CN114437801B - Two-stage hydrocracking method - Google Patents
Two-stage hydrocracking method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 130
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000007791 liquid phase Substances 0.000 claims abstract description 36
- 238000005194 fractionation Methods 0.000 claims abstract description 33
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- 239000012071 phase Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003921 oil Substances 0.000 claims description 61
- 238000005984 hydrogenation reaction Methods 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 15
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- 239000002808 molecular sieve Substances 0.000 claims description 15
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- 239000001993 wax Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010779 crude oil Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 25
- 239000007788 liquid Substances 0.000 abstract description 14
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- 239000002994 raw material Substances 0.000 description 20
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- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
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- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000010724 circulating oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a two-stage hydrocracking method, which comprises the following steps: the effluent of the first-stage hydrocracking reaction enters a flash separator to separate a liquid phase flow and a gas phase flow, the liquid phase flow enters a fractionation system to separate heavy naphtha and tail oil, the gas phase flow is mixed with the tail oil and then undergoes a second-stage hydrocracking reaction, the gas phase separated from the effluent of the second-stage hydrocracking reaction is used as circulating hydrogen of the first-stage hydrocracking reaction after gas-liquid separation, and the liquid phase enters the fractionation system to separate gas phase products, light naphtha, heavy naphtha and tail oil. The process can allow the deactivation rate of the two-stage hydrocracking catalyst to be reduced while increasing the selectivity of the premium heavy naphtha product.
Description
Technical Field
The invention relates to a two-stage hydrocracking method, in particular to a two-stage hydrocracking method for producing heavy naphtha in a more yield.
Background
Hydrocracking technology is the core of the combination of "oiled" and "oiled", and is a key tie for conversion, and has been increasingly concerned. In particular, the effect of the chemical raw materials is becoming larger and larger at present when the chemical raw materials are highly demanded. At present, the fuel demand of the domestic market is low, compared with the annual rising of the processing amount of crude oil, the proportion of fuel oil products in the oil refining product structure is reduced year by year, and most of crude oil is necessarily required to be converted into chemical raw materials with more vigorous market demands. The trend of product structure adjustment of oil refining enterprises is that the conversion from fuel type to chemical type becomes necessary, and a hydrocracking device is required to provide more high-quality chemical raw materials such as catalytic reforming raw materials and ethylene raw materials prepared by steam cracking, and the two-stage hydrocracking technology of the maximum mass production of chemical materials is developed as a necessary way along with the enlargement of the device.
At present, the two-stage hydrocracking technology is in vigorous demand, the product structure is also required to be adjusted to the maximum production of chemical raw materials while raw materials are processed, and high-quality raw materials are provided for the catalytic reforming device and the ethylene device while fuel oil is reduced, so that the method is suitable for the rapid increase of the demands of basic chemical raw materials such as aromatic hydrocarbon, ethylene and the like in domestic markets. In addition, for the requirement of aromatic hydrocarbon, two-stage hydrocracking of heavy naphtha with high yield becomes the most hot process unit, and how to further improve the yield of heavy naphtha to provide high-quality feed for the catalytic reforming device has become a key judgment of technical advancement.
CN201517589. X discloses a two-stage full-cycle hydrogenation method to overcome the defects of high energy consumption, environmental damage to generated flue gas and the like of the existing hydrogenation device. The method comprises the following steps: fresh feed and a first-stage reaction product exchange heat and are heated and then enter a first-stage hydrofining reactor for reaction; and the first-stage refined product and the second-stage mixed feed are subjected to heat exchange and then enter a first-stage hydrocracking reactor, the first-stage reaction product of the first-stage hydrocracking reactor is mixed with the second-stage reaction product, and then the mixture is cooled by a steam generator and then sequentially enters a reaction part separation system and a fractionation part separation system for separation to obtain a hydrogenation product.
CN201210408340.9 discloses a hydrocracking process for producing high quality jet fuel from poor quality feedstock. The inferior raw oil is subjected to hydrofining reaction, the hydrofining effluent is subjected to gas-liquid separation, liquid is subjected to fractionation, tail oil obtained by fractionation is subjected to hydrocracking reaction, and a cracking reaction zone comprises two hydrocracking catalysts I and II with different molecular sieve contents. In the method, the upstream catalyst I in the cracking reaction zone has stronger aromatic hydrocarbon conversion capability, can convert aromatic hydrocarbon in the raw material heavy components into smaller molecules, and is distributed into naphtha and aviation kerosene fractions, and the downstream catalyst II has stronger alkane cracking capability.
