System and method for grading, processing and utilizing full-fraction coal tar
阅读说明：本技术 一种全馏分煤焦油分级加工利用的系统和方法 (System and method for grading, processing and utilizing full-fraction coal tar ) 是由 朱永红 黄传峰 杨天华 李伟 杨涛 杨程 刘亚青 戴鑫 任彩玲 于 2019-12-25 设计创作，主要内容包括：本发明涉及一种全馏分煤焦油分级加工利用的系统和方法,该系统主要由焦油精制部分、石脑油催化重整部分、航空煤油加氢改质部分以及油渣气化制氢部分构成,主要工艺过程为：以全馏分煤焦油为原料,油气混合后通过加氢精制得到石脑油馏分、航空煤油馏分、船舶残渣燃料油产品以及尾油,之后石脑油馏分经催化重整得到BTX产品,航空煤油馏分经过加氢改质得到合格航空煤油产品,尾油采用油渣气化工艺制氢气,本发明能够在显著降低反应苛刻度的条件下,实现装置低成本、目标产品高转化率、处理量增大的目的,大大提高了煤焦油利用的经济价值。(The invention relates to a system and a method for grading, processing and utilizing full-range coal tar, wherein the system mainly comprises a tar refining part, a naphtha catalytic reforming part, an aviation kerosene hydro-upgrading part and an oil residue gasification hydrogen production part, and the main process comprises the following steps: the method is characterized in that full-range coal tar is used as a raw material, naphtha fraction, aviation kerosene fraction, ship residual fuel oil products and tail oil are obtained through hydrofining after oil and gas are mixed, then the naphtha fraction is catalytically reformed to obtain BTX products, the aviation kerosene fraction is hydro-modified to obtain qualified aviation kerosene products, and the tail oil is used for preparing hydrogen through an oil residue gasification process.)
1. The system for grading, processing and utilizing the full-range coal tar is characterized by comprising a coal tar pretreatment device (1), wherein an inlet of the coal tar pretreatment device (1) is communicated with a coal tar pipeline, an outlet of the coal tar pretreatment device is communicated with a new hydrogen pipeline and an input port of a tar heating furnace (2), an outlet of the tar heating furnace (2) is communicated with an oil way inlet of a first-stage super-diffusion gas-liquid mixing device (3), a gas path inlet of the first-stage super-diffusion gas-liquid mixing device (3) is communicated with an outlet pipeline of a hydrogen heating furnace (4), and an inlet of the hydrogen heating furnace (4) is communicated with the new hydrogen pipeline; the oil-gas mixing outlet of the primary super-diffusion gas-liquid mixing device (3) is communicated with the inlet of a coal tar primary reactor (5), the outlet of the coal tar primary reactor (5) is communicated with the inlet of a tar heating furnace (6), the tar heating furnace (6) is communicated with the oil circuit inlet of a secondary super-diffusion gas-liquid mixing device (7), the gas circuit inlet of the secondary super-diffusion gas-liquid mixing device (7) is communicated with the outlet pipeline of the hydrogen heating furnace (4), the oil-gas mixing outlet of the secondary super-diffusion gas-liquid mixing device (7) is communicated with the inlet of a coal tar secondary reactor (7), and the outlet of the coal tar secondary reactor (8) is respectively connected with a circulating hydrogen pipeline and the inlet of an atmospheric fractionating tower (10) through a generated oil high-pressure separating tower (9; a fraction output pipeline at the temperature of less than 145 ℃ is arranged at the upper part of the atmospheric fractionating tower (10), a fraction output pipeline at the temperature of 145-280 ℃ is arranged at the middle part, and a fraction output pipeline at the temperature of more than 280 ℃ is arranged at the lower part;
the outlet of the fraction pipeline at the temperature of less than 145 ℃ is connected with the inlet of the catalytic reforming device (11), the hydrogen outlet at the upper part of the catalytic reforming device (11) is connected with a circulating hydrogen pipeline, the liquid product outlet at the lower part is connected with the inlet of the BTX extraction tower (12), and the BTX extraction tower (12) is provided with a BTX product outlet pipeline and a high-octane gasoline component, namely a raffinate oil outlet pipeline;
an outlet of the 145-280 ℃ fraction pipeline is connected with a fresh hydrogen pipeline, the outlet of the 145-280 ℃ fraction pipeline is communicated with an inlet of a aviation kerosene hydrogenation modifying device (13) after hydrogen mixing, an outlet of the aviation kerosene hydrogenation modifying device (13) is connected with an inlet of an atmospheric fractionating tower (14), an outlet at the upper part of the atmospheric fractionating tower (14) is provided with a byproduct outlet pipeline, and an aviation kerosene product outlet pipeline is arranged at the lower part of the atmospheric fractionating tower;
