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When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given e.g. AUTHOR (year of submission) "Full thesis title", University of Southampton, name of the University School or Department, PhD Thesis, pagination http://eprints.soton.ac.uk UNIVERSITY OF SOUTHAMPTON Faculty of Engineering and the Environment NITROGEN CONTROL IN SOURCE SEGREGATED DOMESTIC FOOD WASTE ANAEROBIC DIGESTION USING STRIPPING TECHNOLOGIES by Alba Serna-Maza Thesis for the degree of Doctor of Philosophy November_2014 UNIVERSITY OF SOUTHAMPTON ABSTRACT FACULTY OF ENGINEERING AND THE ENVIRONMENT Doctor of Philosophy NITROGEN CONTROL IN SOURCE SEGREGATED DOMESTIC FOOD WASTE ANAEROBIC DIGESTION USING STRIPPING TECHNOLOGIES Alba Serna-Maza Anaerobic digestion of source segregated domestic food waste (SS-DFW) offers a sustainable management route for reclaiming potential energy in the form of a fuel gas, and nutrients which can be recycled back to land. However, the biochemical characteristics of SS-DFW can lead to free ammonia nitrogen (FAN) concentrations that are inhibitory to the digestion process causing unstable operation and in some cases complete process failure, particularly in thermophilic systems. With the purpose of reducing the total ammoniacal nitrogen (TAN) in the digester, side-stream and in situ biogas stripping technologies were tested. Mesophilic and thermophilic temperatures were evaluated under moderate and complete biogas mixing rates (0.4 l min-1 – 2.6 l min-1) in a batch system. Laboratory investigations showed that TAN reductions in an in situ bubbling reactor with moderate and complete gas mixing rates were non-existent at mesophilic temperatures and minimal at thermophilic temperatures. For this reason, it is unlikely that in situ biogas stripping would be adequate to prevent TAN concentrations greater than 2500 mg N l-1 in a food waste digester and thus will not mitigate ammonia inhibition in a thermophilic system. Semi-continuous trials carried out on SS-DFW in laboratory-scale digesters, fed daily at an organic loading rate (OLR) of 2 kg VS m-3 day-1 and coupled to stripping columns at low bleed rates (2 – 3.5 % digester volume per day treated in the stripping process) were effective in reducing ammonia concentrations to below thermophilic toxic levels (TAN concentration of 2500 – 3500 mg N l-1). The experiments also confirmed that removal of a proportion of the digester contents and their exposure to thermophilic conditions with pH adjustment to 10 had no adverse effects on performance in terms of biogas production (0.83 ± 0.03 l g-1 VS without stripping, 0.84 ± 0.05 l g-1 VS with stripping) or VS destruction (81.8 % without stripping, 88.5 % with stripping). The process required high pH and temperature (≥70 ⁰C) to achieve a TAN concentration below the toxic threshold for thermophilic digestion, and it is unlikely that stripping at 55 ⁰C and pH 10 would achieve the target reduction. The research showed the way forward for the application of side-stream stripping to prevent the build-up of ammonia under thermophilic conditions, if the digester is started up with a non-inhibitory FAN concentration in the inoculum. Keywords: Anaerobic digestion; source segregated domestic food waste; ammonia removal; in situ stripping; side-stream stripping Contents ABSTRACT ................................................................................................................................ i Contents ................................................................................................................................... i List of tables ...................................................................................................................... vii List of figures ......................................................................................................................ix DECLARATION OF AUTHORSHIP ............................................................................x iii Acknowledgements ........................................................................................................ xv Definitions and Abbreviations ..............................................................................x vii 1. Introduction.................................................................................................................1 1.1 Background ................................................................................ 2 1.2 Aims and objectives .................................................................... 4 1.2.1 Aims ........................................................................................... 4 1.2.2 Objectives ................................................................................... 5 2. Literature review ......................................................................................................7 2.1 Principles of anaerobic digestion................................................. 7 2.1.1 Degradation route ....................................................................... 7 2.1.2 Environmental factors ............................................................... 10 2.1.2.1 Temperature ........................................................................ 10 2.1.2.2 pH and alkalinity .................................................................. 12 2.1.2.3 Nutrients ............................................................................. 14 2.1.2.4 Inhibitors ............................................................................. 15 2.2 Ammonia inhibition of anaerobic digestion ............................... 15 2.2.1 Impact of ammonia toxicity to methanogenesis pathway in anaerobic digestion ................................................................................. 16 2.2.2 Mechanisms of ammonia inhibition ........................................... 19 2.2.2.1 Free ammonia nitrogen ........................................................ 19 i 2.2.2.2 Ammonium ion .................................................................... 21 2.2.3 Inhibition levels ......................................................................... 22 2.3 Ammonia inhibition mitigation methods ................................... 30 2.3.1 Acclimation of microflora .......................................................... 30 2.3.2 Temperature and pH control ..................................................... 31 2.3.3 Substrate dilution ...................................................................... 31 2.3.4 Trace element supplementation ................................................ 33 2.3.5 C/N ratio adjustment ................................................................ 34 2.3.6 N removal ................................................................................. 35 2.3.7 Stripping ................................................................................... 37 2.3.7.1 Introduction ......................................................................... 37 2.3.7.2 Physicochemical effects of biogas stripping .......................... 40 2.3.7.3 Stripping configurations ....................................................... 44 Pre-digestion ..................................................................................... 44 Post-hydrolysis .................................................................................. 