US20140318013A1

US20140318013A1 - Simultaneous reactions with gasification of biomass

Info

Publication number: US20140318013A1
Application number: US14/325,701
Authority: US
Inventors: Wayne W. Simmons; Christopher Perkins; Zoran Radojica Zovanovic
Original assignee: Sundrop Fuels Inc
Current assignee: Sundrop Fuels Inc
Priority date: 2009-06-09
Filing date: 2014-07-08
Publication date: 2014-10-30
Also published as: WO2010144554A1; US20160024403A1; WO2010144542A1; WO2010144540A1; AU2010258843A1; US8771387B2; WO2010144537A9; US9150803B2; AU2010258857A1; AU2010258852A1; US20170137284A1; US20100242352A1; AU2010258845A1; CN102460039A; US20100243961A1; WO2010144556A1; US20100249251A1; US8709112B2; WO2010144554A4; AU2010258840B2

Abstract

A method, apparatus, and system for a solar-driven chemical plant that may include a solar thermal receiver having a cavity with an inner wall, where the solar thermal receiver is aligned to absorb concentrated solar energy from one or more of 1) an array of heliostats, 2) solar concentrating dishes, and 3) any combination of the two. Some embodiments may include a solar-driven chemical reactor having multiple reactor tubes located inside the cavity of solar thermal receiver, wherein a chemical reaction driven by radiant heat occurs in the multiple reactor tubes, and wherein particles of biomass are gasified in the presence of a steam (H2O) carrier gas and methane (CH4) in a simultaneous steam reformation and steam biomass gasification reaction to produce reaction products that include hydrogen and carbon monoxide gas using the solar thermal energy from the absorbed concentrated solar energy in the multiple reactor tubes.

Description

RELATED APPLICATIONS

This Divisional application claims the benefit of priority to U.S. Pat. No. 8,771,387, issued Jul. 8, 2014, from U.S. Non-Provisional application Ser. No. 12/796,045, filed on Jun. 8, 2010, titled “SYSTEMS AND METHODS FOR SOLAR-THERMAL GASIFICATION OF BIOMASS”, which claimed priority of both U.S. Provisional Patent Application Ser. No. 61/248,282, filed Oct. 2, 2009 and entitled “VARIOUS METHODS AND APPARATUSES FOR SUN DRIVEN PROCESSES”, and U.S. Provisional Patent Application Ser. No. 61/185,492, titled “VARIOUS METHODS AND APPARATUSES FOR SOLAR-THERMAL GASIFICATION OF BIOMASS TO PRODUCE SYNTHESIS GAS” filed Jun. 9, 2009, all of which are hereby incorporated herein by reference in their entireties.

NOTICE OF COPYRIGHT

A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the software engine and its modules, as it appears in the Patent and Trademark Office Patent file or records, but otherwise reserves all copyright rights whatsoever.

FIELD OF THE INVENTION

Embodiments of the invention generally relate to systems, methods, and apparatus for refining biomass and other materials. More particularly, an aspect of an embodiment of the invention relates to solar-driven systems, methods, and apparatus for refining biomass and other materials.

BACKGROUND OF THE INVENTION

Biomass gasification is an endothermic process; energy must be put into the process to drive it forward. Typically, this is performed by partially oxidizing (burning) the biomass itself. Between 30% and 40% of the biomass must be consumed to drive the process, and at the temperatures which the process is generally limited to (for efficiency reasons), conversion is typically limited, giving still lower yields. In contrast, the proposed solar-driven biorefinery uses an external source of energy (solar) to provide the energy required for reaction, so none of the biomass need be consumed to achieve the conversion. This can result in significantly higher yields of gallons of gasoline per biomass ton than previous technologies, as the energy source being used to drive the conversion is renewable and carbon free. In addition, chemical reactors are generally engineered to operate at constant conditions around the clock.

SUMMARY OF THE INVENTION

Some embodiments relate to a solar-driven chemical plant, including a solar thermal receiver having a cavity with an inner wall, where the solar thermal receiver can be aligned to absorb concentrated solar energy from one or more of 1) an array of heliostats, 2) solar concentrating dishes, and 3) any combination of the two.
In some embodiments, a solar-driven chemical reactor having multiple reactor tubes is located inside the cavity of a solar thermal receiver. A chemical reaction driven by radiant heat occurs in the multiple reactor tubes. Particles of biomass may be gasified in the presence of a steam (H2O) carrier gas and methane (CH4) in a simultaneous steam reformation and steam biomass gasification reaction to produce reaction products that include hydrogen and carbon monoxide gas using the solar thermal energy from the absorbed concentrated solar energy in the multiple reactor tubes.
In some embodiments, a solar-driven reactor may be located inside a receiver, which is a cavity that transforms solar radiant energy into thermal energy. The receiver can include multiple reactor tubes that allow methane or natural gas and steam to pass through a fluidized bed of inert particles to cause a steam methane reaction. When natural gas is passed through a stream methane reaction occurs with a dry reforming of methane with CO2 occurs. Additionally, multiple reactors may be incorporated in the receiver.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings refer to embodiments of the invention in which:

FIG. 1 illustrates a block diagram of an embodiment of an example process flow in accordance with the systems and methods described herein;

FIG. 2 illustrates a diagram of an embodiment of an example multiple tube reactor in accordance with the systems and methods described herein;

FIG. 3 illustrates a diagram of an embodiment of an example solar tower with receivers and heliostat field in accordance with the systems and methods described herein;

FIG. 4 illustrates results from simulations of the solar-thermal gasification of biomass with methane;

FIG. 5 illustrates a diagram of an embodiment of a solar thermal receiver with gasifier tubes in accordance with the systems and methods described herein;

FIG. 6 illustrates a block diagram of an embodiment of a feed system in accordance with the systems and methods described herein;

FIG. 7 illustrates a diagram of an embodiment of a solar-driven bio-refinery in accordance with the systems and methods described herein; and

FIG. 8 illustrates a flow diagram of an embodiment of the systems and methods described herein.

