High-solids biomass slurry generation for enhanced efficiency hydrolysis processing and equipment design to yield the same
10501765 ยท 2019-12-10
Assignee
Inventors
Cpc classification
C08L97/02
CHEMISTRY; METALLURGY
B01F25/721
PERFORMING OPERATIONS; TRANSPORTING
C12P2201/00
CHEMISTRY; METALLURGY
B02C23/18
PERFORMING OPERATIONS; TRANSPORTING
B01F27/271
PERFORMING OPERATIONS; TRANSPORTING
B01F23/565
PERFORMING OPERATIONS; TRANSPORTING
C08H8/00
CHEMISTRY; METALLURGY
B01F27/50
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08L97/02
CHEMISTRY; METALLURGY
C08H8/00
CHEMISTRY; METALLURGY
C12P19/14
CHEMISTRY; METALLURGY
B02C23/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
This disclosure provides a high solids biomass slurry that is readily pumpable and transportable to downstream processing units, such as chemical and/or biochemical processing units. The slurry is amenable to saccharification efficiencies of >70 % in processing times of <36 hours. Also provided are devices for processing materials, such as the high solids biomass slurry.
Claims
1. A device for mixing, homogenizing, dispersing, and processing materials, comprising the following components: a. One or more stages of shear cutting elements configured to initially process incoming solids by shear cutting and dispersion prior to or in tandem with water introduction; wherein the one or more stages of shear cutting elements comprises a series of alternating rotor and stator plates; a series of two or more impeller stages positioned in between the shear cutting stages and a discharge impeller stage to enhance mixing and homogenization; c. a pumping ring to direct material flow from an outlet of the discharge impeller stage to a discharge port, wherein the discharge port is configured tangentially to the device's diameter to enhance the delivery pressure of the hydrated biomass.
2. The device of claim 1, further comprising a downstream milling device configured to reduce particle sizes and further homogenize the materials to a pretreated state suitable for downstream enzymatic hydrolysis processing.
3. The device of claim 2, wherein the downstream milling device is a colloidal mill, and the material processed is corn stover or sugarcane bagasse.
4. The device of claim 2, wherein the mixing, homogenizing, dispersing, and processing are accomplished in a hybrid device constructed in a single housing.
5. A device or tandem device(s) for mixing, homogenizing, dispersing, milling and processing of biomass materials, derived from corn stover or sugarcane bagasse, for generating a homogenous, hydrated slurry of biomass solids comprising >20% (by weight) solid material that is readily pumpable and transportable to downstream chemical processing and/or biochemical processing unit operations, comprising the following components: a. One or more stages of shear cutting elements to initially process incoming solids by shear cutting and dispersion prior to or in tandem with water introduction, wherein the shear cutting elements comprise a series of alternating rotor and stator plates; and wherein the rotor and stator plates have oblong slots or holes; b. a series of two or more impeller stages positioned between the shear cutting stages and a discharge impeller stage to enhance mixing and homogenization; c. a pumping ring to direct slurry flow from an outlet of the discharge impeller to a discharge port; d. one or more colloidal mills or colloidal mill stages that reduces particle size and further enhances slurry phase dispersion; thereby generating a slurry capable of saccharification efficiencies of >70% in processing times of <24 hours.
6. A device or tandem device(s) of claim 5, wherein saccharification enzymes are added into one or more of the shear zone, pumping zone, discharge impeller outlet, or discharge port of the device(s).
7. A device or tandem device(s) of claim 6, wherein the saccharification enzymes introduced directly into one or more of the shear zone, pumping zone, discharge impeller outlet or discharge port of the device(s) are comprised of one or more of the enzyme classes of cellulases, glucanases, xylanases, ligninases, or peroxidases.
8. The device of claim 1, further comprising an isolation disk positioned between the shear cutting stages and the two or more impeller stages.
