CN110257101B - Device and method for preparing chemicals through reaction-separation-reaction of coal tar distillate - Google Patents
Device and method for preparing chemicals through reaction-separation-reaction of coal tar distillate Download PDFInfo
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- CN110257101B CN110257101B CN201910596238.8A CN201910596238A CN110257101B CN 110257101 B CN110257101 B CN 110257101B CN 201910596238 A CN201910596238 A CN 201910596238A CN 110257101 B CN110257101 B CN 110257101B
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- 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
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Abstract
A device and a method for preparing chemicals through coal tar distillate reaction-separation-reaction take single polycyclic aromatic hydrocarbon (bicyclic, tricyclic and tetracyclic) components in coal tar as a core, coal tar distillate oil rich in polycyclic aromatic hydrocarbon after the distillate is cut is subjected to dealkylation normalization treatment, so that the single polycyclic aromatic hydrocarbon components in the coal tar are effectively enriched, and the separation difficulty and the energy consumption of a separation section are remarkably reduced. The polycyclic aromatic hydrocarbons (bicyclic, tricyclic and tetracyclic) are separated by constant temperature condensation and centrifugal filtration by utilizing large freezing point difference among the polycyclic aromatic hydrocarbons. The separation process is normal pressure and low temperature, and the energy consumption of the separation section is effectively reduced. Aiming at improving the high added value utilization of the polycyclic aromatic hydrocarbon in the coal tar, the high-purity fraction obtained by the polycyclic aromatic hydrocarbon separator can be further processed into a polycyclic aromatic hydrocarbon partial hydrogenation chemical product with higher added value through hydrogenation reaction.
Description
Technical Field
The invention belongs to the technical field of energy deep processing, and relates to a device and a method for preparing chemicals through reaction-separation-reaction of coal tar polycyclic aromatic hydrocarbon fractions.
Background
China is rich in coal resources, a large amount of coal tar, which is a byproduct associated in the coal chemical production process, is a valuable chemical raw material, and various chemical products with high added values can be extracted from the coal tar. The research on the composition structure of the coal tar and the classification and quality-based utilization of the coal tar are of great significance for utilizing coal resources to the maximum extent and promoting the economic development of China. Coal tar is extremely complex in composition, and its family composition contains aromatic hydrocarbon, aliphatic hydrocarbon, oxygen-containing and nitrogen-containing compound and heteroatom compound. At present, how to realize the high added value utilization of polycyclic aromatic hydrocarbon in coal tar is a difficult point in industrial production. Polycyclic aromatic hydrocarbon is the most basic chemical raw material of organic chemical industry and can be used for producing various fine chemical products. For example, biphenyl is used as a heat carrier in chemical processes, naphthalene is used to manufacture dyes and plasticizers, phenanthrene is used to produce dyes and synthetic drugs, pyrene is used for dyes, synthetic resins, disperse dyes and engineering plastics, and also to make pesticides, plasticizers, etc. The polycyclic aromatic hydrocarbon has high added value and wide application, and a plurality of downstream products have low yield and higher added value. For example: tetrahydronaphthalene belongs to a hydrogenation intermediate of naphthalene and is an important hydrogen donor solvent; the method is widely applied to the process research of direct coal liquefaction, coal pitch hydrogenation, biomass liquefaction and the like. Compared with the prices of naphthalene (500g, 180 yuan) and decahydronaphthalene (250mL, 69.6 yuan), tetrahydronaphthalene (250mL, 695 yuan) is obviously a high-value product. Similar to polycyclic aromatic hydrocarbons such as phenanthrene and pyrene, the value of products can be improved by preparing corresponding intermediates (such as dihydrophenanthrene and hexahydropyrene) by partial hydrogenation. Coal tar is one of the main sources of aromatic hydrocarbon compounds, however, the aromatic hydrocarbon in the existing coal tar contains various side chain derivatives, and the derivatives are various in types, small in content and not concentrated in distribution, so that the separation is difficult, and the effective processing and utilization of the derivatives cannot be realized. Taking naphthalene as an example, the two-ring compounds with the content of more than 1 percent in coal tar are mainly as follows: naphthalene (8-12%), 1-methylnaphthalene (0.8-1.2%), 2-methylnaphthalene (1.0-1.8%). Therefore, the existing coal tar processing method has the defects of low efficiency utilization of high-value components of the coal tar, resource waste and environmental pollution due to the limitation of a separation method and the simplification of a processing process.
Disclosure of Invention
The invention aims to provide a device and a method for preparing chemicals through reaction-separation-reaction of polycyclic aromatic hydrocarbon fractions in coal tar.
