CN118909659B - A solvent oil, its preparation method and uses - Google Patents
A solvent oil, its preparation method and usesInfo
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- CN118909659B CN118909659B CN202410992501.6A CN202410992501A CN118909659B CN 118909659 B CN118909659 B CN 118909659B CN 202410992501 A CN202410992501 A CN 202410992501A CN 118909659 B CN118909659 B CN 118909659B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
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- Civil Engineering (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
本发明提供一种溶剂油及其制备方法和用途，采用本发明提供的溶剂油进行煤液化沥青的精制处理，固液分离效果好，溶剂油易于回收重复利用，能够在较低的溶剂油消耗率的情形下，获得兼顾高收率、低灰分和低喹啉不溶物含量的精制沥青，能够满足高端碳材料的应用要求。所述溶剂油中含有C10～C16链烷烃、环数为1～3的环烷烃、单环芳烃、二环芳烃和三环芳烃；基于溶剂油的总质量，所述C10～C16链烷烃的含量为5.0～10.5wt％，所述环烷烃的含量为10.0～25.3wt％，所述单环芳烃的含量为30.0～44.0wt％，所述二环芳烃的含量为20.0～50.0wt％，所述三环芳烃的含量为0.5～5.0wt％；所述溶剂油的氮含量为200～2500ppm，硫含量为5～500ppm，所述溶剂油的馏程在170～350℃之间。This invention provides a solvent oil, its preparation method, and its uses. Using the solvent oil provided by this invention for the refining of coal liquefaction pitch results in good solid-liquid separation, easy recycling and reuse of the solvent oil, and the ability to obtain refined pitch with high yield, low ash content, and low quinoline insoluble content with a low solvent oil consumption rate, thus meeting the application requirements of high-end carbon materials. The solvent oil contains C10 - C16 alkanes, cycloalkanes with 1-3 rings, monocyclic aromatics, dicyclic aromatics, and tricyclic aromatics; based on the total mass of the solvent oil, the content of the C10 - C16 alkanes is 5.0-10.5 wt%, the content of the cycloalkanes is 10.0-25.3 wt%, the content of the monocyclic aromatics is 30.0-44.0 wt%, the content of the dicyclic aromatics is 20.0-50.0 wt%, and the content of the tricyclic aromatics is 0.5-5.0 wt%; the nitrogen content of the solvent oil is 200-2500 ppm, the sulfur content is 5-500 ppm, and the distillation range of the solvent oil is between 170 and 350°C.
Description
Technical Field
The invention relates to an extraction and refining treatment technology of coal liquefied asphalt, in particular to solvent oil and a preparation method and application thereof.
Background
The coal liquefied asphalt is a special byproduct in the direct coal liquefaction oil production process, and accounts for about 20-30% of the liquefaction coal feeding amount, and the coal liquefied asphalt mainly comprises asphaltene, liquefied heavy oil, unreacted coal, minerals and catalysts and has the characteristics of high ash, high sulfur and high heat value. The 108 ten thousand tons/year coal direct liquefaction demonstration device produces about 70 ten thousand tons of coal liquefied asphalt in one year, is mainly used for coal blending gasification or combustion, has extensive utilization mode, and influences technical and economic benefits and industrial green development. Because the coal liquefied asphalt is subjected to high-temperature hydrogenation, the coal liquefied asphalt has the characteristics of high hydrogen-carbon ratio and high coking value, is a high-quality raw material of high-end carbon materials such as mesophase asphalt carbon fibers, high-quality needle coke and the like, but the components of the coal liquefied asphalt are complex, the ash content and the solid content are high, and the refined asphalt with the ash content and the quinoline insoluble content lower than 1000ppm and even 50ppm can be obtained through refining separation, so that the requirements of the high-end carbon materials can be met.
Solvent extraction is an effective coal liquefied asphalt refining and separating method, and solvent selection is the first key. The conventional extraction solvent mainly comprises four types, namely one or more mixtures of chemical reagents such as methanol, N-heptane, N-hexane, cyclohexane, carbon disulfide, acetone, benzene, toluene, tetrahydrofuran, furfural, N-methylpyrrolidone, pyridine, N-dimethylacetamide and quinoline, one or more mixtures of aliphatic solvent oils such as petroleum ether, gasoline, kerosene and diesel oil, and the like, a third type of coal tar distillate such as one or more mixtures of light oil, phenolate oil, decalin oil, wash oil and anthracene oil, and a fourth type of distillate oil in the direct coal liquefaction process such as one or more of a coal liquefaction crude oil fraction and hydrogenation stabilization distillate oil.
The patent CN202311729937.8 discloses an extraction method of coal liquid residues, which comprises the following steps of S1, grinding, primary drying, deashing and secondary drying the coal liquid residues, S2, adding an extractant into the coal liquid residues treated in the step S1, obtaining filter cakes and extract liquid after ultrasonic treatment and filtration, S3, repeating the step S2 on the filter cakes obtained in the step S2 to obtain the extract liquid and raffinate residues, and collecting all the extract liquid for rotary evaporation to obtain an extract, wherein in the step S2, the extractant is selected from any one of petroleum ether, methanol, cyclohexane, CS 2, benzene, acetone and CS 2.
Patent CN202110614074.4 discloses a method for extracting coal direct liquefaction oil residue by using coking crude benzene, which comprises the steps of mixing the coking crude benzene with the coal direct liquefaction oil residue, extracting, and then carrying out solid-liquid separation on the mixture obtained by extraction to obtain asphalt substances and mixed benzene. According to the invention, the direct coal liquefaction oil residue is mixed with the coking crude benzene and then extracted, the olefin and the sulfur-containing compound in the coking crude benzene can further destroy the association structure in the direct coal liquefaction oil residue in the extraction process, meanwhile, the purification of the coking crude benzene can be realized in the solvent recovery process, the coking crude benzene is refined, the high-efficiency extraction of the direct coal liquefaction oil residue is realized, and the asphalt substance with excellent quality is obtained, and the cost is low.
Patent CN201810812618.6 discloses a separation system and a separation method for directly liquefying coal to oil residues. The separation system comprises an extraction device, a horizontal screw centrifugal device, a disc centrifugal device and a distillation device. The extractant is a tar solvent with a distillation range of 200-320 ℃, preferably wash oil and/or anthracene oil.
Patent CN201811649445.7 discloses a high-efficiency deashing method for coal liquefaction residues, which adopts a two-stage standing sedimentation separation technology to remove ash content of the coal liquefaction residues to below 100ppm, so that the method can meet the conditions for preparing high-added-value carbon materials, further improves the production benefits of enterprises and saves resources. The invention has the advantages of reasonable and economical agent, easy recycling of the needed solvent, simple and easy treatment process, good deashing effect, high efficiency, low energy consumption, environmental protection and the like. Solves a series of problems of long settling time, high energy consumption, low ash removal rate and the like faced by the current process. The composite solvent is a mixture of an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent in a mass ratio of 1:0.10-1, wherein the aliphatic hydrocarbon solvent is any one or more of n-heptane, no. 120 solvent oil, gasoline, kerosene and diesel oil, and the aromatic hydrocarbon solvent is any one or more of light oil, phenol oil, naphthalene oil, wash oil and anthracene oil.
