CN113046129B - Energy-saving kerosene co-refining method and device - Google Patents
Energy-saving kerosene co-refining method and device Download PDFInfo
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- CN113046129B CN113046129B CN202110301684.9A CN202110301684A CN113046129B CN 113046129 B CN113046129 B CN 113046129B CN 202110301684 A CN202110301684 A CN 202110301684A CN 113046129 B CN113046129 B CN 113046129B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
Abstract
The invention relates to the technical field of coal and heavy oil co-processing methods and devices, in particular to a kerosene energy-saving co-refining method and a device, wherein the kerosene energy-saving co-refining device comprises a dry distillation unit, a heavy oil pyrolysis unit, a suspension bed hydrogenation unit, a secondary hydrogenation unit and the like. According to the energy-saving kerosene co-refining method and the device, the high-temperature coal powder is used as a raw material for subsequent hydrogenation and also used as a high-activity metal catalyst carrier for cracking the heavy oil, so that the heavy oil and the high-activity metal catalyst are in full contact reaction, the heavy oil is cracked in a heavy oil pyrolysis unit, the heavy oil and the coal powder are completely fused into the kerosene slurry, the problem of poor intersolubility of the kerosene is thoroughly solved, the coal and the oil are fused to form the kerosene slurry, the activity of the high-activity metal catalyst is greatly reduced, the kerosene slurry obtained by subsequent separation is in a suspension bed hydrogenation reactor and is beneficial to catalytic liquefaction of the coal under the condition of high hydrogen partial pressure and internal and external catalysis of an iron catalyst, and the aim of hydrogenation co-refining is fulfilled.
Description
Technical Field
The invention relates to the technical field of coal and heavy oil co-processing methods and devices, in particular to a kerosene energy-saving co-refining method and device.
Background
The kerosene co-refining aims to realize the coordination effect of oil and coal, and two problems are solved by realizing coordination corresponding to the key point, namely the problem of the solubility of the coal and the oil, so that the oil and the coal are integrated and mutually fused. Secondly, the problem of co-catalysis of the catalyst is solved, at present, heavy oil cracking mostly adopts a high-activity noble metal catalyst, coal liquefaction mostly adopts an iron-based catalyst, the high-activity noble metal catalyst is not ideal for the catalyst of coal, however, the co-refining effect of catalytic slurry oil and coal is good, so that the activity of the catalyst of heavy oil residue (namely the high-activity noble metal catalyst) is reduced, the coal and the oil are integrated, and the purpose of co-refining the kerosene can be realized.
Disclosure of Invention
The invention provides a kerosene energy-saving co-refining method and a device, which overcome the defects of the prior art and can effectively solve the problem that the existing kerosene co-refining technology has poor kerosene intersolubility in the process of kerosene co-refining; the coal and oil catalysts have large activity difference and cannot realize catalytic complementation; the continuous complementarity of each unit is poor, and the heat energy can not be fully utilized.
One of the technical schemes of the invention is realized by the following measures: an energy-saving co-refining method for kerosene comprises the following steps:
mixing an iron catalyst and coal powder, and then entering a dry distillation unit for dry distillation, wherein the dry distillation temperature is 500-600 ℃, volatile components and tar of the coal powder subjected to dry distillation are distilled, so that the coal powder is changed into high-temperature coal powder with a porous structure, a high-activity metal catalyst is mixed with heavy oil to obtain heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is contacted with the heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is used as a catalyst carrier for cracking the heavy oil, the high-activity metal catalyst is loaded on the surface and inside of the high-temperature coal powder, the heavy oil is subjected to cracking reaction under the action of the high-activity metal catalyst on the surface and inside of the high-temperature coal powder in a heavy oil pyrolysis unit, light components of the heavy oil are distilled, and the heavy components of the heavy oil and the coal powder are completely fused into oil coal slurry;
mixing hydrogen bubble droplets with the oil coal slurry, then feeding the mixture into a suspension bed hydrogenation unit, carrying out hydrogenation co-refining on the oil coal slurry under the action of an iron catalyst in a high hydrogen partial pressure environment in the suspension bed hydrogenation unit, separating a product of the hydrogenation co-refining to obtain a gas phase component, a liquid phase component and residues, hydrogenating the liquid phase component through a secondary hydrogenation unit, separating a secondary hydrogenation product to obtain a secondary hydrogenation light component and a secondary hydrogenation heavy component, wherein the secondary hydrogenation heavy component is a circulating solvent with the fraction temperature of 270-450 ℃;
after heat exchange and temperature rise of a circulating solvent with the fraction temperature of 270-450 ℃ and high-temperature synthesis gas, atomizing and mixing the circulating solvent with hydrogen to form hydrogen bubble fog drops, mixing the hydrogen bubble fog drops with the coal oil slurry, then feeding the mixture into a suspension bed hydrogenation unit, and in the suspension bed hydrogenation unit, carrying out hydrogenation co-refining on the coal oil slurry under the high-hydrogen partial pressure environment and the action of an iron catalyst;
the high-temperature synthesis gas subjected to primary temperature reduction by the circulating solvent provides a loosening power source and a reaction heat source for the oil pyrolysis reactor in the heavy oil pyrolysis unit, meanwhile, a heat source is provided for the dry distillation tower in the dry distillation unit, and raw coke oven gas generated after pulverized coal dry distillation and the high-temperature synthesis gas subjected to secondary temperature reduction by the dry distillation unit and the heavy oil pyrolysis unit are also used as heat sources of the fractionation device for the light components of the dry distillation unit and the light components of the heavy oil pyrolysis unit.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the synthetic gas or dry gas obtained by fractionation of the fractionation device corresponding to the dry distillation unit and the heavy oil pyrolysis unit is sent to the hydrogen production unit to produce hydrogen, the hydrogen produced by the hydrogen production unit is divided into two paths, one path is atomized and mixed with the circulating solvent to form hydrogen bubble fog drops, and the other path is sent to the secondary hydrogenation unit to hydrogenate.
