe₂O₃	Al₂O₃	SiO₂	Cl	SO₃	P₂O₅	TiO₂
DJG	1.91	10.80	5.14	3.37	1.30	2.29	66.60	2.61	2.36	2.64	0.12
YMJG	0.41	26.43	14.26	9.59	0.93	0.99	36.68	4.13	2.52	3.74	0.05

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表 3 生物质灰熔融特征温度

Table 3 Ash fusion temperatures of biomass

Sample	Temperature t/℃
Sample	DT	ST	HT	FT
DJG	826	1010	1188	1269
YMJG	976	1033	1048	1076

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表 4 稻秸秆中矿物质在高温下可能发生的反应^[9-11]

Table 4 Possible reactions of rice straw mineral matters at high temperatures^[9-11]

Temperature t/℃	Possible reaction
550-800	quartz [SiO₂]→cristobalite [SiO₂], Na₂O+Al₂O₃+2SiO₂→2NaAlSiO₄, 3CaO+P₂O₅→Ca₃(PO₄)₂,
	Fe₂O₃+CO→2FeO+CO₂, FeO+SiO₂→FeSiO₃, MgO+SiO₂→MgSiO₃, CaO+ MgSiO₃→CaMgSiO₄
800-900	Al₂O₃+SiO₂→Al₂SiO₅, K₂O+Al₂O₃+2SiO₂→2KAlSiO₄,
	CaO+SiO₂→CaSiO₃, CaSiO₃+ CaO→Ca₂SiO₄, Ca₂SiO₄+MgSiO₃→Ca₂MgSi₂O₇
900-1000	Ca₂SiO₄+Al₂O₃→Ca₂Al₂SiO₇, 2MgO+2Al₂O₃+5SiO₂→Mg₂Al₄Si₅O₁₈
1000-1100	enstatite [MgSiO₃]→clinoenstatite [MgSiO₃]
1100-1200	2Al₂SiO₅+Al₂O₃→Al₆Si₂O₁₃
1200-1300	Al₆Si₂O₁₃+5FeO→2FeSiO₃+3FeAl₂O₄, Al₆Si₂O₁₃+CaO→CaAl₂Si₂O₈+2Al₂O₃

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表 5 玉米秸秆中矿物质在高温下可能发生的反应^[9]

Table 5 Possible reactions of corn stalk mineral matters at high temperatures^[9]

Temperature t/℃	Possible reaction
550-800	puartz [SiO₂]→cristobalite [SiO₂], CaO+SiO₂→CaSiO₃, 3CaO+P₂O₅→Ca₃(PO₄)₂,
	K₂O+Al₂O₃+2SiO₂→2KAlSiO₄, K₂O+SiO₂→K₂Si₂O₅, Fe₂O₃+CO→2FeO+CO₂,
	FeO+SiO₂→FeSiO₃, FeO+ FeSiO₃→Fe₂SiO₄, MgO+SiO₂→MgSiO₃, CaSiO₃+ MgSiO₃→CaMgSi₂O₆
800-900	Al₂O₃+SiO₂→Al₂SiO₅, K₂O+Al₂O₃+2SiO₂→2KAlSiO₄, Na₂O+SO₃→Na₂SO₄, MgO+MgSiO₃→Mg₂SiO₄
900-1100	0.15KAlSiO₄+0.35K₂O+0.35Al₂O₃→K_0.85Al_0.85Si_0.15O₂

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