Patent CN201510317246.6 provides a treatment method of direct coal liquefaction residues. The method comprises the steps of extracting coal direct liquefaction residues by using an extraction solvent to obtain an extraction mixture, carrying out primary solid-liquid separation on the extraction mixture to obtain primary clear liquid and a primary concentrated phase, carrying out secondary solid-liquid separation on part or all of the primary clear liquid to obtain secondary clear liquid and a secondary concentrated phase, carrying out tertiary solid-liquid separation on part or all of the secondary clear liquid to obtain tertiary clear liquid and a tertiary concentrated phase, carrying out secondary solid-liquid separation on part of the primary clear liquid, carrying out clear liquid solvent recovery treatment on the rest of the primary clear liquid to obtain primary asphalt, carrying out tertiary solid-liquid separation on part of the secondary clear liquid, carrying out clear liquid solvent recovery treatment on the rest of the secondary clear liquid to obtain secondary asphalt, and carrying out clear liquid solvent recovery treatment on all of the tertiary clear liquid to obtain tertiary asphalt. The method can obtain three asphalt products, and is beneficial to improving the additional benefit value of asphalt in coal liquefaction residues. The extraction solvent includes, but is not limited to, one or more of the group consisting of tetrahydrofuran, furfural, N-methylpyrrolidone, quinoline, toluene, coal direct liquefaction distillate, or coal tar distillate.
Patent CN201310211245.4 provides a method and application for separating asphaltic substances from direct coal liquefaction residues. The method comprises the following steps of S1, mixing coal direct liquefaction residues with an extraction solvent, carrying out hot-melt extraction to obtain a hot-melt extraction mixture, S2, carrying out solid-liquid separation on the hot-melt extraction mixture to obtain an extraction liquid, and S3, carrying out solvent recovery on the extraction liquid to obtain asphalt substances, wherein the extraction solvent is coal tar or coal tar distillate. The coal tar or coal tar distillate oil is used as an extraction solvent to separate coal direct liquefaction residues to prepare the pitch substances, so that the extraction rate is improved, the cost is reduced, the pitch substance mixture with moderate volatile components and higher softening point is obtained, and the pitch substance mixture can be used as raw materials of different grades of carbon materials according to different properties of the pitch substances in the mixture.
Patent CN201310209911.0 discloses a method for separating liquefied heavy oil and asphaltic substances from direct coal liquefaction residues. The method comprises the steps of S1, mixing coal direct liquefaction residues with an extraction solvent, stirring, performing hot-melt extraction to obtain a hot-melt extraction mixture, S2, performing primary solid-liquid separation on the hot-melt extraction mixture to obtain primary extraction liquid and primary raffinate, S3, performing secondary solid-liquid separation on the primary extraction liquid to obtain secondary extraction liquid and secondary raffinate, S4, performing solvent recovery on the secondary extraction liquid to obtain an extract, and S5, mixing the extract with a subcritical anti-precipitation solvent, performing subcritical anti-solvent precipitation, and separating to obtain liquefied heavy oil and asphalt substances. The invention utilizes the difference of the dissolution capability of subcritical anti-precipitation solvent to organic matters in the direct coal liquefaction residues in a subcritical state, and effectively realizes the separation of liquefied heavy oil and asphalt substances by combining a solid-liquid separation process. The extraction solvent is one or more of normal side secondary oil, reduced primary oil and hydrogenated stable side oil generated in the direct coal liquefaction process, the distillation range of the extraction solvent is 120-280 ℃, the subcritical anti-precipitation solvent is one or more of normal top oil, reduced top oil and hydrogenated stable top oil generated in the direct coal liquefaction process, and the distillation range of the subcritical anti-precipitation solvent is 40-160 ℃.
Aiming at the composition and physical properties of the coal liquefied asphalt, the extraction solvent oil which has high efficiency, low cost and easy recycling and reuse and is suitable for industrial scale production is developed, and has important significance.
Disclosure of Invention
The solvent oil provided by the invention is used for refining coal liquefied asphalt, has good solid-liquid separation effect, is easy to recycle, can obtain refined asphalt with high yield, low ash content and low quinoline insoluble content under the condition of low solvent oil consumption rate, and can meet the application requirements of high-end carbon materials.
The invention provides the following technical scheme for achieving the purpose:
The invention provides solvent oil, which contains C 10～C16 alkane, naphthene with the ring number of 1-3, monocyclic arene, bicyclic arene and tricyclic arene;
Based on the total mass of the solvent oil, the content of the C 10～C16 alkane is 5.0-10.5wt%, the content of the cycloalkane is 10.0-25.3wt%, the content of the monocyclic arene is 30.0-44.0wt%, the content of the bicyclic arene is 20.0-50.0wt%, and the content of the tricyclic arene is 0.5-5.0wt%;
the nitrogen content of the solvent oil is 200-2500 ppm, the sulfur content is 5-500 ppm, and the distillation range of the solvent oil is 170-350 ℃.
Further, the density of the solvent oil is 0.93-1.02 g/cm 3.
The invention also provides a preparation method of the solvent oil, which comprises the following steps:
And mixing the coal tar distillate oil and the coal direct liquefaction crude oil according to the mass ratio of 10:90-90:10, then carrying out hydrogenation reaction, and then carrying out distillation and cutting to obtain a distillate section with the distillation range of 170-350 ℃ to obtain the solvent oil.
In some embodiments, the coal tar distillate is a coal tar distillate with a distillation range of 170-400 ℃;
The coal direct liquefaction crude oil is coal direct liquefaction crude oil fraction with a distillation range of 200-450 ℃.
In a preferred embodiment, the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises a carrier and an active component, the active component comprises Ni, mo and P, and the mass contents of the Ni, the Mo and the P in the hydrogenation catalyst are respectively 4.71-5.89%, 8.87-10.93% and 0.74-0.87% in sequence;
in some embodiments, the support is an Al 2O3-SiO2 support, for example, wherein the Al 2O3 content is 45-72 wt% and the SiO 2 content is 28-55 wt%.
In some embodiments, the hydrogenation reaction conditions comprise a temperature of 350-380 ℃, a pressure of 8-15 MPa, a hydrogen-oil ratio (v/v) of 500-1000 and a volume space velocity of 0.6-1.5 h -1;
preferably, the hydrogenation reaction is carried out in a fixed bed reactor, a suspended bed reactor or an ebullated bed reactor.
The invention also provides application of the solvent oil or the solvent oil prepared by the preparation method in refining treatment of coal liquefied asphalt.
The invention also provides a refining treatment method of the coal liquefied asphalt, which comprises the following steps:
(1) Uniformly mixing coal liquefied asphalt and solvent oil according to a mass ratio of 1:2-4, heating to 80-130 ℃, and stirring at constant temperature for 0.5-2 hours to obtain mixed slurry, wherein the solvent oil is the solvent oil or the solvent oil prepared by the preparation method;
(2) Centrifugally separating the mixed slurry to obtain a light phase and a heavy phase;
(3) Separating solvent oil in the light phase to obtain refined coal liquefied asphalt;
preferably, in the step (2), the centrifugal separation is performed in a decanter centrifuge, and preferably, the centrifugal separation factor of the decanter centrifuge is 600-1800 g.
Preferably, heating the heavy phase to 200-250 ℃ to soften the heavy phase into fluid, and then recovering solvent oil therein;
Preferably, the solvent oil separated from the light phase and the solvent oil recovered from the heavy phase are recycled to the step (1) after being mixed.
The technical scheme provided by the invention has the following beneficial effects:
(1) Compared with the prior art, the solvent oil provided by the invention can realize low-cost and high-efficiency industrial production of coal liquefied asphalt refining, and can prepare the refined asphalt with the characteristics of high yield, low ash content, low quinoline insoluble content and the like on the premise of low solvent oil consumption rate, for example, the refined asphalt with the ash content lower than 1000ppm, even lower than 100ppm and the quinoline insoluble content lower than 2000ppm can be obtained, and meanwhile, the yield reaches 48-58%, and the application requirements of high-end carbon materials can be met.
