CN111378501B - Coal tar hydrotreating method - Google Patents

Coal tar hydrotreating method Download PDF

Info

Publication number
CN111378501B
CN111378501B CN201811618730.2A CN201811618730A CN111378501B CN 111378501 B CN111378501 B CN 111378501B CN 201811618730 A CN201811618730 A CN 201811618730A CN 111378501 B CN111378501 B CN 111378501B
Authority
CN
China
Prior art keywords
coal tar
oil
temperature
hydrotreating process
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811618730.2A
Other languages
Chinese (zh)
Other versions
CN111378501A (en
Inventor
孟兆会
陈博
刘玲
杨涛
朱慧红
其他发明人请求不公开姓名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201811618730.2A priority Critical patent/CN111378501B/en
Publication of CN111378501A publication Critical patent/CN111378501A/en
Application granted granted Critical
Publication of CN111378501B publication Critical patent/CN111378501B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure

Abstract

The invention discloses a coal tar hydrotreating method, which comprises the steps of firstly fractionating coal tar to obtain distillate oil at a temperature of less than 210 ℃, distillate oil at a temperature of 210-; dephenolizing distillate oil at the temperature of less than 210 ℃ to obtain dephenolized oil and crude phenol; naphthalene removal treatment is carried out on the distillate oil with the temperature of 210 ℃ and 230 ℃ to obtain naphthalene removal oil and crude naphthalene; the distillate oil with the temperature higher than 230 ℃, dephenolized oil, decalin oil and the auxiliary agent enter a pretreatment tank to be mixed, insoluble substances are separated after uniform mixing to obtain a blending component A, the obtained blending component A enters a fluidized bed hydrogenation reaction unit to be reacted, the obtained hydrogenation reaction effluent is subjected to gas-liquid separation to obtain a gas-phase material and a liquid-phase material, and part of the liquid-phase material is circulated to the pretreatment tank; and fractionating the rest liquid phase material to obtain a light component, a medium component and a tail oil component. The method can convert heavy components in the coal tar into high-value light components while efficiently recovering the phenol oil and the naphthalene oil, and realizes long-period stable operation of the device.

