CN112175656A - Suspension bed enhanced reaction system and method for direct coal liquefaction - Google Patents
Suspension bed enhanced reaction system and method for direct coal liquefaction Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 81
- 239000000725 suspension Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000001257 hydrogen Substances 0.000 claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 80
- 239000003250 coal slurry Substances 0.000 claims abstract description 51
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 42
- 238000012546 transfer Methods 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 56
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- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention provides a suspension bed enhanced reaction system and a method for direct coal liquefaction, which comprises the following steps: the feeding unit is used for preparing coal slurry and conveying the coal slurry and hydrogen; a liquefaction reaction unit connected to the feed unit; a catalytic hydrogenation unit connected to the liquefaction reaction unit; the micro-interface generator is respectively arranged between the liquefaction reaction unit and the catalytic hydrogenation unit, and is used for crushing hydrogen into micron-sized bubbles before the liquefaction reaction and the catalytic hydrogenation so as to increase the mass transfer area of a phase boundary between the hydrogen and a corresponding reactant in the processes of the liquefaction reaction and the catalytic hydrogenation and enhance the reaction efficiency.
Description
Technical Field
The invention relates to the technical field of direct coal liquefaction, in particular to a suspension bed enhanced reaction system and method for direct coal liquefaction.
Background
The direct coal liquefaction technology has been studied as early as the 19 th century. In 1914, the German chemist Curgis studied the liquefaction of coal under hydrogen pressure, and in the same year, together with Bilviller, patented the test. In 1926, the german law company developed a high-efficiency hydrogenation catalyst, and built a plant for preparing liquid fuel from lignite through high-pressure hydrogenation liquefaction by using the bages method. Before world war II, Germany produces liquid fuel from coal and low-temperature carbonization coal tar, which reaches the annual production level of 1.5Mt in 1938, and the total production capacity reaches 4Mt in the later period of world war II; in 1935 England chemical industry, Bilingham, England, also established a hydrogenation plant for producing liquid fuels from coal and coal tar, 150kt annually. In addition, some laboratories have been built in japan, france, canada, and the united states. After a war, due to the decrease of the price of the petroleum, the coal liquefaction product cannot compete with the natural petroleum economically, and the coal liquefaction product is closed in sequence, even the experimental device stops the test. In the early 60 s, especially in 1973, after the price of petroleum was greatly increased, the direct coal liquefaction work was also regarded and a new series of processes such as solvent refining coal method, exxon hydrogen supply solvent method, hydrogen coal method and the like in the U.S. were developed.
Axens North American Limited had a long history of development and demonstration of direct coal liquefaction technology, originating in the last 60 th century. The development of the direct coal liquefaction technology is based on the industrial hydrogen-oil process and proves that the suspended bed reactor technology has remarkable universality. These technologies, including hydrogen-oil processes, CTSL (two-stage catalytic liquefaction), and coal/oil hybrid processing, are the leading positions of coal liquefaction technology in the world today.
However, in the reaction process of directly liquefying coal using a suspension bed reactor, hydrogen gas does not sufficiently react with coal slurry, thereby reducing reaction efficiency.
Disclosure of Invention
In view of the above, the invention provides a suspension bed enhanced reaction system and method for direct coal liquefaction, and aims to solve the problem of low reaction efficiency in the direct coal liquefaction process due to the fact that hydrogen cannot fully react with coal slurry in the prior art.
In one aspect, the present invention provides a suspension bed enhanced reaction system for direct coal liquefaction, comprising:
the feeding unit is used for preparing coal slurry and conveying the coal slurry and hydrogen;
the liquefaction reaction unit is connected with the feeding unit and is used for carrying out liquefaction reaction on the coal slurry and the hydrogen, and separating and rectifying a liquefaction reaction product to obtain a light fraction, distillate oil and hydrogen;
the catalytic hydrogenation unit is connected with the liquefaction reaction unit and is used for carrying out catalytic hydrogenation reaction on the light fraction, the distillate oil and the hydrogen to finally obtain a hydrogen-donating solvent and product oil;
and the micro-interface generators are respectively arranged between the liquefaction reaction unit and the catalytic hydrogenation unit and are respectively used for crushing the hydrogen into micron-sized bubbles before the liquefaction reaction and the catalytic hydrogenation so as to increase the phase boundary mass transfer area between the hydrogen and the corresponding reactant in the liquefaction reaction and the catalytic hydrogenation processes, reduce the thickness of a liquid film, reduce the mass transfer resistance and enhance the reaction efficiency.
