Pitch composition and method relating to the pitch composition

Abstract

Pitch compositions having controlled pitch composition properties, and methods of making and using same. Pitch properties are predicted based on infrared structural parameters, and two or more pitch compositions can be blended to achieve desired pitch properties including softening point, microcarbon residue, hydrogen / carbon ratio, and % pitch volatiles. Predicting these properties aids in end use optimization, particularly in the production of spinnable pitches for carbon fibers, mesocarbon microbeads, matrices for carbon / carbon composites, and other pitch-derived carbon products.

Description

[Technical Field]

[0001] This disclosure relates to pitch compositions, and more particularly to the properties of controlled pitch compositions and methods for manufacturing and using them. [Background technology]

[0002] Pitch is a carbon-containing raw material that can be classified as either isotropic pitch or mesophase pitch. Both isotropic and mesophase pitches can be complex mixtures of aromatic molecules, but the aromatic molecules in isotropic pitch are randomly oriented, whereas in mesophase pitch, at least some of these aromatic molecules are ordered. Mesophase pitch may have a heterogeneous two-phase structure containing the ordered aromatic molecules (e.g., anisotropic regions) and isotropic regions. Generally, the formation of isotropic pitch precedes the formation of mesophase pitch. In this specification, unless otherwise specified, both types of pitch are collectively referred to as "pitch".

[0003] Pitch can be produced, for example, from acid-catalyzed oligomerization of petroleum, coal tar, biomaster, or low molecular weight (e.g., naphthalene) raw materials. Typical chemical components of pitch include, but are not limited to, alkanes, cycloalkanes, aromatics, hydroaromatics, phenols, alkenes, ketones, carboxylic acids, sulfur-containing compounds, oxygen-containing compounds, and nitrogen-containing compounds. These components vary depending on the starting materials and process conditions.

[0004] Pitch is used in many product applications, including carbon fiber, binder pitch, and impregnation pitch. Major markets for pitch include high-performance and general-purpose carbon fiber, refractories, carbon / carbon composite materials, artificial graphite, graphite components, binders and impregnation pitch for electrodes, binders and impregnation pitch for anodes and cathodes in aluminum manufacturing, impregnation pitch for electric furnace electrodes in steelmaking, mesocarbon microbeads for lithium-ion battery anodes, and thermal conductivity applications. 12,13This includes, but is not limited to, carbon foam for sound absorption, roofing products, lubricants, and consumer products (such as cosmetics).

[0005] Given the chemical diversity of pitch, its properties depend, but are not limited to, on its raw materials, manufacturing (e.g., pyrolysis), and separation (e.g., distillation) conditions. Different pitch properties are specified for specific end-uses, each with its own defined range of acceptable specifications. These include, but are not limited to, the softening point, microcarbon residue (or residual, or residue), mesophase percentage (%), and other applicable property ranges. However, currently, there is no way to predict or control these properties, and the typical means of obtaining pitch property specifications suitable for a particular end-use is simply trial and error and based on past experience, which is at least costly in terms of manufacturing time and raw materials (such as pitch material). Indeed, such a trial-and-error approach requires many sets of experiments under multiple different conditions and product characteristics before the desired pitch properties are achieved. Significant research and development efforts have been expended to identify suitable feedstocks and processes for producing specific commercial pitches, such as ASHLAND A240, or suitable pitch blends, such as binder pitches, but this has proven impossible when the pitch raw materials are immutable. Furthermore, this trial-and-error approach does not consider the pitch composition and is only effective when the pitch composition is nearly constant. When a large market is desired for new pitch products such as carbon fiber composite materials for infrastructure applications, fluctuations in raw materials are unavoidable, and therefore the pitch composition fluctuates consistently, making the trial-and-error approach even more undesirable.

[0006] Therefore, there is a strong need for methods to adjust the characteristics and enable the production of controlled pitch compositions with reproducible properties. [Overview of the project]

[0007] In non-limiting embodiments of this disclosure, examples include compositions comprising a pitch composition having either or both an A-factor in the range of about 0.4 to about 0.8 and / or an aromaticity in the range of about 0.3 to about 1.3.

[0008] In non-limiting embodiments of this disclosure, a method is provided comprising thermally decomposing at least a first pitch composition and a second pitch composition, wherein the thermal decomposition of the first and second pitch compositions is carried out separately, the first pitch composition being a composition from a first pitch feed and the second pitch composition being a composition from a second pitch feed. A first infrared spectrum is obtained from at least the first pitch composition, and at least one first infrared parameter is selected based on (1) the first infrared spectrum and a calibration curve or (2) the first infrared spectrum and chemometric (or chemometric) modeling. A second infrared spectrum is obtained from at least the second pitch composition, and at least one second infrared parameter is selected based on (1) the second infrared spectrum and a calibration curve or (2) the second infrared spectrum and chemometric modeling. The selected first and second infrared parameters are at least one or both of an A-factor in the range of about 0.4 to about 0.8 and / or aromaticity in the range of about 0.3 to about 1.3, and the first and second pitch compositions are blended (or mixed or formulated) in a ratio that achieves the selected first and second infrared parameters, thereby forming a blended pitch composition.

[0009] In non-limiting embodiments of this disclosure, a method is provided comprising extruding a pitch composition to produce green (or environmentally friendly; green) carbon fibers, and then stabilizing the extruded pitch composition. Stabilization comprises obtaining an infrared spectrum of the extruded pitch composition and selecting at least one infrared parameter based on (1) a first infrared spectrum and a calibration curve, or (2) a first infrared spectrum and chemometric modeling, wherein the at least one infrared parameter is at least the A-factor and aromaticity. Stabilization is stopped based on the at least one infrared parameter.

[0010] These and other features and attributes of the disclosed method for producing a pitch composition having the adjusted and reproducible properties of this disclosure, as well as their advantageous applications and / or uses, will become apparent from the detailed description below. [Brief explanation of the drawing]

[0011] The accompanying drawings are provided for assistance to the ordinary articulators in the relevant field in manufacturing and using the subject matter of this specification. The following drawings are included to illustrate specific aspects of this disclosure and should not be considered exclusive. The disclosed subject matter can be substantially modified, altered, combined, and equivalent in form and function, as can be conceived by any person skilled in the art and interested in this disclosure.

