WO2008114139A2 - System and methods for biomass processing - Google Patents

System and methods for biomass processing Download PDF

Info

Publication number
WO2008114139A2
WO2008114139A2 PCT/IB2008/000714 IB2008000714W WO2008114139A2 WO 2008114139 A2 WO2008114139 A2 WO 2008114139A2 IB 2008000714 W IB2008000714 W IB 2008000714W WO 2008114139 A2 WO2008114139 A2 WO 2008114139A2
Authority
WO
WIPO (PCT)
Prior art keywords
biomass
swelling agent
steam
swelling
contacted
Prior art date
Application number
PCT/IB2008/000714
Other languages
French (fr)
Other versions
WO2008114139A3 (en
Inventor
David Senyk
Tonya Tiedje
Darold F. Mccalla
Farzaneh Teymouri
Original Assignee
Mbi International
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mbi International filed Critical Mbi International
Publication of WO2008114139A2 publication Critical patent/WO2008114139A2/en
Publication of WO2008114139A3 publication Critical patent/WO2008114139A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/08Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00Macromolecular compounds derived from lignocellulosic materials
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/14Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Definitions

  • This invention relates to biomass processing.
  • this invention is to a process for treating or swelling cellulosic biomass using a swelling agent to swell at least a portion of the biomass.
  • AFEX ammonia fiber nsion
  • the AFEX process treats iass with ammonia at moderate temperature under pressure followed by explosive pressure .release to rupture the biomass and enhance the conversion of structural carbohydrate (cellulose and hemicellulose) to fermentable sugar.
  • the AFEX treatment effectuates a physico/chemical alteration in the biomass micro and macro structure.
  • AFEX increase the digestibility of the biomass by de-crystallization of cellulose (Laureano-Perez, L., Teymouri, F., Alizadeh, H., Dale, B. (2005), Applied Biochemistry and Biotechnology. 121-124, pp 1081-1099; Gollapalli, L., Dale, B., Rivers, D. (2002), Applied Biochemistry and Biotechnology.
  • AFEX process for treatment of several different lignocellulosic biomasses such as corn stover (Teymouri, F., Laureano-Perez, L., Alizadeh, H., Dale, B. (2004), Applied Biochemistry and Biotechnology.113-116, pp., 951-963), switchgrass (Alizadeh, H., Teymouri, F., Gilbert, Th., Dale, B. (2005) Applied Biochemistry and Biotechnology.121-124, pp., 1133-1142), corn fiber (Hanchar, R., Teymouri, F., Nielson, Ch., McCalla , D., Stowers, M.
  • corn stover Teymouri, F., Laureano-Perez, L., Alizadeh, H., Dale, B. (2004), Applied Biochemistry and Biotechnology.113-116, pp., 951-963
  • switchgrass Alizadeh, H., Teymo
  • distiller's dried grains with solubles (DDGS) (BaIs 1 B., Dale, B., Balan, V., (2006) Energy & Fuels, 20, pp., 2,732-2,736), and bagasse have been evaluated and shown that this pretreatment helps increase enzymatic digestibility several fold over the untreated biomass.
  • AFEX pretreatment process ti ⁇ ards making commercially viable ethanol.
  • the major AFEX operating parameter variations include: temperature (70-110 0 C), moisture content (20-80 wt%), ammonia loading (0.5-2.5 g ammonia per gram of dry biomass), residence time (5-30min).
  • the most effective conditions are en based on the highest glucose and xylose yield from enzymatic hydrolysis of the treated iass.
  • the present invention provides a biomass pretreatment system and fermentation processes incorporating a biomass or cellulose treatment system in a simple and scalable design.
  • the invention may be practiced using a plug flow reactor capable of accomplishing several of the desired functions simultaneously while meeting desired or predetermined process conditions.
  • An advantage of the present invention is the ability to continuously provide required residence time and expansion.
  • residence time is provided
  • the process incorporates a retention coil or auger and ammonia expansion occurs across a pressure reduction device (valve, orifice, or other mechanical devices).
  • a process for swelling biomass includes contacting the biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system.
  • the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a of the biomass.
  • a ientation process there is provided.
  • the fermentation process includes a pretreatment system in which nass is contacted with a swelling agent as the biomass and swelling agent are transported ugh a reactor system.
  • the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a portion of the biomass. At least a portion of the biomass that has been contacted with the swelling agent is then fermented. f ⁇ [00015]
  • steam is applied to the biomass to achieve a total moisture content of from 20 wt% to 90 wt% as the steam mixes with the biomass.
  • steam is applied to the biomass to achieve a temperature of from 6O 0 C to 200 0 C as the swelling agent mixes with the biomass.
  • the steam is applied to the biomass prior to contacting with the swelling agent.
  • the steam is applied to the biomass after contacting with the swelling agent.
  • the steam is applied to the biomass during contacting with the swelling agent, which means that at or near concurrent application of steam and swelling agent with biomass can also be utilized.
  • the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1 : 1 to 2.5 : 1 dry weight basis (dwb).
  • the ' " ⁇ steam can be applied by way of a mixing device to mix the steam with the biomass or by way of a transport device to transport the biomass.
  • the steam is applied by way of a mixing and transport device to mix and transport the biomass.
  • the biomass is contacted with the swelling agent for at least one minute to swell the biomass.
  • the swelled biomass is dried to provide a vapor stream and a dried biomass stream such that the vapor stream contains at least a portion of the swelling agent and moisture from the biomass.
  • FIG. 1 is a schematic diagram depicting a system for continuous biomass essing in accordance with an embodiment of the present invention
  • FIG. 2 is a schematic diagram depicting an overall system for continuous biomass processing in accordance with an embodiment of the present invention
  • FIGs. 3-9 are schematic diagrams depicting alternate embodiments of a system for continuous biomass processing in accordance with an embodiment of the present invention.
  • Fig. 10 is a schematic diagram depicting components that could be used for a system for continuous biomass processing in accordance with an embodiment of the present invention using a heating heat exchanger to heat ammonia to, at or near reaction temperature;
  • FIGs. 11-13 are schematic diagrams depicting components and system variations that could be used for a system for continuous or semi-continuous biomass processing in accordance with an embodiment of the present invention.
  • the present invention relates to the use of a process for treatment of cellulosic biomass using a swelling agent to swell the biomass.
  • the swelling of the biomass increases the chemical and biological reactivity of biomass for subsequent processing.
  • the invention incorporates the use of the pretreatment system in fermentation processes.
  • the present invention is capable of providing a variety of functions desired for treatment of biomass with swelling agent. These functions include: 1) pressurizing tfee'biomass and swelling agent, 2) mixing and generating a homogeneous mixture of swelling agent and biomass, 3) heating the biomass and swelling agent, 4) providing adequate residence time, 5) releasing the pressure quickly.
  • One embodiment of the present invention is providing for a reactor system that uses a plug flow reactor while meeting desired process conditions.
  • an ammonia addition system its by running pressurized ammonia, from a pressurized ammonia tank 100, through a ing heat exchanger 102, then through a metering pump 104, followed by a flow meter 106, through a heating heat exchanger 108 to add in heat, then proceeding into a reactor 110.
  • cooling heat exchanger is configured to cool the ammonia below a vaporization point, therefore keeping it predominantly in liquid form through the metering pump. This allows for accurate measurement of the ammonia.
  • the heat exchanger is configured to heat the measured ammonia flowing through the system to at or near reaction temperature prior to flowing through the reactor.
  • FIGs. 11-13 Other components and process schematics are shown at Figs. 11-13.
  • Fig. 11 a continuous or semi-continuous reactor is illustrated.
