Method for treating carbonaceous material and apparatus therefor

Abstract

To provide a method for treating a carbonaceous material.SOLUTION: A method includes the steps of: feeding a carbonaceous material into a reactor; feeding a catalyst into the reactor; and treating the carbonaceous material at a relatively low temperature within the reactor to decompose the carbonaceous material into a base compound.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure generally relates to a method for treating carbonaceous materials, particularly materials containing halide elements, and more particularly to a method for treating carbonaceous materials in a reactor and related systems, the method including a low-temperature pyrolysis reaction involving in-situ or separate-step catalytic partial oxidation and a method for recovering at least a portion of the products of the method.

Background Art

[0002] Pyrolysis reactors provide thermochemical decomposition of organic materials at high temperatures in the absence of oxygen or halogens. Pyrolysis involves simultaneous changes in chemical composition and physical phase and is irreversible. Reactor design can use direct, indirect, or a combination of both as two main heat transfer modes to provide energy for thermochemical conversion. Indirect heating relies on a metal heat transfer surface, which is a limiting factor when scaling up this type of device, and as a result, multiple units are operated in parallel to achieve a reasonable plant throughput. This results in high capital costs, high maintenance costs, high operating costs, and low thermal efficiency. Examples of this type of equipment are rotary kilns, drum kilns, retorts (fixed beds), augers, melters, and vacuum reactors. Some novel indirect heating methods include electricity (radiation and / or conduction), plasma, microwaves, and solar energy. These methods typically require inexpensive electricity and an inert carrier gas. Furthermore, these complex heating methods have high operating and capital costs.

[0003] Direct heat transfer can be achieved using a flow of hot spent combustion gas or recycle of an inert gas (usually syngas). Using hot spent combustion gas results in significant dilution of the syngas with carbon dioxide and nitrogen, and as a result, a very low-calorie syngas is obtained. This has little utility value as once cooled, it does not have sufficient fuel value for self-combustion. Using recycle of syngas has the drawback that it requires the off-gas cleaning system to be much larger to handle the extra recycle gas volume and the gas has to be recompressed. Further, the pyrolysis off-gas (raw syngas) has to be wet scrubbed (cooled) to condense and remove tar and oil. Thus, the recycle gas has to be recompressed and reheated from about 80°C to +800°C per cycle, resulting in low thermal efficiency and high operating costs. Further, the recycled syngas has to be reheated using an indirect heat exchanger, resulting in high capital costs. A high gas flow through the pyrolysis reactor reduces the yield of biochar. Examples of this technology are fixed bed retorts, multi-hearth furnaces, fluid beds and entrained flow reactors.

[0004] The above reference to the background art is not an admission that the art forms part of the common general knowledge of a person skilled in the art. The above reference is also not intended to limit the actuators, methods of manufacturing actuators, and their application to compositions as disclosed herein.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] The present disclosure generally relates to the treatment of carbonaceous materials including contaminated organic materials, PFAS, and other waste materials containing halide elements. It should be understood that the disclosed methods are also applicable to other carbonaceous materials.

[0006] In some forms, the method is utilized to process organic materials using pyrolysis to break down the organic material feedstock into base components. In some forms, the method is the production of a processed product such as carbon It is a low-cost treatment of organic materials that includes some recovery of products or outputs. This method can be used to treat a wide range of organic compositions such as PFAS, PVC, lignite, animal waste, wood chips, straw, and biosolids. In some forms of the method, the method results in the treatment of waste / contaminants (such as PFAS, biosolids, PVC, etc.), heat recovery, energy recovery, clean syngas recovery, biochar recovery, water recovery, hydrogen recovery, and soil recovery.

[0007] However, it will be understood that this method is not limited to these applications or outputs. This method can handle the variability of feedstocks and can be applied over a wide range of conditions.

Means for Solving the Problem

[0008] According to a first aspect, a method for treating a carbonaceous material is disclosed, the method including the steps of sending the carbonaceous material to a reactor, sending a catalyst to the reactor, and treating the carbonaceous material at a relatively low temperature in the reactor to liberate and decompose organic compounds within the carbonaceous material.

[0009] In some forms, the method includes sending a catalyst in the form of hot sand. In some forms the sand includes loose or fine particulate material. In some forms, the hot sand or catalyst is sent at a plurality of spaced points along the length of the reactor. In some forms, the hot sand or catalyst is mechanically mixed with the feedstock.

