CN116064082A - Two-stage hydrocracking method for producing high-yield low-freezing diesel oil - Google Patents
Two-stage hydrocracking method for producing high-yield low-freezing diesel oil Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a two-stage hydrocracking method for producing high-yield low-freezing diesel oil. The method comprises a first hydrogenation reaction zone and a second hydrogenation reaction zone, wherein raw oil and hydrogen firstly enter the first hydrogenation reaction zone to react, the single-pass conversion rate of the first hydrogenation reaction zone is controlled to be 60% -70%, the effluent of the first hydrogenation reaction zone enters a flash separation high-pressure device, the flash separation high-pressure device is controlled to obtain a gas phase component at the top of the flash separation high-pressure device, the mass ratio of the hydrogen to the hydrocarbons is controlled to be 0.40-0.90, the liquid phase component obtained at the bottom is separated and fractionated to obtain light hydrocarbons, light naphtha, heavy naphtha, diesel oil and tail oil, the tail oil and the gas phase component obtained at the top of the flash separation high-pressure device are together fed into the second hydrogenation reaction zone to react, the single-pass conversion rate of the second hydrogenation reaction zone is controlled to be 35% -75%, and the effluent of the second hydrogenation reaction zone is separated and fractionated. The method only slightly adjusts the process, not only can achieve the purpose of increasing the yield of the low-freezing diesel oil, but also has the advantage of stable long-period operation.
Description
Technical Field
The invention relates to a two-stage hydrocracking method, in particular to a two-stage hydrocracking method for producing high-yield low-freezing diesel oil.
Background
In the secondary processing technology of crude oil, the distillate oil hydrocracking technology has the characteristics of strong raw material adaptability, flexible production operation, various product schemes, good product quality and the like, and can directly convert various heavy and inferior raw materials into high-quality jet fuel, diesel oil, lubricating oil base stock, chemical naphtha, tail oil steam cracking ethylene raw materials and the like which are urgently needed in the market. The method plays a role of a product distribution and product quality regulator in the whole factory production flow, is a core of oil-chemical-fiber combination, and has become one of the final heavy oil deep processing technologies in the modern oil refining and petrochemical industry.
Among the numerous products of hydrocracking, diesel has taken up a certain market share as an important component thereof, the most important use of which is for diesel engines for vehicles, ships. Compared with gasoline, the fuel oil has high energy density, low fuel consumption and low power consumption, so that diesel oil is used for some small-sized automobiles and even high-performance automobiles. According to the difference of the use places and the environment, the required low-temperature fluidity is different, the light diesel oil is classified according to the condensation point, the light diesel oil has six marks of 5, 0, -10, -20, -35 and 50, and the heavy diesel oil has three marks of 10, 20 and 30. The winter in the three north and Tibetan areas of China is long, and the demand for low-freezing point diesel oil (low-grade light diesel oil) is large. At present, the main production means of low-freezing diesel oil is mainly cutting and blending light diesel oil fraction.
Among the hydrocracking processes, the process can be divided into a single-stage process, a two-stage process, and other different types of processes, wherein the two-stage hydrocracking process is the greatest feature of the hydrocracking process in terms of high selectivity to the target product, although the hydrocracking process is not advantageous in terms of investment and structure. In the long term, short term investment will bring long term returns, so it is now increasingly applied in the hydrocracking market. How to organically combine two-stage hydrocracking flow with the aim of producing high-quality diesel oil at maximum is an important research and development direction in the future and is also the aim of the efforts in the field.
CN103102966a discloses a hydrocracking method for high nitrogen raw material, which uses high nitrogen heavy distillate oil as raw material, adopts two-stage process flow, under hydrofining condition, heavy distillate oil raw material and hydrogen gas are mixed and enter into first-stage reaction zone, hydrofining catalyst is used in first-stage reaction zone, denitrification rate is controlled to 60% -95%, gas phase after gas-liquid separation of effluent of first-stage reaction zone is recycled after impurity removal, and light oil product and tail oil are obtained by liquid phase fractionation; mixing tail oil with hydrogen gas, entering a second-stage reaction zone, using a hydrofining catalyst and a hydrocracking catalyst in the second-stage reaction zone, and enabling reaction effluent of the second-stage reaction zone to enter a separation system. The method can be operated under relatively mild conditions, is beneficial to improving the operation period of the hydrogenation device, but has limited yield increase for diesel oil.
Disclosure of Invention
The inventor of the present invention has found through a great deal of researches that by adopting a two-stage hydrocracking method, the conversion depth of hydrocracking in one stage (i.e. the first hydrogenation reaction zone) is controlled to realize the output of the whole fraction of the hydrocracking product, and the whole fraction is reasonably separated and optimized through one-time flash evaporation, the hydrogen-hydrocarbon ratio of the separated gas phase component is controlled, and the gas phase component is used as the gas phase feed of the second stage (i.e. the second hydrogenation reaction zone) due to the specific hydrogen-hydrocarbon ratio, hydrogen sulfide and ammonia contained in the gas phase component, and is matched with the recycling of the non-ideal component, the performance of the second hydrocracking catalyst can be improved, the concentration of the target product can be increased, the excessive cracking of the reactant can be inhibited, thereby organically combining the first stage reactant and the second stage reaction mechanism, realizing the yield increase of low-freezing diesel in the overall reaction effect, and being capable of stably running for a long period, and realizing the present invention. When the conventional two-stage hydrocracking method is adopted, the existing high-fraction gas is directly utilized to enter the second stage as a reaction material, the problem that the flash separation working condition is not matched with the high-fraction working condition exists, the adjustment flexibility is poor, the pressure difference cannot return to the current thermal high fraction after the second stage is removed, the existing equipment cannot realize direct pressurization of the mixed material flow and the reacted light components are difficult to discharge out of the device due to the adoption of the pressurizing equipment, so that the series connection of the processing flow is difficult to realize by directly utilizing the high-fraction gas, and the device cannot be produced.