the outlet of the distillate pipeline with the temperature of more than 280 ℃ is connected with a reduced pressure fractionating tower (15), the upper part of the reduced pressure fractionating tower (15) is provided with a distillate with the temperature of 280-510 ℃, namely a ship residue fuel oil product output pipeline, and the lower part of the reduced pressure fractionating tower (15) is provided with a distillate with the temperature of more than 510 ℃, namely a tail oil output pipeline.
2. The system for fractional processing and utilization of full range coal tar according to claim 1, characterized in that the outlet of the tail oil output pipeline is connected with the inlet of the oil residue gasification device (16), and the outlet of the oil residue gasification device (16) is connected with a circulating hydrogen pipeline.
3. The system for fractional processing and utilization of full-range coal tar according to claim 1, characterized in that the coal tar pretreatment device (1) comprises electric desalting, dewatering and deslagging treatment processes, and the pretreated tar meets the feeding requirements of the system.
4. The system for fractional processing and utilization of whole coal tar according to claim 1, characterized in that the coal tar primary reactor (5) and the secondary reactor (8) are fixed bed reactors.
5. The system for fractional processing and utilization of full-range coal tar according to claim 1, characterized in that the lower part of the coal tar primary reactor (5) is filled with a protective agent, the upper part is filled with a demetallizing agent, and olefin saturation demetallization reaction is mainly performed, the upper part of the coal tar secondary reactor (8) is filled with a refining agent 1, and the lower part is filled with a refining agent 2, and desulfurization, denitrification, aromatic saturation, and a small amount of deasphalting and carbon residue removal reactions are mainly performed.
6. A method for grading, processing and utilizing full-range coal tar is characterized by comprising the following steps;
(1) mixing the pretreated coal tar and hydrogen for the first time, heating to 220-260 ℃, and then entering a first-stage super-diffusion gas-liquid mixing device (3) for secondary gas-liquid efficient diffusion mixing; introducing the mixed oil gas into a coal tar primary reactor (5) for primary hydrofining to obtain primary hydrofined oil;
(2) heating the primary hydrofined oil obtained in the step (1) to 290-320 ℃, introducing the heated primary hydrofined oil into a secondary super-diffusion gas-liquid mixing device (7) for three-time gas-liquid efficient diffusion mixing; introducing the mixed oil gas into a coal tar secondary reactor 8 for deep hydrofining to obtain secondary hydrofined oil;
(3) separating hydrogen from the secondary hydrofined oil obtained in the step (2) by a high-pressure separator 9 at the temperature of 30-50 ℃, introducing the hydrogen into a circulating hydrogen pipe network, introducing the separated oil into an atmospheric fractionating tower (10), and separating the separated oil into tower top purge gas, distillate oil with a lateral line of less than 145 ℃, distillate oil with a temperature of 145-280 ℃ and distillate oil with a temperature of more than 280 ℃ at the bottom of the tower by the atmospheric fractionating tower (10);
(4) mixing hydrogen with the fraction oil obtained in the step (3) at the temperature of less than 145 ℃, introducing the mixture into a catalytic reforming device (11), and performing catalytic reforming reaction to obtain aromatic-rich reformed oil; then introducing the aromatic-rich reformed oil into an aromatic extraction tower (12) for aromatic extraction, obtaining a BTX product from the lateral line of the aromatic extraction tower (12), and obtaining raffinate oil at the bottom of the tower;
(5) mixing the 145-280 ℃ distillate oil obtained in the step (3) with hydrogen, introducing the mixture into a aviation kerosene hydrogenation modification device (13), introducing the oil product subjected to hydrogenation modification into an atmospheric fractionating tower (14), discharging a byproduct from an upper outlet of the atmospheric fractionating tower (14), and obtaining a high-quality aviation kerosene product from a lower outlet;
