Agave Residues as a Potential Lignocellulosic feedstock for Biofuels and Animal feed.

A Review.
Carlos Alberto Flores-Gomez, Leonardo da Costa Sousa, Andrea Orjuela, Eleazar Escamilla, Bruce
Dale, Venkatesh Balan.

ABSTRACT
Agave residues are regionally-important agroindustrial residues in Mexico and can become potential
feedstocks for sustainable liquid biofuel production. Spirit Beverages, nutraceuticals and sweeteners
industries generates tons of these residues in both factories and land (crop residues). The use of this
residues is important to avoid potential negative environmental impacts, and also to promote rural
economic development. Furthermore, the interest in Agave plant is getting attention in the recent days
because its crassulacean acid metabolism (CAM) are able to adapt to grow under drought conditions
since it can fix CO2 at night reducing evapotranspiration. Utilization of this lignocellulosic biomass for
biofuels requires an effective pretreatment to deconstruct the lignin-carbohydrate complex network and
yield fermentable sugars. Low severity pretreatments are required to obtain digestible and fermentable
material, prevent loss of available sugars, and avoid the formation of inhibitory byproducts that affect
subsequent hydrolysis and fermentation steps. AFEX pretreatment are a prospective dry-technology
suitable for exploit this low lignin biomass in the production of biofuels, animal feed and chemicals.

INTRODUCTION
The worlds continued dependence on fossil fuels as an energy source causes that greenhouse gas
levels are steadily increasing in the atmosphere and warming the Earth. The transport sector is the
second energy related CO2 emitter with 23% of the global emissions, behind of the power sector (42%).
(Leal, Horta Nogueira et al. 2013), (Casper 2010).
Lignocellulosic biofuelsliquid fuels made from inedible parts of plants called Second generation
biofuels (2ndGenB) offer the most environmentally attractive and technologically feasible near-term
alternative to fossil fuels. Lignocellulosic materials (also called biomass) is the most abundant
renewable resource on Earth, and it constitutes a large component of the residues/wastes originating
from municipal, agricultural, forestry, and some industrial sources. The use of biomass for biofuels
production would minimize the conflict between land use for food / feed production and energy
feedstock production. This raw material is less expensive than conventional agricultural feedstock and
can be produced with lower input of fertilizers, pesticides, and energy. 2 ndGenB can be made from
several sources as wood residues (i.e. sawdust and construction debris), agricultural residues (corn
stover, wheat or rice straw, sugarcane bagasse) or energy crops woody and non woody materials that
are grown expressly to serve as feedstocks (fast growing grasses, poplar, willow coppice) that can grow
on marginal lands that would not otherwise be used as farmland. Besides, energy-crops could are able
to decontaminate soil that has been polluted with wastewater or heavy metals as it grows (Huber and
Dale 2009), (Soccol, Faraco et al. 2011).
Eff orts are underway to transform the petroleum-based economy to a bio-based economy.1,2 As the
name implies, a bio-based economy is focused on deriving fuels and chemicals from renewable plant-,

algal-, or microbial-based materials such as lignocellulosic biomass. T e development of new processes

for fuels and chemicals from lignocellulosic feedstocks represents an extremely important fi eld for R&D
and industrial innovation n within the bioenergy sector today.
In general, major motivations to launch second-generation technologies into full-scale commercial
applications will increase the sustainability of biofuel production (compared to first-generation biofuels
that are produced from food-grade materials).
The growing interest in biofuels from lignocellulosic feedstock in the United States (US) and the
European Union (EU) can provide a path forward toward replacing petroleum-based fuels with
sustainable biofuels which have the potential to lower greenhouse gas (GHG) emissions.
(Balan, Chiaramonti et al. 2013).
Agricultural crop residues include field residues and processing residues. They are renewable and
abundant resources. Field residues represent materials left in an agricultural field after harvesting the
crop, and they include straw and stalks, leaves, and seed pods. Processing residues, such as husks,
seeds, bagasse and roots, are those materials left by factories after processing of the crop. In addition
to the crops cultivated globally, some crops have local importance. And, they can be very significant for
the region economy and a substantial source of biomass for biofuel. A major concern in the utilization of
crop residues is the residue collection methodology and efficiency. (Hadar 2013).