49 In situ ............................................................................................... 51 Post-digestion and side-stream ......................................................... 54 2.3.7.4 Nitrogen recovery: reasons and methodology ....................... 57 3. Methodology ............................................................................................................ 59 3.1 General ..................................................................................... 59 3.2 Monitoring and analytical methods ............................................ 59 3.2.1 Total and Volatile Solids ............................................................ 59 3.2.2 pH ............................................................................................. 60 3.2.3 Alkalinity ................................................................................... 61 3.2.4 Total ammonia nitrogen ............................................................ 62 3.2.5 Total Kjeldahl Nitrogen ............................................................. 63 3.2.6 Volatile Fatty Acids .................................................................... 64 ii 3.2.7 Trace metals extraction and analysis ......................................... 64 3.2.8 [2-14C] Sodium acetate labelled analysis to determine the methanogenic pathway ............................................................................ 65 3.2.9 Capillarity Suction Time ............................................................ 66 3.2.10 Frozen Image Centrifuge Test ................................................... 66 3.2.11 Gas composition ....................................................................... 67 3.2.12 Gas volume ............................................................................... 67 3.2.13 Rotameter and pump calibration ............................................... 68 3.3 Materials ................................................................................... 69 3.3.1 Feedstocks................................................................................ 69 3.3.2 Trace element solution ............................................................. 70 3.4 Equipment ................................................................................ 70 3.4.1 75-L CSTR digesters .................................................................. 70 3.4.2 35-L CSTR digesters .................................................................. 73 3.4.3 Side-stream stripping columns .................................................. 74 3.4.4 Batch stripping columns ........................................................... 76 3.5 Experimental plan ..................................................................... 77 3.6 Calculation methods ................................................................. 78 3.6.1 VS destruction .......................................................................... 78 3.6.2 Ammonia removal rate .............................................................. 79 3.6.3 Ammonia stripping efficiency .................................................... 79 3.6.4 N mass balance ......................................................................... 81 3.6.4.1 N mass balance: Batch stripping column .............................. 81 3.6.4.2 N mass balance: Continuous digester ................................... 82 Control reactor ................................................................................. 82 Side-stream stripping system ............................................................ 83 4. Results and discussion ...................................................................................... 87 iii 4.1 75-L CSTR digesters for anaerobic digestion of food waste ........ 88 4.1.1 Methodology for food waste anaerobic digestion trial ............... 88 4.1.2 Results of food waste anaerobic digestion trial .......................... 90 4.1.3 Conclusion ................................................................................ 92 4.2 In situ stripping......................................................................... 92 4.2.1 Methodology for in situ stripping experiments .......................... 93 4.2.2 Results of in situ stripping experiments .................................... 94 4.2.2.1 In situ stripping at mesophilic temperature .......................... 94 4.2.2.2 In situ stripping at thermophilic temperature ....................... 96 4.2.2.3 Results of batch stripping test for synthetic and real digestates ............................................................................................ 99 4.2.3 Conclusions ............................................................................ 101 4.3 Batch ammonia stripping experiments .................................... 101 4.3.1 Methodology ........................................................................... 102 4.3.2 Results of comparison of alkaline compounds for pH control .. 102 4.3.3 Overview of results of batch stripping experiments ................. 105 4.3.3.1 Nitrogen mass balances ..................................................... 111 4.3.3.2 Comparison of time constants. ........................................... 116 4.3.4 Analysis of the effects of temperature, pH, biogas flow analysis .... ............................................................................................... 117 4.3.4.1 Conclusions ....................................................................... 119 4.3.5 Ammonia stripping efficiency .................................................. 119 4.3.6 Hydrolysis experiment ............................................................ 122 4.4 Side-stream stripping .............................................................. 125 4.4.1 Methodology ........................................................................... 125 4.4.1.1 Phase 1: Establishing a digestion baseline .......................... 126 4.4.1.2 Phase 2: Ammonia removal by side-stream stripping .......... 127 4.4.2 Results .................................................................................... 128 iv 4.4.2.1 Phase 1: Baseline performance and stability assessment .... 128 4.4.2.2 Phase 2: Side-stream ammonia stripping ............................ 128 Digesters performance ................................................................... 129 Short-term effects of return of stripped digestate ........................... 140 Stripping columns .......................................................................... 143 Digestate solids separation and dewaterability results .................... 145 14C assay for dominant methanogenic pathway ............................... 147 4.4.2.3 Digester N mass balance .................................................... 149 Control reactor ............................................................................... 149 Side-stream stripping system .......................................................... 150 5. Conclusions and further work ................................................................... 153 5.1 Conclusions ............................................................................ 153 5.2 Further work ........................................................................... 155 References ........................................................................................................................ 157 v
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