9. The device of claim 5, wherein the stator comprises (i) circular, rectangular or hexagonal holes, or (ii) slots.
10. The device of claim 5, wherein the discharge port is configured tangentially to the device's diameter to enhance the delivery pressure of the hydrated biomass.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
Introduction
(10) Devices have been manufactured to accomplish the generation of slurries from a range of solids, and to achieve the qualitative attributes of slurry mixing and hydration, as well as solids dispersion. A primary example is the MHD-2000 product offered by IKA Works (Wilmington, N.C.). Novel and non-obvious improvements to this existing art have been developed in the present application to further enable these devices to process low-density, hydration resistant (i.e., recalcitrant) solids, enable solids loadings at levels greater than those previously achieved, and thus facilitate capital- and energy-efficient downstream hydrolysis (i.e., saccharification) of these materials in the production of biofuels and/or biochemicals.
(11) The key embodiment of the present invention is the production of the desired high-solids, homogeneous slurry that can be readily transported and further processed with high-efficiencyincluding saccharification, product separation, and water recovery and recycle. Specific modifications to the existing equipment art have been achieved that yield hybrid equipment functionalitynotably including inlet solids particle shearing and size reduction, with combined attribute improvement of increased wettability and increased reactivity toward both hydration and hydrolysis. Additional improvements to the existing art improve pumpability of resultant slurries out of the mixing stage at very high solids loading levelsloading levels novel for biomass processing in these applications.
(12) Equipment has been developed and applied for the processing of slurried solids (usually aqueous slurries) to include the functionalities of mixing, hydration, dispersion, homogenization, and milling/sizing. More specifically, for the handling of cellulosic biomass materials in high-loading processing, with the combined purposes of all of the above functionalitiesand enabling high-conversion, low-residence time downstream hydrolysis reactions (e.g., enzymatic saccharification), specific mixing/hydration/dispersion and slurry homogenization and milling equipment has been customized for this application and deployed in tandem to achieve these targeted attributes. High-loading processing or high-solids slurries are biomass mixtures with greater than 10% wt solids on a dry mass basis, greater than 12% wt solids, greater than 15% wt solids, greater than 18% wt solids, greater than 20% wt solids, greater than 22% wt solids, greater than 25% wt solids, and greater than 30% wt solids.
(13) A mixing-hydration-dispersion processor (MHD; for example, from IKA Works USAWilmington, N.C.) has been developed specifically for this application. One embodiment of this device 100 is conceptually shown in
(14) Alternative embodiments of the device 200 are illustrated in
(15) The paddle mixing bars 233, centrifugal impeller 255 and the discharge impeller 236 are all assembled on the rotating shaft 241 providing a direct drive constant speed of rotation for all components. In some embodiments these are all rotating at the same rotational speed, but in some embodiments the direct drive gear transitions are used between the shaft 241 and the component to decrease the rotational speed of a specific component. For example the discharge impeller 236 can be geared to rotate at 50% or 75% or 85% or 95% of the speed of the centrifugal impeller to enhance the compression of the hydrated biomass against the wall before it is sweeps around to the outlet port 204. This feature helps to compress the biomass of entrained air and to generate denser slurry of biomass delivered from the device. This embodiment also enhances the compositional characteristic of the hydrated biomass which can be important for downstream operations such as but not limited to wet milling with the Cellunator or other rotor stator type mills such as colloidal mills and others including typical paper making process mills such as plate type mills. The direct drive gear transition can be implemented to reverse the rotational direction of the discharge impeller 236 with respect to the centrifugal pump impeller and change the movement of material out of the device.
(16) Alternative embodiments of the device 200 can include auger feed mechanisms assembled to the drive shaft 241 and located in the center of the feed zone 222 above the paddle mixing bars 233 to enhance the reliable movement of biomass into the hydration zone 223. All of these alternative configurations are enhanced by the inclusion of the discharge impeller 236 and the tangential flow exit 204. In some embodiments of the device 200 the isolation plate 245 is equipped with a vertically downward facing fingers or interrupted stator wall (as shown) that is positioned between the centrifugal pump impeller 255 and the sweep bar 236 creating additional shear force on the biomass for particle size reduction and mixing and hydration.
