# Patent

## Title
Locally-regulated pressurized pretreatment of lignocellulosic biomass

## Abstract

Described are methods for pretreating lignocellulosic biomass that comprise passing a hot aqueous biomass slurry through a heat exchange passage from an inlet to an outlet and locally regulating pressure in the passage by feed of a pressurized liquid medium to one or more intermediate locations of the passage. Also described are methods for producing ethanol from the pretreated biomass.

## Background
REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/US2009/048856, which is hereby incorporated by reference, which claims the benefit of U.S. Provisional Application No. 61/076,034 filed Jun. 26, 2008, which is hereby incorporated by reference.


BACKGROUND
The present invention relates generally to the utilization of lignocellulosic biomass, and in certain embodiments to systems and processes useful for treating aqueous slurries of lignocellulosic biomass at elevated temperatures to render cellulose therein more susceptible to hydrolysis.
As further background, increasing emphasis has been placed in recent years upon finding ways to efficiently produce fuels from renewable, non-petroleum resources. In one field of interest, fuel ethanol has been produced by fermentation of biomass feedstocks derived from plants. Currently, fuel ethanol is commercially produced from feedstocks of cornstarch, sugar cane and sugar beets. These materials, however, find significant competing uses in the food industry, and their expanded use to make fuel ethanol is met with increased prices and disruption of other industries. Alternative fermentation feedstocks and viable technologies for their utilization are thus highly sought after.
Lignocellulosic biomass feedstocks are available in large quantities and are relatively inexpensive. Such feedstocks are available in the form of agricultural wastes such as corn stover, corn fiber, wheat straw, barley straw, oat straw, oat hulls, canola straw, soybean stover, grasses such as switch grass, miscanthus, cord grass, and reed canary grass, forestry wastes such as aspen wood and sawdust, and sugar processing residues such as bagasse and beet pulp. Cellulose from these feedstocks is converted to sugars, which are then fermented to produce the ethanol.
A difficulty in using lignocellulosic feedstocks is that the cellulose content of the biomass is caught up in a structure that inhibits the accessibility of the cellulose to agents that convert it to sugars. For this reason, research has focused upon methods for pretreating lignocellulosic biomass to enhance the susceptibility of the cellulose to conversion to sugars. Such pretreatment processes are designed to break the lignin seal protecting the cellulose and to disrupt the crystalline structure of the cellulose. A variety of pretreatment methodologies have been explored for this purpose; including physical processes such as size reduction, steam explosion, liquid hot water, irradiation, cryomilling, and freeze explosion; and chemical processes such as acid hydrolysis, buffered solvent pumping, alkali or alkali/H2O2 delignification, solvents, ammonia; and microbial or enzymatic methods.
Despite previous efforts relating to pretreatments for lignocellulosic biomass feedstocks and its ultimate use in the production of ethanol, needs remain for improved and alternative biomass pretreatment processes and follow-on production of ethanol. In certain of its aspects, the present invention is addressed to these needs.
SUMMARY
In one embodiment, provided is a method for processing lignocellulosic biomass. The method includes passing an aqueous slurry including the lignocellulosic biomass through a first passage of a heat exchange device from an inlet opening to an outlet opening, with the aqueous slurry having a temperature above 100° C. and being subjected to a pressure substantially at or above its saturation vapor pressure so as to facilitate maintaining water of the aqueous slurry in liquid form. The method also includes feeding a liquid aqueous medium under pressure into the first passage through at least one additional opening at a position intermediate the inlet opening and the outlet opening so as to locally control pressure within the passage. In preferred embodiments, the liquid aqueous medium is fed under pressure through a plurality of additional openings into the first passage occurring between the first opening or inlet and second opening or outlet. In this manner, improved pressure control can be achieved along the length of the first passage. Such pressure control may be beneficial, for example, in preventing localized flashing of water of the aqueous slurry which could have a deleterious effect on the pretreatment process, and/or in equalizing pressure within the passage to prevent or at least reduce the incidence of phenomena such as “bump” or “water hammer”.
Additional embodiments of the invention as well as features and advantages thereof will be apparent from the descriptions herein.



BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a schematic diagram of a heat exchange system with localized pressure control.
FIG. 2 is a schematic diagram of a lignocellulosic biomass pretreatment and heat recovery system with a plurality of heat exchangers having localized pressure control.
FIG. 3 provides a perspective view of a heat exchange tube arrangement of the invention with a helical groove in an outer passage.



