CN115216337A - Production method of high-octane gasoline - Google Patents
Production method of high-octane gasoline Download PDFInfo
- Publication number
- CN115216337A CN115216337A CN202110403341.3A CN202110403341A CN115216337A CN 115216337 A CN115216337 A CN 115216337A CN 202110403341 A CN202110403341 A CN 202110403341A CN 115216337 A CN115216337 A CN 115216337A
- Authority
- CN
- China
- Prior art keywords
- zone
- reaction
- hydrofining
- liquid
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 133
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 68
- 239000002283 diesel fuel Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011344 liquid material Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 56
- 239000007791 liquid phase Substances 0.000 claims description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 239000012530 fluid Substances 0.000 abstract description 3
- 238000006757 chemical reactions by type Methods 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 description 13
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910017313 Mo—Co Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (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 production method of high-octane gasoline. The method comprises the following steps: hydrogen enters from the lower part of the fixed bed reactor, a catalytic diesel oil raw material enters from the upper part of the fixed bed reactor, and gas-liquid material flows are in contact reaction in the reactor to obtain a high-octane gasoline component and a diesel oil blending component; wherein the fixed bed reactor is internally provided with a gasoline hydrofining area, a raw material pretreatment area, a hydrocracking reaction area, a gas-liquid contact area and a diesel hydrofining area from top to bottom in sequence. According to the invention, according to the characteristic that the raw materials consist of light to heavy hydrocarbons, high-octane components in each reaction process are retained to the maximum extent by controlling the fluid state, the reaction phase state, the reaction conditions and the reaction type in a subarea manner, so that the poor-quality catalytic diesel oil raw material is efficiently converted into high-octane gasoline.
Description
Technical Field
The invention belongs to the field of oil refining and chemical engineering, and particularly relates to a production method of high-octane gasoline.
Background
In China, catalytic cracking is a main processing means for converting heavy oil into light oil, and one of the products, namely catalytic diesel oil, accounts for about 30% of a diesel oil pool. Along with the gradual heaviness and deterioration of crude oil, the operation severity of a catalytic cracking unit needs to be improved, so that the quality of catalytic cracking diesel oil is further deteriorated, and huge pressure is caused on subsequent processing and conversion.
The main processing means of catalytic diesel include hydrofinishing and hydrocracking. Through hydrofining, S, N and other impurities in the raw materials can be removed, the content of aromatic hydrocarbon is reduced, and the blending component of the diesel oil for vehicles is produced. However, the aromatic hydrocarbon content in the catalytic diesel oil is up to more than 60%, and more than half of the catalytic diesel oil is polycyclic aromatic hydrocarbon, so that the cetane number of a refined diesel oil product is far away from the quality standard, and the refined diesel oil product can only be blended with other relatively high-quality diesel oil raw materials. The hydrocracking technology can convert a large amount of polycyclic aromatic hydrocarbon into monocyclic aromatic hydrocarbon, paraffin hydrocarbon and the like through hydrogenation saturation, ring opening and cracking of macromolecular aromatic hydrocarbon, thereby realizing the production of high-quality diesel oil and gasoline products. However, the hydrocracking technology also has the problems of high hydrogen consumption of the device and high operation energy consumption.