  • Fig. 12 illustrates another variation of a schematic for a process that uses a heat exchanger to bring ammonia to at or near reaction temperature. It is noted that the given components in line in this process may also involve various other combinations including heating exchangers and/or including steam to increase the biomass to reaction temperature. All possible heating heat exchange combinations are contemplated to fall within the design and scope of the present invention.
  • the pressurization and transport of the biomass utilizes a positive displacement pump.
  • Possible mixing devices can include mechanically powered inline mixers, annular jet pumps, externally and internally modulated steam injection heaters. Annular jet pumps and steam injection heaters may also serve multiple functions in the continuous reactor. For example, these devices can act as one or more of a heating device, a transport device and a mixing device. Residence time is preferably provided by a retention pipe or auger.
  • biomass is contacted with a swelling agent, and this mix of biomass and swelling agent are continuously transported through a reactor system.
  • continuous it is meant that the mix does not need to be collected in a vessel. Rather, the biomass and swelling agent are flowed at a relatively constant rate through the reaction system.
  • the reaction system can include a vessel, but the flow of the mixture is relatively uninterrupted as at least a portion of the biomass is swelled during the flow.
  • Biomass refers to living and recently dead biological material that can be used as fuel or for industrial production. Generally, biomass refers to plant matter grown for use ⁇ el, but it also includes plant or animal matter that can be used for production of fibers, nicals or heat. Biomass may also include biodegradable wastes that can be burned as fuel. It udes organic material which has been transformed by geological processes into substances i as coal or petroleum.
  • Particularly suitable biomass includes such plant matter containing a relatively high content of cellulose.
  • biomass or plant matter include miscanthus, switchgrass, hemp, com (e.g., stover or cob), poplar, willow, sugarcane and oil palm (palm oil).
  • com e.g., stover or cob
  • poplar poplar
  • sugarcane sugarcane
  • oil palm palm
  • biomass examples include stems, leaves, hulls, husks, wood, wood chips, wood pulp, and sawdust.
  • paper waste include discard photocopy paper, computer printer paper, notebook paper, notepad paper, typewriter paper, newspapers, magazines, cardboard, and paper-based packaging materials.
  • the biomass is predominantly one or more C4 grasses.
  • C 4 grasses are classified by their pathway of carbon dioxide metabolism, which involves intermediates with 4 carbon atoms. This is described in Biology of Plants, by Raven, Evert, and Curtis, Worth Publishing Co., second edition, 1976, pages 116-117, incorporated herein by reference.
  • Particularly preferred C4 grasses are C 4 perennial grasses. Perennial grasses do not require yearly planting and fertilization and are therefore more suitable for fermentation and ethanol production than annual grasses.
  • Particularly preferred C 4 perennial grasses include switchgrass, miscanthus, cord grass, and rye grass. These grasses are particularly fast growing. Cord grass is classified as a C 4 grass even though a portion of its growth cycle uses C 3 metabolism.
  • the pressure of the reaction system i.e., the portion of the system in which there is contact of the biomass and swelling agent and swelling of at least a portion of the biomass occurs
  • the pressure of the reaction system is at a pressure sufficient to prevent substantial vaporization of the swelling agent.
  • the swelling agent should remain predominantly in the liquid phase while contacting the biomass, and while swelling of at least a portion of the biomass occurs.
  • the conditions of the system are such that the swelling agent will be considered to be ined predominantly in the liquid phase.
  • the pressure condition of the reaction system will end upon the type of swelling agent.
  • TM _mples of swelling agents include: 1) water soluble amines having the structure NRR 1 R 2 where R, R'and R 2 are either the same or different and are selected from ' he group consist of H or hydrocarbons containing 1—60 carbons, optionally substituted with oxygen, nitrogen, sulfur or phosphorous, or where two or more of the R groups are attached to form a cyclic group, Preferred examples of swelling agents include ammonia, methyl amine, dimethylamine, N- methyl, ethylamine, tripropylamine, and morpholine; 2) water soluble ammonium ions having Hie structure +NRR 1 R 2 R 3 where R,R !
  • R 2 andR 3 are either the same or different and are selected from the group consisting of H or hydrocarbons containing l ⁇ 60 carbons, optionally substituted with oxygen, nitrogen, sulfur or phosphorous, or where two or more of the R groups are attached to form a cyclic group.
  • Preferred examples include, ammonium hydroxide, ammonium chloride, arid trimethylammonium chloride; 3) hydroxides, carbonates, and bicarbonates of lithium, sodium, potassium, magnesium, and calcium, such as sodium hydroxide, magnesium carbonate, and calcium carbonate (lime); 4) water soluble mono, or poly carboxylic acids containing l ⁇ 20 carbons such as carbonic, acetic, trifloroacetic, succinic and citric; 5) inorganic acids such as sulfuric, sulfurous, nitric, nitrous, phosphoric, and hydrochloric, including agents that form inorganic acids when dissolved in water such as sulfur dioxide, which forms sulfurous acid when dissolved in water.
  • the reactor system is at a pressure of from 50 psig to 600 psig.
  • the reaction system is at a pressure of from 100 psig to 450 psig.
  • the contact of the biomass with the swelling agent is also for a period of time sufficient to swell at least a portion of the biomass.
  • the swelling agent contacts the biomass for at least one minute, more preferably for at least two minutes, and most preferably for at least five minutes.
  • steam is applied to the biomass.
  • the steam is applied to the biomass.
  • ⁇ T , K - applied before, during or after the biomass is first contacted with the swelling agent.
  • the s preferably saturated steam.
  • the steam is applied to the biomass to maintain the opriate moisture content as the steam mixes with the biomass.
  • the presence of moisture in Momass allows faster and more even distribution of the swelling agent in the biomass.
  • the in the biomass particularly affects hydrolysis of hemicellulose in the biomass, and thereby enhances the overall effect of the pretreatment.
  • too high of a moisture content will dilute the overall swelling agent content in the process and also pose an unnecessary burden on any recovery of the swelling agent and on any drying of the biomass that has been contacted with the swelling agent and steam.
  • steam is applied to maintain a moisture content of from 20 wt% to 90 wt% on a total weight basis as the steam mixes with the biomass. More preferably, steam is applied to maintain a moisture content of from 60 ⁇ vt% to 90 wt%, and most preferably from 70 wt% to 85 wt% on a total weight basis as the steam mixes with the biomass.
  • the steam is applied to the biomass to maintain the appropriate temperature as the swelling agent mixes with the biomass. Too low of a temperature will have little if any swelling effect on the biomass. Too high of a temperature can issult in undesirable chemical reactions and generate potential inhibitory compounds that adversely affect downstream processes such as hydrolysis and fermentation.
  • steam is applied to achieve a temperature of from 60 0 C to 200 0 C as the steam mixes with the biomass. More preferably, steam is applied to achieve a temperature of from 80 0 C to 120 0 C, and most preferably from 90 0 C to 110 0 C as the stream mixes with the biomass. ⁇ " -
  • the biomass is contacted with the swelling agent at a predetermined weight ratio of swelling agent to biomass.
  • the weight ratio should be high enough to swell at least a significant portion of the biomass within an acceptable amount of time. The weight ratio need not be too high, however. Otherwise, excessive swelling can result such that the swelling agent can cause cellulose in the biomass to plasticize, thereby reducing chemical and biological reactivity of the biomass contacted with the swelling agent on downstream processes. Downstream processes that can be particularly impacted include hydrolysis and fermentation reaction processes.
  • the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1:1 to 2.5:1 dwb. More Dreferably, the biomass is contacted with the swelling agent at a ratio of swelling agent to
