微藻与塑料混合热解的热解特性和动力学研究

唐紫玥; 陈伟; 陈旭; 陈应泉; 胡强; 成伟; 杨海平; 陈汉平

doi:10.19906/j.cnki.JFCT.2023008

微藻与塑料混合热解的热解特性和动力学研究

doi: 10.19906/j.cnki.JFCT.2023008

唐紫玥^1,,
陈伟^2,,
陈旭^3,,
陈应泉^1,,
胡强^1,,
成伟^1,,
杨海平^1, ,,
陈汉平^1,

1.
华中科技大学能源与动力工程学院煤燃烧国家重点实验室, 湖北武汉 430074
2.
南京农业大学工学院, 江苏南京 210095
3.
武汉轻工大学硒科学与工程现代产业学院, 湖北武汉 430023

基金项目: 国家自然科学基金杰出青年项目(52125601)和国家重点研发计划项目 (2018YFB1501403)资助

详细信息

通讯作者:
Tel: 027-87542417-8211, E-mail: yhping2002@163.com

中图分类号: TK6
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出版历程
- 收稿日期: 2022-10-29
- 修回日期: 2022-12-07
- 录用日期: 2022-12-27
- 网络出版日期: 2023-01-18
- 刊出日期: 2023-08-01

Pyrolysis characteristics and kinetics of co-pyrolysis of microalgae and plastics

TANG Zi-yue^1
,,
CHEN Wei^2
,,
CHEN Xu^3
,,
CHEN Ying-quan^1
,,
HU Qiang^1
,,
CHENG Wei^1
,,
YANG Hai-ping^{1
, ,},
CHEN Han-ping^1
,

1.
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
2.
College of Engineering, Nanjing Agricultural University, Nanjing 210095, China
3.
School of Modern Industry for Selenium Science and Engineering, Wuhan Polytechnic University, Wuhan 430023, China

Funds: The project was supported by the National Natural Science Foundation of China Outstanding Youth Program (52125601) and National Key Research and Development Program (2018YFB1501403)

摘要

摘要: 本研究利用TG-FTIR研究了微藻和聚乙烯（PE）、聚苯乙烯（PS）和聚丙烯（PP）混合热解特性，探讨了塑料添加比及塑料结构对热解失重和挥发分释放特性以及动力学的影响。微藻与塑料混合热解存在交互作用，使塑料的热解温度升高，并抑制焦炭形成，其中，PE能有效地减少残余物产率，而PS混合热解时其热解温度明显升高。并且微藻与塑料混合热解能降低热解过程中的平均活化能，且在较低比例塑料添加时作用较强。此外，微藻与聚乙烯混合会促进CO₂的释放以及聚乙烯断键生成–CH₃和C=C–H。微藻与聚丙烯混合却抑制CO₂的释放，加剧了聚丙烯生成芳烃C–H。而微藻与聚苯乙烯混合会轻微促进C=O和NH₃生成，并加剧微藻的氢转移和聚苯乙烯苯环断裂释放–CH₃。
- 微藻 /
- 塑料 /
- 混合热解 /
- TG-FTIR /
- 动力学
Abstract: Plastics as co-feeding can effectively improve the quality of microalgae pyrolysis oil. The effects of co-pyrolysis of microalgae and polyethylene (PE), polystyrene (PS) and polypropylene (PP) on pyrolysis characteristics and kinetics were investigated by TG-FTIR. There is an interaction between microalgae and plastic, which increases the pyrolysis temperature of plastic and inhibits the formation of coke. PE can effectively reduce the residual yield, while the pyrolysis temperature of PS obviously transfers to high temperature during co-pyrolysis. In addition, co-pyrolysis reduces the average activation energy, especially low proportion of plastic. Besides, the co-pyrolysis of microalgae with PE promotes C−C fracture to release CO₂ and −CH₃ and C=C−H. However, the co-pyrolysis of microalgae and PP inhibits the release of CO₂, and intensifies the formation of aromatic hydrocarbon C−H from polypropylene. Moreover, the co-pyrolysis of microalgae and PS can slightly promote the formation of C=O and NH₃, and aggravate the hydrogen transfer of microalgae to break aromatic ring of polystyrene and release CH₃.
- microalgae /
- plastics /
- co-pyrolysis /
- TG-FTIR /
- kinetics

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FIG. 2580. FIG. 2580.