And gasifying the residue, coal slurry and oxygen obtained by separating the hydrogenation co-refining product through a gasification unit to generate high-temperature synthesis gas.
The second technical scheme of the invention is realized by the following measures: the device for implementing the energy-saving kerosene co-refining method comprises a gasification unit, a dry distillation unit, a heavy oil pyrolysis unit, a suspended bed hydrogenation unit, a secondary hydrogenation unit, a fractionation unit and a preheater, wherein the gasification unit adopts a gasification furnace, the dry distillation unit adopts a dry distillation reactor, the heavy oil pyrolysis unit adopts a heavy oil pyrolysis reactor, the suspended bed hydrogenation unit adopts a suspended bed hydrogenation reactor, the secondary hydrogenation unit adopts a suspended bed hydrogenation reactor or a fixed bed hydrogenation reactor, and the fractionation unit comprises a normal-pressure fractionation tower, a first fractionation tower and a second fractionation tower; the high-temperature synthesis gas outlet of the gasification furnace is communicated with the first side inlet of the preheater, the first side outlet of the preheater is respectively communicated with a dry distillation reactor and a synthesis gas inlet end at the lower part of a heavy oil pyrolysis reactor, the upper part of the dry distillation reactor is provided with a coal powder inlet end, the high-temperature coal powder outlet end at the bottom of the dry distillation reactor is communicated with the high-temperature coal powder inlet end of the heavy oil pyrolysis reactor through a communicating pipe, the upper part of an atmospheric fractionating tower is provided with an oil inlet end for feeding heavy oil containing a high-activity metal catalyst, the top of the dry distillation reactor is communicated with the middle part of the atmospheric fractionating tower, the bottom of the atmospheric fractionating tower is communicated with the lower part of the heavy oil pyrolysis reactor, the top of the heavy oil pyrolysis reactor is communicated with the lower part of a first fractionating tower, the bottom of the first fractionating tower is communicated with the bottom of a suspension bed hydrogenation unit through an oil-coal slurry pipeline, a separation device is communicated between the suspension bed hydrogenation unit and a second hydrogenation unit, the top of the second preheater is communicated with the upper part of the second fractionating tower through a circulating solvent pipeline, and the second side outlet of the preheater is communicated with the oil-coal slurry pipeline through an atomization pipeline.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the dry distillation reactor comprises a cylinder body and a heat exchange body, wherein a driving mechanism is fixed at the top of the cylinder body, the heat exchange body comprises an upper tube plate and a lower tube plate, the upper tube plate and the lower tube plate are vertically and alternately sleeved in the cylinder body in a sealing manner, a coal powder inlet end is arranged at the position of the cylinder body above the upper tube plate, a dry distillation tube is fixedly communicated between the upper tube plate and the lower tube plate, main shaft holes are respectively arranged at the centers of the upper tube plate and the lower tube plate, main shafts are arranged in the main shaft holes of the upper tube plate and the lower tube plate through sliding keys, the power output end of the driving mechanism is connected with the top of the main shafts, bosses are respectively fixed at the inner walls of the cylinder body at the bottom of the upper tube plate and the lower tube plate at intervals along the circumference, and supporting slide blocks capable of sliding on the bosses are respectively fixed at the bottoms of the upper tube plate and the lower tube plate at intervals along the circumference; the cylinder corresponding to the lower tube plate is provided with a synthesis gas inlet end, the upper part of the shell pass between the upper tube plate and the lower tube plate is communicated with the lower part of the atmospheric fractionating tower, and the tube pass above the upper tube plate is communicated with the lower part of the atmospheric fractionating tower.
A spiral baffle is arranged in the cylinder corresponding to the shell pass of the cylinder; a distribution baffle is arranged in the barrel above the coal powder inlet end of the barrel; a supporting bearing is fixed in the cylinder body below the lower tube plate, and the bottom of the main shaft is arranged in the supporting bearing.
The boss is in a triangular shape with a wide left part and a narrow right part, the rear side face of the boss is fixed on the inner wall of the cylinder body, and the supporting slide block is in a trapezoidal shape with a narrow top and a wide bottom.
The synthesis gas inlet end of the barrel is communicated with the first side outlet of the preheater through a first synthesis gas pipe, the lower part of the heavy oil pyrolysis reactor is provided with at least one synthesis gas inlet end, the synthesis gas inlet end of the heavy oil pyrolysis reactor is communicated with the first synthesis gas pipe through a second synthesis gas pipe, more than two synthesis gas inlet ends are arranged at the left side and the right side of the communicating pipe at intervals, and the synthesis gas inlet end of the communicating pipe is communicated with the second synthesis gas pipe.
More than two material feeding throat pipes communicated with the bottom of the atmospheric tower are arranged at the lower part of the heavy oil pyrolysis reactor at intervals up and down.
Be provided with the injection atomizer on the above-mentioned atomizing pipeline, the injection atomizer includes atomizing injection cavity, hydrogen injector head and micropore blender, and in the hydrogen injector head stretched into the atomizing injection cavity from a left side and the right side, the export of atomizing injection cavity and micropore blender's import intercommunication, first fractionating tower bottom and micropore blender passed through the oil coal slurry pipeline intercommunication.