CN20110353765. X discloses a two-stage hydrogenation process for producing solvent oils. Biological grease is used as raw oil, the raw oil and hydrogen are mixed under the hydrogenation condition and pass through a first stage hydrogenation reaction zone, hydrogen-rich gas obtained by separating hydrogenation generated material flows is recycled in the first stage, liquid obtained by separation enters a second stage hydrocracking reaction zone, secondary hydrogen gas obtained by separating oil generated by second stage hydrogenation is recycled in the second stage, and liquid products obtained by separation are fractionated to obtain various solvent oil products.
The invention relates to a two-stage hydrocracking method of a high-nitrogen raw material, which takes high-nitrogen heavy distillate oil as a raw material, adopts two-stage process flow, mixes the heavy distillate oil raw material and hydrogen into a first-stage reaction zone under the condition of hydrofining, and the effluent of the first-stage reaction zone enters a separation system; the liquid phase separated from the effluent of the first stage reaction zone and hydrogen enter a second stage reaction zone, and the reaction effluent enters a separation system to obtain a hydrocracking reaction product.
In the prior art, the energy consumption of the two-stage process is optimized, the aromatic hydrocarbon of the product is removed, and the running period of the device is prolonged, but the method for improving the yield of the heavy naphtha of the two-stage process is not involved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention discloses a two-stage hydrocracking method, which can reduce the deactivation rate of a two-stage hydrocracking catalyst and increase the selectivity of a high-quality heavy naphtha product.
A two-stage hydrocracking process comprising the following: the effluent of the first-stage hydrocracking reaction enters a flash separator to separate a liquid phase flow and a gas phase flow, the liquid phase flow enters a fractionation system to separate heavy naphtha and tail oil, the gas phase flow is mixed with the tail oil and then undergoes a second-stage hydrocracking reaction, the gas phase separated from the effluent of the second-stage hydrocracking reaction is used as circulating hydrogen of the first-stage hydrocracking reaction after gas-liquid separation, and the liquid phase enters the fractionation system to separate gas phase products, light naphtha, heavy naphtha and tail oil.
In the above method, the raw oil is wax oil or diesel oil component, preferably wax oil, the final distillation point of the wax oil is generally 450-540 ℃, preferably 480-530 ℃, and the density is generally 0.93g/cm 3 Hereinafter, it is preferably 0.92g/cm 3 Hereinafter, the nitrogen content is generally 0.08% by weight or more, preferably 0.10% by weight or more, and the sulfur content is generally 0.5% by weight or more, preferably 0.8% wt% or more. The wax oil can be various straight-run wax oil obtained by processing naphthenic base crude oil, intermediate base crude oil or paraffin base crude oil or secondary processed wax oil, and the like, or can be an oil product obtained by mixing the various wax oils, and can be any liquid-phase oil product suitable for being used as a raw material of a hydrocracking deviceThe application range is within.
In the method, the hydrocracking catalyst filled in the first-stage hydrocracking reaction zone and the second-stage hydrocracking reaction zone contains hydrogenation active metal and acidic molecular sieve components, and the hydrocracking catalyst can be selected from various existing commercial catalysts and can also be prepared according to the prior art.
In the method, the first-stage hydrocracking reaction is provided with a first-stage hydrocracking reaction zone and a first-stage hydrocracking reaction zone, the first-stage hydrocracking reaction zone is filled with a hydrotreating catalyst, and the first-stage hydrocracking reaction zone is filled with a hydrocracking reaction zone.