Description

Coal tar hydrotreating method
Technical Field
The invention belongs to the field of oil refining, relates to a coal tar treatment method, and particularly relates to a coal tar hydrotreating method.
Background
The high-temperature coal tar is one of the main secondary chemical products recovered from the coking gas, is rich in specific aromatic compounds, and is a valuable chemical resource. In the existing rectification separation processing process, the yield of coal pitch is as high as more than 55%, and the export of coal pitch is always a bottleneck problem which restricts the development of coal tar processing industry. The low price seriously affects the economic benefit of tar processing enterprises, and forces a large amount of coal tar, especially high-temperature coal tar with high coal pitch content to be directly burnt as fuel, so that the special chemical raw materials of the coal tar cannot be effectively utilized.
The high-temperature coal tar has the characteristics of high carbon residue and metal content, and also contains a large amount of coke powder, carbon powder and other granular substances, and the granular substances have small particle size and are difficult to treat by conventional means. In the actual processing process, the situation that pipelines or equipment are blocked due to particulate matter deposition often occurs.
In order to fully utilize the high-temperature coal tar resources, the property characteristics of the coal tar raw materials need to be analyzed, and a special processing route is created according to the property characteristics, so that the purpose of making the best use of the materials is finally realized. In view of the characteristics of large distillation range, complex composition, high content of polycyclic aromatic hydrocarbon and the like of the high-temperature coal tar, compared with the traditional separation route for purification or the currently popular route for producing light fuel oil by pure hydrogenation, the method aims at the characteristic of high-temperature coal tar, such as 'hydrocarbon is suitable and then hydrocarbon' and 'oil is suitable and then oil' to achieve higher economical efficiency and higher resource utilization rate. But relatively few reports about the production of light fuel oil from high-temperature coal tar as chemical raw materials are reported at present.
Patent CN10271927A describes a method for preparing diesel oil by hydrogenation of high temperature coal tar. In the method, high-temperature coal tar is subjected to reduced pressure distillation pretreatment to obtain hydrofined raw oil, the raw oil is introduced into a reactor for hydrogenation reaction, coal tar fractions passing through the hydrofined reactor are condensed, distillate oil is separated from hydrogen, the hydrogen is recycled, and fractions at 200-360 ℃ are collected to obtain the diesel. According to the method, only the normal-pressure fraction in the high-temperature coal tar is subjected to hydrofining to produce a diesel product or a blending component, so that the purpose of extracting high-value phenol naphthalene oil cannot be realized, and meanwhile, the heavy component in the coal tar is not effectively utilized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a coal tar hydrotreating method, which can convert heavy components in coal tar into high-value light components while efficiently recovering phenol oil and naphthalene oil, realizes long-period stable operation of a device, and solves the problem of low overall resource utilization rate in the existing coal tar treating method.
The invention provides a coal tar hydrotreating method, which comprises the following steps:
(1) fractionating the coal tar raw material to obtain distillate oil at the temperature of less than 210 ℃, distillate oil at the temperature of 210-;
(2) dephenolizing the distillate oil with the temperature of less than 210 ℃ obtained in the step (1) to obtain dephenolized oil and crude phenol;
(3) naphthalene removing treatment is carried out on the distillate oil with the temperature of 210-;
(4) enabling distillate oil with the temperature of more than 230 ℃ obtained in the step (1), dephenolized oil obtained in the step (2), dinaphthalene removed oil obtained in the step (3) and an auxiliary agent to enter a pretreatment tank for mixing, and separating out insoluble substances after uniform mixing to obtain a blending component A;
(5) the blending component A obtained in the step (4) enters a fluidized bed hydrogenation reaction unit, and hydrogenation reaction is carried out in the presence of hydrogen and a fluidized bed hydrogenation catalyst;
(6) carrying out gas-liquid separation on the hydrogenation reaction effluent obtained in the step (5), and separating to obtain a gas-phase material and a liquid-phase material, wherein the liquid-phase material is divided into a first liquid-phase material and a second liquid-phase material, and the first liquid-phase material is recycled to the pretreatment tank;
(7) and (4) fractionating the second liquid-phase material obtained in the step (6) to obtain a light component, a medium component and a tail oil component.
In the coal tar hydrotreating method, the fractionation in the step (1) can adopt any one of normal pressure fractionation, reduced pressure fractionation and supercritical extraction fractionation, and in order to avoid the damage of the coal tar condensation coke formation and valuable components in the system caused by overhigh heating temperature in the coal tar fractionation process, the fractionation preferably adopts a supercritical extraction fractionation technology. When supercritical extraction fractionation is adopted, the extraction temperature is 180-250 ℃, the extraction pressure is 7-15 MPa, and the extractant is CO2One or more of propane and pentane, preferably CO2. The mass ratio of the extracting agent to the coal tar raw material to be treated is 0.01-10: 1, preferably 0.05 to 1:1.