The above separation device. The separating device comprises a hot high-pressure separator, a cold high-pressure separator, a low-pressure separator and a pressure-reducing separator, the top of the suspension bed hydrogenation unit is communicated with the middle of the hot high-pressure separator, the light component outlet at the top of the hot high-pressure separator is communicated with the middle of the cold high-pressure separator, the bottom of the cold high-pressure separator is communicated with the middle of the low-pressure separator, the heavy component outlet at the bottom of the hot high-pressure separator is communicated with the middle of the pressure-reducing separator, the light component outlet of the pressure-reducing separator, the heavy component outlet of the low-pressure separator is communicated with the bottom of the secondary hydrogenation unit, and the heavy component outlet of the pressure-reducing separator is communicated with the gasification furnace.
The device also comprises a hydrogen production unit, wherein the hydrogen production unit adopts a hydrogen production pressure swing adsorption device, and the hydrogen outlet end of the hydrogen production unit is respectively communicated with the hydrogen inlet ends of the jet atomizer, the secondary hydrogenation unit and the cold high-pressure separator.
According to the energy-saving kerosene co-refining method and the device, the high-temperature coal powder is used as a raw material for subsequent hydrogenation and also used as a high-activity metal catalyst carrier for cracking the heavy oil, so that the heavy oil and the high-activity metal catalyst are in full contact reaction, the heavy oil is cracked in a heavy oil pyrolysis unit, the heavy oil and the coal powder are completely fused into the kerosene slurry, the problem of poor intersolubility of the kerosene is thoroughly solved, the coal and the oil are fused to form the kerosene slurry, the activity of the high-activity metal catalyst is greatly reduced, the kerosene slurry obtained by subsequent separation is in a suspension bed hydrogenation reactor and is beneficial to catalytic liquefaction of the coal under the condition of high hydrogen partial pressure and internal and external catalysis of an iron catalyst, and the aim of hydrogenation co-refining is fulfilled.
Drawings
FIG. 1 is a schematic general flow chart of example 4 of the present invention.
FIG. 2 is a schematic flow diagram of a dry distillation unit and a heavy oil pyrolysis unit.
Fig. 3 is an enlarged schematic view of the spray atomizer.
FIG. 4 is an enlarged top view of the upper tube plate of the retort unit.
Fig. 5 is a schematic view of the boss in a main view.
FIG. 6 is an enlarged top view of the boss.
Fig. 7 is a main view enlarged structure diagram of the supporting slide block.
Fig. 8 is an enlarged top view of the supporting slider.
FIG. 9 is a schematic view of the enlarged structure of the material feeding throat.
FIG. 10 is an enlarged top view of the boss mounted on the barrel.
The codes in the figures are respectively: the system comprises a dry distillation reactor 1, a heavy oil pyrolysis reactor 2, a suspended bed hydrogenation reactor 3, a secondary hydrogenation unit 4, a preheater 5, an atmospheric pressure fractionating tower 6, a first fractionating tower 7, a second fractionating tower 8, a communicating pipe 9, a coal slurry pipeline 10, a circulating solvent pipeline 11, an atomization pipeline 12, a stripping tower 13, a cylinder 14, a driving mechanism 15, an upper tube plate 16, a lower tube plate 17, a dry distillation tube 18, a main shaft hole 19, a sliding key 20, a main shaft 21, a boss 22, a support slider 23, a spiral baffle 24, a distribution baffle 25, a support bearing 26, a first synthesis gas tube 27, a second synthesis gas tube 28, a material feeding throat 29, an injection atomizer 30, an atomization injection cavity 31, a hydrogen injection head 32, a micropore mixer 33, a hot high-pressure separator 34, a cold high-pressure separator 35, a low-pressure separator 36, a hydrogen production separator 37, a hydrogen production unit 38, a catalyst preparation tank 39, a coal slurry drying tank 40, a coal slurry feeding machine 44, a hydrogen feeding machine 46 and a gasification furnace 46.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention.
In the present invention, for convenience of description, the description of the relative position relationship of the components is described according to the layout mode of the attached drawing 1 in the specification, such as: the positional relationship of front, rear, upper, lower, left, right, etc. is determined in accordance with the layout direction of fig. 1 of the specification.
The high-activity metal catalyst is a heavy oil catalyst, and can adopt a high-activity noble metal catalyst. The reactors, apparatuses, devices and the like are all reactors, apparatuses and devices which are common in the art unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1: as shown in the attached figure 1, the energy-saving kerosene refining method is carried out as follows:
after the iron catalyst and the coal powder are mixed, the iron catalyst is loaded on the surface of the coal powder and enters a dry distillation unit for dry distillation, the dry distillation temperature is 500-600 ℃, volatile components and tar of the coal powder after dry distillation are distilled off, the coal powder is changed into high-temperature coal powder with a porous structure, the high-activity metal catalyst and heavy oil are mixed to obtain heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is contacted with the heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is used as a catalyst carrier for cracking the heavy oil, the high-activity metal catalyst is loaded on the surface and inside of the high-temperature coal powder, in a heavy oil pyrolysis unit, the heavy oil is subjected to cracking reaction under the action of the high-activity metal catalyst on the surface and inside of the high-temperature coal powder, light components of the heavy oil are distilled off, and heavy components of the heavy oil and the coal powder are completely fused into oil coal slurry;
mixing hydrogen bubble fog drops and oil coal slurry, then entering a suspension bed hydrogenation unit, carrying out hydrogenation co-refining on the oil coal slurry under the action of an iron catalyst in a high hydrogen partial pressure environment in the suspension bed hydrogenation unit, separating a product of the hydrogenation co-refining to obtain a gas-phase component, a liquid-phase component and residues, entering the gas-phase component into a dry gas system, hydrogenating the liquid-phase component through a secondary hydrogenation unit 4 (a fixed bed hydrogenation reactor or a suspension bed hydrogenation reactor 3), removing heteroatoms and simultaneously saturating the liquid by hydrogenation, separating a secondary hydrogenation product to obtain a secondary hydrogenation light component and a secondary hydrogenation heavy component, and separating the secondary hydrogenation heavy component into a circulating solvent with the fraction temperature of 270-450 ℃;
after heat exchange and temperature rise of a circulating solvent with the fraction temperature of 270-450 ℃ and high-temperature synthesis gas, atomizing and mixing the circulating solvent with hydrogen to form hydrogen bubble fog drops, mixing the hydrogen bubble fog drops with the coal oil slurry, then feeding the mixture into a suspension bed hydrogenation unit, and in the suspension bed hydrogenation unit, carrying out hydrogenation co-refining on the coal oil slurry under the high-hydrogen partial pressure environment and the action of an iron catalyst;
the high-temperature synthesis gas subjected to primary temperature reduction by the circulating solvent provides a loosening power source and a reaction heat source for the oil pyrolysis reactor in the heavy oil pyrolysis unit, meanwhile, a heat source is provided for the dry distillation tower in the dry distillation unit, and the raw coal gas generated after the pulverized coal is subjected to dry distillation and the high-temperature synthesis gas subjected to secondary temperature reduction by the dry distillation unit and the heavy oil pyrolysis unit are also used as heat sources of the fractionating devices for the light components of the dry distillation unit and the light components of the heavy oil pyrolysis unit.