In the above method, the one-stage hydrogenation pretreatment catalyst comprises a carrier and a supported hydrogenation active metal. Typically comprising a metal component of group VIB of the periodic Table of elements, such as tungsten and/or molybdenum, in an oxide amount of 10% to 35%, preferably 15% to 30%, based on the weight of the catalyst; the group VIII metal, such as nickel and/or cobalt, is present in an amount of 1% to 7%, preferably 1.5% to 6% by weight of the oxide. The carrier is inorganic refractory oxide and may be selected from alumina, amorphous silica-alumina, silica, titania, etc. Wherein the hydrocracking pretreatment catalyst can be selected from various conventional commercial catalysts, such as FF-36, FF-46, FF-56, FF-66 and other hydrocracking pretreatment catalysts developed by Dalian petrochemical institute (FRIPP); or may be prepared according to the common sense in the art according to actual needs.
In the above method, the operating conditions of the first-stage hydrotreatment reaction zone are as follows: the operating pressure is 11.5-14.5 MPa, the hydrogen-oil volume ratio is 600:1-1100:1, and the volume airspeed is 0.3-5.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the operation pressure is 12.0-14.0 MPa, and the hydrogen-oil volume ratio is 600:1-1000:1.
In the method, the hydrocracking catalyst filled in the first-stage hydrocracking reaction zone contains 10% -30%, preferably 15% -25%, of hydrogenation active metal oxide and more than 50% of molecular sieve by weight, wherein the hydrogenation active metal comprises one or more of Wo, mo, co, ni, and the molecular sieve comprises but is not limited to Y-type or USY molecular sieve. Hydrocracking catalysts such as FC-24, FC-46, FC-52 developed by Dalian petrochemical institute (FRIPP); or may be prepared according to the common sense in the art according to actual needs.
In the method, the reaction condition of the first-stage hydrocracking reaction zone is that the operating pressure is 11.5-14.5 MPa, the hydrogen-oil volume ratio is 700:1-1200:1, and the volume airspeed is 0.4-6.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the operation pressure is 12.0-14.0 MPa, and the hydrogen-oil volume ratio is 700:1-1100:1.
In the method, the flash separator can be a flash tank, the operation pressure is 11-14 MPa, preferably 11.5-13.5 MPa, and the temperature is 80-120 ℃, preferably 85-115 ℃. The flash evaporation condition can flash hydrogen sulfide, ammonia and light hydrocarbon components, and the inventor discovers that the crystallization of the hydrogen sulfide and the ammonia can be inhibited in the presence of the light hydrocarbon, so that the pipeline is prevented from being blocked, and the operation period is prevented from being influenced.
In the method, a hydrocracking reaction zone is arranged in the two-stage hydrocracking reaction, and the hydrocracking catalysts filled in the hydrocracking reaction zone can be the same or different as the hydrocracking catalysts adopted in the same-stage hydrocracking reaction. The hydrocracking catalyst contains 10% -30%, preferably 15% -25%, of hydrogenation active metal oxide and more than 50% of molecular sieve by weight, wherein the hydrogenation active metal comprises one or more of Wo, mo, co, ni, and the molecular sieve comprises but is not limited to Y-type or USY molecular sieve. Hydrocracking catalysts such as FC-24, FC-46, FC-52 developed by Dalian petrochemical institute (FRIPP); or may be prepared according to the common sense in the art according to actual needs.
In the method, the reaction condition of the two-stage hydrogenation reaction is that the operating pressure is 10.5-13.5 MPa, the volume ratio of hydrogen to oil is 700:1-1200:1, and the volume airspeed is 0.5-6.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the operation pressure is 11.0-13.0 MPa, and the hydrogen-oil volume ratio is 700:1-1000:1.
In the method, the conversion rate of the first-stage hydrocracking reaction is controlled to be 50-75%, preferably 55-70%, and the conversion rate of the second-stage hydrocracking reaction is controlled to be 50-75%, preferably 55-70%. The conversion is defined as the conversion of the fraction at >177 ℃ in one stage, [1- (unconverted oil amount/fresh feed amount) ]. Times.100%, and the conversion of the recycle oil at >177 ℃ in the second stage, generally {1- [ recycle oil amount/(fresh feed amount+recycle oil amount) ] }. Times.100%.
In the method, a fractionating tower can be adopted in the fractionating system, specific operation conditions are not described in detail, products produced by the fractionating system mainly comprise gas-phase products, light naphtha and heavy naphtha, and fractions heavier than the heavy naphtha are used as circulating oil for carrying out secondary hydrocracking reaction.
