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{{Short description|Ethanol produced from cellulose}}
'''Cellulosic ethanol''' (also called ceetol) is a
'''Cellulosic ethanol''' is ] (ethyl alcohol) produced from ] (the stringy fiber of a plant) rather than from the plant's ]s or ]. It can be produced from ]es, ], ], or other plants. It is generally discussed for use as a ]. The ] that plants ] offsets some of the carbon dioxide emitted when ethanol made from them is ], so cellulosic ethanol fuel has the potential to have a lower ] than ]s.
] produced from wood, grasses, or the non-edible parts of plants. <ref>http://frwebgate.access.gpo.gov/cgi-bin/getdoc.cgi?dbname=110_cong_bills%26docid=f:h2419enr.txt.pdf</ref>


Interest in cellulosic ethanol is driven by its potential to replace ] or ]. Since these plants are also used for food products, diverting them for ethanol production can cause food prices to rise; cellulose-based sources, on the other hand, generally do not compete with food, since the fibrous parts of plants are mostly inedible to humans. Another potential advantage is the high diversity and abundance of cellulose sources; grasses, trees and algae are found in almost every environment on Earth. Even ] components like paper could conceivably be made into ethanol. The main current disadvantage of cellulosic ethanol is its high cost of production, which is more complex and requires more steps than corn-based or sugarcane-based ethanol.
It is a type of ] produced from ], a structural material that comprises much of the mass of plants. Lignocellulose is composed mainly of ], ] and ]. ], ], ] and ]s are some of the more popular cellulosic materials for ethanol production. Cellulosic ethanol is chemically identical to ] from other sources, such as ] starch or ], but has the advantage that the lignocellulose raw material is highly abundant and diverse. (The word "cellulosic" simply refers to the source material.) However, it differs in that it requires a greater amount of processing to make the sugar monomers available to the microorganisms that are typically used to produce ethanol by fermentation.


Cellulosic ethanol received significant attention in the 2000s and early 2010s. The ] government in particular funded research into its commercialization and set targets for the proportion of cellulosic ethanol added to vehicle fuel. A large number of new companies specializing in cellulosic ethanol, in addition to many existing companies, invested in ]. However, the much cheaper manufacturing of grain-based ethanol, along with the low ] in the 2010s, meant that cellulosic ethanol was not competitive with these established fuels. As a result, most of the new refineries were closed by the mid-2010s and many of the newly founded companies became insolvent. A few still exist, but are mainly used for demonstration or research purposes; as of 2021, none produces cellulosic ethanol at scale.
Switchgrass and Miscanthus are the major biomass materials being studied today, due to high levels of cellulose. Cellulose, however, is contained in nearly every natural, free-growing plant, tree, and bush, in meadows, forests, and fields all over the world without agricultural effort or cost needed to make it grow.


==Overview==
According to U.S. Department of Energy studies<ref> {{Dead link|date=May 2008}}</ref> conducted by the Argonne Laboratories of the University of Chicago, one of the benefits of cellulosic ethanol is that it reduces ] emissions (GHG) by 85% over reformulated gasoline. By contrast, starch ethanol (e.g., from corn), which most frequently uses ] to provide energy for the process, may not reduce GHG emissions at all depending on how the starch-based feedstock is produced.<ref>{{cite journal|url=https://www.environmentcalifornia.org:443/newsletter/fall07/clean-cars-cool-fuels|title=Clean cars, cool fuels|accessdate=2007-11-28|publisher=Environment California|volume=5|issue=2|date=2007}}</ref> A study by Nobel Prize winner ] found ethanol produced from corn, rapeseed (canola), and sugarcane had a "net climate warming" effect when compared to oil.<ref>Crutzen, P.J., A.R. Mosier, K.A. Smith, and W. Winiwarter. “Nitrous oxide release from agro-biofuel production negates global warming reduction by replacing fossil fuels” Atmospheric Chemistry and Physics. Disucss., 7 11191–11205, 2007.</ref>
Cellulosic ethanol is a type of ] produced from ], a structural material that comprises much of the mass of plants and is composed mainly of ], ] and ]. Popular sources of lignocellulose include both agricultural waste products (e.g. ] or ]s) and grasses like ] and '']'' species.<ref>{{cite book | vauthors = Ziolkowska JR | chapter = Biofuels technologies: An overview of feedstocks, processes, and technologies|date=2020 | title = Biofuels for a More Sustainable Future|pages=1–19|publisher=Elsevier|language=en|doi=10.1016/b978-0-12-815581-3.00001-4|isbn=978-0-12-815581-3 | s2cid = 202100623| url = https://repositorio.unal.edu.co/handle/unal/82239}}</ref> These raw materials for ethanol production have the advantage of being abundant and diverse and would not compete with food production, unlike the more commonly used corn and cane sugars.<ref>{{cite web|title=The pros and cons of biofuels - Cellulosic ethanol|url=https://archive.fortune.com/galleries/2008/fortune/0804/gallery.green_biofuels.fortune/4.html|url-status=dead|access-date=2021-05-03|website=Fortune|archive-url=https://web.archive.org/web/20160122002604/http://archive.fortune.com:80/galleries/2008/fortune/0804/gallery.green_biofuels.fortune/4.html |archive-date=2016-01-22 }}</ref> However, they also require more processing to make the sugar monomers available to the microorganisms typically used to produce ethanol by fermentation, which drives up the price of cellulos-derived ethanol.<ref>{{cite web| vauthors = Markings S |date=April 25, 2017|title=The Disadvantages of Cellulose Biofuel|url=https://sciencing.com/disadvantages-cellulose-biofuel-5906.html|url-status=live|access-date=2021-05-03|website=Sciencing|language=en|archive-url=https://web.archive.org/web/20170313061409/http://sciencing.com:80/disadvantages-cellulose-biofuel-5906.html |archive-date=2017-03-13 }}</ref>

Cellulosic ethanol can reduce ] by 85% over reformulated gasoline.<ref>{{cite conference | vauthors = Wang M | conference = The 15th International Symposium on Alcohol Fuels | location = San Diego, CA | date = September 2005 |url=http://www.transportation.anl.gov/pdfs/TA/354.pdf |title=Updated Energy and Greenhouse Gas Emissions Results of Fuel Ethanol<!-- Bot generated title --> |access-date=2013-03-02 |archive-url=https://web.archive.org/web/20130216035905/http://www.transportation.anl.gov/pdfs/TA/354.pdf |archive-date=2013-02-16 |url-status=dead }}</ref> By contrast, starch ethanol (e.g., from corn), which most frequently uses ] to provide energy for the process, may not reduce greenhouse gas emissions at all depending on how the starch-based feedstock is produced.<ref>{{cite journal |url=https://www.environmentcalifornia.org:443/newsletter/fall07/clean-cars-cool-fuels |title=Clean cars, cool fuels |access-date=2007-11-28 |publisher=Environment California |volume=5 |issue=2 |year=2007 |url-status=dead |archive-url=https://web.archive.org/web/20071103010613/http://www.environmentcalifornia.org/newsletter/fall07/clean-cars-cool-fuels |archive-date=2007-11-03 }}</ref> According to the ] in 2011, there is no commercially viable bio-refinery in existence to convert lignocellulosic biomass to fuel.<ref>{{citation | url = http://www.nap.edu/openbook.php?record_id=13105&page=3 | title = Renewable Fuel Standard: Potential Economic and Environmental Effects of U.S. Biofuel Policy | page = 3 of "Summary" | author = National Research Council of the National Academies | year = 2011 | publisher = The National Academies Press | location = Washington, D.C. | isbn = 978-0-309-18751-0| doi = 10.17226/13105 }}</ref> Absence of production of cellulosic ethanol in the quantities required by the regulation was the basis of a ] decision announced January 25, 2013, voiding a requirement imposed on car and truck fuel producers in the United States by the Environmental Protection Agency requiring addition of cellulosic biofuels to their products.<ref name="NYT012513">{{cite news|title=Court Overturns E.P.A.'s Biofuels Mandate|url=https://www.nytimes.com/2013/01/26/business/energy-environment/court-overturns-epas-biofuels-mandate.html|access-date=January 26, 2013|newspaper=The New York Times|date=January 25, 2013| vauthors = Wald ML |quote=wishful thinking rather than realistic estimates}}</ref> These issues, along with many other difficult production challenges, led ] policy researchers to state that "in the short term, ethanol cannot meet the energy security and environmental goals of a gasoline alternative."<ref>{{cite journal |vauthors=Somma D, Lobkowicz H, Deason JP | year = 2010 | title = Growing America's fuel: an analysis of corn and cellulosic ethanol feasibility in the United States | url = http://www.gwu.edu/~eemnews/previousissues/f11_art4_growing%20america.s%20fuel.pdf| journal = Clean Techn Environ Policy | volume = 12 | issue = 4| pages = 373–380 | doi = 10.1007/s10098-009-0234-3 | bibcode = 2010CTEP...12..373S | s2cid = 111303200 }}</ref>


== History == == History ==
The French chemist, ], was the first to discover that cellulose could be hydrolyzed into sugars by treatment with ] in 1819.<ref>{{cite journal | vauthors = Braconnot H | title = Verwandlungen des Holzstoffs mittelst Schwefelsäure in Gummi, Zucker und eine eigne Säure, und mittelst Kali in Ulmin | year = 1819 | journal = Annalen der Physik | volume = 63 | issue = 12 | page = 348 | doi = 10.1002/andp.18190631202 | bibcode = 1819AnP....63..347B | url = https://zenodo.org/record/2325740 }}</ref> The hydrolyzed sugar could then be processed to form ethanol through fermentation. The first commercialized ethanol production began in Germany in 1898, where acid was used to hydrolyze cellulose. In the United States, the Standard Alcohol Company opened the first cellulosic ethanol production plant in South Carolina in 1910. Later, a second plant was opened in Louisiana. However, both plants were closed after World War I due to economic reasons.<ref>{{cite journal| vauthors = Solomon BD, Barnes JR, Halvorsen KE |title=Grain and cellulosic ethanol: History, economics, and energy policy|journal=Biomass and Bioenergy|date=June 2007|volume=31|issue=6|pages=416–425|doi=10.1016/j.biombioe.2007.01.023|bibcode=2007BmBe...31..416S }}</ref>


The first attempt at commercializing a process for ethanol from wood was done in Germany in 1898. It involved the use of dilute acid to hydrolyze the cellulose to glucose, and was able to produce 7.6 liters of ethanol per 100 kg of wood waste (18&nbsp;gal per ton). The Germans soon developed an industrial process optimized for yields of around 50 gallons per ton of biomass. This process soon found its way to the United States, culminating in two commercial plants operating in the southeast during World War I. These plants used what was called "the American Process" — a one-stage dilute sulfuric acid hydrolysis. Though the yields were half that of the original German process (25&nbsp;gallons of ethanol per ton versus 50), the throughput of the American process was much higher. A drop in lumber production forced the plants to close shortly after the end of World War I. In the meantime, a small, but steady amount of research on dilute acid hydrolysis continued at the USDA's Forest Products Laboratory.<ref>Saeman, J.F., "Kinetics of Wood Saccharification: Hydrolysis of Cellulose and Decomposition of Sugars in dilute Acid at High Temperature", ''Industrial and Engineering Chemistry'', 37(1): 43–52 (1945). </ref><ref> Harris, E.E., Beglinger, E., Hajny, G.J., and Sherrard, E.C., "Hydrolysis of Wood: Treatment with Sulfuric Acid in a Stationary Digester", Industrial and Engineering Chemistry, 37(1): 12–23 (1945) </ref><ref>Conner, A.H. and Lorenz, L.F., "Kinetic Modeling of Hardwood Prehydrolysis. Part&nbsp;III. Water and Dilute Acetic Acid Prehydrolysis of Southern Red Oak, Wood and Fiber Science, 18(2): 248–263 (1986).</ref> The first attempt at commercializing a process for ethanol from wood was done in Germany in 1898. It involved the use of dilute acid to hydrolyze the cellulose to glucose, and was able to produce 7.6 liters of ethanol per 100&nbsp;kg of wood waste ({{convert|18|USgal|L|abbr=on}} per ton). The Germans soon developed an industrial process optimized for yields of around {{convert|50|USgal|L}} per ton of biomass. This process soon found its way to the US, culminating in two commercial plants operating in the southeast during World War I. These plants used what was called "the American Process" — a one-stage dilute sulfuric acid hydrolysis. Though the yields were half that of the original German process ({{convert|25|USgal|L}} of ethanol per ton versus 50), the throughput of the American process was much higher. A drop in lumber production forced the plants to close shortly after the end of World War I. In the meantime, a small but steady amount of research on dilute acid hydrolysis continued at the ]'s ].<ref>{{cite journal | vauthors = Saeman JF | year = 1945 | title = Kinetics of wood saccharification: Hydrolysis of cellulose and decomposition of sugars in dilute acid at high temperature | journal = Industrial and Engineering Chemistry | volume = 37 | issue = 1| pages = 43–52 | doi = 10.1021/ie50421a009 }}</ref><ref>{{cite journal | vauthors = Harris EE, Beglinger E, Hajny GJ, Sherrard EC | year = 1945 | title = Hydrolysis of Wood: Treatment with Sulfuric Acid in a stationary digester | journal = Industrial and Engineering Chemistry | volume = 37 | issue = 1| pages = 12–23 | doi = 10.1021/ie50421a005 }}</ref><ref>{{cite journal | vauthors = Conner AH, Lorenz LF | year = 1986 | title = Kinetic modeling of hardwood prehydrolysis. Part&nbsp;III. Water and dilute acetic acid Prehydrolysis of southern red oak | journal = Wood and Fiber Science | volume = 18 | issue = 2 | pages = 248–263 | url = https://www.fpl.fs.fed.us/documnts/pdf1986/conne86a.pdf | access-date = 2021-05-04 | archive-date = 2021-05-04 | archive-url = https://web.archive.org/web/20210504033330/https://www.fpl.fs.fed.us/documnts/pdf1986/conne86a.pdf | url-status = dead }}</ref> During World War II, the US again turned to cellulosic ethanol, this time for conversion to ] to produce synthetic rubber. The Vulcan Copper and Supply Company was contracted to construct and operate a plant to convert sawdust into ethanol. The plant was based on modifications to the original German Scholler process as developed by the Forest Products Laboratory. This plant achieved an ethanol yield of {{convert|50|USgal|L|abbr=on}} per dry ton, but was still not profitable and was closed after the war.<ref>{{cite book | vauthors = Katzen R, Schell DJ | chapter = Lignocellulosic feedstock Biorefinery: History and Plant Development for Biomass Hydrolysis | pages = 129–138 | title = Biorefineries - Industrial processes and Products | volume = 1 | veditors = Kamm B, Gruber PR, Kamm M | publisher = Wiley-VCH | location = Weinheim | date = 2006 | doi = 10.1002/9783527619849.ch6 | isbn = 978-3-527-61984-9 }}</ref>

{{Newsrelease|date=May 2008}}
In April 2004, ], a Canadian biotechnology firm, became the first business to commercially sell cellulosic ethanol, though in very small quantities. The primary consumer thus far has been the Canadian government, which, along with the United States government (particularly the ]'s ]), has invested millions of dollars into assisting the commercialization of cellulosic ethanol.

Another company which appears to be nearing commercialization of cellulosic ethanol is Spain's Abengoa Bioenergy.<ref>{{cite web |url=http://www.abengoabioenergy.com/NewTechnologies/index.cfm?page=3 |title=Starch Conversion to Bioethanol |accessdate=2007-06-17 |publisher=Abengoa Bioenergy}}</ref> Abengoa has and continues to invest heavily in the necessary technology for bringing cellulosic ethanol to market. Using process and pre-treatment technology from ] (multiple class-action lawsuits have been filed by shareholders against SunOpta), Abengoa is building a 5 million gallon cellulosic ethanol facility in Spain and has recently entered into a strategic research and development agreement with , to create a new and better enzyme mixture which may be used to improve both the efficiencies and cost structure of producing cellulosic ethanol.

'''Verenium Corporation''' operates one of the USA’s first cellulosic ethanol pilot plants, an R&D facility, in Jennings, Louisiana and expects to achieve mechanical completion of a 1.4&nbsp;million gallon-per-year, demonstration-scale facility to produce cellulosic ethanol by the end of the first quarter of 2008. In addition, the Company’s process technology has been licensed by Tokyo-based Marubeni Corp. and Tsukishima Kikai Co., LTD and has been incorporated into BioEthanol Japan’s 1.4&nbsp;million liter-per-year cellulosic ethanol plant in Osaka, Japan – the world’s first commercial-scale plant to produce cellulosic ethanol from wood construction waste.

On ], ], announced a with , Canada's largest ethanol producer. The joint venture will build a series of large-scale plants that will make ethanol from wood chips, with ] and GreenField each taking 50% ownership. The first of these plants will be 10 million gallons per year, which appears to be the first true "commercial scale" cellulosic ethanol plant in the world. Under 1&nbsp;million gallons per year (MMgy) is considered "Pilot Scale", greater than 1–10&nbsp;MMgy is defined as "commercial demonstration", while a plant that produces 10&nbsp;MMgy or greater is true "commercial scale". Despite the commercial demonstration cellulosic ethanol plants SunOpta has been involved with, media reports continue to state that cellulosic ethanol is an unproven, "experimental" technology. The 10&nbsp;MMgy SunOpta/GreenField cellulosic ethanol plant is intended to demonstrate that large-scale cellulosic ethanol is commercially viable immediately.