(2) The solvent oil provided by the invention has the advantages of low preparation cost, wide raw material sources, high extraction efficiency on coal liquefied asphalt, good solid-liquid separation effect, easiness in recycling and repeated utilization, and suitability for large-scale industrial application.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
The invention provides solvent oil, which contains C 10～C16 alkane, naphthene with the ring number of 1-3, monocyclic arene, bicyclic arene and tricyclic arene;
Based on the total mass of the solvent oil, the content of the C 10～C16 alkane is 5.0-10.5wt%, the content of the cycloalkane is 10.0-25.3wt%, the content of the monocyclic arene is 30.0-44.0wt%, the content of the bicyclic arene is 20.0-50.0wt%, and the content of the tricyclic arene is 0.5-5.0wt%;
The nitrogen content of the solvent oil is 200-2500 ppm, the sulfur content is 5-500 ppm, and the distillation range of the solvent oil is 170-350 ℃.
Further, the density of the solvent oil is 0.93-1.02 g/cm 3.
The term "cycloalkane having a ring number of 1 to 3" specifically means monocycloalkane, bicycloalkane and tricycloalkane.
Aiming at the problems that the components of the coal liquefied asphalt are complex, asphaltene is difficult to extract, nano-scale particles are difficult to separate and an extraction solvent is difficult to recycle, the invention provides the refined asphalt which mainly comprises C 10～C16 alkane, cycloalkane with the ring number of 1-3, monocyclic arene, bicyclic arene and tricyclic arene, has the distillation range of 170-350 ℃, preferably has the density of 0.93-1.02 g/cm 3, and the inventor discovers that the solvent oil is used for the extraction and refining of the coal liquefied asphalt, can realize the efficient extraction and refining separation of the coal liquefied asphalt, is easy to recycle, has good solid-liquid separation effect, high extraction rate, low solvent oil consumption, and can obtain the refined asphalt with the characteristics of high yield, low ash content, low quinoline insoluble content and the like.
The invention also provides a preparation method of the solvent oil, which comprises the following steps:
And mixing the coal tar distillate oil and the coal direct liquefaction crude oil according to the mass ratio of 10:90-90:10, then carrying out hydrogenation reaction, and then carrying out distillation and cutting to obtain a distillate section with the distillation range of 170-350 ℃ to obtain the solvent oil.
Preferably, the coal tar distillate oil is coal tar distillate with a distillation range of 170-400 ℃. The specific preparation process of the coal tar distillate is well known in the art, and can be obtained by adopting a conventional process well known in the art, for example, coal tar is obtained by dry distillation of coal, and the coal tar distillate with the distillation range of 170-400 ℃ is obtained by carrying out pretreatment such as dehydration, desalination, desolventizing and the like, and then carrying out atmospheric distillation or vacuum distillation or atmospheric and vacuum distillation.
Preferably, the coal direct liquefaction crude oil is a coal direct liquefaction crude oil fraction with a distillation range of 200-450 ℃. The specific preparation process of the crude oil directly liquefied by coal is well known in the art, and can be obtained by adopting the conventional process well known in the art, for example, coal is washed, dried, ground and screened to be less than 100 microns, then the coal is mixed with a catalyst (for example, a nanoscale iron-based catalyst) and a circulating solvent for directly liquefying the coal to prepare coal slurry with a certain concentration, for example, 45 weight percent of the coal slurry, and the coal slurry is hydrogenated and liquefied under the conditions of 450-460 ℃ and 19MP, and the liquefied product is distilled by a high-pressure separator, a medium-pressure separator and a normal-pressure distillation to obtain the crude oil liquefied by the coal with the distillation range of 200-450 ℃.
Further, the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst. In a preferred embodiment, the hydrogenation catalyst comprises a carrier and an active component, wherein the active component comprises Ni, mo and P, the mass content of the Ni, the Mo and the P in the hydrogenation catalyst is 4.71-5.89%, 8.87-10.93% and 0.74-0.87% respectively in sequence, and the carrier is preferably an Al 2O3-SiO2 carrier, for example, the content of Al 2O3 is 45-72 wt% and the content of SiO 2 is 28-55 wt%.
In a preferred embodiment, the hydrogenation reaction conditions comprise a temperature of 350-380 ℃, a pressure of 8-15 MPa, a hydrogen-oil ratio (v/v) of 500-1000 and a volume space velocity of 0.6-1.5 h -1;
preferably, the hydrogenation reaction is carried out in a fixed bed reactor, a suspended bed reactor or an ebullated bed reactor.
The solvent oil provided by the invention is prepared from the coal direct liquefaction crude oil fraction and the coal tar distillate oil according to the mass ratio of 10:90-90:10, and is obtained through hydrogenation, distillation and cutting, and has the characteristics of low cost and strong operability compared with a pure chemical reagent, has the characteristics of stable property, high extraction rate, good swelling property and the like compared with the single coal direct liquefaction crude oil, and has the characteristics of low sulfur and nitrogen content, good solid-liquid separation effect, easiness in recycling and the like compared with the single coal tar distillate oil.
The solvent oil prepared by the preparation method is particularly suitable for high-efficiency extraction of asphalt soluble substances in coal liquefied asphalt and rapid removal of nano-scale solid particles. The monocyclic aromatic hydrocarbon, the bicyclic aromatic hydrocarbon, the tricyclic aromatic hydrocarbon and the like contained in the solvent oil are beneficial to guaranteeing the efficient extraction of asphaltene, pre-asphaltene and other asphalt substances in the coal liquefied asphalt, and the alkane, the cycloalkane and the like contained in the solvent oil are beneficial to reducing the viscosity of a coal liquefied asphalt extraction system on one hand, and play roles in flocculating heavy component asphalt, carrying nano-scale particles, enhancing the solid-liquid separation effect and improving the solid particle removal rate on the other hand. The main components of the solvent oil provided are C 10～C16 alkane, monocycloalkane, bicycloalkane, tricycloalkane, monocycloarene, bicycloarene, tricycloarene and the like, the solvent oil with the specific components has a distillation range of 170-350 ℃ and a density of 0.93-1.02 g/cm 3, the solvent oil has better swelling property on insoluble matters of raffinate solid while realizing efficient extraction, refining and separation of coal liquefied asphalt, the flowability and the transportation property of materials are ensured, meanwhile, the solvent oil is not easy to volatilize and lose, easy to operate, easy to distill and recycle, and the guarantee is provided for the industrialized and large-scale application of the coal liquefied asphalt extraction and refining technology.
In another aspect, the invention also provides the use of the solvent oil described above or the solvent oil produced by the production method described above in the refining treatment of coal liquefied asphalt.
The invention also provides a refining treatment method of coal liquefied asphalt, which comprises the following steps:
(1) Uniformly mixing coal liquefied asphalt and solvent oil according to a mass ratio of 1:2-4, and stirring at a constant temperature of 80-130 ℃ for 0.5-2 hours to obtain mixed slurry, wherein the solvent oil is the solvent oil or the solvent oil prepared by the preparation method;
(2) The solvent oil is adopted to extract the coal liquefied asphalt through the step (1), then solid-liquid separation is realized through continuous horizontal screw centrifugation, and solid insoluble matters such as unreacted coal, mineral matters, catalysts and the like are removed, so that a centrifugal light phase and a centrifugal heavy phase are obtained, wherein the solid insoluble matters are enriched in the heavy phase.
(3) Separating solvent oil in the light phase to obtain refined coal liquefied asphalt. Specifically, the solvent oil is separated and recovered from the light phase by, for example, distillation, thereby obtaining refined coal-liquefied asphalt.