While the invention is subject to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and will herein be described in detail. The invention should be understood to not be limited to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

DETAILED DISCUSSION

In the following description, numerous specific details are set forth, such as examples of specific data signals, named components, connections, number of reactor tubes, etc., in order to provide a thorough understanding of the present invention. It will be apparent, however, to one of ordinary skill in the art that the present invention may be practiced without these specific details. In other instances, well known components or methods have not been described in detail but rather in a block diagram in order to avoid unnecessarily obscuring the present invention. Further, specific numeric references such as first reactor tube, may be made. However, the specific numeric reference should not be interpreted as a literal sequential order but rather interpreted that the first reactor tube is different from a second reactor tube. Thus, the specific details set forth are merely exemplary. The specific details may be varied from and still be contemplated to be within the spirit and scope of the present invention. The term coupled is defined as meaning connected either directly to the component or indirectly to the component through another component.
In some embodiments, a solar-driven chemical reactor may have multiple reactor tubes located inside the cavity of a solar thermal receiver. Within the cavity, a chemical reaction can be driven by radiant heat. The reaction may occur in the multiple reactor tubes. Additionally, particles of biomass can be gasified in the presence of a steam (H2O) carrier gas and methane (CH4) in a simultaneous steam reformation and steam biomass gasification reaction. This can produce reaction products that include hydrogen and carbon monoxide gas using the solar thermal energy from the absorbed concentrated solar energy in the multiple reactor tubes.
In some embodiments, a solar-driven reactor is located inside a receiver, which is a cavity that transforms solar radiant energy into thermal energy. The receiver can include multiple reactor tubes allowing methane or natural gas and steam to pass through a fluidized bed of inert particles to cause a steam methane reaction. When natural gas is passed through a stream, a methane reaction occurs with a dry reforming of methane with CO2 occurs.
FIG. 1 illustrates a block diagram of an example process flow in accordance with the systems and methods described herein. Some embodiments encompass a solar-driven-biomass gasification to a liquid fuel/electrical process. The process might also include generation, chemical processing, or bio-char, for solar generated syngas derivative products or other similar technical process. In a specific example implementation the process described is a solar-driven-biomass gasification to ‘green’ liquid fuel process. In an embodiment, this process includes one or more of the following process steps.
Biomass grinding or densification, transport and offload 100 may be part of the overall process. Bales of the biomass can be compressed and densified by a compactor to facilitate transport to on-site via the densification achieved by the double compression. The bales are sized to dimensions that may, for example, fit within a standard box car size or fit within standard compactor size. The entrained-flow biomass feed system can be preceded by a grinding system equipped with mechanical cutting device and a particle classifier, such as a perforated screen or a cyclone, to control the size of the particles that are. The grinding system that has a mechanical cutting device such as a screw and set of filters with micron sized holes/screen diameter sized holes to control particle size. The mechanical screw and set of filters cooperate to grind and pulverize the stock biomass to particles to the micron sized holes of the filters, and the particles of biomass are then fed into and gasified in the solar-driven chemical reactor. The biomass may be in an embodiment non-food stock biomass. In other cases, food stock biomass or a combination of the two might also be processed.
The biomass may be stored 102. As needed, the biomass might be feed 104 into an example system or apparatus of the instant application. For example, after grinding and pulverizing the biomass to particles, the particles of biomass can be fed into and gasified in the solar-driven chemical reactor. Two or more feed line supply the particles of biomass having an average smallest dimension size between 50 microns (um) and 2000 um to the chemical reactor. An entrained gas biomass feed system uses an entrainment carrier gas to move a variety of biomass sources fed as particles into the solar driven chemical reactor.
A solar receiver and gasifier 106 may be used to break down the biomass. An example biomass gasifier design and operation can include a solar chemical reactor and solar receiver to generate components of syngas.
Quenching, gas clean up, and ash removal 108 from biomass gasifier 106 may be provided for. Some non-pilot syngas may exit the system 112. Some gasses may be a waste product, while other gasses can be compressed 114 prior to storage 118 or e.g., methanol synthesis 116. Methanol may then be stored 120 for later methanol to gasoline conversion 122.
An on-site fuel synthesis reactor that is geographically located on the same site as the chemical reactor and integrated to receive the hydrogen and carbon monoxide products from the gasification reaction can be used in some embodiments. Additionally, the on-site fuel synthesis reactor has an input to receive the hydrogen and carbon monoxide products and use them in a hydrocarbon fuel synthesis process to create a liquid hydrocarbon fuel. The on-site fuel synthesis reactor may be connected to the rest of the plant facility by a pipeline that is generally less than 15 miles in distance. The on-site fuel synthesis reactor may supply various feedback parameters and other request to the control system. For example, the on-site fuel synthesis reactor can request the control system to alter the H2 to CO ratio of the syngas coming out of the quenching and gas clean up portion of the plant and the control system will do so.
In various embodiments, synthesis gas may be fed to another technical application. Examples include a syngas to other chemical conversion process. The other chemical or chemicals produced can include liquefied fuels such as transportation liquefied fuels. In an example hydrocarbon based fuel, methanol 116 may be formed from syngas. The methanol may be further converted to gasoline or other fuels 122 and various products may be separated out from the gasoline 124 or syngas. These products, e.g., gasoline, may then be stored for later use as an energy source.
As noted, these biomass feedstock resources can include energy crops such as miscanthus and switchgrass, which are high-impact and high-yield energy crops. A biomass with low lignin content will make it easier to gasify and process in the solar gasifier.
The stock biomass, such as rice straw, rice hulls, corn stover, high biomass sorghum, switchgrass, miscanthus, bales can be double compressed to facilitate transport via the densification achieved by the double compression allowing very high loadings on the train cars.