in the coal tar hydrotreating method, the coal tar raw material in the step (1) is preferably subjected to solid removal treatment and dehydration treatment before being fractionated, wherein the solid removal treatment mainly removes solid impurities (such as mechanical impurities) in the coal tar raw material, and any one of the coal tar solid removal methods in the prior art can be adopted, such as filtration separation or centrifugal separation, so that the purpose of purifying the coal tar is achieved. The dehydration treatment aims at removing free water in the coal tar and water-soluble salts dissolved in the free water, any one of methods which can realize the dehydration treatment of the coal tar in the prior art can be adopted, if coalescence dehydration can be adopted, deionized water is firstly adopted to dilute and clean the coal tar, the salts in the coal tar are transferred into water as far as possible, then oil-water separation is realized by means of different lipophilicity and hydrophilicity of materials in a coalescer, and the salts in the coal tar are reduced while the oil content of the coal tar is reduced. The selection of the particular mode of the de-consolidation and dehydration process is well known to those skilled in the art.
In the coal tar hydrotreating method, the coal tar in the step (1) can be one or more of medium-low temperature coal tar and high temperature coal tar, and preferably is high temperature coal tar.
In the coal tar hydrotreating method, the dephenolizing treatment in the step (2) and the naphthalene removing treatment in the step (3) can adopt one or more of an alkali washing method and a continuous rectification method. Wherein, the crude naphthalene oil is purified and separated by mainly adopting a continuous rectification method, and the adopted process comprises one or more of processes such as double-furnace double-tower continuous rectification, single-furnace single-tower continuous rectification, single-furnace double-tower pressurized continuous rectification and the like, and preferably adopts double-furnace double-tower continuous rectification; the purification and separation of the crude phenol oil mainly adopt an alkaline washing method, and the specific processing process comprises the working procedures of alkaline phenol washing, purification of crude sodium phenolate, decomposition of clean sodium phenolate and the like. The dephenolizing treatment and the naphthalene removing treatment can be reasonably selected by a person skilled in the art according to the properties of raw materials and the requirements of products.
In the coal tar hydrotreating method, the auxiliary agent in the step (4) is one or more of catalytic slurry oil and catalytic slurry oil clarified oil.
In the coal tar hydrotreating method, the addition amount of the auxiliary agent in the step (4) is 1-100%, preferably 2-50% of the total weight of the distillate oil with the temperature higher than 230 ℃ obtained in the step (1), the dephenolized oil obtained in the step (2) and the dephenolized oil obtained in the step (3).
In the coal tar hydrotreating method, the pretreatment tank in the step (4) can be a static mixer or a container containing the static mixer, the static mixer can be one or more of an SV type static mixer, an SX type static mixer, an SL type static mixer, an SH type static mixer and an SK type static mixer, and the static mixer mainly has the functions of changing the shape and the sectional area of the fluid and rotating the fluid to achieve the aim of fully mixing different fluids.
In the coal tar hydrotreating method, any one of liquid-solid two-phase separation modes in the field can be adopted for separating insoluble substances in the step (4), and for example, one or more of centrifugal separation, standing sedimentation separation and filtration separation can be adopted.
In the coal tar hydrotreating method, the fluidized bed hydrogenation catalyst in the step (5) comprises hydrogenation active metal components and a carrier, wherein the active metal components are selected from VIII group and/or VIB group metals, the VIII group metals are one or more of cobalt, nickel and iron, and preferably cobalt and/or nickel; the VIB group metal is one or more of molybdenum, tungsten and chromium, and molybdenum and/or tungsten are preferred; the carrier is a porous refractory inorganic oxide.
In the coal tar hydrotreating method of the invention, the reaction conditions of the fluidized bed hydrogenation reaction unit in the step (5) are as follows: the reaction temperature is 300-400 ℃, the preferable temperature is 340-380 ℃, the reaction pressure is 6-18 MPa, the preferable pressure is 8-12 MPa, and the volume space velocity is 0.8-8.0 h-1Preferably 1.0 to 4.0 hours-1The volume ratio of hydrogen to oil is 100: 1-1500: 1, preferably 600: 1-1200: 1.
In the coal tar hydrotreating method, the fluidized bed hydrogenation reaction unit in the step (5) is provided with more than one fluidized bed reactor, and the fluidized bed reactors are different from conventional fluidized bed reactors in the current market.
In the coal tar hydrotreating method, the material is fed from the bottom of the fluidized bed reactor, and the catalyst can be filled in the fluidized bed reactor in advance or can enter the fluidized bed reactor along with the fed material.
In the coal tar hydrotreating method, the gas-liquid separation of the hydrogenation reaction effluent obtained in the step (5) in the step (6) is preferably carried out in a hot high-pressure separator, and the gas-phase material obtained after the separation is subjected to heat exchange and air cooling and then is further subjected to desulfurization treatment, and then is mixed with fresh hydrogen by a recycle hydrogen compressor to be used as a hydrogen source.
