Patent Publication Number: US-2013252297-A1

Title: Method for Controlling Butanol Concentration in Fermentation Broth

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims benefit of priority from Provisional Application No. 61/007,665, filed Dec. 14, 2007. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to a two stage process involving stripping and absorption to remove butanol from fermentation broth. 
     BACKGROUND 
     There is much interest in converting fermentable renewable sources of carbon to other useful chemicals, such as, but not limited to fuel or fuel additives or specialty or commodity chemicals. 
     Currently, much industrial fermentation involves the manufacture of ethanol for either chemical or fuel use. However, there is advantage to producing butanol by fermentation. For use in fuel, butanol is superior to ethanol, namely butanol has lower vapor pressure and decreased solubility in water. Hence, it would be desirable to have an economical fermentation process by which butanol could be obtained. 
     An advantageous butanol fermentation process would encompass a complete, or substantially complete, conversion of sugars to butanol without reaching a butanol titer that causes the rate of butanol production to fall below an undesirable predetermined rate (the “tolerance level”, usually influenced by economic considerations). One way of achieving this goal is to limit sugar loadings to a level whereby batch fermentation does not result in butanol titers that cause the rate of butanol production to fall below the predetermined rate. However, this approach is undesirable because limited sugar loadings result in dilute solutions that are economically undesirable to process. Therefore, there is a need for a process that achieves the aforementioned goal in a way that does not require a limitation on sugar loading. 
     One means by which a butanol-producing fermentation process might be made more efficient would be to continuously remove butanol from the fermentation medium (broth), so that the tolerance level of the butanol producing mircoorganism is not reached. This should allow high loadings of sugar to be charged to the fermentation vessel, allowing favorable economics to be achieved. Such a removal process, when associated with fermentation, is generally termed an “In situ Product Removal” process, or an “ISPR” process for short. For an ISPR process to be useful, it needs to be integrated with, compatible with, or easily segregated from, the fermentation process itself. For example, simple distillation of the fermentation broth at atmospheric pressure would not be useful as an ISPR technique because the fermentation microorganisms would most likely be damaged by the temperature in the base of the distillation column. 
     The present invention represents a means by which In situ Product Removal (ISPR) can be successfully carried out to control butanol concentrations in fermentation broth at or below the tolerance level of the fermentation microorganism. Hence, the current invention is believed to enable butanol fermentation to be carried out using a microorganism, concentrations of sugars and other nutrients which result in favorable economics. 
     The present invention provides an ISPR process which solves the problem of toxic butanol levels which can destroy a microorganism in a fermentation process by ensuring that butanol concentration in a fermentation broth can be maintained below the tolerance level of the fermentation microorganisms and allowing for subsequent recycle of the fermentation microorganisms back to the fermentation vessel consequently enhancing the efficiency of the process. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
         FIG. 1  shows an apparatus having stripping and absorption sections for removing butanol from a fermentation broth, where the fermentation broth is contacted counter-currently by the stripping gas. 
         FIG. 2  shows an apparatus having stripping and absorption sections for removing butanol from a fermentation broth, where the fermentation broth is contacted co-currently by the stripping gas. 
         FIG. 3  shows an apparatus having a column having a stripping section and a column having an absorption section for removing butanol from fermentation broth. 
         FIG. 4  shows an apparatus having a column having a series of associated pairs of stripping and absorption sections for removing butanol from fermentation broth. 