DETAILED DESCRIPTION
For the purposes of promoting an understanding of the principles of the invention, reference will now be made to certain embodiments and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated device, and such further applications of the principles of the invention as described herein being contemplated as would normally occur to one skilled in the art to which the invention relates.
As disclosed above, certain aspects of the present invention relate to methods and systems for pretreating lignocellulosic biomass in an aqueous slurry. Such methods and systems involve the utilization of a pressurized liquid-form medium, fed at one or more points intermediate an inlet and an outlet of a passage of a heating device such as a heat exchanger, to provide localized pressure control. Such localized control may be used to prevent or reduce localized flash of water from the aqueous slurry and/or to prevent or reduce localized pressure differentials that could cause undesired mechanical phenomena in the pretreatment system commonly termed “water hammer” or “bump”. Additional aspects of the invention relate to methods for producing products, including fermentation products such as ethanol, from the pretreated biomass materials.
As used herein, the term “lignocellulosic biomass”, is meant to refer to any type of biomass comprising lignin and cellulose such as, but not limited to, non-woody plant biomass, agricultural wastes and forestry residues and sugar-processing residues. For example, the cellulosic feedstock can include, but is not limited to, grasses, such as switch grass, cord grass, rye grass, miscanthus, mixed prairie grasses, or a combination thereof; sugar-processing residues such as, but not limited to, sugar cane bagasse and sugar beet pulp; agricultural wastes such as, but not limited to, soybean stover, corn fiber from grain processing, corn stover, oat straw, rice straw, rice hulls, barley straw, corn cobs, wheat straw, canola straw, oat hulls, and corn fiber; and forestry wastes, such as, but not limited to, paper sludge, recycled wood pulp fiber, sawdust, hardwood, softwood, or any combination thereof. Further, the lignocellulosic biomass may comprise lignocellulosic waste or forestry waste materials such as, but not limited to, newsprint, cardboard and the like. Lignocellulosic biomass may comprise one species of fiber or, alternatively, a lignocellulosic biomass feedstock may comprise a mixture of fibers that originate from different lignocellulosic materials.
Typically, the lignocellulosic material will comprise cellulose in an amount greater than about 2%, 5%, or 10% and preferably greater than about 20% (w/w) to produce a significant amount of glucose. The lignocellulosic material can be of higher cellulose content, for example at least about 30% (w/w), 35% (w/w), 40% (w/w) or more. Therefore, the lignocellulosic material may comprise from about 2% to about 90% (w/w) cellulose, or from about 20% to about 80% (w/w) cellulose, or from 25% to about 70% (w/w) cellulose, or about 35% to about 70% (w/w) cellulose, or more, or any amount therebetween.
Prior to pretreatment, the lignocellulosic biomass can be mechanically processed to increase its surface area. Such mechanical processing may include, for example, reducing the biomass to a particulate by grinding, milling, agitation, shredding, or other types of mechanical action.
In certain aspects, the lignocellulosic biomass will be used to create a pumpable slurry in combination with a suitable liquid, preferably an aqueous medium. The aqueous medium may be water alone, but in other embodiments can include additives to enhance the pretreatment process such as acids or bases to adjust or maintain the pH of the aqueous medium, or another chemical additive beneficial to the pretreatment process. Aspects of the present invention are also applicable to systems which employ dilute acid pretreatment processes. Suitable acids for these or other purposes herein include, for example, inorganic or organic acids, e.g. sulfuric, hydrochloric, phosphoric, nitric, acetic, citric or formic acid. Suitable bases for these purposes include, for example, alkali or alkaline earth metal hydroxides, e.g. sodium or potassium hydroxide, or other hydroxide bases such as ammonium hydroxide. In certain preferred forms, the aqueous medium will be adjusted initially and/or during a thermal pretreatment process by the addition of acid or base to provide a pH that is near neutral, so as to avoid the occurrence of any significant acid- or base-catalyzed autohydrolysis of the lignocellulosic material, for example a pH in the range of about 5 to about 8. Additional information as to suitable conditions for pH-controlled lignocellulosic biomass pretreatments is found in U.S. Pat. No. 5,846,787, which is hereby incorporated herein by reference in its entirety. Other additives that may be present in the aqueous biomass slurry include, as illustrations, surfactants, e.g. vegetable oils such as soybean oil, canola oil, and others, to serve as intercalating agents.
