CN112175646A - System and method for liquefying coal by direct hydrogenation to produce aromatic hydrocarbon in rich yield - Google Patents
System and method for liquefying coal by direct hydrogenation to produce aromatic hydrocarbon in rich yield Download PDFInfo
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
Abstract
The invention provides a system and a method for liquefying coal by direct hydrogenation to produce aromatic hydrocarbon in a rich way, which comprises the following steps: the micro-interface generator is respectively arranged among the liquefaction reaction unit, the liquefaction reaction unit and the quality improvement unit and between the quality improvement unit and the catalytic reforming unit and is used for crushing the hydrogen into micron-sized bubbles before hydrogenation liquefaction reaction, hydrogenation quality improvement and hydrogenation catalytic reforming so as to increase the phase boundary mass transfer area between the hydrogen and corresponding reactants in the processes of hydrogenation liquefaction reaction, hydrogenation quality improvement and hydrogenation catalytic reforming and enhance the reaction efficiency. The system and the method for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon rich solve the problem that in the prior art, the preparation efficiency of the aromatic hydrocarbon is reduced because hydrogen cannot fully react with oil coal slurry.
Description
Technical Field
The invention relates to the technical field of clean utilization of coal, in particular to a system and a method for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon in a rich way.
Background
Aromatic hydrocarbons (BTX) are a large amount of basic organic chemical raw materials and are widely applied to the fields of rubber, resin, textile, chemical fiber, plastics and the like. Particularly, with the rapid development of an aromatic hydrocarbon industry chain mainly comprising PX-Purified Terephthalic Acid (PTA) -Polyester (PET) -polyester fiber (terylene) and polyester plastic (polyester film and polyester packaging bottle), the petroleum resource used as an aromatic hydrocarbon production raw material faces an increasingly serious shortage situation and becomes one of the main bottlenecks restricting the development of aromatic hydrocarbon in China.
At present, the annual consumption of aromatic hydrocarbon in China exceeds 2000 ten thousand tons, and the external dependence of Paraxylene (PX) in 2016 is as high as 56%. Industrially, more than 97% of the aromatic hydrocarbons are derived from petroleum feedstocks and aromatic products are produced by ethylene cracking. Compared with petroleum, the raw material coal macromolecules are rich in 1-3 ring aromatic ring structures, the coal-based oil obtained through conversion processes such as coal pyrolysis, gasification and direct hydrogenation liquefaction still fully retains the aromatic ring molecular structures, and the coal-based oil has the characteristic of high content of aromatic hydrocarbons and naphthenic hydrocarbons, is about 60-80% higher than the content of the aromatic hydrocarbons and the naphthenic hydrocarbons in petroleum fractions. The technology for producing the aromatic hydrocarbon by taking the coal as the raw material is developed, the coal resource is utilized to make up the deficiency of the petroleum resource to produce the basic chemicals such as the aromatic hydrocarbon, the basic chemicals not only accord with the current situation of energy resource endowment of China, but also can realize the clean and efficient utilization of the coal, and become the beneficial supplement of the petrochemical industry.
In the prior art, the coal oil slurry and hydrogen are directly used for carrying out corresponding reaction in a reactor to prepare the aromatic hydrocarbon, and in the method, only the hydrogen and the coal oil slurry are mixed, so that hydrogen molecules cannot fully react with the coal oil slurry, the reaction efficiency is reduced, and the preparation efficiency of the aromatic hydrocarbon is reduced.
Disclosure of Invention
In view of the above, the invention provides a system and a method for direct coal hydrogenation liquefaction to produce aromatic hydrocarbons in a rich manner, and aims to solve the problem that in the prior art, the preparation efficiency of the aromatic hydrocarbons is reduced because hydrogen cannot fully react with oil coal slurry.
In one aspect, the present invention provides a system for direct coal hydroliquefaction to produce aromatics rich in aromatics, including:
the feeding unit is used for preparing the coal oil slurry and conveying the coal oil slurry and the hydrogen;
the liquefaction reaction unit is connected with the feeding unit and is used for carrying out hydrogenation liquefaction reaction on the coal oil slurry and the hydrogen, and carrying out gas-liquid separation on a hydrogenation liquefaction reaction product to obtain a first gas phase material, a light phase oil product, a distillate oil and solid-containing oil residue;
the upgrading unit is connected with the liquefaction reaction unit and is used for carrying out hydrogenation upgrading on the light-phase oil product, the distillate oil and the hydrogen, and carrying out gas-liquid separation on the hydrogenation upgrading product to obtain a second gas-phase material, a light-phase oil fraction, a diesel oil fraction and heavy oil;
the catalytic reforming unit is connected with the quality improving unit, and is used for mixing the light oil fraction with hydrogen, performing catalytic reforming and gas-liquid separation to obtain a third gas-phase material, a light aromatic hydrocarbon product and raffinate oil;
and the micro-interface generators are respectively arranged among the liquefaction reaction unit, the liquefaction reaction unit and the quality improving unit and between the quality improving unit and the catalytic reforming unit and are respectively used for crushing the hydrogen into micron-sized bubbles before liquefaction reaction, quality improvement and catalytic reforming so as to increase the phase boundary mass transfer area between the hydrogen and corresponding reactants in the processes of hydrogenation liquefaction reaction, hydrogenation quality improvement and hydrogenation catalytic reforming, reduce the thickness of a liquid film, reduce the mass transfer resistance and enhance the reaction efficiency.
