废FCC催化剂与高炉灰催化木屑热解特性研究

张玉明; 管俊涛; 乔沛; 李国通; 李家州; 张炜; 刘明华

doi:10.1016/S1872-5813(22)60045-8

废FCC催化剂与高炉灰催化木屑热解特性研究

doi: 10.1016/S1872-5813(22)60045-8

张玉明^1, ,,
管俊涛¹,
乔沛¹,
李国通¹,
李家州¹,
张炜¹,
刘明华^2, ,

1.
中国石油大学(北京) 重质油国家重点实验室, 北京 102249
2.
福州大学环境与安全工程学院, 福建福州 350108

基金项目: 国家重点研发计划（2018YFE0183600）和中国石油大学（北京）科研基金（2462020YXZZ043, 2462021QNXZ007）资助

详细信息

通讯作者:
E-mail: ymzhcup@163.com

mhliu2000@fzu.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2022-03-09
- 修回日期: 2022-04-25
- 录用日期: 2022-04-27
- 网络出版日期: 2022-08-06
- 刊出日期: 2022-11-30

Study on the pyrolysis characteristics of sawdust catalyzed by spent FCC catalyst and blast furnace ash

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China
2.
College of Environment & Safety Engineering, Fuzhou University, Fuzhou 350108, China

Funds: The project was supported by the National Key R&D Program of China (2018YFE0183600) and Science Foundation of China University of Petroleum, Beijing (2462020YXZZ043, 2462021QNXZ007).

摘要

摘要: 将炼油废FCC催化剂（sFCCc）和炼钢高炉灰（BFA）两种典型工业废弃物作为催化剂应用于木屑快速热解过程中，探究了400−700 ℃木屑的催化热解反应特性。结果表明，两种催化剂均促进了液相产物向气相产物的转化，700 ℃、BFA催化条件下的气相产率最高为52.60%。sFCCc在500−600 ℃时具有更强的脱氧活性，气体产物中CO和CO₂产量更高。BFA在600−700 ℃时具有更高的缩聚脱氢活性，催化生成了更大量的多环芳香类化合物和H₂。热解油主要由酚类物质组成，sFCCc促进了甲氧基酚向苯二酚类物质转化。热解油FT-IR解析结果表明，sFCCc促进了C−O和C=O的脱除，导致酸类和酯类化合物减少，CO₂产率增加。
- 生物质 /
- 热解 /
- 废FCC催化剂 /
- 高炉灰
Abstract: Two industrial wastes, spent FCC catalyst (sFCCc) and blast furnace ash (BFA), were used as catalysts in the fast pyrolysis of sawdust, and the catalytic pyrolysis reaction characteristics of sawdust in the temperature range of 400−700 ℃ were explored. The results showed that both catalysts promoted the conversion from liquid products to gaseous products, and the highest gas yield was 52.60% at 700 ℃ catalyzed by BFA. The sFCCc had stronger deoxygenation activity at 500−600 ℃, resulting in higher CO and CO₂ production in gaseous products. While BFA had higher polycondensation and dehydrogenation activity at 600−700 ℃, and promoted the formation of polycyclic aromatic compounds and H₂. Pyrolysis oil was mainly composed of phenols. The sFCCc promoted the conversion of methoxy phenol to benzenediol. FT-IR analysis of pyrolysis oil showed that sFCCc promoted the removal of C−O and C=O, resulting in decreased acid and ester compounds and increased CO₂ yield.
- biomass /
- pyrolysis /
- spent FCC catalyst /
- blast furnace ash

HTML全文

FIG. 1994. FIG. 1994.

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图 1 实验装置流程示意图

Figure 1 Schematic diagram of experimental apparatus

1: Nitrogen cylinder; 2: Reducing valve; 3: Mass flowmeter; 4: Quartz reactor; 5: Thermocouple; 6: Biomass; 7: Temperature control thermocouple; 8: Furnace; 9: Condenser tube; 10: Erlenmeyer flask; 11: Ice water bath; 12: Acetone bottle washing set; 13: Sleeve filter; 14: Gas cylinder; 15: Graduated cylinder

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图 2 500 ℃下不同比例sFCCc（a）和BFA（b）对木屑热解产物产率的影响

Figure 2 Influence of different proportions of sFCCc (a) and BFA (b) on product yield at 500 ℃

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图 3 不同温度与催化条件下木屑热解产物产率的变化

Figure 3 Changes of pyrolysis product yield of sawdust under different temperature and catalytic conditions

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图 4 不同温度与催化条件下气体组分产率变化

Figure 4 Changes in gas component yield under different temperature and catalytic conditions

