anaerobic digestion for methane generation and ammonia .anaerobic digestion for methane generation
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Anaerobic digestion for methane generation andammonia reforming for hydrogen production:A thermodynamic energy balance of a modelsystem to demonstrate net energy feasibility
David M. Babson a, Karen Bellman b, Shaurya Prakash b,*,Donna E. Fennell a,**aDepartment of Environmental Sciences, Rutgers University, 14 College Farm Road, New Brunswick, NJ 08901,
United StatesbDepartment of Mechanical and Aerospace Engineering, The Ohio State University, 201 W. 19th Ave., Columbus,
OH 43210, United States
a r t i c l e i n f o
Article history:
Received 6 October 2012
Received in revised form
6 May 2013
Accepted 24 May 2013
Available online
Keywords:
Anaerobic digestion
Ammonia
Bioenergy
Bioammonia
Hydrogen
Anaerobic digestion-bioammonia
to hydrogen (ADBH)
* Corresponding author. Tel.: 1 614 688 404** Corresponding author. Tel.: 1 848 932 574
E-mail addresses: prakash.31@osu.edu (S0961-9534/$ e see front matter 2013 Elsevhttp://dx.doi.org/10.1016/j.biombioe.2013.05.
a b s t r a c t
During anaerobic digestion, organic matter is converted to carbon dioxide and methane,
and organic nitrogen is converted to ammonia. Generally, ammonia is recycled as a fer-
tilizer or removed via nitrificationedenitrification in treatment systems; alternatively it
could be recovered and catalytically converted to hydrogen, thus supplying additional fuel.
To provide a basis for further investigation, a theoretical energy balance for a model sys-
tem that incorporates anaerobic digestion, ammonia separation and recovery, and con-
version of the ammonia to hydrogen is reported. The model Anaerobic Digestion-
Bioammonia to Hydrogen (ADBH) system energy demands including heating, pumping,
mixing, and ammonia reforming were subtracted from the total energy output from
methane and hydrogen to create an overall energy balance. The energy balance was
examined for the ADBH system operating with a fixed feedstock loading rate with C:N
ratios (gC/gN) ranging from 136 to 3 which imposed corresponding total ammonia nitrogen
(TAN) concentrations of 20e10,000 mg/L. Normalizing total energy potential to the
methane potential alone indicated that at a C:N ratio of 17, the energy output was greater
for the ADBH system than from anaerobic digestion generating only methane. Decreasing
the C:N ratio increased themethane content of the biogas comprising primarily methane to
>80% and increased the ammonia stripping energy demand. The system required 23e34%
of the total energy generated as parasitic losses with no energy integration, but when
internally produced heat and pressure differentials were recovered, parasitic losses were
reduced to between 8 and 17%.
2013 Elsevier Ltd. All rights reserved.
5; fax: 1 614 292 3163.8; fax: 1 732 932 8644.. Prakash), fennell@envsci.rutgers.edu (D.E. Fennell).ier Ltd. All rights reserved.024
b i om a s s a n d b i o e n e r g y 5 6 ( 2 0 1 3 ) 4 9 3e5 0 5494
1. Introduction
1.1. Anaerobic digestion processes and applications
In recent years, major attitudinal shifts have occurred in
modern society to allow wastes to be considered resources
rather than just materials requiring disposal [1e3]. Waste as a
resource can be envisioned as a means of reducing energy
consumption by minimizing the need for producing raw ma-
terials, reducing pre-disposal processing, and extracting us-
able energy from the waste as a feedstock [4e6]. One
established technology for extracting energy from waste is
anaerobic digestion (for recent reviews see Refs. [7e11]).
Anaerobic digestion of crop biomass, agricultural wastes
and residuals, and source-separated mixed organic wastes
have been employed at full scale for decades in Europe (nearly
200 digesters, 2010 [12]), China (10,000 digesters, 1986 [13]) and
India (2,000,000 digesters, 2000 [14]), among other places [15,16].