In order to achieve the purpose, the invention adopts the following technical scheme:
a device for preparing chemicals through coal tar distillate reaction-separation-reaction comprises a distillate separation tower, a distillate oil buffer tank, a dealkylation reactor, a primary polycyclic aromatic hydrocarbon separator, a secondary polycyclic aromatic hydrocarbon separator, a first deep processing reactor, a second deep processing reactor and a third deep processing reactor;
the fraction separation tower is connected with a distillate oil buffer tank, the distillate oil buffer tank is connected with a dealkylation reactor, the dealkylation reactor is connected with an inlet of a first-level polycyclic aromatic hydrocarbon separator, an outlet of the first-level polycyclic aromatic hydrocarbon separator is divided into two paths, one path of the outlet is connected with an inlet of a second-level polycyclic aromatic hydrocarbon separator, the other path of the outlet is connected with an inlet of a first deep processing reactor, an outlet of the second-level polycyclic aromatic hydrocarbon separator is divided into two paths, the other path of the outlet is connected with an inlet of a second deep processing reactor, and the other path of the outlet is connected with an.
The invention is further improved in that the fraction separation tower is also connected with a coal tar feeding storage tank.
The invention has the further improvement that inlets of the first deep processing reactor, the second deep processing reactor and the third deep processing reactor are connected with a gas storage tank;
the outlet of the first deep processing reactor is connected with the first secondary product refining tower, and the second deep processing reactor is connected with the second secondary product refining tower; the third deep processing reactor is connected with a third secondary product refining tower.
The invention is further improved in that a first secondary product refining tower is connected to the first secondary product storage tank, a second secondary product refining tower is connected to the second secondary product storage tank, and a third secondary product refining tower is connected to the third secondary product storage tank.
The invention has the further improvement that the polycyclic aromatic hydrocarbon separator comprises a separator body, a feed inlet, a stirring paddle, a jacket, a constant temperature box, a centrifugal cylinder, a filter membrane and a separation controller; wherein, a thermostat and a centrifugal cylinder are arranged in the jacket; a stirring paddle is arranged in the constant temperature box, a feed inlet is arranged at the top of the constant temperature box, the constant temperature box is arranged on a centrifugal cylinder, the centrifugal cylinder comprises an inner cylinder and an outer cylinder, the inner cylinder is sleeved in the outer cylinder, and a filter membrane is arranged between the inner cylinder and the outer cylinder; the centrifugal cylinder and the thermostat are both connected with a separation controller.
The invention is further improved in that the pore size of the filter membrane is 4-5 μm; the bottom of the inner cylinder is provided with a solid-phase discharge hole, and the bottom of the outer cylinder is provided with a liquid-phase discharge hole.
According to the method for preparing the chemicals based on the device, the coal tar is conveyed to enter a fraction separation tower, and mixed distillate oil with the temperature of 210-360 ℃ is obtained through distillation; or the coal tar is conveyed into a fraction separation tower, and single distillate oil is obtained through distillation side line discharging and is respectively naphthalene oil, naphthalene oil or anthracene oil;
conveying the single distillate oil or the mixed distillate oil to a dealkylation reactor filled with a dealkylation catalyst, conveying the mixture to a first-stage polycyclic aromatic hydrocarbon separator after the mixture reacts in the dealkylation reactor (5), separating out solids at the temperature of 145-148 ℃, and then filtering and separating to obtain the solids which are pyrene; the obtained liquid phase enters a secondary polycyclic aromatic hydrocarbon separator, solid is separated out at the temperature of 98-100 ℃, and the obtained solid is phenanthrene after centrifugal filtration; the obtained liquid phase enters a third deep processing reactor filled with a selective hydrogenation catalyst, and is reacted in the third deep processing reactor to obtain tetrahydronaphthalene;
adding pyrene into a first deep processing reactor filled with a selective hydrogenation catalyst, and reacting in the first deep processing reactor to obtain hexahydropyrene;
and adding phenanthrene into a second deep processing reactor filled with a selective hydrogenation catalyst, and reacting in the second deep processing reactor to obtain dihydrophenanthrene.
A further improvement of the invention is that the conditions under which the reaction is carried out in the dealkylation reactor are: the mass-air speed ratio is 2-3WHSV h-1The reaction is carried out for 2 to 8 hours at the temperature of 400 ℃ and 520 ℃ and the initial reaction pressure of 1 to 4 MPa;
the conditions for carrying out the reaction in the first further processing reactor, the reaction in the second further processing reactor and the reaction in the third further processing reactor are as follows: the mass-air speed ratio is 2-3WHSV h-1The temperature is 160-240 ℃, the initial reaction pressure is 4-8MPa, and the reaction time is 4-8 h.
In a further development of the invention, the dealkylation catalyst is prepared by the following process: loading the active component and the auxiliary agent on a carrier by adopting an equal-volume impregnation method, standing for 4-6h, drying, and roasting at the temperature of 450-550 ℃ for 4-6h to obtain a dealkylation catalyst; wherein, the loading capacity of the active component is 3-9% and the loading capacity of the auxiliary agent is 0.07-0.5% by mass fraction;
the selective catalytic hydrogenation catalyst is prepared by the following processes: loading the active component on a catalyst carrier by adopting an equal-volume impregnation method, performing ultrasonic treatment and standing, drying, and roasting at the temperature of 450-550 ℃ for 4-6h to obtain a selective catalytic hydrogenation catalyst; wherein, the loading amount of the active component is 12-36 percent by mass fraction.
