A steam cracking process for converting crude oil into pitch compositions that can be spun into carbon products

Abstract

The present invention relates to a steam cracking process to convert crude oil into pitch compositions that can be spun into carbon products. The pitch compositions can be obtained by steam cracking one or more crude oils. A process to produce pitch compositions suitable for spinning into fibers from steam cracking of crude oil can include steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous products and liquid products, and a third effluent comprising one or more bottoms products; pre-treating and thermal treating the first, second, and / or third effluents to produce a pitch composition having an mesophase content of 0 vol% to 100 vol% based on the total volume of the pitch product, an MCR in the range of about 40 wt% to about 95 wt%, and a softening point T sp in the range of about 50 °C to about 400 °C.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / US2021 / 072317, international application date November 10, 2021, Chinese national phase application number 202180080250.9, and invention title "Steam cracking method for converting crude oil into a bitumen composition that can be spun into carbon products". Technical Field

[0002] This invention relates to a steam cracking method for converting crude oil into a bitumen composition suitable for spinning carbon products. Specifically, this invention relates to a method for producing bitumen compositions from the steam cracking of crude oil, and bitumen compositions suitable for spinning into fibers. Background Technology

[0003] The carbon fiber industry has been steadily growing to meet demand from a wide range of sectors, including: automotive (e.g., body parts such as trunk lids, roofs, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), aerospace (e.g., aircraft and space systems), high-performance marine vessels (e.g., yacht and racing boat hulls), aircraft, sports equipment (e.g., golf clubs, tennis rackets, bicycles, skateboards, skis, helmets, rowing or waterskiing equipment), construction (non-structural and structural systems), military (e.g., flying drones, armor, armored vehicles, military aircraft), wind energy industry, energy storage applications, refractories, carbon-carbon composites, carbon fibers, and many insulation and sealing materials used in building and road construction (e.g., concrete), turbine blades, lightweight cylinders and pressure vessels, offshore moorings and drilling risers, and medical applications. The non-limiting properties of carbon fiber make it suitable for high-performance applications: high bulk modulus and tensile modulus (depending on the morphology of the carbon fiber), high electrical and thermal conductivity, high specific strength, etc. However, despite the impressive properties exhibited by carbon fiber and carbon fiber composites, their high cost limits their application and widespread use. Therefore, developing low-cost technologies has always been a major challenge for researchers and major manufacturers.

[0004] Pitch-based carbon fibers are typically produced from coal tar or petroleum pitch. However, most carbon fibers are produced from polyacrylonitrile (PAN). Due to raw material variability and process variations, petroleum pitch-based carbon fibers are subject to batch dependence, resulting in a lack of a widespread and reliable commercial supply of isotropic pitch and / or mesophase pitch. Historically, isotropic petroleum pitch used for carbon fiber production was primarily sourced from a single refinery (e.g., Ashland Petroleum). Summary of the Invention

[0005] In at least one embodiment, the present invention provides a method for producing an asphalt composition from crude oil via steam cracking, and an asphalt composition suitable for spinning into fibers. The method includes: steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous and liquid products, and a third effluent comprising one or more bottom products; optionally introducing at least a portion of the first effluent downstream of the steam cracking zone and / or at least a portion of the second effluent downstream of the steam cracking zone and / or at least a portion of the third effluent downstream of the steam cracking zone into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product; and introducing the first effluent, the first effluent pretreatment product, the second effluent, and the third effluent into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product. The pretreated effluent, the third effluent, the pretreated third effluent, or any combination thereof are introduced into the reaction zone; and the first effluent, the pretreated first effluent, the second effluent, the pretreated second effluent, the third effluent, the pretreated third effluent, or any combination thereof are heat-treated in the reaction zone at a temperature ranging from approximately 200°C to approximately 800°C to produce a first reaction effluent comprising asphalt products and a second reaction effluent comprising a mixture of gaseous and liquid products, wherein the asphalt products have an interphase content of 0% to 100% by volume based on the total volume of the asphalt products, an MCR ranging from approximately 40% to approximately 95% by weight, and a softening point T ranging from approximately 50°C to approximately 400°C. sp .

[0006] In at least one embodiment, the present invention provides a method for producing an asphalt composition from crude oil via steam cracking, and an asphalt composition suitable for spinning into fibers. The method includes: steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous and liquid products, and a third effluent comprising one or more bottom products, wherein the first effluent is directly fed to a reaction zone for heat treatment and the first reaction effluent and / or the second reaction effluent are fed to a separation zone to produce at least one asphalt product and a separated reaction effluent comprising gaseous and liquid hydrocarbons; and discharging the first effluent, the first effluent pretreated product, the second effluent, the second effluent pretreated product, the third effluent, and the third effluent pretreated product... The first effluent, or any combination thereof, is introduced into the reaction zone; and the first effluent, the first effluent pretreated product, the second effluent, the second effluent pretreated product, the third effluent, the third effluent pretreated product, or any combination thereof are heat-treated in the reaction zone at a temperature ranging from about 200°C to about 800°C to produce a first reaction effluent comprising asphalt products and a second reaction effluent comprising a mixture of gaseous and liquid products, wherein the asphalt products have an interphase content of 0% to 100% by volume based on the total volume of the asphalt products, an MCR ranging from about 40% to about 95% by weight, and a softening point T ranging from about 50°C to about 400°C. sp . Attached Figure Description

[0007] The following figures are included to illustrate specific aspects of the invention and should not be considered as exclusive embodiments. The disclosed subject matter is capable of numerous variations, changes, combinations, and equivalents in form and function, as will be apparent to those skilled in the art and those who benefit from the invention.

[0008] Figure 1 This is a non-limiting example flowchart of a method 100 for producing spinnable bitumen from crude oil by steam cracking according to the present invention.

[0009] Figure 2 This is a flowchart of another non-limiting example of the method 200 for producing spinnable bitumen from crude oil by steam cracking according to the present invention.

[0010] Figure 3 This is a flowchart of another non-limiting example of the method 300 of the present invention for producing spinnable bitumen from crude oil by steam cracking.

[0011] Figure 4This is another non-limiting example flowchart of the method 400 for producing spinnable bitumen from crude oil by steam cracking according to the present invention.

[0012] Figure 5 This is a thermogravimetric analysis (TGA) plot, illustrating the weight loss of various bitumens as a function of temperature (°C).

[0013] Figure 6A This is a graph illustrating room-temperature X-ray scattering data of HDT-SCT isotropic asphalt and its corresponding anisotropic asphalt as a function of pyrolysis time.

[0014] Figure 6B This is an example of the molecular d of HDT-SCT isotropic asphalt as a function of pyrolysis time. π-π Or a curve of d(002) and the interlayer spacing between the corresponding anisotropic bitumen. Detailed Implementation

[0015] The present invention relates to a method for producing bitumen compositions from crude oil by steam cracking, suitable for bitumen compositions spun into fibers, and a method for characterizing said bitumen compositions.

[0016] Generally, the methods described herein relate to the steam cracking of crude oil for the production of isotropic bitumen compositions and / or mesophase bitumen compositions, and further for the production of fibers, fiber webs, carbon composites and carbon products.

[0017] Furthermore, the method of the present invention advantageously produces cost-effective bitumen suitable for spinning into fibers, fiber webs, carbon fibers, carbon fiber composites, and carbon products, the bitumen being derived from the steam cracking of crude oil. Advantageously, the method of the present invention achieves significant feed flexibility and enables the production of bitumen on a scale never before achieved.

[0018] Definition and testing methods

[0019] The new periodic table symbols used are described in Chemical & Engineering News, 63(5), 27 (1985).

[0020] The abbreviations used in this article are as follows: DSC stands for Differential Scanning Calorimetry; TGA stands for Thermogravimetric Analysis; T g It is the glass transition temperature, T sp This is the softening point temperature; QI is quinoline insolubles; PAH is polycyclic aromatic hydrocarbons; SCF / B is standard cubic feet hydrogen / barrel total feed; MCR is microcarbon residue; N is the number of molecules; MCRT is microcarbon residue test; RPM is revolutions per minute; Pa s is Pascal-second; weight% is weight percentage; mole% is mole percentage; volume% is volume percentage; hr is hour; psig is pound per square inch gauge pressure; LHSV is liquid hourly space velocity; N / A is not applicable; N / D is undetermined.

[0021] All numerical values ​​in the specific embodiments and claims herein are modified by “about” or “approximately” and take into account experimental errors and variations that would be expected by one of ordinary skill in the art. Unless otherwise indicated, the ambient temperature (room temperature) is from about 18°C ​​to about 20°C.

[0022] As used in this invention and the claims, the singular forms “a,” “an,” “the,” and “the” include the plural forms, unless the context clearly specifies otherwise.

[0023] The term “and / or” as used in this article, such as in the phrase “A and / or B”, is intended to include “A and B”, “A or B”, and “A” and “B”.

[0024] When the term "between" is used in this document to refer to a range, the term includes the endpoints of the range. That is, "between 2% and 10%" refers to 2%, 10%, and all percentages between these terms.

[0025] When the term "independently" refers to selecting multiple items from a given Markush group, it means that the selection of the first item does not necessarily affect the selection of any second or subsequent items. In other words, independently selecting multiple items within a given Markush group means that the items can be the same as or different from each other.

[0026] As used herein, the term "asphalt" refers to hydrocarbons with a softening point exceeding 50°C, primarily composed of aromatic and alkyl-substituted aromatic compounds. These aromatic compounds are primarily hydrocarbons, but heteroatoms and trace metals may be present within these materials. When cooled from a melt, asphalt can solidify into an amorphous solid. Asphalt can include petroleum asphalt, coal tar pitch, natural asphalt, asphalt contained as a byproduct in the naphtha cracking industry, high-carbon asphalt obtained from petroleum asphalt, and other substances with asphalt properties produced as products in various industrial processes. Asphalt exhibits a wide softening temperature range and is typically derived from petroleum, coal tar, plants, or catalytic oligomerization reactions of small molecules (e.g., acid-catalyzed oligomerization reactions). Asphalt can also be called tar, geoasphalt, or tar. When asphalt is produced from plants, it is also referred to as resin. Various asphalts can be obtained as a product of carbonaceous residue oil in the gasoline or naphtha cracking industry, which consists of a complex mixture primarily of aromatic organic compounds, and the asphalt is solid at room temperature and exhibits a relatively wide softening temperature range. Therefore, bitumen can be obtained from the heat treatment and distillation of petroleum fractions. "Petroleum bitumen" refers to the residual carbonaceous material obtained from the distillation of crude oil and the catalytic cracking of petroleum distillates. "Coal tar bitumen" refers to the material obtained through the distillation of coal.

[0027] As used herein, the term "mesophase" refers to a disk-shaped liquid crystal material composed of planar aromatic molecules with a broad molecular weight distribution. "Mesophase pitch" consists of the "mesophase" and optionally an isotropic phase. When examined using a polarized light microscope, the mesophase exhibits optical anisotropy (birefringence). For example, based on the total volume of the pitch, mesophase pitch can be pitch containing more than about 10% by volume of mesophase. The mesophase content of the pitch can be measured from reflected polarized light microscopy images according to ASTM D4616 (Standard Test Method for the Analysis and Determination of Mesophases in Pitch by Reflected Light Microscopy), by embedding various pitch samples in epoxy resin and then polishing the samples until they become highly reflective. A series of images can be recorded to quantify the content of said anisotropy.

[0028] As used herein, the term "blend" refers to a mixture of two or more types of bitumen. Blends can be produced, for example, by solution blending, melt blending in a heated mixer, physical blending of liquid bitumen and different types of bitumen in solid form, or physical blending of bitumen in solid form. Suitable solvents for solution blending may include benzene, toluene, naphthalene, xylene, pyridine, quinoline, aromatic fractions from refining or chemical processes such as clarified oils, reformed oils, tar distillates, etc. Solution blending, solid blending, and / or melt blending can occur at temperatures from about 20°C to about 400°C.

[0029] As used herein, "thermosetting matrix" refers to a synthetic polymer-reinforced material that typically transforms from a liquid to a solid state through an irreversible chemical change. Thermosetting matrices can also include cement, concrete, ceramics, glass, asphalt, metals, or metal alloys. Thermosetting matrices can be combined with resins such as polyesters, vinyl esters, epoxy resins, bismaleimides, cyanate esters, polyimides, or phenolic resins. When cured by heat and / or chemicals (catalysts or co-catalysts) or other means, thermosetting matrices become substantially infusible and insoluble. Once cured, thermosetting matrices cannot be returned to their uncured state. Composites made with thermosetting matrices are robust and exhibit good fatigue strength. Such composites can be extremely brittle and may result in low impact toughness. For example, thermosetting matrices can be used in high-temperature applications and / or situations requiring chemical resistance.