According to the coal tar hydrotreating method, the first liquid phase material obtained by separating the fluidized bed hydrogenation reaction liquid phase material in the step (6) is recycled to the pretreatment tank for treatment, and the mass ratio of the first liquid phase material to the total feeding amount of the pretreatment tank is 1: 20-1: 5, preferably 1: 15-1: 8.
In the coal tar hydrotreating method, the cutting point temperature of the light component and the middle component in the step (7) is 210-300 ℃, and preferably 230-250 ℃; the cutting temperature of the middle component and the tail oil component is 380-480 ℃, and preferably 420-450 ℃.
In the coal tar hydrotreating method, the light component obtained in the step (7) is used for preparing chemical raw materials such as BTX and the like, and the light component obtained in the step (7) is separated from C6-C8 components through an aromatic hydrocarbon extraction device.
In the coal tar hydrotreating method, the medium components obtained in the step (7) can enter a coking device to be used for producing needle coke, or further subjected to hydrotreating to produce fuel oil. When entering a coking device to produce needlesWhen coke is formed, the reaction conditions of the coking device are as follows: the reaction temperature is 430-530 ℃, preferably 480-510 ℃; the reaction pressure is 0.1-0.8 MPa, preferably 0.1-0.3 MPa, and the circulation ratio is 0.05-8, preferably 1-3. When further performing hydrotreatment, the hydrogenation reaction conditions are as follows: the reaction temperature is 360-440 ℃, the reaction pressure is 14-19 MPa, and the volume space velocity is 0.5-1.5 h-1The volume ratio of hydrogen to oil is 800-1600, and the preferred operation conditions are as follows: the reaction temperature is 370-420 ℃, the reaction pressure is 15-18 MPa, and the volume space velocity is 0.6-1.2 h-1The volume ratio of hydrogen to oil is 900-1400.
In the coal tar hydrotreating method, the tail oil component obtained in the step (7) can be used as a raw material for producing carbon materials (such as carbon microspheres and carbon fiber materials).
Compared with the prior art, the coal tar hydrotreating method has the following advantages:
1. in the coal tar hydrotreating method, a first liquid-phase material obtained after the effluent of the fluidized bed hydrogenation reaction is separated by a hot high-pressure separator is circulated back to a pretreatment tank, and is mixed with raw materials (including distillate oil with the temperature of more than 230 ℃ obtained in step (1), dephenolized oil obtained in step (2), and decalcified oil obtained in step (3)) and an auxiliary agent for treatment, under the combined action of the auxiliary agent and the first liquid-phase material, large-particle substances in the raw materials are gathered and precipitated, and a prerequisite condition is provided for next solid-liquid separation; and the first liquid phase material is recycled to the pretreatment tank for use, and due to the high-temperature and high-pressure property of the first liquid phase material, the overall temperature of the mixture flow can be greatly improved, the viscosity of the mixed fluid is greatly reduced along with the temperature increase, the resistance on solid particle sedimentation is greatly reduced, and the solid sedimentation speed and the separation efficiency are improved.
2. In the coal tar hydrotreating method, a first liquid-phase material obtained by gas-liquid separation of the effluent of the fluidized bed hydrogenation reaction returns to a pretreatment tank, and by means of the characteristics of high aromatic hydrocarbon content of the coal tar and large heat release of the hydrogenation reaction, the high-temperature and high-pressure properties of the first liquid-phase material are utilized to directly contact with a low-temperature raw material for mixing and heat exchange, so that the temperature of the raw material is increased, the temperature requirement of the reaction feeding can be met, can save a raw oil heating furnace and/or a heat exchanger (only one heating furnace for start-up is arranged, and the device can be shut down after the temperature is operated), greatly reduces the investment cost of the device, and solves the problems that the content of alkadiene and arene in the coal tar is high, the problem that the heating furnace and the wall of the heat exchanger are easy to coke in the heating stage of the heat exchanger and the heating furnace greatly prolongs the running period of the device and reduces the risk of forced shutdown of the device caused by equipment coking.
3. The coal tar hydrotreating method can recover high-value components of naphthalene oil and phenol oil in coal tar resources, can improve the quality and utilize dephenolized oil, decalin oil and heavy components, and greatly improves the utilization rate of the coal tar resources. In addition, according to the property characteristics of each component of the coal tar, the high-value utilization of oil and hydrocarbon of the coal tar is realized; and the high-end carbon materials such as needle coke, carbon fiber and the like which are urgently needed by the market can be produced while producing part of light fuel oil.
Detailed Description
The invention is further described below by means of specific embodiments without limiting the scope of protection of the invention.
The ebullated bed reactors used in the examples and comparative examples of the present invention are ebullated bed reactors having a three-phase separator and no circulation system built in reactors developed by the petrochemical research institute, and the reactor structure of ZL 200810012191.8 may be used as a specific reactor structure.
