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)

1

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


Contents

• Introduction – Scope

• Experimental Analysis

• Process simulation results ‐mass and energy balance

• Conclusions

• Future Work

2

5th International Conference on Sustainable Solid Waste Management 3

Idea Lab & Pilot

ProcessModeling

Industry

Introduction

scale

Demo

Environmental assessment

Economic analysis

Scope


Idea Lab & Pilot

ProcessModeling

Industry

Introduction

scale

Demo


Economic analysis

Scope

Current Study


Idea

Introduction

Scope

Lab & Pilot

ProcessModeling

Industry

scale

Demo


Economic analysis

Current Study


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


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


GrindingHemicellulose‐freeBiomass:

HMF

Hydrolysis (Hexose

Extraction)

HMF Synthesis Bio‐Tar

Heat

Lignin

C6 sugars

Introduction – Process Overview


Lab & Pilot

Introduction

Scope scale

Idea

ProcessModeling

IndustryDemo


Economic analysis

Current Study


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.


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)


Introduction

Scope

ProcessModeling

Current Study

scale

Lab & Pilot

Idea IndustryDemo


Economic analysis


HMF Production Process

13

Process configuration



14




15


Cellulose HydrolysisTemperature= 175 °CPressure= 8.2 barCatalyst 1= acid catalyst Mass ratio H2O/ biomass= 9



16




17


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™



18




19


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%


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


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

21

• 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)




22

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


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

23

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.


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

24

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.


Thank you for your attention!

25

E‐mail:[email protected]

Centre for Research & Technology Hellas (CERTH)


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


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


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%

production of hmf from cellulosic biomass: experimental...

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