Biochar production via Low Temperature Conversion (LTC) technology using a Thermocatalytic Loop Type Reactor

Transcription

1 Biochar production via Low Temperature Conversion (LTC) technology using a Thermocatalytic Loop Type Reactor 3rd International Biochar Conference IBI 2010 Progressing from Terra Preta de Indios to the Whole World September 2010, Rio de Janeiro, Brasil Andreas Frank, Walter Grimmel 1, Ernst A. Stadlbauer 2, Bernd Weber 2, Marc P. Bayer 3, Klaus Albert 3 1 Werkstoff+Funktion Grimmel Wassertechnik GmbH, Ober-Moerlen, Germany 2 University of Applied Sciences Giessen-Friedberg, Giessen, Germany 3 University Tuebingen, Tuebingen, Germany 1

2 Outline Objective LTC Principle + Potentials LTC of Animal Meal Reactor and Pilot Plant Lab & Pilot scale results: LTC-Conversion of Animal Meal Economics Conclusions 2

3 Primary Objective Established Recycling Path Animal & Meat and Bone Meal Cat 1 Cat 2 Cat 3 Incineration Incineration Incineration Level of Added Value Secondary substance fertilizer Secondary substance fertilizer Animal feed (restricted) Any other recycling path available? 3

4 Principle of LTC C a H b O c N d S e - (CO 2 + NH 3 + H 2 S + H 2 O) T 400 C, l O2 = 0, p atm. in-situ/external catalysts C x H y + C + minerals Removal of functional groups from organic molecules in the presence of catalysts and elevated temperatures. Disfunctionalizing - Decarboxylation - Disproportionation Radical Splitting - Random Scission LTC versus Pyrolysis (T < 500 C, preservation of C-C bonds, Decision of Federal Court of Justice, DE) Preservation of natural synthesis preliminary work. Note p atm. : ΔG = ΔH - S x ΔT (forced by temperature) 4

5 Overview LTC Potential Ingredients Process Products Utilization Animal meal Animal fat (Free) Fatty acids Yellow grease Gases Energy recovery Process gas Cake / Extract Oil plant processing Malt residuum in situ/external catalysts absence of oxygen LTC-oil Commercalization Chemical building blocks Energy recovery Marc (dry) Pomace (dry) p atm T = C Reaction water + salt Biological treatment Feedstock recycling Sewage sludge (dry) municipal+industrial via LTC-char Solid residue C, minerals Commercalization Energy recovery Feedstock recycling Thermo-Catalytic Loop Reactor (pat.) 5

6 LTC of Animal meal Animal Meal C 233 H 400 N 38 O 25 P 1.5 S 1 Ca H/C=1,7 in-situ catalyzed Lipids/Protein T = C Crude oil CH 3 -(CH 2 ) n -CH 3 CH 3 -(CH 2 ) n -COOH Non condensable gas (NCG) Reaction water (RW) Char Carbonhydrate [C(H 2 O)n] n H 2 O + C C + P + Ca 6

7 Specification Animal Meal NCV Water Ash V.M. mf (maf) C H N S O calc. P [MJ/kg] [%] [%] [%] [%] [%] [%] [%] [%] [%] Animal Meal AM (95,3) TG /% Thermogravimetry as Mini-LTC Mass Change: % DTG /(%/min) 0 [1.1] 90 Peak: 97.1 C Mass Change: % Mass Change: % Peak: C [1.1] Temperatura / C 7

8 Potential LTC of Animal Meal Animal & Meat and Bone Meal (org. substance + inorg. material) Gas scrubbing NCG (CO 2, C x H y <C=4 Conversion (LTC) LTC- Crude oil Reaction water (RW) directly NO x removal via SNCR Phosphate potential: ton/year (STN 2008, Germany) LTC- Char C + inorg. material Absorption RW Stripping (NH 3 and Org. acids Air NH 3 -dilution NO x removal via SCR Organic acids Water treatment 8

9 Plant Scheme Perfect substrate: e.g. Animal Meal - dry (<10 % H 2 O) - homogeneous, not any impurity - rich in organic (Fat, protein, carbonhydrate) M Buffer Filling Additive M Dedusting Product gas Cooling water Condensation Gravity separator Cooling water Non condensable gas Thermo Catalytic Loop Reactor Advantage: continuous/automated single-stage/internal recirculation Solid product LTC- Char Reaction water Liquid oil LTC Crude oil September 13 th, Biochar production via Low Temperature Conversion (LTC) technology using a Thermocatalytic Loop Type Reactor - Andreas Frank 9

