Production of HMF from cellulosic biomass: Experimental...
Transcript of Production of HMF from cellulosic biomass: Experimental...
5th International Conference on Sustainable Solid Waste Management
Production of HMF from cellulosic biomass: Experimental results and integrated process
simulation
Athens2017Conference23/6/2017
M.A.Kougioumtzis1,2,A.Marianou1,3,K.Atsonios1,C.Michailof1,N.Nikolopoulos1,N.Koukouzas1,K.Triantafyllidis3,A.Lappas1,E.Kakaras1
E‐mail:[email protected]
Centre for Research & Technology Hellas (CERTH)
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1ChemicalProcessandEnergyResourcesInstitute,CentreforResearchandTechnologyHellas,Thessaloniki,6thkm.Charilaou –Thermi Road,GR‐57001Thermi,Greece
2 LaboratoryofSteamBoilersandThermalPlants,NationalTechnicalUniversityofAthens,Athens,Heroon Polytechniou 9,15780,Greece
3 DepartmentofChemistry,AristotleUniversityofThessaloniki,Thessaloniki,54124,Greece
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Contents
• Introduction – Scope
• Experimental Analysis
• Process simulation results ‐mass and energy balance
• Conclusions
• Future Work
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Idea Lab & Pilot
ProcessModeling
Industry
Introduction
scale
Demo
Environmental assessment
Economic analysis
Scope
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Idea Lab & Pilot
ProcessModeling
Industry
Introduction
scale
Demo
Environmental assessment
Economic analysis
Scope
Current Study
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Idea
Introduction
Scope
Lab & Pilot
ProcessModeling
Industry
scale
Demo
Environmental assessment
Economic analysis
Current Study
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What is 5‐HMF and Why is it so important?
Introduction
Listed as one of the top 10 value added biobased chemicals by the US Department of Energy
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How do we get 5‐HMF?
Current state‐of‐the‐art
Disadvantages:1. Expensive2. Less abundant than glucose
Advantages:1. More easily converted to 5‐HMF
New feed
Advantages:1. Abundant2. Cheaper
Disadvantages:1. Lower 5‐HMF yields
Introduction
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GrindingHemicellulose‐freeBiomass:
HMF
Hydrolysis (Hexose
Extraction)
HMF Synthesis Bio‐Tar
Heat
Lignin
C6 sugars
Introduction – Process Overview
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Lab & Pilot
Introduction
Scope scale
Idea
ProcessModeling
IndustryDemo
Environmental assessment
Economic analysis
Current Study
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1st step Cellulose hydrolysis (175oC, 8.2 bar)
Acid hydrolysis
Glucose rich solution43% mass yield, 60.5% selectivity
(cellulose based)
Lignin
Experimental Analysis Various catalysts and conditions were tested in order to find the optimum conditions
for the glucose and HMF production (in cellulose sample and glucose rich sample). The optimum conditions were applied into real hemicellulose‐free biomass to obtain
the yields.
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Glucose rich solution 5‐Hydroxymethyl furfural (5‐HMF)
2nd step Glucose dehydration (150oC, 8.2 bar)
Solid catalyst
Solvent: DMSO+H2O
Synthesis of a heterogeneous γ‐Al2O3 based catalyst
One‐step conversion of glucose to 5‐HMF
Determination of the optimum reaction conditions
Catalyst can be reused
Experimental Analysis
20.6% mass yield, 25% selectivity (glucose based)
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Introduction
Scope
ProcessModeling
Current Study
scale
Lab & Pilot
Idea IndustryDemo
Environmental assessment
Economic analysis
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HMF Production Process
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Process configuration
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HMF Production Process
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Process configuration
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HMF Production Process
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Process configuration
Cellulose HydrolysisTemperature= 175 °CPressure= 8.2 barCatalyst 1= acid catalyst Mass ratio H2O/ biomass= 9
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HMF Production Process
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Process configuration
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HMF Production Process
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Process configuration
Evaporation step Increase glucose
concentration to 7.8 wt% (100.5°C)
