Biogas productie Uit afvalwater van de chemische industrie

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1 Inhoud Biogas productie Uit afvalwater van de chemische industrie 1. Introductie anaerobe afvalwaterzuivering 2. Technieken voor anaerobe afvalwaterzuivering 3. Nieuwe ontwikkelingen 4. Voorbeelden uit de chemische industrie 26/11/2010 Technology development 2 1 Introductie anaerobe afvalwaterzuivering Wat is anaerobe afvalwaterzuivering? Afvalwaterzuivering in afwezigheid van zuurstof Met behulp van anaerobe bacterien / archae worden organische componenten (CZV/COD) gereduceerd tot methaangas Anaerobe afvalwaterzuivering is energie-neutraal, of zelfs netto energie productie 1

2 Anaeroob versus Aeroob Geschiedenis anaerobe afvalwaterzuivering 100 kg BODCOD Air (O 2) to Aerobic Aeration (100 kwh) Heat loss 45% Carbon Dioxide 50% Biomass 2-10 kg COD Sludge, kg BOD 100 kg COD (25 O C 35 O C) to Anaerobic CH Nm 3 CO Nm 3 75% Biogas (75% Methane) 5% Biomass Sludge, 5 kg kg COD Eén van eerste toepassingen anaerobe technologie: Sewer gas destructor lamp, brandt op methaangas gevormd in riool Gepattenteerd in 1895 door Joseph Edmund Webb Veelvulding toegepast in UK Rond 1930 eerste wetenschappelijke onderzoek naar anaerobe afvalwaterzuivering Sindsdien eerste municipale slibvergisters in bedrijf 1 kg COD removed 0.35 Nm 3 CH 4 or 3.8 kwh Geschiedenis anaerobe afvalwaterzuivering Vier stappen in anaerobe degradatie Jaren 70: ontwikkeling anaerobe korrelslib technologie door professor Gatze Lettinga, Universiteit Wageningen Biomassa groeit in korrels, zodoende kunnen ze in reactor blijven Eerste industriële anaerobe korrelslib reactor bij CSM, Breda 1976: 200 m3 1978: 800 m3 1973: 30 m3 26/11/

3 Optimale temperatuur / ph Aantal anaerobe reactoren wereldwijd Temperaturerange anaerobic treatment Minimum Optimum Maximum temperature temperature temperature Psychrophylic Mesophylic Thermophylic /11/ /11/ Anaerobie in verschillende industriën 2 Food, 39% Other, 2% Pulp & Paper, 8% Pharmaceutical, 1% Beverage, 6% Breweries, 23% Technieken voor anaerobe afvalwaterzuivering Fermentation, 13% Chemical, 8% 3

4 Anaerobe processen Continuous Stirred Tank Reactor (compleet gemixed) influent Completely mixed biogas effluent Physical retention Immobilised biomass Expanded bed / blanket Lange retentietijd: dagen Lage volumetrische belasting: 2-5 kg COD/m3/d Gesuspendeerde biomassa SRT = HRT Typische toepassing: Vergister bij McCain Afvalwater/slurrie met hoog gehalte aan (biodegradeerbare) zwevende stof Afvalwater/slurrie met veel vet Mestvergister in Warmenhuizen Vergisting van actief slib Vergisting van mest, etc. 26/11/ Contactproces Fixed bed technologie Anaerobe equivalent van actief slib systeem Gesuspendeerde biomassa Terugvoer van slib naar reactor ontkoppeling HRT & SRT Scheiding slib en effluent in bezinker, DAF, TPS, centrifuge, etc. Biomassa groeit op dragermateriaal (zand, plastic deeltjes, etc.) Ontkoppeling HRT & SRT Belasting tot 10 kg COD/m3/d Vaak problemen met verstopping biofilm influent biogas effluent support (pumice) 26/11/

5 Korrelslibtechnologie Technologie gebaseerd op biomassa die goed bezinkt door groei in korrels / vlokken Ontkoppeling HRT & SRT Meest bekende systemen: UASB Upflow Anaerobic Sludge Bed EGSB Expanded Granular Sludge Bed UASB Ontwikkeld in jaren 70 Driefasenscheider bovenin reactor Belasting tot 15 kg COD/m3/d Met name geschikt voor verwijdering van opgeloste COD uit afvalwater 26/11/ /11/ EGSB Typisch flow diagram UASB / EGSB Ontwikkeld in de jaren 80 Belasting tot 30 kg COD/m3/d Hogere reactor kleiner oppervlak Met name geschikt voor verwijdering opgeloste COD uit afvalwater caustic acid N P FeCl 3+ micro heat Flare Biogas Scrubber biogas to factory raw wastewater Pretreatment Buffer Tank Conditioning Tank Biobed EGSB anaerobic effluent Biomass Storage Tank 26/11/ /11/

6 3 Waterhergebruik Unilever Marmite Nieuwe ontwikkelingen 26/11/ Energiefabriek Diageo Triumph Biomass Boiler Biogas Boiler Anaerobe MBR Draff Dewatering Distillery Pot Ale Biogas Centrifuge Wash Waters Spent Lees High-rate anaerobic plant Membrane bio-reactor Reuse and/or Discharge Copper removal 6

