Patent Application: US-201013378602-A

Abstract:
a unique , integrated non - obvious pathway to convert biomass to biofuels using integration of chemical processes is described herein . the present invention is simple , direct , and provides for the shortest or minimum path between biomass and transportation fuels with alcohols as intermediates , while avoiding hydrogen use during processing . furthermore , the present invention allows the manufacture of “ drop - in ” substitutable fuels to be used as - is without modifications instead of conventional petroleum based fuels . the processing described herein is done under mild conditions , under relatively low pressures and temperatures , and under non - corrosive conditions obviating use of special equipment or materials . the novel integration heat and mass generated during the process increases overall process efficiency and lowers financial costs for processing and capital equipment , manages environmental impact , and enables a relatively high degree of yield by an enhanced usage of fresh water and thermal energy in comparison to the amount of biomass processed .

Description:
while the making and using of various embodiments of the present invention are discussed in detail below , it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts . the specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention . to facilitate the understanding of this invention , a number of terms are defined below . terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention . terms such as “ a ”, “ an ” and “ the ” are not intended to refer to only a singular entity , but include the general class of which a specific example may be used for illustration . the terminology herein is used to describe specific embodiments of the invention , but their usage does not delimit the invention , except as outlined in the claims . before any embodiments of the invention are described in detail , it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description . the invention is capable of other embodiments and of being practiced or of being carried out in various ways . also it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting . the use of “ including ,” “ comprising ,” or “ having ” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof , as well as additional items . as used herein , the term “ hydrocarbon ” refers to any molecule consisting of carbon and hydrogen in any combination . as such , “ hydrocarbon ” includes straight - chain , branched , and cyclic alkanes , alkenes , alkynes , and aromatics . as used herein , the term “ alcohol ” and “ alcohols ” refers to any of a number of carbon / hydrogen - containing molecules having one or more singly - bonded hydroxyl ( oh ) groups . the term “ alcohol ” encompasses both primary ( e . g . oh on terminal carbon ) and secondary ( e . g . oh not on terminal carbon ) alcohols . the number of carbon atoms in the alcohols of the present invention is typically ( but not necessarily ) less than 10 , more typically less than 6 , however longer - chain alcohols may be produced perhaps , in smaller amounts , and incorporated into the systems of the present invention . the present invention describes methods and systems for the production of a bio - fuel . the process described herein comprises : converting biomass to alcohol ( s ) and residual biomass ; gasifying the residual biomass to produce carbon monoxide , hydrogen , or mixtures thereof , thereby producing thermal energy ; synthesizing a liquid hydrocarbon fuel from the alcohol ( s ) using some of the thermal energy produced by gasifying the residual biomass , integrating water from alcohol concentration to biomass pretreatment and hydrolysis , and integrating thermal energy from alcohol concentration and gasification to biomass pretreatment , hydrolysis , alcohol concentration , gasification , dehydration , and oligomerization . the individual steps or the building blocks have been previously shown to work independently , however the present invention provides a novel and unique way to combine the individual building blocks listed above to produce transportation fuels from a biomass . furthermore , the instant invention discloses specific integration embodiments leading to increased mass and energy efficiency . these include : a . residue integration : the fermentation residue ( e . g ., lignin , unreacted cellulose and hemi - cellulose ) is gasified and the syngas is fed to a cogeneration unit , which produces steam , heat , and electric power . the steam is used in the two reboilers and in the gasifier . the heat is used for dehydration and oligomerization . b . water integration : the hot wastewater streams leaving the reboilers of the stripping and distillation columns are used for mass and heat integration by using them in pretreatment and hydrolysis thereby saving fresh water and heat needed in biomass pretreatment and hydrolysis c . offgas integration : the offgases from oligomerization are burned to provide steam needed in the process ( e . g ., pretreatment ). the methods and systems of the present invention enable the efficient production of liquid hydrocarbon fuels from biomass . hydrocarbon fuels created by the present invention may include , but need not be limited to gasoline , diesel , kerosene , jet / aviation fuel , light heating oils , and drop - in substitutes for conventional transport fuels wherein these fuels meet the various standards set out by astm international and the u . s . e . p . a . in most cases , however , the fuels will not contain sulfur compounds and heavy metals at the levels found in conventional petroleum fuels . the systems and methods of the present invention also allow for the production of organic chemicals such as olefins , paraffins , aromatics , and naphthenes . of particular value are chemicals that may be used as feedstocks to the petrochemical industry such as ethylene , acetylene , benzene , cyclohexene , xylene , toluene , ethylbenzene , etc . to counter depleting energy resources growing attention has been devoted to the conversion of biomass into fuel ethanol , considered as a fuel alternative or an additive to fossil fuels . significant advances have been made towards the technology of ethanol fermentation including converting xylose to ethanol , utilization of cellulase enzyme in the hydrolysis of lignocellulosic materials , immobilization of microorganisms in large systems , simultaneous saccharification and fermentation ( ssf ) and sugar conversion into ethanol ( lin and tanaka , 2006 , relevant portions incorporated herein by reference ). the alcohol produced by the fermentation of the biomass can be catalytically converted to hydrocarbons , for e . g . costa et al . ( 1985 ), relevant portions incorporated herein by reference , who studied the conversion of ethanol to hydrocarbons by use of a zsm - 5 zeolite catalyst . the effects of zeolite si / al ratio , ethanol dilution , and process variables ( temperature , space velocity , pressure , and recycle rate of gaseous products ) were also studied . in addition to catalytic conversion to hydrocarbons whitcraft ( 1983 ) disclosed a method to directly recover gasoline from ethanol in fermentation broths . the method is a two - step process involving distilling a fermenter broth containing 8 - 10 wt % ethanol to a 90 wt % solution followed by dehydration wherein the concentrated ethanol solution is dehydrated to diethyl ether or fed directly to a conversion reactor where either the ether or ethanol is converted to gasoline by use of a suitable catalyst . the alcohol produced by the fermentation as discussed above can be converted to gasoline - boiling - range hydrocarbons as described for the case of ethanol in , e . g ., u . s . pat . no . 4 , 621 , 164 ( relevant portions incorporated herein by reference ). the &# 39 ; 164 patent involved contacting the ethanol in the vapor phase at dehydrating temperature with a bifunctional zeolite catalyst in the presence of an equimolar proportion of water . the catalyst induces simultaneous dehydration of the ethanol to reactive intermediates and recombination to a spectrum of hydrocarbons in the c1 to c10 range . higher and lower proportions of water lead to higher yields of gaseous hydrocarbons . alternatively , the alcohols produced from the fermentation of the biomass are recovered and can be converted to other commercially valuable products and as starting materials for other reactions . ethylene produced by the dehydration of ethanol in the presence of different catalysts ( acid catalysts , metals , etc .) has been previously studied ( xiao et al ., 2009 , ouyang et al ., 2009 , and takahara et al ., 2005 , relevant portions incorporated herein by reference ). the olefins ( ethylene , propylene , butene , etc .) undergo further reactions to yield commercially important compounds . for example , n - butenes can be dimerized to yield high octane gasoline components ( golombok and bruijn , 2000 , relevant portions incorporated herein by reference ) or ethylene can be oligomerized catalytically in the presence of ni - containing dealuminated y - zeolites to yield linear and branched higher olefins , which are valuable feedstock , used in the manufacture of detergents , petrochemicals , oil additives , high - octane ecologic gasoline , etc . ( lallemand et al ., 2006 , relevant portions incorporated herein by reference ). the present invention may use a process for the production of a gasoline blending fraction rich in isooctane by the dimerization of isobutylene using tertiary butyl alcohol modifier and isoalkane diluent , such as that disclosed in u . s . pat . no . 