mw assisted activation of biomass · case study 4. paper waste biorefinery. hydrothermal treatment...
TRANSCRIPT
26-04-18
MW assisted activation of
biomass
Dr. Vitaliy Budarin
Microwave
TP MW
Extraction
MW
pyrolysis
Analysis
MW
hydrothermal
pyrolysis
MW assisted
Synthesis
>10years experience 3 postdocs 3 PhDs More than 25 publications 2 patents 3 patent applications
Microwave TP proposals 1. Carbon Trust £500,000
2. ERDF £1,000,000
3. EPSRC: Renewable Chemicals from Sustainable Feedstocks
via High-Throughput Methods; 2013-2017; £817,686.
4. 7th Framework Programme; ALTEREGO (Alternative
Energy Forms for Green Chemistry); 2012-2014; £524,000
5. Industrial fund; Company 1: 2013-2015; £450,00
6. Industrial fund; Company 2: 2013; £27,000
7. Industrial fund; Company 3: 2014-2015; £300,00
8. White Rose University Consortium; Collaboration Fund:
Energy and fuels from thermal chemical conversion of
biomass; 2013; £15,000.
9. SPARK awards: Development of a novel seaweed derived
cytokinin-based plant growth promoter, 2013; £5,000.
10. EPSRC: IB Cat £1,200,000
Why Microwaving biomass?
Biomass is very low heat transfer material (volumetric heating has advantages)
Biomass contained physisorbed and chemisorbed water (high efficiency)
Biomass is heterogeneous (specific heating)
Advantages:
Disadvantage:
At room temperature biomass structural components transparent fpr MR radiation
Biomass
Microwave
processor
Energy
Extracted
oil
Pyrolysis
Oil
Char
Wide range of
feedstock + = Wide range of
products
Flexibility of Microwave
Parameters
(time, temperature, power)
Low Temperature
Microwave Treatment of Biomass
6
www.greenchemistry.net
Heat of
combustion
30 kJ g-1
Case Study 1. Rape Seed Pyrolysis
Model Compounds Whole Biomass
Cellulose Soft Wood Rape Straw
Hemi-cellulose Hard Wood Citrus waste
Lignin Wheat Straw Grass
Oat straw Seaweed
Maltodextrin Barley Straw Microalgae
Glucose Barley Dust Whisky production waste
DDGS DRAFT
Alginic Acid Rape Straw
Pectin Cocoa husks
Waste Paper Bracken
Investigated biomass
Microwave activation of Biomass
Hydrolysis product Pyrolysis products
Biomass Food waste; Forestry waste
Agricultural waste; Marine resources
Bio-fuel Chemicals Materials
140-160oC 160-260oC 180oC
Hemicellulose Cellulose Lignin
H2O Bio
mas
s st
ruct
ure
co
mp
on
en
ts
N2
Research achievements. Relation between
phase transition and MW DSC, Cellulose
DSC, Hemicellulose
MW experiment
181oC
184oC
167oC
Versatile platform technology with two key
approaches:
Hydrothermal
Microwave treatment in
water (100 – 260 ˚C)
Key benefits:
• Suitable for all
biomass, especially
wet
• Efficient hydrolysis of
polysaccharides to
produce fermentable
sugars
• Extraction and gelation
of polysaccharides
(e.g. pectin)
Pyrolysis
Microwave treatment
under inert atmosphere
(140 – 300 ˚C)
Key benefits:
• Applicable to all
biomass
• One-step formation
of biofuels – biogas,
biochar and bio-oil
• In-situ fractionation
results in low-acidity
stable bio-naptha
• Can specifically
target components of
biomass
Microwave pyrolysis
Microwave results in pyrolysis at lower temperature for all biomass and
biomass components studied reduced energy
Microwave Assisted Wheat Straw
Pyrolysis
Heating rate is very informative parameter of MW pyrolysis
Microwave Assisted Barley dust Pyrolysis
Influence of heating rate
• High calorific value ~30kJ/g
• Good grindability
• Good hydrophobicity
• Co-firing with coal
Characteristics of MW Bio-Char
Calorific value of MW Bio-Char
Temperature of pyrolysis is 210oC
Property Crude
Oil[1]
Pyrolysis
oil
Microwave oil
Ruan[2] Current York
Water (%) <1 10-20 15.2 <1
C (wt %) 85-87 45-55 60.1 58.9
H (wt %) 10-14 6-7 7.70 6.85
N (wt %) 0.1-2 0.3 2.02 1.15
S (wt%) 0 0.5-5 0.15 0.02
Acid number <1 70-150 pH= 2.87 1.4 (pH=7)
Alkali metal 50 100 7.6 6
CV (kJ/g) 42 16 - 21 17.4 16-22
[1] Report 40661. The Exploitation of Pyrolysis Oil in the Refinery Main Report. Prepared For: The Carbon Trust. March 2008. [2] Yu F., Deng S., Chen P, LIU Y., Wan Y., Olson A., Kittelson D., and Ruan R. “Physical and Chemical Properties
of Bio-Oils. From Microwave Pyrolysis of Corn Stover”, Applied Biochemistry and Biotechnology, 2007, 136–140,
pp 957-950.