Further, in the suspension bed enhanced reaction system for direct coal liquefaction, 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-mentioned suspension bed enhanced reaction system for direct coal liquefaction, the liquefaction reaction unit includes: the system comprises a first suspended bed reactor, a high-temperature separator, a low-temperature separator, an atmospheric distillation tower and a vacuum distillation tower.
Further, in the suspension bed enhanced reaction system for direct coal liquefaction, the micro-interface generator of the liquefaction reaction unit is a first micro-interface generator, and the first micro-interface generator is arranged in the first suspension bed reactor.
Further, in the above-mentioned suspension bed enhanced reaction system for direct coal liquefaction, the catalytic hydrogenation unit includes: a second suspended bed reactor, a gas-liquid separator and a product fractionating tower.
Further, in the suspension bed enhanced reaction system for direct coal liquefaction, the micro-interface generator between the liquefaction reaction unit and the catalytic hydrogenation unit is a second micro-interface generator, and the second micro-interface generator is connected with an inlet of the second suspension bed reactor.
The suspension bed enhanced reaction system for direct coal liquefaction has the beneficial effects that the micro-interface generators are respectively arranged between the liquefaction reaction unit and the catalytic hydrogenation unit. 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 liquefaction reaction and the catalytic hydrogenation reaction so as to increase the phase boundary mass transfer area between the hydrogen and the corresponding reactant in the reaction process, reduce the thickness of a liquid film, reduce the mass transfer resistance and improve the mass transfer efficiency between reaction phases, thereby solving the problem of low reaction efficiency in the direct coal liquefaction process due to the fact that the hydrogen cannot fully react with coal slurry in the prior art. In addition, the range of the operation conditions 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 liquefaction reaction unit is provided with a high-temperature separation tower, a low-temperature separator, an atmospheric distillation tower and a reduced-pressure distillation tower, and can separate and distill the products of the liquefaction reaction to generate light fraction, distillate oil and hydrogen and simultaneously remove waste and solid residues from the system, so that the reaction efficiency of the system is improved, and the utilization efficiency of resources is increased.
On the other hand, the invention also provides a suspension bed enhanced reaction method for direct coal liquefaction, which comprises the following steps:
preparing raw material coal into coal slurry, feeding the coal slurry into a first suspension bed reactor, and introducing hydrogen into a first micro-interface generator;
the first micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, and conveying the micron-sized bubbles into the first suspension bed reactor to carry out liquefaction reaction with the coal slurry;
carrying out gas-liquid separation on the liquefied reaction product in a separator, wherein a liquid phase part forms a light fraction and a distillate oil through a rectifying tower, and the light fraction and the distillate oil are mixed and then are sent to the interior of the second micro-interface generator together with hydrogen;
the second micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, carrying out gas-liquid mixing on the micron-sized bubbles and the mixture of the light fraction and the distillate oil to form a gas-liquid emulsion, and conveying the emulsion into a second suspension bed reactor for catalytic hydrogenation reaction;
the catalytic hydrogenation product is separated into hydrogen-donating solvent and other product oil by a fractionating tower.
Further, in the above-mentioned suspension bed enhanced reaction method for direct coal liquefaction, the micro-interface generator converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of bubbles and transfers the surface energy to the hydrogen bubbles, so that the hydrogen is broken into micron-sized bubbles.
Further, in the suspension bed enhanced reaction method for direct coal liquefaction, the temperature of the liquefaction reaction is 400-460 ℃, and the pressure is 1-12 MPa.
Further, in the suspension bed enhanced reaction method for direct coal liquefaction, the temperature of the catalytic hydrogenation reaction is 320-380 ℃, and the pressure is 2-15 MPa.