  • the ruptured biomass is preferably dried to provide a vapor stream and a d biomass stream.
  • the vapor stream contains at least a portion of the swelling agent and sture from the ruptured biomass.
  • the vapor can be condensed or recycled or both in the r — -sess.
  • the swelling agent in the vapor is recovered and reused in the recycle stream.
  • the ruptured biomass in dried or undried form, is a highly desirable feed for fermentation, as the ruptured biomass will have a significant amount of cellulose available for fermentation compared to the untreated or unruptured biomass.
  • Fermentation can be anaerobic (deficient in oxygen) as well as aerobic (oxygenated). Under aerobic conditions, microorganisms such as yeast cells can break down sugars to end products such as CO2 and H 2 O. Under anaerobic conditions, yeast cells utilize an alternative pathway to produce CO 2 and ethanol.
  • the fermentation reaction of the present invention is preferably anaerobic, i.e., partially or completely deficient in oxygen. Fermentation can also be used to refer to the bulk growth of microorganisms on a growth medium where no distinction is made between aerobic and anaerobic metabolism.
  • the ruptured biomass is preferably contacted with one or more cellulase enzymes in an aqueous mixture.
  • the cellulase can be provided as a purified enzyme or can be provided by a ceJlulase-producing microorganism in the aqueous mixture.
  • Cellulase can include any enzyme that effects the hydrolysis or otherwise solubilizes cellulose (including insoluble cellulose and soluble products of cellulose). Suitable sources of cellulase include such commercial cellulase products as SpezymeTM CP, CytolaseTM M104, and MultifectTM CL (Genencor, South San Francisco, Calif.).
  • the conditions for cellulase hydrolysis are typically selected in consideration of the conditions suitable for the specific cellulase source, e.g, bacterial or fungal.
  • cellulase hydrolysis can be carried out at a temperature of from 30 0 C to 6O 0 C and a pH of from 4.0 to 8.0.
  • cellulase hydrolysis is carried out at a temperature of from 30 ⁇ C to 48°C and a pH between of from 4.0 to 6.0.
  • the aqueous mixture of biomass and enzyme can further advantageously se an ethanologenic microorganism for fermentation.
  • the microorganism in that has the ability to convert a sugar or oligosaccharide to ethanol.
  • the hydrolysis luct can be separated and then fermented with the microorganism.
  • Examples of ethanologenic microorganisms include ethanologenic bacteria and yeast.
  • the microorganisms are ethanologenic by virtue of their ability to express one or more enzymes which, individually or together, convert a sugar to ethanol.
  • Saccharomyces such as S. cerevisiae
  • Other examples of microorganisms that convert sugars to ethanol include species of Schizosaccharomyces (such as S. pombe), Zymomonas (including Z. mobilis), Pichia (P. stipitis), Candida (C. shehatae) and Pachysolen (P. tannophilus).
  • Preferred examples of ethanologenic microorganisms include ethanologenic microorganisms expressing alcohol dehydrogenase and pyruvate decarboxylase, such as can be obtained with or from Zymomonas mobilis.
  • the ethanologenic microorganism can express xylose reductase and xylitol dehydrogenase, which convert xylose to xylulose.
  • Xylose isomerase converts xylose to xylulose, as well.
  • the ethanologenic microorganism can further express xylulokinase, which catalyzes the conversion of xylulose to xylulose-5-phosphate.
  • Additional enzymes to complete the pathway can include transaldolase and transketolase. These enzymes catri be obtained or derived from microorganisms such as Escherichia coli, Klebsiella oxytoca and Erwinia species.
  • microorganisms capable of fermenting both pentoses and hexoses to ethanol are employed.
  • Particularly preferred microorganisms include Klebsiella oxytoca P2 and Escherichia coli KOl 1.
  • Figure 1 illustrates a schematic diagram of a possible embodiment utilizing the objects of the present invention for a continuous biomass treatment system, and is generally shown at 10.
  • moistened biomass 12 may be pressurized in a positive displacement pump 14 or any other means to pressurize the biomass known in the art.
  • Aqueous or anhydrous ammonia is added to moistened biomass upstream (such as at 16) of an annular jet
  • ammonia when used, it may also alternatively refer to f drous ammonia or other swelling agents known in the art.
  • Steam may be used as a transport, ing and/or moisturizing fluid.
  • steam can be injected by way of an annular jet p 18 to heat the ammonia and biomass suspension, generate a homogeneous suspension, and n transporting the mixture through a retention pipe 20.
  • Retention pipe 20 is illustrated as curved, but may be straight in this and in all variations shown in the all the figures. It is noted that in addition to steam, other types of heat exchangers may be used to heat the ammonia to at or near reaction temperature.
  • the pressure is rapidly decreased such.as across a pressure reduction valve 22, orifice, or other mechanical device allowing for the vaporization of the ammonia and subsequent separation and recycle back into the process.
  • the steam optionally may be introduced upstream of the introduction of the ammonia. Further, steam and ammonia may be introduced simultaneously.
  • Fig 2 shows an example of incorporation of the biomass treatment process with an ethanol manufacturing facility.
  • the treated biomass following enzyme hydrolysis is particularly suitable in any application that utilizesC5, C6 or a mixed C5/C6 sugar solution.
  • FIG. 3 is another schematic of the process illustrated in Fig. 1.
  • FIG. 4 offers a slight variation of the schematic illustrated in Figs. 1 and 3.
  • annular jet pump is replaced by direct-contact steam injection for combined heating and mixing of the biomass/ammonia suspension. This could be accomplished by using spargers, mixing tees and internally modulated steam injection heaters as are known in the art. Steam may also drive the suspension as well as add pressure to the system.
  • Figures 5 and 6 differ from figures 1 and 4 by using a retention auger 30 to replace a retention pipe.
  • the auger would be configured to provide the required residence time for the biomass under pressure prior to depressurizing across a pressure reduction valve, orifice, or other mechanical device.
  • Such configuration and schematic could be developed using methods well known in the art.
  • Figures 7 and 8 show replacement of the annular jet pump or direct- contact steam injectors with an inline mixer 40 or continuous stirred tank reactor (CSTR).
  • the steam and/or ammonia could be added upstream or directly into the inline ir or CSTR.
  • the inline mixer and CSTR could provide mixing and all or some ie required mixing time.
  • Figure 9 is a variation of Fig. 3 in that an auger may optionally be used.
  • an ammonia addition system works by running pressurized ammonia, from a pressurized ammonia tank 100, through a cooling heat exchanger 102, then a metering pump 104, followed by a flow meter 106, then through a heating heat exchanger 108 to add in heat, then proceeding into a reactor 110.
  • the cooling heat exchanger is configured by means known in the art to cool the ammonia below a vaporization point, therefore keeping it predominantly in liquid form through the metering pump. This allows for accurate measurement of the ammonia.
  • the heat exchanger is configured to heat the measured ammonia flowing through the system to at or near reaction temperature prior to flowing through the reactor.
  • Other component and process schematics are shown at Figs. 11-13.
  • Fig. 11 a continuous or semi-continuous reactor system is illustrated.
  • Fig. 12 illustrates another variation of a schematic for a process that uses a heat exchanger to bring the swelling agent to at or near reaction temperature. It is noted that the given components in line in this process may also involve various other combinations including heating exchangers and/or including steam to increase the biomass to reaction temperature. A wide variety of heating heat exchange combinations are contemplated to fall within the design and scope of the present i on ⁇ vention.
  • the reactor system of this invention is energy efficient.
  • mixing energy is provided by steam through a direct steam injection nozzle.
  • the invention is relatively easy to operate and maintain. In one embodiment, there are no moving parts in the reactor. In another embodiment, the reactor has no dynamic seals that could allow ammonia leakage into the work environment.