Comparison microwave oil characteristics with competitors.
Wood Microwave pyrolysis. Oil
fractionation.
Fraction
N T (oC)
3 60-80
4 80-100
5 100-120
• Fraction 4
(sugars) basis for
platform molecules
• Fraction 3
(Phenols, furans)
• Fraction 5
(Phenols, furans)
• Fraction 2
(Water, aldehydes,
acids)
• Fraction 1
(Distilled Water)
CSCs made with silica K60
CSCs made with silica K100
N-doped CSCs made with silica K60
Selective adsorption of gold at a range of concentrations (up to 100% selectivity).
Quantitative gold removal at low concentrations (up to 100% removal).
Temperature-dependent mesoporous materials with tuneable properties (functional
& textural).
08/03/2018 18
Case Study 2. Synthesis of bio-derived
carbon/silica composites for the removal of
gold from aqueous solutions
Microwave assisted pyrolysis
Waste office paper
Mixed with corresponding silica in
acetone
Bio-oil
Carbonisation under nitrogen
Carbon-silica composites
Urea
Processes: 1 tone of Pine
850 kg Dry wood
150 kg H2O
850 kg Dry wood
150 kg H2O
250C
1000C
Heating
850 kg Dry wood
150 kg H2O
1000C
283 kg Char
283 kg H2O
283 kg oil
1800C
Drying
Decomposition
Water heating: 150kg x(100-25)K x 4.2 kJ kg-1K-1 = 50 mJ
Pine wood heating: 850kg x(100-25)K x1.59 kJ kg-1K-1 = 101 mJ
Water Vaporization: 150kg x 2260 kJ/kg = 339 mJ
Water Vaporization: 283kg x 2260 kJ/kg = 640 mJ Steam heat:(283+150) kg x (180-100)K x 2.08 kJ kg-1K-1 = 72 mJ
Oil Vaporization: 283kg x 371 kJ/kg = 104 mJ Oil heating: 283 kg x (180-100)K x 2.85 kJ kg-1K-1 = 64 mJ
Char heating: (283) kg x (180-100) x 1.62 kJ kg-1K-1 = 37 mJ
140 mJ/tone 1.4 kJ/g
Microwave Pyrolysis. Energy Impute
0 50 100 150 200
0
20
40
60
80
100
120
140M
W e
ne
rgy
exp
en
de
d p
er
1 g
of
bio
ma
ss
kJ/g
Sample mass, g
Microwave Pyrolysis. Energy Impute
Pyrolysis. Energy Impute.
Comparison of alternative methods of
estimation
Theoretical calculation 1.36 kJ/g
Experimental. Small scale 1.5 kJ/g
Experimental. Large scale 1.7 kJ/g
Microwave Pyrolysis.
Energy & Mass balance
Products of MW Pyrolysis
Bio-oil
Levoglucosan
Levoglucosenone
HMF
Levulinic acid
Phenol s mixture
Extractives
Limonene
Resins
Wax
Bio-char (30 kJ/g)
Bio-gas (10% energy)
Hydrothermal activation
of bio-mass
Case Study 3. Cellulose Hydrolysis
Sugars yield increases x20 in the presence of microwave irradiation
32%
Fan et al, JACS, 2013, 1178
High selectivity toward glucose. Repeated MW hydrolysis of solid
produces up to 40% yield of sugars at 220oC
Chemical Engineering and Processing, 2013
Case Study 4. Paper Waste biorefinery.
Hydrothermal treatment
High selectivity toward glucose. Repeated MW hydrolysis of
solid produces up to 40% of sugars yield.
Chemical Engineering and Processing , 2013, DOI 10.1016
Cellulose hydrolysis. Salt influence
Case Study 5. Anaerobic Digestion.
Hydrothermal treatment.
Bio-waste Anaerobic
digestion
Post-treatment
Microwave
pretreatment
Biogas
Bio-fertiliser
340%
increase in
bio-gas
yield with
MW
Hydrothermal microwave processing
hydrolyses polysaccharides into
sugars prior to Anaerobic Digestion
resulting in increased biogas yields
Case study 5. MW bio-refinery of Orange
peel. Hydrothermal treatment
Wet orange peel
Process being scaled-up with industrial collaboration
Case study 6. Microalgae biorefinery.
Hydrothermal treatment
Up to 80% of Microalgae was transformed to valuable products
GREEN CHEMISTRY (2012) 14 (12) 3251-3254
Major applications of
MW hydrolysis
Application
1 Hydrolysis of lignocellulosic biomass to fermentable sugars
2 Extraction of pectin from citrus peal
3 Microalgae biorefinery
4 Biomass pre-treatment before AD
5 Waste paper utilisation
6 Extraction high value chemicals from plants