Compared with the prior art, the suspension bed enhanced reaction method for direct coal liquefaction has the beneficial effects that hydrogen is crushed into micron-sized bubbles by the first micro-interface generator and the second micro-interface generator, so that the phase boundary mass transfer area between gas phase and liquid phase in the liquefaction reaction and the catalytic hydrogenation reaction is increased, and the problem of low reaction efficiency in the direct coal liquefaction process due to the fact that hydrogen cannot fully react with coal slurry in the prior art is solved.
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 suspension bed enhanced reaction system and a method for direct coal liquefaction provided by an embodiment of the present invention.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the invention are shown in the drawings, it should be understood that the invention can be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the accompanying figure 1 in conjunction with an embodiment.
Referring to fig. 1, a suspension bed enhanced reaction system for direct coal liquefaction according to an embodiment of the present invention includes: a feeding unit 1, a liquefaction reaction unit 3, a second micro-interface generator 22, a catalytic hydrogenation unit 4: the feeding unit 1 is used for preparing coal slurry and conveying the coal slurry and hydrogen; the liquefaction reaction unit 3 is used for carrying out liquefaction reaction on the coal slurry and the hydrogen, and separating and rectifying a liquefaction reaction product to obtain distillate oil and light fraction, and the liquefaction reaction unit 3 is respectively connected with the inlet ends of the feeding unit 1 and the second micro-interface generator 22. The inlet end of the second micro-interface generator 22 is further connected with the feeding unit 1, the outlet end is connected with the catalytic hydrogenation unit 4, and the second micro-interface generator is used for receiving the light fraction, the distillate oil, the hydrogen in the liquefied reaction product and the hydrogen conveyed by the feeding unit 1, crushing the hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 μm and less than 1mm, mixing the micron-sized bubbles with the light fraction and the distillate oil to form a gas-liquid emulsion after the crushing is completed, and conveying the gas-liquid emulsion to the catalytic hydrogenation unit 4. And the catalytic hydrogenation unit 4 is used for carrying out catalytic hydrogenation reaction on the gas-liquid emulsion, and separating and rectifying a product of the gas-liquid emulsion to finally generate a hydrogen-donating solvent and product oil 8.
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 1 includes: a hydrogen feeding pipeline 11, a coal pretreatment device 12, a catalyst preparation device 13, a coal slurry preparation device 14 and a coal slurry pump 15. One end of the hydrogen feeding pipeline 11 is externally connected with a hydrogen source, and the other end of the hydrogen feeding pipeline is respectively connected with the first micro-interface generator 21, the liquefaction reaction unit 3, the second micro-interface generator 22 and the catalytic hydrogenation unit 4 and used for transporting hydrogen; the coal pre-processor is connected with the inlet end of the coal slurry preparation device 14 and is used for preparing raw material coal powder; the catalyst preparation device 13 is connected with the inlet end of the coal slurry preparation device 14 and is used for preparing catalyst raw materials into ultrafine-particle catalyst powder; the outlet end of the coal slurry preparation device 14 is connected with the inlet of the coal slurry pump 15 and is used for receiving the raw material coal powder and the catalyst powder, and injecting a hydrogen-supplying solvent into the coal slurry preparation device 14, and mixing the raw material coal powder, the catalyst powder and the hydrogen-supplying solvent to form coal slurry; the outlet end of the coal slurry pump 15 is connected with the liquefaction reaction unit 3, and is used for conveying the coal slurry prepared by the coal slurry preparation device 14 to the liquefaction reaction unit 3 for liquefaction reaction.
When the system is in operation, the liquefied raw coal is dried and pulverized by the coal pretreatment device 12 to produce pulverized coal of a certain particle size. The catalyst raw material is made into the catalyst of ultrafine particles by the catalyst preparation device 13. The coal powder and the catalyst are mixed with a hydrogen-donating solvent in the coal slurry preparation device 14 to prepare coal slurry, the coal slurry enters the liquefaction reaction unit 3 after being prepared, and meanwhile, the hydrogen conveying pipeline conveys hydrogen to the first micro-interface generator 21.