Abstract

This invention is directed to biomass processing. In one embodiment, the biomass is processed by contacting the biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system. In another embodiment, the processed biomass is fermented. Steam is also applied in the biomass processing. The steam can be applied before, during or after the biomass is first contacted with the swelling agent.

Description

SYSTEM AND METHODS FOR BIOMASS PROCESSING
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 60/895,673, filed March 19, 2007, which is fiilly incorporated herein by reference.
FIELD OF INVENTION
[0002] This invention relates to biomass processing. In particular, this invention is to a process for treating or swelling cellulosic biomass using a swelling agent to swell at least a portion of the biomass.
BACKGROUND OF THE INVENTION
I - [0003] It is desirable to develop fuels that are cheap, clean, non-petroleum-based, and renewable. It follows that fuels derived from plant materials are becoming more popular. Plant- derived lignocellulosic biomass materials (cellulose) are known in the art to be useful for fermentation processes to produce, for example, ethanol. Brazil has demonstrated the feasibility of producing ethanol and the use of ethanol as a primary automotive fuel for more than 20 years. Similarly, the United States produces a significant amount of fuel ethanol each year. See,
<- generally, US 7,026,152 to Ingram, et al. Ethanol production, fueled by increasing demand, is
- expected to rise sharply.
Λr>!" [0004] Utilization of cellulose in fermentation has traditionally been hindered by its relatively un-reactive nature. The crystalline structure of cellulose and the physical protection , provided by hemicellulose and lignin prevent efficient hydrolysis of these materials. To improve ■ the lignocellulosic hydrolysis, pretreating the biomass to make the cellulose fraction more accessible to a cellulase enzyme has been applied. These processes, developed to increase the chemical and biological reactivity of cellulose, can be physical treatments (such as milling) or chemical treatments (such as use of cellulose swelling and dissolving agents). See generally, US 4,600,590 to Dale, US 5,171,592 to Holtzapple et al., and WO 2006/055362. s [0005] Specifically, chemical pretreatment processes have been developed to reduce the ranee of cellulosic material to hydrolysis and fermentation. The ammonia fiber nsion (AFEX) process has been recognized as one of the most effective processes among the iass pretreatment; (Mosier, N., Wyman, C, Dale, B., Elander, R., Lee, Y. Y., Holtzapple, M., sh, M. (2005), Bioresource Technology. 96, pp. 673-686.). The AFEX process treats iass with ammonia at moderate temperature under pressure followed by explosive pressure .release to rupture the biomass and enhance the conversion of structural carbohydrate (cellulose and hemicellulose) to fermentable sugar. The AFEX treatment effectuates a physico/chemical alteration in the biomass micro and macro structure. AFEX increase the digestibility of the biomass by de-crystallization of cellulose (Laureano-Perez, L., Teymouri, F., Alizadeh, H., Dale, B. (2005), Applied Biochemistry and Biotechnology. 121-124, pp 1081-1099; Gollapalli, L., Dale, B., Rivers, D. (2002), Applied Biochemistry and Biotechnology. 98-100, pp 23-35.), partial depolymerization of hemicellulose and lignin, cleavage of hydrogen bonds that holding cellulose and hemicellulose together, deacetylation of acetyl groups (O'Connor, J.(1972), Tappi - 55:353), cleavage of lignin-carbohydrate complex linkages, lignin C-O-C bond cleavage, and increase in accessible surface area due to structural disruption (Turner, N., McDonough, C, Byers, F., Holtzapple M., Dale, B., Jun, J., Greene, L.(1990), Proceeding Western Section , '* American Society of Animal Science Vol. 41.).
[0006] The applicability of AFEX process for treatment of several different lignocellulosic biomasses such as corn stover (Teymouri, F., Laureano-Perez, L., Alizadeh, H., Dale, B. (2004), Applied Biochemistry and Biotechnology.113-116, pp., 951-963), switchgrass (Alizadeh, H., Teymouri, F., Gilbert, Th., Dale, B. (2005) Applied Biochemistry and Biotechnology.121-124, pp., 1133-1142), corn fiber (Hanchar, R., Teymouri, F., Nielson, Ch., McCalla , D., Stowers, M. (2007), Applied Biochemistry and Biotechnology. In press), distiller's dried grains with solubles (DDGS) (BaIs1 B., Dale, B., Balan, V., (2006) Energy & Fuels, 20, pp., 2,732-2,736), and bagasse have been evaluated and shown that this pretreatment helps increase enzymatic digestibility several fold over the untreated biomass.
. ^K [0007] There is an obvious desire in the art to optimize the AFEX pretreatment process ti^ards making commercially viable ethanol. The major AFEX operating parameter variations include: temperature (70-1100C), moisture content (20-80 wt%), ammonia loading (0.5-2.5 g ammonia per gram of dry biomass), residence time (5-30min). The most effective conditions are en based on the highest glucose and xylose yield from enzymatic hydrolysis of the treated iass.
[0008] It is more economically and commercially desirable in the art to create a scalable Ai1JiX process. Such processes have been attempted using extrusion reactors (Dale, B., Weaver, J., Byers, F.(1999), Applied Biochemistry and Biotechnology, 77-79, pp., 35-45) or in a -Staketech process (commercially available by Stake Technology Ltd., 208 Wyecroft Road, Oakville, Ontario, Canada, L6K 3T8).
[0009] To meet the ever increasing demand for ethanol production, there is a demand and a desire in the art to develop biomass pretreatment systems and methods capable of improving AFEX process conditions in a simple and scalable design.
SUMMARY OF THE INVENTION
[00010] Accordingly, the present invention provides a biomass pretreatment system and fermentation processes incorporating a biomass or cellulose treatment system in a simple and scalable design.
'" . [00011 ] The invention may be practiced using a plug flow reactor capable of accomplishing several of the desired functions simultaneously while meeting desired or predetermined process conditions.
[00012] An advantage of the present invention is the ability to continuously provide required residence time and expansion. In one embodiment, residence time is provided
Λ' by, continuous flow of the ammonia/moistened biomass. In a particular embodiment, the process incorporates a retention coil or auger and ammonia expansion occurs across a pressure reduction device (valve, orifice, or other mechanical devices).
[00013] According to one aspect of the invention, there is provided a process for swelling biomass. The process includes contacting the biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system. In one embodiment, the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a of the biomass. [00014] According to another aspect of the invention, there is provided a ientation process. The fermentation process includes a pretreatment system in which nass is contacted with a swelling agent as the biomass and swelling agent are transported ugh a reactor system. In one embodiment, the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a portion of the biomass. At least a portion of the biomass that has been contacted with the swelling agent is then fermented. f~ [00015] In one embodiment of the invention, steam is applied to the biomass to achieve a total moisture content of from 20 wt% to 90 wt% as the steam mixes with the biomass. In another embodiment, steam is applied to the biomass to achieve a temperature of from 6O0C to 2000C as the swelling agent mixes with the biomass.
[00016] In another embodiment, the steam is applied to the biomass prior to contacting with the swelling agent. In yet another, the steam is applied to the biomass after contacting with the swelling agent. In still another, the steam is applied to the biomass during contacting with the swelling agent, which means that at or near concurrent application of steam and swelling agent with biomass can also be utilized.
[00017] In a preferred embodiment, the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1 : 1 to 2.5 : 1 dry weight basis (dwb). The ' "■ steam can be applied by way of a mixing device to mix the steam with the biomass or by way of a transport device to transport the biomass. Preferably, the steam is applied by way of a mixing and transport device to mix and transport the biomass.
[00018] In one embodiment, the biomass is contacted with the swelling agent for at least one minute to swell the biomass. Preferably, the swelled biomass is dried to provide a vapor stream and a dried biomass stream such that the vapor stream contains at least a portion of the swelling agent and moisture from the biomass.
Uii BRIEF DESCRIPTION OF THE DRAWINGS
[00019] The foregoing features, as well as other features, will become apparent with reference to the description and figures below, in which like numerals represent elements, which: [00020] FIG. 1 is a schematic diagram depicting a system for continuous biomass essing in accordance with an embodiment of the present invention;
[00021] FIG. 2 is a schematic diagram depicting an overall system for continuous biomass processing in accordance with an embodiment of the present invention;
"'• [00022] Figs. 3-9 are schematic diagrams depicting alternate embodiments of a system for continuous biomass processing in accordance with an embodiment of the present invention;
, [00023] Fig. 10 is a schematic diagram depicting components that could be used for a system for continuous biomass processing in accordance with an embodiment of the present invention using a heating heat exchanger to heat ammonia to, at or near reaction temperature; and
.. [00024] Figs. 11-13 are schematic diagrams depicting components and system variations that could be used for a system for continuous or semi-continuous biomass processing in accordance with an embodiment of the present invention.
: DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
[00025] The present invention relates to the use of a process for treatment of cellulosic biomass using a swelling agent to swell the biomass. The swelling of the biomass increases the chemical and biological reactivity of biomass for subsequent processing. Ih one embodiment, the invention incorporates the use of the pretreatment system in fermentation processes.