The method improves the requirements of oil refining enterprises on the target product high-quality heavy naphtha through the optimization and transformation of the flow, fully utilizes the advantages and characteristics of hydrogen sulfide, ammonia and light hydrocarbon components on the reaction process, and improves the reaction effect. Specifically, no extra gas is needed to be introduced, and the optimization effect is achieved only through hydrogen sulfide, ammonia gas and light gas generated by one-stage hydrocracking reaction.
In the conventional two-stage hydrocracking device, the two-stage hydrocracking catalyst has the risk of sulfur loss and relatively high activity loss due to the operation under the sulfur-free condition. In addition, in the conventional two-stage hydrocracking device, the two-stage hydrocracking catalyst is operated under the condition of no ammonia inhibition, so that the reaction is too severe, secondary and repeated cracking side reactions are more, and the heavy naphtha yield is lower. In addition, due to the introduction of light hydrocarbon, the concentration of a reaction product is improved as an ideal component, the heavy naphtha is restrained from being further converted into light components, the hydrogen partial pressure of a system is reduced, and the aromatic potential of the heavy naphtha is improved. In addition, the method avoids the first-stage heavy naphtha from entering the second-stage reactor through the control of the parameters of the flash tank, and removes non-ideal components to the maximum extent to enter the second-stage hydrocracking reaction zone while realizing the advantages, thereby further improving the yield of the heavy naphtha and having strong practical advantages. The invention does not need the help of additional auxiliary materials, can realize the maximum production process of high-quality heavy naphtha by only using the self-processed raw materials and the optimized and improved process, is very in line with the requirement of the current oil refining chemical enterprises on the product structure of the hydrocracking device, and has stronger application value.
Drawings
FIG. 1 is a schematic flow chart of a specific method of the present invention.
Wherein 1 is raw oil, 2 is a first-stage hydrogenation reaction zone, 3 is a first-stage reaction effluent, 4 is a flash separation system, 5 is a separated gas phase component, 6 is a separated liquid phase component, 7 is a fractionation system, 8 is a gas phase product, 9 is light naphtha, 10 is heavy naphtha, 11 is tail oil (circulating oil), 12 is a second-stage reaction zone, 13 is a second-stage reaction effluent, 14 is a separation system, 15 is circulating hydrogen, and 16 is a separated liquid phase.
Detailed Description
The two-stage hydrocracking process of the present invention is described in detail below with reference to the accompanying drawings, which simplify and integrate some conventional and necessary components, such as water injection systems, hydrogen recycle systems, hydrogen chilling systems, etc.
As shown in fig. 1, the process flow of the invention is as follows: the conventional raw oil 1 and the circulating hydrogen 15 are mixed and then enter a first-stage hydrogenation reaction zone 2 for reaction, a first-stage reaction effluent 3 discharged from the bottom enters a flash separation system 4 for gas-liquid separation, a separated gas-phase component 5 is obtained at the upper part, and a separated liquid-phase component 6 obtained at the bottom enters a subsequent fractionation system 7; the gas phase product 8 is discharged from the top of the fractionating system 7, the light naphtha 9 is discharged from the middle upper part, the heavy naphtha 10 is discharged from the middle lower part, the circulating oil 11 obtained from the bottom is mixed with the separated gas phase component 5 and then enters the second-stage reaction zone 12 for reaction, the second-stage reaction effluent 13 discharged from the bottom enters the separating system 14, the obtained circulating hydrogen 15 is mixed with the raw oil 1, and the separated liquid phase 16 enters the fractionating system 7 and then is subjected to the fractionation and circulation process of the product again.
The operation and effects of the method of the present invention will be further described with reference to examples and comparative examples. In the context of the present invention, if not specified,% are mass percentages, the corresponding cut points are 177 ℃, the process of the present invention is used in the examples, and the conventional two-stage hydrocracking process is used in the comparative examples. The properties of the raw oil are shown in Table 1, the main physical and chemical properties of the catalyst are shown in Table 2, the operating conditions are shown in Table 3, and the effect comparison is shown in Table 4.