     
    
    
     SUMMARY OF THE INVENTION 
     A method for controlling the concentration of butanol at or below a predetermined level in one or more fermentation broths comprising butanol and water and contained in one or more respective fermentation vessels, said method comprising:
         (a) continuously removing a portion of at least one of the fermentation broths from its respective fermentation vessel to form a removed fermentation broth;   (b) feeding the removed fermentation broth into a stripping section of an apparatus in which said stripping section is in gaseous communication, but not liquid communication, with an associated absorption section, the apparatus having at least one stripping section with an associated absorption section;   (c) simultaneously feeding an inert gas into the stripping section, thereby causing a portion of the butanol to leave the fermentation broth and form (i) a gaseous mixture comprising butanol and the inert gas and (ii) a reduced-butanol fermentation broth;   (d) returning the reduced-butanol fermentation broth to its respective fermentation vessel, and allowing the gaseous mixture to enter the absorption section of the apparatus that is associated with the stripping section of step (b);   (e) continuously feeding into the absorption section of step (d) an organic liquid absorbent having a lower vapor pressure than that of butanol and an ability to absorb butanol, thereby forming a liquid mixture comprising the liquid absorbent and at least a portion of the butanol from the gaseous mixture, thereby reducing the butanol content in the gaseous mixture to form a reduced-butanol gaseous mixture;   (f) returning the reduced-butanol gaseous mixture to a stripping section of the apparatus;   (g) recovering butanol from the liquid mixture and returning the liquid absorbent to an absorption section of the apparatus;   thereby, as a result of the method, controlling the concentration of butanol in the fermentation broth.       

     Another embodiment provides the process, wherein removal from the same fermentation vessel is simultaneous for two or more fermentation broth streams. 
     Another embodiment provides the process, wherein removal of the two or more fermentation broth streams is non-simultaneous. 
     In yet another embodiment, the process, wherein removal from different fermentation vessels is simultaneous for two or more fermentation broth streams. 
     In yet another embodiment, the process, wherein removal from different fermentation vessels is non-simultaneous for two or more fermentation broth streams. 
     Another embodiment provides the process, wherein removal from different fermentation vessels is separate for two or more fermentation broth streams. 
     Another embodiment provides the process, wherein the inert gas is nitrogen. 
     In yet another embodiment, the process, wherein the inert gas is air. 
     In yet another embodiment, the process, wherein the inert gas is CO 2 . 
     In yet another embodiment, the process, wherein the stripping apparatus is located inside the fermentation vessel. 
     Another embodiment provides the process, wherein the stripping apparatus is located exterior to the fermentation vessel. 
     Another embodiment provides the process, wherein the organic liquid absorbent is a C 8  or higher alcohol. 
     In yet another embodiment, the process, wherein the alcohol is selected from the group consisting of octanol, nonanol, and decanol and mixtures thereof. 
     In yet another embodiment, the process, wherein the alcohol is decanol. 
     Another embodiment provides the process, wherein the butanol is recovered by distillation. 
     In yet another embodiment, the process wherein recovery of butanol is selected from the group consisting of absorption, liquid-liquid extraction and crystallization. 
     An embodiment provides a method for recycling at least one fermentation broth comprising fermentation microorganisms from a fermentation process wherein butanol is produced in at least one fermentation vessel, said method comprising:
         (a) removing a portion of the fermentation broth comprising fermentation microorganisms wherein said butanol is produced from its respective fermentation vessel to form a removed fermentation broth comprising fermentation microorganisms;   (b) feeding the removed fermentation broth comprising fermentation microorganisms into a stripping section of an apparatus in which said stripping section is in gaseous communication, but not liquid communication, with an associated absorption section, the apparatus having at least one stripping section with an associated absorption section;   (c) simultaneously feeding an inert gas into the stripping section, thereby causing a portion of the butanol to leave the removed fermentation broth comprising fermentation microorganisms and form (i) a gaseous mixture comprising butanol and the inert gas and (ii) a reduced-butanol fermentation broth comprising fermentation microorganisms; and   (d) returning the reduced-butanol fermentation broth comprising fermentation microorganisms to its respective fermentation vessel. In yet another embodiment, wherein physical loss of fermentation broth microorganism and sugars is less than 1%.       

     Another embodiment provides the process, wherein the inert gas is nitrogen. 
     In yet another embodiment, the process, wherein the inert gas is CO 2 . 
     An embodiment provides an intermediate composition comprising a butanol-rich absorbent phase comprising about 5% to about 15% butanol and an organic liquid absorbent having a lower vapor pressure than butanol. 