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图 1 微藻与塑料混合热解的TG曲线（a）、（c）、（e）和DTG曲线（b）、（d）、（f）

Figure 1 TG curves and DTG curves of co-pyrolysis of microalgae and plastics

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图 2 共热解过程中TG失重与实验计算结果的偏差

Figure 2 Deviation of TG weight loss between experimental and calculated results during co-pyrolysis process

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图 3 微藻（a）和塑料（b）热解挥发分主要特征峰随温度的变化

Figure 3 Variation of the main volatiles of microalgae (a) and plastic (b) pyrolysis with temperature

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图 4 微藻和塑料混合热解时热解挥发分主要特征峰随温度的变化

Figure 4 Variation of the main volatiles from co-pyrolysis of microalgae and plastic with temperature

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图 5 25%塑料添加比时热解挥发分FT-IR强度差值

Figure 5 FT-IR intensity difference of pyrolytic volatiles at 25% plastic addition ratio

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图 6 微藻和塑料混合热解过程的平均活化能与理论值比

Figure 6 Value of the E_m.cal/ E_m during co-pyrolysis of microalgae and plastics

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表 1 样品的工业分析和元素分析

Table 1 Proximate, ultimate analysis of samples and biochemical constituents of microalgae

Sample	Elemental analysis w_d/%				Proximate analysis w_d/%
Sample	C	H	N	O^①	M	V	FC	A
NS	50.6	7.3	6.7	29.4	4.0	79.6	10.4	6.0
PE	84.3	15.5	−^②	0.2	−	100.0	−	−
PS	91.4	7.5	−	1.1	−	97.2	2.8	−
PP	84.9	14.7	−	0.6	−	99.9	0.1	−
^①: calculated by difference; ^②: undetected

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表 2 基于Doyle 和Coats-Redfern法计算的微藻和塑料混合热解的动力学参数

Table 2 Kinetic parameters for the co-pyrolysis of microalgae and plastics via Doyle and Coats-Redfern method

Sample	Temperature /℃	Coats-Redfern			Doyle			E_m / (kJ·mol⁻¹)
Sample	Temperature /℃	E/(kJ·mol⁻¹)	A/s	R²	E/(kJ·mol⁻¹)	A/s	R²	E_m / (kJ·mol⁻¹)
NS	216–357	47.91	2.7×10	0.9969	54.31	3.4×10²	0.9987	37.04
	357–526	16.15	2.0×10⁻²	0.9856	26.38	2.4	0.9964
25%PE	231–361	41.42	3.6	0.9889	48.31	6.0×10	0.9935	66.21
	361–458	9.65	1.7×10⁻³	0.9752	19.95	4.5×10⁻¹	0.9943
	458–495	149.76	2.3×10⁸	0.9862	154.27	5.9×10⁸	0.9882
50%PE	252–345	37.97	9.2×10⁻¹	0.9892	45.11	1.8×10	0.9937	130.79
	345–442	7.14	4.1×10⁻⁴	0.9766	17.34	1.5×10⁻¹	0.9968
	442–494	205.48	1.9×10¹²	0.9796	207.13	2.7×10¹²	0.9817
75%PE	285–341	32.99	1.4×10⁻¹	0.9872	40.62	3.8	0.9928	208.20
	341–432	7.59	2.2×10⁻⁴	0.9785	17.64	7.4×10⁻²	0.9962
	432–492	267.09	4.3×10¹⁶	0.9862	265.65	3.5×10¹⁶	0.9873
PE	432–486	321.04	3.4×10²⁰	0.9960	316.75	1.9×10²⁰	0.9963	318.89
25%PS	221–352	42.54	5.7	0.9951	49.26	8.9×10	0.9972	46.58
	352–418	16.44	1.3×10⁻²	0.9869	26.04	1.4	0.9949
	418–475	77.71	2.6×10³	0.9790	85.21	2.2×10⁴	0.9843
50%PS	244–337	43.16	4.1	0.9909	49.91	6.4×10	0.9944	74.29
	337–413	18.65	1.3×10⁻²	0.9874	27.97	1.1	0.9945
	413–472	125.05	1.1×10⁷	0.9851	130.13	3.5×10⁷	0.9876
75%PS	290–337	39.31	5.8×10⁻¹	0.9965	46.64	1.1×10	0.9979	176.53
	337–391	16.80	2.8×10⁻³	0.9776	26.04	2.7×10	0.9908
	391–448	221.33	2.7×10¹⁴	0.9831	221.39	2.8×10¹⁴	0.9846
PS	375–431	267.91	2.0×10¹⁸	0.9919	265.33	1.4×10¹⁸	0.9925	266.62
25%PP	174–353	47.90	1.5×10	0.9980	53.89	1.8×10²	0.9988	61.55
	354–453	17.52	1.3×10⁻²	0.9920	27.17	1.3	0.9970
	465–504	118.07	1.7×10⁶	0.9929	123.97	6.6×10⁶	0.9941
50%PP	197–337	49.37	1.3×10	0.9978	55.22	1.4×10²	0.9984	124.06
	354–442	15.65	4.7×10⁻³	0.9925	25.23	5.3×10⁻¹	0.9971
	459–504	179.67	4.7×10¹⁰	0.9912	182.46	8.2×10¹⁰	0.9922
75%PP	229–337	56.23	2.9×10	0.9963	61.63	2.4×10²	0.9976	186.92
	342–427	14.83	1.7×10⁻³	0.9899	24.31	2.1×10⁻¹	0.9961
	449–498	236.05	5.2×10¹⁴	0.9911	235.98	5.3×10¹⁴	0.9918
PP	419–486	321.74	9.5×10²⁰	0.9932	317.14	5.0×10²⁰	0.9936	319.44