[0010] In some forms, the catalyst includes an iron oxide-based catalyst. In some forms, the catalyst includes ilmenite. The method can include the in-situ use of an absorbent with a heat transfer medium catalyst that is tuned to capture halide elements for the purpose of forming more stable compounds and enabling safe disposal. This example is calcium oxide that reacts in the presence of gaseous chlorine to form very stable solid calcium chloride.

[0011] In some forms, the method includes recovering at least a portion of the catalyst from the output material and regenerating the catalyst for reuse in the method.

[0012] In some forms, the reactor method yields an output material. In some forms the output includes a biocchar, and in some forms the biocchar may be separated from the output material.

[0013] In some forms, the method is configured to return some or all of the catalyst and some or all of the carbon or fuel to the reaction chamber.

[0014] In some forms, the method includes sending syngas to a secondary reactor. The secondary reaction stage is provided to ensure further decomposition of the liberated gaseous organic compounds, whereby the offgas from the first stage is contacted with fresh regenerated catalyst. The partial oxidation of these components is sometimes called gasification and can occur at a higher temperature than the pyrolysis of the first stage, forming a clean non-polluting syngas stream.

[0015] In some forms, a method is disclosed for processing multiple streams of carbonaceous material in a parallel process using a single fluidized bed.

[0016] Without excluding any other forms that may fall within the scope of the methods and apparatuses described, specific embodiments are described herein by way of example only, with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017]

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DETAILED DESCRIPTION OF THE INVENTION

[0018] According to a first aspect, a method for treating a carbonaceous material is disclosed, the method comprising the steps of sending the carbonaceous material to a reactor, sending a catalyst to the reactor, and treating the carbonaceous material at a relatively low temperature in the reactor to decompose the carbonaceous material into a base compound.

[0019] Some forms of the method are based on direct heat transfer using a high-temperature solid. In some forms, a free-flowing sand-like material is heated separately and then mixed with biomass or feedstock in a pyrolysis reactor. This method can have the advantage of supplying heat indirectly (but directly to the biomass) from a heat source without diluting the syngas with nitrogen or carbon dioxide.

[0020] In some forms, the method further comprises the steps of recovering at least a portion of the catalyst from the output material and regenerating the catalyst for reuse in the method.

[0021] In some forms, the output material includes biochar.

[0022] In some forms, the catalyst includes an iron oxide-based catalyst. In some forms, the catalyst includes ilmenite.

[0023] In some forms, the catalyst or heat transfer medium can contain reaction components or absorbents. In some forms, the absorbent includes calcium oxide.

[0024] In some forms, the carbonaceous material includes 1 and poly-fluoroalkyl compounds In some forms, the carbonaceous material includes a halide or a halogenated compound contaminated organic material.

[0025] In some forms, the method further includes a step of recovering syngas from the output material of the reactor treatment.

[0026] Also disclosed is a method for treating a carbonaceous material, the method including treating the carbonaceous material in a low-temperature reactor in a reducing environment using an iron-based catalyst.

[0027] Further disclosed is an apparatus for treating a carbonaceous material, the apparatus including a reactor vessel for treating the carbonaceous material, an outlet from the reactor vessel for moving an output material including biocchar and catalyst out of the reactor vessel, a separation vessel for separating at least a portion of the biocchar and catalyst, at least one outlet for sending the biocchar to a biocchar vessel, at least one outlet for sending at least a portion of the catalyst and any alternative material to a combustor, a fluidized bed for receiving at least a portion of the catalyst and any alternative material, and a return for sending at least a portion of the catalyst back to the reactor.

[0028] The carbonaceous material can include, for example, contaminated organic materials such as GAC, or other waste organic materials such as biomass, organic waste, biosolids from wastewater treatment, waste streams from meat processing plants or other organic operations, contaminated soil, and fossil fuel waste. In some forms, the contaminant is PFAS.

[0029] In some forms, the method enables the secondary gasification of oils and tars generated from pyrolysis in another container heated with hot sand. This can have the advantage of having no wasteful waste streams or resulting in no "bad odors".

[0030] Heat transfer is achieved using a sand-like material that is recycled between a free-flowing solid material, i.e., a fluidized bed at 950 °C or similar temperature, and a pyrolysis unit operating at an outlet temperature of about 500 °C. An example of a heat transfer medium that can be used is ilmenite.