The invention has the further improvement that when the dealkylation catalyst is prepared, the active component is one or more of Ni, Mo, Co and W; the auxiliary agent is lanthanum; the carrier is one or a mixture of more of ZSM-5, Beta and HY;
when the selective catalytic hydrogenation catalyst is prepared, the carrier is SiO2、TiO2、Al2O3One or a mixture of more of HY and HZSM-5; the active component is one or more of Co, Mo, Ni and W.
Compared with the prior art, the invention has the beneficial effects that:
the invention is provided with a fraction separation tower, a distillate oil buffer tank, a dealkylation reactor, a primary polycyclic aromatic hydrocarbon separator, a secondary polycyclic aromatic hydrocarbon separator, a first deep processing reactor, a second deep processing reactor and a third deep processing reactor; the fraction separation tower is connected with a distillate oil buffer tank, the distillate oil buffer tank is connected with a dealkylation reactor, the dealkylation reactor is connected with an inlet of a first-level polycyclic aromatic hydrocarbon separator, an outlet of the first-level polycyclic aromatic hydrocarbon separator is divided into two paths, one path of the outlet is connected with an inlet of a second-level polycyclic aromatic hydrocarbon separator, the other path of the outlet is connected with an inlet of a first deep processing reactor, an outlet of the second-level polycyclic aromatic hydrocarbon separator is divided into two paths, the other path of the outlet is connected with an inlet of a second deep processing reactor, and the other path of the outlet is connected. The device provided by the invention can realize that the separated and purified high-purity dicyclic (naphthalene)/tricyclic (phenanthrene)/tetracyclic (pyrene) is subjected to selective hydrogenation deep processing to be a chemical with higher added value. The selective hydrogenation catalyst prepared by the method effectively improves the conversion rate (95.62%) and the selectivity (99.75%) of the selective hydrogenation reaction, and effectively improves the yield of the target product.
Furthermore, compared with the traditional equipment, the separator mainly comprises a constant temperature box, a centrifugal cylinder, a stirring paddle, a jacket, a separation controller and other auxiliary components; the constant temperature box realizes the constant temperature and condensation process of materials, and the centrifugal cylinder realizes the filtering and centrifuging process of the materials; the centrifugal cylinder is positioned at the lower end of the centrifugal cylinder, the two parts are provided with external jackets for providing required temperature, and the separation controller controls the rotating speed of a stirring paddle in the constant temperature box, the rotating speed of the centrifugal cylinder and the temperature of a heating medium in the jackets; one material inlet and two material outlets are arranged, the materials can be continuously fed, and solid-liquid products are respectively discharged.
The method disclosed by the invention maximally separates and utilizes the polycyclic aromatic hydrocarbons in the coal tar, improves the additional value of the coal tar, improves the efficiency of grading and quality-grading utilization of the coal tar, improves the economy and reduces the environmental pollution of the coal tar. Compared with the traditional pre-separation working section of coal tar by fraction cutting, the method is suitable for respective processing and utilization of three fractions of naphthalene oil, wash oil and anthracene oil, and is also suitable for overall processing and utilization of mixed fractions of naphthalene oil, wash oil and anthracene oil. The method has wide applicability due to the large difference between the composition and the property of different coal tar. The remaining light oil fraction can be used for phenol extraction, gasoline production, while the heavy oil at the bottom of the column can be used for asphalt production, hydro-upgrading processing, etc. Compared with the traditional fraction oil separation and purification section, the method has the advantages that dealkylation reaction is carried out before separation, fraction oil rich in polycyclic aromatic hydrocarbon is dealkylated and normalized, and a large amount of single components in the polycyclic aromatic hydrocarbon can be enriched. Moreover, the hydrodealkylation catalyst prepared by the method effectively improves the conversion rate (81.23%) and the selectivity (64.22%) of the dealkylation reaction. The polycyclic aromatic hydrocarbon after dealkylation effectively reduces the component amount in the coal tar and simultaneously improves the content of the target component, and avoids the interference of various derivatives on the separation process, namely, the separation difficulty of the polycyclic aromatic hydrocarbon in the coal tar is reduced, the separation process is shortened, and the energy consumption of the separation section is obviously reduced. Compared with the traditional separation and purification section, the polycyclic aromatic hydrocarbon is separated after dealkylation by adopting a polycyclic aromatic hydrocarbon separator, and the polycyclic aromatic hydrocarbon mixture is subjected to multi-stage constant temperature-condensation-centrifugation-filtration separation to obtain the polycyclic aromatic hydrocarbon single component. Compared with other separation modes such as rectification and the like, the separation process is carried out at normal pressure and lower temperature (lower than 150 ℃), the equipment is simple to operate, and the energy consumption and the operation cost can be effectively reduced. Compared with the traditional coal tar processing technology, the separated and purified high-purity dicyclic (naphthalene)/tricyclic (phenanthrene)/tetracyclic (pyrene) is further processed into a chemical with higher added value by adopting selective hydrogenation. The selective hydrogenation catalyst prepared by the method effectively improves the conversion rate (95.62%) and