CN113122329B - Method and system for co-producing needle coke and low-sulfur petroleum coke - Google Patents
Method and system for co-producing needle coke and low-sulfur petroleum coke Download PDFInfo
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- CN113122329B CN113122329B CN201911417740.4A CN201911417740A CN113122329B CN 113122329 B CN113122329 B CN 113122329B CN 201911417740 A CN201911417740 A CN 201911417740A CN 113122329 B CN113122329 B CN 113122329B
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention discloses a method and a system for co-producing needle coke and low-sulfur coke, wherein the method comprises the steps of feeding refined oil obtained by hydrotreating catalytic slurry oil into a reduced pressure distillation system, and separating to obtain light fraction, middle distillate and heavy distillate; the oil gas product of the middle distillate oil after coking reaction enters a pressure stabilizing tower, and non-condensable gas, distillate oil and tower bottom oil are obtained after separation; the tower bottom oil is divided into two paths after being buffered, wherein one path of tower bottom oil returns to the pressure stabilizing tower after being subjected to temperature adjustment, and the other path of tower bottom oil enters a fractionation system; and feeding the light fraction and the heavy fraction oil into a low-sulfur petroleum coke production device, and separating the reaction oil gas product in a fractionation system to obtain gas, light oil and wax oil. The process uses a portion of the components in the catalytic slurry to produce needle coke and the remaining components to produce low sulfur petroleum coke, which maximizes feedstock conversion.
Description
Technical Field
The invention relates to a method for producing petroleum coke, in particular to a method and a system for simultaneously producing needle coke and low-sulfur petroleum coke by using catalytic slurry oil as a raw material.
Background
The catalytic slurry oil has high aromatic hydrocarbon content, poor cracking performance and difficult deep processing. Many domestic oil refining enterprises use the catalytic oil slurry as a blending component of fuel oil or as a raw material for producing road asphalt and the like, so that the economic benefit is low. In the present year, the transformation development of the steel industry in China, the steel making development of an electric arc furnace are rapid, the demand on graphite electrodes is increasing day by day, the prices of needle coke and low-sulfur petroleum coke are high, and the market is in a short supply and demand state. Needle coke and low sulfur petroleum coke have many commonalities, such as low sulfur, low ash content, low metal content, high density, etc., and the greatest difference is that the national standard for low sulfur petroleum coke has no limitation on the thermal expansion coefficient, so that the low sulfur petroleum coke has loose requirements on raw materials and a much simpler production process. CN103184057A, CN104560152A, etc. disclose methods for producing needle coke by using catalytic slurry oil as raw material, but the requirements of needle coke on raw material are high, and not all components in catalytic slurry oil can be used for producing needle coke. CN1872963A, CN103789028A and the like disclose needle coke raw material production methods, which enrich and catalyze aromatic hydrocarbons such as tricyclic, tetracyclic and the like in oil slurry as raw materials for producing needle coke by various means, but the rest components are still not well utilized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a system for co-producing needle coke and low-sulfur coke by using catalytic slurry oil as a raw material. The process uses a portion of the components in the catalytic slurry to produce needle coke and the remaining components to produce low sulfur petroleum coke, which maximizes feedstock conversion.
In a first aspect, the present invention provides a process for the co-production of needle coke and low sulphur petroleum coke, said process comprising the steps of:
(1) mixing the catalytic slurry oil with hydrogen, feeding the mixture into a hydrogenation reaction zone, reacting in the presence of a hydrogenation catalyst, and separating reaction products to obtain gas, naphtha and refined oil;
(2) feeding the refined oil obtained in the step (1) into a reduced pressure distillation system for separation to obtain light fraction, middle distillate and heavy distillate;
(3) feeding the middle distillate oil obtained in the step (2) into a needle coke production device, feeding a reaction oil gas product into a pressure stabilizing tower, and separating to obtain non-condensable gas, distillate oil and tower bottom oil;
(4) the tower bottom oil obtained in the step (3) enters a buffer tank, is buffered and then is divided into two paths A and B, wherein the tower bottom oil of the path A returns to a pressure stabilizing tower after temperature adjustment, and the tower bottom oil of the path B enters a fractionation system;
(5) and (3) feeding the light fraction and the heavy fraction oil obtained in the step (2) into a low-sulfur petroleum coke production device, feeding the reaction oil gas product into a fractionation system, and separating to obtain gas, light oil and wax oil.