The aqueous slurry of the lignocellulosic biomass will typically be relatively highly concentrated in solids. In certain embodiments, the aqueous slurry will be comprised at least about 10 grams per liter (g/l) of lignocellulosic biomass solids, preferably at least about 50 g/l, more preferably at least about 100 g/l, and typically in the range of about 100 g/l to about 300 g/l. It will be understood, however, that other solids concentrations may be used in broader aspects of the invention.
In aspects of the invention, the aqueous biomass slurry will be subjected to thermal heating and cooling cycles during pressurized flow through the inlets and outlets of a plurality of (two or more) heat exchangers. In such processing, the treatment system will be designed to facilitate maintaining the aqueous slurry under a pressure substantially at or above its saturation vapor pressure, so as to maintain the water and/or other liquid(s) of the slurry in liquid form as much as possible. However, at times, including during startup, passages within the system may encounter localized reductions in pressure due at least in part to the extended nature of the passages within the heat exchangers. This in turn may result in localized vaporization of water or other liquids which may cause undesired chemical changes in the biomass slurry and undesired phenomena in the system components. To address this problem, in certain embodiments, systems of the invention include one or more feed points at position(s) between the inlet and outlet of a heat exchanger passage, into which a pressurized liquid medium, suitably an aqueous medium, is fed into the heat exchanger passage carrying the aqueous biomass slurry. This feed of a pressurized liquid can serve to locally regulate the pressure in the passage and reduce the incidence of localized pressure drops in the system. Alternatively, a feed of pressurized gas, e.g. nitrogen or carbon dioxide gas can be employed.
A wide variety of heat exchangers may be used in systems and methods of the present invention. These include, for example, simple tube-in-tube heat exchangers and core-and-shell heat exchangers. In preferred embodiments, the aqueous biomass slurry flow will be provided in the outer passage or passages of the heat exchanger, for example, the annular outer passage in a simple tube-in-tube exchanger, or the shell of a core-and-shell heat exchanger, while the heat exchange fluid flow will be provided within the inner passage or passages. On the other hand, in other embodiments of the invention, the situation can be reversed—the aqueous slurry flow can occur in the inner passage(s) while the heat exchange fluid flow can occur in the outer passage(s). Combinations of these flow patterns in multiple heat exchange devices, e.g. connected in series, may also be used. As well, the flow of materials in the inner and outer passages can be co-current or counter-current in a given heat exchanger. Further, in certain preferred aspects, in at least one heat exchanger of the system, and optionally multiple heat exchangers, to effect heat recovery, a first amount of aqueous biomass slurry at a relatively lower temperature is passed through the inner passage(s) while a second amount of aqueous biomass slurry at a relatively higher temperature is passed through the outer passage(s), so as to exchange heat between the first and second amounts of aqueous biomass slurry.
With reference now to FIG. 1 shown is one embodiment of a heat exchange system having localized pressure control that is useful for pretreating a lignocellulosic biomass slurry. Heat exchange system 11 includes a core-and-shell heat exchanger 12 having a core portion 13 including one or more fluid passages and a shell portion 14 including one or more fluid passages and encompassing the core portion 13. Heat exchanger 12 includes a core inlet end 15 including one or more openings communicating with the passage or passages of core 13 and a core outlet end 16 including one or more outlet openings communicating with the passage or passages of core 13. The shell portion 14 of heat exchanger 12 includes a shell inlet end 17 having one or more openings communicating with the one or more passages in shell portion 14 and a shell outlet end 18 having one or more openings communicating with the one or more passages in shell portion 14.
In accordance with aspects of the present invention, heat exchanger 12 also includes one or more openings, and preferably a plurality of openings 19, positioned between the shell inlet end 17 the shell outlet end 18. A source of pressurized liquid, such as a pressurized aqueous medium, is fluidly coupled to the one or more openings 19. Opening(s) 19 are preferably relatively small, so as to minimize dilution of the aqueous slurry by the added pressurized liquid. Preferably, within a given heat exchanger, opening(s) 19 will be sized and numbered sufficiently small so as to result in a dilution of the aqueous slurry in that heat exchanger by no more than 5% (w/w), more preferably no more than 2% (w/w). For these purposes, in certain embodiments, the opening(s) 19 will have a cross-sectional area (considered together) of less than about 20% of the cross-sectional area of the shell (or outer) passage portion 14 of the heat exchanger, more preferably less than about 10%.