the selectivity (99.75%) of the selective hydrogenation reaction, and effectively improves the yield of the target product. The method is characterized in that firstly, the coal tar aromatic hydrocarbon fraction is normalized, and the polycyclic aromatic hydrocarbon single component is obtained through separation after enrichment, and the polycyclic aromatic hydrocarbon single component can be sold as a high value-added chemical product and can be further processed into a high value-added chemical product. The method can effectively enrich the content of single component of the polycyclic aromatic hydrocarbon, separate the polycyclic aromatic hydrocarbon in a low-energy-consumption mode, and meanwhile, the high-added-value chemicals obtained by deep processing have higher economical efficiency. The method effectively improves the yield of the polycyclic aromatic hydrocarbon single component in the coal tar, the value of the high value-added chemical obtained by deep processing is higher, and the technical problems of low component enrichment effect, difficult processing of high value-added substances, low utilization rate and the like in the existing coal tar processing process are solved.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing chemicals by reacting-separating-reacting polycyclic aromatic hydrocarbon fractions in coal tar according to the present invention;
FIG. 2 is a schematic structural diagram of an apparatus for preparing chemicals by reacting-separating-reacting polycyclic aromatic hydrocarbon fractions in coal tar according to the present invention;
FIG. 3 is a schematic diagram of a polycyclic aromatic hydrocarbon separator;
FIG. 4 is a graph showing the effect of hydrodealkylation catalysis;
FIG. 5 is a diagram showing the effect of selective hydrogenation catalysis (A: SiO)2、B:TiO2、C:Al2O3、D:HY、E:HZSM-5)。
In the figure, 1, a coal tar feeding storage tank, 2, a gas storage tank, 3, a fraction separation tower, 4, a distillate oil buffer tank, 5, a dealkylation reactor, 6, a polycyclic aromatic hydrocarbon separator, 7, a second-stage polycyclic aromatic hydrocarbon separator, 8, a first polycyclic aromatic hydrocarbon storage tank, 9, a second polycyclic aromatic hydrocarbon storage tank, 10, a third polycyclic aromatic hydrocarbon storage tank, 11, a first deep processing reactor, 12, a second deep processing reactor, 13, a third deep processing reactor, 14, a first secondary product refining tower, 15, a second secondary product refining tower, 16, a third secondary product refining tower, 17, a first secondary product storage tank, 18, a second secondary product storage tank 19, a third secondary product storage tank, 20, a mixed material inlet, 21, a stirring paddle, 22, a jacket, 23, a constant temperature tank, 24, a centrifugal cylinder, 25, a filter membrane, 26, a liquid phase discharge port, 27, a solid phase discharge port, 28, a dealkylation reactor, a second deep processing reactor, a second deep, A separator controller.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments in conjunction with the accompanying drawings.
Referring to fig. 1 and 2, a device for preparing chemicals through reaction-separation-reaction of polycyclic aromatic hydrocarbon fractions in coal tar comprises a coal tar feeding storage tank 1, a gas storage tank 2, a fraction separation tower 3, a distillate oil buffer tank 4, a dealkylation reactor 5, a primary polycyclic aromatic hydrocarbon separator 6, a secondary polycyclic aromatic hydrocarbon separator 7, a first polycyclic aromatic hydrocarbon storage tank 8, a second polycyclic aromatic hydrocarbon storage tank 9, a third polycyclic aromatic hydrocarbon storage tank 10, a first deep processing reactor 11, a second deep processing reactor 12, a third deep processing reactor 13, a first secondary product refining tower 14, a second secondary product refining tower 15, a third secondary product refining tower 16, a first secondary product storage tank 17, a second secondary product storage tank 18 and a third secondary product storage tank 19.
The coal tar feeding storage tank 1 is connected with a fraction separation tower 3, the fraction separation tower 3 is connected with a distillate oil buffer tank 4, the distillate oil buffer tank 4 is connected with a dealkylation reactor 5, the dealkylation reactor 5 is connected with an inlet of a first-stage polycyclic aromatic hydrocarbon separator 6, an outlet of the first-stage polycyclic aromatic hydrocarbon separator 6 is divided into two paths, one path is connected with an inlet of a second-stage polycyclic aromatic hydrocarbon separator 7, the other path is connected with a first polycyclic aromatic hydrocarbon storage tank 8, an outlet of the second-stage polycyclic aromatic hydrocarbon separator 7 is divided into two paths, one path is connected with a second polycyclic aromatic hydrocarbon storage tank 9, and the other path is connected with a third polycyclic aromatic hydrocarbon; a first polycyclic aromatic hydrocarbon storage tank 8 is connected with an inlet of a first deep processing reactor 11, a second polycyclic aromatic hydrocarbon storage tank 9 is connected with an inlet of a second deep processing reactor 12, a third polycyclic aromatic hydrocarbon storage tank 10 is connected with an inlet of a third deep processing reactor 13, a gas storage tank 2 is connected with inlets of the first deep processing reactor 11, the second deep processing reactor 12 and the third deep processing reactor 13, an outlet of the first deep processing reactor 11 is connected with a first secondary product refining tower 14, and the first secondary product refining tower 14 is connected with a first secondary product storage tank 17; the second deep processing reactor 12 is connected with a second secondary product refining tower 15, and the second secondary product refining tower 15 is connected with a second secondary product storage tank 18; the third deep processing reactor 13 is connected with a third secondary product refining tower 16, and the third secondary product refining tower 16 is connected with a third secondary product storage tank 19.