It is known in the art that coal is a raw material having a high carbon content and a low hydrogen content, heavy oil is a raw material having a low carbon content and a high hydrogen content, and heavy metals such as nickel and vanadium, which easily poison highly active metal catalysts, are contained in the heavy oil.
According to the kerosene energy-saving co-refining method, high-temperature coal powder is used as a raw material for subsequent hydrogenation and a high-activity metal catalyst carrier for cracking heavy oil, so that the heavy oil and the high-activity metal catalyst are in full contact reaction, after the heavy oil is cracked in a heavy oil pyrolysis unit, the heavy oil and the coal powder are completely fused into the kerosene slurry, the problem of poor intersolubility of the kerosene is thoroughly solved, the coal and the oil are fused to form the kerosene slurry, the activity of the high-activity metal catalyst is greatly reduced, and the kerosene slurry obtained by subsequent separation is in a suspension bed hydrogenation reactor 3 (suspension bed hydrogenation unit) and is beneficial to catalytic liquefaction of the coal under the condition of high hydrogen partial pressure and under the condition of internal and external catalysis (catalytic complementation) of an iron catalyst, so that the aim of hydrogenation co-refining is fulfilled.
The high-temperature synthesis gas is a total heat source of the device, provides heat for each unit, and is cooled, so that heat energy is fully utilized in a gradient manner.
The high-activity metal catalyst and the heavy oil can be mixed by the catalyst preparation tank 39, and the heavy oil prepared by the catalyst preparation tank 39 is sent into the atmospheric fractionating tower 6 through the oil inlet end.
Example 2: as the optimization of the embodiment, the synthetic gas or dry gas obtained by fractionation of the fractionation devices corresponding to the dry distillation unit and the heavy oil pyrolysis unit is sent to the hydrogen production unit 38 for hydrogen production, or sent to the downstream process, the hydrogen produced by the hydrogen production unit 38 is divided into two paths, one path is atomized and mixed with the circulating solvent to form hydrogen bubble fog drops, and the other path is sent to the secondary hydrogenation unit 4 for hydrogenation.
The fractionation means refers to the subsequent atmospheric fractionation column 6 and the first fractionation column 7.
Example 3: as the optimization of the above embodiment, the residue obtained by separating the hydrogenation co-refining product, the coal slurry and the oxygen are gasified by the gasification unit to generate the high-temperature synthesis gas.
The coal slurry in example 3 is prepared by directly processing raw material coal with the coal grinding drier 40 and then using the coal slurry preparation tank 45.
Example 4: as shown in fig. 1 to 3, the apparatus for implementing the energy-saving kerosene co-refining method according to the above embodiment includes a gasification unit, a dry distillation unit, a heavy oil pyrolysis unit, a suspended bed hydrogenation unit, a secondary hydrogenation unit 4, a fractionation unit, and a preheater 5, where the gasification unit employs a gasification furnace 46, the dry distillation unit includes a dry distillation reactor 1, the heavy oil pyrolysis unit employs a heavy oil pyrolysis reactor 2, the suspended bed hydrogenation unit employs a suspended bed hydrogenation reactor 3, the secondary hydrogenation unit 4 employs a suspended bed hydrogenation reactor 3 or a fixed bed hydrogenation reactor, and the fractionation unit includes an atmospheric fractionation tower 6, a first fractionation tower 7, and a second fractionation tower 8; the high-temperature synthesis gas outlet of the gasification furnace 46 is communicated with the first side inlet of the preheater 5, the first side outlet of the preheater 5 is respectively communicated with the carbonization reactor 1 and the synthesis gas inlet end at the lower part of the heavy oil pyrolysis reactor 2, the upper part of the carbonization reactor 1 is provided with a coal powder inlet end, the high-temperature coal powder outlet end at the bottom of the carbonization reactor 1 is communicated with the high-temperature coal powder inlet end of the heavy oil pyrolysis reactor 2 through a communicating pipe 9, the upper part of the atmospheric fractionating tower 6 is provided with an oil inlet end for feeding heavy oil containing a high-activity metal catalyst, the top of the carbonization reactor 1 is communicated with the middle part of the atmospheric fractionating tower 6, the bottom of the atmospheric fractionating tower 6 is communicated with the lower part of the heavy oil pyrolysis reactor 2, the top of the heavy oil pyrolysis reactor 2 is communicated with the lower part of the first fractionating tower 7, the bottom of the first fractionating tower 7 is communicated with the bottom of the suspension bed hydrogenation unit through an oil coal slurry pipeline 10, a separating device is communicated between the suspension bed hydrogenation unit and the secondary hydrogenation unit 4, the top of the secondary hydrogenation unit 4 is communicated with the upper part of the second fractionating tower 8, the bottom of the second fractionating tower 8 is communicated with the side inlet of the preheater 5 through a two-pass circulation solvent pipeline 11, and the side inlet of the preheater 5 are communicated with the side inlet of the second preheater 5 through an atomization pipeline 12.