5 , 877 , 372 issued to evans et al . ( 1999 ) relevant portions incorporated herein by reference ; advantageously , the isobutylene is derived from the dehydration of tertiary butyl alcohol and the isoalkane used as diluent in the dimerization is the product formed by hydrogenation of the oligomerization product . from the discussion hereinabove it is clear that biomass fermentation leading to the production of alcohol ( s ) is a starting point for a myriad of processes and reactions resulting in the production of commercially valuable products selected from the group consisting of hydrocarbons , gasoline , acids , ketones , ethers , alkylbenzenes , fuel additives , biopolymers , proteins for animal and human consumption , and surfactants . while these processes ( or building blocks ) generating these products have been individually studied and are functional , there is no common integrated unifying process design or method that combines all or elements of these individual building blocks . the present invention addresses this issue by describing a comprehensive integrated biofuel processing system to go from biomass to transportation fuel . biomass suitable for use with the systems and methods of the present invention may include , but need not be limited to , animal manures , kitchen waste , food processing waste , beverage waste , thin and whole stillage , wet distillers grain , raw human sewage , municipal solid waste , treated sewage sludges , fats , oils , greases , meat packing waste , paunche , tallows , processed lignocellulosic waste , pulp and paper sludges , wood wastes , landfill gas , digester gas , energy crops ( cane , sorghum , miscanthus , switch grass or other ), timber ( poplar , aspen , willow , alder ), crop residues ( corn stover , wheat or rice straw , palm ), algae , diatoms , seaweed , and other discarded vegetation including municipal grass and timber wastes . municipal solid waste may include items that are not of ( recent ) biological origin but , nonetheless , may be processed by the systems of the invention . such non - biological materials may include , but need not be limited to , plastics , solvents , used motor oil , and construction debris . residual biomass typically comprises the solid materials that remain after biomass has undergone a biomass conversion process described herein . in some cases the biomass is “ fractionated ” before undergoing the conversion process described herein . “ fractionation ” involves decomposing the biomass into its constituent parts of cellulose , hemi - cellulose , and lignin . if biomass fractionation is purposely used before fermentation to separate cellulose , hemicelluloses , and lignin , then the residual biomass may include a specific cut such as lignin . residual biomass typically has lower cellulose content in comparison to virgin biomass because the biomass conversion process preferentially results in the degradation of cellulose . briefly , a biomass prior to the conversion process described herein is subjected to a pretreatment and a hydrolysis step . the pretreatment step liberates cellulose and hemicellulose from the lignin and involves , e . g ., the use of thermal , physical , and chemical methods such as hot - water pretreatment , steam explosion , ozonolysis , ammonia fiber expansion , weak - and strong - acid hydrolysis , alkaline wet oxidation and supercritical co2 extraction . the hydrolysis step breaks down the cellulosic and hemicellulosic chains to simple sugars ( e . g ., glucose , xylose , etc .). the process can also treat the hemi - cellulose to produce c5 sugars that are different from those obtained from cellulose and these require different subsequent treatments for conversion to alcohols . hydrolysis may be carried out via chemical methods ( e . g ., the use of dilute or concentrated acids ) or enzymatic methods . conversion into alcohols ( preferably but not necessarily ethanol ) ( e . g ., using anaerobic fermentation ), concentration of the alcohol using stripping and distillation , membrane separation , or molecular sieves . dehydration of the alcohol into the corresponding olefin ( ethanol could be converted into ethylene ) can be accomplished by , e . g ., vapor phase reaction over a solid acid catalyst , and oligomerization of the ethylene into transportation fuels ( e . g ., using zsm - 5 or other catalysts possibly containing metals or non - metals in their matrices ). the different processes in the integrated biofuel processing system of the present invention is described herein below and is also depicted schematically in fig1 . the system comprises the following main subsystems or processes : pretreatment : breaks down the cellulose and hemicellulose materials in the biomass by a cavitation method , micronization methods , chemical treatment methods , grinding methods or any other suitable method . hydrolysis : the hydrolysis step converts the pretreated cellulose and hemicellulose materials into sugars . fermentation : in this step the mixture of water and processed feedstocks are typically allowed to ferment at elevated temperatures to produce alcohols . the fermentation proceeds until the alcohol