Referring to fig. 3, the polycyclic aromatic hydrocarbon separator 6 includes a separator body, a feed inlet 20, a stirring paddle 21, a jacket 22, a thermostat 23, a centrifugal cylinder 24, a filter membrane 25 (the aperture on the filter membrane is 4-5 μm), a liquid phase discharge outlet 26, a solid phase discharge outlet 27, and a separation controller 28.
Wherein, a constant temperature box 23 and a centrifugal cylinder 24 are arranged in the jacket 22; a stirring paddle 21 is arranged in the constant temperature box 23, a feed inlet 20 is arranged at the top of the constant temperature box 23, the constant temperature box 23 is arranged on a centrifugal cylinder 24, the centrifugal cylinder 24 comprises an inner cylinder and an outer cylinder, the inner cylinder is sleeved in the outer cylinder, a filter membrane 25 is arranged between the inner cylinder and the outer cylinder, a solid phase discharge port 27 is arranged at the bottom of the inner cylinder, and a liquid phase discharge port 26 is arranged at the bottom of the outer cylinder; the centrifugal cylinder 24 and the thermostat 23 are both connected to a separation controller 28.
Specifically, the stirring paddle 21 is located in the center of the constant temperature box 23, so that the uniform heat transfer of the materials in the constant temperature process is ensured. Jacket 22 heating medium provides the temperature required for the separation process. A centrifugal cylinder 24 is arranged below the constant temperature box 23 and is of a double-layer sleeve structure, the inner cylinder is used for receiving and centrifugally filtering and separating the polycyclic aromatic hydrocarbon solid-liquid mixture, the solid phase is retained in the inner cylinder, and the liquid phase enters the outer cylinder through a filter membrane 25. The feed inlet 20 is located at the top end of the constant temperature box 23, the liquid phase discharge port 26 is located at the lower end of the outer cylinder of the centrifugal cylinder 24, and the solid phase discharge port 27 is located at the lower end of the inner cylinder of the centrifugal cylinder 24. The separation controller 28 has a temperature and rotational speed control system for controlling the temperature of the thermostat and the rotational speed of the centrifuge bowl 24.
Referring to figure 1, the polycyclic aromatic hydrocarbon in the coal tar is reacted and separated based on the deviceThe method for preparing chemicals by the separation-reaction comprises the following steps: the coal tar in the coal tar feeding storage tank 1 is conveyed to enter a fraction separation tower 3, and mixed distillate oil (210-. Or the coal tar in the coal tar feeding storage tank 1 is conveyed to enter a fraction separation tower 3, single distillate oil is obtained through distillation lateral line discharging and is respectively naphthalene oil (210-. The single distillate or the mixed distillate is then conveyed to a dealkylation reactor 5 filled with dealkylation catalyst and fully contacted with the dealkylation catalyst (the mass-air speed ratio is 2-3WHSV h)-1) The reaction is carried out for 2-8h at the temperature of 400-520 ℃ and the initial reaction pressure of 1-4 MPa. The distillate oil normalized by dealkylation in the dealkylation reactor 5 is conveyed to a first-stage polycyclic aromatic hydrocarbon separator 6, the freezing point is utilized for multi-stage separation, the temperature of an insulation box in the first-stage polycyclic aromatic hydrocarbon separator 6 is controlled at 145-3000 r.min by a jacket, at the moment, the tetracyclic aromatic hydrocarbon-pyrene is firstly separated out, and the mixed material enters a centrifugal cylinder (2000-3000 r.min.)-1) And (4) filtering and separating, wherein the pyrene is sent out from a solid phase discharge port of the first-stage polycyclic aromatic hydrocarbon separator 6 and enters a first polycyclic aromatic hydrocarbon storage tank 8. And the liquid phase mixture is sent out from a liquid phase discharge port, enters a secondary polycyclic aromatic hydrocarbon separator 7, is subjected to multi-stage separation by utilizing a freezing point, the temperature of the heat preservation box is controlled to be 98-100 ℃ by a jacket, at the moment, tricyclic aromatic hydrocarbon-phenanthrene are separated out, and are sent out from a solid phase discharge port of the secondary polycyclic aromatic hydrocarbon separator 7 after centrifugal filtration, and enter a second polycyclic aromatic hydrocarbon storage tank 9. The liquid phase-naphthalene is sent out from the liquid phase discharge port and enters a third polycyclic aromatic hydrocarbon storage tank 10.