Example 1
The feedstock in Table 1 was processed, with a primary reaction zone grading using FF-66 hydrocracking pretreatment and FC-46 hydrocracking catalyst, the loading volume ratio of the two being 3:2, with a primary conversion of 60% being controlled, and the resultant liquid components entering a flash separator at an operating pressure of 13.5MPa and a temperature of 99 ℃. The liquid phase at the bottom of the separator enters a fractionation system, the liquid phase at the bottom of the fractionation system and the gas phase at the top of the separator enter a second-stage reaction zone together, the second-stage is filled with an FC-46 hydrocracking catalyst, the single pass conversion rate of the second-stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Example 2
The feedstock in Table 1 was processed using FF-66 and FC-46 hydrocracking catalysts in a single stage reaction zone configuration at a loading volume ratio of 3:2, with a single stage conversion of 60% and a resultant liquid fraction entering a flash separator at an operating pressure of 13.5MPa and a temperature of 99 ℃. The liquid phase at the bottom of the separator enters a fractionation system, the liquid phase at the bottom of the fractionation system and the gas phase at the top of the separator enter a second-stage reaction zone together, the second-stage is filled with an FC-46 hydrocracking catalyst, the single pass conversion rate of the second-stage is controlled to be 70%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Example 3
The feedstock in Table 1 was processed using FF-66 and FC-46 hydrocracking catalysts in a single stage reaction zone configuration at a loading volume ratio of 3:2, with a 50% conversion in the single stage, and the resultant liquid components entering a flash separator at an operating pressure of 13.5MPa and a temperature of 101 ℃. The liquid phase at the bottom of the separator enters a fractionation system, the liquid phase at the bottom of the fractionation system and the gas phase at the top of the separator enter a second-stage reaction zone together, the second-stage is filled with an FC-46 hydrocracking catalyst, the single pass conversion rate of the second-stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Example 4
The feedstock in Table 1 was processed using FF-66 and FC-46 hydrocracking catalysts in a single stage reaction zone configuration at a loading volume ratio of 3:2, with a single stage conversion of 60% and a resultant liquid fraction entering a flash separator at an operating pressure of 13.5MPa and a temperature of 99 ℃. The liquid phase at the bottom of the separator enters a fractionation system, the liquid phase at the bottom of the fractionation system and the gas phase at the top of the separator enter a second-stage reaction zone together, the second-stage is filled with an FC-52 hydrocracking catalyst, the single pass conversion rate of the second-stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Example 5
The feedstock in Table 1 was processed using FF-66 and FC-46 hydrocracking catalysts in a single stage reaction zone configuration at a loading volume ratio of 3:2, with a single stage conversion of 60% and the resultant liquid component entering a flash separator at an operating pressure of 13.5MPa and a temperature of 109 ℃. The liquid phase at the bottom of the separator enters a fractionation system, the liquid phase at the bottom of the fractionation system and the gas phase at the top of the separator enter a second-stage reaction zone together, the second-stage is filled with an FC-46 hydrocracking catalyst, the single pass conversion rate of the second-stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Comparative example 1
The raw materials in the table 1 are processed, the first-stage reaction zone is graded by using FF-66 and FC-46 hydrocracking catalysts, the filling volume ratio of the FF-66 and the FC-46 hydrocracking catalysts is 3:2, the conversion rate of the first stage is controlled to be 60%, the produced liquid component enters a separation and fractionation device, the bottom liquid phase enters a second-stage reaction zone, the second-stage reaction adopts pure hydrogen, the second-stage is filled by using the FC-46 hydrocracking catalysts, the single-pass conversion rate of the second-stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Comparative example 2
The raw materials in the table 1 are processed, the first-stage reaction zone is graded by using FF-66 and FC-46 hydrocracking catalysts, the filling volume ratio of the FF-66 and the FC-46 hydrocracking catalysts is 3:2, the conversion rate of the first stage is controlled to be 60%, the produced liquid component enters a separation and fractionation device, the bottom liquid phase enters a second-stage reaction zone, the second-stage gas phase is subjected to sulfur supplementing operation, the concentration of hydrogen sulfide is controlled to be 1000 mu l/l, the second-stage filling is performed by using the FC-46 hydrocracking catalysts, the single-pass conversion rate of the second stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Comparative example 3
The raw materials in the table 1 are processed, the first-stage reaction zone is graded by using FF-66 and FC-46 hydrocracking catalysts, the filling volume ratio of the FF-66 and the FC-46 hydrocracking catalysts is 3:2, the conversion rate of the first stage is controlled to be 60%, the produced liquid component enters a separation and fractionation device, the bottom liquid phase enters a second-stage reaction zone, sulfur and ammonia supplementing operation is carried out in the second-stage gas phase, the concentration of hydrogen sulfide is controlled to be 1000 mu l/l, the concentration of ammonia is controlled to be 500 mu l/l, the second-stage filling is carried out by using FC-46 hydrocracking catalysts, the single-pass conversion rate of the second stage is controlled to be 60%, and the reacted liquid phase enters a subsequent separation and fractionation system.