content reaches approximately 16 %. at the end of this step the resultant mixture of water , feedstock and alcohol is then separated , with the residual biomass being fed to the gasification subsystem stripping and distillation : in this step the water and alcohol mixture without the biomass is passed through a stripping column and the distillation column to produce a clean stream of alcohol that can be fed to the a dehydration subsystem and / or the fuel conversion subsystem . dehydration : in this step the alcohol received from the biomass conversion system is converted to form an alkene ( olefin ) and includes a water separator . when ethanol is received it is converted to ethylene or other chemicals . oligomerization : the fuel conversion system produces a mixture of liquid hydrocarbons ( e . g . gasoline ) from the alcohols . the fuel conversion system utilizes an oligomerization process to perform the conversion of olefins ( such as ethylene ) to fuel . gasification : in this step the residual biomass from the fermenter is converted to heat and product gases by thermal conversion at high temperatures . gasification typically involves the conversion of residual biomass to a mixture of carbon monoxide and hydrogen , generally known as “ syngas .” cogeneration : the syngas produced from gasification is fed to a cogeneration unit which produces steam , energy as heat ( from the hot off - gasses ) and electric power . the steam from the cogeneration system can be used by the gasifier and by reboiler systems . the heat from the hot - gasses of the cogeneration system can be used by the dehydration and fuel generation subsystems . the hot water produced from the reboilers can be used by the stripping and distillation columns and can also be used for mass and heat integration in the pretreatment system and the hydrolysis system , thereby saving fresh water and heat needed in the pretreatment and hydrolysis systems . thus , from the above description it can be seen that some of the interconnections represent the transport of materials , such as the transfer of residual biomass from the biomass conversion subsystem to the gasification subsystem . some of the other interconnections the transfer of thermal energy between the interdependent subsystems . such transfer may include , but need not be limited to , the recovery of “ waste heat ” from the gasification subsystem to meet the heating needs of the biomass conversion system . thermal energy may be recovered from a number of other process steps present in the biomass conversion , gasification , or fuel conversion subsystems . an overview of the system and methods of the present invention are shown in fig1 . integrated biofuel production systems of the invention 10 may be visualized as at least four interdependent subsystems symbiotically sharing by - product or waste materials and / or thermal energy that have traditionally been discarded . the four subsystems are a biomass conversion subsystem 12 , a gasification subsystem 14 , a dehydration subsystem 16 , and a fuel conversation subsystem 18 . while the production system may be conceptualized as four interdependent subsystems ( 12 - 18 ), a given embodiment of the invention may not have readily recognizable subsystems because of the need to interconnect sinks and sources of materials and thermal energy in order to maximize efficiency . however , the interconnections allow the integrated biofuel production systems 10 of the present invention to use materials and thermal energy most efficiently , thus making it possible to produce more liquid fuel from less biomass , while using less external energy to drive the process . the biomass conversion subsystem 12 of the present invention may entail any of a number of known methods suitable for converting biomass into an alcohol and residual biomass . such methods may include , but need not be limited to , the fermentation of biomass to alcohols 20 , and enzymatic conversion of sugars to alcohols or acids . the acids can then be further converted to alcohols . the methods of the present invention need not be limited to a singular biomass conversion system 12 , as it may be beneficial to incorporate more than one type of biomass conversion system 12 into a given biofuel processing system . in one embodiment the biomass conversion subsystem 12 consists of a pretreatment subsystem , a hydrolysis subsystem 24 and a fermentation subsystem 20 . the pretreatment process may be any known process that works to break down cellulose and hemicellulose materials , such as cavitation methods , micronization methods , chemical treatment methods , grinding methods or any other suitable method . for example , biomass grains can be crushed , ground or enzymatically treated to make the sugars in the feedstock more accessible for the microorganism ( e . g ., yeast ) that will ferment the sugars to alcohol . an additional hydrolysis subsystem 26 may be used to acid hydrolyze