The primary products (pyrene, phenanthrene and naphthalene) are further reacted, processed and separated into chemicals with higher added values. The primary products in the first polycyclic aromatic hydrocarbon storage tank 8, the second polycyclic aromatic hydrocarbon storage tank 9 and the third polycyclic aromatic hydrocarbon storage tank 10 respectively enter a reactor filled with a selective hydrogenation catalyst (12% -36% -Ni/Mo-Al)2O3HY/HZSM-5) and a first deep processing reactor 11, a second deep processing reactor 12 and a third deep processing reactor 13 which are fully contacted with a selective hydrogenation catalyst (the mass-air speed ratio is 2-3WHSV h)-1) At the temperature of 160 ℃ and 240 ℃, the initial reaction pressure is 4-8MPa, and the reaction pressure is 4-8h；
Wherein, hexahydropyrene is obtained by reaction in the first deep processing reactor 11, and dihydrophenanthrene is obtained by reaction in the second deep processing reactor 12; and reacting in the third deep processing reactor 13 to obtain the tetrahydronaphthalene.
Selective hydrogenation is adopted for deep processing, reaction products (namely hexahydropyrene, dihydrophenanthrene and tetrahydronaphthalene) respectively enter a first secondary product refining tower 14, a second secondary product refining tower 15 and a third secondary product refining tower 16 for separation and impurity removal, and obtained chemicals (tetrahydronaphthalene, dihydrophenanthrene and hexahydropyrene) enter a first secondary product storage tank 17, a second secondary product storage tank 18 and a third secondary product storage tank 19.
H required for the reaction2And the gas enters the first deep processing reactor 11, the second deep processing reactor 12 and the third deep processing reactor 13 from the gas storage tank 2, and stop valve control gas switches are arranged.
The dealkylation catalyst comprises a carrier, an active component and a cocatalyst, wherein the carrier is one or a mixture of more of ZSM-5, Beta and HY; the active component is one or more of Ni, Mo, Co and W; the loading amount of the oxide of the active component is 3-9% (by mass fraction); the auxiliary agent is lanthanum with the load of 0.07-0.5%; loading the active component and the auxiliary agent on a catalyst carrier by adopting an equal-volume impregnation method, standing for 4-6h, drying at 120 ℃ for 4-6h, and roasting at 550 ℃ for 4-6h at 450-.
The selective catalytic hydrogenation catalyst comprises a carrier and an active component, wherein the carrier is SiO2、TiO2、Al2O3One or a mixture of more of HY and HZSM-5; the active component is one or more metals of Co, Mo, Ni and W; the loading amount of the oxide of the active component is 12-36%. Loading the active component on a catalyst carrier by an equal-volume impregnation method, performing ultrasonic treatment and standing, drying, and roasting at the temperature of 450-550 ℃ for 4-6h to obtain the selective catalytic hydrogenation catalyst.
The dealkylated and normalized polycyclic aromatic hydrocarbon material enters a polycyclic aromatic hydrocarbon separator 6 from a feed inlet 20 and is firstly put in a constant temperature box 23The polycyclic aromatic hydrocarbon with high solidifying point begins to be separated out in internal cooling, is uniformly mixed under the action of the stirring paddle 21 and enters a centrifugal cylinder 24 (the rotating speed is 2000-3000 r.min)-1) And the wall of the centrifugal cylinder is provided with a filter membrane 25. The solid phase product stays in the inner cylinder and is sent out from the solid phase discharge port 27 to enter the product storage tank. The liquid phase passes through the filter membrane and enters the outer cylinder, and is sent out from a liquid phase discharge port 26 and enters the secondary polycyclic aromatic hydrocarbon separator. And performing multistage separation to obtain single-component products of the polycyclic aromatic hydrocarbon.
The coal tar in the invention is low-temperature coal tar, medium-low temperature coal tar, medium-temperature coal tar or high-temperature coal tar.
The method has strong process applicability, and the coal tar storage tank is connected with a fraction separation tower. The fraction separation part is suitable for naphthalene, wash and anthracene oil mixed distillate (210-360 ℃) and is also suitable for single distillate of naphthalene oil (210-230 ℃), wash oil (230-280 ℃) and anthracene oil (280-360 ℃). The fraction separation tower is one, and the side discharge can realize single fraction discharge.
The distillate oil buffer tank 4 is connected with a dealkylation reactor. The number of the dealkylation reactors 5 is 1, and a catalyst bed layer is arranged in each dealkylation reactor.
The polycyclic aromatic hydrocarbon separator 6 is adopted for the separation of the bicyclo (naphthalene)/the tricyclic (phenanthrene)/the tetracyclic (pyrene). The polycyclic aromatic hydrocarbon separators 6 are two and adopt multi-stage constant temperature-condensation-centrifugation-filtration separation. The polycyclic aromatic hydrocarbon storage tank is connected with a first deep processing reactor 11, a second deep processing reactor 12 and a third deep processing reactor 13. And after separation, the high-purity dicyclic (naphthalene)/tricyclic (phenanthrene)/tetracyclic (pyrene) is continuously subjected to selective hydrogenation deep processing to obtain chemicals (tetrahydronaphthalene, dihydrophenanthrene and hexahydropyrene) with higher added values. The number of the deep processing reactors is 3, and a catalyst bed layer is arranged in the deep processing reactors.