United States President ], in his ] address delivered ], ], proposed to expand the use of cellulosic ethanol. In his State of the Union Address on ], ], President Bush announced a proposed mandate for 35 billion gallons of ethanol by 2017. It is widely recognized that the maximum production of ethanol from corn starch is 15 billion gallons per year, implying a proposed mandate for production of some 20 billion gallons per year of cellulosic ethanol by 2017. Bush's proposed plan includes $2 billion funding (from 2007-2017?) for cellulosic ethanol plants, with an additional $1.6 billion (from 2007-2017?) announced by the USDA on ], ].

In March 2007, the US government awarded $385 million in grants aimed at jumpstarting ethanol production from nontraditional sources like wood chips, switchgrass and citrus peels. Half of the six projects chosen will use thermo-chemical methods and half will use ] methods.<ref>{{cite web |url=http://www.cbsnews.com/stories/2007/03/04/ap/tech/mainD8NLISJ80.shtml |title=Gasification May Be Key to U.S. Ethanol|date=March 4, 2007|accessdate=2007-11-28|author=Dirk Lammers|publisher=CBS News}}</ref>


With the rapid development of enzyme technologies in the last two decades, the acid hydrolysis process has gradually been replaced by enzymatic hydrolysis. Chemical pretreatment of the feedstock is required to hydrolyze (separate) hemicellulose, so it can be more effectively converted into sugars. The dilute acid pretreatment is developed based on the early work on acid hydrolysis of wood at the ]'s ]. In 2009, the ] together with the ] developed a sulfite pretreatment to overcome the recalcitrance of lignocellulose for robust enzymatic hydrolysis of wood cellulose.<ref name=zhu>{{cite journal | vauthors = Zhu JY, Pan XJ, Wang GS, Gleisner R | title = Sulfite pretreatment (SPORL) for robust enzymatic saccharification of spruce and red pine | journal = Bioresource Technology | volume = 100 | issue = 8 | pages = 2411–8 | date = April 2009 | pmid = 19119005 | doi = 10.1016/j.biortech.2008.10.057 | bibcode = 2009BiTec.100.2411Z }}</ref>
The American company Range Fuels announced in July 2007 that it was awarded a construction permit from the state of Georgia to build the first commercial-scale 100-million-gallon-per-year cellulosic ethanol plant in the United States.<ref>{{cite web |url=http://www.rangefuels.com/Range-Fuels-awarded-permit-to-construct-the-nations-first-commercial-cellulosic-ethanol-plant| title=Range Fuels awarded permit to construct the nation’s first commercial cellulosic ethanol plant |publisher=Range Fuels|accessdate=2007-11-28|date=July 2, 2007}}
</ref> Construction began in November, 2007.<ref>{{cite web|url=http://www.npr.org/templates/story/story.php?storyId=16019184|title=Georgia Plant Is First for Making Ethanol from Waste|accessdate=2007-11-28|date=November 5, 2007|publisher=NPR|author=Kathleen Schalch}}</ref>


In his 2007 ] on January 23, 2007, US President ] announced a proposed mandate for {{convert|35|e9USgal|e9litre}} of ethanol by 2017. Later that year, the ] awarded $385 million in grants aimed at jump-starting ethanol production from nontraditional sources like wood chips, switchgrass, and citrus peels.<ref>{{cite news |url=http://www.cbsnews.com/stories/2007/03/04/ap/tech/mainD8NLISJ80.shtml |title=Gasification may be key to U.S. Ethanol |date=2007-03-04
In April 2008, George Huber of the University of Massachusetts Amherst received a $400,000 CAREER grant from the National Science Foundation to pursue his revolutionary new method for making biofuels, or "green gasoline," (Energy Daily 2008). The U.S. could potentially produce 1.3&nbsp;billion dry tons of cellulosic biomass per year, which has the energy content of four billion barrels of crude oil. This translates to 65% of American oil consumption.<ref name="energy-daily"/>
|access-date=2007-11-28 | vauthors = Lammers D |work=CBS News |archive-url = https://web.archive.org/web/20071122145559/http://www.cbsnews.com/stories/2007/03/04/ap/tech/mainD8NLISJ80.shtml <!-- Bot retrieved archive --> |archive-date = 2007-11-22}}</ref>


== Production methods == == Production methods ==
] for ] research.]]
There are two ways of producing alcohol from ]:
* Cellulolysis processes which consist of ] on pretreated lignocellulosic materials followed by fermentation and distillation.
* ] that transforms the ] raw material into gaseous carbon monoxide and hydrogen. These gases can be converted to ethanol by fermentation or chemical catalysis.


The stages to produce ethanol using a biological approach are:<ref name=":1" />
They both include distillation as the final step to isolate the pure ethanol.
# A "pretreatment" phase to make the lignocellulosic material such as wood or straw amenable to hydrolysis
# Cellulose ] (]) to break down the molecules into sugars
# Microbial fermentation of the sugar solution
# Distillation and dehydration to produce pure alcohol


In 2010, a genetically engineered yeast strain was developed to produce its own cellulose-digesting enzymes.<ref name="N.Crassa">{{cite journal | vauthors = Galazka JM, Tian C, Beeson WT, Martinez B, Glass NL, Cate JH | title = Cellodextrin transport in yeast for improved biofuel production | journal = Science | volume = 330 | issue = 6000 | pages = 84–6 | date = October 2010 | pmid = 20829451 | doi = 10.1126/science.1192838 | s2cid = 20444539 | bibcode = 2010Sci...330...84G }}</ref> Assuming this technology can be scaled to industrial levels, it would eliminate one or more steps of cellulolysis, reducing both the time required and costs of production.
=== Cellulolysis (biological approach) ===


Although lignocellulose is the most abundant plant material resource, its usability is curtailed by its rigid structure. As a result, an effective pretreatment is needed to liberate the cellulose from the lignin seal and its crystalline structure so as to render it accessible for a subsequent hydrolysis step.<ref>{{cite journal | vauthors = Mosier N, Wyman C, Dale BE, Elander R, Lee YY, Holtzapple M, Ladisch M | year = 2005 | title = Features of promising technologies for pretreatment of lignocellulosic biomass | journal = Bioresour Technol | volume = 96 | issue = 6| pages = 673–686 | doi=10.1016/j.biortech.2004.06.025| pmid = 15588770 | bibcode = 2005BiTec..96..673M | s2cid = 6661080 }}</ref> By far, most pretreatments are done through physical or chemical means. To achieve higher efficiency, both physical and chemical pretreatments are required. Physical pretreatment involves reducing biomass ] by mechanical processing methods such as ] or ]. Chemical pretreatment partially ] the lignocellulose so enzymes can access the cellulose for microbial reactions.<ref>{{cite journal| vauthors = Taylor MJ, Alabdrabalameer HA, Skoulou V |date=2019-06-30|title=Choosing Physical, Physicochemical and Chemical Methods of Pre-Treating Lignocellulosic Wastes to Repurpose into Solid Fuels |journal=Sustainability |language=en |volume=11 |issue=13 |pages=3604 |doi=10.3390/su11133604 |issn=2071-1050|doi-access=free }}</ref>
There are four or five stages to produce ethanol using a biological approach:
# A "pretreatment" phase, to make the lignocellulosic material such as wood or straw amenable to hydrolysis,
# Cellulose hydrolysis (cellulolysis), to break down the molecules into sugars;
# Separation of the sugar solution from the residual materials, notably ];
# Microbial fermentation of the sugar solution;
# Distillation to produce 99.5% pure alcohol.


Chemical pretreatment techniques include ], ], ammonia fiber expansion, organosolv, ],<ref name="zhu"/> SO2-ethanol-water fractionation,<ref>{{cite journal | vauthors = Iakovlev M, van Heiningen A | year = 2012 | title = Efficient fractionation of spruce by SO2-Ethanol-Water (SEW) treatment: closed mass balances for carbohydrates and sulfur | journal = ChemSusChem | volume = 5 | issue = 8| pages = 1625–1637 | doi = 10.1002/cssc.201100600 | pmid = 22740146 | bibcode = 2012ChSCh...5.1625I }}</ref> alkaline wet oxidation and ozone pretreatment.<ref>{{cite journal |vauthors=Klinke HB, Thomsen AB, Ahring BK | year = 2004 | title = Inhibition of ethanol-producing yeast and bacteria by degradation products produced during pre-treatment of biomass | journal = Appl Microbiol Biotechnol | volume = 66 | issue = 1| pages = 10–26 | doi = 10.1007/s00253-004-1642-2 | pmid = 15300416 | s2cid = 41941145 }}</ref> Besides effective cellulose liberation, an ideal pretreatment has to minimize the formation of degradation products because they can inhibit the subsequent hydrolysis and fermentation steps.<ref>{{cite journal | vauthors = Olsson L, Hahn-Hägerdal B | year = 1996 | title = Fermentation of lignocellulosic hydrolysates for ethanol fermentation | journal = Enzyme Microb Technol | volume = 18 | pages = 312–331 | doi = 10.1016/0141-0229(95)00157-3 }}</ref> The presence of inhibitors further complicates and increases the cost of ethanol production due to required detoxification steps. For instance, even though acid hydrolysis is probably the oldest and most-studied pretreatment technique, it produces several potent inhibitors including ] and ].<ref>{{cite journal | vauthors = Palmqvist E, Hahn-Hägerdal B | year = 2000 | title = Fermentation of lignocellulosic hydrolysates. I. Inhibition and deoxification | journal = Bioresour Technol | volume = 74 | issue = 1 | pages = 17–24 | doi=10.1016/s0960-8524(99)00160-1| bibcode = 2000BiTec..74...17P }}</ref> Ammonia Fiber Expansion (AFEX) is an example of a promising pretreatment that produces no inhibitors.<ref name=lynd>{{cite journal | vauthors = Lynd LR | year = 1996 | title = Overview and evaluation of fuel ethanol from cellulosic biomass: technology, economics, the environment, and policy | journal = ] | volume = 21 | pages = 403–465 | doi = 10.1146/annurev.energy.21.1.403| doi-access= }}</ref>
==== Pretreatment ====


Most pretreatment processes are not effective when applied to feedstocks with high lignin content, such as forest biomass. These require alternative or specialized approaches. ], SPORL ('sulfite pretreatment to overcome recalcitrance of lignocellulose') and SO2-ethanol-water (AVAP®) processes are the three processes that can achieve over 90% cellulose conversion for forest biomass, especially those of softwood species. SPORL is the most energy efficient (sugar production per unit energy consumption in pretreatment) and robust process for pretreatment of forest biomass with very low production of fermentation inhibitors. Organosolv pulping is particularly effective for hardwoods and offers easy recovery of a hydrophobic lignin product by dilution and precipitation.<ref>{{cite book | vauthors = Macfarlane AL, Farid MM, Chen JJ | publisher = Lambert Academic Press | title = Organosolv delignification of willow | date = 2010 |isbn=978-3-8383-9155-7}}</ref> AVAP® process effectively fractionates all types of lignocellulosics into clean highly digestible cellulose, undegraded hemicellulose sugars, reactive lignin and lignosulfonates, and is characterized by efficient recovery of chemicals.<ref>{{cite thesis | vauthors = Iakovlev M | title = SO2-Ethanol-Water Fractionation of Lignocellulosics | degree = Ph.D. | publisher = Aalto University, Finland | date = 2011 | url = http://lib.tkk.fi/Diss/2011/isbn9789526043142/isbn9789526043142.pdf }}</ref><ref>{{cite patent | inventor = Retsina T, Pylkkanen V | country = US | number = 8030039 | title = Method for the production of fermentable sugars and cellulose from lignocellulosic material | assign1 = American Process, Inc. | pubdate = 2011-10-04 | status = patent}}</ref>
Although cellulose is the most abundant plant material resource, its susceptibility has been curtailed by its rigid structure. As the result, an effective pretreatment is needed to liberate the cellulose from the lignin seal and its crystalline structure so as to render it accessible for a subsequent hydrolysis step.<ref> Mosier N, Wyman C, Dale BE, Elander R, Lee YY, Holtzapple M, Ladisch M (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 96:673-686 </ref> By far, most pretreatments are done through physical or chemical means. In order to achieve higher efficiency, some researchers seek to incorporate both effects.<ref> McMillan JD (1994) Pretreatment of lignocellulosic biomass. In: Himmel ME, Baker JO, Overend RP, Enzymatic Conversion of Biomass for Fuels Production, ACS Symposium Series, vol. 556. ACS, Washington, DC, 292–324. </ref>


=== Cellulolytic processes ===
To date, the available pretreatment techniques include acid hydrolysis, steam explosion, ammonia fiber expansion, alkaline wet oxidation and ozone pretreatment.<ref> Klinke HB, Thomsen AB, Ahring BK (2004) Inhibition of ethanol-producing yeast and bacteria by degradation products produced during pre-treatment of biomass. Appl Microbiol Biotechnol 66:10–26.</ref> Besides effective cellulose liberation, an ideal pretreatment has to minimize the formation of degradation products because of their inhibitory effects on subsequent hydrolysis and fermentation processes.<ref> Olsson L, Hahn-Hägerdal B (1996) Fermentation of lignocellulosic hydrolysates for ethanol fermentation. Enzyme Microb Technol 18:312–331. </ref> The presence of inhibitors will not only further complicate the ethanol production but also increase the cost of production due to entailed detoxification steps. Even though pretreatment by acid hydrolysis is probably the oldest and most studied pretreatment technique, it produces several potent inhibitors including ] and hydroxymethyl furfural (HMF) which are by far regarded as the most toxic inhibitors present in lignocellulosic hydrolysate.<ref> Palmqvist E, Hahn-Hägerdal B (2000) Fermentation of lignocellulosic hydrolysates. I. Inhibition and deoxification. Bioresour Technol 74:17–24. </ref> In fact, Ammonia Fiber Expansion (AFEX) is the sole pretreatment which features promising pretreatment efficiency with no inhibitory effect in resulting hydrolysate.<ref name=lynd> Lynd LR (1996) Overview and evaluation of fuel ethanol from cellulosic biomass: technology, economics, the environment, and policy. Annu Rev Energy Environ 21:403–465. </ref>
The ] of cellulose (]) produces ] that can be fermented into alcohol. There are two major cellulolysis processes: chemical processes using acids, or ] reactions using ]s.<ref name=":1">{{cite journal| vauthors = Amezcua-Allieri MA, Sánchez Durán T, Aburto J |date=2017|title=Study of Chemical and Enzymatic Hydrolysis of Cellulosic Material to Obtain Fermentable Sugars |journal=Journal of Chemistry|language=en|volume=2017|pages=1–9|doi=10.1155/2017/5680105|issn=2090-9063|doi-access=free}}</ref>


==== Cellulolytic processes ==== ==== Chemical hydrolysis ====
In the traditional methods developed in the 19th century and at the beginning of the 20th century, hydrolysis is performed by attacking the cellulose with an acid.<ref>{{cite book | url = http://journeytoforever.org/biofuel_library/wood_alcohol.html | trans-title = Wood Alcohol | language = fr | vauthors = Boullanger E |translator-last1= Marc de Piolenc |translator-first1= F | name-list-style = vanc | title = Distillerie Agricole et Industrielle | location = Paris | publisher = Ballière | date = 1924 }}</ref> Dilute acid may be used under high heat and high pressure, or more concentrated acid can be used at lower temperatures and atmospheric pressure. A decrystallized cellulosic mixture of acid and sugars reacts in the presence of water to complete individual sugar molecules (hydrolysis). The product from this hydrolysis is then neutralized and yeast fermentation is used to produce ethanol. As mentioned, a significant obstacle to the dilute acid process is that the hydrolysis is so harsh that toxic degradation products are produced that can interfere with fermentation. ] uses concentrated acid because it does not produce nearly as many fermentation inhibitors, but must be separated from the sugar stream for recycle to be commercially attractive.{{Citation needed|date=January 2021}}
The ] molecules are composed of long chains of sugar molecules. In the ], these chains are broken down to free the sugar, before it is fermented for alcohol production.


] scientists found they can access and ferment almost all of the remaining sugars in ] straw. The sugars are located in the plant's cell walls, which are notoriously difficult to break down. To access these sugars, scientists pretreated the wheat straw with alkaline peroxide, and then used specialized enzymes to break down the cell walls. This method produced {{convert|93|USgal|L}} of ethanol per ton of wheat straw.<ref>{{cite web | vauthors = Perry A | date = 9 April 2010 | url=http://www.ars.usda.gov/is/pr/2010/100409.htm | title = Cellulosic Ethanol: Expanding Options, Identifying Obstacles | work = Agricultural Research Service (ARS) | publisher = U.S. Department of Agriculture }}</ref>
There are two major cellulose hydrolysis (cellulolysis) processes: a chemical reaction using acids, or an ] reaction.