(6) introducing distillate oil with the temperature of more than 280 ℃ at the bottom of the tower obtained in the step (3) into a vacuum fractionating tower (15), obtaining the distillate oil with the temperature of 280-510 ℃, namely a ship residue fuel oil product, from the lateral line of the vacuum fractionating tower (15), and obtaining the distillate oil with the temperature of more than 510 ℃, namely a tail oil fraction, at the bottom of the vacuum fractionating tower (15); and then the obtained tail oil fraction is introduced into an oil residue gasification device (16) and is subjected to gasification reaction to obtain high-purity hydrogen and ultrahigh-pressure steam with high added value.
7. The method for fractional processing and utilization of full-range coal tar according to claim 6, characterized in that in the step (1), the pressure of the coal tar primary reactor 5 is 4-12 MPa, the volume ratio of hydrogen to oil is 300-2000, and the liquid space velocity is 0.2-2 h-1The average reaction temperature is 230-290 ℃.
8. The method for fractional processing and utilization of full-range coal tar according to claim 6, characterized in that in the step (2), the pressure of the coal tar secondary reactor (8) is 4-12 MPa, the volume ratio of hydrogen to oil is 300-2000, and the liquid space velocity is 0.2-2 h-1The average reaction temperature is 300-410 ℃.
Technical Field
The invention relates to the technical field of coal tar hydrogenation, in particular to a system and a method for grading, processing and utilizing full-range coal tar.
Background
The coal tar is a liquid product in the processing and modifying process of low-rank coal such as coal pyrolysis and the like, contains a large amount of heteroatoms such as sulfur, nitrogen, oxygen and the like, and metal and condensed ring aromatic substances, wherein colloid and asphaltene account for more than 50 percent. At present, the coal tar hydrogenation technology becomes an effective method for utilizing the coal tar, and has obvious economic and social benefits. The coal tar hydrogenation technology is mainly used for removing impurities such as sulfur, nitrogen, oxygen, metal and the like through hydrogenation reaction to produce clean fuel oil or fine chemical raw materials, and mainly comprises a coal tar full-fraction fixed bed hydrogenation technology, a wide-fraction hydrogenation technology, a delayed coking hydrocracking technology, a suspension bed hydrogenation technology and the like. The coking reaction is a side reaction in the hydrogenation process caused by excessive dehydrogenation of olefin and condensation ring aromatic polycondensation of asphaltene and the like, and in the present stage, along with the continuous implementation of national environmental protection and safety policies, how to inhibit the coking to realize long-period stable operation of a device and the safe production under high-pressure reaction conditions is various coal tar hydrogenation technologies, especially the full-fraction coal tar hydrogenation technology is urgently needed to solve.
Benzene, toluene, xylene (BTX) are important basic organic chemicals, and about 70% of the BTX required worldwide comes from catalytic reforming. The naphtha fraction prepared by coal tar hydrogenation contains a large amount of aromatic hydrocarbon and naphthenic hydrocarbon, the aromatic hydrocarbon potential value is very large, the aromatic hydrocarbon potential value can generally reach 70-85 percent and is far higher than that of straight-run naphtha, hydrocracked naphtha and the like, and the naphtha fraction is an ideal raw material for catalytic reforming. The composition and the properties of the coal-based naphtha are greatly different from those of the traditional petroleum-based naphtha, the components of the coal-based naphtha are more complex, but the development of the coal-based naphtha can be more products. The products which can be extended and separated at present comprise pure benzene, toluene, dimethylbenzene, trimethylbenzene, gasoline blending material and the like, the product chain is further extended, and the application field is wider.