These digesters operate to generate biogas, comprising pri-
marily of methane, as a fuel source. In the US, anaerobic
digestion is primarily used for wastewater treatment plant
(WWTP) sludges [17], animal manures [18], andmunicipal solid
waste (MSW) in landfills [19]. There aremore than 500 large (>5
million gallons per day) municipal wastewater treatment fa-
cilities [20] and 176 animalmanure digesters in the US [18]. One
of the most prevalent large-scale applications of anaerobic
digestion in the US is in landfills where anaerobic conditions
dominate the operational timeline [21]. However, as of June
2012, 594 of more than 1700 US landfills utilized biogas for en-
ergy production while the remainder flared biogas without
recovering biogas energy [22]. The active landfill projects lead to
generation of over 1800 MW of equivalent energy [15].
Compared to several other countries around the world,
anaerobic digestion has been relatively under-utilized in the
US for a variety of economic and technical reasons. These
include traditionally low energy and/or fuel prices, lack of
governmental incentives for implementing new anaerobic
power plants, the need for abundant and suitable land for site
development facilities and disposal of residuals, the need to
provide high quality reliable heat for the process to achieve
acceptable or commercially viable conversion efficiencies,
and the reputation of anaerobic processes as odor-generating
and difficult to operate [23e26]. The purpose of this paper is to
show through amodel system that when part of an integrated
system, anaerobic digestion can be a powerful resource for
wastemanagement and energy extraction. Specifically, in this
paper, a thermodynamic energy balance for amodel system is
presented demonstrating that anaerobic processing of waste
for harvesting both methane and ammonia as multiple fuel
sources in contrast to methane alone can provide an addi-
tional avenue to a net increase in extracted usable energy
from waste processing.
1.2. Inorganic nitrogen mitigation and removal
The environmental advantages of in-vessel anaerobic di-
gesters include stabilization of biochemical oxygen demand,
generation of biogas, production of digestate as a soil
amendment, and reduction of the environmental footprint
associated with land-filling [15,27,28]. However, several envi-
ronmental concerns as discussed below dictate post-
treatment steps needed for the digestate produced during
anaerobic digestion of organic feedstocks [29,30]. Of particular
concern is ammonia which is toxic to aquatic organisms,
causes eutrophication, and exerts oxygen demand in surface
waters [31]. Further, processes to remove ammoniaenitrogen
from aqueous effluent can require energy-intensive treatment
with large reaction vessels and long holding times [32e34].
Theammonia that accumulates inanaerobicdigesters exists
in two forms, ammonium ion NH4 and free ammonia (NH3),and is in equilibrium in aqueous systems (Equation (1)) [17].
NH44NH3 H (1)Total ammonia nitrogen (TAN) is the sum of NH4 and NH3expressed as total N on a mass basis. The ratio of NH3-N to
NH4 N in an aqueous system is governed by pH and tem-perature (Equation (2)) [17].
NH3 N TAN1 HKa
(2)
where NH3-N is the free ammonia nitrogen concentration and
Ka is the temperature dependent dissociation coefficient for
Equation (2). TAN accumulates in digesters when proteins,
urea, nucleic acids, and other nitrogen-containing com-
pounds degrade, and its concentration must be controlled by
removal or by altering feedstock carbon to nitrogen (C:N) ra-
tios to prevent inhibition of the microbial process by higher
concentrations of free ammonia [35,36].
Anaerobic digestate is frequently used as a soil amend-
ment. However, application of anaerobic digestate to land as a
soil amendment must be carefully managed to avoid release
of excess nitrogen to surface waters, infiltration to ground
water, and the atmosphere. Particularly affected by these
problems are swine, poultry, and dairy operations, where land
application of digestate is an important disposal route [37e43].
Ma et al. (2005), for example, estimated that for Tompkins
County, NY, USAwith a total dairy herd of 9500 approximately
20,000 acres of suitable land would be needed to house di-
gesters and solids/liquids handling systems and to provide a
land sink for the resulting digestate [24]. With increasing
population pressures throughout the world, demand for such
large land resources can pose a significant problem for post-
processing of N or ammonia-rich waste feedstock. In addi-
tion, large domestic WWTP digesters located in metropolitan
environments are often at considerable distances from suit-
able land (>10 km). Consequently, these WWTPs must treat
ammonia onsite via nitrification/denitrification or haul
nitrogen-rich digestate to distant land sinks for disposal [24]
causing challenges for energy efficient waste management.
Anaerobic digester supernatant currently recycled to the
influent of some WWTPs may account for as much as 30% of
the incoming nitrogen loading to the facility [44] and also