Intermediate Compositions

STATEM ENT REGARDING RIGHTS TO INVENTION MADE UN DER FEDERALLY-SPONSORED RES EARCH AN D DEVELOPM ENT

This invention was made with Government support under Contract DE-AC05-76RLO1 830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.

TECHN ICAL FI ELD

The present disclosure relates to liquefaction processes and system as well as liquefaction process intermediate compositions. These systems and processes can be used in the form of hydrothermal liquefaction and they can be used to perform hydrothermal liquefaction on biomass solutions to create a bio-oil. BACKG ROUN D

Bio-oils can be created from the hydrothermal liquefaction of a biomass slurry. These processes present many challenges for performing the process efficiently on many levels. One challenge is the pumping of biomass slu rries through process systems, as well as the separation of the bio-oils from the reaction solutions. The present disclosure provides liquefaction process systems and intermediate compositions that overcome drawbacks of the prior art.

SUMMARY OF TH E DISCLOSU RE

Liquefaction processes are provided that can include: providing a biomass slu rry solution having a temperature of at least 300 °C at a pressu re of at least 2000 psig ; cooling the solution to a temperature of less than 150 °C ; and depressurizing the solution to release carbon dioxide from the solution and form at least part of a bio-oil foam.

Liquefaction processes are also provided that can include: filtering the biomass slurry to remove particulates; and cooling and depressurizing the filtered solution to form a bio-oil foam. Liquefaction systems are provided that can include: a heated biomass slurry reaction zone maintained above 300 °C and at least 2000 psig and in continuous fluid commu nication with a flash cooling/depressu rization zone maintained below 1 50 °C and about atmospheric pressure.

Liquefaction systems are also provided that can include a flash depressurization zone maintained between about 1 25 psig and about atmospheric pressure in fluid commu nication with foam/liquid separation system. Liquefaction process intermediate compositions are provided that can include a bio-oil foam phase separated from an aqueous biomass solids solution.

DRAWINGS

Embodiments of the disclosu re are described below with reference to the following accompanying drawings.

Fig. 1 is a depiction of a process system according to an embodiment.

Fig. 2 is a depiction of a process system according to an embodiment. Fig. 3 is a depiction of a process system according to an embodiment.

Fig. 4 is a depiction of a process system according to an embodiment.

Fig. 5 is a depiction of a process system according to an embodiment.

Fig. 6 is a depiction of a process system according embodiment. Fig. 7 is a depiction of an intermediate composition according to an embodiment of the disclosure.

DESCRI PTION

The process systems and intermediate compositions of the present disclosure will be described with reference to Figs. 1 -7. Referring first to Fig. 1 , a process system 10 is shown that includes a reaction zone 12 in fluid commu nication with a production zone 14, yielding a process intermediate 1 6. Entering the reaction zone 1 2 but not shown can be a biomass slurry solution. This biomass slu rry solution can be provided to reaction zone 12, and this biomass slurry solution can include biomass and water, for example.

Biomass sources suitable for use in this solution include but are not limited to agricultural residues (e.g., corn stover), forest residue (e.g., pine), industrial/municipal sludges, aquatic biomass sources (e.g., algae, kelp), high moistu re biomass slurries, biosludge from wastewater treatment systems, sewage sludge from mu nicipal treatment systems, wet biproducts from biorefinary operations, wet byproducts and residues from food processing, animal waste and waste from centralized animal raising facilities, organic chemical manufacturing wastewater streams, other organic contaminated industrial wastewaters. These biomass materials may be derived from, for example, organic materials, plants, algae, macroalgae, microalgae, photosynthetic cyanobacteria, animal waste, food processing wastes including, e.g., trimmings, culls, pomace, cooking water, washings, fermentation residuals, meat solid wastes, dairy liquid wastes, wood and other biomass materials, raw materials such as fruits, vegetables, fish, poultry, livestock, and combinations of these raw materials and others sources and feedstock materials including combinations of these various sources. Biomass slu rry solution can be substantially liquid and have density of from 0.95 mg/ml to about 1 .15 mg/ml. Wood oils are examples of liquid biomass slu rry solutions and this liquid biomass may have a density within the 0.95 to 1 .1 5 range.