Jet kerosene is mainly used as a fuel for jet engines and is required to have good low-temperature flow properties, higher net calorific value and density, higher combustion degree and good stability. With the rapid development of national economy and aviation technology, the demand of aviation kerosene is increasing day by day, and the requirements on the product quality are more strict. The aviation kerosene fraction mainly comes from cutting components of an atmospheric distillation unit and heavy oil catalytic or hydrocracking fractions. The aviation kerosene fraction needs to be subjected to hydrofining to remove mercaptan sulfur and impurity components, so that the corrosivity to a jet engine fuel system is reduced, and the stability of the aviation kerosene is improved.
In recent years, in order to reduce the pressure of increasing fuel costs, marine fuels have been gradually upgraded, and blended. The quality of the marine fuel oil must comply with the standards set by the international maritime organization, which is similar to the case of aviation kerosene. The International Maritime Organization (IMO) will impose environmental restrictions on all ships worldwide since 2020, and from the world at 1 month and 1 day of 2020, the standards for fuel oil sulfur content of 0.5% are enforced, while the standards for fuel oil sulfur content of 0.1% are still enforced by controlled emission areas (ECAs). At present, China has more strict requirements on environmental protection of coastal berthing ships than IMO. The marine vessel enters the emission control area from 1 month and 1 day in 2019, the marine fuel oil with the sulfur content of not more than 0.5 percent is used, and the marine fuel oil with the sulfur content of not more than 0.1 percent is used from 1 month and 1 day in 2020, when the marine vessel enters the inland river control area. With the rapid increase of the consumption of the marine fuel oil and the limitation of the environmental protection policy, the demand of the domestic and foreign markets for the low-sulfur marine fuel oil will further increase.
CN 105419864A discloses a system and a method for preparing high-octane gasoline, aviation kerosene and naphthenic base oil by using total hydrogen coal tar, wherein the system is composed of a coal tar refining device, a distillate oil deep refining device, an isomeric pour point depressing and post-refining device, and a naphtha dehydrogenation and aromatic extraction device. The technological process is complicated, and the reaction condition is very high in severity, which also results in high system device cost.
CN 101892078A discloses a process for producing catalytically reformed naphtha with high aromatic potential, but it is limited to producing naphtha feedstock for catalytic reforming and no study has been made on the catalytic reforming process and the later liquid products with high aromatics content. In addition, the method adopts a hydrofining mode of combining an expansion bed and a fixed bed when the full-fraction liquefied oil produced by directly liquefying coal is subjected to twice hydrofining and primary hydrofining, so that the investment is high, and the obtained effect is not obvious.
CN 103789034B discloses a method for producing large-specific-gravity aviation kerosene by hydrogenation of medium-low temperature coal tar, wherein the medium-low temperature coal tar is fractionated to obtain light fractions and heavy fractions, the light fractions are subjected to hydrofining reaction to obtain kerosene fractions at the temperature of 140-290 ℃, and the kerosene fractions are subjected to hydro-upgrading and supplementary refining reaction and then separated to obtain the large-specific-gravity aviation kerosene.
CN 102888244B discloses a method for producing marine fuel oil, which comprises the technical processes of catalytic slurry oil filtration, hydrorefining, hydrocracking and the like. The method has the disadvantages of complicated process, low utilization rate of oil slurry, and poor indexes and performances of the blended oil.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a system and a method for fractional processing and utilization of full-range coal tar, and aims to develop a system and a method for fractional processing and utilization of full-range coal tar with low cost and high efficiency to produce aromatic hydrocarbon, aviation kerosene, marine fuel oil products and hydrogen under the condition of low severity.