     In yet another embodiment, the composition, wherein the liquid absorbent is a C 8  or higher alcohol. 
     In yet another embodiment, the composition, wherein the alcohol is selected from the group consisting of octanol, nonanol, decanol and mixtures thereof. 
     In yet another embodiment, the composition, wherein the alcohol is decanol. 
     DETAILED DESCRIPTION 
     As used above and throughout the description of the invention, the following terms, unless otherwise indicated, shall be defined as follows: 
     “In Situ Product Removal” as used herein means the selective removal of a specific fermentation product from a biological process such as fermentation to control the product concentration in the biological process. 
     “Counter-currently” as used herein refers to the internal arrangement of process streams within a unit operation that can be divided into several sub sections by which the process streams flow in opposite directions to each other. In particular in this application the stripping and absorbing sections in the contacter will have liquid put to the top of the section which will flow down through gravity and vapor introduced into the bottom of the section and will flow up through pressure gradient. 
     “Co-currently” as used herein refers to the internal arrangement of process streams within a unit operation that can be divided into several sub sections by which the process streams flow in the same direction as each other. In particular in this application the stripping and absorbing sections in the contacter will have liquid put to the top of the section which will flow down through gravity and vapor will also be introduced into the top of the section and will flow down through pressure gradient. This is opposite to the normal arrangements. 
     “Butanol” as used herein means 1-butanol, 2-butanol, isobutanol, and mixtures thereof. 
     “Inert Gas” as used herein means a gas that does not ineract with the process of fermentation and has low solubility in the both the fermentation broth and the absorbent. The inert gas may be a mixture of compounds that might include but not be limited to N 2  and CO 2 . 
     “Fermentation broth” as used herein means the mixture of water, sugars, dissolved solids, suspended solids, microorganisms producing butanol, product butanol and all other constituents of the material held in the fermentation vessel in which product butanol is being made by the reaction of sugars to butanol, water and CO 2  by the micro organisms present. 
     “Fermentation vessel” as used herein means the vessel in which the fermentation reaction by which product butanol is made from sugars is carried out. 
     “Stripping” as used herein means the action of transferring all or part of a volatile component from a liquid stream into a gaseous stream. 
     “Stripping section” as used herein means that part of the contacting device in which the stripping operation takes place. 
     “Gaseous communication” as used herein means a gaseous phase that is a product from one piece of equipment or operation is then passed to a second piece of equipment or operation to which it is in communication. 
     “Liquid communication” as used herein means that a liquid phase that is a product from one piece of equipment or operation is then passed to a second piece of equipment or operation to which it is in communication. 
     “Absorption” as used herein means the action of transferring all or part of a component from a gaseous stream into a liquid stream. 
     “Absorption section” as used herein means the part of the contacting device in which the absorption operation takes place. 
     “Reduced-butanol fermentation broth” as used herein means material that has a similar composition to the fermentation broth but has been acted upon in such a way to preferentially reduce the composition of the butanol in the material. 
     “Concentration of butanol” as used herein means the amount of butanol contained within a stream compared to the amount of the whole stream. 
     “Absorbent” as used herein means a liquid that is able to absorb another species from a gas phase. Such as for example this may be heavy a alcohol that is then able to absorb butanol from a gaseous phase. 
     The fermentation of sugar to butanol produces two other products: a mole of water per mole of sugar, and two moles of CO 2 . Typically, in a batch fermentation, the water that is made remains in the fermentation vessel, while the CO 2  is vented as a gas. A small amount of the butanol will also be vented with the CO 2 , but at the temperatures of the fermentation, the rate of butanol removal is small compared to its production rate. 
     The current invention is generally described below with reference to  FIG. 1  through  FIG. 4 . 