cellulosic materials to produce free sugars . the pretreated and hydrolyzed biomass and sugars are fed into the fermentation subsystem 20 . in the fermentation subsystem 20 , a mixture of water and processed feedstocks are typically allowed to ferment at elevated temperatures until the alcohol content reaches approximately 16 %. the resultant mixture of water , feedstock and alcohol is then separated , with the residual biomass being fed to the gasification subsystem 28 , and the water and alcohol mixture passing through a stripping column 30 and the distillation column 32 to produce a clean stream of alcohol that can be fed to the a dehydration subsystem 16 and / or the fuel conversion subsystem 18 . other separation methods ( e . g ., membranes ) may be used to concentrate the alcohols . the alcohols need not be concentrated to high levels of purity . for instance , in the case of ethanol , there is no need to exceed the azeotropic concentration . suitably , the ethanol concentration on the resulting ethanol / water mixture after stripping and distillation may be 94 % ethanol or less . suitably , the distillation column 32 has a partial condenser that allows the top product to leave the distillation column as azeotropic ethanol vapor . the gasification subsystem 18 of the present invention may entail any number of known methods suitable for converting residual biomass to heat and product gases by thermally converting the residual biomass at high temperatures . gasification typically involves the conversion of residual biomass to a mixture of carbon monoxide and hydrogen , generally known as “ syngas .” in the gasification process 20 , residual biomass from the biomass conversion subsystem is collected and dried to achieve approximately 10 % moisture content . the dried biomass is then preheated using a steam driven heat exchanger . the hot , dried , residual biomass is then injected into a gasification reactor where the residual biomass is burned in the presence of air and / or steam at approximately a temperature of 800 - 1400 ° c ., preferably at a temperature of 950 - 1150 ° c . because of the higher temperatures and the presence of oxygen , the residual biomass is converted almost entirely to a clean syngas , leaving only a small amount of char that can be sold as a byproduct . the addition of steam enhances the hydrogen yield in the produced syngas . the resultant syngas can be cooled by a heat exchanger , the thermal energy captured in the heat exchanger being circulated to another subsystem of the biofuel processing system , where the thermal energy can be used to preheat other processes . gasification reactors suitable to be used as subsystems for the present invention may be obtained commercially . the syngas produced from gasification is used in a cogeneration unit 34 which produces steam , energy as heat ( from the hot off - gasses ) and electric power . the steam from the cogeneration system can be used by the gasifier and by reboiler systems . the heat from the hot - gasses of the cogeneration system 34 can be used by the dehydration 20 and fuel generation subsystems 18 . the hot water produced from the reboilers can be used by the stripping 30 and distillation columns 32 and can also be used for mass and heat integration in the pretreatment system 24 and the hydrolysis system 26 , thereby saving fresh water and heat needed in the pretreatment 24 and hydrolysis systems 26 . the interconnections between subsystems of the biofuel processing system 10 are also shown in fig1 . some of the interconnections represent the transport of materials , such as the transfer of residual biomass from the biomass conversion subsystem 12 to the gasification subsystem 18 . some of the other interconnections the transfer of thermal energy between the interdependent subsystems . such transfer may include , but need not be limited to , the recovery of “ waste heat ” from the gasification subsystem 14 to meet the heating needs of the biomass conversion system 12 . thermal energy may be recovered from a number of other process steps present in the biomass conversion 12 , gasification 14 , or fuel conversion sub systems 18 . one of skill in the art appreciates that capturing and transporting thermal energy as well as residual biomass and gasses requires transfer systems that are not shown in fig1 . for example , a number of conveyors and pumps will be needed to move materials and thermal loads between subsystems . heat transfer systems may rely on pressurized water or other known heat - transfer fluids to recover the heat and to serve as a heat - transfer medium between the various components of the subsystems . heat transfer systems may also include exchanging heat directly between process hot streams and process cold streams . heat transfer systems appropriate for use in the invention are known to those of skill in the art , and are commercially available . in some embodiments , it may be