JP2021500461A - Integrated process for mesophase pitch and petrochemicals - Google Patents

Abstract

An integrated method for the production of mesophase pitch and petrochemical products. This method involves supplying crude oil to a reaction vessel, heating the crude oil in the reaction vessel to a predetermined temperature for a predetermined time, and causing a polymerization reaction in the reaction vessel at high pressure in the absence of oxygen. To reduce the asphaltene content of, produce a three-phase upgrade hydrocarbon product containing gas, liquid, and solid hydrocarbon components, with liquid hydrocarbon components containing deasphalt oil and solid hydrocarbon components containing mesophase pitch. To separate gas, liquid, and solid hydrocarbon components, to utilize liquid hydrocarbon components directly for the production of petroleum chemicals, to directly utilize the solid hydrocarbon components for the production of carbon artifacts. Including. [Selection diagram] Fig. 1

Description

Embodiments of the present disclosure relate to crude oil and crude oil residue upgrades. In particular, embodiments of the present disclosure relate to upgrading crude oil and crude oil residues to produce mesophase pitches and additional petrochemicals in an integrated process.

Crude oil and crude oil residues can be processed by an energy-consuming refining process to produce mesophase pitch (also called MP). Since the condensed aromaticity of the pitch provides thermal stability, the mesophase pitch can be melt-spun for carbon fiber applications. In some cases, melt spinning is preferred over wet / dry spinning used in the production of polyacrylonitrile (PAN) -based fibers, with large amounts of solvent and waste by-products. High quality carbon fibers can be produced from optically anisotropic pitch or mesophase pitch (MP), but since the production of this carbon fiber precursor requires extensive purification and complex processing, from mesophase pitch. It is desired to produce carbon fiber on a PAN basis rather than producing carbon fiber.

Carbon fibers have high strength and high tensile elasticity, as well as other desirable properties such as light weight, chemically inertness, low coefficient of thermal expansion, excellent electrical and thermal conductivity. Smaller structural defects in fiber morphology and enhanced molecular orientation enable these properties, making carbon fibers suitable for many structural and functional applications.

In the technology of producing chemicals directly from crude oil (C2C), heavy or asphaltene fractions of crude oil are often a problem, stains on reactors and thermal surfaces, catalyst deactivation, reduced degradation activity, and overall performance. Causes a decrease in. Separating these heavy fractions before the decomposition reactor reduces the economic advantage of directly decomposing crude oil into chemicals, in other words, C2C produces refined products such as reduced gas oil (VGO) and naphtha. It costs more than disassembling.

Challenges related to crude decomposition, such as increased catalytic caulking rates and metal poisoning, accelerate certain research efforts towards steam decomposition (pyrolysis) and FCC. In some cases, the economics of energy-consuming steam crackers are more favorable for lower value, heavier feedstocks such as crude oil. However, in practice, the asphalt and non-volatile fractions of these feedstocks are deposited in the pipes of the convection section of the pyrolysis furnace, impairing heat transfer and requiring frequent shutdowns. Some literature discusses dealing with heavy residues in crude oil before steam cracking, and many references disclose a pre-separation step for non-volatile fractions in crude oil. ..

Direct catalytic cracking of crude oil is rarely discussed, as harmful metals such as sulfur and nitrogen in crude oil are harmful to cracking catalysts and equipment. Decomposition of conventional feedstocks such as naphtha is relatively easier than cracking down heavier feedstocks with crude oil and residues, so applying a pre-separation step of asphaltene and metal in the C2C process will crack down. The economic and competitive benefits of skipping crude oil refining before are significantly lost.

The present disclosure is for the direct production of high quality mesophase pitch (MP) from crude oil or crude oil residues, with or without hydrogenation, with the simultaneous removal of asphaltene, which lowers the viscosity and boiling point of heavy crude oil or residues. The heat treatment system and method of the above are presented. Solid (MP), liquid (de-asphalt oil, DAO), and gaseous moieties of the products of such systems and methods are fractionated into refinery products and in C2C processes including cracking and catalytic cracking processes. Can be used as a feedstock for. It is desirable to treat crude oil and crude oil residues to produce mesophase pitches with lower boiling points, which can be used to produce high quality carbon fibers. The DAO product can be used directly as light oil and can be used as a feedstock for cracking processes such as fluid catalytic cracking (FCC) or thermal cracking.

New preheat treatment methods, processes, and systems for producing high quality MPs directly from crude oil or their residues, with or without hydrogenation (HT), are disclosed. Embodiments of the present disclosure can directly use the deasphalt oil (DAO) produced during the methods of the present disclosure as a feedstock to a cracking furnace and thus solve certain caulking problems directly associated with crude oil cracking. Demonstrate what you can do. The mesophase pitch is produced by the embodiments of the present disclosure and is a valuable by-product of increasing the efficiency of the process.

