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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2019, Vol. 13 Issue (1) : 11    https://doi.org/10.1007/s11783-019-1096-5
RESEARCH ARTICLE
Augmented hydrogen production by gasification of ball milled polyethylene with Ca(OH)2 and Ni(OH)2
Giovanni Cagnetta1, Kunlun Zhang1, Qiwu Zhang2, Jun Huang1(), Gang Yu1
1. State Key Joint Laboratory of Environment Simulation and Pollution Control (SKJLESPC), Beijing Key Laboratory of Emerging Organic Contaminants Control (BKLEOCC), School of Environment, POPs Research Center, Tsinghua University, Beijing 100084, China
2. School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China
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Abstract

PE ball milling pretreatment induces higher H2 production and purity by gasification.

Ca(OH)2 reacts at solid state with PE boosting H2 and capturing CO2.

Ca(OH)2 significantly reduces methanation side-reaction.

Polymer thermal recycling for hydrogen production is a promising process to recover such precious element from plastic waste. In the present work a simple but efficacious high energy milling pre-treatment is proposed to boost H2 generation during polyethylene gasification. The polymer is co-milled with calcium and nickel hydroxides and then it is subjected to thermal treatment. Results demonstrate the key role played by the calcium hydroxide that significantly ameliorates hydrogen production. It reacts in solid state with the polyethylene to form directly carbonate and hydrogen. In this way, the CO2 is immediately captured in solid form, thus shifting the equilibrium toward H2 generation and obtaining high production rate (>25 L/mol CH2). In addition, high amounts of the hydroxide prevent excessive methane formation, so the gas product is almost pure hydrogen (~95%).
Keywords Hydrogen production      Gasification      Plastic waste      High energy ball milling     
Corresponding Author(s): Jun Huang   
Issue Date: 18 December 2018
 Cite this article:   
Giovanni Cagnetta,Kunlun Zhang,Qiwu Zhang, et al. Augmented hydrogen production by gasification of ball milled polyethylene with Ca(OH)2 and Ni(OH)2[J]. Front. Environ. Sci. Eng., 2019, 13(1): 11.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1096-5
https://academic.hep.com.cn/fese/EN/Y2019/V13/I1/11
Fig.1  Gas generation from milled PE with various reagent molar ratios (PE:Ca(OH)2:Ni(OH)2), obtained by TG-MS analysis.
Fig.2  Gas generation volume (a) and molar composition (b) from the gasification batch tests of milled PE with different molar PE:Ca(OH)2:Ni(OH)2 ratios.
Fig.3  XRD diffractograms of solid residue after gasification batch tests at 350°C of PE with various reagent molar ratios (PE:Ca(OH)2:Ni(OH)2).
Fig.4  Raman spectra of solid residue after the gasification batch tests at 350°C of PE with various reagent molar ratios (PE:Ca(OH)2:Ni(OH)2).
Compound PE:Ca(OH)2:Ni(OH)2 = 6:1:1
Atomic amount (mmol)		 PE:Ca(OH)2:Ni(OH)2 = 6:3:1
Atomic amount (mmol)		 PE:Ca(OH)2:Ni(OH)2 = 6:6:1
Atomic amount (mmol)
C H Ca Ni C H Ca Ni C H Ca Ni
Reagents PE 160.7 321.4 128.6 257.1 98.9 197.8
Ca(OH)2 10.1 5.1 24.3 12.1 37.4 18.7
Ni(OH)2 8.1 4.0 6.5 3.2 5.0 2.5
Products H2 29.3 44.8 65.1
CH4 8.6 34.2 8.6 34.6 4.3 17.5
CO 0.1 0.1 0.1
CO2 0.1 0.1 0.1
Others* 2.1 4.2 2.6 5.2 2.4 4.8
CaCO3 5.0 5.0 11.5 11.5 14.8 14.8
CaO 0.7 0.4 3.8
Ni 4.0 3.4 2.6
Char 0.0 0.1 0.0
Discrepancy
(reagents ? products)		 144.8 271.9 -0.6 0.0 105.6 203.3 0.2 -0.2 77.2 152.8 0.1 -0.1
Tab.1  Molar balance for milling-gasification experiments with different PE:Ca(OH)2:Ni(OH)2 ratios
Fig.5  Volumetric production and molar composition of gaseous product during the gasification batch test at various temperatures, with PE:Ca(OH)2:Ni(OH)2=6:3:1.
Temperature ξ1 (mol) ξ2 (mol) ξ2 /( ξ1+ξ2)) (mol)
350°C 0.0371 0.1371 78.70
400°C 0.0446 0.1384 75.63
450°C 0.0453 0.1385 75.35
500°C 0.0554 0.1402 71.70
550°C 0.0591 0.1409 70.44
Tab.2  Molar extents of reactions (1) and (2)
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