In recent years, along with gradual slow growth of the market demand of the diesel for vehicles, the reduction of the diesel-gasoline ratio is the main aim of improving the quality and increasing the efficiency by adjusting the refining structure of each oil refinery. Wherein, the high-efficient utilization and conversion of the poor-quality diesel creates a new profit margin for the refinery to reduce the diesel and increase the production of high added-value products. For example, technologies of converting catalytic cracking diesel into high-octane gasoline and aromatic hydrocarbon raw materials, converting coking diesel into ethylene raw materials and the like are all based on the property and composition characteristics of inferior diesel, and are reasonably utilized and converted to produce target products. The technology for producing high-octane gasoline by using catalytic diesel oil as a raw material is to convert the high-octane gasoline into monocyclic aromatic hydrocarbon without further cracking by using an acidic catalyst by utilizing the characteristic of high content of bicyclic aromatic hydrocarbon, and the monocyclic aromatic hydrocarbon is used as a proper high-octane gasoline component. The technology has already realized industrial application at present, and can realize the production of gasoline and diesel oil blending components by taking catalytic diesel oil as a raw material, wherein the octane number of the gasoline is over 90, and the S content of the diesel oil can be less than 10ppm. However, the chemical hydrogen consumption of the technology is more than 3 percent, wherein the hydrogen is consumed in the necessary reactions of conversion of polycyclic aromatic hydrocarbon to monocyclic aromatic hydrocarbon, desulfurization, denitrification and the like,the catalyst also inevitably generates saturation reaction with the olefin originally contained in the catalytic diesel oil, and since the catalytic cracking follows the reaction of a carbonium ion mechanism, the olefin has high proportion of isomeric compounds and is a high-quality high-octane component, and certain hydrocarbon resources are wasted when the olefin is saturated. In addition, hydrocracking is a traditional trickle bed reaction system, and requires a large amount of hydrogen recycle and cold hydrogen injection to reduce the H exposure of the reaction process 2 S and NH 3 The influence of the cracking reaction and the control of bed temperature rise caused by heat release in the cracking reaction process, and the energy consumption of the whole reaction system is higher.
CN104611062B discloses a method for producing high-octane gasoline, which utilizes the characteristics of hydrocracking and reactive distillation processes to reduce the secondary cracking of light fractions and improve the yield of gasoline.
CN108624356A discloses a catalytic diesel hydroconversion process, which reduces the hydrogenation saturation in gasoline components and improves the gasoline octane number by grading a refining agent and a cracking agent. However, the catalytic diesel oil full-fraction contact refining agent provided by the invention can greatly saturate isoolefins (high-octane-value components) enriched in light components in catalytic diesel oil, so that hydrogen resources are consumed unnecessarily, and the retention of the octane value of gasoline components is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a production method of high-octane gasoline. According to the invention, according to the characteristic that the raw materials consist of light to heavy hydrocarbons, high-octane components in each reaction process are retained to the maximum extent by controlling the fluid state, the reaction phase state, the reaction conditions and the reaction type in a subarea manner, so that the poor-quality catalytic diesel oil raw material is efficiently converted into high-octane gasoline.
The production method of the high-octane gasoline comprises the following steps: hydrogen enters from the lower part of the fixed bed reactor, a catalytic diesel oil raw material enters from the upper part of the fixed bed reactor, and gas-liquid material flows are in contact reaction in the reactor to obtain a high-octane gasoline component and a diesel oil blending component; wherein a gasoline hydrofining zone, a raw material pretreatment zone, a hydrocracking reaction zone, a gas-liquid contact zone and a diesel hydrofining zone are arranged in the fixed bed reactor from top to bottom in sequence;
the method comprises the following specific steps: hydrogen firstly enters a gas-liquid contact zone at the lower part of the fixed bed reactor and contacts with a liquid-phase product flowing out from the bottom of a hydrocracking reaction zone, and the hydrogen flows upwards and sequentially passes through the hydrocracking reaction zone, a raw material pretreatment zone and a gasoline hydrofining zone; the liquid phase product enters a hydrocracking reaction zone, the liquid phase product downwards enters a diesel oil hydrofining zone for liquid phase hydrogenation reaction, and the reaction effluent is discharged from the bottom of the reactor;
the catalytic diesel oil raw material enters a raw material pretreatment area at the upper part of a fixed bed reaction area, part of the material is converted into a gas phase raw material under certain conditions, the gas phase raw material and gas phase components from a hydrocracking reaction area enter a gasoline hydrofining area together for reaction, reaction products are discharged from the top of a reactor, and high-octane gasoline is obtained through condensation;
the residual liquid-phase component in the catalytic diesel oil raw material flows downwards to enter a hydrocracking reaction zone and is in countercurrent contact reaction with hydrogen from a gas-liquid contact zone to obtain a liquid-phase product.
In the method, the distillation range of the catalytic diesel raw material is 180-380 ℃, S is no more than 15000 mu g/g, N is no more than 500 mu g/g, and polycyclic aromatic hydrocarbon is no more than 70wt%.