With continued reference to fig. 1, the liquefaction reaction unit 3 includes a first suspended bed reactor 31, a high temperature separator 32, a low temperature separator 33, an atmospheric distillation column 34, and a vacuum distillation column 35. The first micro-interface generator 21 is positioned inside the first suspended bed reactor 31, is connected with the hydrogen feeding pipeline 11, and is used for crushing hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 μm and less than 1mm and conveying the micron-sized bubbles into the first suspended bed reactor 31; the inlet end of the first suspension bed reactor 31 is respectively connected with the coal slurry pump 15 and the catalytic hydrogenation unit 4, and the outlet end of the first suspension bed reactor 31 is connected with the inlet of the high-temperature separator 32, and is used for receiving coal slurry and hydrogen micron-sized bubbles and serving as a reaction chamber for liquefaction reaction of the coal slurry and the hydrogen micron-sized bubbles; the outlet end of the high-temperature separator 32 is connected with the inlet ends of the low-temperature separator 33 and the normal-pressure rectifying tower 34 respectively, and is used for performing gas-liquid separation on the liquefied reaction product to obtain a gas-phase product which enters the low-temperature separator 33 and a liquid-phase product which enters the normal-pressure rectifying tower 34; the outlet end of the low-temperature separation tower is respectively connected with a hydrogen feeding pipeline 11 and an atmospheric distillation tower 34 and is used for receiving the gas-phase product separated from the high-temperature separator 32 and further carrying out gas-liquid separation on the gas-phase product, the generated gas-phase product enters the hydrogen feeding pipeline 11 to be mixed with hydrogen for recycling, part of the waste gas 5 is discharged from the system, and the generated liquid-phase product enters the atmospheric distillation tower; the outlet end of the atmospheric fractionating tower is respectively connected with the second micro-interface separator and the vacuum rectification tower 35, and is used for fractionating the liquid-phase products generated by the high-temperature separator 32 and the low-temperature separator 33 to obtain light fractions, the light fractions enter the second micro-interface generator 22, and the tower bottom materials enter the vacuum rectification tower 35; the outlet end of the reduced pressure rectifying tower 35 is connected with the inlet end of the second micro-interface generator 22 and is used for removing asphalt and solid from the tower bottom material generated by the atmospheric pressure rectifying tower 34 to obtain distillate oil which enters the second micro-interface generator 22 and the liquefied residue 6 removal system.
Hydrogen enters the first micro-interface generator 21, is crushed into micron-sized bubbles, enters the first suspended bed reactor 31, and is subjected to a liquefaction reaction with coal slurry entering the first suspended bed reactor 31, a liquefaction reaction product generated by the first suspended bed reactor 31 enters the high-temperature separator 32 for gas-liquid separation, a gas-phase product obtained by the separation of the high-temperature separator 32 enters the low-temperature separator 33 for further gas-liquid separation, the gas-phase product obtained by the low-temperature separator 33 is mixed with the hydrogen for recycling, and 5 parts of waste gas are discharged out of the system. Liquid phase products of the high-temperature separator 32 and the low-temperature separator 33 enter the atmospheric distillation tower 34 to separate light fractions, tower bottom materials of the atmospheric distillation tower 34 enter the vacuum distillation tower 35 to remove asphalt and solids, the tower bottom materials of the vacuum distillation tower 35 are liquefaction residues 6, and the liquefaction residues 6 are discharged out of the system. In order to ensure that the residue can be removed smoothly at a certain temperature, the solids content of the residue is generally controlled to 50-55 wt.%. The light fractions and the distillate oil generated in the atmospheric pressure rectifying tower 34 and the vacuum rectifying tower 35 enter the inside of the second micro-interface generator 22, and the hydrogen gas is supplied to the inside of the second micro-interface generator 22 through the hydrogen gas supply line 11.