The light components separated from the atmospheric pressure fractionation column 6 and the first fractionation column 7 can be stripped by a stripping column 13 to separate naphtha, diesel, and a gas component containing synthesis gas.
The atmospheric fractionating tower 6 of the fractionating unit can adopt various forms such as trays or fillers, and the like, and utilizes the dry distillation gas and the synthesis gas after heat exchange with the 18 bundles of dry distillation pipes as heating heat sources, so that in the process of gas-liquid contact in the tower, the coal powder carried by the gas phase is washed, and the light components in the heavy oil are fractionated.
The following are further optimizations or/and improvements to the device:
as shown in fig. 2 and 4, the dry distillation reactor 1 comprises a cylinder 14 and a heat exchange body, wherein a driving mechanism 15 is fixed on the top of the cylinder 14, the heat exchange body comprises an upper tube plate 16 and a lower tube plate 17, the upper tube plate 16 and the lower tube plate 17 are vertically sealed and sleeved in the cylinder 14 at intervals, a coal dust inlet end is arranged at the cylinder 14 above the upper tube plate 16, a dry distillation tube 18 is fixedly communicated between the upper tube plate 16 and the lower tube plate 17, main shaft holes 19 are respectively arranged at the centers of the upper tube plate 16 and the lower tube plate 17, a main shaft 21 is arranged in the main shaft holes 19 of the upper tube plate 16 and the lower tube plate 17 through a sliding key 20, the power output end of the driving mechanism 15 is connected with the top of the main shaft 21, bosses 22 are circumferentially fixed at intervals on the inner walls of the cylinder 14 at the bottoms of the upper tube plate 16 and the lower tube plate 17, and supporting sliders 23 capable of sliding on the bosses 22 are circumferentially fixed at intervals at the bottoms of the upper tube plate 16 and the lower tube plate 17; the cylinder 14 corresponding to the lower tube plate 17 is provided with a synthesis gas inlet end, the upper part of the shell side between the upper tube plate 16 and the lower tube plate 17 is communicated with the lower part of the atmospheric fractionating tower 6, and the tube side above the upper tube plate 16 is communicated with the lower part of the atmospheric fractionating tower 6.
As shown in fig. 5 to 6 and 10, the boss 22 has a triangular shape with a wide left side and a narrow right side, and as shown in fig. 5 and 10, the rear side surface of the boss 22 is fixed to the inner wall of the cylinder 14. As shown in fig. 7 to 8, the support slider 23 has a trapezoidal shape with a narrow top and a wide bottom.
The driving mechanism 15 may be a motor driving mechanism commonly known in the art. The main shaft 21 is driven to rotate by the driving mechanism 15, the main shaft 21 drives the heat exchange body to rotate by the sliding key 20, the supporting slide block 23 moves relative to the boss 22 in the rotating process of the heat exchange body, when the supporting slide block 23 moves to the boss 22, the lower end face of the supporting slide block 23 upwards slides along the upper inclined face of the boss 22, and the coal powder is used as a sliding lubricant, so that the whole heat exchange body rises relative to the cylinder 14, and after the supporting slide block 23 passes through the boss 22, the whole heat exchange body falls relative to the cylinder 14, so that the heat exchange body is fluctuated and jumped in the low-speed rotating process, coking of the coal powder in a tube bundle 18 of the carbonization tube is avoided, and the carbonization gas is favorable for rising.
The upper tube plate 16 and the lower tube plate 17 can be sealed and sleeved in the cylinder 14 in a comb tooth sealing mode, and fine leakage dust and dry distillation gas enter the atmospheric fractionating tower 6 together to be washed and recovered.
A radiation level meter can be arranged at the upper part of the cylinder 14 to detect the material level change.
The cylinder 14 may be vertical or inclined, etc., and the inclination angle may be between 15 degrees and 90 degrees for heavy oil.
As shown in fig. 2, a spiral baffle 24 is arranged in the cylinder 14 corresponding to the shell pass of the cylinder 14; a distribution baffle 25 is arranged in the cylinder 14 above the coal powder inlet end of the cylinder 14; a support bearing 26 is fixed in the cylinder 14 below the lower tube plate 17, and the bottom of the main shaft 21 is installed in the support bearing 26.
As shown in fig. 2, the synthesis gas inlet end of the cylinder 14 is communicated with the first side outlet of the preheater 5 through a first synthesis gas pipe 27, the lower portion of the heavy oil pyrolysis reactor 2 is provided with at least one synthesis gas inlet end, the synthesis gas inlet end of the heavy oil pyrolysis reactor 2 is communicated with the first synthesis gas pipe 27 through a second synthesis gas pipe 28, the communication pipe 9 is provided with more than two synthesis gas inlet ends at left and right intervals, and the synthesis gas inlet end of the communication pipe 9 is communicated with the second synthesis gas pipe 28.
As shown in fig. 2 and 9, two or more material feeding throats 29 are provided at an upper and lower interval in the lower portion of the heavy oil pyrolysis reactor 2 to communicate with the bottom of the atmospheric tower.
A vortex and low-pressure mixing area is formed at the bell mouth on the inner side of the material feeding throat pipe 29, and the full contact between heavy oil and high-temperature coal powder is guaranteed.