In the method, the raw material pretreatment area is used for converting the fraction below 220 ℃ in the raw material into a gas-phase component to enter a gasoline hydrofining area, and the unconverted component enters a hydrocracking reaction area in a liquid phase state.
The operation conditions of the raw material pretreatment zone are as follows: the pressure is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 45 to 80 percent of the total pressure; the feed temperature is from 200 to 380 ℃ and preferably from 260 to 320 ℃.
In the method, the gasoline hydrofining area is used for carrying out selective hydrodesulfurization reaction on gas-phase components from the raw material pretreatment area, a gasoline selective hydrodesulfurization catalyst is filled in the reaction area, mo-Ni or Mo-Co is generally used as a catalyst active metal, and Al 2 O 3 Is used as a carrier, and the metal loading amount is 10-20 wt%. The FGH-11/FGH-20 catalyst grading system developed by FRIPP is preferred. The filling volume proportion of the catalyst in the gasoline hydrofining area is 1-60 percent, preferably 5 percent based on the total filling amount of the catalyst in the reactor40 percent; the operating conditions of the gasoline hydrofining zone are as follows: the pressure is 1.0 to 8.0MPa, preferably 2.0 to 6.0MPa, wherein the hydrogen partial pressure accounts for 40 to 70 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 6.0 hours -1 (ii) a The reaction temperature is 100 to 300 ℃, preferably 150 to 260 ℃; hydrogen-oil volume ratio 10:1 to 400:1, preferably 100:1 to 200:1.
in the method, the hydrocracking reaction zone is used for carrying out deep desulfurization, denitrification and hydrocracking on the unconverted liquid-phase component in the raw material pretreatment zone. The hydrogenation cracking reaction zone is internally graded and filled with hydrogenation refining and hydrogenation cracking catalysts, wherein the hydrogenation refining catalyst is a commercial catalyst which is generally sold in the market, mo-Ni or Mo-Co is generally used as a catalyst active metal, and Al 2 O 3 Is used as a carrier, and the metal loading is 20-35 wt%. FHUDS series catalysts, as developed by FRIPP, are preferred FHUDS-6, FHUDS-10 catalysts. The hydrocracking catalyst is a commercial hydrocracking catalyst, generally takes W-Ni as catalyst active metal and Al 2 O 3 Is used as a carrier, and the metal loading is 20-40 wt%, such as FC series catalyst developed by FRIPP. It can also be prepared according to the existing methods such as the method in CN 201710182260.9. The filling volume proportion of the catalyst in the hydrocracking reaction zone is 1-80%, preferably 30-60%. Wherein, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 5:1 to 1:5. the hydrocracking reaction zone is generally operated under the following conditions: the pressure is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 50 to 90 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 5.0 hours -1 (ii) a The reaction temperature is 220 to 400 ℃, and preferably 300 to 360 ℃; hydrogen-oil volume ratio 10:1 to 400:1, preferably 100:1 to 200:1.
in the method, the gas-liquid contact zone is used for the contact heat exchange of the hydrogen and the liquid phase effluent of the hydrocracking reaction zone, and a commercially available gas-liquid distribution inner member is generally arranged; the gas-liquid contact zone is communicated with a hydrogen source, so that parameters such as hydrogen flow, temperature and the like can be flexibly controlled according to needs, and the full contact between the ascending hydrogen and the descending liquid phase component and the mass transfer enhancement are realized. The operating condition of the gas-liquid contact zone is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the partial pressure of hydrogen accounts for 100 percent of the total pressure; the feeding temperature is 30 to 400 ℃, and preferably 200 to 340 ℃.
In the method, the diesel oil hydrofining area is used for liquid-phase hydrofining reaction of liquid-phase products in the hydrocracking reaction area, the diesel oil hydrofining area is filled with a diesel oil hydrofining catalyst, mo-Ni or Mo-Co is generally used as a catalyst active metal, and Al 2 O 3 Is used as a carrier, and the metal loading is 15% -30%. Like the FH-40 series of catalysts developed by FRIPP, preferably FH-40B catalysts. The filling volume proportion of the catalyst in the diesel oil hydrofining area is 1-40%, preferably 10-20% based on the total filling amount of the catalyst in the reactor. The diesel oil hydrofining zone is generally operated under the following conditions: the pressure is 1.0 to 6.0MPa, preferably 2.0 to 5.0MPa, the reaction zone is a pure liquid phase reaction zone, and the volume ratio of standard hydrogen to oil is 2 to 50, preferably 10 to 30; the volume airspeed is 0.1 to 8.0h -1 Preferably 0.5 to 6.0 hours -1 (ii) a The reaction temperature is 100 to 300 ℃, preferably 180 to 260 ℃.
