生物质与催化裂化油浆共热解协同作用研究

doi:10.11949/0438-1157.20220475

摘要/Abstract

摘要：

基于生物质焦油氧含量高、品质差的缺陷，本文提出将生物质与重油共转化利用的方法。以催化裂化油浆（FCC）、稻壳（RH）、木屑（PS）为原料，通过低温固定床热解实验对其共热解产物分布进行了研究。结果表明，在FCC的供氢作用下，共热解有利于焦油中含氧化合物的脱除，随着生物质比例增加，反应过程中脱羧基、脱羰基反应减弱，脱羟基反应增强，产物中CO、CO₂产率较计算值增加幅度减小，水的产率较计算值逐渐增大。焦油中烃类物质增加，其中芳香烃以二元环和四元环增加为主，脂肪烃中以C₁₃~C₂₀增加为主。整体上，共热解过程促进了半焦产率的增加，焦油产率虽无明显改变但品质得到了显著提升。

关键词: 生物质, 催化裂化油浆, 共热解, 协同作用, 共热解焦油

Abstract:

Based on the defects of high oxygen content and poor quality of biomass tar, this paper proposes a method for co-conversion and utilization of biomass and heavy oil. The distribution of co-pyrolysis products of FCC slurry (FCC), rice husk (RH) and wood chip (PS) was studied by fixed bed pyrolysis at low temperature. The results show that the co-pyrolysis process is not conducive to the formation of tar in general, and the polymerization reaction in the system is strong, which promotes the increase of char yield. However, under the action of hydrogen supply by FCC, co-pyrolysis is beneficial to the removal of oxygen-containing compounds in tar. With the increase of biomass ratio, decarboxylation and decarbonylation reactions were weaken and dehydroxyl reaction was strengthen in the reaction process, and the increase of CO and CO₂ in the product decreases compared with the calculated value, while the yield of water gradually increases compared with the calculated value. The increase of hydrocarbons in tar is dominated by the increase of two-rings aromatic and four-rings aromatic in aromatic hydrocarbons and the increase of C₁₃-C₂₀ in aliphatic hydrocarbons. The quality of tar was improved after co-pyrolysis.

Key words: biomass, FCC, co-pyrolysis, synergistic effect, co-pyrolysis tar

中图分类号:

TQ 530

郝泽光, 张乾, 高增林, 张宏文, 彭泽宇, 杨凯, 梁丽彤, 黄伟. 生物质与催化裂化油浆共热解协同作用研究[J]. 化工学报, 2022, 73(9): 4070-4078.

Zeguang HAO, Qian ZHANG, Zenglin GAO, Hongwen ZHANG, Zeyu PENG, Kai YANG, Litong LIANG, Wei HUANG. Study on synergistic effect of biomass and FCC slurry co-pyrolysis[J]. CIESC Journal, 2022, 73(9): 4070-4078.

图/表 12

表1 稻壳与木屑工业分析和元素分析

Table 1 Proximate and ultimate analysis of the rice husk and pine sawdust

原料	工业分析/%(mass)				元素分析/%(mass,daf)					高位发热量/ (MJ/kg)
原料	Mad	A_d	V_daf	FC_d	C	H	O^①	N	S_t	高位发热量/ (MJ/kg)
RH	10.93	14.06	81.12	16.22	50.23	5.46	43.23	0.99	0.09	17.58
PS	1.54	36.49	90.95	5.75	43.31	4.61	51.09	0.98	0.01	8.72

表2 稻壳与木屑灰成分分析

Table 2 Ash composition analyses of the rice husk and pine sawdust

样品	灰成分分析/%(mass)
样品	SiO₂	Fe₂O₃	Al₂O₃	CaO	MgO	K₂O	Na₂O	SO₃	P₂O₅
稻壳灰	78.29	0.54	1.18	1.42	1.72	6.92	0.26	0.85	1.21
木屑灰	16.00	0.71	1.56	27.36	19.49	0.43	0.23	0.09	0.08

表3 FCC的四组分分析和元素分析

Table 3 Four-component analysis and ultimate analysis of the FCC

四组分分析/%(mass)					元素分析/%(mass)
饱和分	芳香分	胶质	沥青质		C	H	N	O	S
26.52	44.89	23.03	5.56		90.02	9.04	0.30	1.11	0.32

图1 FCC、RH和PS单独热解TG (a)和DTG (b)曲线

Fig.1 TG (a) and DTG (b) curves of FCC, RH, and PS pyrolysis alone

表4 生物质与FCC单独热解特征温度

Table 4 Characteristic temperatures of single pyrolysis of biomass and FCC

样品	起始温度/℃	峰值温度/℃	结束温度/℃	最大峰值速率/（%/min）	残焦剩余量/%
FCC	283	354	490	6.70	5.84
RH	233	329	380	7.48	35.82
PS	258	340	385	4.60	63.72

图2 生物质和FCC共热解产物分布

Fig.2 Distribution of co-pyrolysis products of biomass and FCC

图3 生物质和FCC共热解产物协同程度

Fig.3 Synergy degree of co-pyrolysis products of biomass and FCC

图4 3种物料单独热解焦油组分分布

Fig.4 Components distribution of tar from three materials pyrolysis separately

图5 不同生物质与FCC共热解油中不同种类物质实验值与计算值对比

Fig.5 Comparison of experimental and calculated values of different kinds of substances in different biomass and FCC co-pyrolysis tar

图6 不同生物质和FCC共热解气体组成分布

Fig.6 Composition distribution of co-pyrolysis gases of different biomass and FCC

图7 不同生物质和FCC共热解气体组分协同程度

Fig.7 Synergistic degree of different biomass and FCC co-pyrolysis gas components

图8 生物质与FCC共热解可能的反应机制

Fig.8 Possible reaction mechanism of biomass and FCC co-pyrolysis

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