The invention provides a two-stage hydrocracking method for producing low-freezing diesel oil in a high yield. The method only slightly adjusts the process, not only can achieve the purpose of increasing the yield of the low-freezing diesel oil, but also has the advantage of stable long-period operation.
The invention provides a two-stage hydrocracking method for producing high-yield low-freezing diesel oil, which comprises a first hydrogenation reaction zone and a second hydrogenation reaction zone, wherein the upper part of the first hydrogenation reaction zone is a hydrogenation pretreatment zone, the lower part of the first hydrogenation reaction zone is a hydrocracking zone, the upper part of the second hydrogenation reaction zone is a hydrocracking zone, the lower part of the second hydrogenation reaction zone is a hydrogenation post-treatment zone, and the process comprises the following steps: the method comprises the steps of firstly, enabling raw oil and hydrogen to enter a first hydrogenation reaction zone to react, controlling the single pass conversion rate of the first hydrogenation reaction zone to be 60% -70%, enabling effluent of the first hydrogenation reaction zone to enter a flash separation high-pressure device, controlling the mass ratio of hydrogen to hydrocarbon in gas phase components obtained from the top of the flash separation high-pressure device to be 0.40-0.90, preferably 0.41-0.85, separating and fractionating liquid phase components obtained from the bottom of the flash separation high-pressure device to obtain light hydrocarbons, light naphtha, heavy naphtha, diesel oil and tail oil, enabling the tail oil obtained from fractionation to enter a second hydrogenation reaction zone together with the gas phase components obtained from the top of the flash separation high-pressure device to react, controlling the single pass conversion rate of the second hydrogenation reaction zone to be 35% -75%, preferably 60% -70%, and separating and fractionating effluent of the second hydrogenation reaction zone to obtain the light hydrocarbons, the light naphtha, the heavy naphtha, the diesel oil and the tail oil.
In the hydrocracking process described above, the pressure controlled in the flash separation high pressure vessel is lower than the reaction pressure in the first hydrogenation reaction zone and the temperature is 185 to 215 ℃, preferably 190 to 210 ℃.
In the hydrocracking method, the obtained diesel oil is low-freezing diesel oil.
In the hydrocracking method, a fixed bed hydrogenation process is adopted, and the first hydrogenation reaction zone and the second hydrogenation reaction zone both adopt an operation mode of upper feeding and lower discharging.
In the hydrocracking method, the effluent of the second hydrogenation reaction zone is separated and fractionated with the liquid phase component discharged from the primary flash separation high-pressure device by adopting the same separation and fractionation device.
In the hydrocracking method, in the first hydrogenation reaction zone, a hydrogenation pretreatment section is filled with a hydrogenation pretreatment catalyst, and a hydrocracking section is filled with a hydrocracking catalyst; in the second hydrogenation reaction zone, the hydrocracking section is filled with a hydrocracking catalyst, and the post-hydrogenation treatment section is filled with a post-hydrogenation treatment catalyst.
In the above hydrocracking method, the hydrotreating catalyst packed in the first hydrogenation reaction zone or the hydrotreating catalyst packed in the second hydrogenation reaction zone may be a hydrotreating catalyst. The hydrotreating catalyst packed in the second hydrogenation reaction zone may be the same or different from the hydrotreating catalyst in the first hydrogenation reaction zone, and the same catalyst is preferably used in the present invention. The hydrotreating catalyst comprises a support and a hydrogenating active metal component, the hydrogenating active metal comprises at least one of the group VIB and/or the group VIII of the periodic table of elements, preferably one or more of tungsten, molybdenum, nickel and cobalt, the support comprises inorganic refractory oxide, preferably one or more selected from alumina, amorphous silica-alumina, silica and titania, and further preferably alumina. The content of the VIB group metal in terms of the oxide thereof is 10% -35%, preferably 15% -30%, and the content of the VIII group metal in terms of the oxide thereof is 1% -7%, preferably 1.5% -6% based on the weight of the catalyst. The hydrogenation pretreatment catalyst can be selected from various commercial catalysts, and can also be prepared according to the knowledge in the field, wherein the commercial catalysts are HC-K, HC-T, HC-P developed by UOP company, FF-46, FF-56, FF-66 developed by FRIPP, and the like.