Some embodiments use steam reforming of natural gas, sometimes referred to as steam methane reforming (SMR). SMR is a method to produce hydrogen and carbon monoxide for syngas. At high temperatures (700-1500° C.) and in the presence of, for example, a metal-based catalyst (nickel), steam reacts with methane to yield carbon monoxide and hydrogen. In some examples, natural gas may be a mixture of methane and other gases found in deposits under the earth and may contain small amounts of CO2.
Energy+CH4+H2O→CO+3H2
Additional hydrogen can be recovered by a lower-temperature gas-shift reaction with the carbon monoxide produced. The reaction is summarized by: CO+H2O→CO2+H2. However, sometimes it is beneficial to eliminate this water gas shift reaction in order to reduce the amount of CO2 present in the generated synthesis gas. The elimination of the water gas shift reaction may be accomplished by a rapid quenching of the generated products from the reactor at an exit temperature of greater than 900 centigrade to 400 degree or less within 10 seconds.
In some embodiments, carbon dioxide reforming (also known as dry reforming of methane with CO2) is a method of producing synthesis gas (mixtures of hydrogen and carbon monoxide) from the reaction of carbon dioxide with hydrocarbons such as methane.
The methane carbon dioxide reforming reaction may be represented by: CO2+CH4→2H2+2CO
In some embodiments using biomass gasification, the carbonaceous biomass material particles are fed from the entrained flow biomass feed system. The particles can undergo several distinct chemical processes of the gasification reaction prior to exiting the reactor tubes including the following. For example, initially, pyrolysis of the carbonaceous biomass particles can produce carbonaceous char and volatile components vaporized into gas products.
In some embodiments, complete gasification of the carbonaceous char including lignin fractions produce gaseous products including carbon monoxide, hydrogen, and tars as well as greater than 99% pure carbonaceous ash. Additionally, cracking of the tars, including larger hydrocarbons and aromatic compounds collectively known as tars, may occur at greater than 1000 degrees C. to produce the substantial tar destruction to less than below 50 mg/m̂3 and complete gasification of greater than 90% of the biomass particles into reaction products including hydrogen and carbon monoxide gas.
The steps of at least the complete gasification and cracking of tars starts and finishes within the residence time of the biomass particles in the reaction zone in the chemical reactor between the range of 0.01 and 5 seconds. The pyrolysis may start with a low temperature of 300 degree C. or less preheating by the carrier gas prior to entering the reactor tubes.
Solar heat+C6H10O5 (Cellulose)+H2O (Steam)->6CO+6H2
Solar heat+C10H12O3 (Lignin)+7H2O (Steam)->10CO+13H2
This thermochemical process allows conversion of the entire biomass feedstock (cellulose, hemi-cellulose, and lignin), thereby reducing the amount of ash present in reaction products and producing a flexible synthesis gas. At least two of the above reactions occur in some embodiments and generally in an embodiment all three reactions occur simultaneously in the reactor tubes.
Some embodiments may use a fixed bed of carbonaceous fuel (e.g. biomass) through which the gasification agent, e.g., steam, oxygen, air, and/or any combination, flows in a co-current configuration with the fuel downwards. Additionally, a steam blown fluidized bed gasifier may be used to produce a CO2 free gas with a high energy value. Alternatively, small particles of the biomass may be entrained in the gas streams of natural gas and/or gasification agent to mix in the biomass gasification process. Either way, the gasification zone may have steam, biomass, and potentially a methane type reactant which generates biomass gasification reactions as described herein.
The receiver generally encloses multiple reactor tubes. In an embodiment, the reactor tubes allow methane or natural gas and steam to pass through a heat transfer aid to cause a solar driven steam methane reaction to occur. The heat transfer aid is used to heat the reactant gases. The heat transfer aid may be one or more of the following located inside each reactor tube: a fluidized bed of inert particles, reticulate porous ceramic (RPC) foam, a ceramic monolith, ceramic tubes or aerogels, open structured packed rings such as Raschig rings, or gauze or wire constructed of a high temperature-resistant material. Radiation is the primary mode of heat transfer to the heat transfer aids from the reactor tube walls, and conduction, convection, or some combination of the two are secondary modes of heat transfer.
Some embodiments may add methane to the biomass. When compared to systems that do not add methane may include the following:
(1) The energy requirement of the solar reactor to produce the equivalent amount of syngas is 33% lower, thus lowering the cost of solar capital components. The energy released in going from 1:1 H2:CO syngas to a H2:CO 2:1 syngas may be contained in the gas stream (as sensible energy). Practically, it can take more solar energy in a pure biomass gasification case to get to the same amount of syngas, but only because you can't practically get the sensible heat back into the feed stream before gasification; and
(2) The above results confirm that various biomass sources (“Kentucky Bluegrass,” lignin, corn stover, sorghum) can be gasified at high temperature within seconds using a solar-heated transport tube reactor and that tar formation can be substantially reduced or eliminated.
FIG. 2 illustrates a diagram of an example multiple tube chemical reactor 200 that may be used in a solar driven system. Reactor 200 has multiple reactor tubes 202, 204, 206, 208 and a separate entrainment line may be used for each of the gasifier reactor tubes 202, 204, 206, 208 in the chemical reactor 200. This may allow for independent temperature control and balancing of the amount of particles of biomass flowing in each of the reactor tubes 202, 204, 206, 208 in the multiple tube solar driven chemical reactor 200. The particles of biomass feed can be distributed to the reactor tubes 202, 204, 206, 208 by a lock hopper rotary feed system, such as a Rotofeed® lock hopper rotary feed system. Such a system can allow for balanced feeding to individual reactor tubes 202, 204, 206, 208 and feed rate of the particles is controlled by a weight measuring metering device such as load cells. It may also allow for controlling the rotational rate of the screw or auger that can move set amounts of biomass along the axis of rotation of the auger. The auger may be located at the base of the lock hopper and can be controlled by a computerized control system such as a Programmable Logic Controller, PC, MAC, CNC, etc, to respond to feed demands of the system. In an embodiment, the computerized control system controls the feed rate of particles of stock biomass in the solar driven chemical reactor based on an amount of solar energy available indicated by sensors including temperature sensors and/or light meters.
A solar-driven bio-refinery can include a solar driven chemical reactor that has a cyclic operation rather than a continuous steady state operation. Additionally, a computerized control system with sensors may control the feed rate of the biomass material into the multiple reactor tubes with well controlled feed rates that can respond by changing the feed rate of the biomass material based on changing solar availability.