[0030] As used herein, "thermoplastic matrix" refers to a polymer that can be molded, melted, and reshaped without altering its physical properties. In some cases, thermoplastic matrices may be tougher and less brittle than thermoset materials, exhibiting excellent impact resistance and damage tolerance. In other cases, thermoplastic matrices can remain below their glass transition temperature, thus becoming glassy and very brittle. Because the matrix can be melted, the composite material is easier to repair and can be readily reshaped and recycled. The density of thermoplastic matrices can be lower than that of thermoset matrices, making them a viable alternative for weight-critical applications.

[0031] As used herein, “tensile strength” refers to the amount of stress required to cause a sample to break. It is expressed in Pascals or pounds per square inch (Psi). ASTM D3379 can be used to determine the tensile strength of articles made from polymers.

[0032] The numerical ranges used in this article include the numbers listed within the range. For example, the numerical range “from 1 wt% to 10 wt%” includes 1 wt% and 10 wt% within the listed range, as well as all points within that range.

[0033] As used in this article, “glass transition temperature (T)” g "T" refers to the midpoint of the temperature at which the continuous step change in heat capacity (or the peak at the first derivative of the heat flux) is recorded on the second heating scan in a differential scanning calorimeter (DSC) experiment at a heating and cooling rate of 10°C / min. For the purposes of this invention, T can be measured using a thermal analysis TAINSTRUMENTS Q2000™ as indicated. g .

[0034] The "softening point" refers to the temperature or temperature range at which a substance softens. Here, the softening point is measured using a METTLER TOLEDO dropping point instrument, such as the METTLER TOLEDO DP70, according to a procedure similar to ASTM D3104.

[0035] The "Micro Carbon Residue Test," also known as the "MCRT," is a standard test method (micro-method) for determining micro carbon residue. The micro carbon residue (MCR) value for various petroleum materials serves as an approximate tendency for the material to form carbonaceous deposits under degradation conditions similar to those used in this test method, and can be used as a guide for the manufacture of certain feedstocks. However, caution should be exercised when interpreting the results. This test method involves determining the amount of carbon residue formed after evaporation and pyrolysis of petroleum feedstocks under specific conditions and aims to provide some indication of the relevant coke formation trends of such materials. Here, the MCRT is measured according to the ASTM D4530-15 standard test method.

[0036] Unless otherwise indicated, all figures used in this specification and related claims to represent amounts of components, properties such as molecular weight, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and claims are approximate values ​​that may vary depending on the desired properties sought to be obtained through embodiments of the invention. At least, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0037] This document presents one or more exemplary embodiments in conjunction with the embodiments of the invention disclosed herein. For clarity, not all features of the physical implementation are described or shown in this application. It should be understood that in the development of physical implementations in conjunction with the embodiments of the invention, many implementation-specific decisions must be made to achieve the developer's objectives, such as complying with system-related, business-related, governmental-related, and other constraints, which vary depending on the implementation and at different times. While the developer's efforts may be time-consuming, such efforts are routine for those skilled in the art and benefit from the invention.

[0038] Although the compositions and methods described herein are described as “comprising” or “having” various components or steps, the compositions and methods may also be “substantially composed of various components and steps” or “composed of various components and steps.”

[0039] This article also discusses various applications of carbon fiber composites formed from the bitumen compositions of the present invention. Such carbon fiber composites can be used in many applications requiring weight reduction while increasing strength and stiffness. These carbon fiber composites can also be used in offshore drilling (e.g., offshore drilling for oil and gas production) to improve corrosion resistance, fatigue resistance, and heat resistance, producing components including, but not limited to, platforms, risers, mooring lines, anchors, drill pipes, or related equipment and systems. Other product applications may include, for example, automotive (e.g., body parts such as trunk lids, roofs, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), aerospace (aircraft and space systems), sports equipment (e.g., golf clubs, tennis rackets, bicycles, skateboards, skis, helmets, boating or waterskiing equipment), construction (non-structural and structural systems), military (e.g., flying drones, armor, armored vehicles, military aircraft), wind energy industry, energy storage applications, refractory materials, carbon-carbon composites, carbon fibers, and in many insulation and sealing materials (e.g., concrete) used in building and road construction, turbine blades, lightweight cylinders and pressure vessels, offshore mooring lines and drilling risers, and medical equipment.

[0040] Methods and compositions

[0041] As described above, the present invention relates to a process for producing pitch compositions suitable for spinning fibers, binder pitch, graphitizable carbon microspheres, solid lubricants, activated carbon fibers, battery anodes, and carbon foam.

[0042] This invention provides a method comprising: steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous and liquid products, and a third effluent comprising one or more bottom products; optionally introducing at least a portion of the first effluent downstream of the steam cracking zone and / or at least a portion of the second effluent downstream of the steam cracking zone and / or at least a portion of the third effluent downstream of the steam cracking zone into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product; and distributing the first effluent, the first effluent pretreatment product, and the second effluent... The second effluent pretreatment product, the third effluent, the third effluent pretreatment product, or any combination thereof are introduced into the reaction zone; the first effluent, the first effluent pretreatment product, the second effluent, the second effluent pretreatment product, the third effluent, the third effluent pretreatment product, or any combination thereof are heat-treated in the reaction zone at a temperature ranging from approximately 200°C to approximately 800°C to produce a first reaction effluent comprising asphalt products and a second reaction effluent comprising a mixture of gaseous and liquid products, wherein the asphalt products have an interphase content of 0% to 100% by volume based on the total volume of the asphalt products, an MCR ranging from approximately 40% to approximately 95% by weight, and a softening point T ranging from approximately 50°C to approximately 400°C. sp .

[0043] Figure 1This is a non-limiting example flow diagram of a method 100 for producing an asphalt composition from crude oil via steam cracking according to the present invention. The asphalt composition is suitable for spinning fibers, binder asphalt, graphitizable carbon microspheres, solid lubricants, activated carbon fibers, battery anodes, and carbon foam. Generally, the method for producing an asphalt composition according to the present invention may include: steam cracking one or more crude oils 102 in a steam cracking zone to produce a first effluent 108 comprising a heavy oil mixture containing steam cracked tar, a second effluent 106 comprising a mixture of gaseous and liquid products, and a third effluent 110 comprising one or more bottom products (e.g., vacuum residue); optionally introducing at least a portion of the first effluent 108 and / or at least a portion of the second effluent 106 downstream of the steam cracking zone 104 into one or more pretreatment zones 112 to produce a first effluent pretreatment product 116 and / or a second effluent pretreatment product (not shown); and introducing the first effluent 108, the first effluent pretreatment product 116, and / or the second effluent pretreatment product 116 into one or more pretreatment zones 112 to produce a first effluent pretreatment product 116 and / or a second effluent pretreatment product (not shown); and introducing the first effluent 108, the first effluent pretreatment product 116, and the second effluent pretreatment product 116 into one or more pretreatment zones 112. 6. A second effluent 106, a second effluent pretreatment product (not shown), or any combination thereof are introduced into a reaction zone 118; and the first effluent 108, the first effluent pretreatment product 116, the second effluent 106, the second effluent pretreatment product (not shown), or any combination thereof are heat-treated in the reaction zone 118 to a temperature in the range of 200°C to 800°C to produce a first reaction effluent comprising bituminous product 122 and a second reaction effluent 120 comprising a mixture of gaseous and liquid products, wherein the bituminous product 122 has an interphase content of 0% to 100% based on the total volume of the bituminous product 122, an MCR in the range of about 40% to about 95% based on the total weight of the bituminous product 122, and a softening point T in the range of about 50°C to about 400°C. sp (For example, the bitumen product may have a temperature of, for example, about 100°C or higher.) sp In some cases, the asphalt product may have an intermediate phase content of about 10% by volume or less, based on the total volume of the asphalt product. In other cases, the asphalt product may have an intermediate phase content of about 10% by volume to 100% by volume, based on the total volume of the asphalt product. Furthermore, the quinoline insoluble (QI) content of the asphalt product may be about 60% by weight or less (or about 50% by weight or less, or about 40% by weight or less, or about 30% by weight or less, or about 20% by weight or less, or about 10% by weight or less).

[0044] The first effluent 108 can be directly fed to the reaction zone 118 for heat treatment, and the first reaction effluent and / or the second reaction effluent (not shown) containing asphalt product 122 can be fed to the separation zone to produce at least one asphalt product and a separated reaction effluent containing gaseous and liquid hydrocarbons (not shown); and wherein the at least one asphalt product has an interphase content of 0% to 100% based on the total volume of the at least one asphalt product, an MCR of about 40% to about 95% based on the total weight of the at least one asphalt product, and a softening point T in the range of about 50°C to about 400°C. sp The at least one bituminous product can be used to spin fibers, binder bitumen, graphitizable carbon microspheres, solid lubricants, activated carbon fibers, battery anodes, and carbon foams.

[0045] The T50 of the one or more crude oils 102 can be in the range of about 240°C to about 440°C, and based on the total weight of the one or more crude oils 102, the MCR is about 25% by weight or less, and the sulfur content is about 5% by weight or less.

[0046] The T10 of the one or more crude oils 102 can be in the range of about 50°C to about 350°C, the T90 can be in the range of about 300°C to about 700°C, and based on the total weight of the one or more crude oils 102, the hydrogen content is about 20% by weight or less, and the n-heptane asphaltenes content is about 15% by weight or less.

[0047] The first effluent 108 is a hydrocarbon mixture comprising one or more aromatic components, wherein at least about 70% by weight of the mixture has a boiling point above about 200°C at atmospheric pressure, and based on the total weight of the first effluent, the MCR is about 5% to about 55% by weight, the hydrogen content is about 4% to about 10% by weight, and the sulfur content is about 5% by weight or less.

[0048] The method of the present invention may further include combining the first effluent 108 with a flux (not shown) to produce a fluxed effluent. Suitable examples of fluxes may be selected from: reformate, steam cracked naphtha, steam cracked gas oil (SCGO), atmospheric gas oil (AGO), atmospheric heavy gas oil (HAGO), vacuum gas oil (VGO), vacuum heavy gas oil, coking naphtha, coking light gas oil, coking heavy gas oil, main tower oil residue, light circulating oil, heavy diesel oil (HDO), and any combination thereof.

[0049] The first effluent 108 may contain asphalt products with an intermediate phase content of about 10% by volume or less, based on the total volume of the asphalt products. (or about 9% by volume or less, or about 8% by volume or less, or about 6% by volume or less, or about 5% by volume or less, or about 4.5% by volume or less, or about 4% by volume or less, or about 3.5% by volume or less, or about 3% by volume or less, or about 2.5% by volume or less, or about 2% by volume or less, or about 1.5% by volume or less, or about 1% by volume or less, or about 0.5% by volume or less, for example, 0% by volume of intermediate phase).

[0050] The first effluent 108 may contain asphalt products with an MCR of about 20% to about 99% by weight, for example, about 30% to about 99% by weight, for example, about 40% to about 99% by weight, for example, about 50% to about 99% by weight, for example, about 50% to about 95% by weight, for example, about 50% to about 90% by weight, for example, about 50% to about 85% by weight, for example, about 50% to about 80% by weight.

[0051] The first effluent 108 may contain bituminous products with a QI content of about 60% by weight or less, or about 50% by weight or less, or about 40% by weight or less, or about 30% by weight or less, or about 20% by weight or less, or about 10% by weight or less.

[0052] The first effluent 108 may contain a pitch product suitable for spinning, the softening point T of which is determined according to a procedure similar to ASTM D 3104 test method. sp Below approximately 400°C (or approximately 350°C or lower, or approximately 300°C or lower, or approximately 250°C or lower, or approximately 200°C or lower, or approximately 150°C or lower, or approximately 100°C or lower), wherein the procedure can be carried out under nitrogen at a heating rate of 2°C / min up to a temperature of 400°C. The first effluent 108 may contain T sp Asphalt products at about 100°C or higher (or about 150°C or higher, or about 200°C or higher, or about 250°C or higher, or about 300°C or higher, or about 350°C or higher).

[0053] The first effluent 108 may contain a glass transition temperature (T). gAsphalt products at temperatures below about 350°C (or about 325°C or lower, or about 300°C or lower, or about 275°C or lower, or about 235°C or lower, or about 195°C or lower, or about 155°C or lower, or about 115°C or lower, or about 75°C or lower, or about 70°C or lower), determined by a second heating scan of a differential scanning calorimetry (DSC) experiment conducted under an inert atmosphere (N2) at a heating and cooling rate of 10°C / min.

[0054] The reaction effluents 120 and / or 122 can be separated by distillation, deasphalting, chromatographic separation, membrane filtration, or any combination thereof. For example, deasphalting can be performed using a solvent selected from ethane, propane, butane, pentane, hexane, heptane, octane, or any combination thereof.

[0055] The one or more pretreatment zones 112 may be one or more hydrogenation treatment zones, wherein at least a portion of the first effluent may be hydrogenated to produce a first effluent pretreatment product 116, and wherein the first effluent pretreatment product 116 is a hydrogenated first effluent product.