[0031] Using this heat transfer method, since it is not diluted with atmospheric nitrogen, high-calorie synthesis gas can be co-produced. The raw synthesis gas from pyrolysis is "superheated" in a separate vessel using additional hot sand to decompose (gasify) residual tar and oil, or to further decompose the halide organic compounds released in the first stage, thus producing clean synthesis gas without any normal tar, oil or hazardous waste for disposal or treatment. This also reduces common plant odors and fugitive emissions. Approximately 30% of the synthesis gas is used to heat the fluidized bed, and the excess is available for heating or power generation.

[0032] The waste heat from the fluidized bed is used to dry the input biomass feedstock, thereby achieving a high overall thermal efficiency. The final off-gas is wet scrubbed to remove particulate matter and water-soluble components.

[0033] The reactor may include multiple injection points for hot sand. This can have the advantage of providing controlled low-rate auto-pyrolysis that provides maximum temperature control for char, improved synthesis gas yields, and pollutant removal. In one form, a hot sand distribution assembly is used, which supplies hot sand to a series of spaced inputs within the reactor. The hot sand distribution assembly may include a single hot sand input and multiple outputs that can be controlled by adding sufficient fluidizing air to reduce the density in the riser chamber and move the hot sand into the multiple outputs.

[0034] In some forms, the reactor can use heat treatment of a catalytic sand material or mineral to provide additional product streams.

[0035] In some forms, the reactor is mechanically agitated to achieve good mixing, uniform temperature, good residence time management, and avoid clogging. Partial fluidization with some recycle of the syngas can assist in temperature control and material movement through the reactor and can enhance the resulting biochar properties. This method can have the advantage that the expansion of the pyrolysis reactor is limited only by the mechanical design and not by the heat transfer area.

[0036] The reuse of spent sand can be achieved using special elevators or pneumatic transfer without the need to cool the sand.

[0037] The waste energy from the reheating of the sand can, in some forms, be used to dry the input biomass feedstock, which maximizes the thermal efficiency and increases the syngas quality.

[0038] The advantages of this technology can include the following. · It has high energy efficiency as all waste heat is utilized for pre-drying the feed biomass and / or pre-heating the combustion air. · It has a high yield of biochar due to favorable reactor conditions (low-rate pyrolysis). · Control of biochar properties (to enable sales to different applications) is possible. · Some oil and tar are present in the raw syngas, which is processed in a separate gasification reactor, which also uses hot sand to convert these oil and tar into more syngas, thus eliminating the need to deal with by-products and odors. · The pyrolysis gas is not diluted by any inert gas or combustion products. · Good steady-state control of residence time without processing conditions, temperature, hot spots or cold spots is possible, thus resulting in more consistent product quality. · There is no risk of clogging or becoming clogged in the gas flow, and a wide variety of raw material types and sizes can be processed. ·It can be started and stopped simply (when it is necessary to suddenly stop the plant, condensation of oil and tar in the piping does not occur). ·The equipment is simple and easy to maintain. ·Using a catalyst material can assist in pyrolysis and reduce emissions. ·Some of the product biochar may be utilized for syngas cleaning (such as activated carbon) and then returned to the system for treatment. ·Safe operation and low leakage emissions are possible. ·In some forms, the system can have the advantage of using a length that is one-fifth or one-tenth inside the reactor. ·Since nitrogen is not added to the system, the syngas output can be in a clean state with nitrogen removed.

[0039] Next, referring to the figures, FIGS. 1 and 2 show a reactor assembly of one embodiment of the disclosure.

[0040] In assembly 1, a material feeder 10 including a delivery chute 11 and a screw feeder 12 delivers biomass or other materials for processing in assembly 1. The screw feeder 12 extends into the primary pyrolysis reactor 14 and provides a gas seal for restricting backflow of syngas from the reactor. The reactor extends longitudinally. The material is processed in the primary reactor 14, and the processed material is moved from the primary pyrolysis reactor 14 to the separator 15.

[0041] The used sand and biochar are separated by the separator 15. The used sand moves through the elevator 16 to the combustor riser 17 and then to the fluidized bed 19. The off-gas from the fluidized bed 19 passes to the cyclone 22. The syngas moves from the primary reactor 14 through the syngas cyclone 21 to the secondary gasification reactor 20.

[0042] Both the primary and secondary reactors 14 and 20 are supplied with sand in the form of alternative fine high-temperature sand from the ilmenite or sand distribution system 23.

[0043] Next, referring to FIG. 3, the material feeder 10 includes a delivery chute 11 and a screw feeder 12 arranged to receive the material. The delivery chute 11 can be closed using a sliding lid or by any other means.

