A method for processing carbon ten crude aromatic hydrocarbon based on reducing low added value recombination components

Abstract

The application provides a method for treating carbon ten crude aromatic hydrocarbon based on reducing low-value heavy components, which comprises the following steps: feeding the carbon ten crude aromatic hydrocarbon into a tubular reactor provided with a catalyst to perform catalytic hydrogenation reaction; after the reaction is completed, filtering, pumping the filtrate into a rectification system to perform intermittent rectification, and cutting different fractions under the conditions of a certain pressure, a certain temperature and a certain reflux ratio. The method provided by the application is simple in operation, greatly reduces the yield of low-value heavy components, and improves the utilization rate of the carbon ten crude aromatic hydrocarbon.

Description

Technical fields:

[0001] This invention relates to the field of heavy aromatic hydrocarbon processing technology, and specifically to a method for processing C10 crude aromatic hydrocarbons based on reducing low-value-added heavy components. Background technology:

[0002] Heavy aromatics oil is a byproduct of crude oil processing. With the rapid development of the global petrochemical industry in the 21st century, the global production of heavy aromatics oil has increased significantly. In my country, the production of heavy aromatics oil is high, but its utilization efficiency is low. Heavy aromatics oil has many uses; many companies are now using it to develop new products, and it is also being utilized in the chemical and high-tech fields. Rational utilization of heavy aromatics oil can generate substantial economic benefits. As a byproduct of crude oil processing, some heavy aromatics oils contain olefins, which affect their use and necessitate de-oxidation and refining. Currently, the main method for refining heavy aromatics is hydrogenation, which saturates the olefins in the heavy aromatics. The selection of the hydrogenation catalyst is crucial in this process.

[0003] The utilization process of reformed heavy aromatics also includes distillation to obtain different high-value components. The main process is as follows: industrial C10 crude aromatics are distilled through a distillation column under certain pressure, reflux ratio, and temperature to obtain different fractions. The above method has the following drawbacks: the heavy components after distillation have a distillation range >320℃, high density, and high viscosity, resulting in slow flow at the liquidus inlet of the reboiler. This leads to incomplete distillation of some materials and the mixing of some high-value-added materials with low-value-added heavy components, thus affecting the utilization rate of heavy aromatics. Summary of the Invention:

[0004] The technical problem to be solved by the present invention is to provide a method for processing C10 crude aromatics based on reducing low-value-added heavy components, in order to address the shortcomings of the prior art. The method first uses an appropriate amount of catalyst to perform hydrogenation catalytic treatment on C10 crude aromatics, and then performs intermittent distillation on the hydrogenated and catalytically treated material. During the distillation process, a forced circulation pump is set in the distillation column and reboiler to improve the fluidity of heavy components, improve the heat exchange effect, and thus improve the utilization rate of heavy aromatics.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0006] A method for processing C3 crude aromatics based on reducing low-value-added heavy components includes the following steps:

[0007] (1) Pass the C10 crude aromatic hydrocarbon into a tubular reactor containing a catalyst to carry out a catalytic hydrogenation reaction. After the reaction is completed, filter the solution and pump the filtrate into a distillation system for intermittent distillation.

[0008] (2) First, under the conditions of pressure of 0.4-0.5MPa and reflux ratio of (4-6):1, the temperature at the top of the column is controlled at 135±5℃ and the temperature at the bottom of the column is controlled at 170±5℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain light component aromatic solvent.

[0009] (3) Under the conditions of pressure of 0.3-0.4MPa and reflux ratio of (4-7):1, the temperature at the top of the column is controlled at 150±2℃ and the temperature at the bottom of the column is controlled at 180±3℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain a methyltrimethylbenzene enriched liquid.

[0010] (4) Under the conditions of vacuum degree of -0.09MPa and reflux ratio of 5-8:1, the temperature at the top of the column is controlled at 155±5℃ and the temperature at the bottom of the column is controlled at 190±2℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain naphthalene enriched liquid.

[0011] As a preferred embodiment of the above technical solution, in step (1), the catalyst is prepared by: treating H-β zeolite and H-ZSM-5 zeolite in an ammonium nitrate solution, then calcining them once in an air atmosphere, and after calcination, placing them in a mixed solution of nickel nitrate and ammonium heptamolybdate for static treatment, then drying them, and finally calcining them a second time to obtain the catalyst.

[0012] As a preferred embodiment of the above technical solution, the concentration of the ammonium nitrate solution is 1 mol / L, and the mass ratio of H-β zeolite, H-ZSM-5 zeolite, and ammonium nitrate solution is 1:(1-3):10.

[0013] As a preferred embodiment of the above technical solution, the processing temperature is 80-90℃ and the processing time is 2-5h.