Further, in the system for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon in a rich mode, the micro-interface generator converts pressure energy of gas and/or kinetic energy of liquid into bubble surface energy and transmits the bubble surface energy to hydrogen bubbles, and hydrogen is broken into micron-sized bubbles.
Further, in the system for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon in a rich mode, the micro-interface generator is one or more selected from a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
Further, in the system for directly hydrogenating and liquefying coal to produce rich aromatic hydrocarbon, the micron-sized bubbles are micron-sized bubbles with the diameter of more than or equal to 1 μm and less than 1 mm.
Further, in the above system for directly hydrogenating and liquefying coal to enrich and produce aromatic hydrocarbons, the feed unit includes:
the coal oil slurry preparation unit is used for preparing coal oil slurry;
a gas feed line for transporting hydrogen;
the first heating furnace is used for preheating the oil coal slurry;
and the high-pressure coal slurry pump is connected with the oil coal slurry preparation unit and the first heating furnace and is used for conveying the oil coal slurry to the interior of the first heating furnace.
The invention has the advantages that the system for directly hydrogenating and liquefying the coal to produce the aromatic hydrocarbon in rich yield, by arranging micro-interface generators between the feeding unit and the liquefaction reaction unit, between the liquefaction reaction unit and the upgrading unit, and between the upgrading unit and the catalytic reforming unit respectively, the micro interface generator is used for crushing the hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1mm in the micro interface generator before the hydrogenation liquefaction reaction, the hydrogenation quality improvement and the hydrogenation catalytic reforming, so as to increase the mass transfer area of the phase boundary between the hydrogen and the coal oil slurry and the corresponding reactant in the reaction process, reduce the thickness of a liquid film, reduce the mass transfer resistance, improve the mass transfer efficiency between reaction phases, and then the problem that the preparation efficiency of the aromatic hydrocarbon is reduced because the hydrogen can not fully react with the oil coal slurry in the prior art is solved. In addition, the range of the preset operation condition can be flexibly adjusted according to different raw material compositions, different product requirements or different catalysts, so that the full and effective reaction is further ensured, the reaction rate is further ensured, and the purpose of strengthening the reaction is achieved.
Particularly, the high-pressure coal slurry pump is arranged in the feeding unit, and when the system runs, the high-pressure coal slurry pump can provide power for transportation of the oil coal slurry, so that the oil coal slurry can be conveyed to the appointed device at the appointed speed, and the running efficiency of the system is improved.
On the other hand, the invention also provides a method for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon in rich yield, which comprises the following steps:
preparing raw material coal into coal oil slurry, preheating, conveying the coal oil slurry to a hydrogenation liquefaction unit after preheating is finished, and meanwhile conveying hydrogen to the interior of a corresponding micro-interface generator;
the micro-interface generator is used for crushing hydrogen into micron-sized bubbles, conveying the micron-sized bubbles to a liquefaction reaction unit after the micro-interface generator finishes crushing, mixing the micron-sized bubbles with the coal oil slurry to form a gas-liquid emulsion, and carrying out liquefaction reaction after the mixing is finished;
and (3) liquefaction reaction: carrying out deep liquefaction reaction on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a first gas-phase material and a first liquid-phase material, heating the first liquid-phase material and then distilling at normal pressure to obtain a light-phase oil product and a heavy-phase oil product, and carrying out reduced pressure distillation on the heavy-phase oil product to obtain a distillate oil and solid-containing oil residues;
heating the light-phase oil product and the distillate oil, then conveying the heated light-phase oil product and the distillate oil to the corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion of the light-phase oil product, the distillate oil and the hydrogen received by the micro-interface generator, crushing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles with the light-phase oil product and the distillate oil by the micro-interface generator to form a gas-liquid emulsion after the crushing is finished, and conveying the formed gas-liquid emulsion to an upgrading unit after the mixing is finished;
hydrogenation upgrading: carrying out hydrogenation upgrading on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a second gas-phase material and a second liquid-phase material; wherein the second liquid phase material comprises a light oil fraction, a diesel oil fraction and a heavy oil;
heating the light oil fraction, conveying the heated light oil fraction to the inside of a corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion between the light oil fraction and the hydrogen received by the micro-interface generator, smashing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles and the light oil fraction by the micro-interface generator to form a gas-liquid emulsion after smashing, and conveying the formed gas-liquid emulsion to a catalytic reforming unit after mixing;
catalytic reforming: carrying out catalytic reforming on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a third gas-phase material and a third liquid-phase material; and extracting the third liquid phase material by a solvent to obtain a light aromatic hydrocarbon product and raffinate oil.