10 Pilot Plant Pilot Plant Yield Solid product Reaction water Liquid oil Non cond. Gas Installed power (Heating) = 23 kw Mass flow = 50 kg/h 10

11 Results: LTC products LTC- Bio oil NCV C H N S O calc. n 40 C [MJ/kg] [%] [%] [%] [%] [%] [mm²/s] Bio oil AM LTC- Reaction water C H N S NH 4 -N CH 3 COOH ph [%] [%] [%] [%] [%] [%] [-] RW AM GC C-15 Fettsäuren C-17 Fatty Acids 100, %T IR 2358, , , ,49 NH 3 -compensation on NO x removal Carbon Feed for digesters & sludge activation ,0 2956, , , , ,0 cm ,89 695,92 728,79 storable easy to transport Combustion Process heating 11

12 Concentration PO4 [mg/g] Results: Solid product Mol ratio H/C [-] NCV Water Ash C V.M. mf (maf) H N S O calc. P Bulk Density [MJ/kg] [%] [%] [%] [%] [%] [%] [%] [%] [%] [kg/l] Char AM (31,5) Aqua Regia Disintegration Extraction with Citric Acid ,0 van Krevelen - diagram 0 MBM Solid Product AM Solid Product Sludge Solid Product Solid Product Rape Seed 1,6 1,8 LTC-Char of not any heavy metals dry, free flowing briquetting not any protein 1,4 1,2 1,0 0,8 0,6 0,4 0,2 Animal meal 1 Animal meal 2 Meat & Bone Meal 0,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 Mol ratio O/C [-] 12

13 Solubility Results: Fertilizer concept Solubility Water Formic acid 2% Citric acid 2% Total MBM MBM + Soda AM MBM MBM=Meat and Bone Meal TP=Thomas phosphate AM=Animal Meal LTC-Char from AM and MBM have huge phosphate concentration. Formic acid can extract phosphate 80% from AM and 90% from MBM in produced LTC-char. Control MBM TP Special: Sodium Carbonate increase plant availability of phosphate demonstrated with ryegrass (Loleum porenne L.) Thesis B. Weber,

14 Normalized Intensity Results: 13 C NMR spectra* NH R O C NH R O NH R O *determined by Bayer, M P, Albert, K, University Tuebingen % C sp2 elemental carbon NH R O CH NH R O NH R O NH R O C H 2 NH R O NH R O Arom. from Tyrosin % -CH 2 - aliphatic Animal meal with 1% H 2 O LTC-Char of animal meal Chemical Shift (ppm) 14

15 Results: Energy Flow* (Sankey) Verluste Losses (Warm up, (Aufheiz, Cooling Abkühl, Transmission) Q>0,09 GJ H exo <0,03 GJ Non Nichtkond. cond. gas Gas Q<0,03 GJ LTC- NTK-Öl Oil Q=0,66 GJ Substrate Q=1 GJ LTC-NTK-Kok Solid product s Q=0,29 GJ Q therm =0,07 GJ P el =0,02 GJ Reaktions Reaction water wasse r Q=0,02 GJ *normalized on a mole biogenic substrate of a (1) GJ is assigned Thesis B. Weber,

16 Economics Economic process with inclusion the cost of invest Value adding heat (0.02 /kwh) oil: 36 /ton AM char: 29 /ton AM Value adding chemicals e.g. Ammonia (400 /ton): 26 /ton AM Phosphorous recycling (350 /ton P) 31 /ton AM CO 2 -certificate (22 /ton CO 2 ) oil*: 70 /ton AM char: 26 /ton AM *(- H 2 component): Sum But: Actual market price AM (Energy use) max. 218 /ton AM 150 /ton AM Realistic throughput is from 1 ton/hour 16

17 Conclusions Use of Virgin Food Crops for Bio-fuels has Severe Limitation instead Waste to Fuels and Chemical Raw Materials Solid Product from AM and MBM is a Natural Resource for Phosphorous Direct use of char containing phosphate from LTC in Fertilizer Concepts 17

18 Recycling and intelligent use of organic residues are today s challenge and tomorrow s reward. Muito obrigado pela atenção Contact fran.k@gmx.de 18