[0012] [Figure 1A] Figure 1A shows the diffuse reflectance infrared Fourier transform (DRIFT) spectrum of a pitch sample according to one or more embodiments of the present disclosure. [Figure 1B] Figure 1B shows the diffuse reflectance infrared Fourier transform (DRIFT) spectrum of a pitch sample according to one or more embodiments of the present disclosure. [Figure 1C] Figure 1C shows the diffuse reflectance infrared Fourier transform (DRIFT) spectrum of a pitch sample according to one or more embodiments of the present disclosure. [Figure 1D]FIG. 1D shows the diffuse reflectance infrared Fourier transform (DRIFT) spectrum of a pitch sample according to one or more aspects of the present disclosure. [Figure 2A] FIG. 2A is a trend chart of infrared parameters based on the DRIFT spectrum of a pitch sample that changes with pyrolysis according to one or more aspects of the present disclosure. [Figure 2B] FIG. 2B is a trend chart of infrared parameters based on the DRIFT spectrum of a pitch sample that changes with pyrolysis according to one or more aspects of the present disclosure. [Figure 2C] FIG. 2C is a trend chart of infrared parameters based on the DRIFT spectrum of a pitch sample that changes with pyrolysis according to one or more aspects of the present disclosure. [Figure 2D] FIG. 2D is a trend chart of infrared parameters based on the DRIFT spectrum of a pitch sample that changes with pyrolysis according to one or more aspects of the present disclosure. [Figure 3A] FIG. 3A shows a correlation diagram between infrared parameters based on the DRIFT spectrum and the pitch characteristics of a pitch sample according to one or more aspects of the present disclosure. [Figure 3B] FIG. 3B shows a correlation diagram between infrared parameters based on the DRIFT spectrum and the pitch characteristics of a pitch sample according to one or more aspects of the present disclosure. [Figure 3C] FIG. 3C shows a correlation diagram between infrared parameters based on the DRIFT spectrum and the pitch characteristics of a pitch sample according to one or more aspects of the present disclosure. [Figure 3D] FIG. 3D shows a correlation diagram between infrared parameters based on the DRIFT spectrum and the pitch characteristics of a pitch sample according to one or more aspects of the present disclosure. [Figure 4A] FIG. 4A shows a parity plot of predicted pitch characteristics based on the DRIFT structure correlation for the experimental values of FIGS. 3A - 3D according to one or more aspects of the present disclosure. [Figure 4B]Figure 4B shows a parity plot of the predicted pitch characteristics based on DRIFT structure correlation for the experimental values ​​in Figures 3A-3D, according to one or more embodiments of this disclosure. [Figure 4C] Figure 4C shows a parity plot of the predicted pitch characteristics based on DRIFT structure correlation for the experimental values ​​in Figures 3A-3D, according to one or more embodiments of this disclosure. [Figure 4D] Figure 4D shows a parity plot of the predicted pitch characteristics based on DRIFT structure correlation for the experimental values ​​in Figures 3A-3D, according to one or more embodiments of this disclosure. [Figure 5] Figure 5 shows a partial least squares (PLS) model correlation diagram of a representative pitch characteristic of a pitch sample according to one or more embodiments of this disclosure. [Figure 6A] Figure 6A shows a parity plot of the pitch characteristics predicted using PLS model correlations to experimentally determined pitch characteristics, according to one or more embodiments of the present disclosure. [Figure 6B] Figure 6B shows a parity plot of the pitch characteristics predicted using PLS model correlations to experimentally determined pitch characteristics, according to one or more embodiments of the present disclosure. [Figure 6C] Figure 6C shows a parity plot of the pitch characteristics predicted using PLS model correlations to experimentally determined pitch characteristics, according to one or more embodiments of the present disclosure. [Figure 6D] Figure 6D shows a parity plot of the pitch characteristics predicted using PLS model correlations to experimentally determined pitch characteristics, according to one or more embodiments of this disclosure. [Figure 7A] Figure 7A shows a prediction chart of the pitch characteristics of a pitch sample using least squares analysis (LSA) modeled correlation according to one or more aspects of the present disclosure. [Figure 7B] Figure 7B shows a prediction chart of the pitch characteristics of a pitch sample using least squares analysis (LSA) modeled correlation according to one or more aspects of the present disclosure. [Figure 7C]Figure 7C shows a prediction chart of the pitch characteristics of a pitch sample using least squares analysis (LSA) modeled correlation according to one or more aspects of the present disclosure. [Figure 7D] Figure 7D shows a prediction chart of the pitch characteristics of a pitch sample using least squares analysis (LSA) modeled correlation according to one or more aspects of this disclosure. [Modes for carrying out the invention]

[0013] This disclosure relates to pitch compositions, and more particularly to the properties of controlled pitch compositions and methods for manufacturing and using them.

[0014] There is a need for methodologies for producing pitch compositions with tailor-reproducible properties suitable for one or more specific end applications. This disclosure provides a methodology that utilizes compositional details to enable rapid identification of pitch properties. In particular, disclosed herein is a method for tailoring pitch properties based on infrared structural parameters specific to a pitch composition. The method described herein is particularly suitable for enabling the development of pitch blend rules, optimization of carbon fiber spinning, information provision for reaction operations, and scale-up of pitch-based carbon material production.

[0015] As described herein, the method of this disclosure provides for producing pitch compositions having tuned pitch properties; these properties include softening point, microcarbon residue, hydrogen / carbon ratio, and percent pitch volatiles. Predicting these properties can help optimize the end-use of the production of spun pitch for carbon fibers, matrices for carbon / carbon composite materials, and other pitch-derived carbon products as described herein.

[0016] The method of generating tuned pitch characteristics according to this disclosure is advantageously derived based on pitch composition modeling: (1) correlation (prediction) of IR parameters (e.g., ratio of infrared spectral absorbance bands correlated with pitch characteristics) regardless of a specific pitch generation reaction (e.g., thermal decomposition, air oxidation, etc.), and (2) multivariate analysis of the infrared spectrum.

[0017] In other embodiments, the method of generating tuned pitch characteristics according to the present disclosure is favorably derived based on modeling based on the chemometric composition of pitch: (1) correlation (prediction) of IR parameters (e.g., the ratio of infrared spectral absorbance bands correlated with pitch characteristics) regardless of the specific pitch type, (2) multivariate analysis of the infrared spectrum, and (3) partial least squares (PLS) modeling and analysis. Thus, the specific correlations developed can be considered independent of or universal to any particular pitch composition.

[0018] Using the methodology of this disclosure, the properties of a starting pitch composition can be used to determine the composition of a blended pitch in order to satisfy a specific desired pitch value or range. In particular, infrared spectra from various pitch compositions can be summed or a PLS model can be used to produce a pitch blend having a specific desired property or property. Since the pitch blend ratio depends on the starting pitch blend composition, it will be understood that multiple solutions using multiple starting pitch compositions may be advantageously used to achieve the desired final pitch properties. Thus, the method of this disclosure and the compositions produced therefrom enable substantial customization and rapid identification of suitable (and unsuitable) starting pitch compositions and blends without the use of conventional trial-and-error methods that involve substantial resources.

[0019] Definitions and Test Methods All numerical values ​​in the detailed description and claims of this specification are modified with “about” or “approximately” to the indicated values, taking into account the experimental errors and variability that a person skilled in the art would expect. Unless otherwise specified, the ambient temperature (room temperature or “RT”) is approximately 25°C.

[0020] As used in this disclosure and claims, the singular forms "a," "an," and "the" include the plural form unless the context makes it clear otherwise.

[0021] In this specification, the term "and / or" as used in expressions such as "A and / or B" is intended to include "A and B," "A or B," and "A" and "B."

[0022] In this disclosure and its claims, the following definitions are used:

[0023] As used herein, the terms “pitch” or “pitch composition” and their grammatical variations include petroleum pitch, coal tar pitch, natural asphalt, biomass pitch, pitch produced from the oligomerization and / or polymerization of aromatics, and pitch obtained as a byproduct in the naphtha cracking industry.

[0024] The terms "thermal decomposition" or "the act of thermal decomposition," and their grammatical variations, refer to thermal reactions induced by high temperatures (e.g., dehydrogenation, cyclization, cracking, condensation, etc.).

[0025] As used herein, the terms “softening point” or “SP,” and their grammatical variations, refer to the temperature or temperature range at which a substance softens. Here, the softening point is measured using a Mettler-Toledo drop point measuring instrument such as a Mettler-Toledo DP70, following a procedure similar to that of the American Society for Testing and Materials (ASTM) ASTM D3104-14a.

[0026] As used herein, the terms “microcarbon residue” or “MCR” and their grammatical variations refer to the amount of carbonaceous residue formed after the evaporation and thermal decomposition of petroleum materials under specific conditions. As used herein, the terms “microcarbon residue test” or “MCRT” and their grammatical variations refer to a standard method for measuring MCR, which is measured according to ADTM D4530 (2020).

[0027] In this specification, the term "mesocarbon microbeads" refers to porous graphitecarbon materials in which the inner core is composed of amorphous carbon and the outer shell is composed of graphitecarbon. Both the inner core and the outer shell are porous. The diameter of mesocarbon microbeads ranges from 10 microns to 100 microns.

[0028] As used herein, the "hydrogen / carbon ratio" or "H / C ratio" and its grammatical variations refer to the amount of elemental hydrogen relative to elemental carbon in a pitch composition. The H / C ratio is measured according to ASTM D5291-21.

[0029] The terms "percent pitch volatiles" (%PV) or "%PV," and their grammatical variations, relate to the amount of volatile substances that can be suspended in the air within a pitch composition upon heating, such as pyrene, phenanthrene, acridine, chrysene, anthracene, and benzo(a)pyrene. PV% is measured by recording the mass loss after a given thermal decomposition reaction. Because the temperature and time used vary from experiment to experiment, %PV will differ from experiment to experiment. When pitch volatiles % are measured by weight, they are referred to as "wt%PV" in this specification.

[0030] In this specification, the H / C ratio may be referred to as “elemental analysis.”

[0031] As used herein, the terms “infrared parameters” or “infrared structural parameters,” or simply “IR parameters,” and their grammatical variations, refer to the methyl-to-methylene ratio, A-factor, aromaticity, and degree of condensation determined from the infrared spectrum.

[0032] In this specification, the terms “Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectrum” or “DRIFT spectroscopy,” and their grammatical variations, refer to an FTIR spectrometer equipped with a DRIFT peripheral. DRIFT spectra can provide both chemical and structural information about the sample being measured. The FTIR used in the examples described herein was a Thermo Fisher Scientific Inc. NICOLET® 3700 FTIR spectrometer (Waltham, Massachusetts), and the DRIFT peripheral used in the examples described herein was a Pike Technologies DIFFUSIR® (Madison, Wisconsin). The FTIR spectrometer was further equipped with a Thermo Fisher Scientific Inc. deuterated triglyceride sulfate (DGTS) detector.