The fluidized bed hydrogenation catalysts used in the examples and comparative examples of the present invention are microspherical catalysts developed by the research institute of petrochemical engineering, wherein the microspherical catalysts are supported on alumina, the active metal components are molybdenum and nickel, the weight of the catalysts is used as a reference, and MoO is used3The content was 12.8wt%, and the NiO content was 6.5 wt%. The bulk density of the catalyst was 0.75g/cm3Surface area 198m2The catalyst particles had an average diameter of 0.32 mm/g. The catalyst was prepared using the method disclosed in patent CN 200710010377.5.
The properties of the coal tar raw materials in the examples and the comparative examples of the invention are shown in table 1, the used auxiliary agent is catalytic slurry oil, the specific properties are shown in table 1, the yield results of the phenol oil, the naphthalene oil and the light components (in terms of BTX) produced by the fluidized bed are shown in table 2, the properties of the needle coke are shown in table 3, and the properties of tail oil are shown in table 4.
In the embodiment of the invention, the boiling bed hydrogenation reaction unit is provided with a boiling bed hydrogenation reactor.
The invention relates to a coal tar hydrotreating method, which comprises the following steps: fractionating the coal tar raw material to obtain distillate oil at the temperature of less than 210 ℃, distillate oil at the temperature of 210-; dephenolizing distillate oil at the temperature of less than 210 ℃ to obtain dephenolized oil and crude phenol; naphthalene removing treatment is carried out on the distillate oil with the temperature of 210 ℃ and 230 ℃ to obtain naphthalene removing oil and crude naphthalene; distillate oil with the temperature of more than 230 ℃, dephenolized oil, decalin oil and an auxiliary agent enter a pretreatment tank to be mixed, and insoluble substances are separated after uniform mixing to obtain a blending component A; the blending component A enters a fluidized bed hydrogenation reaction unit, and hydrogenation reaction is carried out in the presence of hydrogen and a fluidized bed hydrogenation catalyst; carrying out gas-liquid separation on the hydrogenation reaction effluent to obtain a gas-phase material and a liquid-phase material after separation, wherein the liquid-phase material is divided into a first liquid-phase material and a second liquid-phase material, and the first liquid-phase material is circulated back to the pretreatment tank to be mixed with the blending component A; and fractionating the second liquid-phase material to obtain a light component, a medium component and a tail oil component. The light component is extracted by aromatic hydrocarbon to obtain BTX, the medium component is fed into a coking device to produce needle coke, and the tail oil component is used for producing carbon fiber or carbon microsphere material.
Example 1
In example 1, the supercritical extraction technology is adopted to realize the cutting separation of different fractions of the coal tar raw material, wherein the supercritical extraction is carried out by using CO2Is an extracting agent, the extraction ratio (the ratio of the extracting agent to the raw materials) is 0.2, the extraction temperature is 195 ℃, and the extraction pressure is 8.5 MPa; the auxiliary agent is catalytic slurry oil, and the weight of the catalytic slurry oil is 10 percent of the weight of heavy components (distillate oil with the temperature of more than 230 ℃) of coal tar and the weight of mixed oil of the dephenolized oil and the dephenolized oil; the crude phenol is purified by an alkali washing method and Na2CO3As alkali for alkali washing, crude phenol and Na2CO3The mass ratio is 1: 1; the crude naphthalene is purified by adopting double-furnace double-tower continuous rectification; the mixed components enter a fluidized bed reactor to carry out hydrogenation reaction, and a hydrogenation reaction stripA piece: the reaction temperature is 350 ℃, the reaction pressure is 9MPa, the hydrogen-oil volume ratio is 600, and the volume space velocity is 3h-1(ii) a The blended coal tar and the hot high-temperature synthetic oil circulating oil of the boiling bed are heated in a direct contact mode, and the circulation ratio is 13: 1; the cutting temperature of the light component and the medium component of the oil generated by the fluidized bed hydrogenation is 240 ℃, and the cutting temperature of the medium component and the tail oil component is 430 ℃. The light component enters an aromatic extraction device to be separated to obtain BTX, the solvent used in the aromatic extraction process is furfural, and the solvent ratio is that the raw materials: the weight ratio of the furfural to the furfural is 1:0.5, the temperature of the top of an aromatic extraction tower is 80 ℃, the temperature of the tower is 60 ℃, and the temperature of the bottom of the tower is 35 ℃; the medium component enters a coking device to produce needle coke, the coking reaction temperature is 490 ℃, the circulation ratio is 1.3, the reaction pressure is 0.13Mpa, and the heavy component is used as a material for producing carbon microspheres or carbon fibers. Wherein the yields of phenol oil, naphthalene oil and light components produced in the fluidized bed (in BTX) are shown in Table 2, the properties of needle coke are shown in Table 3 and the properties of tail oil are shown in Table 4.
Example 2