HMF SynthesisTemperature= 150 °CPressure= 8.2 barSolid Catalyst ratio/Glucose = 1/1 (wt)Solvent= H2O with DMSO
ASPEN PLUS™
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HMF Production Process
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Process configuration
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HMF Production Process
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Process configuration
ASPEN PLUS™
HMF ExtractionVia Liquid Liquid extraction at 1 bar. Input 1/10/1= solution/CH2Cl2/H2O
HMF PurificationThree stage separationTemperature(°C)= 40/45/75Pressure(bar)= 1/0.8/0.1HMF purity= 96.5%HMF recovery= 98%
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Mass Balance
Biom
ass
1500
kg/hr
Hydrolysis
Hydrolysis
byproducts’vapors
49.3 kg/hr
Others: 1.9 %
HMFSynthesis
Combustion
HMFRecovery
Glucose Evaporation
HMF:54.0 kg/hr
Waste Water:149.8 kg/hr
Biotar:1246.9 kg/hr
• 54 kg of HMF (96.5% purity) recovered ~ 3.6% of initial biomass• ~13% of initial biomass converted into byproducts (e.g. levulinic acid, mannitol, leviglucosan,
mannose, fructose, mannitol, acetic acid, formic acid etc.)• ~83% of initial biomass is used as biotar
Process simulation results
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16034100
7
1732
33417444
166131843
9540
2014
0 5000 10000 15000 2000007
14212835424956637077849198
105112119126133140147154161168175
Heat (kWth)
Temp
eratu
re (o C)
rejected heat
heat demand
cellulose preheating
first step reactor
glucose preheating
evaporator
HMF purification 1
vapors cooling
HMF condensationHMF cooling
HMF purification 2
HMF purification 3
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• Biotar is burnt in combustor. Steam generationfor heat demands coverage
Section/ component kWe
grinder 4.2
air blowers 32.1
water pumps (heating system) 2.6
cooling water pumps and vapors compressor 137.5
HMF production pumps 333.6
heat pumps 756.2
total consumptions 1266.1
Power Demands (electricity from grid)
Energy System (dual boiler)
Process simulation results
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Process simulation results
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Energy Balance (Sankey diagram) • External fuel (e.g. natural gas) is necessary for the proper operation of heat demanding process. Most of excess heat cannot be used for coverage of heat demands
• 306 kg/hr of NG is used.• 8.3 MWth from biotar (HHV 24.75
MJ/kg d.b.)• Total heat demands at 11.8 MWth• Heat pump used to exploit the low
temperature rejected heat from HMF condensation
Chemical energy (HHV)
Thermal energy
Electricity
Total heat demands
Hydrolysis
bio‐tar 1
feedstock
vapors cooling
heat for hydrolysis
HMF synthesis
HMF condensation
bio‐tar 2
steam boiler
steam
flue gas
natural gas
glucose preheating
HMF cooling
HMF recovery
rejected heat
heat pump
heat pump consumption
recycling heat
HMF
pumps consumption
8.1 MWth 10.8 MWth
9.5 MWth7.2 MWth
1.1 MWth
1.7 MWth
0.5 MWth
1.8 MWth
1.5 MWth
11.8 MWth
4.6 MWth
9.5 MWth
vapors cooling
0.8 MWe
0.3 MWe
5.8 MWth
6.6 MWth
10.8 MWth
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Heat Integration of the process and identification of energy demands. External heat(NG) consumptions at 85.2 kWhth/kgHMF and power demands at 22.2 kWhe/kgHMF.
Conclusions
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Detailed modeling of process for commercial production of HMF in ASPEN Plus™ fromhemicellulose‐free biomass.
Production of 3.6% HMF of the biomass input. Around 13% of the initial biomassconverted into byproducts.
A dual fuel boiler was implemented to cover the energy demands. A heat pump wasimplemented to exploit the low temperature rejected heat of the system.
Higher HMF yields will increase the economic feasibility of the refinery (bettercatalysts/ solvents)
Experiments on cellulose hydrolysis and glucose dehydration into HMF.
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Process modeling of the whole process (conversion of both cellulosic andhemicellulosic part of the biomass into added value biochemicals). Recovery of otherchemicals (acetic acid, formic acid, levulinic acid, etc.) produced in the process will beincluded in the analysis
Techno‐ economic analysis of such biorefinery.
Future Work
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Examination of converting the hemicellulose part into furfural along with the HMFproduction from the cellulosic part of the biomass.
Improved Heat Integration and optimization of such system.
Environmental Analysis of such biorefinery.
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Thank you for your attention!