(17) The hydration zone 223 can be configured to include additional stages and mixing vanes that further mix the solids and water, enabling hydration, while providing centrifugal driving force for solids dispersion and slurry homogenization. After two or more stages of mixing blades in series, the slurry reaches the discharge sections or the centrifugal pumping zone 225 and discharge impeller zone 226 from which it is pumped out of the unit. The inclusion of the discharge wipers or pumping rings help clear the solids and slurry from the zone, and direct concentrated slurry flow into the discharge port 204. The discharge impeller can consist of any number of configurations including a sweep bar assembly with 2, 3, 4, or more vertical bars to sweep the solids off the inside circumference of the housing 246. Alternative embodiments include two rotating bar assemblies, one that sweeps the hydrated biomass off the outside diameter of the centrifugal impeller 255 and one that sweeps the solids off the inside diameter of the housing 246. As described previously, the rotational speed and direction of these multiple sweeping discharge impeller 236 can be the same or different from the rotational characteristics of the centrifugal impeller 255.
(18) Depending on the feedstock and the form of the feedstock, such as pellets, long fibers, medium fibers, or fine fibers, the specific configuration the device 100 or 200 may vary for optimum performance and biomass mixing, hydration, and dispersion. In some embodiments the feed zone 122 or 222 is equipped with rotating auger elements that help transport the biomass from the feed zone 122 or 222 into the hydration zones 123 or 224. In the case of pellets this auger element is useful, but in the case of loose, longer fibers the auger element is less effective.
(19) In some embodiments of the device and the process configuration a slurry milling device, such as a colloid mill, can be installed in series with the mixing, hydration and dispersion device. This provides the serial functionality of hydrating the biomass followed by milling and particle size reduction, taking advantage of the highly dispersed solids in the hydrated slurry provided directly from the device. The combined effect generates a fine-particle, high-loading, homogenous biomass solids aqueous slurry. The biomass solids aqueous slurry can have optimal characteristics for downstream processing. This intermediate product is ideally suited for hydrolysis processing of very high efficiency: i.e., high-conversion, low-residence time requirement enzymatic saccharification. The slurry can have homogeneous hydration with solids levels of 10%, 15%, 20%, 25%, 30%, 35%, or greater weight percent solids. The consistency of the homogeneous hydrated solids can be maintained using this device by managing the constant solids feed rate of dry solids into the device using the feed hopper assembly 103 and managing the constant liquid feed rate into the device. Alternative biomass hydration processes such as batch mixing or semi-batch mixing of biomass into a tank with water cannot produce continuous operation with consistently controlled levels of hydration. Dried biomass can be extremely hydrophobic and initial wetting and hydration can be inconsistent with some material floating on the tank and some fibers being wetted and having a density greater than water allowing them to sink to the bottom of the tank. Even with controlled water and biomass feeds into a bulk batch hydration tank the consistency of the delivered or extracted solids can vary and fluctuate greatly. Introducing recirculation and in tank shear mixing can improve the consistency, but inconsistency of the initial, incoming hydrophobic material remains a critical issue. Even using an inline hydration device within a recirculation loop around the tank results in inconsistency of solids levels especially when the target solids are greater than 15% or greater than 20% because the solids level of the slurry in the tank has to been less than the solids level out of the device because of the fresh dry biomass being feed into the device. As higher solid levels are targeted the mixing of the recycled solids and the bulk solids in the tank become the critical control factor for the consistency of the delivered solids. This innovative hydration configuration 199 of managing dry biomass feed with the feed hopper assembly 103 into the mixing, hydration and dispersion device 100 provides a unique solution to delivering a controlled mass flow rate and degree of hydration for downstream processes.