The source of pressurized liquid (or gas) can include a feed line or lines 20 connected via a valve 21 to a pressurized tank 22. Pressurized tank 22 can include an incompressible liquid 23 such as an aqueous medium, and a pressurized gaseous atmosphere 24 exerting pressure upon the liquid 23. Pressurized atmosphere 24 can, for example, comprise water vapor, air, nitrogen, or any suitable gas or combination of gases for providing a gaseous environment that exerts pressure on liquid 23. A pressure relief valve 25 can be provided on tank 22, as well as a bleed valve 26 for bleeding the system as necessary.
Heat exchange system 11 also includes a source 27 of an aqueous slurry of a lignocellulosic biomass material, and a pump 28 for pumping the aqueous slurry under pressure through the shell side of heat exchanger 12. System 11 includes a source 29 of a heat exchange fluid coupled to the core side of heat exchanger 12. Source 29 can provide the heat exchange fluid in gaseous or liquid form and at a temperature that is higher or lower than that of the aqueous biomass slurry. In certain embodiments disclosed herein, the source 29 provides the heat exchange fluid in the form of a liquid aqueous medium or steam. The heat exchange fluid from source 29 is circulated through the core portion 13 from core inlet end 15 to the core outlet end 16.
In use, the aqueous biomass slurry from source 27 can be circulated through the shell portion 14 of heat exchanger 12 at a pressure substantially at or exceeding its saturation vapor pressure in order to facilitate maintaining the water and/or other liquid of the slurry in liquid form. However, as the aqueous biomass slurry passes through the shell portion 14 of heat exchanger 12, localized pressure drops may develop which may lead to vaporization or flashing of water and/or other liquid from the aqueous slurry. This in turn interrupts the desired liquid-form modification of the lignocellulosic biomass and decreases the overall efficiency of the pretreatment process, and also may tend to cause “water hammer” or “bump” in the system which exerts unnecessary stresses on systems components. To ameliorate the occurrence of localized pressure drops, an incompressible liquid medium such as an aqueous liquid medium, suitably water alone, is fed under pressure from tank 22 through the openings 19 at intermediate locations within heat exchanger 12. This intermediate feed will be conducted at a pressure sufficient to reduce the incidence of localized pressure drops, typically at a pressure at or above the initial feed pressure of the aqueous biomass slurry into the shell inlet end 17 of heat exchanger 12. Such localized pressure regulation with an incompressible liquid may be used at any desired time during processing of the aqueous biomass slurry through heat exchanger 12, and may be particularly beneficial when used during start-up operations.
It will be understood that the source of pressurized fluid for intermediate feed to heat exchanger 12 can vary from that shown in FIG. 1 in other embodiments. For example, pressurized liquid can be provided by a pump or any other suitable mechanism. Further, it will be understood that intermediate, localized pressure control within the spirit and scope of the present invention can also be provided to the aqueous slurry in situations where the aqueous slurry is passed through the core portion 13 of the heat exchanger 12, rather than through the shell portion 14 thereof. In such situations, openings would be provided at one or more locations intermediate the core inlet end 15 and the core outlet end 16. In such situations, the source 29 of heat exchange fluid would circulate the fluid through the shell portion 14 of heat exchanger 12. Still further, in accordance with additional aspects of the invention, the pressured liquid for intermediate feed to the heat exchanger can contain additives for modifying the aqueous biomass slurry as it passes through the heat exchanger system. Such additives can include, for example, any of those discussed herein, including acid or base for adjusting pH, surfactants, e.g. vegetable oils such as soybean oil, canola oil, and others, to serve as intercalating agents. In certain embodiments, such additives can be added to the pressurized liquid feed at selected times under control of appropriate valving and supply systems. Other embodiments, such additives can be included as a standard measure in the pressurized liquid feed. In these embodiments, additional control and variation of the pretreatment conditions for the lignocellulosic biomass can be provided during the process. These and other variations of embodiments of the present invention will be apparent to those skilled in the art from the descriptions herein.
With reference now to FIG. 2, shown is a lignocellulosic biomass pretreatment system 30 that includes a plurality of heat exchangers. In system 30, an aqueous slurry of a lignocellulosic biomass is passed through the shell sides of the heat exchangers and a heat exchange fluid is passed through the core sides of the heat exchangers. In particular, system 30 includes heat exchanger 31, heat exchanger 32, heat exchanger 33, heat exchanger 34, heat exchanger 35, and heat exchanger 36, having their shell sides coupled in series. As examples, core and shell or simple tube-in-tube heat exchangers may be used. In the illustrated embodiment, each heat exchanger is fluidly coupled to a source 37 of pressurized liquid through feed lines 38 that open into a corresponding plurality of openings in the shell sides 40 of the heat exchangers. The heat exchangers also include a core side 39 encompassed by the shell side 40. This source of pressurized incompressible liquid can be such as that described in the proceeding passages and can be useful to locally regulate pressures within the system 30.