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参考文献(27)

[1]	CHEN X, LI S J, LIU Z H, CHEN Y Q, YANG H P, WANG X H, CHE Q F, CHEN W, CHEN H P. Pyrolysis characteristics of lignocellulosic biomass components in the presence of CaO[J]. Bioresour Technol,2019,287:7.
[2]	ROSS, A B, P BILLER, M L KUBACKI, H LI, A LEA-LANGTON, J M JONES. Hydrothermal processing of microalgae using alkali and organic acids[J]. Fuel,2010,89(9):2234−2243. doi: 10.1016/j.fuel.2010.01.025
[3]	LI F H, SRIKANTH C S, SANKAR B. A review on catalytic pyrolysis of microalgae to high-quality bio-oil with low oxygeneous and nitrogenous compounds[J]. Renewable Sustainable Energy Rev,2019,108:481−497. doi: 10.1016/j.rser.2019.03.026
[4]	BACH, QUANG-VU, CHEN W H. Pyrolysis characteristics and kinetics of microalgae via thermogravimetric analysis (TGA): A state-of-the-art review[J]. Bioresour Technol,2017,246:88−100. doi: 10.1016/j.biortech.2017.06.087
[5]	AYSU T, MAROTO-VALER M M, SANNA A. Ceria promoted deoxygenation and denitrogenation of Thalassiosira weissflogii and its model compounds by catalytic in-situ pyrolysis[J]. Bioresour Technol,2016,208:140−148. doi: 10.1016/j.biortech.2016.02.050
[6]	AZIZI K, MOSTAFA K M, HAMED A N. A review on bio-fuel production from microalgal biomass by using pyrolysis method[J]. Renewable Sustainable Energy Rev,2018,82:3046−3059. doi: 10.1016/j.rser.2017.10.033
[7]	张泽, 赵洪君, 孟洁, 洪晨, 李益飞. 生物质的热解及生物油提质的研究进展[J]. 环境工程,2021,39(3):161−171. doi: 10.13205/j.hjgc.202103023 ZHANG Ze, ZHAO Hong-Jun, MENG Jie, HONG Chen, LI Yi-Fei. Reseach progess of biomass pyrolysis and bio oil upgrading[J]. Environ Eng,2021,39(3):161−171. doi: 10.13205/j.hjgc.202103023
[8]	CAMPANELLA A, HAROLD M P. Fast pyrolysis of microalgae in a falling solids reactor: Effects of process variables and zeolite catalysts[J]. Biomass Bioenergy,2012,46:218−232. doi: 10.1016/j.biombioe.2012.08.023
[9]	王文燕, 张光义, 孟辉波, 朱新宇, 张建岭, 许光文. 糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用[J]. 化工学报,2021,72(11):5770−5778. doi: 10.11949/0438-1157.20211028 WANG Wen-yan, ZHANG Guang-yi, MENG Hui-bo, ZHU Xin-yu, ZHANG Jian-ling, XU Guang-wen. Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NOx emission from its combustion flue gas[J]. CIESC J,2021,72(11):5770−5778. doi: 10.11949/0438-1157.20211028
[10]	NANDAKUMAR T, DWIVEDI U, PANT K K. KUMAR S, BALARAMAN E. Wheat straw/HDPE co-reaction synergy and enriched production of aromatics and light olefins via catalytic co-pyrolysis over Mn, Ni, and Zn metal modified HZSM-5[J]. Catal Today,2023,408:111−126.
[11]	TIAN F J, YU J L, MCKENZIE L J, J HAYASHI, LI C Z. Conversion of fuel-N into HCN and NH3 during the pyrolysis and gasification in steam: A comparative study of coal and biomass[J]. Energy Fuels,2007,21(2):517−521. doi: 10.1021/ef060415r
[12]	RANJEET K M, KAUSTUBHA M. Co-pyrolysis of waste biomass and waste plastics (polystyrene and waste nitrile gloves) into renewable fuel and value-added chemicals[J]. Carbon Res Conv,2020,3:145−155. doi: 10.1016/j.crcon.2020.11.001
[13]	毛俏婷, 胡俊豪, 赵雨佳, 闫舒航, 杨海平, 陈汉平. 生物质和废塑料混合热解协同特性研究[J]. 燃料化学学报,2020,48(3):286−292. doi: 10.3969/j.issn.0253-2409.2020.03.004 (MAO Qiao-ting, HU Jun-hao, ZHAO Yu-jia, YAN Shu-hang, YANG Hai-ping, CHEN Han-ping. Synergistic effect during biomass and waste plastics co-pyrolysis[J]. J Fuel Chem and Technol,2020,48(3):286−292. doi: 10.3969/j.issn.0253-2409.2020.03.004