In the above hydrocracking process, the hydrocracking catalyst packed in the first hydrogenation reaction zone or the hydrocracking catalyst packed in the second hydrogenation reaction zone may be a commercial catalyst or may be prepared according to the prior art in the art. The hydrocracking catalyst packed in the second hydrogenation reaction zone may be the same as or different from the hydrocracking catalyst packed in the first hydrogenation reaction zone, and the same hydrocracking catalyst is preferably used in the present invention. The hydrocracking catalyst comprises a cracking component and a hydrogenation active metal component; the hydrogenation active metals include group VIB metals (such as tungsten and/or molybdenum) and group VIII metals (such as nickel and/or cobalt); the cracking component includes molecular sieves including, but not limited to, beta-type molecular sieves; the hydrocracking catalyst also contains a binder, typically alumina or silica. Based on the weight of the catalyst, the weight of the VIB group metal oxide is 10-35%, preferably 15-30%, the weight of the VIII group metal oxide is 1-7%, preferably 1.5-6%, and the content of the molecular sieve is 10-30%. Commercial catalysts such as FC-14, FC-20, etc., developed by FRIPP.
In the hydrocracking method, the operating conditions of the first hydrogenation reaction zone are as follows:
hydrogenation pretreatment section: the pressure is 10.0MPa to 16.5MPa, the reaction temperature is 280 ℃ to 435 ℃ and the liquid hourly space velocity is 0.1h -1 ～4.0h -1 The volume ratio of hydrogen to oil is 300:1-900:1; preferably, the pressure is 11.0MPa to 16.0MPa, the reaction temperature is 290 ℃ to 410 ℃ and the liquid hourly space velocity is 0.2h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 400:1-800:1.
Hydrocracking section: the pressure is 9.9MPa to 16.4MPa, the reaction temperature is 320 ℃ to 440 ℃, and the liquid hourly space velocity is 0.2h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 600:1-1300:1; preferably, the pressure is 10.9 MPa-15.9 MPa, the reaction temperature is 330-430 ℃ and the liquid hourly space velocity is 0.4h -1 ～3.0h -1 The volume ratio of hydrogen to oil is 700:1-1200:1.
In the hydrocracking method, the loading volume ratio of the hydrocracking catalyst to the post-hydrotreating catalyst in the second hydrogenation reaction zone is 7-13, preferably 8-12, and the operating conditions of the second hydrogenation reaction zone are as follows:
the pressure is 9.0MPa to 15.5MPa, the reaction temperature is 260 ℃ to 370 ℃ and the liquid hourly space velocity is 0.4h -1 ～4.5h -1 The volume ratio of hydrogen to oil is 500:1-1200:1; preferably, the pressure is 10.0 MPa-15.0 MPa a, the reaction temperature is 270-360 ℃, and the liquid hourly space velocity is 0.5h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 600:1-1100:1. Wherein the hydrogen-oil volume ratio refers to the volume ratio of hydrogen in the mixed feed to the volume ratio of the liquid feed.
In the above hydrocracking process, the feedstock oil may be selected from various distillate oils suitable as a hydrocracking feedstock, such as one or more of Vacuum Gas Oil (VGO) (also referred to as vacuum wax oil) obtained from petroleum, coker Gas Oil (CGO), heavy Gas Oil (HGO), and catalytic cracking Heavy Cycle Oil (HCO), preferably vacuum gas oil, and the base property of the feedstock is not limited and may be one or more of cycloalkyl, intermediate or paraffinic crude oils. The property of the raw oil is preferably that the dry point is not more than 530 ℃, the initial distillation point is 250-350 ℃, the final distillation point is 450-530 ℃, and the density is not more than 0.92g/cm 3 Generally 0.87 to 0.92g/cm 3 The nitrogen content is not more than 1800ug/g, generally 400-1800 mug/g, and the sum of Fe, ca, ni, V content is not more than 1.0 mug/g, generally 0.1-1.0 mug/g.
In the hydrocracking method, the first hydrogenation reaction zone and the second hydrogenation reaction zone are controlled to have a single-pass conversion rate (in terms of mass), and a certain temperature point is required to be corresponding to the conversion rate. In the invention, the temperature point corresponding to the single-pass conversion rate of the first hydrogenation reaction zone is 335-365 ℃, preferably 345-355 ℃, and the conversion depth can be realized by adjusting the reaction temperature of the hydrocracking section of the first hydrogenation reaction zone; the temperature point corresponding to the single-pass conversion rate of the second hydrogenation reaction zone is 330-390 ℃, the preferable temperature point is 340-380 ℃, and the conversion depth can be realized by adjusting the reaction temperature of the hydrocracking section of the second hydrogenation reaction zone.