System 30 includes a source of lignocellulosic biomass 41 and pump 42 for pumping the biomass in slurry form through the system 30. As illustrated, the biomass slurry is pumped through the shell sides 40 of the heat exchangers of system 30, whereas various heat exchange fluids (in some cases potentially including another amount of aqueous biomass slurry or a fraction thereof) are passed through the cores 39 of the heat exchangers. As will be discussed further below, in one module of the heat exchange fluid side, a source of heated, liquid-form water 43 is pumped by pump 44 through the cores 39 of heat exchangers 32 and 34 of system 30. In another module of the heat exchange fluid side of system 30, a source of steam 45, such as a boiler, is provided to circulate steam through the core 39 of heat exchanger 33.
Generally in system 30, as the aqueous biomass slurry is pumped through heat exchangers 31, 32, and 33, it is subjected to increasing temperatures. For example, the temperature ST1 of the initial dry lignocellulosic biomass can be room temperature, for example about 20° C. to about 25° C. After being combined with heated liquids such as a heated aqueous medium, the temperature ST2 of the aqueous biomass slurry can be about 50° C. to about 90° C. The temperature ST3 of the aqueous biomass slurry after exiting the first heat exchanger 31 will be higher than ST2, typically in the range of about 70° C. to about 120° C. The temperature ST4 of the aqueous slurry after exiting heat exchanger 32 can typically be about 120° C. to about 170° C. The temperature ST5 of the aqueous biomass slurry after exiting heat exchanger 33 can typically be in the range of about 150° C. to about 220° C. From this point, the aqueous biomass slurry is passed through a series of heat exchangers which decrease its temperature. Thus, the temperature ST6 of the aqueous slurry as it exits heat exchanger 34 can be in the range of about 100° C. to about 150° C., the temperature ST7 of the aqueous slurry after exiting heat exchanger 35 can be about 50° C. to about 100° C., and the temperature ST8 after exiting heat exchanger 36 can typically be about 30° C. to about 70° C.
On the heat exchange fluid side of the system, the temperature XT1 of the heat exchange fluid exiting heat exchanger 31 can typically range from about 70° C. to about 100° C., where as the temperature XT2 of the heat exchange fluid entering heat exchanger 31 can typically be in the range of about 90° C. to about 120° C. The temperature XT3 of the heat exchange fluid exiting heat exchanger 32 can typically be in the range of about 100° C. to about 150° C., whereas the temperature XT4 of the heat exchange fluid entering heat exchanger 32 can typically be about 130° C. to about 180° C. The temperature XT5 of the heat exchange fluid exiting heat exchanger 33 can typically be in the range of about 140° C. to about 180° C., whereas the temperature XT6 of the heat exchange fluid entering heat exchanger 33 can typically in the range of about 150° C. to about 230° C. The temperature XT7 of the heat exchange fluid exiting heat exchanger 34 can typically be about 130° C. to about 180° C., while the temperature XT8 of the heat exchange fluid entering heat exchanger 34 can typically be about 100° C. to about 150° C. The temperature XT9 of the heat exchange fluid exiting heat exchanger 35 can typically be in the range of about 90° C. to about 120° C., where as the temperature XT10 of the heat exchange fluid entering heat exchanger 35 can typically be about 60° C. to about 110° C. The temperature XT11 of the heat exchange fluid exiting heat exchanger 36 can typically be about 60° C. to about 110° C. The temperature XT12 of the heat exchange fluid entering heat exchanger 36 can typically be in the range of about 20° C. to about 70° C. It will be understood that the temperatures XT and ST discussed herein can apply to cases in which the biomass is processed in either a core side or a shell side of a heat exchanger, with the heat transfer fluid correspondingly being passed through the opposite side. It will also be understood that in such processing, where multiple heat exchangers are utilized, some of the exchangers can process the biomass in the shell side while others process it in the core side, or all of the exchangers can process the biomass in the shell side or in the core side, with the heat transfer fluid correspondingly in the opposite side. These and other variations will be within the purview of those skilled in the art given the descriptions herein.
In certain processes of the invention, the lignocellulosic biomass utilized will be corn stover or corn fiber (derived from the hulls of corn kernels). In preferred such processes, the temperatures given in Table 1 below are applied in a system such as that described in connection with FIG. 2:








