FUTURE WORK4

ACKNOWLEDGMENTS: The authors thank the Spanish Ministry of Economy an Competitiveness for the Project CTQ2013-44143-R. C. M. M. thanks Junta de Castilla y León for her research fellowship.

INTRODUCTION1

RESULTS3

EXPERIMENTAL SET-UP2

DEMONSTRATION OF AN EFFECTIVE BIOMASS TO SUGARS TRANSFORMATION PROCESS

BY ULTRA-FAST REACTORS IN SUPERCRITICAL WATER

Celia M. Martínez a, Danilo A. Cantero b, MJosé Cocero a

a High Pressure Processes Group – Department of Chemical Engineering and Environmental Technology, University of Valladolid, SpainbDepartment of Chemical and Biomolecular Engineering, Energy Institute, Cornell University, Ithaca, United States

National project: CTQ-2013-44143-R

FastSugars Project responds to

the challenge of developing a

selective technology to transform

biomass into sugars and chemicals

using supercritical water (SCW) as

hydrolysis medium, with reaction

times of milliseconds.

AIM

1. Design, build and operate a demonstration plant to hydrolyse biomass in SCW

2. Study biomass pre-treatments for the hydrolysis process

3. Apply the obtained results to biomass of industrial interest: cellulosic biomass

and lignocellulosic biomass

4. Study the production of added value compounds from biomass by SCW

CV: Check Valve

HE: Heat Exchanger

M: Mixer

P: Pump

PI: Pressure Indicator

PT: Pressure Transducer

SV: Selection Valve

TT: Temperature Transducer

V: Valve

GT: Gate Valve

P-1

P-2

Biomass

Tank

Water

Tank

CV-1

CV-2

PI-1

PI-2

V-1

PT-1

HE-4

Flash

HE-3

H-1SV-1

SV-2

Vapor

Outlet

Liquid

Outlet

TT

TT

TTTTTT

TT

TT

TT

PI-3

H-2 H-3

TT

HE-1

SV-3

HE-2

F2

F1

GV2

GV1

SCV

SCV

SV-3

FeaturesSCALE UP

LABORATORY PLANT PILOT PLANT

Capacity 8 kg/h (max 3 kg/h biomass) 50 kg/h (up to 15 kg/h biomass)

Solid retention (filters) NO YES

SCW heating 1 problematic step 3 steps

dp biomass Max 150 µm Up to 500 µm

Depressurization system Manual Manual or automatic

Design conditions Up to 30 MPa and 420 ºC

OBJECTIVE 1 of FASTSUGARS project was already accomplish by designing,

building and starting up the pilot plant to carry out the hydrolysis of biomass in SCW.

The design project was focused on improving and scaling up the current laboratory

plant from a previous project. Start up experiments were carried out with tobacco scrap.

Hydrolysis of cellulose in supercritical water: Reagent

concentration as a selectivity factor

Cellulose hydrolysis in SCW was carried out at 400ºC, 25MPa with

reaction times between 0.07 and 1.5 s and inlet concentrations of

cellulose between 1.5 to 6.5 % w/w.

Reaction time showed a strong effect over selectivity, yielding

sugars (low tR) or derived products (high tR).

It was proved that inlet concentration of biomass affected the

conversion rate of cellulose in SCW.

Selective production of sugars and glycoaldehyde from

sugar beet pulp (SBP) by supercritical water hydrolysis

SBP hydrolysis in SCW was carried out at 390ºC and 25MPa with

reaction times between 0.11 and 1 s. Maximum recovery for

cellulose and hemicellulose fractions was achieved at 0.15 s,

completely recovering cellulose as C-6 sugars and 70% of

hemicellulose recovered as C-5 sugars. Lignin was recovered as

solid residue.

Sugars yield was enhanced at low reaction times (up to a

maximum) and then increasing the reaction time other interesting

products as glycoaldehyde were yielded. Glycoaldehyde was used

for ethylene glycol production through hydrogenation (Alberto

Romero`s work).

CHAPTER 1

CHAPTER 2 CHAPTER 3

Acidity and alkalinity effects on bio-oil production by

hydrothermal liquefaction (HTL) of dairy manure and food

waste

CELLULOSE

HYDROLYSIS

BIOMASS

CHARACT.

SBP SCW

HYDROLYSIS

LAB PLANT

DESIGN

PILOT PLANT

STAY

ABROAD:

CORNELL

SBP SCW

HYDROLYSIS

PILOT PLANT

CHAPTER 1: PUBLISHED CHAPTER 2: WRITING CHAPTER 3: WRITING CHAPTER 4 CHAPTER 5 CHAPTER 6

BIO-OIL

UPGRADING

PATACA SCW

HYDROLYSIS

PILOT PLANT

14/15 15/16 16/17

BUILDING AND

STARTING UP

PILOT PLANT

SCW hydrolysis

Reaction

time

Cellulose

concentration

Effect

over

kinetics

Effect over

selectivity

Ru

MCM-48

Oligosaccharides

C-6 sugars

C-5 sugars

Glycoaldehyde

Ethyleneglycol

Hexitols

HTL of wet biomass was carried out at 300ºC for 1h in a batch

reactor located at Cornell University (USA). Natural, alkaline and

acidic conditions were tested in order to study pH effect on bio-oil

production.

It was found that acid addition improved the oil yield (up to 59% for

manure and 44% for food waste). On the other hand, alkaline

addition seemed to enhance the gas production and therefore

reducing the oil yield.

This bio-oil is going to be shipped to Valladolid to upgrade it through

a hydrogenation step (chapter 5).

HTL

PROCESS

GAS

OIL

AQUEOUS

SOLID

Ru

MCM-48

CHAPTER 5

Finishing writing Chapter 2 and 3.

Improvements in the pilot plant (heating and pumping systems, starting up automatic valve).

To accomplish with the rest of objectives of FASTSUGARS project:

Collaborating with Gianluca Gallina, the extraction of hemicelluloses as a pretreatment for the biomass before SCW hydrolysis will be studied (OBJECTIVE 2).

SCW hydrolysis of both sugar beet pulp and “pataca”, studying different parameters as particle size and inlet concentration (OBJECTIVE 3, Chapter 4 and 6).

Collaborating with Alberto Romero, the upgrading of the bio-oil from Cornell will be carried out via catalyzed hydrogenation (Chapter 5).