杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃

蔡伟; 黄明; 朱亮; 郑宇博; 蔡博; 马中青

doi:10.19906/j.cnki.JFCT.2023004

杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃

doi: 10.19906/j.cnki.JFCT.2023004

浙江农林大学化学与材料工程学院国家木质资源综合利用工程技术研究中心, 浙江杭州 311300

基金项目: “领雁”研发攻关计划（2022C03092），浙江省自然科学基金（LY21E060001），浙江省属高校基本科研业务费专项资金（2020YQ006），国家林业和草原局科技创新青年拔尖人才项目（2019132617)和浙江大学能源清洁利用国家重点实验室开放基金（ZJU-CEU2020021）资助

详细信息

作者简介:
蔡伟（1999—），男，硕士研究生，caiwei962464@163.com

通讯作者:
E-mail: mazq@zafu.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2022-11-17
- 修回日期: 2022-12-29
- 录用日期: 2022-12-30
- 网络出版日期: 2023-01-10
- 刊出日期: 2023-08-01

Enhancement of the production of light aromatics from poplar wood by combined approach of wet torrefaction pretreatment and catalytic fast pyrolysis using metal modified hierarchical zeolite

College of Chemistry and Materials Engineering, National Engineering Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang A & F University, Hangzhou 311300, China

Funds: The project was supported by the Key R & D Program of Zhejiang Province (2022C03092）, Natural Science Foundation of Zhejiang Province (LY21E060001), the Fundamental Research Funds for the Provincial Universities of Zhejiang (2020YQ006), the Youth Talent Support Program by National Forestry and Grassland Administration (2019132617), the Open Foundation from the State Key Laboratory of Clean Energy Utilization (ZJU-CEU2020021)

摘要

摘要: 轻质芳烃是化工领域重要的基础有机原料，生物质催化热解的技术路线可制取生物基的轻质芳烃化学品。首先，采用湿法烘焙预处理，对杨木进行协同脱氧和脱灰改性提质；其次，采用NaOH脱硅预处理和负载活性金属（Zn、Ga和Fe），对微孔HZSM-5进行修饰改性，构建金属改性多级孔HZSM-5催化剂，并将其用于湿法烘焙杨木催化热解，研究烘焙温度、催化剂改性、催化剂与原料质量比和热解温度等参数对轻质芳烃产率的影响。结果表明，随着湿法烘焙温度的升高，杨木的脱氧率和碱/碱土金属脱除率逐渐增加，其中，O、K、Mg、Ca和Na的最大脱除率分别为47.96%、90.99%、86.65%、66.09%和36.29%。与HZSM-5相比，采用NaOH脱硅后的多级孔HZSM-5（Hie-H）及金属改性的多级孔HZSM-5（Ga/Hie-H、Zn/Hie-H和Fe/Hie-H），均促进了轻质芳烃的形成，其中，Zn/Hie-H对杨木湿法烘焙后固体产物催化热解制取轻质芳烃产率最高；在湿法烘焙温度为220 ℃，Zn/Hie-H与烘焙杨木质量比为3∶1，热解温度为850 ℃时，轻质芳烃的产率达到最大值，为7.83 × 10⁷ p.a./mg。
- 生物质 /
- 湿法烘焙 /
- 协同脱氧脱灰 /
- 分子筛 /
- 催化热解 /
- 芳烃
Abstract: Light aromatics are extremely important building blocks in the chemical industry which can be produced from the catalytic fast pyrolysis (CFP) of biomass. In this work, wet torrefaction pretreatment (WTP) was employed to improve the quality of poplar wood (PW) in terms of the synergetic deoxygenation and demineralization. Then, metal-modified hierarchical HZSM-5 was prepared by the combined approach of NaOH desilication pretreatment and metal (Zn, Ga, and Fe) modification. At last, the CFP of torrefied PW was carried out by using the metal-modified hierarchical HZSM-5 as catalyst to produce light aromatics. Results showed that the deoxygenation and demineralization rates gradually increased with the increase of WTP temperature from 180 to 260 ℃, the maximum removal rates of oxygen, K, Mg, Ca, and Na were 47.96%, 90.99%, 86.65%, 66.09%, and 36.29%, respectively. NaOH desilication pretreatment and metal modification on HZSM-5 promoted the formation of light aromatics. The Zn-modified hierarchical HZSM-5 presented the highest yield of light aromatics. The yield of aromatics increased first with the raise of catalyst-to-torrefied PW ratio from 1:1 to 1∶3, then decreased slightly at the highest catalyst-to-torrefied PW ratio of 1∶5. At last, the operation parameter of WTP and CFP was optimized which the maximum yield of light aromatics was 7.83 × 10⁷ p.a./mg at WTP temperature of 220 ℃, catalyst-to-biomass ratio of 3∶1, and CFP temperature of 850 ℃.
- biomass /
- wet torrefaction /
- synergetic deoxygenation and demineralization /
- zeolite /
- catalytic fast pyrolysis /
- aromatics

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FIG. 2578. FIG. 2578.