[00026] The present invention is capable of providing a variety of functions desired for treatment of biomass with swelling agent. These functions include: 1) pressurizing tfee'biomass and swelling agent, 2) mixing and generating a homogeneous mixture of swelling agent and biomass, 3) heating the biomass and swelling agent, 4) providing adequate residence time, 5) releasing the pressure quickly. One embodiment of the present invention is providing for a reactor system that uses a plug flow reactor while meeting desired process conditions.
[00027] Several types of reactors can be utilized with the systems and methods of sent invention. In one basic form illustrated in Fig. 10, an ammonia addition system its by running pressurized ammonia, from a pressurized ammonia tank 100, through a ing heat exchanger 102, then through a metering pump 104, followed by a flow meter 106, through a heating heat exchanger 108 to add in heat, then proceeding into a reactor 110. cooling heat exchanger is configured to cool the ammonia below a vaporization point, therefore keeping it predominantly in liquid form through the metering pump. This allows for accurate measurement of the ammonia. The heat exchanger is configured to heat the measured ammonia flowing through the system to at or near reaction temperature prior to flowing through the reactor. Other components and process schematics are shown at Figs. 11-13. In Fig. 11 a continuous or semi-continuous reactor is illustrated. Fig. 12 illustrates another variation of a schematic for a process that uses a heat exchanger to bring ammonia to at or near reaction temperature. It is noted that the given components in line in this process may also involve various other combinations including heating exchangers and/or including steam to increase the biomass to reaction temperature. All possible heating heat exchange combinations are contemplated to fall within the design and scope of the present invention.
[00028] In one embodiment of the present invention, the pressurization and transport of the biomass utilizes a positive displacement pump. Possible mixing devices can include mechanically powered inline mixers, annular jet pumps, externally and internally modulated steam injection heaters. Annular jet pumps and steam injection heaters may also serve multiple functions in the continuous reactor. For example, these devices can act as one or more of a heating device, a transport device and a mixing device. Residence time is preferably provided by a retention pipe or auger.
^ [00029] According to one aspect of the invention, biomass is contacted with a swelling agent, and this mix of biomass and swelling agent are continuously transported through a reactor system. By continuous, it is meant that the mix does not need to be collected in a vessel. Rather, the biomass and swelling agent are flowed at a relatively constant rate through the reaction system. The reaction system can include a vessel, but the flow of the mixture is relatively uninterrupted as at least a portion of the biomass is swelled during the flow.
[00030] Biomass refers to living and recently dead biological material that can be used as fuel or for industrial production. Generally, biomass refers to plant matter grown for use ιel, but it also includes plant or animal matter that can be used for production of fibers, nicals or heat. Biomass may also include biodegradable wastes that can be burned as fuel. It udes organic material which has been transformed by geological processes into substances i as coal or petroleum.
[00031 ] Particularly suitable biomass includes such plant matter containing a relatively high content of cellulose. Examples of such biomass or plant matter include miscanthus, switchgrass, hemp, com (e.g., stover or cob), poplar, willow, sugarcane and oil palm (palm oil). Even municipal wastes such as newspaper can all be used as suitable biomass material.
[00032] Other examples of biomass include stems, leaves, hulls, husks, wood, wood chips, wood pulp, and sawdust. Particular examples of paper waste include discard photocopy paper, computer printer paper, notebook paper, notepad paper, typewriter paper, newspapers, magazines, cardboard, and paper-based packaging materials.
[00033] In one embodiment, the biomass is predominantly one or more C4 grasses.
C4 grasses are classified by their pathway of carbon dioxide metabolism, which involves intermediates with 4 carbon atoms. This is described in Biology of Plants, by Raven, Evert, and Curtis, Worth Publishing Co., second edition, 1976, pages 116-117, incorporated herein by reference. Particularly preferred C4 grasses are C4 perennial grasses. Perennial grasses do not require yearly planting and fertilization and are therefore more suitable for fermentation and ethanol production than annual grasses. Particularly preferred C4 perennial grasses include switchgrass, miscanthus, cord grass, and rye grass. These grasses are particularly fast growing. Cord grass is classified as a C4 grass even though a portion of its growth cycle uses C3 metabolism.
c *
'"" [00034] In this invention, the pressure of the reaction system (i.e., the portion of the system in which there is contact of the biomass and swelling agent and swelling of at least a portion of the biomass occurs) is at a pressure sufficient to prevent substantial vaporization of the swelling agent. This means that the swelling agent should remain predominantly in the liquid phase while contacting the biomass, and while swelling of at least a portion of the biomass occurs. Of course, it is not intended that there will be no vapor space within the reaction system, it the conditions of the system are such that the swelling agent will be considered to be ined predominantly in the liquid phase. [00035] It is also understood that the pressure condition of the reaction system will end upon the type of swelling agent. For example, when the swelling agent is ammonia, the jsure condition will be that at which ammonia is predominantly in the liquid phase. Other _mples of swelling agents include: 1) water soluble amines having the structure NRR1R2 where R, R'and R2 are either the same or different and are selected from 'he group consist of H or hydrocarbons containing 1—60 carbons, optionally substituted with oxygen, nitrogen, sulfur or phosphorous, or where two or more of the R groups are attached to form a cyclic group, Preferred examples of swelling agents include ammonia, methyl amine, dimethylamine, N- methyl, ethylamine, tripropylamine, and morpholine; 2) water soluble ammonium ions having Hie structure +NRR1R2R3 where R,R!,R2 andR3 are either the same or different and are selected from the group consisting of H or hydrocarbons containing l~60 carbons, optionally substituted with oxygen, nitrogen, sulfur or phosphorous, or where two or more of the R groups are attached to form a cyclic group. Preferred examples include, ammonium hydroxide, ammonium chloride, arid trimethylammonium chloride; 3) hydroxides, carbonates, and bicarbonates of lithium, sodium, potassium, magnesium, and calcium, such as sodium hydroxide, magnesium carbonate, and calcium carbonate (lime); 4) water soluble mono, or poly carboxylic acids containing l~20 carbons such as carbonic, acetic, trifloroacetic, succinic and citric; 5) inorganic acids such as sulfuric, sulfurous, nitric, nitrous, phosphoric, and hydrochloric, including agents that form inorganic acids when dissolved in water such as sulfur dioxide, which forms sulfurous acid when dissolved in water.
;LJT [00036] In one embodiment of the invention, the reactor system is at a pressure of from 50 psig to 600 psig. Preferably, the reaction system is at a pressure of from 100 psig to 450 psig.
[00037] The contact of the biomass with the swelling agent is also for a period of time sufficient to swell at least a portion of the biomass. Preferably, the swelling agent contacts the biomass for at least one minute, more preferably for at least two minutes, and most preferably for at least five minutes.
[00038] According to the invention, steam is applied to the biomass. The steam
^T, K- applied before, during or after the biomass is first contacted with the swelling agent. The s preferably saturated steam. [00039] In one embodiment, the steam is applied to the biomass to maintain the opriate moisture content as the steam mixes with the biomass. The presence of moisture in Momass allows faster and more even distribution of the swelling agent in the biomass. The in the biomass particularly affects hydrolysis of hemicellulose in the biomass, and thereby enhances the overall effect of the pretreatment. However, too high of a moisture content will dilute the overall swelling agent content in the process and also pose an unnecessary burden on any recovery of the swelling agent and on any drying of the biomass that has been contacted with the swelling agent and steam. Preferably, steam is applied to maintain a moisture content of from 20 wt% to 90 wt% on a total weight basis as the steam mixes with the biomass. More preferably, steam is applied to maintain a moisture content of from 60 \vt% to 90 wt%, and most preferably from 70 wt% to 85 wt% on a total weight basis as the steam mixes with the biomass.
[00040] In another embodiment, the steam is applied to the biomass to maintain the appropriate temperature as the swelling agent mixes with the biomass. Too low of a temperature will have little if any swelling effect on the biomass. Too high of a temperature can issult in undesirable chemical reactions and generate potential inhibitory compounds that adversely affect downstream processes such as hydrolysis and fermentation. Preferably, steam is applied to achieve a temperature of from 600C to 2000C as the steam mixes with the biomass. More preferably, steam is applied to achieve a temperature of from 800C to 1200C, and most preferably from 900C to 1100C as the stream mixes with the biomass. Λ " -
