PRODUCTION AND CHARACTERISATION OF BIO-OIL OIL FROM CATALYTIC BIOMASS PYROLYSIS

Transcription

1 PRODUCTION AND CHARACTERISATION OF BIO-OIL OIL FROM CATALYTIC BIOMASS PYROLYSIS E.V. Antonakou*, V.S. Dimitropoulos and A.A. Lappas Chemical Process Engineering Research Institute (), Center for Research and Technology Hellas (), Thermi, Thessaloniki, Greece

2 Overview Introduction Experimental Unit Description Experimental Results Conclusions

3 Introduction Biomass is the plant material created by photosynthesis (H 2 O and CO 2 into organic matter) Biomass exploitation processes are considered CO * 2 neutral -the reverse of photosynthesis It can contribute to cover energy needs and also to provide a wide range of chemicals * Originates from harvested or processed plants which have absorbed it from the atmosphere-no additional emissions

4 Introduction Pyrolysis, as a basic biomass thermochemical process for the production of liquid, solid and gaseous products, has been studied in a variety of reactor types A biomass pyrolysis pilot plant unit operates in for the catalytic pyrolysis of various biomass species

5 Introduction Catalytic Pyrolysis Use of a solid catalyst as a heat carrier for the in-situ upgrading of the pyrolysis products aiming at the production of liquids with increased stability and concentration in high value chemicals Aim Presentation of operation and results of the pilot plant unit in and the effect of catalyst in the main pyrolysis products

6 Experimental Unit Description The catalytic biomass pyrolysis pilot plant unit in

7 Pilot Plant Overview

8 Solids Feed Feed hopper for storing raw biomass Load cell support that continuously weights the biomass Screw feeder is used to continuously supply the biomass to the injector. Biomass Feed: 5-20 g/min FEED TANK BIOMASS SCREW FEEDER INJECTOR Heat carrier vessel (up to 815 C) Four thermocouples measuring the temperature inside the bed of the vessel Differential pressure controller Slide valve that controls the flow of solids to the injector through a heat traced line Catalyst Feed: g/min HEAT CARRIER VESSEL FLUIDIZING GAS SLIDE VALVE

9 Reactor A bottom part or injector where the biomass comes in contact with the catalyst Riser type reactor (15ft* 3/8 ) Wire heaters that supply heat while the temperature is controlled and measured in many parts (up to 600 C) Fluidization system using nitrogen (Ν 2 ) for the transport of solids through the reactor

10 Solids Recovery System Stripper vessel with a cyclonic stripper head Series of cyclones and filters for the removal of particles Heating up to 600 C Stripper Gas: Ν 2 STRIPPER/ DISENGAGER FILTER CYCLONE TO PRODUCT RECOVERY STRIPPING GAS SLIDE VALVE

11 Liquid Product Recovery System Air-cooled vertical heat exchanger Stabilizer column, which serves also as a secondary condenser (-15 C) Activated carbon filters that trap the remaining oil and heavier gas compounds from the gaseous stream

12 Pilot Plant Specifications PARAMETER Operating Range Regenerator Temperature( o C) < 680 Reactor Temperature( o C) Reactor Pressure(atm) Regenerator Capacity(Lt) < 30 Solids Rate(g/min) Feed Hopper Capacity(Lt) < 3 Biomass Feed Rate(ml/min) Biomass Particle Size (µm) Vapor Residence Time in Riser (sec) < 1

13 Process Mass Balances Satisfactory mass balances both from conventional and catalytic pyrolysis experiments

14 Product Analysis Gas Analysis HP 6890 GC, equipped with four columns (Precolumn:OV-101; Columns: Porapak N, Molecular Sieve 5A and Rt-Qplot(30m x 0.53mm ID) TLP Analysis Total Liquid Products(TLP) are separated in organic and aqueous phase Organic Phase Analysis HP 5989 MS ENGINE equipped with a column:hp-5ms(30m x 0.25mmID x 0.25 µm) HP 5890 GC, equipped with a HP-5 column (10m x 0.53mmID x 2.65m) and a FID detector

15 Product Analysis Physical Characterization Standard analytical techniques (based on conventional fuels): ASTM 4052 (density) ASTM D1744 (H 2 O) ASTM D445 (viscosity at 50 o C) ASTM D4530 (MCRT) ASTM D97 (pour point) ASTM D93 (flash point) ASTM D4809 (calorific value)

16 Experimental Results Biomass Feedstock Lignocel (beech wood) Ash (wt %) C (wt %) H (wt %) N (wt %) O (wt %) GHV (MJ/kg kg) Na (mg/kg) K (mg/kg) Moisture (%) 0,53 49,41 6,73 0,16 42,96 18,22 43, ,25

17 Experimental Results Heat Carriers Silica sand FCC APS(µm) BD (g/ml) TSA (m 2 /g) ZA (m 2 /g) 58.5 UCS(A O ) 24.26

18 Experimental Results Product Yields Water (wt%on bio-oil) T=450C T=500C sand FCC The use of catalyst causes a decrease in the production of liquids and an increase in the production of water in the bio-oil in both temperatures

19 Experimental Results Product Yields Catalytic pyrolysis leads to increased gas and coke production Higher temperatures favor the production of gases

20 Experimental Results Physical Characterisation of Bio-oil oil Flash Point T=450oC T=500oC Density T=450oC T=500oC o C sand FCC 0.9 sand FCC Decrease in flash point and density of the catalytically produced bio-oil- due to the extensive cracking in the presence of catalyst

21 Experimental Results Physical Characterisation of Bio-oil oil Viscosity T=450oC T=500oC Mj/kg of bio-oil HHV T=450oC T=500oC 0 sand FCC 0 sand FCC With the use of catalyst the values of viscosity and heating value are also decreased Phase separation maybe desirable in order to obtain more condensed fractions with desirable fuel properties

22 Experimental Results Thermal Stability Studies of Bio-oil oil Stability test, 450 o C NON CAT FCC Hours of heating at 80 o C Stability Test 500 o C Hours of heating at 80 o C NON CAT FCC Thermal stability studies indicate a more stable bio-oil in the presence of the FCC catalyst

23 Conclusions The pilot plant exhibited good operating stability and flexibility with different heat carriers and under different operating conditions The type of heat carrier plays a significant role in the yield and composition of the produced bio-oil The introduction of catalysts in the biomass pyrolysis process causes bio-oil vapors decomposition into gaseous and solid products and also water Although the main physical properties of bio-oil deteriorate in the presence of the FCC catalyst, promising results were obtained from the stability tests of the catalytically produced oil