[0044] The screw feeder 12 includes an inclined tube extending upward. In the illustrated form, the screw feeder 12 forms an angle of about 10 degrees to 45 degrees with respect to the horizontal. This can have the advantage of avoiding backfire of the biomass. A chain drive or other system connects a motor to a rotating twin screw 13 located within the screw feeder. The rotating screw 13 rotates to send the biomass to the reactor at a controlled speed. In some forms, the speed can be manually controlled to provide an average outlet temperature to the reactor. The upper end of the screw feeder does not include a screw shape to allow plug formation to limit backflow of the raw syngas. The biomass is supplied from the screw feeder 12 to the primary reactor 14. In some forms, cold sand or ilmenite is also added to the material feeder 10 as needed based on the replenishing fluidized bed leveling way.

[0045] Referring to FIG. 4, the combustor riser in the illustrated form includes a generally cylindrical upright combustion vessel 25 and a plurality of outlets 26. The waste heat from the fluidized bed 19 can be utilized to preheat the return sand or to combust the fuel in place to provide heat or an alternative.

[0046] Next, referring to FIGS. 5 and 6, the sand distribution system 23 includes a single input section and a plurality of output sections 27 controlled by non-mechanical valves. In an alternative embodiment, large-scale mechanical valves can be utilized. In one form, the delivery of hot sand is manually controlled in response to the heat within a given zone of the reactor. In an alternative embodiment, this can be automated. The control of the sand moving to the output sections is actuated through the amount of fluidizing air sent to a given area of the distribution assembly that results in the movement of sand to a given output section. The hot sand is distributed (only at startup) from the water distribution system 23 to the primary reactor 14, secondary reactor 20, and combustor riser as required. The output sections can be controlled by manually controlling the input section, or the output sections can be automated by controlling the input section.

[0047] Referring to FIG. 7, the elevator 16 includes an elevator with a gas lock between the oxidation system and the reduction system. The fluidized bed vessel is shown in FIG. 8.

[0048] Referring to FIG. 9, the secondary reactor includes a vessel 30 capable of mixing hot sand with the input synthesis gas. In the illustrated form, it has double-angle pipes 31 that meet at a predetermined angle. By further having a V-shaped funnel-shaped vessel 32, mixing is enabled. The hot sand and the synthesis gas are mixed within the reactor, and the interior of the reactor is hot enough to gasify residual oil and tar from the synthesis gas. This has the advantage of reducing clogging of the system. In an alternative embodiment, a series of risers and cyclones can be used. The intention is to pass the synthesis gas through areas that could potentially cause blockages. The synthesis gas needs to be heated to 850 °C or more at the outlet.

[0049] Referring to FIG. 10, the primary reactor has an input end 5 where materials from the feeder are supplied to the reactor It includes an elongated container 50 extending from 1. The container 50 extends through a plurality of inlets 53 that enable the entry of hot sand from the high-temperature sand distribution system in the illustrated form. This divides the reactor into reaction zones. A double-shaft paddle wheel auger disposed within the reaction vessel 50 rotates to mix the biomass supplied from the supply device with the hot sand.

[0050] In one form, by measuring the temperature constantly, the input of hot sand and biomass can be controlled. In some forms, the residence time is allowed by changing the shape of the paddle or the rotational speed at the outlet end of the reactor. Then, the material from the reactor is moved to a separator. In some forms, the reaction stage is a separate mixer and may include an independent separation of the used sand.

[0051] Referring to FIG. 11, the separator may include a separator container 58 incorporating one or more screens of various types or apertures. Magnetic separation and physical separation may be used.

[0052] Further, referring to FIGS. 12-16, a further embodiment of an apparatus for processing a carbonaceous material is disclosed. The apparatus 200 includes an infeed 201 for entering the carbonaceous material into a reactor 202. The reactor may be a pyrolysis reactor. The product from the reactor 202 is moved to a separator 203 where the materials are separated. At this point, make-up ilmenite may be added. Then, a catalyst such as ilmenite proceeds to a combustor riser 204 where it is lifted in a fluidized bed 205, recovered, and returned to the reactor to catalyze further reactions within the reactor. The biochar is separated into a biochar bin 206. The combustor riser 204 includes a cylindrical combustion vessel 208 and a pipe 209 that extends upward to a cyclone 210 connected to the fluidized bed 205. The method of separation includes removing the syngas from the reactor 202 to a tar cracker and then to a water quench / scrubber. Excess syngas is flared through a stack 209.