[0014] As a preferred embodiment of the above technical solution, the temperature of the first calcination treatment is 500℃ and the time is 5-6 hours.

[0015] As a preferred embodiment of the above technical solution, the concentrations of nickel nitrate and ammonium heptamolybdate in the mixed solution are 2-5 wt% and 5-10 wt%, respectively, and the ratio of the mixed solution to the solid after the first calcination treatment is 100 ml: 5-20 g.

[0016] As a preferred embodiment of the above technical solution, the static treatment is performed at room temperature for 10-20 hours.

[0017] As a preferred embodiment of the above technical solution, the temperature of the secondary calcination treatment is 500℃ and the time is 2-5h.

[0018] As a preferred embodiment of the above technical solution, in step (1), the loading volume of the catalyst is 10-20 ml; the pressure of the catalytic hydrogenation reaction is 2-4 MPa, the temperature is 300-400℃, the hydrogen-to-oil volume ratio is 300-400, and the weight hourly space velocity is 2-3 h⁻¹. -1 .

[0019] As a preferred embodiment of the above technical solution, the distillation system includes a reboiler and a distillation column; the heat exchange material outlet of the reboiler is connected to the distillate inlet of the distillation column, the material outlet at the bottom of the distillation column is connected to the reboiler, and a shut-off valve and a forced circulation pump are installed on the pipeline connecting the material outlet and the reboiler.

[0020] By adopting the above technical solution, the present invention has the following beneficial effects:

[0021] This invention uses C10 crude aromatics as raw material and distills different fractions of the product through a distillation column under certain pressure, reflux ratio and temperature. With the setting of a forced reflux pump and a shut-off valve, the heavy components with high density and high viscosity are circulated to the reboiler for heat exchange again, which improves the flowability of the liquid between the reboiler and the distillation column, improves the heat exchange effect, thereby reducing the output of low value-added heavy components and increasing the output of high value-added materials, thus improving the utilization rate of C10 crude aromatics.

[0022] This invention employs a catalyst to hydrocracking crude C10 aromatics before distillation, thereby improving the utilization rate of these aromatics. The hydrogenation catalyst used in this invention utilizes H-β zeolite and H-ZSM-5 zeolite as supports, with nickel-molybdenum oxide as the catalytically active component. Through acidic sites on the catalyst surface, it interacts with heavy aromatic molecules, enabling hydrogenation at these sites and conversion into lighter aromatics or saturated hydrocarbons. The nickel and molybdenum elements in the catalyst provide active sites, facilitating the hydrogenation reaction. Furthermore, the zeolite support framework provides a stable environment, maintaining the catalyst's activity during the hydrogenation reaction. Simultaneously, the pore structure of the zeolite support can also regulate the active sites and distribution of the catalyst, improving its hydrogenation performance. Attached image description:

[0023] Figure 1 This is a schematic diagram of the distillation system.

[0024] In the diagram, 1 is the reboiler; 2 is the distillation column; 3 is the shut-off valve; 4 is the forced circulation pump; and 5 is the material output pump. Detailed implementation method:

[0025] To better understand the present invention, the following embodiments are provided for further illustration. These embodiments are only for explaining the present invention and do not constitute any limitation on the present invention.

[0026] The distillation system described in the following embodiments has the following structure: Figure 1 As shown, the distillation system includes a reboiler 1 and a distillation column 2; the heat exchange material outlet of the reboiler 1 is connected to the distillate inlet of the distillation column 2, the material outlet at the bottom of the distillation column 2 is connected to the reboiler 1, a shut-off valve 3 and a forced circulation pump 4 are installed on the pipe connecting the material outlet and the reboiler 1, and a material output pump 5 is also installed on the discharge pipe of the distillation column 2.

[0027] During distillation, the feed liquid is heated by reboiler 1 and then enters distillation column 2 for distillation. The forced circulation pump 4 and the shut-off valve 3 enable the feed liquid at the bottom of distillation column 2 to be circulated back to reboiler 1, which improves the flowability of the material and the heat exchange effect of the feed liquid, thereby reducing the output of low value-added heavy components and increasing the output of high value-added materials.

[0028] In the following examples, H-β zeolite was purchased from Beijing Huaye Huanyu Chemical Co., Ltd., and H-ZSM-5 zeolite was purchased from Yingkou Zhongbao Molecular Sieve Co., Ltd.