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图 1 湿法烘焙温度对碱和碱土金属含量（a）、结晶度（b）和表面官能团（c）的影响

Figure 1 Effect of wet torrefaction temperature on the contents of alkali and alkali earth metals, crystallinity, and the surface chemical functional groups

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图 2 金属改性前后多级孔HZSM-5催化剂的 N₂吸附-脱附等温曲线（a），孔径分布（b）和NH₃-TPD谱图（c）

Figure 2 N₂ adsorption-desorption isotherms (a), pore size distribution curves (b), and NH₃-TPD profiles of the parent and metal modified hierarchical HZSM-5

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图 3 湿法烘焙温度对杨木非催化热解生物油组分的影响

Figure 3 Effect of wet torrefaction temperature on the components in bio-oil derived from non-CFP of PW

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图 4 碱改性处理和金属修饰HZSM-5催化剂对烘焙杨木催化热解生物油组分分布的影响

Figure 4 Effect of the NaOH and metal modified HZSM-5 on the compound distribution in bio-oil during CFP of torrefied PW

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图 5 催化剂与烘焙杨木的质量比对催化热解生物油组分的影响

Figure 5 Effect of the mass ratio of catalyst and wet torrefied PW on the compound distribution in bio-oil during CFP of torrefied PW

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图 6 催化热解温度对生物油组分的影响

Figure 6 Effect of pyrolysis tempearture on the compound distribution in bio-oil during CFP of torrefied PW

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表 1 湿法烘焙温度对杨木基本特性的影响

Table 1 Effect of wet torrefaction temperature on the yield of torrefied products and the basic properties of torrefied PW

Temp. /℃	Mass yields of torrefied product /%			Ultimate analysis /%			Proximate analysis /%			Other properties
Temp. /℃	gas	liquid	solid	C	H	O	A	V	FC	Q_HHV / (MJ·kg⁻¹)	O/C ratio	deoxygenation rate /%	energy yield /%
Raw	−	−	−	46.69	6.20	47.02	4.32	82.17	13.51	16.23	0.76	−	−
180	2.07	27.02	70.94	49.33	6.19	44.37	0.09	84.08	15.83	17.62	0.67	5.64	77.02
200	3.41	32.58	64.01	52.07	6.00	41.71	0.34	81.06	18.60	18.58	0.60	11.29	73.28
220	12.46	35.54	52.00	52.89	5.91	41.16	2.08	72.86	25.06	18.99	0.58	12.46	60.84
240	14.91	37.19	47.90	60.28	5.78	33.92	2.60	62.70	34.70	22.61	0.42	27.86	56.23
260	16.50	40.17	43.33	70.15	5.37	24.47	3.40	57.48	39.12	27.06	0.26	47.96	49.76

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表 2 金属改性前后多级孔HZSM-5催化剂的孔结构特征和酸量

Table 2 Pore structural characteristics and acid amount of the parent and metal modified hierarchical HZSM-5

Catalyst	^aS_BET / (m²·g⁻¹)	^bv_Total / (cm³·g⁻¹)	^cv_Micro / (cm³·g⁻¹)	^dv_Meso / (cm³·g⁻¹)	^ed_Pore / nm	Weak acid / (mmol·g⁻¹)	Strong acid / (mmol·g⁻¹)	Total acid / (mmol·g⁻¹)
HZSM-5	288.490	0.212	0.136	0.076	2.365	0.460	0.600	1.060
Hie-H	357.729	0.271	0.117	0.153	3.030	0.625	0.230	0.855
Ga/Hie-H	309.839	0.252	0.102	0.151	3.257	0.769	0.105	0.874
Fe/Hie-H	296.613	0.231	0.105	0.125	3.113	0.680	0.139	0.819
Zn/Hie-H	298.396	0.226	0.102	0.125	3.036	0.748	0.102	0.850
^aS_BET: Specific surface area, ^bv_Total: Total pore volume, ^cv_Micro: Micropore volume, ^dv_Meso: Mesopore volume, ^ed_Pore: Average pore diameter

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