In the method for co-producing needle coke and low-sulfur petroleum coke, the catalytic slurry oil in the step (1) is subjected to solid removal treatment in advance, and the solid removal treatment can be one or more of filtration, sedimentation, centrifugal separation, reduced pressure distillation and the like. The slurry-solid content of the catalytic oil after the de-solidification treatment is less than 0.01 wt%.
In the method for co-producing needle coke and low-sulfur petroleum coke, the hydrogenation reaction zone in the step (1) comprises at least one hydrogenation reactor and a reaction product separation system; the hydrogenation reactor can adopt one or more of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, a suspended bed hydrogenation reactor and a moving bed hydrogenation reactor, and preferably adopts a fixed bed hydrogenation reactor. The reaction product separation system is a separation system adopted in the prior art, and can comprise one or more of a hot high-pressure separator, a cold high-pressure separator, a hot low-pressure separator and a cold low-pressure separator, and the separation system can be selected by a person skilled in the art according to actual needs and according to the existing knowledge. The hydrogenation catalyst carrier is generally inorganic oxide such as alumina, and the active component is oxide of metal in VIB group and/or VIII group. The hydrogenation catalyst can adopt the existing heavy oil hydrogenation treatment catalyst, such as FZC series hydrogenation catalyst developed by the research institute of petrochemical industry.
In the method for co-producing needle coke and low-sulfur petroleum coke, the operating conditions of the hydrogenation reaction zone in the step (1) are as follows: the reaction temperature is 300-480 ℃, the preferable temperature is 330-400 ℃, the reaction pressure is 3-20 MPa, the preferable pressure is 5-10 MPa, the volume ratio of hydrogen to oil is 100-2500, the preferable pressure is 500-1500, wherein the volume ratio of hydrogen to oil is the volume ratio of hydrogen to catalytic slurry oil, and the liquid hourly space velocity is 0.1h when the catalytic slurry oil is used for metering liquid-1～2.0h-1Preferably 0.5h-1～1.0h-1。
In the method for coproducing needle coke and low-sulfur petroleum coke, the sulfur content of the refined oil in the step (1) is not more than 0.5wt%, and preferably not more than 0.4 wt%.
In the method for coproducing needle coke and low-sulfur petroleum coke, the 5 percent distillation temperature of the middle distillate oil in the step (2) is 320-420 ℃, and preferably 340-380 ℃; the 95 percent distillation temperature of the middle distillate is 450-520 ℃, preferably 460-490 ℃.
In the method for co-producing needle coke and low-sulfur petroleum coke, the needle coke production device in the step (3) comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage. The middle distillate oil is heated by a heating furnace and then fed into a coke tower, the generated needle coke is deposited at the bottom of the tower, and the generated oil gas is discharged from the top of the tower to a pressure stabilizing tower. The outlet temperature of the heating furnace is 400-550 ℃, preferably 440-520 ℃, and the heating rate is 1-50 ℃/h, preferably 2-10 ℃/h; the top pressure of the coke tower is 0.01 MPa-2.5 MPa, preferably 0.2 MPa-1.5 MPa, and the coke tower can be operated at constant pressure and variable pressure, if variable pressure operation is adopted, the variable pressure rate is 0.1 MPa/h-5 MPa/h; the reaction period is 10-50 h, preferably 30-50 h.
In the method for co-producing needle coke and low-sulfur petroleum coke, the pressure control system is arranged at the top of the pressure stabilizing tower in the step (3), and the pressure of the pressure stabilizing tower is associated with the pressure of the coke tower, namely the pressure of the coke tower is controlled by adjusting the pressure of the pressure stabilizing tower.
In the method for co-producing needle coke and low-sulfur petroleum coke, the 95 percent distillation temperature of distillate oil obtained by the pressure stabilizer in the step (3) is 150-430 ℃, preferably 230-370 ℃, and more preferably 230-330 ℃. The 95% distillation temperature of the distillate can be constant or can fluctuate within a certain range, preferably within a certain range.
In the method for co-producing needle coke and low-sulfur petroleum coke, the liquid level of the pressure stabilizing tower in the step (3) accounts for 10-80% of the total height of the tower.