[0053] Referring to FIGS. 17 - 19, a reaction vessel including a plurality of mixing zones is disclosed. The mixing zones are arranged and set via high - temperature solid entry points. The zones perform temperature control. The reaction vessel further includes a plow for improving fluidization. Reactor 202 extends from supply section 284 through auger 285 to discharge section 286. The in - feed includes an inlet conduit 288 and an auger 285 for guiding materials into the reactor body 270. The reactor body 270 includes a mechanically assisted fluidized bed / mixer 273 configured in the illustrated form of a biaxial 274 with paddles that can be angled to assist or retard the flow.

[0054] When materials enter through the in - feed 284, the raw synthesis gas can exit through the synthesis gas outlet 275. High - temperature sand or alternative materials are injected at a plurality of high - temperature solid entry points 277. Thereby, zones are formed within the reactor 202.

[0055] Next, referring to FIG. 20, a simple flowchart of one embodiment of the disclosure is shown. The illustrated method 301 for processing a carbonaceous material 302 includes the step of sending the carbonaceous material 302 to a reactor 303.

[0056] This method further includes introducing a fuel 306, air 307, and a catalyst 308 into the reactor. The fuel can consist of any commercially available clean - burning gaseous or liquid hydrocarbon fuel, or a solid fuel such as biomass, coal, or charcoal. In some forms, the fuel may be synthesis gas. The catalyst may be in the form of an iron oxide catalyst such as ilmenite, for example. The fuel 306, air 307, and catalyst 308 can be sent to a fluidized bed 311 including an outlet to the reactor 303. The combustion exhaust gas 309 is removed from the fluidized bed. The organic material 302 and the high - temperature catalyst 308 merge within the reactor 303.

[0057] Reactor 303 can include a pyrolysis reactor that in some forms acts to partially combust the organic material by contact with a heated solid medium. In some forms, the heated solid medium includes ilmenite. In some forms, the reactor may be configured to subject the organic material to several heating steps. In the illustrated form, the heating steps are maintained at a relatively low temperature of 500 to 900 °C.

[0058] The product of the reactor is sent from the reactor to a separation chamber 310 where the clean material 312 and the recoverable material are separated from each other. The clean material 312 proceeds through an outlet while the recovered material is sent to a fluidized bed 311 where it can be sent back to the reactor 303. In some forms, the recovered material includes at least some of the spent catalyst and fuel. In some forms, the separator includes screening. Some of the spent catalyst may be discarded to maintain the integrity of the catalyst.

[0059] The material further proceeds from both the reactor and the fluidized bed to at least one scrubber. In the illustrated form, the gaseous material proceeds through a dry scrubber 314 where secondary gasification occurs and reaches a wet scrubber 315. A neutralizing agent 317 such as CaCO3 can be added to the wet scrubber 315. The clean off-gas 318 and the precipitated solids 319 are removed from the wet scrubber.

[0060] This method has the advantage of treating contaminated organic materials, particularly contaminated halides, at relatively low temperatures and thus requiring less energy input than prior art systems. By keeping the reaction temperature below approximately 900 °C, the temperature is kept relatively low compared to other systems that require temperatures in excess of 1100 °C. Further, this method utilizes ilmenite as a medium for heat transfer and as a catalyst. Some forms of the method enable release at approximately 500 °C and destruction of volatile contaminants at approximately 1000 °C, while in some forms carbon can be recovered and reactivated. In some forms, the system can enable recovery of the catalyst for reuse of at least a portion of the catalyst.

[0061] Referring now to FIG. 21, a second embodiment of a method for the treatment of a carbonaceous material is disclosed. The method includes feeding a carbonaceous material 321 to a reactor 322 via a dryer 323. The dryer can utilize standard processing equipment including an off-gas cyclone 325 in some forms.

[0062] Within the reactor 322, the material is heated to a temperature above 200° C., tempering is initiated at a temperature above 300° C., and finally pyrolysis is initiated at a temperature above 500° C. In some forms, the temperature of the reactor remains below 800° C. to 900° C.

[0063] This method may further include feeding a fuel, which may be in the form of synthesis gas, and a catalyst, which may be in the form of an iron oxide catalyst such as ilmenite, to the reactor 322 via a fluidized bed 327, a primary scrubber 328 (which is the same as the dry scrubber described above), a riser 330, and a plurality of cyclones including a riser cyclone 331, a fluidized bed off-gas cyclone 332, and a synthesis gas cyclone 333.