In the embodiments of the present disclosure, heavy crude oils, such as Arabian heavy (AH) crude oil, are directly converted into valuable compounds using heat and pressure. The product obtained in the treatment vessel has a solid phase corresponding to about 10 weight percent ± 5 weight percent (depending on feed, temperature, and polymerization time) of the carbon fraction obtained at room temperature. contains. The liquid phase (cut) represents about 80 weight percent ± 5 weight percent of the obtained carbon fraction and the gas phase is about 10 weight percent ± 5 weight percent of the obtained carbon fraction. The liquid and gaseous moieties of the products of such processes can be fractionated into petrochemical feedstocks or used as feedstocks for direct C2C processes involving steam pyrolysis and catalytic cracking processes (such as FCC). obtain.

Accordingly, disclosed herein is an integrated method for mesophase pitch and petrochemical products, in which the steps of supplying crude oil to the reaction vessel and the crude oil in the reaction vessel are defined at a given temperature. A step of heating for a period of time, a step of reducing the asphaltene content in crude oil by causing a polymerization reaction in a reaction vessel at high pressure in the absence of oxygen, and a liquid hydrocarbon containing gas, liquid, and solid hydrocarbon components. Steps to produce three-phase upgrade hydrocarbon products, where the hydrogen component contains deasphalt oil and the solid hydrocarbon component contains mesophase pitch, and steps to separate gas, liquid, and solid hydrocarbon components, and petrochemical products. It includes a step of directly utilizing the liquid hydrocarbon component for production and a step of directly utilizing the solid hydrocarbon component for the production of carbon artifacts.

In some embodiments of the method, the crude oil is the crude oil that is separated from the natural gas, dehydrated and then received directly from the wellhead, but without pretreatment prior to the step of supplying the crude oil to the reactor vessel. In yet another embodiment, the predetermined temperature is from about 350 ° C to about 575 ° C. In some embodiments, the predetermined temperature is between about 400 ° C and about 450 ° C. In yet another embodiment, the method applies an initial pressure of about 145 pounds per square inch gauge (psig) to about 870 psig prior to the step of heating the crude oil in the reaction vessel to a given temperature for a given time. It further includes a step of pressing.

In yet another embodiment, the step of pressurizing the vessel to the initial pressure comprises the step of expelling oxygen from the reaction vessel using a gas containing nitrogen. In certain embodiments, the method further comprises the step of pressurizing the vessel to an initial pressure of about 435 psig to about 725 psig prior to the step of heating the crude oil in the reaction vessel to a predetermined temperature for a predetermined time. In some embodiments, the step of pressurizing the vessel to the initial pressure comprises the step of expelling oxygen from the reaction vessel using a gas containing nitrogen. In yet another embodiment, the predetermined time is about 2 hours to about 15 hours. In certain embodiments of the method, the predetermined time is from about 4 hours to about 8 hours.

In another embodiment, the step of reducing the asphalt content reduces the asphalt content in the de-asphalt oil to less than about 2% by weight. In certain other embodiments, the high pressure exceeds about 1,000 psig. In yet another embodiment, the high pressure is about 1,800 psig to 1,900 psig. In certain embodiments of the method, the step of directly utilizing the liquid hydrocarbon component for the production of petrochemical products comprises supplying deasphalt oil to a fluid cracking process. In certain embodiments, the step of directly utilizing the liquid hydrocarbon component for the production of petrochemicals comprises supplying deasphalt oil to the steam cracking process.

In yet another embodiment, the step of directly utilizing the solid hydrocarbon component for the production of carbon artifacts comprises the step of producing carbon fibers from the mesophase pitch. In certain embodiments, crude oil comprises at least one hydrocarbon selected from the group consisting of heavy crude oil, light crude oil, and crude oil residues having a boiling point above about 500 ° C.

In yet another embodiment, the asphalt compound content of the deasphalt oil is reduced by at least about 50% by weight with respect to the asphalt compound content of the crude oil. In certain embodiments, the asphalt compound content of the deasphalt oil is reduced by at least about 90% by weight with respect to the asphalt compound content of the crude oil. In yet another embodiment, the metal content in the liquid hydrocarbon component is less than the metal content in the crude oil. In some embodiments, the solid hydrocarbon component is at least about 90% pure mesophase pitch. Further, in another embodiment, the step of causing a polymerization reaction at high pressure in the reactor in the absence of oxygen to reduce the asphaltene content in the crude oil increases the pressure in the reactor to about 1,700 psig to about 2. , Increase to 500 psig.

Further disclosed herein is an integrated system for mesophase pitch and petrochemical products, which includes a crude oil source fluid-coupled to the reaction vessel, where the reaction vessel is defined. It can operate to be heated to a predetermined temperature for a period of time, and can operate to reduce the asphaltene content in the crude oil source by causing a polymerization reaction in the reaction vessel at high pressure in the absence of oxygen. , Including a gas-liquid solid three-phase separator, the gas-liquid solid three-phase separator can operate to separate the three-phase upgrade hydrocarbon products produced in the reaction vessel, the three-phase upgrade hydrocarbon products. Consists of gas, liquid, and solid hydrocarbon components, the liquid hydrocarbon component contains deasphalt oil, the solid hydrocarbon component contains a mesophase pitch, and also contains a decomposition unit, which is a decomposition unit. It receives the liquid hydrocarbon component and is fluidly linked to decompose the liquid hydrocarbon component for petrochemical products.