In example 2, the supercritical extraction technology is adopted to realize the cutting and separation of different fractions of the coal tar raw material, wherein the supercritical extraction is carried out by using CO2Is an extracting agent, the extraction ratio is 0.5, the extraction temperature is 215 ℃, and the extraction pressure is 11.5 Mpa; the auxiliary agent is catalytic slurry oil, and the weight of the catalytic slurry oil is 30% of the weight of heavy components of coal tar and the weight of the mixed oil of the dephenolized oil and the dephenolized oil; the crude phenol is purified by an alkali washing method and Na2CO3As alkali for alkali washing, crude phenol and Na2CO3The mass ratio is 1: 1.2; the crude naphthalene is purified by adopting double-furnace double-tower continuous rectification; feeding the mixed components into a fluidized bed reactor for hydrogenation reaction, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 360 ℃, the reaction pressure is 10MPa, the volume ratio of hydrogen to oil is 600, and the volume airspeed is 2h-1(ii) a The blended coal tar and the hot high-temperature synthetic oil circulating oil of the boiling bed are heated in a direct contact mode, and the circulation ratio is 10: 1; the cutting temperature of the light component and the medium component of the oil generated by the fluidized bed hydrogenation is 240 ℃, and the cutting temperature of the medium component and the tail oil component is 430 ℃. The light component enters an aromatic extraction device to be separated to obtain BTX, the solvent used in the aromatic extraction process is furfural, and the solvent ratio is that the raw materials: the weight ratio of the furfural to the furfural is 1:0.6, the temperature of the top of the aromatic extraction tower is 85 ℃, the temperature of the middle of the tower is 65 ℃, and the temperature of the bottom of the tower is 37 ℃; the middle component isThe coking device produces needle coke, the coking reaction temperature is 500 ℃, the circulation ratio is 1.8, the reaction pressure is 0.14Mpa, and the heavy component is used as a material for producing carbon microspheres or carbon fibers. Wherein the yields of phenol oil, naphthalene oil and light components produced in the fluidized bed (in BTX) are shown in Table 2, the properties of needle coke are shown in Table 3 and the properties of tail oil are shown in Table 4.
Example 3
In example 3, CO was used2Is an extracting agent, the extraction ratio is 0.8, the extraction temperature is 235 ℃, and the extraction pressure is 13.5 Mpa; the auxiliary agent is catalytic slurry oil, and the weight of the catalytic slurry oil is 40 percent of the weight of heavy components of high-temperature coal tar and the weight of the mixed oil of the dephenolized oil and the dephenolized oil; the crude phenol is purified by an alkali washing method and Na2CO3As alkali for alkali washing, crude phenol and Na2CO3The mass ratio is 1: 1.3; the crude naphthalene is purified by adopting double-furnace double-tower continuous rectification; feeding the mixed components into a fluidized bed reactor for hydrogenation reaction, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 11MPa, the volume ratio of hydrogen to oil is 600, and the volume space velocity is 1h-1(ii) a The blended coal tar and the hot high-temperature synthetic oil circulating oil of the boiling bed are heated in a direct contact mode, and the circulation ratio is 8: 1; the cutting temperature of the light component and the medium component of the oil generated by the fluidized bed hydrogenation is 240 ℃, and the cutting temperature of the medium component and the tail oil component is 430 ℃. The light component enters an aromatic extraction device to be separated to obtain BTX, the solvent used in the aromatic extraction process is furfural, and the solvent ratio is that the raw materials: the weight ratio of the furfural to the furfural is 1:0.6, the temperature of the top of the aromatic extraction tower is 88 ℃, the temperature of the middle of the tower is 68 ℃, and the temperature of the bottom of the tower is 42 ℃; the medium components enter a coking device to produce needle coke, the reaction temperature of the coking device is 505 ℃, the circulation ratio is 2.0, the reaction pressure is 0.15Mpa, and the heavy components are used as materials for producing carbon microspheres or carbon fibers. Wherein the yields of phenol oil, naphthalene oil and light components produced in the fluidized bed (in BTX) are shown in Table 2, the properties of needle coke are shown in Table 3 and the properties of tail oil are shown in Table 4.
Comparative example 1
The method is basically the same as the method in the example 1, except that a pretreatment tank is not arranged, no auxiliary agent is added, the boiling bed heat high-molecular generated oil is not circulated, and the heat is extracted by adopting a conventional heat exchange and heating furnace heating mode. Wherein the yields of phenol oil, naphthalene oil and light components produced in the fluidized bed (in BTX) are shown in Table 2, the properties of needle coke are shown in Table 3 and the properties of tail oil are shown in Table 4.
Comparative example 2
The same as example 1 except that no pretreatment tank was provided and no auxiliary agent was added. Wherein the yields of phenol oil, naphthalene oil and light components produced in the fluidized bed (in BTX) are shown in Table 2, the properties of needle coke are shown in Table 3 and the properties of tail oil are shown in Table 4.
TABLE 1 Properties of the stock oils
Figure DEST_PATH_IMAGE001
TABLE 2 yield of phenol oil, naphthalene oil and light components (in BTX) from ebullated bed
Figure 549114DEST_PATH_IMAGE002
TABLE 3 needle coke Properties
Figure DEST_PATH_IMAGE003
TABLE 4 properties of tail oil fractions from ebullated bed
Figure 745216DEST_PATH_IMAGE004
As can be seen from the comparison of the comparative examples and the comparative examples, the method provided by the invention can extract high-value chemical raw materials such as phenol oil, naphthalene oil and the like on one hand; on the other hand, after hydrofining by a fluidized bed, light components can produce more light aromatics such as BTX and the like; the intermediate component can be used for producing high-quality needle coke, and the heavy component can be used as a raw material for producing high-end materials, so that the value of high-temperature coal tar is comprehensively improved.

