载镧白云石催化剂对松木催化气化性能的研究

牛永红; 宋子曌; 李义科; 王文才; 温建军; 郑坤灿

doi:10.1016/S1872-5813(21)60005-1

载镧白云石催化剂对松木催化气化性能的研究

doi: 10.1016/S1872-5813(21)60005-1

牛永红^{1, 2, 3, ,},
宋子曌¹,
李义科^1, ,,
王文才²,
温建军¹,
郑坤灿¹

1.
内蒙古科技大学能源与环境学院，内蒙古包头 014010
2.
内蒙古科技大学矿业研究院，内蒙古包头 014010
3.
内蒙古自治区高效洁净燃烧重点实验室，内蒙古包头 014030

基金项目: 国家自然科学基金（51768054, 51764046, 51764044），内蒙古自治区科技创新引导项目（KCBJ2018077），内蒙古自然科学基金（2017MS(LH)0524），内蒙古科学技术厅项目（20180823）和包头市中科发展科技有限责任公司项目（ZK2018H003）资助

详细信息

通讯作者:
E-mail：niuyonghong@imust.edu.cn

liyk@imust.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2020-08-01
- 修回日期: 2020-10-04
- 刊出日期: 2021-01-29

Performance research of lanthanum-loaded dolomite catalyst for pine catalytic gasification

1.
School of Energy and Environment, Inner Mongolia University of Science and Technology, Baotou 014010, China
2.
Mining Research Institute, Inner Mongolia University of Science and Technology, Baotou 014010, China
3.
Inner Mongotia Key Laboratory of Efficient and Clean Combustion, Baotou 014030, China

Funds: The project was supported by the National Natural Science Foundation of China (51768054, 51764046, 51764044)，Inner Mongolia Autonomous Region Science and Technology Innovation Guidance Project (KCBJ2018077)，Inner Mongolia Natural Science Foundation (2017MS(LH)0524)，Inner Mongolia Science and Technology Department Project (20180823) and Baotou Zhongke Development Technology Limited Liability Company Project (ZK2018H003)

摘要

摘要: 为增强白云石的催化效果，以La(NO₃)₃为助剂，采用浸渍法对白云石进行改性研制La/Dol催化剂，通过BET、SEM、XRD对其进行了表征。以松木燃料棒为生物质原料，La/Dol为重整催化剂，采用自制的两段式生物质气化重整试验炉对比分析了不同气化温度、不同载La量催化剂对松木屑催化气化结果的影响。结果表明，少量的La（2%）可明显促进水煤气反应的正向进行，改善催化重整效果。2-La/Dol在催化剂蒸汽流量为10 g/min，重整温度为750 ℃ 的工况下，随着气化温度的升高，产H₂量显著增加，H₂体积分数的最高值从28.51%（0-La/Dol）增加到41.72%（2-La/Dol）。催化剂内的La₂O₃促进了焦油的二次裂解，使得液相产物焦油含量明显减少，官能团数目减少，分布在白云石表面的La₂O₃占据了活性位点，使得碳丝不宜集聚，抑制了积炭的生成，同时存在于催化剂中的碳酸盐（La₂O₂CO₃）亦与表面的积炭发生反应，减缓催化剂积炭问题，提高了催化剂活性和使用寿命。
- 生物质 /
- La/Dol催化剂 /
- 催化气化 /
- 水蒸气气化
Abstract: To enhance the catalytic effect of dolomite, La/Dol catalyst was prepared by impregnation modification of dolomite with La (NO₃)₃ as additive. The catalyst was characterized by BET, SEM and XRD. With pine rods as raw materials and La/Dol as reforming catalysts, the effects of gasification temperature and La amount of catalysts on the catalytic gasification of pine were compared and analyzed in a self-made two-stage biomass gasification reforming experimental furnace. The results show that a small amount of La (2%) can obviously promote the forward progress of water gas reaction and perfect the catalytic reforming effect. Under the working condition of steam flow rate of 10 g/min, 2-La/Dol catalyst and reforming temperature of 750℃, with the increase of gasification temperature, the amount of H₂ increases significantly, and the highest volume fraction of H₂ increases from 28.51% (0-La/Dol) to 41.72% (2-La/Dol). La₂O₃ in the catalyst promotes the secondary cracking of tar. As a result, the tar content of liquid phase product is obviously reduced, and the number of functional groups is also reduced. La₂O₃ on dolomite surface occupies active sites, so carbon filaments are not suitable for accumulation and carbon deposition is inhibited. Carbonate (La₂O₂CO₃) in the catalyst can react with carbon to slow down the carbon deposition on the surface and improve the activity and service life of the catalyst.
- biomass /
- La/dolomite catalyst /
- catalystic gasification /
- steam gasification