Compared with the prior art, the method of the invention has the following advantages:
(1) The method further enriches light components such as monocyclic aromatic hydrocarbon, isoolefine and micromolecule sulfide in the catalytic diesel oil raw material and monocyclic aromatic hydrocarbon generated in the hydrocracking reaction into gasoline components through the combined action of the raw material feeding mode, the raw material pretreatment area and the hydrocracking reaction area, reserves the monocyclic aromatic hydrocarbon and the isoolefine to the maximum extent through the reaction of the gasoline hydrofining area on the upper part of the reactor, and effectively improves the octane number of the gasoline. Meanwhile, the liquid phase material in the hydrocracking reaction zone is rich in hydrocarbons with more than bicyclic aromatics, so that the hydrocracking reaction is more targeted, the reaction airspeed can be further improved, and the device treatment capacity is increased. In the hydrofining reaction zone, only the olefin saturation reaction of the effluent material from the hydrogen cracking reaction zone occurs, and because the chemical hydrogen consumption required in the zone is low, the condition can be met only by carrying dissolved hydrogen, the dissolved hydrogen is fully utilized for hydrogenation reaction, and the material flow flowing out of the reactor is not required to be cooled and separated from excessive hydrogen, so that the heat exchange equipment in the conventional technology is omitted.
(2) The hydrogen in the invention meets the chemical requirement of each reaction zoneBesides hydrogen consumption, the amount of hydrogen at the inlet can be flexibly adjusted according to the properties of raw materials and the requirements of products, so that the effects of stabilizing the reaction phase state of each reaction zone, adjusting the partial pressure of the hydrogen and reducing the content of impurities are achieved. The hydrogen inlet is arranged in a gas-liquid contact zone below the hydrocracking reaction zone, the proportion of the hydrogen which ascends in a gas phase state and descends in a liquid phase state can be controlled by adjusting the operation conditions, and the hydrogen exists in a gas phase form in the gasoline hydrofining zone and the hydrocracking reaction zone, and the hydrogen exists in a liquid phase form in the diesel hydrofining zone. The hydrocracking reaction zone has the highest requirement on hydrogen partial pressure, and the position of a hydrogen inlet can meet the requirement that the hydrogen partial pressure is highest in the zone, so that the optimization of the environment for the hydrocracking reaction of the bicyclic aromatic hydrocarbon is facilitated. In the process that hydrogen flows upwards and downwards, with the generation of light hydrocarbon and impurities and the consumption of reaction, the hydrogen partial pressure in the gasoline hydrofining area and the diesel hydrofining area is gradually reduced, but the hydrogen consumption of chemical reaction can be still met, a large amount of hydrogen surplus is not needed from top to bottom like the hydrogen consumption of a traditional fixed bed reactor, and the hydrogen consumption of the device is greatly reduced. In the hydrocracking reaction zone, hydrogen gas and reaction raw material are in counter-current flow contact, and gas-phase components (including hydrogen gas, small molecular hydrocarbon and H) 2 S, etc.) to contact with the raw oil going upwards and going downwards in the raw material pretreatment area, the mass transfer and separation are carried out, the separation effect of light and heavy components in the raw material can be enhanced, impurities are carried to quickly flow upwards and flow out of the reactor, and H is avoided 2 S、NH 3 The catalyst also carries light components such as monocyclic aromatic hydrocarbon generated by the reaction to a gasoline hydrofining zone to be used as high-octane components to enter a gasoline product, thereby increasing the yield of the gasoline, avoiding further cracking caused by too long retention time of the gasoline on the cracking catalyst and reducing excessive hydrogenation reaction. Meanwhile, the hydrogen amount is adjustable, so that the gas velocity can be adjusted according to the change of the gasification rate and the liquid fraction of the raw material in the reactor, and the flooding of a hydrocracking reaction zone is avoided.