beneficial to produce steam from excess thermal energy , which may be used for both heating processes and to provide electrical energy ( by driving a turbine ) to power the transfer systems . while it is possible to produce electricity to drive the heat and material transfer processes with steam , in many cases it is more efficient to use the thermal energy produced by the subsystems for heating rather than electrical production . optimally , if additional heat and power are needed , the heat and material transfer systems can be powered from other renewable energy sources amenable to the production of electricity , such as wind turbines , solar panels , or a biogas - powered electrical generator . however , the transfer systems can also be powered with electricity from the local power grid . a dehydration subsystem 36 may be used to convert the alcohol received from the biomass conversion system to form an alkene ( olefin ) and includes a water separator 38 . when ethanol is received it is converted to ethylene or other chemicals . the fuel conversion subsystem 18 can be adapted to create liquid hydrocarbon fuel , such as gasoline , jet fuel , and / or diesel from the alcohol or olefin received from the dehydration subsystem . olefins may be directly oligomerized to hydrocarbons in high temperatures ( 300 - 450 ° c .) and moderate pressures ( 1 - 40 atm ) in the presence of a catalyst in an oligomerization reactor 40 . suitably the catalyst is a zeolite catalyst or other solid acid catalyst , possibly with added metals or rare earths . by controlling the temperature and pressure of the oligomerization process and / or the composition of the catalyst , it is possible to direct the production of longer or shorter chain hydrocarbons . it is also possible to control the amount of alkane branching in the final product . the thermal energy required for the oligomerization process may be augmented with thermal energy taken from the gasification sub system 14 . in some embodiments , oligomerization reactor 40 may produce an amount of residual light hydrocarbons ( light - ends ), e . g . short chain liquid and gaseous hydrocarbons including those for combustion 42 . these light ends may be thermally reformed with steam to produce methanol and other primary alcohols , which can be fed into the oligomerization reactor in order to boost the fuel output . in other embodiments , the light ends may be recycled to create methanol and the methanol converted to long chain liquid hydrocarbons using the mobil methanol to fuel process . the gasification system described above is intended to be illustrative , and is not intended to limit the scope of the invention . other methods of producing energy as heat and process gasses from residual biomass are also known to those of skill in the art . for example , the residual biomass may be dried and pelletized for use directly in burners and or boilers to provide heat for various processes requiring the additional of thermal energy . additionally , it is anticipated that new methods for producing heat and process gasses are likely to be discovered in the near future . the biomass conversion systems 10 detailed above are intended to be illustrative , and are not intended to limit the scope of the invention . other methods of producing useful feedstocks for the fuel conversion subsystem are also known to those of skill in the art . additionally , it is anticipated that new methods for converting biomass to methane or alcohol and residual biomass are likely to be discovered in the near future . in conclusion , the present invention permits , for the first time , the integration of existing / known technologies in a unique , non - obvious way to create an overall pathway from biomass to bio - fuels that others have not recognized . the present inventors have found that the present invention allows for the shortest or minimum path between biomass and fuels , that is , the simplest , most direct and shortest path from biomass to transportation fuels with alcohols as intermediates , while avoiding the use of hydrogen during the processing steps . furthermore , the present invention allows the user to “ drop - in ” substitutable fuels because the products produced hereby ( bio - gasoline , bio jet and bio - diesel ) are direct substitutes for conventional petroleum based fuels . they can be used as - is without modifications to engines or distribution infrastructure . additionally , the integration of mass and energy in novel ways throughout the process enhance the overall efficiency of the process . the efficiency of the conversion process is enhanced by utilizing heat and mass from one process as an ingredient to another process . thus , the biomass processing system may enable a relatively high degree of yield and an enhanced usage of fresh water and thermal energy in relation to the amount of biomass introduced into the biofuel processing system . although the present