[0056] The method of the present invention may further include: separating the first effluent pretreatment product 116 to produce at least one distillable product and one non-distillable product. The first effluent pretreatment product 116 can be separated by distillation.

[0057] The method of the present invention may further include: heat-treating the non-distillable product to produce a reaction effluent; separating the reaction effluent to produce a heat-treated asphalt product and a separated reaction effluent, wherein the separated reaction effluent comprises gaseous and liquid hydrocarbons; and wherein the heat-treated asphalt product has an interphase content of 0% to 100% based on the total volume of the heat-treated asphalt product, an MCR in the range of about 40% to about 95% by weight, and a softening point T in the range of about 50°C to about 400°C. sp The reaction effluent can be separated by distillation, deasphalting, chromatographic separation, membrane filtration, or any combination thereof.

[0058] A third effluent 110, comprising one or more bottom products, can be directly fed to a reaction zone 118 for heat treatment to produce a heat-treated reaction effluent. The method of the present invention may further include: separating the heat-treated reaction effluent in a separation zone to produce at least one bituminous product, and a separated reaction effluent comprising gaseous and liquid hydrocarbons, wherein the at least one bituminous product has an interphase content of 0% to 100% based on the total volume of the at least one bituminous product, an MCR in the range of about 40% to about 95% by weight, and a softening point T in the range of about 50°C to about 400°C. sp .

[0059] The reaction effluent from the heat treatment can be separated by distillation, deasphalting, chromatographic separation, membrane filtration, or any combination thereof.

[0060] A third effluent 110 comprising one or more bottom products can be sent to a first separation zone to produce at least a first separation product and a second separation product, wherein at least a portion of the first separation product or at least a portion of the second separation product can be sent to a reaction zone to produce a reaction effluent. The method of the invention may further include: separating the reaction effluent generated from at least a portion of the first separation product or at least a portion of the second separation product to a second separation zone to produce at least one bituminous product, and a separated reaction effluent comprising gaseous and liquid hydrocarbons, wherein the at least one bituminous product has an interphase content of 0% to 100% based on the total volume of the at least one bituminous product, an MCR in the range of about 40% to about 95% by weight, and a softening point T in the range of about 50°C to about 400°C. sp .

[0061] The first and second separation zones can be independently selected from distillation, deasphalting, chromatographic separation, membrane filtration, or any combination thereof.

[0062] The reaction zone is a tubular, batch, semi-batch, or continuous stirred tank reactor, and is either a thermal or catalytic process. Furthermore, the reaction zone can be either a thermal or catalytic process.

[0063] The first effluent 108 containing the aforementioned bitumen products may be sent to one or more heat treatment zones to produce MCR and T. sp Both are greater than the MCR and T of the first effluent 108 sp The heat-treated pitch product, and the pitch product and / or the heat-treated pitch product are suitable for spinning into carbon fibers.

[0064] The heat-treated asphalt product may have one or more of the following: based on the total volume of the heat-treated asphalt product, the mesophase content is about 50% by volume or higher (or about 55% by volume or higher, or about 60% by volume or higher, or about 65% by volume or higher, or about 70% by volume or higher, or about 75% by volume or higher, or about 80% by volume or higher, or about 85% by volume or higher, or about 90% by volume or higher); based on the total weight of the heat-treated asphalt product, the QI content is about 1% by weight or higher (or about 5% by weight or higher, or about 10% by weight or higher, or about 20% by weight or higher, or about 25% by weight or higher, or about 30% by weight or higher, or about 40% by weight or higher, or about 50% by weight or higher, or about 60% by weight or higher, or about 70% by weight or higher, or about 80% by weight or higher, or about 90% by weight or higher, or about 95% by weight or higher); and T sp The temperature is approximately 200°C or higher (or approximately 225°C or higher, or approximately 250°C or higher, or approximately 275°C or higher, or approximately 300°C or higher, or approximately 325°C or higher, or approximately 350°C or higher).

[0065] The hydrogenation treatment of the first effluent 108 in the hydrogenation treatment zone 112 can be carried out by catalysis, heat, or a combination thereof. Suitable hydrogenation conditions may include one or more of the following: a hydrogen partial pressure of about 3,500 psig or less (or about 3,250 psig or less, or about 3,000 psig or less, or about 2,500 psig or less, or about 2,000 psig or less, or about 1,500 psig or less, or about 1,000 psig or less, or about 500 psig or less, or about 250 psig or less, or about 100 psig or less, or about 50 psig or less), a temperature in the range of about 200°C to about 500°C (or about 225°C to about 490°C, or about 250°C to about 480°C, or about 275°C to about 470°C), and a pressure in the range of about 72 psig to about 3,000 psig (or about 600 psig to about 1,900 psig). psig, or about 700 psig to about 1,800 psig, or about 800 psig to about 1,700 psig, or about 900 psig to about 1,600 psig, or about 1,000 psig to about 1,500 psig, with a stay of about 5 minutes or longer (or about 10 minutes or longer, or about 15 minutes or longer, or about 20 minutes or longer, or about 25 minutes or longer, or about 30 minutes or longer, or about 1 hour or longer, or about 2 hours or longer, or about 3 hours or longer, or about 4 hours or longer, or about 5 hours or longer, or about 6 hours or longer, or about 7 hours or longer, or about 8 hours or longer, or about 9 hours or longer, or about 10 hours or longer), and LHSV at about 0.1 hr -1 approximately 12 hours -1 Within the range (or approximately 0.5 hr) -1 approximately 10 hours -1 or approximately 0.75 hr -1 approximately 8 hours -1 or about 1 hour -1 Approximately 6 hours -1 or about 1 hour -1 approximately 4 hours -1 The hydrogenation process can be continuous, semi-batch, or intermittent.

[0066] During hydrotreating, a hydrogen stream 114 can be fed or injected into the hydrotreating zone 112, where a catalyst or catalyst system can be added. Hydrogen that can be contained in a hydrogen treatment gas (not shown) can be supplied to the hydrotreating zone 112. Hydrotreating can be a continuous fixed-bed process. The treatment gas, as referred to herein, can be pure hydrogen or a hydrogen-containing gas, which is a stream containing a sufficient amount of hydrogen for the target reaction, optionally containing one or more other gases (e.g., nitrogen and light hydrocarbons such as methane) that will not adversely interfere with or affect the reaction or the products. Impurities, such as H2S and NH3, are undesirable and are typically removed from the treatment gas before it is directed to the hydrotreating zone 112. The treatment gas introduced into the hydrotreating zone 112 will preferably contain at least about 25% by volume, for example at least about 50% by volume, more preferably at least about 75% by volume, of hydrogen.

[0067] Hydrogen can be supplied at a rate of about 100 SCF / B to about 20,000 SCF / B (or about 500 SCF / B to about 15,000 SCF / B, or about 750 SCF / B to about 10,000 SCF / B, or about 1,000 SCF / B to about 8,000 SCF / B, or about 1,500 SCF / B to about 6,000 SCF / B, or about 2,000 SCF / B to about 5,000 SCF / B).

[0068] Hydrogen can be supplied simultaneously with the first effluent 108 and / or the solvent, or separately to the hydrogenation treatment zone 112 via a separate gas conduit (not shown). Specifically, when the hydrogenation treatment is catalytic, the contact of the first effluent 108, the solvent, the catalyst, and the hydrogen can produce a total product, which may include the hydrogenation treatment product effluent 116 and, in some embodiments, a gas. The catalytic hydrogenation treatment of the first effluent 108 will be further described below.

[0069] The total pressure in the hydrogenation treatment zone 112 can range from about 72 psig to about 5,000 psig, for example from about 400 psig to about 4,000 psig, or from about 500 psig to about 2,000 psig, or from about 600 psig to about 1,500 psig. Preferably, the first effluent 108 can be hydrogenated under low hydrogen partial pressure conditions. In such an aspect, the hydrogen partial pressure during hydrogenation treatment can be from about 100 psig to about 1,500 psig, for example from about 150 psig to about 1,000 psig, or for example from about 200 psig to about 800 psig. Additionally or alternatively, the hydrogen partial pressure can be at least about 200 psig, or at least about 400 psig, or at least about 600 psig. Additionally or alternatively, the hydrogen partial pressure may be about 1,000 psig or lower, for example, about 900 psig or lower, or about 850 psig or lower, or about 800 psig or lower, or about 750 psig or lower. In such aspects with low hydrogen partial pressure, the total pressure in the hydrogenation processing zone 112 may be about 1,200 psig or lower, preferably about 1,000 psig or lower, for example, about 900 psig or lower, or about 800 psig or lower, or about 700 psig or lower, or about 600 psig or lower, or about 500 psig or lower, or about 400 psig or lower, or about 300 psig or lower, or about 200 psig or lower, or about 100 psig or lower.

[0070] The liquid hourly space velocity (LHSV) of the first effluent 108, optionally combined with the recovered component (not shown), can be obtained in approximately 0.1 h. -1 approximately 50 h -1 The range, or approximately 0.5 h -1 approximately 25 hours -1 The range, or approximately 0.75 h -1 approximately 10 h -1 The range. In some respects, LHSV is at least about 20 h. -1 or at least about 15 hours -1 or at least about 10 hours -1 or at least about 5 hours -1 or at least about 2 hours -1 Or, in some respects, LHSV is approximately 5 hours. -1 Or lower, or about 4 hours -1 Or lower, or about 3 hours -1 Or lower, or about 2 hours -1 Or lower, or about 1 hour -1 Or lower.

[0071] In some cases, a catalyst system can be used to catalyze hydrogenation, the catalyst system comprising: one or more transition metal catalysts comprising group 5, 6, 9, or 10 transition metals; and one or more supports.

[0072] The one or more transition metal catalysts may contain transition metals selected from V, Mo, W, Co, Ni, Pt, Pd, or any combination thereof.

[0073] The one or more carriers may be selected from: alumina, silicon dioxide, silicon dioxide-alumina, porous carbon, zeolite, zirconium oxide, titanium dioxide, and refractory oxides.

[0074] Hydrogenation can be carried out in the presence of a hydrogen-donating solvent. The hydrogen-donating solvent may contain at least one monocyclic aromatic compound.

[0075] The T10 of the bottom product effluent 122 can be in the range of about 500°C to about 600°C (or about 510°C to about 590°C, or about 520°C to about 580°C, or about 530°C to about 570°C, or about 540°C to about 560°C).

[0076] The T50 of the hydrotreated product effluent 116 can be in the range of about 225°C to about 375°C, and the hydrogen content is about 7% to about 12% by weight and the sulfur content is 0% to about 1% by weight based on the total weight of the treated product effluent 116.

[0077] The T50 of the hydrotreated product effluent 116 can be in the range of about 225°C to about 375°C, with a hydrogen content of about 7% to about 12% by weight and a sulfur content of 0% to about 1% by weight, based on the total weight of the treated product effluent.

[0078] The first reaction effluent containing bituminous product 122 may include a bottoms product, which may be separated by deasphalting in the presence of a solvent to produce a first portion containing the solvent and a soluble compound, and a second portion containing the solvent and the deasphalted bottoms product. The deasphalted bottoms product may include a third bituminous product, the third bituminous product having a softening point T. sp The temperature is about 25°C or higher, the hydrogen content is about 4% to about 12% by weight based on the total weight of the third pitch product, and the MCR is about 10% to about 60% by weight based on the total weight of the third pitch product, wherein the third pitch product is suitable for spinning into carbon fibers.

[0079] The T50 of the bottom product effluent 122 can be in the range of about 500°C to about 650°C (or about 525°C to about 625°C, or about 550°C to about 600°C), and the hydrogen content is about 4 wt% to about 8 wt% (or about 4.5 wt% to about 8 wt%, or about 5 wt% to about 8 wt%, or about 5.2 wt% to about 7.8 wt%, or about 5.4 wt% to about 7.6 wt%, or about 5.6 wt% to about 7.4 wt%, or about 5.8 wt% to about 7.2 wt%, or about 6 wt% to about 7 wt%) based on the total weight of the heat-treated asphalt.

[0080] The method of the present invention may further include: separating the hydrotreating product effluent 116 downstream of the hydrotreating zone to generate at least a liquid effluent (not shown); and recovering the liquid effluent back upstream of the hydrotreating zone 112 (not shown). Figure 1 In a configuration not shown, the first effluent 108 may be combined with a recovered portion of the liquid effluent that has been separated from the hydrotreated product effluent 116, and the mixture then enters the hydrotreated zone 112. Alternatively, the recovered portion of the liquid effluent may be mixed with one or more crude oils 102 before entering the steam cracking zone 104. Alternatively, a separate solvent may be added to replace or supplement the recovered portion of the liquid effluent. The weight ratio of the liquid effluent to the first effluent 108 may be from about 0.1 to about 10 (or from about 0.4 to about 8, or from about 0.6 to about 6, or from about 0.8 to about 4, or from about 1 to about 2). The hydrotreated product effluent 116 may be separated by one or more of distillation, deasphalting, chromatographic separation, membrane filtration, or a combination thereof. The bituminous composition may be characterized as relatively free of impurities and ash.