Further, in the method for directly hydrogenating and liquefying the coal to produce the rich aromatic hydrocarbon, the temperature of the hydrogenation and liquefaction reaction is 400-460 ℃, and the reaction pressure is 5-15 MPa.
Further, in the method for directly hydrogenating and liquefying the coal to produce the rich aromatic hydrocarbon, the reaction temperature of hydrogenation upgrading is 300-380 ℃, and the reaction pressure is 2-15 MPa.
Further, in the method for directly hydrogenating and liquefying coal to produce rich aromatic hydrocarbon, the catalytic reforming reaction pressure is 0.2-1MPa, and the reaction temperature is 450-530 ℃.
Further, in the method for directly hydrogenating and liquefying coal to produce rich aromatic hydrocarbon, the diesel fraction is subjected to hydrocracking to obtain a fourth gas-phase material and a fourth liquid-phase material; and the fourth liquid-phase material is subjected to hydrogenation upgrading and distillation separation.
The method for producing the aromatic hydrocarbon in a rich manner by direct coal hydrogenation liquefaction has the beneficial effects that the hydrogen is crushed to form micron-sized bubbles in a micron scale, and the micron-sized bubbles are mixed with the direct coal liquefaction oil to form a gas-liquid emulsion, so that the phase boundary mass transfer area between the hydrogen and the corresponding reactant in the reaction process is increased, the mass transfer efficiency between reaction phases is improved, and the problem of low aromatic hydrocarbon preparation efficiency caused by the fact that the hydrogen cannot fully react with the coal oil slurry in the prior art is solved.
The coal is rich in 1-5 aromatic ring structures, and a large amount of hydrogen is consumed for preparing the clean fuel oil by directly hydrogenating and opening the rings, so that the aromatic hydrocarbon is prepared by directly liquefying the coal, the unique characteristics of the aromatic hydrocarbon structures in the coal are fully utilized, the utilization rate of coal resources is improved, the economy of coal hydrogenation liquefaction is improved, and the competitiveness of the coal hydrogenation liquefaction and the petrochemical industry is improved.
The invention integrates the direct coal liquefaction, catalytic reforming and hydrocracking technologies in a coupling way, and achieves the aim of maximally producing high-added-value light aromatic hydrocarbons by direct coal liquefaction through secondary hydrocracking of a small amount of diesel oil fraction.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic structural diagram of a system and a method for direct coal hydroliquefaction rich aromatic hydrocarbon production according to an embodiment of the present invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Referring to fig. 1, a system for directly hydroliquefying coal to enrich and produce aromatic hydrocarbons according to an embodiment of the present invention includes: a feeding unit, a first micro-interface generator 21, a liquefaction reaction unit, a second micro-interface generator 22, an upgrading unit, a third micro-interface generator 23, a catalytic reforming unit: the device comprises a liquefaction reaction unit, a feeding unit, a hydrogen storage unit and a hydrogen storage unit, wherein the feeding unit is connected with the liquefaction reaction unit and used for preparing coal oil slurry and conveying the coal oil slurry and hydrogen; the first micro-interface generator 21 is connected with the feeding unit and the liquefaction reaction unit respectively, and is used for receiving hydrogen and crushing the hydrogen to a micron scale to form micron-sized bubbles with the diameter of more than or equal to 1 micrometer and less than 1mm, and after the crushing is finished, the hydrogen is conveyed to the liquefaction reaction unit to be mixed with the oil coal slurry for liquefaction reaction; the liquefaction reaction unit is used for carrying out liquefaction reaction on the coal oil slurry and the hydrogen and carrying out gas-liquid separation on a liquefaction reaction product to obtain a first gas phase material, a light phase oil product, distillate oil and solid-containing oil residue; a second micro-interface generator 22, one end of which is connected with the liquefaction reaction unit and the feeding unit and the other end of which is connected with the hydrogenation upgrading reaction unit, and is used for receiving the light-phase oil product, the distillate oil and the hydrogen and crushing the hydrogen to a micron scale to form micron-sized bubbles with the diameter of more than or equal to 1 micron and less than 1mm, and conveying the light-phase oil product, the distillate oil and the hydrogen to the upgrading unit after the crushing is finished; the upgrading unit is used for carrying out hydrogenation upgrading on the light-phase oil product, the distillate oil and the hydrogen, and carrying out gas-liquid separation on the hydrogenation upgrading product to obtain a second gas-phase material, a light oil fraction, a diesel oil fraction and heavy oil; a third micro-interface generator 23, one end of which is connected with the upgrading unit and the feeding unit and the other end of which is connected with the catalytic reforming unit, for receiving the light oil fraction and hydrogen and crushing the hydrogen to micron scale to form micron-sized bubbles with the diameter of more than or equal to 1 μm and less than 1mm, and delivering the crushed light oil fraction and hydrogen to the catalytic reforming unit; and the catalytic reforming unit is used for mixing the light oil fraction with hydrogen, performing catalytic reforming, and performing gas-liquid separation to obtain a third gas-phase material, a light aromatic hydrocarbon product and raffinate oil.