High-temperature coal powder enters the heavy oil pyrolysis reactor 2 under the pushing of pressure and loose hot synthesis gas to form an upward flow, a swirling flow is formed under the combined action of a negative pressure region formed by high-speed jet flow at a throat volute (a bell mouth at the inner side of a material feeding throat 29), the high-temperature coal powder is contacted with high-speed jet heavy oil under the action of a high-activity metal catalyst, heavy oil pyrolysis reaction is carried out on the surface of the coal powder and the inside of the coal powder, light components are distilled off along with a gas phase, and heavy components and the high-activity metal catalyst with greatly reduced activity invade the inside and the surface of the coal powder to form a new fused body.
As shown in fig. 1 and 3, a spray atomizer 30 is arranged on the atomization pipeline 12, the spray atomizer 30 includes an atomization spray cavity 31, a hydrogen spray head 32 and a micropore mixer 33, the hydrogen spray head 32 extends into the atomization spray cavity 31 from left to right, an outlet of the atomization spray cavity 31 is communicated with an inlet of the micropore mixer 33, and the bottom of the first fractionating tower 7 is communicated with the micropore mixer 33 through an oil-coal slurry pipeline 10.
The circulating solvent exchanges heat with the high-temperature synthesis gas in the preheater 5 and then enters the atomizing injection cavity 31, high-pressure hydrogen forms high-speed airflow through the hydrogen injection head 32, a low-pressure area is formed in the atomizing injection cavity 31, small droplets are formed under the impact of the hydrogen flow due to certain viscosity of the circulating solvent, hydrogen is wrapped in each droplet to form hydrogen bubble fog droplets, the hydrogen content in the circulating solvent is greatly increased, and the co-refining of kerosene is promoted.
As shown in the attached figure 1, the separation device comprises a hot high-pressure separator 34, a cold high-pressure separator 35, a low-pressure separator 36 and a pressure reduction separator 37, the top of the suspension bed hydrogenation unit is communicated with the middle of the hot high-pressure separator 34, a light component outlet at the top of the hot high-pressure separator 34 is communicated with the middle of the cold high-pressure separator 35, the bottom of the cold high-pressure separator 35 is communicated with the middle of the low-pressure separator 36, a heavy component outlet at the bottom of the hot high-pressure separator 34 is communicated with the middle of the pressure reduction separator 37, both the light component outlet of the pressure reduction separator 37 and the heavy component outlet of the low-pressure separator 36 are communicated with the bottom of the secondary hydrogenation unit 4, and a heavy component outlet of the pressure reduction separator 37 is communicated with a gasification furnace 46.
The residue at the heavy component outlet of the pressure reducing separator 37 is used as fuel of the gasification furnace 46, the gas phase component at the top outlet of the low pressure separator 36 enters a dry gas system, and the liquid phase component at the light component outlet of the pressure reducing separator 37 and the liquid phase component at the heavy component outlet of the low pressure separator 36 are subjected to secondary hydrogenation in a fixed bed or a suspended bed.
As shown in fig. 1, the hydrogen production unit 38 employs a hydrogen production pressure swing adsorption device, and a hydrogen outlet end of the hydrogen production unit 38 is respectively communicated with hydrogen inlet ends of the jet atomizer 30, the secondary hydrogenation unit 4 and the cold high-pressure separator 35.
A new hydrogen compressor 43 and a recycle hydrogen compressor 44 can be arranged on the hydrogen outlet end pipeline of the hydrogen production unit 38.
The fluid flow of each unit and each device of the invention is as follows:
1. dry distillation unit
As shown in fig. 2, the pulverized coal is dried by a coal mill dryer 40 to obtain pulverized coal with a particle size of 80 to 100 microns, and the pulverized coal is fed into a micro-positive pressure bunker 41 through a coal feeder 42, the bunker realizes intermittent feeding of the micro-positive pressure bunker 41 through pressure regulation and control of a lower cock valve, and meanwhile, the micro-positive pressure bunker 41 can be provided with a vibration system to prevent the pulverized coal from being hardened and blocked. Coal powder enters an upper tube plate 16 at the upper part of the dry distillation reactor 1 through a plug valve at the lower part of a micro-positive pressure bin 41, then uniformly enters a dry distillation tube 18 of the dry distillation reactor 1 through a distribution baffle 25, hot synthesis gas outside the dry distillation tube 18 heats the coal powder in the dry distillation tube 18 to 500-600 ℃ through a spiral baffle 24, and volatile components and coal tar in the coal powder carry a small amount of coal powder to enter the bottom of the atmospheric fractionating tower 6. The hot synthesis gas outside the tube enters the bottom of the atmospheric fractionating tower 6 after exchanging heat with the dry distillation tube 18;
2. atmospheric fractionating tower
As shown in figure 1, crude oil is pumped into an atmospheric fractionating tower 6, and is contacted with dry distillation gas and part of synthesis gas in the tower, the other part of synthesis gas is adjusted according to heat, and the redundant part of synthesis gas is sent to a synthesis gas rear pipe network. Fractionating light components of heavy oil, washing coal dust by the heavy oil, and then sending the coal dust into a heavy oil pyrolysis unit;
3. heavy oil pyrolysis unit
As shown in the attached figure 1, the high-temperature coal powder from the dry distillation unit enters a heavy oil pyrolysis reactor 2 from the bottom under the pressure difference and the conveying of the synthesis gas. The heavy oil from the atmospheric fractionating tower 6 is sprayed into the heavy oil pyrolysis reactor 2 through the material feeding throat 29, fully contacts with the hot pulverized coal to perform a cracking reaction, enters the first fractionating tower 7 after the reaction, and the light component of the atmospheric fractionating tower 6 are mixed and enter the stripping tower 13 to fractionate products. The coal slurry components are pressurized and sent out by a first fractionating tower 7 tower bottom pump and are used as the feed for the hydrogenation of the suspension bed;
4. hydrogenation unit
The oil coal slurry is subjected to a hydrogenation liquefaction reaction in a suspension bed hydrogenation reactor 3 under the action of hydrogen and a catalyst (a high-activity metal catalyst and an iron catalyst), a product after the reaction is separated by a separation device, residues are used as a fuel of a gasification furnace 46, a gas-phase component enters a dry gas system, a liquid-phase component is subjected to fixed bed or suspension bed secondary hydrogenation, heteroatoms are removed, liquid is subjected to hydrogenation saturation at the same time, a light component is separated in the separation system, and a heavy component is used as a circulating solvent;
5. spray atomizer