With continued reference to FIG. 1, the catalytic hydrogenation unit 4 includes: a second suspended bed reactor 41, a gas-liquid separator 42, and a product fractionating tower 43. Wherein the inlet end of the second suspended bed reactor 41 is connected with the outlet end of the second micro interface generator 22, and the outlet end thereof is connected with the inlet end of the gas-liquid separator 42, and is used for receiving the gas-liquid emulsion generated by the second micro interface generator 22 and taking the gas-liquid emulsion as a catalytic hydrogenation reaction chamber of the gas-liquid emulsion; the outlet end of the gas-liquid separator 42 is respectively connected with the product fractionating tower 43 and the hydrogen feeding pipeline 11, and is used for performing gas-liquid separation on the catalytic hydrogenation product, the obtained gas-phase product and hydrogen are mixed and recycled, the waste part is removed from the system, and the obtained liquid-phase product enters the product fractionating tower 43; the product fractionating tower 43 is further connected to the first suspended bed reactor 31, and is configured to fractionate the liquid-phase product produced by the gas-liquid separator 42 to obtain the product oil 8 and the circulating solvent 7, and the circulating solvent 7 is circulated to the first suspended bed reactor 31 to perform the secondary liquefaction reaction.
The second micro-interface generator 22 crushes the hydrogen into micron-sized bubbles and mixes the micron-sized bubbles with the light fraction and the distillate oil to form a gas-liquid emulsion, the gas-liquid emulsion is conveyed to the inside of the second suspended bed reactor 41, the second suspended bed reactor 41 is subjected to catalytic hydrogenation for the purpose of improving the hydrogen supply performance of the gas-liquid emulsion, the outlet material of the second suspended bed reactor 41 enters the gas-liquid separator 42 for gas-liquid separation, the gas-phase product generated by the gas-liquid separator 42 is mixed with the hydrogen for recycling, and 5 parts of the waste gas are discharged out of the system. The liquid phase material produced by the gas-liquid separator 42 enters a product fractionating tower 43, and the product oil 8 and the circulating solvent 7 are fractionated. Wherein the circulating solvent 7 is circulated to the first suspension bed reactor 31 for the second liquefaction reaction. The product oil 8 is all gasoline and diesel oil fractions.
According to the suspension bed enhanced reaction system for direct coal liquefaction, the first micro-interface generator 21 is arranged in the first suspension bed reactor 31, the second micro-interface generator 22 is arranged at the inlet end of the second suspension bed reactor 41, hydrogen is broken into micron-sized bubbles in the corresponding micro-interface generator before liquefaction reaction and catalytic hydrogenation reaction, the phase boundary mass transfer area between reactants such as hydrogen and coal slurry in the reaction process is effectively increased, the thickness of a liquid film is reduced, the mass transfer resistance is reduced, the mass transfer efficiency between reaction phases is improved, and the problem of low reaction efficiency in the direct coal liquefaction process due to the fact that hydrogen cannot fully react with the coal slurry in the prior art is solved.
The specific method and effect of the system of the present invention will be further described with reference to fig. 1.
A suspension bed enhanced reaction method for direct coal liquefaction comprises the following steps:
preparing raw material coal into coal slurry, feeding the coal slurry into a first suspension bed reactor, and introducing hydrogen into a first micro-interface generator;
the first micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, and conveying the micron-sized bubbles into the first suspension bed reactor to carry out liquefaction reaction with the coal slurry;
carrying out gas-liquid separation on the liquefied reaction product in a separator, wherein a liquid phase part forms a light fraction and a distillate oil through a rectifying tower, and the light fraction and the distillate oil are mixed and then are sent to the interior of the second micro-interface generator together with hydrogen;
the second micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, carrying out gas-liquid mixing on the micron-sized bubbles and the mixture of the light fraction and the distillate oil to form a gas-liquid emulsion, and conveying the emulsion into a second suspension bed reactor for catalytic hydrogenation reaction;
the catalytic hydrogenation product is separated into hydrogen-donating solvent and other product oil by a fractionating tower. Wherein the reaction temperature of the liquefaction reaction is 400-460 ℃, and the pressure is 1-12 MPa. The temperature of the catalytic hydrogenation reaction is 320-380 ℃ and the pressure is 2-15 MPa. It can be understood that the range of the operation conditions can be flexibly adjusted according to different raw material compositions, different product requirements or different catalysts, so as to ensure the full and effective reaction, further ensure the reaction rate and achieve the purpose of strengthening the reaction. 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, a cobalt-based catalyst, and a tungsten-based catalyst, as long as the strengthening reaction can be smoothly performed.
