5.

Renewable feedstock's and

energy resources

Química verda
Curs 2023-2024
5. Renewable feedstock's and energy resources

5.1. Introduction
5.1.1. Fossil fuels
5.1.2. Biomass as a renewable resource

5.2. Energy renewable sources

5.2.1. Energy from biomass
Bioethanol
Biodiesel
5.2.2. Fuel cells
5.2.3. Other energy resources
Solar energy
Eolic energy
Hydraulic energy

5.3. Renewable feedstock's

5.1. Introduction
5.1.1. Fossil fuels
During the last 80 years fossil fuels and natural gas have been the source of energy and chemicals
This is not sustainable at least for two reasons:
- Oil reserves are consumed at a higher rhythm than their regeneration and will be eventually
exhausted (energy and feedstock’s). No clear when they will be finished since the existing
resources are not know.
- Fossil fuels cause an increase in CO2 concentration (greenhouse effect).

Currently, fossils fuels provide 40% of the

required energy for the planet and are the main
source of chemicals.
90% are used for energy while 8% are used
for chemicals.
Therefore, from an energetic and feedstock’s
point of view it is necessary to change the
current status (based in oil) for a new one based
in renewable resources.
5.1. Introduction
5.1.2. Biomass as a renewable resource
Any living organism can be considered biomass but usually the term refers to non animal resources
such as trees and plants
Biomass originates from CO2 and water by means of photosynthesis. Once consumed, it returns to
atmosphere as CO2 and water, via biodegradation. Thus, biomass consumption can be
considered as a neutral process from the point of view of CO2 generation. (CO2 neutrality).
Biomass is an alternative to fossil fuels. Despite biomass amount is small, it regenerates easily on
human lifetime (renewable resource).
James R. Stoppert: “the chemical industry is based on carbon and it does not matter if the carbon was fixed 2
million years ago or 6 months ago”

CO2 H2 O

energy
Feedstock’s Photosynthesis

biomass
5.1. Introduction
5.1.2. Biomass as a renewable resource
It is estimated that the amount of biomass produced in the EEUU suffices to produce all the
necessary chemicals. Besides, an important amount of the fuels required for transportation can be
produced:
For example, 1 ton of wheat Straw produces 600 kg de carbohydrates and 200 kg of lignin.
Carbohydrates can be converted via fermentation in 180 kg ethanol, that can then be burnt to
generate energy
average world
raw materials market price (€/kg)
crude oil 0.175
coal 0.035
corn 0.080
wheat straw 0.020
sugar 0.180
ethanol 0.400
ethylene 0.400

Currently, there is a transition era and some products are already produced from biomass ( for
example, lactic acid is produced from starch from corn). However, a sustainable process will only be
possible if it is based in the residues from plants (lignocellulose). Competition with agriculture for
food production and agriculture needs to be avoided.
5.2. Renewable energy resources
5.2.1. Energy from biomass
Most of biomass used to produce energy is burnt (production of heat and electricity).
But there are other processes that permit to obtain energy (direct or indirect) from biomass
5.2. Renewable energy resources
5.2.1. Energy from biomass
Bioethanol
Ethanol can be produced by fermentation of carbohydrates. Usually from sugar cane (Brazil) or el
corn (US) as a source of carbohydrates, in combination with the yeast Saccharomyces.
Less tan 10% of the world production of ethanol is made by chemical synthesis

The maximum concentration of ethanol during fermentation is 12-20% and can be recovered by a
distillation (important consumption of energy)
5.2. Renewable energy resources
5.2.1. Energy from biomass
Bioethanol
From a “green chemistry” perspective, the optimum solution will be the use of plant residues
(lignocellulose, 1011 tons/year) to produce ethanol since there will be no competition with food
agriculture.
Lignocellulose has a complex structure (35-50% cellulose, 20-35% hemicellulose, 20-25% lignin)
and is resistant to enzymatic hydrolysis (pentoses are resistant to yeast Saccharomyces).
Because of that, before starting the fermentation, a digestion of the hemicellulose is required in
order to make it susceptible to hydrolysis. However, these processes are still not well resolved, which
limits the use of hemicellulose

