Coal tar full-fraction hydrogenation upgrading method and system
阅读说明：本技术 一种煤焦油全馏分加氢提质的方法及其系统 (Coal tar full-fraction hydrogenation upgrading method and system ) 是由 吴昊 李猛 梁家林 胡志海 于 2019-04-30 设计创作，主要内容包括：一种煤焦油全馏分加氢提质的方法及其系统,所述方法包括煤焦油全馏分原料与加氢尾油混合后依次进入分离系统,固定床脱金属反应器和脱水系统,脱除固体颗粒物、金属和水后,得到净化混合物物料,所得净化混合物进入加氢单元进行反应,分离反应产物得到石脑油馏分、柴油馏分和加氢尾油。本发明提供的方法和系统能有限实现煤焦油全馏分的最大化利用,并且显著延长加氢单元装置的运行周期。(A coal tar full-fraction hydrogenation upgrading method and a coal tar full-fraction hydrogenation upgrading system are provided, the method comprises the steps of mixing a coal tar full-fraction raw material and hydrogenation tail oil, sequentially feeding the mixture into a separation system, a fixed bed demetallization reactor and a dehydration system, removing solid particles, metals and water to obtain a purified mixture material, feeding the purified mixture into a hydrogenation unit for reaction, and separating reaction products to obtain naphtha fraction, diesel fraction and hydrogenation tail oil. The method and the system provided by the invention can realize the maximum utilization of the whole fraction of the coal tar in a limited way, and obviously prolong the operation period of the hydrogenation unit device.)
1. A coal tar whole fraction hydrogenation upgrading method comprises the following steps:
(1) mixing the coal tar full-fraction raw material with the hydrogenated tail oil, feeding the obtained mixture into a separation system, separating solid particles out of the mixture to obtain a solid-removed mixture material,
(2) mixing the solid-removed mixture material obtained in the step (1) with steam, then feeding the mixture into a heating furnace, heating the mixture, then feeding the mixture into a fixed bed demetallization reactor, contacting with a metal catching agent to remove metals in the mixture to obtain the demetallized mixture material, wherein the metal catching agent is a supported catalyst loaded with at least one metal of Fe, Ti and Co, the carrier is selected from one or more of alumina, silica and active carbon,
(3) the demetallization mixture material obtained in the step (2) enters a dehydration system to remove water in the demetallization mixture material to obtain a purified mixture material,
(4) the method comprises the steps of mixing a purified mixture material with hydrogen, then feeding the mixture into a hydrogenation unit, wherein the hydrogenation unit is provided with a first reaction area, a second reaction area, a gas-liquid separation area and a fractionation area, a hydrogenation refining catalyst is filled in the first reaction area, a hydrocracking catalyst is filled in the second reaction area, and a hydrogenation reaction product passes through the gas-liquid separation area and the fractionation area to obtain hydrogen-rich gas, water, naphtha fraction, diesel fraction and hydrogenation tail oil.
2. The method according to claim 1, wherein a gas-liquid separation zone is arranged in the hydrogenation unit in the step (4), and the reaction effluent of the first reaction zone and the reaction effluent of the second reaction zone enter the gas-liquid separation zone together;
the purified mixture material and hydrogen enter a first reaction zone together to contact with a hydrofining catalyst for reaction, the reaction effluent enters a gas-liquid separation zone, hydrogen-rich gas, water and liquid material flow are obtained by separation, the liquid material flow enters a fractionation zone, and naphtha fraction, diesel fraction and hydrogenated tail oil are obtained by fractionation; and (3) allowing part of the hydrogenated tail oil to enter a second reaction zone to contact with a hydrocracking catalyst for reaction, allowing the reaction effluent to enter a gas-liquid separation zone for separation, and returning the other part of the hydrogenated tail oil to the step (1) to be mixed with the coal tar full-distillate raw material.