[0064] After being processed in the reactor 322, the material is sent to a separation chamber 335. The separation chamber may include a rotary screen or an alternative separator in some forms. The material from the separation chamber is sent to an anaerobic cooler and a material including a bioreactor 336, some calcined mineral catalysts 337, and cooling water 338. Materials such as mineral / heat transfer media or catalysts are moved through a riser 340 to a riser cyclone 331 and then to a fluidized bed 327.

[0065] Referring to FIG. 22, a method for treating a carbonaceous material is disclosed. The method includes feeding biomass 401 to a feeder 402 including a twin-screw feeder and feeding the biomass to a primary reactor 403. The primary reactor in the illustrated form includes a double-shaft paddle wheel within a container. The reactor can increase the heat of the biomass from 160° C. to 300° C. to 500° C.

[0066] Hot sand or ilmenite is sent from the hot sand distribution assembly 404 to the reactor 403. The hot sand is sent in a plurality of inlets that effectively divide the reactor into zones having different temperatures. The double shaft paddle wheel mixes the biomass and the sand. Periodic temperature measurements enable the controlled feeding of the sand from the hot sand flow assembly.

[0067] In some forms, the hot sand is a catalyst such as ilmenite or an alternative iron-based catalyst.

[0068] The raw synthesis gas is discharged from the primary reactor and sent to the secondary reactor 410 for syngasification. This continues to heat the exhaust gas and decomposes the tar and oil into components of smaller molecular weight, reducing condensation and blockage by the oil and tar. The clean synthesis gas is discharged to a compressor and may be flared, discharged, or reused as fuel.

[0069] An important objective of the plant is to determine the syngas composition.

[0070] The processed biomass is sent to a separator that may include a plurality of screens for separating the biochar product and the roasted sand from the stream. Nitrogen can also be purged from the separator. The material follows from the separator to the old's elevator 406 and then enters the combustor riser 407. The combustor riser in the illustrated form raises the temperature to 750 °C. Air is injected to control the rate of rise.

[0071] The material is moved to a fluidized bed 411 that may be higher than 900 °C. A plurality of cyclones are used to separate off-gas from the material for further processing.

[0072] Referring to FIG. 23, more details of the pyrolysis in the primary reactor 403 are shown. The biomass feed 401 is sent to the primary reactor 403. Inside the primary reaction vessel 420, there is a twin-shaft paddle wheel 421 for mixing the biomass with the high-temperature sand catalyst in the reactor. The high-temperature sand catalyst is sent from a high-temperature sand catalyst distribution system 404 equipped with a plurality of non-mechanical valves that operate either manually or automatically according to the temperature measurement in the reactor.

[0073] The high-temperature sand catalyst is supplied from the distributor assembly 404 to various zones of the reactor 403 through a series of pipes 423. The reactor is loosely divided into several zones. In the illustrated form, the zones include a heating zone, a calcination zone, a pyrolysis zone, and a self-generation zone. These are defined by the input of high-temperature sand. The temperature of the zones indicates the time when additional high-temperature sand is required from the multi-vessel high-temperature sand distribution system 403. Some forms of high-temperature sand distribution systems have a single input 425 and multiple outputs. In the illustrated form, the multiple output parts include seven output parts. Four output parts send high-temperature sand to the primary pyrolysis reactor 403, and the other three output parts 426 send high-temperature sand to the fluidized beds of the secondary reactor and the rest of the processing system.

[0074] The material from the primary reactor is sent to the separator 405, separated, returned to the reactor, and discharged as biochar or used sand.

[0075] Referring to FIG. 24, more details of the gasification of the secondary reactor and the synthesis gas are shown. The raw synthesis gas 501 from the primary reactor is sent to the secondary reactor 502. The secondary reactor in the illustrated form is shaped as a double-angle pipe that meets at an angle. High-temperature sand and synthesis gas are mixed inside the reactor, and the inside of the reactor is hot enough to gasify residual oil and tar from the synthesis gas. This has the advantage of reducing clogging in the system. At the meeting point of the double pipes of the reactor, a diverter valve 505 is included to enable a change in the direction of the high-temperature sand flow. The material proceeds to the funnel-shaped container 506 and the synthesis gas cyclone 507.