Preferably, the micro-interface generator converts pressure energy of gas and/or kinetic energy of liquid into bubble surface energy and transmits the bubble surface energy to hydrogen bubbles, so that hydrogen is crushed into micron-sized bubbles, and the micron-sized bubbles are divided into a pneumatic micro-interface generator, a hydraulic micro-interface generator and an air-liquid linkage micro-interface generator according to an energy input mode or a gas-liquid ratio, wherein the pneumatic micro-interface generator is driven by gas, and the input gas amount is far greater than the liquid amount; the hydraulic micro-interface generator is driven by liquid, and the input air quantity is generally smaller than the liquid quantity; the gas-liquid linkage type micro-interface generator is driven by gas and liquid at the same time, and the input gas amount is close to the liquid amount. The micro-interface generator can be one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and an air-liquid linkage micro-interface generator.
With continued reference to fig. 1, the feed unit includes: coal slurry preparation unit, gas feed pipe 14, high-pressure coal slurry pump 12, first heating furnace 13: wherein one end of the gas feed pipeline 14 is externally connected with a hydrogen source, and the other end is respectively connected with the first micro-interface generator 21, the liquefaction reaction unit, the upgrading unit and the catalytic reforming unit, and is connected with the first micro-interface generator 21, the second micro-interface generator 22, the third micro-interface generator 23, the liquefaction reaction unit, the upgrading unit and the catalytic reforming unit by delivering hydrogen to the first micro-interface generator 21, the second micro-interface generator 22, the third micro-interface generator 23; the coal oil slurry preparation unit is used for preparing coal oil slurry; one end of the high-pressure coal slurry pump 12 is connected with the oil coal slurry preparation unit, and the other end of the high-pressure coal slurry pump is connected with the first heating furnace 13, so that the oil coal slurry is transported to the inside of the first heating furnace 13; and the first heating furnace 13 is connected with the liquefaction reaction unit and used for preheating the oil-coal slurry and conveying the oil-coal slurry to the liquefaction reaction unit.
Preferably, the coal slurry preparation unit comprises a coal slurry preparation tank, a coal slurry metering tank, a stirring device, a coal slurry circulating pump and the like, and is provided with an external solvent oil inlet when the circulating solvent is insufficient to prepare the coal slurry according to different coal types, liquefaction reaction conditions and distillation process conditions; when the circulating solvent is enough to prepare the coal slurry, the coal slurry preparation unit does not have an external solvent oil inlet.
When the system is started, fresh hydrogen and circulating hydrogen are mixed in the gas feed pipeline 14 to obtain mixed hydrogen; the raw material coal is pretreated, dried and crushed into coal powder, and added with solvent catalyst and cocatalyst circulating solvent according to a certain proportion, and the coal powder and the solvent are added into a coal slurry preparation unit, and stirred and mixed into oil coal slurry with the viscosity of less than 500cp (60 ℃) in the coal slurry preparation unit. The oil coal slurry from the coal slurry preparation unit enters a first heating furnace 13 for preheating after being pressurized by a high-pressure coal slurry pump 12, the preheated oil coal slurry enters a first micro-interface generator 21, and meanwhile, a gas feeding pipeline 14 conveys hydrogen to the first micro-interface generator 21.
With continued reference to fig. 1, the liquefaction reaction unit includes a liquefaction reactor 31, a first gas-liquid separator 32, a second heating furnace 33, an atmospheric distillation column 34, a third heating furnace 35, a reduced-pressure distillation column 36, a liquid-phase oil feed pump, and a fourth heating furnace 38. Wherein, the liquefaction reactor 31 is internally provided with a first micro-interface generator 21, the inlet is connected with the first heating furnace 13, the outlet is connected with the inlet of the first gas-liquid separator 32, and the outlet of the first gas-liquid separator 32 is connected with the second heating furnace 33. The inlet of the atmospheric distillation tower 34 is connected with the second heating furnace 33, and the outlet is respectively connected with the third heating furnace 35 and the liquefied crude oil feeding pump 37. The inlet of the fourth heating furnace 38 is connected with a liquefied crude oil feeding pump 37, and the outlet is connected with the second micro-interface generator 22.
Preferably, the number of the liquefaction reactors 31 is 1-3, the connection form is a series connection, and the reactors can be bubble bed reactors without internal components, loop reactors with guide cylinders, or forced circulation reactors with circulating pumps.