In the hydrocracking method, the flash separation high-pressure device can separate the gas phase and the liquid phase of the material flow entering the flash separation high-pressure device through the control of the operation condition, namely the adjustment of the temperature and the pressure, the gas phase components discharged from the upper part comprise light hydrocarbon, ammonia, hydrogen sulfide and hydrogen, and the liquid components mainly comprising low-freezing point diesel oil and tail oil are discharged from the lower part. The inventor finds through experimental study that the mass ratio of hydrogen to hydrocarbon in the gas phase component at the top of the flash separation high-pressure device is controlled to be 0.40-0.90, preferably 0.41-0.85, and the gas phase component enters the second hydrogenation reaction zone to be used as gas phase feed, so that the yield of low-freezing diesel oil is increased, and the low-freezing diesel oil can stably run for a long period. The internal pressure of the separator is between the pressure of the first hydrogenation reaction zone and the pressure of the second hydrogenation reaction zone, and the flow of reactants is ensured according to the energy level difference of the normal flow of the flows, and the method is not particularly limited. The specific operating conditions of the flash separation high pressure vessel are as follows: the pressure is 9.5MPa to 16.0MPa, the preferable range is 10.5MPa to 15.5MPa, the temperature is 185 ℃ to 215 ℃, and the preferable range is 190 ℃ to 210 ℃.
In the hydrocracking method, the separation and fractionation units are common knowledge of those skilled in the art, and are not necessary to be described, while the products of the discharging system of the method comprise dry gas, liquefied gas, light naphtha, heavy naphtha and low-freezing diesel oil, and the tail oil is discharged from the bottom of the fractionation tower and recycled to the second hydrogenation reaction zone to be processed and re-reacted together with gas phase components entering the top of the flash separation high-pressure device of the second hydrogenation reaction zone, so that the low-freezing diesel oil of the desired target product is produced through further deep hydrocracking reaction.
Compared with the prior art, the method has the following beneficial effects:
according to the hydrocracking method, a two-stage hydrocracking flow is adopted, a flash separation high-pressure device is additionally arranged behind the first hydrogenation reaction zone, the gas phase is used as the gas phase feed of the second hydrogenation reaction zone by controlling the hydrogen-hydrocarbon ratio in the gas phase obtained from the top of the flash separation high-pressure device, the circulating tail oil is used as the liquid phase feed of the second hydrogenation reaction zone, and the coexistence gas of hydrogen sulfide, ammonia gas, hydrogen with specific hydrogen-hydrocarbon ratio and light hydrocarbon in the gas phase component is utilized, so that the performance of the hydrocracking catalyst in the second hydrogenation reaction zone can be improved, and the introduction of the light hydrocarbon belongs to non-ideal products for the second hydrogenation reaction zone, but the fraction thereof is balanced, so that the further cracking of low-freezing diesel oil can be restrained, the cracking of the circulating tail oil to the low-freezing diesel oil is accelerated, and the promotion and optimization effects on the hydrocracking reaction in the second hydrogenation reaction zone are realized, so that the yield of the low-freezing diesel oil is improved. The invention utilizes the existing logistics to carry out reasonable configuration, fully utilizes the characteristics of different reaction sections, not only can stably operate for a long period, but also realizes the yield increase of the low-freezing diesel oil, and meets the market demand for the low-freezing diesel oil.
Drawings
FIG. 1 is a schematic flow diagram of a two-stage hydrocracking process principle of the invention for producing high yield low freezing point diesel;
FIG. 2 is a schematic flow diagram of the principle of a conventional two-stage hydrocracking process.
Detailed Description
The process of the present invention is described below with reference to the accompanying drawings, integrated in some conventional unit figures, which are not necessarily described, and generalized as a separation system and fractionation system.
In the invention, the high-quality diesel oil mainly refers to wide-fraction diesel oil, has a low condensation point, can be used as low-condensation diesel oil, and has an initial distillation point of 160-190 ℃ and a final distillation point of 360-380 ℃. The low-freezing point diesel oil can be used as-35 # diesel oil product.
In the present invention, conversion is defined as:
conversion (%) = [1- (unconverted oil amount/fresh feed amount) ]×100% in the first hydrogenation reaction zone;
the conversion (%) = {1- [ amount of recycle oil/(amount of fresh feed+amount of recycle oil) ] } x 100% in the second hydrogenation reaction zone.
As shown in fig. 1, the process flow of the invention is as follows:
the raw material 1 and hydrogen 17 are mixed and then enter a first hydrogenation reaction zone 2 for reaction, the zone contains a hydrogenation pretreatment process and a hydrocracking process, a reaction effluent 3 enters a flash separation high-pressure device 4 for gas-liquid phase separation, a separated gas component 5 is discharged at the top, and a separated liquid component 6 enters a subsequent separation system 7 and a fractionation system 9 to obtain various gas-liquid phase products, such as light hydrocarbon 10, light naphtha 11, heavy naphtha 12, high-quality diesel 13 and tail oil 14. Wherein the tail oil 14 and the gas component 5 are mixed and then enter a second hydrogenation reaction zone 15 for hydrocracking reaction, a reaction effluent 16 enters a subsequent separation system 7, a separated gas phase 17 is used as circulating hydrogen, and a separated liquid phase 8 enters a fractionation system 9 to obtain various gas-liquid phase products such as light hydrocarbon 10, light naphtha 11, heavy naphtha 12, high-quality diesel 13 and tail oil 14. In the present invention, the tail oil 14 is not discharged, thereby realizing the maximized yield increase of high-quality diesel oil.