The solvent oil provided by the invention is particularly suitable for being used as a high-efficiency refining and separating solvent for coal liquefied asphalt, and can realize high-efficiency extraction of asphalt and other soluble substances in the coal liquefied asphalt and rapid removal of nano-scale solid particles. The solvent oil contains monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon, tricyclic aromatic hydrocarbon and the like, which is beneficial to the efficient extraction of asphaltene, preapitch and other asphalt substances in the coal liquefied asphalt, and the solvent oil contains alkane, naphthene and the like, which is beneficial to the reduction of the viscosity of a coal liquefied asphalt extraction system, and has the effects of flocculating heavy component asphalt, carrying nano-scale particles, enhancing the solid-liquid separation effect and improving the removal rate of solid particles. The distillation range of the solvent is 170-350 ℃ and the density is 0.93-1.02 g/cm 3, so that the high-efficiency extraction, refining and separation of the coal liquefied asphalt are realized, meanwhile, the solvent has good swelling property on insoluble matters of raffinate solids, the flowability and the transportation property of the materials are guaranteed, meanwhile, the solvent is not easy to volatilize and lose, the solvent is easy to distill, recycle and reuse, the operability is strong, and the industrialization and large-scale application of the coal liquefied asphalt extraction and refining technology can be realized.
The solvent oil provided by the invention is used for extracting and refining coal liquefied asphalt according to the refining treatment method, so that solid-liquid efficient separation can be realized, most of the solvent oil can be recovered, the solvent consumption is low, the refined asphalt which has the characteristics of high yield, low ash content, low quinoline insoluble content and the like can be obtained, and the application requirements of high-end carbon materials can be met. For example, the refined coal liquefied asphalt with ash content of 50-1000 ppm, quinoline insoluble content of 80-2000 ppm, softening point of 150-190 ℃ and yield of 48-58% can be obtained by the refining treatment method.
Preferably, in the step (2), the centrifugal separation is performed in a decanter centrifuge, and preferably, the centrifugal separation factor of the decanter centrifuge is 600-1800 g.
Preferably, the heavy phase obtained in the step (2) is heated to 200-250 ℃ so as to soften the heavy phase into fluid, then solvent oil in the fluid is recovered, the solvent oil is adopted to carry out refining treatment on coal liquefied asphalt, the heavy phase with higher solid insoluble matter content is separated and obtained, the fluid can be softened, the viscosity is 200-2000 cp (measured at 200-250 ℃ by adopting a rotary viscometer), the solvent is easy to convey and recover, and for example, the solvent can be recovered by continuously conveying the fluid into a decompression spray drying device or a belt drying device for solvent recovery, and raffinate solid residues with the solvent residue amount of <2.5% and the yield of about 42.0-52.5% can be obtained after the solvent is recovered.
Preferably, the solvent oil separated from the light phase and the solvent oil recovered from the heavy phase are recycled to the step (1) after being mixed. The solvent oil is used for refining the coal liquefied asphalt, the consumption rate of the solvent oil is low, the solvent oil is stable, the solvent oil is easy to recycle, and the consumption rate of the solvent oil is 0.2-1.0wt% of the treatment capacity of the coal liquefied asphalt.
The formation process of coal liquefied asphalt is well known in the art, specifically, coal is subjected to washing, drying, grinding and screening (for example, screening to below 100 micrometers) to prepare coal oil slurry, for example, the coal oil slurry is prepared with a catalyst (for example, a nanoscale iron-based catalyst) and a coal direct liquefaction circulating solvent to prepare the coal oil slurry with required concentration (for example, 45 weight percent), the heavy products obtained after the processes of hydrogenation liquefaction, separation and the like are subjected to hydrogenation liquefaction at the temperature of 450-460 ℃ and 19MP, and the heavy products obtained after the gas phase and the liquid products are separated by a high-pressure separator, a medium-pressure separator and a normal-pressure distillation and a reduced-pressure distillation are obtained, namely the coal liquefied asphalt. The coal liquefied asphalt mainly comprises asphalt substances, heavy liquefied oil, unconverted coal, mineral substances and catalysts. The coal liquefied asphalt without refining has an ash content of 15.0-20.0 wt%, a quinoline insoluble content of 40.0-50.0 wt%, and a softening point of 165-195 deg.C.
Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the following examples and comparative examples:
yield of refined coal liquefied asphalt: wherein m R is the mass of the refined coal liquefied asphalt, and m o is the mass of the coal liquefied asphalt raw material;
Yield of raffinate solid residue: Wherein m s is the mass of raffinate solid slag, and m o is the mass of coal liquefied asphalt raw material;
Solvent oil consumption rate: wherein G o is the feeding mass of the solvent oil, G R is the recovery mass of the solvent oil, and m o is the mass of the coal liquefied asphalt raw material.
The catalyst NiMoP/Al 2O3-SiO2 used in the following examples was prepared as follows:
Mixing pseudo-boehmite powder, siO 2 sol, dilute nitric acid (the concentration is 31.68 wt%), sesbania powder and water according to the mass ratio of 2:1:0.5:0.5:1, pulping and kneading in a kneader, extruding into a cylinder with the diameter of 1.5-2.5 mm and the length of 5-10 mm, drying in a 120 ℃ oven for 6h, and roasting in a muffle furnace for 6h at 550 ℃ to obtain the Al 2O3-SiO2 carrier (the mass ratio of Al 2O3 to SiO 2 is 60:40). Preparing an aqueous solution containing nickel nitrate, (NH 4)6Mo7O24·4H2 O and phosphoric acid), immersing the Al 2O3-SiO2 carrier obtained in the above in a medium volume for 16h, airing at room temperature, drying in a 120 ℃ oven for 6h, and roasting at 550 ℃ for 4h to obtain the NiMoP/Al 2O3-SiO2 hydrogenation catalyst, wherein the mass contents of Ni, mo and P are 5.3%, 9.8% and 0.8% respectively.