[00041] In another embodiment, the biomass is contacted with the swelling agent at a predetermined weight ratio of swelling agent to biomass. The weight ratio should be high enough to swell at least a significant portion of the biomass within an acceptable amount of time. The weight ratio need not be too high, however. Otherwise, excessive swelling can result such that the swelling agent can cause cellulose in the biomass to plasticize, thereby reducing chemical and biological reactivity of the biomass contacted with the swelling agent on downstream processes. Downstream processes that can be particularly impacted include hydrolysis and fermentation reaction processes. Preferably, the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1:1 to 2.5:1 dwb. More Dreferably, the biomass is contacted with the swelling agent at a ratio of swelling agent to
3 of from 0.3:1 to 1.5:1 dwb, most preferably from 0.9:1 to 1.1:1 dwb. [00042] The ruptured biomass is preferably dried to provide a vapor stream and a d biomass stream. The vapor stream contains at least a portion of the swelling agent and sture from the ruptured biomass. The vapor can be condensed or recycled or both in the r— -sess. Preferably, the swelling agent in the vapor is recovered and reused in the recycle stream.
[00043] The ruptured biomass, in dried or undried form, is a highly desirable feed for fermentation, as the ruptured biomass will have a significant amount of cellulose available for fermentation compared to the untreated or unruptured biomass. Fermentation can be anaerobic (deficient in oxygen) as well as aerobic (oxygenated). Under aerobic conditions, microorganisms such as yeast cells can break down sugars to end products such as CO2 and H2O. Under anaerobic conditions, yeast cells utilize an alternative pathway to produce CO2 and ethanol. The fermentation reaction of the present invention is preferably anaerobic, i.e., partially or completely deficient in oxygen. Fermentation can also be used to refer to the bulk growth of microorganisms on a growth medium where no distinction is made between aerobic and anaerobic metabolism.
J1- [00044] As a part of the fermentation process, the ruptured biomass is preferably contacted with one or more cellulase enzymes in an aqueous mixture. The cellulase can be provided as a purified enzyme or can be provided by a ceJlulase-producing microorganism in the aqueous mixture. Cellulase can include any enzyme that effects the hydrolysis or otherwise solubilizes cellulose (including insoluble cellulose and soluble products of cellulose). Suitable sources of cellulase include such commercial cellulase products as Spezyme™ CP, Cytolase™ M104, and Multifect™ CL (Genencor, South San Francisco, Calif.).
[00045] The conditions for cellulase hydrolysis are typically selected in consideration of the conditions suitable for the specific cellulase source, e.g, bacterial or fungal. For example, cellulase hydrolysis can be carried out at a temperature of from 300C to 6O0C and a pH of from 4.0 to 8.0. Preferably, cellulase hydrolysis is carried out at a temperature of from 30^C to 48°C and a pH between of from 4.0 to 6.0.
[00046] The aqueous mixture of biomass and enzyme can further advantageously se an ethanologenic microorganism for fermentation. Preferably, the microorganism in that has the ability to convert a sugar or oligosaccharide to ethanol. Likewise, the hydrolysis luct can be separated and then fermented with the microorganism.
[00047] Examples of ethanologenic microorganisms include ethanologenic bacteria and yeast. The microorganisms are ethanologenic by virtue of their ability to express one or more enzymes which, individually or together, convert a sugar to ethanol. For example, Saccharomyces (such as S. cerevisiae) can be employed in the conversion of glucose to ethanol. Other examples of microorganisms that convert sugars to ethanol include species of Schizosaccharomyces (such as S. pombe), Zymomonas (including Z. mobilis), Pichia (P. stipitis), Candida (C. shehatae) and Pachysolen (P. tannophilus). Preferred examples of ethanologenic microorganisms include ethanologenic microorganisms expressing alcohol dehydrogenase and pyruvate decarboxylase, such as can be obtained with or from Zymomonas mobilis.
[00048] In another embodiment, the ethanologenic microorganism can express xylose reductase and xylitol dehydrogenase, which convert xylose to xylulose. Xylose isomerase converts xylose to xylulose, as well. The ethanologenic microorganism can further express xylulokinase, which catalyzes the conversion of xylulose to xylulose-5-phosphate. Additional enzymes to complete the pathway can include transaldolase and transketolase. These enzymes catri be obtained or derived from microorganisms such as Escherichia coli, Klebsiella oxytoca and Erwinia species.
[00049] In one embodiment, microorganisms capable of fermenting both pentoses and hexoses to ethanol are employed. Particularly preferred microorganisms include Klebsiella oxytoca P2 and Escherichia coli KOl 1.
[00050] Referring now to the figures, Figure 1 illustrates a schematic diagram of a possible embodiment utilizing the objects of the present invention for a continuous biomass treatment system, and is generally shown at 10.
[00051 ] hi Fig. 1 , moistened biomass 12 may be pressurized in a positive displacement pump 14 or any other means to pressurize the biomass known in the art. Aqueous or anhydrous ammonia is added to moistened biomass upstream (such as at 16) of an annular jet
18. It is noted that when the term ammonia is used, it may also alternatively refer to fdrous ammonia or other swelling agents known in the art. Steam may used as a transport, ing and/or moisturizing fluid. For example, steam can be injected by way of an annular jet p 18 to heat the ammonia and biomass suspension, generate a homogeneous suspension, and n transporting the mixture through a retention pipe 20. Retention pipe 20 is illustrated as curved, but may be straight in this and in all variations shown in the all the figures. It is noted that in addition to steam, other types of heat exchangers may be used to heat the ammonia to at or near reaction temperature. Once the suspension has passed through the retention pipe, the pressure is rapidly decreased such.as across a pressure reduction valve 22, orifice, or other mechanical device allowing for the vaporization of the ammonia and subsequent separation and recycle back into the process. It is also noted that in this Fig. and in all figures which use steam and ammonia, that the steam optionally may be introduced upstream of the introduction of the ammonia. Further, steam and ammonia may be introduced simultaneously.
ΪH [000S2] Fig 2 shows an example of incorporation of the biomass treatment process with an ethanol manufacturing facility. The treated biomass following enzyme hydrolysis is particularly suitable in any application that utilizesC5, C6 or a mixed C5/C6 sugar solution.
[00053] Fig. 3 is another schematic of the process illustrated in Fig. 1.
[00054] Fig. 4 offers a slight variation of the schematic illustrated in Figs. 1 and 3.
In Fig. 4 the annular jet pump is replaced by direct-contact steam injection for combined heating and mixing of the biomass/ammonia suspension. This could be accomplished by using spargers, mixing tees and internally modulated steam injection heaters as are known in the art. Steam may also drive the suspension as well as add pressure to the system.
[00055] Figures 5 and 6 differ from figures 1 and 4 by using a retention auger 30 to replace a retention pipe. The auger would be configured to provide the required residence time for the biomass under pressure prior to depressurizing across a pressure reduction valve, orifice, or other mechanical device. Such configuration and schematic could be developed using methods well known in the art.
[00056] Figures 7 and 8 show replacement of the annular jet pump or direct- contact steam injectors with an inline mixer 40 or continuous stirred tank reactor (CSTR). In xampies the steam and/or ammonia could be added upstream or directly into the inline ir or CSTR. In these cases the inline mixer and CSTR could provide mixing and all or some ie required mixing time.
[00057] Figure 9 is a variation of Fig. 3 in that an auger may optionally be used.
[00058] Any of a variety of reactors are suitable for use with the systems and methods of the present invention. In one basic form illustrated in Fig. 10, an ammonia addition system works by running pressurized ammonia, from a pressurized ammonia tank 100, through a cooling heat exchanger 102, then a metering pump 104, followed by a flow meter 106, then through a heating heat exchanger 108 to add in heat, then proceeding into a reactor 110. The cooling heat exchanger is configured by means known in the art to cool the ammonia below a vaporization point, therefore keeping it predominantly in liquid form through the metering pump. This allows for accurate measurement of the ammonia. The heat exchanger is configured to heat the measured ammonia flowing through the system to at or near reaction temperature prior to flowing through the reactor. Other component and process schematics are shown at Figs. 11-13. In Fig. 11 a continuous or semi-continuous reactor system is illustrated. Fig. 12 illustrates another variation of a schematic for a process that uses a heat exchanger to bring the swelling agent to at or near reaction temperature. It is noted that the given components in line in this process may also involve various other combinations including heating exchangers and/or including steam to increase the biomass to reaction temperature. A wide variety of heating heat exchange combinations are contemplated to fall within the design and scope of the present i on<vention.
[00059] The reactor system of this invention is energy efficient. In one embodiment of the present invention, mixing energy is provided by steam through a direct steam injection nozzle.
[00060] The invention is relatively easy to operate and maintain. In one embodiment, there are no moving parts in the reactor. In another embodiment, the reactor has no dynamic seals that could allow ammonia leakage into the work environment.
[00061 ] The description of the present invention herein is presented to enable any person skilled in the art to make and use the invention and is provided in the context of particular tions of the invention and their requirements. Various modifications to the disclosed odiments will be readily apparent to those skilled in the art, and the general principles led herein may be applied to other embodiments and applications without departing from the all functions of the invention. Thus, the present invention is not intended to be literallyed to the embodiments as claimed.