[0076] Figure 25 shows a block diagram of a combination of fluidized beds for heating sand. The fluidized beds include a first fluidized bed 515 and a second fluidized bed 516. The hot sand from the high-temperature sand distribution assembly is sent to the first fluidized bed 515. Fluidizing air, solids, and fuel are added to heat the fluidized bed to approximately 750°C. Substances flow into the second fluid layer, and combustion air, fluidizing air, and fuel are added. The temperature is raised to approximately 950°C. The hot sand is sent to the distribution system through conduit 517 while the combustion off-gas is discharged.

[0077] (Example) Table 1 shows exemplary feedstocks and temperatures for the reaction, along with the percentage yields for the biocrude. [Table 1]

[0078] (Example 2) Additional test work was completed with a residence time of 15 minutes and an operating pressure of atmospheric pressure.

[0079] In some forms, the residence time is up to 1 hour. In some forms, the temperature of the pyrolysis is between approximately 600°C and approximately 900°C. In some forms, the final decomposition step (either in a primary scrubber or a dry scrubber) can operate at approximately 750 - 1000°C. In some forms, the temperature of the final decomposition step is approximately 800°C.

[0080] As shown in Table 2, the solid results of the PFAS treatment confirm the removal of PFAS compounds at low operating temperatures. Removal. [Table 2]

[0081] Table 3 shows water samples from the off-gas scrubber. [Table 3]

[0082] These results indicate that the PFAS compounds were thermally desorbed at much lower temperatures than expected, followed by complete thermal decomposition of only the contaminant fraction.

[0083] Figure 26 shows a flowchart diagram of a further embodiment of a method for processing two or more types or streams of carbonaceous materials in parallel. This system allows for two separate feeders and two separate reactors, but includes a single source of hot sand that can be sampled from each reactor system. In the illustrated method 601, a first stream of contaminants in the form of carbonaceous material 604 is sent to a first reactor 605. The processed material from the first reactor 605 flows outward from the first reactor 605 in two channels. The first one is screened by a first screen 606 and output as processed material 608. During screening at the first screen 606, the material obstructed by the first screen 606 is sent to a common fluidized bed 613 for further processing.

[0084] A second stream of material is sent to a second reactor 611, reacted, and sent to a scrubber 612. An additional substance 613 in the form of CaCO3 is sent to the scrubber 612. The output of 612 is discharged at a discharge point 614 as clean off-gas.

[0085] A second stream of material in the form of biomass 615 is sent to a third reactor 617. From the third reactor 617, the material is sent to either a fourth reactor 619 or a second screen 622. The output of the reactor is screened at the second screen 622 and output as processed material 608. During screening at the second screen 622, the material obstructed by the second screen 622 is sent to the common fluidized bed 613 as biocchar fuel.

[0086] The output supplied to the fourth reactor 619 is processed through the second scrubber 620 and returned to the common fluidized bed as clean syngas fuel.

[0087] The common fluidized bed outputs the spent combustion off-gas 625 and enables the flow of hot sand to the four reactors.

[0088] The screen may be in the form of a magnetic separator, a physical screen, or any other screening system.

[0089] The technical advantage of this system is to provide a common fluidized bed for both pollutant treatment and biomass treatment. The biomass is converted into syngas for fuel, biochar for fuel or soil additives or carbon sequestration of any required size. The gas flows from different feedstocks do not mix, enabling the supply of clean syngas.

[0090] A further embodiment of the system is shown in Figure 27. A feed material such as biochar 701 is sent to a mixing and feeding system 702 and then to a primary reactor 703. The primary reactor processes the material by pyrolysis at 500 - 700 °C by mixing with a high-temperature medium such as high-temperature catalytic sand. The reactor also includes four zones or stages through which the material moves. The high-temperature medium is sent from the fluidized bed 705 to the reactor 703 via a derivation system.

[0091] The processed material from the reactor 703 is moved to a separator 707 including one or more screens. The biochar product is discharged while the return medium is returned to the fluidized bed 705 via the preheater / riser 708.

[0092] The raw syngas from the reactor 703 is supplied to a secondary reactor 709 to gasify the volatile hydrocarbons at about 900 °C. Once gasified and separated through a cyclone, the effluent can be sent through a series of scrubbers and heat exchangers so that exhaust gas, warm water, solids, and spent biochar can be discharged.

[0093] A further embodiment of the method is shown in FIG. 28. In this embodiment, contaminated soil 901 or GAC is sent to the primary reactor via a feed system 902 for thermal desorption of PFAS at 500 - 700 °C. A heat exchanger 903 and an anaerobic cooler 904 are used to exchange heat.