In Mexico, agave crop spices has a great importance in the economy; it is cultivated from the north of
the country from Bacanora region in Sonora State, to the south in Yucatan state as fiber source
(henequen). Including the 2 major agroindustrial aplications for agave, Tequila and Mezcal. Tequila,
Mezcal and Bacanora, are spirit beberages with export to the world, and each one has its own
protected Designation of Origin (DO) region(protected geographical indication). Figure 1.
**************************
Table__ Agave Taxonomic relations within the Angiosperms.
Class
Subclass
Order
Family
Angiospermae
Monocotyledonea
Liliales
Agavaceae
e
Adapted from (Nobel 2003)
***************************************************

Subfamily
Agavoideae

Figure 1. Mexicos Protected Designation of Origin (DO) regions for Agave Spirit Beverages.
The Tequila beverage made from Agave tequilana, is the main intensive agriculture, exporting 152 ML
of tequila. In 2008 there were a peak in a national production with 312.1 ML (40 % Alcohol Vol.).
Jalisco state has the high density for both, agave farmers and tequila factories, with more of the 90 %
of the total production. Oaxaca is the state with a large acreage for agave mapisaga for mexcal
production. Due, The potential for the agave residues is high, in the other states for the DO authorized.
The supply chain of Agave Tequila has 17,500 agave farmers, and more than 152 companies in the
DOO. In 2009 there were 76.6 MHa with more than 2.41 million of plants.
Additional to this activities, there are small-size producers of other spices of agave, called Maguey
Pulquero. This farmersare in central Mexico (states of Hidalgo, Tlaxcala, Estado de Mxico and
Puebla), that produce Aguamiel1 and Pulque2. In recent years,some small producers, are producing a
natural syrup (sweetener) called Maguey Honey, that is a healthy option from Aguamiel concentrated.
With a major economy benefits for this rural regions.
In the same option, recently are increasing well-technified Inulin powder producers, a nutraceutic
complement from the juice of pia or agave heart (stem), mainly from Agave tequilana spices. And
Agave-Syrup industrial producers, that is a concentrated hydrolyzed stem-extracted agave tequilana
juice (>95 % fructose).
Other Mexicos States like Morelos and Veracruz, is having important attention to agave activities.
All of this activities produce agroindustrial residues, agave leaves a crop residue and agave bagasse,
that is an industrial residue from the fibrous stem after cooking, shredding and extracting the juice.
1 Aguamiel is Honey Water that is collected after cut the flowering stalk from Maguey
( Agavesalmiana, atrovirenz, etc.)
2Pulque, is an alcoholic beverage from Aguamiel fermentation. It has economic
importance until mid last century.

Agave bagasse is the residual fiber remaining after cooked agave heads are shredded, milled and the
sugars water-extracted. Iiguez-Covarrubias, Lange et al. (2001). Agave tequilana is an economically
important CAM species cultivated in Mexico and is the only one of the species of Agavaceae that is
appropriate for the production of tequila.
The leaves of the agave plant are left in the field after harvesting the heads for tequila production.
The commercially important part of A. tequilana for tequila production is the stem, commonly termed
head or pia because it resembles a pineapple fruit. Leaves are cut off near their bases. They are
harvested 6-9 years after planting but before the inflorescence is produced by this monocarpic
perennial.
Agave tequilana is cultivated only in very restricted regions established as protected territories by the
tequila denomination of origin. These territories include Jalisco state and some municipalities in the
states of Nayarit (8 municipalities), Guanajuato (6 municipalities), Michoacn (29 municipalities) and
Tamaulipas (12 municipalities). The major land surface where A. tequilana is cultivated is in the Jalisco
state covering more than 482 millions m2, where produces about 90% of the total tequila production,
concentrated in the regions of Amatitn, Arandas, Atotonilco, El Arenal, Tepatitln and Tequila.
54% of the wet agave plant represents the agave head, which is the raw material for tequila production.
The rest of the wet plant or 46% is left in the fields and is not utilized.
Iiguez 2 2001Iiguez-Covarrubias, Daz-Teres et al. (2001), Iiguez-Covarrubias, Lange et al. (2001)
Agroindustrial residues as a Lignocellulosicfeedstocks(Petrova and Ivanova 2010, Quintero, Rincon et
al. 2011)Amarasekara(Amarasekara 2013) To avoid conflicts between human food use and industrial
use of crops, only the wasted crop, could be is considered as feedstock.
Rice straw, wheat straw, corn stover, and sugarcane bagasse are the major agricultural wastes in terms
of quantity of biomass availability (Kim and Dale 2004). Kim and Dale (2004) estimated that there are
73.9 Tg of dry wasted crops in the world that could potentially produce 49.1 GL year-1 of bioethanol.
About 1.5 Pg ton year-1 of dry lignocellulosic biomass from seven crops is also available for conversion
to bioethanol. The total potential bioethanol production from crop residues and wasted crops is 491 GL
year-1 (Kim and Dale 2004). (Kim and Dale 2004)
In other hand in the arid and semi-arid areas, there are a potential to grow some Agave spices as a
Energy Crop. Agave as an Energy Crop is receiving increased attention in the world (Davis, Dohleman
et al. 2011, Holtum, Chambers et al. 2011, Escamilla-Trevino 2012) , as CAM plant (crassulacean acid
metabolism), they are adapted to grow under conditions of low water availability in arid and semiarid
lands and they can fix CO2 at night by CAM pathway to reduce evapotranspiration, and have a higher
Water Use Efficiency (WUE) measured as the amount of CO2 fixed by photosynthesis relative to the
amount of water lost through transpiration (Nobel 1991, Garcia-Moya, Romero-Manzanares et al.
2011). In arid conditions, the greater WUE of CAM species results in theoretical biomass yield
potentials that are 147% greater than C4 species. (Davis, LeBauer et al. 2014). Moreover, many CAM
plants have other attractive qualities for biofuel production such as a relatively low lignin content and
high amount of soluble carbohydrates. (Bartlett, Vico et al. 2014)
GARCIA-MOYA (Garcia-Moya, Romero-Manzanares et al. 2011)