Claims (26)

1. A coal tar hydrotreating process comprising the following:
(1) fractionating the coal tar raw material to obtain distillate oil at the temperature of less than 210 ℃, distillate oil at the temperature of 210-;
(2) dephenolizing the distillate oil with the temperature of less than 210 ℃ obtained in the step (1) to obtain dephenolized oil and crude phenol;
(3) naphthalene removing treatment is carried out on the distillate oil with the temperature of 210-;
(4) mixing distillate oil with the temperature of more than 230 ℃ obtained in the step (1), dephenolized oil obtained in the step (2), and the decalcified oil obtained in the step (3) and an auxiliary agent in a pretreatment tank, uniformly mixing, and separating out insoluble substances to obtain a blending component A, wherein the auxiliary agent is one or more of catalytic oil slurry and catalytic oil slurry clarified oil;
(5) the blending component A obtained in the step (4) enters a fluidized bed hydrogenation reaction unit, and hydrogenation reaction is carried out in the presence of hydrogen and a fluidized bed hydrogenation catalyst;
(6) carrying out gas-liquid separation on the hydrogenation reaction effluent obtained in the step (5), and separating to obtain a gas-phase material and a liquid-phase material, wherein the liquid-phase material is divided into a first liquid-phase material and a second liquid-phase material, and the first liquid-phase material is recycled to the pretreatment tank;
(7) and (4) fractionating the second liquid-phase material obtained in the step (6) to obtain a light component, a medium component and a tail oil component.
2. The coal tar hydrotreating process according to claim 1 characterized in that: the fractionation in the step (1) adopts any one of atmospheric fractionation, vacuum fractionation and supercritical extraction fractionation.
3. The coal tar hydrotreating process according to claim 1 characterized in that: and (2) performing fractionation in the step (1) by using supercritical extraction.
4. The coal tar hydrotreating process according to claim 3 characterized in that: when supercritical extraction fractionation is adopted, the extraction temperature is 180-250 ℃, the extraction pressure is 7-15 MPa, and the extractant is CO2One or more of propane and pentane; the extractantThe mass ratio of the coal tar to the coal tar raw material is 0.01-10: 1.
5. the coal tar hydrotreating process according to claim 4 characterized in that: the extractant is CO2(ii) a The mass ratio of the extracting agent to the coal tar raw material is 0.05-1: 1.
6. the coal tar hydrotreating process according to claim 1 characterized in that: the coal tar raw material in the step (1) is firstly subjected to solid removal treatment and dehydration treatment before being fractionated.
7. The coal tar hydrotreating process according to claim 1 characterized in that: the coal tar in the step (1) is one or more of medium-low temperature coal tar and high-temperature coal tar.
8. The coal tar hydrotreating process according to claim 1 characterized in that: the coal tar in the step (1) is high-temperature coal tar.
9. The coal tar hydrotreating process according to claim 1 characterized in that: and (3) adopting one or more of an alkali washing method and a continuous rectification method for dephenolizing treatment in the step (2) and naphthalene removing treatment in the step (3).
10. The coal tar hydrotreating process according to claim 1 characterized in that: the addition amount of the auxiliary agent in the step (4) is 1-100% of the total weight of the distillate oil with the temperature higher than 230 ℃ obtained in the step (1), the dephenolized oil obtained in the step (2) and the dephthalized oil obtained in the step (3).
11. The coal tar hydrotreating process according to claim 1 characterized in that: the addition amount of the auxiliary agent in the step (4) is 2-50% of the total weight of the distillate oil with the temperature higher than 230 ℃ obtained in the step (1), the dephenolized oil obtained in the step (2) and the deparaffinized oil obtained in the step (3).
12. The coal tar hydrotreating process according to claim 1 characterized in that: and (4) separating by adopting one or more of centrifugal separation, standing sedimentation separation and filtration separation.
13. The coal tar hydrotreating process according to claim 1 characterized in that: the reaction conditions of the ebullated bed hydrogenation reaction unit in the step (5) are as follows: the reaction temperature is 300-400 ℃, the reaction pressure is 6-18 MPa, and the volume airspeed is 0.8-8.0 h-1The volume ratio of hydrogen to oil is 100: 1-1500: 1.
14. The coal tar hydrotreating process according to claim 1 characterized in that: the reaction conditions of the ebullated bed hydrogenation reaction unit in the step (5) are as follows: the reaction temperature is 340-380 ℃, the reaction pressure is 8-12 MPa, and the volume space velocity is 1.0-4.0 h-1The volume ratio of hydrogen to oil is 600: 1-1200: 1.
15. The coal tar hydrotreating process according to claim 1 characterized in that: and (5) arranging more than one fluidized bed reactor in the fluidized bed hydrogenation reaction unit, wherein the fluidized bed reactor is a circulating pump-free fluidized bed reactor with a three-phase separator.
16. The coal tar hydrotreating process according to claim 1 characterized in that: and (3) carrying out gas-liquid separation on the hydrogenation reaction effluent obtained in the step (5) in the step (6) in a hot high-pressure separator, carrying out heat exchange and air cooling on the separated gas-phase material, further carrying out desulfurization treatment, and mixing the gas-phase material with fresh hydrogen by a recycle hydrogen compressor to be used as a hydrogen source.
17. The coal tar hydrotreating process according to claim 1 characterized in that: the mass ratio of the first liquid-phase material to the total feeding amount of the pretreatment tank in the step (6) is 1: 20-1: 5.
18. The coal tar hydrotreating process according to claim 1 characterized in that: the mass ratio of the first liquid-phase material to the total feeding amount of the pretreatment tank in the step (6) is 1: 15-1: 8.
19. The coal tar hydrotreating process according to claim 1 characterized in that: in the step (7), the cutting point temperature of the light component and the middle component is 210-300 ℃, and the cutting temperature of the middle component and the tail oil component is 380-480 ℃.
20. The coal tar hydrotreating process according to claim 1 characterized in that: the cutting point temperature of the light component and the middle component in the step (7) is 230-250 ℃; the cutting temperature of the middle component and the tail oil component is 420-450 ℃.
21. The coal tar hydrotreating process according to claim 1 characterized in that: and (4) using the light component obtained in the step (7) to prepare a BTX chemical raw material, and using the obtained tail oil component as a raw material for producing a carbon material.
22. The coal tar hydrotreating process according to claim 1 characterized in that: and (4) feeding the medium components obtained in the step (7) into a coking device for producing needle coke, or further carrying out hydrotreating to produce fuel oil.
23. The coal tar hydrotreating process of claim 22 characterized in that: when the medium components obtained in the step (7) enter a coking unit for producing needle coke, the reaction conditions of the coking unit are as follows: the reaction temperature is 430-530 ℃, the reaction pressure is 0.1-0.8 MPa, and the circulation ratio is 0.05-8.
24. The coal tar hydrotreating process of claim 22 characterized in that: when the medium components obtained in the step (7) enter a coking unit for producing needle coke, the reaction conditions of the coking unit are as follows: the reaction temperature is 480-510 ℃; the reaction pressure is 0.1-0.3 MPa, and the circulation ratio is 1-3.
25. The coal tar hydrotreating process of claim 22 characterized in that: when the medium component obtained in the step (7) is further subjected to hydrotreating, the hydrogenation reaction conditions are as follows: the reaction temperature is 360-440 ℃, the reaction pressure is 14-19 MPa, and the volume space velocity is 0.5-1.5 h-1The volume ratio of hydrogen to oil is 800-1600.
26. The coal tar hydrotreating process of claim 22 characterized in that: when the medium component obtained in the step (7) is further subjected to hydrotreating, the hydrogenation reaction conditions are as follows: the reaction temperature is 370-420 ℃, the reaction pressure is 15-18 MPa, and the volume space velocity is 0.6-1.2 h-1The volume ratio of hydrogen to oil is 900-1400.
CN201811618730.2A 2018-12-28 2018-12-28 Coal tar hydrotreating method Active CN111378501B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811618730.2A CN111378501B (en) 2018-12-28 2018-12-28 Coal tar hydrotreating method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811618730.2A CN111378501B (en) 2018-12-28 2018-12-28 Coal tar hydrotreating method