Some embodiments of the system further include a unit that produces carbon fibers from the mesophase pitch. In some embodiments, the predetermined temperature is between about 350 ° C and about 575 ° C. In yet another embodiment, the predetermined temperature is between about 400 ° C and about 450 ° C. In yet another embodiment, the predetermined time is about 2 hours to about 15 hours. In certain embodiments, the predetermined time is from about 4 hours to about 8 hours. In some embodiments, the asphalt content in the deasphalt oil is less than about 2% by weight. In yet another embodiment, the high pressure exceeds about 1,000 psig. In certain embodiments, the high pressure is from about 1,800 psig to 1,900 psig. In yet another embodiment, the cracking unit comprises a fluid catalytic cracking process.

In certain embodiments, the decomposition unit comprises a steam decomposition process. In yet another embodiment, the crude oil comprises at least one hydrocarbon selected from the group consisting of heavy crude oil, light crude oil, and crude oil residues having a boiling point above about 500 ° C. In embodiments of the system, the asphalt compound content of the deasphalt oil is reduced by at least about 50% by weight with respect to the asphalt compound content of the crude oil source. In yet another embodiment, the asphalt compound content of the deasphalt oil is reduced by at least about 90% by weight with respect to the asphalt compound content of the crude oil source. In some embodiments, the metal content in the liquid hydrocarbon component is less than the metal content in the crude oil source.

In another embodiment of the system, the solid hydrocarbon component is at least about 90% pure mesophase pitch. In a more specific embodiment, the high pressure in the reaction vessel is from about 1,700 psig to about 2,500 psig.

These and other features, aspects, and advantages of the present disclosure will be better understood with respect to the following description, claims, and accompanying drawings. However, it should be noted that the drawings show only some embodiments of the present disclosure and therefore other equally valid embodiments can be acknowledged and should not be considered to limit the scope of the present disclosure.

FIG. 1 is a mechanical flow chart showing a system and method of one exemplary embodiment of a direct C2C manufacturing process.

FIG. 2 is a mechanical diagram showing experimental settings for the disassembly experiments of the present disclosure.

FIG. 3 shows light microscopy images of mesophase pitches obtained using the embodiments of the present disclosure on scales of 100 micrometers (μm), 50 μm, and 20 μm, where the crude oil and crude oil residue samples are 425 degrees Celsius. The treatment was carried out at a temperature of (° C.) and a stirring rate of 650 rpm (rpm) for 6 hours.

FIG. 4 is a graph showing X-ray diffraction (XRD) data for mesophase pitches obtained using the embodiments of the present disclosure, where the crude oil and crude oil residue samples are rotated 650 rpm at a temperature of 425 ° C. The treatment was carried out at a stirring speed of / min (rpm) for 6 hours.

It forms part of this specification so that the features and advantages of embodiments of integrated process systems and methods for mesophase pitches and petrochemicals, as well as other features and benefits, can be understood in more detail. A more detailed description of the embodiments of the present disclosure, briefly summarized above, may be provided by reference to the embodiments shown in the accompanying drawings. However, it should be noted that the drawings show only the various embodiments of the present disclosure and therefore other valid embodiments may be included as well and should not be considered to limit the scope of the present disclosure.

First referring to FIG. 1, a mechanical flow chart is provided showing a system and method for one exemplary embodiment of a direct crude oil-chemical (C2C) manufacturing process. In the embodiments of the present disclosure, an integrated heat pretreatment process for producing mesophase pitch (MP) in addition to upgraded crude oil with very low concentrations of asphaltene and heavy metals, also called deasphalt oil or DAO. Give a different overview of. Products such as MP can be used directly in carbon fiber production and DAO can be used as a direct feed material in C2C techniques such as fluid cracking (FCC) and thermal cracking (steam cracking). Embodiments of the thermal pretreatment step include prolonged thermal polymerization under mild decomposition conditions. The result is MP, gaseous decomposition products, and liquid DAO. Liquid and gaseous products can be fractionated into petrochemical raw materials or used as raw materials for direct C2C processes. These processes can be integrated with conventional steam / catalytic cracking systems to provide solutions to the problems cited above, such as metal poisoning of catalysts and coke precursors.

The term crude oil in the present disclosure includes references to liquid crude oil from wellheads separated from natural gas. As defined, the crude oil feedstocks of the present disclosure can undergo a processing process to make them transportable feedstocks such as desalting, but in certain embodiments distillation of any kind at the crude oil feedstock inlet. Or, it does not undergo pre-distillation treatment. Crude oil has Arabian gas oil, Arabic gas oil, Arabian heavy oil, and the American Petroleum Institute (API) degree, which varies from about 6 ° to about 39 °, or from about 6 to about 30 °, or from about 6 ° to about 21 °. Other types of crude oil can be included. In some of the examples described herein, the "heat" pretreatment of crude oil occurs in a substantially inert atmosphere, such as nitrogen, or at high temperatures and pressures, such as under argon, but for some preheat treatment steps. In the examples, no solvent and other chemical reactants are added to the crude oil.

