Prof. Rafael Luque - UESTuest.ntua.gr/iwwatv/proceedings/presentations/21... · Mechanochemistry (milling) Transformations of platform molecules Biomass valorisation Biofuels production

Possibilities for Waste valorisation: the

concept of modular biorefineries

Prof. Rafael Luque

DEPARTAMENTO DE QUÍMICA ORGÁNICA,

UNIVERSIDAD DE CÓRDOBA

http://www.uco.es/~q62alsor/

Produce Use Dispose

ITS ALWAYS THE SAME THING………

Produce Use Dispose

Reduce

Re-use

Recycle

Something wrong with this?

What do we do?

Heterogeneous catalysis

(acid-base, redox, C-C y

C-heteroatom couplings)

Microwave assisted

catalysis

Flow Chemistry

Supramolecular gels

Nanomaterials

Supported nanoparticles

Microwave nanocatalysis

Mechanochemistry (milling)

Transformations of

platform molecules

Biomass valorisation

Biofuels production

Waste valorisation

(biorefineries)

Group leader: Alina M. Balu

Group Leader:

Weiyi Ouyang

Group Leader:

Sudipta De

Feedstock(s)

biological raw materials

Environmentally benign

Processing Technologies

Food, chemical products and

energy

• Food and feed grain

• Ligno-cellulosic biomass

• Waste

• Green Chemical Processes

• Bio-processes

• Thermal processes

• Physical processes

Integrated facilities that can convert a variety of bio-feedstocks into energy,

chemicals and other valuable materials cleanly and efficiently maximising

the value of the biomass and minimizing waste

BIOREFINERIES

WASTE TO WEALTH: FROM RESIDUES TO MARKETABLE PRODUCTS

Paint additives Biodegradable plastics

Personal care products

Coatings and unguents Other derivatives (chemicals, fuels, etc.)

Green technologies (e.g. microwaves, extraction, fractionation)

http://www.cbme.ust.hk/rafaluque.html

http://images.google.co.uk/imgres?imgurl=www.ethnicbeauty.co.uk/living_nature/images/wavelips.jpg&imgrefurl=http://www.ethnicbeauty.co.uk/living_nature/ls9.htm&h=375&w=375&sz=11&tbnid=f-yhb_OVHUwJ:&tbnh=118&tbnw=118&prev=/images?q=carnauba&start=40&hl=en&lr=&ie=UTF-8&oe=UTF-8&sa=N

Biorefinery: The big picture

HEMICELLULOSE

LIGNIN CELLULOSE

MINOR CONSTITUENTS

Knowing chemical composition is the

key to success!!!

Lignocellulosics

ChemSocRev 2011

Green Chem 2014

ChemSocRev 2014

FUELS

CHEMICALS

Wheat

BioreactionDownstream processing Succinic

acid

Derivatives

Upstream processing

Succinic acid as a C4 building block

HO

OH

H2N

NH2

O

O

H2N

NH2

NC

CN

O

O

O

O

H3C

CH3

O

OO

NO

H

NO

CH3

HO

OH

O

O Succinic acid

Tetrahydrofuran (THF)

2-Pyrrolidone

N-Methyl-2-Pyrrolidone

(NMP)

Succinonitrile

1,4-Diaminobutane

Succindiamide

1,4-Butanediol

(BDO)γ-Butyrolactone

(GBL)

Dimethyl succinate

(DBE)

4,4-Bionolle

(polyester)

Applications: solvents, adhesives, printing inks, magnetic tapes, coating resins, plasticizer/emulsifier,

de-icing compounds, herbicide ingredient, chemical and pharmaceutical intermediates

properties

applications

Ability to functionalise

i.e. acid, basic, metallic

Different forms including

particles & monoliths

Range of composites

High to low conductivity

Fuel cells

adsorbency

catalysis

Water purification

chromatography

Higher temperature materials stable

to hot water & organic solvents

High mesoporosity, surface areas

and surface energies

From Starch to Starbon®

With the mighty team

at York (UK)

Extraction of Phytosterols

(cholesterol-reducing agents)

Biores. Technol. 2012, Carb. Polym. 2013; Green Chem 2013; JMaterChem B 2014; Nature Commun. 20155

BIOMASS VALORISATION (II)… with

INCAR (Oviedo) MIP concept

RSC Adv. 2014

Gracillaria gracilis

Table 1. Biochemical composition (% d.w.) of Gracilaria

gracilis sampled in the Lesina lagoon (Italy).

Total Lipids 1.98

Fatty Acids Methyl Esters 0.47

Proteins 30.93

Carbohydrates 27.54

Ashes 27.89

(EES 2012)

http://www.cbme.ust.hk/rafaluque.html

http://www.uco.es/~q62alsor/

Green Chem. 2011, 13, 3162

FOOD WASTE VALORISATION (I)… with Rick

Arancon (Ateneo Uni)

2 FOOD WASTE RESIDUES:

CORNCOBS, WASTE BREAD, OTHERS

+

WASTE COOKING OILS

2 VALUABLE PRODUCTS:

CARBONACEOUS MATERIAL (CATALYST)

+

BIODIESEL

Gasification

residue

J. Natural Gas Chem.

2012, 21, 246

http://www.uco.es/~q62alsor/

Materials 2013, 6, 1599

Materials 2013, 6, 4641

FOOD WASTE VALORISATION (II)… with

Jaume Cot (IQAC)

FROM SLAUGHTER WASTE TO BIO-HEALING NATURAL POLYMERS (BIO-COLLAGEN)

TREATMENT OF WOUND HEALING IN RATS

Green Chem. 2012, 14, 308

PCT Patent 2013

http://www.uco.es/~q62alsor/

Porous materials

FOOD WASTE VALORISATION (III):

Microwave-assisted

extraction:

-simple

-rapid (5-10 min)

-efficient

Unique form of

mesoporous

cellulose

ChemSusChem, 2012; Energy Env. Sci. 2013

ChemSusChem 2013

Green Chem. 2013

Conclusions

Biomaterials Speciality chemicals

CHEMICAL INDUSTRIAL

PRODUCTS

MATERIALS, CHEMICALS &

FUELS

Biopolymers

Platform molecules

BIOMASS &

WASTE

Commodity chemicals

T. U. Gerngross, Nature Biotechnology, 17, (1999), 541 - 544

Some food for thought….

• The synthesis of 1 kg of

polystyrene requires a total of 2.26

kg of fossil oil (1 kg to generate

electricity and 1.26 kg to serve as

feedstocks for polymer production).

• The production of 1 kg of PHAs

requires 2.39 kg of fossil resources.

Simply deriving chemical

products from renewable

resources is NOT ENOUGH!

Real environmental benefit?

Biodegradability?

Toxicity?

SAFETY!!!

Many thanks for your attention!!