[0033] The terms “methyl-to-methylene ratio” or “CH3 / CH2 ratio” used herein, and their grammatical variations, relate to an infrared parameter obtained by dividing the asymmetric stretching of CH3 by the asymmetric stretching of CH2 in a sample, based on the infrared spectrum. The CH3 / CH2 ratio is an indicator of the length of the aliphatic chain approximated by the asymmetric stretching vibrations of CH3 and CH2, and / or the degree of branching of the aliphatic portion. The height (intensity) or integral area of ​​the infrared absorption band can be used to derive the calculated ratio. For example, based on the integral center in wavenumber space, the CH3 / CH2 ratio = 12960 ÷ 12918.

[0034] In this specification, the term "A-factor" and its grammatical variations relate to infrared parameters that correlate the aliphatic and aromatic content of a sample based on its infrared spectrum. The A-factor represents the change in the integrated intensity of absorbance from aliphatic CH2 with respect to the aromatic C=C ring stretching vibration of the sample. Based on the integration center in wavenumber space, the A-factor = [I2850 + I2918] ÷ [I2850 + I2918 + I1600].

[0035] As used herein, "aromaticity" and its grammatical variations refer to infrared parameters representing the ratio of aromatic CH stretching to absorbance from CH3 and CH2 vibrations of a sample based on infrared spectroscopy. Aromaticity is an index indicating the relative content of aromatic carbon and aliphatic carbon in a sample. Based on the integration center in wavenumber space, aromaticity = I3000 / [I2960+I2918+I2870+I2850].

[0036] As used herein, the terms “Degree of Condensation” or “DoC” and their grammatical variations refer to the ratio of aromatic CH stretching to aromatic C=C ring stretching of a sample based on infrared spectroscopy. DoC represents the number of hydrogens directly bonded to the ring structure and indicates the degree of aromatic substitution versus ring condensation in the sample. Based on the center of integration in wavespace, DoC = I3000 / I1600.

[0037] The integration center of the wavenumber space term "I2960" represents the asymmetric stretching of CH3, and in this specification, for example, it is 2941 cm. -1 ~2991cm -1 The calculation can extend up to this point, but is not limited to this.

[0038] The integration center of the wavenumber space term "I2918" represents the asymmetric stretching of CH2, and in this specification, for example, it is 2902 cm. -1 ~2941cm -1 The calculation is performed within this range, but is not limited to it.

[0039] The integration center of the wavenumber space term "I2850" represents the symmetric stretching of CH2. In this specification, for example, it is calculated within the range of 2819~2864 cm -1 but is not limited thereto.

[0040] The integration center of the wavenumber space term "I1600" represents the aromatic C=C ring stretching. In this specification, for example, it is calculated within the range of 1570~1632 cm -1 but is not limited thereto.

[0041] The integration center of the wavenumber space term "I3000" represents the aromatic C-H stretching. In this specification, for example, it is calculated within the range of 2991 cm -1 ~3101 cm -1 but is not limited thereto.

[0042] The integration center of the wavenumber space term "I2870" represents the symmetric stretching of CH3. In this specification, for example, it is calculated within the range of 2864 cm -1 ~2889 cm -1 but is not limited thereto.

[0043] Method for manufacturing pitch composition The present disclosure provides a method that includes blending two or more prepared pitch compositions, measuring their infrared structural parameters, and selecting at least one final structural infrared parameter based on a calibration curve or chemometric modeling. Then, blend two or more prepared pitch compositions to obtain a blended pitch composition having the desired final infrared structural parameter.

[0044] Pitch, as described above, is prepared (or otherwise is the residual product) from the pyrolysis of various raw material sources such as petroleum, coal tar, and biomaster, or from the acid-catalyzed oligomerization of low molecular weight materials (e.g., naphthalene), and is itself an intermediate product. The pyrolysis of pitch for use in the various methods described herein is carried out in a pyrolysis reactor at temperatures in the range of about 200°C to about 600°C, encompassing any value and subsets therein, for example, about 200°C to about 500°C, or about 200°C to about 400°C, or about 200°C to about 300°C, or about 300°C to about 600°C, or about 400°C to about 500°C, or about 500°C to about 600°C. A gas may be present in the reactor, and the gas may include one or more or all of, for example, hydrogen, air, oxygen, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, nitrogen dioxide, and / or ozone. Without departing from the scope of this disclosure, other suitable pyrolysis gases may also be suitable. Furthermore, the pyrolysis reactor is operated at pressures ranging from about 0.3 to about 2,500 pounds / square inch (psi), or about 0.3 to about 100 psi, or about 1 to about 75 psi, or about 5 to about 50 psi, or about 10 to about 25 psi, or about 50 to about 2,000 psi, or about 100 to about 1,500 psi, or about 200 to about 1,000 psi, or about 400 to about 1,000 psi, or about 500 to about 1,000 psi. After pyrolysis, the resulting pitch effluent can be further separated to obtain the desired pitch, such as by distillation separation, deasphalt separation, membrane separation, and any combination thereof. Accordingly, this disclosure provides the preparation of pitch compositions as described herein for further analysis to determine pitch properties and appropriate blend ratios based on desired structural parameters.

[0045] In one or more embodiments of this disclosure, a pyrolysis reaction may be used to prepare a pitch composition having one or more undesirable structural properties, as described herein below. That is, a particular pitch feed (or feed) (also interchangeably referred herein as “raw material” or “feedstock”) may have one or more particular undesirable IR parameters, and the feed is pyrolyzed to achieve a desired IR parameter (and the resulting pitch properties) by adjusting the pyrolysis reaction conditions. For example, in one or more embodiments, the desired pitch preferably has one or both an A-factor in the range of about 0.6 to about 0.8 and / or an aromaticity in the range of about 0.3 to about 0.6, but the pitch feed has different IR parameters; or the desired pitch preferably has one or both an A-factor in the range of about 0.4 to about 0.6 and / or an aromaticity in the range of about 0.5 to about 0.8, but the pitch feed has different IR parameters. In each case, the feed can be supplied to the pyrolysis reactor at a temperature in the range of about 200°C to about 600°C and a pressure exceeding about 0.3 psi to achieve specific desired pitch IR parameters (i.e., structural properties). The pitch effluent can then be separated as described herein. When at least two pitch compositions are blended, two pyrolysis reactions are carried out on separate pitch feeds, two arbitrary separations are carried out separately, two infrared spectra are measured separately, and two selections of desired IR parameters are carried out separately before blending.

[0046] Furthermore, the structural properties of the present disclosure may be measured after the prepared pitch composition has left the reactor (using DRIFT or other IR techniques, or other techniques capable of measuring or approximating the intensity of the vibrational bands described above, e.g., Raman spectroscopy, photothermal techniques, photoacoustic techniques, multivariate optical computing, spectrophotometers, filter photometer towers), including those used inline in a carbon fiber (e.g., green carbon fiber) manufacturing process. Here, after the carbon fiber has left the extrusion die, while stabilization is carried out in a carbon fiber stabilization process in which it is brought into contact with the reaction gas (i.e., the reaction zone), the infrared spectrum is measured (using DRIFT or other IR techniques) and IR parameters are selected. The IR parameters can be used to stop stabilization when a desired IR parameter is reached, as described later herein. The reactive gas may include, without limitation, any combination of any of the oxidizing gases listed herein, as well as hydrogen peroxide and nitrogen dioxide.

[0047] The spinning zone may be a spinneret operating in an inert environment within a temperature range of about Tsp-10°C to about Tsp+50°C, typically about 50°C to about 500°C, possibly 350°C, encompassing any value and subsets in between, which is the temperature range relative to the pitch softening point. A spinneret is a type of die for extruding carbon fiber filaments through a small hole. In some embodiments, the pitch composition may be blown (or sprayed) through an extrusion die such as a spinneret or other suitable die. After the filament or extruded article is formed, it can be oxidized in a reaction zone. The reaction zone may be an oven, such as a batch oven or a continuous oven, which can heat the fiber or article to a temperature in the range of about -5°C to about 50°C, encompassing any value and subsets in between, in the presence of a reactive gas. In one or more embodiments, the extruded pitch composition for forming carbon fibers may be spooled (or wound) before contact with the reactive gas.