3. The method of claim 1, wherein two gas-liquid separation zones are arranged in the hydrogenation unit in the step (4), and the reaction effluent of the first reaction zone and the reaction effluent of the second reaction zone enter different gas-liquid separation zones respectively;
the method comprises the following steps that a purified mixture material and hydrogen enter a first reaction area together to contact with a hydrofining catalyst for reaction, reaction effluent enters a gas-liquid separation area I for separation to obtain hydrogen-rich gas, water and a liquid material flow I, the liquid material flow I enters a second reaction area to contact with a hydrocracking catalyst for reaction, the reaction effluent enters a gas-liquid separation area II for separation to obtain hydrogen-rich gas, water and a liquid material flow II, and the liquid material flow II enters a fractionation area for fractionation to obtain naphtha fraction, diesel fraction and hydrogenation tail oil; and (3) returning part of the hydrogenated tail oil to the second reaction zone to contact with a hydrocracking catalyst, and returning the other part of the hydrogenated tail oil to the step (1) to be mixed with the coal tar whole fraction raw material.
4. The process according to any one of claims 1 to 3, wherein in step (1) the coal tar whole fraction feedstock is mixed with a hydrogenated tail oil, the temperature of the resulting mixture being 50 to 100 ℃, preferably 70 to 90 ℃; the mass ratio of the hydrogenated tail oil to the coal tar whole-fraction raw material is 1:9-5:5, preferably 2:8-4: 6.
5. The method according to any one of claims 1 to 3, wherein the separation system in step (1) is one or more selected from the group consisting of a filter, a decanter centrifuge, and a disk centrifuge.
6. A method according to any one of claims 1-3, characterized in that in step (2) the steam pressure is 0.5-4.0Mpa, preferably 0.5-2.0Mpa, with the amount of steam being 1-8%, preferably 1-3% by weight of the solids mixture mass.
7. A method according to any one of claims 1 to 3, characterized in that the metal capturing agent is obtained by using one or more of alumina, silica and activated carbon as a matrix, impregnating the matrix with one or more of Fe, Ti and Co metal salt solutions, and drying the impregnated matrix at a temperature of 120 ℃ to 180 ℃, preferably at a temperature of 130 ℃ to 150 ℃.
8. The method of claim 7, wherein the Fe metal salt solution is 0.01-0.1mol/L FeSO 4Solution of Ti metal salt solution of 0.1-1.0mol/L TiCl4The solution is Co with a Co metal salt solution of 0.01-0.1mol/L2(NO)3And (3) solution.
9. The process according to any one of claims 1 to 3, characterized in that the fixed-bed demetallization reactor is operated under the following conditions: the pressure is 0.5-4.0MPa, the temperature is 180 ℃ and the volume space velocity is 0.3-3.0h-1；
The content of metal in the demetallization mixture material is not higher than 20 mu g/g.
10. The method according to any one of claims 1 to 3, wherein the dehydration system is a high temperature dehydration column and/or a centrifuge, and the water content in the purge mixture material is not higher than 300 μ g/g.
11. The process of any of claims 1-3, wherein the reaction conditions in the first reaction zone of the hydrogenation unit are: the average reaction temperature is 350-420 ℃, the hydrogen partial pressure is 10.0-15.0MPa, and the volume space velocity is 0.3-0.8h-1Hydrogen-oil volume ratio of 1000-;
preferably the average reaction temperature is 360-400 ℃, the hydrogen partial pressure is 12.0-15.0MPa, and the volume space velocity is 0.3-0.5h-1The hydrogen-oil volume ratio is 1200-1800.
12. According to claim1-3, wherein the reaction conditions in the second reaction zone of the hydrogenation unit are: the average reaction temperature is 330- -1The hydrogen-oil volume ratio is 500-1000;
preferably the average reaction temperature is 340--1The volume ratio of hydrogen to oil is 600-800.
13. The method of any one of claims 1-3, wherein the hydrogenated tail oil has a paraffin content of no greater than 15% and a total aromatics content of no less than 10%.