===== Chemical hydrolysis ===== ==== Enzymatic hydrolysis ====
Cellulose chains can be broken into ] molecules by ] ]s. This reaction occurs at body temperature in the stomachs of ]s such as cattle and sheep, where the enzymes are produced by microbes. This process uses several enzymes at various stages of this conversion. Using a similar enzymatic system, lignocellulosic materials can be enzymatically hydrolyzed at a relatively mild condition (50&nbsp;°C and pH 5), thus enabling effective cellulose breakdown without the formation of byproducts that would otherwise inhibit enzyme activity. All major pretreatment methods, including dilute acid, require an enzymatic hydrolysis step to achieve high sugar yield for ethanol fermentation.<ref name="lynd" />
In the traditional methods developed in the 19th century and at the beginning of the 20th century, hydrolysis is performed by attacking the cellulose with an acid.<ref>. Translation from E. Boullanger: Distillerie Agricole et Industrielle (Paris: Ballière, 1924).</ref> Dilute acid may be used under high heat and high pressure, or more concentrated acid can be used at lower temperatures and atmospheric pressure. A decrystalized cellulosic mixture of acid and sugars reacts in the presence of water to complete individual sugar molecules (hydrolysis). The product from this hydrolysis is then neutralized and yeast fermentation is used to produce ethanol. As mentioned, a significant obstacle to the dilute acid process is that the hydrolysis is so harsh that toxic degradation products are produced that can interfere with fermentation. Concentrated acid must be separated from the sugar stream for recycle (simulated moving bed (SMB) chromatographic separation for example) to be commercially attractive.


Fungal enzymes can be used to hydrolyze cellulose. The raw material (often wood or straw) still has to be pre-treated to make it amenable to hydrolysis.<ref>{{cite journal | vauthors = Dashtban M, Schraft H, Qin W | title = Fungal bioconversion of lignocellulosic residues; opportunities & perspectives | journal = International Journal of Biological Sciences | volume = 5 | issue = 6 | pages = 578–95 | date = September 2009 | pmid = 19774110 | pmc = 2748470 | doi = 10.7150/ijbs.5.578 }}</ref> In 2005, Iogen Corporation announced it was developing a process using the ] '']'' to secrete "specially engineered enzymes" for an enzymatic ] process.<ref>
===== Enzymatic hydrolysis =====
{{cite web
Cellulose chains can be broken into ] molecules by ] ]s.
|url=http://www.iogen.ca/cellulose_ethanol/what_is_ethanol/process.html
|publisher=]
|title=Iogen technology makes it possible (process overview)
|year=2005
|access-date=2007-11-28
|url-status=dead
|archive-url=https://web.archive.org/web/20060203050630/http://www.iogen.ca/cellulose_ethanol/what_is_ethanol/process.html
|archive-date=2006-02-03
}}</ref>


Another Canadian company, SunOpta, uses ] pretreatment, providing its technology to Verenium (formerly Celunol Corporation)'s facility in ], Abengoa's facility in ], and a China Resources Alcohol Corporation in ]. The CRAC production facility uses ] as raw material.<ref>{{cite web | url = http://phx.corporate-ir.net/phoenix.zhtml?c=82712&p=irol-newsArticle&t=Regular&id=951516 | title = Sunopta updates current cellulosic ethanol projects | work = Sunopta press release | date = 2007 }}</ref>
This reaction occurs at body temperature in the stomach of ruminants such as cows and sheep, where the enzymes are produced by bacteria. This process uses several enzymes at various stages of this conversion. Using a similar enzymatic system, lignocellulosic materials can be enzymatically hydrolyzed at a relatively mild condition (50<sup>o</sup>C and pH5), thus enabling effective cellulose breakdown without the formation of byproducts that would otherwise inhibit enzyme activity. By far, all major pretreatment methods, including dilute acid pretreatment, require enzymatic hydrolysis step to achieve high sugar yield for ethanol fermentation<ref name="lynd"/>


=== Microbial fermentation ===
{{Newsrelease|date=May 2008}}
{{Main|Ethanol fermentation}}
A start-up American environmental company , has discovered a purely organic hydrolysis process for ] that generates 4.4&nbsp;times the ethanol product from trash, at a rate that is oil-independent capable<ref>{{cite web |title=Wise Landfill (Ethanol Market Share) |url=http://www.wiselandfill.com/Ethanol20%Market.html }}</ref> without process-intensive genetically modified microbes. Their method also boasts of being not merely ], but carbon negative.<ref> "WLRM Celebrates Completion of its Cellulosic Ethanol Breakthrough" press release, 2007.</ref>


Traditionally, baker's yeast ('']''), has long been used in the brewery industry to produce ethanol from ]s (six-carbon sugars). Due to the complex nature of the ]s present in ], a significant amount of ] and ] (five-carbon sugars derived from the hemicellulose portion of the lignocellulose) is also present in the hydrolysate. For example, in the hydrolysate of ], approximately 30% of the total fermentable sugars is xylose. As a result, the ability of the fermenting microorganisms to use the whole range of sugars available from the hydrolysate is vital to increase the economic competitiveness of cellulosic ethanol and potentially biobased proteins.{{Citation needed|date=January 2021}}
Various enzyme companies have also contributed significant technological breakthroughs in cellulosic ethanol through the mass production of enzymes for hydrolysis at competitive prices.


At the turn of the millennium, ] for microorganisms used in fuel ethanol production showed significant progress.<ref>{{cite journal |vauthors=Jeffries TW, Jin YS | year = 2004 | title = Metabolic engineering for improved fermentation of pentoses by yeasts | journal = Appl Microbiol Biotechnol | volume = 63 | issue = 5| pages = 495–509 | doi = 10.1007/s00253-003-1450-0 | pmid = 14595523 | s2cid = 26069067 }}</ref> Besides ''Saccharomyces cerevisiae'', microorganisms such as ''Zymomonas mobilis'' and ''Escherichia coli'' have been targeted through metabolic engineering for cellulosic ethanol production. An attraction towards alternative fermentation organism is its ability to ferment five carbon sugars improving the yield of the feed stock. This ability is often found in bacteria <ref>{{cite web | vauthors = McMillan JD | date = January 1993 | work = National Renewable Energy Laboratory | publisher = U.S. Department of Energy |url=https://www.nrel.gov/docs/legosti/old/4944.pdf |title=Xylose Fermentation to Ethanol: A Review}}</ref> based organisms.{{Citation needed|date=January 2021}}
] is a Canadian producer of enzymes for an enzymatic hydrolysis process that uses "specially engineered enzymes".<ref>{{cite web |url=http://www.iogen.ca/cellulose_ethanol/what_is_ethanol/process.html |publisher=Iogen |title=Iogen Technology Makes it Possible (Process Overview) |date=2005 |accessdate=2007-11-28}}</ref> The raw material (wood or straw) has to be pre-treated to make it amenable to hydrolysis.


In the first decade of the 21st century, engineered yeasts have been described efficiently fermenting xylose,<ref>{{cite journal | vauthors = Brat D, Boles E, Wiedemann B | year = 2009 | title = Functional expression of a bacterial xylose isomerase in Saccharomyces cerevisiae | journal = Appl. Environ. Microbiol. | volume = 75| issue = 8| pages = 2304–2311| doi = 10.1128/AEM.02522-08 | pmid=19218403 | pmc=2675233| bibcode = 2009ApEnM..75.2304B }}</ref><ref>{{cite journal | vauthors = Ohgren K, Bengtsson O, Gorwa-Grauslund MF, Galbe M, Hahn-Hagerdal B, Zacchi G | year = 2006 | title = Simultaneous saccharification and co-fermentation of glucose and xylose in steam-pretreated corn stover at high fiber content with Saccharomyces cerevisiae TMB3400 | journal = J Biotechnol | volume = 126 | issue = 4| pages = 488–98 | doi=10.1016/j.jbiotec.2006.05.001| pmid = 16828190 }}</ref> and arabinose,<ref>{{cite journal |vauthors=Becker J, Boles E | year = 2003 | title = A modified Saccharomyces cerevisiae strain that consumes L-Arabinose and produces ethanol | journal = Appl Environ Microbiol | volume = 69 | issue = 7| pages = 4144–50 | doi = 10.1128/AEM.69.7.4144-4150.2003 | pmid = 12839792 | pmc = 165137 | bibcode = 2003ApEnM..69.4144B }}</ref> and even both together.<ref name="Karhumaa_2006">{{cite journal | vauthors = Karhumaa K, Wiedemann B, Hahn-Hägerdal B, Boles E, Gorwa-Grauslund MF | title = Co-utilization of L-arabinose and D-xylose by laboratory and industrial Saccharomyces cerevisiae strains | journal = Microbial Cell Factories | volume = 5 | issue = | pages = 18 | date = April 2006 | pmid = 16606456 | pmc = 1459190 | doi = 10.1186/1475-2859-5-18 | doi-access = free }}</ref> Yeast cells are especially attractive for cellulosic ethanol processes because they have been used in biotechnology for hundreds of years, are tolerant to high ethanol and inhibitor concentrations and can grow at low pH values to reduce bacterial contamination.{{Citation needed|date=January 2021}}
] is used by ].


=== Combined hydrolysis and fermentation ===
Another Canadian company, SunOpta Inc. markets a patented technology known as "Steam Explosion" to pre-treat cellulosic biomass, overcoming its "recalcitance" to make cellulose and hemicellulose accessible to enzymes for conversion into fermenatable sugars. SunOpta designs and engineers cellulosic ethanol ] and its process technologies and equipment are in use in the first 3 commercial demonstration ]s in the world:<ref> . Sunopta press release, 2007.</ref> Verenium (formerly Celunol Corporation)'s facility in Jennings, Louisiana, Abengoa's facility in Salamanca, Spain, and a facility in China owned by China Resources Alcohol Corporation (CRAC). The CRAC facility is currently producing cellulosic ethanol from local corn stover on a 24-hour a day basis utilizing SunOpta's process and technology.
Some species of bacteria have been found capable of direct conversion of a cellulose substrate into ethanol. One example is '']'', which uses a complex ] to break down cellulose and synthesize ethanol. However, ''C.&nbsp;thermocellum'' also produces other products during cellulose metabolism, including ] and ], in addition to ethanol, lowering the efficiency of the process. Some research efforts are directed to optimizing ethanol production by ] bacteria that focus on the ethanol-producing pathway.<ref>{{cite web | url = http://www.rochester.edu/news/show.php?id=2803 | work = University of Rochester Press Release | title = Genome Sequencing Reveals Key to Viable Ethanol Production | date = 2 March 2007 }}</ref>


=== Gasification process (thermochemical approach) ===
and are two other companies that have received United States government Department of Energy funding for research into reducing the cost of cellulase, a key enzyme in the production of cellulosic ethanol by enzymatic hydrolysis.
] ] ]]]
The gasification process does not rely on chemical decomposition of the cellulose chain (cellulolysis). Instead of breaking the cellulose into sugar molecules, the carbon in the raw material is converted into ], using what amounts to partial combustion. The carbon monoxide, carbon dioxide and hydrogen may then be fed into a special kind of ]. Instead of sugar fermentation with yeast, ] uses '']'' bacteria.<ref>{{cite web |url=http://www.brienergy.com/index.html |archive-url=https://web.archive.org/web/20060421183908/http://www.brienergy.com/index.html |url-status=dead |archive-date=2006-04-21 |title=Providing for a Sustainable Energy Future by producing clean RENEWABLE liquid energy and green power |access-date=2007-11-28 |publisher=Bioengineering Resources Inc. }}</ref> This microorganism will ingest carbon monoxide, carbon dioxide and hydrogen and produce ethanol and water. The process can thus be broken into three steps:
# ] — Complex carbon-based molecules are broken apart to access the carbon as carbon monoxide, carbon dioxide and hydrogen
# Fermentation — Convert the carbon monoxide, carbon dioxide and hydrogen into ethanol using the ''Clostridium ljungdahlii'' organism
# Distillation — Ethanol is separated from water


A 2002 study has found another ''Clostridium'' bacterium that seems to be twice as efficient in making ethanol from carbon monoxide as the one mentioned above.<ref>{{cite journal | vauthors = Rajagopalan S, Datar R, Lewis RS| year = 2002 | title = Formation of Ethanol from Carbon Monoxide via New Microbial Catalyst | journal = Biomass & Energy | volume = 23 | issue = 6| pages = 487–493 | doi = 10.1016/s0961-9534(02)00071-5 | bibcode = 2002BmBe...23..487R }}</ref>
Other enzyme companies, such as , are developing genetically engineered ] which would produce large volumes of cellulase, xylanase and hemicellulase enzymes which can be utilized to convert agricultural residues such as corn stover, distiller grains, wheat straw and sugar cane bagasse and ]s such as ] into fermentable sugars which may be used to produce cellulosic ethanol.


Alternatively, the synthesis gas from gasification may be fed to a catalytic reactor where it is used to produce ethanol and other higher alcohols through a thermochemical process.<ref>{{cite web |url=http://www.powerenergy.com/ |title=Power Energy Fuels Homepage |publisher=Power Energy Fuels, Inc. | work = Enerkem |access-date=2007-11-28 |url-status=dead |archive-url=https://web.archive.org/web/20071212011334/http://www.powerenergy.com/ |archive-date=2007-12-12 }}</ref> This process can also generate other types of liquid fuels, an alternative concept successfully demonstrated by the Montreal-based company ] at their facility in Westbury, Quebec.<ref>{{cite web |url=http://www.enerkem.com/en/our-locations/plants/westbury-quebec-canada.html |title=Westbury, Quebec |access-date=2011-07-27 |url-status=dead |archive-url=https://web.archive.org/web/20110806232704/http://www.enerkem.com/en/our-locations/plants/westbury-quebec-canada.html |archive-date=2011-08-06 }}</ref>
] , the new name of recently merged ] and Celunol Corporations, operates a pilot cellulosic ethanol plant in Jennings, Louisiana and is building a 1.4&nbsp;million gallon per year demonstration plant on adjacent land to be completed by the end of 2007 and begin operation in early 2008. Vernium is the first publicly traded company with integrated, end-to-end capabilities to make cellulosic biofuels.


==Hemicellulose to ethanol==
==== Microbial fermentation ====
{{Main|Ethanol fermentation}}


Studies are intensively conducted to develop economic methods to convert both cellulose and ] to ethanol. Fermentation of glucose, the main product of cellulose hydrolyzate, to ethanol is an already established and efficient technique. However, conversion of xylose, the pentose sugar of hemicellulose hydrolyzate, is a limiting factor, especially in the presence of glucose. Moreover, it cannot be disregarded as hemicellulose will increase the efficiency and cost-effectiveness of cellulosic ethanol production.<ref name="Sakamoto_2012">{{cite journal | vauthors = Sakamoto T, Hasunuma T, Hori Y, Yamada R, Kondo A | title = Direct ethanol production from hemicellulosic materials of rice straw by use of an engineered yeast strain codisplaying three types of hemicellulolytic enzymes on the surface of xylose-utilizing Saccharomyces cerevisiae cells | journal = Journal of Biotechnology | volume = 158 | issue = 4 | pages = 203–10 | date = April 2012 | pmid = 21741417 | doi = 10.1016/j.jbiotec.2011.06.025 }}</ref>
Traditionally, ] (''Saccharomyces cerevisiae''), has long been used in brewery industry to produce ethanol from ]s (6-carbon sugar). Due to the complex nature of the ]s present in ], a significant amount of ] and ] (5-carbon sugars derived from the hemicellulose portion of the lignocellulose) is also present in the hydrolysate. For example, in the hydrolysate of ], approximately 30% of the total fermentable sugars is xylose. As a result, the ability of the fermenting microorganisms to utilize the whole range of sugars available from the hydrolysate is vital to increase the economic competitiveness of cellulosic ethanol and potentially bio-based chemicals.


Sakamoto (2012) et al. show the potential of genetic engineering microbes to express hemicellulase enzymes. The researchers created a recombinant Saccharomyces cerevisiae strain that was able to:
In recent years, metabolic engineering for microorganisms used in fuel ethanol production has shown significant progress.<ref> Jeffries TW, Jin YS (2004) Metabolic engineering for improved fermentation of pentoses by yeasts. Appl Microbiol Biotechnol 63: 495–509. </ref> Besides ''Saccharomyces cerevisiae'', microorganisms such as ''Zymomonas mobilis'' and ''Escherichia coli'' have been targeted through metabolic engineering for cellulosic ethanol production.


# hydrolyze hemicellulase through codisplaying endoxylanase on its cell surface,
Recently, engineered yeasts have been described efficiently fermenting xylose<ref> Ohgren K, Bengtsson O, Gorwa-Grauslund MF, Galbe M, Hahn-Hagerdal B, Zacchi G (2006) Simultaneous saccharification and co-fermentation of glucose and xylose in steam-pretreated corn stover at high fiber content with Saccharomyces cerevisiae TMB3400. J Biotechnol. 126(4):488–98. </ref> and arabinose,<ref> Becker J, Boles E (2003) A modified Saccharomyces cerevisiae strain that consumes L-Arabinose and produces ethanol. Appl Environ Microbiol. 69(7):4144–50.</ref> and even both together.<ref> Karhumaa K, Wiedemann B, Hahn-Hagerdal B, Boles E, Gorwa-Grauslund MF (2006) Co-utilization of L-arabinose and D-xylose by laboratory and industrial Saccharomyces cerevisiae strains. Microb Cell Fact. 10;5:18.</ref> Yeast cells are especially attractive for cellulosic ethanol processes as they have been used in biotechnology for hundred of years, as they are tolerant to high ethanol and inhibitor concentrations and as they can grow at low pH values which avoids bacterial contaminations.
# assimilate xylose by expression of xylose reductase and xylitol dehydrogenase.