(20) Integrating the shear functions of the paddle mixing bars 233 into the hydration zone 223 provides additional benefits of improving the effectiveness of the hydration achieved with the device. As defined water mixed with biomass can be bulk water or retained water. Bulk water can be removed from the biomass by centrifugal forces while retained water is fully hydrated into the fiber and fibril structures of the biomass. The innovative device provides biomass hydration that enhances both the bulk water and the retained water. The latter is most important effective downstream processing such as enzymatic saccharification The device produces hydrated biomass with an increased retained water content of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or greater than 13%. The device achieves the mixing, hydration, and dispersion of the biomass solids and liquid such that the hydrated biomass achieves a retained water content of greater than 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, or greater than 65% and delivers the hydrated biomass solids with a controlled bulk solids content of greater than 15% wt solids, 20% wt solids, 25% wt solids, or greater than 30% solids. The controlled biomass solids level out of the device is continuously managed to maintain the bulk solids level within less than 20%, less than 15%, less than 10%, or less than 5% variability from minute to minute or from hour to hour on a continuous bases. The device provides an ability to produce up to 75 psi of discharge pressure or less based on downstream losses and pressure requirements. When the device is used upstream of a device such as the Cellunator, discharge pressures produced are managed between 0 and 15 psi, or 15 and 40 psi, or 40 and 65 psi. Pressure delivery is similar to that of a centrifugal pump, where solids particle size, concentration, and other properties of the liquid that make up viscosity or rheology all affect potential discharge pressure capabilities.
(21) An alternative embodiment of the device is shown in
(22) Illustrated in this embodiment 300 is a shear cutting and particle size reduction assembly 334 which is consistent with the shear zone 124 of
(23) The high shear rotor stator assembly 334 is further illustrated in
(24) In some embodiments of the assembly the design, materials of construction, and spacing of the rotors and stators are such that the replacement cost of the high shear assembly 334 is relatively low so that periodic replacement of the assembly does not contribute significantly to the overall operating cost of the process. The replacement cost for a stack of cutting disk rotor and stators can be approximately $300-500 per assembly. The alternative to this configuration is to use a colloidal mill downstream of the HMD device for the function of particle size reduction. Replacement cost for equivalent capacity wear component in this equipment may be in the range of $20 k to $40 k per year. If the cutting disks required replace 10 times per year, the cost of the replacement components would be less than 25% of the colloidal mill alternative. The embodiment of the MHD with the high shear cutting elements provides lower reoccurring costs on the order of less than 25%, less than 20% or less than 10% of the colloidal mill alternative.
(25) The biomass fibers can be introduced into the device as a relatively long strands of fiber for example as received corn stover and the advantage of the mixing, hydrating, and dispersion device 300 with the high shear cutting assembly 334 is a single step process that reduces the fiber to short pieces and hydrating the fiber and fibril sub structures of the biomass. The feedstock can consist of a mixture of fibers with 10% by weight of the fibers having lengths greater than 2 cm, or greater than 3 cm, or 4 cm or 5 cm or 6 cm or longer. The feedstock can also consist of material that has be preprocessed by dry milling steps (e.g., hammer mills, roller mills, grinders, etc.) such that 90% by weight of the material has a particle size less than 3 mm but still contains a 5 to 20% of the material with particles greater than 1 mm in size. The mechanical shear during the hydration process rips, cuts, and disturbs the fiber structure such that 95% wt of the particles (or greater) are less than 1 mm in size or less than 0.5 mm, or such that 97% of the particles (or greater) are less than 1 mm in size or less than 0.5 mm. The mechanical shear during the hydration process results in producing an exit hydrated biomass with greater than 50%, greater than 55%, or greater than 60% retained moisture. Bulk solids loading is in the controlled ranges of greater than 15%, greater than 20%, greater than 25%, or greater than 30% bulk solids. In addition the device hydrates biomass with the combination of particle size reduction, retained moisture content and bulk solids.