14. A coal tar full-fraction hydrogenation upgrading system comprises a separation system, a heating furnace, a fixed bed demetalization reactor, a dehydration system and a hydrogenation unit;
the coal tar full-fraction raw material pipeline is communicated with a hydrogenation tail oil pipeline and is communicated with an inlet pipeline of a separation system, and at least one outlet of the separation system is communicated with a solid-removing mixture material pipeline;
the solid-removing mixture material pipeline is communicated with a steam pipeline and an inlet pipeline of a heating furnace, an outlet pipeline of the heating furnace is communicated with an inlet pipeline of a fixed bed metal-removing reactor, a metal catching agent is filled in the fixed bed metal-removing reactor, the metal catching agent is a supported catalyst loaded with at least one metal of Fe, Ti and Co, a carrier is selected from one or more of alumina, silica and active carbon, and an outlet of the fixed bed metal-removing reactor is communicated with an inlet of a dehydration system through a pipeline;
At least one outlet of the dehydration system is communicated with a purified mixture material pipeline, the purified mixture material pipeline is communicated with a hydrogen pipeline and is communicated with an inlet pipeline of the hydrogenation unit, the hydrogenation unit is provided with a first reaction zone, a second reaction zone, a gas-liquid separation zone and a fractionation zone, a hydrogen refining catalyst is filled in the first reaction zone, a hydrogen cracking catalyst is filled in the second reaction zone, the gas-liquid separation zone is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material outlet, and the fractionation zone is provided with a naphtha fraction outlet, a diesel fraction outlet and a hydrogenation tail oil outlet and is respectively communicated with corresponding pipelines.
15. The system of claim 14, wherein the purge mixture feed line is in communication with the hydrogen line and with the inlet line of the first reaction zone of the hydrogenation unit, the outlet line of the first reaction zone and the outlet line of the second reaction zone are both in communication with the inlet line of the vapor-liquid separation zone, the liquid stream outlet of the vapor-liquid separation zone is in communication with the inlet of the fractionation zone; the hydrogenation tail oil pipeline is divided into two paths, one path is communicated with the inlet of the second reaction zone, and the other path is communicated with the coal tar whole fraction raw material pipeline.
16. The system of claim 14, wherein the purified mixture material line is communicated with a hydrogen line and is communicated with an inlet line of a first reaction zone of the hydrogenation unit, an outlet of the first reaction zone is communicated with the gas-liquid separation zone I, the gas-liquid separation zone I is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material flow I outlet, the liquid material flow I outlet is communicated with an inlet of a second reaction zone through a pipeline, an outlet of the second reaction zone is communicated with an inlet line of the gas-liquid separation zone II, the gas-liquid separation zone II is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material flow II outlet, and the liquid material flow II outlet is communicated with an inlet of the fractionation zone; the hydrogenation tail oil pipeline is divided into two paths, one path is communicated with the inlet of the second reaction zone, and the other path is communicated with the coal tar whole fraction raw material pipeline.
Technical Field
The invention relates to a coal tar whole fraction hydrogenation quality-improving method and a coal tar whole fraction hydrogenation quality-improving system.
Background
With the continuous and high-speed development of social economy, the demand of China on petroleum products is increasing day by day. However, petroleum is an irrenewable energy source and is facing a crisis of increasing exhaustion. In contrast, Chinese coal reserves are abundant, and therefore, the preparation of liquid fuel from coal has become a fundamental direction for coal processing and utilization.
On the other hand, with the rapid growth of the international and domestic steel industry and the coal grading utilization, the coking and pyrolysis industry shows a high growth trend, the yield of the coal tar is larger and larger, and the clean processing and the effective utilization of the coal tar are more and more important. At present, the conventional processing method is to cut various fractions with concentrated components through pretreatment distillation, and then treat the various fractions by acid-base washing, distillation, polymerization, crystallization and other methods to extract pure products; and part of the coal tar is directly combusted as inferior fuel oil after being subjected to acid-base refining, or is directly combusted as emulsified fuel after being directly emulsified. Impurities such as sulfur, nitrogen and the like in coal tar are changed into oxides of sulfur and nitrogen in the combustion process and released into the atmosphere to cause atmospheric pollution, and a large amount of sewage is generated in the acid-base refining process to seriously pollute the environment. Therefore, from the viewpoint of environmental protection and comprehensive utilization of the environment, an effective chemical processing way is expected to be found, so that the coal tar is upgraded, and the utilization value of the coal tar is expanded. Therefore, coal tar is upgraded more and more in recent years by adopting a hydrogenation means, but at present, cut fraction hydrogenation upgrading is mainly adopted, namely, coal tar is firstly fractionated, about 20% of coal pitch is separated from coal tar, and about 80% of light fraction coal tar is subjected to hydrogenation upgrading. Although the hydrogenation difficulty is reduced by adopting the cut fraction hydrogenation process route, the yield of light oil of about 20 percent is lost, so the method is not an optimal scheme in economy. Related organizations have researched the hydrogenation of the whole fraction of coal tar in China.