In order to further verify the processing method provided by the invention, the beneficial effects of the invention are further illustrated by combining the examples and the comparative examples.
The following is the liquefaction result of direct liquefaction of an enhanced coal under three different reaction conditions using the preferred embodiment of the present invention.
The first embodiment is as follows:
the reactor temperature: the first suspension bed reactor is 400 ℃, and the second suspension bed reactor is 320 ℃.
Reaction pressure: the first suspension bed reactor is 1MPa, and the second suspension bed reactor is 2 MPa.
Coal slurry concentration: 40/50 (dry coal/solvent, mass ratio).
The addition amount of the catalyst is as follows: liquefaction catalysis aid: 1.0wt% (iron/dry coal).
The addition amount of sulfur: S/Fe =2 (molar ratio).
Gas-liquid ratio: 400 coal slurry.
In this example, the conversion of coal was 80.57%, the oil yield in the product was 50.24%, and the hydrogen consumption was 8.36%.
Comparative example one:
comparative experiments on direct coal liquefaction were conducted using the prior art using the reaction conditions described in example one.
In this example, the conversion of coal was 75.36%, the oil yield in the product was 43.56%, and the hydrogen consumption was 8.54%.
Example two:
the reactor temperature: the first suspension bed reactor is 430 ℃ and the second suspension bed reactor is 350 ℃.
Reaction pressure: the first suspension bed reactor is 6MPa, and the second suspension bed reactor is 8 MPa.
Coal slurry concentration: 40/50 (dry coal/solvent, mass ratio).
The addition amount of the catalyst is as follows: liquefaction catalysis aid: 1.0wt% (iron/dry coal).
The addition amount of sulfur: S/Fe =2 (molar ratio).
Gas-liquid ratio: 600 coal slurry.
In this example, the conversion of coal was 85.46%, the oil yield in the product was 55.98%, and the hydrogen consumption was 7.32%.
Comparative example two:
comparative experiments on direct coal liquefaction were conducted using the prior art using the reaction conditions described in example two.
In this example, the conversion of coal was 80.25%, the oil yield in the product was 48.36%, and the hydrogen consumption was 7.56%.
Example three:
the reactor temperature: the first suspension bed reactor is 460 ℃ and the second suspension bed reactor is 380 ℃.
Reaction pressure: the first suspended bed reactor is 12MPa, and the second suspended bed reactor is 15 MPa.
Coal slurry concentration: 40/50 (dry coal/solvent, mass ratio).
The addition amount of the catalyst is as follows: liquefaction catalysis aid: 1.0wt% (iron/dry coal).
The addition amount of sulfur: S/Fe =2 (molar ratio).
Gas-liquid ratio: 800 coal slurry.
In this example, the conversion of coal was 93.36%, the oil yield in the product was 60.79%, and the hydrogen consumption was 6.53%.
Comparative example three:
comparative experiments on direct coal liquefaction were conducted using the prior art using the reaction conditions described in example three.
In this example, the conversion of coal was 87.59%, the oil yield in the product was 52.36%, and the hydrogen consumption was 6.89%.
The data show that compared with the prior art, the suspension bed enhanced reaction system and the method for direct coal liquefaction provided by the invention have the advantages that under the same reaction conditions, the oil yield and the conversion rate of direct coal liquefaction are obviously increased, the hydrogen consumption is reduced, the utilization rate of energy sources is effectively improved, and the production cost is reduced.