The first micro-interface generator 21 crushes the hydrogen to micron scale, the crushed hydrogen is conveyed into the liquefaction reactor 31 to be subjected to liquefaction reaction with the kerosene slurry conveyed by the first heating furnace 13, the reaction product flowing out of the liquefaction reactor 31 is conveyed into the first gas-liquid separator 32 to be subjected to gas-liquid separation, one part of the first gas-phase material separated by the first gas-liquid separator 32 is mixed with fresh hydrogen and then recycled, and the other part of the first gas-phase material is discharged out of the system as the waste gas 6. The first liquid phase material separated by the first gas-liquid separator 32 is heated by the second heating furnace 33 after being mixed, and then enters the atmospheric distillation tower 34 to separate light fraction, the heavy fraction at the bottom of the atmospheric distillation tower 34 is heated to a certain temperature by the third heating furnace 35 and then enters the vacuum distillation tower 36 to remove the solid 7, the material at the bottom of the vacuum distillation tower 36 is the solid-containing oil residue, and in order to ensure that the solid-containing oil residue can be smoothly discharged at a certain temperature, the solid content in the solid-containing oil residue is generally controlled to be 40-55 wt%. Distillate oil from the atmospheric distillation tower 34 and the vacuum distillation tower 36 enters a fourth heating furnace 38 through a liquefied crude oil feeding pump 37 to be heated, and then enters the second micro-interface generator 22, and meanwhile, the gas feeding pipeline 14 conveys hydrogen to the second micro-interface generator 22.
The upgrading unit comprises a hydrogenation upgrading reactor 41, a second gas-liquid separator 42, a fractionating tower 43, a diesel fraction feed pump 44, a naphtha fraction feed pump 45, a fifth heating furnace 46, a hydrocracking reactor 47 and a third gas-liquid separator 48. Wherein, the inlet of the hydrogenation upgrading reactor 41 is connected with the second micro interface generator 22, the outlet is connected with the inlet of the second gas-liquid separator 42, and the outlet end of the second gas-liquid separator 42 is respectively connected with the inlet ends of the gas feeding pipeline 14 and the fractionating tower 43. The inlet end of the fractionating tower 43 is also connected to the outlet end of a third gas-liquid separator 48, and the outlets are connected to the inlet end of a naphtha fraction feed pump 45 and the inlet end of a diesel fraction feed pump 44, respectively. The outlet end of the diesel fraction feed pump 44 is connected to the inlet end of the hydrocracking reactor 47, and the inlet end of the hydrocracking reactor 47 is also connected to the gas feed line 14. The outlet end of the hydrocracking reactor 47 is connected with the inlet end of a third gas-liquid separator 48, and the outlet end of the third gas-liquid separator 48 is connected to the gas feed pipe 14. The fifth heating furnace 46 has an inlet connected to a naphtha fraction feed pump 45 and an outlet connected to the third micro-interface generator 23.
Preferably, the number of the hydrogenation upgrading reactors 41 is 1-2, the connection mode is in series connection, and the reactors are in the form of fixed bed reactors or boiling bed reactors. The number of the hydrocracking reactors 47 is 1-3, the connection mode is series connection, and the reactors are fixed bed reactors or boiling bed reactors or suspension bed reactors.
The second micro-interface generator 22 crushes the hydrogen to micron scale, and then conveys the light-phase oil product, the distillate oil and the hydrogen to the hydrogenation upgrading reactor 41 for hydrogenation refining reaction aiming at aromatic saturation, desulfurization, denitrification and other heteroatoms after the crushing; the material at the outlet of the hydrogenation upgrading reactor 41 enters a third gas-liquid separator 48 for gas-liquid separation, one part of the second gas-phase material generated by the third gas-liquid separator 48 is mixed with hydrogen and then recycled, and the other part of the second gas-phase material is discharged out of the system as waste gas 6; the second liquid phase material generated by the third gas-liquid separator 48 enters the fractionating tower 43, naphtha with high potential aromatic hydrocarbon content and diesel oil fraction are fractionated, and heavy oil at the bottom of the fractionating tower 43 is used as a circulating solvent to enter a coal slurry preparation unit to prepare coal slurry. The diesel fraction is mixed with hydrogen by a diesel fraction feeding pump 44 and enters a hydrocracking reactor 47 for catalytic hydrocracking reaction, the product oil of the hydrocracking reactor 47 enters a third gas-liquid separator 48 for gas-liquid separation, a fourth gas-phase material of the third gas-liquid separator 48 is sent into a gas feeding pipeline 14, a fourth liquid-phase material generated by the third gas-liquid separator 48 enters a fractionating tower 43 for secondary distillation separation, and heavy fraction at the bottom of the fractionating tower 43 enters the cracking reactor for further hydrocracking. Naphtha with high potential aromatic content can be used as a product, or can be used as catalytic reforming raw oil, and enters the third micro-interface generator 23 after being preheated by the fifth heating furnace 46 after passing through the naphtha fraction feed pump 45, and meanwhile, the gas feed pipeline 14 conveys hydrogen to the first micro-interface generator 23.
The catalytic reforming unit includes a catalytic reforming reactor 51, a fourth gas-liquid separator 52, and an aromatic extraction column 53. The inlet of the catalytic reforming reactor 51 is connected to the third micro-interface generator 23 and the outlet is connected to the inlet of the fourth gas-liquid separator 52. The outlet of the fourth gas-liquid separator 52 is connected to an aromatics extraction column 53.