[0029] Example 1

[0030] A method for processing C3 crude aromatics based on reducing low-value-added heavy components includes the following steps:

[0031] (1) 1g of H-β zeolite and 1g of H-ZSM-5 zeolite were placed in 10g of ammonium nitrate solution with a concentration of 1mol / L and treated at 85℃ for 2h. Then, they were calcined in air at 500℃ for 5h. After calcination, they were placed in a mixed solution of nickel nitrate and ammonium heptamolybdate and allowed to stand at room temperature for 12h. The concentrations of nickel nitrate and ammonium heptamolybdate in the mixed solution were 3wt% and 6wt%, respectively. Then, they were dried at 80℃ for 10h. Finally, they were calcined in air at 500℃ for 2h to obtain the catalyst.

[0032] (2) 10 ml of catalyst was packed into a tubular reactor, and 1000 g of C10 crude aromatics was introduced into the tubular reactor containing the catalyst. The reactor was subjected to a pressure of 3 MPa, a temperature of 370 °C, a hydrogen-to-oil volume ratio of 300, and a weight hourly space velocity of 2 h⁻¹. -1 Under certain conditions, a catalytic hydrogenation reaction is carried out. After the reaction is completed, the mixture is filtered, and the filtrate is pumped into a distillation system for intermittent distillation.

[0033] (3) First, under the conditions of pressure of 0.4MPa and reflux ratio of 4:1, the temperature at the top of the column is controlled at 135±5℃ and the temperature at the bottom of the column is controlled at 170±5℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain light component aromatic solvent.

[0034] (4) Under the conditions of pressure of 0.3MPa and reflux ratio of 5:1, the temperature at the top of the column is controlled at 150±2℃ and the temperature at the bottom of the column is controlled at 180±3℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain a methyltrimethylbenzene enriched solution.

[0035] (5) Under the conditions of vacuum degree of -0.09MPa and reflux ratio of 7:1, the temperature at the top of the column is controlled at 155±5℃ and the temperature at the bottom of the column is controlled at 190±2℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain naphthalene-enriched liquid.

[0036] Example 2

[0037] A method for processing C3 crude aromatics based on reducing low-value-added heavy components includes the following steps:

[0038] (1) 1g of H-β zeolite and 2g of H-ZSM-5 zeolite were placed in 10g of ammonium nitrate solution with a concentration of 1mol / L and treated at 85℃ for 3.5h. Then, they were calcined in air at 500℃ for 5h. After calcination, they were placed in a mixed solution of nickel nitrate and ammonium heptamolybdate and allowed to stand at room temperature for 15h. The concentrations of nickel nitrate and ammonium heptamolybdate in the mixed solution were 4wt% and 6wt%, respectively. Then, they were dried at 80℃ for 10h. Finally, they were calcined in air at 500℃ for 3h to obtain the catalyst.

[0039] (2) 15 ml of catalyst was packed into a tubular reactor, and 1000 g of C10 crude aromatics was introduced into the tubular reactor containing the catalyst. The reactor was subjected to a pressure of 3 MPa, a temperature of 375 °C, a hydrogen-to-oil volume ratio of 300, and a weight hourly space velocity of 3 h⁻¹. -1 Under certain conditions, a catalytic hydrogenation reaction is carried out. After the reaction is completed, the mixture is filtered, and the filtrate is pumped into a distillation system for intermittent distillation.

[0040] (3) First, under the conditions of pressure of 0.5MPa and reflux ratio of 4:1, the temperature at the top of the column is controlled at 135±5℃ and the temperature at the bottom of the column is controlled at 170±5℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain light component aromatic solvent.

[0041] (4) Under the conditions of pressure of 0.4MPa and reflux ratio of 5:1, the temperature at the top of the column is controlled at 150±2℃ and the temperature at the bottom of the column is controlled at 180±3℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain a methyltrimethylbenzene enriched solution.

[0042] (5) Under the conditions of vacuum degree of -0.09MPa and reflux ratio of 6:1, the temperature at the top of the column is controlled at 155±5℃ and the temperature at the bottom of the column is controlled at 190±2℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain naphthalene-enriched liquid.

[0043] Example 3

[0044] A method for processing C3 crude aromatics based on reducing low-value-added heavy components includes the following steps:

[0045] (1) 1g of H-β zeolite and 3g of H-ZSM-5 zeolite were placed in 10g of ammonium nitrate solution with a concentration of 1mol / L and treated at 85℃ for 3h. Then, they were calcined in air at 500℃ for 5h. After calcination, they were placed in a mixed solution of nickel nitrate and ammonium heptamolybdate and allowed to stand at room temperature for 15h. The concentrations of nickel nitrate and ammonium heptamolybdate in the mixed solution were 3wt% and 8wt%, respectively. Then, they were dried at 80℃ for 10h. Finally, they were calcined in air at 500℃ for 3h to obtain the catalyst.