The jet atomizer 30 is a core component of solvent circulation and has two functions, namely, three times of hydrogenation supersaturation is carried out on the circulating solvent, the circulating solvent liquid is impacted by high-speed hydrogen flow, gas is divided into countless fine bubbles, the hydrogen supersaturation amount in the circulating solvent is increased, the hydrogenation effect is increased in the hydrogenation reaction, and the hydrogenation pressure is reduced; and secondly, a liquid and gas exchange place is provided, and due to the low heat transfer coefficient of gas, the gas is cut and wrapped by the liquid, so that the gas and the liquid can quickly reach the consistent temperature.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (7)
1. An energy-saving kerosene co-refining method is characterized by comprising the following steps:
mixing an iron catalyst and coal powder, and then entering a dry distillation unit for dry distillation, wherein the dry distillation temperature is 500-600 ℃, volatile components and tar of the coal powder subjected to dry distillation are distilled, so that the coal powder is changed into high-temperature coal powder with a porous structure, a high-activity metal catalyst is mixed with heavy oil to obtain heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is contacted with the heavy oil containing the high-activity metal catalyst, the high-temperature coal powder is used as a catalyst carrier for cracking the heavy oil, the high-activity metal catalyst is loaded on the surface and inside of the high-temperature coal powder, the heavy oil is subjected to cracking reaction under the action of the high-activity metal catalyst on the surface and inside of the high-temperature coal powder in a heavy oil pyrolysis unit, light components of the heavy oil are distilled, and the heavy components of the heavy oil and the coal powder are completely fused into oil coal slurry;
mixing hydrogen bubble fog drops with the oil coal slurry, then feeding the mixture into a suspension bed hydrogenation unit, carrying out hydrogenation co-refining on the oil coal slurry under the action of an iron catalyst in a high hydrogen partial pressure environment in the suspension bed hydrogenation unit, separating a product of the hydrogenation co-refining to obtain a gas-phase component, a liquid-phase component and residues, carrying out hydrogenation on the liquid-phase component through a secondary hydrogenation unit, separating a secondary hydrogenation product to obtain a secondary hydrogenation light component and a secondary hydrogenation heavy component, wherein the secondary hydrogenation heavy component is a circulating solvent with a fraction temperature of 270-450 ℃, and the circulating solvent with the fraction temperature of 270-450 ℃ exchanges heat with high-temperature synthesis gas and is heated to form hydrogen bubble fog drops after being atomized and mixed with hydrogen;
one part of the high-temperature synthesis gas subjected to primary temperature reduction by the circulating solvent provides a loosening power source and a reaction heat source for the oil pyrolysis reactor in the heavy oil pyrolysis unit, and the other part of the high-temperature synthesis gas provides a heat source for the dry distillation reactor in the dry distillation unit; the hydrogen produced by the hydrogen production unit is divided into two paths, one path is atomized and mixed with a circulating solvent to form hydrogen bubble fog drops, and the other path is fed into a secondary hydrogenation unit for hydrogenation; and gasifying the residue obtained by separating the hydrogenation co-refining product, the coal slurry and oxygen by a gasification unit to generate high-temperature synthesis gas.
2. An apparatus for implementing the energy-saving kerosene co-refining method according to claim 1, comprising a gasification unit, a dry distillation unit, a heavy oil pyrolysis unit, a suspended bed hydrogenation unit, a secondary hydrogenation unit, a fractionation unit and a preheater, wherein the gasification unit adopts a gasification furnace, the dry distillation unit adopts a dry distillation reactor, the heavy oil pyrolysis unit adopts a heavy oil pyrolysis reactor, the suspended bed hydrogenation unit adopts a suspended bed hydrogenation reactor, the secondary hydrogenation unit adopts a suspended bed hydrogenation reactor or a fixed bed hydrogenation reactor, and the fractionation unit comprises an atmospheric fractionation tower, a first fractionation tower and a second fractionation tower; a high-temperature synthesis gas outlet of the gasification furnace is communicated with a side inlet I of the preheater, the side outlet I of the preheater is respectively communicated with a carbonization reactor and a synthesis gas inlet end at the lower part of a heavy oil pyrolysis reactor, a coal powder inlet end is arranged at the upper part of the carbonization reactor, a high-temperature coal powder outlet end at the bottom of the carbonization reactor is communicated with a high-temperature coal powder inlet end of the heavy oil pyrolysis reactor through a communicating pipe, an oil inlet end for feeding heavy oil containing a high-activity metal catalyst is arranged at the upper part of an atmospheric fractionating tower, the top of the carbonization reactor is communicated with the middle part of the atmospheric fractionating tower, the bottom of the atmospheric fractionating tower is communicated with the lower part of the heavy oil pyrolysis reactor, the top of the heavy oil pyrolysis reactor is communicated with the lower part of a first fractionating tower, the bottom of the first fractionating tower is communicated with the bottom of a suspension bed hydrogenation unit through an oil coal slurry pipeline, a separation device is communicated between the suspension bed hydrogenation unit and the secondary hydrogenation unit, the top of the secondary hydrogenation unit is communicated with the upper part of a second fractionating tower, the bottom of the second fractionating tower is communicated with a circulating solvent pipeline through a circulating pipeline, and a side outlet II of the preheater is communicated with the oil coal slurry pipeline;
the dry distillation reactor comprises a cylinder and a heat exchange body, a driving mechanism is fixed at the top of the cylinder, the heat exchange body comprises an upper tube plate and a lower tube plate, the upper tube plate and the lower tube plate are vertically sealed and sleeved in the cylinder at intervals, a coal powder inlet end is arranged at the position of the cylinder above the upper tube plate, a dry distillation tube is fixedly communicated between the upper tube plate and the lower tube plate, main shaft holes are respectively arranged at the centers of the upper tube plate and the lower tube plate, main shafts are arranged in the main shaft holes of the upper tube plate and the lower tube plate through sliding keys, the power output end of the driving mechanism is connected with the top of the main shaft, bosses are circumferentially fixed at intervals at the inner walls of the cylinder at the bottom of the upper tube plate and the bottom of the lower tube plate, and supporting slide blocks capable of sliding on the bosses are circumferentially fixed at intervals at the bottoms of the upper tube plate and the lower tube plate; the cylinder corresponding to the lower tube plate is provided with a synthesis gas inlet end, the upper part of the shell side between the upper tube plate and the lower tube plate is communicated with the lower part of the atmospheric fractionating tower, and the tube side above the upper tube plate is communicated with the lower part of the atmospheric fractionating tower.