A. salmiana and A. mapisaga can have high nocturnal net CO2 uptake rates and high productivities
averaging 40 tonnes (dry weight) /hayr
E . GARCIA-MOYA*, A. ROMERO-MANZANARES* and P. S .NO B E L. GCB Bioenergy (2011) 3, 4
14, Highlights for Agave Productivity.

From: Escamilla-Trevio(Escamilla-Trevino 2012). Bioenerg. Res. (2012) 5:19

Achievable productivities of certain CAM plants: basis for high values compared with C3 and C4 plants

The annual aboveground dry-weight productivity was 42 Mg ha-1year-1 for agave salmiana
near to Mexico city. An even higher productivity would be expected under irrigation.
Nevertheless, this productivities exceed those reports for virtually all natural ecosystems
crops, and trees. Nobel PS, Valenzuela AG (1987

Reference (36) Nobel PS, Garcia Moya E, Quero E (1992) High annual productivity of
certain agaves and cacti under cultivation. Plant Cell Environ 15:329335

Agave Yields
An agave variety with stems of 150 kg and 27 percent sugar content, grown at a density of 3,000 plants
per hectare and harvested in six years has a potential annual ethanol yield of 7,500 liters per hectare.
This yield is highly superior to those reported for corn and sugarcane. Higher yielding varieties of agave
still can be developed from elite plants seldom found in the plantations. Second-generation ethanol
production from cellulose contained in leaves and the waste pulp of the agave stem will considerably
increase the yield. (Madrigal-Lugo , et al)

Overcoming lignocellulosic biomass recalcitrance followed by enzymatic hydrolysis ofstructural

polymeric carbohydrates (i.e., cost-efficient liberation of fermentable sugars) isperhaps the most
challenging technical and economic barrier to success of biorefineries. (Percival Zhang, Berson et al.
2009).The AFEX pretreatment is more effective on agricultural residues and herbaceous crops, (Harun,
Balan et al. 2013)

Cellulose susceptibility to hydrolysis is restricted due to the rigid lignin and hemicellulose protection
surrounding the cellulose micro fibrils. Therefore, an effective pretreatment is necessary to liberate the
cellulose from the ligninhemicellulose seal andalso reduce cellulosic crystallinity. Some of the
available pretreatment techniques include acid hydrolysis, steam explosion, ammonia fiber expansion
(AFEX), alkaline wet oxidation, and hot water pretreatment. Besides reducing lignocellulosic
recalcitrance, an ideal pretreatment must also minimize formation of degradation products that inhibit
subsequent hydrolysis and fermentation.
AFEX is an important pretreatmenttechnology that utilizes both physical (high temperature and
pressure) and chemical (ammonia)processes to achieve effective pretreatment. Besides increasing the
surface accessibility for hydrolysis,AFEX promotes cellulose decrystallization and partial hemicellulose
depolymerization and reduces thelignin recalcitrance in the treated biomass.(Balan, Bals et al. 2009).

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Advanced biofuels produced from lignocellulosic biomass offer an exciting
opportunity to produce renewable liquid transportation fuels, biochemicals, and
electricity from locally available agriculture and forest residues. The growing
interest in biofuels from lignocellulosic feedstock in the United States (US) and the
European Union (EU) can provide a path forward toward replacing petroleum-based
fuels with sustainable biofuels which have the potential to lower greenhouse gas
(GHG) emissions. The selection of biomass conversion technologies along with
feedstock development plays a crucial role in the commercialization of nextgeneration biofuels. There has been synergy and, even with similar basic process
routes, diversity in the conversion technologies chosen for commercialization in the
EU and the US. The conversion technologies for lignocellulosic biomass to advanced
biofuels can be broadly classified in three major categories: biochemical,
thermochemical, and hybrid conversions. The objective of this review is to discuss
the US and EU biofuel initiatives, feedstock availability, and the state-of-art
conversion technologies that are potentially ready or are already being deployed for
large-scale applications. The review covers and compares the developments in
these areas in the EU and the USA and provides a comprehensive list of the most
relevant ongoing development, demonstration, and commercialization activities in
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traditional crop displacement), impacts on biodiversity and on the environment (soil,
water and air). Today, biofuels use only a little more than 2% of the world arable
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ChapingoAutonomus University. http://ethanolproducer.com/articles/8573/researchers-evaluateagaveundefineds-potential-for-ethanol

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