The biomass slurry solution can have a minimu m wt % of about 8 wt/wt % and can range up to as high as 35 wt/wt % with the balance being water. The balance can also include saltwater and/or mixtures of water and inorganics. The slurry solutions can be maintained at this concentration to allow efficient pumping of these solutions in a continuous or steady state reaction system as disclosed herein.

This biomass slurry solution can be provided to reaction zone 1 2, and within reaction zone 1 2, the biomass slu rry solution can be increased to a temperature of at least 300 °C and a pressure of at least 2000 psig. According to example implementations, reaction zone 12 can also be configu red to maintain the slurry from about 300 °C to about 350 °C and a pressure of from about 2000 psig to about 3000 psig. The biomass slu rry solution can be processed at a liquid hourly space velocity in zone 12 from about 1 to about 10 L/L/h

From reaction zone 1 2, the reacted slurry solution can proceed to production zone 14. Production zone 14 can provide for the cooling, (which may be via heat exchange) of the reacted slurry solution to a temperatu re of less than 1 50 °C and/or the depressurizing of the solution to about atmospheric pressure. The reacted slurry solution can be cooled to below 110 °C as well. Upon depressurization, carbon dioxide can be released from the reacted slu rry solution and form at least part of process intermediate 1 6 as a bio-oil foam. The bio-oil foam 17 that is formed resides above or is phase separated from the reacted aqueous solution 1 8 of the biomass slu rry solution. The bio-oil foam composition 1 6 can be provided from production zone 14 as shown in Fig. 1 .

Referring next to Fig. 2, production zone 14 may have a subzone such as filter zone 20 as shown in system 20 of Fig. 2. Filter zone 20 can be configured to receive heated and pressurized biomass slu rry solution from reactant zone 12 for example and filter same. According to one embodiment of the disclosure, the slurry solution at temperatures between 300 °C and 350 °C and pressu res between 2000 psig and 3000 psig can be filtered to remove solids and particulates. This filtering can minimize the formation of emulsions du ring the preparation of intermediate composition 16. The filter device can include a high crush rating or strength such as a stainless steel filter device. The device can have a filter breakthrough rating selected in the range between about 0.5% to about 2%. Example devices can have an internal filter with selected pore sizes including, e.g., 5 urn pores rated to remove up to 98% of solids such as organic or inorganic solids including organic char.. In alternative embodiments, filter zone 20 can include an internal filter with 1 8 μιη pores configu red to remove up to 1 00% of inorganic solids and precipitates from the solution that is passed from the reaction zone. Filtration zone 20 may include a top-down filter zone and may also include a woven filter design.

Referring next to Fig. 3, process system 30 can include as part of the production zone 14 as depicted in system 30, cooling zone 32 in fluid communication with depressurization zone 34 to yield product intermediate 1 6. As shown in Fig. 3, cooling zone 32 can include a zone that is configured to receive reacted biomass slurry at a temperature above 300 °C and reduce the temperature of that solution to below 150 °C or 110 °C in some embodiments, and in other embodiments, to a temperature of from between about 20 °C and 110 °C. In certain specific implementations, the temperature can be reduced to 60 °C to 70 °C as well, for example.

Cooling zone 32 can be in fluid communication with, for example, filter zone 20 of Fig. 2 as part of production zone 14, for example. Cooling zone 32 can be in fluid communication with a depressurization zone 34 wherein upon cooling, the pressure applied to the solution is rapidly changed from at least 2000 psig to less than 125 psig to about atmospheric pressure. According to some implementations, during this rapid depressu rization, exsolvation of saturated CO ₂ formed as a product in the reaction zone evolves and brings with it bio-oils from the aqueous solution to form a bio-oil foam or froth. The terms "bio-oil froth" and "bio-oil foam" are used interchangeably herein.

It has been discovered that this bio-oil foam or froth resides above the aqueous solution at atmospheric pressure and provides intermediate composition 1 6 that can be exploited to separate the foam from the liquid solution, and thereby acquire the bio-oil produced during the reaction phase. This foam can be separated from the solution in a separation zone that can be coupled in fluid communication to the production zone.