Uses
Bioethanol is basically used as fuel for transportation
Since ethanol has an energetic content approx. 33% inferior than gasoline, it is normally used as
additive to gasoline. The use of bioethanol has some advantages:
- Reduce the use of fossil fuels
- reduces CO2 emissions of traffic
- Improves the quality of the gases in the exhaust tubes
5.2. Renewable energy resources
5.2.1. Energy from biomass
Biodiesel
Biodiesel originate from fatty acids of vegetable oils. Advantages:
- Since it originates from plants, it is neutral from a CO2 emission perspective
- easily biodegradable
- Reduction in CO, SOx and particles emissions
The main component of vegetal oils are triglycerides. These compounds can not be directly used
because they have an elevate viscosity.
Biodiesel is prepared by transesterification of triglycerides with methanol:
- process catalyzed by simple bases as NaOH and KOH (oils free from water and free fatty acids)
- process catalyzed by immobilized Lypases (Novozyme 435) and scCO2 as solvent

Renovable feedstock’s
biodiesel
5.2. Renewable energy resources
5.2.2. Fuel cells
A “fuel cell” is an electrochemical system that permits to convert H2 and O2 in electricity and water
(only byproduct)

Advantages of fuel cells to produce energy:

- Highly efficient systems
- Minimum pollution (water as the only
byproduct)
- H2, fuel of the fuel cells, can be obtained
from renewable resources

Problems of the use of H2 as a fuel:

- Low energetic content per volume unit. H2
liquid is difficult to liquefy and to transport
safely
5.2. Renewable energy resources
5.2.2. Fuel cells
H2 is not a natural resource and must be produced:
- From methanol or methane: reaction at high temp with a catalyst (usually Ni) producing CO
and H2. Since CO is very toxic, it is reacted at high temps (400ºC) with an iron catalyst to
produce more H2 and CO2.

- From biomass: some biomass processes (pyrolysis, gasification) produce H2 or methane.

Nocera’s artificial leaf

- water-splitting: this process corresponds to the breakage

of water in O2 and H2. This methodology will be a very
secure way of store and produce energy (from water).

http://www.nature.com/news/2011/110929/full/news.2011.564.html
5.2. Renewable energy resources
5.2.3. Other sources
Solar energy
Energy can be used in two manners:
- As a heat source: to heat water, for example.
Domestic use.
- To convert it in electricity: photovoltaic
energy. Photovoltaic panels are contain
semiconductor materials based in Si.

Eolic energies Energy consumption in Spain in 2015

Using aero generators, electricity can be Source of energy consumption (%)
produced from wind. 20015
Problems: environmental impact, noises, birds... Oil 42.3
Natural gas 19.9
Hydraulic energies nuclear 12.1
carbon 11.6
Energy from falling of water from a high to a
biomass and residues 7.4
low level (potential energy).Potential energy is
eolic, solar 7.5
used to move turbines that generate electricity. Hydraulic 2.4
5.2. Renewable energy resources

January 2014 (Spain)

5. Feedstock’s and renewable energy resources

5.1. Introduction

5.2. Renewable energy resources

5.3. Renewable feedstock’s

5.3.1. Products from fermentation of glucose
Lactic acid
1,3-Propandiol
3-hydroxypropanoic acid
aromatic -amino acid
Other products
5.3.2. Chemical transformations of carbohydrates
5.3.3. Fatty acids
5.3.4. Terpenes
5.3.5. Polymers from renewable feedstock’s
5.3. Renewable Feedstock’s
Biomass is the only renewable feedstock (only alternative to oil).

5.3.1. Products derived from glucose fermentation

Fermentation of glucose is known for long for obtaining different products:
- Primary metabolites : acetone
- Chemicals that are more efficiently produced by fermentation tan by chemical means: citric acid,
L-glutamic acid, L-proline
- Complex chemicals that can not be prepared by chemical means: β-lactam antibiotics, vitamin B12
In order for a biological process to compete with a chemical process it must have a minimum “space-
time yield” (STY) of 100 g·L-1·d-1. Usually, fermentation processes are less productive (regulation,
toxicity)
→ improvement of the strain (increase of yield, product concentration and STY)

There are different methods to improve the efficiency of an strain:

- Classical methodologies
- genome shuffling
- Metabolic engineering
5.3. Renewable Feedstock’s
5.3.1. Products derived from glucose fermentation
- Classical methodology: random mutations under different conditions and selections of the
mutant with the desired properties. Natural sequence of mutations is accelerated with mutagenic
chemical agents or UV- radiation.
- Genome shuffling: amplification of the genetic diversity of a population via genetic
recombination. Then selection of mutants with the desired properties.
- Metabolic engineering: rational approach targeting specific genes or enzymes. This methodology
implies reprograming the metabolic chain from DNA recombination, and knowledge of the
genome. The objective is to optimize the biosynthesis of a given product. There are three basic
strategies:
- Eliminate the determining steps of the route: eliminating the regulation or amplifying the
gens that code the enzymes that determine the reaction.
- To direct the metabolic route favoring the transformation of an intermediate towards the
desired product via overexpression of the enzyme that favors this specific metabolic path.
- Reprograming the metabolism, if necessary, to provide the red-ox equivalents and the
required energy (ATP).
- Modulating the enzymes of the biosynthetic path in order to avoid intermediates
accumulation.
Problems in biosynthesis of chemicals: High operational costs and high cost of the separation and
purification of the product.
5.3. Renewable Feedstock’s
5.3.1. Products derived from glucose fermentation
Lactic acid
Lactic acid constitutes and interesting intermediate for different processes and the monomer for the
synthesis of the polymer polylactic acid (PLA). PLA presents interesting properties that can make it a
suitable substitute for polyethylene (PE).
Lactic acid can be produced from fermentation of corn starch