In the method for co-producing needle coke and low-sulfur petroleum coke, the operation mode of returning the tower bottom oil of the path A to the pressure stabilizing tower in the step (4) is determined by the 95 percent distillation temperature of distillate oil in the pressure stabilizing tower and the liquid level of the tower bottom of the pressure stabilizing tower. When the liquid level at the bottom of the pressure stabilizer is increased to more than 60 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is increased to more than 310 ℃, the tower bottom oil of the path A is cooled and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is increased; when the liquid level at the bottom of the pressure stabilizer is increased to more than 60 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is reduced to below 240 ℃, the tower bottom oil of the path A is heated and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is increased; when the liquid level at the bottom of the pressure stabilizer is reduced to be lower than 20 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is increased to be higher than 310 ℃, the tower bottom oil of the path A is cooled and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is reduced; when the liquid level at the bottom of the pressure stabilizer is reduced to be lower than 20 percent of the total tower height and the 95 percent distillation temperature of distillate oil is reduced to be lower than 240 ℃, the tower bottom oil of the path A is heated and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is reduced.
In the method for co-producing the needle coke and the low-sulfur petroleum coke, the fractionating system in the step (5) separates gas, light oil and wax oil; the 95 percent distillation temperature of the light oil is 300-440 ℃, and the optimal temperature is 320-380 ℃. The 5% distillation temperature of the wax oil is higher than the 95% distillation temperature of the light oil by more than 3 ℃.
In the method for co-producing needle coke and low-sulfur petroleum coke, the wax oil in the step (5) is recycled to the needle coke production device, the wax oil is preferably subjected to solid removal treatment in advance and then recycled to the needle coke production device, and the solid removal treatment process can be one or more of filtration, sedimentation, centrifugation and the like, and is preferably filtration.
In the method for co-producing needle coke and low-sulfur petroleum coke, the light oil obtained in the step (5) is polymerized, and the polymer obtained after polymerization is recycled to the low-sulfur petroleum coke production device; and (4) carrying out polymerization treatment on the distillate oil obtained in the step (3), and recycling the polymer obtained after the polymerization treatment to a low-sulfur petroleum coke production device. The polymerization treatment is carried out in a polymerization unit, the polymerization unit comprises at least one polymerization reactor, a catalyst is filled in the reactor, and the polymerization reactor is a fixed bed reactor. The polymerization reactor reaction conditions are as follows: the reaction temperature is 380-550 ℃, preferably 400-450 ℃, the reaction pressure is 0.01-10 MPa, preferably 1-4 MPa, and the retention time is 0.1-20 h, preferably 2-5 h. The catalyst takes one or more of kaolin, montmorillonite, alumina, silicon-containing alumina and the like as a carrier, and loads one or more of oxides of metals in IVB group and/or VIB group, such as Zr, W, Mo and the like. The metal content of the catalyst is 0.1-40 wt%, preferably 3-25 wt%. The shape of the catalyst can be one or more grading compositions of a sphere, a cylinder, clover, raschig ring and the like.
In the method for co-producing needle coke and low-sulfur petroleum coke, the low-sulfur petroleum coke production device in the step (5) comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage. The outlet temperature of the heating furnace is 470-550 ℃, preferably 490-505 ℃. The coke tower top pressure is 0.01 MPa-2.5 MPa, preferably 0.5 MPa-1.0 MPa, and the coke tower top pressure can be operated at constant pressure or variable pressure, preferably constant pressure; when pressure swing operation is adopted, the pressure change rate is 0.01 MPa/h-50 MPa/h, preferably 0.2 MPa/h-5 MPa/h. The reaction period is 10-50 h, preferably 30-50 h, and preferably the same as the coking period of the needle coke in the step (3).
In a second aspect the present invention provides a system for co-producing needle coke and low sulphur petroleum coke, the system comprising:
the hydrogenation reaction zone comprises at least one hydrogenation reactor and a reaction product separation system, and is used for receiving catalytic slurry oil and hydrogen and obtaining refined oil after treatment;
the reduced pressure distillation tower is used for receiving the refined oil from the hydrogenation reaction zone and separating to obtain light fraction, middle distillate and heavy distillate;
a needle coke production unit for receiving and processing middle distillate from a vacuum distillation column;
the pressure stabilizing tower is used for receiving oil gas products from the needle coke production device and obtaining non-condensable gas, distillate oil and tower bottom oil after treatment;
the buffer tank is used for receiving tower bottom oil from the pressure stabilizing tower, dividing the tower bottom oil into tower bottom oil in a path A and tower bottom oil in a path B after buffer treatment, and circulating the tower bottom oil in the path A back to the pressure stabilizing tower through a pipeline;
a low sulfur petroleum coke production unit for receiving and processing light and heavy distillate oils from a vacuum distillation column;
and the fractionating system is used for receiving the B path tower bottom oil from the buffer tank and the reaction oil gas products from the low-sulfur petroleum coke production device, and obtaining gas, light oil and wax oil after treatment.