[0081] Figure 2 This is another non-limiting example flow diagram of a method 200 for producing a bitumen composition suitable for spinning fibers from crude oil via steam cracking. In this method, the bottom product effluent 122 can be separated by deasphalting in the presence of a solvent in a deasphalting unit 226 to produce a first portion 228 containing a solvent and a soluble compound, and a second portion 230 containing a solvent and deasphalted bottom product. Here, the deasphalted bottom product of the second portion 230 may contain a third bitumen product, the softening point T of which is... sp At approximately 350°C or lower (or softening point T) spThe hydrogen content is from about 4 wt% to about 12 wt% (or from about 4 wt% to about 11 wt%, or from about 4 wt% to about 10 wt%, or from about 5 wt% to about 9 wt%, or from about 5 wt% to about 8 wt%, or from about 5.2 wt% to about 7.8 wt%, or from about 5.4 wt% to about 7.6 wt%, or from about 5.6 wt% to about 7.4 wt%, or from about 5.8 wt% to about 7.2 wt%, or from about 6 wt% to about 7 wt%) based on the total weight of the third pitch product, and the MCR is from about 20 wt% to about 95 wt% (or from about 25 wt% to about 75 wt%, or from about 25 wt% to about 55 wt%, or from about 30 wt% to about 50 wt%, or from about 35 wt% to about 45 wt%) based on the total weight of the third pitch product, wherein the third pitch product is suitable for spinning into carbon fibers. The solvent may be selected from ethane, propane, butane, pentane, hexane, benzene, heptane, toluene, octane, xylene, or any isomer thereof or any combination thereof.

[0082] The method of the present invention may further include: vacuum distilling at least a portion of the deasphalted bottom product to produce a vacuum gas oil product and a vacuum bottom product; and producing fuel oil from at least a portion of the vacuum gas oil product, wherein the sulfur content of the fuel oil is 1% by weight or less.

[0083] Figure 3 This is another non-limiting example flow diagram of a method 300 for producing a bitumen composition suitable for spinning fibers from crude oil via steam cracking. Here, the method of the invention further includes solvent deasphalting at least a portion of the third effluent 110 in a deasphalting unit 334 to produce a deasphalted oil fraction 338 and a deasphalted residue oil 336.

[0084] The T50 of the deasphalted oil fraction 338 may be in the range of about 250°C to about 650°C (or about 300°C to about 640°C, or about 325°C to about 630°C, or about 350°C to about 620°C, or about 375°C to about 610°C, or about 400°C to about 600°C), and based on the total weight of the deasphalted oil fraction, the MCR is about 10 wt% to about 50 wt% (or about 15 wt% to about 45 wt%, or about 20 wt% to about 40 wt%, or about 25 wt% to about 30 wt%), and the hydrogen content is about 6 wt% to about 20 wt% (or about 6). The content is 5% by weight to about 18% by weight, or about 7% by weight to about 16% by weight, or about 7.5% by weight to about 14% by weight, or about 8% by weight to about 12% by weight, or about 8.5% by weight to about 11% by weight, with a sulfur content of about 5% by weight or less (or about 4.5% by weight or less, or about 4% by weight or less, or about 3.5% by weight or less, or about 3% by weight or less, or about 2.5% by weight or less, or about 2% by weight or less, or about 1.5% by weight or less, or about 1% by weight or less, or about 0.5% by weight or less, or about 0.2% by weight or less, or about 0.1% by weight or less).

[0085] The method of the present invention may further include: at least partially removing the deasphalted residue 336 for further processing (e.g., producing HDT Rock VR, POX, or bitumen).

[0086] like Figure 3As illustrated, the method of the present invention may further include: hydrotreating the deasphalted oil fraction 338 in the presence of hydrogen 340 in a hydrotreating zone 342 to produce an effluent 344 comprising a mixture of gaseous and liquid compounds (formed from the hydrotreating process in the hydrotreating zone 342) and a hydrotreating product effluent 348 comprising heavy hydrocarbons (e.g., HDT Rock VR). The T50 of the hydrotreated product effluent 348 can be in the range of about 300°C to about 800°C (or about 400°C to about 700°C, or about 425°C to about 675°C), and based on the total weight of the hydrotreated product effluent 348 fraction, the MCR is about 20 wt% to about 80 wt% (or about 30 wt% to about 70 wt%, or about 40 wt% to about 60 wt%), and the hydrogen content is about 6 wt% to about 20 wt% (or about 6.5 wt% to about 18 wt%, or about 7 wt% to about 16 wt%). The content of sulfur is about 5% by weight or less (or about 4.5% by weight or less, or about 4% by weight or less, or about 3.5% by weight or less, or about 3% by weight or less, or about 2.5% by weight or less, or about 2% by weight or less, or about 1.5% by weight or less, or about 1% by weight or less, or about 0.5% by weight or less, or about 0.2% by weight or less, or about 0.1% by weight or less). The method of the present invention may further include: at least partially removing the hydrotreating product effluent 348 for further processing 346 (e.g., HDTRock VR deasphalting; HDT Rock VR pyrolysis to produce mesophase and isotropic bitumen).

[0087] The method of the present invention may further include solvent deasphalting of a hydrotreated product effluent 348 containing heavy hydrocarbons in a deasphalting unit 350 to produce a deasphalted oil fraction 352 and a deasphalted residue oil 354. The deasphalted oil fraction 352 and the deasphalted residue oil 354 may also be further processed to produce, for example, isotropic asphalt and mesophase asphalt.

[0088] Solvent deasphalting of the hydrogenation product effluent 348 can occur in the presence of a solvent. Suitable examples of solvents include ethane, propane, butane, pentane, hexane, benzene, heptane, toluene, octane, xylene, any isomer thereof, or any combination thereof.

[0089] Here, hydrotreating the deasphalted oil fraction 338 in the hydrotreating zone 342 may include introducing a hydrogen stream 340 into the hydrotreating zone 342. The hydrotreating conditions in the hydrotreating zone 342 may be the same as those in the hydrotreating zone 112. For example, the hydrotreating of the deasphalted oil fraction 338 may be carried out by catalysis, heat, or a combination thereof.

[0090] The hydrotreating of the deasphalted oil fraction 338 may include one or more of the following: a hydrogen partial pressure of about 3,500 psig or less (or about 3,250 psig or less, or about 3,000 psig or less, or about 2,500 psig or less, or about 2,000 psig or less, or about 1,500 psig or less, or about 1,000 psig or less, or about 500 psig or less, or about 250 psig or less, or about 100 psig or less, or about 50 psig or less), a temperature in the range of about 200°C to about 500°C (or about 225°C to about 490°C, or about 250°C to about 480°C, or about 275°C to about 470°C), and a pressure in the range of about 72 psig to about 3,000 psig (or about 600 psig to about 1,900 psig). The concentrations of psig, or about 700 psig to about 1,800 psig, or about 800 psig to about 1,700 psig, or about 900 psig to about 1,600 psig, or about 1,000 psig to about 1,500 psig, with a stay of about 5 minutes or longer (or about 10 minutes or longer, or about 15 minutes or longer, or about 20 minutes or longer, or about 25 minutes or longer, or about 30 minutes or longer, or about 1 hour or longer, or about 2 hours or longer, or about 3 hours or longer, or about 4 hours or longer, or about 5 hours or longer, or about 6 hours or longer, or about 7 hours or longer, or about 8 hours or longer, or about 9 hours or longer, or about 10 hours or longer), and LHSV at about 0.1hr -1 approximately 12 hours -1 (or approximately 0.5 hr) -1 approximately 10 hours -1 or approximately 0.75 hr -1 approximately 8 hours -1 or about 1 hour -1 approximately 6 hours -1 or about 1 hour -1 approximately 4 hours -1 Within the range of ), the hydrogenation process can be continuous, semi-batch, or intermittent.

[0091] The hydrotreating of the deasphalted oil fraction 338 can be carried out catalystically using a catalyst system comprising: one or more transition metal catalysts containing group 5, 6, 9, or 10 transition metals; and one or more supports. The one or more transition metal catalysts comprise transition metals selected from V, Mo, W, Co, Ni, Pt, Pd, or any combination thereof. The one or more supports are selected from: alumina, silica, silica-alumina, porous carbon, zeolite, zirconium oxide, titanium dioxide, and refractory oxides. The hydrotreating of the deasphalted oil fraction 338 can be carried out in the presence of a hydrogen-donating solvent containing at least one aromatic ring.

[0092] Figure 4 This is a flow chart of another non-limiting example of a method 400 for producing a bitumen composition suitable for spinning fibers from crude oil via steam cracking. In this method, at least a portion of the third effluent 110 is hydrotreated in a hydrotreating zone 456 and then solvent-deasphalted in a deasphalting unit 334, thereby producing an effluent 458 containing a gas oil portion and a hydrotreated effluent 460, wherein the hydrotreated effluent 460 contains bitumen products, the MCR of which is based on a total weight of the hydrotreated effluent 460 from 0 wt% to about 60 wt% (or about 1 wt% to about 50 wt%, or about 2 wt% to about 40 wt%, or about 5 wt% to about 30 wt%), and a softening point T. sp The temperature is approximately 400°C or lower (or approximately 350°C or lower, or approximately 300°C or lower, or approximately 250°C or lower, or approximately 200°C or lower, or approximately 150°C or lower, or approximately 100°C or lower), wherein the pitch product of the hydrogenated effluent 460 is suitable for spinning into carbon fibers. As described above, the hydrogenated effluent 460 can then be separated in the solvent deasphalting unit 334 for further processing.

[0093] The structure, optical texture, and composition of the asphalt compositions of the present invention, particularly mesophase asphalt, can be evaluated and analyzed by X-ray scattering and / or optical microscopy. X-ray scattering patterns can be processed to infer the following crystallographic parameters of the asphalt composition: interlayer spacing d (002), packing height (Lc), and layer diameter (L). a ) and the number of molecules packed together (N).

[0094] X-ray scattering measurements can be performed in synchrotron beamlines (e.g., at the Advanced Photon Source 9-ID at Argonne National Laboratory, which combines a Bonse-Hart ultrasmall-angle X-ray scattering (USAXS) (Si 220 crystal) design with pinhole collimated small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) configurations). For beamlines, a standard configuration with an energy of 21 keV can be used. Data represent the q range covered by the SAXS and WAXS detectors. For example, for SAXS / WAXS, data can be acquired with exposure times of 15 seconds and 30 seconds, respectively. Calibration of all generated 2-D SAXS and WAXS patterns can be performed using the silver behenate standard (d-spacing of 58.38 Å) and the LaB6 standard (a = 4.156 Å), respectively. The data can then be integrated to obtain the scattering intensity (…). I ) on the scattering vector q A one-dimensional graph, in which q = 4πsin(θ) / λ, where 2θ is the scattering angle relative to the incident beam direction. For X-ray data processing, the Irena-Nika-USAXS software package (such as that developed by J. Ilavsky and PR Jemian) can be used. Journal of Applied Crystallography Crystallography (2009), Vol. 42, pp. 347-353; and J. Ilavsky in Journal of Applied Crystallography (2012), Vol. 45(2), pp. 324-328, which are incorporated herein by reference). Samples can be prepared in a 1.5 mm diameter kapton tube. The measurements can be performed at room temperature.

[0095] Here, the mesophase bitumen composition may contain polyaramid lamellars that tend to form locally ordered associations (stacking) with more or less parallel and / or equidistant lamellars. Stacking height (L) C The following formula can be used to estimate it; The shape factor K was chosen as uniform. The number of molecules packed (N) can be expressed as N = L. C The interplanar spacing is estimated using / d(002)+1. ;where q That is the maximum peak value.

[0096] The packing height (L) of the mesophase pitch composition of the present invention was determined by X-ray scattering. C The packing height (L) of the mesophase pitch composition of the present invention can be about 2 nm or higher (or about 3 nm or higher, or about 3.5 nm or higher, or about 3.75 nm or higher, or about 4 nm or higher, or about 4.25 nm or higher, or about 4.5 nm or higher).​C The wavelength can be approximately 2 nm to approximately 9 nm (or approximately 2.5 nm to approximately 8.5 nm, approximately 3 nm to approximately 8 nm, approximately 3.5 nm to approximately 7.5 nm, or approximately 4 nm to approximately 7 nm).

[0097] The method of the present invention may further include: producing fibers from any of the aforementioned pitch products, wherein the fibers may be oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphitized fiber webs. The production of fibers, carbon fibers, carbon products, and carbon composite materials is further described.

[0098] Figure 1 , 2 References 3 and 4 provide non-limiting examples and descriptions of the methods and systems of the present invention, wherein the methods and systems can produce a feedstock that can subsequently be converted into mesophase asphalt or isotropic asphalt having a higher softening point than the feedstock. For example, effluent 108 can be pyrolyzed to produce a heat-treated product, which, upon deasphalting, can produce isotropic asphalt. This isotropic asphalt can be further heat-treated to produce mesophase asphalt. Similarly, effluent 122 can be pyrolyzed to produce a heat-treated product, which, upon deasphalting, can produce isotropic asphalt. This isotropic asphalt can be further heat-treated to produce mesophase asphalt.