In order to achieve the purpose, the invention adopts the technical scheme that:
a system for grading, processing and utilizing full-fraction coal tar comprises a coal
the outlet of the fraction pipeline at the temperature of less than 145 ℃ is connected with the inlet of the
an outlet of the 145-280 ℃ fraction pipeline is connected with a fresh hydrogen pipeline, the outlet of the 145-280 ℃ fraction pipeline is communicated with an inlet of a aviation kerosene
an outlet of the distillate pipeline with the temperature of more than 280 ℃ is connected with a vacuum fractionating
and the outlet of the tail oil output pipeline is connected with the inlet of the oil
The coal
The coal tar
The lower part of the coal tar
A method for grading, processing and utilizing full-range coal tar comprises the following steps;
(1) mixing the pretreated coal tar and hydrogen for the first time, heating to 220-260 ℃, and then entering a first-stage super-diffusion gas-
(2) heating the primary hydrofined oil obtained in the step (1) to 290-320 ℃, introducing the heated primary hydrofined oil into a secondary super-diffusion gas-
(3) separating hydrogen from the secondary hydrofined oil obtained in the step (2) by a high-
(4) mixing hydrogen with the fraction oil obtained in the step (3) at the temperature of less than 145 ℃, introducing the mixture into a
(5) mixing the 145-280 ℃ distillate oil obtained in the step (3) with hydrogen, introducing the mixture into a aviation kerosene hydro-upgrading
(6) introducing distillate oil with the temperature of more than 280 ℃ at the bottom of the tower obtained in the step (3) into a vacuum fractionating
In the step (1), the pressure of the coal tar
In the step (2), the pressure of the coal tar
The invention has the beneficial effects that:
the invention adopts the technology of gas-liquid hydrogen mixing by segmentation and super-diffusion, and greatly promotes the efficient dissolution and uniform distribution of hydrogen in coal tar. The adoption of the ultra-diffusion gas-liquid hydrogen mixing technology can provide enough activated hydrogen in a short time, which is beneficial to the implementation of hydrofining and hydrocracking reactions, plays a role in inhibiting condensation coking reactions and is beneficial to the long-period operation of the device.
According to the invention, only two fixed bed reactors connected in series are adopted in the coal tar hydrogenation reaction section, the overall equipment cost of the hydrogenation system is far lower than that of the existing fixed bed hydrogenation technology in the prior art, and the advantage is more remarkable in the period of low oil price.
The raw material coal tar is completely converted into products such as aromatic hydrocarbon, aviation kerosene, ship residual fuel oil, hydrogen and the like after being processed, wherein the aromatic hydrocarbon is an important raw material in the chemical and textile industries, the aviation kerosene and the ship residual fuel oil are currently important strategic oil products in China, and the hydrogen is efficiently recycled. The whole coal tar grading processing and utilizing method has high economical efficiency and high added value of products.
The invention adopts the high-efficiency gas-liquid mixing device, so the severity of the process conditions of the coal tar grading processing and utilizing system is obviously reduced, an ideal reaction effect can be achieved under a lower hydrogen-oil ratio, a lower pressure and a higher airspeed, and a qualified target product is obtained. The reduction of the severity of the process conditions can obviously reduce the cost of the device and improve the treatment capacity of the device on one hand, and also greatly improve and ensure the operation safety of the device on the other hand.
Drawings
FIG. 1 is a schematic structural diagram of a system and a method for grading, processing and utilizing whole-fraction coal tar (example 1 and example 2).
FIG. 2 is a schematic diagram of a system and method for fractional processing and utilization of whole coal tar (comparative example 1).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, the whole coal tar fractionation processing and utilizing system of the present invention is composed of a tar refining section, a naphtha catalytic reforming section, an aviation kerosene hydro-upgrading section, and an oil residue gasification hydrogen production section.