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图 1 实验系统装置示意图

Figure 1 Schematic diagram of the experimental system

1: nitrogen bottle; 2: flow meter; 3: water storage tank; 4: peristaltic water pump; 5: steam generator; 6: gasification furnace; 7: crucible; 8: thermocouple; 9: temperature controller; 10: insulation cotton; 11: bracket; 12: catalytic furnace; 13: catalyst; 14: tar absorption system; 15: drying device; 16: air bag; 17: flame

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图 2 不同负载量的白云石催化剂SEM照片

Figure 2 SEM images of dolomite catalysts with different loadings

（a）：2-La/Dol；（b）：4-La/Dol；（c）：6-La/Dol；（d）：8-La/Dol

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图 3 负载2%的La(NO₃)₃前后催化剂XRD谱图

Figure 3 XRD patterns of catalysts before and after loading 2% La(NO₃)₃

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图 4 负载不同La含量的催化剂 XRD谱图

Figure 4 XRD patterns of catalysts with different La contents

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图 5 白云石催化剂等温吸附-脱附曲线

Figure 5 Dolomite catalyst isothermal adsorption desorption curve

(a): natural dolomite; (b): calcined dolomite

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图 6 天然白云石催化气体产物随气化温度的变化规律

Figure 6 Variation of catalytic gas products of natural dolomite with gasification temperature

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图 7 2-La/Dol 催化作用下气体组分随气化温度变化规律

Figure 7 Gas composition over 2-La/Dol catalysis at different temperatures

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图 8 800 ℃气体组分随负载量变化趋势

Figure 8 Variation trend of gas composition with La loading at 800℃

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图 9 气化产物焦油的FT-IR谱图（800 ℃）

Figure 9 FT-IR spectra of tars from 0-La/Dol （a）and 2-La/Dol（b）catalytic gasification at 800℃

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图 10 气化产物焦油的FT-IR谱图（800 ℃）

Figure 10 FT-IR spectra of gasification tars using recycled 2-La/Dol catalyst

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图 11 2-La/Dol催化剂反应后XRD谱图

Figure 11 XRD patterns of 2-La/Dol catalyst after reaction

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图 12 积炭量随催化剂使用次数的变化

Figure 12 Variation of carbon deposition with catalyst usage times

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表 1 松木棒元素分析及工业分析

Table 1 Element analysis and industrial analysis of pine rod particles

Elemental analysis w/%					Industrial analysis w/%
C_ad	H_ad	O_ad	N_ad	S_ad	FC_d	V_d	A_d
50.54	7.08	41.11	0.15	0.57	17.16	82.29	0.55

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表 2 催化剂的孔结构

Table 2 Pore structure properties of catalysts

Sample	Surface area A/（m²·g⁻¹）	Mean pore diameter d/nm	Total pore volume v/（cm³·g⁻¹）（× 10⁻²）
Natural dolomite	1.4	22.4	0.764
Calcined dolomite	8.6	45.9	9.83
2-La/Dol	4.5	17.3	1.95
4-La/Dol	4.8	17.4	2.11
6-La/Dol	4.9	20.4	2.50
8-La/Dol	4.0	16.2	1.62

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