The process flow for conventional two-stage hydrocracking, as shown in fig. 2, is as follows:
the raw material 1 and hydrogen 17 are mixed and then enter a first hydrogenation reaction zone 2 for reaction, the zone contains a hydrogenation pretreatment process and a hydrocracking process, and a reaction effluent 3 enters a subsequent separation system 7 and a fractionation system 9 to obtain various gas-liquid phase products, such as light hydrocarbon 10, light naphtha 11, heavy naphtha 12, high-quality diesel 13 and tail oil 14. Wherein the tail oil 14 is mixed with circulating hydrogen 17 and then enters a second hydrogenation reaction zone 15 for hydrocracking reaction, the reaction effluent 16 enters a subsequent separation system 7, the separated gas phase 17 is used as circulating hydrogen, and the separated liquid phase 8 enters a fractionation system 9 to obtain various gas-liquid phase products such as light hydrocarbon 10, light naphtha 11, heavy naphtha 12, diesel 13 and tail oil 14. In the present invention, the tail oil 14 is not discharged.
The present process is further described below in conjunction with examples and comparative examples to compare the effects and advantages of a two-stage hydrocracking process embodying the present invention for high quality diesel production.
In the present invention, unless otherwise specified, percentages refer to mass fractions.
In the embodiment and the comparative example of the invention, the conversion temperature corresponding to the first hydrogenation reaction zone is 350 ℃, and the conversion temperature corresponding to the second hydrogenation reaction zone is 360 ℃.
The inventive example operates according to the scheme of fig. 1, whereas the comparative example operates according to a conventional two-stage hydrocracking scheme, as in fig. 2. The properties of the raw oil are shown in Table 1, the main physical indexes of each catalyst are shown in Table 2, the main operating conditions are shown in Table 3 and Table 4, the advantage effect comparison is shown in Table 5, and the properties of the low-freezing diesel oil obtained in each example are shown in Table 6.
Example 1
With the method and flow of the invention as in FIG. 1, feedstock 1, shown in Table 1, is processed, firstThe hydrogenation reaction zone is internally provided with a hydrogenation pretreatment catalyst FF-46 and a hydrogenation cracking catalyst FC-20 which are already mature and industrialized at present, the filling ratio of the hydrogenation pretreatment catalyst FF-46 and the hydrogenation cracking catalyst FC-20 is 6:5, and the second hydrogenation reaction zone is filled with the hydrogenation cracking catalyst FC-20 and the hydrogenation post-treatment catalyst FF-46, wherein the volume ratio of the hydrogenation pretreatment catalyst FF-46 and the hydrogenation post-treatment catalyst FC-20 is 8:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 379 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 385 ℃, the reaction pressure is 14.7MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 65%, the reaction product enters a flash separation high-pressure device for gas-liquid separation operation, the pressure in the device is 14.2MPa, the temperature is 200 ℃, the hydrogen-hydrocarbon ratio in the gas phase is controlled to be 0.44, the liquid phase component discharged from the bottom enters a subsequent separation system and a fractionating system, and is discharged from the bottom of the fractionating tower>Mixing tail oil at 360 ℃ with gas phase components obtained by flash separation, and then entering a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, wherein the reaction temperature is 342 ℃, the reaction pressure is 13.5MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.2h -1 Control of>The single pass conversion rate at 360 ℃ is 60%, the reacted material flow enters the separation system to obtain gas phase as circulating hydrogen, and the liquid phase enters the fractionation system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
Example 2
The method and the flow chart of the invention are shown in figure 1, the raw material 1 shown in the table 1 is processed, a hydrogenation pretreatment catalyst FF-46 and a hydrogenation cracking catalyst FC-20 which are already mature and industrialized at present are used in a first hydrogenation reaction zone, the filling ratio of the hydrogenation pretreatment catalyst FF-46 to the hydrogenation cracking catalyst FC-20 is 6:5, and a hydrogenation reaction zone is filled with the hydrogenation cracking catalyst FC-20 and the hydrogenation post-treatment catalyst FF-46, and the volume ratio of the hydrogenation pretreatment catalyst FF-46 to the hydrogenation reaction zone is 8:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 379 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 700:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 385 ℃, the reaction pressure is 14.7MPa, the hydrogen-oil volume ratio is 900:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 65%,the reaction product enters a flash evaporation separation high-pressure device for gas-liquid separation operation, the pressure in the device is 14.1MPa, the temperature is 190 ℃, the mass ratio of hydrogen to hydrocarbon in gas phase components is controlled to be 0.54, liquid phase components are discharged from the bottom of the device for subsequent separation systems and fractionation systems, and the liquid phase components are discharged from the bottom of the fractionation tower>Mixing tail oil at 360 ℃ with gas phase components obtained by flash separation, and then entering a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, wherein the reaction temperature is 343 ℃, the reaction pressure is 13.4MPa, the hydrogen-oil volume ratio is 900:1, and the liquid hourly space velocity is 1.2h -1 Control of>The single pass conversion rate at 360 ℃ is 63%, the reacted material flow enters the separation system to obtain gas phase as circulating hydrogen, and the liquid phase enters the fractionation system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
Example 3