The strain was able to convert rice straw hydrolyzate to ethanol, which contains hemicellulosic components. Moreover, it was able to produce 2.5x more ethanol than the control strain, showing the highly effective process of cell surface-engineering to produce ethanol.<ref name="Sakamoto_2012"/>
==== Combined hydrolysis and fermentation ====
Some species of bacteria have been found capable of direct conversion of a cellulose substrate into ethanol. One example is '']'', which utilizes a complex ] to break down cellulose and synthesize ethanol. However, ''C.&nbsp;thermocellum'' also produces other products during cellulose metabolism, including ] and ], in addition to ethanol, lowering the efficiency of the process. Some research efforts are directed to optimizing ethanol production by ] bacteria that focus on the ethanol-producing pathway.<ref> Genome Sequencing Reveals Key to Viable Ethanol Production</ref>


== Advantages ==
=== Gasification process (thermochemical approach) ===
] ] ]]]
The gasification process does not rely on chemical decomposition of the cellulose chain (cellulolysis). Instead of breaking the cellulose into sugar molecules, the carbon in the raw material is converted into ], using what amounts to partial combustion. The carbon monoxide, carbon dioxide and hydrogen may then be fed into a special kind of fermenter. Instead of sugar fermentation with yeast, this process uses a microorganism named “''Clostridium ljungdahlii''”.<ref> {{cite web |url=http://www.brienergy.com/index.html |title=Providing for a Sustainable Energy Future by producing clean RENEWABLE liquid energy and green power |accessdate=2007-11-28 |publisher=Bioengineering Resources Inc.}}</ref> This microorganism will ingest (eat) carbon monoxide, carbon dioxide and hydrogen and produce ethanol and water. The process can thus be broken into three steps:
# Gasification — Complex carbon based molecules are broken apart to access the carbon as carbon monoxide, carbon dioxide and hydrogen are produced
# Fermentation — Convert the carbon monoxide, carbon dioxide and hydrogen into ethanol using the ''Clostridium ljungdahlii'' organism
# Distillation — Ethanol is separated from water


=== General advantages of ethanol fuel ===
A recent study has found another ''Clostridium'' bacterium that seems to be twice as efficient in making ethanol from carbon monoxide as the one mentioned above.<ref> "Formation of Ethanol from Carbon Monoxide via New Microbial Catalyst", ''Biomass & Energy'' v. 23 (2002), p. 487–493.</ref>
Ethanol burns more cleanly and more efficiently than gasoline.<ref name="demain">
{{cite journal | vauthors = Demain AL, Newcomb M, Wu JH | title = Cellulase, clostridia, and ethanol | journal = Microbiology and Molecular Biology Reviews | volume = 69 | issue = 1 | pages = 124–54 | date = March 2005 | pmid = 15755956 | pmc = 1082790 | doi = 10.1128/MMBR.69.1.124-154.2005 }}</ref><ref>{{cite web | url = http://www.afdc.energy.gov/fuels/ethanol_benefits.html | work = Alternative Fuels Data Center | title = Ethanol Benefits and Considerations }}</ref> Because plants consume carbon dioxide as they grow, bioethanol has an overall lower carbon footprint than fossil fuels.<ref>{{cite web|title=Alternative Fuels Data Center: Ethanol Benefits and Considerations|url=https://afdc.energy.gov/fuels/ethanol_benefits.html|url-status=live|access-date=2021-05-03|website=afdc.energy.gov|publisher=US Department of Energy|archive-url=https://web.archive.org/web/20120718003935/http://www.afdc.energy.gov:80/fuels/ethanol_benefits.html |archive-date=2012-07-18 }}</ref> Substituting ethanol for oil can also reduce a country's ].<ref name=":5">{{cite web| vauthors = Beck K |date=November 2019|title=Advantages & Disadvantages of Ethanol Biofuel|url=https://sciencing.com/advantages-disadvantages-ethanol-biofuel-21990.html|url-status=live|access-date=2021-05-03|website=Sciencing|language=en|archive-url=https://web.archive.org/web/20170401041453/http://sciencing.com:80/advantages-disadvantages-ethanol-biofuel-21990.html |archive-date=2017-04-01 }}</ref>


=== Advantages of cellulosic ethanol over corn or sugar-based ethanol ===
Alternatively, the synthesis gas from gasification may be fed to a catalytic reactor where the synthesis gas is used to produce ethanol and other higher alcohols through a thermochemical process.<ref> {{cite web |url=http://www.powerenergy.com/ |title=Power Energy Fuels Homepage |publisher=Power Energy Fuels, Inc. |accessdate=2007-11-28}}</ref> This process can also generate other types of liquid fuels, an alternative concept under investigation by at least one biofuels company.<ref>{{cite web |url=http://www.choren.com/en |title=Following Nature's Example |publisher=Chloren Industries |accessdate=2007-11-28}}</ref>
{{See also|Ethanol fuel in the United States#Environmental and social impacts|l1=Environmental and social impacts of ethanol fuel in the U.S.|Indirect land use change impacts of biofuels|Low-carbon fuel standard}}
{| class="wikitable" style="float: right; margin-left: 10px"
! colspan="3" style="background-color: #ABCDEF;" align="center" | ]<br>Draft ] ] reduction results<br> for different ] and discount rate approaches<ref name="EPAdraft">{{cite web|title=EPA Lifecycle Analysis of Greenhouse Gas Emissions from Renewable Fuels - Technical Highlights|url=http://www.epa.gov/otaq/renewablefuels/420f09024.pdf|access-date=2009-06-07}} ''See Table 1''.</ref><br>(includes ])
|-
! style="background-color: #ABCDEF;" | Fuel Pathway || style="background-color: #ABCDEF;" | 100 years +<br> 2% discount<br>rate || style="background-color: #ABCDEF;" | 30 years +<br> 0% discount <br> rate
|-
|] (] dry mill)<sup>(1)</sup>|| style="text-align:center" |-16%|| style="text-align:center" |+5%
|-
|Corn ethanol (Best case NG DM)<sup>(2)</sup> || style="text-align:center" |-39%|| style="text-align:center" |-18%
|-
|Corn ethanol (] dry mill) || style="text-align:center" |+13%|| style="text-align:center" |+34%
|-
| Corn ethanol (] dry mill)|| style="text-align:center" |-39% || style="text-align:center" |-18%
|-
| Corn ethanol (biomass dry mill with <br>combined heat and power) || style="text-align:center" |-47%|| style="text-align:center" |-26%
|-
| ]|| style="text-align:center" |-44%|| style="text-align:center" |-26%
|-
| Cellulosic ethanol from ] || style="background-color:#ffffcc;text-align:center" |-128% || style="background-color:#ffffcc;text-align:center" |-124%
|-
| Cellulosic ethanol from ] || style="background-color:#ffffcc;text-align:center" |-115% || style="background-color:#ffffcc;text-align:center" |-116%
|-
| colspan="3" |<small>Notes: (1) Dry mill (DM) plants grind the entire kernel and generally produce<br> only one primary co-product: ] with solubles (DGS).<br> (2) Best case plants produce wet distillers grains co-product.</small>
|}
Commercial production of cellulosic ethanol, which unlike corn and sugarcane would not compete with food production, would be highly attractive since it would alleviate pressure on these foodcrops.


Although its processing costs are higher, the price of cellulose biomass is much cheaper than that of grains or fruits. Moreover, since cellulose is the main component of plants, the whole plant can be harvested, rather than just the fruit or seeds. This results in much better yields; for instance, switchgrass yields twice as much ethanol per acre as corn.<ref name="grist.org">{{cite web | vauthors = Montenegro M | date = 5 December 2006 | url = http://grist.org/article/montenegro/ | title = The numbers behind ethanol, cellulosic ethanol, and biodiesel in the U.S. | work = Grist }}</ref> Biomass materials for cellulose production require fewer inputs, such as fertilizer, herbicides, and their extensive roots improve ], reduce erosion, and increase nutrient capture.<ref name="nelson">{{cite web| vauthors = Nelson R |year=2007|title=Cellulosic ethanol: bioethanol in Kansas|url=http://kec.kansas.gov/reports/Cellulosic_Ethanol_FINAL.pdf|url-status=dead|archive-url=https://web.archive.org/web/20080910051624/http://kec.kansas.gov/reports/Cellulosic_Ethanol_FINAL.pdf|archive-date=2008-09-10|access-date=2007-12-09}}</ref><ref name="charles_rice">
== Economics==
{{cite web| vauthors = Rice CW |year=2002|title=Storing Carbon in Soil: Why and How?|url=http://www.geotimes.org/jan02/feature_carbon.html|access-date=2008-11-10}}</ref> The overall carbon footprint and ] of cellulosic ethanol are considerably lower (see chart)<ref>{{cite journal | vauthors = Farrell AE, Plevin RJ, Turner BT, Jones AD, O'Hare M, Kammen DM | title = Ethanol can contribute to energy and environmental goals | journal = Science | volume = 311 | issue = 5760 | pages = 506–8 | date = January 2006 | pmid = 16439656 | doi = 10.1126/science.1121416 | bibcode = 2006Sci...311..506F | s2cid = 16061891 }}</ref><ref>{{cite journal | url = http://www.atmos-chem-phys.org/8/389/2008/acp-8-389-2008.pdf | vauthors = Crutzen, PJ, Mosier AR, Smith KA, Winiwarter W | title = Nitrous oxide release from agro-biofuel production negates global warming reduction by replacing fossil fuels | journal = Atmospheric Chemistry and Physics | volume = 8 | issue = 2 | pages = 389–395 | date = 2008 | doi = 10.5194/acp-8-389-2008 | doi-access = free }}</ref><ref name="Solomon_2007">{{cite journal|vauthors=Solomon BD, Barnes JR, Halvorson KE|year=2007|title=History, economics, and energy policy|journal=Biomass Bioenergy|volume=31|issue=6|pages=416–425|doi=10.1016/j.biombioe.2007.01.023|bibcode=2007BmBe...31..416S }}</ref> and the net energy output is several times higher than that of corn-based ethanol.
{{Inappropriate tone|date=December 2007}}
Construction of pilot scale lignocellulosic ethanol plants requires considerable financial support through grants and subsidies. On ] ], the U.S. Dept. of Energy announced $385 million in grant funding to six cellulosic ethanol plants.<ref>{{cite web |url=http://www.doe.gov/news/4827.htm |title=DOE Selects Six Cellulosic Ethanol Plants for Up to $385 Million in Federal Funding|publisher=] |date=2007-02-28}}</ref> This grant funding accounts for 40% of the investment costs. The remaining 60% comes from the promoters of those facilities. Hence, a total of $1&nbsp;billion will be invested for approximately 140&nbsp;million gallon capacity. This translates into $7/annual gallon production capacity in capital investment costs for pilot plants (this would work out to $.35/gal over the 20-year life of a facility); future capital costs are expected to be lower. Corn to ethanol plants cost roughly $1–3/annual gallon capacity, though the cost of the corn itself is considerably greater than for switchgrass or waste biomass.<ref>{{cite web |url=http://www1.eere.energy.gov/biomass/pdfs/37092.pdf |format=PDF |title=Feasibility Study for Co-Locating and Integrating Ethanol Production Plants from Corn Starch and Lignocellulosic Feedstocks |publisher=United States Department of Energy |date=2005-01}}</ref><ref> {{cite web |url=http://www.ethanol-gec.org/information/briefing/16.pdf |format=PDF |title=Determining the Cost of Producing Ethanol from Corn Starch and Lignocellulosic Feedstocks |publisher=U.S. Department of Agriculture and U.S. Department of Energy|date=2000-10}}</ref>


The potential raw material is also plentiful. Around 44% of household waste generated worldwide consists of food and greens.<ref name=":6">{{cite web|title=Trends in Solid Waste Management|url=https://datatopics.worldbank.org/what-a-waste/trends_in_solid_waste_management.html|url-status=live|access-date=2021-05-04|website=]|archive-url=https://web.archive.org/web/20180925220225/http://datatopics.worldbank.org:80/what-a-waste/trends_in_solid_waste_management.html |archive-date=2018-09-25 }}</ref> An estimated 323 million tons of cellulose-containing raw materials which could be used to create ethanol are thrown away each year in US alone. This includes 36.8 million dry tons of urban wood wastes, 90.5 million dry tons of primary mill residues, 45 million dry tons of forest residues, and 150.7&nbsp;million dry tons of corn stover and wheat straw.<ref name="Resource Estimates">{{cite web | vauthors = Walsh M | date = 10 April 2000 | publisher = Oak Ridge National Laboratory | location = Oak Ridge, TN |url=http://bioenergy.ornl.gov/papers/misc/resource_estimates.html |title=Biomass Resource Estimates |url-status=dead |archive-url=https://web.archive.org/web/20080209194101/http://bioenergy.ornl.gov/papers/misc/resource_estimates.html |archive-date=2008-02-09 }}</ref> Moreover, even land marginal for agriculture could be planted with cellulose-producing crops, such as switchgrass, resulting in enough production to substitute for all the current oil imports into the United States.<ref>{{cite news |url= http://www.planetark.com/dailynewsstory.cfm/newsid/46338/story.htm |archive-url= https://web.archive.org/web/20080111050405/http://www.planetark.com/dailynewsstory.cfm/newsid/46338/story.htm |url-status= usurped |archive-date= January 11, 2008 |title= Switchgrass Fuel Yields Bountiful Energy: Study |date=January 10, 2008 |agency= ] |access-date= 2008-02-12}}</ref>
The quest for alternative sources of energy has provided many ways to produce electricity, such as ]s, ], or ]s. However, about 20% of total energy consumption is dedicated to transportation (i.e., cars, planes, lorries/trucks, etc.)<ref>{{cite web |url=http://www.eia.doe.gov/aer/pdf/pages/sec2_4.pdf |format=PDF |title=Energy Consumption by Sector, 1949–2006 |publisher=] |date=2007-01}}</ref> and currently requires energy-dense liquid fuels such as ], ] fuel, or ]. These fuels are all obtained by refining petroleum. This dependency on oil has two major drawbacks: burning fossil fuels such as oil may contribute to ]; and for net-consuming countries like the United States, importing oil creates a dependency on oil-producing countries.


Paper, cardboard, and packaging comprise around 17% of global household waste;<ref name=":6" /> although some of this is recycled. As these products contain cellulose, they are transformable into cellulosic ethanol,<ref name="Resource Estimates" /> which would avoid the production of ], a potent greenhouse gas, during decomposition.<ref>{{cite web | vauthors = McKibben B | work = ] | title = Carbon's New Math | date = October 2007 | url = https://ontd-political.livejournal.com/23729.html }}</ref>
As of 2007, ethanol is produced mostly from sugars or starches, obtained from fruits and grains. In contrast, cellulosic ethanol is obtained from cellulose, the main component of wood, straw and much of the structure of plants. Since cellulose cannot be digested by humans, the production of cellulose does not compete with the production of food, other than conversion of land from food production to cellulose production (which has recently started to become an issue, due to rising wheat prices.) The price per ton of the raw material is thus much cheaper than grains or fruits. Moreover, since cellulose is the main component of plants, the whole plant can be harvested. This results in much better yields per acre — up to 10&nbsp;tons, instead of 4 or 5&nbsp;tons for the best crops of grain.{{Fact|date=August 2007}}


== Disadvantages ==
The raw material is plentiful. Cellulose is present in every plant, in the form of straw, grass, and wood. Most of these "bio-mass" products are currently discarded.
It is estimated that 323 million tons of cellulose containing raw materials
that could be used to create ethanol are thrown away each year.
This includes
36.8 million dry tons of urban wood wastes, 90.5&nbsp;million dry tons of primary mill residues,
45 million dry tons of forest residues, and 150.7&nbsp;million dry tons of corn stover
& wheat straw.<ref name="Resource Estimates">{{cite web |url=http://bioenergy.ornl.gov/papers/misc/resource_estimates.html |title=Biomass Resource Estimates}}</ref>
Transforming them into ethanol using efficient and cost effective hemi(cellulase) enzymes or other processes might provide as much as 30% of the current fuel consumption in the United States — and probably similar figures in other oil-importing regions like China or Europe.{{Fact|date=April 2007}}


=== General disadvantages ===
Moreover, even land marginal for agriculture could be planted with cellulose-producing crops like ], resulting in enough production to substitute for all the current oil imports into the United States.<ref>{{cite web
The main overall drawback of ethanol fuel is its lower fuel economy compared to gasoline when using ethanol in an engine designed for gasoline with a lower compression ratio.<ref name=":5" />
| url= http://www.planetark.com/dailynewsstory.cfm/newsid/46338/story.htm
| title= Switchgrass Fuel Yields Bountiful Energy: Study
| date= ], ] | publisher= ]
|pages= |language= |doi= |archiveurl= |archivedate= |quote=
| accessdate= 2008-02-12}} </ref>


