微波輔助炭基催化劑催化熱解生物質的研究進展

李攀; 胡秋輝; 胡俊豪; 陳志勇; 張永勝; 方書起; 常春

doi:10.13374/j.issn2095-9389.2022.11.16.002

微波輔助炭基催化劑催化熱解生物質的研究進展

doi: 10.13374/j.issn2095-9389.2022.11.16.002

李攀^{1, 2, 3},
胡秋輝^{1, 2,},
胡俊豪^{1, 2, 3},
陳志勇²,
張永勝^{1, 2, ,},
方書起^{1, 2, 3},
常春^{1, 2, 3}

1.
鄭州大學機械與動力工程學院，鄭州 450001
2.
河南省生物基化學品綠色制造重點實驗室，濮陽 457000
3.
生物質煉制技術與裝備河南省工程實驗室，鄭州 450001

基金項目: 國家自然科學基金資助項目（52006200）；河南省杰出外籍科學家工作室資助項目（GZS2022007）；南陽市協同創新重大專項（鄭州大學南陽研究院）資助項目（22XTCX12007）

詳細信息

通訊作者:
E-mail: yzhang@zzu.edu.cn

中圖分類號: TK6
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- 文章訪問數: 302
- HTML全文瀏覽量: 144
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-11-16
- 網絡出版日期: 2023-01-12
- 刊出日期: 2023-09-25

Research progress on biomass catalytic pyrolysis via microwave effects combined with carbon-based catalysts

LI Pan^{1, 2, 3},
HU Qiuhui^{1, 2
,},
HU Junhao^{1, 2, 3},
CHEN Zhiyong²,
ZHANG Yongsheng^{1, 2
, ,},
FANG Shuqi^{1, 2, 3},
CHANG Chun^{1, 2, 3}

1.
School of Mechanical and Power Engineering, Zhengzhou University, Zhengzhou 450001, China
2.
Henan Key Laboratory of Green Manufacturing of Biobased Chemicals, Puyang 457000, China
3.
Henan Engineering Laboratory for Biorefinery Technology and Equipment, Zhengzhou 450001, China

More Information

Corresponding author: E-mail: yzhang@zzu.edu.cn

摘要

摘要: 炭基催化劑具有制備成本低、催化后處理簡單等優點，但存在易積碳失活、產物選擇性低等缺點，結合微波效應，可明顯提高炭基催化劑的競爭力。本文對微波輔助炭基催化劑熱解生物質的研究進展進行了現狀綜述。主要介紹了微波加熱原理，吸波劑和催化劑對于微波熱解的影響機制。分析了不同改性方法（金屬負載法、化學法、磺化等）對炭基催化劑的孔隙結構、含氧官能團和酸性基團及催化反應產物特性的影響。總結了微波輔助改性炭基催化劑在焦油重整和改善生物質熱解產物特性等方面的應用進展。本文對該研究方向存在的問題提出建議并進行展望，為基于微波催化熱解作用下炭基催化劑的選擇、改性和生物質高值化利用提供一定的參考。
- 炭基催化劑 /
- 生物質 /
- 微波催化熱解 /
- 改性 /
- 高值化利用
Abstract: It is critical to discover a clean energy source to replace fossil fuels such as coal to meet the targets of “emission peak” and “carbon neutrality” in 2030 and 2060, respectively. Biomass is a kind of renewable energy that is rich in reserves and can be directly converted into fuel. Pyrolysis is a common way to maximize the value of biomass, and the composition and distribution of products can be adjusted by the addition of catalysts. Carbon-based catalysts have the advantages of low preparation costs and easy treatment after catalysis. However, they have the disadvantages of easy carbon deposition inactivation and low product selectivity. The competitiveness of carbon-based catalysts can be improved when combined with the microwave effect. Herein, the research status of microwave-assisted carbon-based catalysts for the pyrolysis of biomass is reviewed. This study primarily introduces the microwave heating theory principle as well as the microwave absorber and catalyst effect mechanisms on the microwave for pyrolysis. The limitations of metal catalysts and molecular sieve catalysts are analyzed, and the unique advantages of modified carbon-based catalysts in the field of microwave pyrolysis are proposed. Microwave heating uses microwave radiation to create heat in the internal particles of biomass; therefore, microwave pyrolysis has the advantages of a high heating rate, uniform heating, low energy loss, a high energy conversion rate, and instantaneous adjustment. The effects of different modification methods (metal loading method, chemical method, sulfonation, etc.) on the pore structure, oxygen-containing functional groups, and acidic groups of carbon-based catalysts and the characteristics of catalytic products are analyzed. Among them, the preparation method’s precipitation method is difficult to manage, and the repeatability is low. The impregnation method has the advantages of being an easy preparation process, being inexpensive, and having a large production capacity. The chemical process will remarkably alter the oxygen-containing groups and acidity of the biochar. Too much acidity causes carbon deposition and catalyst deactivation, whereas too few acidic oxygen-containing groups induce pyrolysis rate decreasing. Therefore, the raw materials used in sulfonation are not environmentally friendly. The application progress of microwave-assisted modified carbon-based catalysts in tar reforming and improving the properties of biomass pyrolysis products is summarized. Carbon-based catalysts combined with microwave heating can increase the yield of phenols and syngas and improve the quality of pyrolysis products. Herein, some suggestions on the problems existing in this research direction are put forward and prospected, which provides some reference for the selection and modification of carbon-based catalysts and the high-value utilization of biomass based on microwave catalytic pyrolysis.
- carbon-based catalyst /
- biomass /
- microwave catalytic pyrolysis /
- modification /
- high-value utilization