Referring to Fig. 4, according to another embodiment, a process system 40 can include a separation zone 42 down the process from production of the intermediate process composition 16, and this separation zone can be in fluid commu nication, for example, with production zone 14. Separation zone 42 for example of process system 40 can be utilized to separate the bio-oil foam from the aqueous solution upon which it resides. This separation can yield a bio-oil foam which can be collapsed later to form a liquid bio-oil. Separation zone 42 can include, for example, a configuration of weirs, condensers and/or traps that can be utilized to separate the foam from the liquid. According to example implementations, the separation zone can include at least two float traps, and in fluid communication with each of the two float traps can be a condenser, for example.

Referring next to Fig. 5, a more detailed process system is shown according to an embodiment of the disclosure, and this system 50 can include a feed tank and stirrer 52 which can be configured to receive the biomass slurry solution and coupled directly to this feed tank and stirrer can be syringe pumps 54, for example, which are coupled to horizontal oil jacketed preheaters 56 which can be maintained at about 1 60 °C. Horizontal oil jacketed preheaters 56 can have an interior diameter of about 1 /2" and can have a volu me of about 21 0 ml. Coupled to these heaters can be a stir tank reactor 58 that can be heated with electric heat, and then coupled to a tubular reactor 60 which can be a vertical oil jacketed tubular reactor maintained at about 350 °C. This reactor can have an inner diameter of about 1 /2" and a volu me of about 1 27 ml. In fluid communication with the reactor 60 can be reaction zone 1 as item 62. This can be a resistance heated zone and can be maintained at 350 °C and have a 1 /2" interior diameter and have a volume of 60 ml. In fluid communication with this zone can be resistance heated zone 2 as item 64, which can also be a zone having a 1 /2" diameter and an 80 ml volume. The reactors 60, 62 and 64 can form the herein described reaction zone, for example.

In fluid communication with reactor 64 can be an oil jacketed filter system 66 than can have an interior volu me of about 670 ml. One side of this filter can be mixtu re and blow out pot assemblies 68 and 70. In fluid commu nication with the filter can be a heat exchanger outlet 72 which can be maintained at about 60 °C to 70 °C as described in this particular embodiment, but as indicated herein can be maintained at less than 150 °C, or 110 °C or between 20 °C and 100 °C.

In direct fluid commu nication with this heat exchanger outlet can be a bypass direct pressure let down conduit 78 which provides the reacted, filtered, and cooled solution to a separation zone. This bypass system 78 can bypass oil jacketed liquid collectors 76 with valve system 74, for example. Upon providing the cooled reacted solution to a separation zone which can include elements 80-88, the foam from the formed foam intermediate process composition can be separated utilizing a system that includes a back pressure regulator 80 that can be maintained at about 20 °C as well as a float trap 82 which can be in fluid commu nication with a container 84 configu red to receive overfill from float trap 82. In fluid communication with float trap 82 can be sample collection assemblies 86 and 88, for example, which are also coupled to exhaust system 90.

Referring next to Fig. 6, a more detailed view of an example separation zone 1 00 is shown and in this separation zone, heated and reacted solution 102 can be rapidly cooled and then depressurized at section 1 04 after passing through a dome-loaded backpressure regulator 1 06 to produce the intermediate composition described herein. This intermediate composition can then be provided to an assembly that includes a condenser 11 0 in fluid communication with a float trap 108. Gaseous exhaust from condenser 11 0 can be provided to a gas recovery system 112 as well as a second float trap 114. Yields from float traps 1 08 and 114 can be provided to collector 116, for example. As shown in Fig. 7, an example depiction of the intermediate foam bio-oil is shown wherein the foam bio-oil resides above the processed solution. This intermediate solution heretofore has not been known. Utilizing the process systems of the present disclosure, mass yield to bio-oil can range from about 25 to 40 wt% on a dry ash- free biomass basis. As one example, a 20 wt% slurry solution with a mass yield of 35 wt% can produce a process product stream that is 7 wt% bio-oil with the balance being aqueous phase.