Biosyngas from forest product industry by-products and residues

Transcription

1 Biosyngas from forest product industry by-products and residues 1 Presentation at the VETAANI Conference 9 April 2014 Prof Rikard Gebart Luleå University of Technology

2 Feedstock use in the forest product industry Source: Biomassaflöden i svensk skogsnäring 2004, Per Olov Nilsson. Rapport Skogsstyrelsen ISSN *Million tons dry biomass Biomass gasification Fuel& chemicals Felling residues Fuel& Chemicals Black liquor gasification 2

3 BL Energy in Europe = clusters of mills together having a large boiler capacity = important single mill Approx: MW Black Liquor Some 65 large plants 3

4 Feedstock flexible gasification opens up many possibilities CO 2 * Coal FT Diesel Liquid residues Natural gas Biomass Black liquor Gasification Followed by cooling and preliminary cleaning Gas cleaning & Conditioning SYNGAS Ammonia Mixed Alcohols Hydrogen Methanol Ethanol Urea Gasoline Acetic acid DME Waste Methane Esters & Ethers Formaldehyde Olefins 4

5 Swedish pilot scale research on gasification of forest industry by-products Pilot plant projects Budget BLG I 11 M B BLG II Black Liquor 11 M BioDME 28 M B LTU Biosyngas BL + PO + pulverised fuels 20 M B GoBiGas Pellets + wood chips 25 M B PEBG Pulverised fuels 4 M Significant other gasification projects in Sweden Budget SFC 36 M f 3 (system analysis) 8 M 5

6 6 Black liquor and pyrolysis oil gasification

7 Some basics about Black Liquor Black Liquor is a Liquid Easy to feed to a pressurized gasifier Can be atomized to fine droplets Rapid gasification rates Stable properties over time Black Liquor is an efficient gasification fuel Full carbon conversion at ~1000 deg C Virtually no tar formation Low methane formation Black Liquor is available in large quantities World BL capacity about 660 TWh/y Corresponds to production of ~ 10 billion gal gasoline equivalents per year Typically MW of BL per pulp mill 7

8 BLACK LIQUOR OXYGEN AND ATOMIZING MEDIA The Chemrec DP-1 gasifier COOLING WATER PARTLY CLEANED, COOL SYNTHESIS GAS GAS COOLER Probe REACTOR RAW GAS QUENCH GREEN LIQUOR 8 WEAK WASH CONDENSATE Owned and operated by LTU Green Fuels 20 ton BLS/day (3 MW), 30 bar, 1050 C > hours of operation

9 Gas composition for a typical case (p = 27 bar, = 0.3, T = 1050 ºC) Inside reactor (%) Cooled syngas (%) CO2 33.9± ±0.2 H2S 1.65± ±0.02 CH4 1.36± ±0.07 CO 28.7± ±0.2 H2 34.3± ±0.1 COS 468±22 ppm 122±5 ppm H2/CO 1.19± ±0.01 H2/CO2 1.01± ±0.01 CO/CO2 0.85± ± (calculated as N 2 and H 2 O-free, >10 samples per value)

10 Trace elements in the synthesis gas Element Average Gas concentration (ppb by weight) Fe <1.8 K <1.8 Li <0.02 Na <17.4 Ni <0.05 NH 4 -N 89.5 Cl 1297 Br <1.0 I <4.6 CN total <0.5 F <2.6 10

11 Particle mass size distribution in cooled syngas Extremely low particle concentration, typically <0.1 mg/nm 3 Notice lack of bimodal distribution typical of combustion particles 11

12 Conclusions about the DP-1 12 Catalytic action from the cooking chemicals Efficient gasification at low temperature (1050 C) > 99.9 % carbon conversion (based on amount of green liquor sludge) Extremely low tar concentration, easy to clean gas Robust and reliable process, easy to control > hours of operation Industrially acceptable performance from refractory lining (life length >> hours in continuous operation)

13 Widening of feedstock base Catalytic gasification Mixtures of black liquor and pyrolysis oil have the same high reactivity as BL Can double the capacity of a single mill Entrained flow gasification of solid biomass under development (ETC, LTU, Biogreen) Plans for building a second solid biomass gasifier in the LTU Green Fuels pilot plant Liquefaction of organic waste resulting black liquor is highly reactive and can be gasified in existing gasifier 13

14 14 Syngas cleaning and conversion

15 Syngas cleaning in entrained flow gasifiers Low tar concentration no need for tar reforming, insignificant fouling from tars Low concentration of sub-micron particles H 2 S concentration in raw syngas: BL gasification: [H 2 S] app. 1% Solid biomass and PO: [H 2 S] < 100 ppm 15 Requirements: H 2 S and CO 2 (acid gas) removal Need small slip of CO 2 for methanol process All trace components must be below ppm level

16 Syngas cleaning in LTU Green Fuels pilot Raw syngas Carbon filter CO shift Amine wash H 2 S / CO 2 to pulp mill incinerator Clean syngas 16 Active carbon filter for remaining hydrocarbons (mostly benzene) Sour shift integrated with gas cleaning Amine wash for CO 2 and H 2 S removal The offgas is sent to the mill s incinerator where sulfur is captured New, low-cost, high efficiency concept under development

17 Conclusions 17 Black liquor gasification is a mature technology > 99.9 % carbon conversion at 1050 C Containment materials will last for a long time Very low amounts of tars and trace compounds Robust process, easy to control Gasification of mixtures of pyrolysis oil and BL under development Gas cleaning is relatively simple with high temperature entrained flow gasification Continued research is focused on decreasing costs and widening of feedstock base

18 Acknowledgements W2C 18

19 19 Extra slides

20 LTU Biosyngas Program WP2 Powder Torrefied Mtrl Pyrolysis oil Black Liquor WP6 Existing facilities DP-1 Plant ETC EF gasifier Cleaning WP4 Membranes bar > 100 bar Active C Abs Distillation Electrolysis WG Shift O 2 H 2 CO, H 2 Future development The Renewable Syngas Highway WP1 WP3 WP8 Fuel Cells WP1 Pilot scale experiments WP2 Catalytic gasification WP3 Solid fuel gasification WP4 Novel syngas cleaning WP5 Catalytic conversion WP6 Containment materials WP7 Field tests (WP8 Electrofuels and new concepts) Amine Wash CO 2 H 2 O MeOH Synth. Catalytic Process Development DME Synth. WP5 WP7 Others BioMeOH BioDME

21 LTU Green Fuels syngas conversion Runs in 3 week stints, 24 weeks per year Accumulated operation > hours Accumulated production > 500 tons DME Additional experiments are possible on slip stream syngas up to 100 Nm 3 /h 21

22 DP-1 unit Black Liquor Oxygen LTU Green Fuels present syngas conversion Gasification Carbon filter CO shift Amine wash Gas conditioning & Cleaning H 2 S / CO 2 to pulp mill incinerator MeOH Synthesis 2 Syngas Compressor Sulphur guard MeOH Synthesis 1 Raw Methanol First single-pass MeOH synthesis featuring > 95% yield MeOH (recycled) Off gases DME Product DME day tanks DME synthesis DME storage 22 DME synthesis & product purification Water

23 The LTU Green Fuels pilot plant Feedstock and utility connection to the host pulp mill - Office facilities Black liquor gasification pilot plant 23 - Gas conditioning - gas cleaning - synthesis - distillation together converting raw syngas to Methanol/DME O 2 and N 2 storage