The method and the flow chart of the invention are shown in figure 1, the raw material 1 shown in the table 1 is processed, a hydrogenation pretreatment catalyst FF-46 and a hydrogenation cracking catalyst FC-20 which are already mature and industrialized at present are used in a first hydrogenation reaction zone, the filling ratio of the hydrogenation pretreatment catalyst FF-46 to the hydrogenation cracking catalyst FC-20 is 6:5, and a hydrogenation reaction zone is filled with the hydrogenation cracking catalyst FC-20 and the hydrogenation post-treatment catalyst FF-46, and the volume ratio of the hydrogenation pretreatment catalyst FF-46 to the hydrogenation reaction zone is 8:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 381 ℃, the reaction pressure is 14.0MPa, the hydrogen-oil volume ratio is 700:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 383 ℃, the reaction pressure is 13.5MPa, the hydrogen-oil volume ratio is 900:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 60%, the reaction product enters a flash separation high-pressure device to carry out gas-liquid separation operation, the pressure in the device is 12.5MPa, the temperature is 210 ℃, the mass ratio of hydrogen to hydrocarbon in gas phase components is controlled to be 0.62, the liquid phase components are discharged from the bottom to carry out a subsequent separation system and a fractionating system, and the liquid phase components are discharged from the bottom of the fractionating system>Mixing tail oil at 360 ℃ with gas phase components obtained by flash separation, and then entering a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, wherein the reaction temperature is 348 ℃, the reaction pressure is 12.0MPa, the hydrogen-oil volume ratio is 900:1, and the liquid hourly space velocity is 1.2h -1 Control of>The single pass conversion rate at 360 ℃ is 68 percent, and the material flow after the reaction enters the separationThe system obtains gas phase as circulating hydrogen, and the liquid phase enters the fractionating system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
Example 4
Adopting the method and the flow chart of the invention as shown in figure 1, processing the raw material 2 shown in the table 1, wherein a hydrogenation pretreatment catalyst FF-46 and a hydrogenation cracking catalyst FC-20 which are already mature and industrialized at present are used in a first hydrogenation reaction zone, the filling ratio of the two is 6:5, and a hydrogenation cracking catalyst FC-20 and a hydrogenation post-treatment catalyst FF-46 are filled in a second hydrogenation reaction zone, and the volume ratio of the two is 11:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 375 ℃, the reaction pressure is 15.5MPa, the hydrogen-oil volume ratio is 600:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 380 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 61%, the reaction product enters a flash separation high-pressure device to carry out gas-liquid separation operation, the pressure in the device is 14.5MPa, the temperature is 195 ℃, the mass ratio of hydrogen to hydrocarbon in gas phase components is controlled to be 0.68, the liquid phase components are discharged from the bottom to carry out a subsequent separation system and a fractionating system, and the liquid phase components are discharged from the bottom of the fractionating system>Mixing tail oil at 360 ℃ with gas phase components obtained by flash separation, and then entering a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, wherein the reaction temperature is 348 ℃, the reaction pressure is 13.9MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.1h -1 Control of>The single pass conversion rate at 360 ℃ is 65%, the reacted material flow enters the separation system to obtain gas phase as circulating hydrogen, and the liquid phase enters the fractionation system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
Comparative example 1
Adopting a conventional two-stage hydrocracking method and a process shown in FIG. 2, processing a raw material 1 shown in Table 1, wherein the first hydrogenation reaction zone uses FF-46 and FC-20 catalysts which are already mature and industrialized at present, the filling ratio of the two catalysts is 6:5, and the second hydrogenation reaction zone is filled with FC-20 hydrocracking catalyst and hydrogenation post-treatment catalyst FF-46, and the volume ratio of the two catalysts is 8:1; first hydrogenation reaction zone pre-treatmentThe reaction temperature of the treatment section is 379 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 385 ℃, the reaction pressure is 14.7MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 65%, the generated components enter a subsequent separation system and a fractionation system and are discharged at the bottom of the fractionation tower>The tail oil at 360 ℃ and the circulating hydrogen enter a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, the reaction temperature is 333 ℃, the reaction pressure is 14.2MPa, the volume ratio of the hydrogen oil is 1000:1, and the liquid hourly space velocity is 1.2h -1 Control of>The single pass conversion rate at 360 ℃ is 60%, the gas phase after the reaction enters a separation system to obtain the gas phase as circulating hydrogen, and the liquid phase enters a fractionation system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
Comparative example 2
Adopting a conventional two-stage hydrocracking method and a process shown in FIG. 2, processing a raw material 1 shown in Table 1, wherein the first hydrogenation reaction zone uses FF-46 and FC-20 catalysts which are already mature and industrialized at present, the filling ratio of the two catalysts is 6:5, and the second hydrogenation reaction zone is filled with FC-20 hydrocracking catalyst and hydrogenation post-treatment catalyst FF-46, and the volume ratio of the two catalysts is 8:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 379 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 385 ℃, the reaction pressure is 14.7MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 65%, the generated components enter a subsequent separation system and a fractionation system and are discharged at the bottom of the fractionation tower>The tail oil at 360 ℃ and circulating hydrogen enter a second hydrogenation reaction zone to react with an FC-20 catalyst, sulfur supplementing operation is carried out in a gas phase, the concentration of hydrogen sulfide is controlled to be 800 mu l/l, the reaction temperature is 330 ℃, the reaction pressure is 14.2MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.1h -1 Control of>The single pass conversion rate at 360 ℃ is 60%, the reacted material flow enters a separation system to obtain gas phase as circulating hydrogen, and the liquid phase enters a fractionation system to obtain various light hydrocarbonsLight naphtha, heavy naphtha and low-freezing diesel products.