The American Petroleum Institute (API) gravity is a measure of how "heavy" or "light" a petroleum liquid is. The relationship between the API gravity and the specific gravity (SG) at 60 ° F is API = (141.5 / SG) -131.5. Crude oil from Saudi Arabia with an API gravity greater than about 32 ° is called Arabian Light or "AL" and crude oil with an API gravity less than about 28 ° is called Arabian Heavy or "AH". In the present disclosure, the hydrogenated (“HT”) residue of Arabian Light is also referred to as “C2C” (crude oil to chemical) reject, and the term is approximately after hydrogenating Arabian Light. Identify residues obtained at boiling points above 500 ° C. For example, on one scale, Arabian Heavy is about 10 ° ≥ API> 6 °, Arabian Medium is about 21 ° ≥ API> 10 °, Arabian Light is about 30 ° ≥ API> 21 °, Arabian Extra. The light is about 39 ° ≥ API> 30 °.

As shown in FIG. 1, process 100 is separated from natural gas, optionally desalted and stabilized for transport, but otherwise untreated, unfractionated and decomposed. It begins at the untreated crude oil source 102 from the untreated wellhead. An embodiment of the preheat treatment step for the crude oil source 102 comprises heating the untreated crude oil source 102 in an inert or substantially inert atmosphere, the atmosphere being substantially oxygen-free (eg, about). Less than 5% by volume of oxygen, or less than about 1% by volume of oxygen). As shown in FIG. 1, the substantially inert atmosphere can include nitrogen gas in addition to, or in place of, one or more inert gases, such as argon or helium. Hydrogen (H ₂ ) and other treatment additives can optionally be added to the untreated crude oil source 102, but are not always required.

Embodiments of the process of the present disclosure include heat treatment in an atmosphere of inert nitrogen or argon or helium, without additional additives. However, the additive may be added to the inert gas stream or crude oil feedstock to improve the polymerization yield and adjust the mesophase pitch properties (eg, to reduce its softening point). Any additive can include hydrogen in addition to or in place of the organic salt.

The inlet crude oil enters the high pressure high temperature (HPHT) heating reactor 106 from the inlet 104, which is optionally agitated by the stirrer 108. A volume of crude oil enters the HPHT heating reactor 106, allowing a void space near the top of the HPHT heating reactor 106, and the volume of this void space is added to the nitrogen by nitrogen, or instead, is otherwise inert. Can be occupied by gas. Voids with an inert or substantially inert atmosphere occupy about 10% to about 80% by volume of the HPHT heating reactor 106, or about 30% to about 50% by volume of the HPHT heating reactor 106. Can be done. The HPHT heating reactor 106 is heated and maintained at a predetermined (preselected) reaction temperature of about 350 ° C. to about 575 ° C., or about 400 ° C. to about 450 ° C. in some embodiments.

The HPHT heating reactor 106 prior to heating, in the absence of oxygen, in an inert or substantially inert atmosphere, is approximately 145 lbs / square inch gauge (psig) to approximately 870 psig, or approximately 435 psig to approximately 725 psig. The pressure is initially maintained and during heating, the residence time is maintained between about 2 hours and about 15 hours, or between about 4 hours and about 8 hours. During heating, the pressure in the HPHT heating reactor 106 can exceed about 1,000 psig and can be from about 1,700 psig to about 2,500 psig.

The effluent at the reactor outlet 110 proceeds to the gas-liquid solid phase three-phase separator 112, and the effluent is a hydrocarbon-containing gas stream, a liquid DAO stream, and a substantially solid MP in the three-phase separator 112. Separated into products. MP proceeds to MP product collecting unit 116 through outlet 114. MP can be used as an integrated carbon fiber spinning or other carbon artifact, a valuable by-product of equipment, converting MP into valuable carbon fiber and electrode materials for batteries.

Gaseous products include hydrogen, methane, ethane, propylene, propane, butane and butene, in addition to pentane and pentene, decomposition products spanning the C ¹ -C ⁵ paraffins and olefins. The three-phase separator 112 separates the products by density, where the gas product is discharged from near the top of the three-phase separator 112, while solids and liquids are, for example, in addition to or in the precipitate. Instead, it is separated by a method such as centrifugation.

DAOs from the process exit directly into the C2C purification process 120 through outlet 118, which can include, for example, FCC in addition to or instead of steam decomposition (pyrolysis). The DAO in the embodiments of the present disclosure can contain less than about 2% by weight of asphaltene and can be used as a steam / catalytic cracking material for the production of petrochemical products.