Example 1
Preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 171-400 ℃) and the crude oil directly liquefied by coal (with the distillation range of 253-450 ℃) are mixed according to the mass ratio of 10:90, and are subjected to hydrogenation under the conditions of the temperature of 380 ℃ and the pressure of 15MPa, the hydrogen oil ratio of 1000 (v/v) and the volume airspeed of 0.6h -1 in the presence of a catalyst NiMoP/Al 2O3-SiO2 by a fixed bed reactor, and then the distillate section with the distillation range of 171-278 ℃ is cut by distillation, so that the solvent oil with the density of 0.9305g/cm 3 is obtained, wherein the nitrogen element content is 201ppm and the sulfur element content is 5ppm. The solvent oil contains 10.2wt% of C 10～C16 alkane, 25.3wt% of total naphthenes with the ring number of 1-3, 44.0wt% of monocyclic aromatic hydrocarbon, 20.0wt% of bicyclic aromatic hydrocarbon and 0.5wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
Uniformly mixing coal liquefied asphalt with ash content of 19.9wt%, quinoline insoluble matter content of 49.5wt% and softening point of 194 ℃ and solvent oil according to a mass ratio of 1:4, keeping constant temperature at 80 ℃ and stirring for 2 hours to finish extraction, continuously conveying the extracted mixed slurry to a horizontal screw centrifuge with drum inner diameter of 760mm and centrifugal separation factor of 600g at a speed of 6.12t/h to realize separation of soluble asphalt matters and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral matters and catalysts, and obtaining centrifugal light liquid and centrifugal heavy phase, wherein the centrifugal light liquid is distilled to recover the solvent oil to obtain refined coal liquefied asphalt with ash content of 201ppm, quinoline insoluble matter content of 385ppm, softening point of 150.1 ℃ and yield of 48.2%, the centrifugal heavy phase is heated to 200 ℃, softened to fluid with viscosity of 1998cp, continuously conveying the fluid to a decompression spray drying device, and recovering the solvent oil to obtain raffinate residue with solvent oil residue of 0.51wt% and yield of 52.07%;
The solvent oil consumption rate is 0.27wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 175-275 ℃, the density is 0.9304g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 2:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 205-396 ℃ C.) and the crude oil directly liquefied by coal (with the distillation range of 247-443 ℃ C.) are mixed according to the mass ratio of 11.4:88.6, and hydrogenation is completed under the conditions of the temperature of 375 ℃ C., the pressure of 14MPa, the hydrogen-oil ratio of 1000 (v/v) and the volume space velocity of 0.6h -1 in the presence of a catalyst NiMoP/Al 2O3-SiO2 by a fixed bed reactor, and then a distillate section with the distillation range of 179-285 ℃ C is cut by distillation, so that the solvent oil with the density of 0.9482g/cm 3 is obtained, wherein the nitrogen content is 501ppm and the sulfur content is 33ppm. The solvent oil contains 10.5wt% of C 10～C16 paraffin, 22.8wt% of total naphthenes with a ring number of 1-3, 44.0wt% of monocyclic aromatic hydrocarbon, 21.4wt% of bicyclic aromatic hydrocarbon and 1.3wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
Uniformly mixing coal liquefied asphalt with 18.5wt% ash content, 47.8wt% quinoline insoluble matter content and 189 ℃ softening point with solvent oil according to a mass ratio of 1:3.5, keeping constant temperature at 85 ℃ and stirring for 1.5h to finish extraction, continuously conveying the obtained mixed slurry obtained by extraction into a horizontal screw centrifuge with 760mm of inner diameter of a rotary drum and 1300g of centrifugal separation factor at a speed of 6.12t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, minerals and catalysts, obtaining centrifugal light liquid and centrifugal heavy phase, obtaining refined coal liquefied asphalt with 83ppm ash content, 132ppm quinoline insoluble matter content, 152.3 ℃ softening point and 49.1% yield after the solvent oil is recovered by distillation, heating the centrifugal heavy phase to 212 ℃, softening the mixed slurry into a fluid with 1875cp viscosity, continuously conveying the fluid into a decompression belt type drying device, and obtaining raffinate with the solvent oil residue of 0.65wt% and 51.23% yield after the solvent oil is recovered;
The solvent oil consumption rate is 0.33wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 177-283 ℃, the density is 0.9480g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 3:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 198-388 ℃) and the crude oil (with the distillation range of 215-412 ℃) which is directly liquefied by coal are mixed according to the mass ratio of 23.7:76.3, hydrogenation is completed under the conditions of the temperature of 375 ℃, the pressure of 13MPa, the hydrogen-oil ratio of 900 (v/v) and the volume airspeed of 0.7h -1 by a fixed bed reactor in the presence of a catalyst NiMoP/Al 2O3-SiO2, and then the distillate section with the distillation range of 192-305 ℃ is cut by distillation, so that the solvent oil with the density of 0.9647g/cm 3 is obtained, wherein the nitrogen element content is 832ppm and the sulfur element content is 59ppm. The solvent oil contains 9.0wt% of C 10～C16 alkane, 22.1wt% of total naphthenes with the ring number of 1-3, 41.2wt% of monocyclic aromatic hydrocarbon, 25.4wt% of bicyclic aromatic hydrocarbon and 2.3wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
uniformly mixing coal liquefied asphalt with 17.1wt% ash content, 46.1wt% quinoline insoluble matter content and 182 ℃ softening point with solvent oil according to a mass ratio of 1:3.2, keeping the temperature at 91 ℃ and stirring for 1.3h to finish extraction, continuously conveying the obtained mixed slurry obtained by extraction into a horizontal screw centrifuge with a drum inner diameter of 760mm and a centrifugal separation factor of 665g at a speed of 12.38t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, minerals and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, recovering the solvent oil from the centrifugal light liquid by distillation to obtain coal liquefied asphalt with 734ppm ash content, 1369ppm quinoline insoluble matter content, 157.4 ℃ softening point and 51.3% yield, heating the centrifugal heavy phase to 219 ℃, softening the coal liquefied asphalt into fluid with a viscosity of 1734cp, continuously conveying the fluid into a decompression spray drying device, and recovering the solvent oil to obtain raffinate with a solvent oil residue of 0.89wt% and a yield of 49.14%;
The solvent oil consumption rate is 0.44wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 197-303 ℃, the density is 0.9640g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 4:
preparation of solvent oil:
the coal tar distillate oil (with the distillation range of 212-350 ℃) and the crude oil directly liquefied by coal (with the distillation range of 230-398 ℃) are mixed and prepared according to the mass ratio of 37.5:62.5, hydrogenation is completed under the conditions of the temperature of 370 ℃, the pressure of 12MPa, the hydrogen-oil ratio of 800 (v/v) and the volume airspeed of 0.8h -1 by a fixed bed reactor in the presence of a catalyst NiMoP/Al 2O3-SiO2, and then a distillate section with the distillation range of 204-317 ℃ is cut by distillation, so that the solvent oil with the density of 0.9751g/cm 3 is obtained, wherein the nitrogen element content is 1160ppm and the sulfur element content is 87ppm. The solvent oil contains 8.4wt% of C 10～C16 paraffin, 18.5wt% of total naphthenes with a ring number of 1-3, 38.4wt% of monocyclic aromatic hydrocarbon, 31.1wt% of bicyclic aromatic hydrocarbon and 3.6wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
Uniformly mixing coal liquefied asphalt with 16.3wt% ash content, 47.1wt% quinoline insoluble matter content and 188 ℃ softening point with solvent oil according to a mass ratio of 1:3.0, and carrying out constant temperature and stirring for 1h at 95 ℃ to complete extraction, continuously conveying the obtained mixed slurry to a horizontal screw centrifuge with a drum inner diameter of 760mm and a centrifugal separation factor of 915g at a speed of 18.72t/h to realize separation of soluble asphalt substances and heavy liquefied oil and solid insoluble matters such as unreacted coal, mineral substances, catalysts and the like, so as to obtain centrifugal light liquid and centrifugal heavy phase, obtaining refined coal liquefied asphalt with 864ppm ash content, 1796ppm quinoline insoluble matter content, 162.8 ℃ softening point and yield of 52.5% after the solvent oil is recovered by distillation, heating the centrifugal heavy phase to 225 ℃, softening the mixed slurry into fluid with a viscosity of 1598cp, continuously conveying the fluid to a decompression spray drying device, and obtaining raffinate solid with a solvent oil residue with a solvent oil residue content of 1.34wt% and a yield of 48.15%;