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E‐mail:[email protected]
Centre for Research & Technology Hellas (CERTH)
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Table 1. Biotar specifications
C (% d.b) 63.7 H (% d.b) 5.46 N (% d.b) 0.15 O (% d.b) 30.29 S (% d.b) 0.3 ash (% d.b) 0.1 HHV (% d.b.) 24.75 MJ/kg
Table 1. Feedstock (hemicellulose-free biomass) composition (ash free-dry basis) Cellulose 40.48% Hemicellulose 4.65% Lignin 53.05% Unidentified 1.82% Higher Heating Value (dry basis) 19.88 MJ/kg
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stream number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15m (kg/s) 0.42 3.78 4.20 3.90 0.30 2.96 3.73 0.07 4.73 4.73 0.05 50.72 9.65 45.66 0.02T (oC) 25.0 25.0 170.0 175.0 175.0 158.2 25.0 25.0 150.0 150.0 30.0 25.0 25.0 40.0 75.0p (bar) 1.0 1.0 8.2 8.2 8.2 1.6 1.0 15.2 8.2 8.2 8.2 1.0 1.0 0.1 0.1
mass fraction
Acetic acid 1.2E-03 1.3E-03 1.6E-04 2.4E-04 9.1E-05 5.4E-06 7.9E-05
CH2Cl2 9.1E-01 5.3E-02 9.9E-01 2.2E-02
DMSO 1.0 7.9E-01 7.9E-01 3.9E-01 1.9E-07 1.2E-03
Unidentified 1.8E-02 1.8E-03
Formic acid 2.2E-03 2.5E-03 2.5E-04 1.1E-03 5.0E-04 4.9E-06 1.5E-06
Fructose 1.1E-04 1.7E-17 8.8E-05 1.9E-05 9.1E-06 9.5E-24 2.1E-07
Glucose 1.9E-02 5.0E-15 1.5E-02 2.7E-03 1.3E-03 6.0E-21 8.9E-05
Glycolic acid 3.2E-05 1.9E-06 2.5E-05 7.1E-05 3.4E-05 4.4E-08 1.8E-04
H2O9.9E-01 8.9E-01 9.6E-01
1.0E+0
01.7E-01 1.7E-01 9.1E-02 5.5E-01 1.5E-03 5.5E-05
H2SO4 7.4E-03 6.7E-03 7.2E-03 7.1E-06 5.9E-03 5.9E-03 2.9E-03 1.0E-09 3.3E-03
HMF 9.4E-04 1.2E-05 7.7E-04 3.2E-03 2.3E-05 6.6E-06 9.6E-01
Lactic acid 8.6E-05 3.5E-06 6.8E-05 2.2E-03 1.1E-03 2.0E-07 3.7E-03
Levoglucosan 5.8E-04 1.4E-08 4.8E-04 2.4E-05 4.3E-06 1.9E-11 4.8E-03
Levullinic acid 5.2E-03 6.9E-04 3.8E-03 2.5E-03 1.2E-03 1.2E-08 6.2E-04
Mannitol 7.5E-05 1.8E-12 6.2E-05
Mannose 3.5E-04 9.5E-17 2.9E-04 1.7E-05 8.4E-06 3.8E-23 5.7E-07
Propionic acid 8.6E-05 9.2E-05 1.3E-05
SnAl 1.0 1.5E-02 1.5E-02
Xylose 3.3E-04 7.9E-13 2.7E-04
Cellulose 4.0E-01 4.0E-02 1.6E-01
Humins 1.0E-01 9.7E-03 1.0
Lignin 5.3E-01 5.3E-02 7.4E-01
Xylan 4.7E-02 4.6E-03 2.8E-04
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Table 1. Cellulose (in hemicellulose free biomass) Hydrolysis Experimental Results
Conversion Cellulose 71.43% Mass Yields (biomass based wt %)
Glucose 17.44% HMF 0.88% Mannitol 0.07% Levoglucosan 0.54% Xylose 0.31% Mannose 0.33% Fructose 0.10% Galactose 0.004% glycolic acid 0.03% Acetic acid 1.11% Lactic acid 0.08% Formic acid 2.07% Propionic acid 0.08% Levulinic acid 4.86% Lignin 53.05% Unreacted hemicellulose 0.02% Humins 7.47%
Table 1. HMF Synthesis Experimental Results (starting from hemicellulose free biomass)Conversion Glucose 82.46%
Mass Yields (glucose-based wt%) HMF 20.64% Levoglucosan 0.11%Mannose 0.11%Fructose 0.12% Glycolic acid 0.46% Acetic acid 1.54%Lactic acid 14.39% Formic acid 6.99% Levulinic acid 15.97% Humins 22.12%
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