In some embodiments, a solar-driven chemical reactor can have multiple reactor tubes located inside the cavity of a solar thermal receiver. A chemical reaction can be driven by radiant heat. The reaction can occur in the multiple reactor tubes such that particles of biomass are gasified in the presence of a steam (H2O) carrier gas and methane (CH4). This may occur in a simultaneous steam reformation and steam biomass gasification reaction to produce reaction products that include hydrogen and carbon monoxide gas using the solar thermal energy from the absorbed concentrated solar energy in the multiple reactor tubes.
In some embodiments, the solar-thermal chemical reactor converts carbonaceous biomass materials into carbon monoxide and hydrogen by reacting the raw particles of biomass material with the steam (biomass gasification) and the steam. For example, this may occur with the supplemental methane steam reforming at high temperatures, 700-1500 C, with a controlled amount of steam, oxygen, air, and/or any combination, which results in the gas mixture of synthesis gas. Additionally, the steam reacts with both the biomass and the methane, but biomass and methane do not react with each other. A lower amount of steam (H2O) to carbon ratio can be better. In some embodiments, the ratio can be 1:1 to 1:4.
Additionally, a steam reforming process at a high temperature of 700-1500° C. may provide a reaction that avoids a water gas shift reaction that occurs at lower temperatures. This can avoid CO2 creation and still provide a 2:1 H2:CO ratio. For example, a reaction using methane with a steam reforming reaction may allow the reaction in the reactor to generate the correct molar ratio without a water-gas-shift reaction.
In some embodiments, CO2 may generally be formed in the reaction product gas stream as a result of the water-gas-shift reaction occurring, especially with water feed, and the WGS could be used to achieve a desired molar ratio of H2:CO=2. However, by material balancing the steam reforming of the natural gas the desired molar ratio of H2:CO=2 can be achieved without the secondary WGS, which would also generate CO2.
Energy+CO+H2O→CO2+H2 (water gas shift reaction) (2)
wherein the steam reforming reaction is generating a 3:1 H2:CO ratio and the biomass is generating a 1:1 ratio so less biomass is needed to achieve a 2:1 ratio. In some examples, less energy is needed because all of these reactions are endothermic being driven simultaneously by the concentrated solar energy.
As illustrated in FIG. 2, a control system may be used to balance the biomass gasification reaction, stream reforming reaction, and dry reforming reaction. For example, balancing gasification with the amount of concentrated solar energy available directed at the solar thermal receiver and solar chemical reactor to keep a temperature at which the chemical reactor operates high enough to maintain the molar ratio of H2 to CO ratio.
In some embodiments, a control system may be used to keep a reaction temperature high enough for substantially an entire conversion of biomass to product gases and elimination of tar products. For example, the temperature might be at least 1100-1300 degree C. This may provide a reaction that has less than 200 mg/m̂3 while keeping the temperature low enough such that the reactor tube wall temperature can be less than 1600 degrees C. so that the walls are not structurally weakened. Such temperatures may also significantly reduce receiver efficiency. Additionally, the control system may control the amount of H2O, natural gas, and biomass particles to keep the generated syngas within the desired H2:CO ratio while the chemical reaction can be substantially tar free and have less than 7% by volume CO in the generated syngas. For example, a control system may balance mass in verses available solar energy. This may provide for an endothermic reaction that consumes an amount of available energy and controls concentration and an amount of each reactant product into the chemical reactor to control the molarity and ratio of the reactants going into the reactions in order to control the products coming out of the reactions.
Some embodiments can include a synthesis reactor that may use the resultant hydrogen molecules and the carbon monoxide molecules (syngas) in the hydrocarbon fuel synthesis process. This can be catalytically reformed using known processes to produce chemicals, including liquid hydrocarbon fuels. For example, fuels such as syngas can be produced and may also be used to drive a gas turbine to produce electricity via an efficient gas turbine or it can be catalytically reformed to valuable chemicals or liquid fuels. In some embodiments, one or more tubes may be graphite reaction tube with an external SiC coating operating at up to 1500 degree C.
FIG. 3 illustrates a diagram of an example solar tower 300 with receivers 302 and heliostat field 304. In some embodiments solar tower 300 may be used to form a solar-driven bio-refinery with a pneumatic biomass feed system. The feed system can be feedstock flexible via, for example, particle size control of the biomass.
A chemical reactor 306 receives concentrated solar thermal energy from an array of heliostats 304. The chemical reactor 306 can be, for example, a multiple reactor tube, downdraft, solar driven, chemical reactor, which receives concentrated solar thermal energy from the array of heliostats 304.
A solar tower 300 may form a portion of a solar-driven bio-refinery that may also include a biomass feed system that has balancing of the feed lines to each of the reactor tubes in a multiple tube chemical reactor. For example, biomass may be fed to the solar reactor in an operation including three parts: biomass transport and preparation for feeding to the solar tower reactor, biomass transport to the top of the, e.g., 500+ foot tower, and distribution into the specific downdraft tubes of the reactor. The distribution may be performed via multiple stages.
In some embodiments, a solar-driven chemical plant can include a solar thermal receiver having a cavity with an inner wall, where the solar thermal receiver is aligned to absorb concentrated solar energy from one or more of 1) an array of heliostats, 2) solar concentrating dishes, and 3) any combination of the two. The solar driven chemical reactor can include a downdraft geometry with the multiple reactor tubes in a vertical orientation and are located inside the solar thermal receiver.
In some embodiments, the concentrated solar energy may interact with water to convert the water to steam, supply the energy for the reactant gases, and/or interact with other sources to provide heat delivery mechanisms for the heat for the gasification process of the biomass. Additionally, the solar energy may be transferred to the walls of the receiver and walls of the reactor tubes such that the heat is radiantly transferred to the biomass particles. The biomass particles have a lot of surface area to absorb the radiant heat and the particles transfer that heat to the methane molecules.
FIG. 4 illustrate results from simulations of the solar-thermal gasification of biomass with methane. Simulations were carried out for biomass gasification, with and without additive methane, to evaluate the impact of supplemental methane on the solar-thermal process.
As illustrated in FIG. 4 the reactions of an example biomass to syngas may be:
Solar heat+C6H10O5 (Cellulose)+H2O (Steam)->6CO+6H2 (1)
Solar heat+C10H12O3 (Lignin)+7H2O (Steam)->10CO+13H2 (2)
Solar heat+CH4 (Methane)+H2O (Steam)->CO+3H2 (3)