invention has been described with several embodiments , a myriad of changes , variations , alterations , transformations , and modifications may be suggested to one skilled in the art , and it is intended that the present disclosure encompass such changes , variations , alterations , transformation , and modifications as they fall within the scope of the appended claims . it is contemplated that any embodiment discussed in this specification can be implemented with respect to any method , kit , reagent , or composition of the invention , and vice versa . furthermore , compositions of the invention can be used to achieve methods of the invention . it will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention . the principal features of this invention can be employed in various embodiments without departing from the scope of the invention . those skilled in the art will recognize , or be able to ascertain using no more than routine experimentation , numerous equivalents to the specific procedures described herein . such equivalents are considered to be within the scope of this invention and are covered by the claims . all publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains . all publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference . the use of the word “ a ” or “ an ” when used in conjunction with the term “ comprising ” in the claims and / or the specification may mean “ one ,” but it is also consistent with the meaning of “ one or more ,” “ at least one ,” and “ one or more than one .” the use of the term “ or ” in the claims is used to mean “ and / or ” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive , although the disclosure supports a definition that refers to only alternatives and “ and / or .” throughout this application , the term “ about ” is used to indicate that a value includes the inherent variation of error for the device , the method being employed to determine the value , or the variation that exists among the study subjects . as used in this specification and claim ( s ), the words “ comprising ” ( and any form of comprising , such as “ comprise ” and “ comprises ”), “ having ” ( and any form of having , such as “ have ” and “ has ”), “ including ” ( and any form of including , such as “ includes ” and “ include ”) or “ containing ” ( and any form of containing , such as “ contains ” and “ contain ”) are inclusive or open - ended and do not exclude additional , unrecited elements or method steps . the term “ or combinations thereof ” as used herein refers to all permutations and combinations of the listed items preceding the term . for example , “ a , b , c , or combinations thereof ” is intended to include at least one of : a , b , c , ab , ac , bc , or abc , and if order is important in a particular context , also ba , ca , cb , cba , bca , acb , bac , or cab . continuing with this example , expressly included are combinations that contain repeats of one or more item or term , such as bb , aaa , mb , bbc , aaabcccc , cbbaaa , cababb , and so forth . the skilled artisan will understand that typically there is no limit on the number of items or terms in any combination , unless otherwise apparent from the context . all of the compositions and / or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure . while the compositions and methods of this invention have been described in terms of preferred embodiments , it will be apparent to those of skill in the art that variations may be applied to the compositions and / or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept , spirit and scope of the invention . all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit , scope and concept of the invention as defined by the appended claims . united states patent application no . 20050269048 : novel catalytic reactor process for the production of commercial grade pulp , native lignin & amp ; unicellular protein . costa , e ., ugulna , a ., aguado , j . and herndndez , p . j . ethanol to gasoline process : effect of variables , mechanism , and kinetics . ind . eng . chem . process des . dev . 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( 2006 ) 69 : 627 - 642 . ouyang , j ., kong , f ., su , g ., hu , y . and song , q . catalytic conversion of bio - ethanol to ethylene over la - modified hzsm - 5 catalysts in a bioreactor . catalysis letters ( 2009 ) 132 ( 1 - 2 ), 164 - 174 . takahara , i ., saito , m ., inaba , m . and murata , k . dehydration of ethanol into ethylene over solid acid catalysts . catalysis letters ( 2005 ) 105 ( 3 - 4 ) 249 - 252 . xiao , y ., li , x ., yuan , z ., li , j . and chen , y . catalytic dehydration of ethanol to ethylene on tio 2 / 4a zeolite composite catalysts . catal . lett . ( 2009 ) 130 : 308 - 311 . whitcraft , d . r ., veryklos , x . e . and yutharasan , r . recovery of ethanol from fermentation broths by catalytic conversion to gasoline . ind . eng . chem . process des . dev . ( 1983 ) 22 : 452 - 457 .