[0048] As a result of thermal decomposition, significant reactions may occur that can alter the composition and / or properties of the pitch, based on thermal reactions that proceed by radical reactions initiated by the cleavage of homolysis bonds. Such reactions include, but are not limited to, dealkylation (e.g., demethylation), dehydrogenation, cyclization, condensation reactions, and combinations thereof. Separation of low molecular weight compounds from high molecular weight compounds may also occur if off-gassing occurs due to these thermal decomposition reactions. To account for these potentially large changes, this disclosure uses infrared spectroscopy and multivariate analysis to blend pitch compositions and achieve desired compositional and structural properties.

[0049] The type of infrared spectroscopy used to obtain the infrared spectra of pitch compositions according to this disclosure may preferably be multivariate FTIR, including an FTIR spectrometer coupled to a gas handling system (e.g., N2, air, vacuum, etc.), but it will be understood that dispersive infrared spectroscopy may also be used without departing from the scope of this disclosure. In one or more embodiments, the FTIR spectrometer may further include diffuse reflectance infrared Fourier transform (DRIFT) peripheral equipment. The DRIFT peripheral equipment allows for temperature control of the sample up to 1000°C. The DRIFT spectrum can provide both chemical and structural information about the sample diluted with potassium bromide (KBr), but other DRIFT-compatible diluents may be used without departing from the scope of this disclosure.

[0050] In one or more aspects of this disclosure, for DRIFT spectroscopic analysis, the sample may be diluted with KBr in the range of about 0.1 wt% to about 10 wt%, encompassing any value and subsets in between, for example, about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%.

[0051] The DRIFT spectrum used in this disclosure is approximately 200 cm². -1 From approximately 6000cm -1It may be within the range of, and encompass any value and subset within that range, for example, about 200 cm. -1 From approximately 4000cm -1 , or approximately 400cm -1 From approximately 4000cm -1 , or approximately 400cm -1 From approximately 2000cm -1 , or approximately 1000cm -1 From approximately 6000cm -1 It may also be within that range.

[0052] In one or more embodiments of this disclosure, the acquired pitch drift spectrum is evaluated to determine specific structural IR parameters. These IR parameters include, but are not limited to, the methyl-methylene ratio ("CH3 / CH2 ratio"), the A-factor, aromaticity, and degree of condensation (DoC).

[0053] It should be noted that when pitch feedstocks are thermally decomposed, alkyl side chains decompose and are removed from the thermal decomposition system. In many cases, methyl groups remain in the aromatic ring where alkyl groups were present due to weak CC bonds adjacent to the aromatic ring. Generally, the CH3 / CH2 ratio increases at least due to the loss of these CH2 units from the alkyl side chains. However, this is not true for all feedstocks. For example, highly aromatic steam cracker tars (e.g., the SOP2 sample in the following examples) and isotropic pitches (e.g., the M50 sample in the following examples) may generally show the opposite trend in the CH3 / CH2 ratio as the thermal decomposition time increases. Furthermore, the loss of alkyl side chains during thermal decomposition generally results in a decrease in the A-factor. This is because the A-factor is a measure of the size of the alkyl side chains on the aromatic core, and the chain length shortens as decomposition progresses. However, aromaticity generally increases due to the possible removal of these aliphatic side chains and the dehydrogenation of hydroaromatic compounds. As thermal decomposition progresses, DoC decreases due to increased aromaticity resulting from cyclization, dehydrogenation, and condensation reactions. These correlations can also be seen from the results of the examples shown below.

[0054] Furthermore, it was observed that using pitch-specific correlations is optimal for predicting pitch characteristics from structural IR parameters. As described with reference to the examples herein, pitch characteristics, A-factor, and aromaticity were found to be particularly correlated.

[0055] Accordingly, the Disclosure provides a method for determining pitch properties by obtaining an infrared spectrum of a pitch composition (prepared as described herein) and correlating the obtained infrared spectrum with at least one structural IR parameter using a calibration curve. In a further embodiment, the Disclosure provides a method for tuning one or more pitch properties by obtaining a first infrared spectrum of a first pitch composition (prepared as described herein) and at least a second infrared spectrum of a second pitch composition (prepared as described herein), correlating the obtained infrared spectra with at least one structural IR parameter using a calibration curve, and blending the first and second pitch compositions in a certain ratio to obtain a blended pitch composition having at least one desired pitch property.

[0056] As provided above, chemometric modeling of infrared spectra for correlating (predicting) structural IR parameters can be used, but is not limited to, the use of multivariate statistical analysis techniques such as partial least squares (PLS), in accordance with this disclosure. However, it should be understood that other types of chemometric modeling can be used without departing from the scope of this disclosure. Chemometric approaches are particularly useful, for example, for understanding and predicting pitch properties from samples undergoing air oxidation. Air oxidation is a key process used in air-blowing processes (including any reactive gases described herein) used to stabilize green carbon fibers and increase the SP of pitch. In stabilizing green fibers, the objective is to produce an injectable solid that does not flow or adhere to adjacent fibers during subsequent carbonization and graphitization (referred herein to as carbon fiber processing). The objective of air-blowing is to increase the SP of pitch, but still to produce pitch that softens and flows at moderate temperatures. Thus, because the objectives and processes differ, the resulting pitch compositions will be entirely different. Therefore, while chemometric approaches are considered particularly useful for predicting pitch composition properties, including blended pitch compositions, during the stabilization of green carbon fibers, the IR parameter methods described herein can also be used for blended pitch compositions.

[0057] Accordingly, the Disclosure provides a method for determining pitch properties by obtaining an infrared spectrum of a pitch composition (prepared as described herein) and inputting the spectrum into chemometric modeling such as PLS or other modeling techniques. In a further embodiment, the Disclosure provides a method for tuning one or more pitch properties by obtaining a first infrared spectrum of a first pitch composition (prepared as described herein), obtaining at least a second infrared spectrum of a second pitch composition (prepared as described herein), modeling at least one structural IR parameter using the infrared spectrum with chemometric modeling, and blending the first and second pitch compositions in a certain ratio to obtain a blended pitch composition having at least one desired pitch property.

[0058] Pitch composition This disclosure provides various pitch compositions, which may comprise two or more pitch compositions blended in specific ratios according to the methods described herein to obtain their desired structural properties. A single pitch (unblended) can also be evaluated according to the methodology of this disclosure, without limitation.

[0059] In one or more embodiments, the pitch composition or blended pitch composition comprises an A-factor in the range of about 0.4 to about 0.8, encompassing any value and subsets in between, for example, about 0.4 to about 0.7, or about 0.4 to about 0.6, or about 0.4 to about 0.5, or about 0.5 to about 0.8, or about 0.6 to about 0.8, or about 0.7 to about 0.8.

[0060] In various aspects of this disclosure, the pitch composition or blended pitch composition comprises aromaticity in the range of about 0.3 to about 0.9, encompassing any value and subsets in between, for example, about 0.3 to about 0.8, or about 0.3 to about 0.7, or about 0.3 to about 0.6, or about 0.3 to about 0.5, or about 0.4 to about 0.8, or about 0.5 to about 0.8, or about 0.6 to about 0.8, or about 0.7 to about 0.8, or about 0.8 to about 0.9.

[0061] In a particular embodiment, the pitch composition or blended pitch composition includes an A-factor in the range of about 0.6 to about 0.8, encompassing any value and a subset thereof, or an aromaticity in the range of about 0.3 to about 0.6, encompassing any value and a subset thereof. In another particular embodiment, the pitch composition or blended pitch composition includes an A-factor in the range of about 0.4 to about 0.6, encompassing any value and a subset thereof, or an aromaticity in the range of about 0.5 to about 0.8, encompassing any value and a subset thereof.

[0062] The pitch compositions or blended pitch compositions of this disclosure may include SP in the range of about 90°C to about 350°C, encompassing any value and subsets therein, for example, about 90°C to about 300°C, or about 90°C to about 250°C, or about 90°C to about 200°C, or about 90°C to about 150°C, or about 150°C to about 350°C, or about 200°C to about 300°C.

[0063] In various embodiments, the pitch compositions and blended pitch compositions of the Disclosure may include SP below 150°C, for example between 90°C and 150°C, encompassing any value and subsets therein, and mesophase volume (vol%) less than about 20 vol% (including 0%) encompassing any value and subsets therein. In other various embodiments, the pitch compositions and blended pitch compositions of the Disclosure may include SP between about 150°C and about 350°C, encompassing any value and subsets therein, and mesophase volume (vol%) greater than 50% (including 100%) encompassing any value and subsets therein.