[0099] Figure 1 , 2 Sections 3 and 4 provide non-limiting examples and descriptions of the methods and systems of the present invention. Those skilled in the art will recognize that other components may be included for the proper and safe operation of the methods. Examples of other components may include, but are not limited to, flow meters, sensors, heat exchangers, valves, and any combinations thereof.

[0100] The method of the present invention may also include the production of carbon articles comprising the carbon fiber composite material, binder pitch, graphitizable carbon microspheres, solid lubricants, activated carbon fibers, battery anodes, or carbon foams. Examples of carbon articles are further described below.

[0101] Spinning asphalt into fibers

[0102] After separation, the bitumen composition of the present invention can be directly spun into fibers.

[0103] In some cases, the first pitch can be spun in combination with the second pitch, wherein the viscosity of the first pitch at the spinning temperature may differ from that of the second pitch at the spinning temperature. In some cases, the viscosity of the first pitch may be greater than that of the second pitch. In other cases, the viscosity of the first pitch may be lower than that of the second pitch. Blending two or more pitches to control melt spinning or to control the properties (e.g., tensile strength) of the resulting carbon fibers may be desirable and advantageous. More specifically, the first pitch can be spun in combination with the second pitch, wherein the first pitch can form a first carbon fiber as a first layer (i.e., an inner / center layer), and the second pitch can form a second carbon fiber as a second layer (i.e., an outer layer), thereby forming a second carbon fiber on the surface of the first layer. Other non-limiting examples may include: 1) forming a second bitumen on the surface of the first bitumen, wherein the second bitumen reacts with air at a greater rate than the first bitumen to produce an oxide layer, thereby preventing the fibers from sticking together during winding; 2) making the outer bitumen harder than the inner bitumen; 3) making the bitumen more resistant to external surface defects than internal surface defects; 4) using the second bitumen primarily to produce much narrower fibers in the core / inner layer to increase the strength of the core / inner fiber layer; 5) making the second bitumen form a better interface with the matrix. For example, two different bitumens can be used in a two-component spinning machine to produce fibers in which different materials (bitumens) are geometrically arranged along the long axis of the filament (fiber). For example, “side-by-side” fibers can be created, wherein the two bitumens are arranged along the long axis of the fiber. In other examples, other geometric arrangements, such as “sheath and core” fibers, can be produced. Non-limiting examples of arrangements may include “tilted trefoil,” “island in the sea,” or other suitable geometries. In some cases, the bitumen product, the hydrotreated bitumen product, and / or the third bitumen product may have different viscosities.

[0104] The method of the present invention may include: producing carbon fibers from the above-mentioned bitumen composition (based on the total volume of the bitumen composition, an isotropic and / or anisotropic bitumen composition with an intermediate phase content of less than 10% by volume, or an isotropic and / or anisotropic bitumen composition with an intermediate phase content of 10% by volume or higher).

[0105] The spun pitch-based carbon fibers can be produced using a melt spinning process. This process can use a pitch composition with a softening point of 50°C to 400°C (or higher than 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 250°C, 300°C, or 320°C). The pitch composition of this invention can be introduced into an extruder, whereby the pitch composition can be heated, sheared, and extruded through a capillary to form carbon fibers. The spinning process can produce continuous fibers or fiber webs. Subsequently, the spun fibers or fiber webs can be stabilized, carbonized, or graphitized.

[0106] Carbon fiber composite materials and their production methods

[0107] The present invention also provides a method for forming a composite material, wherein carbon fibers can be formed from a single bitumen or a blend of two or more bitumens and a matrix. The matrix can be, for example, a thermosetting matrix, a thermoplastic matrix, or a combination thereof.

[0108] The carbon fiber composite material may comprise carbon fibers produced from the pitch product of the present invention (as described above). Based on the total volume of the carbon fiber composite material, the carbon fiber composite material may contain about 1 vol% to about 70 vol% carbon fibers and about 99 vol% to about 30 vol% matrix.

[0109] The matrix used in this article can be derived from the following substances: thermosetting polymers (e.g., cyclopentadiene, dicyclopentadiene, epoxy resins, bitumen, phenolic resins, vinyl esters, polyimides, and polyesters), thermoplastic polymers (e.g., including one or more of the following thermoplastic polymers: polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyetherimide, and polyphenylene sulfide), cement, concrete, ceramics, metals, metal alloys, or combinations thereof. For example, bitumen itself can be used as a matrix and / or binder for carbon fiber composites by impregnating numerous oxidized fibers, carbon fibers, or graphite fibers, or oxidized, carbonized, or graphitized fiber webs with bitumen and carbonizing the assembly, thereby enabling the production of carbon-carbon composites. In such cases, the carbon fibers are laid in the desired form, then the fibers are impregnated, and then these materials are carbonized at high temperatures to form solid carbon blocks. Impregnation with bitumen is often repeated several times before the final carbon product is formed; this method is commonly used in the production of carbon brakes.

[0110] This invention also relates to a method for manufacturing carbon fiber composite materials, the method comprising: combining at least one composite filler with at least one matrix, the composite filler comprising carbon fibers produced from the aforementioned spinnable pitch composition, wherein the matrix is ​​a thermosetting matrix, a thermoplastic matrix, cement, concrete, ceramic, metal, metal alloy, or a combination thereof. The composite filler may be used in the carbon fiber composite material after stabilization, carbonization, or graphitization processes. The composite filler may be short or continuous, in the form of pads, bundles, unidirectional or multidirectional, woven or nonwoven. The carbon fiber composite material components may be produced using conventional molding, roving, autoclave, and pultrusion processes.

[0111] The carbon fiber composite exhibits superior stiffness, strength, corrosion resistance, density, thermal conductivity, and / or electrical conductivity compared to similar composites without carbon fiber incorporation. Furthermore, carbon fiber-reinforced composites tend to be lighter and exhibit higher specific strength (relative to mass-normalized strength) compared to other reinforcing agents. Additionally, this carbon fiber composite exhibits a low coefficient of thermal expansion, particularly when using fibers with high graphite content; this property can be enhanced by controlling the orientation / texture of the carbon fibers on the pitch.

[0112] In at least one embodiment, the method of the present invention may include: producing fibers from the asphalt product, the hydrotreated asphalt product, the third asphalt product, or any combination thereof, wherein the asphalt product, the hydrotreated asphalt product, and / or the third asphalt product may be obtained as described in methods 100, 200, 300, and / or 400, and wherein the fibers may be oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphitized fiber webs.

[0113] In other embodiments, the method of the present invention may include producing fibers from a pitch product obtained by heat-treating the material produced in methods 100, 200, 300 and / or 400, wherein the fibers may be oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs or graphitized fiber webs.

[0114] The method of the present invention may further include: producing carbon articles comprising carbon fibers produced from the pitch product, the hydrogenated pitch product, and / or the third pitch product of methods 100, 200, 300, and / or 400. Additionally, a T value lower than or equal to that of the pitch product, the hydrogenated pitch product, and / or the third pitch product may be used. SP The fiber is stabilized at a stabilization temperature.

[0115] The method of the present invention may further include: producing high-modulus, high-strength carbon fibers, comprising: spinning one or more pitch products to produce spun fibers; stabilizing the spun fibers with an oxygen-containing oxidizing gas to produce stabilized fibers; carbonizing the stabilized fibers to produce carbonized fibers; and graphitizing the carbonized fibers. The carbonization of the stabilized fibers may be carried out at a carbonization temperature of about 1,000°C or higher. The diameter of the carbon fibers is about 50 µm or less. The weight loss (wt%) of any of the pitch products at the spinning temperature may be about 1 wt% or less (or about 0.75 wt% or less, or about 0.5 wt% or less, or about 0.25 wt% or less). Here, the carbon fibers can be produced by meltblowing or melt spinning processes.

[0116] The method of the present invention may further include: producing high modulus, high strength carbon fiber fabric, comprising: spinning one or more pitch products to produce spun fibers; stabilizing the spun fibers with an oxygen-containing oxidizing gas to produce stabilized fibers; weaving a fabric from the stabilized fibers to produce a stabilized fabric; carbonizing the stabilized fabric to produce a carbonized fabric; and optionally graphitizing the carbonized fabric.

[0117] The method of the present invention may further include: producing a composite material comprising: generating carbon fibers from the bitumen product, the hydrotreated bitumen product, the third bitumen product, or any combination thereof; generating a first fabric from the carbon fibers; generating a first fiber-reinforced matrix material from the first fabric and a first matrix material; generating at least a second fiber-reinforced sheet from a second fabric, wherein the second fabric is generated from a second fiber and a second matrix material, and wherein the second fabric is generated from the same or different carbon fibers; and laminating the first fiber-reinforced sheet together with the second fiber-reinforced sheet.

[0118] The first matrix material or the second matrix material may be a thermosetting resin, a thermoplastic resin, cement, concrete, ceramics, metal, metal alloy, asphalt product, or a combination thereof.

[0119] The first matrix material may be a thermoplastic resin selected from polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyester, epoxy resin, phenolic resin, vinyl ester, polyurethane, silicone, polyamide, or any combination thereof. The second fiber may be selected from glass fiber, carbon fiber, aramid fiber, ceramic fiber, boron fiber, or any combination thereof.

[0120] The second matrix material may be a resin selected from polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyester, epoxy resin, phenolic resin, vinyl ester, polyurethane, silicone, polyamide, or any combination thereof.

[0121] The first matrix material or the second matrix material may be the asphalt product, the hydrogenated asphalt product, the third asphalt product, or any combination thereof.

[0122] The composite material may include fillers, wherein the fillers are selected from carbon fibers, glass fibers, metal fibers, boron fibers, or carbon black.

[0123] End use

[0124] Non-limiting examples of carbon products may include vehicle body parts (e.g., trunk lids, roofs, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), marine moorings and drilling risers, wind turbine blades, insulation and sealing materials (e.g., concrete) for building and road construction, aircraft and aerospace systems, high-performance seagoing vessels, aircraft, sports equipment, unmanned aerial vehicles, armor, armored vehicles, military aircraft, energy storage systems, refractory materials, lightweight cylinders and pressure vessels, and medical devices. Furthermore, the fibers of this invention (e.g., filaments or webs) can be used as insulation materials (e.g., thermal insulation or sound insulation), or as shielding materials (e.g., electromagnetic shielding or radio frequency shielding), or as friction control surfaces (e.g., brake pads, such as aircraft brake pads). Other examples of applications for carbon products may include graphite foam for heat dissipation, explosion protection, etc. Additional uses may include binder bitumen, graphitizable carbon microspheres, solid lubricants, activated carbon fibers, and battery anodes.

[0125] According to at least one embodiment of the present invention, in order to form the asphalt composition and further form the carbon fiber composite material, the asphalt composition can be mixed according to any suitable mixing method to produce the above-described spinnable asphalt composition and spun into asphalt fibers. The initially spun asphalt fibers can then be oxidized to form stabilized asphalt fibers, and can further undergo carbonization and graphitization processes under inert conditions to produce carbon fiber filler. Stabilization, carbonization, and graphitization conditions can be used according to methods readily apparent to those skilled in the art. The carbon fiber filler may comprise the stabilized, carbonized, or graphitized carbon fibers. Additionally, the carbon fiber filler may comprise a fiber web, a stabilized fiber web, a carbonized fiber web, or a graphitized fiber web. The carbon fiber filler can then be used to form the carbon product and / or the associated asphalt composition.

[0126] The implementation methods disclosed herein include: A method for manufacturing an asphalt composition. The method includes: steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous and liquid products, and a third effluent comprising one or more bottom products; optionally introducing at least a portion of the first effluent downstream of the steam cracking zone and / or at least a portion of the second effluent downstream of the steam cracking zone and / or at least a portion of the third effluent downstream of the steam cracking zone into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product; and introducing the first effluent, the first effluent pretreatment product, the second effluent, and the third effluent into one or more pretreatment zones. The pretreated effluent, the third effluent, the pretreated third effluent, or any combination thereof are introduced into the reaction zone; and the first effluent, the pretreated first effluent, the second effluent, the pretreated second effluent, the third effluent, the pretreated third effluent, or any combination thereof are heat-treated in the reaction zone at a temperature ranging from approximately 200°C to approximately 800°C to produce a first reaction effluent comprising asphalt products and a second reaction effluent comprising a mixture of gaseous and liquid products, wherein the asphalt products have an interphase content of 0% to 100% by volume based on the total volume of the asphalt products, an MCR ranging from approximately 40% to approximately 95% by weight, and a softening point T ranging from approximately 50°C to approximately 400°C. sp .