=== Disadvantages of cellulosic ethanol over corn or sugar-based ethanol ===
Paper, cardboard, and packaging comprise a substantial part of the solid waste sent to landfills in the United States each day, 41.26% of all organic municipal solid waste (MSW) according to 's city profiles. These city profiles account for accumulation of 612.3 tons daily per landfill where an average population density of 2,413 per square mile persists. Organic waste consists of 0.4%&nbsp;Manures, 1.6%&nbsp;Gypsum Board, 4.2%&nbsp;Glossy Paper, 4.2%&nbsp;Paper Ledger, 9.2%&nbsp;Wood, 10.5%&nbsp;Envelopes, 11.9%&nbsp;Newsprint, 12.3%&nbsp;Grass & Leaves, 30.0%&nbsp;Food Scrap, 34.0%&nbsp;Office Paper, 35.2%&nbsp;Corrugated Cardboard, and 46.4%&nbsp;Agricultural Composites, makes up 71.51% of land fill. All these except Gypsum Board contain cellulose which is transformable into cellulosic ethanol<ref name="Resource Estimates"/> because they are the leading cause of ] plumes. Methane, a greenhouse gas, is 21&nbsp;times more potent than carbon-dioxide.<ref> '']'', 'Carbon's New Math', October 2007</ref>
The main disadvantage of cellulosic ethanol is its high cost and complexity of production, which has been the main impediment to its commercialization.<ref name=":3" /><ref name=":2" />


==Economics==
Reduction of the disposal of solid waste through cellulosic ethanol conversion would reduce solid waste disposal costs by local and state governments. It is estimated that each person in the US throws away {{convert|4.4|lb|abbr=on}} of trash each day, of which 37% contains waste paper which is largely cellulose. That computes to 244&nbsp;thousand tons per day of discarded waste paper that contains cellulose.<ref></ref> The raw material to produce cellulosic ethanol is not only free, it has a negative cost — i.e., ethanol producers can get paid to take it away.<ref> {{cite web |url=http://www.des.state.nh.us/SWPlan/SWGeneration.pdf |format=PDF |title=Solid Waste Generation}}</ref>
Although the global ] market is sizable (around 110 billion liters in 2019), the vast majority is made from ] or ], not cellulose.<ref>{{cite web|date=May 2020|title=Alternative Fuels Data Center: Maps and Data - Global Ethanol Production|url=https://afdc.energy.gov/data/10331|url-status=live|access-date=2021-05-03|website=afdc.energy.gov|publisher=US Department of Energy|archive-url=https://web.archive.org/web/20130919052713/http://www.afdc.energy.gov:80/data/10331 |archive-date=2013-09-19 }}</ref> In 2007, the cost of producing ethanol from cellulosic sources was estimated ca. USD&nbsp;2.65 per gallon (€0.58 per liter), which is around 2–3 times more expensive than ethanol made from corn.<ref name=":4">{{cite news| vauthors = Osborne S |date=November 2007|title=Energy in 2020: Assessing the Economic Effects of Commercialization of Cellulosic Ethanol|publisher=US Department of Commerce |url=https://www.trade.gov/sites/default/files/2020-12/Energy%20in%202020_Assessing%20the%20Economic%20Effects%20of%20Commercialization%20of%20Cellulosic%20Ethanol.pdf |access-date=2021-05-03}}</ref> However, the cellulosic ethanol market remains relatively small and reliant on government subsidies.<ref name=":2">{{cite web| vauthors = Rapier R |title=Cellulosic Ethanol Falling Far Short Of The Hype|url=https://www.forbes.com/sites/rrapier/2018/02/11/cellulosic-ethanol-falling-far-short-of-the-hype/|access-date=2021-05-03|website=Forbes|language=en}}</ref> The US government originally set cellulosic ethanol targets gradually ramping up from 1 billion liters in 2011 to 60 billion liters in 2022.<ref name="technologyreview.com">{{cite web | vauthors = Orcutt M | date = 9 May 2012 | url = http://www.technologyreview.com/news/427874/us-will-be-hard-pressed-to-meet-its-biofuel-mandates/ | archive-url = https://web.archive.org/web/20140429222808/http://www.technologyreview.com/news/427874/us-will-be-hard-pressed-to-meet-its-biofuel-mandates/ | archive-date = 29 April 2014 | title = U.S. Will Be Hard-Pressed to Meet Its Biofuel Mandates | work = MIT Technology Review }}</ref> However, these annual goals have almost always been waived after it became clear there was no chance of meeting them.<ref name=":3">{{cite web| vauthors = Loyola M |date=2019-11-23|title=Stop the Ethanol Madness|url=https://www.theatlantic.com/ideas/archive/2019/11/ethanol-has-forsaken-us/602191/|access-date=2021-05-03|website=The Atlantic|language=en}}</ref> Most of the plants to produce cellulosic ethanol were canceled or abandoned in the early 2010s.<ref name=":2" /><ref>{{cite web| vauthors = Bullis K |date=November 2012|title=BP Plant Cancellation Darkens Cellulosic Ethanol's Future|url=https://www.technologyreview.com/2012/11/02/181923/bp-plant-cancellation-darkens-cellulosic-ethanols-future/|url-status=live|access-date=2021-05-03|website=MIT Technology Review|language=en|archive-url=https://web.archive.org/web/20200812072458/https://www.technologyreview.com/2012/11/02/181923/bp-plant-cancellation-darkens-cellulosic-ethanols-future/ |archive-date=2020-08-12 }}</ref> Plants built or financed by ], ] and ], among many others, were closed or sold.<ref>{{cite web| vauthors = Mayer A |date=2018-01-02|title=Cellulosic Ethanol Push Stalls In The Midwest Amid Financial, Technical Challenges|url=https://www.kcur.org/agriculture/2018-01-02/cellulosic-ethanol-push-stalls-in-the-midwest-amid-financial-technical-challenges|url-status=live|access-date=2021-05-03|website=KCUR 89.3 - NPR in Kansas City. Local news, entertainment and podcasts.|language=en|archive-url=https://web.archive.org/web/20201203175141/https://www.kcur.org/agriculture/2018-01-02/cellulosic-ethanol-push-stalls-in-the-midwest-amid-financial-technical-challenges |archive-date=2020-12-03 }}</ref> As of 2018, only one major plant remains in the US.<ref name=":2" />


In order for it to be grown on a large-scale production, cellulose biomass must compete with existing uses of agricultural land, mainly for the production of crop commodities. Of the United States' 2.26&nbsp;billion acres (9.1&nbsp;million km<sup>2</sup>) of unsubmerged land,<ref>The World Fact Book, www.cia.org, 01 May 2008</ref> 33% are forestland, 26% pastureland and grassland, and 20% crop land. A study by the U.S. Departments of Energy and Agriculture in 2005 suggested that 1.3&nbsp;billion dry tons of biomass is theoretically available for ethanol use while maintaining an acceptable impact on forestry, agriculture.<ref name="usdoe1">
The environmental company Wise Landfill Recycling Mining<ref></ref> expects to start generating cellulosic ethanol product from trash early 2008.<ref> "WLRM Celebrates Completion of its Cellulosic Ethanol Breakthrough" press release, 2007.</ref>. Their method also boasts of being not merely ], but oil independent.<ref>{{cite web|title=Wise Landfill (Ethanol Market Share)|url=http://www.wiselandfill.com/Ethanol20%Market.html}}</ref>
{{cite web|year=2007|title=Cellulosic Ethanol: Benefits and Challenges. Genomics: GTL|url=http://genomicsgtl.energy.gov/biofuels/benefits.shtml|url-status=dead|archive-url=https://web.archive.org/web/20071221032949/http://genomicsgtl.energy.gov/biofuels/benefits.shtml|archive-date=2007-12-21|access-date=2007-12-09|publisher=U.S. Department of Energy Office of Science}}</ref>


=== Comparison with corn-based ethanol ===
In June 2006, a U.S. Senate hearing was told that the current cost of producing cellulosic ethanol is US $2.25 per US gallon (US $0.59/litre). This is primarily due to the current poor conversion efficiency.{{Fact|date=December 2007}} <!-- the following blog ref is not within Misplaced Pages standards for reference. Blogs are not suitable refs:<ref name="http://i-r-squared.blogspot.com/2006/11/cellulosic-ethanol-reality-check.html">{{cite web | title= R-Squared Energy Blog | url= http://i-r-squared.blogspot.com/2006/11/cellulosic-ethanol-reality-check.html | accessmonthday=November 19 | accessyear=2006 }}</ref> --> At that price it would cost about $120 to substitute a barrel of oil (42&nbsp;gallons), taking into account the lower energy content of ethanol. However, the Department of Energy is optimistic and has requested a doubling of research funding. The same Senate hearing was told that the research target was to reduce the cost of production to US $1.07 per US gallon (US $0.28/litre) by 2012. "The production of cellulosic ethanol represents not only a step toward true energy diversity for the country, but a very cost-effective alternative to fossil fuels. It is advanced weaponry in the war on oil,” said Vinod Khosla, managing partner of Khosla Ventures, who recently told a Reuters Global Biofuels Summit that he could see cellulosic fuel prices sinking to $1&nbsp;per gallon within ten years.
Currently, cellulose is more difficult and more expensive to process into ethanol than corn or sugarcane. The US Department of Energy estimated in 2007 that it costs about $2.20 per gallon to produce cellulosic ethanol, which is 2–3 times much as ethanol from corn. Enzymes that destroy plant cell wall tissue cost US$0.40 per gallon of ethanol compared to US$0.03 for corn.<ref name=":4" /> However, cellulosic biomass is cheaper to produce than corn, because it requires fewer inputs, such as energy, fertilizer, herbicide, and is accompanied by less soil erosion and improved soil fertility. Additionally, nonfermentable and unconverted solids left after making ethanol can be burned to provide the fuel needed to operate the conversion plant and produce electricity. Energy used to run corn-based ethanol plants is derived from coal and natural gas. The ] estimates the cost of cellulosic ethanol from the first generation of commercial plants will be in the $1.90–$2.25 per gallon range, excluding incentives. This compares to the current cost of $1.20–$1.50 per gallon for ethanol from corn and the current retail price of over $4.00 per gallon for regular gasoline (which is subsidized and taxed).<ref name="Putting the Pieces Together:Commercializing Ethanol from Cellulose">{{cite web|year=2007|title=Cellulosic ethanol: fuel of the future?|url=http://www.newrules.org/agri/celluloseethanol.pdf|url-status=dead|archive-url=https://web.archive.org/web/20060927113144/http://www.newrules.org/agri/celluloseethanol.pdf|archive-date=2006-09-27|publisher=ILSR Daily}}</ref>


===Enzyme-cost barrier===
University of Massachusetts at Amherst researchers have developed a streamlined technique which uses "catalytic fast pyrolysis" (heating to 400–600&nbsp;°C followed by rapid cooling) and ] as a catalyst to produce cellulosic ethanol in about 60&nbsp;seconds. They estimate improvements in the process should be able to generate ethanol at the equivalent of $1–$1.70/gal of gasoline. As of April 2008, the process has only been developed to work at laboratory scales.<ref name="energy-daily"> {{cite web
Cellulases and hemicellulases used in the production of cellulosic ethanol are more expensive compared to their first generation counterparts. Enzymes required for maize grain ethanol production cost 2.64-5.28 US dollars per cubic meter of ethanol produced. Enzymes for cellulosic ethanol production are projected to cost 79.25 US dollars, meaning they are 20-40 times more expensive.<ref name="Sainz_2009">{{cite journal | vauthors = Sainz MB | title = Commercial cellulosic ethanol: the role of plant-expressed enzymes. | journal = In Vitro Cellular & Developmental Biology - Plant | date = June 2009 | volume = 45 | issue = 3 | pages = 314–29 | doi = 10.1007/s11627-009-9210-1 | s2cid = 23080785 }}</ref> The cost differences are attributed to quantity required. The cellulase family of enzymes have a one to two order smaller magnitude of efficiency. Therefore, it requires 40 to 100 times more of the enzyme to be present in its production. For each ton of biomass it requires 15-25 kilograms of enzyme.<ref name="Yang, B. 2007">{{cite journal | vauthors = Yang B, Wyman CE | year = 2007 | title = Pretreatment: the key to unlocking low-cost cellulosic ethanol | journal = Biofuels, Bioproducts and Biorefining | volume = 2 | issue = 1| pages = 26–40 | doi = 10.1002/bbb.49 | s2cid = 9015244 }}</ref> More recent estimates<ref name=":0">{{cite journal| vauthors = Johnson E |date=18 Feb 2016|title=Integrated enzyme production lowers the cost of cellulosic ethanol|journal=Biofuels, Bioproducts and Biorefining|doi=10.1002/bbb.1634|volume=10|issue=2|pages=164–174|doi-access=free}}</ref> are lower, suggesting 1&nbsp;kg of enzyme per dry tonne of biomass feedstock. There is also relatively high capital costs associated with the long incubation times for the vessel that perform enzymatic hydrolysis. Altogether, enzymes comprise a significant portion of 20-40% for cellulosic ethanol production. A 2016 paper<ref name=":0" /> estimates the range at 13-36% of cash costs, with a key factor being how the cellulase enzyme is produced. For cellulase produced offsite, enzyme production amounts to 36% of cash cost. For enzyme produced onsite in a separate plant, the fraction is 29%; for integrated enzyme production, the fraction is 13%. One of the key benefits of integrated production is that biomass instead of glucose is the enzyme growth medium. Biomass costs less, and it makes the resulting cellulosic ethanol a 100% second-generation biofuel, i.e., it uses no ‘food for fuel’.{{Citation needed|date=January 2021}}
| url= http://www.energy-daily.com/reports/New_Method_Rapidly_Produces_Low_Cost_Biofuels_From_Wood_Grass_999.html
| title= New Method Rapidly Produces Low-Cost Biofuels From Wood, Grass
|date= 14 Apr 2008 |work= |publisher= Energy Daily
| accessdate= 2008-05-15 }} </ref>


==Feedstocks==
== Environmental effects: corn-based vs. grass-based==
In general there are two types of feedstocks: '''forest (woody) Biomass''' and '''agricultural biomass'''. In the US, about 1.4 billion dry tons of biomass can be sustainably produced annually. About 370 million tons or 30% are forest biomass.<ref>{{cite report | vauthors = Perlack RD | date = 2005 | title = Biomass as feedstock for a bioenergy and bioproducts Industry: the technical feasibility of a billion-ton annual supply. | work = Oak Ridge National Laboratory Report ORNL/TM-2005/66 | publisher = US Department of Energy | location = Oak Ridge, TN }}</ref> Forest biomass has higher cellulose and lignin content and lower hemicellulose and ash content than agricultural biomass. Because of the difficulties and low ethanol yield in fermenting pretreatment hydrolysate, especially those with very high 5 carbon hemicellulose sugars such as xylose, forest biomass has significant advantages over agricultural biomass. Forest biomass also has high density which significantly reduces transportation cost. It can be harvested year around which eliminates long-term storage. The close to zero ash content of forest biomass significantly reduces dead load in transportation and processing. To meet the needs for biodiversity, forest biomass will be an important biomass feedstock supply mix in the future biobased economy. However, forest biomass is much more recalcitrant than agricultural biomass. In 2009, the ] together with the ] developed efficient technologies<ref name="zhu"/><ref>{{cite journal | vauthors = Wang GS, Pan XJ, Zhu JY, Gleisner R, Rockwood D | title = Sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL) for robust enzymatic saccharification of hardwoods | journal = Biotechnology Progress | volume = 25 | issue = 4 | pages = 1086–93 | year = 2009 | pmid = 19551888 | doi = 10.1002/btpr.206 | s2cid = 18328577 }}</ref> that can overcome the strong recalcitrance of forest (woody) biomass including those of softwood species that have low xylan content. Short-rotation intensive culture or tree farming can offer an almost unlimited opportunity for forest biomass production.<ref>{{cite book | vauthors = Foody BE, Foody KJ | date = 1991 | chapter = Development of an integrated system for producing ethanol from biomass. | veditors = Klass DL | title = Energy from Biomass and Waste. | publisher = Institute of Gas Technology | location = Chicago | pages = 1225–1243 }}</ref>
Today, there is only a small amount of switchgrass dedicated for ethanol production. In order for it to be grown on a large-scale production it must compete with existing uses of agricultural land, mainly for the production of crop commodities. Of the United States' 2.26&nbsp;billion acres (9.1&nbsp;million km²) of unsubmerged land,<ref>The World Fact Book, www.cia.org, 01May2008</ref> 33% are forestland, 26% pastureland and grassland, and 20% crop land. A study done by the U.S. Departments of Energy and Agriculture in 2005, determined whether there were enough available land resources to sustain production of over 1&nbsp;billion dry tons of biomass annually to replace 30% or more of the nation’s current use of liquid transportation fuels. The study found that there could be 1.3&nbsp;billion dry tons of biomass available for ethanol use, by making little changes in agricultural and forestry practices and meeting the demands for forestry products, food, and fiber.<ref name=usdoe1">{{cite web |publisher=U.S. Department of Energy Office of Science |date=2007 |title=Cellulosic Ethanol: Benefits and Challenges. Genomics: GTL| url=http://genomicsgtl.energy.gov/biofuels/benefits.shtml|accessdate=2007-12-09}}</ref> A recent study done by the University of Tennessee reported that as many as 100&nbsp;million acres (400,000&nbsp;km², or 154,000 sq.&nbsp;miles), of cropland and pasture will need to be allocated to switchgrass production in order to offset petroleum use by 25&nbsp;percent.<ref name=montenegro> {{cite web |author=Montenegro, M. |date=2006 |title=The Big Three |publisher=Grist Environmental News |url=http://grist.org/news |accessdate=2007-12-10}}</ref>


