Abstract
This paper presents the quantitative bomb calorimetric high heat values (HHV) for residue samples collected from the Anaerobic Pump (®TAP) and a continuous flow stirred tank reactor (CFSTR) anaerobically digesting a 50:50 wastewater sludge substrate. TAP, an advanced anaerobic digestion (AD) process, features biogas plasticization that greatly increases gas production and leaves a mineralized residual. Measured residue HHVs are compared to HHV estimates from literature empirical relationships. Two empirical formulations, the Meraz thermodynamic formulation (with 7.4% moisture) (Meraz et al. The Chemical Educator, 7(2), 66–70, (2002) and the Channiwala Universal formulation (Channiwala et al. Fuel, 81(8), 1051–1063, (2002), compared favorably (within ± 3% mean value) with the bomb measured HHV values. A stoichiometric ICC description for Ucells is derived. The thermodynamic formation potentials of all measured residues are derived including Ucells. An empirical method was used to calculate the entropy of formation (∆fS) for all residues and Ucells. Krevelen plots show residue molar ratios of oxygen and hydrogen to carbon (H/C, O/C) are linearly correlated with HHV and formation potentials (∆fG’, ∆fH’, ∆fS’) with strong statistical coefficients of determination (R2). Residue H/C and O/C ratios fell across the peat classification on the biomass coalification diagram. A wide AD methane fermentation zone ≤ 18.6 MJ/kg is identified. The methods and correlation relationships presented enable the computation of accurate HHV and thermodynamic formation potentials without the necessity of direct thermal measurement. These quantitative results confirm that steady state AD of a well-known heterogeneous solid substrate (WWTP sludge) is a linear thermodynamic process.
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Abbreviations
- HHV:
-
High heat value (kJ/kg or kJ/mol).
- GCV:
-
Gross Caloric value (kJ/kg or kJ/mol).
- IFUCF:
-
Ion-free unit carbon formula.
- ICUCF:
-
Ion-containing, unit-carbon formula.
- ICUCFW:
-
Ion containing unit carbon formula weight.
- C-mol:
-
Unit carbon mol mass (g/mol).
- ICC-mol:
-
Ion containing carbon mol mass (g/mol).
- WAS:
-
Waste activated sludge substrate.
- ΔcHbiomass :
-
Heat of biomass combustion (kJ/kg or kJ/mol).
- U:
-
Thermodynamic internal energy (kJ/kg or kJ/mol).
- F:
-
Thermodynamic Helmholtz force function (kJ/kg or kJ/mol, kJ/cm2).
- G:
-
Thermodynamic Gibb’s free energy function (kJ/kg or kJ/mol).
- H:
-
Thermodynamic enthalpy heat function (kJ/kg or kJ/mol).
- S:
-
Thermodynamic entropy (J/mol °K).
- ∆Hc,s°:
-
Standard change in Enthalpy during oxygen bomb combustion reaction.
- ∆Uc,s°:
-
Standard change in internal energy during combustion reaction.
- dNi :
-
Change in the number of moles of species i during a reaction (∆ moles).
- Rf :
-
Refractory coefficient that represents the fraction of particulate COD that is nonbiodegradable at infinite digestion time (gram resistant COD/gram input substrate COD).
- R2 :
-
Correlation coefficient of determination (no units).
- V:
-
Volume (liters).
- T:
-
Absolute temperature, (°K).
- μi :
-
Thermodynamic chemical potential of chemical species i (kJ/mol).
- ni :
-
Number of moles of chemical species i (moles).
- dni :
-
Change in the number of moles of species i produced in a chemical reaction (Δ moles).
- AE:
-
Available electrons transferred during a biological fermentation reaction.
- eeq:
-
Total electron equivalents transferred during biological or bomb combustion reactions.
- ∆fGo ∆fHo ∆fSo :
-
Change free energy, enthalpy, or entropy of formation, respectively, of a specified quantity 1 mol of a pure substance in its standard state (zero superscript o) at 298.15 °K and one atmosphere.
- ∆fG’ ∆fH’ ∆fS’:
-
Change free energy, enthalpy, or entropy of formation, respectively, of a specified quantity of an impure (apostrophe superscript ‘) substance in aqueous solution or suspension, not having a standard state at 298.15 K and 1 atm and activity of 0.001 M.
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Acknowledgments
My special thanks goes to Dr. Standard Methods, Myrton (Mike) C. Rand [70], whose knowledge of fundamental processes helped envision a way of completing wet solid biomass AD conversion to methane long before it became “obvious.” His vision and technical and intellectual rigor inspired me to accept the challenge in the early years of creating the Anaerobic Pump.
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Schimel, K.A. Biogas Plasticization Coupled Anaerobic Digestion: Anaerobic Pump Calorimetry. Appl Biochem Biotechnol 189, 511–540 (2019). https://doi.org/10.1007/s12010-019-03007-z
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DOI: https://doi.org/10.1007/s12010-019-03007-z