[0127] B. A method for manufacturing an asphalt composition. The method includes: steam cracking one or more crude oils in a steam cracking zone to produce a first effluent comprising a heavy oil mixture containing steam cracked tar, a second effluent comprising a mixture of gaseous and liquid products, and a third effluent comprising one or more bottom products, wherein the first effluent is directly fed to a reaction zone for heat treatment and the first reaction effluent and / or the second reaction effluent are fed to a separation zone to produce at least one asphalt product and a separated reaction effluent comprising gaseous and liquid hydrocarbons; and discharging the first effluent, the first effluent pretreated product, the second effluent, the second effluent pretreated product, the third effluent, and the third effluent pretreated product... The first effluent, or any combination thereof, is introduced into the reaction zone; and the first effluent, the first effluent pretreated product, the second effluent, the second effluent pretreated product, the third effluent, the third effluent pretreated product, or any combination thereof are heat-treated in the reaction zone at a temperature ranging from about 200°C to about 800°C to produce a first reaction effluent comprising asphalt products and a second reaction effluent comprising a mixture of gaseous and liquid products, wherein the asphalt products have an interphase content of 0% to 100% by volume based on the total volume of the asphalt products, an MCR ranging from about 40% to about 95% by weight, and a softening point T ranging from about 50°C to about 400°C. sp .

[0128] Implementation methods A and B may each have one or more of the following elements in any combination: Element 1: wherein the first effluent is directly fed to the reaction zone for heat treatment and / or the first reaction effluent and / or the second reaction effluent are fed to the separation zone to produce at least one asphalt product and a separated reaction effluent containing gaseous and liquid hydrocarbons; and wherein the at least one asphalt product has an interphase content of 0% to 100% based on the total volume of the at least one asphalt product, an MCR of about 40% to about 95% based on the total weight of the at least one asphalt product, and a softening point T in the range of about 50°C to about 400°C. sp .

[0129] Element 2: The reaction effluent is separated by distillation, deasphalting, chromatographic separation, membrane filtration or any combination thereof.

[0130] Element 3: Deasphalting is carried out using a solvent selected from ethane, propane, butane, pentane, hexane, heptane, octane, or any combination thereof.

[0131] Element 4: wherein the one or more pretreatment zones are one or more hydrogenation treatment zones, wherein at least a portion of the first effluent is hydrogenated to produce a first effluent pretreatment product, and wherein the first effluent pretreatment product is a hydrogenated first effluent product.

[0132] Element 5: Separate the first effluent pretreatment product to produce at least one distillable product and one non-distillable product.

[0133] Element 6: The first effluent pretreatment product is separated by distillation.

[0134] Element 7: The non-distillable product is heat-treated to produce a reaction effluent; the reaction effluent is separated to produce a heat-treated asphalt product and a separated reaction effluent; wherein the separated reaction effluent comprises gaseous and liquid hydrocarbons; and wherein the heat-treated asphalt product has an interphase content of 0% to 100% based on the total volume of the heat-treated asphalt product, an MCR of about 40% to about 95% based on the total weight of the heat-treated asphalt product, and a softening point T in the range of about 50°C to about 400°C. sp .

[0135] Element 8: The reaction effluent is separated by distillation, deasphalting, chromatographic separation, membrane filtration or any combination thereof.

[0136] Element 9: The stacking height (L) of the asphalt product, determined by X-ray scattering. C The wavelength ranges from approximately 2 nm to approximately 9 nm.

[0137] Element 10: Separating the heat-treated reaction effluent in a separation zone to produce at least one bituminous product, and a separated reaction effluent comprising gaseous and liquid hydrocarbons, wherein the at least one bituminous product has an interphase content of 0% to 100% based on the total volume of the at least one bituminous product, an MCR of about 40% to about 95% based on the total weight of the at least one bituminous product, and a softening point T in the range of about 50°C to about 400°C. sp .

[0138] Element 11: The reaction effluent from the heat treatment is separated by distillation, deasphalting, chromatographic separation, membrane filtration, or any combination thereof.

[0139] Element 12: wherein the third effluent containing one or more bottom products is fed to a first separation zone to produce at least a first separation product and a second separation product, wherein at least a portion of the first separation product or at least a portion of the second separation product is fed to a reaction zone to produce a reaction effluent.

[0140] Element 13: Separating the reaction effluent generated from at least a portion of the first separation product or at least a portion of the second separation product to a second separation zone to produce at least one bituminous product, and a separated reaction effluent comprising gaseous and liquid hydrocarbons, wherein the at least one bituminous product has an interphase content of 0 vol% to 100 vol% based on the total volume of the at least one bituminous product, an MCR of about 40 wt% to about 95 wt% based on the total weight of the at least one bituminous product, and a softening point T in the range of about 50°C to about 400°C. sp .

[0141] Element 14: wherein the first and second separation zones are independently selected from distillation, deasphalting, chromatographic separation, membrane filtration or any combination thereof.

[0142] Element 15: The reaction zone is a tubular, batch, semi-batch, or continuous stirred tank reactor, and is a thermal or catalytic process.

[0143] Element 16: The reaction zone described therein is a thermal process or a catalytic process.

[0144] Element 17: The T50 of said one or more crude oils is in the range of about 240°C to about 440°C, and based on the total weight of said one or more crude oils, the MCR is about 25% by weight or less, and the sulfur content is about 5% by weight or less.

[0145] Element 18: wherein the T10 of said one or more crude oils is in the range of about 50°C to about 350°C, the T90 is in the range of about 300°C to about 700°C, and based on the total weight of said one or more crude oils, the hydrogen content is about 20% by weight or less, and the n-heptane asphaltenes content is about 15% by weight or less.

[0146] Element 19: wherein, based on the total weight of the first effluent, at least about 70% by weight of the mixture in the first effluent has a boiling point above about 200°C at atmospheric pressure, an MCR of about 5% to about 55% by weight, a hydrogen content of about 4% to about 10% by weight, and a sulfur content of about 5% by weight or less.

[0147] Element 20: The first effluent is combined with flux to produce a fluxed effluent.

[0148] Element 21: The flux is selected from: reforming oil, steam cracked naphtha, steam cracked gas oil (SCGO), atmospheric gas oil (AGO), atmospheric heavy gas oil (HAGO), vacuum gas oil (VGO), vacuum heavy gas oil, coking naphtha, coking light gas oil, coking heavy gas oil, main tower oil foot, light circulating oil, heavy diesel oil (HDO) and any combination thereof.

[0149] Element 22: wherein, based on the total volume of the asphalt product, the content of the intermediate phase of the asphalt product is about 10% by volume or less.

[0150] Element 23: wherein, based on the total volume of the asphalt product, the intermediate phase content of the asphalt product is from about 10% to 100% by volume.

[0151] Element 24: The content of quinoline insolubles (QI) in the bitumen product is about 60% by weight or less.

[0152] Element 25: The T of the asphalt product thereon sp At approximately 100°C or higher.

[0153] Element 26: The T of the asphalt product thereon g At approximately 70°C or higher.

[0154] Element 27: The bitumen product is sent to one or more heat treatment zones to produce MCR and T. sp Both are greater than the MCR and T of the asphalt product. sp The heat-treated pitch product, and the pitch product and / or the heat-treated pitch product are suitable for spinning into carbon fibers.

[0155] Element 28: The heat-treated bitumen product wherein the heat-treated bitumen product has one or more of the following characteristics: based on the total volume of the heat-treated bitumen product, the mesophase content is about 50% by volume or higher; based on the total weight of the heat-treated bitumen product, the quinoline insoluble (QI) content is about 10% by weight or higher; and T sp At approximately 200°C or higher.

[0156] Element 29: Wherein the hydrogenation process is carried out by catalysis, heat, or a combination thereof.

[0157] Element 30: The hydrotreating process includes one or more of the following: a hydrogen partial pressure of about 3,500 psig or less, a temperature in the range of about 200°C to about 500°C, a pressure in the range of about 72 psig to about 3,000 psig, a residence time of about 5 minutes or longer, and an LHSV of about 0.1 hr. -1 approximately 12 hours -1 Within the range.

[0158] Element 31: The hydrogenation process is carried out by catalysis using a catalyst system comprising: one or more transition metal catalysts comprising group 5, 6, 9, or 10 transition metals; and one or more supports.

[0159] Element 32: The one or more transition metal catalysts therein comprise a transition metal selected from V, Mo, W, Co, Ni, Pt, Pd or any combination thereof.

[0160] Element 33: wherein one or more of the carriers are selected from: alumina, silicon dioxide, silicon dioxide-alumina, porous carbon, zeolite, zirconium oxide, titanium dioxide and refractory oxides.

[0161] Element 34: The hydrogenation process is carried out in the presence of a hydrogen-donating solvent.

[0162] Element 35: The hydrogen-donating solvent contains at least one monocyclic aromatic compound.

[0163] Element 36: wherein the T50 of the hydrogenation product effluent is in the range of about 225°C to about 375°C, and based on the total weight of the treated product effluent, the hydrogen content is about 7% to about 12% by weight, and the sulfur content is 0% to about 1% by weight.

[0164] Element 37: The T10 of the heat-treated bitumen product is in the range of about 500°C to about 650°C, and the hydrogen content is about 4% by weight to about 8% by weight.

[0165] Element 38: The hydrogenation process described therein is a continuous fixed-bed process.

[0166] Element 39: Separating the hydrotreating product effluent downstream of the hydrotreating zone to produce at least a liquid effluent; and recycling the liquid effluent back upstream of the hydrotreating zone.

[0167] Element 40: The weight ratio of the liquid effluent to the first effluent may be from about 0.1 to about 10.

[0168] Element 41: The separation of the hydrogenation product effluent is carried out by one or more of distillation, deasphalting, chromatographic separation, membrane filtration, or a combination thereof.

[0169] Element 42: The effluent of the bottom product is separated by deasphalting in the presence of a solvent to produce a first portion comprising a solvent and a soluble compound, and a second portion comprising a solvent and deasphalted bottom product, wherein the deasphalted bottom product comprises a third asphalt product, the softening point T of which is... sp The temperature is about 25°C or higher, the hydrogen content is about 4% to about 12% by weight based on the total weight of the third pitch product, and the MCR is about 10% to about 60% by weight based on the total weight of the third pitch product, wherein the third pitch product is suitable for spinning into carbon fibers.

[0170] Element 43: The solvent is selected from ethane, propane, butane, pentane, hexane, benzene, heptane, toluene, octane, xylene or any isomer thereof or any combination thereof.

[0171] Element 44: Vacuum distilling at least a portion of the deasphalted bottom product to produce a vacuum gas oil product and a vacuum bottom product; and producing fuel oil from at least a portion of the vacuum gas oil product, wherein the fuel oil has a sulfur content of about 1% by weight or less.

[0172] Element 45: Solvent deasphalting of at least a portion of the third effluent in the deasphalting unit to produce deasphalted oil fraction and deasphalted residue oil.

[0173] Element 2: wherein the T50 of the deasphalted oil fraction is in the range of about 250°C to about 650°C, and based on the total weight of the deasphalted oil fraction, the MCR is about 10% to about 50% by weight, the hydrogen content is about 6% to about 20% by weight, and the sulfur content is about 5% by weight or less.

[0174] Element 46: At least partially remove the deasphalted oil for further processing.

[0175] Element 47: Hydrotreating the deasphalted oil fraction in a hydrotreating zone to produce a hydrotreating product effluent containing heavy hydrocarbons.

[0176] Element 48: The hydrotreating of the deasphalted oil fraction is carried out by catalysis, heat, or a combination thereof.

[0177] Element 49: The hydrotreating of the deasphalted oil fraction comprises one or more of the following: a hydrogen partial pressure of about 3,500 psig or less, a temperature in the range of about 200°C to about 500°C, a pressure in the range of about 72 psig to about 3,000 psig, a residence time of about 5 minutes or longer, and an LHSV of about 0.1 hr. -1 approximately 12 hours -1 Within the range.

[0178] Element 50: The hydrotreating of the deasphalted oil fraction is carried out by catalysis using a catalyst system, the catalyst system comprising: one or more transition metal catalysts comprising group 5, 6, 9, and 10 transition metals; and one or more supports.

[0179] Element 51: The one or more transition metal catalysts therein comprise a transition metal selected from V, Mo, W, Co, Ni, Pt, Pd or any combination thereof.

[0180] Element 52: wherein one or more carriers are selected from: alumina, silicon dioxide, silicon dioxide-alumina, porous carbon, zeolite, zirconium oxide, titanium dioxide and refractory oxides.

[0181] Element 53: The hydrotreating of the deasphalted oil fraction is carried out in the presence of a hydrogen-donating solvent containing at least one aromatic ring.

[0182] Element 54: The hydrotreated product is separated into at least one oil foot fraction by distillation; and the hydrotreated oil foot fraction containing heavy hydrocarbons is solvent deasphalted in a deasphalting unit to produce a deasphalted oil fraction and a deasphalted residue oil.