Preferably, the catalytic reforming reactor 51 is a fixed bed reactor.
The third micro-interface generator 23 crushes the hydrogen gas to a micron scale, the naphtha with high potential aromatic hydrocarbon content and the hydrogen gas are conveyed to the catalytic reforming reactor 51 for aromatic hydrocarbon isomerization reaction after the crushing is finished, the catalytic reforming reaction product enters the fourth gas-liquid separator 52 for gas-liquid separation, the hydrogen-rich gas separated by the fourth gas-liquid separator 52 enters the hydrogen circulation system, the third liquid phase material separated by the fourth gas-liquid separator 52 enters the aromatic hydrocarbon extraction tower 53, and the light aromatic hydrocarbon product and the raffinate oil byproduct are obtained after the solvent extraction.
The specific method and effect of the system of the present invention will be further described with reference to fig. 1.
A method for directly hydrogenating and liquefying coal to produce aromatic hydrocarbons in rich yield comprises the following steps:
preparing raw material coal into coal oil slurry, preheating, conveying the coal oil slurry to a hydrogenation liquefaction unit after preheating is finished, and meanwhile conveying hydrogen to the interior of a corresponding micro-interface generator;
the micro-interface generator is used for smashing hydrogen into micron-sized bubbles, the micro-interface generator is used for conveying the micron-sized bubbles to the liquefaction reaction unit after smashing is completed, so that the micron-sized bubbles and the coal oil slurry are mixed to form a gas-liquid emulsion, and the liquefaction reaction is performed after mixing is completed;
and (3) liquefaction reaction: carrying out deep liquefaction reaction on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a first gas-phase material and a first liquid-phase material, heating the first liquid-phase material and then distilling at normal pressure to obtain a light-phase oil product and a heavy-phase oil product, and carrying out reduced pressure distillation on the heavy-phase oil product to obtain a distillate oil and solid-containing oil residues;
heating the light-phase oil product and the distillate oil, then conveying the heated light-phase oil product and the distillate oil to the corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion of the light-phase oil product, the distillate oil and the hydrogen received by the micro-interface generator, crushing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles with the light-phase oil product and the distillate oil by the micro-interface generator to form a gas-liquid emulsion after the crushing is finished, and conveying the formed gas-liquid emulsion to an upgrading unit after the mixing is finished;
hydrogenation upgrading: carrying out hydrogenation upgrading on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a second gas-phase material and a second liquid-phase material; wherein the second liquid phase material comprises a light oil fraction, a diesel oil fraction and a heavy oil;
heating the light oil fraction, conveying the heated light oil fraction to the inside of a corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion between the light oil fraction and the hydrogen received by the micro-interface generator, smashing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles and the light oil fraction by the micro-interface generator to form a gas-liquid emulsion after smashing, and conveying the formed gas-liquid emulsion to a catalytic reforming unit after mixing;
catalytic reforming: carrying out catalytic reforming on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a third gas-phase material and a third liquid-phase material; and extracting the third liquid phase material by a solvent to obtain a light aromatic hydrocarbon product and raffinate oil.
Preferably, the temperature of the hydrogenation liquefaction reaction is 400-460 ℃, the reaction pressure is 5-15MPa, the gas-liquid ratio is 600-1200, and the air speed of the oil-coal slurry is as follows: 0.5-4.0h-1。
Preferably, the reaction temperature of hydrogenation upgrading is 300-380 ℃ for reactionThe pressure is 2-15MPa, the gas-liquid ratio is 500-1200, and the space velocity is 0.5-3.5h-1。
Preferably, the catalytic reforming reaction pressure is 0.2-1MPa, the reaction temperature is 450-530 ℃, and the liquid volume space velocity is 1-3.0h-1The gas-liquid ratio is 600-1200, the gas-liquid separation condition temperature is 20-40 ℃, and the pressure is 1.0-1.8 MPa.
Specifically, hydrocracking the diesel fraction to obtain a fourth gas-phase material and a fourth liquid-phase material; and the fourth liquid-phase material is subjected to hydrogenation upgrading and distillation separation.
In order to further verify the processing method provided by the invention, the beneficial effects of the invention are further illustrated by combining the embodiment and comparing the embodiment with the comparative example in which the micro-interface generator is not arranged in the system. Meanwhile, in the present embodiment, the kind of the catalyst is not particularly limited, and may be one or a combination of several of an iron-based catalyst, a molybdenum-based catalyst, a nickel-based catalyst, an aluminum-based catalyst, a silicon-based catalyst, a cobalt-based catalyst, and a tungsten-based catalyst, as long as the strengthening reaction can be smoothly performed.
Table 1 shows the main parameters of examples 1 to 3 and comparative examples 1 to 3, table 2 shows the liquefaction test results and naphtha property data of examples 1 to 3 and comparative examples 1 to 3, and table 3 shows the analysis results of the products after catalytic reforming of examples 1 to 3 and comparative examples 1 to 3.