CN104449842A discloses a coal tar whole fraction hydrogenation method, which comprises the following steps: (1) coal tar is hydrogenated through a slurry bed reactor at the temperature of 400 ℃ and 500 ℃ and under the pressure of 15-20 MPa; (2) separating the hydrogenation product in the slurry bed by a vacuum tower, and discharging part of heavy components from the bottom; (3) the stream at the top of the vacuum tower enters a fixed bed hydrogenation reactor, and is subjected to hydrofining and hydrocracking at the temperature of 380-500 ℃ and the pressure of 13-18 MPa; (4) the fixed bed hydrogenation product is separated into naphtha, diesel oil, wax oil and heavy oil by a fractionating tower, wherein the heavy oil circulates back to the slurry bed reactor, and the wax oil circulates back to the fixed bed reactor.
CN102796560B discloses a method for hydrogenating coal tar whole fraction. The method comprises the following specific steps: (1) purifying the whole fraction of coal tar to remove water, metals and solid impurities in the coal tar; (2) mixing the purified coal tar with hydrogen for 15-40 minutes at the temperature of 150-250 ℃ and under the pressure of 3-8MPa to obtain a liquid material with balanced gas and liquid; (3) the liquid material with gas-liquid balance enters a fixed bed hydrogenation reactor for hydrogenation, the reaction temperature is 260-410 ℃, the pressure is 9-14MPa, the volume space velocity is 0.28-2.6h < -1 >, and the hydrogen-oil volume ratio is 1000-1800; (4) and distilling the reaction product of the fixed bed to obtain gasoline fraction, diesel oil fraction and tail oil.
Disclosure of Invention
The invention provides a method and a system for upgrading coal tar whole fraction through hydrogenation aiming at the problems in the prior art, and provides a method and a system for upgrading coal tar whole fraction through hydrogenation, wherein the method and the system are high in conversion rate of coal tar whole fraction, low in cost and long in device operation period.
The method provided by the invention comprises the following steps:
(1) mixing the coal tar full-fraction raw material with the hydrogenated tail oil, feeding the obtained mixture into a separation system, separating solid particles out of the mixture to obtain a solid-removed mixture material,
(2) mixing the solid-removed mixture material obtained in the step (1) with steam, then feeding the mixture into a heating furnace, heating the mixture, then feeding the mixture into a fixed bed demetallization reactor, contacting with a metal catching agent to remove metals in the mixture to obtain the demetallized mixture material, wherein the metal catching agent is a supported catalyst loaded with at least one metal of Fe, Ti and Co, the carrier is selected from one or more of alumina, silica and active carbon,
(3) the demetallization mixture material obtained in the step (2) enters a dehydration system to remove water in the demetallization mixture material to obtain a purified mixture material,
(4) the method comprises the steps of mixing a purified mixture material with hydrogen, then feeding the mixture into a hydrogenation unit, wherein the hydrogenation unit is provided with a first reaction area, a second reaction area, a gas-liquid separation area and a fractionation area, a hydrogenation refining catalyst is filled in the first reaction area, a hydrocracking catalyst is filled in the second reaction area, and a hydrogenation reaction product passes through the gas-liquid separation area and the fractionation area to obtain hydrogen-rich gas, water, naphtha fraction, diesel fraction and hydrogenation tail oil.
In one embodiment of the invention, in the hydrogenation unit in the step (4), a gas-liquid separation zone is arranged in the hydrogenation unit in the step (4), and the reaction effluent of the first reaction zone and the reaction effluent of the second reaction zone enter the gas-liquid separation zone together; the purified mixture material and hydrogen enter a first reaction zone together to contact with a hydrofining catalyst for reaction, the reaction effluent enters a gas-liquid separation zone, hydrogen-rich gas, water and liquid material flow are obtained by separation, the liquid material flow enters a fractionation zone, and naphtha fraction, diesel fraction and hydrogenated tail oil are obtained by fractionation; and (3) allowing part of the hydrogenated tail oil to enter a second reaction zone to contact with a hydrocracking catalyst for reaction, allowing the reaction effluent to enter a gas-liquid separation zone for separation, and returning the other part of the hydrogenated tail oil to the step (1) to be mixed with the coal tar full-distillate raw material.