Comparative example 3
Adopting a conventional two-stage hydrocracking method and a process shown in FIG. 2, processing a raw material 1 shown in Table 1, wherein the first hydrogenation reaction zone uses FF-46 and FC-20 catalysts which are already mature and industrialized at present, the filling ratio of the two catalysts is 6:5, and the second hydrogenation reaction zone is filled with FC-20 hydrocracking catalyst and hydrogenation post-treatment catalyst FF-46, and the volume ratio of the two catalysts is 8:1; the reaction temperature of the pretreatment section of the first hydrogenation reaction zone is 379 ℃, the reaction pressure is 15.0MPa, the hydrogen-oil volume ratio is 800:1, and the liquid hourly space velocity is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the cracking section is 385 ℃, the reaction pressure is 14.7MPa, the hydrogen-oil volume ratio is 1000:1, and the liquid hourly space velocity is 1.2h -1 First hydrogenation reaction zone control>The conversion rate at 350 ℃ is 65%, the generated components enter a subsequent separation system and a fractionation system and are discharged at the bottom of the fractionation tower>Introducing 360 ℃ tail oil and circulating hydrogen into a second hydrogenation reaction zone to react with FC-20 and FF-46 catalysts, performing sulfur and ammonia supplementing operation in a gas phase, controlling the concentration of hydrogen sulfide to be 800 mu l/l, controlling the concentration of ammonia to be 250 mu l/l, controlling the reaction temperature to be 339 ℃, controlling the reaction pressure to be 14.2MPa, and controlling the hydrogen oil volume ratio to be 1000;1, liquid hourly space velocity 1.1h -1 Control of>The single pass conversion rate at 360 ℃ is 60%, the reacted material flow enters a separation system to obtain gas phase as circulating hydrogen, and the liquid phase enters a fractionation system to obtain various light hydrocarbon, light naphtha, heavy naphtha and low-freezing diesel products.
TABLE 1 Properties of raw oil
| Raw material source | Reduced pressure wax oil | Reduced pressure wax |
| Numbering device | ||
| 1 | 2 | |
| Density (20 ℃ C.)/g.cm -3 | 0.9104 | 0.9088 |
| Distillation range/. Degree.C | 315～519 | 300～489 |
| Sulfur/. Mu.g.g -1 | 13800 | 9800 |
| Nitrogen/. Mu.g.g -1 | 1150 | 980 |
TABLE 2 Primary physicochemical Properties of the catalysts used in examples
| Project | FF-46 | FC-20 |
| Active metal composition | Mo-Ni | W-Ni |
| MoO 3 ，wt％ | 24.5 | - |
| NiO，wt％ | 4.0 | 7.5 |
| WO 3 ，wt％ | - | 25.1 |
| Beta molecular sieve content, wt% | - | 25.0 |
| Physical Properties | ||
| Appearance shape | Clover strip | Cylindrical strip |
| Crush strength, N/cm | ≥150 | >180 |
| Particle diameter, mm | 1.1～1.4 | 1.5～1.7 |
TABLE 3 principal reaction conditions for each example
Table 4 main reaction conditions of examples
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Conversion in the first hydrogenation reaction zone% | 65 | 65 | 65 |
| Hydrogen to hydrocarbon mass ratio of the gas phase feed to the second hydrogenation reaction zone | 1.28 | 1.31 | 1.30 |
TABLE 5 comparison of effects of different conditions used in examples
TABLE 6 principal Properties of the Low-freezing Diesel oil obtained in the examples
As can be seen from Table 6, the low-freezing point diesel oil obtained in the examples of the present invention meets the standard.
Claims (12)
1. The two-stage hydrocracking process for producing high yield low freezing point diesel oil includes the first hydrogenating reaction area with upper hydrogenating pretreatment stage and lower hydrocracking stage and the second hydrogenating reaction area with upper hydrocracking stage and lower hydrogenating post-treatment stage, and the process includes: the method comprises the steps of firstly, enabling raw oil and hydrogen to enter a first hydrogenation reaction zone to react, controlling the single pass conversion rate of the first hydrogenation reaction zone to be 60% -70%, enabling effluent of the first hydrogenation reaction zone to enter a flash separation high-pressure device, controlling the mass ratio of hydrogen to hydrocarbon in gas phase components obtained from the top of the flash separation high-pressure device to be 0.40-0.90, preferably 0.41-0.85, separating and fractionating liquid phase components obtained from the bottom of the flash separation high-pressure device to obtain light hydrocarbons, light naphtha, heavy naphtha, diesel oil and tail oil, enabling the tail oil obtained from fractionation to enter a second hydrogenation reaction zone together with the gas phase components obtained from the top of the flash separation high-pressure device to react, controlling the single pass conversion rate of the second hydrogenation reaction zone to be 35% -75%, preferably 60% -70%, and separating and fractionating effluent of the second hydrogenation reaction zone to obtain the light hydrocarbons, the light naphtha, the heavy naphtha, the diesel oil and the tail oil.