] from slashes and tree tops and ] from saw mills, and ] are forest biomass feedstocks for cellulosic ethanol production.<ref>{{cite web | vauthors = Patel P | date = 9 September 2008 | url = http://www.technologyreview.com/Energy/21347/?nlid=1325 | archive-url = https://web.archive.org/web/20110608002312/http://www.technologyreview.com/Energy/21347/?nlid=1325 | archive-date = 8 June 2011 | title = Better Bug to Make Cellulosic Ethanol: A new strain of bacteria could make cellulosic ethanol cheaper. | work = MIT Technology Review }}</ref>
Currently, corn is easier and less expensive to process into ethanol in comparison to cellulosic ethanol. The Department of Energy estimates that it costs about $2.20 per gallon to produce cellulosic ethanol, which is twice as much as ethanol from corn. Enzymes that destroy plant cell wall tissue cost 30 to 50&nbsp;cents per gallon of ethanol compared to 3&nbsp;cents per gallon for corn.<ref name=Weeks>{{cite web|author=Weeks, J. |date=2006 |title=Are We There Yet? Not quite, but cellulosic ethanol may be coming sooner than you think |publisher=Grist Magazine |url=http://www.grist.org/news/maindish/2006/12/11/weeks/index.html |accessdate=2007-12-08}}</ref> The Department of Energy hopes to reduce this cost to $1.07 per gallon by 2012 to be effective. However, cellulosic biomass is cheaper to produce than corn, because it requires fewer inputs, such as energy, fertilizer, herbicide, and is accompanied by less soil erosion and improved soil fertility. Additionally, nonfermentable and unconverted solids left after making ethanol can be burned to provide the fuel needed to operate the conversion plant and produce electricity. Energy used to run corn-based ethanol plants is derived from coal and natural gas. The estimates the cost of cellulosic ethanol from the first generation of commercial plants will be in the $1.90–$2.25 per gallon range, excluding incentives. This compares to the current cost of $1.20–$1.50 per gallon for ethanol from corn and the current retail price of over $3.00 per gallon for Regular Gasoline (which is subsidized and taxed).<ref name="Putting the Pieces Together:Commercializing Ethanol from Cellulose">{{cite web |publisher=ILSR Daily |date=2007 |title=Cellulosic Ethanol: Fuel of the Future? |url=http://www.newrules.org/agri/celluloseethanol.pdf}}</ref>


'''Switchgrass''' ('']'') is a native ] grass. Known for its hardiness and rapid growth, this perennial grows during the warm months to heights of 2–6&nbsp;feet. Switchgrass can be grown in most parts of the United States, including swamplands, plains, streams, and along the shores & ''interstate highways''. It is ''self-seeding'' (no tractor for sowing, only for mowing), resistant to many diseases and pests, & can produce high yields with low applications of fertilizer and other chemicals. It is also tolerant to poor soils, flooding, & drought; improves soil quality and prevents erosion due its type of root system.<ref name="Rinehart">{{cite web | vauthors = Rinehart L |year=2006 |title=Switchgrass as a Bioenergy Crop. National Sustainable Agriculture Information Service |url=http://attra.ncat.org/attra-pub/PDF/switchgrass.pdf#xml=http://search.ncat.org/texis/search/pdfhi.txt?query=Rinehart&pr=ATTRAv2&prox=page&rorder=500&rprox=500&rdfreq=500&rwfreq=500&rlead=500&rdepth=0&sufs=0&order=r&cq=&id=4770e3036d |access-date=2007-12-10 |archive-url=https://web.archive.org/web/20070715192013/http://attra.ncat.org/attra-pub/PDF/switchgrass.pdf#xml=http://search.ncat.org/texis/search/pdfhi.txt?query=Rinehart&pr=ATTRAv2&prox=page&rorder=500&rprox=500&rdfreq=500&rwfreq=500&rlead=500&rdepth=0&sufs=0&order=r&cq=&id=4770e3036d |archive-date=2007-07-15 |url-status=dead }}</ref>
One of the major reasons for increasing the use of biofuels is to reduce greenhouse gas emissions.<ref name=sciencedaily">{{cite web |publisher=Science Daily |date=2007 |title=Cellulosic Ethanol: Fuel of the Future? |url=http://www.sciencedaily.com/releases/2007/02/070218140448.htm |accessdate=2007-12-10}}</ref> In comparison to gasoline, ethanol burns cleaner with a greater efficiency, thus putting less carbon dioxide and overall pollution in the air. Additionally, only low levels of smog are produced from combustion.<ref name="demain">{{cite journal |author=Demain A., Newcomb M. , Wu D.|date=March 2005 |title= Cellulase, Clostridia, and Ethanol. Microbiology |journal=Molecular Biology Reviews |issue=69 |pages=124–154}}</ref> According to the U.S. Department of Energy, ethanol from cellulose reduces green house gas emission by 90&nbsp;percent, when compared to gasoline and in comparison to corn-based ethanol which decreases emissions by 10 to 20&nbsp;percent.<ref name=montenegro/> Carbon dioxide gas emissions are shown to be 85%&nbsp;lower than those from gasoline. Cellulosic ethanol contributes little to the greenhouse effect and has a five times better net energy balance than corn-based.<ref name="demain"/> When used as a fuel, cellulosic ethanol releases less sulfur, carbon monoxide, particulates, and greenhouse gases. Cellulosic ethanol should earn producers carbon reduction credits, higher than those given to producers who grow corn for ethanol, which is about 3 to 20&nbsp;cents per gallon.<ref name=Weeks/>

It takes 0.76 J of energy from fossil fuels to produce 1 J worth of ethanol from corn.<ref name=farrell>{{cite journal | author = Farrell A.E., Plevin R.J., Turner B.T., Jones A.D., O’Hare M., Kammen D.M. | date=27 January 2006 | title = Ethanol Can Contribute to Energy
and Environmental Goals | journal = Science | volume = 311 | pages = 506-508}}</ref>
This total includes the use of fossil fuels used for fertilizer, tractor fuel, ethanol plant operation, etc. Research has shown that 1 gallon of fossil fuel can produce over 5&nbsp;gallons of ethanol from prairie grasses, according to Terry Riley, President of Policy at the Theodore Roosevelt Conservation Partnership. The United States Department of Energy concludes that corn-based ethanol provides 26&nbsp;percent more energy than it requires for production, while cellulosic ethanol provides 80&nbsp;percent more energy.<ref name=montenegro/> Cellulosic ethanol yields 80 percent more energy than is required to grow and convert it.<ref name=ratliff>{{cite journal |author=Ratliff, E. 2007 |title=One Molecule Could Cure our Addiction to Oil |journal=Wired Magazine |issue=10 |volume=15}}</ref> The process of turning corn into ethanol requires about 1,700&nbsp;gallons of water for every 1&nbsp;gallon of ethanol produced. Additionally, each gallon of ethanol leaves behind 12&nbsp;gallons of waste that must be disposed.<ref name="marshall">{{cite journal|author=Marshall, B.|date=October 2007|title=Gas From the Grass| journal=Field and Stream|page 40–42}}</ref> Grain ethanol uses only the edible portion of the plant. Expansion of corn acres for the production of ethanol poses threats to biodiversity. Corn lacks a strong root system, therefore, when produced, it causes soil erosion. This has a direct effect on soil particles, along with excess fertilizers and other chemicals, washing into local waterways, damaging water quality and harming aquatic life. Planting riparian areas can serve as a buffer to waterways, and decrease runoff.

Cellulose is not used for food and can be grown in all parts of the world. The entire plant can be used when producing cellulosic ethanol. Switchgrass yields twice as much ethanol per acre than corn.<ref name=montenegro/> Therefore, less land is needed for production and thus less habitat fragmentation. Biomass materials require fewer inputs, such as fertilizer, herbicides, and other chemicals that can pose risks to wildlife. Their extensive roots improve soil quality, reduce erosion, and increase nutrient capture. Herbaceous energy crops reduce soil erosion by greater than 90%, when compared to conventional commodity crop production. This can translate into improved water quality for rural communities. Additionally, herbaceous energy crops add organic material to depleted soils and can increase soil carbon, which can have a direct effect on climate change.<ref name="nelson">{{cite web|author=Nelson, R.|date=2007|title=Cellulosic Ethanol/ Bioethanol in Kansas |url=http://kec.kansas.gov/reports/Cellulosic_Ethanol_FINAL.pdf |format=PDF |accessdate=2007-12-09}}</ref> As compared to commodity crop production, biomass reduces surface runoff and nitrogen transport. Switchgrass provides an environment for diverse wildlife habitation, mainly insects and ground birds. Conservation Resource Program (CRP) land is composed of perennial grasses, which are used for cellulosic ethanol, and may be available for use.

==Feedstocks==
Switchgrass is a native prairie grass of "the tall grass prairie", in contrast to the short grass of the "high plains". Known for its hardiness and rapid growth, this perennial grows during the warm months to heights of 2–6&nbsp;feet. Switchgrass can be grown in most parts of the United States, including swamplands, plains, streams, and along the shores & ''interstate highways''. It is ''self-seeding'' (no tractor for sowing, only for mowing), resistant to many diseases and pests, & can produce high yields with low applications of fertilizer and other chemicals. It is also tolerant to poor soils, flooding, & drought; improves soil quality and prevents erosion due its type of root system.<ref name="Rinehart">{{cite web |author=Rinehart, L. |date=2006 |title=Switchgrass as a Bioenergy Crop. National Sustainable Agriculture Information Service| url=http://attra.ncat.org/attra-pub/PDF/switchgrass.pdf#xml=http://search.ncat.org/texis/search/pdfhi.txt?query=Rinehart&pr=ATTRAv2&prox=page&rorder=500&rprox=500&rdfreq=500&rwfreq=500&rlead=500&rdepth=0&sufs=0&order=r&cq=&id=4770e3036d | accessdate=2007-12-10}}</ref>


Switchgrass is an approved cover crop for land protected under the federal ] (CRP). CRP is a government program that pays producers a fee for not growing crops on land on which crops recently grew. This program reduces soil erosion, enhances water quality, and increases wildlife habitat. CRP land serves as a habitat for upland game, such as pheasants and ducks, and a number of insects. Switchgrass for biofuel production has been considered for use on Conservation Reserve Program (CRP) land, which could increase ecological sustainability and lower the cost of the CRP program. However, CRP rules would have to be modified to allow this economic use of the CRP land.<ref name="Rinehart"/> Switchgrass is an approved cover crop for land protected under the federal ] (CRP). CRP is a government program that pays producers a fee for not growing crops on land on which crops recently grew. This program reduces soil erosion, enhances water quality, and increases wildlife habitat. CRP land serves as a habitat for upland game, such as pheasants and ducks, and a number of insects. Switchgrass for biofuel production has been considered for use on Conservation Reserve Program (CRP) land, which could increase ecological sustainability and lower the cost of the CRP program. However, CRP rules would have to be modified to allow this economic use of the CRP land.<ref name="Rinehart"/>


''']''' is another viable feedstock for cellulosic ethanol production. This species of grass is native to Asia and is a sterile ] of '']'' and '']''. It has high crop yields, is cheap to grow, and thrives in a variety of climates. However, because it is sterile, it also requires ], making it more expensive.<ref>{{cite journal| vauthors = Christian DG, Riche AB, Yates NE |date= November 2008 |title=Growth, yield and mineral content of Miscanthus×giganteus grown as a biofuel for 14 successive harvests |journal=Industrial Crops and Products|language=en|volume=28|issue=3|pages=320–327|doi=10.1016/j.indcrop.2008.02.009}}</ref>
==Cellulosic ethanol commercialization==
{{Main|Cellulosic ethanol commercialization}}
Cellulosic ethanol commercialization can contribute to a successful renewable fuels future.


It has been suggested that ] may become a valuable source of biomass.<ref>{{cite journal | vauthors = Lugar RG, Woolsey RJ | year = 1999 | title = The New Petroleum | journal = Foreign Affairs | volume = 78 | issue = 1| pages = 88–102 | doi=10.2307/20020241| jstor = 20020241 }}</ref>
Companies such as ], Broin, and ] are all building refineries that can process biomass and turn it into ethanol, while companies such as ], ], and Dyadic are producing enzymes and ]<ref> http:www.butalco.com</ref> is developing improved yeast strains, which could enable a cellulosic ethanol future. The shift from food crop feedstocks to waste residues and native grasses offers significant opportunities for a range of players, from farmers to biotechnology firms, and from project developers to investors.<ref> Pernick, Ron and Wilder, Clint (2007). '']'' p.&nbsp;96.</ref>


==Cellulosic ethanol commercialization==
A biorefinery built to produce 1.4 million gallons of ethanol a year from cellulosic biomass has opened in ]. Built by ], based in ], the plant makes ethanol from agricultural waste left over from processing ]. <ref>http://www.technologyreview.com/Energy/20828/?nlid=1099</ref>
Fueled by subsidies and grants, a boom in cellulosic ethanol research and ]s occurred in the early 2000s. Companies such as ], ], and ] built refineries that can process biomass and turn it into ethanol, while companies such as ], ], ], and ] invested in enzyme research. However, most of these plants were canceled or closed in the early 2010s as technical obstacles proved too difficult to overcome. As of 2018, only one cellulosic ethanol plant remained operational.<ref name=":2" />


In the later 2010s, various companies occasionally attempted smaller-scale efforts at commercializing cellulosic ethanol, although such ventures generally remain at experimental scales and often dependent on subsidies. The companies Granbio, ] and the ] each run a pilot-scale facility operate in Brazil, which together produce around 30 million liters in 2019.<ref>{{Cite book| vauthors = Barros S |title=Biofuels Annual|publisher=]|year=2020|pages=33}}</ref> ], which started as an enzyme maker in 1991 and re-oriented itself to focus primarily on cellulosic ethanol in 2013, owns many patents for cellulosic ethanol production<ref>{{Cite web|title=Novozymes acquires Iogen Bio-Products - Manure ManagerManure Manager|date=11 February 2013 |url=https://www.manuremanager.com/novozymes-acquires-iogen-bio-products-30139/|access-date=2021-05-05|language=en-US}}</ref> and provided the technology for the Raízen plant.<ref>{{Cite web|date=2021-03-18|title=Raízen planeja mais três usinas de etanol 2G|url=https://www.argusmedia.com/en/news/2197446-raízen-planeja-mais-três-usinas-de-etanol-2g|url-status=live|access-date=2021-05-05|website=Argus Media|language=en|archive-url=https://web.archive.org/web/20210318213520/https://www.argusmedia.com/en/news/2197446-ra%C3%ADzen-planeja-mais-tr%C3%AAs-usinas-de-etanol-2g |archive-date=2021-03-18 }}</ref> Other companies developing cellulosic ethanol technology as of 2021 are ] (Denmark); companies operating or planning pilot production plants include New Energy Blue (US),<ref>{{Cite web| vauthors = Rischar H | date=September 19, 2020|title=New Energy Blue converts agricultural waste to alternative fuels, cuts emissions|url=https://www.wastetodaymagazine.com/article/new-energy-blue-converts-agricultural-waste-to-alternative-fuels-cuts-emissions/|url-status=live|access-date=2021-05-05|website=Waste Today|language=en|archive-url=https://web.archive.org/web/20201002032550/https://www.wastetodaymagazine.com/article/new-energy-blue-converts-agricultural-waste-to-alternative-fuels-cuts-emissions/ |archive-date=2020-10-02 }}</ref> Sekab (Sweden)<ref>{{Cite web|date=2020-03-09|title=Sekab and Vertoro to build large-scale demo plant to produce "Goldilocks"|url=https://bioenergyinternational.com/biofuels-oils/sekab-and-vertoro-to-build-large-scale-demo-plant-to-produce-goldilocks|access-date=2021-05-05|website=Bioenergy International|language=en-US}}</ref> and ] (in Romania).<ref>{{Cite news| vauthors = Scott A |date=September 30, 2018|title=Clariant bets big on cellulosic ethanol|work=Chemical & Engineering News|url=https://cen.acs.org/business/agriculture/Clariant-bets-big-cellulosic-ethanol/96/i39}}</ref> Abengoa, a Spanish company with cellulosic ethanol assets, became insolvent in 2021.<ref>{{Cite news| vauthors = Garcia Perez I |date=2021-02-23|title=Spanish Renewable Energy Firm Files for Insolvency|language=en|work=Bloomberg.com|url=https://www.bloomberg.com/news/articles/2021-02-23/abengoa-insolvency-filing-marks-spain-s-biggest-company-failure|access-date=2021-05-05}}</ref>
== Related Fields To Cellulosic Ethanol ==
*]