The method comprises the following steps: the inlet of the coal tar pretreatment device is communicated with a coal tar pipeline, the outlet of the coal tar pretreatment device is communicated with a fresh hydrogen pipeline and an inlet of a tar heating furnace, the outlet of the tar heating furnace is communicated with the inlet of an oil way of a primary ultra-diffusion gas-liquid mixing device, the inlet of a gas path of the primary ultra-diffusion gas-liquid mixing device is communicated with the outlet pipeline of a hydrogen heating furnace, and the inlet of the hydrogen heating furnace is communicated with the fresh hydrogen pipeline; the oil-gas mixing outlet of the primary ultra-diffusion gas-liquid mixing device is communicated with the inlet of the coal tar primary reactor, the outlet of the coal tar primary reactor is communicated with the inlet of the tar heating furnace, the tar heating furnace is communicated with the oil path inlet of the high-efficiency mixing device, the gas path inlet of the ultra-diffusion gas-liquid mixing device is communicated with the outlet pipeline of the hydrogen heating furnace, and the oil-gas mixing outlet of the high-efficiency mixing device is communicated with the inlet of the coal tar secondary; the coal tar primary reactor and the coal tar secondary reactor are fixed bed reactors, wherein the lower part of the coal tar primary reactor is filled with a protective agent, the upper part of the coal tar primary reactor is filled with a demetallizing agent, olefin saturation demetallization reaction is mainly carried out, the upper part of the coal tar secondary reactor is filled with a
The method for realizing the grading processing and utilization of the full-range coal tar by utilizing the system can be realized by the following steps:
(1) mixing the pretreated coal tar with hydrogen for the first time, heating to 220-260 ℃, and then entering a super-diffusion gas-liquid mixing device for primary gas-liquid efficient diffusion mixing; introducing the mixed oil gas into a coal tar first-stage reactor for primary hydrofining to obtain first-stage hydrofined oil;
(2) heating the primary hydrofined oil obtained in the step to 290-320 ℃, introducing the heated primary hydrofined oil into a mixing device, and performing secondary gas-liquid efficient diffusion mixing; introducing the mixed oil gas into a coal tar secondary reactor for deep hydrofining to obtain secondary hydrofined oil;
(3) separating hydrogen from the secondary hydrofined oil obtained in the step at the temperature of 30-50 ℃ by a high-pressure separator, introducing the hydrogen into a circulating hydrogen pipe network, and introducing the separated oil into a normal-pressure fractionating tower and a normal-pressure fractionating tower (the separation is tower top purge gas, distillate oil with the lateral line of less than 145 ℃, distillate oil with the temperature of 145-280 ℃ and distillate oil with the temperature of more than 280 ℃ at the bottom of the tower;
(4) introducing the distillate oil obtained in the step (below 145 ℃) after hydrogen mixing into a catalytic reforming device, and obtaining aromatic-rich reformed oil after catalytic reforming reaction; then introducing the aromatic-rich reformed oil into an aromatic extraction tower for aromatic extraction, obtaining a BTX product from the side line of the aromatic extraction tower, and obtaining raffinate oil (high-octane gasoline component) at the bottom of the tower;
(5) mixing the 145-280 ℃ distillate oil obtained in the step, introducing the mixture into a aviation kerosene hydrogenation modification device, introducing the oil product subjected to hydrogenation modification into an atmospheric fractionating tower, discharging a byproduct from an upper outlet of the atmospheric fractionating tower, and obtaining a high-quality aviation kerosene product from a lower outlet;
(6) introducing distillate oil with the temperature of more than 280 ℃ at the bottom of the tower obtained in the step (A) into a vacuum fractionating tower, obtaining the distillate oil with the temperature of 280-510 ℃, namely a ship residue fuel oil product, from the lateral line of the vacuum fractionating tower, and obtaining the distillate oil with the temperature of more than 510 ℃, namely a tail oil fraction, at the bottom of the vacuum fractionating tower; and introducing the obtained tail oil fraction into an oil residue (residual oil and heavy and poor coal tar) gasification device, and obtaining high-purity hydrogen and high-added-value ultrahigh-pressure steam through a gasification reaction device.
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