Example 1
Coal tar of a certain coke-oven plant in northern Shaanxi is used as a raw material, and the basic properties and the element analysis results are shown in Table 1. Distilling to obtain naphthalene oil, wash oil, anthracene oil and their mixture (mixture of 3 single fractions). The yields obtained are shown in table 2. The mixed fraction obtained in the test is analyzed by gas chromatography-mass spectrometry.
The basic properties and elemental analysis of the coal tar used in example 1 are shown in table 1.
TABLE 1 basic Properties and elemental analysis of coal tar
TABLE 2 yield of coke fractions
Example 2
Coal tar of a certain coking plant in northern Shaanxi is used as a raw material, wherein the contents of naphthalene, phenanthrene and pyrene are respectively 11.84%, 4.67% and 1.52%. Distilling to obtain mixed distillate (210--1) And reacting for 4 hours at 480 ℃ and under the condition that the initial reaction pressure is 2 MPa. The content distribution of naphthalene, phenanthrene and pyrene in the reaction product is improved to 14.09%, 6.12% and 2.48%. The distillate oil normalized by dealkylation is conveyed to a multi-stage polycyclic aromatic hydrocarbon separator for separation, and the yields of naphthalene, phenanthrene and pyrene in the materials are respectively 13.81%, 5.94% and 2.36%. The results are shown in table 3, the content of the polycyclic aromatic hydrocarbon single component in the coal tar is effectively improved by the hydrodealkylation reaction, and the yield of the polycyclic aromatic hydrocarbon single component separated by the separator is still higher than that of the raw material. The single component of polycyclic aromatic hydrocarbon is respectively subjected to selective hydrogenation reaction and then separated and purified to obtain chemical products of tetrahydronaphthalene, dihydrophenanthrene and hexahydropyrene, the yield of the chemical products is respectively 13.53%, 5.69% and 2.10%, and the yield of the chemical products is still higher than that of the naphthalene, phenanthrene and pyrene in the raw materials. The results are shown in Table 4.
TABLE 3 polycyclic aromatic hydrocarbons yield in the feed of each section
TABLE 4 chemical yields
Example 3
The hydrodealkylation section in this example hydrodealkylates the alkyl polycyclic aromatic hydrocarbons (alkyl naphthalene, alkyl phenanthrene, alkyl pyrene) in the crude oil. The effect of the hydrodealkylation catalyst on the hydrodealkylation of alkyl polycyclic aromatic hydrocarbon into polycyclic aromatic hydrocarbon in the method is investigated by taking 2-methylnaphthalene (model compound) as a raw material. The hydrodealkylation catalyst in the embodiment comprises a carrier, an active component and a cocatalyst, wherein the carrier is one or a mixture of more of ZSM-5, Beta and HY; the active component is one or more of Ni, Mo, Co and W; the loading amount of the oxide of the active component is 3-9% (by mass fraction); the auxiliary agent is lanthanum with the load of 0.07-0.5%; loading the active component and the auxiliary agent on a catalyst carrier by adopting an equal-volume impregnation method, standing for 4-6h, drying at 120 ℃ for 4-6h, and roasting at 450 ℃ and 550 ℃ for 4-6h to obtain the hydrodealkylation catalyst. When the catalyst is applied, the reaction temperature is 480 ℃, the initial reaction pressure is 2MPa, and the reaction time is 4 hours. The reaction effect is shown in figure 4, and the hydrodealkylation catalyst prepared by the method can effectively remove the side chain of alkyl naphthalene. The selectivity of naphthalene can reach 64.22%, and the conversion rate can reach 81.23%. The conversion rate and the selectivity can obviously show that the yield of the naphthalene is improved, the alkyl naphthalene is effectively converted into the naphthalene, and the content of the naphthalene in the raw material coal tar is effectively improved.
Example 4
The selective hydrogenation section in this example selectively hydrogenates polycyclic aromatic hydrocarbons (naphthalene, phenanthrene, pyrene) in crude oil, and takes naphthalene (model compound) as a raw material to investigate the effect of the catalyst on the selective hydrogenation of polycyclic aromatic hydrocarbons. The selective catalytic hydrogenation catalyst in the embodiment comprises a carrier and an active component, wherein the carrier is Al2O3One or a mixture of more of HY and HZSM-5; oxides of active componentsThe loading amount of the catalyst is 12-36 percent, and the ratio of nickel to molybdenum is 1: 5. The active component is loaded on the catalyst carrier by adopting an equal-volume impregnation method, and is subjected to ultrasonic standing for 12h after 0.5-1h, and then is dried at 120 ℃ for 4-6h and then is roasted at 550 ℃ for 4-6h, so that the selective hydrogenation catalyst can be obtained. When the catalyst is applied, the reaction temperature is 200 ℃, the reaction time is 8H, and the initial H2 pressure is 6 MPa. The results are shown in FIG. 5, where the naphthalene conversion was 95.62% and the tetrahydronaphthalene selectivity was 99.75%. The improvement of the yield of the tetrahydronaphthalene is obviously seen from the conversion rate and the selectivity.