Claims

CLAIMSit is claimed is:
1. A process for swelling biomass, comprising: contacting the biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system, wherein the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a portion of the biomass; and applying steam to the biomass to achieve a total moisture content of from 20 wt% to 90 wt% as the steam mixes with the biomass.
2. The process of claim 1 , wherein the steam is applied to the biomass prior to contacting with the swelling agent.
3. The process of claim 1 , wherein the steam is applied to the biomass after contacting with the swelling agent.
4. The process of claim 1 , wherein the steam is applied to the biomass during contacting with the swelling agent
5. The process of claim 1 , wherein the steam is applied to achieve a temperature of from 600C to 2000C as the steam mixes with the biomass.
6. The process of claim 1 , wherein the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1:1 to 2.5:1 dwb.
7. The process of claim 1 , wherein the steam is applied by way of a mixing device to mix the steam with the biomass.
8. The process of claim 1 , wherein the steam is applied by way of a transport device ansport the biomass.
9. The process of claim 1 , wherein the steam is applied by way of a mixing and transport device to mix and transport the biomass.
10. The process of claim 1 , wherein the biomass is contacted with the swelling agent for at least one minute to swell the biomass.
11. The process of claim 1 , wherein the swelled biomass is dried to provide a vapor stream and a dried biomass stream such that the vapor stream contains at least a portion of the swelling agent and moisture from the biomass.
12. The process of claim 1 , further comprising fermenting at least a portion of the biomass that has been contacted with the swelling agent.
13. A process for swelling biomass, comprising: contacting the biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system, wherein the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a portion of the biomass; and applying steam to the biomass to achieve a temperature of from 600C to 2000C as the swelling agent mixes with the biomass.
14. The process of claim 13, wherein the steam is applied to the biomass prior to contacting with the swelling agent.
15. The process of claim 13, wherein the steam is applied to the biomass after contacting with the swelling agent.
16. The process of claim 13 , wherein the steam is applied to the biomass during acting with the swelling agent.
17. The process of claim 13, wherein the steam is applied to achieve a total moisture content of from 20 wt% to 90 wt% as the steam mixes with the biomass.
18. The process of claim 13, wherein the biomass is contacted with the swelling agent at a ratio of swelling agent to biomass of from 0.1:1 to 2.5:1 dwb.
19. The process of claim 13 , wherein the steam is applied by way of a mixing device to mix the steam with the biomass.
20. The process of claim 13, wherein the steam is applied by way of a transport device to transport the biomass.
*".L 21. The process of claim 13 , wherein the steam is applied by way of a mixing and transport device to mix and transport the biomass.
22. The process of claim 13, wherein the biomass is contacted with the swelling agent for at least one minute to swell the biomass.
23. The process of claim 13, wherein the swelled biomass is dried to provide a vapor stream and a dried biomass stream such that the vapor stream contains at least a portion of the swelling agent and moisture from the biomass.
24. The process of claim 13, further comprising fermenting at least a portion of the biomass that has been contacted with the swelling agent.
25. A fermentation process, comprising: contacting biomass with a swelling agent as the biomass and swelling agent are rted through a reactor system, wherein the reactor system is at a pressure sufficient to itain the swelling agent predominantly in the liquid phase, and the contact is for a time cient to allow the swelling agent to swell at least a portion of the biomass; applying steam to the biomass to achieve a total moisture content of from 20 wt% to ^v wt% as the steam mixes with the biomass; and fermenting at least a portion of the biomass that has been contacted with the swelling agent.
26. A fermentation process, comprising: contacting biomass with a swelling agent as the biomass and swelling agent are transported through a reactor system, wherein the reactor system is at a pressure sufficient to maintain the swelling agent predominantly in the liquid phase, and the contact is for a time sufficient to allow the swelling agent to swell at least a portion of the biomass; ς applying steam to the biomass to achieve a temperature of from 600C to 2000C as the swelling agent mixes with the biomass; and qt fermenting at least a portion of the biomass that has been contacted with the swelling agent.
PCT/IB2008/000714 2007-03-19 2008-03-19 System and methods for biomass processing WO2008114139A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89567307P 2007-03-19 2007-03-19
US60/895,673 2007-03-19

Publications (2)

Publication Number Publication Date
WO2008114139A2 true WO2008114139A2 (en) 2008-09-25
WO2008114139A3 WO2008114139A3 (en) 2008-12-11

Family

ID=39766556

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2008/000714 WO2008114139A2 (en) 2007-03-19 2008-03-19 System and methods for biomass processing

Country Status (2)

Country Link
US (1) US20080229657A1 (en)
WO (1) WO2008114139A2 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013163271A1 (en) * 2012-04-27 2013-10-31 Michigan Biotechnology Institute Process for treating biomass
US8945245B2 (en) 2009-08-24 2015-02-03 The Michigan Biotechnology Institute Methods of hydrolyzing pretreated densified biomass particulates and systems related thereto
US8968515B2 (en) 2006-05-01 2015-03-03 Board Of Trustees Of Michigan State University Methods for pretreating biomass
US9039792B2 (en) 2009-08-24 2015-05-26 Board Of Trustees Of Michigan State University Methods for producing and using densified biomass products containing pretreated biomass fibers
US9175323B2 (en) 2012-04-27 2015-11-03 The Michigan Biotechnology Institute Process for treating biomass
US9206446B2 (en) 2006-05-01 2015-12-08 Board Of Trustees Of Michigan State University Extraction of solubles from plant biomass for use as microbial growth stimulant and methods related thereto
US9650657B2 (en) 2010-04-19 2017-05-16 Board Of Trustees Of Michigan State University Methods for producing extracted and digested products from pretreated lignocellulosic biomass
US10202660B2 (en) 2012-03-02 2019-02-12 Board Of Trustees Of Michigan State University Methods for increasing sugar yield with size-adjusted lignocellulosic biomass particles
US10457810B2 (en) 2009-08-24 2019-10-29 Board Of Trustees Of Michigan State University Densified biomass products containing pretreated biomass fibers