- Synthesis gas=nCO+mH2, where n and m variable amounts of moles.

Even if some CO2 is present in the natural gas consisting mainly of the methane above, the CO2 and CH4 react with the high heat via dry reforming to produce hydrogen and carbon monoxide.
CH4+CO2==>2H2+2CO (4)
The methane addition in FIG. 4 eliminates the water gas shift reaction in reactions without methane in order to get to the desired molar H2/CO=2. Note, when operating the reforming process with concentrated solar radiation, the solar energy is converted into chemical energy and therefore, it increases the energy content of the gas.
An example biomass to syngas reaction without methane may be:
Solar heat+C6H10O5 (Cellulose)+H2O (Steam)->6CO+6H2 (1)
Solar heat+C10H12O3 (Lignin)+7H2O (Steam)->10CO+13H2 (2)
Solar heat+CO+H2O (Steam)<-->CO2+H2 (3)

- Synthesis gas=nCO+mH2, where n and m variable amounts of moles.

FIG. 5 illustrates a diagram of a solar thermal receiver 500 with gasifier tubes 502. Solar thermal receiver 500 can form a portion of a solar-driven bio-refinery in accordance with the systems and methods described herein. The solar-driven bio-refinery can include a solar driven chemical reactor, a solar thermal receiver such as receiver 500, or both. In some embodiments, solar thermal receiver 500 can be a multiple reaction tube downdraft solar thermal receiver as well as solar driven chemical reactor. Additionally, the feed system may feed biomass particles into the multiple reaction tubes 502, in which the particles of biomass may be gasified in the presence of steam at a temperature exceeding 950 degrees C. from an exit of a gasification reaction zone of the reactor tubes.
In some embodiments, a solar-driven chemical plant may use methane from natural gas. Additionally, the biomass and natural gas may be co-fed with steam heated by the solar energy to dry reform heated CO2 with CH4 the methane with the CO2 into syngas, such that, even if some CO2 is present in the natural gas consisting mainly of methane, the CO2 and CH4 react with the high heat via dry reforming to produce hydrogen and carbon monoxide substantially free of CO2.
For example, the reaction may include:
Energy from H2O+CH4+CO2==>2H2+2CO+H2O.
In some cases, small amounts of CO2 in the natural gas can react with methane to produce additional synthesis gas. Additionally, thermodynamics indicate that a CO2-free syngas can be produced when biomass and methane are co-fed with steam at 1200 degree C. in stoichiometric proportions to produce a molar ratio of H2:CO=2 (two moles of hydrogen gas-carbon monoxide per liter). The majority of the reduction of carbon dioxide present in the generated syngas from the reactor comes from that concentrated solar energy, which can externally drive the steam reforming of the methane and biomass gasification of the carbon in the biomass reactions. Additional CO2 reduction may occur by rapid quenching of the reactor products to avoid the water gas shift reaction and a dry reforming of methane reaction simultaneous with the steam reforming to consume CO2 present and/or generated during the reactions in the reactor tubes. Also the 2:1 H2:CO molar ratio can be in a range from 2.0 to 2.8.
In some examples, when natural gas is used, it is possible for the plant to produce 5 to 10% of the syngas on demand via oxidation of NG using high temperature oxidizers (O2, not air) that essentially fits into a tee (T) just before the downstream syngas catalytic reforming synthesis. Thus, in a partial oxidation system, the system can have a catalytic oxidizer. A reaction that may take place is: CH4+0.5O2=CO+2H2 (partial oxidation reforming). Additionally, this supplemental source may be used to raise the amount of H2 present in H2:CO syngas. This process may be run in parallel with the main solar driven reactor.
In some examples, the co-feeding of methane, potentially in natural gas, with water and biomass, produces a CO2-free synthesis gas. In such an example CO2 levels may be less than 7% (by volume) of the syngas stream and have a desirable molar ratio of H2:CO=2. Such a reaction may also avoid a water-gas-shift reaction that may otherwise produce CO2. Tar formation may also be avoided at an approximately 1100-1300 degree C. operating temperature. In some examples, use of biomass carbon can produce CO2-free syngas. Substantially 100% of the biomass carbon may produce the useful CO component of syngas. Additionally, with CO2 levels at less than 7% (by volume) of the syngas stream, a downstream amine train to remove CO2 prior to catalytic reforming of the syngas might no longer be necessary. Operation in temperature regimes where tar may be eliminated and reaction can be extremely fast due to radiation heat transfer may be used.
In some embodiments, co-feeding of methane (CH4) with the biomass may be used such that particles of biomass facilitate the radiation heat transfer. This can raise the temperature in the tubes to a level to reform the methane and cause the biomass gasification reaction. In other systems, separate streams mighty be required and a separate solid particle addition might be needed to accomplish this such that the conversion of methane is combined with biomass gasification using steam heated by the solar energy to generate the synthesis gas.
In some embodiments, a solar-driven reactor may be located inside a receiver. A receiver is a cavity that transforms solar radiant energy into thermal energy. The receiver can comprise multiple reactor tubes. The reactor tubes may allow methane or natural gas and steam to pass through a fluidized bed of inert particles to cause a steam methane reaction. Natural gas can be passed through a stream such that a methane reaction occurs with a dry reforming of methane with CO2 occurs. Additionally, multiple reactors can be incorporated in a receiver. To increase the size of a plant, more receivers may be added. Each reactor may be a downdraft tube.
FIG. 6 illustrates a block diagram of a feed system 600. The grinding system 603 has a mechanical cutting device used to grind the biomass into primary particles, which are to be fed into the solar driven chemical reactor. The grinding system supplies primary particles that have an average smallest dimension size between 200 microns (um) and 2000 um, with a general range of between 500 um and 1000 um to a lock hopper system 604 with a standard belt conveyer. The biomass particles are then fed across a pressure boundary into a pressurized entrainment gas for feeding into in the solar driven chemical reactor. The feeding vessel may use an Auger/Screw feeder or an airlock-type rotational solids feeding/rate metering device.
The entrainment-flow biomass feed system 600 can include a pressurized lock hopper 604 that feeds the biomass to a rotating screw conveyor 602 and a metering device and then into an entrainment gas pipe at the lock hopper exit 606. A flow splitter distributes the particles of biomass into multiple entrainment gas lines to feed at least two or more of the multiple reactor tubes making up the solar driven chemical reactor. The entrainment gas for the pneumatic biomass feed system may be a pressurized dry steam generated from waste heat recovered from either 1) the methanol/Methanol-To-Gasoline (MTG) units in the hydrocarbon fuel synthesis process or 2) the products from the gasification reaction in the solar driven chemical reactor. The entrainment gas may also be CO2, natural gas, an inert gas, steam generated in any fashion, or other similar entrainment gas.