Publications (2)

Publication Number Publication Date
CN111378501A CN111378501A (en) 2020-07-07
CN111378501B true CN111378501B (en) 2021-07-09

Family

ID=71214867

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811618730.2A Active CN111378501B (en) 2018-12-28 2018-12-28 Coal tar hydrotreating method

Country Status (1)

Country Link
CN (1) CN111378501B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102465033A (en) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 Processing method of medium-low temperature coal tar
CN108102710A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of method for preparing needle coke
CN108102692A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of process of coal-based feedstocks production needle coke

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102465033A (en) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 Processing method of medium-low temperature coal tar
CN108102710A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of method for preparing needle coke
CN108102692A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of process of coal-based feedstocks production needle coke

Also Published As

Publication number Publication date
CN111378501A (en) 2020-07-07

Similar Documents

Publication Publication Date Title
US9994775B2 (en) Process for producing mesophase pitch by hydrogenation of high-temperature coal tar
JP4866351B2 (en) Process for direct coal liquefaction
CN103013566B (en) A kind of technique utilizing coal-tar pitch to prepare needle-shape coke raw material
JPH02187495A (en) Hydrocracking of heavy oil
RU2010120474A (en) METHOD FOR HYDRAULIC PROCESSING OF HEAVY AND EXTREME OIL AND OIL RESIDUES
CN103265971A (en) Heterogeneous coal tar suspension bed hydrogenation method
CN102796559A (en) Method and apparatus for producing fuel oil by hydrocracking
CN107267186B (en) The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon
CN111378490B (en) Coal tar full-fraction fluidized bed-fixed bed combined treatment process
CN109111950B (en) Method for producing liquid fuel by hydrogenating full-fraction tar
CN109749778A (en) A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling
CN110643391B (en) Method for converting coal tar/heavy oil into liquefied gas, naphtha and diesel oil
CN205152158U (en) Coal tar suspension bed hydrocracking unit
CN111378501B (en) Coal tar hydrotreating method
CN110229694A (en) The online fixed bed hydrogenation method of hydrocarbon material floating bed hydrogenation product temperature high score gas and middle matter hydrocarbon
CN105623724A (en) Hydrogenation thermal cracking method for producing low-carbon-number single-six-membered ring hydrocarbon from high aromatic hydrocarbon
CN113755208B (en) High aromatic hydrocarbon oil material and preparation method and application thereof
CN111378491B (en) Inferior heavy oil hydrotreating process
CN108504378B (en) Preparation method of coal hydropyrolysis hydrogen-donating solvent oil, hydrogen-donating solvent oil prepared by same and application thereof
CN112877090A (en) Coal direct liquefaction circulating solvent and preparation method and system thereof
CN108003935B (en) Method for producing clean diesel oil by Fischer-Tropsch synthesis of light and heavy product combination
CN111575049A (en) Use of solvent deasphalted oil in upflow hydrocracking process of heavy oil
CN110964560A (en) Method for combining poor-quality hydrocarbon hydrogenation thermal cracking reaction section with post-positioned hydrofining reaction section
CN111154505B (en) Coal tar hydrotreating process
CN111849552B (en) Coal tar full-fraction hydrogenation upgrading method and system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230606

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right