TABLE 1







Corn Fiber
Corn Stover










ST
XT
ST
XT


Temperature
Temperature
Temperature
Temperature


(± 10° C.)
(± 10° C.)
(± 10° C.)
(± 10° C.)

















ST1
 20° C.
XT1 
 80° C.
ST1
 20° C.
XT1 
100° C.


ST2
 70° C.
XT2 
105° C.
ST2
 90° C.
XT2 
135° C.


ST3
 95° C.
XT3 
105° C.
ST3
125° C.
XT3 
135° C.


ST4
140° C.
XT4 
150° C.
ST4
170° C.
XT4 
180° C.


ST5
160° C.
XT5 
160° C.
ST5
190° C.
XT5 
190° C.


ST6
115° C.
XT6 
170° C.
ST6
145° C.
XT6 
200° C.


ST7
 80° C.
XT7 
150° C.
ST7
110° C.
XT7 
180° C.


ST8
 50° C.
XT8 
105° C.
ST8
 80° C.
XT8 
135° C.




XT9 
105° C.


XT9 
135° C.




XT10
 70° C.


XT10
100° C.




XT11
 70° C.


XT11
100° C.




XT12
 50° C.


XT12
 80° C.









It will be understood that the temperature ranges given herein for the biomass slurry (ST) and heat exchange fluids (XT) at various points in the system can vary in accordance with the particular process at hand. Appropriate temperatures for a given process will depend upon system requirements, pretreatment requirements, the particular lignocellulosic biomass undergoing pretreatment, and other factors. It will also be understood that while those temperature ranges given above illustrate certain embodiments of the invention, other embodiments with other temperature ranges are also encompassed by broader aspects of the invention. As well, the number of heat exchangers and stages of heating and cooling in the system can vary from those disclosed in system 30 without departing from the spirit and scope of broader aspects of the present invention.
The aqueous lignocellulosic biomass slurry can be passed through the heat exchanger(s) of the system at any suitable flow rate. Flow rates of about 5 gallons (US) per minute (gal/min) to about 200 gal/min will be typical, with flow rates of about 40 gal/min to about 100 gal/min being more preferred. In addition, in portions of the pretreatment system (e.g. in some or all heat exchangers) in which the biomass slurry is processed at pressures above the saturation vapor pressure of water or other liquid, the pressure will typically be in the range of about 50 to about 500 pounds per square inch (psi).
Other preferred aspects of the system 30 are illustrated in FIG. 2. For example, countercurrent heat recovery can be incorporated into the system. In particular, a single heat exchange fluid can be circulated through heat exchangers 35 and 36 during which the heat exchange fluid picks up heat from the aqueous biomass slurry during its cooling phase, and that same fluid can then be circulated through heat exchanger 31 to transfer heat to the aqueous slurry during its heating phase. Also, hot water from liquid water source 43 can be circulated through heat exchanger 32 during which it transfers heat to the aqueous biomass slurry during its heating phase, and then through heat exchanger 34 during which the liquid water picks up heat from the aqueous slurry during its cooling phase. These and other arrangements of the heating and cooling stages of the system 30 will be apparent to those skilled in the art from the descriptions herein, and can be used in embodiments of the invention. Further, it will be understood that pretreatment processes as described herein can be used in combination with other pretreatment processes designed to increase the susceptibility of the biomass to enzymatic hydrolysis, including for example chemical, mechanical and/or microbiological pretreatment processes.
In additional embodiments of the invention, a heat exchanger useful for pretreating a biomass slurry defines at least one helical groove along at least a portion of its length, and potentially the entire length of an outer flow passage of the heat exchanger. With reference to FIG. 3, shown is a perspective view of a tube-in-tube arrangement of one embodiment of such a heat exchanger. The arrangement for heat exchanger 50 thus includes at least one outer passage 51, at least one inner passage 52, and a helical groove 53 defined along an outer wall 54 of outer passage 51. Helical groove 53 can, for example, provide a secondary, helical passage 55 having a radial dimension R1 that is at least about 10% of that of the radial dimension R2 of the primary outer passage 56, with radial dimension R1 typically being in the range of about 10% to about 50% of that of radial dimension R2, more typically in the range of about 10% to about 20%. Helical groove 53 can serve to enhance mixing of the aqueous biomass slurry as it passes through the overall outer passage 51 including primary passage 56 and helical passage 55, so as to help to prevent plugging of outer passage 51. It will be understood that helical groove 53 can be used instead of or in addition to fins, baffles, or other turbulence-inducing members located in outer passage 51. Heat exchanger(s) 50 can be used in overall systems containing a plurality of heat exchangers, e.g. a system 30 as disclosed in FIG. 2, and in so doing can be used for one, two or more, or all heat exchangers of the system.
In any given heat exchanger used in processes of the invention, or in some or all such heat exchangers, it is desirable that the volume of the passage in which the biomass is being processed be larger than the volume of the passage through which the heat exchange fluid is passed. Thus, in certain embodiments, the volume ratio of the biomass-processing passage of the heat exchanger(s) (e.g. a shell or core portion, as the case may be) to the heat transfer fluid passage of the heat exchanger(s) (e.g. correspondingly a core or shell portion, as the case may be) is at least about 3:1, or at least about 5:1, typically in the range of about 5:1 to about 50:1 and preferably in the range of about 10:1 to about 30:1.
In accordance with other aspects of the invention, lignocellulosic biomass that has been pretreated as described herein can be utilized to produce useful products, such as ethanol. In the production of ethanol, the pretreated biomass can be subjected to enzymatic hydrolysis with a cellulase enzyme. In this regard, a cellulase enzyme is an enzyme that catalyzes the hydrolysis of cellulose to products such as glucose, cellobiose, and/or other cellooligosaccharides. Cellulase enzymes may be provided as a multienzyme mixture comprising exo-cellobiohydrolases (CBH), endoglucanases (EG) and beta-glucosidases (betaG) that can be produced by a number of plants and microorganisms. The process of the present invention can be carried out with any type of cellulase enzymes, regardless of their source; however, microbial cellulases provide preferred embodiments. Cellulase enzymes can, for example, be obtained from fungi of the genera Aspergillus, Humicola, and Trichoderma, and from the bacteria of the genera Bacillus and Thermobifida. 
Following enzymatic hydrolysis of the pretreated biomass, an aqueous medium containing the resulting sugars can be subjected to fermentation to produce useful products, such as ethanol. In certain modes of practice, unhydrolyzed solids, typically including lignin, can be separated from liquids as a byproduct, for example by centrifugation or in a settling tank. The unhydrolyzed solids can be sold into commercial channels such as feed industries or combusted to generate thermal energy to be provided to systems and methods of the invention.
The fermentation of the sugars to produce ethanol and/or other useful chemicals can be conducted with any of a wide variety of fermentive microorganisms such as yeast or bacteria, including genetically modified versions thereof, and using known techniques. The ethanol can then be purified from the fermented medium, for example by distillation.
The uses of the terms “a” and “an” and “the” and similar references in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiment has been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected. In addition, all references cited herein are indicative of the level of skill in the art and are hereby incorporated by reference in their entirety.