Table 1 table of raw oil properties
TABLE 2 Primary physicochemical Properties of catalysts
TABLE 3 hydrogenation reaction conditions
TABLE 4 comparison of effects of different conditions
As can be seen from the above examples and comparative examples, the two-stage hydrocracking apparatus not employing the present invention has problems of lower heavy naphtha yield, poorer quality and faster catalyst deactivation. The hydrocracking device provided by the invention can fully exert the benefits of hydrogen sulfide, ammonia and light hydrocarbon in the primary reaction process through reasonable utilization of the primary reaction process gas, and achieves the purposes of long-period operation and high-quality heavy naphtha yield increase. From the effect, the bottleneck of maximizing the heavy naphtha yield of the conventional two-stage hydrocracking device is broken through, the vigorous demand of a refining enterprise on gasoline or aromatic hydrocarbon raw materials is further met, and the problems of short period and reduced hydrogenation performance caused by sulfur loss of the two-stage catalyst are solved to the greatest extent.
The flash separator is additionally arranged in the process flow and is assisted in the means of temperature control, so that the secondary reaction of the high-quality target components is reduced, the inhibition effect of the target components is improved, the high-quality heavy stone yield is further improved, and the ideal comprehensive processing effect can be obtained. The method has the advantages of low operation cost, simple flow and the like in practical application, and has wide application prospect.
Claims (18)
1. A two-stage hydrocracking process characterized by: the method comprises the following steps: the effluent of the first-stage hydrocracking reaction enters a flash separator to separate a liquid phase flow and a gas phase flow, the liquid phase flow enters a fractionation system to separate heavy naphtha and tail oil, the gas phase flow is mixed with the tail oil and then undergoes a second-stage hydrocracking reaction, the gas phase separated from the effluent of the second-stage hydrocracking reaction is used as circulating hydrogen of the first-stage hydrocracking reaction, and the liquid phase enters the fractionation system to separate gas phase products, light naphtha, heavy naphtha and tail oil; the raw oil is wax oil or diesel oil; the hydrocracking catalyst filled in the first-stage hydrocracking reaction zone and the second-stage hydrocracking reaction zone contains hydrogenation active metal and an acidic molecular sieve component; the first-stage hydrocracking reaction is provided with a first-stage hydrocracking reaction zone and a first-stage hydrocracking reaction zone, wherein the first-stage hydrocracking reaction zone is filled with a hydrocracking catalyst, and the first-stage hydrocracking reaction zone is filled with a hydrocracking catalyst; the reaction condition of the first-stage hydrocracking reaction zone is that the operating pressure is 11.5-14.5 MPa, the hydrogen-oil volume ratio is 700:1-1200:1, and the reaction pressure is highThe product space velocity is 0.4 to 6.0. 6.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction condition of the two-stage hydrogenation reaction is that the operating pressure is 10.5-13.5 MPa, the volume ratio of hydrogen to oil is 700:1-1200:1, and the volume airspeed is 0.5-6.0 h -1 。
2. The method according to claim 1, characterized in that: the raw oil is wax oil with the final distillation point of 450-540 ℃ and the density of 0.93g/cm 3 The nitrogen content is 0.08wt% or more and the sulfur content is 0.5wt% or more.
3. The method according to claim 2, characterized in that: the final distillation point of the wax oil is 480-530 ℃ and the density is 0.92g/cm 3 The nitrogen content is 0.10% or more and the sulfur content is 0.8. 0.8 wt% or more.