(3) In the traditional gas-liquid-solid three-phase reaction, gas-phase hydrogen can reach the surface of a solid-phase catalyst only by penetrating liquid-phase raw oil, and the reaction efficiency is influenced due to diffusion limitation. The upper, middle and lower reaction zones are ingeniously arranged into a gas-solid reaction zone, a gas-liquid-solid reaction zone and a liquid-solid reaction zone, wherein two hydrofining zones are subjected to two-phase reaction with higher mass transfer efficiency, and the middle hydrocracking zone adopts gas-liquid reverse contact, so that the gas-liquid mass transfer driving force is enhanced, the reaction efficiency is integrally improved, and the hydrogen utilization rate is further improved. Meanwhile, the three reaction zones arranged in the invention can make the reaction system more stable under the coupling action. When gas-liquid reverse contact strengthens the mass transfer process in the hydrocracking reaction zone, along with backmixing, need stable pressure control, the gasoline hydrofining zone of the top has great compressible gas phase space, has good cushioning effect to stable bed pressure and stable fluid flow state, just can adjust the gas phase velocity of flow and the liquid layer thickness in hydrocracking reaction zone through nimble control export tolerance, has improved the gas velocity scope that takes place the flooding. The hydrocracking reaction effluent (refined liquid-phase component) is contacted with pure hydrogen through a gas-liquid contact zone, then is subjected to heat exchange and temperature reduction, and quickly enters a liquid-phase hydrogenation reaction zone (diesel oil hydrogenation reaction zone) below the hydrocracking reaction effluent, so that hydrogen escapes after entering a reactor in the hydrogen mixing process of the conventional liquid-phase hydrogenation process, and meanwhile, the diesel oil hydrogenation reaction zone below is a liquid-phase space, so that the material flow state at the outlet of the reactor can be well controlled, and if the zone does not exist, the problem that the hydrogen is carried out of the reactor without reaction through a catalyst bed layer can be caused, a high-pressure separator in the conventional process flow can be omitted, and the flow is simplified.
Drawings
FIG. 1 is a schematic diagram of a process for producing high octane gasoline according to the present invention.
In the figure: 1-raw material, 2-hydrogen, 3-gasoline hydrofining zone, 4-raw material pretreatment zone, 5-hydrocracking reaction zone, 6-gas-liquid contact zone, 7-diesel hydrofining zone, 8-gasoline hydrofining zone effluent, 9-high octane gasoline, 10-diesel hydrofining zone effluent and 11-diesel blending component.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.
The process of the invention for producing high octane gasoline is illustrated by the accompanying figure 1: the reaction raw material 1 enters the hydrogenation reactor from the raw material pretreatment zone 4. Separated into a gas phase and a liquid phase in the raw material pretreatment zone 4. The gas phase flows upwards and enters a gasoline hydrofining zone 3, and the liquid phase flows downwards and enters a hydrocracking reaction zone 5. The hydrogen 2 enters the hydrogenation reactor in the gas-liquid contact zone 6, is mixed and contacted with the liquid phase material flowing out downwards in the hydrocracking reaction zone 5, then flows upwards to enter the hydrocracking reaction zone 5, and flows downwards to enter the diesel oil hydrofining zone 7 with the hydrogen liquid phase material.
The gasoline hydrogenation refining zone 3 is subjected to gas phase reaction, mainly selective hydrodesulfurization reaction for catalyzing fractions below bicyclic aromatic hydrocarbons in diesel oil to generate an effluent 8 of the gasoline hydrogenation refining zone, and the effluent is condensed to be used as high-octane gasoline 9. The hydrocracking reaction zone 5 has gas-liquid two-phase reaction, the liquid phase is used for catalyzing the downward flow of double-ring aromatic hydrocarbon and above fraction in the diesel oil, the gas phase is used for catalyzing the upward flow of hydrogen, and the gas-liquid reverse contact is used for carrying out hydrofining and hydrocracking reaction. H formed by reaction 2 S、NH 3 And the low molecular hydrocarbon flows upwards along with the gas phase material flow to enter a hydrocracking reaction zone 5 and a gasoline hydrofining zone 3, and finally flows out of the device from the top of the reactor. The liquid phase material flow after the reaction in the hydrocracking reaction area 5 flows downwards to enter a gas-liquid contact area 6, and enters a diesel oil hydrofining area 7 after contacting with hydrogen for heat exchange, the liquid phase reaction in the diesel oil hydrofining area 7 is a supplementary refining reaction for generating olefin in the cracking process, and the diesel oil blending component 11 is obtained after the effluent 10 of the diesel oil hydrofining area flows out of the device.