For the purpose of thermal integration, in one example, the crude oil is below the decomposition temperature, eg, about 100 ° C., in the convection section of the pyrolysis oven or in the regeneration section of the FCC unit, depending on the type of crude oil feed. It can first be preheated to ~ about 350 ° C., or about 250 ° C. to about 350 ° C., or about 200 ° C. to about 300 ° C., or less than about 200 ° C. The preheated oil is then fed to a de-asphalt unit, eg HPHT heat treatment reactor 106, where it is heat-treated under pressure to produce mesophase pitch, liquid de-asphalt oil, and gas decomposition products, which It is separated by a three-phase separator, for example, a three-phase separator 112. In some embodiments, the DAO utilizes any superheated steam stream 122, eg, as shown in FIG. 1, to mix with superheated steam (from the convection zone or regeneration section of the FCC) and prior to severe decomposition. It can be supplied to the final preheating zone.

In addition to or instead of that residue, upgraded de-asphalt crude oil can be used as a feedstock for hydrocarbon decomposition processes such as steam pyrolysis and catalytic flow decomposition, while asphaltene in crude oil residues. Is removed at the same time as the production of high quality MP. Removal of asphaltene from DAOs is advantageous as these compounds cause coking of the reactor in vapor pyrolysis and FCC processes. Excellent selectivity for light olefins, especially ethylene and propylene, was observed when DAO from the exemplary heat treatment steps of the present disclosure was used as a feedstock for the decomposition process.

[Test example]
In one test example, Arabian heavy crude oil was injected into a 10 liter autoclave reactor, leaving a void space above the autoclave with a substantially inert atmosphere. The autoclave was flushed with nitrogen gas (N ₂ ) several times to remove oxygen from the reaction environment. The autoclave, _{N 2} pressures was maintained at about 600 lbs / square inch gauge (psig) at room temperature. The reactor temperature was raised by 6 ° C./min (° C./min) to the desired temperature (eg, about 400 ° C., 410 ° C., and 425 ° C.) with stirring at about 600 rpm. Once the desired reaction temperature was reached, the heat treatment was maintained for a predetermined polymerization time, optionally for about 6 to about 17 hours. The time for heat treatment can also be from about 2 hours to about 15 hours, or from about 4 hours to about 8 hours. The pressure in the autoclave reactor exceeded 1,000 psig and reached from about 1,800 psig to about 1,900 psig. The product obtained consisted of three separate phases, a gas phase, a liquid phase, and a solid phase at room temperature. Decomposition gas was discharged and MP was separated from DAO by centrifugation.

For certain other similar test examples, Table 1 shows Arabian Heavy, Heated Arabian Heavy, Hydrogenated Crude Oil Residues, and Saturated Hydrocarbons, Fragrances for Heated, Hydrogenated Crude Oil Residues. Values for group compounds, resins, and asphaltene are shown.

Crude oils or derivatives thereof can be separated into four chemical groups: saturated substances such as alkanes and cycloparaffins, aromatics, resins, and asphaltene, the so-called SARA fraction. SARA analysis is used to determine the distribution of saturateds, aromatics, resins, and asphaltene in top petroleum samples. The procedure is divided into two stages: the first stage involves precipitation and quantification of asphaltene, while the second stage follows the ASTM D-2007 method, saturated fraction of deasphalt oil, aromatic fraction, and Open column chromatography separation into resin fractions.

In particular, Table 1 shows that the Arabian Heavy (AH) heat treatment product was deasphalated, with about 90% of the asphaltene removed. As shown in Table 1, most of the asphaltene content is removed after processing the crude oil. Table 1 also shows that the resin content of Arabian heavy crude oil has been reduced to about half. For Arabian Heavy, the aromatic content increased by more than 100% from 35% to 78% by weight.

Table 2 shows the elemental analysis of both Arabian Heavy Crude Oil and its heat treatment products. The resulting mesophase pitch hydrocarbon product (liquid + solid) also contains much less sulfur, nickel, and other metals such as vanadium than its precursors, mesophase pitch (solid) and deasphalt oil (solid). Liquids) will be suitable for techniques for obtaining chemicals directly from crude oil via either steam cracking or catalytic cracking processes for DAOs, as well as carbon fiber production for solid MPs. In an inductively coupled plasma (ICP) mass spectrometer used to detect metals, the actual quantification limit (QPL) of the sample weight (30 mg, mg) used is nickel = 0.05 mg, sulfur = 0.4 mg. , And vanadium = 0.05 mg.

As shown in Table 2, no heavy metal content (Ni and V) was detected in the liquid phase of the obtained product (DAO) (treated Arabian heavy). The sulfur content in the liquid phase was also significantly reduced. The liquid composition analyzed by SIMDIS showed that 100% of the components had a boiling point of less than 500 ° C. after Arabian Heavy treatment and 96% of the components had a boiling point of less than 500 ° C. after residue treatment. The volatility of different components in crude oil and residues, as well as in heat-treated crude oil and heat-treated residues, was measured by an Agilent Automated Distillation (“SIMDIS”) system from Agilent Technologies, Sugar Land, Texas. SIMDIS complies with ASTM D7169 according to the Standard Operating Procedure (SOP) described in the Reference Manual.