4. The method according to claim 1, characterized in that: the wax oil is various straight-run wax oil or secondary processed wax oil obtained by processing naphthenic base crude oil, intermediate base crude oil or paraffin base crude oil, or is oil products obtained by mixing various wax oils.
5. The method according to claim 1, characterized in that: the first-stage hydrogenation pretreatment catalyst comprises a carrier and supported hydrogenation active metal, wherein the weight of the catalyst is taken as a reference, and the catalyst comprises 10% -35% of metal components of VIB group in the periodic table in terms of oxide; the content of the group VIII metal is 1% -7% in terms of oxide.
6. The method according to claim 1, characterized in that: the first-stage hydrogenation pretreatment catalyst comprises a carrier and supported hydrogenation active metal, wherein the weight of the catalyst is taken as a reference, and the catalyst comprises 15% -30% of metal components of VIB group in the periodic table in terms of oxide; the content of the metal of the VIII family is 1.5% -6% calculated by oxide.
7. The method according to claim 1, characterized in that: the operating conditions of the first-stage hydrogenation pretreatment reaction zone are as follows: the operating pressure is 11.5-14.5 MPa, the hydrogen-oil volume ratio is 600:1-1100:1, and the volume airspeed is 0.3-5.0 h -1 。
8. The method according to claim 1, characterized in that: the operating conditions of the first-stage hydrogenation pretreatment reaction zone are as follows: the operating pressure is 12.0-14.0 MPa, and the hydrogen-oil volume ratio is 600:1-1000:1.
9. The method according to claim 1, characterized in that: the hydrocracking catalyst filled in the first-stage hydrocracking reaction zone contains 10% -30% of hydrogenation active metal oxide and more than 50% of molecular sieve by weight, wherein the hydrogenation active metal comprises one or more of Wo, mo, co, ni, and the molecular sieve comprises Y-type or USY molecular sieve.
10. The method according to claim 9, wherein: the hydrocracking catalyst filled in the first-stage hydrocracking reaction zone contains 15-25% of hydrogenation active metal oxide by weight.
11. The method according to claim 1, characterized in that: the reaction condition of the first-stage hydrocracking reaction zone is that the operating pressure is 12.0-14.0 MPa, and the volume ratio of hydrogen to oil is 700:1-1100:1.
12. The method according to claim 1, characterized in that: the flash separator is a flash tank, the operating pressure is 11-14 MPa, and the temperature is 80-120 ℃.
13. The method according to claim 1, characterized in that: the flash separator is a flash tank, the operating pressure is 11.5-13.5 MPa, and the temperature is 85-115 ℃.
14. The method according to claim 1, characterized in that: the second-stage hydrocracking reaction is provided with a hydrocracking reaction zone, the hydrocracking catalyst contains 10% -30% of hydrogenation active metal oxide and more than 50% of molecular sieve by weight, the hydrogenation active metal comprises one or more of W, mo, co, ni, and the molecular sieve comprises Y-type or USY molecular sieve.
15. The method according to claim 12, wherein: the second-stage hydrocracking reaction is provided with a hydrocracking reaction zone, and the hydrocracking catalyst contains 15-25% of hydrogenation active metal oxide by weight.
16. The method according to claim 1, characterized in that: the reaction condition of the two-stage hydrogenation reaction is that the operating pressure is 11.0-13.0 MPa, and the volume ratio of hydrogen to oil is 700:1-1000:1.
17. The method according to claim 1, characterized in that: the conversion rate of the first-stage hydrocracking reaction is controlled to be 50-75%, and the conversion rate of the second-stage hydrocracking reaction is controlled to be 50-75%.
18. The method according to claim 1, characterized in that: the conversion rate of the first-stage hydrocracking reaction is controlled to be 55-70%, and the conversion rate of the second-stage hydrocracking reaction is controlled to be 55-70%.
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| CN101173189A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
| CN109777509A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of two-segment hydrocracking method |
| CN109777500A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of two-segment hydrocracking method of gas-liquid counter current |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173189A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
| CN109777509A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of two-segment hydrocracking method |
| CN109777500A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of two-segment hydrocracking method of gas-liquid counter current |
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