The solvent oil consumption rate is 0.65wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 210-312 ℃, the density is 0.9746g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 5:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 245-360 ℃) and the crude oil directly liquefied by coal (with the distillation range of 217-378 ℃) are mixed and prepared according to the mass ratio of 67.8:32.2, hydrogenation is completed under the conditions of the temperature of 365 ℃, the pressure of 11MPa, the hydrogen-oil ratio of 700 (v/v) and the volume airspeed of 1.0h -1 by a fixed bed reactor in the presence of a catalyst NiMoP/Al 2O3-SiO2, and then a distillate section with the distillation range of 209-324 ℃ is cut by distillation, so that the solvent oil with the density of 0.9804g/cm 3 is obtained, wherein the nitrogen element content is 1504ppm and the sulfur element content is 174ppm. The solvent oil contains 7.2wt% of C 10～C16 alkane, 14.6wt% of total naphthenes with the ring number of 1-3, 35.6wt% of monocyclic aromatic hydrocarbon, 38.3wt% of bicyclic aromatic hydrocarbon and 4.3wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
Uniformly mixing coal liquefied asphalt with 15.5wt% ash content, 43.6wt% quinoline insoluble matter content and 177 ℃ softening point with solvent oil according to a mass ratio of 1:3.0, keeping the temperature at 104 ℃ and stirring for 1h to finish extraction, continuously conveying the obtained mixed slurry to a horizontal screw centrifuge with 760mm of inner diameter of a rotary drum and 1783g of centrifugal separation factor at a rate of 6.01t/h to realize separation of soluble asphalt matters and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral matters and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, obtaining refined coal liquefied asphalt with 51ppm ash content, 94ppm quinoline insoluble matter content, 169.5 ℃ softening point and 54.4% yield after the solvent oil is recovered by distillation, heating the centrifugal heavy phase to 234 ℃, softening the mixed slurry into fluid with 1321cp viscosity, continuously conveying the fluid to a decompression belt type drying device, and recovering the solvent oil to obtain raffinate solid with 1.87wt% solvent oil residue and 46.47% yield;
The solvent oil consumption rate is 0.87wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 215-325 ℃, the density is 0.9798g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 6:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 172-350 ℃) and the crude oil (with the distillation range of 205-380 ℃) which is directly liquefied by coal are mixed according to the mass ratio of 79.3:20.7, hydrogenation is completed under the conditions of the temperature of 360 ℃, the pressure of 10MPa, the hydrogen-oil ratio of 600 (v/v) and the volume airspeed of 1.2h -1 by a fixed bed reactor in the presence of a catalyst NiMoP/Al 2O3-SiO2, and then a distillate section with the distillation range of 217-332 ℃ is cut by distillation, so that the solvent oil with the density of 0.9933g/cm 3 is obtained, wherein the nitrogen element content is 1848ppm and the sulfur element content is 297ppm. The solvent oil contains 6.5wt% of C 10～C16 paraffin, 11.8wt% of total naphthenes with a ring number of 1-3, 32.8wt% of monocyclic aromatic hydrocarbon, 44.1wt% of bicyclic aromatic hydrocarbon and 4.8wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
uniformly mixing coal liquefied asphalt with 15.0wt% ash content, 42.4wt% quinoline insoluble matter content and 171 ℃ softening point with solvent oil according to a mass ratio of 1:2.8, keeping constant temperature at 117 ℃ and stirring for 0.8h to finish extraction, continuously conveying the obtained mixed slurry to a horizontal screw centrifuge with a drum inner diameter of 760mm and a centrifugal separation factor of 1530g at a speed of 19.97t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, recovering the solvent oil from the centrifugal light liquid by distillation to obtain refined coal liquefied asphalt with 552ppm ash content, 1074ppm quinoline insoluble matter content, a softening point of 174.7 ℃ and a yield of 55.5%, heating the centrifugal heavy phase to 238 ℃, softening to a fluid with a viscosity of 689cp, continuously conveying the fluid to a decompression spray drying device, and recovering the solvent oil to obtain raffinate solid with a solvent oil residue with a yield of 2.06wt% and a yield of 45.44%;
The solvent oil consumption rate is 0.94wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 215-330 ℃, the density is 0.9926g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 7:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 171-300 ℃) and the crude oil directly liquefied by coal (with the distillation range of 203-448 ℃) are mixed and prepared according to the mass ratio of 86.2:13.8, hydrogenation is completed under the conditions of the temperature of 355 ℃, the pressure of 9MPa, the hydrogen-oil ratio of 600 (v/v) and the volume space velocity of 1.3h -1 by a fixed bed reactor in the presence of a catalyst NiMoP/Al 2O3-SiO2, and then a distillate section with the distillation range of 228-336 ℃ is cut by distillation, so that the solvent oil with the density of 1.0101g/cm 3 is obtained, wherein the nitrogen content is 2165ppm and the sulfur content is 426ppm. The solvent oil contains 5.8wt% of C 10～C16 alkane, 11.2wt% of total naphthenes with the ring number of 1-3, 31.8wt% of monocyclic aromatic hydrocarbon, 46.5wt% of bicyclic aromatic hydrocarbon and 4.7wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
uniformly mixing coal liquefied asphalt with 15.3wt% ash content, 40.4wt% quinoline insoluble matter content and 166 ℃ softening point with solvent oil according to a mass ratio of 1:2.7, stirring at a constant temperature of 128 ℃ for 0.5h to complete extraction, continuously conveying the obtained mixed slurry obtained by extraction into a horizontal screw centrifuge with 760mm of inner diameter of a rotating drum and 1200g of centrifugal separation factor at a speed of 9.09t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, obtaining coal liquefied asphalt with 667ppm ash content, 1245ppm quinoline insoluble matter content, 186.2 ℃ softening point and 57.8% yield after the solvent oil is recovered by distillation, heating the centrifugal heavy phase to 246 ℃, continuously conveying the obtained mixed slurry into a fluid with 387cp viscosity, and continuously conveying the mixed slurry into a decompression spray drying device to obtain raffinate with the solvent oil residue of 2.23wt% and the yield of 43.16%;
the solvent oil consumption rate is 0.96wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 225-333 ℃, the density is 1.005g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Example 8:
preparation of solvent oil:
The coal tar distillate oil (with the distillation range of 300-396 ℃ and the crude oil directly liquefied by coal (with the distillation range of 204-350 ℃) are mixed and prepared according to the mass ratio of 90:10, hydrogenation is completed under the conditions of the temperature of 350 ℃ and the pressure of 8MPa, the hydrogen-oil ratio of 500 (v/v) and the volume airspeed of 1.5h -1 in the presence of a catalyst NiMoP/Al 2O3-SiO2 by a fixed bed reactor, and then a distillate section with the distillation range of 247-349 ℃ is cut by distillation to obtain the solvent oil with the density of 1.0196g/cm 3, wherein the nitrogen element content is 2490ppm and the sulfur element content is 500ppm. The solvent oil contains 5.0wt% of C 10～C16 alkane, 10.5wt% of total naphthenes with the ring number of 1-3, 30.0wt% of monocyclic aromatic hydrocarbon, 49.5wt% of bicyclic aromatic hydrocarbon and 5.0wt% of tricyclic aromatic hydrocarbon.
Refining treatment of coal liquefied asphalt:
Uniformly mixing coal liquefied asphalt with 17.9wt% ash content, 40.1wt% quinoline insoluble matter content and 165 ℃ softening point with solvent oil according to a mass ratio of 1:2.5, keeping the temperature at 130 ℃ and stirring for 0.5h to finish extraction, continuously conveying the obtained mixed slurry obtained by extraction into a horizontal screw centrifuge with a drum inner diameter of 760mm and a centrifugal separation factor of 1800g at a speed of 19.85t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, minerals and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, obtaining refined coal liquefied asphalt with 998ppm ash content, 1992ppm quinoline insoluble matter content, 190.0 ℃ softening point and 58.0% yield after the solvent oil is recovered by distillation, heating the centrifugal heavy phase to 250 ℃, softening the mixed slurry into fluid with a viscosity of 201cp, continuously conveying the fluid into a decompression spray drying device, and obtaining raffinate with a solvent oil residue of 2.28wt% and a solvent oil residue of 42.98% after the solvent oil is recovered;
The solvent oil consumption rate is 0.98wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 245-353 ℃, the density is 1.0196g/cm 3, the property is relatively stable, and the recovered solvent can be recycled.