(26) One embodiment of the process is to have a feed hopper deliver biomass fibers to the MHD hardware in which the material is mixed, hydrated (e.g., mixed with water or liquid), and dispersed to create a biomass mixture with a bulk solids level of greater than 15% solids, or greater than 20% solids, or greater than 30% or greater than 40% solids and has a WRV of greater than 2.5 or greater than 3.0 or greater than 3.5. One embodiment of the process is a feed hopper feeding the MHD, which creates a hydrated biomass mixture that with a bulk solids level of greater than 15% solids, or greater than 20% solids, or greater than 30% or greater than 40% solids and has sufficient delivery pressure capability to feed a downstream colloidal mill, which provides high shear particle size reduction capability such that the delivery pressure of the MHD is greater than 30 psig, or greater than 40 psig, or greater than 50 psig in steady state operation or has the capability to achieve greater than 120 psig if deadheaded. One embodiment of the process is to have a feed hopper deliver biomass pellets of bulk density greater than 0.5 kg/lit to a MHD configuration that breaks up the pellets and hydrates the biomass such that the hydrated biomass has a WRV of greater than 2.5, or greater than 3.0 or greater than 3.5 and with a bulk solids level of greater than 15% solids, or greater than 20% solids, or greater than 30% or greater than 40% solids. One embodiment of the process is a MHD configuration containing a high shear zone with alternating stator cutting disks and rotor cutting disks with at least two stators or at least three stators or at least four stators or at least five stators such that feed biomass with a mixture of fiber lengths and greater than 5% of the fibers are longer than 1 inch or longer than 2 inches or longer than 3 inches is mixed, hydrated, and dispersed and exits the MHD with a particle size reduction such that less than 1% of the fiber mass has a length of greater than 0.05 inches or greater than 0.04 inches or greater than 0.03 inches or greater than 0.02 inches and or has a WRV of greater than 2.5 or greater than 3.0 or greater than 3.5 and has a bulk solids level of greater than 15%, or greater than 20%, or greater than 30% or greater than 40%. One embodiment of the process is a feed hopper or biomass conveyor unit delivers biomass fibers to a MHD that delivers hydrated biomass to a colloidal mill, such that the hydrated biomass with a WRV of greater 2.0 or greater than 2.5 or greater than 3.0, can flow to the colloidal mill and has a measurable pressure head of greater than 30 psig, greater than 40 psig, or greater than 50 psig as it exits the MHD, such that no pump is required between the MHD and the colloidal mill.
(27) In one embodiment of the system the mechanical pretreatment (MPT) function for preparing biomass for saccharification consists of two individual pieces of equipment. The first is the MHD device of various configurations, which provides initial mixing, hydration and dispersion of the biomass, and the second is the colloid mill or rotor stator device, which provides the particle size reduction and optimization while producing a homogeneous slurry for downstream processes. In some embodiments the MPT function consists of an integrated device, which incorporates both the elements required for mixing, hydration and dispersion and also includes the rotor stator high shear milling elements as illustrated in
(28) The resulting equipment tandem customization including units tailored for biomass in both MHD and milling unit operationscan be ideally used for the pretreatment of cellulosic biomass substrates in the generation of cellulosic sugars, the key intermediate to either ethanol or other biofuels and biochemicals. Two such substrates of immediate commercial interest are corn stover and sugarcane bagasse, as primary examples. The elements of the device in various embodiments will include a combination of the functional elements outlined in Table 1. For example the device can comprise combination of 1-4-5-7-8-13-14-15-16-18-20 if the biomass feedstock is dry pellets, or can comprise combination of 1-2-3-4-5-9-10-13-14-16-19-20 if the biomass feedstock is dry loose fibers. In another embodiment the device can comprise combination 1-4-5-9-10-14-16-19-20 if the feedstock is dry loose fibers or various lengths and minimal preprocessing.