Additionally, an entrained-flow biomass feed system having one or more feed lines to feed the biomass particles into the multiple reactor tubes, in which a separate entrainment line and metering device of the entrained-flow biomass feed system is used for each of the gasifier reactor tubes in the chemical reactor. This may allow for balancing of 1) amount of particles of biomass flowing through the feed line to each reactor tube to 2) an amount of solar energy available for that reactor tube in the multiple tube solar driven chemical reactor. Feed rate of the biomass particles can be controlled by a metering device and controlling a rotational rate of a screw 602 at a base of the lock hopper 604, which responds to a feed demand signal received from the control system.
Thus, control of the rotational rate of the screw or auger 602 can move set amounts of biomass along the axis of rotation of the auger 602. The auger 602 may be located at the base of the lock hopper 604 and can be controlled by a control system to respond to feed demand of the system. As discussed, the control system controls the feed rate of particles of biomass in the solar driven chemical reactor based on an amount of solar energy available indicated by sensors including temperature sensors and/or light meters.
In some embodiments, additional biomass may be used in a biomass methane gasification reformation as compared to biomass gasification. For example, in some embodiments (about 2.5×) to produce a given mass of the required H2/CO=2 molar ratio. In this example embodiment, the reaction is substituting carbon in the natural gas for carbon sourced from the biomass carbon. In addition, there may be excess water in the reactor for the straight biomass gasification route. Hence, reactor materials may be oxidation resistant and steam resistant.
Some embodiments include an entraining gas biomass feed system that uses an entrainment carrier gas comprising natural gas, steam, oxygen, air, and/or any combination of these and supplies a variety of feed stock biomass sources fed as particles into the solar driven chemical reactor. The entrainment carrier gas can be natural gas, steam, or any combination of natural gas and steam. Additionally, the entraining gas biomass feed system may receive ground and pulverized biomass with a particle size that is between 150 and 300 microns. The particle size has an average smallest dimension size between 200 microns um and 2000 um in diameter, such to fit through the holes in the filters, with a general range of between 500 um and 1000 um. Similar particle size, and use of the multiple tube design with the external concentrated solar thermal energy driving the biomass gasification reaction, steam reforming reaction, and dry reforming reaction may be used to allow the process to be feedstock flexible, with no major equipment redesign required to change feedstocks.
In some embodiments, two or more types of biomass may be fed. These biomasses may be fed individually or in combinational mixtures, from the group consisting of cellulose, lignin, pine sawdust, rice straw, corn stover, switch grass, energy crops, source separated green wastes, sorghum, Algae, and other similar biomass sources. This may be done as long as a few parameters are controlled, such as particle size of the stock biomass and operating temperature range of the reactor tubes.
FIG. 7 illustrates a diagram of a solar-driven bio-refinery 700 in accordance with the systems and methods described herein. An array of heliostats 702 can be used to focus light onto a window 704 of a reactor 706. In reactor 706 biomass particles can be reduced to syngas, which in turn can be synthesized into liquid fuel in liquid fuel synthesizer 708.
For example, in some embodiments, an on-site fuel synthesis reactor 708 may receive the hydrogen and carbon monoxide products from the gasification reaction and use the hydrogen and carbon monoxide products in a hydrocarbon fuel synthesis process to create a liquid hydrocarbon fuel. The fuel synthesis reactor 706 may be geographically located on the same site as the chemical reactor and integrated into the process to utilize the hydrogen and carbon monoxide products from the gasification reaction.
In some embodiments, the addition of methane (CH4 i.e. primary constituent in natural gas) can be used at the solar-thermal operating temperatures to stretch the use of biomass carbon to produce essentially CO2-free syngas (at less than CO2 levels at less than 7% (by volume) of the syngas stream) via dry reforming of methane with the carbon dioxide. The biomass and the supplemental natural gas are rapidly gasified and reformed with steam, and all are heated by the solar energy concentrated into the solar-thermal gasifier, which primarily uses radiant heat to drive the chemical reaction.
In some embodiments, an on-site chemical plant that is geographically located on the same site as the chemical reactor and integrated to receive the hydrogen and carbon monoxide products from the gasification reaction may be used. The on-site chemical plant can have an input to receive the hydrogen and carbon monoxide products and use them in a hydrocarbon fuel synthesis process to create a liquid hydrocarbon fuel, or other chemical product.
Additionally, down stream of the reactor, one or more knock out drums may exist to remove excess water from the generated syngas. For biomass/methane, less than an amount of 2-5% of CO2 is formed.
FIG. 8 illustrates a flow diagram in accordance with the systems and methods described herein. In step 800, biomass grinding can occur. Equipment generally used for grinding biomass includes impact mills (e.g. hammer mills), attrition mills, and kinetic disintegration mills (e.g. flail mills). A hammer mill system can be used to grind the bales (loaded by conveyer) into primary particles, which are to be fed into the solar thermal gasifier. The re-ground particles have an average size between 500 um and 1000 um, and are loaded into the lock hopper system with a standard belt conveyer.
In step 802 biomass feeding occurs. In some embodiments, high pressure feeding may be used. High pressure feeding of solids of biomass with gasification at pressure may reduce capital cost due to the ability to use smaller compressors in some such systems. Additionally, operating cost may be reduced because energy for pressurizing carrier gas comes from the sun, as opposed to from electricity. The lock hopper system can feed the reactor processes at pressure. For example, the feeding system can entrain the biomass materials in steam at high pressure, successfully disengage the particulates in the cyclone system, and distribute flow appropriately to the reactor tubes.
In step 804, gasification occurs. For example, in some embodiments, concentrated solar thermal energy drives gasification of the particles of the stock biomass to generate at least hydrogen and carbon monoxide products from the gasification reaction.
In step 806 fuel synthesis occurs. An on-site fuel synthesis reactor can receive the hydrogen and carbon monoxide products from the gasification reaction and use the hydrogen and carbon monoxide products in a hydrocarbon fuel synthesis process to create a liquid hydrocarbon fuel. The fuel synthesis reactor may be geographically located on the same site as the chemical reactor and integrated into the process to utilize the hydrogen and carbon monoxide products from the gasification reaction.