Preferably, the hydrogen-rich gas is returned to the first reaction zone and/or the second reaction zone as recycle hydrogen.
In another embodiment of the invention, two gas-liquid separation zones are arranged in the hydrogenation unit in the step (4), and the reaction effluent of the first reaction zone and the reaction effluent of the second reaction zone enter different gas-liquid separation zones respectively; the method comprises the following steps that a purified mixture material and hydrogen enter a first reaction area together to contact with a hydrofining catalyst for reaction, reaction effluent enters a gas-liquid separation area I for separation to obtain hydrogen-rich gas, water and a liquid material flow I, the liquid material flow I enters a second reaction area to contact with a hydrocracking catalyst for reaction, the reaction effluent enters a gas-liquid separation area II for separation to obtain hydrogen-rich gas, water and a liquid material flow II, and the liquid material flow II enters a fractionation area for fractionation to obtain naphtha fraction, diesel fraction and hydrogenation tail oil; and (3) returning part of the hydrogenated tail oil to the second reaction zone to contact with a hydrocracking catalyst, and returning the other part of the hydrogenated tail oil to the step (1) to be mixed with the coal tar whole fraction raw material.
Preferably, the hydrogen-rich gas is returned to the first reaction zone and/or the second reaction zone as recycle hydrogen.
The coal tar of the invention refers to coal tar produced by coal pyrolysis, coal gasification or other processes. The coal tar whole fraction raw material can be low-temperature coal tar generated by coal gas production, or low-temperature coal tar or medium-temperature coal tar or high-temperature coal tar whole fraction raw material generated in a coal pyrolysis process (including low-temperature coking, medium-temperature coking and high-temperature coking processes), and mixed oil of the coal tar whole fraction raw materials.
In the invention, the coal tar full fraction raw material and the hydrogenated tail oil in the step (1) are mixed and enter a separation system after being mixed. Preferably the temperature of the resulting mixture is from 50 to 100 deg.C, more preferably from 70 to 90 deg.C; the mass ratio of the hydrogenated tail oil to the coal tar whole-fraction raw material is 1:9-5:5, and more preferably 2:8-4: 6.
In a preferable case, the separation system in the step (1) is one or more of a filter, a horizontal screw centrifuge and a disc centrifuge, and further preferably the horizontal screw centrifuge. Preferably, the mechanical impurities content of the solids-depleted mixture mass is reduced to less than 0.01% by weight.
In a preferred case, the steam pressure in step (2) is between 0.5 and 4.0MPa, preferably between 0.5 and 2.0MPa, the amount of steam being between 1% and 8%, preferably between 1% and 3%, by weight of the feed of the solid-free mixture.
In a preferable case, the metal catching agent is obtained by taking one or a mixture of more of alumina, silicon oxide and activated carbon as a matrix, impregnating the matrix with one or more metal salt solutions of Fe, Ti and Co, and drying the impregnated matrix at 120-180 ℃, and more preferably at 130-150 ℃.
Further preferably, the Fe metal salt solution is 0.01-0.1mol/L of FeSO4Solution of Ti metal salt solution of 0.1-1.0mol/L TiCl4The solution is Co with a Co metal salt solution of 0.01-0.1mol/L2(NO)3And (3) solution.
In a preferred case, the operating conditions of the fixed-bed demetallization reactor are: the pressure is 0.5-4.0MPa, the temperature is 180 ℃ and the volume space velocity is 0.3-3.0h-1. The content of metal in the obtained demetallization mixture material is not higher than 20 mu g/g.
In a preferable case, the dehydration system in the step (3) is a high-temperature dehydration tower and/or a centrifuge, and the water content in the purified mixture material is not higher than 300 mu g/g.