Comparative example 1 (direct liquefaction of crude oil fraction with coal having a lower distillation range alone compared to example 1)
And (3) distilling the crude oil directly liquefied by coal to obtain a distillate section with a distillation range of 70-171 ℃ to obtain the solvent oil with a density of 0.7678g/cm 3, wherein the nitrogen content is 77ppm and the sulfur content is 5ppm. In the obtained solvent oil, the content of C 6～C16 alkane is 36.1wt%, the total amount of naphthenes with the ring number of 1-3 is 38.9wt%, the content of monocyclic aromatic hydrocarbon is 24.7wt%, and the content of bicyclic aromatic hydrocarbon is 0.3wt%.
The method comprises the steps of mixing coal liquefied asphalt with ash content of 19.9wt%, quinoline insoluble matter content of 49.5wt% and softening point of 194 ℃ with solvent oil uniformly according to a mass ratio of 1:4, stirring at constant temperature of 80 ℃ for 2h to complete extraction, continuously conveying the extracted mixed slurry to a horizontal screw centrifuge with drum inner diameter of 760mm and centrifugal separation factor of 600g at a rate of 6.12t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts, obtaining refined coal liquefied asphalt with ash content of 190ppm, quinoline insoluble matter content of 367ppm, softening point of 110.1 ℃ and yield of 13.1% after the solvent oil is recovered by distillation of the centrifugal light liquid, wherein the solvent content of the centrifugal heavy phase is 19.3% and is difficult to soften into fluid recovery solvent, so that the solvent consumption rate is up to 16.81wt% (based on the treatment amount of the coal liquefied asphalt), and the distillation range of recovered solvent is 70-150 ℃ and density is 0.7432g/cm 3, so that the property is not reusable.
The solvent oil in the comparative example has low content of monocyclic aromatic hydrocarbon and bicyclic aromatic hydrocarbon, higher content of alkane and naphthene, low extraction yield of coal liquefied asphalt, poor swelling property of raffinate, incapability of continuously conveying centrifugal heavy phase and difficulty in industrial scale application.
Comparative example 2 (compared with example 1, the mass ratio of coal tar distillate to coal direct liquefaction crude oil is different)
The coal tar distillate oil (with the distillation range of 171-400 ℃) and the crude oil directly liquefied by coal (with the distillation range of 253-450 ℃) are mixed according to the mass ratio of 3:97, and are hydrogenated under the conditions of the temperature of 380 ℃ and the pressure of 15MPa, the hydrogen oil ratio of 1000 (v/v) and the volume airspeed of 0.6h -1 in the presence of a catalyst NiMoP/Al 2O3-SiO2 by a fixed bed reactor, and then the distillate section with the distillation range of 170-280 ℃ is cut by distillation, so that the solvent oil with the density of 0.8347g/cm 3 is obtained, wherein the nitrogen element content is 101ppm and the sulfur element content is 15ppm. The solvent oil contains 26.5wt% of C 10～C16 paraffin, 49.3wt% of total naphthenes with a ring number of 1-3, 20.3wt% of monocyclic aromatic hydrocarbon and 3.9wt% of bicyclic aromatic hydrocarbon.
The coal liquefied asphalt with the ash content of 19.9wt percent, the quinoline insoluble matter content of 49.5wt percent and the softening point of 194 ℃ is uniformly mixed with the solvent oil according to the mass ratio of 1:4, the mixture is stirred for 2 hours at the constant temperature of 80 ℃ to finish the extraction, the mixed slurry obtained by the extraction is continuously conveyed into a horizontal screw centrifuge with the inner diameter of a rotary drum of 760mm and the centrifugal separation factor of 600g at the speed of 6.12t/h, the separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts is realized, the centrifugal light liquid and the centrifugal heavy phase are obtained, the refined coal liquefied asphalt with the ash content of 198ppm, the quinoline insoluble matter content of 380 ℃ and the softening point of 135.3 ℃ and the yield of 30.1% is obtained after the solvent oil is recovered by distillation, the solvent content of 25.7% of the centrifugal heavy phase is difficult to soften into fluid recovery solvent, the solvent consumption rate is high up to 18.03wt% (based on the treatment capacity of the coal asphalt), the distillation range of the recovery solvent is 175-260 ℃ and the density is 0.8128 g/3 g/cm, and the recycling property is not changed greatly.
The solvent has low content of monocyclic aromatic hydrocarbon and bicyclic aromatic hydrocarbon, higher content of alkane and naphthene, low extraction yield of coal liquefied asphalt, poor swelling property of raffinate, incapability of continuously conveying centrifugal heavy phase and difficulty of industrial scale application.
Comparative example 3 (compared to example 8, coal tar distillate alone was used)
And (3) hydrogenating the coal tar distillate oil (with the distillation range of 300-396 ℃ C.) in the presence of a catalyst NiMoP/Al 2O3-SiO2 by a fixed bed reactor under the conditions of the temperature of 350 ℃ C., the pressure of 8MPa, the hydrogen-oil ratio of 500 (v/v) and the volume space velocity of 1.5h -1, and then cutting a distillate section with the distillation range of 240-330 ℃ C. By distillation to obtain the solvent oil with the density of 1.0467g/cm 3, wherein the nitrogen content is 5210ppm and the sulfur content is 2167ppm. The solvent oil contains 2.4wt% of C 10～C16 alkane, 4.2wt% of total naphthene with a ring number of 1-3, 18.8wt% of monocyclic aromatic hydrocarbon, 72.1wt% of bicyclic aromatic hydrocarbon and 2.5wt% of tricyclic aromatic hydrocarbon.
The method comprises the steps of uniformly mixing coal liquefied asphalt with 17.9wt% of ash content, 40.1wt% of quinoline insoluble matter content and 165 ℃ of softening point with solvent oil according to a mass ratio of 1:2.5, stirring at a constant temperature of 130 ℃ for 0.5h to finish extraction, continuously conveying the obtained mixed slurry to a horizontal screw centrifuge with 760mm of inner diameter of a rotating drum and 1800g of centrifugal separation factor at a speed of 19.85t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, obtaining refined coal liquefied asphalt with 10150ppm of ash content, 22480ppm of quinoline insoluble matter content, 187.4 ℃ of softening point and 59.7% of yield after the solvent oil is distilled and recovered from the centrifugal light liquid, heating the centrifugal heavy phase to 250 ℃, softening the mixed slurry into fluid with 187cp of viscosity, continuously conveying the mixed slurry to a decompression spray drying device, and recovering the solvent oil to obtain raffinate solid with a solvent oil residue content of 4.56wt% and 42.23%;
the solvent oil consumption rate is 1.93wt% of the coal liquefied asphalt treatment capacity, the consumption is large, the cost is high, and the ash content of the extracted and refined asphalt is more than 10000ppm, so that the raw material requirement of high-end carbon materials cannot be met.
Comparative example 4 (compared to example 3, solvent oil was prepared without hydrogenation)
The coal tar distillate oil (with the distillation range of 198-388 ℃) and the crude oil (with the distillation range of 215-412 ℃) which are directly liquefied by coal are mixed according to the mass ratio of 23.7:76.3, and then the distillate section with the distillation range of 200-305 ℃ is cut by distillation to obtain the solvent oil with the density of 0.9947g/cm 3, wherein the nitrogen content is 2759ppm and the sulfur content is 1341ppm. The solvent oil contains 5.0wt% of C 10～C16 alkane, 17.1wt% of total naphthenes with a ring number of 1-3, 28.8wt% of monocyclic aromatic hydrocarbon, 44.0wt% of bicyclic aromatic hydrocarbon and 5.1wt% of tricyclic aromatic hydrocarbon.