TABLE 1
TABLE 2
| Case(s) | Example 1 | Comparative example 1 | Example 2 | Comparative example 2 | Example 3 | Comparative example 3 |
| Coal conversion (wt%, daf coal) | 94.78 | 93.56 | 96.65 | 94.23 | 98.23 | 95.64 |
| Naphtha yield | 35.56 | 24.68 | 38.23 | 27.53 | 42.68 | 28.56 |
| Density (20 deg.C), kg/m | 779.35 | 765.23 | 787.32 | 775.25 | 798.36 | 767.25 |
| Viscosity (20 ℃ C.), mm2/s | 0.79 | 0.82 | 1.12 | 0.81 | 0.78 | 0.87 |
| S,mg/kg | 1.24 | 0.68 | 0.45 | 0.71 | 1.32 | 0.89 |
| N,mg/kg | 0.56 | 0.13 | 0.33 | .019 | 0.46 | 0.56 |
| Potential content of aromatic hydrocarbons,%) | 78.59 | 66.32 | 81.32 | 73.65 | 83.56 | 63.56 |
| IBP/5% | 65/88 | 69/86 | 72/89 | 75/86 | 74/96 | 65/86 |
| 10%/30% | 95/108 | 96/109 | 96/115 | 95/109 | 99/108 | 93/106 |
| 50%/70% | 114/130 | 115/132 | 114/130 | 115/130 | 115/137 | 110/128 |
| 90%/95% | 137/156 | 137/157 | 135/150 | 140/152 | 136/150 | 136/145 |
| FBP | 152 | 152 | 157 | 154 | 156 | 152 |
TABLE 3
| Example 1 | Comparative example 1 | Example 2 | Comparative example 2 | Example 3 | Comparative example 3 | |
| Liquid yield (C)5 +）/% | 97.52 | 86.54 | 98.64 | 88.53 | 98.43 | 86.75 |
| Aromatic hydrocarbon/wt% | 92.32 | 78.62 | 95.56 | 85.32 | 97.56 | 80.32 |
| Conversion of aromatics/%) | 116.54 | 102.35 | 120.32 | 110.32 | 125.23 | 115.36 |
| Benzene/wt.% | 12.11 | 6.89 | 15.35 | 10.56 | 17.32 | 11.68 |
| Toluene/wt.% | 20.64 | 13.56 | 24.12 | 15.23 | 27.55 | 16.23 |
| Xylene/wt.% | 20.56 | 19.65 | 22.56 | 20.35 | 24.14 | 20.36 |
| >C9 aromatics/wt.% | 32.70 | 41.78 | 36.35 | 44.23 | 38.26 | 42.98 |
As can be seen from the data in Table 2, compared with the process without a micro-interface generator in the system, the system and the method for directly liquefying coal to produce aromatics in a rich way provided by the invention have the advantages that under the same reaction conditions, the coal conversion rate is high, the obtained naphtha yield is high, the potential content of aromatics is high, the naphtha is an excellent catalytic reforming raw oil, and the purpose of producing aromatics in a rich way is achieved.
As can be seen from the data in Table 3, the product obtained by catalytic reforming of naphtha with high potential content of aromatic hydrocarbon obtained by the invention has high liquid yield, high aromatic hydrocarbon content and high aromatic hydrocarbon conversion rate under the same reaction conditions compared with the result obtained by catalytic reforming of naphtha, and the content of light aromatic hydrocarbon (BTX) in the liquid product is improved by 5-20%, so that the method has obvious economic benefit.
In view of the above, the invention provides a system and a method for direct coal hydrogenation liquefaction to produce aromatic hydrocarbons in a rich manner, and solves the problem that in the prior art, the preparation efficiency of the aromatic hydrocarbons is reduced because hydrogen cannot fully react with oil coal slurry.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A system for coal direct hydrogenation liquefaction rich aromatic hydrocarbon production is characterized by comprising:
the feeding unit is used for preparing the coal oil slurry and conveying the coal oil slurry and the hydrogen;
the liquefaction reaction unit is connected with the feeding unit and is used for carrying out hydrogenation liquefaction reaction on the coal oil slurry and the hydrogen, and carrying out gas-liquid separation on a hydrogenation liquefaction reaction product to obtain a first gas phase material, a light phase oil product, a distillate oil and solid-containing oil residue;
the upgrading unit is connected with the liquefaction reaction unit and is used for carrying out hydrogenation upgrading on the light-phase oil product, the distillate oil and the hydrogen, and carrying out gas-liquid separation on the hydrogenation upgrading product to obtain a second gas-phase material, a light-phase oil fraction, a diesel oil fraction and heavy oil;
the catalytic reforming unit is connected with the quality improving unit, and is used for mixing the light oil fraction with hydrogen, performing catalytic reforming and gas-liquid separation to obtain a third gas-phase material, a light aromatic hydrocarbon product and raffinate oil;
and the micro-interface generators are respectively arranged among the liquefaction reaction unit, the liquefaction reaction unit and the quality improving unit and between the quality improving unit and the catalytic reforming unit and are respectively used for crushing the hydrogen into micron-sized bubbles before liquefaction reaction, quality improvement and catalytic reforming so as to increase the phase boundary mass transfer area between the hydrogen and corresponding reactants in the processes of hydrogenation liquefaction reaction, hydrogenation quality improvement and hydrogenation catalytic reforming, reduce the thickness of a liquid film, reduce the mass transfer resistance and enhance the reaction efficiency.