[0183] Element 55: Solvent deasphalting occurs in the presence of a solvent.

[0184] Element 57: The solvent is selected from ethane, propane, butane, pentane, hexane, benzene, heptane, toluene, octane, xylene or any isomer thereof or any combination thereof.

[0185] Element 58: Producing fibers from the bitumen product, the hydrotreated bitumen product, the third bitumen product, or any combination thereof, wherein the fibers are oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphitized fiber webs.

[0186] Element 59: The bitumen product, the hydrotreated bitumen product, the third bitumen product, or any combination thereof, are mixed with needle coke to produce carbon articles capable of forming electrodes for the production of iron and / or aluminum.

[0187] Element 60: The bitumen product, the hydrogenated bitumen product, the third bitumen product, or any combination thereof are mixed with carbon fibers to produce carbon articles capable of forming carbon-carbon composite materials.

[0188] Element 61: wherein the asphalt product, the hydrogenated asphalt product and / or the third asphalt product have different viscosities.

[0189] Element 62: wherein the asphalt product, the hydrogenated asphalt product, and the third asphalt product each have a different softening point T. sp .

[0190] Element 63: Producing carbon products containing the carbon fibers.

[0191] Element 64: wherein the T value is lower than or equal to that of the asphalt product, the hydrogenated asphalt product, or the third asphalt product. sp The fiber is stabilized at a stabilization temperature.

[0192] Element 65: Producing high-modulus, high-strength carbon fibers includes: spinning one or more pitch products to produce spun fibers; stabilizing the spun fibers with an oxygen-containing oxidizing gas to produce stabilized fibers; and carbonizing the stabilized fibers to produce carbonized fibers.

[0193] Element 66: Graphitize the carbonized fibers.

[0194] Element 67: The carbonization of the stabilized fibers is carried out at a carbonization temperature of about 1,000°C or higher.

[0195] Element 68: The diameter of the carbon fiber is approximately 50 µm or less.

[0196] Element 69: wherein the weight loss (wt%) of any of the said pitch products at the spinning temperature is about 1 wt% or less.

[0197] Element 70: The carbon fiber thereon is produced by a meltblown process.

[0198] Element 71: Producing high-modulus, high-strength carbon fiber fabrics includes: spinning one or more pitch products to produce spun fibers; stabilizing the spun fibers with an oxygen-containing oxidizing gas to produce stabilized fibers; weaving a fabric from the stabilized fibers to produce a stabilized fabric; carbonizing the stabilized fabric to produce a carbonized fabric; and optionally graphitizing the carbonized fabric.

[0199] Element 72: Production of a composite material comprising: producing carbon fibers from the bitumen product, the hydrotreated bitumen product, the third bitumen product, or any combination thereof; producing a first fabric from the carbon fibers; producing a first fiber-reinforced matrix material from the first fabric and a first matrix material; producing at least a second fiber-reinforced sheet from a second fabric, wherein the second fabric is produced from a second fiber and a second matrix material; and laminating the first fiber-reinforced sheet together with the second fiber-reinforced sheet.

[0200] Element 73: wherein the first matrix material or the second matrix material is a thermosetting resin, a thermoplastic resin, cement, concrete, ceramic, metal, metal alloy, bitumen product, or a combination thereof.

[0201] Element 74: The first matrix material is a thermoplastic resin selected from polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, or any combination thereof.

[0202] Element 75: wherein the second fiber is selected from: glass fiber, carbon fiber, aramid fiber, ceramic fiber, boron fiber, or any combination thereof.

[0203] Element 76: The second matrix material is a resin selected from polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyester, epoxy resin, phenolic resin, vinyl ester, polyurethane, silicone, polyamide, or any combination thereof.

[0204] Element 77: wherein the first matrix material or the second matrix material is the bitumen product, the hydrogenated bitumen product, the third bitumen product, or any combination thereof.

[0205] Element 78: The composite material comprises a filler selected from carbon fiber, glass fiber, metal fiber, boron fiber or carbon black.

[0206] Element 79: Introducing at least a portion of the first effluent from downstream of the steam cracking zone and / or at least a portion of the second effluent from downstream of the steam cracking zone and / or at least a portion of the third effluent from downstream of the steam cracking zone into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product.

[0207] As a non-limiting example, exemplary combinations applicable to A include, but are not limited to: 1 and 2; 1 and 3; 1, 3 and 4; 1 and 3-5; 1, 3 and 5; 1, 4 and 5; 1 and 3-6; 1, 3, 5 and 6; 1, 4, 5 and 6; 1 and 4; 1 and 5; 1 and 7; 1 and 3-7; 1, 3, 5 and 7; 1, 4, 5 and 7; 1 and 8; 1 and 9; 1 and 10; 1 and 11; 3 and 4; 3-5; 3 and 5; 3-6; 3-7; 3, 4 and 7; 3 and 8; 3 and 9; 3 and 10; 3 and 11; 4 and 5; 4 and 6; 4-6; 4-7; 4 and 8; 4 and 9; 4 and 10; 4 and 11; 5 and 6; 5-7; 5 and 8; 5 and 9; 5 and 10; 5 and 11; 7 and 8; 7 and 9; 7 and 10; 7 and 11; 8 and 9; 8 and 10; 8 and 11; 9 and 10; 9 and 11; and 10 and 11; 1 or 2, and 3; 1 or 2, and 4; 1 or 2, and 5; 1 or 2, and 6; 1 or 2, and 6 and 7; 1 or 2, and 7; 1 or 2, and 8; 1 or 2, and 6-8; 1 or 2, and 7 and 8; 1 or 2, and 15; 1 or 2, and 16-32; 1 or 2, and 25-78.

[0208] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are provided. These examples should not in any way be construed as limiting or restricting the scope of the invention.

[0209] Example

[0210] A series of bitumen is produced from the steam cracking of crude oil.

[0211] Comparison of the generation of asphalt compositions: Commercial isotropic petroleum bitumen was used as a comparative example (sample 1) and had the following properties: T10 = 402°C, T50 = 569°C, T87 = 750°C, MCR of 52.5 wt%, 93.45 wt% C, 5.50 wt% H, 0.23 wt% N, 0.51 wt% S based on the total weight of the bitumen, and a softening point of 127°C.

[0212] Representative conditions for heat treatment: Approximately 2 grams of feed were placed in a glass vial and placed in a PAC microcarbon residue analyzer (MCRT). The sample was heated to 100°C over 10 minutes with a nitrogen flow (600 mL / min). Immediately thereafter, the sample was heated to 400°C at a heating rate of 30°C / min and a nitrogen flow rate of 600 mL / min. Once at 400°C, the flow rate was reduced to 150 mL / min. The sample was held at 400°C for a specified period of time under a continuous nitrogen flow rate of 150 mL / min (see Table 1-9). After the 400°C heat soaking, the sample was cooled to ambient temperature under a nitrogen atmosphere at a flow rate of 600 mL / min for several hours. Typically, after about 15 minutes, the temperature is about 350°C; after about 25 minutes, the temperature is about 300°C; after about 66 minutes, the temperature is about 200°C; and after about 157 minutes, the temperature is about 100°C.

[0213] Table 1 illustrates the results obtained after heat treatment of commercial comparative bitumen (sample 1).

[0214] Table 1.

[0215] Table 1 (continued).

[0216] Table 2 illustrates the results obtained after heat treatment of hydrotreated steam cracked tar (sample 10).

[0217] Table 2.

[0218] Table 2 (continued).

[0219] Table 3 illustrates the results obtained after heat treatment of steam cracked tar 1 (sample 21). The Tg of steam cracked tar 1 increases with increasing heat treatment time. spIncreased MCR and mesophase content (see samples 21-28).

[0220] Table 3.

[0221] Table 3 (continued).

[0222] Table 4 illustrates the results obtained after heat treatment of steam cracked tar 2 (sample 29). With increasing heat treatment time, the MCR and mesophase content of steam cracked tar 2 increased (see samples 29-31).

[0223] Table 4.

[0224] Table 4 (continued).

[0225] Table 5 illustrates the results obtained after heat treatment of steam-cracked tar 3 (sample 35).

[0226] Table 5.

[0227] Table 5 (continued).

[0228] Table 6 illustrates the results obtained after heat treatment of hydrotreated steam cracked tar 2 (sample 35).

[0229] Table 6.

[0230] Table 7 illustrates the results obtained after heat treatment of hydrotreated steam cracked tar 3 (sample 43).

[0231] Table 7.

[0232] HDT isotropic pitch (sample 50), based on the total weight of sample 50, has an elemental composition of 92.3 wt% C, 7.55 wt% H, <0.10 wt% N, and 0.551 wt% S, with T10 of 516.11°C (961°F), T50 of 617.22°C (1143°F), and T90 of 727.78°C (1342°F), spun into carbon fibers. The MCRT indication of sample 50, based on the total weight of sample 50, is 38.8 wt% T. sp The temperature is 170°C, and T g The temperature is 103°C. Figure 5 This is a TGA plot of the weight loss (wt%) versus temperature (T, °C) for example sample 50. Figure 5 As shown, the TGA of sample 50 revealed minimal weight loss at around 180°C, suggesting that this could be a suitable spinning temperature due to the low number of volatile species present.

[0233] HDT isotropic pitch (sample 50) was spun into carbon fibers: The carbon fibers were spun on a benchtop extruder at 180°C, a spinning speed of 20 RPM, a winding speed of 10 m / min, and a nozzle diameter of 1 mm. Due to the low softening point of sample 50, stabilization was performed in an oven by slowly increasing the temperature from 95°C to 100°C and maintaining that temperature for 1 hour. The temperature was then increased to 105°C and maintained for 1 hour. This process was repeated in 5°C increments and maintained at that temperature for 1 hour before moving to the next temperature. The final stabilization temperature was 220°C.

[0234] Heat treatment of steam cracked tar: Steam cracked tar (sample 51) was pyrolyzed in an autoclave at 250 psig under flowing nitrogen using the conditions summarized in Table 8. At room temperature, using a 10:1 n-heptane:filtered product ratio, the steam cracked tar showed 30.5 wt% n-heptane insolubles, and elemental analysis revealed 89.30 wt% carbon, 6.46 wt% hydrogen, and 0.18 wt% nitrogen. Following pyrolysis, the remaining liquid product was filtered at 150°C and deasphalted with n-heptane at room temperature using a 10:1 n-heptane:filtered product ratio. Table 8 illustrates the yield and properties of the n-heptane insolubles generated after the pyrolysis of steam cracked tar (sample 51). Sulfur was not independently measured in these samples, but it is expected that the majority of the remaining elemental balance will be sulfur.

[0235] Table 8.

[0236] Table 8 (continued).

[0237] The n-heptane insolubles shown in Table 8 were then further heat-treated for 30 minutes in a sand bath at 400°C using a Swagelok cap-plug microbomb reactor. Table 9 lists the properties of the resulting heat-treated samples.

[0238] Table 9.

[0239] Table 9 (continued).

[0240] X-ray scattering: X-ray scattering measurements were performed in the synchrotron beamline at the Advanced Photon Source 9-ID at Argonne National Laboratory, which combines a Bonse-Hart USAXS (Si 220 crystal) design with pinhole collimated SAXS and WAXS configurations. A standard configuration with an energy of 21 keV was used for the beamline. Data represent the q range covered by the SAXS and WAXS detectors, acquired for SAXS / WAXS with exposure times of 15 seconds and 30 seconds, respectively. Calibration of all generated 2-D SAXS and WAXS patterns was performed using the silver behenate standard (d-spacing 58.38 Å) and the LaB6 standard (a = 4.156 Å), respectively. The data were then integrated to obtain the scattering intensity (…). I ) on the scattering vector q A one-dimensional graph, in which q = 4πsin(θ) / λ, where 2θ is the scattering angle relative to the incident beam direction. For X-ray data processing, the Irena-Nika-USAXS software package (as used by J. Ilavsky and PR Jemian) is employed. Journal of Applied Crystallography (2009), Vol. 42, pp. 347-353; and J. Ilavsky in Journal of Applied Crystallography (2012), Vol. 45(2), pp. 324-328, which are incorporated herein by reference). Samples were prepared in a 1.5 mm diameter Kapton tube. The Kapton tube background scattering was subtracted from the data to obtain the individual sample scattering. Measurements were performed at room temperature. The X-ray data (see Figure 6) showed characteristic reflections in the wide angle due to π-intermolecular interactions, which was evident in the mesophase pitch samples (see peak (002)). The X-ray data were deconvolved into two peak distributions: the Lorentz peak distribution capturing the mesophase domains and the isotropic portion represented by a Gaussian distribution (the two isotropic contributions provided a better fit for samples with higher mesophase content). Multiple peaks were required in the small-angle region (three Gaussian functions). The width of the mesophase Lorentz peak ( q), through the following formula Estimate stacking height (L) C The shape factor K was chosen as uniform. The number of molecules packed (N) is determined by N = L. C The interplanar spacing is estimated using / d(002)+1. ;where q That is the maximum peak value.