The ], along with state and local governments, partially funded a pilot plant in 2017 and 2020 in ] as part of efforts to diversify the regional economy away from coal mining.<ref>{{Cite web| vauthors = Kirkwood I |date=2020-05-25|title=Muswellbrook council considering $10m grant to early stage bio-fuel plant after Chinese investor withdraws|url=https://www.newcastleherald.com.au/story/6766041/muswellbrook-council-considering-10m-grant-to-early-stage-bio-fuel-plant-after-chinese-investor-withdraws/|access-date=2021-05-05|website=Newcastle Herald|language=en-AU}}</ref>
==Prominent cellulosic ethanol researchers==
{{Unreferencedsection|date=August 2007}}
* , ]
** 2007 USDA Sterling B. Hendricks memorial lecturer
** 1996 Charles D. Scott awardee
** The Inventor of Ammonia Fiber Expansion (AFEX) pretreatment
** Fourteen US international patent holder
** Among the group of ten experts from industry, academia and government lab who was invited to brief President Bush on biofuels
* , ]
* , ]
** 1996 Presidential Green Chemistry awardee
* , University of Florida ]
** 2007 Charles D. Scott awardee
** Member of U.S. National Academy of Sciences (2001)
** Fellow of Society of Industrial Microbiology (2001)
** Twelve U.S. Patents holder including the landmark patent 5,000,000 on an important breakthrough on metabolic engineering of ''Escherichia coli'' to utilize virtually all sugars from lignocellulosic materials for ethanol production
* , ]
* , ]
*
** Seven international patents holder including the patent describing the first recombinant yeast able to ferment the lignocellulosic sugar L-arabinose
*
*
*
* , ]


=== US Government support ===
==Development timeline==
From 2006, the US Federal government began promoting the development of ethanol from cellulosic feedstocks. In May 2008, Congress passed a new farm bill that contained funding for the commercialization of ], including cellulosic ethanol. The ''Food, Conservation, and Energy Act of 2008'' provided for grants covering up to 30% of the cost of developing and building demonstration-scale biorefineries for producing "advanced biofuels," which effectively included all fuels not produced from corn kernel starch. It also allowed for loan guarantees of up to $250 million for building commercial-scale biorefineries.<ref></ref>


In January 2011, the USDA approved $405 million in loan guarantees through the 2008 Farm Bill to support the commercialization of cellulosic ethanol at three facilities owned by ], ] and ]. The projects represent a combined {{convert|73|e6USgal|m3}} per year production capacity and will begin producing cellulosic ethanol in 2012. The USDA also released a list of advanced biofuel producers who will receive payments to expand the production of advanced biofuels.<ref>{{cite web |url=http://www.ethanolproducer.com/articles/7433/usda-approves-loan-guarantees-for-3-cellulosic-projects |title=USDA approves loan guarantees for 3 cellulosic projects |author=Bevill, Kris |date=January 20, 2011 |work=Ethanol Producer Magazine }}</ref> In July 2011, the US Department of Energy gave in $105 million in loan guarantees to ] for a commercial-scale plant to be built ].<ref>{{cite news|title=U.S. Backs Project to Produce Fuel From Corn Waste|url=https://www.nytimes.com/2011/07/07/business/energy-environment/us-backs-plant-to-make-fuel-from-corn-waste.html|access-date=July 7, 2011|newspaper=The New York Times|date=July 6, 2011|author=Matthew L. Wald|quote=The Energy Department plans to provide a $105 million loan guarantee for the expansion of an ethanol factory in Emmetsburg, Iowa, that intends to make motor fuel from corncobs, leaves and husks. }}</ref>
* 1998 US Patent # 5,811,381 — Cellulase Compositions And Methods Of Use. - Methods of use for the cellulase compositions of the saccharification of lignocellulose biomass from agriculture, forest products, muicipal solid waste and other sources.
* 2003 US Patent # 6,573,086 — Transformation System In The Field Of Filamentous Fungal Hosts. - Engineering filamentous fungi to produce low cost efficient enzyme mixtures to convert lignocellulose (biomass or energy crops) into fermntable sugars such as glucose and xylose
* 2005 — Fungus functions as lab and factory for protein
* 2006 — Design of Highly Efficient Cellulase Mixtures for Enzymatic Hydrolysis of Cellulose
* 2006 — US Patent # 7,122,330 - High-Throughput Screening of Expressed DNA Libraries in Filamentous Fungi — use of robotics to identify and create new and better genes that encode for cellulase and hemicellulase enzymes that can be inserted into fungi or other organisms for use in the conversion of lignocellulose (biomass or energy crops) into fermentable sugars
* 2006 — BIO CEO and Investor Conference, February 13-15, 2006 at The Waldorf Astoria Hotel in New York City.
* 2006 — Industrial Biotech Gains Momentum, Growth of commercial enzyme-mediated processes points to the future of the chemical industry; ], ]
* 2006 — Exploiting Fungal Factories for Future Energy
* 2006 — Cradle of innovation Although it's starting late, Florida has minds and the raw materials tobecome a leader in alternative energy research and a.. ], ]
* - Beyond corn: Ethanol's next generation, Scientists seek cheap, plentiful energy alternatives October,13 2006
* 2006 — Bear Stearns Second Annual Commodities and Capital Goods Conference, Wednesday, ] and Thursday, ], ] - Biofuels – Prospect of Future Technologies
* 2006 — "US biofuels: A field in ferment" - Nature 444, 673-676 (] ]) | doi:10.1038/444673a; Published online ] ]
* 2006 — Put A Termite In Your Tank ], ]
* 2007 — Ethanol Producer Magazine January 2007 "The Discoverer's Game"
* 2007 — BIO CEO & Investor Conference ], ] at the Waldorf-Astoria Hotel in New York City,
* 2007 — World Biofuels Markets Congress, Brussels,Belgium March 12-14 2008 -
* 2007 — Dyadic, Int.: The Making of Cellulosic Ethanol
* 2007 — The Energy Challenge A Renewed Push for Ethanol, Without the Corn, NY Times ], ]


== See also == ==See also==
{{Portal|Renewable energy}}
{{EnergyPortal}}
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* ] *]
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==References== ==References==
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== External links == ==External links==
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* — P.C. Badger, 2002 * — P.C. Badger, 2002
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* The by Environment Canada, 1999, re-published by the web site.
* , including current costs and expected costs of producing cellulosic ethanol.
* ], ]]
* by Maywa Montenegro, Grist Magazine, ] ]
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* {{Webarchive|url=https://web.archive.org/web/20100106114400/http://www.fpl.fs.fed.us/ |date=2010-01-06 }}
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== Further reading ==
{{Bioenergy}}
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* {{cite book | vauthors = Mansoori GA, Enayati N, Agyarko LB | date = 2016 | url = http://www.worldscientific.com/worldscibooks/10.1142/9699 | title = Energy: Sources, Utilization, Legislation, Sustainability, Illinois as Model State | publisher = World Sci. Pub. Co. | doi = 10.1142/9699 | isbn = 978-981-4704-00-7}}
{{refend}}


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Latest revision as of 07:43, 3 December 2024

Ethanol produced from cellulose

Cellulosic ethanol is ethanol (ethyl alcohol) produced from cellulose (the stringy fiber of a plant) rather than from the plant's seeds or fruit. It can be produced from grasses, wood, algae, or other plants. It is generally discussed for use as a biofuel. The carbon dioxide that plants absorb as they grow offsets some of the carbon dioxide emitted when ethanol made from them is burned, so cellulosic ethanol fuel has the potential to have a lower carbon footprint than fossil fuels.

Interest in cellulosic ethanol is driven by its potential to replace ethanol made from corn or sugarcane. Since these plants are also used for food products, diverting them for ethanol production can cause food prices to rise; cellulose-based sources, on the other hand, generally do not compete with food, since the fibrous parts of plants are mostly inedible to humans. Another potential advantage is the high diversity and abundance of cellulose sources; grasses, trees and algae are found in almost every environment on Earth. Even municipal solid waste components like paper could conceivably be made into ethanol. The main current disadvantage of cellulosic ethanol is its high cost of production, which is more complex and requires more steps than corn-based or sugarcane-based ethanol.

Cellulosic ethanol received significant attention in the 2000s and early 2010s. The United States government in particular funded research into its commercialization and set targets for the proportion of cellulosic ethanol added to vehicle fuel. A large number of new companies specializing in cellulosic ethanol, in addition to many existing companies, invested in pilot-scale production plants. However, the much cheaper manufacturing of grain-based ethanol, along with the low price of oil in the 2010s, meant that cellulosic ethanol was not competitive with these established fuels. As a result, most of the new refineries were closed by the mid-2010s and many of the newly founded companies became insolvent. A few still exist, but are mainly used for demonstration or research purposes; as of 2021, none produces cellulosic ethanol at scale.

Overview

Cellulosic ethanol is a type of biofuel produced from lignocellulose, a structural material that comprises much of the mass of plants and is composed mainly of cellulose, hemicellulose and lignin. Popular sources of lignocellulose include both agricultural waste products (e.g. corn stover or wood chips) and grasses like switchgrass and miscanthus species. These raw materials for ethanol production have the advantage of being abundant and diverse and would not compete with food production, unlike the more commonly used corn and cane sugars. However, they also require more processing to make the sugar monomers available to the microorganisms typically used to produce ethanol by fermentation, which drives up the price of cellulos-derived ethanol.

Cellulosic ethanol can reduce greenhouse gas emissions by 85% over reformulated gasoline. By contrast, starch ethanol (e.g., from corn), which most frequently uses natural gas to provide energy for the process, may not reduce greenhouse gas emissions at all depending on how the starch-based feedstock is produced. According to the National Academy of Sciences in 2011, there is no commercially viable bio-refinery in existence to convert lignocellulosic biomass to fuel. Absence of production of cellulosic ethanol in the quantities required by the regulation was the basis of a United States Court of Appeals for the District of Columbia decision announced January 25, 2013, voiding a requirement imposed on car and truck fuel producers in the United States by the Environmental Protection Agency requiring addition of cellulosic biofuels to their products. These issues, along with many other difficult production challenges, led George Washington University policy researchers to state that "in the short term, ethanol cannot meet the energy security and environmental goals of a gasoline alternative."

History

The French chemist, Henri Braconnot, was the first to discover that cellulose could be hydrolyzed into sugars by treatment with sulfuric acid in 1819. The hydrolyzed sugar could then be processed to form ethanol through fermentation. The first commercialized ethanol production began in Germany in 1898, where acid was used to hydrolyze cellulose. In the United States, the Standard Alcohol Company opened the first cellulosic ethanol production plant in South Carolina in 1910. Later, a second plant was opened in Louisiana. However, both plants were closed after World War I due to economic reasons.

The first attempt at commercializing a process for ethanol from wood was done in Germany in 1898. It involved the use of dilute acid to hydrolyze the cellulose to glucose, and was able to produce 7.6 liters of ethanol per 100 kg of wood waste (18 US gal (68 L) per ton). The Germans soon developed an industrial process optimized for yields of around 50 US gallons (190 L) per ton of biomass. This process soon found its way to the US, culminating in two commercial plants operating in the southeast during World War I. These plants used what was called "the American Process" — a one-stage dilute sulfuric acid hydrolysis. Though the yields were half that of the original German process (25 US gallons (95 L) of ethanol per ton versus 50), the throughput of the American process was much higher. A drop in lumber production forced the plants to close shortly after the end of World War I. In the meantime, a small but steady amount of research on dilute acid hydrolysis continued at the USFS's Forest Products Laboratory. During World War II, the US again turned to cellulosic ethanol, this time for conversion to butadiene to produce synthetic rubber. The Vulcan Copper and Supply Company was contracted to construct and operate a plant to convert sawdust into ethanol. The plant was based on modifications to the original German Scholler process as developed by the Forest Products Laboratory. This plant achieved an ethanol yield of 50 US gal (190 L) per dry ton, but was still not profitable and was closed after the war.

With the rapid development of enzyme technologies in the last two decades, the acid hydrolysis process has gradually been replaced by enzymatic hydrolysis. Chemical pretreatment of the feedstock is required to hydrolyze (separate) hemicellulose, so it can be more effectively converted into sugars. The dilute acid pretreatment is developed based on the early work on acid hydrolysis of wood at the USFS's Forest Products Laboratory. In 2009, the Forest Products Laboratory together with the University of Wisconsin–Madison developed a sulfite pretreatment to overcome the recalcitrance of lignocellulose for robust enzymatic hydrolysis of wood cellulose.

In his 2007 State of the Union Address on January 23, 2007, US President George W. Bush announced a proposed mandate for 35 billion US gallons (130×10^ L) of ethanol by 2017. Later that year, the US Department of Energy awarded $385 million in grants aimed at jump-starting ethanol production from nontraditional sources like wood chips, switchgrass, and citrus peels.

Production methods

Bioreactor for cellulosic ethanol research.

The stages to produce ethanol using a biological approach are:

  1. A "pretreatment" phase to make the lignocellulosic material such as wood or straw amenable to hydrolysis
  2. Cellulose hydrolysis (cellulolysis) to break down the molecules into sugars
  3. Microbial fermentation of the sugar solution
  4. Distillation and dehydration to produce pure alcohol

In 2010, a genetically engineered yeast strain was developed to produce its own cellulose-digesting enzymes. Assuming this technology can be scaled to industrial levels, it would eliminate one or more steps of cellulolysis, reducing both the time required and costs of production.

Although lignocellulose is the most abundant plant material resource, its usability is curtailed by its rigid structure. As a result, an effective pretreatment is needed to liberate the cellulose from the lignin seal and its crystalline structure so as to render it accessible for a subsequent hydrolysis step. By far, most pretreatments are done through physical or chemical means. To achieve higher efficiency, both physical and chemical pretreatments are required. Physical pretreatment involves reducing biomass particle size by mechanical processing methods such as milling or extrusion. Chemical pretreatment partially depolymerizes the lignocellulose so enzymes can access the cellulose for microbial reactions.

Chemical pretreatment techniques include acid hydrolysis, steam explosion, ammonia fiber expansion, organosolv, sulfite pretreatment, SO2-ethanol-water fractionation, alkaline wet oxidation and ozone pretreatment. Besides effective cellulose liberation, an ideal pretreatment has to minimize the formation of degradation products because they can inhibit the subsequent hydrolysis and fermentation steps. The presence of inhibitors further complicates and increases the cost of ethanol production due to required detoxification steps. For instance, even though acid hydrolysis is probably the oldest and most-studied pretreatment technique, it produces several potent inhibitors including furfural and hydroxymethylfurfural. Ammonia Fiber Expansion (AFEX) is an example of a promising pretreatment that produces no inhibitors.

Most pretreatment processes are not effective when applied to feedstocks with high lignin content, such as forest biomass. These require alternative or specialized approaches. Organosolv, SPORL ('sulfite pretreatment to overcome recalcitrance of lignocellulose') and SO2-ethanol-water (AVAP®) processes are the three processes that can achieve over 90% cellulose conversion for forest biomass, especially those of softwood species. SPORL is the most energy efficient (sugar production per unit energy consumption in pretreatment) and robust process for pretreatment of forest biomass with very low production of fermentation inhibitors. Organosolv pulping is particularly effective for hardwoods and offers easy recovery of a hydrophobic lignin product by dilution and precipitation. AVAP® process effectively fractionates all types of lignocellulosics into clean highly digestible cellulose, undegraded hemicellulose sugars, reactive lignin and lignosulfonates, and is characterized by efficient recovery of chemicals.

Cellulolytic processes

The hydrolysis of cellulose (cellulolysis) produces simple sugars that can be fermented into alcohol. There are two major cellulolysis processes: chemical processes using acids, or enzymatic reactions using cellulases.

Chemical hydrolysis

In the traditional methods developed in the 19th century and at the beginning of the 20th century, hydrolysis is performed by attacking the cellulose with an acid. Dilute acid may be used under high heat and high pressure, or more concentrated acid can be used at lower temperatures and atmospheric pressure. A decrystallized cellulosic mixture of acid and sugars reacts in the presence of water to complete individual sugar molecules (hydrolysis). The product from this hydrolysis is then neutralized and yeast fermentation is used to produce ethanol. As mentioned, a significant obstacle to the dilute acid process is that the hydrolysis is so harsh that toxic degradation products are produced that can interfere with fermentation. BlueFire Renewables uses concentrated acid because it does not produce nearly as many fermentation inhibitors, but must be separated from the sugar stream for recycle to be commercially attractive.

Agricultural Research Service scientists found they can access and ferment almost all of the remaining sugars in wheat straw. The sugars are located in the plant's cell walls, which are notoriously difficult to break down. To access these sugars, scientists pretreated the wheat straw with alkaline peroxide, and then used specialized enzymes to break down the cell walls. This method produced 93 US gallons (350 L) of ethanol per ton of wheat straw.

Enzymatic hydrolysis

Cellulose chains can be broken into glucose molecules by cellulase enzymes. This reaction occurs at body temperature in the stomachs of ruminants such as cattle and sheep, where the enzymes are produced by microbes. This process uses several enzymes at various stages of this conversion. Using a similar enzymatic system, lignocellulosic materials can be enzymatically hydrolyzed at a relatively mild condition (50 °C and pH 5), thus enabling effective cellulose breakdown without the formation of byproducts that would otherwise inhibit enzyme activity. All major pretreatment methods, including dilute acid, require an enzymatic hydrolysis step to achieve high sugar yield for ethanol fermentation.