[0064] In a particular embodiment, a pitch composition or a blended pitch composition, (1) an A-factor in the range of approximately 0.4 to approximately 0.8 encompassing any value and its subsets, or an aromaticity in the range of approximately 0.3 to approximately 1.3 encompassing any value and its subsets, and (2) SP in the range of approximately 90°C to approximately 150°C that encompass any value and subsets thereof, (3) Includes less than approximately 20% (including 0%) of mesophase vol% encompassing any value and its subsets. In other various specific embodiments, pitch compositions or blended pitch compositions, (1) an A-factor in the range of approximately 0.4 to approximately 0.6 encompassing any value and subsets in between, or an aromaticity in the range of approximately 0.5 to approximately 0.8 encompassing any value and subsets therein, and (2) SP in the range of approximately 250°C to approximately 350°C that encompass any value and subsets thereof, (3) Includes any value and a subset thereof, including mesophase vol% greater than approximately 30% (including 100%).

[0065] In various aspects of this disclosure, the pitch composition or blended pitch composition has an MCR in the range of about 45 wt% to about 100 wt%, encompassing any value and subsets in between, for example, in the range of about 55 wt% to about 95 wt%, or about 60 wt% to about 90 wt%, or about 65 wt% to about 85 wt%, or about 70 wt% to about 80 wt%.

[0066] In one or more embodiments, the Disclosure provides pitch compositions or blended pitch compositions having a wt% PV of less than about 70 wt%, such as in the range of 0 wt% to about 70 wt%, encompassing any value and subsets in between, for example, 5 wt% to about 65 wt%, or 10 wt% to about 60 wt%, or 15 wt% to about 55 wt%, or about 20 wt% to about 50 wt%.

[0067] In one or more embodiments of the present disclosure, the pitch or blended pitch composition has an H / C ratio in the range of about 0.5 to about 1.0, encompassing any value and subsets therein, for example, about 0.5 to about 0.9, or about 0.5 to about 0.8, or about 0.5 to about 0.7, or about 0.5 to about 0.6, or about 0.6 to about 0.7, or about 0.7 to about 0.8, or about 0.8 to about 0.9, or about 0.9 to about 1.0.

[0068] It will be understood that any combination of SP, MCR, wt%PV, and H / C ratio values ​​may be applied to a particular pitch based on the values ​​and ranges provided herein, without limitation. That is, a pitch composition or blended pitch composition according to this disclosure may have one or more of the following: SP in the range of about 90°C to about 350°C, MRC in the range of about 5°C to about 100°C, wt%PV less than about 90 wt%, and H / C ratio in the range of about 0.5 to about 1.0.

[0069] Applications of carbon fiber This disclosure also relates to a method for producing carbon fibers, including green carbon fibers, which involves combining one or more carbon fibers derived from a pitch composition or blended pitch composition prepared in accordance with this disclosure. In some embodiments, carbon fibers derived from pitch can be combined with thermosetting polymers (e.g., cyclopentadiene, dicyclopentadiene, epoxy, pitch, phenolic resins, vinyl esters, polyimides, and polyesters), thermoplastic polymers (e.g., thermoplastic polymers comprising one or more of polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyaryletherketone, polyetherimide, and polyphenylene sulfide), cement, concrete, ceramics, metals, metal alloys, or combinations thereof. In other examples, pitch itself can be used as a matrix and / or binder for producing carbon fibers, enabling the production of carbon-carbon composite materials.

[0070] In addition to carbon fibers, other suitable products can also be prepared from the pitch composition or blended pitch composition in accordance with this disclosure. For example, mesocarbon microbeads, graphite, and / or needle coke can be produced from the pitch composition or blended pitch composition. Any suitable technique can be used to produce mesocarbon microbeads, including a condensation process that involves the thermal polycondensation of the pitch composition or blended pitch composition. Other techniques for producing mesocarbon microbeads include emulsion or suspension processes.

[0071] Accordingly, this disclosure provides two methods using the IR spectroscopy described herein to predict pitch characteristics using structural IR parameters. The first method involves investigating structural IR parameters for predicting pitch characteristics from a given pitch raw material, while the second method involves using a wide variety of different raw materials and IR parameters to develop a feed-independent model for predicting pitch characteristics.

[0072] Exemplary Embodiments Non-limiting exemplary embodiments of this disclosure include:

[0073] Embodiment A: A composition comprising a pitch composition having an A-factor in the range of about 0.4 to about 0.8 and / or an aromaticity in the range of about 0.3 to about 1.3, or both.

[0074] A non-limiting exemplary embodiment A may include one or more of the following elements:

[0075] Element 1: Here, the A-factor is in the range of approximately 0.6 to 0.8, and the aromaticity is in the range of approximately 0.3 to 0.6.

[0076] Element 2: Furthermore, it includes a softening point in the range of approximately 90°C to approximately 150°C and less than approximately 20% by volume of mesophase (or intermediate phase).

[0077] Element 3: Here, the A-factor is in the range of approximately 0.4 to 0.6, and the aromaticity is in the range of approximately 0.5 to 0.8.

[0078] Element 4: Furthermore, it includes a softening point in the range of approximately 250°C to approximately 350°C and more than approximately 30% by volume of mesophase.

[0079] Element 5: Furthermore, it includes a softening point in the range of approximately 150°C to approximately 350°C and more than approximately 50% by volume of mesophase.

[0080] Element 6: The pitch composition comprises a blend of pitches including at least a first pitch composition and a second pitch composition.

[0081] As a non-limiting example, exemplary combinations applicable to Embodiment A include: A having 1 and 2, A having 1 and 4, A having 1 and 5, A having 1 and 6, A having 1, 2 and 6, A having 1, 4 and 6, A having 1, 5 and 6, A having 2 and 3, A having 2 and 6, A having 2, 3 and 6, A having 3 and 4, A having 3 and 5, A having 3 and 6, A having 3, 4 and 6, A having 4 and 6, and A having 5 and 6.

[0082] Embodiment B: A method comprising the following: At least the first pitch composition and the second pitch composition are thermally decomposed; Here, the thermal decomposition of the first pitch composition and the second pitch composition is carried out separately. The aforementioned first pitch composition is a composition derived from a first pitch feed, The aforementioned second pitch composition is a composition derived from a second pitch feed, Obtaining a first infrared spectrum of at least a first pitch composition; selecting at least one first infrared parameter based on (1) the first infrared spectrum and a calibration curve or (2) the first infrared spectrum and chemometric modeling; and Obtain a second infrared spectrum of at least a second pitch composition; (1) select at least one second infrared parameter based on the second infrared spectrum and a calibration curve or (2) the second infrared spectrum and chemometric modeling; and Here, the selected first and second infrared parameters are at least one or both of the A-factor in the range of about 0.4 to about 0.8 and / or aromaticity in the range of about 0.3 to about 1.3; and Blending first and second pitch compositions in a ratio that achieves selected first and second infrared parameters, thereby forming a blended pitch composition.

[0083] Non-limiting exemplary embodiments A, B, C, or D may include one or more of the following elements:

[0084] Element 7: The selected first and second infrared parameters further include a softening point in the range of approximately 90°C to approximately 150°C and less than approximately 20% by volume of mesophase.

[0085] Element 8: Herein, the selected first and second infrared parameters further include a softening point in the range of about 250°C to about 350°C and a mesophase exceeding about 30% by volume.

[0086] Element 9: Herein, the selected first and second infrared parameters further include a softening point in the range of about 150°C to about 350°C and a mesophase exceeding about 50% by volume.

[0087] Element 10: Further comprising spinning or manufacturing one or both carbon fibers and / or carbon fiber composite materials using blended pitch.

[0088] Element 11: Further comprising using blended pitch to produce one or more mesocarbon microbeads, graphite, and / or needle coke.

[0089] Element 12: Before thermal decomposition, the following is also included: Obtain a first initial infrared spectrum of a first pitch feeder, and select at least one first initial infrared parameter based on (1) the first initial infrared spectrum and a calibration curve, or (2) the first initial infrared spectrum and chemometric modeling; Obtain a second initial infrared spectrum of a second pitch feeder; (1) select at least one second initial infrared parameter based on the second initial infrared spectrum and a calibration curve, or (2) the second initial infrared spectrum and chemometric modeling; and The selected first and second initial infrared parameters are either or both the initial A-factor and / or initial aromaticity, excluding the range of approximately 0.4 to approximately 0.8.