     The current invention consists of a two stage ISPR process of stripping and absorption to remove butanol from the fermentation broth. The operating conditions, including temperatures and pressures, of the stripping operation of the ISPR process are similar to those used in the fermentation vessel, enabling the viability of the fermentation microorganism. In the first stage, butanol is stripped from the fermentation broth in a stripping unit by a gas stream comprising an inert carrier gas. The inert carrier gas can comprise nitrogen, CO 2 , air, or mixtures thereof. The inert carrier gas can further comprise at least one additional gas so long as the presence of the additional gas is not deleterious to the process. The selection of the inert carrier gas can be based on availability and cost, for example. 
     The volatility of butanol under these conditions is much greater than water and hence an increase in the concentration of butanol in the gas stream, relative to water, will occur. The rate of stripping needs to be such that butanol levels in the fermentation vessel are maintained at or below the tolerance level. The amount of carrier gas required at the temperature of the fermentation is much greater than the amount of CO 2  that is given off by the fermentation process, consequently, a source of carrier gas will be required. This stripping process could take place in the fermentation vessel itself, but is more likely carried out outside of this vessel in an external stripping unit. The liquid resulting from the stripping process is returned to the fermentation vessel where the microorganisms can continue to convert unused sugar to butanol, CO 2  and water. Physical loss of the microorganism and sugars from the fermentation broth as a result of the stripping process should be minimal, for example less than about 1%, because of their low volatilities. The stripping process is operated in such a manner that it is not deleterious to the microorganism and the sugars in the fermentation broth. Meanwhile, the butanol-containing carrier gas stream is passed to an absorption unit where it is contacted with a low volatility organic absorbent, having a lower vapor pressure than that of butanol, such as an ether, aldehyde, ester, ketone, or alcohol, preferably an alcohol having eight or more carbon atoms, for example octanol, nonanol, or decanol, and mixtures thereof, wherein the butanol is preferentially absorbed from the carrier gas to form a butanol-rich absorbent phase. A butanol rich absorbent phase is one where the butanol content is about 5% to 15%. 
     The butanol-rich absorbent phase is then processed by means known in the art for example distillation, absorption, liquid-liquid extraction, crystallization) to regenerate a substantially butanol-free absorbent for reuse in the absorption unit and to produce a product butanol stream. The resulting carrier gas stream from the absorption process is low in butanol content and can be recycled to the front of the process (the stripping unit) by use of suitable mechanical compression equipment, such as a fan, blower, or compressor, thereby forming a gas loop. If CO 2  is the preferred carrier gas, the CO 2  generated from the reactor can be introduced into the gas loop, with excess CO 2  in the loop being purged from the remainder of the process via a suitable scrubbing system. 
       FIG. 1 , depicts an apparatus for carrying out an embodiment of the present invention. Such apparatus can be purchased from commercial vendors or assembled by one skilled in the art. The apparatus comprises a column  10  that includes an absorption section  20  and a stripping section  22 . Typically, sections  20  and  22  will comprise trays or packing, as is well known in the art. In addition, gas exits at or near the top of column  10  via line  16  and is raised in pressure by mechanical compression equipment  14 , such as a fan, blower or compressor, and is returned to, or near to, the bottom of column  10  via line  18 . Maintenance of sufficient gas in the system is controlled by purge or make-up in a conventional manner (not shown). The process is operated by passing fermentation broth from a fermentation vessel (not shown) via line  36  into, or near to, the top of stripping section  22 , wherein the broth is then contacted counter-currently by gas entering column  10  via line  18 . A fraction of the butanol contained in the fermentation broth is transferred into the gas and is passed from the top of the stripping section  22  to the bottom of the absorption section  20 , resulting in a stripped fermentation broth that is formed in section  22 . The stripped fermentation broth is returned to the fermentation vessel via line  38 . Butanol that is contained in the gas passing from section  22  to section  20  is absorbed in section  20  by a low volatility organic absorbent, having a lower vapor pressure than that of butanol, such as an ether, aldehyde, ester, ketone, or alcohol, preferably an alcohol having eight or more carbon atoms, for example octanol, nonanol, or decanol, and mixtures thereof, that is introduced into the top of the absorption section via line  32  wherein the butanol is preferentially absorbed from the carrier gas to form a butanol-rich absorbent phase. A butanol rich absorbent phase is one where the butanol content is about 5% to 15%. 