In the system for co-producing needle coke and low-sulfur petroleum coke, the wax oil obtained from the fractionation system is circulated back to the needle coke production device through a pipeline, and a solid removal device is arranged on the pipeline and can be one or more of a filter, a centrifugal separator and a settler.
The system for coproducing needle coke and low-sulfur petroleum coke comprises a polymerization unit, wherein the polymerization unit is used for receiving light oil from a fractionation system and optional distillate oil from a pressure stabilizing tower, and a polymer obtained after polymerization treatment is recycled to a low-sulfur petroleum coke production device through a pipeline.
In the above system for co-producing needle coke and low sulfur petroleum coke, the needle coke production apparatus comprises at least one heating furnace and two coke drums, and at least one coke drum is always in the reaction stage and at least one coke drum is in the decoking stage.
In the above system for co-producing needle coke and low-sulfur petroleum coke, the low-sulfur petroleum coke production apparatus comprises at least one heating furnace and two coke drums, and at least one coke drum is always in the reaction stage and at least one coke drum is in the decoking stage.
Compared with the prior art, the method and the system for co-producing needle coke and low-sulfur petroleum coke provided by the invention have the following advantages:
(1) the overall utilization rate of the catalytic oil slurry is improved, the sulfur content of the low-sulfur petroleum coke is required to be less than 0.5wt%, and the contents of impurities such as ash, metal and the like are low, so that the low-sulfur petroleum coke can be produced as long as the impurities such as sulfur, ash, metal and the like in the raw oil meet the requirements under normal conditions. In contrast, the needle coke has strict requirements on impurities and has strict limit indexes on macro morphology, micro morphology and application performance, so the needle coke has more strict requirements on raw materials. The invention divides the catalytic slurry oil into two parts, one part of which has moderate distillation range and is used for producing needle coke, and the other part of which consists of over-light and over-heavy fractions in the catalytic slurry oil and is used for producing low-sulfur petroleum coke, thereby not only improving the overall utilization rate of the catalytic slurry oil, but also being beneficial to improving the quality of the needle coke product.
(2) Improve needle coke production system stability, in whole needle coke production cycle, the coke drum gas discharge amount is undulant great, and prior art adjusts coke drum pressure through the pressure control system at the coke drum top of the tower, and this pressure control system operating range is wider, and the operation of low reaches fractionating system is undulant also great moreover, is unfavorable for device steady operation. The pressure stabilizing tower is arranged between the coke tower and the fractionating system, the pressure control system is arranged at the top of the pressure stabilizing tower, and the top pressure of the coke tower is controlled by adjusting the top pressure of the pressure stabilizing tower; the non-condensable gas and part of light oil in the coking oil gas are removed from the tower bottom oil of the pressure stabilizing tower, so that the feeding property of the fractionating tower is relatively stable, and the tower bottom oil can be quantitatively delivered to the fractionating system, thereby eliminating the adverse effect of unstable feeding on the operation of the fractionating system and greatly improving the operation stability of the fractionating system.
(3) The yield of low-sulfur petroleum coke is improved, the catalytic slurry oil is rich in aromatic hydrocarbon, and the generated coking light oil has the characteristics of high aromatic hydrocarbon content, unstable property and the like after coking treatment, and has low utilization value. According to the invention, the light oil is used as the low-sulfur petroleum coke raw material again after being subjected to polymerization reaction and heavy, so that the problem of difficulty in processing aromatic-rich oil products is solved, and the yield of the low-sulfur petroleum coke is favorably improved.
Drawings
Fig. 1 is a schematic diagram of a process and system for co-producing needle coke and low sulfur petroleum coke according to the present invention.
FIG. 2 is a graph showing the relationship between the 5% distillation temperature of wax oil separated by the fractionation system and the reaction time in example 1.
FIG. 3 is a graph showing the relationship between the 5% distillation temperature of wax oil separated by the fractionation system of comparative example 1 and the reaction time.
FIG. 4 is a graph showing the relationship between the 5% distillation temperature of wax oil separated by the fractionation system and the reaction time in example 2.
FIG. 5 is a graph showing the relationship between the 5% distillation temperature of wax oil separated by the fractionation system of comparative example 2 and the reaction time.
Detailed Description
The following examples are provided to further illustrate the process and effects of the present invention, but are not to be construed as limiting the scope of the present invention.