[0090] Element 13: The pyrolysis further comprises contacting the first and second pitch feeds with a reactive gas at a temperature in the range of about 200°C to about 600°C and a pressure greater than 0.3 psi, thereby producing a first pitch effluent (or eluate, or effluent) consisting of the first pitch composition and a second pitch effluent consisting of the second pitch composition.

[0091] Element 14: After thermal decomposition: Separating the first pitch composition from the first pitch spill, and separating the second pitch composition from the second pitch spill. Here, the separation is selected from distillation separation, deasphalt separation, membrane separation, or any combination thereof.

[0092] Element 15: The reactive gas is selected from the group consisting of hydrogen, air, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, nitrogen dioxide, and any combination thereof.

[0093] As a non-limiting example, exemplary combinations applicable to Embodiment B include: B having 7 and 10; B having 7 and 11; B having 7, 10 and 12; B having 7, 11 and 12; B having 7, 12 and 13; B having 7, 10, 12 and 13; B having 7, 11, 12 and 13; B having 7, 12, 13 and 14; B having 7, 10, 12 and 13 and 14; B having 7, 11, 12 and 13 and 14; B having 7, 12, 13, 14 and 15; B having 7, 10, 12 and 13, 14 and 15; B having 7, 11, 12 and 13, 14 and 15 B; B with 7, 10, 12, 13, and 15; B with 7, 11, 12, 13, and 15; B with 7, 12, 13, and 15; B with 8 and 10; B with 8 and 11; B with 8, 10, and 12; B with 8, 11, and 12; B with 8, 12, and 13; B with 8, 10, 12, and 13; B with 8, 11, 12, and 13; B with 8, 12, 13, and 14; B with 8, 11, 12, 13, and 14; B with 8, 12, 13, 14, 14, and 15; B with 8, 10, 12, 13, 14, and 15; B with 8 and 1 B with 1, 12, 13, 14, and 15; B with 8, 10, 12, 13, and 15; B with 8, 11, 12, 13, and 15; B with 8, 12, 13, and 15; B with 9 and 10; B with 9 and 11; B with 9, 10, and 12; B with 9, 11, and 12; B with 9, 12, and 13; B with 9, 10, 11, 12, and 13; B with 9, 12, 13, and 14; B with 9, 10, 12, 13, and 14; B with 9, 11, 12, 13, and 14; B with 9, 12, 13, 14, and 15; B with 9, 10, and 12 B with 13, 14 and 15; B with 9, 11, 12, 13, 14 and 15; B with 9, 10, 12, 13 and 15; B with 9, 11, 12, 13 and 15; B with 9, 12, 13 and 15; B with 10 and 12; B with 11 and 12; B with 10, 12 and 13; B with 11, 12 and 13; B with 10, 12, 13 and 14; B with 10, 12, 13 and 14; B with 11, 12, 13 and 14; B with 10, 12, 13 and 14; B with 11, 12, 13 and 14; B with 11, 12, 13 and 14; B with 11, 12, 13 and 14B having 10, 12, 13, and 15; B having 11, 12, 13, and 15; B having 12, 13, and 15; B having 12 and 13; B having 12 and 15; B having 12, 13, and 14; B having 12, 13, 14, and 15.

[0094] Embodiment C: A method comprising the following: Extruding a pitch composition to produce green carbon fiber; and Subsequently, the extruded pitch composition is stabilized; Here, stabilization involves obtaining an infrared spectrum of the extruded pitch composition and selecting at least one infrared parameter based on (1) a first infrared spectrum and a calibration curve, or (2) a first infrared spectrum and chemometric modeling. Here, at least one infrared parameter is at least the A-factor and aromaticity, and Stop stabilization based on at least one infrared parameter.

[0095] As a non-limiting example, exemplary combinations applicable to Embodiment C include:

[0096] Element 15: The pitch composition is extruded through a spinneret, and the method further comprises spooling the extruded pitch composition before stabilization, the stabilization being carried out using a reactive gas.

[0097] Element 16: Extrusion includes blowing a pitch composition through an extrusion die.

[0098] Element 17: The reactive gas is selected from the group consisting of hydrogen, air, oxygen, ozone, nitrogen dioxide, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, and any combination thereof.

[0099] Element 18: At least one selected infrared parameter is at least one or both of the A-factor and aromaticity, and stabilization is stopped when the A-factor is in the range of about 0.4 to about 0.8 and / or aromaticity is in the range of about 0.3 to about 1.3.

[0100] As a non-limiting example, exemplary combinations applicable to Embodiment C include: C having 15 and 17; C having 16 and 17; C having 15 and 18; C having 16 and 18; C having 15, 17 and 18; C having 16, 17 and 18; C having 17 and 18.

[0101] Embodiment D. A method comprising the following: Thermal decomposition of the pitch composition from the pitch feed; Obtaining the infrared spectrum of a first pitch composition, and selecting at least one infrared parameter based on (1) the infrared spectrum and a calibration curve or (2) the infrared spectrum and chemometric modeling. At least one selected infrared parameter is at least one or both of the A-factor in the range of approximately 0.4 to approximately 0.8 and / or aromaticity in the range of approximately 0.3 to approximately 1.3.

[0102] As a non-limiting example, exemplary combinations applicable to Embodiment D include:

[0103] Element 18: At least one selected infrared parameter further includes a softening point in the range of about 90°C to about 150°C and less than about 20% by volume of mesophase.

[0104] Element 19: At least one selected infrared parameter further includes a softening point in the range of approximately 250°C to approximately 350°C, and a mesophase greater than approximately 30% by volume.

[0105] Element 20: At least one selected infrared parameter further includes a softening point in the range of approximately 150°C to approximately 350°C and a mesophase greater than approximately 50% by volume.

[0106] Element 21: Further comprises spinning or manufacturing one or both carbon fibers and / or carbon fiber composite materials using a pitch composition.

[0107] Element 22: Before thermal decomposition, The method further includes obtaining the initial infrared spectrum of the pitch feed and selecting at least one initial infrared parameter based on (1) the initial infrared spectrum and a calibration curve, or (2) the initial infrared spectrum and chemometric modeling; At least one selected initial infrared parameter is either the initial A-factor outside the range of approximately 0.4 to approximately 0.8 and / or the initial aromaticity outside the range of approximately 0.3 to approximately 1.3, or both.

[0108] Element 23: Pyrolysis further comprises contacting a pitch feed with a reactive gas at a temperature in the range of about 200°C to about 600°C and a pressure exceeding 0.3 psi, thereby producing a pitch effluent consisting of a pitch composition.

[0109] Element 24: Further comprising separating the pitch composition from the pitch spill after thermal decomposition, wherein the separation is selected from distillation separation, deasphalt separation, membrane separation, or any combination thereof.

[0110] Element 25: The reactive gas is selected from the group consisting of hydrogen, air, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, nitrogen dioxide, and any combination thereof.

[0111] As a non-limiting example, exemplary combinations applicable to Embodiment D include: D having 18 and 21; D having 18 and 22; D having 18, 21 and 22; D having 18, 22 and 23; D having 18, 21, 22 and 23; D having 18, 22 and 23 and 24; D having 18, 21, 22 and 23 and 24; D having 18, 21, 22 and 23 and 24; D having 18, 21, 22 and 23 and 24; D having 19 and 21; D having 19 and 22; D having 19, 21 and 22; D having 19, 22 and 23; D having 19, 21 and 22 and 23 and 24; D having 19 and 21 and D having 22, 24, and 25; D having 19, 21, 22, 23, 24, and 25; D having 18 and 21; D having 18 and 22; D having 18, 21, and 22; D having 18, 22, and 23; D having 18, 21, 22, and 23; D having 18, 22, 23, and 24; D having 18, 21, 22, 23, and 24; D having 18, 21, 22, and 2 D having 3, 24, and 25; D having 18, 21, 22, 23, 24, and 25; D having 21 and 22; D having 21, 22, and 23; D having 21, 22, 23, and 24; D having 21, 22, 23, and 25; D having 22, 23, and 24; D having 22, 23, and 25; D having 22, 23, 24, and 25.

[0112] To facilitate understanding of the embodiments of the present invention, examples of preferred or representative embodiments are shown below. In no sense should the following examples be read to limit or define the scope of the present invention.

