JP2020533471A - Systems and methods for refining coal into high-value products - Google Patents

Abstract

An integrated thermochemical process for the conversion of coal to high value products using a combination of pyrolysis and solvent extraction is described herein. The systems and methods described are versatile, chemical products (aromatic compounds, asphaltene, naphthenes, phenols, polyamides, polyurethanes, polyesters), polymer composite products (resins, coatings), graphite. It can be used to produce a variety of high value products, including products, agricultural materials, building materials, carbon fiber, and other products that are substantially more valuable than the energy produced by combustion. In addition, these systems and methods are specifically designed to be highly branched and highly flexible, allowing for high selectivity and optimization to increase the value of the product compared to raw materials. [Selection diagram] Fig. 1

Description

Detailed description of the invention

[Cross-reference of related applications]
[0001] This patent application claims the interests and priority of US Patent Provisional Application No. 62/557804, filed September 13, 2017, which application is hereby incorporated by reference, unless inconsistent with this specification. Incorporated into the book.

[Background of invention]
[0002] Coal mining and coal production are large, valuable industries both in the United States and abroad. Most of this coal is burned to produce energy. Currently, there is a lot of economic and political pressure on the construction of new coal-fired power plants. Thus, it includes methods for the production of chemicals, plastics, building materials, and products that can have significantly higher value than the value of energy produced by power plants, in order to further utilize coal outside of combustion. Considering its use as a raw material for other methods is becoming more and more attractive.

[0003] Research and development of coal as a raw material for the production of chemical products and other materials has been around for more than 50 years. Interest in this area has typically increased during the period, as in the 1970s, when traditional petroleum raw materials became expensive due to high crude oil prices. For example, US Pat. No. 4,346,077 describes the thermal decomposition of liquid hydrocarbons and coals that produce vapors. U.S. Pat. No. 9074139 describes the production of aromatic compounds from coal utilizing liquefaction and hydrocracking. What these references and most coal conversion technologies have in common is that coal is converted to coal tar in order to mimic petroleum hydrocarbons so that coal tar can later be processed in petroleum refineries. .. Coal, which produces larger amounts of solid products and typically contains high sulfur content and some metals, is often a relatively poor price for processes designed for oil-based raw materials. It is an article.

[0004] Systems and methods for the systematic thermochemical conversion of coal into intermediate and finished high-value products, thereby producing materials that are much more valuable than the considerable carboniferous energy produced by combustion. It can be understood from the above that there are still requirements in the relevant technical field. In addition, separation and separation considering the production of outstanding commodities that are specifically adapted and / or personalized for coal and carboniferous raw materials to achieve effective conversion into products, yields, efficiencies, conversion rates, and can be sold. Process systems and methods are needed.

[Outline of Invention]
[0005] An integrated thermochemical process for the planned decomposition, extraction and conversion of coal into high value products and commodities using a combination of pyrolysis and solvent extraction is described herein. The systems and methods described are versatile, planned, and of chemical products (aromatic compounds; asphaltene; naphthalenes; phenols; and polyamides, polyurethanes, polyesters, graphite materials. Precursors for production), polymer composite products (resins, coatings, adhesives), agricultural materials, building materials, carbon fiber, graphene products, and other materials that are substantially more valuable than the energy produced by combustion. It can be used to produce a variety of intermediate and finished high value products, including. Moreover, these systems and methods are highly branched (ie, process steps suitable for producing a wide range of product types and specifications from the same raw material together) and synergistically (ie). For example, it is possible to combine a resin system produced from coal with a solid carbon material derived from coal to produce a composite material), especially designed. Therefore, the systems and methods are highly adaptable to the market and meet product requirements. Therefore, it allows for high selectivity and optimization to increase the value of the actual product compared to the raw material. Some of these products may be coal extracts such as metals and rare earth elements.

[0006] The thermochemical process provided converts most of the coal raw material and extracts from coal into value-added products, with a high percentage of the solid material (eg, greater than 50% on a dry basis). You can focus on the conversion to fluid. These systems and methods can avoid expensive, energy-intensive hydrocracking and hydrotreating processes. The thermochemical processes described herein can be optimized to achieve favorable manufacturing motivated by the total price of the goods produced using an integrated combination of thermal and chemical processes. It provides a controlled planned conversion of coal and extraction from coal into a selective and switchable mixture of high value products.

[0007] In one embodiment, a method for converting coal into a plurality of high value coal products, i) a step of preparing a raw material derived from coal at least partially; ii) pyrolysis and solvent extraction. Provided are methods in which thermal decomposition and solvent extraction are integrated and performed under conditions for producing multiple high value coal products, including the steps of processing the raw material, including the combination of. Percentages of high-value coal products that are liquid at standard temperature and pressure may be 50% or more, 60% or more, or optionally 70% or more on a dry basis. The steps to be machined may be highly divergent, discriminatory, and extensive, and yet highly selective.

[0008] Pyrolysis is commonly used in the systems described to reduce the size or length of complex molecules commonly found in coal and to concentrate the extract. The thermal decomposition described herein may refer to, for example, flash thermal decomposition at high temperatures and having a short residence time (in seconds). The pyrolysis process described herein may specifically exclude the use of catalysts in some embodiments and may specifically include the use of catalysts in some embodiments. The thermal decomposition process described herein may be highly selective in some embodiments.

[0009] Pyrolysis is a combination of single-step pyrolysis, multiple single-step pyrolysis, single multi-step pyrolysis, multiple multi-step pyrolysis or single-step and multi-step pyrolysis steps. May be good. Each pyrolysis or pyrolysis step may be independently performed at a pressure selected from the range of 0.5 atm to 15 atm, 0.9 atm to 15 atm or 0.9 atm to 10 atm. Each pyrolysis or pyrolysis step may be carried out at a temperature selected from the range of 400 ° C. to 1200 ° C., 750 ° C. to 1200 ° C. or optionally 900 ° C. to 1100 ° C. In one embodiment, the residence time for thermal decomposition is selected over the range of 30 minutes to 0.1 seconds and optionally 10 seconds or less, 5 seconds or less, 2 seconds or less or 1 second or less. Pyrolysis may be integrated with solvent extraction as a pretreatment or posttreatment. Each pyrolysis or pyrolysis step may be independently performed at a pressure selected from the range of 0.5 atm to 15 atm, 0.9 atm to 15 atm or 0.9 atm to 10 atm.

[0010] Solvent extraction may exclude water vapor to produce a gas with a mass percentage of 25% or less, 15% or less, 10% or less, 5% or less, or optionally 3% or less. Solvent extraction may produce a liquid with a mass percentage that may contain up to 100% of the solvent itself or may be excluded, and the liquid itself may be a precursor or intermediate for further processing into commodities and products. Become a body. Pyrolysis may be carried out in a hydrogen donating environment such as in the presence of nitrogen, air or hydrogen gas, methane, syngas or any combination thereof. The pyrolysis may be flash pyrolysis.

[0011] Solvent extraction is commonly used to remove and / or separate various components of solid raw materials, including intermediates and final products. It should be noted that in some cases solvent extraction can facilitate chemical reactions, including the conversion of solid materials to liquids, and chemically convert the various components processed. Various solvents known in the art can be used, including aliphatic, aromatic, hydrogen donating, non-polar solvents, protic solvents and ionic liquid solvents. Solvent extraction may include multi-step extraction and multiple solvent extraction steps before or after thermal decomposition. Solvent extraction may include a supercritical fluid step. Solvent extraction may also utilize fractionation or the use of multiple solvent extraction steps at various temperatures and pressures. Various uses of solvent recovery, including solvent reuse, can provide additional efficiency and cost savings, in addition to the solvent itself being a precursor or intermediate product for further processing.

