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