[0094] Used sand and clean soil are separated by a separator 907 through screening and magnetic separation, and the used sand moves to a fluidized bed 909 through a combustor riser 908. Clean soil 910 is discharged when the product off-gas from the fluidized bed 909 passes through a cyclone 22. The syngas from the primary reactor 902 and the fluidized bed 909 moves to a secondary reactor 911 for thermal decomposition of PFAS at 900 - 1100 °C. A syngas cyclone 913 separates the syngas for further reaction in the secondary reactor 911 or moves the treated syngas to a wet quench 914, wet scrubber 915, and dry scrubber 916 system, from which clean off-gas and used GAC are discharged.

[0095] In some forms not shown, a full-scale commercial plant includes preheating and drying of the feed by waste heat from cooling of the discharged soil. The treated soil is advantageously at about 80 °C for magnetic separation. This makes it possible to return ilmenite or other catalysts for reuse.

[0096] Those skilled in the art will understand that many other modifications can be made without departing from the spirit and scope of the methods and apparatuses disclosed herein.

[0097] In the following claims and the foregoing description, unless the context requires otherwise due to express language or necessary implication, the word "comprising" or variations of the word "comprising" are used in an inclusive sense, that is, used to specify the presence of the stated features, but not to exclude the presence or addition of further features in the various embodiments of the methods and apparatuses disclosed herein.

Claims

1. A method for treating a carbonaceous material, comprising: feeding the carbonaceous material into a reactor; feeding a catalyst into the reactor; treating the carbonaceous material at a relatively low temperature in the reactor to decompose the carbonaceous material into a base compound. Method.

2. The method according to claim 1, further comprising recovering at least a portion of the catalyst from the output material and regenerating the catalyst for reuse.

3. The method according to claim 2, wherein the catalyst comprises an iron oxide-based catalyst.

4. The method according to claim 2 or claim 3, wherein the catalyst comprises ilmenite.

5. The method according to any one of claims 1 to 4, comprising feeding the catalyst in the form of high-temperature sand or sand in another solid medium.

6. The method according to claim 5, wherein the catalyst is fed through a plurality of inlets provided along the length of the reactor.

7. The method according to claim 5 or claim 6, wherein the catalyst and the carbonaceous material are mechanically mixed in the reactor.

8. The method according to any one of claims 1 to 7, wherein the carbonaceous material contains perfluoroalkyl compounds and polyfluoroalkyl compounds as contaminants.

9. The method according to any one of claims 1 to 7, wherein the carbonaceous material contains contaminated organic materials.

10. The method according to any one of claims 1 to 9, further comprising recovering synthesis gas from the output material treated by the reactor.

11. The method according to any one of claims 1 to 10, further comprising separating biocchar from the output material.

12. The method according to any one of claims 1 to 11, further comprising feeding the synthesis gas output from the reactor to a secondary reactor.

13. The method according to claim 12, wherein the secondary reactor contains a catalyst in the form of high-temperature sand.

14. A method for treating a carbonaceous material containing a halide element, comprising: feeding the carbonaceous material containing the halide element into a reactor; feeding a catalyst into the reactor; treating the carbonaceous material at a relatively low temperature in the reactor to partially decompose the carbonaceous material, completely volatilize it, release and capture the halide element. Method.

15. An apparatus for treating a carbonaceous material, comprising: a reactor vessel for treating the carbonaceous material; an outlet from the reactor vessel for moving an output material containing biocchar and a catalyst out of the reactor vessel. A separation vessel for separating at least a part of the biocatalyst and the catalyst, At least one outlet for sending the biocatalyst to a biocatalyst container, At least one outlet for sending at least a part of the catalyst and any alternative material to a preheater, A fluidized bed for receiving at least a part of the catalyst and any alternative material, A return for sending at least a part of the catalyst to a reactor, An apparatus comprising.

16. A system for treating two or more types of carbonaceous materials, A first reactor assembly including a first reactor and one or more separators, A second reactor assembly including one or more reactors and one or more separators, A fluidized bed, and is provided with, The system is configured such that a first type of carbonaceous material is treated through a first treatment stream including at least the first reactor assembly, and a second type of carbonaceous material is treated through a second treatment stream including at least the second reactor assembly, and the fluidized bed is utilized in both the first treatment stream and the second treatment stream System.

17. The system according to claim 16, wherein contaminants are treated through the first treatment stream.

18. The system according to claim 16 or claim 17, wherein biomass is treated through the second treatment stream.

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