Characterization of SIMDIS reveals that the resulting DAO liquid contains hydrocarbons with a significantly lower boiling point than the original Arabian Heavy Crude Oil. Therefore, hydrocarbon products can be suitable feedstocks for refining processes, hydrogenation processes, and especially direct crude oil-chemical processes. In certain embodiments, different precursors are being tested, including Arabian Heavy and hydrothermally treated Arabian Light with a cut temperature above 500 ° C. In some embodiments, the starting pressure of a pressure vessel, such as an autoclave or any high pressure processing unit, is at least about 600 psig (at room temperature), then the temperature gradually rises to about 420 ° C. During the process, the pressure in the high pressure vessel can reach from about 1700 psig to about 2500 psig, depending on the volume of the starting material and the temperature reached.

The decomposition of DAO is discussed with respect to FIG. 2 as follows, but with respect to the MP produced in the test examples of the present disclosure, FIG. 3 shows light microscope images of solid mesophase pitches obtained on the 100 μm, 50 μm, and 20 μm scales. Here, the mesophase pitch was obtained after processing the sample at a temperature of 425 ° C. and a stirring speed of 650 rpm for 6 hours. The mesophase pitch produced using the embodiments of the present disclosure is a high quality precursor suitable for pitch-based carbon fibers. The resulting mesophase pitch was found by polarizing light microscopy and X-ray diffraction (XRD) to have an appropriate amount of alkyl side chains, lower softening points, and an advantageous and consistent crystal structure. The image in FIG. 3 shows that the mesophase pitch is beneficially uniform throughout. Similar results were obtained with light microscopy images for both Arabian Heavy and Arabian Light (C2C rejected) starting material HT residues.

The purity of the mesophase pitch was determined by a polarizing microscope by counting the percentage of mesophase regions that reflect light differently than the "non-mesophase" regions. The purity of the mesophase pitch in the embodiments of the present disclosure can exceed about 90% and can exceed about 99%.

FIG. 4 is a graph showing X-ray diffraction (XRD) data for the mesophase pitch obtained using the embodiments of the present disclosure, where the mesophase pitch is 650 rpm (650 rpm) at a temperature of 425 ° C. It was obtained by stirring for 6 hours at a stirring speed of (rpm). The XRD graph shows a peak at 25.6, which identifies it as a mesophase pitch carbon material. The mesophase pitch obtained using the method described here has less asphaltene than mesophase pitch precursors such as crude oil and crude oil residues. In some embodiments, asphaltene removal was achieved up to about 90%, resulting in a mesophase pitch suitable for C2C applications such as carbon fiber. The characterization of the final product by XRD shows a normal diffraction graph for the mesophase pitch, which indicates that the aromatic and resin compounds in the crude oil undergo heat polymerization to become molecules of higher molecular weight.

In certain embodiments of the technique, the heat treatment is performed in addition to one or more inert gases, or in the absence of nitrogen, or in the absence of additives other than nitrogen, to pressurize the heat treatment process. .. In some embodiments, more than about 90% pure mesophase pitch product is obtained after heat treatment, and in some embodiments, more than about 99% pure mesophase pitch product is obtained after heat treatment. The pressure treatment of the present disclosure can be used to simultaneously upgrade and de-asphalt crude oil and HT crude oil residues.

With reference to FIG. 2, a mechanical diagram showing experimental settings for the direct C2C decomposition experiments of the present disclosure is provided. In the experimental apparatus 200, a syringe pump 202 was used to supply DAO from the DAO inlet 204 as carrier gas from the helium tank 206 together with helium (in addition to or instead of the nitrogen gas in the nitrogen tank 208). DAOs were generated using the embodiments described in the test examples described above. The weight space velocity (WHSV) used in the decomposition experiment was 61 / hour (h ^-1 ). The experimental apparatus 200 further included an electric furnace 210, a decomposition catalyst 212, a gas chromatograph 214, and a condenser 216. The liquid product was collected at product outlet 218. The gas was analyzed by gas chromatography (GC). Carbon monoxide, carbon dioxide, oxygen, nitrogen, methane, light olefins, C ₁ to C ₇ hydrocarbons and BT (benzene and toluene) can be quantified.

The cracking temperature may be in the range of, for example, about 450 ° C. to about 850 ° C., for catalytic cracking such as FCC, about 500 ° C. to about 650 ° C. depending on the type of raw material to be supplied, and for steam cracking, about 650 ° C. to about 850 ° C. It may be. Decomposition catalysts used in some embodiments include solid acid catalysts. In one or more embodiments, the solid acid catalyst bed may comprise aluminosilicate zeolite, silicate (eg, silicalite), or titanosilicate. In a further embodiment, the solid acid catalyst is an aluminosilicate zeolite having a mordenite-type (MFI) structure.