[0113] Examples In the following non-limiting embodiments, a typical methodology of the present disclosure for adjusting pitch characteristics is provided.

[0114] Background infrared spectra - Examples 1 and 2 Infrared spectra of various prepared pitch compositions were obtained using DRIFT. Pitch samples were prepared by filling glass vials with approximately 2 grams (g) of the raw materials described later, and placing them in a PAC® Micro Carbon Residue Tester. Nitrogen gas (600 mL min) -1 The sample was heated to 100°C for 10 minutes while flowing (a solution) through it. Immediately afterward, it was heated to 30°C. -1 The heating rate and 600 mL min -1 The sample was heated to 400°C using a nitrogen flow rate of 150 mL min. Once 400°C was reached, the flow rate was increased to 150 mL min. -1 The temperature was lowered, and the sample was held at 400°C for 0-6 hours (hr). After a predetermined heat soak time, it was heated in an oven for several hours in nitrogen gas at a flow rate of 600 mL min. -1 The sample was then cooled to room temperature.

[0115] The results and pyrolysis parameters (heating time (hr) and temperature (°C)) are shown in Table 1 below. The pitch composition of the sample was obtained from the following raw materials: (1) Solvent-assisted tar conversion (SATC) bottom stream samples (labeled SATC-1 to SATC-8); (2) "Seed" SATC PDU bottom stream samples (indicated as sSATC-1 to s-SATC-8) formed from a mixture of 0-hour unheated SATC bottom stream (SATC-1) and 5-hour treated SATC bottom stream (SATC-6); (3) Tar derived from steam crackers (indicated as SOP2-1 to SOP2-5); (4) Heavy vacuum diesel pitch (bottom stream at temperatures of 986°F to 1038°F, or 524°C to 559°C) (indicated as HVGO-1 and HVGO-2); (5) Bitumen pitch derived from Kerl (indicated as KB-1 to KB-6); (6) Hydrogenated mesocarbon microbead pitch (indicated as MCB-1 and MC-2); and (8) Isotropic petroleum pitch available from Marathon Oil Corporation (Findlay, Ohio) (labeled M-50, M50-1 to M50-4).

[0116] Elemental analysis of SP, MCR, H / C ratio, and %PV was measured as defined herein. “N / A” in Table 1 indicates that a specific pitch characteristic was not measured or that an unknown measurement error occurred. A superscript “*” in Table 1 indicates that the instrument failed to measure at the given temperature, resulting in the material not being fully softened and therefore the value being at its lower limit. [Table 1]

[0117] Each sample in Table 1 was diluted with potassium bromide (KBr) in a 2 wt% pitch sample packing, and the respective DRIFT spectra were measured by RT (using an FT-IR spectrometer equipped with the DRIFT peripherals and detector provided herein). DRIFT data were obtained at 400–4000 cm⁻¹. -1 The spectral range was collected, and the ratio of the sample spectrum to the room-temperature spectrum of KBr was used, according to Thermo Fisher Scientific Inc. OMNIC. TM The values ​​were converted to absorbance using software (version 9). Measurements were taken using the Happ-Genzel decay function with a resolution of 4 cm. -1 Each sample was acquired using 256 scans.

[0118] Representative results are shown in Figures 1A-1D. Figure 1A shows the drift spectra of samples HVGO-1 and HVGO-2, Figure 1B shows the drift spectra of samples KB-1 to KB-6, Figure 1C shows the drift spectra of samples MCB-1 and MCB-2, and Figure 1D shows the drift spectra of samples M50-1 to M50-4.

[0119] As shown in Figure 1A-1D, the drift spectrum shows an increase in aromatic CH stretching (approximately 2991–3100 cm) as the heat treatment progresses (i.e., as the time at 400°C increases). -1 (range) Simultaneously, there is a decrease in aliphatic CH elasticity (approximately 2820-3000 cm) -1 This shows spectral changes related to the range. Similar results were observed in the DRIFT spectra of the remaining samples in Table 1.

[0120] Example 1 - Drift Spectrum Analysis + Infrared Parameters Representative DRIFT spectra were obtained as described above for samples SATC-1 to SATC-6 and SATC-8 (represented by diamond-shaped labels); and samples sSATC-1 to sSATC-8 (represented by circular labels). Subsequently, based on the obtained DRIFT spectra, the infrared structural parameters of the CH3 / CH2 ratio, A-factor, aromaticity, and DoC, as defined above, were measured. Figure 2A shows the measurement results for the infrared parameter CH3 / CH2 ratio, Figure 2B shows the measurement results for the infrared parameter A-factor, Figure 2C shows the measurement results for the infrared parameter aromaticity, and Figure 2D shows the measurement results for the infrared parameter DoC.

[0121] As shown in Figures 2A-2D, the CH3 / CH2 ratio and aromaticity increase with increasing thermal decomposition time (at 400°C in this example), while the A-factor and DoC decrease with increasing thermal decomposition time. The decrease in DoC with increasing thermal conversion time indicates an increase in ring condensation. Similar results were observed for the infrared parameters of the remaining samples in Table 1 (not shown).

[0122] As described above, DRIFT spectra were obtained for each sample shown in Table 1, and infrared parameters (CH3 / CH2 ratio, A-factor, aromaticity, and DoC) were measured. Subsequently, each infrared parameter was correlated with each pitch characteristic (SP, MCR, H / C ratio, and %PV). The infrared parameters were used to track the various major structural changes that occur during the thermal decomposition of pitch.

[0123] From the correlation between infrared parameters and the structural properties of pitch, it was observed that the most fitting correlation was based on the A-factor and aromaticity. Figures 3A-3D show representative correlation diagrams for each sample in Table 1 between the A-factor and MCR (Figure 3A); the A-factor and SP (Figure 3B); aromaticity and MCR (Figure 3C); and aromaticity and SP. As shown in Figures 3A-3D, infrared parameters and pitch properties correlate, but this correlation differs depending on the pitch type; therefore, this embodiment is pitch type dependent. As described above, the average of the A-factor and / or aromaticity is used to predict specific structural pitch properties.

[0124] Based on the determined average A-factor and average aromaticity, parity plots were created for each of the pitch characteristics: MCR (%), SP (°C), H / C ratio, and %PV, between the predicted and measured values ​​of the A-factor and aromaticity characteristics. Representative samples were selected that contained sufficient data and sufficient reference (measured) data. The parity plots are shown in Figures 4A to 4D, with Figure 4A showing the parity plot for MCR, Figure 4B showing the parity plot for SP (the dashed line indicates the limit of the measuring instrument above 380°C), Figure 4C showing the parity plot for the H / C ratio, and Figure 4D showing the parity plot for %PV. As can be observed, for all infrared parameters, there is significant parity between the predicted pitch characteristics and the actual pitch characteristics.

[0125] Therefore, this embodiment demonstrates the methodology of this disclosure, which utilizes the correlation between DRIFT infrared parameters and pitch-type predictions of their structural properties.

[0126] Example 2 - Drift Spectrum Analysis + Chemometric Analysis In this example, chemometric modeling was used to predict pitch characteristics based on the DRIFT spectrum, as shown in Table 1 and representative Figures 1A-1B. The chemometric method enables the prediction of pitch characteristics that are independent of the pitch type ("independent (or agnostic) pitch model"), as described herein.

[0127] Each of the four pitch characteristics described herein (MCR, SP, H / C ratio, and %PV) was evaluated using the PLS modeling technique described above.

[0128] Referring to Figure 5, a correlation diagram of the PLS model for a typical pitch characteristic MCR is shown, where the MCR is predicted based on PLS and compared with the actual MCR values ​​in Table 1. As shown in Figure 5, there is a significant correlation between the MCR predicted by PLS and the actual MCR values.

[0129] Similar to Example 1, parity plots were created for this example, and the results are shown in Figures 6A to 6D. Figure 6A shows the parity plot for MCR, Figure 6B shows the parity plot for SP, Figure 6C shows the parity plot for H / C ratio, and Figure 6D shows the parity plot for %PV. As can be observed, for all infrared parameters, there is significant parity between the predicted pitch characteristics and the actual pitch characteristics.

[0130] Figures 7A-7D show the predicted pitch characteristics based on the chemometric approach of this embodiment, using IR structural parameter least squares analysis (LSA) (polynomial degree 2) for the SATC-1, SATC-4, SATC-8, sSATC-1, sSATC-4, and sSATC-8 samples from Table 1. Compared with the values ​​in Table 1, the predicted values ​​were within the range of the measured values ​​for each sample.