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图 6 不同催化条件下热解油品烃类组成

Figure 6 Hydrocarbon composition under different catalytic conditions at 700 ℃

（MAH: Monocyclic aromatic hydrocarbons, PAH: Polycyclic aromatic hydrocarbons）

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图 5 温度和催化条件对热解油品组成的影响

Figure 5 Influence of temperature and catalytic conditions on the composition of pyrolysis oil (a): 500 ℃, 600 ℃ and 700 ℃; (b): 500 ℃+sFCCc/BFA; (c): 600 ℃+ sFCCc /BFA; (d): 700 ℃+ sFCCc /BFA; (e): 700 ℃+ sFCCc /Al₂O₃; (f): 700 ℃+BFA/Fe₂O₃

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图 7 木屑热解油傅里叶变换红外光谱谱图

Figure 7 Fourier transform infrared spectra of sawdust pyrolysis oil

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图 8 木屑油傅里叶红外变换光谱的高斯拟合峰

Figure 8 Fitting Gaussian peaks of Fourier transform infrared spectrum for sawdust oil

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表 1 杨木屑的工业分析和元素分析

Table 1 Proximate and ultimate analyses of the poplar sawdust

Proximate analysis w_ad/%				Ultimate analysis w_daf/%
A	V	FC	M	C	H	S	N	O*
1.50	77.71	17.90	2.89	46.80	6.73	0.14	0.23	46.10
ad: air-dried basis; daf: dried ash-free basis; *: calculated by difference

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表 2 BFA和sFCCc所含主要金属氧化物

Table 2 Main metal oxides in BFA and SFCCc

Industrial waste	Fe₂O₃	Al₂O₃	SiO₂	K₂O	CaO	Na₂O	MgO
BFA/% (mass)	60.60	3.85	9.73	4.74	7.67	3.33	2.02
sFCCc/% (mass)	0.56	45.56	44.20	0.15	0.16	0.26	0.16

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表 3 不同温度和催化条件下主要酚类物质绝对峰面积

Table 3 Absolute peak area of main phenols under different temperature and catalytic conditions

Name	Experimental condition /Absolute peak area (×10⁶)
Name	500 ℃	500 ℃ sFCCc	500 ℃ BFA	600 ℃	600 ℃ sFCCc	600 ℃ BFA	700 ℃	700 ℃ sFCCc	700 ℃ BFA
Phenol	5.85	4.31	6.17	6.39	13.85	15.17	19.46	52.08	57.10
Phenol-methyl, 2-	8.75	5.76	6.64	8.48	15.12	14.93	19.02	37.40	31.77
Phenol, 3-methyl-	Na	Na	Na	11.16	25.79	19.38	27.16	32.53	48.02
Phenol, 2,3-dimethyl-	4.11	3.89	Na	3.77	34.01	15.89	6.15	7.58	16.67
Phenol, 3,5-dimethyl-	5.44	8.78	Na	11.02	6.91	7.78	16.28	26.38	20.55
Phenol, 2-methoxy-4-methyl-	17.86	7.78	25.81	Na	Na	Na	Na	Na	Na
Phenol, 2,6-dimethoxy-	51.95	37.31	52.34	Na	Na	Na	Na	Na	Na
Phenol, 2,6-dimethoxy-4-(2-propenyl)-	40.20	11.70	44.94	Na	Na	Na	Na	Na	Na
Phenol, 2-methoxy-	75.78	30.49	37.77	Na	Na	Na	Na	Na	Na
1,2-benzenediol	15.36	50.24	46.36	42.64	54.83	56.85	44.30	17.03	35.85
1,2-benzenediol, 4-methyl-	Na	Na	Na	59.81	21.14	20.41	8.61	Na	12.60
*Na: not available

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表 4 红外光谱波段分配^[36-39]和拟合峰面积

Table 4 Band assignments derived from FT-IR spectra^[36-39] and fitting peaks area

Peak positions /cm⁻¹	Half peak width/cm⁻¹	Functional groups	Peak area
Peak positions /cm⁻¹	Half peak width/cm⁻¹	Functional groups	500 ℃	600 ℃	700 ℃	600 ℃- sFCCc	600 ℃- BFA
3444 3286	106 167	O−H stretching vibration band	48.27	28.87	39.85	48.41	50.00
2939 2854 1461 1446	50 23 9 44	C−H stretching and bending vibration peaks	21.02	13.59	8.73	10.41	11.40
1773 1718	27 30	C=O vibration peaks	12.04	8.41	5.61	4.93	7.31
1660 1607 1514	23 25 9	C=C stretching vibration peak in aromatic rings	7.97	5.00	5.58	7.28	7.65
1363 1325 1283 1214 1154 1113 1054	27 15 27 43 13 27 34	C−O stretching vibration peak	34.34	25.01	21.60	23.65	30.43

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