Uniformly mixing coal liquefied asphalt with 15.3wt% ash content, 40.4wt% quinoline insoluble matter content and 166 ℃ softening point with solvent oil according to a mass ratio of 1:2.7, stirring at a constant temperature of 128 ℃ for 0.5h to complete extraction, continuously conveying the obtained mixed slurry obtained by extraction into a horizontal screw centrifuge with 760mm of inner diameter of a rotating drum and 1200g of centrifugal separation factor at a speed of 9.09t/h to realize separation of soluble asphalt substances and heavy liquefied oil from solid insoluble matters such as unreacted coal, mineral substances and catalysts to obtain centrifugal light liquid and centrifugal heavy phase, distilling the centrifugal light liquid to recover the solvent oil to obtain 859ppm ash, 1731ppm quinoline insoluble matter content, 175.2 ℃ softening point and 57.9% yield of refined coal liquefied asphalt, heating the centrifugal heavy phase to 248 ℃, softening the liquid with 299cp viscosity, continuously conveying the liquid into a decompression spray drying device, and recovering the solvent oil to obtain raffinate with 4.05wt% solvent oil residue and 43.89% yield;
The solvent oil consumption rate is 1.78wt% of the coal liquefied asphalt treatment capacity, the distillation range of the recovered solvent is 155-270 ℃, the density is 0.9256g/cm 3, the property is greatly changed, and the recovered solvent cannot be recycled.
The solvent is not subjected to hydrogenation treatment, and the coal liquefied crude oil is easy to crack and coke in the processes of extraction, distillation and temperature rise and fall, so that the consumption rate is high, the property is changed, and the recycling can not be realized.
Table 1 summary of experimental results
From the experimental results, compared with the comparative example, the solvent oil of the invention is adopted for refining the coal liquefied asphalt, so that the yield of the refined asphalt (more than 48 percent) can be relatively high under the condition of lower solvent oil consumption rate, and the solvent oil residue in the raffinate solid residue is low while the ash content (50-1000 ppm) and the quinoline insoluble content (80-2000 ppm) are relatively low. The solvent oil disclosed by the embodiment of the invention has a good solid-liquid separation effect when treating the coal liquefied asphalt, is easy to recycle, can realize good balance of low-solvent oil consumption, high yield, low ash content and low quinoline insoluble content of the refined asphalt, and has a softening point of 150-190 ℃.
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (12)
1. The solvent oil is characterized by comprising C 10~C16 alkane, naphthene with the ring number of 1-3, monocyclic arene, bicyclic arene and tricyclic arene;
Based on the total mass of the solvent oil, the content of the C 10~C16 alkane is 5.0-10.5wt%, the content of the cycloalkane is 10.0-25.3wt%, the content of the monocyclic arene is 30.0-44.0wt%, the content of the bicyclic arene is 20.0-50.0wt%, and the content of the tricyclic arene is 0.5-5.0wt%;
The nitrogen content of the solvent oil is 200-2500 ppm, the sulfur content is 5-500 ppm, the distillation range of the solvent oil is 170-350 ℃, and the density of the solvent oil is 0.93-1.02 g/cm 3;
the preparation method of the solvent oil comprises the following steps:
And mixing the coal tar distillate oil and the coal direct liquefaction crude oil according to the mass ratio of 10:90-90:10, then carrying out hydrogenation reaction, and then carrying out distillation and cutting to obtain a distillate section with the distillation range of 170-350 ℃ to obtain the solvent oil.
2. The solvent oil of claim 1, wherein the coal tar distillate is a coal tar distillate with a distillation range of 170-400 ℃;
The coal direct liquefaction crude oil is coal direct liquefaction crude oil fraction with a distillation range of 200-450 ℃.
3. The solvent naphtha according to claim 1, wherein the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst comprising a carrier and an active component, wherein the active component comprises Ni, mo and P, and the mass contents of Ni, mo and P in the hydrogenation catalyst are 4.71-5.89%, 8.87-10.93% and 0.74-0.87% respectively.
4. The solvent oil of claim 3, wherein the carrier is an Al 2O3-SiO2 carrier, wherein the Al 2O3 content is 45-72 wt% and the SiO 2 content is 28-55 wt%.
5. The solvent naphtha of any one of claims 1-4 wherein the hydrogenation reaction conditions include a temperature of 350-380 ℃, a pressure of 8-15 mpa, a hydrogen-to-oil ratio v/v of 500-1000, and a volume space velocity of 0.6-1.5 h -1.
6. The mineral spirits of claim 5, wherein the hydrogenation reaction is carried out in a fixed bed reactor, a suspended bed reactor or an ebullated bed reactor.
7. Use of the solvent oil according to any one of claims 1 to 6 in a refining process of coal liquefied asphalt.
8. The refining treatment method of the coal liquefied asphalt is characterized by comprising the following steps of:
(1) Uniformly mixing coal liquefied asphalt and solvent oil according to a mass ratio of 1:2-4, heating to 80-130 ℃, and stirring at constant temperature for 0.5-2 hours to obtain mixed slurry, wherein the solvent oil is the solvent oil according to any one of claims 1-6;
(2) Centrifugally separating the mixed slurry to obtain a light phase and a heavy phase;
(3) Separating solvent oil in the light phase to obtain refined coal liquefied asphalt.
9. The method for purifying a coal liquefied asphalt according to claim 8, wherein in step (2), the centrifugal separation is performed in a decanter centrifuge.
10. The method for purifying coal liquefied asphalt according to claim 9, wherein the centrifugal separation factor of the decanter centrifuge is 600 to 1800 g.
11. The method for purifying coal liquefied asphalt according to any one of claims 8 to 10, wherein the heavy phase is heated to 200 to 250 ℃ so that the heavy phase is softened into a fluid, and then the solvent oil therein is recovered.
12. The method for purifying a coal liquefied asphalt according to claim 11, wherein the solvent oil separated from the light phase and the solvent oil recovered from the heavy phase are mixed and recycled to the step (1).
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| JPS62277491A (en) * | 1986-05-26 | 1987-12-02 | Maruzen Petrochem Co Ltd | How to make mesophasic pitch |
| US5437780A (en) * | 1993-10-12 | 1995-08-01 | Conoco Inc. | Process for making solvated mesophase pitch |
| WO2013019418A2 (en) * | 2011-07-29 | 2013-02-07 | Saudi Arabian Oil Company | Process for stabilization of heavy hydrocarbons |
| CN103242881B (en) * | 2013-05-30 | 2015-08-12 | 神华集团有限责任公司 | The method of separate bitumen class material from coal directly-liquefied residue |
| CN108690650A (en) * | 2017-04-09 | 2018-10-23 | 何巨堂 | A kind of combined method of Coal Liquefaction process and high aromatic hydrogenation thermal cracking process |
| CN114752410B (en) * | 2022-03-28 | 2024-03-26 | 中国神华煤制油化工有限公司 | Metal rolling base oil and preparation method thereof |
| CN116987523A (en) * | 2023-07-28 | 2023-11-03 | 西北大学 | Method for preparing monocyclic aromatic hydrocarbons and naphtha using thermal decarburization of medium-low temperature coal tar |
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Effective date of registration: 20260309 Address after: Block C, Shenhua building, 16 ande Road, Dongcheng District, Beijing, 100011 Patentee after: CHINA SHENHUA COAL TO LIQUID AND CHEMICAL Co.,Ltd. Country or region after: China Patentee after: Guoneng Cornerstone Chemical Technology (Shanghai) Co.,Ltd. Address before: Block C, Shenhua building, 16 ande Road, Dongcheng District, Beijing, 100011 Patentee before: CHINA SHENHUA COAL TO LIQUID AND CHEMICAL Co.,Ltd. Country or region before: China Patentee before: SHANGHAI RESEARCH INSTITUTE OF CHINA SHENHUA COAL TO LIQUID AND CHEMICAL Corp.,Ltd. |