     Butanol is removed from absorption section  20 , along with the low volatility absorbent via line  34  and then separated from the low volatility absorbent using conventional separation techniques such as distillation, decantation, absorption, liquid-liquid extraction, crystallization (not shown). 
     An alternative embodiment to the apparatus shown in  FIG. 1  is one in which the vertical relationship of the absorption and stripping sections of column  10  is reversed, i.e., the stripping section  22  resides above the absorption section  20 . 
       FIG. 2  depicts an apparatus for carrying out a further embodiment of the present invention. The apparatus comprises a column  10  that includes an absorption section  20  and a stripping section  22 . Typically, sections  20  and  22  will comprise trays or packing, as is well known in the art. In addition, gas exits at or near the bottom of column  10  via line  16  and is raised in pressure by mechanical compression equipment  14 , such as a fan, blower or compressor, and is returned to, or near to, the top of column  10  via line  18 . Maintenance of sufficient gas in the system is controlled by purge or make-up in a conventional manner (not shown). 
     The process is operated by passing fermentation broth from a fermentation vessel (not shown) via line  36  into, or near to, the top of the stripping section  22 , wherein the broth is then contacted co-currently by gas entering column  10  via line  18 . A fraction of the butanol contained in the fermentation broth is transferred into the gas and is passed from the bottom of the stripping section  22  to the top of the absorption section  20 , resulting in a stripped fermentation broth that is formed in section  22 . The stripped fermentation broth is returned to the fermentation vessel via line  38 . Butanol that is contained in the gas passing from section  22  to section  20  is absorbed in section  20  by a low volatility organic absorbent, having a lower vapor pressure than that of butanol, such as an ether, aldehyde, ester, ketone, or alcohol, preferably an alcohol having eight or more carbon atoms, for example octanol, nonanol, or decanol, and mixtures thereof, that is introduced into the top of the absorption section via line  32  wherein the butanol is preferentially absorbed from the carrier gas to form a butanol-rich absorbent phase. A butanol rich absorbent phase is one where the butanol content is about 5% to 15%. Butanol is removed from the absorption section  20 , along with the low volatility absorbent via line  34  and then separated from the low volatility absorbent using conventional separation techniques such as distillation, decantation, absorption, liquid-liquid extraction, crystallization (not shown). 
     An alternative embodiment of the apparatus shown in  FIG. 2  is one in which the vertical relationship of the absorption and stripping sections of column  10  is reversed, i.e., the absorption section  20  resides above the stripping section  22 . 
       FIG. 3 , depicts an apparatus for carrying out a further embodiment of the present invention. The apparatus comprises a column  10  containing absorption section  20  and column  12  containing stripping section  22 . Typically, sections  20  and  22  will comprise trays or packing, as is well known in the art. The columns are connected via line  13  by which gas can pass from the top, or near the top, of column  12  to the bottom, or near the bottom, of column  10 . In addition gas exits at or near the top of column  10  via line  16  and is raised in pressure by mechanical compression equipment  14 , such as a fan, blower or compressor, and is returned to, or near to, the bottom of column  12  via line  18 . Maintenance of sufficient gas in the system is controlled by purge or make-up in a conventional manner (not shown). 