As can be seen from figure 1, the invention provides a method and a system for coproducing needle coke and low-sulfur petroleum coke, catalytic slurry oil 1 is mixed with hydrogen and enters a hydrogenation reaction zone 2, refined oil 3 in reaction effluent is sent to a vacuum distillation tower 4, and middle distillate oil 5 and other distillate oil are obtained by separation, wherein the other distillate oil comprises light fraction 6 and heavy fraction oil 7. Feeding the middle distillate oil 5 to a needle coke production device 10, and sending oil gas 11 generated by reaction to a pressure stabilizing tower 12; light components discharged from the top of the pressure stabilizing tower 12 comprise non-condensable gas 13 and distillate oil 14, and bottom oil 15 is sent to a buffer tank 16; the tower bottom oil in the buffer tank 16 is divided into two paths, the tower bottom oil 18 in the path A is circulated back to the pressure stabilizing tower, and the tower bottom oil 17 in the path B is sent to a fractionation system 19. The light fraction 6 and the heavy fraction 7 are fed to a low sulfur petroleum coke production unit 26, and the oil gas 27 generated by the reaction is sent to a fractionation system 19. The fractionation system 19 separates gas 20, light oil 23 and wax oil 21, wherein the wax oil 21 is processed by a filter 22 to obtain purified oil 8 which is recycled to the needle coke production device 10; the light oil 23 is sent to a polymerization unit 24, the noncondensable gas 25 obtained after the polymerization reaction is discharged, and the polymer 9 is returned to a low sulfur petroleum coke production facility 26. The distillate 14 obtained at the top of the stabilizer 12 can also be sent, partially or totally, to the polymerization unit 24.
The properties of the catalytic slurry oils used in the following examples and comparative examples are shown in Table 1.
Example 1
Example 1 Using the method provided by the present invention, catalytic slurry oil and hydrogen were mixed and fed into a hydrogenation reaction zone to contact with a catalyst of FCZ-34 type at a reaction temperature of 370 ℃, a reaction pressure of 7.8MPa, a hydrogen-to-oil volume ratio of 900, and a liquid hourly space velocity of 0.7h-1(ii) a The obtained hydrofined oil is sent to a vacuum distillation device to be separated into middle distillate oil and other distillate oil, wherein the 5 percent distillation temperature of the middle distillate oil is 358.6 ℃, and the 95 percent distillation temperature of the middle distillate oil isThe temperature is 472.8 ℃; the middle distillate oil is sent to a needle coke production system, the outlet temperature of a coking heating furnace is 465-505 ℃, the heating rate is 4 ℃/h, a coke tower adopts pressure swing operation, the initial pressure of the tower top is 1.0MPa, when the feeding time reaches 60% of the reaction period, the pressure of the tower top is reduced to 0.2MPa at the rate of 0.3MPa/h, the reaction period is 38h, oil gas generated by coking is sent to a pressure stabilizing tower, non-condensable gas and distillate oil are discharged from the tower top, the tower bottom oil is sent to a buffer tank, the oil at the tower bottom is divided into two streams, the first stream is circulated back to the pressure stabilizing tower, and the second stream is sent to a fractionation system; other distillate oil is sent to a low-sulfur petroleum coke production system, the outlet temperature of a coking heating furnace is 495 ℃, a coke tower adopts constant pressure operation, the pressure at the top of the tower is 0.7MPa, the reaction period is 38h, and oil gas generated by coking is sent to a fractionation system; and gas, light oil and wax oil are separated out by the fractionation system, the wax oil circulates back to the needle coke tower, the light oil and distillate oil separated by the pressure stabilizer are sent to the polymerization unit together, the light oil and the distillate oil are contacted with a Zr/Mo-based catalyst, the reaction temperature is 420 ℃, the reaction pressure is 2MPa, the reaction time is 4h, and the generated polymer returns to the low-sulfur petroleum coke tower. The specific reaction conditions are shown in Table 2. The product distribution is shown in Table 3. The corresponding relationship between the 5% distillation temperature of the wax oil separated by the fractionation system and the reaction time is shown in FIG. 2.
Comparative example 1
The needle coke and the low-sulfur petroleum coke are produced by adopting the prior art, wherein the needle coke production system is not provided with a pressure stabilizing part, the generated oil gas is directly sent to a fractionation system, the low-sulfur petroleum coke production system is not provided with a polymerization part, and the coking light oil is directly discharged.