In step (4) of the present invention, the purified mixture material is mixed with hydrogen and then enters the hydrogenation unit for reaction, and preferably, the reaction conditions of the first reaction zone in the hydrogenation unit are as follows: the average reaction temperature is 350-420 ℃, the hydrogen partial pressure is 10.0-15.0MPa, and the volume space velocity is 0.3-0.8h-1Hydrogen-oil volume ratio of 1000-; more preferably the average reaction temperature is 360-400 ℃, the hydrogen partial pressure is 12.0-15.0MPa, and the volume space velocity is 0.3-0.5h -1The hydrogen-oil volume ratio is 1200-1800.
Preferably, the reaction conditions in the second reaction zone of the hydrogenation unit are: the average reaction temperature is 330--1The hydrogen-oil volume ratio is 500-1000; more preferably the average reaction temperature is 340-370 ℃, the hydrogen partial pressure is 12.0-15.0MPa, and the volume space velocity is 0.8-1.5h-1The volume ratio of hydrogen to oil is 600-800.
In the present invention, the first reaction zone is filled with a hydrofinishing catalyst, optionally with a hydrogenation protecting agent upstream of the hydrofinishing catalyst. The purified mixture material contacts with a hydrofining catalyst in the presence of hydrogen to carry out hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation and partial aromatic hydrocarbon saturation reactions. The hydrofining catalyst is a conventional hydrofining catalyst, can be a commercially available hydrofining catalyst, and can also be a laboratory agent.
In the invention, the second reaction zone is filled with a hydrocracking catalyst, and at least part of the hydrogenation tail oil is subjected to selective ring-opening and cracking reaction under the action of the hydrocracking catalyst. The hydrocracking catalyst is a conventional hydrocracking catalyst, can be a commercial hydrocracking catalyst, and can also be a laboratory agent.
In a preferable case, the invention adjusts the composition in the hydrogenation tail oil by controlling the hydrogenation depth of the hydrogenation reaction zone, the distillation range of the hydrogenation tail oil is 280-480 ℃, the paraffin content in the hydrogenation tail oil is not higher than 15 percent, and the total aromatic hydrocarbon content is not lower than 10 percent. According to the invention, the hydrogenated tail oil and the coal tar are mixed, and the obtained mixture is subjected to effective pretreatment and then hydrogenation reaction, so that the conversion rate of the whole fraction of the coal tar can be effectively improved, and the maximum utilization of the whole fraction of the coal tar is realized.
The invention also provides a coal tar full-fraction hydrogenation upgrading system, which comprises a separation system, a heating furnace, a fixed bed demetalization reactor, a dehydration system and a hydrogenation unit;
the coal tar full-fraction raw material pipeline is communicated with a hydrogenation tail oil pipeline and is communicated with an inlet pipeline of a separation system, and at least one outlet of the separation system is communicated with a solid-removing mixture material pipeline;
the solid-removing mixture material pipeline is communicated with a steam pipeline and an inlet pipeline of a heating furnace, an outlet pipeline of the heating furnace is communicated with an inlet pipeline of a fixed bed metal-removing reactor, a metal catching agent is filled in the fixed bed metal-removing reactor, the metal catching agent is a supported catalyst loaded with at least one metal of Fe, Ti and Co, a carrier is selected from one or more of alumina, silica and active carbon, and an outlet of the fixed bed metal-removing reactor is communicated with an inlet of a dehydration system through a pipeline;
At least one outlet of the dehydration system is communicated with a purified mixture material pipeline, the purified mixture material pipeline is communicated with a hydrogen pipeline and is communicated with an inlet pipeline of the hydrogenation unit, the hydrogenation unit is provided with a first reaction zone, a second reaction zone, a gas-liquid separation zone and a fractionation zone, a hydrogen refining catalyst is filled in the first reaction zone, a hydrogen cracking catalyst is filled in the second reaction zone, the gas-liquid separation zone is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material outlet, and the fractionation zone is provided with a naphtha fraction outlet, a diesel fraction outlet and a hydrogenation tail oil outlet and is respectively communicated with corresponding pipelines.
In one embodiment of the invention, the purified mixture material pipeline is communicated with a hydrogen pipeline and is communicated with an inlet pipeline of a first reaction zone of the hydrogenation unit, an outlet pipeline of the first reaction zone and an outlet pipeline of a second reaction zone are both communicated with an inlet pipeline of the gas-liquid separation zone, and a liquid material flow outlet of the gas-liquid separation zone is communicated with an inlet of the fractionation zone; the hydrogenation tail oil pipeline is divided into two paths, one path is communicated with the inlet of the second reaction zone, and the other path is communicated with the coal tar whole fraction raw material pipeline.