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0722418B1 (en) * 2006-05-01 2023-10-10 Dartmouth College Process for treating lignocellulosic biomass with ammonia and water vapors
EP1889870A1 (en) * 2006-08-16 2008-02-20 BIOeCON International Holding N.V. Stable suspensions of biomass comprising inorganic particulates
US20100206499A1 (en) * 2009-02-13 2010-08-19 Zilkha Biomass Acquisitions Company L.L.C. Methods for Producing Biomass-Based Fuel With Pulp Processing Equipment
US8236173B2 (en) 2011-03-10 2012-08-07 Kior, Inc. Biomass pretreatment for fast pyrolysis to liquids
US9850512B2 (en) 2013-03-15 2017-12-26 The Research Foundation For The State University Of New York Hydrolysis of cellulosic fines in primary clarified sludge of paper mills and the addition of a surfactant to increase the yield
US9951363B2 (en) 2014-03-14 2018-04-24 The Research Foundation for the State University of New York College of Environmental Science and Forestry Enzymatic hydrolysis of old corrugated cardboard (OCC) fines from recycled linerboard mill waste rejects
WO2018191176A2 (en) * 2017-04-09 2018-10-18 Locus Ip Company, Llc Efficient production of bioethanol in mobile reactors
CA3081329A1 (en) 2017-10-31 2019-05-09 Locus Ip Company, Llc Matrix fermentation systems and methods for producing microbe-based products

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171592A (en) * 1990-03-02 1992-12-15 Afex Corporation Biomass refining process
WO2006034590A1 (en) * 2004-09-30 2006-04-06 Iogen Energy Corporation Continuous flowing pre-treatment system with steam recovery
WO2006055362A1 (en) * 2004-11-12 2006-05-26 Michigan Biotechnology Institute Process for treatment of biomass feedstocks
EP1076488B1 (en) * 1998-04-30 2008-05-14 Michigan State University Process and apparatus for treating cellulosic materials

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4644060A (en) * 1985-05-21 1987-02-17 E. I. Du Pont De Nemours And Company Supercritical ammonia treatment of lignocellulosic materials
BRPI0722418B1 (en) * 2006-05-01 2023-10-10 Dartmouth College Process for treating lignocellulosic biomass with ammonia and water vapors

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171592A (en) * 1990-03-02 1992-12-15 Afex Corporation Biomass refining process
EP1076488B1 (en) * 1998-04-30 2008-05-14 Michigan State University Process and apparatus for treating cellulosic materials
WO2006034590A1 (en) * 2004-09-30 2006-04-06 Iogen Energy Corporation Continuous flowing pre-treatment system with steam recovery
WO2006055362A1 (en) * 2004-11-12 2006-05-26 Michigan Biotechnology Institute Process for treatment of biomass feedstocks

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9644222B2 (en) 2006-05-01 2017-05-09 Board Of Trustees Of Michigan State University Methods for pretreating biomass
US8968515B2 (en) 2006-05-01 2015-03-03 Board Of Trustees Of Michigan State University Methods for pretreating biomass
US9206446B2 (en) 2006-05-01 2015-12-08 Board Of Trustees Of Michigan State University Extraction of solubles from plant biomass for use as microbial growth stimulant and methods related thereto
US8945245B2 (en) 2009-08-24 2015-02-03 The Michigan Biotechnology Institute Methods of hydrolyzing pretreated densified biomass particulates and systems related thereto
US10457810B2 (en) 2009-08-24 2019-10-29 Board Of Trustees Of Michigan State University Densified biomass products containing pretreated biomass fibers
US9039792B2 (en) 2009-08-24 2015-05-26 Board Of Trustees Of Michigan State University Methods for producing and using densified biomass products containing pretreated biomass fibers
US9458482B2 (en) 2009-08-24 2016-10-04 The Michigan Biotechnology Institute Methods of hydrolyzing pretreated densified biomass particulates and systems related thereto
US9650657B2 (en) 2010-04-19 2017-05-16 Board Of Trustees Of Michigan State University Methods for producing extracted and digested products from pretreated lignocellulosic biomass
US10202660B2 (en) 2012-03-02 2019-02-12 Board Of Trustees Of Michigan State University Methods for increasing sugar yield with size-adjusted lignocellulosic biomass particles
CN104508137A (en) * 2012-04-27 2015-04-08 密歇根生物技术研究所 Process for treating biomass
US9175323B2 (en) 2012-04-27 2015-11-03 The Michigan Biotechnology Institute Process for treating biomass
CN104508137B (en) * 2012-04-27 2017-08-15 密歇根生物技术研究所 Method for handling biomass
US9938662B2 (en) 2012-04-27 2018-04-10 The Michigan Biotechnology Institute Process for treating biomass
US9102964B2 (en) 2012-04-27 2015-08-11 The Michigan Biotechnology Institute Process for treating biomass
WO2013163271A1 (en) * 2012-04-27 2013-10-31 Michigan Biotechnology Institute Process for treating biomass

Also Published As

Publication number Publication date
WO2008114139A3 (en) 2008-12-11
US20080229657A1 (en) 2008-09-25

Similar Documents

Publication Publication Date Title
US20080229657A1 (en) System and methods for continuous biomass processing
Tayyab et al. Bioethanol production from lignocellulosic biomass by environment-friendly pretreatment methods: a review.
Balat Production of bioethanol from lignocellulosic materials via the biochemical pathway: a review
Khan et al. A review on the role of pretreatment technologies in the hydrolysis of lignocellulosic biomass of corn stover
US10421667B2 (en) Process for treating lignocellulosic feedstock comprising wet oxidation
US20120201947A1 (en) Advanced biorefinery process
US20110171709A1 (en) Product Recovery From Fermentation of Lignocellulosic Biomass
Haq et al. Recent progress in bioethanol production from lignocellulosic materials: A review
US10513715B2 (en) Wet oxidation of biomass
Jayakumar et al. Bioethanol production from agricultural residues as lignocellulosic biomass feedstock's waste valorization approach: A comprehensive review
KR20110067992A (en) Method for pretreating biomass using internal heat and apparatus for pretreating biomass
Fan et al. Integrating sugarcane molasses into sequential cellulosic biofuel production based on SSF process of high solid loading
US9102965B2 (en) Saccharide-solution producing apparatus, fermentation system, saccharide-solution producing method, and fermentation method
Awoyale et al. Harnessing the potential of bio‐ethanol production from lignocellulosic biomass in Nigeria–a review
US20150047629A1 (en) Counter-current diffuser technology for pretreatment of lignocellulosic substrates
Kahr et al. Bioethanol production from steam explosion pretreated straw
Kuhad et al. Bioethanol production from lignocellulosics: an overview
Yang The use of lignocellulosic biomass for fermentative butanol production in biorefining processes
Ezeoha et al. The prospects, impacts, and research challenges of enhanced cellulosic ethanol production: a review
Kapoor et al. Bioethanol from crop residues, production forecasting and economics: An Indian perspective
Konur Second Generation Industrial Waste-based Bioethanol Fuels
Gao ABE fermentation from low cost substrates
Awoyale Paper 1, HPBPLB, Accepted and Published Journal Paper of Biofuels, Bioproducts and Biorefining, John Wiley & Sons, Ltd Awoyale Adeolu A. and Lokhat, David (2019) Harnessing the Potential of bioethanol production from lignocellulosic biomass in Nigeria–a review
Anuradha et al. Recent Technologies for the Production of Biobutanol from Agricultural Residues
Kumneadklang Development of bioethanol production process from oil palm trunk with ethanol membrane separation.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08750841

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08750841

Country of ref document: EP

Kind code of ref document: A2