2. The system for direct coal hydroliquefaction rich in aromatics of claim 1, wherein the micro-interface generator breaks hydrogen into micron-sized bubbles by converting pressure energy of gas and/or kinetic energy of liquid into bubble surface energy and transferring the energy to hydrogen bubbles.
3. The system for direct coal hydroliquefaction rich aromatic hydrocarbon production according to claim 2, wherein the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
4. The system for direct coal hydroliquefaction rich in aromatics of any one of claims 1-3, wherein the micron-sized bubbles are micron-sized bubbles with a diameter of 1 μm or more and less than 1 mm.
5. The system for direct coal hydroliquefaction rich in aromatics of claim 1, wherein the feed unit comprises:
the coal oil slurry preparation unit is used for preparing coal oil slurry;
a gas feed line for transporting hydrogen;
the first heating furnace is used for preheating the oil coal slurry;
and the high-pressure coal slurry pump is connected with the oil coal slurry preparation unit and the first heating furnace and is used for conveying the oil coal slurry to the interior of the first heating furnace.
6. A method for directly hydrogenating and liquefying coal to produce aromatic hydrocarbon in rich yield is characterized by comprising the following steps:
preparing raw material coal into coal oil slurry, preheating, conveying the coal oil slurry to a hydrogenation liquefaction unit after preheating is finished, and meanwhile conveying hydrogen to the interior of a corresponding micro-interface generator;
the micro-interface generator is used for crushing hydrogen into micron-sized bubbles, conveying the micron-sized bubbles to a liquefaction reaction unit after the micro-interface generator finishes crushing, mixing the micron-sized bubbles with the coal oil slurry to form a gas-liquid emulsion, and carrying out liquefaction reaction after the mixing is finished;
and (3) liquefaction reaction: carrying out deep liquefaction reaction on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a first gas-phase material and a first liquid-phase material, heating the first liquid-phase material and then distilling at normal pressure to obtain a light-phase oil product and a heavy-phase oil product, and carrying out reduced pressure distillation on the heavy-phase oil product to obtain a distillate oil and solid-containing oil residues;
heating the light-phase oil product and the distillate oil, then conveying the heated light-phase oil product and the distillate oil to the corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion of the light-phase oil product, the distillate oil and the hydrogen received by the micro-interface generator, crushing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles with the light-phase oil product and the distillate oil by the micro-interface generator to form a gas-liquid emulsion after the crushing is finished, and conveying the formed gas-liquid emulsion to an upgrading unit after the mixing is finished;
hydrogenation upgrading: carrying out hydrogenation upgrading on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a second gas-phase material and a second liquid-phase material; wherein the second liquid phase material comprises a light oil fraction, a diesel oil fraction and a heavy oil;
heating the light oil fraction, conveying the heated light oil fraction to the inside of a corresponding micro-interface generator, meanwhile conveying hydrogen to the inside of the micro-interface generator, controlling the proportion between the light oil fraction and the hydrogen received by the micro-interface generator, smashing the hydrogen into micron-sized bubbles, mixing the micron-sized bubbles and the light oil fraction by the micro-interface generator to form a gas-liquid emulsion after smashing, and conveying the formed gas-liquid emulsion to a catalytic reforming unit after mixing;
catalytic reforming: carrying out catalytic reforming on the gas-liquid emulsion and carrying out gas-liquid separation to obtain a third gas-phase material and a third liquid-phase material; and extracting the third liquid phase material by a solvent to obtain a light aromatic hydrocarbon product and raffinate oil.
7. The method as claimed in claim 6, wherein the temperature of the hydrogenation liquefaction reaction is 400-460 ℃, and the reaction pressure is 5-15 MPa.
8. The method for direct coal hydrogenation liquefaction of aromatics rich in yield as claimed in claim 6, wherein the hydrogenation upgrading reaction temperature is 300-380 ℃ and the reaction pressure is 2-15 MPa.
9. The method as claimed in claim 6, wherein the pressure of the catalytic reforming reaction is 0.2-1MPa, and the reaction temperature is 450-530 ℃.
10. The method for directly hydroliquefying coal to enrich aromatic hydrocarbons according to claim 6, wherein the diesel fraction is hydrocracked to obtain a fourth gas phase material and a fourth liquid phase material; and the fourth liquid-phase material is subjected to hydrogenation upgrading and distillation separation.
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