In view of the above, the invention provides a suspension bed enhanced reaction system and method for direct coal liquefaction, which solve the problem of low reaction efficiency in the direct coal liquefaction process in the prior art because hydrogen cannot fully react with 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. It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (10)
1. A suspension bed enhanced reaction system for direct coal liquefaction is characterized by comprising:
the feeding unit is used for preparing coal slurry and conveying the coal slurry and hydrogen;
the liquefaction reaction unit is connected with the feeding unit and is used for carrying out liquefaction reaction on the coal slurry and the hydrogen, and separating and rectifying a liquefaction reaction product to obtain a light fraction, distillate oil and hydrogen;
the catalytic hydrogenation unit is connected with the liquefaction reaction unit and is used for carrying out catalytic hydrogenation reaction on the light fraction, the distillate oil and the hydrogen to finally obtain a hydrogen-donating solvent and product oil;
and the micro-interface generator is respectively arranged between the liquefaction reaction unit and the catalytic hydrogenation unit, and is respectively used for crushing the hydrogen into micron-sized bubbles before the liquefaction reaction and the catalytic hydrogenation so as to increase the phase boundary mass transfer area between the hydrogen and the corresponding reactant in the liquefaction reaction and the catalytic hydrogenation processes, reduce the thickness of a liquid film, reduce the mass transfer resistance and enhance the reaction efficiency.
2. The suspension bed enhanced reaction system for direct coal liquefaction according to claim 1, wherein the micro-bubbles are micro-bubbles with a diameter of 1 μm or more and less than 1 mm.
3. The suspension bed enhanced reaction system for direct coal liquefaction according to claim 1, wherein the liquefaction reaction unit comprises: the system comprises a first suspended bed reactor, a high-temperature separator, a low-temperature separator, an atmospheric distillation tower and a vacuum distillation tower.
4. The suspension bed enhanced reaction system for direct coal liquefaction according to claim 1, wherein the micro-interface generator of the liquefaction reaction unit is a first micro-interface generator, and the first micro-interface generator is arranged inside the first suspension bed reactor.
5. The suspended bed enhanced reaction system for direct coal liquefaction according to claim 1, wherein the catalytic hydrogenation unit comprises: a second suspended bed reactor, a gas-liquid separator and a product fractionating tower.
6. The suspension bed enhanced reaction system for direct coal liquefaction according to claim 1, wherein the micro-interface generator between the liquefaction reaction unit and the catalytic hydrogenation unit is a second micro-interface generator, and the second micro-interface generator is connected with an inlet of the second suspension bed reactor.
7. A suspension bed enhanced reaction method for direct coal liquefaction is characterized by comprising the following steps:
preparing raw material coal into coal slurry, feeding the coal slurry into a first suspension bed reactor, and introducing hydrogen into a first micro-interface generator;
the first micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, and conveying the micron-sized bubbles into the first suspension bed reactor to carry out liquefaction reaction with the coal slurry;
carrying out gas-liquid separation on the liquefied reaction product in a separator, wherein a liquid phase part forms a light fraction and a distillate oil through a rectifying tower, and the light fraction and the distillate oil are mixed and then are sent to the interior of the second micro-interface generator together with hydrogen;
the second micro-interface generator is used for crushing the hydrogen into micron-sized bubbles with micron scale, carrying out gas-liquid mixing on the micron-sized bubbles and the mixture of the light fraction and the distillate oil to form a gas-liquid emulsion, and conveying the emulsion into a second suspension bed reactor for catalytic hydrogenation reaction;
the catalytic hydrogenation product is separated into hydrogen-donating solvent and other product oil by a fractionating tower.
8. The suspension bed enhanced reaction method for direct coal liquefaction according to claim 7, wherein the micro-interface generator breaks the hydrogen into micro-sized bubbles by converting pressure energy of gas and/or kinetic energy of liquid into bubble surface energy and transferring the energy to the hydrogen bubbles.
9. The method as claimed in claim 7, wherein the liquefaction reaction temperature is 400-460 ℃ and the pressure is 1-12 MPa.
10. The suspension bed enhanced reaction method for direct coal liquefaction as claimed in claim 7, wherein the temperature of the catalytic hydrogenation reaction is 320-380 ℃ and the pressure is 2-15 MPa.
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