Mixing the catalytic slurry oil after the de-solidification treatment with hydrogen, entering a hydrogenation reaction zone to contact with a catalyst, wherein the type of the catalyst is FCZ-34, the reaction temperature is 370 ℃, the reaction pressure is 7.8MPa, the volume ratio of hydrogen to oil is 900, and the liquid hourly space velocity is 0.7h-1(ii) a Sending the obtained hydrofined oil to a reduced pressure distillation device, and separating the hydrofined oil into middle distillate oil and other distillate oil, wherein the 5 percent distillation temperature of the middle distillate oil is 358.6 ℃, and the 95 percent distillation temperature is 472.8 ℃; the middle distillate oil is sent to a needle coke production system, the outlet temperature of a coking heating furnace is 465-505 ℃, the heating rate is 4 ℃/h, a coke tower adopts pressure swing operation, the initial pressure of the tower top is1.0MPa, when the feeding time reaches 60 percent of the reaction period, the pressure at the top of the tower is reduced to 0.2MPa at the speed of 0.3MPa/h, the reaction period is 38h, and oil gas generated by coking is sent to a fractionation system; other distillate oil is sent to a low-sulfur petroleum coke production system, the outlet temperature of a coking heating furnace is 495 ℃, a coke tower adopts constant-pressure operation, the pressure at the top of the tower is 0.7MPa, the reaction period is 38h, and oil gas generated by coking is sent to a fractionation system; the fractionation system separates the gas, light oil, and wax oil, wherein the wax oil is recycled to the needle coke drum. The specific reaction conditions are shown in Table 2. The product distribution is shown in Table 3. The corresponding relationship between the 5% distillation temperature of the wax oil separated by the fractionation system and the reaction time is shown in FIG. 3.
Example 2
Example 2 the process of the present invention was carried out under substantially the same operating conditions as in example 1, except that the needle coke drum was operated at a constant pressure. The specific reaction conditions are shown in Table 2. The product distribution is shown in Table 3. The corresponding relationship between the 5% distillation temperature of the wax oil separated by the fractionation system and the reaction time is shown in FIG. 4.
Comparative example 2
Comparative example 2 needle coke was produced using the prior art, under substantially the same operating conditions as comparative example 1, except that: the needle coke tower is operated at a constant pressure of 0.8 MPa. The product distribution is shown in Table 3. The corresponding relationship between the 5% distillation temperature of the wax oil separated by the fractionation system and the reaction time is shown in FIG. 5.
TABLE 1 Properties of the catalytic slurries subjected to the de-solidification treatment
TABLE 2 reaction conditions
TABLE 3 product distribution
Claims (29)
1. A process for co-producing needle coke and low sulfur petroleum coke, the process comprising:
(1) mixing the catalytic slurry oil with hydrogen, feeding the mixture into a hydrogenation reaction zone, reacting in the presence of a hydrogenation catalyst, and separating reaction products to obtain gas, naphtha and refined oil;
(2) feeding the refined oil obtained in the step (1) into a reduced pressure distillation system for separation to obtain light fraction, middle distillate and heavy distillate;
(3) feeding the intermediate distillate oil obtained in the step (2) into a needle coke production device, feeding a reaction oil gas product into a pressure stabilizing tower, separating to obtain non-condensable gas, distillate oil and tower bottom oil, polymerizing the distillate oil, and circulating the polymer obtained after polymerization back to the low-sulfur petroleum coke production device;
(4) the tower bottom oil obtained in the step (3) enters a buffer tank, is buffered and then is divided into two paths A and B, wherein the tower bottom oil of the path A returns to a pressure stabilizing tower after temperature adjustment, and the tower bottom oil of the path B enters a fractionation system;
(5) feeding the light fraction and the heavy distillate obtained in the step (2) into a low-sulfur petroleum coke production device, feeding the reaction oil gas product into a fractionation system, and separating to obtain gas, light oil and wax oil; and polymerizing the light oil, and recycling the polymer obtained after polymerization treatment to the low-sulfur petroleum coke production device.
2. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the slurry solid content of the catalytic oil in the step (1) is less than 0.01 wt%.
3. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the operating conditions of the hydrogenation reaction zone in the step (1) are as follows: the reaction temperature is 300-480 ℃, the reaction pressure is 3-20 MPa, the volume ratio of hydrogen to oil is 100-2500, wherein the volume ratio of hydrogen to oil is the volume ratio of hydrogen to catalytic slurry oil, and the liquid hourly space velocity is 0.1h when the catalytic slurry oil is used for metering liquid-1～2.0h-1。
4. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 3, wherein: the operating conditions of the hydrogenation reaction zone in the step (1) are as follows: the reaction temperature is 330-400 ℃, the reaction pressure is 5-10 MPa, the hydrogen-oil volume ratio is 500-1500, wherein the hydrogen-oil volume ratio is the volume ratio of hydrogen to catalytic slurry oil, and the liquid hourly space velocity is 0.5h when the catalytic slurry oil is used for liquid measurement-1～1.0h-1。
5. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the sulfur content of the refined oil in the step (1) is not more than 0.5 wt%.
6. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 5, wherein: the sulfur content of the refined oil in the step (1) is not more than 0.4 wt%.
7. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: in the step (2), the distillation temperature of 5 percent of the middle distillate oil is 320-420 ℃, and the distillation temperature of 95 percent of the middle distillate oil is 450-520 ℃.
8. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 7, wherein: the 5 percent distillation temperature of the middle distillate oil in the step (2) is 340 to 380 ℃; the 95 percent distillation temperature of the middle distillate is 460-490 ℃.
9. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the needle coke production device in the step (3) comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage; the outlet temperature of the heating furnace is 400-550 ℃, the heating rate is 1-50 ℃/h, the top pressure of the coke tower is 0.01-2.5 MPa, and the reaction period is 10-50 h.
10. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 9, characterized in that: the needle coke production device in the step (3) comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage; the outlet temperature of the heating furnace is 440-520 ℃, and the heating rate is 2-10 ℃/h; the top pressure of the coke tower is 0.2MPa to 1.5MPa, and the reaction period is 30h to 50 h.
11. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (4) arranging a pressure control system at the top of the pressure stabilizing tower in the step (3), wherein the top pressure of the pressure stabilizing tower is related to the top pressure of the coke tower, namely the top pressure of the coke tower is controlled by adjusting the top pressure of the pressure stabilizing tower.
12. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (3) the 95 percent distillation temperature of distillate oil obtained by the pressure stabilizing tower is 150-430 ℃.
13. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 12, wherein: the 95 percent distillation temperature of distillate oil obtained by the pressure stabilizing tower in the step (3) is 230-370 ℃.
14. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 13, wherein: the 95 percent distillation temperature of the distillate oil obtained by the pressure stabilizing tower in the step (3) is 230-330 ℃.
15. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (3) the liquid level of the pressure stabilizing tower accounts for 10-80% of the total height of the tower.
16. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (4) the operation mode of returning the tower bottom oil of the path A to the pressure stabilizing tower is determined by the 95 percent distillation temperature of distillate oil in the pressure stabilizing tower and the liquid level of the tower bottom of the pressure stabilizing tower.
17. The process for co-producing needle coke and low sulfur petroleum coke of claim 16, wherein: when the liquid level at the bottom of the pressure stabilizer is increased to more than 60 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is increased to more than 310 ℃, the tower bottom oil of the path A is cooled and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is increased; when the liquid level at the bottom of the pressure stabilizer is increased to more than 60 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is reduced to below 240 ℃, the tower bottom oil of the path A is heated and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is increased; when the liquid level at the bottom of the pressure stabilizer is reduced to be lower than 20 percent of the total tower height and the 95 percent distillation temperature of the distillate oil is increased to be higher than 310 ℃, the tower bottom oil of the path A is cooled and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is reduced; when the liquid level at the bottom of the pressure stabilizer is reduced to be lower than 20 percent of the total height of the pressure stabilizer and the 95 percent distillation temperature of the distillate oil is reduced to be lower than 240 ℃, the tower bottom oil of the path A is heated and then returns to the pressure stabilizer, and the discharge rate of the tower bottom oil of the pressure stabilizer is reduced.
18. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (5) the 95 percent distillation temperature of the light oil is 300-440 ℃, and the 5 percent distillation temperature of the wax oil is higher than the 95 percent distillation temperature of the light oil by more than 3 ℃.
19. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1 or 18, wherein: the 95 percent distillation temperature of the light oil in the step (5) is 320-380 ℃; the 5% distillation temperature of the wax oil is higher than the 95% distillation temperature of the light oil by more than 3 ℃.
20. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: and (5) circulating the wax oil back to the needle coke production device.
21. The process for co-producing needle coke and low sulfur petroleum coke according to claim 1 or 20, wherein: and (5) recycling the wax oil subjected to solid removal treatment in advance to the needle-shaped coke production device.
22. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the polymerization treatment is carried out in a polymerization unit, the polymerization unit comprises at least one polymerization reactor, the interior of the reactor is filled with a catalyst, and the reaction conditions of the polymerization reactor are as follows: the reaction temperature is 380-550 ℃, the reaction pressure is 0.01-10 MPa, and the retention time is 0.1-20 h.
23. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1 or 22, wherein: the polymerization treatment is carried out in a polymerization unit, the polymerization unit comprises at least one polymerization reactor, the interior of the reactor is filled with a catalyst, and the reaction conditions of the polymerization reactor are as follows: the reaction temperature is 400-450 ℃, the reaction pressure is 1-4 MPa, and the retention time is 2-5 h.
24. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the low-sulfur petroleum coke production device in the step (5) comprises at least one heating furnace and two coke towers, wherein at least one coke tower is always kept in a reaction stage, and at least one coke tower is kept in a decoking stage; the outlet temperature of the heating furnace is 470-550 ℃, the top pressure of the coke tower is 0.01-2.5 MPa, and the reaction period is 10-50 h.
25. The process for co-producing needle coke and low sulfur petroleum coke as claimed in claim 1, wherein: the low-sulfur petroleum coke production device in the step (5) comprises at least one heating furnace and two coke towers, wherein at least one coke tower is always kept in a reaction stage, and at least one coke tower is kept in a decoking stage; the outlet temperature of the heating furnace is 490-505 ℃; the top pressure of the coke tower is 0.5MPa to 1.0MPa, and the reaction period is 30h to 50h, which is the same as the coking period of the needle coke in the step (3).
26. A system for co-producing needle coke and low sulfur petroleum coke, the system comprising:
the hydrogenation reaction zone comprises at least one hydrogenation reactor and a reaction product separation system, and is used for receiving catalytic slurry oil and hydrogen and obtaining refined oil after treatment;
the reduced pressure distillation tower is used for receiving the refined oil from the hydrogenation reaction zone and separating to obtain light fraction, middle distillate and heavy distillate;
a needle coke production unit for receiving and processing middle distillate from a vacuum distillation column;
the pressure stabilizing tower is used for receiving oil gas products from the needle coke production device and obtaining non-condensable gas, distillate oil and tower bottom oil after treatment;
the buffer tank is used for receiving tower bottom oil from the pressure stabilizing tower, dividing the tower bottom oil into tower bottom oil in a path A and tower bottom oil in a path B after buffer treatment, and circulating the tower bottom oil in the path A back to the pressure stabilizing tower through a pipeline;
a low sulfur petroleum coke production unit for receiving and processing light and heavy distillate oils from a vacuum distillation column;
the fractionating system is used for receiving the B path tower bottom oil from the buffer tank and the reaction oil gas products from the low-sulfur petroleum coke production device, and obtaining gas, light oil and wax oil after treatment;
and the polymerization unit is used for receiving light oil from the fractionation system and optional distillate oil from the pressure stabilizing tower, and the polymer obtained after the polymerization treatment is recycled to the low-sulfur petroleum coke production device through a pipeline.
27. The system for co-producing needle coke and low sulfur petroleum coke of claim 26, wherein: and circulating wax oil obtained by the fractionating system to the needle coke production device through a pipeline, wherein a solid removal device is arranged on the pipeline, and the solid removal device is one or more of a filter, a centrifugal separator and a settler.
28. The system for co-producing needle coke and low sulfur petroleum coke of claim 26, wherein: the needle coke production plant comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage.
29. The system for co-producing needle coke and low sulfur petroleum coke of claim 26, wherein: the low sulfur petroleum coke production plant comprises at least one heating furnace and two coke drums, wherein at least one coke drum is always kept in a reaction stage, and at least one coke drum is kept in a decoking stage.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666556A (en) * | 2012-09-03 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of petroleum coke |
| CN110093181A (en) * | 2018-01-29 | 2019-08-06 | 湖南长岭石化科技开发有限公司 | Catalytic cracked oil pulp takes off solid method |
| CN110283612A (en) * | 2019-07-12 | 2019-09-27 | 山东滨化滨阳燃化有限公司 | A kind of production method of the ripe coke of oil system needle coke |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103666556A (en) * | 2012-09-03 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of petroleum coke |
| CN110093181A (en) * | 2018-01-29 | 2019-08-06 | 湖南长岭石化科技开发有限公司 | Catalytic cracked oil pulp takes off solid method |
| CN110283612A (en) * | 2019-07-12 | 2019-09-27 | 山东滨化滨阳燃化有限公司 | A kind of production method of the ripe coke of oil system needle coke |
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