Claims

1-20. (canceled)

21. A method of producing chemicals in an integrated plant to produce a fuel, comprising:

providing a chemical reactor having multiple reactor tubes located inside a cavity of a thermal receiver, wherein a simultaneous biomass gasification reaction and steam methane reforming reaction is driven by radiant heat, wherein the simultaneous chemical reaction occurs in the multiple reactor tubes in the chemical reactor, wherein particles of biomass are gasified in a presence of steam to produce products that include hydrogen and carbon monoxide gas using thermal energy from the radiant heat, where the products from the biomass gasification reaction that include hydrogen and carbon monoxide gas are mixed with products from the steam methane reforming reaction, where the products from both reactions are then commonly fed through a first input into a first on-site fuel synthesis reactor, which is configured to produce the fuel;

supplying the particles of biomass from forestry wastes, forestry thinnings, or another woody source from a feed system to the multiple reactor tubes; and

causing the simultaneous steam methane reformation reaction and biomass gasification reaction to produce reaction products that include the hydrogen and carbon monoxide gas using the thermal energy in the multiple reactor tubes, where the feed system, the chemical reactor, and the first on-site fuel synthesis reactor are part of the integrated plant.

22. The method of claim 21, further comprising:

controlling operating parameters for the simultaneous biomass gasification reaction and the steam methane reformation at high temperatures between 700-1500 degrees C., with a controlled amount of i) steam, ii) particles of biomass, iii) methane, and iv) any combination these three, which results in a gas mixture of synthesis gas that contains the products from both reactions supplied to the first input into the first on-site fuel synthesis reactor.

23. The method of claim 21, further comprising:

where the methane in the steam methane reformation reaction is provided from natural gas along with any CO2 contained in the natural gas;

co-feeding the particles of biomass and the natural gas with steam heated by the radiant heat energy to dry reform the methane with CO2 either contained within the natural gas or fed as a separate feedstock, such that even if some CO2 is present in the natural gas, the CO2 and methane react with in a presence of high heat greater than 750 degrees C. via dry reforming to produce hydrogen and carbon monoxide gas from the steam methane reforming reaction; and

wherein a synthesis gas having less than 7% of CO2 by volume syngas is produced when the particles of biomass and the methane are co-fed with steam at temperature ranges of 750-1300 degrees C. in the stoichiometric proportions to produce a molar H2:CO ratio of H2:CO in a range from 1.0 to 3.0.

24. The method of claim 21, further comprising:

co-feeding of the methane in natural gas form with the steam and the particles of biomass within the multiple reactor tubes to produce a low CO2 synthesis gas with CO2 levels at less than 7% by volume in the syngas stream and having a molar H2:CO ratio in a range between 2.0-3.0; and

wherein tar formation in the products from both reactions is mitigated to less than 200 mg/m̂3 by the radiant heat keeping an approximately 1100-1300 degrees C. operating temperature in the chemical reactor and by the multiple reactor tubes separating the heat source from the particles of biomass.

25. The method of claim 21, further comprising:

where the first fuel synthesis reactor is geographically located on the same site as the chemical reactor and the first fuel synthesis reactor is a methanol synthesis reactor, wherein the methanol synthesis reactor is configured to create methanol, and a second fuel synthesis reactor connected downstream of the first fuel synthesis reactor is configured to receive the methanol from the methanol synthesis reactor, where the second fuel synthesis reactor is configured to produce a liquid hydrocarbon chemical product, where the methanol synthesis reactor and the second fuel synthesis reactor are both geographically located on the same site as the chemical reactor and form part of the integrated plant.

26. The method of claim 21, further comprising:

wherein the thermal receiver having the inner cavity has a geometric arrangement specifically shaped and configured with the multiple reactor tubes to exchange the radiant energy to create an oven effect, which gives rise to a fairly uniform temperature profile along the reactor tubes to heat chemical reactants to produce a substantial tar destruction to less than below 50 mg/m̂3 in the reaction products that include the hydrogen and carbon monoxide gas.

27. The method of claim 21, further comprising:

where the feed system is an entraining gas biomass feed system that uses an entrainment carrier gas comprising natural gas, steam, air, and/or any combination of these and supplies the particles of biomass into the chemical reactor; and

controlling a particle size distribution of the particles of biomass to have an average smallest dimension the particles of equal to or less than 2000 um, and where the chemical reactor and feed system of the integrated plant are configured to be feedstock flexible, with no major equipment redesign required to change biomass feedstock via use of a simple multiple reactor tube design with radiant heat driving the biomass gasification reaction and control over the particle size distribution of the particles of biomass.

28. The method of claim 21, further comprising:

oxidizing natural gas to produce a syngas with a ratio of equal to greater than a 2:1 H2:CO ratio on demand that is to be combined with the hydrogen and carbon monoxide products from the chemical reactor to raise an amount of H2 present in the products from both reactions to a desired H2:CO ratio for methanol synthesis in the first on-site fuel synthesis reactor.

29. The method of claim 21, further comprising:

passing the methane and steam to pass through a fluidized bed of inert particles to cause the steam methane reformation reaction.

30. The integrated plant of claim 21, further comprising:

controlling temperature in the thermal receiver by factoring an amount of particles of biomass and methane feed rate against available energy from the heat source such that the temperature in the thermal receiver is maintained at a desired set point in the range of 800-1600 degrees C. by a balance of energy consumed by the simultaneous chemical reaction and reactant sensible heat, and thermal losses from the thermal receiver by radiation, convection and/or conduction;

keeping the temperature high enough at 1000-1300 degrees C. for substantially an entire conversion of the particles of biomass to product gases and causes an elimination of tar products to a concentration of less than 200 mg/m̂3; and

keeping the temperature low enough, <1600 degrees C., for the walls of the multiple reactor tubes to not structurally weaken or significantly reduce thermal receiver efficiency, and to control the amounts of steam, methane, and the particles of biomass to keep a generated syngas within a desired H2:CO ratio, where a control system for the first on-site fuel synthesis reactor is configured to communicate with the control system to alter the desired H2 to CO ratio of the products coming out of the chemical reactor.

