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Efficient CO2 capture by nitrogen-doped biocarbons derived from rotten strawberry Limin Yue, Linli Rao, Liwei Wang, Linlin Wang, Jiayi Wu, Xin Hu, Herbert DaCosta, Jie Yang, and Maohong Fan Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b02692 • Publication Date (Web): 08 Nov 2017 Downloaded from http://pubs.acs.org on November 13, 2017
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Industrial & Engineering Chemistry Research
Efficient CO2 capture by nitrogen-doped bio-carbons derived from rotten strawberry Limin Yuea, Linli Raoa, Liwei Wanga, Linlin Wangb, Jiayi Wua, Xin Hu*,a Herbert DaCostac, Jie Yanga, Maohong Fand, a
College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua
321004, PR China b
College of Engineering, Zhejiang Normal University, 688 Yingbin Ave. Jinhua
321004, PR China c
Math, Science, and Engineering Division, Illinois Central College, 1 College Drive
East Peoria, IL 61635, USA d
Department of Chemical and Petroleum Engineering, University of Wyoming,
Laramie, Wyoming 82071, USA *
Corresponding author’s e-mail:
[email protected]; phone: 86-151-0579-0257; fax:
86-579-8228-8269
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Abstract
In this study, rotten strawberry was used as carbon precursor to prepare nitrogen-doped porous bio-carbons for CO2 capture. The sorbents were synthesized by hydrothermal treatment of rotten strawberry, followed by KOH activation. The nitrogen in the resulting sorbents is inherited from the rotten strawberry precursor. This series of samples demonstrates high CO2 uptake at 1 bar, up to 4.49 mmol g-1 at 25 °C, and 6.35 mmol g-1 at 0 °C. In addition to narrow micropore volume and nitrogen content, the pore size of narrow micropores also plays a key role in determining the CO2 capture capacity under ambient condition. Furthermore, these sorbents possess stable reusability, moderate heat of CO2 adsorption, quick CO2 adsorption kinetics, reasonable CO2/N2 selectivity, and high dynamic CO2 capture capacity under simulated flue gas conditions. All these merits along with the zero-cost and wide availability of rotten strawberry precursor make this type of sorbents highly promising in CO2 capture form combustion flue gas.
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1. Introduction
CO2 is one of the most dominant greenhouse gases, its emission has a key responsibility in global warming1. To mitigate CO2 emission, different techniques have been extensively researched including amine scrubbing2, membrane separation3, and ionic liquid absorption4, to name a few. Among the various CO2 capture technologies, adsorption via solid adsorbents shows great promise due to its merits of low capital investment, simple operation, low energy consumption, and avoidance of equipment corrosion5-10. A key factor for the success of this technique is to find sorbents with superior CO2 adsorption properties, such as high CO2 uptake and CO2/N2 selectivity, rapid CO2 adsorption kinetics, medium heat of adsorption, and outstanding chemical and mechanical stability. Among various solid porous sorbents such as carbons11-17, silica18,
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, porous metal oxide20, zeolites21, metal
organic frameworks (MOFs)22, 23, and porous polymers24, 25, porous carbonaceous sorbents have revealed great promise in CO2 capture. The advantages of porous carbons include easy synthesis, low production cost, large accessible surface area, easy control of porosity, favorable surface chemistry, low chemical reactivity, high chemical, thermal and mechanical stability, and high resistance to moisture11, 14, 17. An attractive feature for porous carbons is that they can be synthesized from readily available and low-cost precursors, such as coal26-28, petroleum coke29-31, carbon-rich polymer32, 33, wood34, and various biomass sources35-42. In light of wide availability, low cost, renewability, biomass-derived porous carbons have obtained significant 4
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attention and showed great potential for CO2 capture under ambient conditions. For example, Mokaya and co-workers synthesized a series of Jujun grass and Camellia japonica-derived porous carbons
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. The maximum CO2 uptake at 25ºC and 1 bar
was up to 5.0 mmol/g for these carbonaceous sorbents. In another work, they reported even higher CO2 adsorption capacity under the same testing conditions, i.e. 5.8 mmol/g for porous carbons prepared from sawdust and lignin43. Sevilla et al. also prepared porous carbon using sawdust as the precursor and the maximum CO2 uptake was 4.8 mmol/g under 25ºC and 1 bar44. Deng et al. developed pine nut shell-derived porous carbons, with the maximum CO2 uptake of 5.0 mmol/g at 25ºC and 1 bar45. As one of the most commonly consumed fruits, strawberry is rich in nutritional value and contains a variety of vitamins that are beneficial to human health. Strawberries also have plentiful output, of which the strawberry production of China in market year 2011-2012 is estimated to be 2,100,000 tons46. Fresh strawberries are available from late November to June. However, strawberry is not easy to preserve, any slight collision, even slight touch by fingers could damage the skin and further lead to its decomposition. Rotten strawberry is usually discarded, which further increases the burden of environmental protection. It would be of high value if this waste biomass source could be used to achieve more valuable adsorbents. In fact, there are approximately up to 7.68 g of carbohydrates, including sugar and dietary fibers, per 100 g of strawberries, making it a potential carbon precursor. In addition, 5
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strawberry contains a variety of vitamin B, such as Thiamine (B1), Ribofavin (B2), Niacin (B3), Pantothenic acid (B5), vitamin B6, and some amount of proteins, which is attractive with respect to the potential addition of nitrogen within the carbon structure. In this study, hydrochar is first obtained by hydrothermal treatment of rotten strawberries, and then the resulting hydrochar were activated by KOH to synthesize nitrogen-doped porous carbons. Compared with the tedious post-synthesis nitrogen-doping process reported in previous studies29,
30, 38, 47
, synthesis of
N-enriched porous carbon by one-step KOH activation of hydrochar can further reduce the sorbent preparation costs. The effect of two preparation parameters, i.e. activation temperature and KOH/hydrochar, on the porous properties/surface chemical properties will be investigated. The goal is to synthesis carbonaceous sorbents with high amount of narrow micropore (