[0012] The solvent extraction described herein may be carried out with at least one liquid solvent. At least one solvent can be selected from the group consisting of aliphatic solvents, aromatic solvents, polar solvents, hydrogen donor solvents, ionic liquid solvents and any combination thereof. At least two kinds of liquid solvents may be used for solvent extraction. The first solvent may be a combination of solvents that may include polar solvents, separately applied polar solvents and aromatic solvents. The second solvent may be a hydrogen donating solvent and vice versa. The solvent extract itself may be an intermediate that is further processed into the final product.

[0013] Solvent extraction may be a combination of single-step solvent extraction, multiple single-step solvent extraction, single multi-step solvent extraction, multiple multi-step solvent extraction or single-step and multi-step solvent extraction. Good. Solvent extraction may be performed at a temperature below the critical temperature of the solvent. Each solvent extraction or step may be independently performed at a temperature of 400 ° C. or lower, 350 ° C. or lower, or optionally 300 ° C. or lower. Solvent extraction may exclude water vapor to produce a gas with a mass percentage of 10% or less, 5% or less, or optionally 1% or less.

[0014] The solvents described herein may include tetralin (1,2,3,4-tetrahydronaphthalene), 1-methyl-naphthalene, toluene, dimethylformamide (DMF) or any combination thereof. .. The solvent may be impure, for example due to reuse or separation inefficiency.

[0015] The systems and methods described are flexible and the solvent extraction step may be performed prior to the pyrolysis step and vice versa. Further, more complex systems may utilize any combination of multiple pyrolysis steps and / or multiple solvent extraction steps, eg, a first pyrolysis step followed by a first solvent extraction and then a second. The pyrolysis step of may be continued. In addition, a portion of the output from one step (either thermal decomposition or solvent extraction) is reused as input for the previous step, next step or current step, or as part of the input. Reuse streams may be used as they may be used. The solvent extraction and thermal decomposition steps can be considered as an integrated achievement result in which thermal decomposition and / or solvent extraction cannot be achieved alone.

[0016] Solvent extraction may be performed upstream of thermal decomposition. Pyrolysis may be carried out upstream of solvent extraction. Some of the products from the pyrolysis step may be reused for solvent extraction. Some of the products from solvent extraction may be reused for pyrolysis or transferred to further downstream processing. The processing step may include multiple solvent extractions, and the solvent from the subsequent solvent extraction may be reused in the earlier solvent extraction or pyrolysis step.

[0017] The main raw materials described herein are generally coals or coal-based materials, including cutting coal and / or coal, which may include physicochemical, chemical and / / Alternatively, it may be thermally preprocessed. Pre-processing includes milling, ash removal and / or drying. The systems and methods described are flexible and may be used with any main ingredient, including lignite, bituminous coal and bituminous coal. Auxiliary raw material inclusions include other hydrocarbon sources such as biomass and oil shale, and / or inclusions in secondary reuse streams from downstream processes, such as syngas and other reactive mineral resources such as sodium bicarbonate It may be included.

[0018] The high value coal products described herein have significantly higher monetary or economic value than the value of the energy produced by burning or burning the main raw material. High-value coal products are fuel products and / or small-quantity manufactured products of mixed components, for example, 10% or less fuel products and / or mixed products, 5% or less fuel products and / or mixed products, or optionally the following: It may include fuel products and / or mixed products. High value coal products may contain polymers or polymer precursors. High value coal products may include polyurethane. High value coal products may include composite polyurethane foam. High value coal products may include polyamides. High value coal products may include polyesters. High value coal products may contain aromatic compounds. High-value coal products include benzene, toluene, xylenes (including isomers), phenols, cresols, xylenolic acids (including isomers), naphthenols, and C9 monocyclic aromatic compounds (isomers). Includes), C10 monocyclic aromatic compounds (including isomers) or any combination thereof. High-value coal products may include paraffins, olefins, asphaltenes, naphthenes or combinations thereof. High value coal extracts may contain metal and rare earth elements.

[0019] High value coal products may include asphaltene intermediates and / or final products. High value coal products may include intermediates, additives or final products for road paving and roofing. High value coal products may include coal tar, distillates, pitches, asphalts, graphite materials, carbon fibers or any combination thereof. High value coal products may include soil conditioners and fertilizer products. High value coal products may include building materials. A significant portion of high value coal products can be solids, such as 10% or more solids, 20% or more solids or optionally 30% or more solids. Solids can be combined with resins, liquids, or other by-products produced by the methods described herein into graphite materials, building materials, composites, liquid additives or any combination thereof. May be converted. High value products may include syngas, urea, CO ₂ and / or acetylene.

[0020] In one embodiment, a method for converting coal into a plurality of high value coal products, i) a step of preparing a main raw material derived from coal at least partially; ii) processing the main raw material. Steps, the order of processing is a) a thermal decomposition step performed in a hydrogen-rich atmosphere with a time of 10 seconds or less; and b) performed with at least one liquid solvent, where the liquid solvent is a polar solvent and / or hydrogen. Includes a solvent extraction step, a processing step, selected from the group consisting of donor solvent and / or any combination thereof; c) The thermal decomposition step is the first process step performed on the main ingredient. , The solvent extraction process is a second process step performed on solid chars produced from thermal decomposition; d) The thermal decomposition and solvent extraction processes are integrated and carried out under conditions to produce multiple high value coal products. A method is provided.

[0021] The pyrolysis step may be a flash pyrolysis process. The solvent extraction step may be a combination of single-step solvent extraction, multiple single-step solvent extraction, single multi-step solvent extraction, multiple multi-step solvent extraction or single-step and multi-step solvent extraction. Two or more solvents may be used in the solvent extraction step. Processing of the raw material may further include one or more separation steps performed after thermal decomposition, after the solvent extraction process or between the solvent extractions.

[0022] Without being bound by any particular theory, there may be an explanation herein regarding the belief or understanding of the underlying principles of the devices and methods disclosed herein. Regardless of the final accuracy of any mechanical explanation or hypothesis, it is recognized that embodiments of the present invention can nevertheless be valid and useful.

FIG. 5 outlines the process described, including additional post-processing to produce liquid and solid products. It is a figure which shows an example of the processing step in which solvent extraction follows thermal decomposition. It is a figure which shows an example of the multi-step solvent extraction step in which two different solvents are used to increase the extraction effectiveness. It is a figure which shows the outline including input and output. It is a figure which shows an example of the highly branched highly selective process utilizing solvent extraction and thermal decomposition. It is a figure which shows an example of the highly branched highly selective process utilizing solvent extraction and thermal decomposition. It is a figure which shows an example of the outline which has the details about a product and an additional process. It is a figure which shows the additional example of the integrated multi-step machining step. It is a figure which shows the example of a thermochemical processing step.

[Detailed description of the invention]
[0032] In general, the terms and phrases used herein have meanings recognized in their art, and the meanings refer to standard texts, journal references and contexts known to those of skill in the art. Can be found by doing. The following definitions are given to clarify their particular use in the context of the present invention.

[0033] As used herein, "raw material derived at least partially from coal" refers to solids, powders, slurries, liquids, fluids or other materials produced from raw coal sources. For example, raw coal may be ground into powder before processing. The raw material may have various physical, thermal and chemical pretreatments known in the art to further accelerate the processing of the raw material, for example by flash pyrolysis and solvent extraction. Also, the raw material is a downstream process or intermediate (eg, solvent extraction) so that additional products, such as liquid products, can be promoted by reworking less valuable or unnecessary intermediate products. It may function as a reusable stream from one or more of the remaining solid materials).

[0034] "Coal" refers to a predominantly solid hydrocarbon that may contain some amount of fluid material. Coal generally consists of hydrogen, carbon, sulfur, oxygen and nitrogen. Coal may refer to bituminous charcoal, sub-bituminous charcoal and sub-coal, as described herein. Coal may also refer to ash or peat.

[0035] As used herein, "flash pyrolysis" refers to a thermal process in which a raw material or intermediate product is exposed to sufficient energy to quickly heat the raw material or intermediate. Flash pyrolysis may, for example, supply heat above 750 ° C., above 900 ° C., above 1050 ° C., or optionally above 1200 ° C., or heat the material to be processed. Flash thermal decomposition may refer to heating or resonance time of less than 60 seconds, less than 10 seconds, less than 5 seconds, less than 1 second, or optionally less than 0.5 seconds. Flash pyrolysis may be carried out under vacuum, in the presence of air, or optionally in the presence of a purified gas such as hydrogen or methane or a syngas. Further, the flash pyrolysis may be carried out in an inert atmosphere, particularly at a very high temperature exceeding 1200 ° C.

[0036] “Solvent extraction” is a substance that is mediated by extraction of components of a material through a chemical reaction and / or solubility in a solvent by flowing a liquid solvent through or over raw materials or intermediate products. Refers to the process of facilitating movement. As described herein, solvent extraction is carried out in one or more solvent extraction steps, including solvent extraction steps in multi-step solvent extraction in which the same or similar solvent is repeatedly used for the material. One or more solids may be utilized. The solvent may be a mixture containing a mixture of liquid hydrocarbons produced by the processes described herein, as described herein. The solvent may be a mixture of several solvents, as described herein. The solvent may be reused and reused as is known in the art. Solvent extraction may be at subcritical temperature. Solvent extraction may be performed under reduced pressure, atmospheric pressure or increased pressure.

[0037] As used herein, the term "solvent" refers to a liquid or mixture or mixture of liquids that is soluble in hydrocarbons or other species and molecules present in coal. Solvents may refer to complex mixtures of liquids, including hydrocarbon mixtures generally defined by the boiling range. The solvent may be polar, paraffinic, aromatic, alcoholic, ionic and / or hydrogen donating in nature. In embodiments that utilize two or more solvents, the solvents can be distinguished by composition, additives, molecular design, boiling range or a combination thereof.

[0038] "High-value coal products" are chemical products and materials (solids and liquids) produced by the processes described herein that are more valuable than coal or at least partially coal-derived raw materials. Both) will be described. High-value coal products may refer to liquid products produced primarily from solid coal. The high value coal products described herein are 1.5 times, 2 times, 3 times, 5 times, 10 times or at least 50 times optionally compared to the coal or raw coal material supplied as raw material. May have double the monetary value. High-value coal products are coal products that are 1.5 times, 2 times, 3 times, 5 times, 10 times, or optionally at least 50 times more valuable than the energy that can be produced through burning coal. Sometimes. High-value coal products may refer to products that are not fuel (eg, created for the purpose of burning to generate energy). Examples of high-value coal products include polymers (eg polyurethanes, polyesters, polyamides), high-value chemical products (BTX, paraffins, olefins, asphaltenes), composites, carbon fibers, graphenes, building materials, road pavements. And roofing materials and soil improving materials. High-value coal products are small portions of all materials converted from raw materials, such as 50% of total products on a dry basis, 70% of total products on a dry basis, 80% of total products on a dry basis. % Or optionally 90% of the total product on a dry basis.

[0039] The "hydrogen-rich environment" refers to an atmosphere containing a large composition of hydrogen gas. A hydrogen-rich environment may refer to an atmosphere containing 50 mol percent or more of hydrogen, or, in some embodiments, 70 mol percent or more of hydrogen. The hydrogen-rich environment may refer to the atmosphere or condition of a chamber or container in which thermal decomposition takes place.

[0040] The "inactive atmosphere" refers to an environment in which the gas phase is chemically inert to the raw materials (s) present.

[0041] The pressure values described herein are shown as absolute pressure values unless otherwise specified.

[0042] The following examples further illustrate the invention, but of course should not be construed in any way to limit the scope of the invention.

(Example 1-Outline of coal refining process)
[0043] This embodiment illustrates a high level overview of methods for thermochemical decomposition of coal or carboniferous raw materials into a systematically selected high value product. FIG. 1 shows a schematic diagram. In FIG. 1, the raw material, at least partially derived from coal, is fed to processing step 100, which includes thermal decomposition and solvent extraction. In general, the pyrolysis and solvent extraction steps may occur in any order and may include a multi-step process, an additional step of pyrolysis and / or solvent extraction, a reuse flow and separation. From a process and method perspective, solvent extraction and pyrolysis steps are integrated. The main machining step 100 produces at least one solid and liquid output, but may generate multiple solid and liquid output streams based on the configuration of the main machining step 100. In some cases, the liquid undergoes additional liquid processing 102 and optionally the liquid recycling stream 106 returns a particular liquid fraction to main processing 100. In some cases, the liquid recycling stream 106, including the solvent recycling stream, may be useful as an intermediate in downstream processes or as a product and may be sold or processed separately. Similarly, the solids may undergo additional solids processing 104 with an optional reuse stream 104. The end result is at least one high-value liquid product and at least one high-value solid product, but typically the processes described are various high-value products and lower-value products (with raw material costs). (Compare) to produce, lower value products may or may not be reprocessed or sold.

[0044] An example of machining step 100 is shown in FIG. First, the coal-based raw material is processed via thermal decomposition 200, which reduces the carbon chain length and liquefies or vaporizes a part of the raw material. In this example, the thermal decomposition is carried out at 400-1200 ° C. and at atmospheric pressure. Flash pyrolysis (eg, resonance time less than 1 minute) or low resonance time (eg, less than 15 minutes) reduces energy requirements and therefore costs while increasing efficiency, product manufacturing and It may be used to change yields and / or reduce processing time. The fluid from the pyrolysis process 200 may be further processed (eg, separation, polymerization, etc.) in the downstream process. The solid from the pyrolysis process 200 is transferred to the solvent extraction unit 210. The solvent extraction 210 is part of a chemical reaction that further removes fluid components from a solid material to reduce carbon chain length, a chemical reaction that increases the hydrogen / carbon ratio, or a chemical reaction that interacts with sulfur and oxygen bonds. May provide chemical reactions and recovery of metals and rare earth elements. Residual solids from solvent extraction step 210 may be further treated as described herein, reused through a process for additional conversion to lighter compounds, and other high. It may be converted into a value product. The fluid flow from the solvent extractor 210 may be separated, for example, by a distillation column 220. The fluid stream may be split into one or more product streams based on volatility, and the solvent may be recovered and returned to the solvent extractor 210. FIG. 8 shows an additional example of an integrated multi-step machining step, further exemplifying its versatility in the order of various process steps.

(Example 2-Pyrolysis)
[0045] The pyrolysis used in the systems and methods described provides the complex hydrocarbon pyrolysis found in coal and assists in converting some of the solid coal material into liquids and vapors. The pyrolysis described herein is generally performed at a high temperature but low enough to avoid combustion, eg, above 400 ° C., above 800 ° C., or optionally above 1000 ° C. Moreover, in order to increase efficiency and reduce energy costs, the pyrolysis of the described methods generally has a low residence time, eg, less than 1 hour, or in some cases less than 15 minutes. Some embodiments of the present invention utilize flash pyrolysis, which can have a residence time of less than 1 minute, or preferably less than 15 seconds. The pyrolysis steps described may be performed at or near atmospheric pressure, or in a pressurized environment, and in some embodiments, of hydrogen-rich gas, including hydrogen gas, methane, natural gas or syngas. Including doing in the presence.

[0046] Certain pyrolysis parameters depend on the input or supply flow. For example, in an embodiment of the first step of the method described by pyrolysis, the feed material is primarily coal or coal-derived material. However, if one or more solvent extractions are performed, the residual solid material may have a significantly different composition and therefore the process parameters need to be changed.

[0047] Coal pyrolysis experiments were performed on Cordero Rojo subbituminous coal. 25 g of coal was dried under argon at 100 ° C. overnight. Determine the weight of dry coal, which is the basis for the following yield calculations. The contents were then heated to 500 ° C. for 40 minutes in a vertical tube furnace. The generated thermal decomposition steam was transferred to a cooling trap at 0 ° C. to concentrate the tar and aerate the residual gas.

[0048] The following are weight-based yield results for dry coal based on the above experimental procedure:

(Example 3-solvent extraction)
Solvent extraction provides an effective cost-effective method for recovering desirable and valuable fluid components primarily from solid raw materials or intermediates. In addition, solvent selection and design may confer some chemical reactivity, reducing the size or length of complex hydrocarbon molecules often found in coal, and / or practical recovery of metals and rare earth elements. May give the realization of.

[0050] Various solvents are useful in treating coal-based raw materials or intermediate coal products (eg, after pyrolysis). Polar solvents, hydrogen donor solvents, aliphatic solvents, aromatic solvents, ionic liquid solvents and supercritical fluid extractions (including other solvents) are all highly adapted in promoting the production of certain products or product types. Allowing the nature, changes in solvent system or process parameters can explain the differences between various coal sources and types. The temperature and pressure of solvent extraction are often tied to the solvent used, but both subcritical and supercritical solvent extractions may be performed.

Multiple solvent extractions with various solvent systems and / or process parameters allow for higher efficiency in converting solid materials into more easily processed and potentially more valuable fluid outputs. To. An example of multiple single-step solvent extractions is shown in FIG. Feed material 201 (which can be a pyrolysis product or an intermediate that has undergone multiple process steps, including both coal-based raw materials, thermal decomposition and solvent extraction) is supplied to the first solvent extractor 210. The solvent extractor 210 uses a polar solvent that targets a particular solvent type, eg, a particular coal component, such as an aromatic compound. The first extract is then divided in one or more separation steps 220, such as a distillation column, to provide both light and heavy fluid power. The solvent may be reused and returned to the solvent extractor 210. The solids remaining after solvent extraction 210 are then processed in a second solvent extraction process 211 using a different solvent type, eg, a hydrogen donating solvent, to extract additional fluid remaining in the solids. Importantly, the order of the solvent extraction process may be reversed or changed to increase the amount of a particular hydrocarbon and allow for a variety of product choices. Also, the extract from the second solvent extraction 211 is fed to separation step 221 (s), providing both light and heavy fluid output, as well as the ability to reuse the solvent. The solids remaining after multi-step solvent extraction may be further processed (eg, pyrolysis or additional solvent extraction) or processed as a solid product as described herein.

[0052] Multi-step solvent extraction, in which a single solvent is applied multiple times to increase total extraction and fractionation and the single solvent is applied at various temperatures, is also available in some embodiments. ..

[0053] A solvent extraction experiment was performed to investigate the extraction efficiency of tetralin and 1-methyl-naphthalene in Cordero Rojo's subbituminous coal (the same coal as described in Example 2 and Table 1). The experimental procedure was to dry the coal under a stream of fluid argon at 90 ° C. for 36 hours; this resulted in coal with a moisture content of less than 1 (weight)%. After drying, the dried coal is weighed, which is the basis for the following yield calculations, assuming 0% moisture. About 100 g of coal was placed in a pressure vessel and the pressure vessel was then placed in the oven. The desired solvent is pumped at a rate of 0.1 ml / min / 1 g of dry coal to a pressure above the boiling point at the desired temperature. Turn on the oven and heat the container to controlled 360 ° C. The solvent flow is continued for 2 hours after reaching this temperature. A slight (assumed to be 0) gas flow was observed. After 2 hours, the solvent flow is stopped, the oven is turned off and the container is cooled in this way. The pressure drops to atmospheric pressure. After cooling to below the boiling point of the solvent, argon is allowed to flow through the vessel for 36 hours to remove the residual solvent from the solid residue. The resulting residue is weighed to determine the yield.

[0054] The following are weight-based yield results for dry coal based on the above experimental procedure:

(Example 4-Integrated thermochemical processing)
[0055] The solids collected from the pyrolysis (Example 2) and solvent extraction (Example 3) experiments were then subjected to a second processing option. In other words, the solvent-extracted solid residue was pyrolyzed and the pyrolyzed char was solvent-extracted. See FIGS. 1, 2 and 8.

[0056] Solvent extraction experimental procedures and conditions were the same as those described in Solvent Extraction (Examples), except that drying was not required.

[0057] Pyrolysis experimental procedures and conditions were the same as those described in the Pyrolysis Examples, except that drying was not required.

[0058] The following are weight-based tetralin solvent extraction yield results for dry pyrolysis char based on the above experimental procedure:

[0059] The following are weight-based pyrolysis yield results for tetralin-based solvent-extracted dry residues based on the above experimental procedure:

[0060] The following are weight-based yield results for the combined two-step method as a whole, based on the above results and the results from coal pyrolysis and coal solvent extraction examples. The solvent used was tetralin.

It should be noted that in both cases, the tar yield from the two-step method is higher than the yield from the pyrolysis-only or solvent-extraction-only process.

(Example 5-branch process)
[0062] By including additional processing steps, including steps after the combination of pyrolysis and solvent extraction may produce a range of products, or have different specifications and functionality for the same family of product types manufactured. Realize a highly branched process that can bring about. These additional processes convert the intermediate products obtained from the thermochemical treatment (shown in FIG. 2). The final product manufacturing process (formulation) supplied by the intermediate exhibits performance that ensures economic stability, with product distribution and adjustments to conditions that allow it to meet market demands based on the product. Achieve high selectivity ability to manufacture quantity of products.

[0063] FIG. 9 shows an example of a highly branched, highly selective process with additional post-processing to produce a variety of high value and useful products. The processes described are three integrated steps: thermal and chemical decomposition, steam-liquid separation, and further processing to produce high value derivatives or final products after the formation of a single direct process or intermediate product. Consists of product manufacturing / formulation which can be.

[0064] The thermal and chemical decomposition section consists of a minimum of two processing steps, thermal decomposition and solvent extraction, with the potential for additional post-treatment steps, which are carried out in succession. This process achieves maximum liquid intermediate yield (from the separation section), which is the main feed material for vapor-liquid product manufacturing or formulation. The thermal and chemical decomposition steps consist of thermal decomposition of the solvent-extracted solid residue after solvent extraction of the thermal decomposition char after thermal decomposition or after solvent extraction of the main raw material. Pyrolysis is direct or indirect heating of the main raw material or solvent extraction residue in a neutral or hydrogen donating atmosphere (such as hydrogen-rich gas, syngas or methane). Gas and solid products result from thermal decomposition. Solvent extraction consists of contacting the main raw material, or coal pyrolysis char, which can be a plurality of steps, with various solvents. The solvent is recovered in the separation section and the solvent-rich flow is reused for solvent extraction. The solvent carried over to the next processing step is minimized. Solvent extraction produces little gas and operates at temperatures below the pyrolysis temperature to produce a solvent containing an extraction liquid stream and solid residual logistics. FIG. 8 illustrates an integrated thermal and chemical decomposition step.

[0065] The separation section processes vapor and liquid intermediates from the thermal and chemical decomposition sections to produce the intermediates supplied to the product formulation section. Depending on the type of atmosphere in the pyrolysis reactor, the gas from the separation section may be processed and reused in the pyrolysis reactor. The solvent-rich flow is recovered in the separation section and reused in the solvent extraction section or used as an intermediate product for further processing into the final product. The separation section depends on both the conversion section (temperature, pressure, processing sequence, pyrolysis atmosphere and solvent scheme) and the product formulation section. Pyrolysis vapor and solvent extraction extracts are mixed into a single separation section, depending on which high value products are systematically selected and which are by-products or co-products. It may be fed, or the pyrolysis vapor and solvent extract extracts may be fed in separate parallel separation sections. The distillation column may be the first unit step in the separation section for removing gas products from the thermal and chemical decomposition sections and producing various liquid intermediates. Side strippers and side absorbers may be present. The lower part (residual product) from this first column can be transferred to a high vacuum distillation column for further purification of the heaviest material. Depending on the product formulation specifications, the liquid intermediate may be further separated or processed to produce the desired intermediate feed material for a particular product formulation. These downstream separations may consist of adsorption, fractionation, crystallization, azeotropic fractionation, extraction distillation, liquid-liquid decantation and extraction, including combinations thereof. Intermediates that have not been used (for product formulation) (eg, intermediates in the higher boiling range) are reused in the thermal and chemical decomposition sections to further process this material into more usable intermediates. You may.

[0066] The product formulation consists of two main subsections: intermediate (liquid) and gaseous product formulations and solids, which are processed in post-treatment formulations to produce the final product. The final formulation processes the intermediates from the separation section to produce 2-10 high value products and optionally additional lower value products. Examples of these high value products may be petrochemicals, carbon fibers, polymers, composites, asphaltenes, binders, coke and others. Each of these high value products is produced in a separate processing unit that uses a personalized feed material from the separation section. Solids from the thermal and chemical decomposition sections are transferred to the solids formulation. Again, some products are manufactured in separate processing units. Examples of lower value products include water, minerals and clay with flue gas. Examples of high value product extracts include metals and rare earth elements.

The process described herein is somewhat similar to crude oil refining, in which crude oil is fed, with multiple conversion steps, many separation (particularly fractionation) steps, and many produced. There are a number of inductive products produced using the intermediates, and generally distillation as the main process step, to produce the intermediates, followed by discontinuous hydrocracking, hydrotreating and hydrotreating. To manufacture the final product. However, the processes described herein are particularly adapted for solid, high carbon content feedstocks that require a separate and unique integration of thermochemical processes, which are technical or economical. Produces significant amounts of solid, high-value products, liquid products that cannot be derived by petroleum refining, or both, and conversely produces small amounts of fuel products and / or fuel mixture components.

[0068] Figures 5-7 show more detailed examples of possible process integrations that provide specific examples of high value products. In FIG. 7, the coal-based raw material is placed in a dryer to remove about 90% of the water content. The dried coal is then converted in a thermochemical processing step consisting of two fully integrated solvent extraction steps and a single pyrolysis step in this example. The first solvent extraction utilizes polar solvents (eg, DMF, ethanol, water) to recover oxygen-containing molecules. The second solvent extraction uses a non-polar solvent (eg, mixed hydrogenated oil, tetralin, supercritical fuel, 1-methyl-naphthalene). Pyrolysis of solvent extraction residues is performed at 400-1200 ° F to produce soil conditioner products and building materials, as well as worthy hydrocarbons containing vapors as intermediates for further processing.

[0069] After thermochemical processing, the various streams are separated by known techniques including, for example, distillation, vacuum distillation, solvent extraction, crystallization, wipe-film evaporation, liquid-liquid extraction and decantation. In some embodiments, the separated product may be reused for thermochemical processing steps until the desired composition, conversion or boiling range is achieved. In some cases, separation may be performed during the thermochemical processing step (ie, solvent extraction 1-separation-pyrolysis-solvent extraction 2). For tar streams, vacuum distillation may be used to produce various products based on the boiling point of the stream. The fuel gas from the separation step (s) may be processed in a gas cleanup step such as amine treatment, scrubbing or membrane filtration to remove unwanted gases (eg carbon dioxide and SOx and NOx contaminants). Good. After cleaning, the fuel gas may be further converted using dry methane reforming (DMR) or methane steam reforming (SMR) and placed in the processing step or sold.

[0070] The solid product from the thermochemical processing step may be incorporated into the final product or used as an intermediate in which the final product can be manufactured or sold. Examples of products are carbon filter by-products for building materials, which can be further processed to produce activated carbon products for environmental management, or used to produce soil conditioners, or even more. Calcination to produce coke.

(Example 6-Branch from thermochemical coal processing)
[0071] With reference to FIGS. 5 and 6, this example produces a number of unique product manufacturing outcomes based on the unique integrated and synergistic steps of the thermochemical process defined herein. In order to explain how the thermochemical processing of coal can be adapted and how the thermochemical processing of coal is flexible. The examples describe laboratory-scale experiments demonstrating the proof of concept and the feasibility of additional conversion of coal-based materials to high-demand, high-value products.

[Coal stripper]
[0072] Coal solids, in which polar and non-polar molecules have been extracted with high exfoliation properties and high surface region foam, are described, which are soil purification additives, gas / fluid absorbers, graphene oxide spray slurries, and vaporization. And can be used as a char for hydrogenation.

[0073] Experimentally, the two-step experimental process was mediated by 1) removal of polar molecules via continuous extraction using DMF at 140 ° C. at 1 atm, and 2) supercritical CO2 extraction at 40 ° C. at 75 atm. Includes removal of non-polar molecules. The two steps can be applied in any order.

[Room temperature urethane foam composite material synthesis]
[0074] Organic filled with reinforcing particles with sufficient structural strength to function as a filler in skin / matrix composites or as a stand-alone foam for acoustic modulation, adiabatic, ballistic impact mitigation or buoyancy. An organic composite consisting of a matrix is described. These coal-based functionalized carbon particles, along with coal-derived urethane matrices, can produce low-cost polymer matrix composites (PMCs) with highly desirable properties.

[0075] By reacting the two solutions at room temperature to form a significantly large amount of durable foam within minutes, with intermediate separation of the extract into its individual chemical or boiling range components. Instead, the process of producing urethane composites from organic coal extracts is described herein. This process does not require causative or dangerous reagents during the foam synthesis step, uses the alcohol / phenol OH groups of the extract and reacts them with diisocyanate crosslinkers in a standard manner for superior thermal performance. It also produces non-differentiated polyurethane with moderate toughness, tensile strength and elasticity. The process also utilizes the alcohol / phenol OH groups of graphene oxide produced from coal via the Hummer method or graphitic coal char produced from coal. The addition of graphene oxide or graphitic coal char can greatly increase the strength of coal PMC.

[0076] The experimentally produced coal extract is produced in a continuous Soxhlet process using a standard evaporator, condenser and filter / siphon scheme with dimethylformamide as the solvent. A portion of the coal extract is then wet pyrolyzed at 850 ° C. for 10 to 15 minutes and then milled to a size of 200 mesh. As a laboratory example, graphene oxide is produced from coal via the standard Hummer method. Prepare a mixture of 0.5 g of water and 1% (w / w%) graphene oxide or 1% (w / w%) graphitic coal char, 0.1 g of dibutyltin dilaurate and 2 g of coal extract. Approximately 14 g of toluene d-isocyanate is added to the mixture and manually stirred vigorously to foam the solution and then cool to room temperature.

[Production of polyamide from coal]
[0077] A process for producing a polyamide from an organic coal extract is described, without any intermediate separation of the extract into its individual chemical or boiling range components. This process utilizes the carboxylic acid groups of the extract and reacts them with diamine crosslinkers in a standard manner to produce non-differentiated polyamides with excellent thermal performance as well as moderate toughness, tensile strength and elasticity.

[0078] A coal extract is produced by suspending coal in high temperature, high pressure tetralin. Reducing temperature and pressure causes the dissolved extract to precipitate from the solution. As an example on a laboratory scale, then 0.5 g of solid extract is dissolved in DMF and heated at 130 ° C. for 4 hours while refluxing with 0.5 g of hexamethylenediamine. The solution is then placed in a heated Petri dish and the DMF is evaporated to produce a polyamide precipitate.

[0079] A second sample of polyamide is prepared by suspending 10 g of coal in dimethylformamide at room temperature. The dissolved extract is separated from the solid by filtration and then reacted directly with 0.5 g of hexamethylenediamine at 150 ° C. and 1 atm. The solution was refluxed for 4 hours and placed in a heated Petri dish to form a polyamide precipitate as described above.

[0080] Modified polyamides with a variety of physical, chemical and intrinsic properties, such as the flexibility, tensile strength and glass transition temperature of the resulting polymer by varying the chemical composition, reaction conditions and solvent system. Can be generated.

[Coal-derived conductive composite material]
[0081] There are currently technical requirements for organic composites having sufficient electrical conductivity to shield electromagnetic radiation generated from computer CPUs, mobile phones, microwave ovens and the like. High-cost thermoplastics filled with medium-cost carbon black are commonly used, but the market is looking for fillers with lower filling volumes and higher conductivity. Graphene and multi-walled or single-walled carbon nanotubes work perfectly in this role; however, due to their high price, they cannot achieve widespread use. Coal-based carbon particles with oblong or oblate shapes can achieve lower volume filling in electrically conductive composites at a significantly lower cost.

[0082] Manufactures an electrically conductive organic composite of a coal-based polymer matrix composite (PMC) that forms an electrically conductive composite using a coal-based polymer base and a second coal-based carbon filler. A three-step method for doing so is described.

The process scheme consists of three steps: 1) extraction of organic residues, 2) conversion of the resulting solids into functionalized graphite-like chars, and 3) reaction of the residues and functionalized chars with diisocyanate. It consists of manufacturing a urethane-based polymer composite material.

[0084] Experimentally, coal residues were extracted using DMF as a solvent at temperatures up to 450 ° C., where temperatures above 150 ° C. required a pressure vessel and of the extract volume. Increased yields can be achieved at high temperatures. This solution is then used in the production of composites. The solids remaining after extraction of the residue are thermally decomposed at 850 ° C. for 10 to 15 minutes, after which the char is ground to a size of 200 mesh, ethanol is added as a carrier fluid and further ground with a ball mill. After 16 hours of milling, the char is filtered to remove the solvent and then placed in a stainless steel bomblet with 1/10 equal weight of diisocyanate. The bomblet is sealed and heated to 400 ° C to make the char functional. The char is then washed with some aliquots of acetone to remove excess diisocyanate and dried.

[Coal-derived polyester]
[0085] Described is the process of producing a polyester from an organic coal extract without intermediate separation of the extract into its individual chemical constituents. This process utilizes the carboxylic acid groups of the extract and reacts them with diol crosslinkers in a standard manner to produce non-differentiated polyesters with excellent thermal performance as well as moderate toughness, tensile strength and elasticity.

[0086] A coal extract is produced by suspending coal in high temperature, high pressure tetralin. Reducing temperature and pressure causes the dissolved extract to precipitate from the solution. Experimentally, 0.5 g of solid extract is dissolved in DMF and heated at 130 ° C. for 4 hours while refluxing with 0.35 g of ethylene glycol. The solution is then placed in a heated Petri dish and the DMF is evaporated to produce a polyester precipitate.

[0087] A second sample of urethane was prepared by suspending 10 g of coal in dimethylformamide at room temperature, the extract was separated from the solid by filtration, followed by 0.35 g of ethylene glycol and 150 ° C. And react directly at 1 atm. The solution was refluxed for 4 hours and placed in a heated Petri dish to form a polyester precipitate as described above.

[0088] Substitution with other glycols such as polyethylene glycol, benzenediol or bisphenol can result in similar polymers to control the desired properties, which can be combined with a mixture of diols of the resulting polymer. It can be used to control desirable properties such as flexibility, tensile strength, glass transition temperature.

[Structural foam (STUCTURAL FOAM) composite material]
[0089] 1) Liquid extraction of polar organic residues from lower coals, 2) Distillation or other separation of polar extracts to recover highly volatile organics and toluene and other selected aromatic compounds, 3 ) Acid nitration, then conversion of these residual aromatic compounds to diisocyanates via hydrogenation, then phosgene carboxylation, 4) conversion of residual solids to functionalized graphite-like chars and 5) residues, diisocyanates and A multi-step method comprising reacting a functionalized char to produce a urethane-based polymer composite is described.

[0090] Coal residues are extracted using DMF as a solvent at temperatures up to 450 ° C., where temperatures above 150 ° C. require a pressure vessel and the yield of extract volume is: It increases with temperature. Prior to the reaction to form the composite, the residue concentration in the solvent should be close to 1 g of residue / 2 g of solvent, i.e. as close to saturation as possible. This solution is used to make composites.

[0091] Toluene is nitrated in HNO ₃ / H2SO ₄ solution and dinitrate is hydrogenated with hydrogen at 500 ° C. in a pressure vessel to diamine. Diamines are converted to diisocyanates by exposure to phosgene at 250 ° C.

[0092] The solids remaining after the residue extraction are then wet pyrolyzed at 850 ° C. for 10 to 15 minutes and then ground to a size of 200 mesh. This powder is further ground with a ball mill by adding ethanol as a carrier fluid. After 16 hours of milling, the char is filtered to remove the solvent and then placed in a stainless steel bomblet with an equal weight of the extracted residue and an equal weight (residue + char) of diisocyanate. The bomblet is sealed and heated to 180 ° C. to form a composite.

[0093] The resulting foam had a density of 0.33 g / cc and a crush strength of over 150 PSI.

[Coal-derived urethane]
[0094] A process for producing urethane from an organic coal extract is described, without intermediate separation of the extract into its individual chemical constituents. This process reacts the alcohol / phenol OH groups of the extract with a diisocyanate crosslinker to produce a non-differentiated polyurethane with excellent thermal performance as well as moderate toughness, tensile strength and elasticity.

[0095] Experimentally, a coal extract was produced by suspending coal in a hot, high pressure tetraline solution, whereby the dissolved extract precipitated from the solution at reduced temperature and pressure. Experimentally, 0.5 g of the solid extract is then dissolved in acetone and heated at 60 ° C. for 4 hours while refluxing with 0.25 g of toluene diisocyanate. The solution is then placed in a heated Petri dish and the acetone is evaporated to produce a urethane film. A second sample of urethane is prepared by suspending 10 g of coal in dimethylformamide at room temperature. The dissolved extract is separated from the solid by filtration and then reacted directly with 0.5 g of toluene diisocyanate at 150 ° C. and 1 atm. The solution is refluxed for 4 hours and placed in a heated Petri dish to form a urethane film as described above.

[0096] Similar to Sample 2, except that two drops of dibutyltin dilaurate as a catalyst are added to the isocyanate mixture and the solution is refluxed for only one hour before placing in the dish to evaporate the solvent. 3 Samples are produced.

Substitution with other diisocyanates such as 1,6-diisocyanate hexanes can result in similar polymers, the mixture of isocyanates of the resulting polymer with flexibility, tensile strength, glass transition temperature. Can be used to control desirable properties, such as.

[Coal-derived graphene / graphene oxide film and powder]
[0098] A multi-step method for the synthesis of graphene powder and film from coal is described, and the route for synthesizing graphite oxide powder and reduced graphene oxide film from coal is outlined. The process was via 1) burning off volatiles of organic material from coal for 30 minutes at 850 ° C. and 2) induction heating (above 2500 ° C.) of a graphite crucible containing the solids obtained from step 1. , Including high temperature graphitization of the resulting solid in an inert vacuum environment.

[0099] Then, 3) chip / bath sonication of the resulting material in a spray-affinitive solvent (ethanol and isopropyl alcohol), 4) a material for selecting the nanoflake material in the supernatant. Centrifugation, then decantation of the solution to remove the lower solid material, 5) vacuum drying of the supernatant to produce graphene flake powder (powder synthesis), 6) from step 4 on a heated substrate. By forced spraying of the supernatant of, to form a conductive film of variable thickness and conductivity, and 7) the synthesized film is then further annealed via a tubular furnace at 800-1450 ° C. Graphene powder or film is produced by annealing (film synthesis).

[00100] Alternatively, the graphite oxide powder and graphene oxide film can be formed through 3) variable time using a strong oxidant or oxidation of the material until strong oxidation of the solution occurs. The oxidation solution consisted of 98% sulfuric acid, potassium permanganate and sodium nitrate. 4) The solids were collected by centrifugation, washed with deionized water three times, centrifuged after each wash, washed, 5) the solution supernatant was discarded, and the solids were dried by freeze-drying (powder synthesis). ..

(Example 7-industrial analysis and elemental analysis)
[Analysis of pyrolysis char]
[00101] Sample number: CE-16-Pc (char)

[0100] The reported hydrogen and oxygen values do not include hydrogen and oxygen in the adhering moisture associated with the sample. The reported results are calculated by ASTM D3180. The result is the average of two times.

[Analysis of pyrolysis char from solvent-extracted coal pyrolysis residue]
[0101] Sample number: CE-13-Res-Pc (char)

[0102] The reported hydrogen and oxygen values do not include hydrogen and oxygen in the adhering water associated with the sample. The reported results are calculated by ASTM D3180. The result is the average of two times.

[Analysis of residues from solvent extraction of pyrolysis char tested in Table 6]
[0103] Sample number: CE-16-Res

[0104] The reported hydrogen and oxygen values do not include hydrogen and oxygen in the adhering water associated with the sample. The reported results are calculated by ASTM D3180. The result is the average of two times.

(Explanation of built-in and modified forms by reference)
[0105] All references, including publications, patent applications and patents cited herein, have been shown to be incorporated individually and specifically by reference, and are incorporated herein by reference in their entirety. Is incorporated herein by reference as indicated.

[0106] The terms "a" and "an" and "the" and "at least one (species)" and similar instructions in the context of describing the present invention (particularly in the context of the following patent claims). Use of material should be construed as including both singular and plural, unless otherwise specified herein or explicitly denied by the context. The use of the term "at least one" followed by an enumeration of one or more items (eg, "at least one of A and B") is specified separately herein or is apparent. Unless denied by the context, it should be construed to mean one item (A or B) selected from the listed items or any combination of two or more of the listed items (A and B). is there. The terms "comprising", "having", "inclusion" and "containing" are unrestricted terms (ie, include "including" unless otherwise specified. However, it should be interpreted as "meaning not limited to these"). The enumeration of ranges of values herein is merely intended to serve as a simplification to individually refer to each separate value that falls within the range, unless otherwise specified herein. , The values are incorporated herein as they are individually cited herein. All methods described herein can be performed in any suitable order, unless specified separately herein or otherwise explicitly denied by the context. The use of any and all examples or exemplary languages (eg, "such as") set forth herein is solely intended to better reveal the invention and unless otherwise requested. There is no limitation on the range of. The language herein should not be construed as indicating any unclaimed element as essential to the practice of the present invention.

[0107] Preferred embodiments of the invention are described herein, including the best known embodiments of the invention for performing the invention. Modifications of those preferred embodiments can be apparent to those skilled in the art by reading the above description. We anticipate that skilled artisans will use such variants as appropriate, and we have practiced the invention differently than specifically described herein. Is intended to be. Accordingly, the present invention includes all modified and equivalent forms of the subject matter listed in the claims herein as permitted by applicable law. Moreover, any combination of the above elements, in all possible variations thereof, is included in the present invention unless specified separately herein or otherwise explicitly denied by the context.

[0108] All references throughout the application, such as patent documents or equivalents, including issued or licensed patents; patent application publications; and non-patent literature documents or other sources, are described in their respective references. They are incorporated herein by reference in their entirety, as they are individually incorporated by reference, at least partially consistent with the disclosures in this application (eg, in part). Conflicting references are incorporated by reference, except for partially conflicting references).

[0109] The terms and expressions used herein are used as descriptive terms and not as limiting terms, and in the use of such terms and expressions, the features shown and described or the features thereof. It is not intended to exclude any equivalent form of the portion, but it is recognized that various modifications are possible within the scope of the claimed invention. Thus, although the invention has been disclosed in detail by preferred embodiments, one of ordinary skill in the art may rely on exemplary embodiments of the concepts disclosed herein as well as optional features, modifications and variations. It should be understood that such modifications and variations are considered to be within the scope of the invention as defined by the appended claims. The particular embodiments presented herein are examples of useful embodiments of the present invention, and the present invention uses a number of variants of the devices, device components, and method steps presented herein. It is clear to those skilled in the art that it can be done. As will be apparent to those skilled in the art, methods and devices useful in this method may include a number of optional compositions and processing elements and steps.

[0110] When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomer, are disclosed separately. .. When the Markush group or other groups are used herein, it is intended that all individual members of the group and all possible and subordinate combinations of the group are individually included in the present disclosure. To. If a compound is described herein as a particular isomer of the compound, eg, not specified by formula or chemical name, the description is for each isomer of the individually described compound or optionally. Is intended to contain isomers of the combination of. In addition, unless otherwise specified, all isotopic variants of the compounds disclosed herein are intended to be incorporated herein. For example, it is understood that any one or more hydrogens in the disclosed molecule can be replaced with deuterium or tritium. Isotopic variants of molecules are generally useful as standards in molecular assays and in chemical and biological studies of molecules or their use. Methods for producing such isotope variants are known in the art. Specific names for compounds are intended to be exemplary, as it is known to those skilled in the art that the same compound can be named differently.

[0111] Many of the molecules disclosed herein are one or more ionizable groups [groups from which protons can be removed (eg, -COOH) or groups to which protons can be added (eg, amines) or four. It contains a group that can be graded (eg, amine)]. All possible ionic forms of such molecules and salts thereof are intended to be individually included in the disclosure herein. For salts of the compounds herein, one of ordinary skill in the art can select from a wide variety of available counterions suitable for the preparation of the salts of the invention for a given application. In certain applications, the choice of a given anion or cation for the preparation of a salt can result in an increase or decrease in the solubility of that salt.

[0112] Any combination or combination of components described or exemplified herein can be used to carry out the invention unless otherwise indicated.

[0113] If ranges are given herein, eg, temperature range, pressure range, time range or composition or concentration range, then all intermediate and subranges and all individual within those given ranges. The values are intended to be included in this disclosure. It is understood that any subrange, or individual values within the range or subrange, contained in the description herein may be excluded from the scope of the claims herein.

[0114] All patents and publications referred to herein represent the level of one of ordinary skill in the art to which the present invention belongs. References cited herein are incorporated herein by reference in their entirety and indicate the state of the art in their publication or filing date, and this information may precede, if necessary. It is intended that it can be used herein to exclude certain embodiments that exist in the art. For example, when a material composition is requested, it is known and used in the art prior to the applicant's invention, including compounds for which disclosures that provide special functionality are provided in the references cited herein. It should be understood that possible compounds are intended not to be included in the claims for material composition herein.

[0115] As used herein, "comprising" is synonymous with "including," "containing," or "featuring." It is inclusive or unrestricted and does not exclude additional unlisted elements or method steps. As used herein, "consisting of" excludes any element, step or component not specified in the claims. As used herein, "becomes essential from" does not exclude materials or steps that do not substantially affect the underlying and novel features of the claims. In each case of the present specification, any of the terms "comprising", "consisting of" and "consisting of" may be replaced with any of the other two terms. it can. The invention exemplified herein can be appropriately implemented in the absence of any element (s), limitation (s), which is not specifically disclosed herein. ..

[0116] Those skilled in the art will not rely on undue experimentation for starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods and biological methods other than those specifically exemplified. , Understand that it can be used in the practice of the present invention. All of the functionally equivalent forms of any such material and method known in the art are intended to be included in the present invention. The terms and expressions used are used as descriptive terms and not as limiting terms, and in the use of such terms and expressions, any equivalent form of the feature or part thereof shown and described. Although not intended to be excluded, it is recognized that various modifications are possible within the scope of the claimed invention. Thus, although the invention has been disclosed in detail by preferred embodiments, one of ordinary skill in the art can rely on optional features, modifications and variations of the concepts disclosed herein, such modifications. It should be understood that the forms and variants are considered to be within the scope of the invention as defined by the appended claims.

Claims (50)

A method for converting coal into multiple high-value coal products and extracts.
The step of preparing raw materials derived from coal at least partially,
Including steps to process the raw material, including a combination of thermal decomposition and solvent extraction.
A method in which the pyrolysis and solvent extraction are integrated and performed under conditions for producing a plurality of high value coal products. The method according to claim 1, wherein 50% by mass or more is a liquid at a standard temperature and pressure based on the dry amount of the high-value coal product. The method of claim 1 or 2, wherein the steps to be machined are highly branched and highly selective. The method according to any one of claims 1 to 3, wherein the thermal decomposition is carried out at a pressure selected from the range of 0.5 atm to 15 atm. The method according to any one of claims 1 to 4, wherein the thermal decomposition is carried out at a temperature selected from the range of 400 ° C. to 1200 ° C. The method according to any one of claims 1 to 5, wherein the thermal decomposition is carried out for a time of 5 seconds or less. The method according to any one of claims 1 to 6, wherein the thermal decomposition is integrated with the solvent extraction. The method according to any one of claims 1 to 7, wherein the thermal decomposition excludes water vapor to produce a gas having a mass percentage of 25% or less. The method according to any one of claims 1 to 8, wherein the thermal decomposition is carried out in the presence of hydrogen gas, methane, syngas or any combination thereof. The method according to any one of claims 1 to 9, wherein the thermal decomposition is a flash thermal decomposition. The method according to any one of claims 1 to 10, wherein the solvent extraction is carried out with at least one liquid solvent. Any of claims 1 to 11, wherein the at least one solvent is selected from the group consisting of an aliphatic solvent, an aromatic solvent, a polar solvent, a hydrogen donating solvent, an ionic liquid solvent, and any combination thereof. The method described in paragraph 1. The method according to any one of claims 1 to 12, wherein the solvent extraction is carried out with at least two kinds of liquid solvents. 13. The method of claim 13, wherein the first solvent is a polar solvent and the second solvent is a hydrogen donating solvent or vice versa. 1. The solvent extraction is a combination of a single-step solvent extraction, a plurality of single-step solvent extractions, a single multi-step solvent extraction, a plurality of multi-step solvent extractions, or a single-step and multi-step solvent extraction. The method according to any one of ~ 14. The method according to any one of claims 11 to 15, wherein the solvent extraction is performed at a temperature lower than the critical temperature of the at least one solvent. The method according to any one of claims 1 to 16, wherein the solvent extraction is performed at a temperature of 350 ° C. or lower. The method according to any one of claims 1 to 17, wherein the solvent extraction excludes water vapor to produce a gas having a mass percentage of 5% or less. Claimed that one of the at least one solvent comprises tetralin (1,2,3,4-tetrahydronaphthalene), 1-methyl-naphthalene, toluene, dimethylformamide (DMF) or any combination thereof. Item 10. The method according to any one of Items 11 to 18. The method according to any one of claims 1 to 19, wherein the solvent extraction is performed upstream of the thermal decomposition. The method according to any one of claims 1 to 20, wherein the thermal decomposition is carried out upstream of the solvent extraction. The method according to any one of claims 1 to 21, wherein a part of the product of the thermal decomposition step is reused for the solvent extraction. The processing step comprises multiple solvent extractions, and the product from the later solvent extraction is reused for the earlier solvent extraction or the thermal decomposition, or used as an intermediate for further processing upstream. 22. The method of claim 22. The method according to any one of claims 1 to 23, wherein the raw material derived from coal at least partially is 90% by weight or more of unrefined coal. 24. The method of claim 24, wherein the unrefined coal is physically, chemically or thermally preprocessed prior to the step of processing. The method according to any one of claims 1 to 25, wherein a part of the raw material is one or more physical distributions from the thermal decomposition, the solvent extraction, a reuse flow, or a combination thereof. The method according to any one of claims 1 to 26, wherein the raw material, which is at least partially derived from coal, comprises subbituminous coal. The method according to any one of claims 1 to 27, wherein the raw material, which is at least partially derived from coal, is derived from cut coal. The method according to any one of claims 1 to 28, wherein the high-value coal product comprises 10% or less of a fuel product. The method of any one of claims 1-29, wherein the high value coal product comprises a polymer or a polymer precursor. The method according to any one of claims 1 to 30, wherein the high-value coal product comprises polyurethane. The method according to any one of claims 1 to 31, wherein the high-value coal product comprises a composite polyurethane foam. The method according to any one of claims 1 to 22, wherein the high-value coal product contains polyamides. The method according to any one of claims 1 to 33, wherein the high-value coal product contains polyesters. The method according to any one of claims 1 to 34, wherein the high-value coal product contains an adhesive. The method according to any one of claims 1 to 35, wherein the high-value coal product contains an aromatic compound. The high value coal products include benzene, toluene, xylene, phenols, cresols, xylenolic acids, naphthenols, C9 monocyclic aromatic compounds, C10 monocyclic aromatic isomers or any combination thereof. , The method of claim 36. The method according to any one of claims 1 to 37, wherein the high-value coal product comprises paraffins, olefins or a combination thereof. The method according to any one of claims 1 to 38, wherein the high-value coal product comprises asphaltenes. The method of any one of claims 1-39, wherein the high value coal product comprises coal tar, distillate, pitch, carbon fiber or any combination thereof. The method according to any one of claims 1 to 40, wherein the high-value coal product comprises a soil conditioner. The method according to any one of claims 1 to 41, wherein the high-value coal product comprises a building material. The method of any one of claims 1-42, wherein a significant portion of the high value coal product is solid. When the resin, liquid or other by-product produced by the method according to any one of claims 1 to 43 is combined, the solid material is used as a building material, a composite material, a liquid additive or any of these. 43. The method of claim 43, which can be converted into a combination of. 44. The method of claim 44, wherein the extract may contain metals and rare earth elements. A method for converting coal into multiple high-value coal products,
With the step of preparing the main raw material derived from coal at least partially;
It is a step of processing the main raw material, and the order of processing is
A pyrolysis step performed in a hydrogen-rich atmosphere for a time of 10 seconds or less; and performed in at least one liquid solvent, wherein the liquid solvent consists of a group consisting of polar solvents, hydrogen donor solvents and any combination thereof. Includes steps, which are solvent extraction steps selected.
The pyrolysis step is a first process step performed on the main raw material, and the solvent extraction step is a second process step performed on the solid char generated from the pyrolysis step.
A method in which the pyrolysis step and the solvent extraction step are integrated and carried out under conditions for producing a plurality of high value coal products. 46. The method of claim 46, wherein the pyrolysis step is a flash pyrolysis process. Claim that the solvent step process is a combination of single-step solvent extraction, multiple single-step solvent extraction, single multi-step solvent extraction, multiple multi-step solvent extraction or single-step and multi-step solvent extraction. 46 or 47. The method according to any one of claims 46 to 48, wherein the solvent extraction step uses two or more kinds of solvents. Any one of claims 46-49, wherein the step of processing the raw material further comprises one or more separation steps performed after the thermal decomposition step, after the solvent extraction step, or between the solvent extractions. The method described in the section.

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