Examples 1 to 3
In this example, a 100mL fixed bed hydrogenation reactor is used, and a catalyst bed layer is disposed in a gasoline hydrofining zone, a hydrocracking reaction zone and a diesel hydrofining zone from top to bottom. A selective hydrodesulfurization catalyst system A (Mo-Co type catalyst 2. The volume filling ratio of the catalyst according to the volume of the reactor A: b: c: d =20:30:40:10. catalytic diesel oil is used as raw material. The catalyst properties are shown in Table 1, the feedstock properties are shown in Table 2, and the reaction process conditions and results are shown in Table 3.
Comparative example 1
The FD2G technology for producing high-octane naphtha by catalyzing diesel oil is adopted, and raw materials are introduced into a 100mL fixed bed hydrogenation reactor and then enter a fractionating tower to obtain naphtha fraction and diesel oil fraction. The properties of the raw materials are the same as those of the embodiment, the Ni-Mo type pretreatment catalyst B and the hydrocracking catalyst C are graded and filled, the filling volume is equal to the sum of the filling of the catalysts A, B, C and D of the embodiment, and the filling volume ratio of B: c =1:1. the reaction conditions were the same as in the hydrocracking reaction zone of example 3.
Comparative example 2
A fixed bed reactor is connected with a liquid-phase hydrogenation reactor in series, the fixed bed reactor comprises a gasoline hydrofining zone, a raw material pretreatment zone and a hydrocracking reaction zone from top to bottom, raw materials enter from the raw material pretreatment zone, and hydrogen enters from the bottom of the fixed bed reactor. The top effluent of the fixed bed reactor is a high-octane gasoline product, the bottom effluent directly enters the liquid phase hydrogenation reactor without any treatment and enters from the top of the liquid phase hydrogenation reactor, a diesel oil hydrofining area is arranged in the reactor, and the bottom effluent is a diesel oil blending component. The gasoline hydrogenation refining zone, the hydrocracking reaction zone and the diesel oil hydrogenation refining zone are all provided with a catalyst bed layer. A selective hydrodesulfurization catalyst A is filled in a gasoline hydrofining area, a Ni-Mo type hydrofining catalyst B and a Ni-W type hydrocracking catalyst C are filled in a hydrocracking reaction area, and a Mo-Co type hydrofining catalyst D is filled in a diesel hydrofining area. The catalyst loading volumes and proportions were the same as in examples 1 to 3, and the reaction conditions were the same as in example 3.
TABLE 1 physicochemical Properties of the catalyst
TABLE 2 Properties of the feed oils
TABLE 3 hydrogenation process conditions and results
TABLE 3 (continuous) hydrogenation Process conditions and results
As can be seen from table 3, compared with the hydrocracking technology, the present invention has higher naphtha yield due to the inhibition of the secondary cracking of the small molecule hydrocarbons, and the reduction of the gas yield; the hydrocracking reaction zone is in gas-liquid reverse contact, and the mass transfer driving force is enhanced, so that the reaction effect is improved, the sulfur content of the diesel oil is lower, the cetane number is improved to a greater extent, and a gas-solid and liquid-solid two-phase reaction zone is arranged, so that a large amount of hydrogen is not required to be excessive, and the hydrogen consumption of the device is remarkably reduced. Compared with the process flow of independently arranging a liquid phase reactor, the process flow has the advantages that the material flow flowing out of the hydrocracking reaction zone directly carries hydrogen in the reactor to enter the diesel oil hydrofining zone, so that hydrogen escape is avoided, and in the comparative example 3, because the liquid phase hydrogenation reactor is in an upper feeding mode, part of hydrogen directly escapes from a gas phase outlet at the top of the reactor without passing through a catalyst bed layer, so that the reaction effect is influenced, and the sulfur content of refined diesel oil is influenced. Due to the deep coupling of the three reaction zone environments and the adjustable hydrogen amount, the device is always in a stable state in the test process, the product quality is always qualified, and the flooding phenomenon is not generated.