[0241] ​Figure 6 depicts the room-temperature X-ray scattering data of HDT-STC isotropic asphalt (sample 10, at 0 hours) and compares them with the X-ray scattering data of its corresponding intermediate phase samples (sample 11, at 1 hour; sample 13, at 3 hours; sample 14, at 4 hours; sample 15, at 5 hours) obtained during different time periods (e.g., 0 hours to 5 hours) of pyrolysis of sample 10 at 400°C under N2. Samples 11, 13, 14, and 15 were then cooled to room temperature. The scattered X-ray intensities were plotted against the scattering vector q.

[0242] Figure 6A The scattering data of the HDT-SCT material over pyrolysis time (hours) are illustrated. Figure 6B The example illustrates the interlayer distance between molecules over pyrolysis time (peak 2, d). π-π , also known as d(002)). The small-angle scattering contrast of HDT-STC isotropic bitumen material originates from fused aromatic rings (high electron density moieties) and low electron density side groups (or small aromatic flexible side groups). The position of the scattering peak at a smaller q value determines the intermolecular spacing (i.e., average molecular size). For isotropic materials, the wide-angle scattering peak originates from the liquid-like structure factor. After pyrolysis, the orderliness of the planar aromatic molecules is improved through intermolecular interactions (e.g., non-covalent electrostatic interactions, such as π-π stacking), resulting in the wide-angle peak position shifting to a higher q value (smaller d spacing) and a reduced peak width compared to the starting material of Sample 10. Therefore, the wide-angle ( Approximately 1.8 Å -1 The scattering contrast (or reflection) in the sample is attributed to the interplanar spacing of the mesophase domains. Liquid crystal order is also evident in the (101) peak, which indicates π-packing in the mesophase materials (samples 11, 13, 14, and 15). The (101) peak begins to appear in sample 13, with a portion of mesophase less than 1% by volume observed in the PLM data. A packing height (L) of sample 13 was observed. C The density was approximately 3.6 nm, corresponding to approximately 10 N molecules stacked together. After further heating for 4 hours, the stacking height L was observed. C The density was approximately 4.4 nm (N was approximately 12.5 molecules). After 5 hours, the stacking height L was observed. C It is approximately 4.2 nm (N is approximately 12 molecules).

[0243] The low-intensity diffuse peak of the HDT-STC isotropic asphalt (sample 10) is at 0.4 Å. -1 The left and right (i.e., the position of peak 1) represent the average intermolecular spacing (L) in the ordered portion of the asphalt material. aThis indicates weak lateral spatial correlation (electron density variation) between aromatic molecules. If the side groups are small (or Mw is low), the position of peak 1 also provides an estimate of the average size of the aromatic molecule. A larger peak width also reflects a wider size distribution and weaker electron density variation (or more random ordering) of aromatic compounds in the asphalt material. The position of peak 1 remains almost unchanged during pyrolysis. The aromatic composition in HDT-STC isotropic asphalt produces small density variations in the asphalt material, thus within 0.4 Å. -1 A small signal was generated at that point. It is worth noting that the peak position (e.g., peak 1 position) or average size of the asphalt sample does not necessarily capture a consistent change (or increase) in molecular weight (the same peak position can have different molecular weights).

[0244] As shown in Figure 6, the X-ray scattering data of the HDT-SCT isotropic asphalt (sample 10) shows a scattering peak corresponding to approximately 1.4 Å. -1 The scattering vector q (Peak 2) This is due to the electron density correlation (liquid-like structure factor) resulting from van der Waals separation of the molecules. After pyrolysis, in addition to the decrease in the peak width of the corresponding peak, its relative intensity increases. Furthermore, due to the improvement in aromaticity (molecular growth) and order, at approximately q 1.4 Å... -1 Peak 2 at the pyrolysis site gradually shifts to a higher scattering vector q over time, leading to the formation of an intermediate phase in the later stages (≥3 hours) due to stronger intermolecular interactions. On the other hand, with increasing pyrolysis time, the improved spatial correlation represents L... a The peak height (Å) also increases, while the corresponding peak position remains almost unchanged until 5 hours of pyrolysis. The constant q vector of the small-angle peak position indicates that the planar aromatic molecules in the mesophase do not show significant changes in average molecular size during the mesophase transition.

[0245] In summary, X-ray scattering data, together with optical microscopy measurements, confirmed that the material forms an mesophase (disc-shaped nematic) during pyrolysis, and that the content of this mesophase increases with pyrolysis time. Furthermore, the average molecular size constituting the mesophase domains remains unchanged during pyrolysis. Therefore, these results confirm the importance of the initial molecular composition, which (along with the chemical composition of the pitch) ultimately determines the final pitch morphology. The material has a packing height of approximately 4.5 nm and consists of about 13 molecules, thus providing pitch with improved liquid crystal ordering, which results in a significantly improved graphite content compared to mesophase pitch produced by conventional processes.

[0246] All documents described herein are incorporated herein by reference for use in all jurisdictions where such practices are permitted, including any priority documents and / or test procedures, provided they do not contradict this document. It will be apparent from the foregoing general description and detailed description that while the forms of the invention have been exemplified and described, various modifications may be made without departing from the spirit and scope of the invention. Therefore, the invention is not intended to be limited thereto. For example, compositions described herein may not contain any components or elements not expressly stated or disclosed herein. Any method may omit any steps not listed or disclosed herein. Similarly, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also consider the same composition or group of elements preceded by the transitional phrases “consistently composed of,” “composed of,” “selected from,” or “is,” and vice versa.

[0247] Whenever a numerical range with a lower and upper limit is disclosed, any number falling within that range and any range included therein are specifically disclosed, including the lower and upper limits. In particular, all numerical ranges disclosed herein (in the form of “from about a to about b,” or equivalently, “about from a to b,” or equivalently, “about from ab”) should be understood to list all numbers and ranges contained within that wider range of values. Furthermore, unless the patent holder expressly and clearly defines otherwise, the terms in the claims have their simple, ordinary meaning. Moreover, the indefinite articles “an” or “a” used in the claims are defined herein as referring to one or more elements introduced therein.

[0248] Therefore, the present invention is well suited to achieving the foregoing objects and advantages, and those inherent therein. The specific embodiments disclosed above are merely exemplary, as the invention can be modified and practiced in different but equivalent ways, as will be apparent to those skilled in the art and those who benefit from the teachings herein. Furthermore, no limitation is intended to be made on the details of the constructions or designs shown herein other than those described in the claims. Therefore, it is apparent that the specific exemplary embodiments disclosed above can be changed, combined, or modified, and all such changes are considered to be within the scope and spirit of the invention. The embodiments disclosed herein may be appropriately practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein.

Claims

1. A method for producing an asphalt composition from crude oil via steam cracking, the method comprising: One or more crude oils are steam-cracked in a steam cracking zone to produce a first effluent containing a heavy oil mixture containing steam-cracked tar, a second effluent containing a mixture of gaseous and liquid products, and a third effluent containing one or more bottom products. Optionally, at least a portion of the first effluent from the downstream of the steam cracking zone and / or at least a portion of the second effluent from the downstream of the steam cracking zone and / or at least a portion of the third effluent from the downstream of the steam cracking zone are introduced into one or more pretreatment zones to produce a first effluent pretreatment product and / or a second effluent pretreatment product and / or a third effluent pretreatment product. The first effluent, the first effluent pretreatment product, the second effluent, the second effluent pretreatment product, the third effluent, the third effluent pretreatment product, or any combination thereof are introduced into the reaction zone; as well as The first effluent, the first effluent pretreatment product, the second effluent, the second effluent pretreatment product, the third effluent, the third effluent pretreatment product, or any combination thereof are heat-treated in the reaction zone to a temperature ranging from 200°C to 800°C to produce a first reaction effluent containing bitumen products and a second reaction effluent containing a mixture of gaseous and liquid products. The asphalt product has an intermediate phase comprising more than 10% by volume of the total volume of asphalt, and the MCR of the asphalt product is in the range of 40% by weight to 95% by weight and the softening point T0 is [not specified]. sp Within the range of 50°C to 400°C, The intermediate phase is a disk-shaped liquid crystal material composed of planar aromatic molecules with a wide molecular weight distribution.

2. The method of claim 1, wherein the first effluent is directly fed into the reaction zone without the optional pretreatment, and the first reaction effluent, the second reaction effluent, or both the first and second reaction effluents are sent to a separation zone after heat treatment to produce at least one bituminous product and a separated reaction effluent comprising gaseous and liquid hydrocarbons; and The at least one bituminous product, after separation, has an intermediate phase content of 10% to 100% based on the total volume of the at least one bituminous product, an MCR of 40% to 95% based on the total weight of the at least one bituminous product, and a softening point T in the range of 50°C to 400°C. sp .

3. The method of claim 1, wherein the one or more pretreatment zones are one or more hydrogenation treatment zones, wherein at least a portion of the first effluent is hydrogenated to produce the first effluent pretreatment product, and wherein the first effluent pretreatment product is a hydrogenated first effluent product.

4. The method according to any one of claims 1 to 3, wherein the packing height (L) of the asphalt product is determined by X-ray scattering. C The range is from 2 nm to 9 nm.

5. The method according to any one of claims 1 to 4, wherein, based on the total weight of the first effluent, at least 70% by weight of the mixture in the first effluent has a boiling point above 200°C at atmospheric pressure, an MCR of 5% to 55% by weight, a hydrogen content of 4% to 10% by weight, and a sulfur content of 5% by weight or less.

6. The method according to any one of claims 1 to 5, wherein the bitumen product has: (1) a quinoline insoluble (QI) content of 60% by weight or less, and (2) a temperature of 100°C or higher. sp (3) 70°C or higher g , or (4) their combination.

7. The method according to any one of claims 1 to 6, wherein the bitumen product is fed into one or more heat treatment zones to produce MCR and T. sp Both are greater than the MCR and T of the asphalt product. sp The heat-treated pitch product, and wherein the pitch product and / or the heat-treated pitch product is suitable for spinning into carbon fibers, preferably wherein the heat-treated pitch product has one or more of the following: a mesophase content of 50% by volume or higher based on the total volume of the heat-treated pitch product; a quinoline insoluble (QI) content of 10% by weight or higher based on the total weight of the heat-treated pitch product; and T sp 200°C or higher.

8. The method according to any one of claims 3 to 7, wherein the T50 of the hydrotreated product effluent is in the range of 225°C to 375°C, and the hydrogen content is 7% to 12% by weight and the sulfur content is 0% to 1% by weight based on the total weight of the hydrotreated product effluent.

9. The method according to any one of claims 3 to 8, wherein the method further comprises: The hydrotreating product effluent downstream of the hydrotreating zone is separated to produce at least a liquid effluent; as well as The liquid effluent is recycled back upstream of the hydrogenation treatment zone.

10. The method according to any one of claims 1 to 9, wherein the method further comprises: The first reaction effluent product is separated by deasphalting in the presence of a solvent to produce a first portion containing the solvent and soluble compounds, and a second portion containing the solvent and deasphalted bottoms product. The bottom product of the deasphalted tower contains a third bituminous product, the softening point of which is T. sp The temperature is 25°C or higher, the hydrogen content is 4% to 12% by weight based on the total weight of the third pitch product, and the MCR is 10% to 60% by weight based on the total weight of the third pitch product, wherein the third pitch product is suitable for spinning into carbon fibers.

11. The method according to claim 10, further comprising: At least a portion of the deasphalted bottom product is subjected to vacuum distillation to produce vacuum gas oil product and vacuum bottom product; as well as Fuel oil is produced from at least a portion of the vacuum gas oil product, wherein the sulfur content of the fuel oil is 1% by weight or less.

12. The method according to any one of claims 1 to 11, wherein the method further comprises: At least a portion of the third effluent is solvent-deasphalted in the deasphalting unit to produce deasphalted oil fraction and deasphalted residue oil.

13. The method according to any one of claims 1 to 12, wherein the method further comprises: Fibers are produced from the asphalt product, the third asphalt product, the hydrotreated asphalt product under the method of any one of claims 3 to 12, or any combination thereof, wherein the fibers are oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphitized fiber webs.

14. The method according to any one of claims 1 to 13, wherein the method further comprises: The asphalt product, the third asphalt product, the hydrotreated asphalt product in any of the methods described in claims 3 to 13, or any combination thereof, are mixed with needle coke to produce carbon articles capable of forming electrodes for the production of iron and / or aluminum.

15. The method according to any one of claims 1 to 14, wherein the method further comprises: Production of high-modulus, high-strength carbon fiber fabrics, including: Spinning one or more pitch products to produce spun fibers; The spun fibers are stabilized with an oxygen-containing oxidizing gas to produce stabilized fibers; Weaving fabric from the stabilized fibers to produce stabilized fabric; Carbonize the stabilized fabric to produce a carbonized fabric; and Optionally, the carbonized fabric is graphitized.

Images