The method takes the polycyclic aromatic hydrocarbon (bicyclic, tricyclic and tetracyclic) single component in the coal tar as a core, and dealkylation normalization treatment is adopted for the coal tar distillate oil which is rich in polycyclic aromatic hydrocarbon after the cut fraction is cut, so that the single component of polycyclic aromatic hydrocarbon in the coal tar is effectively enriched, and the separation difficulty and the energy consumption of a separation section are obviously reduced. The polycyclic aromatic hydrocarbons (bicyclic, tricyclic and tetracyclic) are separated by constant temperature condensation and centrifugal filtration by utilizing large freezing point difference among the polycyclic aromatic hydrocarbons. The separation process is normal pressure and low temperature, and the energy consumption of the separation section is effectively reduced. Aiming at improving the high added value utilization of the polycyclic aromatic hydrocarbon in the coal tar, the high-purity fraction obtained by the polycyclic aromatic hydrocarbon separator can be further processed into a polycyclic aromatic hydrocarbon partial hydrogenation chemical product with higher added value through hydrogenation reaction. The method solves the problem of separation of components in the existing coal tar, enriches the content of valuable single components in the coal tar, and further processes and utilizes polycyclic aromatic hydrocarbon compounds in the coal tar, thereby effectively improving the utilization value of the coal tar.
Claims (3)
1. A coal tar distillate reaction-separation-reaction chemical preparation method is characterized in that coal tar is conveyed into a distillate separation tower (3) and distilled to obtain 210-360 ℃ mixed distillate oil; the mixed distillate oil is conveyed to a dealkylation reactor (5) filled with dealkylation catalyst, is conveyed to a first-level polycyclic aromatic hydrocarbon separator (6) after being reacted in the dealkylation reactor (5), and is separated out solid at the temperature of 145-148 ℃, and then is filtered and separated, and the obtained solid is pyrene; the obtained liquid phase enters a secondary polycyclic aromatic hydrocarbon separator (7), solid is separated out at the temperature of 98-100 ℃, and the obtained solid is phenanthrene after centrifugal filtration; the obtained liquid phase enters a third deep processing reactor (13) filled with a selective hydrogenation catalyst, and is reacted in the third deep processing reactor (13) to obtain tetrahydronaphthalene;
adding pyrene into a first deep processing reactor (11) filled with a selective hydrogenation catalyst, and reacting in the first deep processing reactor (11) to obtain hexahydropyrene;
phenanthrene is added into a second deep processing reactor (12) filled with a selective hydrogenation catalyst, and reaction is carried out in the second deep processing reactor (12) to obtain dihydrophenanthrene;
the conditions under which the reaction is carried out in the dealkylation reactor (5) are: the mass-air speed ratio is 2-3WHSV h-1The reaction is carried out for 2 to 8 hours at the temperature of 400 ℃ and 520 ℃ and the initial reaction pressure of 1 to 4 MPa;
the conditions for carrying out the reaction in the first further processing reactor (11), the reaction in the second further processing reactor (12) and the reaction in the third further processing reactor (13) are all as follows: the mass-air speed ratio is 2-3WHSV h-1The temperature is 160-240 ℃, the initial reaction pressure is 4-8MPa, and the reaction time is 4-8 h.
2. The method for producing chemicals according to claim 1,
the dealkylation catalyst is prepared by the following process: loading the active component and the auxiliary agent on a carrier by adopting an equal-volume impregnation method, standing for 4-6h, drying, and roasting at the temperature of 450-550 ℃ for 4-6h to obtain a dealkylation catalyst; wherein, the loading capacity of the active component is 3-9% and the loading capacity of the auxiliary agent is 0.07-0.5% by mass fraction;
the selective catalytic hydrogenation catalyst is prepared by the following processes: loading the active component on a catalyst carrier by adopting an equal-volume impregnation method, performing ultrasonic treatment and standing, drying, and roasting at the temperature of 450-550 ℃ for 4-6h to obtain a selective catalytic hydrogenation catalyst; wherein, the loading amount of the active component is 12-36 percent by mass fraction.
3. The method for preparing chemicals according to claim 2, wherein the dealkylation catalyst is prepared such that the active component is one or more of Ni, Mo, Co, W; the auxiliary agent is lanthanum; the carrier is one or a mixture of more of ZSM-5, Beta and HY;
when the selective catalytic hydrogenation catalyst is prepared, the carrier is SiO2、TiO2、Al2O3One or a mixture of more of HY and HZSM-5; the active component is one or more of Co, Mo, Ni and W.
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| EP1165473B1 (en) * | 1999-04-08 | 2004-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing 2,6-dialkylnaphtalene |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
| CN208865285U (en) * | 2018-09-12 | 2019-05-17 | 大闽食品（漳州）有限公司 | One kind standing clarified separation system for concentrate refrigeration |
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| EP1165473B1 (en) * | 1999-04-08 | 2004-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing 2,6-dialkylnaphtalene |
| CN103773489A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrogenation method for treating high-nitrogen high-aromatic hydrocarbon inferior diesel oil raw materials |
| CN208865285U (en) * | 2018-09-12 | 2019-05-17 | 大闽食品（漳州）有限公司 | One kind standing clarified separation system for concentrate refrigeration |
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