Claims (10)
1. A production method of high-octane gasoline is characterized by comprising the following steps: hydrogen enters from the lower part of the fixed bed reactor, a catalytic diesel oil raw material enters from the upper part of the fixed bed reactor, and gas-liquid material flows are in contact reaction in the reactor to obtain a high-octane gasoline component and a diesel oil blending component; wherein the fixed bed reactor is internally provided with a gasoline hydrofining zone, a raw material pretreatment zone, a hydrocracking reaction zone, a gas-liquid contact zone and a diesel hydrofining zone from top to bottom in sequence; the method comprises the following specific steps: hydrogen firstly enters a gas-liquid contact zone at the lower part of a fixed bed reactor and contacts with a liquid-phase product flowing out from the bottom of a hydrocracking reaction zone, the hydrogen flows upwards and sequentially passes through the hydrocracking reaction zone, a raw material pretreatment zone and a gasoline hydrofining zone, the liquid-phase product flows downwards and enters a diesel hydrofining zone to carry out liquid-phase hydrogenation reaction, and a reaction effluent is discharged from the bottom of the reactor; the catalytic diesel oil raw material enters a raw material pretreatment area at the upper part of a fixed bed reaction area, part of the material is converted into a gas phase material under certain conditions, the gas phase material and a gas phase component from a hydrocracking reaction area enter a gasoline hydrofining area to react, a reaction product is discharged from the top of a reactor, and high-octane gasoline is obtained through condensation; the residual liquid-phase component in the catalytic diesel raw material flows downwards to enter a hydrocracking reaction zone and is in countercurrent contact reaction with hydrogen from a gas-liquid contact zone to obtain a liquid-phase product.
2. The method of claim 1, wherein: the distillation range of the catalytic diesel raw material is 180-380 ℃, S is no more than 15000 mu g/g, N is no more than 500 mu g/g, and polycyclic aromatic hydrocarbon is no more than 70wt%.
3. The method of claim 1, wherein: the raw material pretreatment area is used for converting fractions with the temperature of below 220 ℃ in the raw material into gas-phase components to enter a gasoline hydrofining area, and the unconverted components enter a hydrocracking reaction area in a liquid phase state.
4. The method of claim 1, wherein: the operation conditions of the raw material pretreatment zone are as follows: the pressure is 3.0 to 10.0MPa, wherein the hydrogen partial pressure accounts for 45 to 80 percent of the total pressure; the feeding temperature is 200 to 380 ℃.
5. The method of claim 1, wherein: the gasoline hydrogenation refining zone is used for feeding gas-phase components from the raw material pretreatment zoneSelective hydrodesulfurization reaction, namely filling a gasoline selective hydrodesulfurization catalyst in a reaction zone; the filling volume proportion of the catalyst in the gasoline hydrofining area is 1-60% by taking the total filling amount of the catalyst in the reactor as a reference; the operation conditions of the gasoline hydrofining zone are as follows: the pressure is 1.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 40 to 70 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 (ii) a The reaction temperature is 100 to 300 ℃; hydrogen-oil volume ratio 10:1 to 400:1.
6. the method of claim 1, wherein: the hydrocracking reaction zone is used for carrying out deep desulfurization, denitrification and hydrocracking on the unconverted liquid-phase component in the raw material pretreatment zone; the hydrogenation reaction zone is internally graded and filled with hydrogenation refining and hydrocracking catalysts; the filling volume proportion of the catalyst in the hydrocracking reaction zone is 1-80%; the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 5:1 to 1:5.
7. the method of claim 1, wherein: the operating conditions of the hydrocracking reaction zone are as follows: the pressure is 3.0 to 10.0MPa, wherein the hydrogen partial pressure accounts for 50 to 90 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 (ii) a The reaction temperature is 220 to 400 ℃; hydrogen-oil volume ratio 10:1 to 400:1.