     The process is operated by passing fermentation broth from a fermentation vessel (not shown) via line  36  into, or near to, the top of the stripping section  22 , wherein the broth is then contacted counter-currently by gas entering column  12  via line  18 . A fraction of the butanol contained in the fermentation broth is transferred into the gas and is passed from the top of the stripping section  22  to the bottom of the absorption section  20  via line  13 , resulting in a stripped fermentation broth that is formed in section  22 . The stripped fermentation broth is returned to the fermentation vessel via line  38 . Butanol that is contained in the gas passing from section  22  to section  20  is absorbed in section  20  by an organic absorbent having a lower vapor pressure than that of butanol, such as an ether, aldehyde, ester, ketone, or alcohol, preferably an alcohol having eight or more carbon atoms, for example octanol, nonanol, or decanol, and mixtures thereof, that is introduced into the top of the absorption section via line  32  wherein the butanol is preferentially absorbed from the carrier gas to form a butanol-rich absorbent phase. A butanol rich absorbent phase is one where the butanol content is about 5% to 15%. Butanol is removed from the absorption section  20 , along with the low volatility absorbent via line  34  and then separated from the low volatility absorbent using conventional separation techniques such as distillation, decantation, absorption, liquid-liquid extraction, crystallization. 
     An alternative embodiment of the apparatus shown in  FIG. 3  is one where the sequence of operations relative to the gas flow is reversed, i.e., from (1) stripping, then absorption, then mechanical compression to (2) absorption, then stripping, then mechanical compression. 
     Referring now to  FIG. 4 , there is shown apparatus for carrying out a further embodiment of the present invention. The apparatus comprises a column  10  which includes a series of associated pairs of absorption and stripping sections. In  FIG. 4 , three pairs of absorption and stripping sections are shown, but more or fewer are feasible. Sections  20  and  22  form an upper pair of absorption and stripping sections, respectively; sections  40  and  42  form a middle pair of absorption and stripping sections; and sections  60  and  62  form a lower pair of absorption and stripping sections. In addition gas exits at or near the top of column  10  via line  16  and is raised in pressure by mechanical compression equipment  14 , such as a fan, blower or compressor, and is returned to, or near to, the bottom of column  10  via line  18 . Gas will pass up column  10  passing from section  62  to section  60 , from section  60  to section  42 , from section  42  to section  40 , from section  40  to section  22  and from section  22  to section  20 . Maintenance of sufficient gas in the system is controlled by purge or make-up in a conventional manner (not shown). 
     The process is operated by passing fermentation broth from a fermentation vessel (not shown) via line  76  into, or near to, the top of the bottom stripping section  62  which is then contacted counter-currently by gas entering column  10  via line  18 . A fraction of the butanol contained in the fermentation broth is transferred into the gas and is passed from the top of the stripping section  62  to the bottom of the absorption section  60 , resulting in a stripped fermentation broth that is formed in section  62 . The stripped fermentation broth is returned to the fermentation vessel via line  78 . Butanol that is contained in the gas passing from section  62  to section  60  is absorbed in section  60  by a low volatility organic absorbent, having a lower vapor pressure than that of butanol, such as an ether, aldehyde, ester, ketone, or alcohol, preferably an alcohol having eight or more carbon atoms, for example octanol, nonanol, or decanol, and mixtures thereof, that is introduced into the top of the absorption section via line  72  wherein the butanol is preferentially absorbed from the carrier gas to form a butanol-rich absorbent phase. A butanol rich absorbent phase is one where the butanol content is about 5% to 15%. Butanol is removed from the absorption section  60 , along with the low volatility absorbent via line  74  and then separated from the low volatility solvent using conventional separation techniques such as distillation, decantation, absorption, liquid-liquid extraction, crystallization. 
     In like manner, the process can be operated by passing fermentation broth simultaneously from the same vessel or different fermentation vessels (not shown) to the middle and upper stripping section/absorption section pairs. 
     By stacking stripping section/absorption section pairs to operate in series, the diameter of the column can be reduced, although the height will be increased. The volume of CO 2  or other inert gas circulated will be reduced, although at the expense of having to compress over a higher pressure ratio. In a process where multiple fermentation vessels are operating, it is likely to be advantageous to keep the streams of fermentation broth separate, which can be facilitated by having multiple stripping section/absorption section pairs. 
     Although particular embodiments of the present invention have been described in the foregoing description, it will be understood by those skilled in the art that the invention is capable of numerous modifications, substitutions, and rearrangements without departing from the spirit or essential attributes of the invention. Reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.