(29) TABLE-US-00001 TABLE 1 List of Optional Elements used in the Assembly of the Device Section of device Element Location Feed Zone 1. Inlet port Stator 2. Biomass scraper prongs Rotor 3. Feed auger Rotor Hydration Zone 4. Liquid feed port Stator 5. Liquid distribution wall or roof Stator 6. Feed auger Rotor 7. Paddle mixing bars Rotor High Shear Zone 8. Paddle mixing bars Rotor 9. Rotor cutting disks Rotor 10. Stator cutting disks Stator 11. Colloid mill rotor assembly Rotor 12. Colloid mill stator assembly Stator Centrifugal Pump 13. Isolation disk Stator Zone 14. Centrifugal pump impeller Rotor 15. Stator wall barrier Stator Discharge Impeller 16. Sweeping discharge impeller Rotor Zone 17. Variable speed drive assembly Rotor Exit Zone 18. Exit port Stator 19. Tangential exit port Stator Center Rotating 20. Drive shaft for assembling elements Rotor section
(30) Some preferred embodiments of the device are defined in Table 2 which uses the elements defined in Table 1 and the specific cutting plates as shown in
(31) TABLE-US-00002 TABLE 2 Representative Embodiments of MHD device Elements Configured For 1, 4, 5, 9E, 10I, 9D, 10I, 9C, 10I, 9C, 10G, Dry Fibrous material up to 9C, 10H, 9C, 14, 16, 19 6 in length down to 250 micron and above 20% S 1, 9E, 10I, 9D, 10I, 9C, 10I, 9C, 10G, 9C, Wet Fibrous material up to 10H, 9C, 14, 16, 19 6 in length down to 250 micron and below 20% S 1, 4, 5, 9E, 10F, 9D, 10F, 9D, 10I, 9D, 10G, Dry fibrous material up to 9C, 10H, 9C, 14, 16, 19 9 in length down to 250 micron and above 20% S 1, 3, 4, 5, 7, 7, 7, 7, 13, 14, 16, 17, 19 Dry powder materials from 0 to 250 microns in size and above 90% S 1, 4, 5, 9E, 10I, 9D, 10G, 9B, 10H, 9B, 8, Dry fibrous materials up to 8, 14, 16, 19 850 microns in length down to powder and above 20% S
(32) In some embodiments where the mixing, hydration, and dispersion functionalities are combined with shear/particle size reduction functionalities in a single MHD unit, and in particular where the thermal pretreatment (TPT) is not downstream of the mechanical pretreatment (MPT), it is possible and advantageous to integrate the intended saccharification or hydrolysis chemical reaction step with the MHD. This can either be done by direct application of the saccharification enzymes (e.g., cellulases, glucanases, xylanases, ligninases, peroxidases, or various combinations of two or more of these enzyme classes) into the high shear or mixing zone(s) of the MHD device, or by introduction of the same enzyme(s) into the pumping and/or discharge section of the MHD, closely downstream of the high shear or mixing zone(s). This configuration thus includes introduction of active saccharification enzymes into one or more of zone(s) 124, 125, and/or 127 (
EXAMPLES
Example 1
(33) An MHD-20 manufactured by IKA Works, USA (Wilmington, N.C.) was customized via the inclusion of the inlet sheer cutting zones and the t high-solids discharge impeller. This unit was deployed in tandem with the Cellunator by Edeniq, Inc. (Visalia, Calif.), specifically the IKA MK2000/20 unit, for the purpose of tandem processing of corn stover biomass.
(34) The stover had been initially preprocessed to an approximate upper particle size of 6 prior to this treatment. The material was roughly 95% S by weight.
(35) The material was processed through the tandem MHD-Cellunator train continuously at approximately 15 GPM, and a solids loading of 18% S. From here, the propensity for this material to be used effectively in saccharification processing was independently verified in laboratory testing.
Example 2
(36) An MHD-20 manufactured by IKA Works, USA (Wilmington, N.C.) was customized via the inclusion of the inlet sheer cutting zones and the high-solids discharge impeller. This unit was deployed in tandem with the Cellunator by Edeniq, Inc. (Visalia, Calif.), specifically the IKA MK-20 unit, for the purpose of tandem processing of sugarcane bagasse biomass.
(37) The bagasse had been initially preprocessed to an approximate upper particle size of 1.5 mm prior to this treatment, with no upstream thermal treatment processing.
(38) The material was processed through the tandem MHD-Cellunator train continuously at approximately 10 GPM, and a solids loading of 20%. From here, the material was subjected to laboratory thermal pretreatment, and the subsequent propensity for this material to be used effectively in saccharification processing was independently verified in laboratory testing.
Example 3
(39) A configuration of the MHD which incorporated the high shear paddle zone feeding the centrifugal pumping ring, and the sweeping cross bars was operated on both corn stover pellets and loose fiber stover. The processing capabilities of this small scale device (i.e., IKA MHD-20) was partially mapped as a function of total mass flow rate and resulting biomass solids fraction as illustrated in
Example 4
(40) In another example as illustrated in
Example 5
(41) Another example of the effectiveness of the MHD device and MPT function in hydrating biomass is shown in
(42) It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.