## Claims

1. A method for processing lignocellulosic biomass, comprising:
passing an aqueous slurry including the lignocellulosic biomass in a starting physical form through outer passage of a heat exchanger from an inlet opening to an outlet opening spaced horizontally from the inlet opening, while passing a heated exchange medium through one or more inner passages encompassed by said outer passage, said one or more inner passages in heat exchange relationship with said outer passage along a length of the heat exchanger, said outer passage having a volume that is greater than that of said one or more inner passages, and said aqueous slurry having a temperature above 100° C. and being at a first pressure substantially at or above the saturation vapor pressure of water at said temperature;
during said passing step, feeding an amount of liquid aqueous medium under a second pressure into said outer passage through a plurality of additional openings at longitudinally spaced positions along said length of the heat exchanger and intermediate said inlet opening and said outlet opening so as to locally regulate pressure within said outer passage and so that said amount of liquid aqueous medium travels co-current with said aqueous slurry to said outlet opening;
conducting said feeding step sufficiently to reduce or prevent localized vaporization of liquid of said aqueous slurry in said outer passage and resulting occurrence of mechanical water hammer in said heat exchanger that would otherwise occur under conditions of said passing step;
conducting said feeding step so as to control said amount of liquid aqueous medium to result in no more than a 5% by weight dilution of said aqueous slurry as said aqueous slurry passes from said inlet opening to said outlet opening of said outer passage; and
recovering from the outlet opening of the said outer passage an aqueous slurry diluted by said amount of liquid aqueous medium from said feeding step and including the lignocellulosic biomass in a modified physical form, wherein the modified physical form of the lignocellulosic biomass has an increased susceptibility to degradation by a cellulase enzyme relative to the starting physical form of the lignocellulosic biomass.

2. The method of claim 1, wherein the heat exchanger is a core and shell heat exchanger having a shell portion providing said outer passage and a core portion providing said one or more inner passages.

3. The method of claim 1, wherein said feeding comprises (i) providing a vessel containing the liquid aqueous medium as an incompressible liquid and a gaseous atmosphere above a surface of the liquid aqueous medium, and (ii) exerting pressure on the gaseous atmosphere to cause the gaseous atmosphere to exert pressure on the surface of the liquid aqueous medium and feed the liquid aqueous medium through a plurality of feed lines connected to said tank and then through said plurality of additional openings and into said outer passage.

4. The method of claim 1, wherein said plurality of additional openings considered together have a cross-sectional area that is less than 20% of a cross-sectional area of said outer passage.

5. The method of claim 1, wherein said second pressure is equal to or greater than said first pressure.

6. The method of claim 1, wherein during said passing said aqueous slurry is maintained at a pH in the range of 5 to 8.

7. The method of claim 1, wherein said aqueous slurry includes the lignocellulosic biomass at a solids level of at least 50 grams per liter.

8. A method for pretreating lignocellulosic biomass to increase its susceptibility to enzymatic hydrolysis, comprising:
providing particulate lignocellulosic biomass in a starting physical form;
mixing the particulate lignocellulosic biomass with an aqueous medium to prepare an aqueous biomass slurry;
first passing the aqueous biomass slurry through an outer passage of a heat exchanger from an inlet opening to an outlet opening, said aqueous biomass slurry having a temperature above 100° C. and being at a first pressure substantially at or above the saturation vapor pressure of water at said temperature;
second passing a heated exchange medium through one or more inner passages of the heat exchanger encompassed by said outer passage, said one or more inner passages in heat exchange relationship with said outer passage along a length of the heat exchanger, and said outer passage having a volume that is greater than that of said one or more inner passages;
during said first passing, feeding an amount of liquid aqueous medium at a second pressure into said outer passage through a plurality of additional openings at longitudinally spaced positions along said length of the heat exchanger and intermediate said inlet opening and said outlet opening so as to locally regulate pressure within the outer passage and so that said amount of liquid aqueous medium travels co-current with said aqueous biomass slurry to said outlet opening;
conducting said feeding step sufficiently to reduce or prevent localized vaporization of liquid of said aqueous biomass slurry in said outer passage and resulting occurrence of mechanical water hammer in said heat exchanger that would otherwise occur under conditions of said first passing step;
conducting said feeding step so as to control said amount of liquid aqueous medium to result in no more than a 5% by weight dilution of said aqueous biomass slurry as said aqueous biomass slurry passes from said inlet opening to said outlet opening of said outer passage; and
recovering from said outlet opening of said outer passage an aqueous slurry diluted by said amount of liquid aqueous medium from said feeding step and including the lignocellulosic biomass in a modified physical form, wherein the modified physical form of the lignocellulosic biomass has an increased susceptibility to degradation by a cellulase enzyme relative to the starting physical form of the lignocellulosic biomass.