[14]	RAHMAN, M H, P R BHOI, A SAHA, V PATIL, S ADHIKARI. Thermo-catalytic co-pyrolysis of biomass and high-density polyethylene for improving the yield and quality of pyrolysis liquid[J]. Energy,2021,225:120231.
[15]	CHEN W M, SHI S K, CHEN M Z, ZHOU X Y. Fast co-pyrolysis of waste newspaper with high-density polyethylene for high yields of alcohols and hydrocarbons[J]. Waste Manage,2017,67:155−162. doi: 10.1016/j.wasman.2017.05.032
[16]	YUAN H R, FAN H G, SHAN R, HE M Y, GU J, CHEN Y. Study of synergistic effects during co-pyrolysis of cellulose and high-density polyethylene at various ratios[J]. Energy Conv Manag,2018,157:517−526. doi: 10.1016/j.enconman.2017.12.038
[17]	TANG Z Y, CHEN W, HU J H, LI S Q, CHEN Y Q, YANG H P, CHEN H P. Co-pyrolysis of microalgae with low-density polyethylene (LDPE) for deoxygenation and denitrification[J]. Bioresour Technol,2020,311:123502. doi: 10.1016/j.biortech.2020.123502
[18]	DUAN P G, JIN B B, XU Y P, WANG F. Co-pyrolysis of microalgae and waste rubber tire in supercritical ethanol[J]. Chem Eng J, 2015. 269(Supplement C): 262−271.
[19]	XU S N, CAO B, B B UZOEJINWA, E A ODEY, WANG S, SHANG H, LI C H, HU Y M, WANG Q, J N NWAKAIRE. Synergistic effects of catalytic co-pyrolysis of macroalgae with waste plastics[J]. Process Saf Environ Protect,2020,137:34−48. doi: 10.1016/j.psep.2020.02.001
[20]	WU X Y, WU Y L, WU K J, CHEN Y, HU H S, YANG M D. Study on pyrolytic kinetics and behavior: The co-pyrolysis of microalgae and polypropylene[J]. Bioresour Technol,2015,192:522−528. doi: 10.1016/j.biortech.2015.06.029
[21]	CHEN R, ZHANG S, YANG X, LI G, ZHOU H, LI Q, ZHANG Y. Thermal behaviour and kinetic study of co-pyrolysis of microalgae with different plastics[J]. Waste Manage,2021,126:331−339. doi: 10.1016/j.wasman.2021.03.001
[22]	TANG Z Y, CHEN W, CHEN Y Q, YANG H P, CHEN H P. Co-pyrolysis of microalgae and plastic: Characteristics and interaction effects[J]. Bioresour Technol,2019,274:145−152. doi: 10.1016/j.biortech.2018.11.083
[23]	ABOUL-ENEIN, ATEYYA A, FATHI S S, MOHAMED A B. Co-production of hydrogen and carbon nanomaterials using NiCu/SBA15 catalysts by pyrolysis of a wax by-product: Effect of Ni-Cu loading on the catalytic activity[J]. Int J Hydrog Energy,2019,44(59):31104−31120. doi: 10.1016/j.ijhydene.2019.10.042
[24]	HU Q, TANG Z Y, YAO D D, YANG H P, SHAO J A, CHEN H P. Thermal behavior, kinetics and gas evolution characteristics for the co-pyrolysis of real-world plastic and tyre wastes[J]. J Clean Prod,2020,260:121102.
[25]	WANG X, SHENG L L, YANG X Y. Pyrolysis characteristics and pathways of protein, lipid and carbohydrate isolated from microalgae Nannochloropsis sp[J]. Bioresour Technol,2017,229:119−125. doi: 10.1016/j.biortech.2017.01.018
[26]	WANG X, TANG X H, YANG X Y. Pyrolysis mechanism of microalgae Nannochloropsis sp. based on model compounds and their interaction[J]. Energy Conv Manag,2017,140:203−210. doi: 10.1016/j.enconman.2017.02.058
[27]	CHEN H P, XIE Y P, CHEN W, XIA M W, LI K X, CHEN Z Q, CHEN Y Q, YANG H P. Investigation on co-pyrolysis of lignocellulosic biomass and amino acids using TG-FTIR and Py-GC/MS[J]. Energy Conv Manag,2019,196:320−329. doi: 10.1016/j.enconman.2019.06.010