[0046] (2) 20 ml of catalyst was packed into a tubular reactor, and 1000 g of C10 crude aromatics was introduced into the tubular reactor containing the catalyst. The reactor was subjected to a pressure of 4 MPa, a temperature of 300 °C, a hydrogen-to-oil volume ratio of 300-400, and a weight hourly space velocity of 2 h⁻¹. -1 Under certain conditions, a catalytic hydrogenation reaction is carried out. After the reaction is completed, the mixture is filtered, and the filtrate is pumped into a distillation system for intermittent distillation.

[0047] (3) First, under the conditions of pressure of 0.45MPa and reflux ratio of 4:1, the temperature at the top of the column is controlled at 135±5℃ and the temperature at the bottom of the column is controlled at 170±5℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain light component aromatic solvent.

[0048] (4) Under the conditions of pressure of 0.33MPa and reflux ratio of 5:1, the temperature at the top of the column is controlled at 150±2℃ and the temperature at the bottom of the column is controlled at 180±3℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain a methyltrimethylbenzene enriched solution.

[0049] (5) Under the conditions of vacuum degree of -0.09MPa and reflux ratio of 5:1, the temperature at the top of the column is controlled at 155±5℃ and the temperature at the bottom of the column is controlled at 190±2℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain naphthalene enriched liquid.

[0050] Tests showed that the lowest residual oil content after distillation in the above embodiments was 98.5g, and the utilization rate of C10 crude aromatics was as high as 90.15%.

[0051] Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A method for processing C10 crude aromatics based on reducing low-value-added heavy components, characterized in that, Includes the following steps: (1) C10 crude aromatics are introduced into a tubular reactor containing a catalyst to carry out catalytic hydrogenation. After the reaction is completed, the mixture is filtered and the filtrate is pumped into a distillation system for intermittent distillation. (2) First, under the conditions of pressure of 0.4-0.5MPa and reflux ratio of (4-6):1, the temperature at the top of the column is controlled at 135±5℃ and the temperature at the bottom of the column is controlled at 170±5℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain light component aromatic solvent. (3) Under the conditions of pressure of 0.3-0.4MPa and reflux ratio of (4-7):1, the temperature at the top of the column is controlled at 150±2℃ and the temperature at the bottom of the column is controlled at 180±3℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain a methyltrimethylbenzene enriched liquid. (4) Under the conditions of vacuum degree of -0.09MPa and reflux ratio of 5-8:1, the temperature at the top of the column is controlled at 155±5℃ and the temperature at the bottom of the column is controlled at 190±2℃. The vapor phase at the top of the column during distillation is collected after condensation to obtain naphthalene-enriched liquid. The catalyst is prepared by treating H-β zeolite and H-ZSM-5 zeolite in an ammonium nitrate solution, followed by a first calcination at 500°C for 5-6 hours in air. After calcination, the catalyst is placed in a mixed solution of nickel nitrate and ammonium heptamolybdate for static treatment, then dried, and finally subjected to a second calcination at 500°C for 2-5 hours to obtain the catalyst. The concentrations of nickel nitrate and ammonium heptamolybdate in the mixed solution are 2-5 wt% and 5-10 wt%, respectively, and the ratio of the mixed solution to the solid after the first calcination is 100 ml: 5-20 g.

2. The method for processing C10 crude aromatics based on reducing low-value-added heavy components according to claim 1, characterized in that, The concentration of the ammonium nitrate solution is 1 mol / L, and the mass ratio of the H-β zeolite, H-ZSM-5 zeolite, and ammonium nitrate solution is 1:(1-3):

10.

3. The method for processing C10 crude aromatics based on reducing low-value-added heavy components according to claim 1, characterized in that, The treatment is carried out at a temperature of 80-90℃ for 2-5 hours.

4. The method for processing C10 crude aromatics based on reducing low-value-added heavy components according to claim 1, characterized in that, The settling temperature is room temperature, and the time is 10-20 hours.

5. The method for processing C3 crude aromatics based on reducing low-value-added heavy components according to claim 1, characterized in that, In step (1), the catalyst loading volume is 10-20 ml; the catalytic hydrogenation reaction pressure is 2-4 MPa, the temperature is 300-400 °C, the hydrogen-to-oil volume ratio is 300-400, and the weight hourly space velocity is 2-3 h⁻¹. -1 .

6. The method for processing C3 crude aromatics based on reducing low-value-added heavy components according to claim 1, characterized in that, The distillation system includes a reboiler and a distillation column; the heat exchange material outlet of the reboiler is connected to the distillate inlet of the distillation column, the material outlet at the bottom of the distillation column is connected to the reboiler, and a shut-off valve and a forced circulation pump are installed on the pipeline connecting the material outlet and the reboiler.

Images