HTML全文

圖 1 常規加熱和微波加熱方式對比^[13]. (a)常規加熱；(b) 微波加熱

Figure 1. Comparison of conventional and microwave heating^[13]: (a) conventional heating；(b) microwave heating

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圖 2 活性炭基催化劑催化熱解葡萄糖和纖維素制備酚類機理圖^[33]

Figure 2. Diagram of the mechanism of the activated carbon-based catalyst to catalyze the pyrolysis of glucose and cellulose to produce phenols^[33]

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圖 3 催化劑制備流程圖^[42]

Figure 3. Flow chart of catalyst preparation^[42]

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圖 4 不同溫度下木質素的熱解途徑^[51]

Figure 4. Pyrolysis pathway of lignin at different temperatures^[51]

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圖 5 棕櫚仁殼熱解蒸氣催化重整實驗裝置圖^[56]

Figure 5. Experimental setup of the palm kernel shell (PKS) pyrolysis steam catalytic reforming^[56]

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表 1 不同改性方法對炭基催化劑特性及熱解產物的影響

Table 1. Effects of different modification methods on the characteristics and pyrolysis products of carbon-based catalysts

Materials	Catalyst	Result	Reference
Corncob	Gp?SO₃H?H₂O₂	After H₂O₂ modification, the total amount of acidic groups increased from 1.80 mmol·g^?1 to 2.55 mmol·g^?1, and the xylose and glucose produced by corncob increased from 54.7% and 9.3% to 79.7% and 11.5% respectively.	[43]
Pine sawdust, plastics	Ni?CaO?C	Ni?CaO?C was synthesized by the rising pH method. The hydrogen production performance of Ni?CaO?C was better than that of Ni?Al₂O₃, and the co-pyrolysis effect of Ni?CaO?C on H₂ production was HDPE(high density polyethylene) > PP(polypropylene) > PS(polystyrene).	[44]
Douglas fir	MgO/phosphoric acid activated carbon catalyst	The main components of bio-oil produced by catalytic pyrolysis of Douglas Fir were phenols, ketones, aldehydes and furans, accounting for 75.9%–90.5%.	[45]
Peanut shells	HCl and MnCl₂-modified carbon-based catalysts	Carbon-based catalysts inhibited the formation of pyrolytic acids; HCl increased the selectivity of phenols and inhibited the formation of H₂; MnCl₂ improved the selectivity of phenol and alkylated phenols and promoted the formation of H₂ and CH₄.	[46]
Tar	Porous silicon film overcoating biomass char-supported catalyst	SiO₂ film combined with microporous biochar enhanced the adsorption of tar molecules and gas. The formed FeNi₃ nano-alloy particles can prevent the aggregation of nano-metal particles and reduce carbon deposition. After repeated use, the tar conversion rate was stable.	[47]
Tar	Activation of carbon-based catalysts by KOH, H₃PO₄ and ZnCl₂	The tar conversion rates of catalyst-free, RHC(rice husk char), ZnCl₂?RHC, H₃PO₄?RHC and KOH?RHC were 66.9%, 76.7%, 83.4%, 91.6% and 94.2%, respectively. RHC?KOH obtained the maximum yield of the four gas components.	[48]
Xylitol	Metal-modified carbon-based catalyst	The activity of Pt?Ni/C, Pt?Co/C and Pt?Ru/C catalysts and the selectivity of H₂ were close to those of Pt/C	[49]

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表 2 不同微波催化熱解條件下的主要產物

Table 2. Primary products under different microwave catalytic pyrolysis conditions

Materials	Catalyst	Product	Reference
Toluene	Ni/rice husk char	The cracking rate of toluene was 95.12%, and the concentration of hydrogen in the gaseous product was 92.04%.	[63]
Moso bamboo sawdust	Moso bamboo biochar	With the increase of biochar load, CO+H₂ also increased, with the highest yield of 65.31%.	[64]
Rice straw	Rice straw biochar	The tar removal efficiency was 94.03%, and the H₂ and syngas contents were 50.5% and 94.5%, respectively.	[65]
Douglas fir	Acid washed granular activated carbon	After the addition of activated carbon, the contents of total phenol and phenol increased to 66.9% and 39.0%, respectively.	[66]
Palm kernel shell	Activated carbon and lignite char	At 500 ℃, the mass fraction of phenol and total phenol in bio-oil reached 64.58% and 71.24%, respectively.	[67]
Corn cob	Fe/phosphoric acid acidified biochar	The main components of bio-oil obtained by microwave catalytic pyrolysis were phenols, and the yields of bio-oil and phenols were not closely related to the times of use.	[68]
Tar	Ni/ rice husk char	When the load increased to 16.86% (mass fraction), the tar conversion increased from 78.6% to 98.6%. Microwave promoted the removal of tar and the formation of syngas and improved the stability of catalytic cracking of Ni/ rice husk char.	[69]
Douglas fir	Ferrum-modified activated carbon	Under certain conditions, the ketone content accounted for about 38% of the bio-oil, and the organic acid content decreased significantly.	[70]
Lignin, polyethylene	Zn modified lignin-based char	At 450 °C, when the LDPE (low density polyethylene) dosage was 12.5%, the hydrocarbon yield was the highest. At 550 °C, when the LDPE dosage was 20%, the phenolic yield was the highest.	[71]
Dunaliella salina	Na₂CO₃/AC，CaCO₃/AC	The dehydration effect of activated carbon catalyst on microalgae was better than that of Na₂CO₃ and CaCO₃; In the process of microwave pyrolysis, AC/Na₂CO₃ was better than AC/CaCO₃.	[72]

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