8. the method of claim 1, wherein: the gas-liquid contact zone is used for contact heat exchange between hydrogen and a liquid-phase product in the hydrocracking reaction zone; the operating condition of the gas-liquid contact zone is 3.0 to 10.0MPa, wherein the hydrogen partial pressure accounts for 100 percent of the total pressure; the feeding temperature is 30 to 400 ℃.
9. The method of claim 1, wherein: the diesel oil hydrofining area is used for liquid-phase hydrofining reaction of the dissolved hydrogen material flow, and a diesel oil hydrofining catalyst is filled in the diesel oil hydrofining area; the filling volume proportion of the catalyst in the diesel oil hydrofining area is 1-40% by taking the total filling amount of the catalyst in the reactor as a reference.
10. The method of claim 1, wherein: the diesel oil hydrofining area has the following operating conditions: the pressure is 1.0 to 6.0MPa, the reaction zone is a liquid phase reaction zone, and the volume ratio of standard hydrogen to oil is 2 to 50; the volume airspeed is 0.1 to 8.0h -1 (ii) a The reaction temperature is 100 to 300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110403341.3A CN115216337B (en) | 2021-04-15 | 2021-04-15 | Production method of high-octane gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110403341.3A CN115216337B (en) | 2021-04-15 | 2021-04-15 | Production method of high-octane gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115216337A true CN115216337A (en) | 2022-10-21 |
| CN115216337B CN115216337B (en) | 2023-10-10 |
Family
ID=83605317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110403341.3A Active CN115216337B (en) | 2021-04-15 | 2021-04-15 | Production method of high-octane gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115216337B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552819A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Light hydrocarbon hydrogenation method |
| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN101987971A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for producing high-octane petrol by inferior diesel |
-
2021
- 2021-04-15 CN CN202110403341.3A patent/CN115216337B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552819A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Light hydrocarbon hydrogenation method |
| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN101987971A (en) * | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for producing high-octane petrol by inferior diesel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115216337B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1111587C (en) | Process for increased olefin yields from heavy feedstocks | |
| CN103059972B (en) | Combined hydrogenation method of producing chemical materials | |
| CN102465018B (en) | Technological method for hydrogenation of coker full-range distillate | |
| CN102453535A (en) | Hydrocracking method for reforming material yield increase | |
| CN102876371B (en) | Inferior raw material hydrocracking method | |
| CN105754647A (en) | A combined method for catalytic diesel oil hydro-conversion and catalytic gasoline selective hydrogenation | |
| CN103059986A (en) | Hydrocracking method for producing chemical materials | |
| TWI811819B (en) | Reaction System and Reaction Method of Multiphase State Combination | |
| CN108102709A (en) | The processing and treating method of catalytic diesel oil | |
| CN109988631B (en) | Method for producing gasoline and base oil by catalyst grading technology | |
| CN115216341B (en) | Medium-low temperature coal tar processing system and processing method | |
| CN115216337A (en) | Production method of high-octane gasoline | |
| CN108102702A (en) | The processing method of catalytic diesel oil | |
| CN109988651B (en) | Method for producing gasoline by catalyst grading technology | |
| CN100381542C (en) | One-stage tandem combined process for hydrocracking- aryl removal | |
| CN114456838B (en) | Production method of ethylene steam cracking raw material | |
| CN114437804B (en) | Hydrocracking method of high-nitrogen raw oil | |
| CN114437801B (en) | Two-stage hydrocracking method | |
| CN114736708B (en) | Wax oil liquid phase hydrotreating method | |
| CN113122319B (en) | Hydrocracking process for producing high-quality reforming raw material | |
| CN102533327A (en) | Single-stage inferior gasoline fraction hydrotreatment process method | |
| CN114437799B (en) | Hydrocracking method | |
| CN115703978B (en) | Method for producing light aromatic hydrocarbon | |
| CN115216338B (en) | Coking full distillate oil processing method | |
| CN116004282B (en) | Hydrocracking method for producing jet fuel with high smoke point |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231222 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |