An analysis system for hydroprocessed fluid from a hydrocarbon source

Abstract

The present disclosure provides for an analysis system to analyze a hydroprocessed fluid produced from a hydrocarbon source. The analysis system includes a pyrolysis unit, a hydroprocessing unit, a chromatography column and an analytical detector unit. The pyrolysis receives and heats the hydrocarbon source to form an effluent gas that is carried to the hydroprocessing unit using a carrier gas. The hydroprocessing unit includes a hydroprocessing catalyst and a temperature control system that adds heat to the hydroprocessing chamber. In the hydroprocessing unit, the hydroprocessed fluid is formed from the reaction of hydrogen gas and the effluent gas in the presence of a hydroprocessing catalyst. The chromatography column separates the hydroprocessed fluid produced from the hydrocarbon source, which is then analyzed by the analytical detector unit.

Description

[0001] AN ANALYSIS SYSTEM FOR HYDROPROCESSED FLUID FROM A HYDROCARBON SOURCE

[0002] Technical Field

[0003] The present disclosure relates generally to an analysis system and more particularly to an analysis system for hydroprocessed fluid from a hydrocarbon source.

[0004] Background

[0005] Chemical recycling of plastics faces significant hurdles. Plastic waste streams are complex mixtures containing diverse polymer types, contaminants like other materials and additives, and varying degrees of degradation. This heterogeneity significantly impacts the efficiency and quality of chemical recycling processes, such as pyrolysis, gasification, and methanolysis. Furthermore, accurately characterizing the composition and properties of these complex waste streams is both time-consuming and challenging.

[0006] For example, pyrolysis of plastics generates a complex mixture of chemical molecules that differ substantially from conventional fossil-based feedstocks used in the oil and chemicals industry. These pyrolysis oils typically contain a wide array of compounds including a-olefins, i-olefins, diolefins, naphthenes, aromatics, and heteroatoms (e.g., sulfur, oxygen, nitrogen). This complex composition presents significant challenges for downstream processing. Hydroprocessing is important to upgrade these molecules, removing heteroatoms and saturating unsaturated compounds to paraffins. The chemical composition of the hydroprocessed material significantly influences its suitability for further processing, such as steam cracking. For instance, polyethylene pyrolysis primarily yields paraffins and olefins, while aromatic-rich polymers (e.g., polystyrene, polyurethanes) produce more aromatics, hindering the production of light olefins.

[0007] Addressing these challenges necessitates the development of advanced analytical techniques for characterizing both plastic waste and recycled products. Additionally, standardized testing protocols are important for evaluating the performance of different chemical recycling technologies. As a result, there is a need in the art to overcoming these obstacles so as to improve the effectiveness and sustainability of chemical recycling and contribute to a more circular economy for plastics.

[0008] Summary

[0009] The present disclosure addresses the challenges regarding the development of advanced analytical techniques for characterizing both plastic waste and recycled products.The present disclosure provides for testing protocols that play an important role in evaluating the performance of different chemical recycling technologies. The result is an analysis system that helps to overcoming the above obstacles in an effort to improve the effectiveness and sustainability of chemical recycling and contribute to a more circular economy for plastics.

[0010] To that end, the embodiments of the present disclosure provide for an analysis system to analyze a hydroprocessed fluid produced from a hydrocarbon source. The analysis system includes pyrolysis unit, a hydroprocessing unit, a chromatography column and an analytical detector unit, where the analysis system, as discussed herein, analyzes the hydroprocessed fluid produced from the hydrocarbon source. For the various embodiments, the pyrolysis unit includes a pyrolysis chamber and a heating source, where the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form an effluent gas from the hydrocarbon source. A carrier gas conduit, in fluid tight communication with the pyrolysis chamber, supplies a carrier gas to the pyrolysis chamber. The hydroprocessing unit has a hydroprocessing chamber that includes a hydroprocessing catalyst and a temperature control system, where the temperature control system adds heat to the hydroprocessing chamber. An effluent gas conduit couples the pyrolysis chamber and the hydroprocessing chamber in fluid tight communication, where the effluent gas conduit includes an effluent valve to control a flow of the effluent gas and the carrier gas from the pyrolysis chamber into the hydroprocessing chamber. A hydrogen supply conduit is in fluid tight communication with the hydroprocessing chamber, where the hydrogen supply conduit includes a hydrogen supply valve to control a flow of hydrogen gas to the hydroprocessing chamber for hydroprocessing reactions to form the hydroprocessed fluid. The hydroprocessing reactions occur with the hydroprocessing catalyst, the effluent gas and heat added to the hydroprocessing chamber by the temperature control system. The chromatography column has a chromatography column inlet and a chromatography column outlet, where an analysis gas conduit couples the hydroprocessing chamber and the chromatography column inlet in fluid tight communication. An analytical detector conduit couples the chromatography column outlet and the analytical detector in fluid tight communication, where the hydroprocessed fluid from the hydroprocessing chamber passes through the chromatography column to the analytical detector unit to analyze the hydroprocessed fluid produced from the hydrocarbon source.

[0011] Embodiments of the present disclosure also provide for a method of analyzing the hydroprocessed fluid produced from the hydrocarbon source with the analysis system. Themethod includes forming an effluent gas in a pyrolysis unit having a pyrolysis chamber and a heating source, where the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form the effluent gas from the hydrocarbon source; supplying a carrier gas to the pyrolysis chamber to carry the effluent gas to a hydroprocessing chamber of a hydroprocessing unit that includes a hydroprocessing catalyst and a temperature control system to add heat to the hydroprocessing chamber; supplying hydrogen gas to the hydroprocessing chamber; hydroprocessing the effluent gas with the hydroprocessing catalyst, the effluent gas, hydrogen and heat supplied by the temperature control system to form the hydroprocessed fluid; separating the hydroprocessed fluid for analysis; and analyzing the separated hydroprocessed fluid from the hydrocarbon source.

[0012] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.

[0013] Brief Summary of Drawings

[0014] Fig, 1 provides a schematic illustration of an embodiments of an analysis system according to the present disclosure.

[0015] Fig, 2 provides a schematic illustration of an embodiment of an analysis system according to the present disclosure.

[0016] Detailed Description

[0017] The present disclosure provides for an effective way of characterizing plastics or pyrolysis oils through gas chromatography (GC) that avoids separate experiments of hydroprocessing the samples in a separate device. As discussed herein, the present disclosure provides advanced analytical techniques for characterizing and evaluating both plastic waste and recycled products for their capability to be used in chemical recycling processes. The disclosure describes a solution in which microreactors are placed in series together with effluent analysis. The disclosure describes, in particular, a micropyrolyzer cell which is downstream connected to a hydroprocessing reactor, and an optional a steam cracking reactor. The effluent of the reactors can be routed to detectors for chemical characterization. The result is an analysis system that helps to overcoming the obstaclesidentified in the Background in an effort to improve the effectiveness and sustainability of chemical recycling and contribute to a more circular economy for plastics.

[0018] The figures herein follow a numbering convention in which the first digit or digits correspond to the drawing figure number and the remaining digits identify an element in the drawing. Similar elements between different figures may be identified by the use of similar digits. For example, 102 references element “02” in Fig. 1, and a similar element may be referenced as 202 in Fig. 2. It is emphasized that the purpose of the figures is to illustrate and the figures are not intended to be limiting in any way. The figures herein may not be to scale and relationships of elements in the figures may be exaggerated. The figures are employed to illustrate conceptual structures and methods herein described.

[0019] The following is a brief overview of an analysis system 100 and method of its use for the analysis of a hydroprocessed fluid produced from a hydrocarbon source. Further details, embodiments and examples of the various aspects of the analysis system 100 and method are provided herein afterwards.

[0020] Referring now to Fig. 1, there is shown an embodiment of the analysis system 100 according to the present disclosure. For the various embodiments, the analysis system 100 functions to analyze a hydroprocessed fluid produced from a hydrocarbon source. The analysis system 100 includes, among other things, a pyrolysis unit 102, a hydroprocessing unit 104, a chromatography column 106 and an analytical detector unit 108, where the analysis system 100, as discussed herein, analyzes the hydroprocessed fluid produced from the hydrocarbon source.

[0021] For the various embodiments, the pyrolysis unit 102 includes a pyrolysis chamber 110 and a heating source 111, where the pyrolysis chamber 110 receives the hydrocarbon source and the heating source 111 provides heat to the pyrolysis chamber 110 to form an effluent gas from the hydrocarbon source. A carrier gas conduit 112, in fluid tight communication with the pyrolysis chamber 110, supplies a carrier gas to the pyrolysis chamber 110. The hydroprocessing unit 104 has a hydroprocessing chamber 114 that includes a hydroprocessing catalyst 116 and a temperature control system 118, where the temperature control system 118 adds heat to the hydroprocessing chamber 114. An effluent gas conduit 120 couples the pyrolysis chamber 110 and the hydroprocessing chamber 114 in fluid tight communication, where the effluent gas conduit 120 includes an effluent valve 122 to control a flow of the effluent gas and the carrier gas from the pyrolysis chamber 110 into the hydroprocessing chamber 114. A hydrogen supply conduit 124 is in fluid tight communication with the hydroprocessing chamber 114, where the hydrogen supply conduit124 includes a hydrogen supply valve 126 to control a flow of hydrogen gas to the hydroprocessing chamber 114 for hydroprocessing reactions to form the hydroprocessed fluid. The hydroprocessing reactions occur with the hydroprocessing catalyst 116, the effluent gas and heat added to the hydroprocessing chamber 114 by the temperature control system 118.

[0022] The chromatography column 106 has a chromatography column inlet 128 and a chromatography column outlet 130, where an analysis gas conduit 132 couples the hydroprocessing chamber 114 and the chromatography column inlet 128 in fluid tight communication. An analytical detector conduit 134 couples the chromatography column outlet 130 and the analytical detector unit 108 in fluid tight communication, where the hydroprocessed fluid from the hydroprocessing chamber 114 passes through the chromatography column 106 to the analytical detector unit 108 to analyze the hydroprocessed fluid produced from the hydrocarbon source.

[0023] The method of analyzing the hydroprocessed fluid produced from the hydrocarbon source with the analysis system 100 includes forming the effluent gas in the pyrolysis unit 102 having the pyrolysis chamber 110 and a heating source 111. The pyrolysis chamber 110 receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber 110 to form the effluent gas from the hydrocarbon source. The method further includes supplying the carrier gas to the pyrolysis chamber 110 to carry the effluent gas to the hydroprocessing chamber 114 of the hydroprocessing unit 104, where the hydroprocessing chamber 114 includes the hydroprocessing catalyst and the temperature control system 118 to add heat to the hydroprocessing chamber 114. The method further includes supplying hydrogen gas to the hydroprocessing chamber 114 and hydroprocessing the effluent gas with the hydroprocessing catalyst, the effluent gas, hydrogen gas and heat supplied by the temperature control system 118 to form the hydroprocessed fluid. The method then includes separating the hydroprocessed fluid for analysis, and then analyzing the separated hydroprocessed fluid from the hydrocarbon source.

[0024] As used herein, a “hydrocarbon source” can include a synthetic polymer, a wax, pyrolysis oil and combinations thereof. As used herein, a “synthetic polymer” is formed from monomers of any number of known sources using techniques well known in the art, where the molecular weight of the polymer can range from a few thousand to several millions of atomic mass units (amu). Such sources can include, but are not limited to, simple alkyls such as C2-C12 vinyl monomers (e.g., ethylene, propylene, 1-butylene, 1-octene, efc.); dienes; halogen containing monomers, such as vinyl chloride; aromatic containingmonomers, such as styrene; oxygen containing monomers, such as monomers that include an acetate group (e.g., vinyl acetate), monomers that include a carboxylic acid group (-COOH) (e.g., acrylic acid, methacrylic acid, etc.), those containing a methoxy carbonyl group (-COOCH3) (e.g., methyl methacrylate, ethyl methacrylate, e / c.); nitrogen containing monomers, such as those that include a nitrile group (-CN) (e.g., acrylonitrile), or an amide group (-CONH2) (e.g., acrylamide); and cyclic olefins, such as styrene, norbornene, cyclopentene, etc. The above list is not limited, but is provided as an example of known monomers. For the various embodiments, the hydrocarbon source can further include one or more of water and / or organic oxygenates such as alcohols, ketones and aldehydes.

[0025] As used herein, a “wax” includes simple lipids that are an ester of a long-chain alcohol and a fatty acid, where the alcohol may contain from 12-32 carbon atoms.

[0026] As used herein, “pyrolysis oil” is the synthetic product formed from, among other things, a hydrocarbon source and / or a wax, as provided herein, or from any number of other known hydrocarbon sources (e.g., biomass) that has undergone heating in an anaerobic environment (e.g., without oxygen) in a reactor at a temperature of about 400 °C to 800 °C with subsequent cooling, separation from the aqueous phase and other processes known in the art. The resulting pyrolysis oil may or may not have undergone upgrading processes, as are known in the art.

[0027] As used herein, a “conduit” can include pipes, tubes, and / or ducts designed and intended to transport the liquids and / or gases produced at the various stages of the analysis system 100 and method provided herein. The conduit can be made of stainless steel, carbon steel or other alloy steels based on the specific application and temperature requirements. The design and choice of the conduit can vary in diameter and length depending on the flow rate and pressure of the gases. Such conduits include the carrier gas conduit, the effluent gas conduit, the hydrogen supply conduit, the analysis gas conduit and the analytical detector conduit as discussed herein.

[0028] As used herein, the terms “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. The terms “comprises” and “includes” and variations thereof do not have a limiting meaning where these terms appear in the description and claims. Thus, for example, “a” material can be interpreted to mean “one or more” materials, and a composition that “includes” or “comprises” a material can be interpreted to mean that the composition includes things in addition to the material.

[0029] The recitations of numerical ranges by endpoints include all numbers subsumed within that range, e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.The term “about” as used herein means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.

[0030] Whether or not a numerical value or end-point of a range in the specification recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the end-points of each of the ranges are significant both in relation to the other end-point, and independently of the other end-point.

[0031] For the various embodiments, the pyrolysis unit 102 includes a pyrolysis chamber 110 and the heating source 111. The pyrolysis chamber 110 provides an enclosed space in which the hydrocarbon source (e.g., the material being pyrolyzed) is heated. The heating source 111 for the pyrolysis chamber 110 provides the heat to initiate and sustain the pyrolysis process. Examples of the heating source 111 include electric heaters, gas burners and / or indirect heating. The heating source 111 can also be, or include, in internal hearting source, such as resistance heating through the use of electric current passing through the hydrocarbon source itself. Other possible heating sources can include microwave heating. In addition, the heating source 111, the pyrolysis unit 102 can also include additional features, such as a cooling system to facilitate condensing vapors and collect liquid products and controls and instrumentation, as are known, to monitor and control the process parameters (temperature, pressure, flow rates). Preferably, the pyrolysis unit 102 is a micropyrolyzer.

[0032] For the various embodiments, the pyrolysis chamber 110 receives the hydrocarbon source and the heating source 111 provides heat to the pyrolysis chamber 110 to form an effluent gas from the hydrocarbon source. For the various embodiments, the pyrolysis reactions occur in the pyrolysis chamber 110 at temperatures from 200 °C to 800 °C, preferably from 500 °C to 600 °C. In addition, it is noted that the hydrocarbon source provided in the pyrolysis chamber 110 can be a solid material at, for example, room temperature (e.g., 23 °C), but that the hydrocarbon source might alternatively be a pyrolysis liquid. In the case where the hydrocarbon source is a pyrolysis liquid the pyrolysis chamber 110 and the heating source 111 can be at a low temperature (e.g., 20 °C to 100 °C) to avoidpyrolysis. As an option, the hydrocarbon source (e.g., pyrolysis liquid) can be injected together with water or organic oxygenates such as alcohols, ketones and aldehydes.

[0033] During the pyrolysis of the hydrocarbon source, a carrier gas is used to take the pyrolysis effluent to the hydroprocessing unit 104. Referring again to Fig. 1, there is illustrated the carrier gas conduit 112, in fluid tight communication with the pyrolysis chamber 110, where the carrier gas conduit 112 supplies the carrier gas to the pyrolysis chamber 110. For the various embodiments, the carrier gas is selected from the group consisting of helium (He), hydrogen gas (H2,), argon (Ar), nitrogen gas (N2) and combinations thereof.

[0034] The effluent gas conduit 120 couples the pyrolysis chamber 110 and the hydroprocessing chamber 114 in fluid tight communication, where the effluent gas conduit 120 includes an effluent valve 122 to control a flow of the effluent gas and the carrier gas from the pyrolysis chamber 110 into the hydroprocessing chamber 114. For the various embodiments, the effluent valve 122 is a check value, which operates as a “one-way” valve to prevent the effluent gas and the carrier gas from flowing back into the pyrolysis chamber 110. In other words, the effluent valve 122 only allows movement of the effluent gas and / or the carrier gas in one-direction, when open, into the hydroprocessing chamber 114. Such a oneway valve can include a swing check valve, a lift check valve or a ball check valve as are known in the art.

[0035] For the various embodiments, the hydroprocessing chamber 114 of the hydroprocessing unit 104 includes a hydroprocessing catalyst 116 and a temperature control system 118. The temperature control system 118 functions to add heat to or remove heat from the hydroprocessing chamber 114 and the contents therein, as discussed herein. For the various embodiments, the hydroprocessing chamber 114 defines a tubular volume 136 that includes the hydroprocessing catalyst 116 and the temperature control system 118 surrounding the tubular volume 136. For the various embodiments, the hydroprocessing catalyst 116 can include a Group 6 metals (IUPAC Periodic Table of the Elements, 1 December 2018 version) selected from the group consisting of Mo, W and combinations thereof. In addition, the hydroprocessing catalyst 116 can be a solid catalyst that includes a Group 8-10 metals (IUPAC Periodic Table of the Elements, 1 December 2018 version) selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ru and combinations thereof. For the various embodiments, the hydroprocessing catalyst 116 can include an amorphous mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clays, zeolites, and combinations thereof. Examples of such hydroprocessingcatalyst 116 can include, but are not limited to, cobalt-molybdenum (Co-Mo) catalysts, which typically consist of cobalt and molybdenum sulfides supported on alumina. In addition, hydroprocessing catalyst 116 can include nickel -molybdenum (Ni-Mo) catalysts supported on alumina.

[0036] For the various embodiments, the temperature control system 118 surrounding the tubular volume 136 can operate to either provide heat to the tubular volume 136 or remove heat from the tubular volume 136. For the various embodiments, the temperature control system 118 can operate to cool the tubular volume 136 to about -150 °C or heat the tubular volume 136 to about 400 °C, where the two systems can be used to achieve a desired temperature in the range from the -150 °C to the 400 °C. For the various embodiments, the temperature control system of the hydroprocessing unit 104 can be accomplished by means of a double wall jacket surrounding the hydroprocessing chamber 114, where either cooling fluid or heating fluid can either remove or add the heat as discussed herein. For example, the cooling fluid can be liquid nitrogen (N2), liquid carbon dioxide (CO2) and / or light hydrocarbons from Cl to C4. Heating fluid can be steam, super-heated steam or molten salt. In addition, the temperature control system 118 of the hydroprocessing unit 104 can include an electrical heating or gas heating unit surrounding the hydroprocessing chamber 114, where the electrical heating unit or gas heating unit adds heat to the hydroprocessing chamber 114.

[0037] Fig. 1 also shows a hydrogen supply conduit 124 that is in fluid tight communication with the hydroprocessing chamber 114. For the various embodiments, the hydrogen supply conduit 124 includes the hydrogen supply valve 126 to control a flow of hydrogen gas to the hydroprocessing chamber 114 for hydroprocessing reactions to form the hydroprocessed fluid. For the various embodiments, the hydrogen supply valve 126 is a check value, which operates as a “one-way” valve to prevent the hydrogen gas, the effluent gas and the carrier gas from flowing back through the hydrogen supply valve 126. In other words, the hydrogen supply valve 126 only allows movement of the hydrogen gas in one-direction, when open, into the hydroprocessing chamber 114. Such a one-way valve can include a swing check valve, a lift check valve or a ball check valve as are known in the art.

[0038] The analysis system 100 further includes the chromatography column 106, where the chromatography column 106 includes the chromatography column inlet 128 and the chromatography column outlet 130. As illustrated, the analysis gas conduit 132 couples the hydroprocessing chamber 114 and the chromatography column inlet 128 in fluid tightcommunication. For the various embodiments, the chromatography column 106 can be selected from a variety of gas chromatography (GC) columns. Examples include, but are not limited to, capillary columns, including non-polar, polar and / or wax stationary phase columns; packed columns; molecular sieve columns; compound specific columns as are known, and system configurations that include two or more GC columns. Examples can include GCxGC systems that include, besides the two GC columns, a modulator and oven, each as are known in the art.

[0039] The analysis gas conduit 132 further includes a purge valve 138 and an analysis gas valve 140. For the various embodiments, both the purge valve 138 and the analysis gas valve 140 can be in a closed position to allow for a desired pressure to be achieved in the hydroprocessing chamber 114, or in an open position to either purge gases from the hydroprocessing chamber 114, as is the case for the purge valve 138, or to allow the hydroprocessed fluid to proceed to the chromatography column inlet 128 and the chromatography column 106 via analysis gas valve 140. For the various embodiments, both the purge valve 138 and the analysis gas valve 140 can be a ball valve.

[0040] In operation, the effluent gas and the carrier gas enter the hydroprocessing chamber 114 where the effluent value 122 prevents flow back to the pyrolysis chamber 110 (e.g., effluent value 122 is “closed”). In addition, each of the purge valve 138 and analysis gas valve 140

[0041] are “closed” while hydrogen gas is supplied to the hydroprocessing chamber 114 via the hydrogen supply conduit 124 and the hydrogen supply valve 126. It is noted that the hydrogen stream may optionally contain EES when the catalyst used requires catalyst sulfidation. For the various embodiments, the flow of hydrogen gas increases the pressure inside the hydroprocessing chamber 114 to a pressure of 30 to 100 bar (gauge), preferably to a pressure of 30 to 80 bar (gauge). The temperature control system 118 can be used to heat the hydroprocessing chamber 114 to a temperature of 50 °C to 400 °C, and preferably between 200 °C to 380 °C for a time interval of 10 minutes to 180 minutes, and preferably from 60 minutes to 120 minutes to form the hydroprocessed fluid. At these pressures, time and temperatures, hydroprocessing reactions occur, where the hydrogen is chemically consumed. During this process, hydrogen gas can be continually supplied to the hydroprocessing chamber 114 via the hydrogen supply conduit 124 and the hydrogen supply valve 126. During the reaction time, any optionally added organic oxygenate will be converted mainly to a hydrocarbon and water.After the completion of the desired reaction, the temperature control system 118 removes heat from the hydroprocessing chamber 114 to condense the hydroprocessed fluid into a non-gaseous state. This cooling of the hydroprocessing chamber 114 acts to condense and thereby capture the hydroprocessed fluid formed from the reactions with the hydroprocessing catalyst, the hydrogen gas, the effluent gas and heat added to the hydroprocessing chamber 114. For example, the temperature control system 118 cools the hydroprocessing chamber to a temperature of -150 °C. During the cooling, the hydrogen supply valve 126 can be in a closed state while carrier gas is fed through the effluent valve 122 so as to avoid vacuum pressure within the hydroprocessing chamber 114. When the desired cooling temperature is reached (e.g., -150 °C), the hydroprocessing chamber 114 is depressurized to separate at least a portion of the hydrogen gas and light hydrocarbons in the hydroprocessing chamber 114 from the hydroprocessed fluid in the non-gaseous state after the temperature control system 118 removes heat from the hydroprocessing chamber 114. To this end, the purge valve 138 is opened to depressurize the hydroprocessing chamber 114 while also purging hydrogen gas and any light products (e.g., light hydrocarbon products) from the hydroprocessing chamber 114. As used herein, the “depressurized” hydroprocessing chamber 114 can have a pressure of about 1 (or lower) to less than 30 bar (gauge). Preferably, the “depressurized” hydroprocessing chamber 114 can have a pressure of about 1 bar (gauge).

[0042] Once the hydroprocessing chamber 114 is in the depressurized state, purge valve 138 closes, while the effluent valve 122 feeds carrier gas into the hydroprocessing chamber 114. As this occurs, the temperature control system 118 rapidly heats the hydroprocessed fluid in the non-gaseous state to a temperature of 200 to 500 °C, preferably from 200 to 400 °C. While at this temperature, the carrier gas is used to carry the hydroprocessed fluid heated to the temperature of 200 to 500 °C to the chromatography column 106 for separating the hydroprocessed fluid for analysis. As discussed herein, the chromatography column 106 separates the hydroprocessed fluid prior to entering the analytical detector unit 108 for analysis. For the various embodiments, an oven can be used to provide heat to the chromatography column 106 so as to help facilitate the flow of the hydroprocessed fluid through the chromatography column 106.

[0043] As discussed, the analytical detector conduit 134 couples the chromatography column outlet 130 and the analytical detector unit 108 in fluid tight communication, where the hydroprocessed fluid from the hydroprocessing chamber 114 passes through the chromatography column 106 to the analytical detector unit 108 to analyze the hydroprocessedfluid produced from the hydrocarbon source. For the various embodiments, the analytical detector unit 108 can be linked to the chromatography column 106 that is used. Such analytical detector units 108 can include a mass spectrometer (MS), flame ionization detector (FID) and thermal conductivity detector (TCD), the operation of which is known in the art. For the various embodiments, combinations or two or more of the analytical detector units 108 provided herein and / or as are known in the art can be used simultaneously, sequentially, in series, in parallel and in any combination thereof as is known in the art.

[0044] Embodiments of the present disclosure can also include the use of a steam cracking unit that can be used to further process the hydroprocessed fluid from the hydroprocessing chamber 114. For example, referring to Fig. 2 there is shown an embodiment of the analysis system 200 that includes the elements and operates as described herein (e.g., in relation to Figs. 1 and 2). In addition to the elements described and seen in Figs. 1 and 2, the analysis system 200 further includes a steam cracking unit 242. For the various embodiments, the steam cracking unit 242 can be used for steam cracking the hydroprocessed fluid prior to separating the hydroprocessed fluid for analysis.

[0045] As illustrated in Fig. 2, the analysis gas conduit 232 can feed the hydroprocessed fluid from the hydroprocessing unit 204, via conduit 244, to the steam cracking unit 242. For the various embodiments, the steam cracking unit 242 includes a steam cracking chamber 246 and a steam heating source 248. The steam cracking chamber 246 receives the hydroprocessed fluid via conduit 244 and the steam heating source 248 provides heat to the steam cracking chamber 246 to chemically process the hydroprocessed fluid. For the various embodiments, steam cracking the hydroprocessed fluid can occur at a temperature of 750 °C to 950 °C, preferably at a temperature of 800 °C to 860 °C. For the various embodiments, the steam heating source 248 can be an electrical heating unit or a gas fired heating unit that is able to supply steam at the temperatures provided herein.

[0046] Conduit 250 can then be used to supply the hydroprocessed fluid, having been chemically processed in the steam cracking chamber 246, to the analysis gas conduit 232 where it proceeds to the chromatography column 206 for separation and subsequent analysis by the analytical detector unit 208. In addition, a carrier gas, as provided herein, can also be supplied to the steam cracking unit 242 to help facilitate the movement of the hydroprocessed fluid, having been chemically processed, from the steam cracking chamber 246 through the conduit 250 and to the analysis gas conduit 232 where it proceeds to the chromatography column 206 for separation and subsequent analysis by the analytical detector unit 208.In addition to the above discussion, the following aspects of the present invention are provided:

[0047] Aspect 1: an analysis system to analyze a hydroprocessed fluid produced from a hydrocarbon source, comprising: a pyrolysis unit having a pyrolysis chamber and a heating source, where the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form an effluent gas from the hydrocarbon source; a carrier gas conduit in fluid tight communication with the pyrolysis chamber, where the carrier gas conduit supplies a carrier gas to the pyrolysis chamber; a hydroprocessing unit having a hydroprocessing chamber that includes a hydroprocessing catalyst and a temperature control system, where the temperature control system adds heat to the hydroprocessing chamber; an effluent gas conduit coupling the pyrolysis chamber and the hydroprocessing chamber in fluid tight communication, where the effluent gas conduit includes an effluent valve to control a flow of the effluent gas and the carrier gas from the pyrolysis chamber into the hydroprocessing chamber; a hydrogen supply conduit in fluid tight communication with the hydroprocessing chamber, where the hydrogen supply conduit includes a hydrogen supply valve to control a flow of hydrogen gas to the hydroprocessing chamber for hydroprocessing reactions with the hydroprocessing catalyst, the effluent gas and heat added to the hydroprocessing chamber by the temperature control system to form the hydroprocessed fluid; a chromatography column having a chromatography column inlet and a chromatography column outlet; an analysis gas conduit coupling the hydroprocessing chamber and the chromatography column inlet in fluid tight communication; an analytical detector unit; and an analytical detector conduit coupling the chromatography column outlet and the analytical detector in fluid tight communication, where the hydroprocessed fluid from the hydroprocessing chamber passes through the chromatography column to the analytical detector unit to analyze the hydroprocessed fluid produced from the hydrocarbon source.

[0048] Aspect 2: the analysis system of aspect 1, where the temperature control system of the hydroprocessing unit includes an electrical heating unit surrounding the hydroprocessing chamber, where the electrical heating unit adds heat to the hydroprocessing chamber.

[0049] Aspect 3: the analysis system of any one of aspects 1-2, where the hydroprocessing catalyst includes a Group 6 metals (IUPAC Periodic Table of the Elements, 1 December 2018 version) selected from the group consisting of Mo, W and combinations thereof.

[0050] Aspect 4: the analysis system of any one of aspects 1-3, where the hydroprocessing catalyst is a solid catalyst that includes a Group 8-10 metal (IUPAC Periodic Table of theElements, 1 December 2018 version) selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ru and combinations thereof.

[0051] Aspect 5: the analysis system of any one of aspects 1-4, where the hydroprocessing catalyst includes an amorphous mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clays, zeolites, and combinations thereof.

[0052] Aspect 6: the analysis system of aspect 1, where the effluent valve and the hydrogen supply valve are each a check-valve.

[0053] Aspect 7: the analysis system of any one of aspects 1-6, where the temperature control system of the hydroprocessing unit includes a double wall jacket surrounding the hydroprocessing chamber, where a heat transfer fluid in the double wall jacket removes heat from the hydroprocessing chamber.

[0054] Aspect 8: the analysis system of any one of aspects 1-7, where the analysis gas conduit further includes a purge valve that opens to purge fluid that includes hydrogen gas from the hydroprocessing chamber.

[0055] Aspect 9: the analysis system of any one of aspects 1-8, where the analysis gas conduit feeds the hydroprocessed fluid to a steam cracking unit having a steam cracking chamber and a steam heating source, where the steam cracking chamber receives the hydroprocessed fluid and the steam heating source provides heat to the steam cracking chamber to chemically process the hydroprocessed fluid, and where the analysis gas conduit delivers the hydroprocessed fluid having been further chemically processed to the analytical detector unit.

[0056] Aspect 10: a method of analyzing a hydroprocessed fluid produced from a hydrocarbon source with an analysis system, comprising: forming an effluent gas in a pyrolysis unit having a pyrolysis chamber and a heating source, where the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form the effluent gas from the hydrocarbon source; supplying a carrier gas to the pyrolysis chamber to carry the effluent gas to a hydroprocessing chamber of a hydroprocessing unit that includes a hydroprocessing catalyst and a temperature control system to add heat to the hydroprocessing chamber; supplying hydrogen gas to the hydroprocessing chamber; hydroprocessing the effluent gas with the hydroprocessing catalyst, the effluent gas, hydrogen and heat supplied by the temperature control system to form the hydroprocessed fluid; separating the hydroprocessed fluid for analysis; and analyzing the separated hydroprocessed fluid from the hydrocarbon source.Aspect 11 : the method of aspect 10, where the pyrolysis reaction occurs in the pyrolysis chamber at temperatures from 200 °C to 800 °C. Preferably, the pyrolysis reaction occurs in the pyrolysis chamber at temperatures from 500 °C to 600 °C

[0057] Aspect 12: the method of aspect 10, where the carrier gas is selected from the group consisting of He, H2, Ar, N2 and combinations thereof.

[0058] Aspect 13: the method of aspect 10, where supplying hydrogen gas to the hydroprocessing chamber raises the pressure inside the hydroprocessing chamber to 30 to 100 bar. Preferably, supplying hydrogen gas to the hydroprocessing chamber raises the pressure inside the hydroprocessing chamber to 30 to 80 bar

[0059] Aspect 14: the method of aspect 13, where the temperature control system heats the hydroprocessing chamber to a temperature of 50 °C to 400 °C to form the hydroprocessed fluid.

[0060] Aspect 15: the method of aspect 14, where the temperature control system removes heat from the hydroprocessing chamber to condense the hydroprocessed fluid into a non-gaseous state.

[0061] Aspect 16: the method of aspect 15, where the temperature control system cools the hydroprocessing chamber to a temperature of -150 °C.

[0062] Aspect 17: the method of anyone of aspects 15 to 16, where the hydroprocessing chamber is depressurized to separate at least a portion of the hydrogen gas and light hydrocarbons in the hydroprocessing chamber from the hydroprocessed fluid in the non-gaseous state after the temperature control system removes heat from the hydroprocessing chamber.

[0063] Aspect 18: the method of aspect 17, where hydroprocessing the hydroprocessed fluid further includes heating the hydroprocessed fluid in the non-gaseous state to a temperature of 200 to 500 °C; and using the carrier gas to carry the hydroprocessed fluid heated to the temperature of 200 to 500 °C to the chromatography column for separating the hydroprocessed fluid for analysis.

[0064] Aspect 19: the method of aspect 10, where the hydrocarbon source is one of a synthetic polymer, a wax and pyrolysis oil.

[0065] Aspect 20: the method of aspect 10, where the hydrocarbon source can further include one or more of water and / or organic oxygenates such as alcohols, ketones and aldehydes.

[0066] Aspect 21: the method of aspect 10, further including steam cracking the hydroprocessed fluid prior to separating the hydroprocessed fluid for analysis.Aspect 22: the method of aspect 21, where steam cracking the hydroprocessed fluid occurs at a temperature of 750 °C to 950 °C. Preferably, steam cracking the hydroprocessed fluid occurs at a temperature of 800 °C to 860 °C.

[0067] Aspect 23: the method of aspect 22, where carrier gas is used to facilitate the analysis.

Claims

What is claimed is:

1. An analysis system to analyze a hydroprocessed fluid produced from a hydrocarbon source, comprising:a pyrolysis unit having a pyrolysis chamber and a heating source, wherein the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form an effluent gas from the hydrocarbon source;a carrier gas conduit in fluid tight communication with the pyrolysis chamber, wherein the carrier gas conduit supplies a carrier gas to the pyrolysis chamber;a hydroprocessing unit having a hydroprocessing chamber that includes a hydroprocessing catalyst and a temperature control system, wherein the temperature control system adds heat to the hydroprocessing chamber;an effluent gas conduit coupling the pyrolysis chamber and the hydroprocessing chamber in fluid tight communication, wherein the effluent gas conduit includes an effluent valve to control a flow of the effluent gas and the carrier gas from the pyrolysis chamber into the hydroprocessing chamber;a hydrogen supply conduit in fluid tight communication with the hydroprocessing chamber, wherein the hydrogen supply conduit includes a hydrogen supply valve to control a flow of hydrogen gas to the hydroprocessing chamber for hydroprocessing reactions with the hydroprocessing catalyst, the effluent gas and heat added to the hydroprocessing chamber by the temperature control system to form the hydroprocessed fluid;a chromatography column having a chromatography column inlet and a chromatography column outlet;an analysis gas conduit coupling the hydroprocessing chamber and the chromatography column inlet in fluid tight communication;an analytical detector unit; andan analytical detector conduit coupling the chromatography column outlet and the analytical detector in fluid tight communication, wherein the hydroprocessed fluid from the hydroprocessing chamber passes through the chromatography column to the analytical detector unit to analyze the hydroprocessed fluid produced from the hydrocarbon source.

2. The analysis system of claim 1 , wherein the hydroprocessing catalyst includes a Group 6 metals selected from the group consisting of Mo, W and combinations thereof.

3. The analysis system of any one of claims 1-2, wherein the hydroprocessing catalyst is a solid catalyst that includes a Group 8-10 metal selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ru and combinations thereof.

4. The analysis system of claim 1, wherein the effluent valve and the hydrogen supply valve are each a check-valve.

5. The analysis system of any one of claims 1-4, wherein the analysis gas conduit further includes a purge valve that opens to purge fluid that includes hydrogen gas from the hydroprocessing chamber.

6. The analysis system of any one of claims 1-5, wherein the analysis gas conduit feeds the hydroprocessed fluid to a steam cracking unit having a steam cracking chamber and a steam heating source, wherein the steam cracking chamber receives the hydroprocessed fluid and the steam heating source provides heat to the steam cracking chamber to chemically process the hydroprocessed fluid, and wherein the analysis gas conduit delivers the hydroprocessed fluid having been further chemically processed to the analytical detector unit.

7. A method of analyzing a hydroprocessed fluid produced from a hydrocarbon source with an analysis system, comprising:forming an effluent gas in a pyrolysis unit having a pyrolysis chamber and a heating source, wherein the pyrolysis chamber receives the hydrocarbon source and the heating source provides heat to the pyrolysis chamber to form the effluent gas from the hydrocarbon source; supplying a carrier gas to the pyrolysis chamber to carry the effluent gas to a hydroprocessing chamber of a hydroprocessing unit that includes a hydroprocessing catalyst and a temperature control system to add heat to the hydroprocessing chamber;supplying hydrogen gas to the hydroprocessing chamber;hydroprocessing the effluent gas with the hydroprocessing catalyst, the effluent gas, hydrogen and heat supplied by the temperature control system to form the hydroprocessed fluid;separating the hydroprocessed fluid for analysis; andanalyzing the separated hydroprocessed fluid from the hydrocarbon source.

8. The method of claim 7, wherein supplying hydrogen gas to the hydroprocessing chamber raises the pressure inside the hydroprocessing chamber to 30 to 100 bar.

9. The method of claim 8, wherein the temperature control system heats the hydroprocessing chamber to a temperature of 50 °C to 400 °C to form the hydroprocessed fluid.

10. The method of claim 9, wherein the temperature control system removes heat from the hydroprocessing chamber to condense the hydroprocessed fluid into a non-gaseous state.

11. The method of claim 10, wherein the temperature control system cools the hydroprocessing chamber to a temperature of -150 °C.

12. The method of anyone of claims 10 to 11, wherein the hydroprocessing chamber is depressurized to separate at least a portion of the hydrogen gas and light hydrocarbons in the hydroprocessing chamber from the hydroprocessed fluid in the non-gaseous state after the temperature control system removes heat from the hydroprocessing chamber.

13. The method of claim 12, wherein hydroprocessing the hydroprocessed fluid further includes heating the hydroprocessed fluid in the non-gaseous state to a temperature of 200 to 500 °C; andusing the carrier gas to carry the hydroprocessed fluid heated to the temperature of 200 to 500 °C to the chromatography column for separating the hydroprocessed fluid for analysis.

14. The method of claim 7, wherein the hydrocarbon source is one of a synthetic polymer, a wax and pyrolysis oil.

15. The method of claim 7, further including steam cracking the hydroprocessed fluid prior to separating the hydroprocessed fluid for analysis.

Images