7 Anaerobic MBR AnMBR for Dairy -US Application Suitable for high strength biodegradable organic industrial wastewater Membranes Crossflowultra-filtration membranes Low energy consumption and cleaning frequency Key benefits Biomass cannot be washed out No granular biomass requirement COD removal rates > 99% Successfully started in August 2007 on cottage cheese whey and wash water Expanded to full scale operation in October 2009 Design parameters Flow: 190 m 3 /d COD: 60,000 mg/l System performance COD < 200 mg/l TSS < 1mg/L 4 Voorbeelden uit de chemische industrie Anaerobic treatment in chemical industry Selection of Biothane references Industry Country Product DSM Chemicals Netherlands Phenol Shell Netherlands MS/PO Ciba Geigy Korea Dying Baek Hwa Korea Alcohols Petrocel Mexico PTA/DMT Eastman Argentine PET Gist brocades Europe Pharmaceutical Caldic Netherlands Formaldehyde/ methanol Copenor Brazil Formaldehyde VPI Greece PET BorsodChem TDI DuPont Netherlands Delrin in chemical industry Industry Hoechst Castagna Univel Italy Country Product Netherlands DMT Sam Yang co Korea PET Eastman Chemicals Orchid chemicals Ciba CKD Biochem InfreServe Höchst Alembic Chemicals Singapore India India India Solvent recovery OXO SASA Turkey DMT Pharmaceutical Pharmaceutical Pharmaceutical Rotopas Turkey Solvent recovery 7

8 Caldic Europoort Production of formaldehyde and derivates from methanol Discharge wastewater to surface water (CZV < 200 ppm) Feasibility study: Biological treatment lowest capex and opex. Combination anaerobic - aerobic lowest opex Laboratory study to anaerobic treatment: CH 2 O at entrance Anaerobic Reactor must be < 500 ppm CH 2 O raw waste water is 5000 ppm, so high recirculation / mixing needed Full-scale design Biobed EGSB system followed by low loaded activated sludge plant (Carrousel ) Caldic Europoort (NL) Full-scale plant Wastewater characteristicscaldic Europoort Design Actual Flow m 3 /d COD mg/l 20,000 40,000 Formaldehy de mg/l ,000 Methanol mg/l 10,000 20,000 Caldic Europoort Comparison lab test, design and actual Comparisonlab test, design and actual - Results Biobed reactor Labtest Design Actual Volume load kg TCOD/m3/d TCOD reduction % > 98 Efficiency (%) Time (weeks) Biobed Total COD efficiency DuPont Nederland DuPont Dordrecht site Dordrecht Site Doubling of the production of Delrin Waste water containing formaldehyde, acetic acid, formic acid, methanol and octanol Existing aerobic post treatment is too small No space available High sludge handling costs Design stages anaerobic treatment plant Laboratory tests Analysis of the raw waste water Toxicity Test Batch Biodegradability Test Continuous Laboratory Research Design full-scale installation 8

9 DuPont Nederland Conclusions laboratory tests Raw wastewater analysis Formaldehyde and octanol are potential toxic compounds Formaldehyde < 500 ppm biodegradable, otherwise toxic Octanol unknown, toxicity test required Toxicity test Activity of anaerobic biomass inhibited by octanol At octanol > 338 ppm no activity observed Batch biodegradability test SCOD removal > 90 % Within 70 h SCOD < 200 mg/l Anaerobic biomass is not inhibited by low concentrations of octanol present in the raw waste water DuPont Nederland Conclusions laboratory tests Continuous test Adaptation to octanol after 6 weeks Octanol degradation during steady-state 80-90% Peaks in octanol till 600 ppm are allowed COD efficiency > 90% during the entire experiment Steady state load g COD/l.d, peak till 19 g COD/l.d Biobed EGSB very suitable for treatment of this type of waste water DuPont Nederland Full scale installation DuPont Nederland Efficiency Octanol & Formaldehyde + COD removal COD efficiency (%) Time (weeks) Wastewater characteristics Average Peak Flow m 3 /d COD load Formal dehyde kg/d mg/l Octanol mg/l T(S)COD efficiency (%) Octanol Formaldehyde Time (weeks) TCOD removal SCOD removal 9

10 Biothane in PTA industry 15 references worldwide From laboratory to full scale PTA production scheme PTA: Purified Terephtalic acid (para-phtalic acid) Two steps: 1. Crude TA (CTA) production from PX (para-xylene) 2. TA purificiation (PTA) 26/11/ Anaerobic treatment of PTA wastewater Main components wastewater: Results laboratory test with PTA wastewater Biobed EGSB Continuous Laboratory Test COD removal efficiencies para-phthalic acid degradation: ~100 % 25 Para Terephthalic acid Mw 166; COD 1.44 g/g Tri melliticacid Mw 210; COD 1.14 g/g Ortho phthalic acid Mw 166; COD 1.44 g/g CH 3 P-Toluic acid Mw 136; COD 2.12 g/g Iso phthalic acid CH 3 Mw 166; COD 1.44 g/g Acetic acid Mw 60; COD 1.07 g/g Benzoic acid Mw 122; COD 1.97 g/g Adaptation required to phthalic acid isomers: Time required to reach 50% degradation in batch mode Compound Days Benzoic acid 4-10 Orthophthalic acid Terephtalicacid Iso-phtalicacid Removal efficiency (%) 80 ortho and para degradation starts 70 benzoate : 100 % conv TCOD removal 10 SCOD removal load SCOD load kg COD / m3 d 10

11 Vragen? 26/11/