In another embodiment of the invention, the purified mixture material pipeline is communicated with a hydrogen pipeline and is communicated with an inlet pipeline of a first reaction zone of the hydrogenation unit, an outlet of the first reaction zone is communicated with a gas-liquid separation zone I, the gas-liquid separation zone I is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material flow I outlet, the liquid material flow I outlet is communicated with an inlet of a second reaction zone through a pipeline, an outlet of the second reaction zone is communicated with an inlet pipeline of a gas-liquid separation zone II, the gas-liquid separation zone II is provided with a hydrogen-rich gas outlet, a water outlet and a liquid material flow II outlet, and the liquid material flow II outlet is communicated with an inlet of the fractionation zone; the hydrogenation tail oil pipeline is divided into two paths, one path is communicated with the inlet of the second reaction zone, and the other path is communicated with the coal tar whole fraction raw material pipeline.
The invention has the advantages that:
(1) the maximum utilization of the coal tar whole fraction is realized, and the yield of the light oil reaches over 95 percent for the coal tar whole fraction.
(2) A fixed bed demetallization reactor is adopted to carry out impurity removal and demetallization treatment on the whole fraction of the coal tar under low pressure, and the investment cost of the device is low.
(3) The operation period of the hydrogenation unit device is prolonged, the pressure drop rising speed of a reactor in the hydrogenation unit can be obviously reduced by purified coal tar whole fraction, and the operation period of the whole device is effectively prolonged.
Drawings
FIG. 1 is a schematic flow diagram of one embodiment of a coal tar whole fraction hydrogenation upgrading method provided by the invention.
FIG. 2 is a schematic flow diagram of another embodiment of a coal tar whole fraction hydrogenation upgrading method provided by the invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The method provided by the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited thereto.
As shown in FIG. 1, one embodiment of the coal tar full-cut hydrogenation upgrading method provided by the invention is as follows: the coal tar whole fraction raw material from the pipeline 1 is mixed with the hydrogenation tail oil from the
The purified mixture material from the
As shown in fig. 2, another embodiment of the coal tar whole fraction hydrogenation upgrading method provided by the present invention is as follows: the coal tar whole fraction raw material from the pipeline 1 is mixed with the hydrogenation tail oil from the
The purified mixture material from the
The following examples further illustrate the process of the present invention but are not intended to limit the invention thereto.
The properties of the coal tar whole cut feedstock of the following examples are shown in table 1.
TABLE 1 Properties of the stock oils
Density (20 ℃ C.)/(g/cm)3)
0.9998
Carbon residue/weight%
4.97
Nitrogen content/(μ g/g)
6100
Sulfur content/(μ g/g)
2200
H content/weight%
9.61
Asphaltene content/weight%
13.5
Mechanical impurity content/weight%
0.12
Distillation Range ASTM D-1160/. degree.C
IBP
172
50％
370
95％
505
Metal content/(μ g/g)
Fe
46.9
Na
13.3
Ca
130.7
The preparation method of the metal catching agent comprises the following steps: .
Mixing pseudo-boehmite and activated carbon according to the mass ratio of 3:1, and mixingAfter synthesis and drying, the carrier is prepared by roasting for 1-6 hours at 500-1000 ℃ in the air. The support was immersed in TiCl at a concentration of 0.8mol/L4And 0.03mol/LCo2(NO)3After the solution is immersed, the metal catching agent BM-1 is obtained after drying for 6 hours at the temperature of 150 ℃.
The properties of the hydrogenated tail oil used in the test are shown in the following table:
item
Density (20 ℃ C.), g/cm3
0.9040
S content, μ g/g
4.48
N content, μ g/
15
Composition of mass spectrometry/%)
Alkane hydrocarbons
26.9
Cycloalkanes
41.2
Total aromatic hydrocarbons
31.9
Distillation Range ASTM D-86, deg.C
IBP
286
5％
359
10％
363
20％
369
30％
374
40％
379
50％
390
60％
402
70％
413
80％
424
90％
449
95％
473
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