Fungal enzymes can be used to hydrolyze cellulose. The raw material (often wood or straw) still has to be pre-treated to make it amenable to hydrolysis. In 2005, Iogen Corporation announced it was developing a process using the fungus Trichoderma reesei to secrete "specially engineered enzymes" for an enzymatic hydrolysis process.

Another Canadian company, SunOpta, uses steam explosion pretreatment, providing its technology to Verenium (formerly Celunol Corporation)'s facility in Jennings, Louisiana, Abengoa's facility in Salamanca, Spain, and a China Resources Alcohol Corporation in Zhaodong. The CRAC production facility uses corn stover as raw material.

Microbial fermentation

Main article: Ethanol fermentation

Traditionally, baker's yeast (Saccharomyces cerevisiae), has long been used in the brewery industry to produce ethanol from hexoses (six-carbon sugars). Due to the complex nature of the carbohydrates present in lignocellulosic biomass, a significant amount of xylose and arabinose (five-carbon sugars derived from the hemicellulose portion of the lignocellulose) is also present in the hydrolysate. For example, in the hydrolysate of corn stover, approximately 30% of the total fermentable sugars is xylose. As a result, the ability of the fermenting microorganisms to use the whole range of sugars available from the hydrolysate is vital to increase the economic competitiveness of cellulosic ethanol and potentially biobased proteins.

At the turn of the millennium, metabolic engineering for microorganisms used in fuel ethanol production showed significant progress. Besides Saccharomyces cerevisiae, microorganisms such as Zymomonas mobilis and Escherichia coli have been targeted through metabolic engineering for cellulosic ethanol production. An attraction towards alternative fermentation organism is its ability to ferment five carbon sugars improving the yield of the feed stock. This ability is often found in bacteria based organisms.

In the first decade of the 21st century, engineered yeasts have been described efficiently fermenting xylose, and arabinose, and even both together. Yeast cells are especially attractive for cellulosic ethanol processes because they have been used in biotechnology for hundreds of years, are tolerant to high ethanol and inhibitor concentrations and can grow at low pH values to reduce bacterial contamination.

Combined hydrolysis and fermentation

Some species of bacteria have been found capable of direct conversion of a cellulose substrate into ethanol. One example is Clostridium thermocellum, which uses a complex cellulosome to break down cellulose and synthesize ethanol. However, C. thermocellum also produces other products during cellulose metabolism, including acetate and lactate, in addition to ethanol, lowering the efficiency of the process. Some research efforts are directed to optimizing ethanol production by genetically engineering bacteria that focus on the ethanol-producing pathway.

Gasification process (thermochemical approach)

Fluidized Bed Gasifier in Güssing Burgenland Austria

The gasification process does not rely on chemical decomposition of the cellulose chain (cellulolysis). Instead of breaking the cellulose into sugar molecules, the carbon in the raw material is converted into synthesis gas, using what amounts to partial combustion. The carbon monoxide, carbon dioxide and hydrogen may then be fed into a special kind of fermenter. Instead of sugar fermentation with yeast, this process uses Clostridium ljungdahlii bacteria. This microorganism will ingest carbon monoxide, carbon dioxide and hydrogen and produce ethanol and water. The process can thus be broken into three steps:

  1. Gasification — Complex carbon-based molecules are broken apart to access the carbon as carbon monoxide, carbon dioxide and hydrogen
  2. Fermentation — Convert the carbon monoxide, carbon dioxide and hydrogen into ethanol using the Clostridium ljungdahlii organism
  3. Distillation — Ethanol is separated from water

A 2002 study has found another Clostridium bacterium that seems to be twice as efficient in making ethanol from carbon monoxide as the one mentioned above.

Alternatively, the synthesis gas from gasification may be fed to a catalytic reactor where it is used to produce ethanol and other higher alcohols through a thermochemical process. This process can also generate other types of liquid fuels, an alternative concept successfully demonstrated by the Montreal-based company Enerkem at their facility in Westbury, Quebec.

Hemicellulose to ethanol

Studies are intensively conducted to develop economic methods to convert both cellulose and hemicellulose to ethanol. Fermentation of glucose, the main product of cellulose hydrolyzate, to ethanol is an already established and efficient technique. However, conversion of xylose, the pentose sugar of hemicellulose hydrolyzate, is a limiting factor, especially in the presence of glucose. Moreover, it cannot be disregarded as hemicellulose will increase the efficiency and cost-effectiveness of cellulosic ethanol production.

Sakamoto (2012) et al. show the potential of genetic engineering microbes to express hemicellulase enzymes. The researchers created a recombinant Saccharomyces cerevisiae strain that was able to:

  1. hydrolyze hemicellulase through codisplaying endoxylanase on its cell surface,
  2. assimilate xylose by expression of xylose reductase and xylitol dehydrogenase.

The strain was able to convert rice straw hydrolyzate to ethanol, which contains hemicellulosic components. Moreover, it was able to produce 2.5x more ethanol than the control strain, showing the highly effective process of cell surface-engineering to produce ethanol.

Advantages

General advantages of ethanol fuel

Ethanol burns more cleanly and more efficiently than gasoline. Because plants consume carbon dioxide as they grow, bioethanol has an overall lower carbon footprint than fossil fuels. Substituting ethanol for oil can also reduce a country's dependence on oil imports.

Advantages of cellulosic ethanol over corn or sugar-based ethanol

See also: Environmental and social impacts of ethanol fuel in the U.S., Indirect land use change impacts of biofuels, and Low-carbon fuel standard
U.S. Environmental Protection Agency
Draft life cycle GHG emissions reduction results
for different time horizon and discount rate approaches
(includes indirect land use change effects)
Fuel Pathway 100 years +
2% discount
rate
30 years +
0% discount
rate
Corn ethanol (natural gas dry mill) -16% +5%
Corn ethanol (Best case NG DM) -39% -18%
Corn ethanol (coal dry mill) +13% +34%
Corn ethanol (biomass dry mill) -39% -18%
Corn ethanol (biomass dry mill with
combined heat and power)
-47% -26%
Brazilian sugarcane ethanol -44% -26%
Cellulosic ethanol from switchgrass -128% -124%
Cellulosic ethanol from corn stover -115% -116%
Notes: (1) Dry mill (DM) plants grind the entire kernel and generally produce
only one primary co-product: distillers grains with solubles (DGS).
(2) Best case plants produce wet distillers grains co-product.

Commercial production of cellulosic ethanol, which unlike corn and sugarcane would not compete with food production, would be highly attractive since it would alleviate pressure on these foodcrops.

Although its processing costs are higher, the price of cellulose biomass is much cheaper than that of grains or fruits. Moreover, since cellulose is the main component of plants, the whole plant can be harvested, rather than just the fruit or seeds. This results in much better yields; for instance, switchgrass yields twice as much ethanol per acre as corn. Biomass materials for cellulose production require fewer inputs, such as fertilizer, herbicides, and their extensive roots improve soil quality, reduce erosion, and increase nutrient capture. The overall carbon footprint and global warming potential of cellulosic ethanol are considerably lower (see chart) and the net energy output is several times higher than that of corn-based ethanol.

The potential raw material is also plentiful. Around 44% of household waste generated worldwide consists of food and greens. An estimated 323 million tons of cellulose-containing raw materials which could be used to create ethanol are thrown away each year in US alone. This includes 36.8 million dry tons of urban wood wastes, 90.5 million dry tons of primary mill residues, 45 million dry tons of forest residues, and 150.7 million dry tons of corn stover and wheat straw. Moreover, even land marginal for agriculture could be planted with cellulose-producing crops, such as switchgrass, resulting in enough production to substitute for all the current oil imports into the United States.

Paper, cardboard, and packaging comprise around 17% of global household waste; although some of this is recycled. As these products contain cellulose, they are transformable into cellulosic ethanol, which would avoid the production of methane, a potent greenhouse gas, during decomposition.

Disadvantages

General disadvantages

The main overall drawback of ethanol fuel is its lower fuel economy compared to gasoline when using ethanol in an engine designed for gasoline with a lower compression ratio.

Disadvantages of cellulosic ethanol over corn or sugar-based ethanol

The main disadvantage of cellulosic ethanol is its high cost and complexity of production, which has been the main impediment to its commercialization.

Economics

Although the global bioethanol market is sizable (around 110 billion liters in 2019), the vast majority is made from corn or sugarcane, not cellulose. In 2007, the cost of producing ethanol from cellulosic sources was estimated ca. USD 2.65 per gallon (€0.58 per liter), which is around 2–3 times more expensive than ethanol made from corn. However, the cellulosic ethanol market remains relatively small and reliant on government subsidies. The US government originally set cellulosic ethanol targets gradually ramping up from 1 billion liters in 2011 to 60 billion liters in 2022. However, these annual goals have almost always been waived after it became clear there was no chance of meeting them. Most of the plants to produce cellulosic ethanol were canceled or abandoned in the early 2010s. Plants built or financed by DuPont, General Motors and BP, among many others, were closed or sold. As of 2018, only one major plant remains in the US.

In order for it to be grown on a large-scale production, cellulose biomass must compete with existing uses of agricultural land, mainly for the production of crop commodities. Of the United States' 2.26 billion acres (9.1 million km) of unsubmerged land, 33% are forestland, 26% pastureland and grassland, and 20% crop land. A study by the U.S. Departments of Energy and Agriculture in 2005 suggested that 1.3 billion dry tons of biomass is theoretically available for ethanol use while maintaining an acceptable impact on forestry, agriculture.

Comparison with corn-based ethanol

Currently, cellulose is more difficult and more expensive to process into ethanol than corn or sugarcane. The US Department of Energy estimated in 2007 that it costs about $2.20 per gallon to produce cellulosic ethanol, which is 2–3 times much as ethanol from corn. Enzymes that destroy plant cell wall tissue cost US$0.40 per gallon of ethanol compared to US$0.03 for corn. However, cellulosic biomass is cheaper to produce than corn, because it requires fewer inputs, such as energy, fertilizer, herbicide, and is accompanied by less soil erosion and improved soil fertility. Additionally, nonfermentable and unconverted solids left after making ethanol can be burned to provide the fuel needed to operate the conversion plant and produce electricity. Energy used to run corn-based ethanol plants is derived from coal and natural gas. The Institute for Local Self-Reliance estimates the cost of cellulosic ethanol from the first generation of commercial plants will be in the $1.90–$2.25 per gallon range, excluding incentives. This compares to the current cost of $1.20–$1.50 per gallon for ethanol from corn and the current retail price of over $4.00 per gallon for regular gasoline (which is subsidized and taxed).

Enzyme-cost barrier

Cellulases and hemicellulases used in the production of cellulosic ethanol are more expensive compared to their first generation counterparts. Enzymes required for maize grain ethanol production cost 2.64-5.28 US dollars per cubic meter of ethanol produced. Enzymes for cellulosic ethanol production are projected to cost 79.25 US dollars, meaning they are 20-40 times more expensive. The cost differences are attributed to quantity required. The cellulase family of enzymes have a one to two order smaller magnitude of efficiency. Therefore, it requires 40 to 100 times more of the enzyme to be present in its production. For each ton of biomass it requires 15-25 kilograms of enzyme. More recent estimates are lower, suggesting 1 kg of enzyme per dry tonne of biomass feedstock. There is also relatively high capital costs associated with the long incubation times for the vessel that perform enzymatic hydrolysis. Altogether, enzymes comprise a significant portion of 20-40% for cellulosic ethanol production. A 2016 paper estimates the range at 13-36% of cash costs, with a key factor being how the cellulase enzyme is produced. For cellulase produced offsite, enzyme production amounts to 36% of cash cost. For enzyme produced onsite in a separate plant, the fraction is 29%; for integrated enzyme production, the fraction is 13%. One of the key benefits of integrated production is that biomass instead of glucose is the enzyme growth medium. Biomass costs less, and it makes the resulting cellulosic ethanol a 100% second-generation biofuel, i.e., it uses no ‘food for fuel’.

Feedstocks

In general there are two types of feedstocks: forest (woody) Biomass and agricultural biomass. In the US, about 1.4 billion dry tons of biomass can be sustainably produced annually. About 370 million tons or 30% are forest biomass. Forest biomass has higher cellulose and lignin content and lower hemicellulose and ash content than agricultural biomass. Because of the difficulties and low ethanol yield in fermenting pretreatment hydrolysate, especially those with very high 5 carbon hemicellulose sugars such as xylose, forest biomass has significant advantages over agricultural biomass. Forest biomass also has high density which significantly reduces transportation cost. It can be harvested year around which eliminates long-term storage. The close to zero ash content of forest biomass significantly reduces dead load in transportation and processing. To meet the needs for biodiversity, forest biomass will be an important biomass feedstock supply mix in the future biobased economy. However, forest biomass is much more recalcitrant than agricultural biomass. In 2009, the USDA Forest Products Laboratory together with the University of Wisconsin–Madison developed efficient technologies that can overcome the strong recalcitrance of forest (woody) biomass including those of softwood species that have low xylan content. Short-rotation intensive culture or tree farming can offer an almost unlimited opportunity for forest biomass production.

Woodchips from slashes and tree tops and saw dust from saw mills, and waste paper pulp are forest biomass feedstocks for cellulosic ethanol production.

Switchgrass (Panicum virgatum) is a native tallgrass prairie grass. Known for its hardiness and rapid growth, this perennial grows during the warm months to heights of 2–6 feet. Switchgrass can be grown in most parts of the United States, including swamplands, plains, streams, and along the shores & interstate highways. It is self-seeding (no tractor for sowing, only for mowing), resistant to many diseases and pests, & can produce high yields with low applications of fertilizer and other chemicals. It is also tolerant to poor soils, flooding, & drought; improves soil quality and prevents erosion due its type of root system.

Switchgrass is an approved cover crop for land protected under the federal Conservation Reserve Program (CRP). CRP is a government program that pays producers a fee for not growing crops on land on which crops recently grew. This program reduces soil erosion, enhances water quality, and increases wildlife habitat. CRP land serves as a habitat for upland game, such as pheasants and ducks, and a number of insects. Switchgrass for biofuel production has been considered for use on Conservation Reserve Program (CRP) land, which could increase ecological sustainability and lower the cost of the CRP program. However, CRP rules would have to be modified to allow this economic use of the CRP land.

Miscanthus × giganteus is another viable feedstock for cellulosic ethanol production. This species of grass is native to Asia and is a sterile hybrid of Miscanthus sinensis and Miscanthus sacchariflorus. It has high crop yields, is cheap to grow, and thrives in a variety of climates. However, because it is sterile, it also requires vegetative propagation, making it more expensive.

It has been suggested that Kudzu may become a valuable source of biomass.

Cellulosic ethanol commercialization

Fueled by subsidies and grants, a boom in cellulosic ethanol research and pilot plants occurred in the early 2000s. Companies such as Iogen, POET, and Abengoa built refineries that can process biomass and turn it into ethanol, while companies such as DuPont, Diversa, Novozymes, and Dyadic invested in enzyme research. However, most of these plants were canceled or closed in the early 2010s as technical obstacles proved too difficult to overcome. As of 2018, only one cellulosic ethanol plant remained operational.

In the later 2010s, various companies occasionally attempted smaller-scale efforts at commercializing cellulosic ethanol, although such ventures generally remain at experimental scales and often dependent on subsidies. The companies Granbio, Raízen and the Centro de Tecnologia Canavieira each run a pilot-scale facility operate in Brazil, which together produce around 30 million liters in 2019. Iogen, which started as an enzyme maker in 1991 and re-oriented itself to focus primarily on cellulosic ethanol in 2013, owns many patents for cellulosic ethanol production and provided the technology for the Raízen plant. Other companies developing cellulosic ethanol technology as of 2021 are Inbicon (Denmark); companies operating or planning pilot production plants include New Energy Blue (US), Sekab (Sweden) and Clariant (in Romania). Abengoa, a Spanish company with cellulosic ethanol assets, became insolvent in 2021.

The Australian Renewable Energy Agency, along with state and local governments, partially funded a pilot plant in 2017 and 2020 in New South Wales as part of efforts to diversify the regional economy away from coal mining.

US Government support

From 2006, the US Federal government began promoting the development of ethanol from cellulosic feedstocks. In May 2008, Congress passed a new farm bill that contained funding for the commercialization of second-generation biofuels, including cellulosic ethanol. The Food, Conservation, and Energy Act of 2008 provided for grants covering up to 30% of the cost of developing and building demonstration-scale biorefineries for producing "advanced biofuels," which effectively included all fuels not produced from corn kernel starch. It also allowed for loan guarantees of up to $250 million for building commercial-scale biorefineries.

In January 2011, the USDA approved $405 million in loan guarantees through the 2008 Farm Bill to support the commercialization of cellulosic ethanol at three facilities owned by Coskata, Enerkem and INEOS New Planet BioEnergy. The projects represent a combined 73 million US gallons (280,000 m) per year production capacity and will begin producing cellulosic ethanol in 2012. The USDA also released a list of advanced biofuel producers who will receive payments to expand the production of advanced biofuels. In July 2011, the US Department of Energy gave in $105 million in loan guarantees to POET for a commercial-scale plant to be built Emmetsburg, Iowa.

See also

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