2. The process according to claim 1, wherein the pressure controlled in the flash separation high pressure vessel is lower than the reaction pressure in the first hydrogenation reaction zone and the temperature is 185 to 215 ℃, preferably 190 to 210 ℃.
3. The process according to claim 1 or 2, characterized in that the pressure of the flash separation high pressure vessel is 9.5MPa to 16.0MPa, preferably 10.5MPa to 15.5MPa.
4. The process according to claim 1 or 2, wherein the effluent from the second hydrogenation reaction zone is separated and fractionated with the same separation and fractionation means as the liquid phase components exiting the flash separation high pressure vessel.
5. The process of claim 1 wherein in the first hydrogenation reaction zone the hydrotreating zone is charged with a hydrotreating catalyst and the hydrocracking zone is charged with a hydrocracking catalyst; in the second hydrogenation reaction zone, the hydrocracking section is filled with a hydrocracking catalyst, and the post-hydrogenation treatment section is filled with a post-hydrogenation treatment catalyst.
6. A process according to claim 1 or 2, wherein the feedstock oil is selected from one or more of vacuum gas oil, coker gas oil, heavy gas oil, catalytic cracking heavy cycle oil, preferably vacuum gas oil.
7. The method according to claim 1 or 6, characterized in that the properties of the raw oil are as follows: the dry point is not higher than 530 ℃, and the density is not higher than 0.92g/cm 3 The nitrogen content is not more than 1800 mug/g.
8. The process according to claim 2 or 5, characterized in that the content of group VIB metals in terms of their oxides is 10% to 35%, preferably 15% to 30% based on the weight of the catalyst, of the hydrotreatment catalyst packed in the first hydrogenation reaction zone or of the hydrotreatment catalyst packed in the second hydrogenation reaction zone; the group VIII metal is 1% to 7%, preferably 1.5% to 6%, based on the oxide thereof.
9. The process of claim 2 or 5 wherein the first hydrogenation zone is a packed hydrocracking catalyst or the second hydrogenation zone is a packed hydrocracking catalyst, the hydrocracking catalyst comprising a cracking component and a hydrogenation-active metal component; the cracking component comprises a molecular sieve comprising a beta-type molecular sieve; based on the weight of the catalyst, the weight of the VIB group metal oxide is 10-35%, preferably 15-30%, the weight of the VIII group metal oxide is 1-7%, preferably 1.5-6%, and the content of the molecular sieve is 10-30%.
10. The process of claim 2, wherein the operating conditions in the first hydrogenation reaction zone:
hydrogenation pretreatment section: the pressure is 10.0MPa to 16.5MPa, the reaction temperature is 280 ℃ to 435 ℃ and the liquid hourly space velocity is 0.1h -1 ～4.0h -1 The volume ratio of hydrogen to oil is 300:1-900:1; preferably, the pressure is 11.0MPa to 16.0MPa, the reaction temperature is 290 ℃ to 410 ℃ and the liquid hourly space velocity is 0.2h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 400:1-800:1.
Hydrocracking section: the pressure is 9.9MPa to 16.4MPa, the reaction temperature is 320 ℃ to 440 ℃, and the liquid hourly space velocity is 0.2h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 600:1-1300:1; preferably, the pressure is 10.9 MPa-15.9 MPa, the reaction temperature is 330-430 ℃ and the liquid hourly space velocity is 0.4h -1 ～3.0h -1 The volume ratio of hydrogen to oil is 700:1-1200:1.
11. The process according to claim 2 or 10, characterized in that in the second hydrogenation reaction zone the loading volume ratio of hydrocracking catalyst to hydrotreating catalyst is from 7 to 13, preferably from 8 to 12, the operating conditions of the second hydrogenation reaction zone being: the pressure is 9.0MPa to 15.5MPa, the reaction temperature is 260 ℃ to 370 ℃ and the liquid hourly space velocity is 0.4h -1 ～4.5h -1 The volume ratio of hydrogen to oil is 500:1-1200:1; preferably, the pressure is 10.0 MPa-15.0 MPa a, the reaction temperature is 270-360 ℃, and the liquid hourly space velocity is 0.5h -1 ～3.5h -1 The volume ratio of hydrogen to oil is 600:1-1100:1.
12. The process according to claim 1 or 2, characterized in that the first hydrogenation reaction zone has a temperature point corresponding to the per pass conversion of 335 ℃ to 365 ℃, preferably 345 ℃ to 355 ℃; the second hydrogenation reaction zone has a temperature point corresponding to the single pass conversion of 330 ℃ to 390 ℃, preferably 340 ℃ to 380 ℃.
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| CN101724459A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for reducing condensation point of diesel oil |
| US20170335208A1 (en) * | 2015-02-11 | 2017-11-23 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method of hydrotreatment of fischer-tropsch synthesis products |
| CN112143522A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydrogenation method and system for production chemical material |
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| CN101724459A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for reducing condensation point of diesel oil |
| US20170335208A1 (en) * | 2015-02-11 | 2017-11-23 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method of hydrotreatment of fischer-tropsch synthesis products |
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