9. The method of claim 8, wherein said outlet opening is spaced horizontally from said inlet opening.

10. The method of claim 8, wherein said feeding comprises (i) providing a vessel containing the liquid aqueous medium as an incompressible liquid and a gaseous atmosphere above a surface of the liquid aqueous medium, and (ii) exerting pressure on the gaseous atmosphere to cause the gaseous atmosphere to exert pressure on the surface of the liquid aqueous medium and feed the liquid aqueous medium through a plurality of feed lines connected to said tank and then through said plurality of additional openings and into said outer passage.

11. A method for producing ethanol from lignocellulosic biomass, comprising:
(a) pretreating lignocellulosic biomass to increase its susceptibility to hydrolysis by a cellulase enzyme, said pretreating comprising:
providing particulate lignocellulosic plant biomass in a starting physical form;
mixing the particulate lignocellulosic plant biomass with an aqueous medium to prepare an aqueous plant biomass slurry;
first passing the aqueous plant biomass slurry through an outer passage of a heat exchanger from an inlet opening to an outlet opening, said aqueous plant biomass slurry having a temperature above 10020  C. and being at a first pressure substantially at or above the saturation vapor pressure of water at said temperature;
second passing a heated fluid medium through one or more inner passages of the heat exchanger encompassed by the outer passage, said one or more inner passages in heat exchange relationship with said outer passage along a length of the heat exchanger, and said outer passage having a volume that is greater than that of said one or more inner passages;
during said first passing, feeding an amount of liquid aqueous medium at a second pressure into said outer passage through a plurality of additional openings at longitudinally spaced positions along said length of the heat exchanger and intermediate said inlet opening and said outlet opening so as to locally regulate pressure in said outer passage and so that said amount of liquid aqueous medium passes co-current with said aqueous plant biomass slurry to said outlet opening;
conducting said feeding step sufficiently to reduce or prevent localized vaporization of liquid of said aqueous biomass slurry in said outer passage and resulting occurrence of mechanical water hammer in said heat exchanger that would otherwise occur under conditions of said first passing step;
conducting said feeding step so as to control said amount of liquid aqueous medium to result in no more than a 5% by weight dilution of said aqueous slurry as said aqueous slurry passes from said inlet opening to said outlet opening of said outer passage; and
recovering from said outlet opening of said outer passage an aqueous slurry diluted by said amount of liquid aqueous medium from said feeding step and including the lignocellulosic biomass in a modified physical form, wherein the modified physical form of the lignocellulosic biomass has an increased susceptibility to degradation by a cellulase enzyme relative to the starting physical form of the lignocellulosic biomass;

(b) hydrolyzing lignocellulosic biomass subjected to step (a) with a cellulase enzyme so as to produce glucose from cellulose of the biomass;
(c) fermenting a medium including said glucose to produce ethanol; and
(d) purifying the ethanol.

12. The method of claim 11, wherein said outlet opening is spaced horizontally from said inlet opening.

13. The method of claim 11, wherein said feeding comprises (i) providing a vessel containing the liquid aqueous medium as an incompressible liquid and a gaseous atmosphere above a surface of the liquid aqueous medium, and (ii) exerting pressure on the gaseous atmosphere to cause the gaseous atmosphere to exert pressure on the surface of the liquid aqueous medium and feed the liquid aqueous medium through a plurality of feed lines connected to said tank and then through said plurality of additional openings and into said outer passage.

14. The method of claim 11, wherein said plurality of additional openings considered together have a cross-sectional area that is less than 20% of a cross-sectional area of said outer passage.

15. The method of claim 11, wherein said second pressure is equal to or greater than said first pressure.

16. The method of claim 11, wherein said aqueous slurry includes the lignocellulosic biomass at a solids level of at least 50 grams per liter.

17. The method of claim 11, wherein the volume ratio of the outer passage to the one or more inner passages is at least 3:1.

18. The method of claim 11, wherein said liquid aqueous medium comprises an additive to the pretreatment process.

19. The method of claim 18, wherein the additive is an acid or a base.

20. The method of claim 8, wherein the heat exchanger is a core and shell heat exchanger having a shell side providing said outer passage and a core side providing said one or more inner passages.

21. The method of claim 11, wherein the heat exchanger is a core and shell heat exchanger having a shell side providing said outer passage and a core side providing said one or more inner passages.