3. The device of claim 2, wherein a spiral baffle is disposed in the cylinder corresponding to the shell side of the cylinder; or/and a material distribution baffle is arranged in the cylinder above the coal powder inlet end of the cylinder; or/and a support bearing is fixed in the cylinder body below the lower tube plate, and the bottom of the main shaft is arranged in the support bearing; or/and the boss is in a triangular shape with a wide left part and a narrow right part, the rear side surface of the boss is fixed on the inner wall of the cylinder body, and the supporting slide block is in a trapezoidal shape with a narrow top and a wide bottom; or/and the synthesis gas inlet end of the cylinder is communicated with the first side outlet of the preheater through a first synthesis gas pipe, the lower part of the heavy oil pyrolysis reactor is provided with at least one synthesis gas inlet end, the synthesis gas inlet end of the heavy oil pyrolysis reactor is communicated with the first synthesis gas pipe through a second synthesis gas pipe, more than two synthesis gas inlet ends are arranged at the left side and the right side of the communicating pipe at intervals, and the synthesis gas inlet end of the communicating pipe is communicated with the second synthesis gas pipe.
4. The apparatus of claim 2 or 3, wherein two or more material feeding throats are provided at a lower portion of the heavy oil pyrolysis reactor at intervals up and down to communicate with a bottom of the atmospheric tower.
5. The device according to claim 2 or 3, wherein the atomization pipeline is provided with a jet atomizer, the jet atomizer comprises an atomization jet cavity, a hydrogen jet head and a micropore mixer, the hydrogen jet head extends into the atomization jet cavity from left to right, an outlet of the atomization jet cavity is communicated with an inlet of the micropore mixer, and the bottom of the first fractionating tower is communicated with the micropore mixer through a coal oil slurry pipeline.
6. The device according to claim 2 or 3, characterized in that the separation device comprises a hot high-pressure separator, a cold high-pressure separator, a low-pressure separator and a pressure-reducing separator, the top of the suspension bed hydrogenation unit is communicated with the middle part of the hot high-pressure separator, the light component outlet at the top of the hot high-pressure separator is communicated with the middle part of the cold high-pressure separator, the bottom of the cold high-pressure separator is communicated with the middle part of the low-pressure separator, the heavy component outlet at the bottom of the hot high-pressure separator is communicated with the middle part of the pressure-reducing separator, the light component outlet of the pressure-reducing separator and the heavy component outlet of the low-pressure separator are both communicated with the bottom of the secondary hydrogenation unit, and the heavy component outlet of the pressure-reducing separator is communicated with the gasification furnace.
7. The device according to claim 2 or 3, characterized by further comprising a hydrogen production unit, wherein the hydrogen production unit adopts a hydrogen production pressure swing adsorption device, and a hydrogen outlet end of the hydrogen production unit is respectively communicated with a hydrogen inlet end of the jet atomizer, the secondary hydrogenation unit and the cold high-pressure separator.
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| JP3824464B2 (en) * | 1999-04-28 | 2006-09-20 | 財団法人石油産業活性化センター | Method for hydrocracking heavy oils |
| CN101947451A (en) * | 2010-08-25 | 2011-01-19 | 太原理工大学 | Cobalt-based catalyst and preparation method and application thereof |
| CN102453510B (en) * | 2010-10-22 | 2013-11-27 | 中国石油化工股份有限公司 | Combined processing method of copyrolysis of heavy oil and coal |
| CN204051632U (en) * | 2014-08-29 | 2014-12-31 | 上海河图工程股份有限公司 | A kind of Venturi tube-type spreader gas-liquid allotter of high-efficient atomizing |
| CN107892945A (en) * | 2016-10-01 | 2018-04-10 | 何巨堂 | With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups |
| CN107916138A (en) * | 2016-10-11 | 2018-04-17 | 何巨堂 | A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device |
| CN106906001B (en) * | 2017-04-26 | 2020-01-07 | 煤炭科学技术研究院有限公司 | Method for co-processing coal with high content of inert components and heavy oil |
| CN110373228A (en) * | 2019-06-27 | 2019-10-25 | 中国石油大学(华东) | A kind of coal heavy oil two stage hydro coprocessing process |
| CN112175656A (en) * | 2019-07-04 | 2021-01-05 | 南京延长反应技术研究院有限公司 | Suspension bed enhanced reaction system and method for direct coal liquefaction |
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