Synthesis of polylactic acid (PLA)

5.3. Renewable Feedstock’s
5.3.1. Products derived from glucose fermentation
1,3-propandiol
1,3-propandiol (1,3PD) is used in the synthesis of poly(trimethylene terephthalate) (PTT) as a PET
substitute.

Synthesis of PTT
5.3. Renewable Feedstock’s
5.3.1. Products derived from glucose fermentation
3-hydroxypropanoic acid
3-hydroxypropanoic (3HPA) is currently not produced industrially but it may be an entry in the
production of C3 compounds such as acrylic acid or malonic acid.

3HPA as platform for proparation of diverse

products
5.3. Renewable Feedstock’s
5.3.1. Products derived from glucose fermentation
Aromatic -amino acids
L-Phenylalanine (L-Phe) is used in the production sweetener aspartame.
L-Tryptophan (L-Trp) is used as food additive and medical applications
5.3. Renewable feedstock’s
5.3.1. Products derived from glucose fermentation
Other products
5.3. Renewable feedstock’s
5.3.2. Chemical transformations of carbohydrates
L-ascorbic acid (vitamin C)

L-ascorbic acid is produced in 80

kt/year. It is used in food
supplements, in pharma
synthesis, in cosmetics as
antioxidant and also as additive
for animal food.
L-ascorbic is industrially
produced from glucose.

Actually there’s a search for

greener alternatives for its
production, such as
multienzymatic systems in vitro or
by biotechnological design of a
novel fermentation process.
5.3. Renewable feedstock’s
5.3.2. Chemical transformations of carbohydrates
Building blocks C3 and C4 derived from carbohydrates
The optimum size for using chiral “building blocks” are chains of 3 or 4 carbon atoms. So, its necessary to
find efficient methods for breaking up carbohydrates in order to obtain such synthons.
A suitable candidate for preparing chiral “building block” C3 is D-mannitol (obtained from hydrogenation
of fructose). The cleavage of D-mannitol gives an entry to (R)-D-glycerolic acid.
The opposite enantiomer can be obtained from L-ascorbic acid.
5.3. Renewable feedstock’s
5.3.2. Chemical transformations of carbohydrates
5-hydroxymethylfurfural and levulinic acid
Both 5-hidroximetilfurfural (HMF) and levulinic acid (LA) can be obtained from fructose.

FDA is specially interesting in the synthesis of polymers to replace terephthalic acid.

LA is a precursor in the synthesis of diverse products such as polymers, plastics, pharmaceutical
products. Moreover, is a precursor in the synthesis of other interesting chemicals.
5.3. Renewable feedstock’s
5.3.3. Fatty acids

seed crushing and separation

oil

high temperature hydrolysis

distillation glycerol

crude acid mix

crystallization
solvent extraction
supercritical extraction

fractional distillation

Fatty acids can be modified by reactions in the carboxylic acid (COOH) or in the alkene (C=C)
moiety.
5.3. Renewable feedstock’s
5.3.3. Fatty acids
Erucic acid

Ricinoleic acid
5.3. Renewable feedstock’s
5.3.4. Terpenes
A large variety can be obtained from biomass and are interesting building blocks for “fine chemistry”. For
example they are interesting compounds to prepare fragrances and aromas and in the synthesis of vitamins
A and E.

Catalytic transformation of terpenes includes different reactions: hydrogenation, dehydrogenation,

oxidation, hydroformylation, carbonylation, hydration, isomerization, reorganization, cyclization.
5.3. Renewable feedstock’s
5.3.5. Polymers from renewable feedstock’s
Polylactic acid (PLA)
Polystyrene substitute (PE).

Polyhydroxyalkanoates (PHA)
From fermentation of glucose in presence of propanoic acid.
Polymers with properties similar to polyethylene (PE) and polypropylene (PP) are obtained.
PHA was used in the first biodegradable credit card(1998, Greenpeace).

Polycarbonates