31. An integrated plant to produce a fuel, comprising:

a chemical reactor having multiple reactor tubes located inside a cavity of a thermal receiver,

a feed system of particles of biomass connected via two or more feed lines to the chemical reactor to supply the particles of biomass to the chemical reactor, where the particles of biomass are generated from forestry wastes, forestry thinnings, or other woody source,

a heat source thermally coupled to the chemical reactor, wherein a simultaneous biomass gasification reaction and steam methane reforming reaction is driven by radiant heat, and the simultaneous chemical reaction occurs in the multiple reactor tubes in the chemical reactor, and wherein particles of biomass are gasified in the presence of steam to produce products that include hydrogen and carbon monoxide gas using thermal energy from the radiant heat in the multiple reactor tubes, where the products from the biomass gasification reaction that include hydrogen and carbon monoxide gas are mixed with products from the steam methane reforming reaction, where the products from both reactions are then commonly fed through a first input into a first on-site fuel synthesis reactor, which is configured to produce the fuel; and

wherein the multiple tubes are configured with dimensions and material selection to cause the simultaneous steam methane reformation and biomass gasification reaction to produce reaction products that include the hydrogen and carbon monoxide gas using the thermal energy in the multiple reactor tubes, where the feed system, the chemical reactor and the first on-site fuel synthesis reactor are part of the integrated plant.

32. The integrated plant of claim 31, further comprising:

wherein the thermal receiver has cavity walls and is aligned to absorb energy from the heat source; and

a control system for the chemical reactor to control operating parameters for the simultaneous biomass gasification reaction and the steam methane reformation at high temperatures between 700-1500 degrees C., with a controlled amount of steam, and methane, and any combination, which results in a gas mixture of synthesis gas that contains the products from both reactions supplied to the first input into the first on-site fuel synthesis reactor.

33. The integrated plant of claim 31, further comprising:

a natural gas source in fluid communication with the chemical reactor, where the methane in the steam methane reformation reaction is provided from natural gas along with any CO2 contained in the natural gas;

where the chemical reactor is configured to co-feed the particles of biomass and the natural gas with steam heated by the radiant heat energy to dry reform the methane with CO2 either contained within the natural gas or fed as a separate feedstock, such that even if some CO2 is present in the natural gas, the CO2 and methane react with in a presence of high heat greater than 700 degrees C. via dry reforming to produce hydrogen and carbon monoxide gas from the steam methane reforming reaction; and

a control system configured to ensure the first input into the first on-site fuel receives the products from both reactions having less than 7% of CO2 by volume syngas, where the control system controls an amount and when the particles of biomass and the methane are co-fed with steam at temperature ranges of 750-1300 degrees C. in the stoichiometric proportions to produce a molar H2:CO ratio of H2:CO in a range from 1.0 to 3.0.

34. The integrated plant of claim 31, further comprising:

wherein within the multiple reactor tubes the co-feeding of the methane in natural gas form with the steam and the particles of biomass occurs to produce a low CO2 synthesis gas with CO2 levels at less than 7% by volume in the syngas stream and having a molar H2:CO ratio in a range between 2.0-3.0, as well as avoids a water-gas-shift reaction that may otherwise produce CO2; and

35. The integrated plant of claim 31, further comprising:

36. The integrated plant of claim 31, further comprising:

37. The integrated plant of claim 31, further comprising:

where the feed system is an entraining gas biomass feed system that uses an entrainment carrier gas comprising natural gas, steam, air, and/or any combination of these and supplies the particles of biomass into the chemical reactor;

a feed vessel containing the particles of biomass, which supplies the particles of biomass via the two or more feed lines into the chemical reactor; and

wherein a particle size distribution of the particles of biomass has an average smallest dimension the particles of equal to or less than 2000 um, and where the chemical reactor and feed system of the integrated plant are configured to be feedstock flexible, with no major equipment redesign required to change biomass feedstock via use of a simple multiple reactor tube design with radiant heat driving the biomass gasification reaction and control over the particle size distribution of the particles of biomass.

38. The integrated plant of claim 31, further comprising:

one or more high temperature oxidizers configured to oxidize natural gas to produce a syngas with a ratio of equal to greater than a 2:1 H2:CO ratio on demand that is to be combined with the hydrogen and carbon monoxide products from the chemical reactor to raise an amount of H2 present in the products from both reactions to a desired H2:CO ratio for methanol synthesis in the first on-site fuel synthesis reactor.

39. The integrated plant of claim 31, further comprising:

wherein the thermal receiver includes the multiple reactor tubes configured to allow the methane and steam to pass through a fluidized bed of inert particles to cause the steam methane reformation reaction.

40. The integrated plant of claim 31, further comprising:

a control system configured to control temperature in the thermal receiver by factoring an amount of particles of biomass and methane feed rate against available energy from the heat source such that the temperature in the thermal receiver is maintained at a desired set point in the range of 800-1600 degrees C. by a balance of energy consumed by the simultaneous chemical reaction and reactant sensible heat, and thermal losses from the thermal receiver by radiation, convection and/or conduction; and

wherein the control system 1) keeps the temperature high enough at 1000-1300 degrees C. for substantially an entire conversion of the particles of biomass to product gases and causes an elimination of tar products to a concentration of less than 200 mg/m̂3, and 2) keeps the temperature low enough (<1600 degrees C.) for the walls of the multiple reactor tubes to not structurally weaken or significantly reduce thermal receiver efficiency, and to control the amounts of steam, methane, and the particles of biomass to keep a generated syngas within a desired H2:CO ratio, where a control system for the first on-site fuel synthesis reactor is configured to communicate with the control system to alter the desired H2 to CO ratio of the products coming out of the chemical reactor.