[0131] All documents described herein, including priority documents and / or test procedures, are incorporated herein by reference, to the extent that they do not conflict with this Specified, for the purposes of all jurisdictions in which such practice is permitted. As is evident from the general description and specific embodiments set forth herein, the forms of this disclosure are illustrated and described herein, but various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. For example, the compositions described herein may not include components or compositions not expressly described or disclosed herein. Any method may lack any steps not described or disclosed herein. Similarly, the term “comprising” is to be considered synonymous with the term “including.” Whenever there is a transitional clause “comprising” before a method, composition, element or group of elements, it is understood that the same composition or group of elements is also assumed to be preceded by a transitional clause “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is.”

[0132] Unless otherwise indicated, all numerical values ​​used in this specification and the appended claims, such as quantities of components, molecular weights and other properties, and reaction conditions, are understood in all cases to be modified by the term "approximately." Therefore, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired properties to be obtained by embodiments of the present invention. At least, without attempting to limit the application of the doctrine of equivalents to the claims, each numerical parameter should be interpreted by applying common rounding techniques, at least in light of the reported number of significant figures.

[0133] Wherever a numerical range with lower and upper limits is disclosed, any number that falls within that range and any range that is included, including the lower and upper limits, shall be specifically disclosed. In particular, any numerical range disclosed herein (in the form of "about a to about b," or equivalently "about a to b," or equivalently "about ab") shall be understood to define any number and range that is included within a broader numerical range. Furthermore, terms used in the claims shall have plain, ordinary meanings unless explicitly and clearly defined by the patentee. In addition, the indefinite article "a" or "an" used in the claims shall be defined herein as meaning one or more of the elements it introduces.

[0134] This specification provides one or more exemplary embodiments. For clarity, this application does not describe or illustrate all features of the physical embodiments. It is understood that in developing the physical embodiments of this disclosure, numerous embodiment-specific decisions must be made to achieve the developer's objectives, including compliance with system-related, business-related, government-related, and other constraints that vary by embodiment and from time to time. While the developer's efforts may be time-consuming, such efforts will still be routine business for those skilled in the art and who have an interest in this disclosure.

[0135] Accordingly, this disclosure is well adapted to achieve the purposes and benefits mentioned herein, as well as those inherent therein. Since this disclosure can be modified and implemented in different but equivalent ways that will be apparent to those skilled in the art who have an interest in the teachings herein, the specific embodiments disclosed above are merely illustrative. Furthermore, no limitation is intended on any details of the structure or design shown herein other than those described in the following claims. Accordingly, it is apparent that the specific exemplary embodiments disclosed above can be modified, combined, or altered, and all such variations are considered to be within the scope and spirit of this disclosure. The embodiments disclosed herein exemplary can preferably be implemented even without elements not specifically disclosed herein and / or any elements disclosed herein.

Claims

1. A composition comprising a pitch composition having both an A-factor in the range of approximately 0.4 to approximately 0.8 and an aromaticity in the range of approximately 0.3 to approximately 0.

7.

2. The composition according to claim 1, wherein the A-factor is in the range of about 0.6 to about 0.8, and the aromaticity is in the range of about 0.3 to about 0.

6.

3. The composition according to claim 1 or 2, further comprising a softening point in the range of about 90°C to about 150°C and less than about 20% by volume of mesophase.

4. The composition according to claim 1, wherein the A-factor is in the range of about 0.4 to about 0.6, and the aromaticity is in the range of about 0.5 to about 0.

7.

5. The composition according to any one of claims 1, 2, or 4, further comprising a softening point in the range of about 250°C to about 350°C and more than about 30% by volume of mesophase.

6. The composition according to any one of claims 1, 2, or 4, further comprising a softening point in the range of about 150°C to about 350°C and more than about 50% by volume of mesophase.

7. The composition according to claim 1, wherein the pitch composition comprises a blend of pitches including at least a first pitch composition and a second pitch composition.

8. At least the first pitch composition and the second pitch composition are thermally decomposed. Here, the thermal decomposition of the first pitch composition and the second pitch composition is carried out separately. The first pitch composition is a composition derived from the first pitch feed, The aforementioned second pitch composition is a composition derived from the second pitch feed, Obtain a first infrared spectrum of at least a first pitch composition, and select at least one first infrared parameter based on (1) the first infrared spectrum and a calibration curve or (2) the first infrared spectrum and chemometric modeling. Obtain a second infrared spectrum of at least a second pitch composition, select at least one second infrared parameter based on (1) the second infrared spectrum and a calibration curve or (2) the second infrared spectrum and chemometric modeling, and Here, the selected first and second infrared parameters are at least one or both of the A-factor in the range of about 0.4 to about 0.8 and / or aromaticity in the range of about 0.3 to about 1.3, and A method comprising blending first and second pitch compositions in a ratio that achieves selected first and second infrared parameters, thereby forming a blended pitch composition.

9. The method according to claim 8, wherein the selected first and second infrared parameters further include a softening point in the range of about 90°C to about 150°C and less than about 20% by volume of mesophase.

10. The method according to claim 8, wherein the selected first and second infrared parameters further include a softening point in the range of about 250°C to about 350°C and a mesophase exceeding about 30% by volume.

11. The method according to claim 8, wherein the selected first and second infrared parameters further include a softening point in the range of about 150°C to about 350°C and a mesophase exceeding about 50% by volume.

12. The method according to any one of claims 8 to 11, further comprising using blended pitch to spin or manufacture one or both carbon fibers and / or carbon fiber composite materials.

13. The method according to any one of claims 8 to 11, further comprising using blended pitch to produce one or more of mesocarbon microbeads, graphite, and / or needle coke.

14. Before thermal decomposition, Obtain a first initial infrared spectrum of a first pitch feeder, and select at least one first initial infrared parameter based on (1) the first initial infrared spectrum and a calibration curve, or (2) the first initial infrared spectrum and chemometric modeling. The method further includes obtaining a second initial infrared spectrum of a second pitch feeder, and selecting at least one second initial infrared parameter based on (1) the second initial infrared spectrum and a calibration curve, or (2) the second initial infrared spectrum and chemometric modeling, and The method according to claim 8, wherein the selected first and second initial infrared parameters are either or both of the initial A-factor and / or initial aromaticity, except in the range of about 0.4 to about 0.

8.

15. The method according to claim 14, further comprising the thermal decomposition bringing the first and second pitch feeds into contact with a reactive gas at a temperature in the range of about 200°C to about 600°C and at a pressure greater than 0.3 psi, thereby producing a first pitch spill containing a first pitch composition and a second pitch spill containing a second pitch composition.

16. After pyrolysis, The method further includes separating a first pitch composition from a first pitch spill and separating a second pitch composition from a second pitch spill. The method according to claim 15, wherein the separation is selected from distillation separation, deasphalt separation, membrane separation, or any combination thereof.

17. The method according to claim 15 or 16, wherein the reactive gas is selected from the group consisting of hydrogen, air, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, nitrogen dioxide, and any combination thereof.

18. Extruding a pitch composition to produce green carbon fibers, and Subsequently, the extruded pitch composition is stabilized. Here, stabilization includes obtaining an infrared spectrum of the extruded pitch composition and selecting at least one infrared parameter based on (1) a first infrared spectrum and a calibration curve, or (2) a first infrared spectrum and chemometric modeling. Here, at least one infrared parameter is at least the A-factor and aromaticity, and When the A-factor is in the range of approximately 0.4 to approximately 0.8 and / or the aromaticity is in the range of approximately 0.3 to approximately 1.3, A method that includes stopping stabilization.

19. The method according to claim 18, wherein a pitch composition is extruded through a spinneret, and the method further comprises spooling the extruded pitch composition before stabilization, wherein the stabilization is performed using a reactive gas.

20. The method according to claim 18, wherein the extrusion comprises blowing a pitch composition through an extrusion die.

21. The method according to any one of claims 18 to 20, wherein the reactive gas is selected from the group consisting of hydrogen, air, oxygen, ozone, nitrogen dioxide, hydrogen peroxide, carbon monoxide, carbon dioxide, formic acid, and any combination thereof.

22. The method according to claim 18, wherein at least one selected infrared parameter is at least one or both of the A-factor and aromaticity, and stabilization is stopped when the A-factor is in the range of about 0.4 to about 0.8 and / or aromaticity is in the range of about 0.3 to about 1.3.

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