For example, but not limited to, the MFI structured aluminosilicate zeolite catalyst may be a Zeolite Society Mobile-5 (ZSM-5) catalyst. In yet another embodiment, the ZSM-5 catalyst may be an H-ZSM-5 catalyst in which at least a portion of the ZSM-5 catalyst ion exchange site is occupied by H + ions. In addition, aluminosilicate zeolite catalysts, such as H-ZSM-5 catalysts, can have a Si / Al molar ratio of at least 10. In a further embodiment, the aluminosilicate zeolite catalyst may have a Si / Al molar ratio of at least 30, or at least 35, or at least 40. In addition, the aluminosilicate zeolite catalyst may contain one or more additional components used to modify the structure and performance of the aluminosilicate zeolite catalyst. Specifically, the aluminosilicate zeolite catalyst can include phosphorus, boron, nickel, iron, tungsten, other metals, or combinations thereof. In various embodiments, the aluminosilicate zeolite catalyst can comprise 0-10% by weight of additional components, 1-8% by weight of additional components, or 1-5% by weight of additional components.

For example, but not limited to, these additional components may be wet impregnated into ZSM-5, followed by drying and calcination. Aluminosilicate zeolite catalysts may contain mesoporous structures. The catalyst can be sized to have a diameter of 25-2,500 micrometers (μm). In a further embodiment, the catalyst may have a diameter of 400-1200 μm, 425-800 μm, 800-1000 μm, or 50-100 μm. The minimum size of the catalyst particles depends on the design of the reactor to prevent the catalyst particles from passing through the filter along with the reaction product.

In Table 3 below, the feasibility of decomposition of DAO is demonstrated and the production of beneficial products is shown.

In Table 3, the conversion (*) refers to the amount of gas phase formed from DAO in the decomposition reaction carried out in the apparatus of FIG. 2, and C4 olefin (**) refers to 1-butene, cis and trans-2-. Refers to butene, as well as isobutene, and selectivity (***) considers only the vapor phase products formed. In the present disclosure, it is not desired that the processes and steps prior to other downstream chemical manufacturing processes, such as decomposition or carbon fiber production, evaporate or separate unwanted components of the crude oil feedstock. Instead, the goal is to perform long-term thermal polymerization under pressure so that the non-volatile aromatic rings in the asphalt fraction can be easily precipitated and separated, eg, as a mesophase pitch. Reproducibility and flexibility are guaranteed by controlling reaction temperature, pressure, and residence time.

Certain advantages enabled by the methods and systems of the present disclosure are to reduce the problem of coke settling in steam decomposition for crude oil and heavy feedstock, and to reduce the problem of rapid catalytic deactivation due to coke. Decomposition from traditional refining methods such as reducing metal problems in crude oil that poison the decomposition catalyst, increasing process economics by co-producing MP, and using naphtha and gas oil (VGO). It contains higher hydrocarbon yields compared to the product. Treatments at high temperatures above about 400 ° C. decompose the branching of aromatic compounds in addition to or instead of asphaltene to low molecular weight hydrocarbons, making more hydrocarbons available for catalytic cracking. it is conceivable that.

Claims (39)

An integrated method for the production of mesophase pitch and petrochemicals,
Supply of crude oil to the reaction vessel and
A step of heating the crude oil in the reaction vessel to a predetermined temperature for a predetermined time;
In the absence of oxygen, the content of asphaltene in the crude oil can be reduced by causing a polymerization reaction in the reaction vessel at high pressure.
Production of three-phase upgraded hydrocarbon products, which comprises gaseous, liquid, and solid hydrocarbon components, said liquid hydrocarbon component containing deasphalt oil, and said solid hydrocarbon component containing mesophase pitch.
Separation of gas, liquid and solid hydrocarbon components,
The liquid hydrocarbon component is directly used in the production of petrochemical products.
Direct use of the solid hydrocarbon component for the production of carbon artifacts,
A method that includes each step of. The method of claim 1, wherein the crude oil is crude oil that is separated from natural gas, dehydrated and then received directly from the wellhead, but is not pretreated prior to the step of supplying the crude oil to the reactor vessel. The method according to claim 1 or 2, wherein the predetermined temperature is 350 ° C to 575 ° C. The method according to claim 1 or 2, wherein the predetermined temperature is 400 ° C. to 450 ° C. The invention according to any one of claims 1 to 4, further comprising a step of pressurizing the vessel to an initial pressure of 145 psig to 870 psig before the step of heating the crude oil in the reaction vessel to a predetermined temperature for a predetermined time. the method of. The method of claim 5, wherein the step of pressurizing the vessel to an initial pressure comprises the step of discharging oxygen from the reaction vessel using a gas containing nitrogen. Any one of claims 1 to 4, further comprising a step of pressurizing the container to an initial pressure of 435 psig to 725 psig prior to the step of heating the crude oil in the reactor to a predetermined temperature for a predetermined time. The method described in the section. The method according to claim 7, wherein the step of pressurizing the vessel to an initial pressure includes a step of discharging oxygen from the reaction vessel using a gas containing nitrogen. The method according to any one of claims 1 to 8, wherein the predetermined time is 2 hours to 15 hours. The method according to any one of claims 1 to 8, wherein the predetermined time is 4 to 8 hours. The method according to any one of claims 1 to 9, wherein the step of reducing the asphaltene content reduces the asphaltene content in the deasphalted oil to less than 2% by weight. The method according to any one of claims 1 to 11, wherein the high pressure is greater than 1,000 psig. The method according to any one of claims 1 to 12, wherein the high pressure is 1,800 psig to 1,900 psig. The method according to any one of claims 1 to 13, wherein the step of directly utilizing the liquid hydrocarbon component for the production of a petrochemical product includes a step of supplying the deasphalt oil to a fluidized catalytic cracking process. The method according to any one of claims 1 to 14, wherein the step of directly utilizing the liquid hydrocarbon component for the production of a petrochemical product includes a step of supplying the deasphalt oil to a steam decomposition process. The method according to any one of claims 1 to 15, wherein the step of directly utilizing the solid hydrocarbon component for producing carbon artifacts comprises a step of producing carbon fibers from the mesophase pitch. The method of any one of claims 1-16, wherein the crude oil comprises at least one hydrocarbon selected from the group consisting of heavy crude oil, light crude oil, and crude oil residues having a boiling point above 500 ° C. .. The method according to any one of claims 1 to 17, wherein the asphalt compound content of the de-asphalt oil is reduced by at least 50% by mass with respect to the asphalt compound content of the crude oil. The method according to any one of claims 1 to 18, wherein the asphalt compound content of the de-asphalt oil is reduced by at least 90% by mass with respect to the asphalt compound content of the crude oil. The method according to any one of claims 1 to 19, wherein the metal content in the liquid hydrocarbon component is less than the metal content in the crude oil. The method according to any one of claims 1 to 20, wherein the solid hydrocarbon component is at least 90% pure mesophase pitch. The step of reducing the asphaltene content in the crude oil by causing a polymerization reaction in the reaction vessel at high pressure in the absence of oxygen increases the pressure in the reaction vessel from 1,700 psig to 2,500 psig. The method according to claim 1, which is a thing. An integrated system for mesophase pitch and petrochemical manufacturing,
It contains a crude oil source that is fluidly coupled to the reaction vessel, the reaction vessel can be operated to be heated to a predetermined temperature for a predetermined time, and in the reaction vessel at high pressure in the absence of oxygen. By causing a polymerization reaction in the above, it is possible to operate so as to reduce the asphaltene content in the crude oil supply source.
The three-phase upgrade hydrocarbon product comprises a gas-liquid solid three-phase separator that can be operated to separate the three-phase upgrade hydrocarbon product produced in the reaction vessel, the three-phase upgrade hydrocarbon product being a gas, liquid, solid hydrocarbon. Consisting of components, the liquid hydrocarbon component comprises deasphalt oil, the solid hydrocarbon component comprises a mesophase pitch, and
A decomposition unit that receives the liquid hydrocarbon component and is fluid-bonded to decompose the liquid hydrocarbon component for petrochemical products.
System including. 23. The system of claim 23, further comprising a unit for producing carbon fibers from the mesophase pitch. The system according to claim 23 or 24, wherein the predetermined temperature is 350 ° C to 575 ° C. The system according to claim 23 or 24, wherein the predetermined temperature is 400 ° C. to 450 ° C. The system according to any one of claims 23 to 26, wherein the predetermined time is 2 hours to 15 hours. The system according to any one of claims 23 to 26, wherein the predetermined time is 4 hours to 8 hours. The system according to any one of claims 23 to 28, wherein the asphalt content in the deasphalt oil is less than 2% by weight. The system according to any one of claims 23 to 29, wherein the high pressure is greater than 1,000 psig. The system according to any one of claims 23 to 30, wherein the high pressure is 1,800 psig to 1,900 psig. The system according to any one of claims 23 to 31, wherein the cracking unit comprises a fluid catalytic cracking process. The system according to any one of claims 23 to 32, wherein the decomposition unit comprises a steam decomposition process. The system of any one of claims 23-33, wherein the crude oil comprises at least one hydrocarbon selected from the group consisting of heavy crude oil, light crude oil, and crude oil residues having a boiling point above 500 ° C. .. The system according to any one of claims 23 to 34, wherein the asphalt compound content of the de-asphalt oil is reduced by at least 50% by mass with respect to the asphalt compound content of the crude oil source. The system according to any one of claims 23 to 35, wherein the asphalt compound content of the de-asphalt oil is reduced by at least 90% by mass with respect to the asphalt compound content of the crude oil source. The system according to any one of claims 23 to 36, wherein the metal content in the liquid hydrocarbon component is less than the metal content in the crude oil source. The system according to any one of claims 23 to 37, wherein the solid hydrocarbon component is at least 90% pure mesophase pitch. 23. The system of claim 23, wherein the high pressure in the reaction vessel is 1,700 psig to 2,500 psig.